CN1058035C - Preparation of modified polyurethane resin used for artificial leather - Google Patents
Preparation of modified polyurethane resin used for artificial leather Download PDFInfo
- Publication number
- CN1058035C CN1058035C CN96117002A CN96117002A CN1058035C CN 1058035 C CN1058035 C CN 1058035C CN 96117002 A CN96117002 A CN 96117002A CN 96117002 A CN96117002 A CN 96117002A CN 1058035 C CN1058035 C CN 1058035C
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- China
- Prior art keywords
- polyurethane
- leather
- modified
- blend
- make
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000002649 leather substitute Substances 0.000 title claims description 4
- 239000004814 polyurethane Substances 0.000 claims abstract description 38
- 229920002635 polyurethane Polymers 0.000 claims abstract description 19
- 239000004816 latex Substances 0.000 claims abstract description 17
- 229920000126 latex Polymers 0.000 claims abstract description 17
- 229920001084 poly(chloroprene) Polymers 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000002585 base Substances 0.000 claims abstract description 8
- 125000002091 cationic group Chemical group 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000013067 intermediate product Substances 0.000 claims abstract description 4
- 229920003226 polyurethane urea Polymers 0.000 claims abstract description 4
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000010985 leather Substances 0.000 claims description 51
- 238000002156 mixing Methods 0.000 claims description 14
- -1 polyethylene Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 239000010773 plant oil Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 13
- 239000004744 fabric Substances 0.000 abstract description 8
- 229920002873 Polyethylenimine Polymers 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 abstract 1
- 239000012948 isocyanate Substances 0.000 abstract 1
- 150000002513 isocyanates Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 235000015112 vegetable and seed oil Nutrition 0.000 abstract 1
- 239000008158 vegetable oil Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- 239000003795 chemical substances by application Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 241001481789 Rupicapra Species 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- NSEQHAPSDIEVCD-UHFFFAOYSA-N N.[Zn+2] Chemical compound N.[Zn+2] NSEQHAPSDIEVCD-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 238000001467 acupuncture Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 0.000 description 1
- 238000009955 starching Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The present invention relates to a new method for preparing a modified leather-like polyurethane resin by the blend of neoprene latex and waterborne polyurethane. The method comprises the following steps: according to the patent of ZL91108102. X, a polyurethane urea compound is generated by the reaction of a polyurethane prepolymer and excessive polyethylenimine, wherein the polyurethane prepolymer uses isocyanate prepared by polyatomic alcohol as a terminal group, and the polyatomic alcohol is modified by vegetable oil; then, the polyurethane urea compound reacts with epihalohydrin to obtain an intermediate product; afterwards, the intermediate product reacts with cyclic anhydrous carboxylic anhydride to obtain waterborne polyurethane. The present invention is characterized in that the prepared waterborne polyurethane is directly blended with cationic neoprene latex without being neutralized with alkali to obtain the modified leather-like polyurethane resin; in the blend, the two components can be blended in any proportion. The present invention is suitable for producing leather-like products on production lines with difference kinds of base cloth and different technologies.
Description
The present invention relates to the polychloroprene latex that a kind of imitation leather uses and the resins novel method of aqueous polyurethane blending and modifying.
Polyurethane leather (being called for short the PU leather) closely little by little is familiar with by people during the last ten years, is constantly substituting natural leather, satisfies people and goes back to nature to the growing needs of natural leather clothes and articles for use thereof.Because the PU leather artificial polyvinyl chloride leather of changing over has the shortcoming of hot sticky cold crisp.No matter its imitation leather goods are from feel, outward appearance, and still structure internally all has the sense of the corium of exactly liking, and is anti-insect, do not go mouldy characteristics durable in use.Therefore, the development of PU leather is very fast.
But tens of domestic introductions are done, the production line of wet production PU leather, all are to use solvent (DMF, dimethyl methylamine) type PU resin.Because toxicity and the pollution of DMF must be reclaimed usefulness again, producer's investment of producing the PU leather is strengthened, cost improves, and benefit descends.For this reason, force the manufacturer that produces the PU leather to be badly in need of wanting use PU resin to come replace solvents type PU production of resins PU leather.
Though, abroad have much and deliver about the patent of use PU production of resins PU leather.But domestic not introduce one be the imitation leather production line that use PU resin is produced PU leather.Be used for the water-based PU resin that corium is covered with paint, lacquer, colour wash, etc. and retanning is filled although many manufacturer production have been arranged, can not be used for imitation leather, particularly can not be used for non-woven fabrics of imitating.Its major cause: the one, production water-based PU resin cost is higher.The 2nd, the water-based PU resin quality instability of producing, the 3rd, it is still immature that use PU resin carries out the production technique of imitation leather, makes it and can not contend with sophisticated solvent-borne type PU resin imitation leather goods.
