CN108610739A - It is modified amylopectin material and preparation method thereof and includes its water-based ink - Google Patents
It is modified amylopectin material and preparation method thereof and includes its water-based ink 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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- C—CHEMISTRY; METALLURGY
- 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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- 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
- 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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- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- 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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- 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
- 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 present invention provides a kind of modified amylopectin material and preparation method thereof and include its water-based ink, the preparation method includes the following steps：(1) graft reaction is carried out after mixing amylopectin, maleic anhydride and the first initiator；(2) part pH adjusting agent and the second initiator are added in amylopectin and are mixed, then modified monomer is added and carries out graft reaction, it is eventually adding crosslinking agent and carries out cross-linking reaction, then adjust pH value using remaining pH adjusting agent, obtain the modified amylopectin material.Modified amylopectin provided by the invention has higher minimum film formation temperature, and water proofing property is preferable, rub resistance, warping strength, may be used as the binder of water-based ink.
Description
Technical field
The invention belongs to modified material field, be related to a kind of modified amylopectin material and preparation method thereof and comprising its
Water-based ink.
Background technology
Starch is the natural polymers that a kind of amylopectin fraction and amylose component mix naturally, starch
Branch makes a big difference with each comfortable molecular structure of linear component, state of aggregation and performance and application aspect tool, and amylopectin
Then it is widely used in food, packing timber because having the function of anti-aging, freeze-thaw stability, thickening, high-expansion and water imbibition etc.
The fields such as material, water-soluble and Biodegradable films in recent years obtain the isolation technics of amylose and amylopectin in starch
Very big progress, this not only promotes the industrialization high level application to the respective distinctive property of amylose and amylopectin,
Higher technical need to meet each field provides actual capabilities.
Amylopectin has preferable bonding force, resistance to flatiron, high temperature resistant, and starch solution are to face as natural polymer
Material has good stably dispersing effect and levelling effect, and has certain filming performance and toughness, is a kind of complete biodegradable
And reproducible raw material.But amylopectin film forming it is hard it is crisp, extensibility is small, poor water resistance, easily mouldy, split slurry, simple branch
Chain starch starch can not meet the needs of water-based ink binder.Amylopectin can pass through a series of modifications, be endowed excellent
Benign energy, the acrylic acid-graft starch binder that such as organic-natural materials combine have in fields such as papermaking, printing, coating
It is widely used.
CN1709935A discloses the preparation method of a kind of starch grafted polyacrylamide and its derivative reversed-phase emulsion, should
Method includes preparing the connection phase of emulsifier oil solution, prepares the connection phase of solid part solution of amylopectin and acrylamide,
Dispersion is added to connection phase, and starch grafted polyacrylamide and its derivative inverse latex is obtained by the reaction, is prepared by this method
Process is complicated, and grafting rate is relatively low, and modified effect is little.
CN102875742A discloses a kind of using amylopectin as the highly -branched degree acrylamide grafted copolymer of skeleton
Manufacturing method, wherein then being added by the grafting water vinyl monomer on amylopectin using urea as structural adjustment agent
The crosslinking agent that adds the olefinic unsaturation cross-linking monomer of ketocarbonyl-containing and can be reacted with cross-linking monomer is modified to obtain highly -branched
And lightly crosslinked modification amylopectin, although can be applied in water-based ink, minimum film formation temperature is relatively low, dry speed
Rate is excessively slow, therefore printing adaptability is poor, and the water-based ink water proofing property finally obtained is poor.
Need to develop a kind of new modification amylopectin at present as water-based ink binder, to be adapted to water-based ink
It is required that.
Invention content
It is an object of the invention to a kind of modified amylopectin material and preparation method thereof and include its water-based ink.
For this purpose, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of preparation method of modified amylopectin material, the preparation method includes
Following steps：
(1) graft reaction is carried out after mixing amylopectin, maleic anhydride and the first initiator；
(2) part pH adjusting agent and the second initiator are added in amylopectin and are mixed, be then added modified monomer into
Row graft reaction is eventually adding crosslinking agent and carries out cross-linking reaction, then adjusts pH value using remaining pH adjusting agent, obtains described
Modified amylopectin material.
