CN113524933B - Preparation method of modified alkyd resin and application of modified alkyd resin in printing ink - Google Patents
Preparation method of modified alkyd resin and application of modified alkyd resin in printing ink Download PDFInfo
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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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Abstract
The invention discloses a preparation method of modified alkyd resin and application thereof in printing ink, 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 residues, and drying the filter residues to obtain modified cellulose; d2, mixing alkyd resin, the modified cellulose, anhydride and an anti-aging agent, then blending and extruding a blank; and D3, crushing the blank, and sieving to obtain the modified alkyd resin. The modified alkyd resin is mainly used for preparing ink, and the ink prepared by the method has good adhesion fastness and glossiness.
Description
Technical Field
The invention relates to the technical field of ink, in particular to a preparation method of modified alkyd resin and application of the modified alkyd resin in the ink.
Background
The printing industry is a long-history and large-scale system industry. Since the advent of the ancient chinese printing technology, the number and quality of books printed is constantly advancing with the improvement of technology level. With the development of the times and the technology level, more and more industrial and biochemical fields need to use various fine novel printing technologies capable of meeting various severe requirements. Nowadays, printing technology is not just a traditional technology for only serving physical books, and in modern life, advertising, posters, various cultural relics, propaganda products and the like, even including ceramic, wood, metal and the like products, are becoming the range of the printing of the surface of an object. This therefore places not only higher demands on the printing machine, but also new standards and demands on the traditional printing process. How to keep 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 related practitioners in the industry. Thus, the printing technology gradually goes deep into various fields of life, production and the like and gradually grows and grows, and the printing industry is now a modern industry with huge scale.
Today, the standards of the consumer on the living standard, the quality and the living development environment are continuously improved, the green packaging material in the packaging market is increasingly high in call, namely the environment-friendly performance is improved, and the pollution-free packaging material which is energy-saving, low in consumption, nontoxic, pollution-free and easy to degrade is selected. And printing ink is one of the more contaminated materials in packaging materials. Conventional printing inks contain a large amount of toxic and harmful chemicals including heavy metals, residual solvents, organic volatiles, and polycyclic aromatic hydrocarbons. Therefore, developing a new ink that is non-toxic, pollution-free at all times, and that can significantly improve the print quality of printed matter has become a problem of widespread concern to related practitioners in the industry.
Patent CN102618117a provides a single-liquid type environment-friendly general composite ink and a preparation method thereof, which consists of ester-soluble vinyl chloride-acetate resin liquid, a dispersing agent, an ester solvent, rutile titanium dioxide/organic pigment, matting powder, wax powder and ester-soluble polyurethane resin, but the printed matter obtained by printing the composite ink has poor printing quality, low glossiness of a printed pattern and easy degradation and cracking of a printed trace after long-time storage.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of modified alkyd resin and application of the modified alkyd resin in printing ink.
In order to solve the technical problems, the invention adopts the following technical scheme:
the green and environment-friendly printing process method comprises the following steps:
q1 determines plate making parameters;
q2 plate making: processing by adopting a laser engraving mode to obtain a columnar intaglio;
q3 test printing: dipping ink on the cylindrical intaglio, and performing test printing and drying operation on a test printed matter; judging whether the ink needs to be re-prepared or the specification of the cylindrical intaglio is adjusted according to the obtained ink forming effect and printing quality; if the printing ink forming effect and the printing quality meet the specified printing standard, batch printing can be carried out according to the current intaglio specification and the printing ink proportion;
q4 printing: and (3) smearing the ink on the whole plate surface of the cylindrical intaglio, scraping off the excessive ink on the surface layer of the cylindrical intaglio by using a doctor blade, placing a printed matter on the plate surface of the cylindrical intaglio, and then applying pressure to print the ink on the cylindrical intaglio onto the printed matter, wherein the green environment-friendly printing process method is finished.
