CN102977317A - Direct-coating type polyurethane resin base material for waterproof and moisture permeable clothing leather and preparation method thereof - Google Patents
Direct-coating type polyurethane resin base material for waterproof and moisture permeable clothing leather and preparation method thereof Download PDFInfo
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- CN102977317A CN102977317A CN2013100011764A CN201310001176A CN102977317A CN 102977317 A CN102977317 A CN 102977317A CN 2013100011764 A CN2013100011764 A CN 2013100011764A CN 201310001176 A CN201310001176 A CN 201310001176A CN 102977317 A CN102977317 A CN 102977317A
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Abstract
The invention provides a direct-coating type polyurethane resin base material for waterproof and moisture permeable clothing leather. The polyurethane resin base material is prepared by the following components in parts by weight: 5-15 parts of aliphatic or aromatic isocyanate compound, 20-50 parts of dihydroxy hydrophilic polymer polyalcohol, 10-20 parts of dihydroxy hydrophobic polymer polyalcohol, 1.5-5 parts of dihydroxy small molecular weight polyalcohol and 30-70 parts of organic solvent. The hydrolysis-resistant polyurethane resin is simple in preparation method, low in cost, high in moisture permeability, soft in hand feel, good in firmness of bonding with base cloth, high in water pressure resistance and good in washing resistance.
Description
Technical field
The invention belongs to Chemicals and preparation method thereof technical field, particularly a kind of waterproof moisture permeable clothing leather is used the urethane resin bed material, also relates to preparation method and the application thereof of this urethane resin bed material.
Background technology
Raising along with people's living standard, people require more and more higher to garment material, particularly when rainy day, winter or outdoor activity, not only require the clothes of dress to have waterproof, warming effect, also require simultaneously the clothes permeability good, the higher inner of temperature is in time discharged with the hot gas of sweat stain, avoid the snugness of fit variation.
Directly being coated with type polyurethane waterproof moisture permeable clothing leather is exactly the fabric of a kind of good waterproof performance, good permeability, and this fabric adopts fabric is utilized the direct coating of urethane; Because coating has been covered the fiber hole of fabric, so that raindrop can not see through fabric, thereby make fabric have waterproof, saturating wet function; Simultaneously, owing to contain hydrophilic composition in the polyurethane coating component, the sweat of human body is discharged with the form of steam, utilize the hydrophilic composition in the polyurethane coating to be delivered to the outside with the form of adsorbing---desorption---absorption, reach wet function.Yet, the saturating wet clothing leather of polyurethane water-proof on the existing market, the ubiquity Water Vapour Permeability is undesirable, the defective that feel is partially hard; And improve the water-fastness variation of clothing leather of Water Vapour Permeability, feel is too soft, and with the firmness variation of base cloth.
Usually, directly be coated with type polyurethane waterproof moisture permeable clothing leather and comprise that fabric and bed material, fabric have guaranteed preferably feel of clothing leather surface, bed material has guaranteed the firmness between resin and the fabric.The saturating wet fabric technique of height is simple, yet has the saturating bed material that wets of height now because containing a large amount of hydrophilic components, and therefore existence chance water-swellable is large, the shortcoming of water-fastness difference.
Summary of the invention
Goal of the invention: the type that directly the is coated with waterproof moisture permeable clothing leather urethane resin bed material and preparation method thereof that the purpose of this invention is to provide a kind of water-tolerant.
Technical scheme: a kind of type waterproof moisture permeable clothing leather that directly is coated with provided by the invention is used the urethane resin bed material, is made by the component of following weight part: isocyanate compound 5-15 part; Two hydroxyl hydrophilic polymer polyatomic alcohol 20-50 parts; Twoly think hydroxyl hydrophobic polymer polyvalent alcohol 10-20 part; Two hydroxyl small molecular weight polyvalent alcohol 1.5-5 parts; Organic solvent 30-70 part.