Wherein, the modified amylopectin material prepare raw material in parts by weight include following component：
Wherein, the modified monomer includes acrylamide, Methacrylamide, acrylic acid, butyl acrylate, acrylic acid
Sodium, methacrylic acid, methyl methacrylate, butyl methacrylate, monobutyl itaconate, N hydroxymethyl acrylamide, first
In base glycidyl acrylate and trimethylolpropane trimethacrylate any one or at least two combination.
Preparation method provided by the invention first obtains maleic anhydride grafted branches starch, so that amylopectin is provided with certain
Then the degree of polymerization, acid value and reactivity are modified amylopectin using modified monomer, modified amylopectin material is obtained
Material has good water-soluble and higher film-forming temperature, and glossiness is good, and rate of drying is very fast, and adsorption can be high, is suitable for
Water-based ink printing uses.
Preferably, the parts by weight of the amylopectin are 25-40 parts by weight, such as 27 parts by weight, 30 parts by weight, 32 weight
Part, 35 parts by weight, 37 parts by weight etc..
Preferably, the parts by weight of the maleic anhydride are 5-8 parts by weight, such as 6 parts by weight, 7 parts by weight etc..
Preferably, the parts by weight of the pH adjusting agent are 1-5 parts by weight, such as 2 parts by weight, 3 parts by weight, 4 parts by weight etc..
Preferably, the parts by weight of the modified monomer are 10-30 parts by weight, such as 15 parts by weight, 17 parts by weight, 20 weight
Part, 22 weight, 25 parts by weight, 27 parts by weight etc..
Preferably, the parts by weight of first initiator are 0.05-0.2 parts by weight, such as 0.08 parts by weight, 0.1 weight
Part, 0.12 parts by weight, 0.14 parts by weight, 0.16 parts by weight, 0.18 parts by weight etc..
Preferably, the parts by weight of second initiator are 0.05-0.2 parts by weight, such as 0.08 parts by weight, 0.1 weight
Part, 0.12 parts by weight, 0.14 parts by weight, 0.16 parts by weight, 0.18 parts by weight etc..
Preferably, the parts by weight of the crosslinking agent are 0.008-0.65 parts by weight, such as 0.01 parts by weight, 0.05 weight
Part, 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 etc..
Preferably, step (2) described modified monomer is methacrylic acid:Butyl acrylate:Methyl methacrylate:Methyl
Glycidyl acrylate:Trimethylolpropane trimethacrylate is (5-15) according to mass ratio:(35-45):(35-45):(1-
5):The composition of (1-5) composition, such as 5:35:35:1:1、8:40:38:3:3、10:40:40:5:5、15:45:45:5:5 etc..
When modified monomer is above-mentioned monomer composition, the modification amylopectin minimum film formation temperature finally obtained is higher, can
With the rapid draing under film-forming temperature, and there is good printing adaptability and color developing.
Preferably, the mass ratio of the amylopectin and modified 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 waiting.
In the present invention, step (1) first initiator is cumyl peroxide and/or dibenzoyl peroxide.
Preferably, step (1) described graft reaction carries out in mixer.
Preferably, the rotating speed of the mixer is 70-90r/min, such as 75r/min, 80r/min, 85r/min etc..
Preferably, the reaction temperature of the graft reaction is 125-145 DEG C, such as 130 DEG C, 135 DEG C, 140 DEG C etc., reaction
Time is 8-12min, such as 9min, 10min, 11min etc..
Preferably, step (1) further includes that waterproofing agent and plasticizer are added in reaction system.
Preferably, the parts by weight of the waterproofing agent are 2-5 parts by weight, such as 3 parts by weight, 4 parts by weight.
Preferably, the waterproofing agent is zirconium carbonate ammonium.
Waterproofing agent is added in modified amylopectin material, is reacted with remaining hydroxyl, carboxyl in system so that most
The modification liquid obtained afterwards has water-proof function, and when applied to water-based ink, the printing finally obtained has water proofing property.
Preferably, the parts by weight of the plasticizer are 2-5 parts by weight, such as 3 parts by weight, 4 parts by weight.
Preferably, the plasticizer include in lauric acid, stearic acid, glycerine and polyethylene glycol any one or at least
Two kinds of combination.
Plasticizer is added in the material, can be the dry film transparent and homogeneous formed, and can improve water resistance and resistance
The ability of water proof steam.
