CN116731557B - High-water-resistance polyamide printing ink and preparation method thereof - Google Patents

High-water-resistance polyamide printing ink and preparation method thereof Download PDF

Info

Publication number
CN116731557B
CN116731557B CN202310925323.0A CN202310925323A CN116731557B CN 116731557 B CN116731557 B CN 116731557B CN 202310925323 A CN202310925323 A CN 202310925323A CN 116731557 B CN116731557 B CN 116731557B
Authority
CN
China
Prior art keywords
parts
resin liquid
polyamide
printing ink
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202310925323.0A
Other languages
Chinese (zh)
Other versions
CN116731557A (en
Inventor
周艳
余佩玉
权肖琦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Tangcai New Materials Technology Co ltd
Original Assignee
Jiangsu Tangcai New Materials Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Tangcai New Materials Technology Co ltd filed Critical Jiangsu Tangcai New Materials Technology Co ltd
Priority to CN202310925323.0A priority Critical patent/CN116731557B/en
Publication of CN116731557A publication Critical patent/CN116731557A/en
Application granted granted Critical
Publication of CN116731557B publication Critical patent/CN116731557B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • 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
    • 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
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • 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
    • C09D11/08—Printing inks based on natural resins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
    • C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
    • C09F1/04—Chemical modification, e.g. esterification

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention discloses high-water-resistance polyamide printing ink which comprises the following components in parts by weight: 22-30 parts of polyamide resin liquid, 10-20 parts of ternary vinyl chloride-acetate resin liquid, 8-15 parts of rosin modified 2-fluoroacrylic acid resin liquid, 12-20 parts of alcohol-soluble dye, 0.8-1.2 parts of fumed silica, 0.4-0.6 part of dispersing agent, 6-10 parts of ethanol solution with the mass fraction of 95%, 1-4 parts of isopropanol, 2-4 parts of n-butanol and 2-5 parts of ethyl acetate. The printing ink adopts the polyamide resin as the main resin, the resin has good water resistance, the ternary chloroacetic resin and the rosin modified 2-fluoroacrylic resin are used as the auxiliary resin, the auxiliary resin is mixed with the polyamide resin to improve the performance of the ink, the adhesive force and the weather resistance of the ink are enhanced, and meanwhile, ethanol, isopropanol and the like are adopted to replace benzene as solvents, so that the problems of environmental pollution, human body injury and the like of the existing benzene solvent ink are solved.

