CN106753086B - Environment-friendly water-based glue spraying and preparation method thereof - Google Patents
Environment-friendly water-based glue spraying and preparation method thereof Download PDFInfo
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- CN106753086B CN106753086B CN201611127093.XA CN201611127093A CN106753086B CN 106753086 B CN106753086 B CN 106753086B CN 201611127093 A CN201611127093 A CN 201611127093A CN 106753086 B CN106753086 B CN 106753086B
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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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/04—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- 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
- C08F253/00—Macromolecular compounds obtained by polymerising monomers on to natural rubbers or derivatives thereof
-
- 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
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
Abstract
Present invention relates particularly to a kind of environment-friendly water-based glue sprayings and preparation method thereof, belong to adhesives for shoes technical field.The environment-friendly water-based glue spraying is made by following component：Tetren aqueous solution that ammonium hydroxide that Heveatex, acrylate, emulsifier, aqueous tackifier lotion, water-based thickener, clay, aqueous defoamer, mass concentration are 2%, t-butyl hydroperoxide, mass concentration are 10%, deionized water.The present invention environment-friendly water-based glue spraying have stronger initial bonding strength, can cold bonding, good bond effect is all had to polarity and non-polar material, the requirement under various weathers can be met, meanwhile, glue spraying of the present invention is realized to unlike material（Bonding between such as sponge and non-woven fabrics, leather and non-woven fabrics, artificial leather and non-woven fabrics unlike material）Between bonding, and adhesive property is stronger, has effectively expanded application of the water-soluble spraying glue in shoe-making industry and leather industry.
Description
Technical field
The invention belongs to adhesives for shoes technical fields, and in particular to a kind of environment-friendly water-based glue spraying and preparation method thereof.
Background technology
Glue spraying, which is one kind, having suitable viscosity, and two different material interfaces are closely connected, and plays transmission application
The adhesive of effect is widely used in furniture, leather and decoration industry.Currently, glue spraying on the market is mainly with solvent type glue spraying (oil
Property glue spraying) based on.Solvent type glue spraying contains a large amount of organic solvent, such as toluene and chlorinated solvent, or even containing benzene etc. it is carcinogenic at
Point.These organic solvents are easily accessible air, have seriously affected people’s lives environment, damage people's health.In addition, molten
Dosage form glue spraying causes fire again and again there is also inflammable and explosive problem.Therefore, competitively research aqueous solvent replacement has for countries in the world
The environment-friendly type aqueous glue spraying of solvent.In Germany, the developed countries such as the U.S. and Japan are proposed aqueous polyurethane glue spraying and aqueous
Neoprene glue spraying.Wherein, aqueous polyurethane glue spraying could use after needing heat-activated, and still, glue spraying industry is generally all taken cold
It is viscous, therefore, limit the use of aqueous polyurethane glue spraying.And watersoluble neoprene glue spraying is because environmentally safe, to health without
Damage, it is non-toxic and tasteless the advantages that, and one of as adhesive industrial development direction.Watersoluble neoprene glue spraying is using water as solvent, tool
The advantages that having and be free of organic solvent, being free of heavy metal, tasteless, fast drying, heat resistance and all good anti-old property.However, watersoluble neoprene
Glue spraying initial adhesive strength is not high, and frost resistance is again poor.Meanwhile the bonding of impermeability material such as metal, plastics and rubber etc. is imitated
Fruit is undesirable.
Meanwhile existing water-soluble spraying glue is only capable of realizing the bonding between same material at present, such as sponge and sponge, non-woven fabrics
With the bonding between non-woven fabrics, leather and leather, artificial leather and artificial leather, if the material bonded is different, caking property can be big
It is big to reduce, or even can not bond, therefore, water-soluble spraying glue is greatly limited in the use of shoes industry.Therefore, to the aqueous spray of shoes
The research of glue can be effectively improved the limitation that existing water-soluble spraying glue is applied in shoes industry.
Invention content
The purpose of the present invention is to solve the deficiencies in the prior art, and provide a kind of environment-friendly water-based glue spraying and its preparation side
Method, the environment-friendly water-based glue spraying have it is stronger go out viscous force, can cold bonding, to polarity and non-polar material all have it is good bonding imitate
Fruit can meet the requirement under Different climate environment.