Preferably, step (1 ') is carried out after step (1)：Amylopectin and the water mixing that step (1) is obtained are laggard
Row gelatinization is handled.
Preferably, the mass ratio of amylopectin and water is (1.5-2.5) in step (1 '):10, such as 1.7:10、1.9:
10、2:10、2.2:10、2.4:10 etc..
Preferably, step (the 1 ') gelatinization time is 1-5 hours, such as 2 hours, 3 hours, 4 hours etc., gelatinization point
It it is 50-100 DEG C, such as 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C etc..
Preferably, step (2) described pH adjusting agent includes ammonium hydroxide, monoethanolamine, diethanol amine, 2- amino-2-methyls -1-
Propyl alcohol and N, in N- dimethylethanolamines any one or at least two combination.
On the one hand pH adjusting agent can adjust the pH value of solution, on the other hand can increase the guarantor before water-based ink drying
It is moist, water-based ink can be made fully to soak plank, solubility is good, and site is moderate, the drawbacks of avoiding the occurrence of dirty version, scumming.
Preferably, step (2) second initiator is ammonium persulfate and/or potassium peroxydisulfate.
Preferably, step (2) described crosslinking agent includes any one in aziridine, ethylenediamine and hexamethylene diamine or at least two
The combination of kind.
Preferably, step (2) further includes that reactant is added before step (2) described graft reaction in anion conditioning agent
System.
Preferably, the parts by weight of the anion surfactant be 1-5 parts by weight, such as 2 parts by weight, 3 parts by weight,
4 parts by weight etc..
Preferably, the anion surfactant is lauryl sodium sulfate.
Because aqueous color paste is generally the aqueous color paste of anionic, matched therewith using anion surfactant
It closes.
Preferably, step (2) is added part pH adjusting agent and pH is adjusted to 7.5-8.5, such as 7.6,7.8,8.0,8.2
Deng.
Preferably, described be blended at 75-85 DEG C of step (2) carries out, such as 77 DEG C, 78 DEG C, 80 DEG C, 82 DEG C etc..
Preferably, the time of step (2) described mixing is 10-15min, such as 11min, 12min, 13min, 14min etc..
Preferably, the temperature of step (2) described graft reaction is 75-85 DEG C, such as 77 DEG C, 78 DEG C, 80 DEG C, 82 DEG C etc.,
Reaction time is 50-80min, such as 55min, 60min, 65min, 70min, 75min etc..
Preferably, the temperature of step (2) described cross-linking reaction is 60-70 DEG C, such as 62 DEG C, 64 DEG C, 66 DEG C, 68 DEG C etc..
Preferably, step (2) the adjusting pH value is that pH is adjusted to 7.5-8.5, such as 7.6,7.8,8.0,8.2 etc..
In the present invention, the effect of pH adjusting agent is the specific dosage for adjusting pH value, therefore not limiting pH adjusting agent, only
PH adjusting agent need to be added, pH is adjusted to preset pH.
As optimal technical scheme, the preparation method includes the following steps：
(1) it is added and turns after mixing the amylopectin of formula ratio, plasticizer, waterproofing agent, maleic anhydride and the first initiator
Speed is the mixer of 70-90r/min, and graft reaction, reaction time 8-12min are carried out at 125-145 DEG C；
(1 ') is by step (1) amylopectin that obtains that treated and water with mass ratio for (1.5-2.5):After 10 mixing,
It is gelatinized 1-5 hours at 50-100 DEG C；
(2) at 75-85 DEG C, part pH adjusting agent is added in amylopectin and adjusts pH to 7.5-8.5, and anion is added
Then surfactant and the second initiator mixing 10-15min are added formula ratio modified monomer, are grafted at 75-85 DEG C
Reaction, reaction time 50-80min, the crosslinking agent for being eventually adding formula ratio carry out cross-linking reaction at 60-70 DEG C, then sharp
PH to 7.5-8.5 is adjusted with remaining pH adjusting agent, obtains the modified amylopectin material.
Second aspect, the present invention provides a kind of modified amylopectin material, the modified amylopectin material is by first
Preparation method described in aspect obtains.
The third aspect, the present invention provides a kind of water-based ink, the water-based ink includes following component in parts by weight：
In water-based ink, the parts by weight of the modified amylopectin material are 40-50 parts by weight, such as 42 weight
Part, 44 parts by weight, 46 parts by weight, 48 parts by weight etc..
