CN102827570B - High-solid-content aqueous adhesive for shoes and preparation method thereof - Google Patents
High-solid-content aqueous adhesive for shoes and preparation method thereof Download PDFInfo
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- CN102827570B CN102827570B CN201210310648.XA CN201210310648A CN102827570B CN 102827570 B CN102827570 B CN 102827570B CN 201210310648 A CN201210310648 A CN 201210310648A CN 102827570 B CN102827570 B CN 102827570B
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Abstract
The invention discloses a high-solid-content aqueous adhesive for shoes and a preparation method thereof. The aqueous adhesive is prepared from an aqueous resin and a deionized water-emulsified polyurethane prepolymer, wherein the polyurethane prepolymer is synthesized from isocyanate, polylol, a hydrophilic chain extender, a crosslinking agent and a neutralizing agent. The preparation method comprises the following steps of: preparing a polyurethane prepolymer through pre-polymerizing and neutralizing processes; and preparing the aqueous adhesive for a high-solid-content shoe by using an aqueous resin in cooperation with deionized water emulsification. The aqueous adhesive for shoes disclosed by the invention has the advantages of high solid content, low cost, excellent performance and the like.
Description
Technical field
The invention belongs to adhesives for shoes field, be specifically related to a kind of high solids content footwear use sizing agent and preparation method thereof.
Technical background:
China is maximum in the world shoemaking industry state, has every year nearly 7,000,000,000 pairs of footwear to produce, and most of producer adopts sizing agent to produce footwear, and sizing agent group will be divided into solvent-borne type and the large class of water-based adhesives for shoes two.Annual adhesives for shoes consumption can reach more than 20 ten thousand tons, but all take solvent-borne type footwear glue as main, along with the raising day by day of mankind's environmental consciousness, and relevant law sound, environment-friendly aqueous adhesives for shoes will progressively replace solvent-borne type footwear glue.Aqueous polyurethane shoes-used glue, because having economy, safety (not firing not quick-fried), nontoxic, pollution-free, smell is little and by advantages such as rear residue easy to clean, become study hotspot.
The relatively morning of research starting to high-solid content water-based polyurethane abroad, and realized industrialization.As the solid content of Bayer DISPERCOLL Series of Water based polyurethane product mostly designs in 50% left and right.And domestic exploitation to high-solid content water-based polyurethane starts late, compared with external product, also there is on the whole a certain distance, seldom there is factory can produce the aqueous polyurethane adhesives for shoes that good stability, excellent performance and solid content are high.
Summary of the invention
The object of the present invention is to provide high solids content footwear use sizing agent of a kind of high solids content, low cost, excellent performance and preparation method thereof.
For achieving the above object, high solids content footwear use sizing agent of the present invention comprises the isocyanic ester of 4-10%, the polyvalent alcohol of 8-20%, the hydrophilic chain extender of 1-6%, the linking agent of 0.6-1.2%, the neutralizing agent of 0.8-1.1%, the catalyzer of 0.1-0.3%, the resin aqueous emulsion of 40-60%, the solvent of 1-6% by weight percentage, and surplus is deionized water.
Described isocyanic ester is the mixture of one or both arbitrary proportions in isoflurane chalcone diisocyanate, hexamethylene diisocyanate.
Described polyvalent alcohol is the mixture of one or more arbitrary proportions in several equal relative molecular masses polycaprolactone glycol that is 1000-3000, PCDL, polyethylene glycol adipate dibasic alcohol, polytetrahydrofuran diol, polyoxypropyleneglycol, polyester polyol.
Described hydrophilic chain extender is 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid, quadrol base ethyl sulfonic acid sodium or BDO-2-sodium sulfonate.
Described linking agent is TriMethylolPropane(TMP), tetramethylolmethane, two adjacent chlorodiphenyl amine methane or sucrose.
Described neutralizing agent is sodium hydroxide, potassium hydroxide, ammoniacal liquor, triethylamine, Trimethylamine 99 or trolamine.
Described catalyzer is dibutyl tin dilaurate or stannous octoate or triethylamine.
Described resin aqueous emulsion is aqueous polyurethane emulsion, ethene-vinyl acetate copolymer emulsion or carboxy styrene-butadiene rubber emulsion.
Described solvent is acetone, methylethylketone, dioxane, DMF or N-Methyl pyrrolidone.
