CN101831048A - High-gloss polyurethane resins and application thereof - Google Patents
High-gloss polyurethane resins and application thereof Download PDFInfo
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- CN101831048A CN101831048A CN201010163613A CN201010163613A CN101831048A CN 101831048 A CN101831048 A CN 101831048A CN 201010163613 A CN201010163613 A CN 201010163613A CN 201010163613 A CN201010163613 A CN 201010163613A CN 101831048 A CN101831048 A CN 101831048A
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- polyurethane resins
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- gloss polyurethane
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- polytetrahydrofuran
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Abstract
High-gloss polyurethane resins are prepared by polymerizing poly(adipate1,4-butanediol ester), polytetrahydrofuran, castor oil, diphenyl-methane diisocyanate, toluene diisocynate, ethylene glycol, 1,4-butanediol, trimethylopropane, 2,2-dimethyl-1,3-propanediol and other molecules through a body; the prepared resin has narrow molecular chain distribution. After dimethyl silicone oil and butanone are added, the resins can be used as a leather processing agent, has better leveling property on the leather and artificial leather and high luminosity. In addition, the resins have stronger adhesive force and are remarkably superior to common like products.
Description
Technical field
The present invention relates to a kind of leather treatment, relate in particular to a kind of polyurethanes resin, the resin that makes is used for the last optical processing of leather surface.
Background technology
Leather need be handled leather before application usually, as: tanning processes such as fleshing, degrease and dyeing.In the tanning process, need to use multiple treatment agent, so that the surface of leather has actual certain function with the satisfied actual needs that use, as: waterproof, light and color etc.
Patent of invention 200710133165.6 relates to a kind of preparation method of sofa class used for artificial leather aqueous polyurethane hot coating sol, and the hot coating sol that this method is produced is mainly used in the bonding of textile fabric and artificial leather material.Generate end group with vulcabond and ester compound and be-performed polymer of NCO, use hydrophilic monomer, 1 then, the reaction of 4-chain expansion of succinic acid is regulated the pH value to neutrality with amine at last, add deionized water and stirring, promptly obtain sofa class used for artificial leather environment-friendly type aqueous polyurethane hot coating sol.The bonding intensity of this thermosol is big, and intensity is medium, and the soft of leather bonds.
Patent of invention 200510019780.5 relates to a kind of dihydroxy dialkyl siloxane polymer modified Synthesis of Waterborne Polyurethane method.Present method is directly to use dihydroxy dialkyl siloxane polymer to replace partly polyester or polyether Glycols and isophorone diisocyanate or tolylene diisocyanate or 4,4 '-diphenylmethanediisocyanate, dimethylol propionic acid, and glycerine or TriMethylolPropane(TMP) or 1, the 4-butyleneglycol, in the presence of solvent n-formyl sarcolysine base pyrrolidone, acetone or butanone or ethyl acetate, make catalyzer with dibutyl tin laurate, obtain dihydroxy dialkyl siloxane polymer modified aqueous polyurethane performed polymer; Through the alkali neutralization, add the water emulsification pretreatment, add the quadrol chain extension again, obtain the polyaminoester emulsion of solid content at 30-40wt%.Gained aqueous polyurethane emulsion solid content height, sticking power, weathering resistance, water tolerance and glossiness are good, excellent in abrasion resistance.This aqueous polyurethane emulsion is suitable for as fabric, plastics, the printing ink of leather etc.; Suitably regulate hardness, also can be used for paint field.
Patent of invention 00800348.3 relates to all good polyurethane/polyurethane-urea resin of intensity and thermotolerance and preparation method thereof.Polyurethane/polyurethane-urea resin is specially adapted to synthetic leather or elastic yarn.It is after making high molecular contain base polyurethane prepolymer for use as (A) that end that the reaction of compound bearing active hydrogen and polyisocyanate compound obtains has isocyanate group to react in solvent with chain extension agent (B), make the method for polyurethane/polyurethane-urea resin except that desolvating, it is characterized in that, the base polyurethane prepolymer for use as (A) that has an isocyanate group as aforementioned end be with following polyvalent alcohol (1) under the excessive condition of isocyanate group and after the polyisocyanate compound reaction, under the excessive condition of isocyanate group, obtain once more with following polyvalent alcohol (2) reaction.Polyvalent alcohol (1) be hydroxyl value below 70, total degree of unsaturation below 0.07, the polyoxy alkene polyvalent alcohol of oxypropylene group content more than 70 weight %.Polyvalent alcohol (2) is the polyvalent alcohol that is selected from polytetramethylene glycol, polyester polyol, polycaprolactone polyol and polycarbonate polyol.
