CN108517147A - Aqueous writing liquid of anti-ink type and preparation method thereof - Google Patents
Aqueous writing liquid of anti-ink type and preparation method thereof Download PDFInfo
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- CN108517147A CN108517147A CN201810648309.XA CN201810648309A CN108517147A CN 108517147 A CN108517147 A CN 108517147A CN 201810648309 A CN201810648309 A CN 201810648309A CN 108517147 A CN108517147 A CN 108517147A
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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
- C09D11/16—Writing inks
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Abstract
The present invention relates to a kind of writing liquids and preparation method thereof, are made of A agent and B agent more particularly to a kind of aqueous writing liquid of anti-black type and preparation method thereof the writing liquid；The A agent, which is prepared from the following ingredients in percentage by, to be process：Organic silicon modified polyurethane 10 15%, water-soluble dextran 2 8%, dispersant 1 2%, surplus are the ethanol water of volume fraction 50 60%；The B agent, which is prepared from the following ingredients in percentage by, to be process：Polyethylene glycol modified polylactide resin 5 10%；Stabilizer 1 5%, coalescents 2 5%, bleeding agent 1 5%, propolis 2 3%, antioxidant 1 2%, surplus is deionized water；PH adjusting agent is a certain amount of, adjusts B agent pH value 6.0 7.0.The writing liquid of the present invention is combined using water as primary solvent between active ingredient and rice paper fiber, after dry, in paper surface and inside, it generates water repellent high molecular hydrophobic film shape and creates trace, there is high conjugation with rice paper, realization leaves on rice paper stablizes apparent creation trace.
Description
Technical field
The present invention relates to a kind of writing liquid and preparation method thereof, more particularly to a kind of aqueous writing liquid of anti-black type and its
Preparation method.
Background technology
Calligraphy creation, not simple writing behavior, the general performance of consciousness consciousness and handwriting skills.It is
The calligraphic factors such as exaggeration of the technique of writing, the method for the use of ink and water, the art of composition, type posture are naturally combined together, due " the pen and ink feelings of calligraphy are generated
Interest " is to reach melting visual effect.
The present invention is envisioned for writing liquid：Using water as solvent, there is good writing quality, writing liquid is dipped with writing brush
Calligraphy creation is carried out on rice paper, the place that pen and ink pass through needs to leave stable, smooth person's handwriting, in order to very easily declare
The various calligraphy work drafts for having upright stone tablet to open up inversion effect are created on paper.
Realize that aforementioned imagination, the present invention need to solve following at least three technical problem：First, writing liquid has certain
Viscosity and good filming performance, a certain amount of writing liquid can be effectively adsorbed when certain viscosity guarantee is dipped with writing brush, protect
The continuity of calligraphy creation is demonstrate,proved, good filming performance ensures that the trace of calligraphy creation is uniform and smooth, improves the product that upright stone tablet opens up reversion
Matter；Secondly, writing liquid will have certain permeance property and solidifiability, permeance property to ensure that the trace of calligraphy creation can be with a surname
Paper firmly combines, and solidifiability ensures to form stable trace form after forming a film in calligraphy production process, does not drop down liquid, avoids printing
Interference between mark；Finally, it is necessary to have good water repellency after writing liquid film forming is dry, surface forms stable hydrophobic
Film surface, keep away from moisture pollution, grows bacterium.
For above three technical problem, the not systematic writing liquid for solving the technical problem, leads in the prior art
When the writing liquid of the prior art being caused to be used for calligraphy creation, there are more defect or deficiencies, influence calligraphy creation quality, the present invention
It aims to solve the problem that this technical problem, aqueous writing liquid of a kind of anti-black type and preparation method thereof is provided.
Invention content
It is an object of the invention to solve the deficiencies in the prior art, a kind of aqueous writing liquid of anti-black type and its preparation side are provided
Method.There is the writing liquid certain viscosity and good filming performance, certain viscosity guarantee can effectively be inhaled when being dipped with writing brush
Attached a certain amount of writing liquid ensures that the continuity of calligraphy creation, good filming performance ensure the trace uniform light of calligraphy creation
It is sliding, improve the quality that upright stone tablet opens up reversion；Secondly, writing liquid of the invention will have certain permeance property and solidifiability, infiltration
The trace of performance guarantee calligraphy creation can firmly be combined with rice paper, and solidifiability ensures to be formed after forming a film in calligraphy production process
Stable trace form, does not drop down liquid, avoids the interference between trace；In addition, after writing liquid film forming is dry, it is necessary to have good
Water repellency, surface energy form stable hydrophobic film surface, and keep away from moisture pollution, grow bacterium.Writing liquid based on the present invention
The calligraphy work of creation can preserve for a long time, be repeatedly used for upright stone tablet and open up.