Description

High-water-resistance polyamide printing ink and preparation method thereof
Technical Field
The invention relates to the field of printing materials, in particular to high-water-resistance polyamide printing ink and a preparation method thereof.
Background
According to the regulations that benzene solvents are not detected in the new national GB/T10004-2008 standard and the urgent requirements of developing green environment-friendly ink and developing renewable energy sources in China, the development direction is indicated for the plastic ink industry and the food and drug packaging industry of China, the substitution of green ink for benzene-containing ink and the substitution of renewable energy sources for non-renewable energy sources are accelerated, the competing requirements of green ink and environment-friendly printing package use in domestic and foreign markets are met, and the aim of no benzene is fulfilled, so that the method is an important subject and the correct development direction of the current surface printing ink research.
In the prior art, improvement and production of water-based ink are carried out in multiple directions such as gravure ink, flexographic ink, screen printing ink, digital printing, food packaging, anti-counterfeiting ink and the like, the proportioning selection and process optimization of the water-based ink are carried out according to the formula principle and the requirement of the ink, proper connecting agents, solvents and auxiliaries are selected, and the processes such as dispersion, mixing, sanding and defoaming are carried out for debugging and improvement, so that the ink meets the requirements of use scenes on multiple indexes such as viscosity, water resistance, quick drying property, fineness and the like, including but not limited to plastic film printing, tissue printing, overprinting, gold and silver card paper printing, corrugated paper printing, food packaging printing and the like. For example, the alcohol-soluble polyamide gravure plastic surface printing ink disclosed in the patent application with the publication number of CN102585601A comprises 15-25% of alcohol-soluble polyamide resin liquid, 6-15% of alcohol-soluble rosin modified maleic acid resin liquid, 2-4% of alcohol-soluble polyketone resin liquid, 5-10% of alcohol-ester-soluble nitrocotton resin liquid, 0.5-1% of wax powder, 9-30% of pigment, 30-40% of absolute ethyl alcohol and 0.5-1% of anti-settling agent, and the prepared alcohol-soluble polyamide gravure plastic surface printing ink adopts ethanol as a solvent system, abandons the use of benzene solvents, replaces the benzene solvent system surface printing ink used at present, meets the requirements of green environment-friendly ink, has the remarkable characteristics of high solid content, low viscosity, high gloss, low temperature resistance, good adhesive force, strong printing adaptability and the like, but has the defects of weak water resistance, poor weather resistance and small application range.
Disclosure of Invention
In order to solve the technical problems, the invention provides high-water-resistance polyamide printing ink and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the high-water-resistance polyamide printing ink comprises the following components in parts by weight: 22-30 parts of polyamide resin liquid, 10-20 parts of ternary vinyl chloride-acetate copolymer, 8-15 parts of rosin modified 2-fluoroacrylic acid resin liquid, 12-20 parts of alcohol-soluble dye, 0.8-1.2 parts of fumed silica, 0.4-0.6 part of disperger 983 type dispersing agent produced by the Taiwan court of the De of Taiwan, 6-10 parts of ethanol solution with the mass fraction of 95%, 1-4 parts of isopropanol, 2-4 parts of n-butanol and 2-5 parts of ethyl acetate;
the Gao Naishui polyamide printing ink is configured to be prepared by:
