CN1995258A - Aqueous adhesive for shoes and its production method - Google Patents
Aqueous adhesive for shoes and its production method Download PDFInfo
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- CN1995258A CN1995258A CN 200610123630 CN200610123630A CN1995258A CN 1995258 A CN1995258 A CN 1995258A CN 200610123630 CN200610123630 CN 200610123630 CN 200610123630 A CN200610123630 A CN 200610123630A CN 1995258 A CN1995258 A CN 1995258A
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Abstract
The invention discloses an aqueous adhesive of shoe and manufacturing method in the shoe adhesive domain, which comprises the following parts: 8-20% polyacrylacid ester emulsion, 75-90% aqueous polyurethane emulsion, 0-3% acetone and 0.2-1% thickener, wherein the polyacrylacid ester emulsion is composed of butyl acrylate, methyl methacrylate, acrylic acid isooctanoic ester, ethyl acrylate, acrylic acid, emulsifier, buffer, reducer and initiator. The manufacturing method comprises the following steps: emulsifying; prepolymerizing; polymerizing; neutralizing; blending.
Description
Technical field:
The invention belongs to the adhesive for shoes field, be specifically related to a kind of aqueous adhesive and production method thereof that is used in shoe-making industry.
Background technology:
There are tens populations in the whole world, everyone will wear footwear, in state-owned 1,300,000,000 people, it is the maximum country of number that footwear are worn in the whole world, it also is first big country that footwear are already produced, there is family more than 20,000 in the existing shoes manufacturing enterprise of China, and most of producer adopts tackiness agent to produce footwear, and tackiness agent mainly is divided into solvent-borne type footwear and water-based footwear glue two big classes.Annual adhesive for shoes consumption reaches more than 20 ten thousand tons, but all based on solvent-borne type footwear glue, and along with the mankind's environmental consciousness improves day by day, relevant laws and regulations will be severe day by day, and water-based footwear glue free from environmental pollution will progressively replace solvent-borne type footwear glue.
The adhesiveproperties of aqueous polyurethane footwear glue with use the identical of technology and solvent-borne type footwear glue, more external large enterprises, as: Bayer (Bayer) company of Germany, the Huai Keluote of the U.S. (Wyanclotte) chemical company, the big Japanese ink company of Japan etc., the water-based polyurethane adhesive production of their existing multiple trades mark, and it is domestic owing to be subjected to the shortage of raw materials such as fatty isocyanic ester, factor affecting such as the big and production cost height of preparation high-solid content water-based polyurethane technical difficulty, aqueous polyurethane footwear glue is cost an arm and a leg, thereby limited its production and use range.
Summary of the invention:
The object of the present invention is to provide a kind of aqueous adhesive for shoes, and the production method of this tackiness agent is provided.
Prescription of the present invention draws best the composition through scientific experimentation, screening, its production method is: at first prepare polyacrylate dispersion, by some performance of polyacrylate dispersion improvement water-based polyurethane adhesive, secondly, produce high-solid content water-based polyurethane footwear glue.
A kind of component and weight percent of aqueous adhesive for shoes are:
Polyacrylate dispersion: 8～20%,
Aqueous polyurethane emulsion: 75～90%,
Acetone: 0～3%,
Thickening material: 0.2～1%.
Wherein polyacrylate dispersion component and weight percent:
Butyl acrylate 30～40%
Methyl methacrylate 20～30%
Isooctyl acrylate monomer 0.3～1%
Hydroxyethyl acrylate 0～1%
Vinylformic acid 0～1%
Deionized water 30～40%
Emulsifying agent 1～3%
Buffer reagent 0～1%
Reductive agent 0～1%
Initiator 0～1%
Polyacrylate dispersion is that, hard monomer soft by acrylate and functional monomer are made through letex polymerization.
A kind of production method of aqueous adhesive for shoes:
The first, the preparation polyacrylate dispersion.
One) emulsification: emulsifiers dissolve in deionized water, is stirred adding butyl acrylate, vinylformic acid, Isooctyl acrylate monomer and methyl methacrylate down, and stirring and emulsifying evenly obtains the monomer emulsion.
Two) pre-polymerization: in reactor, dissolve buffer reagent, add monomer emulsion in a small amount, be warming up to polymerization temperature (85 ℃), add reductive agent and first initiator solution, make seed emulsion with deionized water.
Three) polymerization: drip residual monomers emulsion, functional monomer and initiator solution in seed emulsion, polymeric reaction temperature is controlled at 80～90 ℃, about 5 hours of total reaction time.