Anti- ink type writing liquid definition：Refer on rice paper in a manner of according to prior art ink (writing liquid) is used into
Row calligraphy creation, but transparent or translucent membranaceous of calligraphy creation trace, have water repellency, and will not cover rice paper from
A kind of writing liquid of right color and texture.
The technical solution adopted by the present invention to solve the technical problems is：
A kind of aqueous writing liquid of anti-black type, the writing liquid are made of A agent and B agent；A agent and B agent separately encapsulate storage, make
The agent of used time A and B agent are with mass ratio 1：The ratio mixing of (3-4), which is mixed thoroughly, obtains aqueous writing liquid；
The A agent, which is prepared from the following ingredients in percentage by, to be process：
Organic silicon modified polyurethane 10-15%
Water-soluble dextran 2-8%
Dispersant 1-2%
Surplus is the ethanol water of volume fraction 50-60%；
The B agent, which is prepared from the following ingredients in percentage by, to be process：
Polyethylene glycol modified polylactide resin 5-10%；
Stabilizer 1-5%
Coalescents 2-5%
Bleeding agent 1-5%
Propolis 2-3%
Antioxidant 1-2%
Surplus is deionized water；
PH adjusting agent is a certain amount of, adjusts B agent pH value 6.0-7.0.
A agent needs have good water repellency for solving the problems, such as after writing liquid film forming is dry in the present invention, uses
After the A agent of the present invention, surface energy forms stable hydrophobic film surface, and keep away from moisture pollution.Writing liquid based on the present invention is created
Calligraphy work, can preserve for a long time, be repeatedly used for upright stone tablet and open up.A certain amount of dispersant is added in A agent, allows organic-silicon-modified poly- ammonia
Ester dispersibility substantially improves, and water repellency is uniform, and there is no the situation that Local Property is very poor, water-soluble dextran is as big point
Son, intermolecular formation bridging action improve the viscosity of A agent, meanwhile, the further phase interaction between organic silicon modified polyurethane
With allowing A dosage forms at stable system, preserving for a long time will not flocculate or settle.
B agent is used to solve permeance property and solidifiability after writing liquid film forming drying, permeance property guaranty in the present invention
The trace of method creation can firmly be combined with rice paper, and solidifiability ensures to form stable trace after forming a film in calligraphy production process
Form does not drop down liquid, avoids the interference between trace.Each component synergistic effect in B agent, realizes splendid permeance property and solidification
Performance.The glutathione being added in B agent is evenly distributed with oxidized form and reduced glutathione after film forming, realizes efficient antioxygen
Change function, calligraphy creation trace is avoided to be aoxidized, runs color, quality decline, in addition, propolis has natural restraining and sterilizing bacteria performance,
It effectively keeps away from moisture mouldy.
The writing liquid of the present invention includes solidification macromolecule water repellent substance, has good writing using water as primary solvent
Can, it dips writing liquid with writing brush and carries out calligraphy creation on rice paper, it is the same with tradition ink, the difference is that：Hair
The place that pen passes through, writing liquid are infiltrated through in rice paper, are combined between active ingredient and rice paper fiber, after dry, in paper table
Face and inside generate water repellent high molecular hydrophobic film shape and create trace, with rice paper there is high conjugation, realization to be stayed on rice paper
It is lower to stablize apparent creation trace.
Preferably, the writing liquid is made of A agent and B agent；A agent and B agent separately encapsulate storage, when use A agent and B agent with
Mass ratio 2：7 ratio mixing, which is mixed thoroughly, obtains aqueous writing liquid；
The A agent, which is prepared from the following ingredients in percentage by, to be process：
Organic silicon modified polyurethane 12%
Water-soluble dextran 5%
Dispersant 1%
Surplus is the ethanol water of volume fraction 60%；
The B agent, which is prepared from the following ingredients in percentage by, to be process：
Polyethylene glycol modified polylactide resin 8%；
Stabilizer 3%
Coalescents 3%
Bleeding agent 3%
Propolis 2%
Antioxidant 1%
Surplus is deionized water；
PH adjusting agent is a certain amount of, adjusts B agent pH value 6.5.
