CN101580577B - Modified waterborne polyurethane resin for artificial leather and preparation method thereof - Google Patents
Modified waterborne polyurethane resin for artificial leather and preparation method thereof Download PDFInfo
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- CN101580577B CN101580577B CN2009100995288A CN200910099528A CN101580577B CN 101580577 B CN101580577 B CN 101580577B CN 2009100995288 A CN2009100995288 A CN 2009100995288A CN 200910099528 A CN200910099528 A CN 200910099528A CN 101580577 B CN101580577 B CN 101580577B
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Abstract
The invention relates to a modified waterborne polyurethane resin for artificial leather and a preparation method thereof. The modified waterborne polyurethane resin comprises formulation: the combination of any two in 6% of polyether polyol N210 with the molecular weight of 1000, 9-14% of polyether polyol N220 with the molecular weight of 2000 or 6% of polyether polyol N240 with the molecular weight of 4000; 6.5-9% of toluene di-isocyanate (TDI), 1.5-1.8% of dimethylol propionic acid, 2-4% of hydroxyl saturated polyester resin, 0.0-1% of dibutyl tin laurate, 0.8-1.5% of diethylene glycol, 0.9-1.3% of triethylamine, 0.4-0.5% of isophorone diamine, 0.5-2% of hydroxyl polyether modified siloxane with the hydroxyl value of 56 and the rest of water. The invention has the advantages of high tensile strength, good elasticity, strong adhesive force, excellent water resistance, solvent resistance and chemical resistance, better leather feeling, high cold resistance and folding strength, good combination property and remarkable environmental protection.
Description
Technical field
The present invention relates to use for synthetic leather modified aqueous polyurethane resin and preparation method thereof, a kind of aqueous polyurethane that is used for leatheroid and preparation method thereof of more specifically saying so.
Background technology
Present national use for synthetic leather urethane resin all is the solvent type polyurethane resin of solvent.The use of these solvents can cause various harm, as the potential safety hazard of operator's health, environmental pollution, storage transportation.The volatilization of solvent and recovery also can cause the waste of the resource and the energy, also do not meet the industry policy of national energy-saving and emission-reduction.Along with expanding economy and global integration environmental protection and energy problem also cause the attention of each country.It is trend of the times that development and use waterborne polyurethane resin substitute present solvent type resin.
Process hides developed countries such as Japan, Germany, Italy have brought into use waterborne polyurethane resin replace solvents type polyurethane resin artificial synthetic at present.China is because the relatively slower waterborne polyurethane resin of non-modified at present of water-based polyurethane exploitation can't be used for leather industry.At present existing many modified waterborne polyurethane rosin productss are as patent No. CN101348554, CN1884335, CN1854165, CN1772786, CN1611522 or the like.Although these waterborne polyurethane resins use raw materials and production technique are different, product can only be used for coating and tackiness agent, can not work as macromolecular resin and be used for synthetic leather; Can not satisfy the physical index of synthetic leather.
Summary of the invention
The objective of the invention is in order to overcome above-mentioned deficiency, and provide that a kind of production technique is simple, raw material is simple and easy to purchase, cost is low, effective is used for aqueous polyurethane of leatheroid and preparation method thereof, replacing existing leather solvent type polyurethane resin slurry, the product tensile strength is big, good springiness, strong, water-fast, the anti-solvent of adhesive power, chemical resistance is good, kishke feel is strong, the folding strength height resists cold.Product of the present invention has the excellent comprehensive performances and the outstanding feature of environmental protection, and the manufacturing and the film that can be used for all kinds of leatheroids shift.
The present invention solves the technical scheme that its technical problem adopts: this modified aqueous polyurethane resin that is used for leatheroid, prescription are that polyether glycol N210 molecular weight 1000 is 6%, polyether glycol N220 molecular weight 2000 be 9～14% or polyether glycol N240 molecular weight 4000 be any two kinds of combinations in 6%; Tolylene diisocyanate TDI is 6.5～9%, dimethylol propionic acid is 1.5～1.8%, the hydroxyl saturated polyester resin is 2～4%, dibutyl tin laurate is 0.01%, Diethylene Glycol is 0.8～1.5%, triethylamine is 0.9～1.3%, isophorone diamine be 0.4～0.5% and hydroxy polyethers modified siloxane hydroxyl value 56 be 0.5～2%, all the other are water (deionized water), need to prove that per-cent of the present invention is mass percent.