The preparation method of this high solids content footwear use sizing agent comprises the steps:
1) pre-polymerization: polyvalent alcohol, isocyanic ester are added in reactor, be warming up to 70-90 ℃ and add again catalyzer, reaction 1-3h;
2) chain extension: add again hydrophilic chain extender and linking agent reaction 1-2h at 70-90 ℃;
3) neutralization: add neutralizing agent after cooling to 30-40 ℃ and make pH value for 7-9;
4) emulsification: add wherein deionized water and resin aqueous emulsion emulsification to stir under high-speed stirring and obtain high solids content footwear use sizing agent.High solids content footwear use sizing agent of the present invention can be used for the bonding of polyvinyl chloride (PVC), urethane (PU), rubber and corium, and technical indicator meets the requirement of < < footwear and case and bag sizing agent GB 19340-2003 > >.
High solids content footwear use sizing agent of the present invention has following advantage:
1, improved the solid content of footwear use adhesive for polyurethane.The solid content of domestic Aqueous Polyurethane Adhesives is generally between 30-40%, and the aqueous polyurethane emulsion solid content of external reputable brand is generally in 50% left and right, the present invention utilizes water-base resin and deionized water is composite that base polyurethane prepolymer for use as is carried out to emulsification, can make footwear use sizing agent solid content bring up to 60-70%, the raising of solid content can improve the rate of drying of water-based adhesives for shoes, it is close with the technical process of solvent-based adhesive when streamline is produced, without changing production unit, be conducive to production and the use of shoes manufacturing enterprise.
The performances such as 2, high solids content footwear use sizing agent of the present invention has remarkable low temperature resistant, water-fast, oil resistant, bonding strength is high, snappiness is good.And in adhesives for shoes of the present invention without phenyl ring and large π bond structure, can there is not xanthochromia problem in adhesive for polyurethane, can not have influence on the attractive in appearance of adhesive product, can be used for the senior article of footwear such as sneakers, sports shoes.
In sum, high solids content footwear use sizing agent of the present invention has high solids content, excellent performance and advantages of environment protection, can replace solvent-based adhesive.The present invention has promoted the technical research of Aqueous Polyurethane Adhesives, has widened adhesives for shoes market.
Embodiment
Embodiment 1:
1) get by weight percentage 4% isocyanic ester, 10% polyvalent alcohol, 3% hydrophilic chain extender, 1.0% linking agent, 0.8% neutralizing agent, 0.1% catalyzer, 50% resin aqueous emulsion, 3% solvent, surplus is deionized water;
2) pre-polymerization: polyvalent alcohol, isocyanic ester are added in reactor, be warming up to 70 ℃ and add again catalyzer, reaction 3h;
3) chain extension: add again hydrophilic chain extender and linking agent reaction 2h at 70 ℃;
4) neutralization: add neutralizing agent after cooling to 30 ℃;
5) emulsification: add wherein deionized water and resin aqueous emulsion emulsification to stir under high-speed stirring and obtain high solids content footwear use sizing agent.
Wherein, isocyanic ester is isoflurane chalcone diisocyanate;
Polyvalent alcohol is the polycaprolactone glycol that several equal relative molecular masses are 1000-3000;
Hydrophilic chain extender is 2,2-dimethylol propionic acid;
Linking agent is TriMethylolPropane(TMP);
Neutralizing agent is sodium hydroxide;
Catalyzer is dibutyl tin dilaurate;
Resin aqueous emulsion is aqueous polyurethane emulsion;
Solvent is acetone.
Embodiment 2:
1) comprise by weight percentage 8% isocyanic ester, 15% polyvalent alcohol, 5% hydrophilic chain extender, 0.8% linking agent, 0.9% neutralizing agent, 0.2% catalyzer, 60% resin aqueous emulsion, 1% solvent, surplus is deionized water;
2) pre-polymerization: polyvalent alcohol, isocyanic ester are added in reactor, be warming up to 90 ℃ and add again catalyzer, reaction 1h;
3) chain extension: add again hydrophilic chain extender and linking agent reaction 1h at 90 ℃;
4) neutralization: add neutralizing agent after cooling to 40 ℃;
5) emulsification: add wherein deionized water and resin aqueous emulsion emulsification to stir under high-speed stirring and obtain high solids content footwear use sizing agent.
Wherein, isocyanic ester is hexamethylene diisocyanate.