Japanese Patent, the spy opens clear 52---and 62357, introduced a kind of resin with anion-type water-thinned polyurethane and anionic polychloroprene latex blending and modifying, dipping napping cotton, make a kind of tool high resilience, but with the imitation leather goods of rubber sense, the softness that lacks corium has the pliable and tough feel of body bone again.
The objective of the invention is according to above-mentioned situation, present inventors are devoted to the research of this respect, find the aqueous polyurethane that the method for the patent ZL91108102.X that applies for present inventors makes, neutralize without alkali, directly carry out blending and modifying, make the modified waterborne polyurethane resin that imitation leather is used with cationic polychloroprene latex.
A kind of imitation leather takes following scheme to realize with the preparation method of modified aqueous polyurethane tree: the base polyurethane prepolymer for use as that the patent 91108102.X " preparation process of anion-type water-thinned polyurethane for tanning " that adopts present inventors to apply for makes, generate the polyurethane-urea compound with excessive polyethylene polyamine reaction, again with epihalohydrins react intermediate product, then with ring-type anhydrous carboxylic acid anhydride reactant, get addition polymer, neutralize without alkali, directly carry out blending and modifying, make imitation leather modified aqueous polyurethane resin with cationic polychloroprene latex.In the composition of blend, two components can any ratio carry out blend.The urethane amount increases, imitation leather goods good hand touch, and the skin sense is strong; The polychloroprene latex consumption increases, and rebound resilience improves, and tenacity strengthens, and the rubber sense increases the weight of.Generally be used for the imitation leather resin, both blending ratios are preferably 30-70%: 70-30% (effective ingredient weight percent).
The modified waterborne polyurethane resin that a kind of imitation leather of the present invention is used is opened clear 52-62357 relatively with the Japanese Patent spy, utilizes polychloroprene latex to improve the rebound resilience and the toughness of imitation leather goods, and it is identical reducing cost.But what the present invention used is cationic polychloroprene latex, and the feel of its imitation leather goods is better than anionic polychloroprene latex.Two component blends are extremely wideer than scope in the blend of the present invention, can adapt to the requirement of the production technique of different imitation leather goods.
Waterborne polyurethane resin to this blending and modifying, both can add vulcanizing agent, vulcanization accelerator, strengthening agent, anti-aging agent etc. by the polychloroprene latex requirement, also can add linking agent, crosslinking accelerator by the aqueous polyurethane requirement, and filler, softening agent, whitening agent, thickening material, tackifier, tinting material, deodorizing composition, reodorant, defoamer, wetting agent, feel modifying agent, whipping agent, fire retardant, flocculation agent, thermosensitizing agent etc.
The waterborne polyurethane resin of this blending and modifying can be used for the imitation leather of base cloths such as the non-woven fabrics that synthon, natural fiber and blend fiber thereof make, woven cloth, looped fabric.Different according to the quality of base cloth and production technique can be made into clothing leather, footwear leather, luggage leather and sofa artificial leather etc.For example, in blending resin, add thermosensitizing agent, just can on the imitation leather production line that has temperature-sensitive cohesion and washing step device, produce the imitation leather goods.In blending resin, add flocculation agent, make the base cloth that contains resin pickup make it cohesion, bake drying, just can on wet production line, produce the imitation leather goods by 60-80 ℃ of hot water.If the base cloth that contains resin pickup bakes drying directly by baking oven, so, all available this dry method is produced the imitation leather goods on the production line of common printing and dyeing mill, leatheroid factory.But, the permeability of the imitation leather goods of dry production is not so good as the good permeability with the imitation leather goods of heat sensitive process and wet production.Because the water-soluble substances in the resin can not be by water elution.But dry production imitation leather goods have the characteristics of production efficiency height, save energy.Its imitation leather goods can improve ventilation property by adding certain feel modifying agent or whipping agent.
Above-mentioned imitation leather goods can be used the transfer process pad pasting, or improve the imitation leather apparent property with the coating cotton ginning technique, also can produce imitative chamois leather goods with the napping method.
Embodiment one
Press patent ZL91108102.X " preparation process of anion-type water-thinned polyurethane for tanning " with castor oil modified polyether glycol, neutralize without alkali, aqueous polyurethane that makes (solid content 25%) and cationic polychloroprene latex (solid content 50%), the blending ratio of aqueous polyurethane and polychloroprene latex was by 30: 70, mixing and stirring, it is 30% that water is regulated solid content.With 100 kilograms of this blend imitation leather resins, 10 kilograms in the 50% water-dispersion slurry of zinc oxide and light calcium carbonate, 10 kilograms of zinc ammonium complex ion type thermosensitizing agents (solid content 50%), 10 kilograms of ammonium chloride and citric acid composite catalysts (solid content 20%), stir, pad acupuncture nylon terylene blend fiber non-woven fabrics, when the temperature-sensitive roller that shines by infrared lamp, be lower than 60 ℃ of following gels.Then,, bake drying by washing, napping, or split, pad pasting just can make the imitation leather goods that feel is flexible, nothing is that crease, no loose side, exactly like corium.
