CN106634685B - A kind of Environmental-friendantistatic antistatic wallpaper glue and preparation method thereof - Google Patents
A kind of Environmental-friendantistatic antistatic wallpaper glue and preparation method thereof Download PDFInfo
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- CN106634685B CN106634685B CN201710001152.7A CN201710001152A CN106634685B CN 106634685 B CN106634685 B CN 106634685B CN 201710001152 A CN201710001152 A CN 201710001152A CN 106634685 B CN106634685 B CN 106634685B
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09J103/04—Starch derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/003—Crosslinking of starch
- C08B31/006—Crosslinking of derivatives of starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Paper (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention provides a kind of Environmental-friendantistatic antistatic wallpaper glues and preparation method thereof, the antistatic wallpaper glue is grouped as by following parts by weight group: 40-50 parts of modified starch, 15-20 parts of polyethylene glycol of mixed etherificate, 3-5 parts of thickener, 8-12 parts of chitosan, 3-6 parts of sodium benzoate, 1-3 parts of emulsifier, 1-3 parts and deionized water 300-400 parts of defoaming agent, the preparation method of the modified starch is by water, starch and alpha-amylase are added in reaction vessel, in 70-80 DEG C reaction 3-5 hours, add silane coupling agent, after continuing insulation reaction 0.5 hour, stop reaction, it is cooled to room temperature, filtering, filter cake drying, grinding, it crosses 60 meshes and obtains modified starch.The advantages of Environmental-friendantistatic antistatic wallpaper glue provided by the present invention has safety and environmental protection, anti-electrical property lasting, good weatherability.
Description
Technical field
The invention belongs to field of adhesive technology, and in particular to a kind of Environmental-friendantistatic antistatic wallpaper glue and preparation method thereof.
Background technique
Wallpaper glue is the abbreviation for the adhesive pasted for wallpaper, can be dissolved in cold water, and aqueous solution is rice white or transparent
Sticky glue.With the gradually enhancing and the formulation of national environmental protection class regulation of people's health consciousness, country is to first in adhesive
The limitation of aldehyde is also increasingly stringenter.Widely used phenolic resin, Lauxite, melamine first in current finishing field
The formaldehyde that urea formaldehyde adhesive volatilizes during production and use is not only contaminated environment but also can jeopardize public affairs
Many health.Therefore, the emphasis studied at present will be the adhesive for developing asepsis environment-protecting friendly.
Starch adhesive makees environmentally protective natural adhesive by more and more focus of attention.Starch itself has polyhydroxy
Based structures are the good materials for preparing starch.The good adhesive property of natural plant starch and its derivative, can satisfy city
Field demand；Secondly, starch is from a wealth of sources, cheap, environmentally friendly, degradable, while there is non-toxic, free from extraneous odour good spy
Point.With the continuous reduction of petroleum resources, the renewable resource of natural environmental-protective will certainly be instead of the chemical industry based on petroleum of relying
Raw material.
Wallpaper, often because electrostatic interaction crimps, seriously affects wallpaper sticking effect and construction personnel in Process of Applying Glue
Working efficiency.Chinese patent CN1041176A discloses a kind of antistatic wallpaper glue, by polyvinyl formal, vinyl acetate cream
Liquid, graphite powder, acetylene black powder and water compound.The antistatic wallpaper glue has effects that antistatic, but antistatic persistence is not
It is good, and wallpaper glue weatherability is bad.
Summary of the invention
The present invention provides a kind of Environmental-friendantistatic antistatic wallpaper glue, have safety and environmental protection, anti-electrical property lasting, good weatherability it is excellent
Point.