As preferably, concrete prescription is that polyether glycol N210 molecular weight 1000 is 6%, polyether glycol N220 molecular weight 2000 is 11%, tolylene diisocyanate TDI is 8.5%, dimethylol propionic acid is 1.6%, the hydroxyl saturated polyester resin is 3%, dibutyl tin laurate is 0.01%, Diethylene Glycol is 1.1%, triethylamine is 1.2%, isophorone diamine be 0.5% and hydroxy polyethers modified siloxane hydroxyl value 56 be 1.5%, all the other are water.
As preferably, concrete prescription is: polyether glycol N220 molecular weight 2000 is 12%, polyether glycol N240 molecular weight 4000 is 6%, tolylene diisocyanate TDI is 6.9%, dimethylol propionic acid is 1.4%, the hydroxyl saturated polyester resin is 2.9%, dibutyl tin laurate is 0.01%, Diethylene Glycol is 0.9%, triethylamine is 1%, isophorone diamine be 0.4% and hydroxy polyethers modified siloxane hydroxyl value 56 be 1.8%, all the other are water.
As preferably, concrete prescription is: polyether glycol N210 molecular weight 1000 is 6%, polyether glycol N220 molecular weight 2000 is 12%, tolylene diisocyanate TDI is 6.5%, dimethylol propionic acid is 1.5%, the hydroxyl saturated polyester resin is 2%, dibutyl tin laurate is 0.01%, Diethylene Glycol is 1.3%, triethylamine is 0.9%, isophorone diamine is 0.4% and hydroxy polyethers modified siloxane hydroxyl value 56 is 1%, all the other are water.
As preferably, concrete prescription is: polyether glycol N210 molecular weight 1000 is 6%, polyether glycol N220 molecular weight 2000 is 14%, tolylene diisocyanate TDI is 9%, dimethylol propionic acid is 1.7%, the hydroxyl saturated polyester resin is 4%, dibutyl tin laurate is 0.01%, Diethylene Glycol is 1.2%, triethylamine is 1.3%, isophorone diamine be 0.5% and hydroxy polyethers modified siloxane hydroxyl value 56 be 0.5%, all the other are water.
The preparation method who is used for the modified aqueous polyurethane resin of leatheroid of the present invention comprises the steps: that elder generation with 120 ℃ of dehydrations of polyether glycol, is cooled to 60 ℃ and adds 85～95 ℃ of pre-polymerizations of toluene diisocyanate 3 hours; Add 75～80 ℃ of reactions of dimethylol propionic acid and hydroxyl saturated polyester resin, dibutyl tin laurate again and carried out chain extending reaction in 2 hours; Add Diethylene Glycol, 3. hours capable chain extensions of 75～80 ℃ of reactions of hydroxy polyethers modified siloxane again; Be cooled to add below 40 ℃ the triethylamine neutralization, add deionized water after 10 minutes and disperse to carry out in 15 minutes emulsification for 2200 rev/mins; Add the leather use urethane resin that the isophorone diamine chain extension disperses promptly to get in 30 minutes solid content 30～40% again.
The mechanism of action of the present invention is:
1, utilize the polyethers flexibility to solve the softness and the feel of resin.
2, aromatic polyisocyanate (tolylene diisocyanate TDI, 4,4 diphenylmethanediisocyanate MDI) is the host of addition reaction.
3, dimethylol propionic acid is done hydrophilic chain extender and is solved water-soluble problem.
4, dibutyl tin laurate is made catalyzer.
5, the poly-hydroxy of hydroxyl saturated polyester resin is done sticking power and gentle bearing property and the physical strength that chain extension and linking agent improve resin, and with saturated polyester resin good luster, good characteristic that sticking power is high.
