CN106488960B - Water-based gravure plastic printing table printing/composite ink, binder and preparation method of water-based gravure plastic printing table printing/composite ink and binder - Google Patents

Water-based gravure plastic printing table printing/composite ink, binder and preparation method of water-based gravure plastic printing table printing/composite ink and binder Download PDF

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CN106488960B
CN106488960B CN201580002486.5A CN201580002486A CN106488960B CN 106488960 B CN106488960 B CN 106488960B CN 201580002486 A CN201580002486 A CN 201580002486A CN 106488960 B CN106488960 B CN 106488960B
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water
binder
reaction kettle
ink
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CN106488960A (en
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孟宪平
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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
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • 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
    • C09D11/023—Emulsion inks
    • 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
    • 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
    • C09D193/00—Coating compositions based on natural resins; Coating compositions based on derivatives thereof
    • C09D193/04—Rosin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate

Abstract

A water-based plastic gravure printing table/composite ink, a binder and a preparation method thereof, wherein the ink is prepared from the following components: 68-88 parts of a connecting material, 10-30 parts of an organic pigment, 0.1-0.15 part of an adhesion promoter, 1-1.5 parts of a drying aid and 0.2-0.5 part of a defoaming agent. The binder is prepared from the following components: 1-8 parts of modified rosin, 1.5-4.5 parts of methacrylic acid monomer or acrylic acid monomer, 4-25 parts of acrylate monomer, 20-28 parts of methacrylate monomer, 0.8-2 parts of azodiisobutyronitrile, 28-30 parts of absolute ethyl alcohol, 4-7 parts of amine or ammonia, 0.5-3 parts of cosolvent and 30-32 parts of distilled water. The modified rosin is adopted to reduce the molecular weight and viscosity of acrylic resin, improve the content of resin in the ink body, adjust the cohesive force of the resin, enable the solvent to be easily released, and enable the ink body to have good fluidity, thereby achieving the purposes of quick drying and smoothness of an ink film.

Description

Water-based gravure plastic printing table printing/composite ink, binder and preparation method of water-based gravure plastic printing table printing/composite ink and binder
Technical Field
The invention relates to the field of plastic printing ink, in particular to water-based gravure plastic printing surface printing/composite ink, a binder and a preparation method of the water-based gravure plastic printing surface printing/composite ink and the binder.
Background
At present, more than 90% of plastic printing enterprises in China still adopt solvent-based ink for printing, and in order to meet the requirements of drying speed and print quality, toxic solvents with extremely high volatility, such as toluene, xylene, ethyl acetate and the like, are widely applied to the solvent-based ink. The solvent-based ink is prepared by compounding chlorinated polymer with aromatic compounds such as benzene as a strong solvent, benzene, lipid and alcohol are used as diluents when the solvent-based ink is used, a large amount of toxic (solvent) gas can volatilize in the production and use processes of the ink, the ozone layer of the atmosphere is seriously damaged, the great environmental pollution is caused, the great harm is caused to the health of people, particularly, the health of operators is directly harmed, and the solvent retention in an operation workshop exceeds the standard (particularly in winter) due to the large volatilization of the solvent, so that the great fire safety hazard is formed. In addition, benzene is easy to remain in the dry printing ink microfilm, the benzene residue is easy to increase by dimethylbenzene, the safety of the printed food flexible package is poor, the physical and psychological health of people is directly affected, and the harm to children is huge.
Although alcohol-soluble ink appearing in the market is relatively environment-friendly, some plastic printing enterprises mostly adopt methanol with low price to replace ethanol with slightly high price as a diluent for reducing cost, gas volatilized from the methanol still pollutes the environment, the long-term use directly influences the health of operators, especially eyes, and the characteristic of strong volatility of the methanol easily causes fire safety hazards.
The water-based plastic printing ink on the market has the defects of low drying speed, poor color spreading, poor adhesion fastness, poor water resistance, wet heat resistance, poor glossiness, poor ink film strength, easy generation of pigment precipitation during storage, no freezing prevention and the like, and cannot meet the requirements of high printing speed and high quality of printed products in the existing plastic printing; the drying problem is solved by increasing the drying tunnel of the printing machine abroad, but the printing cost is increased, so that the drying tunnel is not accepted, popularized and applied by the majority of printing enterprises.