The technical solution adopted by the present invention is as follows：
Environment-friendly water-based glue spraying, by being made according to the following component of mass percent meter：Heveatex 49.30%-
52.01%, methyl methacrylate 17.34%-18.49%, emulsifier 0.87%-1.24%, aqueous tackifier lotion 0.87%-
1.85%, water-based thickener 1.74%-2.47%, clay 0.435%-1.23%, aqueous defoamer 0.095%-0.25%, matter
The ammonium hydroxide 12.32%-13%, t-butyl hydroperoxide 0.12%-0.13%, mass concentration for measuring a concentration of 2% are 10%
Tetren aqueous solution 0.43%-0.51%, deionized water 12.3%-13%.
Further, the emulsifier is methacrylic acid hydroxide sodium dimercaptosulphanatein (emulsifier HPMAS) or 3- allyloxys-
One kind in 2- hydroxyl -1- propane sulfonic acid sodium.
Further, the water-based thickener is the swollen anion thickener PR-328 of acrylic acid series alkali soluble.
Further, grain size≤0.2um of the clay.
Further, the aqueous defoamer is organic silicon antifoaming agent ADEKA NATE B-199.
Further, the t-butyl hydroperoxide is two (1- Methylethyls) phenyl hydroperoxides.
Further, the mass concentration of the ammonium hydroxide is 2%, and the mass concentration of the tetren aqueous solution is
10%.
The present invention also provides the preparation methods of environment-friendly water-based glue spraying, and steps are as follows：
Step a：Prepare mass concentration be 2% ammonium hydroxide, mass concentration be 10% tetren aqueous solution, according to institute
Quality proportioning is stated, it is spare to weigh each component；
Step b：Heveatex, the ammonium hydroxide that mass concentration is 2% are sequentially added in polymeric kettle, stirred at 30-35 DEG C
Uniformly；
Step c：Deionized water, emulsifier are sequentially added into stirring and emulsifying 10-20min in pre-emulsification kettle, methyl-prop is added
E pioic acid methyl ester continues stirring and emulsifying 10-20min, obtains pre-emulsion, and t-butyl hydroperoxide is added, is stirred at 30-35 DEG C
It is uniformly mixed, obtains pre-emulsion mixture；
Step d：The pre-emulsion mixture that step c is obtained is added dropwise in step b, is stirred evenly；
Step e：The tetren solution that mass concentration is 10% is added, continues to stir 10-20min；
Step f：Mixing speed is reduced, continues to stir 15-20h；
Step g：Under the rotating speed of 30-60r/min, aqueous tackifier lotion is added while stirring, after addition, continues to stir
10-20min is mixed, water-based thickener, clay are sequentially added, continues to stir 10-20min, aqueous defoamer is added, continues to stir 5-
15min；
Step h：PH value of solution is adjusted to 9~10, filters to take filtrate to get the environment-friendly water-based glue spraying.
Further, mixing speed described in step b is 80~100r/min, and the mixing time is 20~30min,
Mixing speed described in step c is 80~100r/min, and mixing speed described in step d is 80~100r/min, institute in step e
It is 80~100r/min to state mixing speed, and mixing speed described in step f is 30~60r/min.
Further, in step h pH value of solution is adjusted with ammonium hydroxide.
Compared with prior art, the present invention advantage is：
The present invention provides a kind of environment-friendly water-based glue spraying and preparation method thereof, which has stronger just viscous
Power, can cold bonding, good bond effect is all had to polarity and non-polar material, the requirement under various weathers can be met.
Heveatex has excellent comprehensive performance, and such as film-forming matter is good, and elongation is high, and elasticity is good.But day
Its initial bonding strength is poor, adhesive strength is not high in use, due to lacking polar group, causing as adhesive for right latex, and it is made to answer
With being restricted, the present invention enhances it to polarity by carrying out grafting modification to Heveatex with methyl methacrylate
The bonding of material, to effectively improve the initial bonding strength of lotion, and the addition of clay not only can effectively improve the bonding of glue spraying
Intensity has also speeded up the speed of latex drying and forming-film, to make glue spraying of the present invention realize to unlike material (such as sponge and nonwoven
Bonding between the unlike materials such as cloth, leather and non-woven fabrics, artificial leather and non-woven fabrics) between bonding, and adhesive property is stronger,
Effectively application of the water-soluble spraying glue in shoe-making industry and leather industry is expanded.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail.
It will be understood to those of skill in the art that the following example is merely to illustrate the present invention, and it should not be regarded as limiting this hair
Bright range.In the examples where no specific technique or condition is specified, according to technology or condition described in document in the art
Or it is carried out according to product description.Production firm person is not specified in raw materials used or instrument, is that can be obtained by buying
Conventional products, wherein aqueous tackifier lotion can use aqueous rosin resin Tackified emulsion 918, be purchased from by being commercially available
Jining Hua Kai Co., Ltd, solid content are 54 ± 1%, pH8.0 ± 1.
