CN105524201B - A kind of ink covering emulsion and preparation method thereof - Google Patents
A kind of ink covering emulsion and preparation method thereof Download PDFInfo
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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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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- C08F212/08—Styrene
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- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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Abstract
The present invention relates to covering emulsion technical fields, more particularly to a kind of ink covering emulsion and preparation method thereof, the used raw material of the ink covering emulsion is existing low cost feedstock, and the cost of the ink covering emulsion produced is low, and ink covering emulsion of the invention is free of toxic solvent, low VOV contents, covering without free TDI and each heavy metal species, Environmental Safety, ink covering emulsion of the invention is good, color developing effect is good, and the surface gloss of gained printing layer is high；The preparation method of the present invention, simple for process, operability is strong, can large-scale promotion use, cooperation ink masking emulsion formulations use, and the covering of the ink covering emulsion produced is good, and color developing effect is good, and the surface gloss of gained printing layer is high.
Description
Technical field
The present invention relates to covering emulsion technical fields, and in particular to a kind of ink covering emulsion and preparation method thereof.
Background technology
With the continuous enhancing of people's environmental consciousness, the packing box of more and more commodity starts to print using water-based ink.
Domestic traditional water-based ink manufacturer is usually to use modified soluble rosin resin solution as link stuff, together with mill base
It is configured to water-based ink.Modified soluble rosin resin is cheap, strong coloring force, but weathering, poor water resistance, the oil of preparation
Black comprehensive performance is poor.In recent years, start the link stuff for gradually adopting acrylic emulsion as water-based ink.Acrylic emulsion one
Aspect can promote the dispersion of pigment in water, enhance the printing adaptability of ink；On the other hand, the oil prepared with acrylic emulsion
Black weathering, water-tolerant can greatly improve the class of water-based ink.But some printing materials (such as water lustering oil) are normal
Acrylic emulsion is used for preparing water-based ink, and performance is not so good, after mainly being dried due to existing acrylic emulsion
Very transparent, the ink colorant power of preparation is bad, and covering is poor, needs to add many fillers.In addition printing layer glossiness is low, especially
It is more to seem intensely dark on some corrugated-paper packaging boxes, therefore, it is necessary to the good acrylic emulsions of covering to fill market
Vacancy.
Invention content
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of inks to cover breast
The covering of liquid, the covering emulsion is good, and color developing effect is good, and the surface gloss of gained printing layer is high.
Another object of the present invention is to provide a kind of preparation method of ink covering emulsion, which coordinates this hair
Bright ink covering emulsion formula is used together, and the covering of the ink covering emulsion produced is good, and color developing effect is good, gained
The surface gloss of printing layer is high, the preparation method it is simple for process, operability is strong, can large-scale promotion use.
The purpose of the invention is achieved by the following technical solution：A kind of ink covering emulsion, includes the original of following parts by weight
Material：
Component A：300-450 parts of water；
Component B：0.2-2 parts of sodium bicarbonate, 0.2-2 parts of emulsifier；
Component C：8-12 parts of water, 0.5-2.4 parts of persulfate；
Component D1：Itaconic acid, hydroxyethyl methacrylic acid phosphate, methacrylic acid ethylidene-urea ethoxylated ester, clothing health
The total amount of at least one of dimethyl phthalate, trimethylol-propane trimethacrylate, glyceral methacrylate, addition is
5-15 parts；
Component D2：Acrylic or methacrylic acid, addition are 0.1-25 parts；
Component D3：Hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxyethyl methacrylate, hydroxymethyl acrylamide,
At least one of hydroxypropyl acrylate, it is 0.1-20 parts that total amount, which is added,；
Component D4：0.2-10 parts of chain-transferring agent mixture；
Component D5：At least one of butyl acrylate, Isooctyl acrylate monomer, ethyl acrylate, methyl acrylate are added
Total amount is 20-60 parts；
Component D6:Methyl methacrylate or propionic acid acid methyl esters, addition are 10-40 parts；
Component E：0.5-20 parts of PH conditioning agents, 50-70 parts of water；
Component F：0.2-8 parts of anion emulsifier, 0.2-8 parts of nonionic emulsifier, 15-25 parts of water；
Component G：8-12 parts of water, 1-3 parts of persulfate；
Component H：At least one of styrene, methyl methacrylate, butyl acrylate, Isooctyl acrylate monomer, ethyl alcohol
0.5-2 parts, it is 350-450 parts that total amount, which is added,.
Raw material is existing low cost feedstock used by the ink covering emulsion of the present invention, and the ink produced covers
The cost of lotion is low, and ink covering emulsion of the invention is free of toxic solvent, and low VOV contents are free of free TDI and a various huge sum of moneys
Belong to, the covering of Environmental Safety, ink covering emulsion of the invention is good, and color developing effect is good, the surface gloss of gained printing layer
It is high.