Four) neutralization: cool to 45 ℃ by the jacket water (J.W.) in the equipment, add ammoniacal liquor neutralization (pH value 7-9).
Above flow process is shown in the block diagram of Fig. 1.
The second, the preparation aqueous adhesive for shoes.
Compound method: in polyacrylate dispersion, add and slowly add thickening material under aqueous polyurethane emulsion, acetone, the stirring, after stirring, with obtaining aqueous adhesive for shoes behind the screen filtration.
Use the aqueous adhesive for shoes method:
Add 2～6% (weight percent) aqueous polyurethane solidifying agent when 1, using in aqueous adhesive for shoes of the present invention, then, (using up in 4 hours) just can be used in the back that stirs.
2, the technical process of pressing solvent-based adhesive is used.
The aqueous adhesive for shoes that the present invention makes can be used for polyvinyl chloride (PVC), Polyurethane (PU), and rubber and corium bonding, technical indicator meets the requirement of " footwear and case and bag stick with glue agent GB 19340-2003 ".
Use the aqueous adhesive for shoes of polyacrylate dispersion preparation of the present invention to have following advantage:
1, improves the solids content of footwear use polyurethane adhesive.The solids content of domestic water-based polyurethane adhesive generally exists: between 30～40%, and the solids content of the aqueous polyurethane emulsion of external reputable brand is generally about 50%, can improve solids content after polyacrylate dispersion of the present invention and the aqueous polyurethane emulsion blend, aqueous adhesive for shoes solids content of the present invention is 60～70%, the raising of solids content can improve the rate of drying of water-based footwear glue, it is close with the technical process of solvent-based adhesive when streamline is produced, need not to change production unit, help the use of Shoes Factory.
2, reduce the raw materials cost of footwear use polyurethane adhesive.The price of the aqueous polyurethane of better performances is all higher both at home and abroad at present, amounting to into each weight percent point calculates, every centesimal content, its price 〉=1.1 yuan, and the price of water-and acrylate emulsion is generally all lower, amounts to into each percentage point to calculate, each every centesimal content, its price≤0.2 yuan, therefore, raw materials cost 8～18% can fall in the water-based polyurethane adhesive composite with polyacrylate dispersion of the present invention.
3, aqueous polyurethane emulsion and polyacrylate dispersion blend, urethane resin excellent elasticity, wear resistance, low temperature flexibility can be combined with the polyacrylic acid excellent light stability, learn from other's strong points to offset one's weaknesses, film forming matter has the flexibility of urethane and the overall merits such as weathering resistance, water tolerance and erosion resistance of polyacrylic ester concurrently, in addition, experimental results show that: polyacrylate dispersion has improved the freeze-stable of aqueous polyurethane dispersing liquid.In sum, water-based adhesive for shoes of the present invention has advantages such as high solids content, low cost, excellent performance, can replace molten type tackiness agent.The present invention has promoted the technological development to water-based polyurethane adhesive, has widened adhesive for shoes market.
Embodiment
Embodiments of the invention are described in detail in detail below;
Embodiment one:
The first, the preparation of polyacrylate dispersion.
Polyacrylate dispersion component and weight percent:
Deionized water 34.2% vinylformic acid 0.5%
Butyl acrylate 38% methyl methacrylate 23%
Isooctyl acrylate monomer 1% Hydroxyethyl acrylate 0.5%
Emulsifying agent 2% buffer reagent 0.2%
Reductive agent 0.1% initiator 0.5%
Prepare polyacrylate dispersion as follows:
One) emulsification: emulsifiers dissolve in deionized water, is stirred adding butyl acrylate, vinylformic acid, Isooctyl acrylate monomer and methyl methacrylate down, and stirring and emulsifying evenly obtains the monomer emulsion.
Two) pre-polymerization: in reactor, dissolve buffer reagent, add (5%) monomer emulsion in a small amount, be warming up to polymerization temperature (85 ℃), add (50%) solution of reductive agent and initiator, make seed emulsion with deionized water.
Three) polymerization: drip residual monomers emulsion and remaining (50%) initiator solution in seed emulsion, polymeric reaction temperature is controlled at 80～90 ℃, about 5 hours of total reaction time.
Four) neutralization: cool to 45 ℃ by the jacket water (J.W.) in the equipment, add ammoniacal liquor neutralization (pH value 7-9).
