CN108610739B - Modified amylopectin starch material, preparation method thereof and water-based ink containing modified amylopectin starch material - Google Patents
Modified amylopectin starch material, preparation method thereof and water-based ink containing modified amylopectin starch material Download PDFInfo
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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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
- C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
- C08B30/18—Dextrin, e.g. yellow canari, white dextrin, amylodextrin or maltodextrin; Methods of depolymerisation, e.g. by irradiation or mechanically
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- 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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- 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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two 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
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
Abstract
The invention provides a modified amylopectin starch material, a preparation method thereof and water-based ink containing the modified amylopectin starch material, wherein the preparation method comprises the following steps: (1) mixing amylopectin, maleic anhydride and a first initiator and then carrying out grafting reaction; (2) and adding part of the pH regulator and the second initiator into the amylopectin, mixing, then adding the modified monomer for grafting reaction, finally adding the cross-linking agent for cross-linking reaction, and then regulating the pH value by using the rest of the pH regulator to obtain the modified amylopectin material. The modified amylopectin provided by the invention has the advantages of higher minimum film forming temperature, better waterproofness, friction resistance and flexibility resistance, and can be used as a binder of water-based ink.
Description
Technical Field
The invention belongs to the field of modified materials, and relates to a modified amylopectin starch material, a preparation method thereof and water-based ink containing the modified amylopectin starch material.
Background
Starch is a natural high molecular polymer naturally mixed with amylopectin components and amylose components, the respective amylopectin and amylose components of starch have great differences in molecular structure, aggregation state and performance and application, and amylopectin is widely applied to the fields of food, packaging materials, water-soluble and biodegradable films and the like due to the functions of ageing resistance, freeze-thaw stability, thickening, high expansibility, water absorbability and the like.
The amylopectin as natural polymer has good adhesive force, ironing resistance and high temperature resistance, and the starch solution has good dispersion stability effect and leveling effect on the pigment, has certain film forming property and toughness, and is a completely biodegradable and renewable raw material. However, the amylopectin is hard and brittle in film formation, small in extensibility, poor in water resistance and easy to mildew and crack, and the pure amylopectin cannot meet the requirements of the water-based ink binder. Amylopectin can be subjected to a series of modifications, is endowed with excellent performance, such as acrylic acid-grafted starch connecting materials combined by organic-natural substances, and has wide application in the fields of papermaking, printing, coating and the like.
CN1709935A discloses a preparation method of starch grafted polyacrylamide and derivatives thereof inverse emulsion, which comprises the steps of preparing a connecting phase of an emulsifier oil solution, preparing a connecting phase of a solid solution of amylopectin and acrylamide, adding a dispersed phase into the connecting phase, and reacting to obtain starch grafted polyacrylamide and derivatives thereof inverse latex.
CN102875742A discloses a method for preparing a highly branched acrylamide graft copolymer with amylopectin as a backbone, wherein urea is used as a structure modifier, water-soluble vinyl monomer is grafted on amylopectin, and then an ethylenically unsaturated crosslinking monomer containing a ketone carbonyl group and a crosslinking agent capable of reacting with the crosslinking monomer are added to modify the branched and lightly crosslinked modified amylopectin, which can be applied to water-based ink, but the minimum film-forming temperature is low, the drying rate is too slow, so the printing adaptability is poor, and the water-based ink obtained finally has poor water resistance.
At present, a new modified amylopectin starch needs to be developed as a binder of the water-based ink to meet the requirements of the water-based ink.
Disclosure of Invention
The invention aims at a modified amylopectin starch material, a preparation method thereof and water-based ink containing the modified amylopectin starch material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a modified amylopectin starch material, comprising the steps of:
(1) mixing amylopectin, maleic anhydride and a first initiator and then carrying out grafting reaction;
(2) and adding part of the pH regulator and the second initiator into the amylopectin, mixing, then adding the modified monomer for grafting reaction, finally adding the cross-linking agent for cross-linking reaction, and then regulating the pH value by using the rest of the pH regulator to obtain the modified amylopectin material.