The technical proposal for solving the technical problem of the invention are as follows:
A kind of Environmental-friendantistatic antistatic wallpaper glue is grouped as by following parts by weight group: 40-50 parts of modified starch mixes etherificate
15-20 parts of polyethylene glycol, 3-5 parts of thickener, 8-12 parts of chitosan, 3-6 parts of sodium benzoate, 1-3 parts of emulsifier, defoaming agent 1-3
Part and deionized water 300-400 part, the preparation method of the modified starch is by water, starch and alpha-amylase addition reaction vessel
In, in 70-80 DEG C reaction 3-5 hours, add silane coupling agent, after continuing insulation reaction 0.5 hour, stop reaction, cooling
To room temperature, filtering, filter cake drying, grinding cross 60 meshes and obtain modified starch.
Using alpha-amylase first by Starch Hydrolysis, increases its degree of branching, add silane coupling agent, form it into macromolecule
Network structure, to increase the caking property and weatherability of wallpaper glue.
The polyethylene glycol of mixed etherificate is the fiber in hyper-branched polymer, with wallpaper as a kind of Polymer-metallic Catalyst
Plain molecule compatibility is preferable, can be evenly distributed on the inside and surface layer of wallpaper, avoid antistatic macromolecule in wallpaper
Portion reunites, and when wallpaper surface antistatic agent is because of friction loss, is still able to maintain good antistatic effect, antistatic lasting
Property is good.
Preferably, the emulsifier is nonylphenol polyoxyethylene ether, octyl phenol polyoxyethylene ether or stearic acid polyoxy second
Enester.
Preferably, the defoaming agent is that polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether and polyoxypropylene are poly-
Ethylene oxide glycerin ether or dimethyl silicone polymer.
Preferably, the thickener is methylcellulose, hydroxypropyl methyl cellulose, sodium carboxymethylcellulose or hydroxyl second
Base cellulose.
Preferably, the water, starch, alpha-amylase and silane coupling agent mass ratio be 20-30:1:0.15:0.2-
0.3, the silane coupling agent be gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicane or
γ-(methacryloxypropyl) propyl trimethoxy silicane.The dosage of alpha-amylase with 0.15 times of starch quality be it is best, when low
When the value, the degree of branching of starch is lower, cannot form cross-linked network shape structure, and the weatherability of wallpaper glue is bad；Work as alphalise starch
When the dosage of enzyme is higher than the value, alpha-amylase is excessive branching, then is crosslinked easily solidification, caking property decline through coupling agent.
Preferably, the polyethylene glycol of the mixed etherificate the preparation method comprises the following steps: polyethylene glycol, methanol and butanol are added anti-
It answers in container, acid adjusts PH to 4 ~ 5, keeps the temperature at 45 ~ 50 DEG C to 30 ~ 60min, then adjust PH to 8 ~ 9 with alkali, in 70 ~ 80
DEG C after reaction 1 ~ 2 hour, dimethylbenzene is added, 90 DEG C of distillation dehydrations stop reaction until there is no moisture to steam, and residue is
For mixed etherificate polyethylene glycol.
It is further preferred that the molecular weight of the polyethylene glycol is 400 or 600.
It is further preferred that the mass ratio of the polyethylene glycol, methanol and butanol is 1:0.4-0.5:0.2-0.3, polyethylene glycol, first
The mass ratio that feeds intake of pure and mild butanol determines the mixed etherificate degree of polyethylene glycol, when the dosage of methanol and butanol is lower than the numerical value,
Mixed etherificate degree is lower, mix etherificate polyethylene glycol it is soluble easily in water in, cause antistatic agent to lose；When the dosage of methanol and butanol
When more than the numerical value, mixed etherificate degree is higher, and the compatibility of the cellulosic molecule of antistatic agent and wallpaper is excessively good, causes antistatic
Agent can not normally move to wallpaper surface layer, and when surface layer antistatic agent is because of friction loss, inner antistatic agent can not be replenished in time,
Antistatic property is caused to decline, anti-electricity persistence is bad.