Preferably, the green environmental-friendly printing process method comprises the following steps:
q1 determines plate making parameters: adopting brick-type net points, wherein the number of net wires is 20-25 pieces/cm, and the depth of the plate is 80-100 mu m;
q2 plate making: processing by adopting a laser engraving mode to obtain a columnar intaglio;
q3 test printing: dipping ink on the cylindrical intaglio, and performing test printing and drying operation on a test printed matter; judging whether the ink needs to be re-prepared or the specification of the cylindrical intaglio is adjusted according to the obtained ink forming effect and printing quality; if the printing ink forming effect and the printing quality meet the specified printing standard, batch printing can be carried out according to the current intaglio specification and the printing ink proportion;
q4 printing: and (3) smearing the ink on the whole plate surface of the cylindrical intaglio, scraping off the redundant ink on the surface layer of the cylindrical 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 cylindrical intaglio, and then applying pressure to print the ink on the cylindrical intaglio onto the printed matter, thereby finishing the green printing process.
The preparation method of the ink comprises the following steps:
c1 wetting: mixing carbon black with water, heating, stirring, and performing ultrasonic auxiliary treatment to obtain wet carbon black;
pulping C2: 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 cotton seed oil;
c3 reaction: mixing the wet carbon black and the whey, adding chalk, quartz and clay, stirring, standing and taking a precipitate to obtain an intermediate product A;
and 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, finishing: mixing the intermediate product C, liquid paraffin and a drying inhibitor, and homogenizing to obtain an intermediate product D; the drying inhibitor 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, is chemically stable to acid and alkali, has the characteristics of good viscosity adjustment and thermal stability, and can enhance the luster, adhesive force and durability of the printing ink by being used together with the modified alkyd resin prepared by the specific method, thereby obtaining the printed matter with higher printing quality. Catechol and 2-methoxy-4-methylphenol can effectively prevent the degradation cracking phenomenon caused by the oxidation of the ink system by oxygen in the air. The castor oil and the cotton seed oil have good wettability, and are low in price, safe, nontoxic, wide in source and easy to process.
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 60-65deg.C, stirring at 20-40rpm for 40-60min, and performing ultrasonic auxiliary treatment with power of 300-330W and frequency of 35-37kHz to obtain wet carbon black;
pulping C2: 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 105-115 ℃ at a rotation speed of 70-90rpm for 90-110min to obtain emulsion; the vegetable oil is a mixture of castor oil and cotton seed oil in a mass ratio of (4-6) 1;
c3 reaction: mixing 33-36 parts by weight of the wet carbon black with 38-43 parts by weight of the emulsion, adding 8-11 parts by weight of chalk, 1-3 parts by weight of quartz and 7-9 parts by weight of clay, stirring at 55-62 ℃ for 20-40min at a speed of 240-300rpm, and standing at 12-17 ℃ for 28-35h to obtain a precipitate to obtain an intermediate product A;
and C4, drying: drying the intermediate product A at 110-125 ℃ and vacuum degree (-0.12) - (-0.1) MPa to obtain an intermediate product B;
c5 grinding: grinding the intermediate product B, and sieving with a 2300-2500 mesh sieve to obtain an intermediate product C;
c6, finishing: mixing the intermediate product C, liquid paraffin and a drying inhibitor according to the mass ratio of (38-42): 23-26): 0.8-1.2 at 22-25 ℃ and homogenizing at the rotating speed of 12000-13000rpm for 2-4min to obtain an intermediate product D; the drying inhibitor 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 printing 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 residues, and drying the filter residues to obtain modified cellulose;
d2, mixing alkyd resin, the modified cellulose, anhydride and an anti-aging agent, then blending and extruding a blank;
and D3, crushing the blank, and sieving to obtain the modified alkyd resin.
The alkyd resin can show good gloss and excellent toughness after being cured, has strong adhesive force, and has good wear resistance, weather resistance, insulativity and other excellent characteristics, so 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 matter with higher printing quality is obtained through the green environment-friendly printing process method.
However, if alkyd resin is directly added into an ink system, the ink is easy to embrittle and crack under the stimulus of light and air humidity change after being dried and solidified due to poor compatibility between common alkyd resin and ink raw materials, and the printing quality, transportation, storage and use appearance of a printed matter are extremely affected.