The modified amylopectin starch material comprises the following raw materials in parts by weight:
the modified monomer comprises any one or a combination of at least two of acrylamide, methacrylamide, acrylic acid, butyl acrylate, sodium acrylate, methacrylic acid, methyl methacrylate, butyl methacrylate, monobutyl itaconate, N-methylolacrylamide, glycidyl methacrylate and trimethylolpropane triacrylate.
According to the preparation method provided by the invention, the maleic anhydride grafted amylopectin is obtained firstly, so that the amylopectin has a certain degree of polymerization, acid value and reaction activity, and then the modified amylopectin is modified by using the modified monomer to obtain the modified amylopectin material, so that the modified amylopectin material has good water solubility, higher film forming temperature, good glossiness, higher drying rate and high surface adsorption energy, and is suitable for printing of water-based ink.
Preferably, the amylopectin starch is present in an amount of 25-40 parts by weight, such as 27 parts by weight, 30 parts by weight, 32 parts by weight, 35 parts by weight, 37 parts by weight, and the like.
Preferably, the weight parts of maleic anhydride is 5-8 weight parts, such as 6 weight parts, 7 weight parts, and the like.
Preferably, the pH adjuster is present in an amount of 1 to 5 parts by weight, such as 2 parts by weight, 3 parts by weight, 4 parts by weight, and the like.
Preferably, the modifying monomer is present in an amount of 10 to 30 parts by weight, such as 15 parts by weight, 17 parts by weight, 20 parts by weight, 22 parts by weight, 25 parts by weight, 27 parts by weight, and the like.
Preferably, the first initiator is present in an amount of 0.05 to 0.2 parts by weight, such as 0.08 parts by weight, 0.1 parts by weight, 0.12 parts by weight, 0.14 parts by weight, 0.16 parts by weight, 0.18 parts by weight, and the like.
Preferably, the second initiator is present in an amount of 0.05 to 0.2 parts by weight, such as 0.08 parts by weight, 0.1 parts by weight, 0.12 parts by weight, 0.14 parts by weight, 0.16 parts by weight, 0.18 parts by weight, and the like.
Preferably, the crosslinking agent is present in an amount of 0.008 to 0.65 parts by weight, such as 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, and the like.
Preferably, the modified monomer in the step (2) is a composition comprising (5-15) of butyl methacrylate, methyl methacrylate, glycidyl methacrylate and trimethylolpropane triacrylate in a mass ratio of (35-45) to (1-5), such as 5:35:35:1:1, 8:40:38:3:3, 10:40:40:5:5, 15:45:45:5:5, and the like.
When the modified monomer is composed of the monomers, the finally obtained modified amylopectin has higher minimum film forming temperature, can be quickly dried at the film forming temperature, and has good printing adaptability and color development.
Preferably, the mass ratio of the amylopectin to the modifying monomer is 2 (0.75-1.25), such as 2:0.75, 2:0.85, 2:0.95, 2:1, 2:1.1, 2:1.2, etc.
In the invention, the first initiator in the step (1) is dicumyl peroxide and/or dibenzoyl peroxide.
Preferably, the grafting reaction of step (1) is carried out in an internal mixer.
Preferably, the rotational speed of the internal mixer is 70-90r/min, such as 75r/min, 80r/min, 85r/min and the like.
Preferably, the reaction temperature of the grafting reaction is 125-145 ℃, such as 130 ℃, 135 ℃, 140 ℃ and the like, and the reaction time is 8-12min, such as 9min, 10min, 11min and the like.
Preferably, step (1) further comprises adding a water repellent and a plasticizer to the reaction system.
Preferably, the parts by weight of the water repellent are 2 to 5 parts by weight, for example 3 parts by weight, 4 parts by weight.
Preferably, the water repellent agent is ammonium zirconium carbonate.
The waterproof agent is added into the modified amylopectin material to react with the residual hydroxyl and carboxyl in the system, so that the finally obtained modified liquid has a waterproof function, and when the modified amylopectin material is applied to water-based ink, the finally obtained printing product has waterproofness.
Preferably, the weight parts of the plasticizer are 2 to 5 parts, for example 3 parts, 4 parts.
Preferably, the plasticizer includes any one or a combination of at least two of lauric acid, stearic acid, glycerin, and polyethylene glycol.
