CN1058035C - Preparation of modified polyurethane resin used for artificial leather - Google Patents
Preparation of modified polyurethane resin used for artificial leather Download PDFInfo
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- 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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- polyurethane
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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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