Further, a kind of ink covering emulsion, includes the raw material of following parts by weight：
Component A：300-380 parts of water；
Component B：0.2-1 parts of sodium bicarbonate, 0.2-1 parts of emulsifier；
Component C：8-10 parts of water, 0.5-1.5 parts of persulfate；
Component D1：Itaconic acid, hydroxyethyl methacrylic acid phosphate, methacrylic acid ethylidene-urea ethoxylated ester, clothing health
The total amount of at least one of dimethyl phthalate, trimethylol-propane trimethacrylate, glyceral methacrylate, addition is
5-10 parts；
Component D2：Acrylic or methacrylic acid, addition are 0.1-15 parts；
Component D3：Hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxyethyl methacrylate, hydroxymethyl acrylamide,
At least one of hydroxypropyl acrylate, it is 0.1-10 parts that total amount, which is added,；
Component D4：0.2-3 parts of chain-transferring agent mixture；
Component D5：At least one of butyl acrylate, Isooctyl acrylate monomer, ethyl acrylate, methyl acrylate are added
Total amount is 20-40 parts；
Component D6:Methyl methacrylate or propionic acid acid methyl esters, addition are 10-25 parts；
Component E：0.5-10 parts of PH conditioning agents, 50-60 parts of water；
Component F：0.2-4 parts of anion emulsifier, 0.2-4 parts of nonionic emulsifier, 15-20 parts of water；
Component G：8-10 parts of water, 1-2 parts of persulfate；
Component H：At least one of styrene, methyl methacrylate, butyl acrylate, Isooctyl acrylate monomer, ethyl alcohol
0.5-1 parts, it is 350-400 parts that total amount, which is added,.
Further, a kind of ink covering emulsion, includes the raw material of following parts by weight：
Component A：380-450 parts of water；
Component B：1-2 parts of sodium bicarbonate, 1-2 parts of emulsifier；
Component C：10-12 parts of water, 1.5-2.4 parts of persulfate；
Component D1：Itaconic acid, hydroxyethyl methacrylic acid phosphate, methacrylic acid ethylidene-urea ethoxylated ester, clothing health
The total amount of at least one of dimethyl phthalate, trimethylol-propane trimethacrylate, glyceral methacrylate, addition is
11-15 parts；
Component D2：Acrylic or methacrylic acid, addition are 15-25 parts；
Component D3：Hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxyethyl methacrylate, hydroxymethyl acrylamide,
At least one of hydroxypropyl acrylate, it is 10-20 parts that total amount, which is added,；
Component D4：3-6 parts of chain-transferring agent mixture；
Component D5：At least one of butyl acrylate, Isooctyl acrylate monomer, ethyl acrylate, methyl acrylate are added
Total amount is 40-60 parts；
Component D6:Methyl methacrylate or propionic acid acid methyl esters, addition are 25-40 parts；
Component E：10-20 parts of PH conditioning agents, 60-70 parts of water；
Component F：4-8 parts of anion emulsifier, 4-8 parts of nonionic emulsifier, 20-25 parts of water；
Component G：10-12 parts of water, 2-3 parts of persulfate；
Component H：At least one of styrene, methyl methacrylate, butyl acrylate, Isooctyl acrylate monomer, ethyl alcohol
1-2 parts, it is 400-450 parts that total amount, which is added,.
Further, the persulfate is ammonium persulfate or potassium peroxydisulfate.
Further, the anion emulsifier can be oleate soap, odium stearate, fatty acid polyglycol ether sulfate, the third sulphur
Dialkylaminobenzoic acid benzene sulfonate, alkyl phenol ethoxylates ammonium sulfate or sodium alkyl sulfonate；The nonionic emulsifier can be fat
Sour polyoxyethylene（10）Ester（Emulsifier SE-10）Or half branched fatty alcohol polyoxyethylene ether.
Further, the component D1 is dimethyl itaconate and methacrylic acid ethylidene-urea ethoxylated ester with mass ratio
2-4：The mixture of 1-3 compositions, addition are 5-15 parts.Dimethyl itaconate and methacrylic acid ethylidene-urea ethoxylated ester are matched
It closes and uses, be conducive to the covering performance and colour rendering that improve ink covering emulsion.
Further, the chain-transferring agent mixture in the component D4 is chain-transferring agent, organic formwork agent and molecular weight tune
Agent is saved with mass ratio 4:1-2:The mixture of 1-3 compositions.Component D4 can effectively control the chain length of polymer, and then control poly-
The viscosity of object is closed, chain-transferring agent, organic formwork agent and molecular weight regulator are used cooperatively, the viscosity of gained ink covering emulsion
Good, viscosity controllability is strong.
Further, the PH conditioning agents in the component E are organic amino, ammonium hydroxide, an amine or triamine.Use organic amino, ammonia
The PH conditioning agents of water, an amine or triamine as the present invention, using effect is good, at low cost.
Further, the component H is：1 part of ethyl alcohol, surplus are styrene and butyl acrylate with mass ratio 1:1-3 groups
At mixture, be added total amount be 400-450 parts.
Further, the component H is：2 parts of ethyl alcohol, surplus are methyl methacrylate and Isooctyl acrylate monomer with quality
Than 1:The mixture of 1 composition, it is 400-450 parts that total amount, which is added,.
A kind of preparation method of ink covering emulsion, includes the following steps：Step 1: the raw material for weighing formulation weight part is standby
With；Step 2: component A is added in reaction kettle, agitating and heating heating, while it being slowly added into component B into reaction kettle, waits for temperature
Reach 78-88 DEG C, stops heating；Step 3: component C is added into reaction kettle after 80-85 DEG C after temperature of reaction kettle stabilization, so
After start that component D1, component D2, component D3, component D4, component D5 and component D6, dropping temperature 82- are added dropwise into reaction kettle
86 DEG C, it is added dropwise to complete rear isothermal holding 50-90min；Step 4: after the completion of heat preservation, the temperature of reaction kettle is controlled in 78-86
DEG C, component E is added, adjusts pH value so that the PH in reaction kettle is 6.9-8.8, is then heated to 78-91 DEG C；Step 5:
Stablize after 89-91 DEG C after temperature of reaction kettle, component F is added into reaction kettle, adds component G, is stirred 4-6min；Step
Rapid six, component H is added dropwise into reaction kettle for the dropwise addition mode being at the uniform velocity added dropwise using constant temperature, and the dropping temperature of component H is controlled in 89-91
DEG C, total time for adding control is in 2-2.2h；Step 7: keeping the temperature 1-2h at a temperature of 90-91 DEG C after the completion of waiting for step 6, cool down
Ink covering emulsion is made afterwards.