The modified amylopectin material is the modification amylopectin material described in second aspect.
In water-based ink, the parts by weight of the aqueous color paste are 30-40 parts by weight, such as 32 parts by weight, 34 weight
Part, 36 parts by weight, 38 parts by weight etc..
Preferably, the aqueous color paste includes following component by mass percentage：
In aqueous color paste, the mass percentage of the organic pigment is 35-45%, for example, 37%, 39%, 40%,
41%, 43% etc..
Preferably, the organic pigment includes in dark green, phthalocyanine blue, permanent yellow, biphenyl ammonia Huang, carbon black and titanium dioxide
Any one or at least two combination.
In aqueous color paste, the mass percentage of the acrylic dispersing resin is 35-45%, for example, 37%, 39%,
40%, 41%, 43% etc..
In aqueous color paste, the mass percentage of the deionized water is 5-10%, such as 6%, 7%, 8%, 9%
Deng.
In aqueous color paste, the mass percentage of the dispersant is 3-8%, such as 4%, 5%, 6%, 7% etc..
In aqueous color paste, the mass percentage of the wetting agent is 1-2%, for example, 1.2%, 1.4%, 1.6%,
1.8% etc..
In aqueous color paste, the mass percentage of the antifoaming agent is 0.3-0.8%, for example, 0.4%, 0.5%,
0.6%, 0.7% etc..
In water-based ink, the parts by weight of the deionized water are 5-10 parts by weight, such as 6 parts by weight, 7 parts by weight, 8
Parts by weight, 9 parts by weight etc..
In water-based ink, the parts by weight of the antiwear additive are 1-2 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 etc..
In water-based ink, the parts by weight of the wetting agent are 1-2 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 etc..
In water-based ink, the parts by weight of the preservative are 0.5-1 parts by weight, such as 0.6 parts by weight, 0.7 weight
Part, 0.8 parts by weight, 0.9 parts by weight etc..
In water-based ink, the parts by weight of the antifoaming agent are 0.3-0.8 parts by weight, such as 0.4 parts by weight, 0.5 weight
Measure part, 0.6 parts by weight, 0.7 parts by weight etc..
Water-based ink color saturation provided by the invention is high, and shielding is good, and good waterproof performance, levelability is good, can be suitably used for
High speed printing is suitable for corrugated box printing, plain paper aqueous flexible plate printing, aqueous fluorescent intaglio plate ink print etc..
Compared with the existing technology, the invention has the advantages that：
(1) modified amylopectin viscosity of material provided by the invention is moderate, be 45-50 second, and have it is higher it is minimum at
Film temperature, rate of drying is moderate, is suitable for water-based ink and prints, and water proofing property is preferable, the infiltration time is more than 31min, has
Preferable water resistance may be used as the binder of water-based ink；
(2) when the modified monomer that the present invention selects is methacrylic acid:Butyl acrylate:Methyl methacrylate:Methyl
Glycidyl acrylate:Trimethylolpropane trimethacrylate is (5-15) according to mass ratio:(35-45):(35-45):(1-
5):When the composition of (1-5) composition, minimum film formation temperature is higher, can have good print in rapid draing under film-forming temperature
Brush adaptability；
(3) water-based ink provided by the invention has suitable viscosity and rate of drying, will not cause dirty version, scumming etc.
Phenomenon, and its fineness and tinting strength, tinting power are preferable, are suitable for use as printing ink.
Specific implementation mode
The technical solution further illustrated the present invention below by specific implementation mode.Those skilled in the art should be bright
, the embodiment, which is only to aid in, understands the present invention, should not be regarded as a specific limitation of the invention.
Preparation example 1
A kind of modified amylopectin material, preparation method are as follows：
(1) by 30 parts by weight amylopectin, 3.5 parts by weight waterproofing agents, 3.5 parts by weight of plasticizer, 6.5 parts by weight of maleic
The mixer that rotating speed is 80r/min is added after acid anhydride and the mixing of 0.1 the first initiator of parts by weight, graft reaction is carried out at 135 DEG C,
Reaction time is 10min；
(1 ') is by step (1) amylopectin that obtains that treated and water with mass ratio for 2:After 10 mixing, at 75 DEG C
Gelatinization 3 hours；
At (2) 80 DEG C, part pH adjusting agent is added in amylopectin and adjusts pH to 8.0, and 3 parts by weight anion are added
Surfactant and 0.1 parts by weight the second initiator mixing 13min, then be added 15 part by weight modified monomers, at 80 DEG C into
Row graft reaction, reaction time 65min, the crosslinking agent for being eventually adding 0.3 parts by weight carry out cross-linking reaction at 65 DEG C, then
PH to 8.0 is adjusted using remaining pH adjusting agent, obtains modified amylopectin material.