The second, the preparation aqueous adhesive for shoes:
Recipe ingredient and weight percent:
Polyacrylate dispersion 15% is got 15KG,
The aqueous polyurethane emulsion (U-54) 81% (commodity) of Bayer (Bayer) company is got 81KG,
Acetone 3% is got 3KG, and thickening material 1% is got 1KG
Compound method: in polyacrylate dispersion, add and slowly add thickening material under aqueous polyurethane emulsion, acetone, the stirring, after stirring, with obtaining aqueous adhesive for shoes after the filtration of 300 eye mesh screens.Press the 15KG loading barrel packaging then.
Embodiment two:
The first, the preparation of polyacrylate dispersion.
Polyacrylate dispersion component and weight percent:
Deionized water 34.2% vinylformic acid 0.5%
Butyl acrylate 38%, methyl methacrylate 23%,
Isooctyl acrylate monomer 1%, Hydroxyethyl acrylate 0.5%,
Emulsifying agent 2%, buffer reagent 0.2%,
Reductive agent 0.1%, initiator 0.5%.
Preparation polyacrylate dispersion method is identical with example one.
The second, the preparation aqueous adhesive for shoes:
Recipe ingredient and weight percent:
Polyacrylate dispersion 20% is got 20KG,
The U-88 aqueous polyurethane emulsion 76% (commodity) in Taiwan is got 76KG,
Acetone 3% is got 3KG,
Thickening material 1% is got 1KG.
Compound method is identical with example one.
Embodiment three:
The first, the preparation of polyacrylate dispersion.
Polyacrylate dispersion component and weight percent:
Deionized water 34.2% vinylformic acid 0.5%
Butyl acrylate 38%, methyl methacrylate 23%,
Isooctyl acrylate monomer 1%, Hydroxyethyl acrylate 0.5%,
Emulsifying agent 2%, buffer reagent 0.2%,
Reductive agent 0.1%, initiator 0.5%.
The preparation polyacrylate dispersion is identical with example one.
The second, the preparation aqueous adhesive for shoes:
Recipe ingredient and weight percent:
Polyacrylate dispersion 16% is got 16KG,
Taiwan U-66 aqueous polyurethane dispersing liquid 80% (commodity) is got 80.7KG,
Acetone 3% is got 3KG,
Thickening material 0.3% is got 0.3KG.
Compound method is identical with example one.
Above-mentioned aqueous adhesive for shoes uses through preparation, surveys its technical indicator such as following table:
| Test event | Technical indicator |
| Solids content | ≥50％ |
| The PII value | 7-9 |
| Viscosity | 3000-5000mpa*s |
| Initial stage power | ≥60N/2.5cm |
| Stripping strength | ≥100N/2.5cm |
| Xanthochromia | Not flavescence |
As seen, aqueous adhesive for shoes of the present invention and domestic water-based polyurethane adhesive compare, and the high 10-20% of solids content: raw materials cost falls 8～18%.Experimental results show that: polyacrylate dispersion has improved the freeze-stable of aqueous polyurethane dispersing liquid.
Claims (3)
1, a kind of aqueous adhesive for shoes, its component and weight percent are:
Polyacrylate dispersion: 8～20%,
Aqueous polyurethane emulsion: 75～90%,
Acetone: 0～3%,
Thickening material: 0.2～1%;
Wherein polyacrylate dispersion component and weight percent are:
Butyl acrylate 30～40%,
Methyl methacrylate 20～30%,
Isooctyl acrylate monomer 0.3～1%,
Hydroxyethyl acrylate 0～1%,
Vinylformic acid 0～1%
Deionized water 30～40%
Emulsifying agent 1～3%,
Buffer reagent 0～1%,
Reductive agent 0～1%,
Initiator 0～1%.
2, a kind of aqueous adhesive for shoes according to claim 1, its production method is:
The first, the preparation polyacrylate dispersion;
One) emulsification: emulsifiers dissolve in deionized water, is stirred adding butyl acrylate, vinylformic acid, Isooctyl acrylate monomer and methyl methacrylate down, and stirring and emulsifying evenly obtains the monomer emulsion;
Two) pre-polymerization: in reactor, dissolve buffer reagent, add monomer emulsion in a small amount, be warming up to polymerization temperature (85 ℃), add reductive agent and first initiator solution, make seed emulsion with deionized water;
Three) polymerization: drip residual monomers emulsion, functional monomer and initiator solution in seed emulsion, polymeric reaction temperature is controlled at 80～90 ℃, about 5 hours of total reaction time;
Four) neutralization: cool to 45 ℃ by the jacket water (J.W.) in the equipment, add ammoniacal liquor neutralization (pH value 7-9);
The second, preparation water-based adhesive for shoes
Compound method: in polyacrylate dispersion, add and slowly add thickening material under aqueous polyurethane emulsion, acetone, the stirring, after stirring, with obtaining aqueous adhesive for shoes behind the screen filtration.