The present invention preparation method, preparation process is simple, and operability is strong, can large-scale promotion use, cooperation ink hide
The formula for covering lotion is used together, and the covering of the ink covering emulsion produced is good, and color developing effect is good, gained printing layer
Surface gloss is high；Component D1, component D2, component D3, component D4, component D5, component D6 and component H are using the addition side being added dropwise
Formula, material reaction is abundant, and polymerization uniformity coefficient is high；To ensure that the ink covering emulsion of the present invention has good covering performance,
In the step 4, the pH value that must be strictly controlled material after the completion of component E is added is added dropwise, it is ensured that the PH in reaction kettle exists
Between 6.9-8.8；Component H is added dropwise into reaction kettle for the dropwise addition mode being at the uniform velocity added dropwise using constant temperature, and material reaction is abundant, and polymerization is equal
Even degree is high, and the covering performance of gained ink covering emulsion is good, and color developing is good.
Further, when the heating stop temperature of the step 2 is 80-85 DEG C, after reaction kettle is adjusted in step 4
PH is 6.9-7.2, adjusts PH and is heated to 89-91 DEG C after the completion；
When the heating stop temperature of the step 2 is 78-82 DEG C, the PH after reaction kettle is adjusted in step 4 is 7.2-
7.8, it adjusts PH and is heated to 84-88 DEG C after the completion；
When the heating stop temperature of the step 2 is 85-88 DEG C, the PH after reaction kettle is adjusted in step 4 is 7.8-
8.8, it adjusts PH and is heated to 78-83 DEG C after the completion.
Further, further include step 8 after the step of preparation method seven：Wait for that the temperature in reaction kettle drops to 70 DEG C
When, the pH value of material in test reaction kettle makees cooling processing after keeping the temperature 0.5h.Isothermal holding is being carried out after cooling, it is ensured that anti-
Answer the material reaction completely in kettle abundant, it is ensured that ink covering emulsion obtained has good covering performance and colour rendering.
Further, further include step 9 after the step 8：When reactor temperature drops to 35-40 DEG C, adjust
The viscosity and pH value of section material in reactor, sample detection product quality indicator, after qualified, filtering and discharging.Detection production before discharging
Product adjust the viscosity and pH value of product, it is ensured that the quality index of product is qualified, and product quality stability is good.
The beneficial effects of the present invention are：Raw material used by the ink covering emulsion of the present invention is that existing low cost is former
Material, the cost of the ink covering emulsion produced is low, ink covering emulsion of the invention be free of toxic solvent, low VOV contents,
Covering without free TDI and each heavy metal species, Environmental Safety, ink covering emulsion of the invention is good, and color developing effect is good, institute
The surface gloss for obtaining printing layer is high.
The present invention preparation method, preparation process is simple, and operability is strong, can large-scale promotion use, cooperation ink hide
The formula for covering lotion is used together, and the covering of the ink covering emulsion produced is good, and color developing effect is good, gained printing layer
Surface gloss is high；The covering emulsion of the present invention is in kernel, the multilayered structure of middle stratum nucleare and outer shell, group during production
Point D1, component D2, component D3, component D4, component D5 and component D6 form kernel, and the surface that component E is adsorbed on kernel is formed
Stratum nucleare, the component H-shaped of dropwise addition is at outer shell, and the refractive index of kernel, middle stratum nucleare and outer shell is different, in kernel and center
Interface light between layer, middle stratum nucleare and outer shell can reflect, and along with strong diffusing reflection, light is difficult complete
Through the covering emulsion of the present invention, covering emulsion of the invention has good covering performance；Component D1, component D2, component D3,
Using the feed postition being added dropwise, the thickness for being formed by kernel and outer shell is uniform by component D4, component D5, component D6 and component H
Property is good；To ensure that the ink covering emulsion of the present invention has good covering performance, in the step 4, component E is added dropwise and adds
It must be strictly controlled the pH value of material after the completion of entering, it is ensured that the PH in reaction kettle is between 6.9-8.8.
Specific implementation mode
For the ease of the understanding of those skilled in the art, with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of ink covering emulsion, includes the raw material of following parts by weight：
Component A：300 parts of water；
Component B：0.2 part of sodium bicarbonate, 0.2 part of emulsifier；
Component C：8 parts of water, 0.5 part of persulfate；
Component D1：1 part of itaconic acid, 2 parts of hydroxyethyl methacrylic acid phosphate, methacrylic acid ethylidene-urea ethoxylated ester
2 parts；
Component D2：Acrylic acid, addition are 0.1 part；
Component D3：Hydroxy-ethyl acrylate, addition are 0.1 part；
Component D4：0.2 part of chain-transferring agent mixture；
Component D5：Butyl acrylate, addition are 20 parts；
Component D6:Methyl methacrylate, addition are 10 parts；
Component E：0.5 part of PH conditioning agents, 50 parts of water；
Component F：0.2 part of anion emulsifier, 0.2 part of nonionic emulsifier, 15 parts of water；
Component G：8 parts of water, 1 part of persulfate；
Component H：Styrene, 0.5 part of ethyl alcohol, it is 350 parts that total amount, which is added,.