The addition of the plasticizer to the material can make the film formed by drying uniform and transparent, and can improve the water resistance and the water vapor barrier ability.
Preferably, step (1') is performed after step (1): mixing the amylopectin obtained in the step (1) with water, and then carrying out gelatinization treatment.
Preferably, the mass ratio of amylopectin to water in step (1') is (1.5-2.5):10, e.g. 1.7:10, 1.9:10, 2:10, 2.2:10, 2.4:10, etc.
Preferably, the gelatinization time in step (1') is 1-5 hours, such as 2 hours, 3 hours, 4 hours, etc., and the gelatinization temperature is 50-100 ℃, such as 60 ℃, 70 ℃, 80 ℃, 90 ℃, etc.
Preferably, the pH regulator in step (2) comprises any one or a combination of at least two of ammonia, monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol and N, N-dimethylethanolamine.
The pH regulator can regulate the pH value of the solution on one hand, and can increase the moisture retention before the water-based ink is dried on the other hand, so that the water-based ink can fully wet the plate, the redissolution property is good, the mesh point is moderate, and the defects of plate contamination and plate pasting are avoided.
Preferably, the second initiator in the step (2) is ammonium persulfate and/or potassium persulfate.
Preferably, the crosslinking agent of step (2) comprises any one of aziridine, ethylenediamine and hexamethylenediamine or a combination of at least two thereof.
Preferably, step (2) further comprises adding an anionic modifier to the reaction system prior to the grafting reaction described in step (2).
Preferably, the weight portion of the anionic surfactant is 1 to 5 parts by weight, such as 2 parts by weight, 3 parts by weight, 4 parts by weight, and the like.
Preferably, the anionic surfactant is sodium lauryl sulfate.
Because the water-based color paste is generally anionic water-based color paste, an anionic surfactant is adopted to be matched with the water-based color paste.
Preferably, step (2) adds a portion of the pH adjusting agent to adjust the pH to 7.5-8.5, e.g., 7.6, 7.8, 8.0, 8.2, etc.
Preferably, the mixing in step (2) is carried out at 75-85 deg.C, such as 77 deg.C, 78 deg.C, 80 deg.C, 82 deg.C, etc.
Preferably, the mixing time in step (2) is 10-15min, such as 11min, 12min, 13min, 14min, etc.
Preferably, the temperature of the grafting reaction in step (2) is 75-85 ℃, such as 77 ℃, 78 ℃, 80 ℃, 82 ℃ and the like, and the reaction time is 50-80min, such as 55min, 60min, 65min, 70min, 75min and the like.
Preferably, the temperature of the crosslinking reaction in step (2) is 60-70 deg.C, such as 62 deg.C, 64 deg.C, 66 deg.C, 68 deg.C, etc.
Preferably, the pH adjustment in step (2) is to adjust the pH to 7.5-8.5, e.g. 7.6, 7.8, 8.0, 8.2, etc.
In the present invention, the pH adjuster is used to adjust the pH value, and thus the specific amount of the pH adjuster is not limited, and the pH adjuster may be added to adjust the pH to a predetermined pH.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) mixing the amylopectin, the plasticizer, the waterproof agent, the maleic anhydride and the first initiator according to the formula ratio, adding the mixture into an internal mixer at the rotating speed of 70-90r/min, and carrying out grafting reaction at the temperature of 125-145 ℃ for 8-12 min;
(1') mixing the treated amylopectin obtained in the step (1) with water in a mass ratio of (1.5-2.5):10, and gelatinizing the mixture at 50-100 ℃ for 1-5 hours;
(2) adding a part of pH regulator into amylopectin to regulate the pH value to 7.5-8.5 at 75-85 ℃, adding an anionic surfactant and a second initiator to mix for 10-15min, then adding a formula amount of modified monomer, carrying out grafting reaction at 75-85 ℃, wherein the reaction time is 50-80min, finally adding a formula amount of cross-linking agent to carry out cross-linking reaction at 60-70 ℃, and then regulating the pH value to 7.5-8.5 by using the rest pH regulator to obtain the modified amylopectin material.