Preferably, the preparation method of the organic silicon modified polyurethane is as follows：
S1:Using aminopropyl siloxane coupling agent and hydroxyl-terminated injecting two methyl siloxane as raw material, end aminopropyl poly- two is synthesized
Methylsiloxane oligomer, it is spare using it as chain extender；
S2：It is reacted with polyether polyol with polyisocyanates, base polyurethane prepolymer for use as is made；
S3：The base polyurethane prepolymer for use as of step S2 is dissolved with ethanol solution, is gradually added the chain extender of step S1, at room temperature
1-2h is reacted, organic silicon modified polyurethane ethanol solution is made；
S4：The organic silicon modified polyurethane ethanol solution of step S3 is concentrated in vacuo, and recycles ethyl alcohol, is obtained ethanol content and is less than
2.0% organic silicon modified polyurethane.
Preferably, in the step S1, the molar ratio of aminopropyl siloxane coupling agent and hydroxyl-terminated injecting two methyl siloxane
It is 2:1,100-120 DEG C of reaction temperature persistently stirs in reaction process, reaction time 1-2h；
In step S2, the mass ratio that feeds intake of polyisocyanates and polyether polyol is 1.6-1.8；70-80 DEG C of reaction temperature,
Reaction time 1-2h；
In step S3, the addition mole of chain extender is 1.4-1.6 times of base polyurethane prepolymer for use as mole.
Preferably, in the step S1, the molar ratio of aminopropyl siloxane coupling agent and hydroxyl-terminated injecting two methyl siloxane
It is 2:1,110 DEG C of reaction temperature persistently stirs, reaction time 2h in reaction process；
In step S2, the mass ratio that feeds intake of polyisocyanates and polyether polyol is 1.8；80 DEG C of reaction temperature, when reaction
Between 1h；
In step S3, the addition mole of chain extender is 1.6 times of base polyurethane prepolymer for use as mole；
The molecular weight of organic silicon modified polyurethane is 22000-23000.
Preferably, the dispersant is any one in polyacrylamide, guar gum and fatty acid polyethylene glycol ester.
Preferably, the stabilizer is lignosulfonates, and coalescents are ethylene glycol or ethylene glycol ethyl ether.
Preferably, the bleeding agent is sodium alkyl sulfonate, sodium alkyl benzene sulfonate, alkyl sulfate sodium, sodium secondary alkyl sulfonate
With any one in secondary alkyl sulphate sodium, pH adjusting agent is citric acid or sodium hydroxide.
Preferably, the antioxidant is the reduced glutathione handled through incomplete oxidation, the preparation of antioxidant
Method is as follows：Reduced glutathione is taken, in 40-45 DEG C of dissolving, the reduced glutathione solution of 50-100g/L is obtained, surveys
Its pH value is A1；With barium hydroxide tune pH to A2,7.0≤A2≤7.2；A certain amount of hydrogen peroxide is added, it is stirring while adding, after adding
Continue to be stirred to react 0.2-0.5h；After reaction, a certain amount of manganese dioxide is added, stirs 5-10min, then fully filters off two
Manganese oxide；With sulphur acid for adjusting pH to A3, A1-0.1≤A3≤A1；Barium sulfate precipitate is fully filtered off, spray drying obtains oxidized form
Glutathione；A concentration of the 30% of hydrogen peroxide, additive amount is 0.3-0.5ml/g reduced glutathiones, using precision 0.2-
0.45 μm of miillpore filter essence filtering.
A kind of preparation method of the aqueous writing liquid of anti-black type, steps are as follows for the method：
The first step prepares A agent
The organic silicon modified polyurethane of formula ratio, water-soluble dextran, dispersant and ethanol water is mixed in 40-45 DEG C
Uniform, elimination impurity, vacuum and/or ultrasonic wave degassing post package are closed, A agent is obtained；
Second step prepares B agent
By the polyethylene glycol modified polylactide resin of formula ratio, stabilizer, coalescents, bleeding agent, propolis and anti-oxidant
Agent 1-2% is uniformly mixed in 40-45 DEG C, adjusts pH value, is filtered off impurity, vacuum and/or ultrasonic wave degassing post package, is obtained B agent.