Directly be coated with type waterproof moisture permeable clothing leather as the present invention and use a kind of preferred of urethane resin bed material, described isocyanate ester compound comprises aliphatic isocyanates compounds or aromatic isocyanate compounds; Wherein, the aliphatic isocyanates compounds comprises hexamethylene diisocyanate, xylylene diisocyanate and isophorone diisocyanate etc.; The aromatic diisocyanate compounds comprises tolylene diisocyanate and 4, one or both in 4 '-diphenylmethanediisocyanate; More preferably, described aromatic isocyanate compound comprises tolylene diisocyanate and 4, in 4 '-diphenylmethanediisocyanate one or both, most preferably, described aromatic isocyanate compound comprises that weight percent is 4 of the tolylene diisocyanate of 20-80% and 20-80%, 4 '-diphenylmethanediisocyanate.
It is preferred with the another kind of urethane resin bed material directly to be coated with type waterproof moisture permeable clothing leather as the present invention, and described pair of hydroxyl hydrophilic polymer polyatomic alcohol is polyoxyethylene glycol, and its molecular weight is 1000-6000.
It is preferred with the another kind of urethane resin bed material directly to be coated with type waterproof moisture permeable clothing leather as the present invention, and described pair of hydroxyl hydrophobic polymer polyvalent alcohol comprises that weight percent is the polyether glycol of the pure and mild 10-90% of polyester polyols of 10-90%.
It is preferred with the another kind of urethane resin bed material directly to be coated with type waterproof moisture permeable clothing leather as the present invention, described polyester polyol comprises polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acid, its molecular weight is 1000-6000, made by ethylene glycol, butyleneglycol, hexylene glycol and hexanodioic acid, preferably, be that the ethylene glycol of 20-60 part, the butyleneglycol of 10-40 part, the hexylene glycol of 20-50 part and the hexanodioic acid of 3-70 part are made by weight part; Its preparation method is: with ethylene glycol, butyleneglycol, hexylene glycol and hexanodioic acid after 100-170 ℃ of dehydration reaction, be warming up to 180-200 ℃ of transesterification reaction, reach 20-112, moisture＜0.03% in hydroxyl value, when acid number reaches 0.1-0.8mgKOH/g, stopped reaction, and get final product.
It is preferred with the another kind of urethane resin bed material directly to be coated with type waterproof moisture permeable clothing leather as the present invention, and described polyether glycol comprises one or both of polytetrahydrofuran dibasic alcohol and Polyoxypropylene diol; More preferably, described polyether glycol comprises that weight percent is the polytetrahydrofuran dibasic alcohol of 20%-80% and the Polyoxypropylene diol of 20%-80%, and its molecular weight is 1000-6000.
Directly be coated with another kind of preferred with the urethane resin bed material of type waterproof moisture permeable clothing leather as the present invention, the described pair of hydroxyl small molecular weight polyvalent alcohol comprises one or more in ethylene glycol, neopentyl glycol and the glycol ether; More preferably, described pair of hydroxyl small molecular weight polyvalent alcohol comprises that weight percent is 40-80% ethylene glycol, 10%-50% neopentyl glycol and 10%-50% glycol ether.
It is preferred with the another kind of urethane resin bed material directly to be coated with type waterproof moisture permeable clothing leather as the present invention, and described organic solvent comprises one or more in dimethyl formamide, toluene and the butanone; More preferably, described organic solvent comprises that weight percent is the dimethyl formamide of 30%-70%, the toluene of 20%-60% and the butanone of 10%-50%.
The present invention also provides a kind of above-mentioned method that type waterproof moisture permeable clothing leather is used the urethane resin bed material that directly is coated with for preparing, may further comprise the steps: with aliphatics or aromatic isocyanate compound, two hydroxyl hydrophilic polymer polyatomic alcohols, two hydroxyl hydrophobic polymer polyvalent alcohols, two hydroxyl small molecular weight polyvalent alcohols are dissolved in the organic solvent, under 60-70 ℃, react to viscosity be 18-20cps/25 ℃, the cooling and get final product.