In a second aspect, the present invention provides a modified amylopectin starch material obtained by the preparation method according to the first aspect.
In a third aspect, the invention provides a water-based ink, which comprises the following components in parts by weight:
in the water-based ink, the weight part of the modified amylopectin material is 40-50 parts, such as 42 parts, 44 parts, 46 parts, 48 parts and the like.
The modified amylopectin starch material is the modified amylopectin starch material according to the second aspect.
In the water-based ink, the weight portion of the water-based color paste is 30 to 40 parts, such as 32 parts, 34 parts, 36 parts, 38 parts and the like.
Preferably, the aqueous color paste comprises the following components in percentage by mass:
in the water-based color paste, the mass percentage of the organic pigment is 35-45%, such as 37%, 39%, 40%, 41%, 43%, and the like.
Preferably, the organic pigment includes any one of phthalocyanine green, phthalocyanine blue, permanent yellow, benzidine yellow, carbon black and titanium dioxide or a combination of at least two thereof.
In the water-based color paste, the mass percentage of the acrylic acid dispersion resin is 35-45%, such as 37%, 39%, 40%, 41%, 43%, and the like.
In the water-based color paste, the mass percentage of the deionized water is 5-10%, such as 6%, 7%, 8%, 9% and the like.
In the aqueous color paste, the mass percentage of the dispersant is 3-8%, such as 4%, 5%, 6%, 7%, etc.
In the water-based color paste, the mass percentage of the wetting agent is 1-2%, such as 1.2%, 1.4%, 1.6%, 1.8% and the like.
In the water-based color paste, the mass percentage of the defoaming agent is 0.3-0.8%, such as 0.4%, 0.5%, 0.6%, 0.7% and the like.
In the water-based ink, the deionized water is 5 to 10 parts by weight, such as 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, and the like.
In the water-based ink, the weight part of the antiwear agent is 1-2 parts, such as 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts and the like.
In the water-based ink, the wetting agent is 1 to 2 parts by weight, for example, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, and the like.
In the aqueous ink, the preservative is present in an amount of 0.5 to 1 part by weight, for example 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, and the like.
In the aqueous ink, the defoaming agent is present in an amount of 0.3 to 0.8 parts by weight, for example, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, or the like.
The water-based ink provided by the invention has high color saturation, good shielding property, good waterproofness and good leveling property, can be suitable for high-speed printing, and is suitable for corrugated case printing, water-based flexible printing for common paper, water-based fluorescent gravure ink printing and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) the modified amylopectin material provided by the invention has moderate viscosity of 45-50 seconds, higher minimum film forming temperature, moderate drying rate, good waterproofness, water seepage time of more than 31min and good waterproof performance, is suitable for printing of water-based ink, and can be used as a binder of the water-based ink;
(2) when the modified monomer selected by the invention is a composition consisting of (5-15) of butyl methacrylate, methyl methacrylate, glycidyl methacrylate and trimethylolpropane triacrylate in a mass ratio of (35-45) to (1-5), the lowest film forming temperature is higher, the composition can be quickly dried at the film forming temperature, and the composition has good printing adaptability;
(3) the water-based ink provided by the invention has proper viscosity and drying rate, can not cause the phenomena of plate contamination, plate pasting and the like, has good fineness and tinting strength, and is suitable for being used as printing ink.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
A modified amylopectin starch material is prepared by the following steps:
(1) mixing 30 parts by weight of amylopectin, 3.5 parts by weight of a waterproof agent, 3.5 parts by weight of a plasticizer, 6.5 parts by weight of maleic anhydride and 0.1 part by weight of a first initiator, adding the mixture into an internal mixer at the rotating speed of 80r/min, and carrying out grafting reaction at 135 ℃ for 10 min;
(1') mixing the treated amylopectin obtained in the step (1) with water in a mass ratio of 2:10, and gelatinizing the mixture at 75 ℃ for 3 hours;
(2) adding a part of pH regulator into amylopectin to regulate the pH value to 8.0 at the temperature of 80 ℃, adding 3 parts by weight of anionic surfactant and 0.1 part by weight of second initiator to mix for 13min, then adding 15 parts by weight of modified monomer, carrying out grafting reaction at the temperature of 80 ℃, carrying out crosslinking reaction at the temperature of 65 ℃ by adding 0.3 part by weight of crosslinking agent, and then regulating the pH value to 8.0 by using the rest pH regulator to obtain the modified amylopectin material.