s1: mixing and stirring ethanol solution with the mass fraction of 95%, isopropanol, n-butanol and ethyl acetate uniformly to prepare a mixed solvent;
s2: uniformly mixing and stirring polyamide resin liquid, ternary vinyl chloride-acetate resin liquid and 2-fluoroacrylic acid resin liquid to prepare combined resin liquid;
s3: adding alcohol-soluble dye, combined resin liquid, fumed silica and a disperger 983 dispersing agent produced by the Taiwan court of the Carnis, into a mixed solvent, and uniformly stirring to obtain the high-water-resistance polyamide printing ink.
The polyamide resin liquid is prepared through the following steps:
a1: adding tetrafluorosuccinic anhydride and ethanol into a reaction vessel provided with a stirrer and a thermometer, stirring and mixing uniformly, heating to 50-60 ℃ in an oil bath, dripping divinyl triamine, stirring for 3-5 h, and distilling under reduced pressure to remove a solvent to obtain an intermediate, wherein the molar ratio of tetrafluorosuccinic anhydride to divinyl triamine to ethanol is 0.6-1: 1 to 1.4:20, a step of;
a2: adding ethylenediamine and an intermediate into deionized water, wherein the mol ratio of ethylenediamine to the intermediate to deionized water is 1:2: 5-9, heating to 80-100 ℃, reacting for 4-6 h, distilling under reduced pressure, precipitating and filtering, drying the precipitate in a vacuum drying oven at 50-90 ℃ for 12-48 h, cooling and grinding to obtain solid powder according to the mass ratio of 1:1 is mixed with absolute ethyl alcohol, and the temperature is raised to dissolve the solid powder to obtain the polyamide resin liquid.
Synthesis of AB by reaction of tetrafluorosuccinic anhydride and divinyl triamine 2 The class molecules and the ethylene diamine as the center 'nuclear molecules' are added into the AB according to a definite molar ratio by a fractional method with a nucleus 2 Type molecules, therebySynthesizing hyperbranched polyamide resin containing C=C double bonds, fluorine element groups and amino-terminated groups, and dissolving the hyperbranched polyamide resin in ethanol to obtain the polyamide resin liquid.
The rosin modified 2-fluoroacrylic acid resin liquid is prepared through the following steps:
b1: heating rosin to 150-160 ℃, starting a reaction kettle stirrer, then adding 4,4 '-thiobis (6-tert-butyl-3-methylphenol) into the reaction kettle for reaction, continuously heating to 190-210 ℃, adding 2-fluoroacrylic acid, sealing the reaction kettle, controlling the pressure of the reaction kettle to be 0.1-0.3 MPa, reacting for 2 hours, discharging the pressure of the reaction kettle, continuously heating to 240-260 ℃, adding glycerol, and reacting for 1 hour, wherein the mass ratio of the rosin, the 4' -thiobis (6-tert-butyl-3-methylphenol) to the 2-fluoroacrylic acid and the glycerol is 100:0.05-0.2:7-8:3-5;
rosin and 2-fluoroacrylic acid react with 4,4' -thiobis (6-tertiary butyl-3-methylphenol) respectively to generate rosin ester and 2-fluoroacrylate, and then react with glycerol in an ester exchange manner to obtain rosin modified 2-fluoroacrylic acid resin;
b2: vacuumizing the reaction kettle for 0.5h, then starting to cool to 200 ℃, filtering the material obtained by the esterification reaction in the step B1 by using a 200-mesh filter bag to remove impurities, adding absolute ethyl alcohol with the same mass as the material after removing the impurities, stirring and mixing, and heating to dissolve to obtain the rosin modified 2-fluoroacrylic acid resin liquid.
The invention has the beneficial effects that:
the invention discloses a high water resistance polyamide resin ink which is prepared by taking polyamide resin as a main body, taking mixed resin mixed by ternary vinyl acetate resin and rosin modified 2-fluoro acrylic resin as auxiliary resin as a matrix, taking mixed liquid of ethanol, isopropanol, n-butanol and ethyl acetate as an organic solvent, and taking alcohol-soluble dye, fumed silica and a disperger 983 dispersant produced by Taiwan court as additives.