Wherein, the first initiator of step (1) is cumyl peroxide, and waterproofing agent is zirconium carbonate ammonium, and plasticizer is the moon
Cinnamic acid；The pH adjusting agent of step (2) is diethanol amine, and anion surfactant is lauryl sodium sulfate, the second initiator
For ammonium persulfate, modified monomer is methacrylic acid:Butyl acrylate:Methyl methacrylate:Methyl propenoic acid glycidyl
Ester:Trimethylolpropane trimethacrylate is 10 according to mass ratio:40:40:3:The composition of 3 compositions, crosslinking agent is ethylenediamine.
Preparation example 2-10
Modified monomer with differing only in for preparation example 1, step (2) is methacrylic acid:Butyl acrylate:Methyl-prop
E pioic acid methyl ester:Glycidyl methacrylate:Trimethylolpropane trimethacrylate is 5 according to mass ratio:35:35:1:1
(preparation example 2), 15:45:45:5:5 (preparation examples 3), 1:1:1:The composition of 1 (preparation example 4) composition.
Do not include methacrylic acid (preparation example 5), no in the modified monomer of step (2) with differing only in for preparation example 1
Including butyl acrylate (preparation example 6), not including trimethylolpropane trimethacrylate (preparation example 7), including acrylic acid fourth
Ester and methacrylic acid (preparation example 8) do not include methyl methacrylate, glycidyl methacrylate and trihydroxy methyl third
Alkane triacrylate (preparation example 9), the constant rate of other components.
With differing only in for preparation example 1, step (2) modified monomer is acrylamide (preparation example 10).
Preparation example 11-14
With differing only in for preparation example 1, the parts by weight of step (2) modified monomer be 11.25 parts by weight (amylopectin with
Modified monomer mass ratio is 2:0.75, preparation example 11), (amylopectin and modified monomer mass ratio are 2 to 18.75 parts by weight:
1.25, preparation example 12), 10 parts by weight (preparation example 13), 20 parts by weight (preparation example 14).
Preparation example 15
A kind of modified amylopectin material, preparation method are as follows：
(1) by 25 parts by weight amylopectin, 2 parts by weight waterproofing agents, 2 parts by weight of plasticizer, 5 parts by weight maleic anhydride and
The mixer that rotating speed is 70r/min is added after the mixing of 0.05 the first initiator of parts by weight, graft reaction is carried out at 125 DEG C, instead
It is 8min between seasonable；
(1 ') is by step (1) amylopectin that obtains that treated and water with mass ratio for 1.5:After 10 mixing, at 50 DEG C
Lower gelatinization 1 hour；
At (2) 75 DEG C, part pH adjusting agent is added in amylopectin and adjusts pH to 7.5, and 1 parts by weight anion is added
Surfactant and 0.05 parts by weight the second initiator mixing 10min, then be added 15 part by weight modified monomers, at 75 DEG C into
Row graft reaction, reaction time 50min, the crosslinking agent for being eventually adding 0.008 parts by weight carry out cross-linking reaction at 60 DEG C, so
PH to 7.5 is adjusted using remaining pH adjusting agent afterwards, obtains modified amylopectin material.
Wherein, the first initiator of step (1) is dibenzoyl peroxide, and waterproofing agent is zirconium carbonate ammonium, and plasticizer is poly-
Ethylene glycol；The pH adjusting agent of step (2) is N, and N- dimethylethanolamines, anion surfactant is lauryl sodium sulfate,
Second initiator is potassium peroxydisulfate, and modified monomer is methacrylic acid:Butyl acrylate:Methyl methacrylate:Metering system
Acid glycidyl ester:Trimethylolpropane trimethacrylate is 10 according to mass ratio:40:40:3:The composition of 3 compositions, crosslinking
Agent is aziridine.