The persulfate is ammonium persulfate.
The anion emulsifier can be oleate soap, and the nonionic emulsifier can be aliphatic acid polyethenoxy（10）
Ester（Emulsifier SE-10）.
Chain-transferring agent mixture in the component D4 is chain-transferring agent, organic formwork agent and molecular weight regulator with quality
Than 4:1:The mixture of 1 composition.
PH conditioning agents in the component E are organic amino.
A kind of preparation method of ink covering emulsion, includes the following steps：Step 1: the raw material for weighing formulation weight part is standby
With；Step 2: component A is added in reaction kettle, agitating and heating heating, while it being slowly added into component B into reaction kettle, waits for temperature
Reach 80 DEG C and stops heating；Component C is added into reaction kettle after 80 DEG C Step 3: stablizing after temperature of reaction kettle, then starts
Component D1, component D2, component D3, component D4, component D5 and component D6 are added dropwise into reaction kettle, dropping temperature is 82 DEG C, is added dropwise
Isothermal holding 50min after the completion；Step 4: after the completion of heat preservation, the temperature of reaction kettle is controlled at 78 DEG C, component E is added, is adjusted
PH value so that the PH in reaction kettle is 6.9, is then heated to 89 DEG C；Step 5: waiting for that temperature of reaction kettle is stablized at 89 DEG C
Afterwards, component F is added into reaction kettle, adds component G, is stirred 4min；Step 6: the dropwise addition being at the uniform velocity added dropwise using constant temperature
Component H is added dropwise into reaction kettle for mode, and the dropping temperature of component H is controlled at 89 DEG C, and total time for adding control is in 2h；Step 7:
It waits for keeping the temperature 1h at a temperature of 90 DEG C after the completion of step 6, ink covering emulsion is made after cooling.
Further include step 8 after the step of preparation method seven：When the temperature in reaction kettle drops to 70 DEG C, test is anti-
The pH value of material in kettle is answered, makees cooling processing after keeping the temperature 0.5h.
Further include step 9 after the step 8：When reactor temperature drops to 35 DEG C, object in reaction kettle is adjusted
The viscosity and pH value of material, sample detection product quality indicator, after qualified, filtering and discharging.
Embodiment 2
A kind of ink covering emulsion, includes the raw material of following parts by weight：
Component A：380 parts of water；
Component B：1 part of sodium bicarbonate, 1 part of emulsifier；
Component C：10 parts of water, 1.5 parts of persulfate；
Component D1：3 parts of itaconic acid, 3 parts of hydroxyethyl methacrylic acid phosphate, 4 parts of glyceral methacrylate；
Component D2：Methacrylic acid, addition are 15 parts；
Component D3：Hydroxy propyl methacrylate, addition are 10 parts；
Component D4：5 parts of chain-transferring agent mixture；
Component D5：Isooctyl acrylate monomer, addition are 40 parts；
Component D6:Propionic acid acid methyl esters, addition are 25 parts；
Component E：10 parts of PH conditioning agents, 60 parts of water；
Component F：4 parts of anion emulsifier, 4 parts of nonionic emulsifier, 20 parts of water；
Component G：10 parts of water, 2 parts of persulfate；
Component H：Methyl methacrylate, 1 part of ethyl alcohol, it is 400 parts that total amount, which is added,.
The persulfate is potassium peroxydisulfate.
The anion emulsifier can be odium stearate；The nonionic emulsifier is half branched fatty alcohol polyoxyethylene
Ether.Half branched fatty alcohol polyoxyethylene ether and odium stearate synergistic effect emulsifiability are excellent, and the environment that the two is used cooperatively
Compatibility is good, the property still with good stability and hard water resistance within the scope of wider PH.
Chain-transferring agent mixture in the component D4 is chain-transferring agent, organic formwork agent and molecular weight regulator with quality
Than 4:1.5:The mixture of 2 compositions.
PH conditioning agents in the component E are ammonium hydroxide.
A kind of preparation method of ink covering emulsion, includes the following steps：Step 1: the raw material for weighing formulation weight part is standby
With；Step 2: component A is added in reaction kettle, agitating and heating heating, while it being slowly added into component B into reaction kettle, waits for temperature
Reach 85 DEG C and stops heating；Component C is added into reaction kettle after 81 DEG C Step 3: stablizing after temperature of reaction kettle, then starts
Component D1, component D2, component D3, component D4, component D5 and component D6 are added dropwise into reaction kettle, dropping temperature is 83 DEG C, is added dropwise
Isothermal holding 60min after the completion；Step 4: after the completion of heat preservation, the temperature of reaction kettle is controlled at 80 DEG C, component E is added, is adjusted
PH value so that the PH in reaction kettle is 7.2, is then heated to 91 DEG C；Step 5: waiting for that temperature of reaction kettle is stablized at 90 DEG C
Afterwards, component F is added into reaction kettle, adds component G, is stirred 5min；Step 6: the dropwise addition being at the uniform velocity added dropwise using constant temperature
Component H is added dropwise into reaction kettle for mode, and component H dropping temperatures are controlled at 90 DEG C, and total time for adding control is in 2.1h；Step 7:
It waits for keeping the temperature 1.5h at a temperature of 90 DEG C after the completion of step 6, ink covering emulsion is made after cooling.
Further include step 8 after the step of preparation method seven：When the temperature in reaction kettle drops to 70 DEG C, test is anti-
The pH value of material in kettle is answered, makees cooling processing after keeping the temperature 0.5h.