The beneficial effects of the invention are as follows：
1. this product water white transparency or translucent liquid, after writing, natural room temperature dries, and need not heat, have after dry
Excellent water repellency is write and forms stable calligraphy creation trace in material, while retaining the primary colors and texture of rice paper；
2. good weatherability, can be used under normal domestic room temp, -10 DEG C do not freeze, and long-term preservation is never degenerated；
3. water repellent permeability resistance is strong, moisture-proof unfading；
4. durability is good, not damaged to rice paper material, the rice paper service life is not influenced, wear-resisting folding can open up dye repeatedly, and works can
With long-term preservation；
5. not damaged to the writing brush write, writing brush is rinsed with water after totally to be dried；Good film-forming property, fluent writing
Not stagnant pen, not puckery, bacteriostasis property is good, and long-time preservation will not grow miscellaneous bacteria.
Specific implementation mode
Below by specific embodiment, technical scheme of the present invention will be further explained in detail.
Embodiment 1：
A kind of aqueous writing liquid of anti-black type, the writing liquid are made of A agent and B agent；A agent and B agent separately encapsulate storage, make
The agent of used time A and B agent are with mass ratio 1：3 ratio mixing, which is mixed thoroughly, obtains aqueous writing liquid；
The A agent, which is prepared from the following ingredients in percentage by, to be process：
Organic silicon modified polyurethane 10%
Water-soluble dextran 2%
Dispersant 1%
Surplus is the ethanol water of volume fraction 50%；
The B agent, which is prepared from the following ingredients in percentage by, to be process：
Polyethylene glycol modified polylactide resin 5%；
Stabilizer 1%
Coalescents 2%
Bleeding agent 1%
Propolis 2%
Antioxidant 1%
Surplus is deionized water；
PH adjusting agent is a certain amount of, adjusts B agent pH value 6.0.
In the present invention, the preparation method of the organic silicon modified polyurethane is as follows：
S1:Using aminopropyl siloxane coupling agent and hydroxyl-terminated injecting two methyl siloxane as raw material, end aminopropyl poly- two is synthesized
Methylsiloxane oligomer, it is spare using it as chain extender；
S2：It is reacted with polyether polyol with polyisocyanates, base polyurethane prepolymer for use as is made；
S3：The base polyurethane prepolymer for use as of step S2 is dissolved with ethanol solution, is gradually added the chain extender of step S1, at room temperature
1-2h is reacted, organic silicon modified polyurethane ethanol solution is made；
S4：The organic silicon modified polyurethane ethanol solution of step S3 is concentrated in vacuo, and recycles ethyl alcohol, is obtained ethanol content and is less than
2.0% organic silicon modified polyurethane.
Specifically, in the step S1, mole of aminopropyl siloxane coupling agent and hydroxyl-terminated injecting two methyl siloxane
Than being 2:1,100 DEG C of reaction temperature persistently stirs, reaction time 2h in reaction process；
In step S2, the mass ratio that feeds intake of polyisocyanates and polyether polyol is 1.6；70 DEG C of reaction temperature, when reaction
Between 2h；
In step S3, the addition mole of chain extender is 1.4 times of base polyurethane prepolymer for use as mole.
In the present invention, the dispersant is polyacrylamide, and the stabilizer is lignosulfonates, and coalescents are second
Glycol.The bleeding agent is sodium alkyl sulfonate, and pH adjusting agent is citric acid or sodium hydroxide.The antioxidant is through incomplete
The preparation method of the reduced glutathione of oxidation processes, antioxidant is as follows：Reduced glutathione is taken, is dissolved in 40 DEG C,
The reduced glutathione solution for obtaining 50g/L, it is A1 to survey its pH value；With barium hydroxide tune pH to A2,7.0≤A2≤7.2；Add
Enter a certain amount of hydrogen peroxide, it is stirring while adding, continue to be stirred to react 0.2h after adding；After reaction, a certain amount of titanium dioxide is added
Manganese stirs 5min, then fully filters off manganese dioxide；With sulphur acid for adjusting pH to A3, A1-0.1≤A3≤A1；Fully filter off sulfuric acid
Precipitated barium, spray drying obtain oxidized form of glutathione；A concentration of the 30% of hydrogen peroxide, additive amount are 0.3ml/g reduced form paddy
The sweet peptide of Guang is filtered using 0.2 μm of miillpore filter essence of precision.