The levelling property of the various products that use is relatively poor at present, and low to the luminance brightness of leather or leatheroid, sticking power is not strong yet.
Summary of the invention
The purpose of this invention is to provide a kind of high-gloss polyurethane resins, relatively poor to the thermotolerance of leather or leatheroid to overcome currently available products, luminance brightness is hanged down and problems such as sticking power is not strong.
The invention provides a kind of high-gloss polyurethane resins, contain the poly-(hexanodioic acid 1 of 25wt%-60wt%, the 4-butanediol ester), 5wt%-30wt% polytetrahydrofuran, 3wt%-17wt% Viscotrol C, 20wt%-40wt% diphenylmethanediisocyanate, 10wt%-30wt% tolylene diisocyanate, 0.5wt%-5wt% ethylene glycol, 0.5wt%-5wt%1, the hot pentanediol of 4-butyleneglycol, 0.5wt%-5wt% trimethyl propane and 0.5wt%-5wt%.
Poly-(hexanodioic acid 1,4-butanediol ester) molecular weight is 600-3000Da.
The molecular weight of polytetrahydrofuran is 600-3000Da.
The high-gloss polyurethane resins that makes also needs to add the dimethyl silicone oil of 1-5wt% and the butanone of 10-15wt% before being used for leather surface.
High-gloss polyurethane resins of the present invention is distributed as 45,000 ± 3,150Da through the molecular chain that GPC measures.
High-gloss polyurethane resins forms by mass polymerization.
A kind of preparation method who is used for the high-gloss polyurethane resins of leather provided by the invention, 25wt%-60wt% gathers (hexanodioic acid 1, the 4-butanediol ester), 5wt%-30wt% polytetrahydrofuran and the mixing of 3wt%-17wt% Viscotrol C also are dissolved in dimethyl formamide (DMF), after adding the 10wt%-30wt% tolylene diisocyanate, in 60-90 ℃ of reaction 1-2 hour, add 0.5wt%-5wt% ethylene glycol afterwards, 0.5wt%-5wt%1, the 4-butyleneglycol, behind the hot pentanediol of 0.5wt%-5wt% trimethyl propane and 0.5wt%-5wt%, in 40-70 ℃ of reaction 1-2 hour, add 70-90 ℃ of reaction of 20wt%-40wt% diphenylmethanediisocyanate 2-5 hour afterwards.The butanone that adds 1.5wt%-5wt% dimethyl silicone oil and 10wt%-15wt% at last.
Ethylene glycol, 1,4-butyleneglycol, trimethyl propane and hot pentanediol all are solvent with toluene.
The beneficial effect that technical solution of the present invention realizes:
A kind of high-gloss polyurethane resins disclosed by the invention, by poly-(hexanodioic acid 1, the 4-butanediol ester), polytetrahydrofuran, Viscotrol C, diphenylmethanediisocyanate, tolylene diisocyanate, ethylene glycol, 1,4-butyleneglycol, trimethyl propane and hot pentanediol equimolecular get the molecular resin chain narrowly distributing that makes through the mass polymerization preparation.In resin, be used for leather behind the butanone of the dimethyl silicone oil of interpolation 1-5wt% and 10-15wt%, to having good heat resistance (5 grades heat-resisting), good leveling property, luminance brightness height (reflectivity is greater than 80%) on leather and the leatheroid, and show stronger sticking power, obviously be better than general like product.
Embodiment
Below describe technical scheme of the present invention in detail.