Wherein, the first initiator in the step (1) is dicumyl peroxide, the waterproofing agent is ammonium zirconium carbonate, and the plasticizer is lauric acid; the pH regulator in the step (2) is diethanolamine, the anionic surfactant is sodium dodecyl sulfate, the second initiator is ammonium persulfate, the modified monomer is a composition consisting of methacrylic acid, butyl acrylate, methyl methacrylate, glycidyl methacrylate and trimethylolpropane triacrylate according to the mass ratio of 10:40:40:3:3, and the crosslinking agent is ethylenediamine.
Preparation examples 2 to 10
The only difference from preparation example 1 is that the modifying monomer of step (2) is a composition consisting of methacrylic acid, butyl acrylate, methyl methacrylate, glycidyl methacrylate and trimethylolpropane triacrylate in a mass ratio of 5:35:35:1:1 (preparation example 2), 15:45:45:5:5 (preparation example 3) and 1:1:1:1 (preparation example 4).
The only difference from preparation example 1 was that methacrylic acid was excluded from the modified monomer of step (2) (preparation example 5), butyl acrylate was excluded (preparation example 6), trimethylolpropane triacrylate was excluded (preparation example 7), butyl acrylate and methacrylic acid were excluded (preparation example 8), methyl methacrylate, glycidyl methacrylate and trimethylolpropane triacrylate were excluded (preparation example 9), and the proportions of the other components were unchanged.
The only difference from preparation example 1 is that the modifying monomer of step (2) is acrylamide (preparation example 10).
Preparation examples 11 to 14
The only differences from preparation example 1 are that the modified monomer in step (2) is 11.25 parts by weight (amylopectin to modified monomer mass ratio of 2:0.75, preparation example 11), 18.75 parts by weight (amylopectin to modified monomer mass ratio of 2:1.25, preparation example 12), 10 parts by weight (preparation example 13) and 20 parts by weight (preparation example 14).
Preparation example 15
A modified amylopectin starch material is prepared by the following steps:
(1) mixing 25 parts by weight of amylopectin, 2 parts by weight of a waterproof agent, 2 parts by weight of a plasticizer, 5 parts by weight of maleic anhydride and 0.05 part by weight of a first initiator, adding the mixture into an internal mixer with the rotating speed of 70r/min, and carrying out grafting reaction at the temperature of 125 ℃ for 8 min;
(1') mixing the treated amylopectin obtained in the step (1) with water at a mass ratio of 1.5:10, and gelatinizing at 50 ℃ for 1 hour;
(2) adding a part of pH regulator into amylopectin at 75 ℃ to regulate the pH to 7.5, adding 1 part of anionic surfactant and 0.05 part of second initiator by weight, mixing for 10min, then adding 15 parts of modified monomer by weight, carrying out grafting reaction at 75 ℃ for 50min, finally adding 0.008 part of cross-linking agent by weight, carrying out cross-linking reaction at 60 ℃, and then regulating the pH to 7.5 by using the rest of pH regulator to obtain the modified amylopectin material.
Wherein, the first initiator in the step (1) is dibenzoyl peroxide, the waterproofing agent is ammonium zirconium carbonate, and the plasticizer is polyethylene glycol; the pH regulator in the step (2) is N, N-dimethylethanolamine, the anionic surfactant is sodium dodecyl sulfate, the second initiator is potassium persulfate, the modified monomer is a composition consisting of methacrylic acid, butyl acrylate, methyl methacrylate, glycidyl methacrylate and trimethylolpropane triacrylate according to the mass ratio of 10:40:40:3:3, and the crosslinking agent is aziridine.