Preferably, the preparation method of the modified alkyd resin comprises the following steps:
d1, mixing 3-4 parts by weight of sulfonamide, 7-8 parts by weight of cellulose and 16-19 parts by weight of diethyl ether, then treating the mixture at 83-86 ℃ with ultrasonic waves with the power of 340-360W and the frequency of 35-37kHz for 160-180min, filtering to obtain filter residues, and drying the filter residues for 8-10h under the conditions of 75-80 ℃ and the air pressure of 65-70kPa to obtain modified cellulose;
mixing alkyd resin, modified cellulose, anhydride and an anti-aging agent according to the mass ratio of (63-66) (20-23) (7-9) (1-2), blending at the temperature of 103-108 ℃ at the rotating speed of 600-800rpm for 100-110min, and extruding a blank with the particle size of 1-2mm through an extruder;
and D3, crushing the blank, and sieving with 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-sulfonylaniline. Preferably, the sulfonamide is a mixture of N-methyl-N-nitroso-p-toluenesulfonamide and p-aminotoluene o-sulfonylaniline in the 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 the mass ratio of (1-5).
The mutual infiltration degree and compatibility between the alkyd resin and the raw materials in the ink system can be further enhanced by grafting general cellulose into the alkyd resin, but the ink on a printed matter still tends to be deteriorated, brittle failure and the like when being stored for a long time, so that the alkyd resin is subjected to grafting modification treatment by adopting cyanoethyl cellulose containing cyanoethyl and p-aminobenzyl cellulose containing p-amino as modification aids.
The anhydride is at least one of 4,4' -oxydiphthalic anhydride and 1,4,5, 8-naphthalene tetracarboxylic anhydride. Preferably, the anhydride is a mixture of 4,4' -oxydiphthalic anhydride and 1,4,5, 8-naphthalene tetracarboxylic anhydride in the mass ratio of (1-3). More preferably, the 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 sulfonamide prior to the graft modification; the electronegativity of nitroso in N-methyl-N-nitroso-p-toluenesulfonamide and the relative orientation of para-amino in para-aminotoluene o-sulfonylaniline enable polar groups in the two celluloses to better contact and entangle with alkyd resin, thereby obtaining modified alkyd resin with higher toughness and durability, and further improving the service durability and excellent gloss and adhesion of the ink.
According to the invention, 4' -oxydiphthalic anhydride and 1,4,5, 8-naphthalene tetracarboxylic anhydride are adopted as acid anhydrides in the preparation process of the modified alkyd resin, and the relationship between the polarizability of polar groups and the molecular weight of nonpolar groups in the two acid anhydrides enables the two acid anhydrides to effectively enhance the grafting sufficiency of modified cellulose to the alkyd resin when being compounded as the acid anhydrides of the modified alkyd resin, so that the modified alkyd resin with higher toughness and durability is obtained, and the service durability and excellent gloss and adhesive force of the ink are improved.
The anti-aging agent is at least one of coco dimethyl tertiary amine and dioctyl methyl tertiary amine. Preferably, the anti-aging agent is a mixture of coco dimethyl tertiary amine and dioctyl methyl tertiary amine in the 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 the charges of the 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 further improved.
The ink obtained by the technical scheme of the invention accords with the specification of QB/T2024-2012 composite ink for intaglio plastic films.
The invention has the beneficial effects that:
1. the invention provides a green and environment-friendly printing process method which comprises the steps of determining printing parameters, manufacturing plates, trial printing, printing and the like, wherein printing ink with higher glossiness and adhesive force, which is prepared by the specific method, is adopted to obtain a printed matter with higher printing quality, and the process method is free from toxicity and pollution in the production process, low in cost and waste, and meets the theme requirements of green and environment protection.
2. The invention provides an ink and a preparation method thereof, wherein carbon black, petroleum resin, liquid paraffin, vegetable oil and modified alkyd resin prepared by the specific method are used as raw materials, so that the ink which has higher glossiness, stronger adhesive force and oxidation resistance and can be stored for a long time is obtained, and can be used for the green printing process method to obtain a printed matter with higher printing quality.
3. The modified alkyd resin takes alkyd resin as a matrix, takes cyanoethyl cellulose, p-aminobenzyl cellulose, 4' -oxydiphthalic anhydride, 1,4,5, 8-naphthalene tetracarboxylic anhydride, coco dimethyl tertiary amine and dioctyl methyl tertiary amine as modified materials, and obtains the modified alkyd resin which has better glossiness, stronger mechanical toughness, better oxidation resistance and corrosion resistance, 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 in conjunction with the detailed description, 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 of the raw materials in this application:
petroleum resin, CAS: 64142-16-1, available from Kjeldahl Petroleum resin Co., puyang, molecular weight: 2300.
alkyd resin, CAS:63148-69-6, model number from the company of the chemical industry of Star, chen county: e51, molecular weight: 65 ten thousand.