Disclosure of Invention
The invention aims to overcome the defects in the background technology, and provides a water-based gravure plastic printing surface printing/composite ink, a connecting material and a preparation method of the water-based gravure plastic printing surface printing/composite ink and the connecting material, so as to solve the problems of slow drying speed, poor color development, poor water resistance and humidity resistance of the water-based plastic printing ink and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a water-based gravure plastic printing table printing/composite ink adopts the technical scheme that:
the water-based gravure plastic printing table printing/composite ink is prepared from the following components in parts by weight: 68-88 parts of a connecting material, 10-30 parts of an organic pigment, 0.1-0.15 part of an adhesion promoter, 1-1.5 parts of a drying aid and 0.2-0.5 part of a defoaming agent.
The preparation method of the water-based gravure plastic printing table printing/composite ink adopts the following technical scheme:
the method comprises the following steps: mixing binder resin, organic pigment, adhesion promoter, drying aid and defoaming agent; dispersing and grinding the mixture into tiny particles by a high-speed dispersion machine; and (6) packaging.
The technical scheme adopted by the connecting material is as follows:
the connecting material is prepared from the following components in parts by weight: 1-8 parts of modified rosin, 1.5-4.5 parts of methacrylic acid monomer or acrylic acid monomer, 4-25 parts of acrylate monomer, 20-28 parts of methacrylate monomer, 0.8-2 parts of azodiisobutyronitrile, 28-30 parts of absolute ethyl alcohol, 4-7 parts of amine or ammonia, 0.5-3 parts of cosolvent and 30-32 parts of distilled water.
The technical scheme adopted for preparing the connecting material is as follows:
mixing acrylic acid monomer or methacrylic acid monomer, acrylate monomer, methacrylate monomer and azodiisobutyronitrile according to the weight part ratio to prepare materials, putting the materials into a raw material head tank of a reaction kettle, and uniformly stirring;
putting absolute ethyl alcohol into a reaction kettle with a condenser and a nitrogen inlet pipe, closing a cooling pipe in the kettle, adding modified rosin while stirring, opening a nitrogen pipe valve to introduce nitrogen, replacing the air in the reaction kettle, and simultaneously heating to 80-82 ℃ to melt the modified rosin;
opening a flow meter to dropwise add the prepared materials into the reaction kettle at a constant speed, simultaneously opening a condenser to recover gas, stirring while dropwise adding, controlling the dropwise adding speed at 2-3 hours, and completely dropwise adding the prepared materials in the raw material head tank;
raising the temperature in the reaction kettle to 82-85 ℃, and preserving the temperature for more than 4 hours to prepare a copolymer solution; the mass ratio solid content of the resin in the prepared copolymer solution is 58-62%; the glass transition temperature of the obtained copolymer is in the range of 15-38 ℃;
after the polymerization is completed, opening a cooling device in the reaction kettle, reducing the temperature to 60-65 ℃, adding amines or ammonia, adjusting the pH value of the copolymer to 8.5-9.0, simultaneously adding a cosolvent and distilled water, and adjusting the solid content mass ratio of the resin to 38% -42%, thereby obtaining the water-soluble acrylic resin binder.
Compared with the prior art, the preparation of the water-based gravure plastic printing table printing/composite ink and the binder has the following advantages: the modified rosin is used as a molecular weight regulator in acrylic resin polymerization instead of (n) -tert-dodecyl mercaptan, so that the molecular weight and viscosity of the acrylic resin are effectively reduced, the content of the resin in the ink body is increased, the cohesive force of the resin is adjusted, the solvent is easily released, and the fluidity of the ink body is good, so that the quick drying and the smoothness of an ink film are achieved.
The modified rosin is used as an emulsifier of the acrylic resin, so that bubbles are not easy to generate in an ink body, the glossiness is improved, the consumption of (methyl) acrylic monomers in polymerization is reduced, the water resistance of an ink film is improved, a printed product completely achieves the printing effect of solvent-based ink, and the ink film is high in glossiness and excellent in water resistance and humidity resistance.
The modified rosin is used as the modifier of the acrylic resin, so that the bonding strength and the color-spreading force of the acrylic resin and pigment particles are effectively improved, pigment precipitation is not generated in the long-term storage and use process of the ink body, and the printed product is bright in color.