Environment-friendly water-based glue spraying, by being made according to the following component of mass percent meter：Heveatex 49.30%-
52.01%, methyl methacrylate 17.34%-18.49%, emulsifier 0.87%-1.24%, aqueous tackifier lotion 0.87%-
1.85%, water-based thickener 1.74%-2.47%, clay 0.435%-1.23%, aqueous defoamer 0.095%-0.25%, matter
The ammonium hydroxide 12.32%-13%, t-butyl hydroperoxide 0.12%-0.13%, mass concentration for measuring a concentration of 2% are 10%
Tetren aqueous solution 0.43%-0.51%, deionized water 12.3%-13%, wherein the emulsifier is methacrylic acid
One kind in hydroxide sodium dimercaptosulphanatein (emulsifier HPMAS) or 3- allyloxy -2- hydroxyl -1- propane sulfonic acid sodium, the aqueous thickening
Agent is acrylic acid series alkali soluble swollen anion thickener PR-328, grain size≤0.2um of the clay, and the aqueous defoamer is
Organic silicon antifoaming agent ADEKA N ATE B-199, the t-butyl hydroperoxide are two (1- Methylethyls) phenyl hydrogen mistakes
Oxide.
The preparation method of environment-friendly water-based glue spraying is as follows：
Step a：Prepare mass concentration be 2% ammonium hydroxide, mass concentration be 10% tetren aqueous solution, according to institute
Quality proportioning is stated, it is spare to weigh each component；
Step b：By Heveatex, mass concentration be 2% ammonium hydroxide sequentially add in polymeric kettle, in 30-35 DEG C, 80~
20~30min is stirred under 100r/min, you can stir evenly；
Step c：Deionized water, emulsifier are sequentially added in pre-emulsification kettle, the stirring and emulsifying 10- under 80~100r/min
20min is added methyl methacrylate and continues at stirring and emulsifying 10-20min under 80~100r/min, obtain pre-emulsion, is added
T-butyl hydroperoxide is uniformly mixed under 30-35 DEG C, 80~100r/min, obtains pre-emulsion mixture；
Step d：The pre-emulsion mixture that step c is obtained is added dropwise in step b, is stirred under 80~100r/min equal
It is even；
Step e：The tetren solution that mass concentration is 10% is added, continues under 80~100r/min and stirs 10-
20min；
Step f：Mixing speed is reduced, continues to stir 15-20h under 30~60r/min；
Step g：Under the rotating speed of 30-60r/min, aqueous tackifier lotion is added while stirring, after addition, continues to stir
10-20min is mixed, water-based thickener, clay are sequentially added, continues to stir 10-20min, aqueous defoamer is added, continues to stir 5-
15min；
Step h：PH value of solution is adjusted to 9~10, filtrate is filtered to take to get the environment-friendly water-based glue spraying, ammonium hydroxide tune can be used
Save pH.
The present invention is illustrated by embodiment 1 to 3, what embodiment 1 to embodiment 3 was used when making environmentally friendly glue spraying
The proportioning of each component is as shown in table 1 below：
1 embodiment of table, 1 to 3 each group distribution ratio
The preparation method of each embodiment is as follows：
Embodiment 1
The preparation method of the environment-friendly water-based glue spraying of the present embodiment is as follows：
Step a：Prepare mass concentration be 2% ammonium hydroxide, mass concentration be 10% tetren aqueous solution, according to institute
Quality proportioning is stated, it is spare to weigh each component；
Step b：Heveatex, the ammonium hydroxide that mass concentration is 2% are sequentially added in polymeric kettle, in 35 DEG C, 100r/min
Lower stirring 20min, you can stir evenly；
Step c：Deionized water, emulsifier are sequentially added in pre-emulsification kettle, the stirring and emulsifying 10min under 100r/min,
Methyl methacrylate is added and continues at stirring and emulsifying 10min under 100r/min, obtains pre-emulsion, tertiary butyl hydroperoxidation is added
Object is uniformly mixed under 35 DEG C, 100r/min, obtains pre-emulsion mixture；
Step d：The pre-emulsion mixture that step c is obtained is added dropwise in step b, is stirred evenly under 100r/min；
Step e：The tetren solution that mass concentration is 10% is added, continues under 100r/min and stirs 10min；
Step f：Mixing speed is reduced, continues to stir 18h under 50r/min；
Step g：Under the rotating speed of 50r/min, aqueous tackifier lotion is added while stirring, after addition, continues to stir
15min sequentially adds water-based thickener, clay, continues to stir 15min, aqueous defoamer is added, and continues to stir 10min；
Step h：PH value of solution is adjusted to 9~10, filters to take filtrate to get the environment-friendly water-based glue spraying.