Liquid paraffin, CAS:8042-47-5, available from Anhui Zerni technologies Co., ltd., product number: m5310, brand: sigma-Aldrich.
Castor oil, CAS:8001-79-4, available from Anhui Zernike technologies Co., ltd., product number: l04224, brand: alfa Aesar.
Cottonseed oil, CAS:8001-29-4, available from Anhui Zernike technologies Inc., cat No.: c725303, brand: TRC.
Carbon black, CAS:1333-86-4, available from Anhui Zerni technology Co., ltd., particle size: 800 mesh, goods number: 699632, brand: sigma-Aldrich.
Chalk, purchased from the mineral processing plant of the mineral spirits of the county of life, specification: 2000 meshes, the impurity content is less than or equal to 2 percent.
Quartz, CAS:14808-60-7 from Anhui Zealand technologies Co., ltd., particle size: 800 mesh, goods number: 013024, brand: alfa Aesar.
Argil, CAS:1340-68-7, from the Programme of the mineral processing plant, specification: 2200 mesh, mohs hardness: 6, the impurity content is less than or equal to 4 percent.
N-methyl-N-nitroso-p-toluenesulfonamide, CAS:80-11-5, available from Anhui Zernike technologies, inc., cat: b020026-500g.
Para-aminotoluene o-sulfonylanilines, CAS:79-72-1 from the company of the chemical industry, inc. of Ralston, qu.
Cyanoethyl cellulose, CAS:9004-41-5, available from Anhui Zerni science and technology Co., ltd., product number: 184659.
p-aminobenzyl cellulose, CAS:9032-51-3, available from Anhui Zerni technology Co., ltd., product number: C0064.
4,4' -oxydiphthalic anhydride, CAS:1823-59-2 available from Anhui Zerni technology Co., ltd., product number: a01185-500 g.
1,4,5, 8-naphthalene tetracarboxylic anhydride, CAS:81-30-1, available from Anhui Zernike technologies Inc., cat: l14365, brand: alfa Aesar.
Coco dimethyl tertiary amine, CAS:61788-93-0 from WUHanrong and Brilliant Biotechnology Co.
Bis-octyl methyl tertiary amine, CAS:4455-26-9, available from Anhui Zernike technologies Inc., cat#: m0232.
Catechol, CAS:120-80-9, purchased from Anhui Zernike technologies Co., ltd., product number: 135011, brand: sigma-Aldrich.
2-methoxy-4-methylphenol, CAS:93-51-6, available from Anhui Zealand technologies Co., ltd., product number: w267112, brand: sigma-Aldrich.
Example 1
The green and environment-friendly printing process method comprises the following steps:
q1 determines plate making parameters: adopting brick-type net points, wherein the number of net wires is 22 pieces/cm, and the depth of the plate is 100 mu m;
q2 plate making: processing by adopting a laser engraving mode to obtain a columnar intaglio;
q3 test printing: dipping ink on the cylindrical intaglio, and performing test printing and drying operation on a test printed matter; judging whether the ink needs to be re-prepared or the specification of the cylindrical intaglio is adjusted according to the obtained ink forming effect and printing quality; if the printing ink forming effect and the printing quality meet the specified printing standard, batch printing can be carried out according to the current intaglio specification and the printing ink proportion;
q4 printing: and (3) smearing the ink on the whole plate surface of the cylindrical intaglio, scraping off the redundant ink on the surface layer of the cylindrical intaglio by using a doctor blade to enable the thickness of the ink layer of the ink to be 45 mu m, placing a printed matter on the plate surface of the cylindrical intaglio, and then applying pressure to print the ink on the cylindrical intaglio on the printed matter, wherein the green printing process method is finished.