Preparation example 16
A modified amylopectin starch material is prepared by the following steps:
(1) mixing 40 parts by weight of amylopectin, 5 parts by weight of a waterproof agent, 5 parts by weight of a plasticizer, 8 parts by weight of maleic anhydride and 0.2 part by weight of a first initiator, adding the mixture into an internal mixer with the rotating speed of 90r/min, and carrying out grafting reaction at 145 ℃ for 12 min;
(1') mixing the treated amylopectin obtained in the step (1) with water in a mass ratio of 2.5:10, and gelatinizing the mixture at 100 ℃ for 5 hours;
(2) adding a part of pH regulator into amylopectin to regulate the pH value to 8.5 at 85 ℃, adding 5 parts by weight of anionic surfactant and 0.2 part by weight of second initiator to mix for 15min, then adding 15 parts by weight of modified monomer, carrying out grafting reaction at 85 ℃, wherein the reaction time is 80min, finally adding 0.6 part by weight of cross-linking agent to carry out cross-linking reaction at 70 ℃, and then regulating the pH value to 8.5 by using the rest of pH regulator to obtain the modified amylopectin material.
Wherein, the first initiator in the step (1) is dibenzoyl peroxide, the waterproofing agent is ammonium zirconium carbonate, and the plasticizer is polyethylene glycol; the pH regulator in the step (2) is N, N-dimethylethanolamine, the anionic surfactant is sodium dodecyl sulfate, the second initiator is potassium persulfate, the modified monomer is a composition consisting of methacrylic acid, butyl acrylate, methyl methacrylate, glycidyl methacrylate and trimethylolpropane triacrylate according to the mass ratio of 10:40:40:3:3, and the crosslinking agent is aziridine.
Preparation example 17
The only difference from preparation example 1 is that step (1') is not included.
Comparative preparation example 1
CN102875742A example 1 provides a highly branched starch acrylamide copolymer
And (3) performance testing:
the modified amylopectin starches provided in preparation examples 1 to 17 and comparative preparation example 1 were subjected to a performance test:
(1) viscosity: testing an amylopectin modified solution with the solid content of 40% by a Chua-cup viscometer method, Chua-4 cups at 25 ℃;
(2) minimum film formation temperature: testing is carried out according to GB/T9267 plus 2008, and the testing instrument is a BGD 452 minimum film forming temperature instrument;
(3) and (3) testing the waterproofness: coating a film on paper by using a quantitative sample, completely drying, dripping water on the surface of the coating, and observing the time when the water drops start to permeate the paper;
(4) wear resistance: coating a film on paper by using a quantitative sample, completely drying, testing on a friction-resistant tester under the pressure of 4 pounds, rubbing for 400 times back and forth, and observing the coating smearing degree;
level 1: not dragging flowers;
and 2, stage: slight dragging of flowers;
and 3, level: dragging flowers;
4, level: severe flower dragging;
(5) gloss testing: coating a film on the coated paper by using a quantitative sample, completely drying, and testing by using a gloss meter with the reading of 60 degrees as the standard;
(6) and (3) stability testing: taking one month as an observation period, putting the wet sample into a 50 ℃ oven, and observing whether a precipitate is separated out;
a level: no layering and no precipitation;
b stage: thickening and no precipitation;
c level: slight layering is realized, and no precipitation is caused;
d stage: the viscosity decreased and precipitation occurred.
The test results are shown in table 1:
TABLE 1
According to the preparation examples and data, the modified amylopectin material obtained by the method is moderate in viscosity (for amylopectin with the solid content of 40%, the amylopectin with the viscosity of 45-50 seconds is suitable for being used as a water-based ink binder), high in minimum film forming temperature, moderate in drying rate, suitable for water-based ink printing, long in water seepage time (more than 30 min), good in waterproof performance and good in stability; from examples 1 to 3, it can be seen that when the modified monomer selected by the present invention is a composition comprising (5-15) by mass of butyl methacrylate, methyl methacrylate, glycidyl methacrylate, and trimethylolpropane triacrylate, (35-45) by mass of (1-5), the minimum film forming temperature is high, and the composition can be dried quickly at the film forming temperature and has good printing adaptability.
Examples 1 to 17
The water-based ink comprises the following components in parts by weight:
wherein the modified amylopectin starch material is the modified amylopectin starch material prepared in preparation examples 1-17.