Further include step 9 after the step 8：When reactor temperature drops to 38 DEG C, object in reaction kettle is adjusted
The viscosity and pH value of material, sample detection product quality indicator, after qualified, filtering and discharging.
Embodiment 3
A kind of ink covering emulsion, includes the raw material of following parts by weight：
Component A：450 parts of water；
Component B：2 parts of sodium bicarbonate, 2 parts of emulsifier；
Component C：12 parts of water, 2.4 parts of persulfate；
Component D1：5 parts of itaconic acid, 5 parts of methacrylic acid ethylidene-urea ethoxylated ester, trimethylol propane trimethyl propylene
5 parts of acid esters；
Component D2：Acrylic acid, addition are 25 parts；
Component D3：Hydroxyethyl methacrylate, addition are 20 parts；
Component D4：10 parts of chain-transferring agent mixture；
Component D5：Ethyl acrylate, addition are 60 parts；
Component D6:Propionic acid acid methyl esters, addition are 40 parts；
Component E：20 parts of PH conditioning agents, 70 parts of water；
Component F：8 parts of anion emulsifier, 8 parts of nonionic emulsifier, 25 parts of water；
Component G：12 parts of water, 3 parts of persulfate；
Component H：Butyl acrylate, 2 parts of ethyl alcohol, it is 450 parts that total amount, which is added,.
The persulfate is potassium peroxydisulfate.
The anion emulsifier can be alkylbenzene sulfonate；The nonionic emulsifier is half branched fatty alcohol polyoxy
Vinethene.Half branched fatty alcohol polyoxyethylene ether and alkylbenzene sulfonate synergistic effect emulsifiability are excellent, and the two cooperation makes
Environmental compatibility is good, the property still with good stability and hard water resistance within the scope of wider PH.
Chain-transferring agent mixture in the component D4 is chain-transferring agent, organic formwork agent and molecular weight regulator with quality
Than 4:2:The mixture of 3 compositions.
PH conditioning agents in the component E are an amine.
A kind of preparation method of ink covering emulsion, includes the following steps：Step 1: the raw material for weighing formulation weight part is standby
With；Step 2: component A is added in reaction kettle, agitating and heating heating, while it being slowly added into component B into reaction kettle, waits for temperature
Reach 78 DEG C and stops heating；Component C is added into reaction kettle after 85 DEG C Step 3: stablizing after temperature of reaction kettle, then starts
Component D1, component D2, component D3, component D4, component D5 and component D6 are added dropwise into reaction kettle, dropping temperature is 86 DEG C, is added dropwise
Isothermal holding 90min after the completion；Step 4: after the completion of heat preservation, the temperature of reaction kettle is controlled at 86 DEG C, component E is added, is adjusted
PH value so that the PH in reaction kettle is 7.2, is then heated to 84 DEG C；Step 5: waiting for that temperature of reaction kettle is stablized at 91 DEG C
Afterwards, component F is added into reaction kettle, adds component G, is stirred 6min；Step 6: the dropwise addition being at the uniform velocity added dropwise using constant temperature
Component H is added dropwise into reaction kettle for mode, and the dropping temperature of component H is controlled at 91 DEG C, and total time for adding control is in 2.2h；Step
Seven, it waits for keeping the temperature 2h at a temperature of 91 DEG C after the completion of step 6, ink covering emulsion is made after cooling.
Further include step 8 after the step of preparation method seven：When the temperature in reaction kettle drops to 70 DEG C, test is anti-
The pH value of material in kettle is answered, makees cooling processing after keeping the temperature 0.5h.
Further include step 9 after the step 8：When reactor temperature drops to 40 DEG C, object in reaction kettle is adjusted
The viscosity and pH value of material, sample detection product quality indicator, after qualified, filtering and discharging.
Embodiment 4
The present embodiment and embodiment 1 difference lies in：
The anion emulsifier is fatty acid polyglycol ether sulfate.
The component D3 is hydroxypropyl acrylate, and addition is 0.1 part.
The component D1 is dimethyl itaconate and methacrylic acid ethylidene-urea ethoxylated ester with mass ratio 2：1 composition
Mixture, addition are 5 parts.
PH conditioning agents in the component E are triamine.
The component H is Isooctyl acrylate monomer, and 2 parts of ethyl alcohol, it is 450 parts that total amount, which is added,.
A kind of preparation method of ink covering emulsion, includes the following steps：Step 1: the raw material for weighing formulation weight part is standby
With；Step 2: component A is added in reaction kettle, agitating and heating heating, while it being slowly added into component B into reaction kettle, waits for temperature
Reach 82 DEG C and stops heating；Component C is added into reaction kettle after 85 DEG C Step 3: stablizing after temperature of reaction kettle, then starts
Component D1, component D2, component D3, component D4, component D5 and component D6 are added dropwise into reaction kettle, dropping temperature is 86 DEG C, is added dropwise
Isothermal holding 90min after the completion；Step 4: after the completion of heat preservation, the temperature of reaction kettle is controlled at 86 DEG C, component E is added, is adjusted
PH value so that the PH in reaction kettle is 7.8, is then heated to 88 DEG C；Step 5: waiting for that temperature of reaction kettle is stablized at 91 DEG C
Afterwards, component F is added into reaction kettle, adds component G, is stirred 6min；Step 6: the dropwise addition being at the uniform velocity added dropwise using constant temperature
Component H is added dropwise into reaction kettle for mode, and the dropping temperature of component H is controlled at 91 DEG C, and total time for adding control is in 2.2h；Step
Seven, it waits for keeping the temperature 2h at a temperature of 91 DEG C after the completion of step 6, ink covering emulsion is made after cooling.