Beneficial effect: waterproof moisture permeable clothing leather provided by the invention is simple, with low cost with urethane resin bed material preparation method, and Water Vapour Permeability is high, soft, good with the base cloth firmness, water pressure resistance high, water-wash resistance is good.
Embodiment
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand that the described concrete material proportion of embodiment, processing condition and result thereof only are used for explanation the present invention, and should also can not limit the present invention described in detail in claims.
Embodiment 1
Directly be coated with type waterproof moisture permeable clothing leather and use the urethane resin bed material, made by the component of following weight part:
2 parts of tolylene diisocyanates, 4,8 parts of 4 '-diphenylmethanediisocyanates;
Molecular weight is 30 parts of 3000 polyoxyethylene glycol (PEG);
Molecular weight is 5 parts of 3000 polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acids, and molecular weight is 5 parts of 5 parts of 3000 polytetrahydrofuran dibasic alcohol and Polyoxypropylene diols; Wherein, polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acid is made by ethylene glycol, butyleneglycol, hexylene glycol and hexanodioic acid;
0.6 part of 1.0 parts of ethylene glycol, 0.6 part of neopentyl glycol and glycol ether;
10 parts of 25 parts of dimethyl formamides, 15 parts of toluene and butanone.
Its preparation method, may further comprise the steps: with tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, polyoxyethylene glycol, polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acid, polytetrahydrofuran dibasic alcohol, Polyoxypropylene diol, ethylene glycol, neopentyl glycol and glycol ether are dissolved in the mixing solutions of dimethyl formamide, toluene and butanone, under 60-70 ℃, react to viscosity be 18-20 ten thousand cps/25 ℃, the cooling and get final product.
Embodiment 2
Directly be coated with type waterproof moisture permeable clothing leather and use the urethane resin bed material, made by the component of following weight part:
5 parts of isophorone diisocyanates, 4,5 parts of 4 '-diphenylmethanediisocyanates;
Molecular weight is 30 parts of 4000 polyoxyethylene glycol (PEG);
Molecular weight is 5 parts of 4000 polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acids, and molecular weight is 5 parts of 5 parts of 4000 polytetrahydrofuran dibasic alcohol and Polyoxypropylene diols; Wherein, polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acid is made by ethylene glycol, butyleneglycol, hexylene glycol and hexanodioic acid;
0.7 part of 1.5 parts of ethylene glycol, 0.7 part of neopentyl glycol and glycol ether;
10 parts of 10 parts of dimethyl formamides, 30 parts of toluene and butanone.
Its preparation method is with embodiment 1.
Embodiment 3
Directly be coated with type waterproof moisture permeable clothing leather and use the urethane resin bed material, made by the component of following weight part:
2 parts of tolylene diisocyanates, 8 parts of xylylene diisocyanates;
Molecular weight is 40 parts of 2000 polyoxyethylene glycol (PEG);
Molecular weight is 5 parts of 2000 polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acids, and molecular weight is 8 parts of 2 parts of 2000 polytetrahydrofuran dibasic alcohol and Polyoxypropylene diols; Wherein, polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acid is made by ethylene glycol, butyleneglycol, hexylene glycol and hexanodioic acid;
0.5 part of 2.0 parts of ethylene glycol, 0.5 part of neopentyl glycol and glycol ether;
10 parts of 20 parts of dimethyl formamides, 20 parts of toluene and butanone.
Its preparation method is with embodiment 1.