Invention also provides the preparation method of Environmental-friendantistatic antistatic wallpaper glue, the preparation method includes the following steps:
(1) by water, starch and alpha-amylase be added reaction vessel in, in 70-80 DEG C reaction 3-5 hours, add silane
Coupling agent, continue insulation reaction 0.5 hour after after, stop reaction, be cooled to room temperature, filter, filter cake drying, grinding, cross 60 mesh
Sieve to obtain modified starch；
(2) polyethylene glycol, methanol and butanol are added in reaction vessel, acid adjusts PH to 4 ~ 5, keeps the temperature at 45 ~ 50 DEG C
PH to 8 ~ 9 is adjusted to 30 ~ 60min, then with alkali, after 70 ~ 80 DEG C are reacted 1 ~ 2 hour, dimethylbenzene is added, 90 DEG C of distillations are de-
Water stops reaction until there is no moisture to steam, and residue is mixed etherificate polyethylene glycol；
(3) modified starch, the polyethylene glycol of mixed etherificate and deionized water are added in reaction vessel, in 1500-1800r/
It is stirred 15-30 minutes under min, adds chitosan, sodium benzoate, emulsifier and defoaming agent, stir 20 under 600-800/min
Minute, it is eventually adding thickener, is stirred 20 minutes under 1000-1200/min.
The invention has the benefit that
1, Environmental-friendantistatic antistatic wallpaper glue provided by the present invention is led to using the polyethylene glycol of mixed etherificate as antistatic agent
It crosses methanol and butanol mixes etherification modified polyethylene glycol, reduce the water solubility of polyethylene glycol, increase antistatic agent and wallpaper cellulose
Compatibility, be uniformly distributed it in wallpaper interior skin, it is internal antistatic when wallpaper surface layer antistatic agent is because rubbing impaired
Agent moves to wallpaper surface layer in time, increases antistatic persistence.
2, it using alpha-amylase first by Starch Hydrolysis, then is crosslinked through silane coupling agent and modified starch is made, to improve wall
The caking property and weatherability of paper glue.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments to the present invention
It is further elaborated.
Embodiment 1
(1) 2000g water, 100g starch and 15g alpha-amylase are added in reaction vessel, are reacted 3 hours in 80 DEG C, then
Be added 20g gamma-aminopropyl-triethoxy-silane, continue insulation reaction 0.5 hour after after, stop reaction, be cooled to room temperature, mistake
Filter, filter cake drying, grinding cross 60 meshes and obtain 120g modified starch；
(2) 100g polyethylene glycol 400,40g methanol and 25g butanol are added in reaction vessel, acid adjusts PH to 4, in 45
It keeps the temperature at DEG C to 60min, then adjusts PH to 9 with alkali, after 80 DEG C are reacted 1 hour, 150g dimethylbenzene is added, 90 DEG C of distillations take off
Water stops reaction until there is no moisture to steam, and residue is mixed etherificate polyethylene glycol；
(3) 45g modified starch, the polyethylene glycol of the mixed etherificate of 18g and 350g deionized water are added in reaction vessel, in
It is stirred 30 minutes under 1500r/min, adds 10g chitosan, 5g sodium benzoate, 1g nonylphenol polyoxyethylene ether and 2g polyoxy second
Alkene polyoxy propyl alcohol amidogen ether stirs 20 minutes under 700/min, 3g hydroxypropyl methyl cellulose is eventually adding, under 1000/min
Stirring 20 minutes, the viscosity for measuring made wallpaper glue is 758PaS.
Embodiment 2
(1) 2500g water, 100g starch and 15g alpha-amylase are added in reaction vessel, are reacted 5 hours in 70 DEG C, then
Be added 25g γ-glycidyl ether oxygen propyl trimethoxy silicane, continue insulation reaction 0.5 hour after after, stop reaction, cooling
To room temperature, filtering, filter cake drying, grinding cross 60 meshes and obtain 111g modified starch；
(2) 100g Macrogol 600,45g methanol and 30g butanol being added in reaction vessel, acid adjusts PH to 4.5, in
It keeps the temperature at 48 DEG C to 45min, then adjusts PH to 8.5 with alkali, after 75 DEG C are reacted 1.5 hours, addition 150g dimethylbenzene, 90 DEG C
Distillation dehydration stops reaction until there is no moisture to steam, and residue is mixed etherificate polyethylene glycol.