The preparation method of the ink comprises the following steps:
c1 wetting: mixing carbon black with water according to a bath ratio of 1kg to 3L, heating to 60 ℃, stirring for 50min at a rotating speed of 30rpm, and carrying out ultrasonic auxiliary treatment with power of 300W and frequency of 35kHz to obtain wet carbon black;
pulping C2: 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 ℃ for 100min at a rotation speed of 80rpm to obtain emulsion; the vegetable oil is a mixture of castor oil and cotton seed oil in a mass ratio of 5:1;
c3 reaction: mixing 35 parts by weight of the wet carbon black with 40 parts by weight of the emulsion slurry, adding 10 parts by weight of chalk, 2 parts by weight of quartz and 8 parts by weight of clay, stirring at 60 ℃ for 30min at 260rpm, and standing at 15 ℃ for 30h to obtain a precipitate, thereby obtaining an intermediate product A;
and C4, drying: drying the intermediate product A at 120 ℃ and a vacuum degree of-0.1 MPa to obtain an intermediate product B;
c5 grinding: grinding the intermediate product B, and sieving with a 2500-mesh screen to obtain an intermediate product C;
c6, finishing: mixing the intermediate product C, liquid paraffin and a drying inhibitor according to a mass ratio of 40:25:1 at 25 ℃, and homogenizing at 13000rpm for 3min to obtain an intermediate product D; the drying inhibitor 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 printing ink.
The preparation method of the modified alkyd resin comprises the following steps:
d1, mixing 3 parts by weight of sulfonamide, 7 parts by weight of cellulose and 18 parts by weight of diethyl ether, then treating for 170min at 85 ℃ with ultrasonic waves with power of 350W and frequency of 36kHz, filtering to obtain filter residues, and drying the filter residues for 8h at 80 ℃ under the condition of air pressure of 65kPa to obtain modified cellulose;
d2, mixing alkyd resin, the modified cellulose, anhydride and an anti-aging agent according to a mass ratio of 65:22:8:2, then blending for 105 minutes at 105 ℃ at a rotating speed of 800rpm, and extruding a blank with a particle size of 1mm through an extruder;
and D3, crushing the blank, and sieving the crushed blank with 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-sulfonylaniline 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 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 dioctyl methyl tertiary amine according to the mass ratio of 8:9.
Example 2
Substantially the same as in example 1, the only difference is that:
the preparation method of the modified alkyd resin comprises the following steps:
d1, mixing 3 parts by weight of sulfonamide, 7 parts by weight of cellulose and 18 parts by weight of diethyl ether, then treating for 170min at 85 ℃ with ultrasonic waves with power of 350W and frequency of 36kHz, filtering to obtain filter residues, and drying the filter residues for 8h at 80 ℃ under the condition of air pressure of 65kPa to obtain modified cellulose;
d2, mixing alkyd resin, the modified cellulose, anhydride and an anti-aging agent according to a mass ratio of 65:22:8:2, then blending for 105 minutes at 105 ℃ at a rotating speed of 800rpm, and extruding a blank with a particle size of 1mm through an extruder;
and D3, crushing the blank, and sieving the crushed blank with 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-sulfonylaniline 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 anhydride is 4,4' -oxydiphthalic anhydride.
The anti-aging agent is a mixture of coco dimethyl tertiary amine and dioctyl methyl tertiary amine according to the mass ratio of 8:9.
Example 3
Substantially the same as in example 1, the only difference is that:
the preparation method of the modified alkyd resin comprises the following steps:
d1, mixing 3 parts by weight of sulfonamide, 7 parts by weight of cellulose and 18 parts by weight of diethyl ether, then treating for 170min at 85 ℃ with ultrasonic waves with power of 350W and frequency of 36kHz, filtering to obtain filter residues, and drying the filter residues for 8h at 80 ℃ under the condition of air pressure of 65kPa to obtain modified cellulose;
d2, mixing alkyd resin, the modified cellulose, anhydride and an anti-aging agent according to a mass ratio of 65:22:8:2, then blending for 105 minutes at 105 ℃ at a rotating speed of 800rpm, and extruding a blank with a particle size of 1mm through an extruder;
and D3, crushing the blank, and sieving the crushed blank with 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-sulfonylaniline 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 anhydride is 1,4,5, 8-naphthalene tetracarboxylic anhydride.
The anti-aging agent is a mixture of coco dimethyl tertiary amine and dioctyl methyl tertiary amine according to the mass ratio of 8:9.