Embodiment 4
Directly be coated with type waterproof moisture permeable clothing leather and use the urethane resin bed material, made by the component of following weight part:
2 parts of tolylene diisocyanates, 4,8 parts of 4 '-diphenylmethanediisocyanates;
Molecular weight is 35 parts of 3000 polyoxyethylene glycol (PEG);
Molecular weight is 5 parts of 3000 polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acids, and molecular weight is 5 parts of 5 parts of 3000 polytetrahydrofuran dibasic alcohol and Polyoxypropylene diols; Wherein, polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acid is made by ethylene glycol, butyleneglycol, hexylene glycol and hexanodioic acid;
0.5 part of 1.5 parts of ethylene glycol, 0.5 part of neopentyl glycol and glycol ether;
10 parts of 25 parts of dimethyl formamides, 15 parts of toluene and butanone.
Its preparation method is with embodiment 1.
Embodiment 5
Directly be coated with type waterproof moisture permeable clothing leather and use the urethane resin bed material, made by the component of following weight part:
8 parts of tolylene diisocyanates, 4,2 parts of 4 '-diphenylmethanediisocyanates;
Molecular weight is 30 parts of 4000 polyoxyethylene glycol (PEG);
Molecular weight is 5 parts of 4000 polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acids, and molecular weight is 4 parts of 6 parts of 4000 polytetrahydrofuran dibasic alcohol and Polyoxypropylene diols; Wherein, polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acid is made by ethylene glycol, butyleneglycol, hexylene glycol and hexanodioic acid;
1 part of 2 parts of ethylene glycol, 1 part of neopentyl glycol and glycol ether;
15 parts of 20 parts of dimethyl formamides, 15 parts of toluene and butanone.
Its preparation method is with embodiment 1.
Embodiment 6
Directly be coated with type waterproof moisture permeable clothing leather and use the urethane resin bed material, made by the component of following weight part:
10 parts of tolylene diisocyanates, 4,2 parts of 4 '-diphenylmethanediisocyanates;
Molecular weight is 40 parts of 2000 polyoxyethylene glycol (PEG);
Molecular weight is 5 parts of 2000 polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acids, and molecular weight is 6 parts of 4 parts of 2000 polytetrahydrofuran dibasic alcohol and Polyoxypropylene diols; Wherein, polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acid is made by ethylene glycol, butyleneglycol, hexylene glycol and hexanodioic acid;
0.5 part of 2 parts of ethylene glycol, 2.5 parts of neopentyl glycol and glycol ether;
7 parts of 21 parts of dimethyl formamides, 42 parts of toluene and butanone.
Its preparation method is with embodiment 1.
Embodiment 7
Directly be coated with type waterproof moisture permeable clothing leather and use the urethane resin bed material, made by the component of following weight part:
4,10 parts of 4 '-diphenylmethanediisocyanates;
Molecular weight is 50 parts of 4000 polyoxyethylene glycol (PEG);
Molecular weight is 10 parts of 2500 polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acids, and molecular weight is 8 parts of 2 parts of 2500 polytetrahydrofuran dibasic alcohol and Polyoxypropylene diols; Wherein, polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acid is made by ethylene glycol, butyleneglycol, hexylene glycol and hexanodioic acid;
2.5 parts of 2 parts of ethylene glycol, 0.5 part of neopentyl glycol and glycol ethers;
7 parts of 49 parts of dimethyl formamides, 14 parts of toluene and butanone.
Embodiment 8
Directly be coated with type waterproof moisture permeable clothing leather and use the urethane resin bed material, made by the component of following weight part:
5 parts of hexamethylene diisocyanates;
Molecular weight is 20 parts of 3000 polyoxyethylene glycol (PEG);
Molecular weight is 10 parts of 4000 polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acids, and molecular weight is 2 parts of 8 parts of 4000 polytetrahydrofuran dibasic alcohol and Polyoxypropylene diols; Wherein, polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acid is made by ethylene glycol, butyleneglycol, hexylene glycol and hexanodioic acid;
0.5 part of 4 parts of ethylene glycol, 0.5 part of neopentyl glycol and glycol ether;
30 parts of dimethyl formamides.