(3) 40g modified starch, the polyethylene glycol of the mixed etherificate of 15g and 400g deionized water are added in reaction vessel, in
It is stirred 15 minutes under 1800r/min, adds 8g chitosan, 3g sodium benzoate, 3g octyl phenol polyoxyethylene ether and 3g polyoxy third
Alkene glycerin ether stirs 20 minutes under 800/min, is eventually adding 5g methylcellulose, and 20 minutes are stirred under 1100/min i.e.
Can, the viscosity for measuring made wallpaper glue is 801PaS.
Embodiment 3
(1) 3000g water, 100g starch and 15g alpha-amylase are added in reaction vessel, are reacted 4 hours in 75 DEG C, then
Be added 30g γ-(methacryloxypropyl) propyl trimethoxy silicane, continue insulation reaction 0.5 hour after after, stop reaction, drop
It warms to room temperature, filters, filter cake drying, grinding cross 60 meshes and obtain 115g modified starch；
(2) 100g polyethylene glycol 400,50g methanol and 20g butanol are added in reaction vessel, acid adjusts PH to 5, in 50
It keeps the temperature at DEG C to 30min, then adjusts PH to 8 with alkali, after 70 DEG C are reacted 2 hours, 150g dimethylbenzene is added, 90 DEG C of distillations take off
Water stops reaction until there is no moisture to steam, and residue is mixed etherificate polyethylene glycol.
(3) 50g modified starch, the polyethylene glycol of the mixed etherificate of 20g and 300g deionized water are added in reaction vessel, in
It is stirred 20 minutes under 1600r/min, adds 12g chitosan, 6g sodium benzoate, 2g polyoxyethylene stearic acid ester and 1g polyoxy third
Alkene polyoxyethylene glycerol ether stirs 20 minutes under 600/min, 4g sodium carboxymethylcellulose is eventually adding, under 1200/min
Stirring 20 minutes, the viscosity for measuring made wallpaper glue is 752PaS.
Comparative example 1
(1) 100g polyethylene glycol 400,40g methanol and 25g butanol are added in reaction vessel, acid adjusts PH to 4, in 45
It keeps the temperature at DEG C to 60min, then adjusts PH to 9 with alkali, after 80 DEG C are reacted 1 hour, 150g dimethylbenzene is added, 90 DEG C of distillations take off
Water stops reaction until there is no moisture to steam, and residue is mixed etherificate polyethylene glycol；
(2) 45g starch, the polyethylene glycol of the mixed etherificate of 18g and 350g deionized water are added in reaction vessel, in
It is stirred 30 minutes under 1500r/min, adds 10g chitosan, 5g sodium benzoate, 1g nonylphenol polyoxyethylene ether and 2g polyoxy second
Alkene polyoxy propyl alcohol amidogen ether stirs 20 minutes under 700/min, 3g hydroxypropyl methyl cellulose is eventually adding, under 1000/min
Stirring 20 minutes, the viscosity for measuring made wallpaper glue is 532PaS.
Pass through comparative example 1 and comparative example 1, it can be deduced that, obtained wallpaper adhesiveness is bigger after modified for starch,
Caking property is more preferable.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (8)
1. a kind of Environmental-friendantistatic antistatic wallpaper glue, which is characterized in that the Environmental-friendantistatic antistatic wallpaper glue is by following parts by weight component
Composition: 15-20 parts of polyethylene glycol, 3-5 parts of the thickener, 8-12 parts of chitosan, benzoic acid of 40-50 parts of modified starch, mixed etherificate
3-6 parts of sodium, 1-3 parts of emulsifier, 1-3 parts of defoaming agent and 300-400 parts of deionized water, the preparation method of the modified starch is will
Water, starch and alpha-amylase are added in reaction vessel, in 70-80 DEG C reaction 3-5 hours, silane coupling agent is added, after continuation of insurance
After temperature reaction 0.5 hour, stop reaction, be cooled to room temperature, filter, filter cake drying, grinding cross 60 meshes and obtain modified starch；
The polyethylene glycol of the mixed etherificate the preparation method comprises the following steps: by polyethylene glycol, methanol and butanol be added reaction vessel in, acid adjust
PH to 4 ~ 5 is saved, is kept the temperature at 45 ~ 50 DEG C to 30 ~ 60min, then adjusts pH to 8 ~ 9 with alkali, is reacted 1 ~ 2 hour in 70 ~ 80 DEG C
Afterwards, dimethylbenzene, 90 DEG C of distillation dehydrations are added, until there is no moisture to steam, stop reaction, residue is the mixed poly- second two of etherificate
Alcohol.