Example 4
Substantially the same as in example 1, the only difference is 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 treating the mixture for 170 minutes at 85 ℃ by ultrasonic waves with the power of 350W and the frequency of 36kHz, filtering to obtain filter residues, and drying the filter residues for 8 hours at 80 ℃ under the air pressure of 65kPa to obtain modified cellulose;
d2, mixing alkyd resin, the modified cellulose, anhydride and an anti-aging agent according to a mass ratio of 65:22:8:2, then blending for 105 minutes at 105 ℃ at a rotating speed of 800rpm, and extruding a blank with a particle size of 1mm through an extruder;
and D3, crushing the blank, and sieving the crushed blank with 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 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 dioctyl methyl tertiary amine according to the mass ratio of 8:9.
Example 5
Substantially the same as in example 1, the only difference is that:
the preparation method of the modified alkyd resin comprises the following steps:
d1, mixing alkyd resin, cellulose, anhydride and an anti-aging agent according to a mass ratio of 65:22:8:2, then blending for 105 minutes at 105 ℃ at a rotating speed of 800rpm, and extruding a blank with a particle size of 1mm through an extruder;
and D2, crushing the blank, and sieving the crushed blank with 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 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 dioctyl methyl tertiary amine according to the mass ratio of 8:9.
Example 6
Substantially the same as in example 1, the only difference is that:
the preparation method of the modified alkyd resin comprises the following steps:
d1, mixing 3 parts by weight of sulfonamide, 7 parts by weight of cellulose and 18 parts by weight of diethyl ether, then treating for 170min at 85 ℃ with ultrasonic waves with power of 350W and frequency of 36kHz, filtering to obtain filter residues, and drying the filter residues for 8h at 80 ℃ under the condition of air pressure of 65kPa to obtain modified cellulose;
d2, mixing alkyd resin, the modified cellulose and the anti-aging agent according to a mass ratio of 65:22:2, then blending for 105 minutes at 105 ℃ at a rotating speed of 800rpm, and extruding blanks with a particle size of 1mm through an extruder;
and D3, crushing the blank, and sieving the crushed blank with 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-sulfonylaniline 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 dioctyl methyl tertiary amine according to the mass ratio of 8:9.
Example 7
Substantially the same as in example 1, the only difference is that:
the preparation method of the ink comprises the following steps:
c1 wetting: mixing carbon black with water according to a bath ratio of 1kg to 3L, heating to 60 ℃, stirring for 50min at a rotating speed of 30rpm, and carrying out ultrasonic auxiliary treatment with power of 300W and frequency of 35kHz to obtain wet carbon black;
pulping C2: 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 ℃ for 100min at a rotation speed of 80rpm to obtain a whey; the vegetable oil is a mixture of castor oil and cotton seed oil in a mass ratio of 5:1;
c3 reaction: mixing 35 parts by weight of the wet carbon black with 40 parts by weight of the emulsion slurry, adding 10 parts by weight of chalk, 2 parts by weight of quartz and 8 parts by weight of clay, stirring at 60 ℃ for 30min at 260rpm, and standing at 15 ℃ for 30h to obtain a precipitate, thereby obtaining an intermediate product A;
and C4, drying: drying the intermediate product A at 120 ℃ and a vacuum degree of-0.1 MPa to obtain an intermediate product B;
c5 grinding: grinding the intermediate product B, and sieving with a 2500-mesh screen to obtain an intermediate product C;
c6, finishing: mixing the intermediate product C, liquid paraffin and a drying inhibitor according to a mass ratio of 40:25:1 at 25 ℃, and homogenizing at 13000rpm for 3min to obtain an intermediate product D; the drying inhibitor 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 printing ink.