The aqueous color paste comprises the following components in percentage by mass:
wherein the organic pigment is a combination of phthalocyanine green, phthalocyanine blue and permanent yellow.
Comparative example 1
The only difference from example 1 is that in this comparative example, the modified amylopectin starch material was the modified amylopectin starch provided in comparative preparation example 1.
Performance testing
(1) Viscosity: Chua-En cup viscometer method, Chua-4 cups, 25 ℃;
(2) testing the tinting strength of the water-based ink: referring to GB/T13217.6-2008, a sample and a standard sample are respectively diluted by quantitative white ink, and the concentration of the ink after dilution is compared and expressed by percentage;
(3) and (3) testing the fineness of the water-based ink: testing is carried out according to the GB/T13217.3-2008 standard;
(4) the water-based ink dryness testing method comprises the following steps: testing is carried out according to the GB/T13217.5-2008 standard;
(5) and (3) stability testing: taking one month as an observation period, putting the wet sample into a 50 ℃ oven, and observing whether a precipitate is separated out;
a level: no layering and no precipitation;
b stage: thickening and no precipitation;
c level: slight layering is realized, and no precipitation is caused;
d stage: the viscosity decreased and precipitation occurred.
The test results are shown in table 2:
TABLE 2
As can be seen from the comparison between the examples and the comparative examples, the water-based ink provided by the invention has proper viscosity (18-22 seconds) and drying rate (dryness is less than 18), does not cause phenomena such as dirty printing plate, paste printing plate and the like in the printing process, has good fineness and tinting strength, and is suitable for being used as printing ink; when the modified monomer selected by the invention is a composition consisting of (5-15) of butyl methacrylate, methyl methacrylate, glycidyl methacrylate and trimethylolpropane triacrylate in a mass ratio of (35-45) to (1-5), the water-based ink has proper viscosity and good fineness, and the tinting strength can reach over 90-95%.
The applicant states that the present invention is illustrated by the above examples of the modified amylopectin starch material of the present invention, the preparation method thereof and the aqueous ink comprising the same, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must be implemented by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (25)
1. A preparation method of a modified amylopectin starch material is characterized by comprising the following steps:
(1) mixing amylopectin, maleic anhydride and a first initiator and then carrying out grafting reaction;
(2) adding part of pH regulator and second initiator into the amylopectin processed in the step (1) and mixing, then adding modified monomer for grafting reaction, finally adding cross-linking agent for cross-linking reaction, and then regulating the pH value by using the rest pH regulator to obtain the modified amylopectin material;
the modified amylopectin starch material comprises the following raw materials in parts by weight:
the step (1) also comprises the step of adding a waterproof agent and a plasticizer into a reaction system;
the weight portion of the waterproof agent is 2-5;
the waterproof agent is ammonium zirconium carbonate;
the weight part of the plasticizer is 2-5 parts;
the plasticizer comprises any one or the combination of at least two of lauric acid, stearic acid, glycerol and polyethylene glycol;
the modified monomer in the step (2) is a composition consisting of (5-15) of butyl methacrylate, methyl methacrylate, glycidyl methacrylate and trimethylolpropane triacrylate in a mass ratio of (35-45) to (1-5);
the mass ratio of the amylopectin to the modified monomer is 2 (0.75-1.25).
2. The method according to claim 1, wherein the first initiator in step (1) is dicumyl peroxide and/or dibenzoyl peroxide.
3. The method according to claim 1, wherein the grafting reaction in step (1) is carried out in an internal mixer.
4. The process according to claim 3, wherein the internal mixer is rotated at a speed of 70 to 90 r/min.
5. The method as claimed in claim 1, wherein the grafting reaction in step (1) is carried out at a temperature of 125 ℃ to 145 ℃ for a period of 8-12 min.
6. The method according to claim 1, wherein step (1') is performed after step (1): mixing the amylopectin obtained in the step (1) with water, and then carrying out gelatinization treatment.
7. The method according to claim 6, wherein the mass ratio of amylopectin to water in step (1') is (1.5-2.5): 10.
8. The method according to claim 6, wherein the gelatinization time in the step (1') is 1 to 5 hours, and the gelatinization temperature is 50 to 100 ℃.