Preparation example 16
A kind of modified amylopectin material, preparation method are as follows：
(1) by 40 parts by weight amylopectin, 5 parts by weight waterproofing agents, 5 parts by weight of plasticizer, 8 parts by weight maleic anhydride and
The mixer that rotating speed is 90r/min is added after the mixing of 0.2 the first initiator of parts by weight, graft reaction is carried out at 145 DEG C, reacts
Time is 12min；
(1 ') is by step (1) amylopectin that obtains that treated and water with mass ratio for 2.5:After 10 mixing, at 100 DEG C
Lower gelatinization 5 hours；
At (2) 85 DEG C, part pH adjusting agent is added in amylopectin and adjusts pH to 8.5, and 5 parts by weight anion are added
Surfactant and 0.2 parts by weight the second initiator mixing 15min, then be added 15 part by weight modified monomers, at 85 DEG C into
Row graft reaction, reaction time 80min, the crosslinking agent for being eventually adding 0.6 parts by weight carry out cross-linking reaction at 70 DEG C, then
PH to 8.5 is adjusted using remaining pH adjusting agent, obtains modified amylopectin material.
Wherein, the first initiator of step (1) is dibenzoyl peroxide, and waterproofing agent is zirconium carbonate ammonium, and plasticizer is poly-
Ethylene glycol；The pH adjusting agent of step (2) is N, and N- dimethylethanolamines, anion surfactant is lauryl sodium sulfate,
Second initiator is potassium peroxydisulfate, and modified monomer is methacrylic acid:Butyl acrylate:Methyl methacrylate:Metering system
Acid glycidyl ester:Trimethylolpropane trimethacrylate is 10 according to mass ratio:40:40:3:The composition of 3 compositions, crosslinking
Agent is aziridine.
Preparation example 17
Do not include step (1 ') with differing only in for preparation example 1.
Compare preparation example 1
The highly -branched potato starch acrylamnide copolymer that CN102875742A embodiments 1 provide
Performance test：
Preparation example 1-17 and comparison preparation example 1 the modification amylopectin provided are tested for the property：
(1) viscosity：The amylopectin modification liquid for being 40% to solid content is tested, Cai's grace cup viscometer method, -4 glasss of Cai,
25℃；
(2) minimum film formation temperature：It is tested according to GB/T 9267-2008, test equipment is 452 minimum film forming of BGD
Thermometer；
(3) waterproofing tests：With quantitative sample, film drips in coating surface thoroughly after drying, sees water on paper wood
Drop starts to permeate the paper time；
(4) wearability：With quantitative sample, film is tested, 4 thoroughly after drying on friction-resistant tester on paper wood
Pound pressure, rubs 400 times back and forth, and observation coating drags colored degree；
1 grade：Do not drag flower；
2 grades：Have and slightly drags flower；
3 grades：Drag flower；
4 grades：Seriously drag flower；
(5) measurement of luster：With quantitative sample, film is tested, with 60 ° thoroughly after drying with glossometer on art paper
Subject to reading；
(6) stability test：Wet sample is put into 50 DEG C of baking oven, has seen whether precipitation using one month as the observation time limit
It is precipitated；
A grades：It is not stratified, it is not precipitated；
B grades：There is thickening, is not precipitated；
C grades：Slight layering, is not precipitated；
D grades：Viscosity reduces, and has precipitation.
Test result is shown in Table 1：
Table 1
By preparation example and data it is found that the obtained modification amylopectin viscosity of material of the present invention is moderate (is for solid content
40% amylopectin, viscosity are that the amylopectin between 45-50 seconds is suitable for use as water-based ink binder), and minimum film forming
Temperature is higher, and rate of drying is moderate, is suitable for water-based ink and prints, and the infiltration time is longer (30min or more), has preferable anti-
Aqueous energy, and stability is good；By embodiment 1-3 it is found that when the modified monomer that the present invention selects is methacrylic acid:Acrylic acid fourth
Ester:Methyl methacrylate:Glycidyl methacrylate:Trimethylolpropane trimethacrylate is (5- according to mass ratio
15):(35-45):(35-45):(1-5):When the composition of (1-5) composition, minimum film formation temperature is higher, can be in film-forming temperature
Lower rapid draing has good printing adaptability.