The preparation of embodiment 1 high-gloss polyurethane resins
30wt% gathers (hexanodioic acid 1, the 4-butanediol ester), 6wt% polytetrahydrofuran and 4wt% Viscotrol C mix and are dissolved in dimethyl formamide (DMF), after adding the 20wt% tolylene diisocyanate, in 70 ℃ of reactions 1.5 hours, add 0.5wt% ethylene glycol, 0.5wt%1 afterwards, behind the hot pentanediol of 4-butyleneglycol, 0.5wt% trimethyl propane and 0.5wt%,, add 75 ℃ of reactions of 38wt% diphenylmethanediisocyanate 2.5 hours afterwards in 40 ℃ of reactions 2 hours.Make product and be distributed as 45,000 ± 3,150Da through the molecular chain that GPC measures.
The preparation of embodiment 2 high-gloss polyurethane resins
45wt% gathers (hexanodioic acid 1, the 4-butanediol ester), 6wt% polytetrahydrofuran and 4wt% Viscotrol C mix and are dissolved in dimethyl formamide (DMF), after adding the 20wt% tolylene diisocyanate, in 70 ℃ of reactions 1.5 hours, add 1wt% ethylene glycol, 1wt%1 afterwards, behind the hot pentanediol of 4-butyleneglycol, 1wt% trimethyl propane and 1wt%,, add 75 ℃ of reactions of 21wt% diphenylmethanediisocyanate 2.5 hours afterwards in 40 ℃ of reactions 2 hours.Make product and be distributed as 45,000 ± 3,150Da through the molecular chain that GPC measures.
The preparation of embodiment 3 high-gloss polyurethane resins
55wt% gathers (hexanodioic acid 1, the 4-butanediol ester), 6wt% polytetrahydrofuran and 4wt% Viscotrol C mix and are dissolved in dimethyl formamide (DMF), after adding the 10wt% tolylene diisocyanate, in 70 ℃ of reactions 1.5 hours, add 1wt% ethylene glycol, 1wt%1 afterwards, behind the hot pentanediol of 4-butyleneglycol, 1wt% trimethyl propane and 1wt%,, add 75 ℃ of reactions of 31wt% diphenylmethanediisocyanate 2.5 hours afterwards in 40 ℃ of reactions 2 hours.Make product and be distributed as 45,000 ± 3,150Da through the molecular chain that GPC measures.
The performance test of embodiment 4 high-gloss polyurethane resins
The thermotolerance test
Testing standard is the industry testing standard of leather, synthetic leather, and is specific as follows:
Two specimen surface layers are superimposed together relatively, be clipped between two 60mm * 60mm * 3mm glass, being pressed on glass placing it in 100 ± 2 ℃ the air blast thermostat container with the counterweight of quality 3KG again takes out behind the 1h, remove counterweight, behind room temperature 1h, gently open involutory sample with have gentle hands, test result is 5 grades, surface no change (the industry testing standard is divided into 5 grades, and 5 grades of expressions are the highest, and 1 grade of expression is the poorest)
The luminance brightness test is pressed GJB5023.2-2003 and is measured, and the result is: reflectivity is 83%.
Sticking power test (peeling off test)
Test by 5.9 regulation among the GB/T8949-1995, specific as follows:
With the high-gloss polyurethane resins that makes as bonding two of tackiness agent (size is 70mm for 100mm * 25mm leather or synthetic leather bond length), behind 120 ℃/3min of dry environment, under room temperature environment, place 24h again, strip off sample 20mm during test, drawing machine speed is 100mm/min ± 10mm/min, test result 97 ± 3N/cm
2
Claims (6)
1. high-gloss polyurethane resins, contain the poly-(hexanodioic acid 1 of 25wt%-60wt%, the 4-butanediol ester), 5wt%-30wt% polytetrahydrofuran, 3wt%-17wt% Viscotrol C, 20wt%-40wt% diphenylmethanediisocyanate, 10wt%-30wt% tolylene diisocyanate, 0.5wt%-5wt% ethylene glycol, 0.5wt%-5wt%1, the hot pentanediol of 4-butyleneglycol, 0.5wt%-5wt% trimethyl propane and 0.5wt%-5wt%.
2. high-gloss polyurethane resins according to claim 1 is characterized in that described poly-(hexanodioic acid 1,4-butanediol ester) molecular weight is 600-3000Da.