Steps are as follows for the preparation method of the aqueous writing liquid of anti-black type of the present invention：
The first step prepares A agent
By the organic silicon modified polyurethane of formula ratio, water-soluble dextran, dispersant and ethanol water in 40 DEG C of mixing
Uniformly, impurity, vacuum and/or ultrasonic wave degassing post package are filtered off, A agent is obtained；
Second step prepares B agent
By the polyethylene glycol modified polylactide resin of formula ratio, stabilizer, coalescents, bleeding agent, propolis and anti-oxidant
Agent is uniformly mixed in 40 DEG C, adjusts pH value, is filtered off impurity, vacuum and/or ultrasonic wave degassing post package, is obtained B agent.
Embodiment 2：
A kind of aqueous writing liquid of anti-black type, the writing liquid are made of A agent and B agent；A agent and B agent separately encapsulate storage, make
The agent of used time A and B agent are with mass ratio 1：4 ratio mixing, which is mixed thoroughly, obtains aqueous writing liquid；
The A agent, which is prepared from the following ingredients in percentage by, to be process：
Organic silicon modified polyurethane 15%
Water-soluble dextran 8%
Dispersant 2%
Surplus is the ethanol water of volume fraction 60%；
The B agent, which is prepared from the following ingredients in percentage by, to be process：
Polyethylene glycol modified polylactide resin 10%；
Stabilizer 5%
Coalescents 5%
Bleeding agent 5%
Propolis 3%
Antioxidant 2%
Surplus is deionized water；
PH adjusting agent is a certain amount of, adjusts B agent pH value 7.0.
In the present invention, the preparation method of the organic silicon modified polyurethane is as follows：
S1:Using aminopropyl siloxane coupling agent and hydroxyl-terminated injecting two methyl siloxane as raw material, end aminopropyl poly- two is synthesized
Methylsiloxane oligomer, it is spare using it as chain extender；
S2：It is reacted with polyether polyol with polyisocyanates, base polyurethane prepolymer for use as is made；
S3：The base polyurethane prepolymer for use as of step S2 is dissolved with ethanol solution, is gradually added the chain extender of step S1, at room temperature
1-2h is reacted, organic silicon modified polyurethane ethanol solution is made；
S4：The organic silicon modified polyurethane ethanol solution of step S3 is concentrated in vacuo, and recycles ethyl alcohol, is obtained ethanol content and is less than
2.0% organic silicon modified polyurethane.
Specifically, in the step S1, mole of aminopropyl siloxane coupling agent and hydroxyl-terminated injecting two methyl siloxane
Than being 2:1,120 DEG C of reaction temperature persistently stirs, reaction time 1h in reaction process；
In step S2, the mass ratio that feeds intake of polyisocyanates and polyether polyol is 1.8；80 DEG C of reaction temperature, when reaction
Between 1h；In step S3, the addition mole of chain extender is 1.6 times of base polyurethane prepolymer for use as mole, and the dispersant is Gu Er
Glue, the stabilizer are lignosulfonates, and coalescents are ethylene glycol ethyl ether, and the bleeding agent is sodium alkyl benzene sulfonate, pH
Conditioning agent is citric acid or sodium hydroxide, and the antioxidant is the reduced glutathione handled through incomplete oxidation, antioxygen
The preparation method of agent is as follows：Reduced glutathione is taken, in 45 DEG C of dissolvings, the reduced glutathione for obtaining 100g/L is molten
Liquid, it is A1 to survey its pH value；With barium hydroxide tune pH to A2,7.0≤A2≤7.2；A certain amount of hydrogen peroxide is added, it is stirring while adding,
Continue to be stirred to react 0.5h after adding；After reaction, a certain amount of manganese dioxide is added, stirs 5-10min, then fully filters off
Manganese dioxide；With sulphur acid for adjusting pH to A3, A1-0.1≤A3≤A1；Barium sulfate precipitate is fully filtered off, spray drying is aoxidized
Type glutathione；A concentration of the 30% of hydrogen peroxide, additive amount is 0.5ml/g reduced glutathiones, using 0.45 μm of precision
Miillpore filter essence filters.