6, the alkalescence of triethylamine is made neutralizing agent.
7, deionized water is made the environment-friendly type solvent.
8, can refuse water at surface enrichment because hydroxyl changes the silicon of polyether silicone, and have flexibility and the thick feel of smooth silk concurrently, solve resin hydrolysis and soft smooth silk-like handle.
9, isophorone diamine utilizes amine to make chainextender in the water than the slow principle of other diamine reaction soon than water and isocyano reaction, solves to react the too fast difficult intensity of controlling and increasing urine key solution resin.
This shows that waterborne polyurethane resin of the present invention is to do molecular chain host with polyether glycol and polyisocyanates to solve snappiness and feel, dimethylol propionic acid and do hydrophilic chain extender and solve water-soluble increase molecular weight, the hydroxyl saturated polyester resin is made chain extension, crosslinked chainextender solves sticking power and improves physical strength and the raising molecular weight, hydroxyl changes polyether silicone and further improves molecular weight and solve hydrolysis, and special feel problem isophorone diamine is done, and chainextender advances a raising molecular weight and increases the physical strength that molecule urine key solves resin in the water.
The invention has the advantages that:
1, good hand touch after the product process hides of the present invention, cost low, and can make the PU finished product leather of various styles.
2, product of the present invention can be used for present tanning production line equipment and need not this make, and leather-making technology need not to change substantially.
3, product processes of the present invention, preparation process are simple, and envrionment conditions is not had particular requirement.
Embodiment
Below in conjunction with embodiment the present invention is further described, but should understand these embodiment limits the scope of the invention, under the situation of the spirit and scope of the present invention, those skilled in the art can make changes and improvements so that it is fit to different service conditions, condition and embodiment to the present invention.
Implementation column 1: polyether glycol N210 (6%) N220 (11%), tolylene diisocyanate TDI (8%), dimethylol propionic acid (1.6%), hydroxyl saturated polyester resin (3%), dibutyl tin laurate (0.01%), Diethylene Glycol (1.1%), triethylamine (1.2%), isophorone diamine (0.5%), hydroxy polyethers modified siloxane hydroxyl value 56 (1.5%), surplus are water.
This example formulations can be used for the manufacturing of luggage leather, footwear leather and half PU leather.
Implementation column 2: polyether glycol N220 (12%) N240 (6%), tolylene diisocyanate TDI (6.9%), dihydroxy first saturated polyester resin (1.4%), hydroxyl saturated polyester resin (2.9%), dibutyl tin laurate (0.1%), Diethylene Glycol (0.9%), triethylamine (1%), isophorone diamine (0.4%), hydroxy polyethers modified siloxane hydroxyl value 56 (1.8%), surplus are water.
This example formulations can be used for the manufacturing of clothing leather, soft luggage leather and half PU leather.
Implementation column 3: polyether glycol N210 (6%) N220 (12%), tolylene diisocyanate TDI (6.5%), dimethylol propionic acid (1.5%), hydroxyl saturated polyester resin (2%), dibutyl tin laurate (0.01%), Diethylene Glycol (1.3%), triethylamine (0.9%), isophorone diamine (0.4%), hydroxy polyethers modified siloxane hydroxyl value 56 (1%), surplus are water.
The adhesive linkage of especially suitable PU of this implementation column and PVC leather.
Implementation column 4: polyether glycol N210 (6%) N220 (14%), tolylene diisocyanate TDI (9%), dimethylol propionic acid (1.7%), hydroxyl saturated polyester resin (4%), dibutyl tin laurate (0.01%), Diethylene Glycol (1.2%), triethylamine (1.3%), isophorone diamine (0.5%), hydroxy polyethers modified siloxane hydroxyl value 56 (.0.5%), surplus are water.
Changing colour and directly being coated with embossing of the especially suitable PU leather of this implementation column handled.