Embodiment 5
The present embodiment the difference from example 2 is that：
The anion emulsifier is propane sulfonic acid alkylbenzene sulfonate.
The component D3 is hydroxy-ethyl acrylate and hydroxypropyl acrylate with mass ratio 1:The mixture of 3 compositions, addition
It is 10 parts.
The component D1 is dimethyl itaconate and methacrylic acid ethylidene-urea ethoxylated ester with mass ratio 3：2 compositions
Mixture, addition are 11 parts.
The component H is：1 part of ethyl alcohol, surplus are styrene and butyl acrylate with mass ratio 1:The mixture of 1 composition,
It is 400 parts that total amount, which is added,.
A kind of preparation method of ink covering emulsion, includes the following steps：Step 1: the raw material for weighing formulation weight part is standby
With；Step 2: component A is added in reaction kettle, agitating and heating heating, while it being slowly added into component B into reaction kettle, waits for temperature
Reach 85 DEG C and stops heating；Component C is added into reaction kettle after 85 DEG C Step 3: stablizing after temperature of reaction kettle, then starts
Component D1, component D2, component D3, component D4, component D5 and component D6 are added dropwise into reaction kettle, dropping temperature is 86 DEG C, is added dropwise
Isothermal holding 90min after the completion；Step 4: after the completion of heat preservation, the temperature of reaction kettle is controlled at 86 DEG C, component E is added, is adjusted
PH value so that the PH in reaction kettle is 7.8, is then heated to 78 DEG C；Step 5: waiting for that temperature of reaction kettle is stablized at 91 DEG C
Afterwards, component F is added into reaction kettle, adds component G, is stirred 6min；Step 6: the dropwise addition being at the uniform velocity added dropwise using constant temperature
Component H is added dropwise into reaction kettle for mode, and the dropping temperature of component H is controlled at 91 DEG C, and total time for adding control is in 2.2h；Step
Seven, it waits for keeping the temperature 2h at a temperature of 91 DEG C after the completion of step 6, ink covering emulsion is made after cooling.
Embodiment 6
The present embodiment and embodiment 3 difference lies in：
The anion emulsifier is alkyl phenol ethoxylates ammonium sulfate.
The component D3 is hydroxy propyl methacrylate and hydroxymethyl acrylamide with mass ratio 2:The mixture of 3 compositions,
Addition is 20 parts.
The component D1 is dimethyl itaconate and methacrylic acid ethylidene-urea ethoxylated ester with mass ratio 4：3 compositions
Mixture, addition are 15 parts.
The component H is：1 part of ethyl alcohol, surplus are styrene and butyl acrylate with mass ratio 1:The mixture of 3 compositions,
It is 450 parts that total amount, which is added,.
A kind of preparation method of ink covering emulsion, includes the following steps：Step 1: the raw material for weighing formulation weight part is standby
With；Step 2: component A is added in reaction kettle, agitating and heating heating, while it being slowly added into component B into reaction kettle, waits for temperature
Reach 88 DEG C and stops heating；Component C is added into reaction kettle after 85 DEG C Step 3: stablizing after temperature of reaction kettle, then starts
Component D1, component D2, component D3, component D4, component D5 and component D6 are added dropwise into reaction kettle, dropping temperature is 86 DEG C, is added dropwise
Isothermal holding 90min after the completion；Step 4: after the completion of heat preservation, the temperature of reaction kettle is controlled at 86 DEG C, component E is added, is adjusted
PH value so that the PH in reaction kettle is 8.8, is then heated to 83 DEG C；Step 5: waiting for that temperature of reaction kettle is stablized at 91 DEG C
Afterwards, component F is added into reaction kettle, adds component G, is stirred 6min；Step 6: the dropwise addition being at the uniform velocity added dropwise using constant temperature
Component H is added dropwise into reaction kettle for mode, and the dropping temperature of component H is controlled at 91 DEG C, and total time for adding control is in 2.2h；Step
Seven, it waits for keeping the temperature 2h at a temperature of 91 DEG C after the completion of step 6, ink covering emulsion is made after cooling.
Embodiment 7
The present embodiment and embodiment 3 difference lies in：
The anion emulsifier is alkyl phenol ethoxylates ammonium sulfate.
The component D3 is hydroxy propyl methacrylate and hydroxymethyl acrylamide with mass ratio 2:The mixture of 3 compositions,
Addition is 20 parts.
The component D1 is trimethylol-propane trimethacrylate and glyceral methacrylate with mass ratio 2：1 group
At mixture, addition be 15 parts.
The component H is：2 parts of ethyl alcohol, surplus are methyl methacrylate and Isooctyl acrylate monomer with mass ratio 1:1 composition
Mixture, be added total amount be 400 parts.