Embodiment 9
Directly be coated with type waterproof moisture permeable clothing leather and use the urethane resin bed material, made by the component of following weight part:
15 parts of xylylene diisocyanates;
Molecular weight is 40 parts of 6000 polyoxyethylene glycol (PEG);
Molecular weight is 1 part of 6000 polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acid, and molecular weight is 9 parts of 6000 polytetrahydrofuran dibasic alcohol; Wherein, polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acid is made by ethylene glycol, butyleneglycol, hexylene glycol and hexanodioic acid;
1.5 parts of ethylene glycol;
30 parts of toluene.
Its preparation method is with embodiment 1.
Embodiment 10
Directly be coated with type waterproof moisture permeable clothing leather and use the urethane resin bed material, made by the component of following weight part:
10 parts of isophorone diisocyanates;
Molecular weight is 40 parts of 1000 polyoxyethylene glycol (PEG);
Molecular weight is 9 parts of 1000 polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acids, and molecular weight is 9 parts of 1000 Polyoxypropylene diols;
4 parts of 4 parts of neopentyl glycol or glycol ethers;
50 parts of butanone.
Embodiment 11
Measure the type that directly the is coated with waterproof moisture permeable clothing leather urethane resin bed material Water Vapour Permeability of embodiment 1 to 10, method is GBT12704-1991; Measurement result sees Table 1.
The urethane resin bed material Water Vapour Permeability of table 1 embodiment 1 to 10 sample
Claims (10)
1. one kind directly is coated with type waterproof moisture permeable clothing leather and uses the urethane resin bed material, and it is characterized in that: the component by following weight part is made: isocyanate compound 5-15 part; Two hydroxyl hydrophilic polymer polyatomic alcohol 20-50 parts; Two hydroxyl hydrophobic polymer polyvalent alcohol 10-20 parts; Two hydroxyl small molecular weight polyvalent alcohol 1.5-5 parts; Organic solvent 30-70 part.
2. a kind of type waterproof moisture permeable clothing leather that directly is coated with according to claim 1 is used the urethane resin bed material, and it is characterized in that: described isocyanate compound comprises tolylene diisocyanate and 4, one or both in 4 '-diphenylmethanediisocyanate.
3. a kind of type waterproof moisture permeable clothing leather urethane resin bed material that directly is coated with according to claim 2, it is characterized in that: described isocyanate compound comprises that weight percent is 4 of the tolylene diisocyanate of 20-80% and 20-80%, 4 '-diphenylmethanediisocyanate.
4. a kind of type waterproof moisture permeable clothing leather that directly is coated with according to claim 1 is used the urethane resin bed material, and it is characterized in that: described pair of hydroxyl hydrophilic polymer polyatomic alcohol is polyoxyethylene glycol, and its molecular weight is 1000-6000.
5. a kind of type waterproof moisture permeable clothing leather that directly is coated with according to claim 1 is used the urethane resin bed material, and it is characterized in that: described pair of hydroxyl hydrophobic polymer polyvalent alcohol comprises that weight percent is the polyether glycol of the pure and mild 10-90% of polyester polyols of 10-90%.
6. a kind of type waterproof moisture permeable clothing leather urethane resin bed material that directly is coated with according to claim 5, it is characterized in that: described polyester polyol comprises polyoxyethylene glycol butyleneglycol hexylene glycol hexanodioic acid, its molecular weight is 1000-6000, is made by ethylene glycol, butyleneglycol, hexylene glycol and hexanodioic acid; Described polyether glycol comprises one or both of polytetrahydrofuran dibasic alcohol and Polyoxypropylene diol, and its molecular weight is 1000-6000.
7. a kind of type waterproof moisture permeable clothing leather of directly being coated with according to claim 1 is used the urethane resin bed material, it is characterized in that: the described pair of hydroxyl small molecular weight polyvalent alcohol comprises one or more in ethylene glycol, neopentyl glycol and the glycol ether.