Polyvalent alcohol is the PCDL that several equal relative molecular masses are 1000-3000;
Hydrophilic chain extender is 2,2-dimethylolpropionic acid;
Linking agent is tetramethylolmethane;
Neutralizing agent is potassium hydroxide;
Catalyzer is stannous octoate or triethylamine;
Resin aqueous emulsion is ethene-vinyl acetate copolymer emulsion;
Solvent is methylethylketone.
Embodiment 3:
1) comprise by weight percentage 7% isocyanic ester, 20% polyvalent alcohol, 1% hydrophilic chain extender, 1.2% linking agent, 1.1% neutralizing agent, 0.3% catalyzer, 45% resin aqueous emulsion, 5% solvent, surplus is deionized water;
2) pre-polymerization: polyvalent alcohol, isocyanic ester are added in reactor, be warming up to 75 ℃ and add again catalyzer, reaction 2h;
3) chain extension: add again hydrophilic chain extender and linking agent reaction 1.5h at 75 ℃;
4) neutralization: add neutralizing agent after cooling to 33 ℃;
5) emulsification: add wherein deionized water and resin aqueous emulsion emulsification to stir under high-speed stirring and obtain high solids content footwear use sizing agent.
Wherein, isocyanic ester is the mixture of isoflurane chalcone diisocyanate and hexamethylene diisocyanate;
Polyvalent alcohol is the polyethylene glycol adipate dibasic alcohol that several equal relative molecular masses are 1000-3000;
Hydrophilic chain extender is quadrol base ethyl sulfonic acid sodium;
Linking agent is two adjacent chlorodiphenyl amine methane;
Neutralizing agent is ammoniacal liquor;
Catalyzer is dibutyl tin dilaurate;
Resin aqueous emulsion is carboxy styrene-butadiene rubber emulsion;
Solvent is dioxane.
Embodiment 4:
1) comprise by weight percentage 6% isocyanic ester, 8% polyvalent alcohol, 4% hydrophilic chain extender, 0.7% linking agent, 1.0% neutralizing agent, 0.15% catalyzer, 55% resin aqueous emulsion, 2% solvent, surplus is deionized water;
2) pre-polymerization: polyvalent alcohol, isocyanic ester are added in reactor, be warming up to 80 ℃ and add again catalyzer, reaction 2h;
3) chain extension: add again hydrophilic chain extender and linking agent reaction 1.5h at 80 ℃;
4) neutralization: add neutralizing agent after cooling to 35 ℃;
5) emulsification: add wherein deionized water and resin aqueous emulsion emulsification to stir under high-speed stirring and obtain high solids content footwear use sizing agent.
Wherein, isocyanic ester is isoflurane chalcone diisocyanate;
Polyvalent alcohol is the polytetrahydrofuran diol that several equal relative molecular masses are 1000-3000;
Hydrophilic chain extender is BDO-2-sodium sulfonate;
Linking agent is sucrose;
Neutralizing agent is triethylamine;
Catalyzer is stannous octoate or triethylamine;
Resin aqueous emulsion is aqueous polyurethane emulsion;
Solvent is DMF.
Embodiment 5:
1) comprise by weight percentage 9% isocyanic ester, 13% polyvalent alcohol, 2% hydrophilic chain extender, 0.6% linking agent, 0.8% neutralizing agent, 0.25% catalyzer, 40% resin aqueous emulsion, 4% solvent, surplus is deionized water;
2) pre-polymerization: polyvalent alcohol, isocyanic ester are added in reactor, be warming up to 85 ℃ and add again catalyzer, reaction 3h;
3) chain extension: add again hydrophilic chain extender and linking agent reaction 1h at 85 ℃;
4) neutralization: add neutralizing agent after cooling to 38 ℃;
5) emulsification: add wherein deionized water and resin aqueous emulsion emulsification to stir under high-speed stirring and obtain high solids content footwear use sizing agent.
Wherein, isocyanic ester is hexamethylene diisocyanate;
Polyvalent alcohol is several equal relative molecular masses polyoxypropyleneglycol that is 1000-3000 and the mixture of polyester polyol;
Hydrophilic chain extender is 2,2-dimethylol propionic acid;
Linking agent is TriMethylolPropane(TMP);
Neutralizing agent is Trimethylamine 99;
Catalyzer is dibutyl tin dilaurate;
Resin aqueous emulsion is ethene-vinyl acetate copolymer emulsion;
Solvent is N-Methyl pyrrolidone.