3. high-gloss polyurethane resins according to claim 1, the molecular weight that it is characterized in that described polytetrahydrofuran is 600-3000Da.
4. high-gloss polyurethane resins according to claim 1, its preparation method is as follows: 25wt%-60wt% gathers (hexanodioic acid 1, the 4-butanediol ester), 5wt%-30wt% polytetrahydrofuran and the mixing of 3wt%-17wt% Viscotrol C also are dissolved in dimethyl formamide, after adding the 10wt%-30wt% tolylene diisocyanate, in 60-90 ℃ of reaction 1-2 hour, add 0.5wt%-5wt% ethylene glycol afterwards, 0.5wt%-5wt%1, the 4-butyleneglycol, behind the hot pentanediol of 0.5wt%-5wt% trimethyl propane and 0.5wt%-5wt%, in 40-70 ℃ of reaction 1-2 hour, add 70-90 ℃ of reaction of 20wt%-40wt% diphenylmethanediisocyanate 2-5 hour afterwards.
5. the preparation method of high-gloss polyurethane resins according to claim 4 is characterized in that described ethylene glycol, described 1, and 4-butyleneglycol, described trimethyl propane and described hot pentanediol all are solvent with toluene.
6. a high-gloss polyurethane resins that is used for leather adds the dimethyl silicone oil of 1-5wt% and the butanone of 10-15wt% in the described high-gloss polyurethane resins of claim 1.
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| CN201010163613A CN101831048A (en) | 2010-05-05 | 2010-05-05 | High-gloss polyurethane resins and application thereof |
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| CN201010163613A CN101831048A (en) | 2010-05-05 | 2010-05-05 | High-gloss polyurethane resins and application thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086595A (en) * | 2010-12-09 | 2011-06-08 | 嘉兴市罗星化工有限公司 | Crazy-horse brushed resin taking water-soluble polyurethane as carrier and preparation method thereof |
| CN102154835A (en) * | 2010-12-09 | 2011-08-17 | 嘉兴市罗星化工有限公司 | Pull-up and suede resin using water-soluble polyurethane as carrier and preparation method thereof |
| CN102417573A (en) * | 2011-11-01 | 2012-04-18 | 吴江市北厍盛源纺织品助剂厂 | Method for preparing polyurethane coating agent for artificial chamois leather |
| CN102660197A (en) * | 2012-04-20 | 2012-09-12 | 上海皇宇科技发展有限公司 | Leather brightening agent and leather brightening wet wiper |
| CN103589321A (en) * | 2012-08-16 | 2014-02-19 | 展辰涂料集团股份有限公司 | Polyurethane gloss paint |
| CN103739820A (en) * | 2013-12-16 | 2014-04-23 | 北京服装学院 | Polyurethane waterproof moisture-permeable finishing agent and preparation method thereof |
| CN105369631A (en) * | 2015-12-25 | 2016-03-02 | 江苏宝泽高分子材料股份有限公司 | Non-yellowing high-gloss oil leather for synthetic leather and preparation method of oil leather |
| CN106049077A (en) * | 2016-08-09 | 2016-10-26 | 安徽安利材料科技股份有限公司 | Preparation method of high-gloss PET film transfer mirror-surface polyurethane synthetic leather |
| CN103589321B (en) * | 2012-08-16 | 2016-11-30 | 展辰新材料集团股份有限公司 | A kind of polyurethane light coating |
| WO2017107711A1 (en) * | 2015-12-25 | 2017-06-29 | 江苏宝泽高分子材料股份有限公司 | High-solidity, low-adhesiveness, and high-gloss oiled leather for use in leather synthesis and manufacturing method therefor |
| CN107365408A (en) * | 2017-09-06 | 2017-11-21 | 厦门厦广安工贸有限公司 | Castor oil based polyurethanes resin and its making |
| CN109651585A (en) * | 2018-12-11 | 2019-04-19 | 成都杰晟蜀邦新材料科技有限公司 | A kind of hydroxyl-terminated polyurethane and preparation method thereof |