Wherein the polyamide resin is prepared by synthesizing AB through the reaction of tetrafluorosuccinic anhydride and divinyl triamine 2 The type molecules and the ethylenediamine as the center 'nuclear molecules' are stepped by the nuclear according to the determined molar ratioAdding the AB 2 The hyperbranched polyamide resin containing C=C double bonds, fluorine element groups and terminal amino groups is obtained, the water resistance of the polyamide is enhanced after hyperbranched and fluorinated modification, and ternary vinyl chloride-vinyl acetate resin and rosin modified 2-fluoroacrylic acid resin are auxiliary resins, wherein the ternary vinyl chloride-vinyl acetate resin is hydroxyl ternary vinyl chloride-vinyl acetate resin, and the resin has good adhesion and can endow ink with quick drying property; the 2-fluoro acrylic resin has good weather-proof and waterproof performances, and is enhanced by rosin modification softness, so that the flexibility of the ink is improved, and the ink is not easy to break. Meanwhile, ethanol, isopropanol and the like are adopted to replace benzene as solvents, so that the problems of environmental pollution, human body injury and the like caused by the existing benzene solvent system surface printing ink are solved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
An alcohol-soluble polyamide resin prepared by the steps of:
a1: adding tetrafluorosuccinic anhydride and ethanol into a reaction vessel provided with a stirrer and a thermometer, stirring and mixing uniformly, heating an oil bath to 50 ℃, dropwise adding divinyl triamine, stirring for 3 hours, and distilling under reduced pressure to remove a solvent to obtain an intermediate, wherein the molar ratio of tetrafluorosuccinic anhydride to divinyl triamine to ethanol is 0.6:1.4:20, a step of;
a2: adding ethylenediamine and an intermediate into deionized water, wherein the mol ratio of ethylenediamine to the intermediate to deionized water is 1:2:5, heating to 80 ℃, reacting for 4 hours, decompressing, distilling, precipitating, filtering, putting the precipitate into a vacuum drying oven, drying at 50 ℃ for 12 hours, cooling, and grinding to obtain solid powder according to the mass ratio of 1:1, mixing the mixture with absolute ethyl alcohol, and heating to dissolve solid powder to obtain polyamide resin liquid;
example 2
An alcohol-soluble polyamide resin prepared by the steps of:
a1: adding tetrafluorosuccinic anhydride and ethanol into a reaction vessel provided with a stirrer and a thermometer, stirring and mixing uniformly, heating an oil bath to 55 ℃, dropwise adding divinyl triamine, stirring for 4 hours, and distilling under reduced pressure to remove a solvent to obtain an intermediate, wherein the molar ratio of tetrafluorosuccinic anhydride to divinyl triamine to ethanol is 0.8:1.2:20, a step of;
a2: adding ethylenediamine and an intermediate into deionized water, wherein the mol ratio of ethylenediamine to the intermediate to deionized water is 1:2:7, heating to 90 ℃, reacting for 5 hours, decompressing, distilling, precipitating and filtering, putting the precipitate into a vacuum drying oven, drying at 70 ℃ for 24 hours, cooling and grinding to obtain solid powder according to the mass ratio of 1:1, mixing the mixture with absolute ethyl alcohol, and heating to dissolve solid powder to obtain polyamide resin liquid;
example 3
An alcohol-soluble polyamide resin prepared by the steps of:
a1: adding tetrafluorosuccinic anhydride and ethanol into a reaction vessel provided with a stirrer and a thermometer, stirring and mixing uniformly, heating an oil bath to 60 ℃, dropwise adding divinyl triamine, stirring for 5 hours, and distilling under reduced pressure to remove a solvent to obtain an intermediate, wherein the molar ratio of tetrafluorosuccinic anhydride to divinyl triamine to ethanol is 1:1.4:20, a step of;