2. Environmental-friendantistatic antistatic wallpaper glue as described in claim 1, which is characterized in that the emulsifier is Nonyl pheno
Ether, octyl phenol polyoxyethylene ether or polyoxyethylene stearic acid ester.
3. Environmental-friendantistatic antistatic wallpaper glue as described in claim 1, which is characterized in that the defoaming agent is polyoxyethylene polyoxy third
Alcohol amidogen ether, polypropylene glycerol aether, polyoxyethylene polyoxypropylene glycerin ether or dimethyl silicone polymer.
4. Environmental-friendantistatic antistatic wallpaper glue as described in claim 1, which is characterized in that the thickener is methylcellulose, hydroxyl
Propyl methocel, sodium carboxymethylcellulose or hydroxyethyl cellulose.
5. Environmental-friendantistatic antistatic wallpaper glue as described in claim 1, which is characterized in that the water, starch, alpha-amylase and silane
The mass ratio of coupling agent be 20-30:1:0.15:0.2-0.3, the silane coupling agent be gamma-aminopropyl-triethoxy-silane,
γ-glycidyl ether oxygen propyl trimethoxy silicane or γ-(methacryloxypropyl) propyl trimethoxy silicane.
6. Environmental-friendantistatic antistatic wallpaper glue as described in claim 1, which is characterized in that the molecular weight of the polyethylene glycol is 400
Or 600.
7. Environmental-friendantistatic antistatic wallpaper glue as described in claim 1, which is characterized in that the polyethylene glycol, methanol and butanol
Mass ratio is 1:0.4-0.5:0.2-0.3.
8. the method for preparing Environmental-friendantistatic antistatic wallpaper glue described in claim 1-7 any one, which is characterized in that the preparation side
Method includes the following steps:
(1) by water, starch and alpha-amylase be added reaction vessel in, in 70-80 DEG C reaction 3-5 hours, add silane coupled
Agent after continuing insulation reaction 0.5 hour, stops reaction, is cooled to room temperature, filters, and filter cake drying, grinding, crossing 60 meshes must change
Property starch；
(2) polyethylene glycol, methanol and butanol are added in reaction vessel, acid for adjusting pH to 4 ~ 5, are kept the temperature at 45 ~ 50 DEG C to 30
After ~ 60min, then with alkali adjust pH to 8 ~ 9, in 70 ~ 80 DEG C react 1 ~ 2 hour after, be added dimethylbenzene, 90 DEG C of distillation dehydrations, directly
To there is no moisture to steam, stop reaction, residue is mixed etherificate polyethylene glycol；
(3) modified starch, the polyethylene glycol of mixed etherificate and deionized water are added in reaction vessel, in 1500-1800r/min
Lower stirring 15-30 minutes, adds chitosan, sodium benzoate, emulsifier and defoaming agent, stirs 20 under 600-800 turns/min
Minute, it is eventually adding thickener, is stirred 20 minutes under 1000-1200 turns/min.
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Effective date of registration: 20200707 Address after: 315000 room 315-5, Chuangye building, No.66, academician Road, high tech Zone, Ningbo City, Zhejiang Province Patentee after: NINGBO JEEAO CHUANGYI NEW MATERIALS Co.,Ltd. Address before: 325200, Zhejiang City, Wenzhou province Ruian city on the street looking Patentee before: Huang Qihao |