8. a kind of type waterproof moisture permeable clothing leather that directly is coated with according to claim 7 is used the urethane resin bed material, and it is characterized in that: described pair of hydroxyl small molecular weight polyvalent alcohol comprises that weight percent is 40-80% ethylene glycol, 10%-50% neopentyl glycol and 10%-50% glycol ether.
9. a kind of type waterproof moisture permeable clothing leather that directly is coated with according to claim 1 is used the urethane resin bed material, and it is characterized in that: described organic solvent comprises one or more in dimethyl formamide, toluene and the butanone.
10. one kind prepares each described method that directly is coated with type waterproof moisture permeable clothing leather usefulness urethane resin bed material of claim 1 to 9, it is characterized in that: aliphatics or aromatic isocyanate compound, two hydroxyl hydrophilic polymer polyatomic alcohol, two hydroxyl hydrophobic polymer polyvalent alcohol, two hydroxyl small molecular weight polyvalent alcohol are dissolved in the organic solvent, under 60-70 ℃, react to viscosity be 18-20 ten thousand cps/25 ℃, the cooling and get final product.
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| CN104164790A (en) * | 2014-07-02 | 2014-11-26 | 合肥冠怡涂层织物有限公司 | Waterproof moisture-permeable artificial leather used for clothing and preparing method thereof |
| CN104389190A (en) * | 2014-10-25 | 2015-03-04 | 合肥市安山涂层织物有限公司 | Novel waterproof synthetic leather sizing agent and preparation method thereof |
| CN104513355A (en) * | 2013-09-26 | 2015-04-15 | 苏州富仁化工有限公司 | Preparation method for cold resistant and moisture permeable polyurethane resin |
| CN105017501A (en) * | 2015-07-31 | 2015-11-04 | 旭川化学（苏州）有限公司 | Polyurethane resin fabric for safety shoe leather and preparation method thereof |
| CN106633008A (en) * | 2016-12-24 | 2017-05-10 | 浙江旭川树脂有限公司 | Polyester polyol and polyurethane resin used for super-soft clothing leather |
| CN106928421A (en) * | 2017-04-13 | 2017-07-07 | 合肥科天水性科技有限责任公司 | A kind of clothing leather soft bed material and preparation method thereof |
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| CN104513355A (en) * | 2013-09-26 | 2015-04-15 | 苏州富仁化工有限公司 | Preparation method for cold resistant and moisture permeable polyurethane resin |
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| CN108203491A (en) * | 2016-12-20 | 2018-06-26 | 苏州宇熠新材料科技有限公司 | A kind of cold-resistant hydrolysis can flame retardant type wet method air-moisture-permeable fabric and preparation method |
| CN106633008A (en) * | 2016-12-24 | 2017-05-10 | 浙江旭川树脂有限公司 | Polyester polyol and polyurethane resin used for super-soft clothing leather |
| CN106928421A (en) * | 2017-04-13 | 2017-07-07 | 合肥科天水性科技有限责任公司 | A kind of clothing leather soft bed material and preparation method thereof |
| CN109401282A (en) * | 2018-09-11 | 2019-03-01 | 苏州市雄林新材料科技有限公司 | A kind of dress ornament highly-flexible TPU film and preparation method thereof |
| CN109457496A (en) * | 2018-11-14 | 2019-03-12 | 南京边城体育用品股份有限公司 | A kind of fire-resistant waterproof ventilation moisture-permeable shell fabric and preparation method thereof |
| CN112625211A (en) * | 2020-12-17 | 2021-04-09 | 泉州博银信息科技有限公司 | Waterproof moisture-permeable polyurethane film with environmental response function and preparation method thereof |
| CN113773784A (en) * | 2021-08-31 | 2021-12-10 | 长春艾德斯新材料有限公司 | Composition of high-strength moisture-heat-resistant polyurethane adhesive and preparation method and application thereof |
| CN114181369A (en) * | 2022-01-07 | 2022-03-15 | 浙江华大树脂有限公司 | Preparation method of high-moisture-permeability waterproof coating primer resin for textile |
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