The preparation method of the aqueous writing liquid of anti-black type of the present invention, steps are as follows for the method：
The first step prepares A agent
By the organic silicon modified polyurethane of formula ratio, water-soluble dextran, dispersant and ethanol water in 45 DEG C of mixing
Uniformly, impurity, vacuum and/or ultrasonic wave degassing post package are filtered off, A agent is obtained；
Second step prepares B agent
By the polyethylene glycol modified polylactide resin of formula ratio, stabilizer, coalescents, bleeding agent, propolis and anti-oxidant
Agent is uniformly mixed in 45 DEG C, adjusts pH value, is filtered off impurity, vacuum and/or ultrasonic wave degassing post package, is obtained B agent.
Embodiment 3：
A kind of aqueous writing liquid of anti-black type, the writing liquid are made of A agent and B agent；A agent and B agent separately encapsulate storage, make
The agent of used time A and B agent are with mass ratio 2:7 ratio mixing, which is mixed thoroughly, obtains aqueous writing liquid；
The A agent, which is prepared from the following ingredients in percentage by, to be process：
Organic silicon modified polyurethane 12%
Water-soluble dextran 5%
Dispersant 1%
Surplus is the ethanol water of volume fraction 60%；
The B agent, which is prepared from the following ingredients in percentage by, to be process：
Polyethylene glycol modified polylactide resin 8%；
Stabilizer 3%
Coalescents 3%
Bleeding agent 3%
Propolis 2%
Antioxidant 1%
Surplus is deionized water；
PH adjusting agent is a certain amount of, adjusts B agent pH value 6.5.
In the present invention, the preparation method of the organic silicon modified polyurethane is as follows：
S1:Using aminopropyl siloxane coupling agent and hydroxyl-terminated injecting two methyl siloxane as raw material, end aminopropyl poly- two is synthesized
Methylsiloxane oligomer, it is spare using it as chain extender；
S2：It is reacted with polyether polyol with polyisocyanates, base polyurethane prepolymer for use as is made；
S3：The base polyurethane prepolymer for use as of step S2 is dissolved with ethanol solution, is gradually added the chain extender of step S1, at room temperature
1-2h is reacted, organic silicon modified polyurethane ethanol solution is made；
S4：The organic silicon modified polyurethane ethanol solution of step S3 is concentrated in vacuo, and recycles ethyl alcohol, is obtained ethanol content and is less than
2.0% organic silicon modified polyurethane.
Specifically, in the step S1, mole of aminopropyl siloxane coupling agent and hydroxyl-terminated injecting two methyl siloxane
Than being 2:1,110 DEG C of reaction temperature persistently stirs, reaction time 2h in reaction process；
In step S2, the mass ratio that feeds intake of polyisocyanates and polyether polyol is 1.8；80 DEG C of reaction temperature, when reaction
Between 1h；
In step S3, the addition mole of chain extender is 1.6 times of base polyurethane prepolymer for use as mole；
The molecular weight of organic silicon modified polyurethane is 22000-23000.
In the present invention, the dispersant is fatty acid polyethylene glycol ester, and the stabilizer is lignosulfonates, and film forming helps
Agent is ethylene glycol, and the bleeding agent is alkyl sulfate sodium, and pH adjusting agent is citric acid or sodium hydroxide, and the antioxidant is
The reduced glutathione handled through incomplete oxidation, the preparation method of antioxidant are as follows：Reduced glutathione is taken, in 42
DEG C dissolving, obtain the reduced glutathione solution of 60g/L, survey its pH value be A1；With barium hydroxide tune pH to A2,7.0≤A2
≤7.2；A certain amount of hydrogen peroxide is added, it is stirring while adding, continue to be stirred to react 0.2-0.5h after adding；After reaction, it is added
A certain amount of manganese dioxide stirs 8min, then fully filters off manganese dioxide；With sulphur acid for adjusting pH to A3, A1-0.1≤A3≤A1；
Barium sulfate precipitate is fully filtered off, spray drying obtains oxidized form of glutathione；A concentration of the 30% of hydrogen peroxide, additive amount are
0.4ml/g reduced glutathiones are filtered using 0.35 μm of miillpore filter essence of precision.