| CN110684173A (en) * | 2019-10-14 | 2020-01-14 | 浙江华峰合成树脂有限公司 | Super-soft hydrolysis-resistant wet polyurethane resin and preparation method thereof |
| CN110948971A (en) * | 2019-11-15 | 2020-04-03 | 清远市齐力合成革有限公司 | Super-soft and super-soft rebound synthetic leather fabric and preparation method thereof |
-
2010
- 2010-05-05 CN CN201010163613A patent/CN101831048A/en active Pending
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154835A (en) * | 2010-12-09 | 2011-08-17 | 嘉兴市罗星化工有限公司 | Pull-up and suede resin using water-soluble polyurethane as carrier and preparation method thereof |
| CN102086595B (en) * | 2010-12-09 | 2012-07-25 | 嘉兴市罗星化工有限公司 | Crazy-horse brushed resin taking water-soluble polyurethane as carrier and preparation method thereof |
| CN102086595A (en) * | 2010-12-09 | 2011-06-08 | 嘉兴市罗星化工有限公司 | Crazy-horse brushed resin taking water-soluble polyurethane as carrier and preparation method thereof |
| CN102417573B (en) * | 2011-11-01 | 2013-01-09 | 吴江市北厍盛源纺织品助剂厂 | Method for preparing polyurethane coating agent for artificial chamois leather |
| CN102417573A (en) * | 2011-11-01 | 2012-04-18 | 吴江市北厍盛源纺织品助剂厂 | Method for preparing polyurethane coating agent for artificial chamois leather |
| CN102660197B (en) * | 2012-04-20 | 2014-11-05 | 上海皇宇科技发展有限公司 | Leather brightening agent and leather brightening wet wiper |
| CN102660197A (en) * | 2012-04-20 | 2012-09-12 | 上海皇宇科技发展有限公司 | Leather brightening agent and leather brightening wet wiper |
| CN103589321A (en) * | 2012-08-16 | 2014-02-19 | 展辰涂料集团股份有限公司 | Polyurethane gloss paint |
| CN103589321B (en) * | 2012-08-16 | 2016-11-30 | 展辰新材料集团股份有限公司 | A kind of polyurethane light coating |
| CN103739820B (en) * | 2013-12-16 | 2016-01-20 | 北京服装学院 | A kind of polyurethane water-proof moisture-inhibiting finishing composition and preparation method thereof |
| CN103739820A (en) * | 2013-12-16 | 2014-04-23 | 北京服装学院 | Polyurethane waterproof moisture-permeable finishing agent and preparation method thereof |
| CN105369631A (en) * | 2015-12-25 | 2016-03-02 | 江苏宝泽高分子材料股份有限公司 | Non-yellowing high-gloss oil leather for synthetic leather and preparation method of oil leather |
| WO2017107711A1 (en) * | 2015-12-25 | 2017-06-29 | 江苏宝泽高分子材料股份有限公司 | High-solidity, low-adhesiveness, and high-gloss oiled leather for use in leather synthesis and manufacturing method therefor |
| CN106049077A (en) * | 2016-08-09 | 2016-10-26 | 安徽安利材料科技股份有限公司 | Preparation method of high-gloss PET film transfer mirror-surface polyurethane synthetic leather |
| CN106049077B (en) * | 2016-08-09 | 2018-06-29 | 安徽安利材料科技股份有限公司 | A kind of preparation method of bloom PET film transfer minute surface Synthetic Leather |
| CN107365408A (en) * | 2017-09-06 | 2017-11-21 | 厦门厦广安工贸有限公司 | Castor oil based polyurethanes resin and its making |
| CN109651585A (en) * | 2018-12-11 | 2019-04-19 | 成都杰晟蜀邦新材料科技有限公司 | A kind of hydroxyl-terminated polyurethane and preparation method thereof |
| CN110684173A (en) * | 2019-10-14 | 2020-01-14 | 浙江华峰合成树脂有限公司 | Super-soft hydrolysis-resistant wet polyurethane resin and preparation method thereof |
| CN110948971A (en) * | 2019-11-15 | 2020-04-03 | 清远市齐力合成革有限公司 | Super-soft and super-soft rebound synthetic leather fabric and preparation method thereof |
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Application publication date: 20100915 |