Specific implementation method is: earlier with 120 ℃ of dehydrations of polyether glycol, be cooled to 60 ℃ and add 85～95 ℃ of pre-polymerizations of polyisocyanates 3 hours; Adding dimethylol propionic acid and Hydroxylated acrylic resin, 75～80 ℃ of reactions of dibutyl tin laurate 2 hours; Add 75～80 ℃ of reactions of Diethylene Glycol hydroxy polyethers modified siloxane 3 hours again; Be cooled to add below 40 ℃ in the triethylamine and add deionized water after 10 minutes and disperseed 15 minutes for 2200 rev/mins; Add the leather modified aqueous polyurethane resin that the isophorone diamine chain extension disperses 25 minutes solid contents 30～40% both again.
Using method:
1, gets that product of the present invention adds the waterborne organic silicon flow agent, urethane association type ropiness increasing agent is transferred to suitable viscosity, adding aqueous color paste stirs evenly, be applied on the separate-type paper 130 ℃ then and dry by the fire half-dried commentaries on classics card and dry on bass and get final product, using method is the same with usual vehicle dry method resin.
2, get that product of the present invention adds the waterborne organic silicon flow agent, urethane association type ropiness increasing agent is transferred to suitable viscosity, add mill base and stir evenly, be applied to directly that oven dry gets final product on bass or the base cloth.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.
Claims (5)
1. preparation method who is used for the modified aqueous polyurethane resin of leatheroid is characterized in that: prescription is that polyether glycol N210 molecular weight 1000 is 6%, polyether glycol N220 molecular weight 2000 be 9～14% or polyether glycol N240 molecular weight 4000 be any two kinds of combinations in 6%; Tolylene diisocyanate TDI is 6.5～9%, dimethylol propionic acid is 1.5～1.8%, the hydroxyl saturated polyester resin is 2～4%, dibutyl tin laurate is 0.01%, Diethylene Glycol is 0.8～1.5%, triethylamine is 0.9～1.3%, isophorone diamine be 0.4～0.5% and hydroxy polyethers modified siloxane hydroxyl value 56 be 0.5～2%, all the other are water;
The preparation method comprises the steps: that elder generation with 120 ℃ of dehydrations of polyether glycol, is cooled to 60 ℃ and adds 85～95 ℃ of pre-polymerizations of toluene diisocyanate 3 hours; Add dimethylol propionic acid and hydroxyl saturated polyester resin, 75～80 ℃ of reactions of dibutyl tin laurate 2 hours again; Add Diethylene Glycol, 75～80 ℃ of reactions of hydroxy polyethers modified siloxane 3 hours again; Be cooled to add below 40 ℃ the triethylamine neutralization, add deionized water after 10 minutes and disperseed 15 minutes for 2200 rev/mins; Add the leather use urethane resin that the isophorone diamine chain extension disperses promptly to get in 30 minutes solid content 30～40% again.
2. the preparation method who is used for the modified aqueous polyurethane resin of leatheroid according to claim 1, it is characterized in that: concrete prescription is that polyether glycol N210 molecular weight 1000 is 6%, polyether glycol N220 molecular weight 2000 is 11%, tolylene diisocyanate TDI is 8.5%, dimethylol propionic acid is 1.6%, the hydroxyl saturated polyester resin is 3%, dibutyl tin laurate is 0.01%, Diethylene Glycol is 1.1%, triethylamine is 1.2%, isophorone diamine be 0.5% and hydroxy polyethers modified siloxane hydroxyl value 56 be 1.5%, all the other are water.
3. the preparation method who is used for the modified aqueous polyurethane resin of leatheroid according to claim 1, it is characterized in that: concrete prescription is: polyether glycol N220 molecular weight 2000 is 12%, polyether glycol N240 molecular weight 4000 is 6%, tolylene diisocyanate TDI is 6.9%, dimethylol propionic acid is 1.4%, the hydroxyl saturated polyester resin is 2.9%, dibutyl tin laurate is 0.01%, Diethylene Glycol is 0.9%, triethylamine is 1%, isophorone diamine be 0.4% and hydroxy polyethers modified siloxane hydroxyl value 56 be 1.8%, all the other are water.