The preparation method of the aqueous writing liquid of anti-black type of the present invention, steps are as follows for the method：
The first step prepares A agent
By the organic silicon modified polyurethane of formula ratio, water-soluble dextran, dispersant and ethanol water in 42 DEG C of mixing
Uniformly, impurity, vacuum and/or ultrasonic wave degassing post package are filtered off, A agent is obtained；
Second step prepares B agent
By the polyethylene glycol modified polylactide resin of formula ratio, stabilizer, coalescents, bleeding agent, propolis and anti-oxidant
Agent is uniformly mixed in 42 DEG C, adjusts pH value, is filtered off impurity, vacuum and/or ultrasonic wave degassing post package, is obtained B agent.
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form
Limitation, on the premise of not exceeding the technical scheme recorded in the claims also other variations and modifications.
Claims (10)
1. a kind of aqueous writing liquid of anti-black type, it is characterised in that：The writing liquid is made of A agent and B agent；A agent and B agent are separately sealed
Dress storage, A agent and B agent are with mass ratio 1 when use：The ratio mixing of (3-4), which is mixed thoroughly, obtains aqueous writing liquid；
The A agent, which is prepared from the following ingredients in percentage by, to be process：
Organic silicon modified polyurethane 10-15%
Water-soluble dextran 2-8%
Dispersant 1-2%
Surplus is the ethanol water of volume fraction 50-60%；
The B agent, which is prepared from the following ingredients in percentage by, to be process：
Polyethylene glycol modified polylactide resin 5-10%；
Stabilizer 1-5%
Coalescents 2-5%
Bleeding agent 1-5%
Propolis 2-3%
Antioxidant 1-2%
Surplus is deionized water；
PH adjusting agent is a certain amount of, adjusts B agent pH value 6.0-7.0.
2. the aqueous writing liquid of anti-black type according to claim 1, it is characterised in that：The writing liquid is by A agent and B agent groups
At；A agent and B agent separately encapsulate storage, and A agent and B agent are with mass ratio 2 when use：7 ratio mixing, which is mixed thoroughly, obtains aqueous writing
Liquid；
The A agent, which is prepared from the following ingredients in percentage by, to be process：
Organic silicon modified polyurethane 12%
Water-soluble dextran 5%
Dispersant 1%
Surplus is the ethanol water of volume fraction 60%；
The B agent, which is prepared from the following ingredients in percentage by, to be process：
Polyethylene glycol modified polylactide resin 8%；
Stabilizer 3%
Coalescents 3%
Bleeding agent 3%
Propolis 2%
Antioxidant 1%
Surplus is deionized water；
PH adjusting agent is a certain amount of, adjusts B agent pH value 6.5.
3. the aqueous writing liquid of anti-black type according to claim 1, it is characterised in that：The system of the organic silicon modified polyurethane
Preparation Method is as follows：
S1:Using aminopropyl siloxane coupling agent and hydroxyl-terminated injecting two methyl siloxane as raw material, end aminopropyl poly dimethyl is synthesized
Siloxane oligomer, it is spare using it as chain extender；
S2：It is reacted with polyether polyol with polyisocyanates, base polyurethane prepolymer for use as is made；
S3：The base polyurethane prepolymer for use as of step S2 is dissolved with ethanol solution, the chain extender of step S1 is gradually added, reacts at room temperature
Organic silicon modified polyurethane ethanol solution is made in 1-2h；
S4：The organic silicon modified polyurethane ethanol solution of step S3 is concentrated in vacuo, and recycles ethyl alcohol, is obtained ethanol content and is less than
2.0% organic silicon modified polyurethane.
4. the aqueous writing liquid of anti-black type according to claim 3, it is characterised in that：
In the step S1, the molar ratio of aminopropyl siloxane coupling agent and hydroxyl-terminated injecting two methyl siloxane is 2:1, reaction temperature
100-120 DEG C is spent, is persistently stirred in reaction process, reaction time 1-2h；
In step S2, the mass ratio that feeds intake of polyisocyanates and polyether polyol is 1.6-1.8；70-80 DEG C of reaction temperature, reaction
Time 1-2h；
In step S3, the addition mole of chain extender is 1.4-1.6 times of base polyurethane prepolymer for use as mole.