Embodiment 2
The preparation method of environment-friendly water-based glue spraying is as follows：
Step a：Prepare mass concentration be 2% ammonium hydroxide, mass concentration be 10% tetren aqueous solution, according to institute
Quality proportioning is stated, it is spare to weigh each component；
Step b：Heveatex, the ammonium hydroxide that mass concentration is 2% are sequentially added in polymeric kettle, under 30 DEG C, 80r/min
Stir 30min, you can stir evenly；
Step c：Deionized water, emulsifier are sequentially added in pre-emulsification kettle, the stirring and emulsifying 20min under 80r/min adds
Enter methyl methacrylate and continue at stirring and emulsifying 10min under 80r/min, obtain pre-emulsion, t-butyl hydroperoxide is added,
It is uniformly mixed under 30 DEG C, 80r/min, obtains pre-emulsion mixture；
Step d：The pre-emulsion mixture that step c is obtained is added dropwise in step b, is stirred evenly under 80r/min；
Step e：The tetren solution that mass concentration is 10% is added, continues under 80r/min and stirs 20min；
Step f：Mixing speed is reduced, continues to stir 20h under 30r/min；
Step g：Under the rotating speed of 30r/min, aqueous tackifier lotion is added while stirring, after addition, continues to stir
20min sequentially adds water-based thickener, clay, continues to stir 20min, aqueous defoamer is added, and continues to stir 5min；
Step h：PH value of solution is adjusted to 9~10, filters to take filtrate to get the environment-friendly water-based glue spraying.
Embodiment 3
The preparation method of environment-friendly water-based glue spraying is as follows：
Step a：Prepare mass concentration be 2% ammonium hydroxide, mass concentration be 10% tetren aqueous solution, according to institute
Quality proportioning is stated, it is spare to weigh each component；
Step b：Heveatex, the ammonium hydroxide that mass concentration is 2% are sequentially added in polymeric kettle, under 35 DEG C, 90r/min
Stir 25min, you can stir evenly；
Step c：Deionized water, emulsifier are sequentially added in pre-emulsification kettle, the stirring and emulsifying 15min under 90r/min adds
Enter methyl methacrylate and continue at stirring and emulsifying 15min under 90r/min, obtain pre-emulsion, t-butyl hydroperoxide is added,
It is uniformly mixed under 30 DEG C, 90r/min, obtains pre-emulsion mixture；
Step d：The pre-emulsion mixture that step c is obtained is added dropwise in step b, is stirred evenly under 90r/min；
Step e：The tetren solution that mass concentration is 10% is added, continues under 90r/min and stirs 15min；
Step f：Mixing speed is reduced, continues to stir 15h under 60r/min；
Step g：Under the rotating speed of 60r/min, aqueous tackifier lotion is added while stirring, after addition, continues to stir
15min sequentially adds water-based thickener, clay, continues to stir 15min, aqueous defoamer is added, and continues to stir 15min；
Step h：PH value of solution is adjusted to 9~10, filters to take filtrate to get the environment-friendly water-based glue spraying.
The environment-friendly water-based glue spraying of 1 to 3 gained of the embodiment of the present invention, commercial solvents type glue spraying, application type glue are subjected to physical property ratio
Compared with as a result as shown in table 2 below：
Environment-friendly water-based glue spraying made from 2 embodiment of the present invention 1 of table, commercial solvents type glue spraying and application type glue carry out physical property comparison
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (9)
1. environment-friendly water-based glue spraying, which is characterized in that by being made according to the following component of mass percent meter：Heveatex
49.30%-52.01%, methyl methacrylate 17.34%-18.49%, emulsifier 0.87%-1.24%, aqueous tackifier breast
Liquid 0.87%-1.85%, water-based thickener 1.74%-2.47%, clay 0.435%-1.23%, aqueous defoamer 0.095%-
0.25%, the ammonium hydroxide 12.32%-13%, t-butyl hydroperoxide 0.12%-0.13%, mass concentration that mass concentration is 2%
For 10% tetren aqueous solution 0.43%-0.51%, deionized water 12.3%-13%.
2. environment-friendly water-based glue spraying according to claim 1, which is characterized in that the emulsifier is methacrylic acid hydroxypropyl sulphur
One kind in sour sodium or 3- allyloxy -2- hydroxyl -1- propane sulfonic acid sodium.