4. the preparation method who is used for the modified aqueous polyurethane resin of leatheroid according to claim 1 is characterized in that: concrete prescription is: polyether glycol N210 molecular weight 1000 is 6%, polyether glycol N220 molecular weight 2000 is 12%, tolylene diisocyanate TDI is 6.5%, dimethylol propionic acid is 1.5%, the hydroxyl saturated polyester resin is 2%, dibutyl tin laurate is 0.01%, Diethylene Glycol is 1.3%, triethylamine is 0.9%, isophorone diamine is 0.4% and hydroxy polyethers modified siloxane hydroxyl value 56 is 1%, all the other are water.
5. the preparation method who is used for the modified aqueous polyurethane resin of leatheroid according to claim 1, it is characterized in that: concrete prescription is: polyether glycol N210 molecular weight 1000 is 6%, polyether glycol N220 molecular weight 2000 is 14%, tolylene diisocyanate TDI is 9%, dimethylol propionic acid is 1.7%, the hydroxyl saturated polyester resin is 4%, dibutyl tin laurate is 0.01%, Diethylene Glycol is 1.2%, triethylamine is 1.3%, isophorone diamine be 0.5% and hydroxy polyethers modified siloxane hydroxyl value 56 be 0.5%, all the other are water.
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| CN2009100995288A CN101580577B (en) | 2009-06-18 | 2009-06-18 | Modified waterborne polyurethane resin for artificial leather and preparation method thereof |
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| CN2009100995288A CN101580577B (en) | 2009-06-18 | 2009-06-18 | Modified waterborne polyurethane resin for artificial leather and preparation method thereof |
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| CN101580577B true CN101580577B (en) | 2011-05-18 |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798454A (en) * | 2010-04-06 | 2010-08-11 | 建德市顺发化工助剂有限公司 | Modified waterborne polyurethane for artificial synthetic leather and coatings, and preparation method thereof |
| CN102382278B (en) * | 2011-08-29 | 2013-08-28 | 旭川化学（苏州）有限公司 | Waterborne polyurethane resin and preparation method and application thereof |
| CN105330813B (en) * | 2015-11-03 | 2017-10-20 | 淮安凯悦科技开发有限公司 | A kind of synthetic method of process hides organic silicon modified aqueous polyurethane |
| CN105385148B (en) * | 2015-12-04 | 2018-08-28 | 浙江华峰合成树脂有限公司 | Sulfonated graphene modified aqueous polyurethane resin and preparation method |
| KR102264801B1 (en) * | 2016-04-28 | 2021-06-11 | 아라까와 가가꾸 고교 가부시끼가이샤 | Thermosetting release coating agent, release film and method for producing the release film |
| KR102430050B1 (en) * | 2017-09-19 | 2022-08-05 | 디아이씨 가부시끼가이샤 | Synthetic Leather |
| CN109575220B (en) * | 2017-09-29 | 2021-05-25 | 天津大学 | Quick-rebound aqueous polyurethane urea elastomer and preparation method thereof |
| CN110028776A (en) * | 2019-04-23 | 2019-07-19 | 福建宝利特科技股份有限公司 | A kind of antifouling solvent-free artificial leather |
| CN110934380B (en) * | 2019-11-12 | 2021-09-03 | 浙江老鞋匠鞋业有限公司 | Production process of dampness-clearing antibacterial foot-strengthening balance insole |
| CN111334028B (en) * | 2020-04-26 | 2021-09-28 | 常州邦瑞新材料科技有限公司 | Anti-ultraviolet high-thermal-conductivity modified polyurethane composite film material and preparation method thereof |
| CN111732708B (en) * | 2020-06-04 | 2022-04-12 | 旭川化学（苏州）有限公司 | Soft high-resilience aqueous polyurethane resin and preparation method and application thereof |
| CN113152110A (en) * | 2021-05-18 | 2021-07-23 | 广东欧美斯家具有限公司 | Environment-friendly polyurethane synthetic leather for sofa furniture and preparation method thereof |
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