The preferable scheme adopted by the water-based gravure plastic printing table printing/composite ink is as follows:
the adhesion promoter is polyethyleneimine or titanate coupling agent.
The drying assistant is light calcium carbonate.
The defoaming agent is a mixture of non-organosilicon amides and hydrocarbons.
The organic pigment includes: stabilizing phthalocyanine blue, phthalocyanine green, benzidine yellow, lithol rubine, and titanium dioxide.
The preparation method of the gravure plastic printing table printing/composite ink adopts the following preferred scheme:
the particle size of the particles is less than or equal to 15 microns.
The preferable scheme adopted by the connecting material for the ink is as follows:
the cosolvent is propylene glycol ether,
the amine added after polymerization is triethylamine; the ammonia is ammonia water.
After the heat preservation is carried out for 4 hours, the solid content mass ratio of the resin in the prepared copolymer solution is 60%.
When in use, pollution-free water or distilled water is used as a diluent, so that the pressure of petroleum products is relieved, the printing cost is greatly reduced, a printed product has no solvent residue, and the effect of solvent-based ink printing is achieved; the drying speed (with hot air at 50-60 ℃) is up to 110-150 meters per minute, the adhesion fastness is strong (the printing base material needs to be processed by electric spark), the glossiness is high, the transparency is good, the scratch resistance is strong, the water resistance and the humidity resistance are excellent, the application range is wide, the printing ink can be suitable for various plastic base materials, and the prospect is considerable.
Detailed Description
The invention is described in detail below with reference to examples:
example 1
The preparation method of the binder in the embodiment is carried out according to the following steps:
mixing 28kg of methacrylic acid monomer, 224kg of n-butyl methacrylate monomer, 64kg of methyl methacrylate monomer, 56kg of butyl acrylate monomer and 8kg of azobisisobutyronitrile into a prepared material, putting the prepared material into a raw material elevated tank which is connected to the upper part of a reaction kettle and is provided with a flow agent, and uniformly stirring the material.
Putting 258kg of absolute ethyl alcohol into a reaction kettle which is provided with a condenser and a nitrogen inlet pipe and is internally provided with a water cooling device, closing the cooling pipe in the kettle, adding 28kg of hydrogenated rosin while stirring, opening a nitrogen pipe valve to introduce nitrogen, replacing the air in the reaction kettle, and simultaneously heating to 80 ℃ to melt the hydrogenated rosin.
And opening a flow meter to dropwise add the prepared materials into the reaction kettle at a constant speed, simultaneously opening a condenser to recycle gas, stirring while dropwise adding, and completely dropwise adding the prepared materials in the raw material overhead tank within 2-3 hours at the dropwise adding speed.
Heating the temperature in the reaction kettle to 82 ℃, and preserving the temperature for 4 hours to obtain a copolymer solution with the solid content of 60 percent; the glass transition temperature range of the obtained copolymer is 35-36 ℃.
After the polymerization is completed, opening the cooling device in the reaction kettle, reducing the temperature to 65 ℃, adding 52kg of triethylamine, adjusting the pH value of the copolymer to 8.5-9.0, simultaneously adding 5kg of propylene glycol methyl ether and 277kg of distilled water, and adjusting the mass ratio solid content of the resin to 40% to obtain the water-soluble acrylic resin binder.
Example 2
In this example is a method of mixing the water-soluble acrylic resin vehicle obtained in example 1 and preparing a surface printing/composite ink.
Mixing 68.7 parts by mass of water-soluble acrylic resin binder, 30 parts by mass of titanium dioxide, 0.1 part by mass of titanate coupling agent, 1 part by mass of light calcium carbonate (calcium carbonate with finer and more uniform particles) and 0.2 part by mass of defoaming agent (080 defoaming agent produced by Taiwan Demodest company), dispersing and grinding the mixture by a high-speed dispersion machine until the particle size of the particles is less than or equal to 15 microns, and packaging the mixture; the quick-drying water-soluble gravure plastic printing surface printing/composite ink has the advantages of high adhesion fastness, high glossiness, good transparency, high scratch resistance and excellent water resistance and humidity resistance, and the drying speed (with hot air at 50-60 ℃) reaches 110-150 meters per minute.