Example 8
Substantially the same as in example 7, the only difference is that:
the preparation method of the ink comprises the following steps:
c1 wetting: mixing carbon black with water according to a bath ratio of 1kg to 3L, heating to 60 ℃, stirring for 50min at a rotating speed of 30rpm, and carrying out ultrasonic auxiliary treatment with power of 300W and frequency of 35kHz to obtain wet carbon black;
pulping C2: 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 ℃ for 100min at a rotation speed of 80rpm to obtain emulsion; the vegetable oil is a mixture of castor oil and cotton seed oil in a mass ratio of 5:1;
c3 reaction: mixing 35 parts by weight of the wet carbon black with 40 parts by weight of the emulsion slurry, adding 10 parts by weight of chalk, 2 parts by weight of quartz and 8 parts by weight of clay, stirring at 60 ℃ for 30min at 260rpm, and standing at 15 ℃ for 30h to obtain a precipitate, thereby obtaining an intermediate product A;
and C4, drying: drying the intermediate product A at 120 ℃ and a vacuum degree of-0.1 MPa to obtain an intermediate product B;
c5 grinding: grinding the intermediate product B, and sieving with a 2500-mesh screen to obtain an intermediate product C;
c6, finishing: mixing the intermediate product C, liquid paraffin and a drying inhibitor according to a mass ratio of 40:25:1 at 25 ℃, and homogenizing at 13000rpm for 3min to obtain an intermediate product D; the drying inhibitor 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 printing ink.
Example 9
Substantially the same as in example 1, the only difference is that:
the preparation method of the ink comprises the following steps:
c1 wetting: mixing carbon black with water according to a bath ratio of 1kg to 3L, heating to 60 ℃, stirring for 50min at a rotating speed of 30rpm, and carrying out ultrasonic auxiliary treatment with power of 300W and frequency of 35kHz to obtain wet carbon black;
pulping C2: 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 ℃ for 100min at a rotation speed of 80rpm to obtain a whey; the vegetable oil is a mixture of castor oil and cotton seed oil in a mass ratio of 5:1;
c3 reaction: mixing 35 parts by weight of the wet carbon black with 40 parts by weight of the emulsion slurry, adding 10 parts by weight of chalk, 2 parts by weight of quartz and 8 parts by weight of clay, stirring at 60 ℃ for 30min at 260rpm, and standing at 15 ℃ for 30h to obtain a precipitate, thereby obtaining an intermediate product A;
and C4, drying: drying the intermediate product A at 120 ℃ and a vacuum degree of-0.1 MPa to obtain an intermediate product B;
c5 grinding: grinding the intermediate product B, and sieving with a 2500-mesh screen to obtain an intermediate product C;
c6, finishing: mixing the intermediate product C, liquid paraffin and a drying inhibitor according to a mass ratio of 40:25:1 at 25 ℃, and homogenizing at 13000rpm for 3min to obtain an intermediate product D; the drying inhibitor 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 printing ink.
The preparation method of the modified alkyd resin comprises the following steps:
d1, mixing 3 parts by weight of sulfonamide, 7 parts by weight of cellulose and 18 parts by weight of diethyl ether, then treating for 170min at 85 ℃ with ultrasonic waves with power of 350W and frequency of 36kHz, filtering to obtain filter residues, and drying the filter residues for 8h at 80 ℃ under the condition of air pressure of 65kPa to obtain modified cellulose;
d2, mixing alkyd resin, the modified cellulose, anhydride and an anti-aging agent according to a mass ratio of 65:22:8:2, then blending for 105 minutes at 105 ℃ at a rotating speed of 800rpm, and extruding a blank with a particle size of 1mm through an extruder;
and D3, crushing the blank, and sieving the crushed blank with 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-sulfonylaniline 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 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 dioctyl methyl tertiary amine according to the mass ratio of 8:9.
Test example 1
Ink attachment fastness test: the adhesion fastness of the inks obtained by the examples of the present invention was measured according to GB/T13217.7-2009 method for testing adhesion fastness of liquid inks. For each case, 5 samples were tested and the test results averaged. The test temperature was 23℃and the humidity was 65%. The A-disc speed was 0.8m/s.
The test results are shown in Table 1.
TABLE 1 attachment fastness of ink
Test example 2
Ink gloss test: the gloss of the inks obtained by the examples of the present invention was measured according to GB/T13217.2-2009 method for gloss test of liquid inks. For each case, 5 samples were tested and the test results averaged. The test temperature was 23℃and the humidity was 65%.
The test results are shown in Table 2.