a2: adding ethylenediamine and an intermediate into deionized water, wherein the mol ratio of ethylenediamine to the intermediate to deionized water is 1:2:9, heating to 100 ℃, reacting for 6 hours, decompressing, distilling, precipitating and filtering, putting the precipitate into a vacuum drying oven, drying at 90 ℃ for 48 hours, cooling and grinding to obtain solid powder according to the mass ratio of 1:1, mixing the mixture with absolute ethyl alcohol, and heating to dissolve solid powder to obtain polyamide resin liquid;
example 4
A rosin modified 2-fluoroacrylic acid resin is prepared by the following steps:
b1: heating rosin to 150 ℃, starting a reaction kettle stirrer, adding 4,4 '-thiobis (6-tert-butyl-3-methylphenol) into the reaction kettle for reaction, continuously heating to 190 ℃, adding 2-fluoroacrylic acid, sealing the reaction kettle, controlling the pressure of the reaction kettle to be 0.1MPa, reacting for 2 hours, discharging the pressure of the reaction kettle, continuously heating to 240 ℃, adding glycerin, and reacting for 1 hour, wherein the mass ratio of the rosin, the 4' -thiobis (6-tert-butyl-3-methylphenol), the 2-fluoroacrylic acid and the glycerin is 100:0.05:7:3, a step of;
b2: vacuumizing the reaction kettle for 0.5h, cooling to 200 ℃, filtering the material obtained by the esterification reaction in the step B1 by using a 200-mesh filter bag to remove impurities, adding absolute ethyl alcohol with the same mass as the material after removing the impurities, stirring and mixing, and heating to dissolve to obtain the rosin modified 2-fluoroacrylic acid resin liquid.
Example 5
A rosin modified 2-fluoroacrylic acid resin is prepared by the following steps:
b1: heating rosin to 155 ℃, starting a reaction kettle stirrer, adding 4,4 '-thiobis (6-tert-butyl-3-methylphenol) into the reaction kettle for reaction, continuously heating to 200 ℃, adding 2-fluoroacrylic acid, sealing the reaction kettle, controlling the pressure of the reaction kettle to be 0.2MPa, reacting for 2 hours, discharging the pressure of the reaction kettle, continuously heating to 250 ℃, adding glycerin, and reacting for 1 hour, wherein the mass ratio of the rosin, the 4' -thiobis (6-tert-butyl-3-methylphenol), the 2-fluoroacrylic acid and the glycerin is 100:0.1:7.5:4, a step of;
b2: vacuumizing the reaction kettle for 0.5h, cooling to 200 ℃, and filtering the material obtained by the esterification reaction in the step B1 by using a 200-mesh filter bag to remove impurities, thus obtaining the alcohol-soluble rosin modified 2-fluoroacrylic acid resin.
Example 6
A rosin modified 2-fluoroacrylic acid resin is prepared by the following steps:
b1: heating rosin to 160 ℃, starting a reaction kettle stirrer, adding 4,4 '-thiobis (6-tert-butyl-3-methylphenol) into the reaction kettle for reaction, continuously heating to 210 ℃, adding 2-fluoroacrylic acid, sealing the reaction kettle, controlling the pressure of the reaction kettle to be 0.3MPa, reacting for 2 hours, discharging the pressure of the reaction kettle, continuously heating to 260 ℃, adding glycerin, and reacting for 1 hour, wherein the mass ratio of the rosin, the 4' -thiobis (6-tert-butyl-3-methylphenol), the 2-fluoroacrylic acid and the glycerin is 100:0.2:8:5, a step of;
b2: vacuumizing the reaction kettle for 0.5h, cooling to 200 ℃, and filtering the material obtained by the esterification reaction in the step B1 by using a 200-mesh filter bag to remove impurities, thus obtaining the alcohol-soluble rosin modified 2-fluoroacrylic acid resin.
Example 7
The high-water-resistance polyamide printing ink comprises the following components in parts by weight: 22 parts of the polyamide resin liquid obtained in example 1, 10 parts of the ternary vinyl chloride-acetate copolymer, 8 parts of the rosin-modified 2-fluoroacrylic acid resin liquid obtained in example 4, 12 parts of an alcohol-soluble dye, 0.8 part of fumed silica, 0.4 part of a disperger 983 dispersing agent manufactured by Taiwan Demodex company, 6 parts of an ethanol solution with a mass fraction of 95%, 1 part of isopropanol, 2 parts of n-butanol and 2 parts of ethyl acetate;