Embodiment 1-17
A kind of water-based ink includes following component in parts by weight：
Wherein, modified amylopectin material is the modification amylopectin material in preparation example 1-17.
Aqueous color paste includes following component by mass percentage：
Wherein, organic pigment is the combination of dark green, phthalocyanine blue and permanent yellow.
Comparative example 1
With differing only in for embodiment 1, in this comparative example, modified amylopectin material is that comparison preparation example 1 provides
Modification amylopectin.
Performance test
(1) viscosity：Cai's grace cup viscometer method, -4 glasss of Cai, 25 DEG C；
(2) water-based ink colours force inspecting：With reference to GB/T 13217.6-2008, sample and standard specimen are divided with quantitative chalk
It does not water down, comparison waters down rear printing ink concentration, as a percentage；
(3) water-based ink fineness is examined：It is tested with GB/T 13217.3-2008 standards；
(4) the water-based ink dryness method of inspection：It is tested with GB/T 13217.5-2008 standards；
(5) stability test：Wet sample is put into 50 DEG C of baking oven, has seen whether precipitation using one month as the observation time limit
It is precipitated；
A grades：It is not stratified, it is not precipitated；
B grades：There is thickening, is not precipitated；
C grades：Slight layering, is not precipitated；
D grades：Viscosity reduces, and has precipitation.
Test result is shown in Table 2：
Table 2
Water-based ink provided by the invention has suitable viscosity (18-22 seconds) known to the comparison of embodiment and comparative example
And rate of drying (dryness be less than 18), in printing process, phenomena such as dirty version, scumming will not be caused, and its fineness and
Color power is preferable, is suitable for use as printing ink；When the modified monomer that the present invention selects is methacrylic acid:Butyl acrylate:First
Base methyl acrylate:Glycidyl methacrylate:Trimethylolpropane trimethacrylate is (5-15) according to mass ratio:
(35-45):(35-45):(1-5):When the composition of (1-5) composition, the viscosity of water-based ink is suitable, and fineness is good, and tinting strength, tinting power can
Up to 90-95% or more.
Applicant states that the present invention illustrates modification amylopectin material and its preparation of the present invention by above-described embodiment
Method and water-based ink comprising it, but the invention is not limited in above-described embodiments, that is, do not mean that the present invention has to rely on
Above-described embodiment could be implemented.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to the present invention
The equivalence replacement of each raw material of product and the addition of auxiliary element, the selection etc. of concrete mode, all fall within protection scope of the present invention
Within the open scope.
Claims (10)
1. a kind of preparation method of modified amylopectin material, which is characterized in that the preparation method includes the following steps：
(1) graft reaction is carried out after mixing amylopectin, maleic anhydride and the first initiator；
(2) part pH adjusting agent and the second initiator are added in amylopectin and are mixed, modified monomer is then added and is connect
Branch reaction is eventually adding crosslinking agent and carries out cross-linking reaction, then adjusts pH value using remaining pH adjusting agent, obtain the modification
Amylopectin material；
Wherein, the modified amylopectin material prepare raw material in parts by weight include following component：
Wherein, the modified monomer includes acrylamide, Methacrylamide, acrylic acid, butyl acrylate, sodium acrylate, first
Base acrylic acid, methyl methacrylate, butyl methacrylate, monobutyl itaconate, N hydroxymethyl acrylamide, metering system
In acid glycidyl ester and trimethylolpropane trimethacrylate any one or at least two combination.
2. preparation method according to claim 1, which is characterized in that step (2) described modified monomer is methacrylic acid:
Butyl acrylate:Methyl methacrylate:Glycidyl methacrylate:Trimethylolpropane trimethacrylate is according to quality
Than for (5-15):(35-45):(35-45):(1-5):The composition of (1-5) composition；
Preferably, the mass ratio of the amylopectin and modified monomer is 2:(0.75-1.25).
3. preparation method according to claim 1 or 2, which is characterized in that step (1) first initiator is peroxidating
Diisopropylbenzene (DIPB) and/or dibenzoyl peroxide；
Preferably, step (1) described graft reaction carries out in mixer；
Preferably, the rotating speed of the mixer is 70-90r/min；
Preferably, the reaction temperature of the graft reaction is 125-145 DEG C, reaction time 8-12min；
Preferably, step (1) further includes that waterproofing agent and plasticizer are added in reaction system；
Preferably, the parts by weight of the waterproofing agent are 2-5 parts by weight；
Preferably, the waterproofing agent is zirconium carbonate ammonium；
Preferably, the parts by weight of the plasticizer are 2-5 parts by weight；
Preferably, the plasticizer includes any one in lauric acid, stearic acid, glycerine and polyethylene glycol or at least two
Combination.