Example 3
The preparation method of the binder in the embodiment is carried out according to the following steps:
27kg of acrylic monomer, 95kg of ethyl acrylate monomer, 58kg of n-butyl methacrylate monomer, 125kg of methyl methacrylate monomer, 57kg of n-butyl acrylate monomer and 10kg of azobisisobutyronitrile are mixed to prepare a stock, and the stock is put into a raw material elevated tank connected to the upper part of a reaction kettle and provided with a flow agent and stirred uniformly.
Putting 256.5kg of absolute ethyl alcohol into a reaction kettle which is provided with a condenser and a nitrogen inlet pipe and is internally provided with a water cooling device, closing a cooling pipe in the kettle, adding 38kg of polymerized rosin while stirring, opening a nitrogen pipe valve to introduce nitrogen, replacing the air in the reaction kettle, and simultaneously heating to 80 ℃ to melt the polymerized rosin.
And opening a flow meter to dropwise add the prepared materials into the reaction kettle at a constant speed, simultaneously opening a condenser to recycle gas, stirring while dropwise adding, and completely dropwise adding the prepared materials in the raw material overhead tank within 2-3 hours at the dropwise adding speed.
Heating the temperature in the reaction kettle to 82 ℃, and preserving the temperature for 4 hours to obtain a copolymer solution with the solid content of 60 percent by mass; the vitrification range of the obtained copolymer glass is 32-33 ℃.
After the polymerization is completed, opening a condensation device in the reaction kettle, reducing the temperature to 60-65 ℃, adding 53kg of triethylamine, adjusting the pH value of the copolymer to 8.5-9.0, simultaneously adding 3kg of propylene glycol methyl ether and 275kg of distilled water, and adjusting the solid content to 40% to obtain the water-soluble acrylic resin connecting material.
Example 4
In this example is a method of mixing the water-soluble acrylic resin vehicle obtained in example 3 and preparing a surface printing/composite ink.
Mixing 88 parts by mass of water-soluble acrylic resin binder, 10 parts by mass of phthalocyanine blue BGS, 0.15 part by mass of polyethyleneimine, 1.5 parts by mass of light calcium carbonate and 0.5 part by mass of defoaming agent (080 defoaming agent produced by Taiwan Demodesty), dispersing and grinding the mixture by a high-speed dispersion machine until the particle size of the particles is less than or equal to 15 microns, and packaging the mixture; thus obtaining the water-soluble gravure plastic printing surface printing/composite ink.
Example 5
The preparation method of the binder in the embodiment is carried out according to the following steps:
27kg of acrylic monomer, 103kg of methyl methacrylate monomer, 112kg of n-butyl methacrylate monomer, 101kg of ethyl acrylate monomer, 29kg of n-butyl acrylate monomer and 9.5kg of azobisisobutyronitrile are mixed into a stock, put into a raw material head tank connected to the upper part of a reaction kettle and provided with a flow agent, and stirred uniformly.
Putting 256.5kg of absolute ethyl alcohol into a reaction kettle which is provided with a condenser and a nitrogen inlet pipe and is internally provided with a water cooling device, closing a cooling pipe in the kettle, adding 28kg of polymerized rosin while stirring, opening a nitrogen pipe valve to introduce nitrogen, replacing the air in the reaction kettle, and simultaneously heating to 80 ℃ to melt the polymerized rosin.
And opening a flow meter to dropwise add the prepared materials into the reaction kettle at a constant speed, simultaneously opening a condenser to recycle gas, stirring while dropwise adding, and completely dropwise adding the prepared materials in the raw material overhead tank within 2-3 hours at the dropwise adding speed.
Heating the temperature in the reaction kettle to 82 ℃, and preserving the temperature for 4 hours to obtain a copolymer solution with the solid content of 60 percent by mass; the vitrification range of the obtained copolymer is 32-33 ℃.
After the polymerization is completed, opening the cooling device in the reaction kettle, reducing the temperature to 60-65 ℃, adding 54.8kg of triethylamine, adjusting the pH value of the copolymer to 8.5-9.0, simultaneously adding 5kg of propylene glycol ethyl ether and 274kg of distilled water, and adjusting the solid content to 40% to obtain the water-soluble acrylic resin binder.
Example 6
In this example is a method of mixing the water-soluble acrylic resin vehicle obtained in example 5 and preparing a surface printing/composite ink.