the Gao Naishui polyamide printing ink is prepared by the following steps:
s1: mixing and stirring ethanol solution with the mass fraction of 95%, isopropanol, n-butanol and ethyl acetate uniformly to prepare a mixed solvent;
s2: uniformly mixing and stirring polyamide resin liquid, ternary vinyl chloride-acetate resin liquid and rosin modified 2-fluoroacrylic acid resin liquid to prepare combined resin liquid;
s3: adding alcohol-soluble dye, combined resin liquid, fumed silica and a disperger 983 dispersing agent produced by the Taiwan court of the Carnis, into a mixed solvent, and uniformly stirring to obtain the high-water-resistance polyamide printing ink.
Example 8
The high-water-resistance polyamide printing ink comprises the following components in parts by weight: 26 parts of the polyamide resin liquid obtained in example 2, 15 parts of the ternary vinyl chloride-acetate copolymer, 11 parts of the rosin-modified 2-fluoroacrylic acid resin liquid obtained in example 5, 15 parts of an alcohol-soluble dye, 1 part of fumed silica, 0.5 part of a disperger 983 dispersing agent manufactured by the Demodex of Taiwan, 8 parts of an ethanol solution with a mass fraction of 95%, 2 parts of isopropanol, 3 parts of n-butanol and 3 parts of ethyl acetate;
the Gao Naishui polyamide printing ink is prepared by the following steps:
s1: mixing and stirring ethanol solution with the mass fraction of 95%, isopropanol, n-butanol and ethyl acetate uniformly to prepare a mixed solvent;
s2: uniformly mixing and stirring polyamide resin liquid, ternary vinyl chloride-acetate resin liquid and 2-fluoroacrylic acid resin liquid to prepare combined resin liquid;
s3: adding alcohol-soluble dye, combined resin liquid, fumed silica and a disperger 983 dispersing agent produced by the Taiwan court of the Carnis, into a mixed solvent, and uniformly stirring to obtain the high-water-resistance polyamide printing ink.
Example 9
The high-water-resistance polyamide printing ink comprises the following components in parts by weight: 30 parts of the polyamide resin liquid obtained in example 3, 20 parts of the ternary vinyl chloride-acetate copolymer, 15 parts of the rosin-modified 2-fluoroacrylic acid resin liquid obtained in example 6, 20 parts of an alcohol-soluble dye, 1.2 parts of fumed silica, 0.6 part of a disperger 983 dispersing agent manufactured by Taiwan Demodex company, 10 parts of an ethanol solution with a mass fraction of 95%, 4 parts of isopropanol, 4 parts of n-butanol and 5 parts of ethyl acetate;
the Gao Naishui polyamide printing ink is prepared by the following steps:
s1: mixing and stirring ethanol solution with the mass fraction of 95%, isopropanol, n-butanol and ethyl acetate uniformly to prepare a mixed solvent;
s2: uniformly mixing and stirring polyamide resin liquid, ternary vinyl chloride-acetate resin liquid and 2-fluoroacrylic acid resin liquid to prepare combined resin liquid;
s3: adding alcohol-soluble dye, combined resin liquid, fumed silica and a disperger 983 dispersing agent produced by the Taiwan court of the Carnis, into a mixed solvent, and uniformly stirring to obtain the high-water-resistance polyamide printing ink.
The high water resistant polyamide printing inks obtained in examples 7 to 9 were subjected to adhesion test for adhesion fastness, volatile matter test toxicity, water resistance test and weather resistance test, and specific data are shown in the following table:
the data given in the table show that the printing ink obtained by the invention has good adhesive force, is nontoxic and environment-friendly, has good water resistance, is less influenced by acid-base environment and has wider application range.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.