Embodiment 6:
1) comprise by weight percentage 10% isocyanic ester, 18% polyvalent alcohol, 6% hydrophilic chain extender, 1.1% linking agent, 1.1% neutralizing agent, 0.3% catalyzer, 40% resin aqueous emulsion, 6% solvent, surplus is deionized water;
2) pre-polymerization: polyvalent alcohol, isocyanic ester are added in reactor, be warming up to 80 ℃ and add again catalyzer, reaction 1h;
3) chain extension: add again hydrophilic chain extender and linking agent reaction 2h at 80 ℃;
4) neutralization: add neutralizing agent after cooling to 36 ℃;
5) emulsification: add wherein deionized water and resin aqueous emulsion emulsification to stir under high-speed stirring and obtain high solids content footwear use sizing agent.
Wherein, isocyanic ester is the mixture of isoflurane chalcone diisocyanate and hexamethylene diisocyanate;
Polyvalent alcohol is the mixture of several equal relative molecular masses be 1000-3000 polycaprolactone glycol, polyethylene glycol adipate dibasic alcohol and polyoxypropyleneglycol;
Hydrophilic chain extender is BDO-2-sodium sulfonate;
Linking agent is sucrose;
Neutralizing agent is trolamine;
Catalyzer is stannous octoate or triethylamine;
Resin aqueous emulsion is carboxy styrene-butadiene rubber emulsion;
Solvent is N-Methyl pyrrolidone.
Above-mentioned footwear use adhesive for polyurethane be used for boning corium and rubber, measuring technology index is as following table:
Claims (8)
1. a high solids content footwear use sizing agent, it is characterized in that: comprise by weight percentage the isocyanic ester of 4-10%, the polyvalent alcohol of 8-20%, the hydrophilic chain extender of 1-6%, the linking agent of 0.6-1.2%, the neutralizing agent of 0.8-1.1%, the catalyzer of 0.1-0.3%, the resin aqueous emulsion of 40-60%, the solvent of 1-6%, surplus is deionized water;
The preparation method of this high solids content footwear use sizing agent is as follows:
1) pre-polymerization: polyvalent alcohol, isocyanic ester are added in reactor, be warming up to 70-90 ℃ and add again catalyzer, reaction 1-3h;
2) chain extension: add again hydrophilic chain extender and linking agent reaction 1-2h at 70-90 ℃;
3) neutralization: add neutralizing agent after cooling to 30-40 ℃ and make pH value for 7-9;
4) emulsification: add wherein deionized water and resin aqueous emulsion emulsification to stir under high-speed stirring and obtain high solids content footwear use sizing agent;
Wherein isocyanic ester is the mixture of one or both arbitrary proportions in isoflurane chalcone diisocyanate, hexamethylene diisocyanate;
Resin aqueous emulsion is aqueous polyurethane emulsion, ethene-vinyl acetate copolymer emulsion or carboxy styrene-butadiene rubber emulsion.
2. high solids content footwear use sizing agent according to claim 1, is characterized in that: described polyvalent alcohol is the mixture of one or more arbitrary proportions in several equal relative molecular masses polycaprolactone glycol that is 1000-3000, PCDL, polyethylene glycol adipate dibasic alcohol, polytetrahydrofuran diol, polyoxypropyleneglycol.
3. high solids content footwear use sizing agent according to claim 1, is characterized in that: described hydrophilic chain extender is 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid, quadrol base ethyl sulfonic acid sodium or BDO-2-sodium sulfonate.
4. high solids content footwear use sizing agent according to claim 1, is characterized in that: described linking agent is TriMethylolPropane(TMP), tetramethylolmethane, two adjacent chlorodiphenyl amine methane or sucrose.
5. high solids content footwear use sizing agent according to claim 1, is characterized in that: described neutralizing agent is sodium hydroxide, potassium hydroxide, ammoniacal liquor, triethylamine, Trimethylamine 99 or trolamine.
6. high solids content footwear use sizing agent according to claim 1, is characterized in that: described catalyzer is dibutyl tin dilaurate or stannous octoate or triethylamine.
7. high solids content footwear use sizing agent according to claim 1, is characterized in that: described solvent is acetone, methylethylketone, dioxane, DMF or N-Methyl pyrrolidone.