Mixing 86.7 parts by mass of water-soluble acrylic resin binder, 12 parts by mass of phthalocyanine green G, 0.12 part by mass of polyethyleneimine, 1.2 parts by mass of light calcium carbonate and 0.3 part by mass of defoaming agent, dispersing and grinding the mixture by a high-speed dispersion machine until the particle size of the particles is less than or equal to 15 microns, and packaging; thus obtaining the water-soluble gravure plastic printing surface printing/composite ink.
Example 7
The preparation method of the binder in the embodiment is carried out according to the following steps:
16kg of acrylic monomer, 204kg of isobutyl methacrylate monomer, 32kg of 2-hydroxyethyl methacrylate monomer, 104kg of n-butyl acrylate monomer, 20kg of ethyl acrylate monomer and 9kg of azobisisobutyronitrile are mixed into a prepared material, and the prepared material is put into a raw material elevated tank which is connected to the upper part of a reaction kettle and is provided with a flow agent and is stirred uniformly.
Putting 256.5kg of absolute ethyl alcohol into a reaction kettle which is provided with a condenser and a nitrogen inlet pipe and is internally provided with a water cooling device, closing a cooling pipe in the kettle, adding 24kg of disproportionated rosin under stirring, opening a nitrogen pipe valve to introduce nitrogen, replacing the air in the reaction kettle, simultaneously heating to 80 ℃, and melting the disproportionated rosin.
And opening a flow meter to dropwise add the prepared materials into the reaction kettle at a constant speed, simultaneously opening a condenser to recycle gas, stirring while dropwise adding, and completely dropwise adding the prepared materials in the head tank within 2-3 hours at the dropwise adding speed.
Heating the temperature in the reaction kettle to 82 ℃, and preserving the temperature for 4 hours to obtain a copolymer solution with the solid content of 60 percent by mass; the glass transition temperature of the obtained copolymer is 19-20 ℃.
After the polymerization is completed, opening the cooling device in the reaction kettle, reducing the temperature to 60-65 ℃, adding 55kg of triethylamine, adjusting the pH value of the copolymer to 8.5-9.0, simultaneously adding 4kg of propylene glycol ethyl ether and 274.5kg of distilled water, and adjusting the solid content to 40% to obtain the water-soluble acrylic resin binder.
Example 8
In this example is a method of mixing the water-soluble acrylic resin vehicle obtained in example 7 and preparing a surface printing/composite ink.
Mixing 88.66 parts by mass of water-soluble acrylic resin binder, 10 parts by mass of benzidine yellow G, 0.14 part by mass of titanate coupling agent, 1.3 parts by mass of light calcium carbonate and 0.4 part by mass of defoaming agent (080 defoaming agent manufactured by Taiwan Demodex corporation), dispersing and grinding the mixture by a high-speed dispersion machine until the particle size of the particles is less than or equal to 15 microns, and packaging the mixture; thus obtaining the water-soluble gravure plastic printing surface printing/composite ink.
Example 9
The preparation method of the binder in the embodiment is carried out according to the following steps:
24kg of acrylic monomer, 20kg of methacrylic acid-2-hydroxypropyl ester monomer, 92kg of methyl methacrylate monomer, 124kg of n-butyl methacrylate monomer, 116kg of ethyl acrylate monomer and 9.5kg of azobisisobutyronitrile are mixed into a stock, and the stock is put into a raw material elevated tank which is connected to the upper part of a reaction kettle and is provided with a flow agent and is stirred uniformly.
Putting 256.5kg of absolute ethyl alcohol into a reaction kettle which is provided with a condenser and a nitrogen inlet pipe and is internally provided with a water cooling device, closing a cooling pipe in the kettle, adding 24kg of hydrogenated rosin under stirring, opening a nitrogen pipe valve to introduce nitrogen, replacing the air in the reaction kettle, and simultaneously heating to 80 ℃ to melt the hydrogenated rosin.
And opening a flow meter to dropwise add the prepared materials into the reaction kettle at a constant speed, simultaneously opening a condenser to recycle gas, stirring while dropwise adding, and completely dropwise adding the prepared materials in the high-level feeding tank within 2-3 hours at the dropwise adding speed.
Heating the temperature in the reaction kettle to 82 ℃, and preserving the temperature for 4 hours to obtain a copolymer solution with the solid content of 60 percent by mass; the glass transition temperature of the copolymer is 32-33 ℃.