Claims (5)

1. The high-water-resistance polyamide printing ink is characterized by comprising the following components in parts by weight: 22-30 parts of polyamide resin liquid, 10-20 parts of ternary vinyl chloride-acetate resin liquid, 8-15 parts of rosin modified 2-fluoroacrylic acid resin liquid, 12-20 parts of alcohol-soluble dye, 0.8-1.2 parts of fumed silica, 0.4-0.6 part of dispersing agent, 6-10 parts of ethanol solution with the mass fraction of 95%, 1-4 parts of isopropanol, 2-4 parts of n-butanol and 2-5 parts of ethyl acetate;
the Gao Naishui polyamide printing ink is configured to be prepared by:
s1: mixing and stirring ethanol solution with the mass fraction of 95%, isopropanol, n-butanol and ethyl acetate uniformly to prepare a mixed solvent;
s2: uniformly mixing and stirring polyamide resin liquid, ternary vinyl chloride-acetate resin liquid and rosin modified 2-fluoroacrylic acid resin liquid to prepare combined resin liquid;
s3: adding the alcohol-soluble dye, the combined resin liquid, the fumed silica and the dispersing agent into the mixed solvent, and uniformly stirring to obtain the high-water-resistance polyamide printing ink;
wherein the polyamide resin liquid is prepared by the following steps:
a1: adding tetrafluorosuccinic anhydride and ethanol into a reaction vessel provided with a stirrer and a thermometer, stirring and mixing uniformly, heating to 50-60 ℃ in an oil bath, dripping divinyl triamine, stirring for 3-5 h, and distilling under reduced pressure to remove the solvent to obtain an intermediate;
a2: adding ethylenediamine and an intermediate into deionized water, wherein the mol ratio of ethylenediamine to the intermediate to deionized water is 1:2: 5-9, heating to 80-100 ℃, reacting for 4-6 h, distilling under reduced pressure, precipitating and filtering, drying the precipitate in a vacuum drying oven at 50-90 ℃ for 12-48 h, cooling and grinding to obtain solid powder according to the mass ratio of 1:1 is mixed with absolute ethyl alcohol, and the temperature is raised to dissolve the solid powder to obtain the polyamide resin liquid.
2. The high water resistant polyamide printing ink according to claim 1, wherein the molar ratio of tetrafluorosuccinic anhydride, divinyl triamine and ethanol in step A1 is from 0.6 to 1:1 to 1.4:20.
3. the high water resistant polyamide printing ink according to claim 1, wherein the ternary chlorine-containing resin liquid is a mixed liquid obtained by uniformly mixing and stirring hydroxyl ternary chlorine-containing resin with ethanol.
4. The high water resistant polyamide printing ink of claim 1 wherein the rosin modified 2-fluoroacrylic resin liquid is prepared by:
b1: heating rosin in a reaction kettle, when the temperature is raised to 150-160 ℃, starting a reaction kettle stirrer, then adding 4,4' -thiobis (6-tertiary butyl-3-methylphenol) into the reaction kettle for reaction, continuously heating to 190-210 ℃, adding 2-fluoroacrylic acid, sealing the reaction kettle, controlling the pressure of the reaction kettle to be 0.1-0.3 MPa, reacting for 2h, removing the pressure of the reaction kettle, continuously heating to 240-260 ℃, adding glycerol, and reacting for 1h;
b2: vacuumizing the reaction kettle for 0.5h, cooling to 200 ℃, filtering the material obtained by the esterification reaction in the step B1 by using a 200-mesh filter bag to remove impurities, adding absolute ethyl alcohol with the same mass as the material after removing the impurities, stirring and mixing, and heating to dissolve to obtain the rosin modified 2-fluoroacrylic acid resin liquid.
5. The high water resistant polyamide printing ink as claimed in claim 4, wherein the mass ratio of rosin, 4' -thiobis (6-t-butyl-3-methylphenol), 2-fluoroacrylic acid and glycerin in step B1 is 100:0.05-0.2:7-8:3-5.
CN202310925323.0A 2023-07-26 2023-07-26 High-water-resistance polyamide printing ink and preparation method thereof Active CN116731557B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310925323.0A CN116731557B (en) 2023-07-26 2023-07-26 High-water-resistance polyamide printing ink and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310925323.0A CN116731557B (en) 2023-07-26 2023-07-26 High-water-resistance polyamide printing ink and preparation method thereof