A kind of preparation method of ink covering emulsion, includes the following steps：Step 1: the raw material for weighing formulation weight part is standby
With；Step 2: component A is added in reaction kettle, agitating and heating heating, while it being slowly added into component B into reaction kettle, waits for temperature
Reach 88 DEG C and stops heating；Component C is added into reaction kettle after 85 DEG C Step 3: stablizing after temperature of reaction kettle, then starts
Component D1, component D2, component D3, component D4, component D5 and component D6 are added dropwise into reaction kettle, dropping temperature is 86 DEG C, is added dropwise
Isothermal holding 90min after the completion；Step 4: after the completion of heat preservation, the temperature of reaction kettle is controlled at 86 DEG C, component E is added, is adjusted
PH value so that the PH in reaction kettle is 8.8, is then heated to 83 DEG C；Step 5: waiting for that temperature of reaction kettle is stablized at 91 DEG C
Afterwards, component F is added into reaction kettle, adds component G, is stirred 6min；Step 6: the dropwise addition being at the uniform velocity added dropwise using constant temperature
Component H is added dropwise into reaction kettle for mode, and the dropping temperature of component H is controlled at 91 DEG C, and total time for adding control is in 2.2h；Step
Seven, it waits for keeping the temperature 2h at a temperature of 91 DEG C after the completion of step 6, ink covering emulsion is made after cooling.
Following table is the properties of product detection data table of the embodiment of the present invention 1- embodiments 6：
| Detection project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Existing ink covering emulsion -631 |
| PH value | 7.8 | 8.1 | 8.2 | 8.4 | 8.6 | 8.7 | 8.5 | 8.4 |
| Viscosity（Second, apply 4# glasss, 25 DEG C） | 41 | 40 | 39 | 42 | 41 | 42 | 41 | 39 |
| Tinting strength, tinting power（%） | 98 | 99 | 98 | 97 | 99 | 99 | 98 | 98 |
| Covering（%） | 97 | 97 | 96 | 98 | 98 | 98 | 98 | 97 |
As can be seen from the table, compare existing ink covering emulsion -631 of ink covering emulsion of the invention is impartial
With even more excellent covering performance and better tinting strength, tinting power, covering performance of the invention is good, and color developing is excellent, gained print
The surface gloss of brush layer is high.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other manner,
Any obvious replacement is not departed under the premise of present inventive concept within protection scope of the present invention.
Claims (8)
1. a kind of ink covering emulsion, it is characterised in that：Include the raw material of following parts by weight：
Component A：300-450 parts of water；
Component B：0.2-2 parts of sodium bicarbonate, 0.2-2 parts of emulsifier；
Component C：8-12 parts of water, 0.5-2.4 parts of persulfate；
Component D1：Dimethyl itaconate and methacrylic acid ethylidene-urea ethoxylated ester are with mass ratio 2-4：The mixing of 1-3 compositions
The total amount of object, addition is 5-15 parts；
Component D2：Acrylic or methacrylic acid, addition are 0.1-25 parts；
Component D3：Hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxyethyl methacrylate, hydroxymethyl acrylamide, propylene
At least one of sour hydroxypropyl acrylate, it is 0.1-20 parts that total amount, which is added,；
Component D4：0.2-10 parts of chain-transferring agent mixture；
Component D5：Total amount is added at least one of butyl acrylate, Isooctyl acrylate monomer, ethyl acrylate, methyl acrylate
It is 20-60 parts；
Component D6:Methyl methacrylate or propionic acid acid methyl esters, addition are 10-40 parts；
Component E：0.5-20 parts of pH adjusting agent, 50-70 parts of water；
Component F：0.2-8 parts of anion emulsifier, 0.2-8 parts of nonionic emulsifier, 15-25 parts of water；
Component G：8-12 parts of water, 1-3 parts of persulfate；
Component H：At least one of styrene, methyl methacrylate, butyl acrylate, Isooctyl acrylate monomer, ethyl alcohol 0.5-2
Part, it is 350-450 parts that total amount, which is added,；
Chain-transferring agent mixture in the component D4 is chain-transferring agent, organic formwork agent and molecular weight regulator with mass ratio 4:
1-2:The mixture of 1-3 compositions.
2. a kind of ink covering emulsion according to claim 1, it is characterised in that：Include the raw material of following parts by weight：
Component A：300-380 parts of water；
Component B：0.2-1 parts of sodium bicarbonate, 0.2-1 parts of emulsifier；
Component C：8-10 parts of water, 0.5-1.5 parts of persulfate；
Component D1：Dimethyl itaconate and methacrylic acid ethylidene-urea ethoxylated ester are with mass ratio 2-4：The mixing of 1-3 compositions
The total amount of object, addition is 5-10 parts；
Component D2：Acrylic or methacrylic acid, addition are 0.1-15 parts；
Component D3：Hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxyethyl methacrylate, hydroxymethyl acrylamide, propylene
At least one of sour hydroxypropyl acrylate, it is 0.1-10 parts that total amount, which is added,；
Component D4：0.2-3 parts of chain-transferring agent mixture；
Component D5：Total amount is added at least one of butyl acrylate, Isooctyl acrylate monomer, ethyl acrylate, methyl acrylate
It is 20-40 parts；
Component D6:Methyl methacrylate or propionic acid acid methyl esters, addition are 10-25 parts；
Component E：0.5-10 parts of pH adjusting agent, 50-60 parts of water；
Component F：0.2-4 parts of anion emulsifier, 0.2-4 parts of nonionic emulsifier, 15-20 parts of water；
Component G：8-10 parts of water, 1-2 parts of persulfate；
Component H：At least one of styrene, methyl methacrylate, butyl acrylate, Isooctyl acrylate monomer, ethyl alcohol 0.5-1
Part, it is 350-400 parts that total amount, which is added,.