After the polymerization is completed, opening the cooling device in the reaction kettle, reducing the temperature to 60-65 ℃, adding 38kg of ammonia water, adjusting the pH value of the copolymer to 8.5-9.0, simultaneously adding 5kg of propylene glycol methyl ether and 289kg of distilled water, and adjusting the solid content to 40% to obtain the water-soluble acrylic resin connecting material.
Example 10
In this example, a method of mixing the water-soluble acrylic resin binder obtained in example 9 to prepare a surface printing/composite ink was performed.
Mixing 86 parts by mass of water-soluble acrylic resin binder, 12 parts by mass of lithol rubine BK, 0.13 part by mass of polyethyleneimine, 1.1 part by mass of light calcium carbonate and 0.2 part by mass of defoaming agent, dispersing and grinding the mixture by a high-speed dispersion machine until the particle size of the particles is less than or equal to 15 micrometers, and packaging; thus obtaining the water-soluble gravure plastic printing surface printing/composite ink.
The above examples are illustrative of the present invention, but the present invention is not limited to the examples, and those skilled in the art can make various equivalent formulations and equivalent modifications of the preparation method without departing from the spirit of the present invention, and these equivalent modifications are included in the scope of the present invention defined by the claims.

Claims (5)

1. A preparation method of a binder for water-based plastic gravure printing table printing/composite ink comprises the following steps:
mixing 1.5-4.5 parts of acrylic acid monomer or methacrylic acid monomer, 4-25 parts of acrylate monomer, 20-28 parts of methacrylate monomer and 0.8-2 parts of azodiisobutyronitrile according to the weight part ratio to prepare a material, and putting the material into a raw material head tank of a reaction kettle to be uniformly stirred;
putting 28-30 parts of absolute ethyl alcohol into a reaction kettle with a condenser and a nitrogen inlet pipe, closing a cooling pipe in the kettle, adding 1-8 parts of modified rosin while stirring, opening a nitrogen valve to introduce nitrogen, replacing air in the reaction kettle, and heating to 80-82 ℃ to melt the modified rosin;
opening a flow meter to drip the prepared material into a reaction kettle at a constant speed, simultaneously opening a condenser to recover gas, stirring while dripping, controlling the dripping speed at 2-3 hours, and completely dripping the prepared material in a raw material head tank;
raising the temperature in the reaction kettle to 82-85 ℃, and keeping the temperature for more than 4 hours to prepare a copolymer solution; the mass ratio of resin to solid content in the prepared copolymer solution is 58-62%, and the vitrification temperature of the obtained copolymer is 15-38 ℃;
after the polymerization is completed, opening a cooling device in the reaction kettle, reducing the temperature to 60-65 ℃, adding 4-7 parts of amine or ammonia, adjusting the pH value of the polymerization solution to 8.5-9.0, simultaneously adding 0.5-3 parts of cosolvent and 30-32 parts of distilled water, and adjusting the solid content of the polymerization solution to 38% -42%, thus obtaining the water-soluble acrylic resin binder.
2. The method for preparing the binder for the water-based gravure plastic printing table/composite ink as claimed in claim 1, wherein: the cosolvent is propylene glycol ethers; the amine added after polymerization is triethylamine; the ammonia is ammonia water.
3. The method for preparing the binder for the water-based gravure plastic printing table/composite ink as claimed in claim 1, wherein: after the heat preservation is carried out for 4 hours, the solid content mass ratio of the resin in the prepared copolymer solution is 60%.
4. A method for preparing a water-based gravure plastic printing table/composite ink based on the binder of any one of claims 1 to 3, characterized in that: the composition is prepared from the following components in parts by weight: 68-88 parts of a connecting material, 10-30 parts of an organic pigment, 0.1-0.15 part of an adhesion promoter polyethyleneimine, 1-1.5 parts of a drying aid and 0.2-0.5 part of a defoaming agent; mixing the binder resin, the organic pigment, the adhesion promoter polyethyleneimine, the drying aid and the defoaming agent, and dispersing and grinding the mixture to a particle size of micro particles less than or equal to 15 microns by using a high-speed dispersion machine; and (6) packaging.
5. The method for preparing the water-based gravure plastic printing table/composite ink as claimed in claim 4, wherein: the drying assistant is light calcium carbonate, and the defoaming agent is a mixture of non-organosilicon amides and hydrocarbons.
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