Publications (2)

Publication Number Publication Date
CN116731557A CN116731557A (en) 2023-09-12
CN116731557B true CN116731557B (en) 2024-03-05

Family

ID=87902878

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310925323.0A Active CN116731557B (en) 2023-07-26 2023-07-26 High-water-resistance polyamide printing ink and preparation method thereof

Country Status (1)

Country Link
CN (1) CN116731557B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117586497B (en) * 2023-11-27 2024-05-03 江苏众立生包装科技有限公司 Preparation method of printing ink based on amino-terminated hyperbranched polyamide

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5698662A (en) * 1994-01-28 1997-12-16 Dsm N.V. Dendritic macomolecule and a process for the preparation thereof
KR20050110677A (en) * 2005-09-16 2005-11-23 야스히로 모리 Method for surface preparation of solid substances and surface-prepared solid substances
CN1772357A (en) * 2005-10-31 2006-05-17 浙江大学 Microporous polymer film containing cross-linked super branched molecule and its prepn
CN102585601A (en) * 2012-01-30 2012-07-18 郑州峰源油墨有限公司 Alcohol-soluble polyamide gravure plastic surface printing ink
WO2013053086A1 (en) * 2011-10-10 2013-04-18 金发科技股份有限公司 Heat resistant polyamide composition and application thereof
CN103289092A (en) * 2013-05-20 2013-09-11 西北工业大学 Preparation method of A2+B'B2+B2 type hyperbranched polyimide resin
JP2019065122A (en) * 2017-09-29 2019-04-25 東レ株式会社 Polyamide resin composition and molding containing the same
CN110330634A (en) * 2019-06-18 2019-10-15 湖北大学 A kind of preparation method of the hyperbranched fluorine-containing aqueous polyurethane of novel hydrolysis
CN110467540A (en) * 2019-09-12 2019-11-19 南京工业大学 A kind of synthetic method of fluorine-containing polyethyleneimine
CN111334039A (en) * 2020-04-27 2020-06-26 广东圆融新材料有限公司 Reinforced polyamide 66 composition and method for making same
CN114133565A (en) * 2021-12-08 2022-03-04 江苏艾森半导体材料股份有限公司 Hyperbranched polyimide resin and preparation method and application thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5698662A (en) * 1994-01-28 1997-12-16 Dsm N.V. Dendritic macomolecule and a process for the preparation thereof
KR20050110677A (en) * 2005-09-16 2005-11-23 야스히로 모리 Method for surface preparation of solid substances and surface-prepared solid substances
CN1772357A (en) * 2005-10-31 2006-05-17 浙江大学 Microporous polymer film containing cross-linked super branched molecule and its prepn
WO2013053086A1 (en) * 2011-10-10 2013-04-18 金发科技股份有限公司 Heat resistant polyamide composition and application thereof
CN102585601A (en) * 2012-01-30 2012-07-18 郑州峰源油墨有限公司 Alcohol-soluble polyamide gravure plastic surface printing ink
CN103289092A (en) * 2013-05-20 2013-09-11 西北工业大学 Preparation method of A2+B'B2+B2 type hyperbranched polyimide resin
JP2019065122A (en) * 2017-09-29 2019-04-25 東レ株式会社 Polyamide resin composition and molding containing the same
CN110330634A (en) * 2019-06-18 2019-10-15 湖北大学 A kind of preparation method of the hyperbranched fluorine-containing aqueous polyurethane of novel hydrolysis
CN110467540A (en) * 2019-09-12 2019-11-19 南京工业大学 A kind of synthetic method of fluorine-containing polyethyleneimine
CN111334039A (en) * 2020-04-27 2020-06-26 广东圆融新材料有限公司 Reinforced polyamide 66 composition and method for making same
CN114133565A (en) * 2021-12-08 2022-03-04 江苏艾森半导体材料股份有限公司 Hyperbranched polyimide resin and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
A novel bio-based AB2 monomer for preparing hyperbranched polyamides derived from levulinic acid and furfurylamine;Meng-Ling Yang;POLYMER CHEMISTRY;第10卷(第45期);第6217-6226页 *
超支化聚酰胺合成与研究进展;孙静;;上海化工;第36卷(第06期);第19-24页 *

Also Published As

Publication number Publication date
CN116731557A (en) 2023-09-12

Similar Documents

Publication Publication Date Title
CN116731557B (en) High-water-resistance polyamide printing ink and preparation method thereof
CN102675968B (en) Water-based soybean oil ink and preparation method thereof
CN102382516B (en) Water-based plastic printing ink and preparation method thereof
CN101665638B (en) Aquosity optical variable ink and preparing method thereof
CN110951440A (en) Polyurethane acrylate multi-component curing conductive silver adhesive
CN114806262A (en) High-stability spot color ink and preparation method thereof
CN110563918A (en) Preparation method of modified grafted polyurethane resin
CN106084988B (en) A kind of multifunctional water-based ink
CN102816475B (en) Alcohol soluble white board marker ink easy to dry-erase and preparation method thereof
CN101392043A (en) Method for preparing resin for high water resistant waterborne glass ink
CN114213918A (en) Water-based wood clear primer and preparation method thereof
CN112322107B (en) Silk-screen printing ink for PC (polycarbonate) material
CN111234610B (en) Water-based ink-jet pigment color paste and preparation method and application thereof
CN113072840A (en) Thermal sublimation ink based on compound disperse black dye and preparation method thereof
CN113025163A (en) Laser corrosion-resistant water-based paint for plate making
CN112063232A (en) Blue ink for motor vehicle license plate
CN109021685B (en) Hydrophobic color fixing ink and preparation process thereof
CN111363444A (en) Preparation method of high-adhesion self-crosslinking water-based paint
CN1276398A (en) Water ink of compound resin
CN111087557A (en) Application of alcohol-resistant diluted and grindable gravure emulsion in ink
CN115368798B (en) Electrochemical aluminum laser layer coating and preparation method thereof
CN111138578B (en) Hyperbranched polyvinyl acetate and high-stability writing ink based on same
CN115440412B (en) Cardanol derivative-based conductive paste
CN113201254A (en) Water-based nano anti-counterfeiting ink-jet ink and preparation method thereof
CN117986917B (en) Water-based UV (ultraviolet) ink and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant