CN1058036C - Method for preparing modified anionic water type polyurethane resin used as imitated leather - Google Patents
Method for preparing modified anionic water type polyurethane resin used as imitated leather Download PDFInfo
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- CN1058036C CN1058036C CN98111215A CN98111215A CN1058036C CN 1058036 C CN1058036 C CN 1058036C CN 98111215 A CN98111215 A CN 98111215A CN 98111215 A CN98111215 A CN 98111215A CN 1058036 C CN1058036 C CN 1058036C
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- Prior art keywords
- polyurethane
- leather
- resin used
- polyurethane resin
- make
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- 239000010985 leather Substances 0.000 title claims abstract description 68
- 125000000129 anionic group Chemical group 0.000 title claims abstract description 33
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 23
- 239000004814 polyurethane Substances 0.000 claims abstract description 42
- 229920002635 polyurethane Polymers 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 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
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 7
- 239000013067 intermediate product Substances 0.000 claims abstract description 7
- -1 polyethylene Polymers 0.000 claims abstract description 7
- 239000004698 Polyethylene Substances 0.000 claims abstract description 6
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 6
- 229920000768 polyamine Polymers 0.000 claims abstract description 6
- 229920000573 polyethylene Polymers 0.000 claims abstract description 6
- 229920003226 polyurethane urea Polymers 0.000 claims abstract description 6
- 239000002585 base Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000010773 plant oil Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 24
- 239000011347 resin Substances 0.000 abstract description 24
- 150000001450 anions Chemical class 0.000 abstract description 2
- 239000012948 isocyanate Substances 0.000 abstract 1
- 150000002513 isocyanates Chemical class 0.000 abstract 1
- 150000003672 ureas Chemical class 0.000 abstract 1
- 235000015112 vegetable and seed oil Nutrition 0.000 abstract 1
- 239000008158 vegetable oil Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 21
- 239000004744 fabric Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 241001481789 Rupicapra Species 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002649 leather substitute Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 125000003275 alpha amino acid group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000009955 starching Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The present invention relates to a new method for preparing modified resin by blending anionic neoprene latex with anion aqueous polyurethane for imitating leather. The present invention adopts vegetable oil modified polylol to prepare polyurethane prepolymers with isocyanate as terminal groups, and the polyurethane prepolymers react with excessive polyethylene polyamine to generate polyurethane urea compounds which react with epihalohydrin to obtain intermediate products; afterwards, the intermediate products react with ring anhydrous carboxylic anhydride to obtain aqueous polyurethane. The present invention is characterized in that the prepared aqueous polyurethane is neutralized by alkali and then is directly blended with anionic neoprene latex to prepare the modified anionic aqueous polyurethane resin used for imitating leather; the two components can be blended in any proportion with respect to the composition of blended objects.
Description
The present invention relates to the resins novel method of a kind of imitation leather with anionic polychloroprene latex and anion aqueous polyurethane blending and modifying.
Polyurethane leather (being called for short the PU leather) little by little was familiar with by people over past ten years, was constantly substituting natural leather, satisfied people and went 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 is to use solvent (DMF, dimethyl formamide) 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.
The Japanese Patent spy opens the resin that clear 52-62357 has introduced anion-type water-thinned polyurethane of a kind of usefulness and anionic polychloroprene latex blending and modifying, dipping napping cotton, make a kind of high resilience that has, but with the imitation leather goods of rubber sense, the softness that lacks corium has the pliable and tough feel of body bone again.
" a kind of modified polyurethane resin used for artificial leather preparation method " (the number of patent application ZL96117002.6) of present inventor's application belongs to cationic, obtained good effect in the production application of imitation leather.But, should not be used with auxiliary agent, the pigment paste of anionic resin and anionic.Therefore, limited the application of some aspect.
The objective of the invention is at above-mentioned polyurethane leather production method weak point, a kind of method for preparing modified anionic water type polyurethane resin used as imitated leather is provided, adopt the present inventor apply for a patent aqueous polyurethane that " preparation process of anion-type water-thinned polyurethane for tanning " (patent No. ZL91108102.X) make with in the alkali and after, directly and anionic polychloroprene latex carry out blending and modifying, make the anionic water type polyurethane resin of the modification that imitation leather uses.
A kind of method for preparing modified anionic water type polyurethane resin used as imitated leather takes following scheme to realize: adopt plant oil modified polyvalent alcohol to make the base polyurethane prepolymer for use as that isocyanic ester is an end group, with excessive polyethylene polyamine reaction, generate the polyurethane-urea compound, again with epihalohydrins react intermediate product, make aqueous polyurethane with ring-type anhydrous carboxylic acid anhydride reactant then; The aqueous polyurethane that makes is neutralized with alkali, regulate pH value and reach 7.5～10, direct and anionic polychloroprene latex carries out blending and modifying, makes modified anionic water type polyurethane resin used as imitated leather.In the composition of blend, two components can any ratio carry out blend.Generally be used for the imitation leather resin, both blending ratios are preferably 30-70%: 70-30% (effective ingredient weight percent).
A kind of method for preparing modified anionic water type polyurethane resin used as imitated leather of the present invention and Japanese Patent spy open clear 52-62357 relatively, utilize polychloroprene latex to improve the rebound resilience and the toughness of imitation leather goods, and it is identical reducing cost.And all belong to cloudy subtype.But what we used is the aqueous polyurethane that makes with plant oil modified polyvalent alcohol.This aqueous polyurethane is a kind of amphoteric ion type polymeric surface active agent.PH value can be regulated arbitrarily in 1～14 scope.Therefore, it can with cationic polychloroprene latex blend, by adjust pH value also can with the blend of anionic polychloroprene latex.And blending ratio can be regulated arbitrarily.We know, why urethane can be used for imitation leather, exactly because contain multiple carbamate structural unit in its structure, with the amino acid structure unit class that contains in the natural skin seemingly.Therefore, in this blending resin, the urethane amount increases, imitation leather goods good hand touch, and kishke feel is strong; The polychloroprene latex consumption increases, and rebound resilience improves, and tenacity strengthens, and the rubber sense increases the weight of.And the Japanese Patent spy to open clear 52-62357 be exactly that the polychloroprene latex consumption is many, make the sense of imitation leather goods rubber heavy, the kishke feel deficiency.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.
The Japanese Patent spy opens clear 52-62357 and has only exemplified and be used for the imitative chamois leather technology that teaser is weaved cotton cloth, and the processing condition narrow range is not suitable for being applied to the production of non-woven fabrics of imitating.With the negatively charged ion model waterborne polyurethane resin cooperation 5-30% linking agent of imitation leather of the present invention with modification, 0-20% temperature-sensitive flocculation agent, 0-30% feel modifying agent, immersion non-woven fabrics, the starching amount is 1-6 a times of base cloth, according to the specification of quality of base cloth thickness and product, under 120-160 ℃, bake and solidify 10-60min, can obtain not have the goods that exactly like corium of fine wrinkle at the angle, good garden of " chop line ".
Anionic water type polyurethane resin to this blending and modifying, both can add vulcanizing agent, vulcanization accelerator, strengthening agent, anti-aging agent etc., also can add linking agent, crosslinking accelerator and filler, softening agent, whitening agent, tackifier, tinting material, deodorizing composition, reodorant, defoamer, wetting agent, feel modifying agent, whipping agent, fire retardant, flocculation agent, thermosensitizing agent etc. by the waterborne polyurethane resin requirement by the polychloroprene latex requirement.
The waterborne polyurethane resin of this blending and modifying can be used for the imitation leather of base cloths such as the imitative cloth of nothing 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 have production imitation leather goods on the imitation leather production line that carries out temperature-sensitive cohesion and washing step device under the infrared light irradiation.In blending resin, add the temperature-sensitive 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 is directly by baking oven, roasting oven dry is dry, and 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 the imitation leather goods of dry production have the production efficiency height, save energy, basic three-waste free discharge.But, the imitation leather goods can improve ventilation property by adding certain feel modifying agent or whipping agent.The imitation leather goods are in wearing process, and water-soluble substances is by stripping at leisure, and ventilation property is also better and better.
Above-mentioned imitation leather goods can be used the transfer process pad pasting, or improve imitation leather performance performance with the coating cotton ginning technique, also can produce imitative chamois leather goods with the napping method.
Embodiment 1
Adopt plant oil modified polyvalent alcohol to make the base polyurethane prepolymer for use as that isocyanic ester is an end group,, generate the polyurethane-urea compound with the reaction of excessive polyethylene polyamine, again with epihalohydrins react intermediate product.With ring-type anhydrous carboxylic acid anhydride reactant, make aqueous polyurethane then.Is 8.5 with the aqueous polyurethane that makes with alkali (NaOH) aqueous solution pH value that neutralizes.Then with the blend of anionic polychloroprene latex.Blending ratio mixes by effective ingredient 50: 50 (effective component content ratio), and regulating content is 30%, promptly gets modified anionic water type polyurethane resin used as imitated leather.
100 kilograms of the modified anionic water type polyurethane resin used as imitated leather that makes with aforesaid method, add 15 kilograms in zinc oxide, 10 kilograms of thermosensitizing agents, 10 kilograms of KB resins, 5 kilograms of whipping agents, 0.2 kilogram of pigment, mix, the polyamide fibre non-woven fabrics is flooded, dries, makes the imitation leather goods of good hand touch.