This prescription is adjusted slightly, can on wet method and dry process production line, be produced well behaved imitation leather goods equally.
Embodiment two:
Make aqueous polyurethane (solid content 25%) and cationic polychloroprene latex (solid content 50%) by patent ZL91108102.X " system grass preparation process of anion-type water-thinned polyurethane " without the alkali neutralization with castor oil modified polyether glycol, the blending ratio of aqueous polyurethane and polychloroprene latex was by 50: 50 mixing and stirring, and regulating solid content is 30%.With 100 kilograms of this blend imitation leather resins, 18.2 kilograms in zinc oxide, 18.2 kilograms of KB resins, 36.35 kilograms of nonionogenic tensides, whitening agent DT1.34 kilogram, pure blue pigment 20 grams, mixed grinding, napping through compiling the long-pending terylene base cloth starching of pin, is baked curing, can obtain the soft imitative chamois leather fabric of white that exactly likes corium.
Claims (2)
1, a kind of preparation method of modified polyurethane resin used for artificial leather, make the base polyurethane prepolymer for use as that isocyanic ester is an end group with plant oil modified polyvalent alcohol, with excessive polyethylene polyamine reaction, generate the polyurethane-urea compound, again with epihalohydrins react intermediate product, with ring-type anhydrous carboxylic acid anhydride reactant, make aqueous polyurethane then.It is characterized in that the aqueous polyurethane that will make neutralizes without alkali, directly make imitation leather modified water-soluble vibrin with cationic polychloroprene latex blend, in the composition of blend, two components can any ratio carry out blend.
2, imitation leather according to claim 1 is characterized in that with the preparation method of modified aqueous polyurethane resin aqueous polyurethane and cationic polychloroprene latex blending ratio are preferably 30-70%; 70-30% (effective ingredient weight percent).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117002A CN1058035C (en) | 1996-07-08 | 1996-07-08 | Preparation of modified polyurethane resin used for artificial leather |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117002A CN1058035C (en) | 1996-07-08 | 1996-07-08 | Preparation of modified polyurethane resin used for artificial leather |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1170016A CN1170016A (en) | 1998-01-14 |
| CN1058035C true CN1058035C (en) | 2000-11-01 |
Family
ID=5123947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96117002A Expired - Fee Related CN1058035C (en) | 1996-07-08 | 1996-07-08 | Preparation of modified polyurethane resin used for artificial leather |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1058035C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966578B (en) * | 2005-11-17 | 2010-12-08 | 江苏国信合成革有限公司 | Environment-friendly type high-performance PU synthetic leather and its preparation method |
| CN100341913C (en) * | 2006-04-27 | 2007-10-10 | 南京红宝丽股份有限公司 | Rigid polyurethane foam prepared by using rape seed oil |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5262357A (en) * | 1975-11-18 | 1977-05-23 | Kao Corp | Modification of the polychloroprene latex |
| JPS52155653A (en) * | 1976-06-21 | 1977-12-24 | Kao Corp | Modification of cationic polychloroprene latex |
| JPS57149566A (en) * | 1981-03-05 | 1982-09-16 | Dainippon Printing Co Ltd | Production of regenerated natural leather |
| JPS60239572A (en) * | 1984-05-08 | 1985-11-28 | Teijin Ltd | Synthetic leather |
| JPH04372662A (en) * | 1991-06-24 | 1992-12-25 | Showa Electric Wire & Cable Co Ltd | Curable polymer emulsion |
-
1996
- 1996-07-08 CN CN96117002A patent/CN1058035C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5262357A (en) * | 1975-11-18 | 1977-05-23 | Kao Corp | Modification of the polychloroprene latex |
| JPS52155653A (en) * | 1976-06-21 | 1977-12-24 | Kao Corp | Modification of cationic polychloroprene latex |
| JPS57149566A (en) * | 1981-03-05 | 1982-09-16 | Dainippon Printing Co Ltd | Production of regenerated natural leather |
| JPS60239572A (en) * | 1984-05-08 | 1985-11-28 | Teijin Ltd | Synthetic leather |
| JPH04372662A (en) * | 1991-06-24 | 1992-12-25 | Showa Electric Wire & Cable Co Ltd | Curable polymer emulsion |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1170016A (en) | 1998-01-14 |
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