8. according to the preparation method of the high solids content footwear use sizing agent described in any claim in claim 1-7, it is characterized in that comprising the steps:
1) pre-polymerization: polyvalent alcohol, isocyanic ester are added in reactor, be warming up to 70-90 ℃ and add again catalyzer, reaction 1-3h;
2) chain extension: add again hydrophilic chain extender and linking agent reaction 1-2h at 70-90 ℃;
3) neutralization: add neutralizing agent after cooling to 30-40 ℃ and make pH value for 7-9;
4) emulsification: add wherein deionized water and resin aqueous emulsion emulsification to stir under high-speed stirring and obtain high solids content footwear use sizing agent.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210310648.XA CN102827570B (en) | 2012-08-28 | 2012-08-28 | High-solid-content aqueous adhesive for shoes and preparation method thereof |
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| CN201210310648.XA CN102827570B (en) | 2012-08-28 | 2012-08-28 | High-solid-content aqueous adhesive for shoes and preparation method thereof |
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| CN102827570A CN102827570A (en) | 2012-12-19 |
| CN102827570B true CN102827570B (en) | 2014-04-16 |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103254867A (en) * | 2013-04-26 | 2013-08-21 | 巨石集团有限公司 | Preparation method of sulfonic acid type waterborne polyurethane adhesive |
| CN105238327A (en) * | 2015-09-25 | 2016-01-13 | 安徽大松树脂有限公司 | Polyurethane adhesive for shoes |
| CN105400482A (en) * | 2015-12-28 | 2016-03-16 | 倪协照 | Novel wear-resistant anti-aging dual-component polyurethane adhesive for shoe and preparation method thereof |
| CN106118577A (en) * | 2016-07-04 | 2016-11-16 | 黄淳 | A kind of footwear Bicompenent high solid content polyurethane adhesive and preparation method thereof |
| CN106221649B (en) * | 2016-08-15 | 2019-03-01 | 汕头市龙湖昌丰化工有限公司 | The Waterborne polyurethane shoe adhesive and preparation method thereof of low viscosity high-adhesive-strength |
| CN106700016A (en) * | 2016-11-28 | 2017-05-24 | 中国科学院长春应用化学研究所 | Cationic waterborne polyurethane resin, preparation method of cationic waterborne polyurethane resin and waterborne polyurethane adhesive |
| CN106753163B (en) * | 2016-12-27 | 2020-06-16 | 丽水学院 | Flocking leather injection-moldable waterborne polyurethane flocking glue for shoes and preparation method thereof |
| CN108690518A (en) * | 2017-03-13 | 2018-10-23 | 康得新光学膜材料（上海）有限公司 | A kind of compound fenestrated membrane of water-base cement |
| CN108342180A (en) * | 2018-01-22 | 2018-07-31 | 运研材料科技（上海）有限公司 | A kind of aqueous viscose glue of water resistant low temperature and its application and the method for being bonded two layers of ox-hide product |
| CN108978192B (en) * | 2018-05-23 | 2020-12-04 | 广东德美精细化工集团股份有限公司 | Application process of far infrared negative ion functional coating processing technology on textile |
| CN110713808A (en) * | 2018-07-13 | 2020-01-21 | 重庆韩拓科技有限公司 | High-solid-content polyurethane modified EVA (ethylene-vinyl acetate) composite emulsion and preparation method thereof |
| CN109679543B (en) * | 2018-09-03 | 2021-01-29 | 万华化学集团股份有限公司 | Quick-drying water-based adhesive and preparation method and application thereof |
| CN110372845A (en) * | 2019-07-23 | 2019-10-25 | 潍坊科技学院 | A kind of preparation method of environment-friendly water-based polyurethane adhesive |
| CN111116858A (en) * | 2019-12-05 | 2020-05-08 | 黄晨笛 | High-solid-content polyether type waterborne polyurethane and preparation method thereof |
| CN111909392A (en) * | 2020-07-24 | 2020-11-10 | 合肥科天水性科技有限责任公司 | Ultrahigh-solid-content aqueous polyurethane resin and preparation method thereof |
| CN114181371B (en) * | 2022-01-20 | 2023-11-21 | 星宇医疗科技股份有限公司 | Oil-resistant composite latex and preparation method thereof, and disposable oil-resistant glove and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101173031B (en) * | 2006-11-01 | 2010-11-03 | 北京林氏精化新材料有限公司 | Polyurethane prepolymer, aquosity polyurethane binder and uses thereof |
| CN101838457B (en) * | 2010-05-11 | 2011-12-28 | 陕西科技大学 | Preparation method of high-solid content crosslinking polyurethane aqueous dispersoid |
| DE102010029235A1 (en) * | 2010-05-21 | 2011-11-24 | Evonik Degussa Gmbh | Hydrophilic polyisocyanates |
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