3. environment-friendly water-based glue spraying according to claim 1, which is characterized in that the water-based thickener is acrylic acid series alkali soluble
Swollen anion thickener PR-328.
4. environment-friendly water-based glue spraying according to claim 1, which is characterized in that grain size≤0.2um of the clay.
5. environment-friendly water-based glue spraying according to claim 1, which is characterized in that the aqueous defoamer defoams for organic silicon
Agent ADEKA NATE B-199.
6. environment-friendly water-based glue spraying according to claim 1, which is characterized in that the t-butyl hydroperoxide is two (1-
Methylethyl) phenyl hydroperoxides.
7. the preparation method of environment-friendly water-based glue spraying described in claim 1, which is characterized in that steps are as follows：
Step a：Prepare mass concentration be 2% ammonium hydroxide, mass concentration be 10% tetren aqueous solution, according to the matter
Amount proportioning, it is spare to weigh each component；
Step b：Heveatex, the ammonium hydroxide that mass concentration is 2% are sequentially added in polymeric kettle, stirred evenly at 30-35 DEG C；
Step c：Deionized water, emulsifier are sequentially added into stirring and emulsifying 10-20min in pre-emulsification kettle, methacrylic acid is added
Methyl esters continues stirring and emulsifying 10-20min, obtains pre-emulsion, and t-butyl hydroperoxide is added, is stirred at 30-35 DEG C
Uniformly, pre-emulsion mixture is obtained；
Step d：The pre-emulsion mixture that step c is obtained is added dropwise in step b, is stirred evenly；
Step e：The tetren solution that mass concentration is 10% is added, continues to stir 10-20min；
Step f：Mixing speed is reduced, continues to stir 15-20h；
Step g：Under the rotating speed of 30-60r/min, aqueous tackifier lotion is added while stirring, after addition, continues to stir
10-20min sequentially adds water-based thickener, clay, continues to stir 10-20min, aqueous defoamer is added, and continues to stir 5-
15min；
Step h：PH value of solution is adjusted to 9~10, filters to take filtrate to get the environment-friendly water-based glue spraying.
8. the preparation method of environment-friendly water-based glue spraying according to claim 7, which is characterized in that stir speed described in step b
Degree is 80~100r/min, and the mixing time is 20~30min, and mixing speed described in step c is 80~100r/min, step
Mixing speed described in rapid d is 80~100r/min, and mixing speed described in step e is 80~100r/min, described in step f
Mixing speed is 30~60r/min.
9. the preparation method of environment-friendly water-based glue spraying according to claim 7, which is characterized in that adjusted with ammonium hydroxide in step h
PH value of solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810779223.0A CN109054700B (en) | 2016-12-09 | 2016-12-09 | Environment-friendly water-based spray adhesive |
| CN201611127093.XA CN106753086B (en) | 2016-12-09 | 2016-12-09 | Environment-friendly water-based glue spraying and preparation method thereof |
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| CN201611127093.XA CN106753086B (en) | 2016-12-09 | 2016-12-09 | Environment-friendly water-based glue spraying and preparation method thereof |
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| CN201810779223.0A Division CN109054700B (en) | 2016-12-09 | 2016-12-09 | Environment-friendly water-based spray adhesive |
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| CN111117522A (en) * | 2019-11-26 | 2020-05-08 | 广东东方一哥新材料股份有限公司 | Environment-friendly odorless chlorine-free spray adhesive and preparation method thereof |
| CN111154411A (en) * | 2020-01-03 | 2020-05-15 | 广东东方一哥新材料股份有限公司 | Water-based environment-friendly spray adhesive and preparation method thereof |
| CN113336904B (en) * | 2021-05-28 | 2022-04-26 | 惠州市亨迪树脂制品有限公司 | Water-based chlorinated rubber emulsion and preparation method thereof |
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| JP2008195863A (en) * | 2007-02-14 | 2008-08-28 | Bridgestone Corp | Adhesive composition |
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| CN104946166A (en) * | 2015-06-27 | 2015-09-30 | 广东远东高分子科技有限公司 | Water-based spray gel and preparation method thereof |
| CN105086857A (en) * | 2015-09-06 | 2015-11-25 | 南通宝加利新材料有限公司 | Environment-friendly water-based rubber protection film and preparation method thereof |
| CN105219322A (en) * | 2015-11-14 | 2016-01-06 | 际华三五一五皮革皮鞋有限公司 | Novel environment friendly note pressure footwear use tackiness agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
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| CN109054700A (en) | 2018-12-21 |
| CN106753086A (en) | 2017-05-31 |
| CN109054700B (en) | 2020-10-16 |
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