3. a kind of ink covering emulsion according to claim 1, it is characterised in that：Include the raw material of following parts by weight：
Component A：380-450 parts of water；
Component B：1-2 parts of sodium bicarbonate, 1-2 parts of emulsifier；
Component C：10-12 parts of water, 1.5-2.4 parts of persulfate；
Component D1：Dimethyl itaconate and methacrylic acid ethylidene-urea ethoxylated ester are with mass ratio 2-4：The mixing of 1-3 compositions
The total amount of object, addition is 11-15 parts；
Component D2：Acrylic or methacrylic acid, addition are 15-25 parts；
Component D3：Hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxyethyl methacrylate, hydroxymethyl acrylamide, propylene
At least one of sour hydroxypropyl acrylate, it is 10-20 parts that total amount, which is added,；
Component D4：3-6 parts of chain-transferring agent mixture；
Component D5：Total amount is added at least one of butyl acrylate, Isooctyl acrylate monomer, ethyl acrylate, methyl acrylate
It is 40-60 parts；
Component D6:Methyl methacrylate or propionic acid acid methyl esters, addition are 25-40 parts；
Component E：10-20 parts of pH adjusting agent, 60-70 parts of water；
Component F：4-8 parts of anion emulsifier, 4-8 parts of nonionic emulsifier, 20-25 parts of water；
Component G：10-12 parts of water, 2-3 parts of persulfate；
Component H：At least one of styrene, methyl methacrylate, butyl acrylate, Isooctyl acrylate monomer, ethyl alcohol 1-2
Part, it is 400-450 parts that total amount, which is added,.
4. according to a kind of ink covering emulsion of claim 1-3 any one of them, it is characterised in that：PH in the component E
Conditioning agent is organic amino or ammonium hydroxide.
5. a kind of preparation method of ink covering emulsion of claim 1-4 any one of them, it is characterised in that：Including following step
Suddenly：Step 1: weighing the raw material for standby of formulation weight part；Step 2: component A is added in reaction kettle, agitating and heating heating, together
When component B is slowly added into reaction kettle, wait for that temperature reaches 78-88 DEG C, stop heating；Step 3: waiting for that temperature of reaction kettle is stablized
Component C is added into reaction kettle after 80-85 DEG C, then starts that component D1, component D2, component D3, group are added dropwise into reaction kettle
It is 82-86 DEG C to divide D4, component D5 and component D6, dropping temperature, is added dropwise to complete rear isothermal holding 50-90min；Step 4: heat preservation
After the completion, the temperature of reaction kettle is controlled at 78-86 DEG C, component E is added, adjust pH value so that the pH in reaction kettle is 6.9-
8.8, then it is heated to 78-91 DEG C；Step 5: stablizing after 89-91 DEG C after temperature of reaction kettle, the addition group into reaction kettle
Divide F, adds component G, be stirred 4-6min；Step 6: the dropwise addition mode being at the uniform velocity added dropwise using constant temperature is dripped into reaction kettle
Component H, the dropping temperature of component H is added to control at 89-91 DEG C, total time for adding control is in 2-2.2h；Step 7: waiting for that step 6 is complete
1-2h is kept the temperature at a temperature of 90-91 DEG C after, ink covering emulsion is made after cooling.
6. a kind of preparation method of ink covering emulsion according to claim 5, it is characterised in that：When the step 2
When heating stop temperature is 80-85 DEG C, the pH after reaction kettle is adjusted in step 4 is 6.9-7.2, adjusts pH and heats liter after the completion
Temperature is to 89-91 DEG C；
When the heating stop temperature of the step 2 is 78-82 DEG C, the pH after reaction kettle is adjusted in step 4 is 7.2-7.8,
It adjusts pH and is heated to 84-88 DEG C after the completion；
When the heating stop temperature of the step 2 is 85-88 DEG C, the pH after reaction kettle is adjusted in step 4 is 7.8-8.8,
It adjusts pH and is heated to 78-83 DEG C after the completion.
7. a kind of preparation method of ink covering emulsion according to claim 5, it is characterised in that：The step of the preparation method
Further include step 8 after rapid seven：When the temperature in reaction kettle drops to 70 DEG C, the pH values of material in test reaction kettle, heat preservation
Make cooling processing after 0.5h.
8. a kind of preparation method of ink covering emulsion according to claim 7, it is characterised in that：After the step 8
It further include step 9：When reactor temperature drops to 35-40 DEG C, the viscosity and pH values of material in reactor are adjusted, is sampled
Product quality indicator is detected, after qualified, filtering and discharging.
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| CN108059692A (en) * | 2018-01-02 | 2018-05-22 | 上海保立佳新材料有限公司 | A kind of hydridization covering emulsion used for water color ink |
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| CN102807648A (en) * | 2012-09-05 | 2012-12-05 | 陕西科技大学 | Method for preparing high-elasticity adhesive for fabric by adopting nuclear shell emulsion polymerization method |
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| CN102101901B (en) * | 2010-12-28 | 2012-07-25 | 东莞市英科水墨有限公司 | Core-shell type gold varnish emulsion and preparation method and use thereof |
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| CN102807648A (en) * | 2012-09-05 | 2012-12-05 | 陕西科技大学 | Method for preparing high-elasticity adhesive for fabric by adopting nuclear shell emulsion polymerization method |
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Effective date of registration: 20160606 Address after: Jingyuan Yongxing 5 No. 510800 Guangdong province Guangzhou Xiuquan Street Huadu District Fengshen Avenue Applicant after: Yang Kangying Applicant after: Bi Miaoling Address before: Jingyuan Yongxing 5 No. 510800 Guangdong province Guangzhou Xiuquan Street Huadu District Fengshen Avenue Applicant before: Yang Kangying Applicant before: Lu Shuming Applicant before: Bi Miaoling |
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