Implement 2
Adopt plant oil modified polyvalent alcohol to make the base polyurethane prepolymer for use as that isocyanic ester is an end group,, generate the polyurethane-urea compound with the reaction of excessive polyethylene polyamine, again with epihalohydrins react intermediate product.With ring-type anhydrous carboxylic acid anhydride reactant, make aqueous polyurethane then.Is 7.5 with the aqueous polyurethane that makes with alkali (NaOH) aqueous solution pH value that neutralizes.Then with the blend of anionic polychloroprene latex.Blending ratio mixes by effective ingredient 30: 70 (effective component content ratio), and regulating content is 30%, promptly gets modified anionic water type polyurethane resin used as imitated leather.
100 kilograms of the modified anionic water type polyurethane resin used as imitated leather that makes with aforesaid method, add 20 kilograms in zinc oxide, 10 kilograms of thermosensitizing agents, 5 kilograms of KB resins, 5 kilograms of whipping agents, 0.2 kilogram of pigment, mix, to teaser weave cotton cloth dipping, dry, make the imitation leather goods of good hand touch.
Embodiment 3
Adopt plant oil modified polyvalent alcohol to make the base polyurethane prepolymer for use as that isocyanic ester is an end group,, generate the polyurethane-urea compound with the reaction of excessive polyethylene polyamine, again with epihalohydrins react intermediate product.With ring-type anhydrous carboxylic acid anhydride reactant, make aqueous polyurethane then.Is 10 with the aqueous polyurethane that makes with alkali (NaOH) aqueous solution pH value that neutralizes, then with the blend of anionic polychloroprene latex, blending ratio mixes by effective ingredient 70: 30 (effective component content ratio), and regulating content is 30%, promptly gets modified anionic water type polyurethane resin used as imitated leather.
100 kilograms of the modified anionic water type polyurethane resin used as imitated leather that makes with aforesaid method, add 5 kilograms in zinc oxide, 10 kilograms of thermosensitizing agents, 15 kilograms of KB resins, 0.2 kilogram of pigment mix, and handle the warp-knitting polyester looped fabric, dry, make the imitative chamois leather goods of good hand touch.
Claims (3)
1, a kind of method for preparing modified anionic water type polyurethane resin used as imitated 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, then with ring-type anhydrous carboxylic acid anhydride reactant, make aqueous polyurethane, it is characterized in that the aqueous polyurethane that will make neutralizes with alkali, directly and the blend of anionic polychloroprene latex, make modified anionic water type polyurethane resin used as imitated leather, in the composition of its blend, two components can any ratio carry out blend.
2, method for preparing modified anionic water type polyurethane resin used as imitated leather according to claim 1, it is characterized in that in the composition of its blend anion-type water-thinned polyurethane and anionic polychloroprene latex blending ratio are preferably 30-70%: 70-30% (effective ingredient weight percent).
3, method for preparing modified anionic water type polyurethane resin used as imitated leather according to claim 1 is characterized in that the aqueous polyurethane that will make makes pH value reach 7.5～10 with the alkali neutralization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98111215A CN1058036C (en) | 1998-04-01 | 1998-04-01 | Method for preparing modified anionic water type polyurethane resin used as imitated leather |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98111215A CN1058036C (en) | 1998-04-01 | 1998-04-01 | Method for preparing modified anionic water type polyurethane resin used as imitated leather |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1192448A CN1192448A (en) | 1998-09-09 |
| CN1058036C true CN1058036C (en) | 2000-11-01 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98111215A Expired - Fee Related CN1058036C (en) | 1998-04-01 | 1998-04-01 | Method for preparing modified anionic water type polyurethane resin used as imitated leather |
Country Status (1)
| Country | Link |
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| CN (1) | CN1058036C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103061159A (en) * | 2013-01-14 | 2013-04-24 | 合肥市科天化工有限公司 | Preparation method of aqueous thermal-sensitive synthetic leather bass |
| CN114150509B (en) * | 2021-11-19 | 2024-08-13 | 合肥科天水性科技有限责任公司 | Preparation method of neoprene superfine fiber synthetic leather |
| CN116240737B (en) * | 2023-01-03 | 2025-07-15 | 万华化学集团股份有限公司 | A kind of water-based semi-PU leather and preparation method thereof |
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 |
-
1998
- 1998-04-01 CN CN98111215A patent/CN1058036C/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 |
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| Publication number | Publication date |
|---|---|
| CN1192448A (en) | 1998-09-09 |
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