9. The method according to claim 1, wherein the pH adjusting agent in step (2) comprises any one or a combination of at least two of ammonia, monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol and N, N-dimethylethanolamine.
10. The production method according to claim 1, wherein the second initiator in the step (2) is ammonium persulfate and/or potassium persulfate.
11. The method of claim 1, wherein the crosslinking agent of step (2) comprises any one of aziridine, ethylenediamine and hexamethylenediamine or a combination of at least two thereof.
12. The method according to claim 1, wherein the step (2) further comprises adding an anionic surfactant to the reaction system before the grafting reaction in the step (2).
13. The method according to claim 12, wherein the weight part of the anionic surfactant is 1 to 5 parts by weight.
14. The method of claim 12, wherein the anionic surfactant is sodium lauryl sulfate.
15. The method according to claim 1, wherein the pH is adjusted to 7.5 to 8.5 in step (2) by adding a part of the pH adjusting agent.
16. The method of claim 1, wherein the mixing in step (2) is carried out at 75-85 ℃.
17. The method of claim 1, wherein the mixing in step (2) is carried out for a period of 10-15 min.
18. The method according to claim 1, wherein the temperature of the grafting reaction in step (2) is 75 to 85 ℃ and the reaction time is 50 to 80 min.
19. The method according to claim 1, wherein the temperature of the crosslinking reaction in the step (2) is 60 to 70 ℃.
20. The method according to claim 1, wherein the pH value is adjusted to 7.5 to 8.5 in the step (2).
21. The method of claim 1, comprising the steps of:
(1) mixing the amylopectin, the plasticizer, the waterproof agent, the maleic anhydride and the first initiator according to the formula ratio, adding the mixture into an internal mixer at the rotating speed of 70-90r/min, and carrying out grafting reaction at the temperature of 125-145 ℃ for 8-12 min;
(1') mixing the treated amylopectin obtained in the step (1) with water in a mass ratio of (1.5-2.5):10, and gelatinizing the mixture at 50-100 ℃ for 1-5 hours;
(2) adding a part of pH regulator into amylopectin to regulate the pH value to 7.5-8.5 at 75-85 ℃, adding an anionic surfactant and a second initiator to mix for 10-15min, then adding a formula amount of modified monomer, carrying out grafting reaction at 75-85 ℃, wherein the reaction time is 50-80min, finally adding a formula amount of cross-linking agent to carry out cross-linking reaction at 60-70 ℃, and then regulating the pH value to 7.5-8.5 by using the rest pH regulator to obtain the modified amylopectin material.
22. A modified amylopectin starch material, characterized in that it is obtained by the production method according to any one of claims 1 to 21.
23. The water-based ink is characterized by comprising the following components in parts by weight:
wherein the modified amylopectin starch material is the modified amylopectin starch material according to claim 22.
24. The water-based ink according to claim 23, wherein the water-based color paste comprises the following components in percentage by mass:
25. the aqueous ink according to claim 24, wherein the organic pigment comprises any one of phthalocyanine green, phthalocyanine blue, permanent yellow, benzidine yellow or a combination of at least two thereof.
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| US6423775B1 (en) * | 1999-01-25 | 2002-07-23 | WORLéE-CHEMIE GMBH | Starch-based graft polymer, process for its preparation, and use thereof in printing inks and overprint varnishes |
| CN1834139A (en) * | 2006-03-23 | 2006-09-20 | 邓国权 | All biodegradable branched starch master granulars |
| CN101274975A (en) * | 2008-05-08 | 2008-10-01 | 江南大学 | Method for improving grafting efficiency of grafting starch syrup |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6423775B1 (en) * | 1999-01-25 | 2002-07-23 | WORLéE-CHEMIE GMBH | Starch-based graft polymer, process for its preparation, and use thereof in printing inks and overprint varnishes |
| CN1834139A (en) * | 2006-03-23 | 2006-09-20 | 邓国权 | All biodegradable branched starch master granulars |
| CN101274975A (en) * | 2008-05-08 | 2008-10-01 | 江南大学 | Method for improving grafting efficiency of grafting starch syrup |
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