4. according to the preparation method described in any one of claim 1-3, which is characterized in that walked after step (1)
Suddenly (1 ')：Gelatinization processing is carried out after amylopectin and water that step (1) obtains are mixed；
Preferably, the mass ratio of amylopectin and water is (1.5-2.5) in step (1 '):10；
Preferably, step (the 1 ') gelatinization time is 1-5 hours, and gelatinization point is 50-100 DEG C.
5. according to the preparation method described in any one of claim 1-4, which is characterized in that step (2) described pH adjusting agent
Any one including ammonium hydroxide, monoethanolamine, diethanol amine, 2-amino-2-methyl-1-propanol and N, in N- dimethylethanolamines
Or at least two combination；
Preferably, step (2) second initiator is ammonium persulfate and/or potassium peroxydisulfate；
Preferably, step (2) described crosslinking agent includes any one in aziridine, ethylenediamine and hexamethylene diamine or at least two
Combination；
Preferably, step (2) further includes that reaction system is added before step (2) described graft reaction in anion conditioning agent；
Preferably, the parts by weight of the anion surfactant are 1-5 parts by weight；
Preferably, the anion surfactant is lauryl sodium sulfate.
6. according to the preparation method in claim 1-5, which is characterized in that part pH adjusting agent is added in step (2) will
PH is adjusted to 7.5-8.5；
Preferably, described be blended at 75-85 DEG C of step (2) carries out；
Preferably, the time of step (2) described mixing is 10-15min；
Preferably, the temperature of step (2) described graft reaction is 75-85 DEG C, reaction time 50-80min；
Preferably, the temperature of step (2) described cross-linking reaction is 60-70 DEG C；
Preferably, step (2) the adjusting pH value is that pH is adjusted to 7.5-8.5.
7. according to the preparation method described in any one of claim 1-6, which is characterized in that the preparation method includes as follows
Step：
(1) rotating speed is added after mixing the amylopectin of formula ratio, plasticizer, waterproofing agent, maleic anhydride and the first initiator is
The mixer of 70-90r/min carries out graft reaction, reaction time 8-12min at 125-145 DEG C；
(1 ') is by step (1) amylopectin that obtains that treated and water with mass ratio for (1.5-2.5):After 10 mixing, in 50-
It is gelatinized 1-5 hours at 100 DEG C；
(2) at 75-85 DEG C, part pH adjusting agent is added in amylopectin and adjusts pH to 7.5-8.5, and anionic surface is added
Then formula ratio modified monomer is added in activating agent and the second initiator mixing 10-15min, carry out being grafted at 75-85 DEG C anti-
It answers, reaction time 50-80min, the crosslinking agent for being eventually adding formula ratio carries out cross-linking reaction at 60-70 DEG C, then utilizes
Remaining pH adjusting agent adjusts pH to 7.5-8.5, obtains the modified amylopectin material.
8. a kind of modified amylopectin material, which is characterized in that the modified amylopectin material is by appointing in claim 1-7
Preparation method described in one obtains.
9. a kind of water-based ink, which is characterized in that the water-based ink includes following component in parts by weight：
Wherein, the modified amylopectin material is modified amylopectin material according to any one of claims 8.
10. water-based ink according to claim 9, which is characterized in that the aqueous color paste includes by mass percentage
Following component：
Preferably, the organic pigment includes appointing in dark green, phthalocyanine blue, permanent yellow, biphenyl ammonia Huang, carbon black and titanium dioxide
It anticipates a kind of or at least two combinations.
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| CN112375425A (en) * | 2020-10-29 | 2021-02-19 | 广东佳景科技股份有限公司 | Degradable water-based ink for biodegradable plastics and preparation method and application thereof |
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| CN112375425A (en) * | 2020-10-29 | 2021-02-19 | 广东佳景科技股份有限公司 | Degradable water-based ink for biodegradable plastics and preparation method and application thereof |
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