3, a kind of aqueous adhesive for shoes according to claim 1 is characterized in that making use adhesive for shoes method to be:
Add 2～6% (weight percent) aqueous polyurethane solidifying agent when (1) using in polyacrylate dispersion, then, (using up in 4 hours) just can be used in the back that stirs;
(2) technical process of pressing solvent-based adhesive is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101236303A CN100572484C (en) | 2006-11-17 | 2006-11-17 | A kind of aqueous adhesive for shoes and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101236303A CN100572484C (en) | 2006-11-17 | 2006-11-17 | A kind of aqueous adhesive for shoes and production method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1995258A true CN1995258A (en) | 2007-07-11 |
| CN100572484C CN100572484C (en) | 2009-12-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2006101236303A Expired - Fee Related CN100572484C (en) | 2006-11-17 | 2006-11-17 | A kind of aqueous adhesive for shoes and production method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580682B (en) * | 2008-05-16 | 2011-04-06 | 北京高盟燕山科技有限公司 | Waterborne compound adhesive and preparation method and application thereof |
| CN101691476B (en) * | 2009-09-09 | 2012-07-04 | 中部树脂化工有限公司 | Binding agent, preparation method and application thereof |
| CN102863939A (en) * | 2012-10-17 | 2013-01-09 | 厦门大学 | Waterborne polyurethane shoe adhesive and preparation method thereof |
| CN103910826A (en) * | 2013-01-04 | 2014-07-09 | 开平市齐裕胶粘制品科技有限公司 | Acrylate copolymer rubber viscoelastic body and its preparation method |
| CN106085260A (en) * | 2016-06-30 | 2016-11-09 | 嘉兴市哈妮鞋业有限公司 | Footwear aqueous adhesive |
| CN106084154A (en) * | 2016-06-30 | 2016-11-09 | 嘉兴市哈妮鞋业有限公司 | The footwear preparation method of aqueous adhesive |
| CN107573890A (en) * | 2017-07-28 | 2018-01-12 | 安徽安大华泰新材料有限公司 | A kind of heat-resisting water-repellent modified adhesive for being used to print and preparation method thereof |
| CN109439204A (en) * | 2018-09-18 | 2019-03-08 | 常州市东泰橡塑制品有限公司 | A kind of harness cladding water-based glue and preparation method thereof |
| CN111171737A (en) * | 2020-02-27 | 2020-05-19 | 广东九佛新材料科技有限公司 | Protective film and preparation method thereof |
| CN112608706A (en) * | 2020-12-17 | 2021-04-06 | 东莞市人山精密科技有限公司 | Glue and preparation method thereof |
-
2006
- 2006-11-17 CN CNB2006101236303A patent/CN100572484C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580682B (en) * | 2008-05-16 | 2011-04-06 | 北京高盟燕山科技有限公司 | Waterborne compound adhesive and preparation method and application thereof |
| CN101691476B (en) * | 2009-09-09 | 2012-07-04 | 中部树脂化工有限公司 | Binding agent, preparation method and application thereof |
| CN102863939A (en) * | 2012-10-17 | 2013-01-09 | 厦门大学 | Waterborne polyurethane shoe adhesive and preparation method thereof |
| CN103910826A (en) * | 2013-01-04 | 2014-07-09 | 开平市齐裕胶粘制品科技有限公司 | Acrylate copolymer rubber viscoelastic body and its preparation method |
| CN106085260A (en) * | 2016-06-30 | 2016-11-09 | 嘉兴市哈妮鞋业有限公司 | Footwear aqueous adhesive |
| CN106084154A (en) * | 2016-06-30 | 2016-11-09 | 嘉兴市哈妮鞋业有限公司 | The footwear preparation method of aqueous adhesive |
| CN107573890A (en) * | 2017-07-28 | 2018-01-12 | 安徽安大华泰新材料有限公司 | A kind of heat-resisting water-repellent modified adhesive for being used to print and preparation method thereof |
| CN109439204A (en) * | 2018-09-18 | 2019-03-08 | 常州市东泰橡塑制品有限公司 | A kind of harness cladding water-based glue and preparation method thereof |
| CN111171737A (en) * | 2020-02-27 | 2020-05-19 | 广东九佛新材料科技有限公司 | Protective film and preparation method thereof |
| CN112608706A (en) * | 2020-12-17 | 2021-04-06 | 东莞市人山精密科技有限公司 | Glue and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN100572484C (en) | 2009-12-23 |
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Granted publication date: 20091223 Termination date: 20161117 |