5. the aqueous writing liquid of anti-black type according to claim 4, it is characterised in that：
In the step S1, the molar ratio of aminopropyl siloxane coupling agent and hydroxyl-terminated injecting two methyl siloxane is 2:1, reaction temperature
110 DEG C of degree, is persistently stirred, reaction time 2h in reaction process；
In step S2, the mass ratio that feeds intake of polyisocyanates and polyether polyol is 1.8；80 DEG C of reaction temperature, reaction time 1h；
In step S3, the addition mole of chain extender is 1.6 times of base polyurethane prepolymer for use as mole；
The molecular weight of organic silicon modified polyurethane is 22000-23000.
6. the aqueous writing liquid of anti-black type according to claim 1, it is characterised in that：The dispersant be polyacrylamide,
Any one in guar gum and fatty acid polyethylene glycol ester.
7. the aqueous writing liquid of anti-black type according to claim 1, it is characterised in that：The stabilizer is lignin sulfonic acid
Salt, coalescents are ethylene glycol or ethylene glycol ethyl ether.
8. the aqueous writing liquid of anti-black type according to claim 1, it is characterised in that：The bleeding agent be sodium alkyl sulfonate,
Any one in sodium alkyl benzene sulfonate, alkyl sulfate sodium, sodium secondary alkyl sulfonate and secondary alkyl sulphate sodium, pH adjusting agent is
Citric acid or sodium hydroxide.
9. the aqueous writing liquid of anti-black type according to claim 1, it is characterised in that：The antioxidant is through endless total oxygen
Change the reduced glutathione of processing, the preparation method of antioxidant is as follows：Reduced glutathione is taken, is dissolved in 40-45 DEG C,
The reduced glutathione solution for obtaining 50-100g/L, it is A1 to survey its pH value；With barium hydroxide tune pH to A2,7.0≤A2≤
7.2；A certain amount of hydrogen peroxide is added, it is stirring while adding, continue to be stirred to react 0.2-0.5h after adding；After reaction, it is added one
Quantitative manganese dioxide, stirs 5-10min, then fully filters off manganese dioxide；With sulphur acid for adjusting pH to A3, A1-0.1≤A3≤
A1；Barium sulfate precipitate is fully filtered off, spray drying obtains oxidized form of glutathione；A concentration of the 30% of hydrogen peroxide, additive amount are
0.3-0.5ml/g reduced glutathiones are filtered using 0.2-0.45 μm of miillpore filter essence of precision.
10. a kind of preparation method of the aqueous writing liquid of anti-black type described in any one of claim 1-9, it is characterised in that：Institute
It is as follows to state method and step：
The first step prepares A agent
The organic silicon modified polyurethane of formula ratio, water-soluble dextran, dispersant and ethanol water is equal in 40-45 DEG C of mixing
It is even, impurity, vacuum and/or ultrasonic wave degassing post package are filtered off, A agent is obtained；
Second step prepares B agent
By polyethylene glycol modified polylactide resin, stabilizer, coalescents, bleeding agent, propolis and the antioxidant of formula ratio in
40-45 DEG C is uniformly mixed, and adjusts pH value, filters off impurity, vacuum and/or ultrasonic wave degassing post package, obtains B agent.
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| CN103753908A (en) * | 2013-12-31 | 2014-04-30 | 浙江大学 | Super-hydrophobic coating and preparation method thereof |
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| CN108157957A (en) * | 2017-12-25 | 2018-06-15 | 江南大学（如皋）食品生物技术研究所 | Eye-protecting brain-strengthening Functional Food Formulations and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305053A (en) * | 2013-07-08 | 2013-09-18 | 昆山翔华鲸生物科技有限公司 | Temperature-sensitive color-change water-based ink taking biodegradable resin as carrier and preparation process of ink |
| CN103753908A (en) * | 2013-12-31 | 2014-04-30 | 浙江大学 | Super-hydrophobic coating and preparation method thereof |
| CN106753224A (en) * | 2017-01-23 | 2017-05-31 | 张晨杨 | Environment protection type wallpaper adhesive and preparation method thereof |
| CN108157957A (en) * | 2017-12-25 | 2018-06-15 | 江南大学（如皋）食品生物技术研究所 | Eye-protecting brain-strengthening Functional Food Formulations and preparation method thereof |
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