Table 2 gloss of ink
The alkyd resin can show good gloss and excellent toughness after being cured, has strong adhesive force, and has good wear resistance, weather resistance, insulativity and other excellent characteristics, so 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 matter with higher printing quality is obtained through the green environment-friendly printing process method. However, if alkyd resin is directly added into an ink system, the ink is easy to embrittle and crack under the stimulus of light and air humidity change after being dried and solidified due to poor compatibility between common alkyd resin and ink raw materials, and the printing quality, transportation, storage and use appearance of a printed matter are extremely affected. The mutual infiltration degree and compatibility between the alkyd resin and the raw materials in the ink system can be further enhanced by grafting general cellulose into the alkyd resin, but the ink on a printed matter still tends to be deteriorated, brittle failure and the like when being stored for a long time, so that the alkyd resin is subjected to grafting modification treatment by adopting cyanoethyl cellulose containing cyanoethyl and p-aminobenzyl cellulose containing p-amino as modification aids.
Modifying the two celluloses with the sulfonamide prior to the graft modification; the electronegativity of nitroso in N-methyl-N-nitroso-p-toluenesulfonamide and the relative orientation of para-amino in para-aminotoluene o-sulfonylaniline enable polar groups in the two celluloses to better contact and entangle with alkyd resin, thereby obtaining modified alkyd resin with higher toughness and durability, and further improving the service durability and excellent gloss and adhesion of the ink.
According to the invention, 4' -oxydiphthalic anhydride and 1,4,5, 8-naphthalene tetracarboxylic anhydride are adopted as acid anhydrides in the preparation process of the modified alkyd resin, and the relationship between the polarizability of polar groups and the molecular weight of nonpolar groups in the two acid anhydrides enables the two acid anhydrides to effectively enhance the grafting sufficiency of modified cellulose to the alkyd resin when being compounded as the acid anhydrides of the modified alkyd resin, so that the modified alkyd resin with higher toughness and durability is obtained, and the service durability and excellent gloss and adhesive force of the ink are improved.
The two tertiary amine type anti-aging agents adopted by the invention and the modified alkyd resin are influenced by the charges of the 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, is chemically stable to acid and alkali, has the characteristics of good viscosity adjustment and thermal stability, and can enhance the luster, adhesive force and durability of the printing ink by being used together with the modified alkyd resin prepared by the specific method, thereby obtaining the printed matter with higher printing quality.
Claims (8)
1. The preparation method of the modified alkyd resin is characterized by comprising the following steps of:
d1, mixing sulfonamide, cellulose and diethyl ether, then carrying out ultrasonic treatment, filtering to obtain filter residues, and drying the filter residues to obtain modified cellulose;
d2, mixing alkyd resin, the modified cellulose, anhydride and an anti-aging agent, then blending and extruding a blank;
d3, crushing the blank, and sieving to obtain the modified alkyd resin;
the anhydride is a mixture of 4,4' -oxydiphthalic anhydride and 1,4,5, 8-naphthalene tetracarboxylic anhydride in the mass ratio of (1-3) to (1-3).
2. The method for preparing the 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-sulfonylaniline.
3. The method for preparing the modified alkyd resin according to claim 1, wherein: the anti-aging agent is at least one of coco dimethyl tertiary amine and dioctyl methyl tertiary amine.
4. A modified alkyd resin, characterized by: a process for the preparation of a modified alkyd resin as claimed in any of claims 1 to 3.
5. A method for preparing ink, comprising the steps of:
c1 wetting: mixing carbon black with water, heating, stirring, and performing ultrasonic auxiliary treatment to obtain wet carbon black;
pulping C2: mixing petroleum resin, liquid paraffin, vegetable oil and the modified alkyd resin according to claim 4, and stirring to obtain a whey;
c3 reaction: mixing the wet carbon black and the whey, adding chalk, quartz and clay, stirring, standing and taking a precipitate to obtain an intermediate product A;
and 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, finishing: mixing the intermediate product C, liquid paraffin and a drying inhibitor, and homogenizing to obtain an intermediate product D;
c7, defoaming: and defoaming the intermediate product D to obtain the printing ink.
6. The method for preparing the ink according to claim 5, wherein: the vegetable oil is at least one of castor oil and cotton seed oil.
7. The method for preparing the ink according to claim 5, wherein: the anti-dry agent is at least one of catechol and 2-methoxy-4-methylphenol.
8. An ink, characterized in that: obtained by the method for producing an ink according to any one of claims 5 to 7.
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