CN101585968B - Cationic wax emulsion for leather manufacturing procedure and manufacturing method - Google Patents
Cationic wax emulsion for leather manufacturing procedure and manufacturing method Download PDFInfo
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Abstract
The invention provides a cationic wax emulsion for leather manufacturing procedure and manufacturing method thereof. The wax emulsion is prepared by using wax, simethicone, cetanol as oily materials,via dispersing emulsification of two lipophilic emulsifier compound systems of fatty alcohol polyoxyethylene (3) ether and Span 60, and two lipophilic emulsifier compound systems of fatty alcohol polyoxyethylene (25) ether and Tween 60, stearic acid and hexaalkyl trimethyl ammonium chloride cationic surface active agent, then via dispersing emulsification of de-ionized water and reducing temperature. The invention is good in stability, excellent in emulsification, obvious in performance characteristics, which enhances wet and flexibility of leather; when the invention is to improve leather touch feel, addition of 0.8% to 1.5% of materials according weight percentage may bestow rich touch feel of leather.
Description
Technical field
The invention belongs to the leather chemical industry technical field, particularly relate to cationic wax emulsion of a kind of used in leather processing procedure and preparation method thereof.
Background technology
Oil-in-water type wax is covering with paint auxiliary agent commonly used in the leather processing procedure, and this series products generally is to adopt suitable emulsifying agent, under certain conditions wax emulsification is formed.According to the type of used emulsifying agent, the wax emulsion often is divided into anionic, non-ionic type, cationic and amphoteric ion type four classes.Owing to show electronegativity usually without the skin base surface of covering with paint, lacquer, colour wash, etc., cationic wax emulsion can be followed the leather surface combination quickly and be formed thin film in covering with paint, lacquer, colour wash, etc. processing, preventing effectively that coating and decorating material from too much permeating influences leather hand feeling, makes leather embody performances such as coat fastness is good, the elegant softness of feel.Based on above advantage, cationic wax emulsion is subjected to investigator and user's favor in recent years more and more, and is existing for many years to its research and development abroad, and formed tandem product numerous in variety, excellent performance.Domestic just at the early-stage to the exploitation of wax emulsion especially Study of Cationic Wax in Emulsion, existing range of product is few, and has shortcomings such as easy layering, the water and milk voltinism is bad, performance characteristics is not outstanding more.In addition, limit the use of APEO (alkylphenol polyoxyethylene class emulsifying agent, OP-10 belongs to the APEO series products), more force traditional cationic wax emulsion product to be eliminated in view of European Union puts into effect decree in recent years.Therefore, exploitation is when using in leather processing procedure, stability is higher, the water and milk voltinism is better, performance characteristics is outstanding and environmental protection oil-in-water type cationic wax emulsion product have great importance.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming and defect that prior art exists, first purpose of the present invention provides a kind of good stability, the water and milk voltinism is good, performance characteristics outstanding and environmental protection used in leather processing procedure cationic wax emulsion.
Second purpose of the present invention provides a kind of preparation method of cationic wax emulsion of used in leather processing procedure.
For realizing first purpose of the present invention, technical scheme of the present invention is, contain the oiliness material, the lipophilic emulsifier compound system, the hydrophilic emulsifier compound system, 1631 cats products, described oiliness material includes carnauba wax, OP wax, dimethyl silicone oil, hexadecanol, described lipophilic emulsifier compound system includes aliphatic alcohol polyethenoxy (3) ether and sorbitan monooleate, described hydrophilic emulsifier compound system includes aliphatic alcohol polyethenoxy (25) ether and polyoxyethylene 20 sorbitan monooleate, and the proportioning of each component is as follows:
(1), oiliness material:
It is 85%～95% that carnauba wax accounts for oiliness quality of material per-cent;
It is 5%～15% that OP wax accounts for oiliness quality of material per-cent;
It is 0.5%～5% that dimethyl silicone oil accounts for oiliness quality of material per-cent;
It is 2%～12% that hexadecanol accounts for oiliness quality of material per-cent;
(2), the emulsifying agent material includes lipophilic emulsifier compound system and hydrophilic emulsifier compound system, it is 20%-45% that its total mass accounts for oiliness quality of material per-cent, wherein
1., lipophilic emulsifier compound system: by aliphatic alcohol polyethenoxy (3) ether with sorbitan monooleate is composite forms, it is 20%～45% that its total amount accounts for emulsifying agent quality of material per-cent, in this lipophilic emulsifier compound system, the shared mass percent of aliphatic alcohol polyethenoxy (3) ether is 20%～40%, and the shared mass percent of sorbitan monooleate is 60%～80%;
2., hydrophilic emulsifier compound system: aliphatic alcohol polyethenoxy (25) ether and polyoxyethylene 20 sorbitan monooleate is composite forms, it is 55%～80% that its total amount accounts for emulsifying agent quality of material per-cent, the shared mass percent of aliphatic alcohol polyethenoxy (25) ether is 5%～25% in this hydrophilic emulsifier compound system, and the shared mass percent of polyoxyethylene 20 sorbitan monooleate is 75%～95%;
(3), to account for oiliness quality of material per-cent be 0.5%～10% to 1631 cats products;
All the other are water, and described cationic wax emulsion is according to the requirement of use properties, and solid content can be regulated between 8.0～22%.
Further being provided with is also to include stearic acid, and it is 0%～10% that its addition accounts for oiliness quality of material per-cent.
Further being provided with is that described cats product is the palmityl trimethyl ammonium chloride cats product.
Further being provided with is that the described carnauba wax trade mark is 3#, and fusing point is 82～83 ℃, acid number 9.3～9.6mg KOH/g, saponification value 86.0～87.8mg KOH/g.
Further being provided with is that described OP wax outward appearance is a white particle, density 0.95～0.96g/cm
3, acid number 20～24mg KOH/g.
For realizing second purpose of the present invention, technical scheme of the present invention is may further comprise the steps:
(1), each raw material described in the claim 1 is mixed by each the material rate value thawing described in the claim 1, in proportion oiliness material, aliphatic alcohol polyethenoxy (3) ether, sorbitan monooleate are mixed and be heated to 100-130 ℃ and stir 30min at least, add aliphatic alcohol polyethenoxy (25) ether, polyoxyethylene 20 sorbitan monooleate and 1631 cationic emulsifiers more in proportion and keep 100-130 ℃ to stir 50min at least, mix;
(2) water filling emulsification deionized water more than 80 ℃ is divided into 4～5 equivalent adds, and 30min is at least stirred in emulsification after adding deionized water each time;
(3) cooling emulsification obtains finished product, is cooled to below 35 ℃, and the stirring velocity that slows down continues emulsification and stirs 30min at least, makes the cationic wax emulsion finished product of used in leather processing procedure.
Further be provided with is to be added into also in the described step (1) that to account for oiliness quality of material per-cent be that 0%～10% stearic acid is with the heating and melting mixing in proportion of oiliness material, aliphatic alcohol polyethenoxy (3) ether, sorbitan monooleate.
When the present invention prepares cationic wax emulsion, performance requriements according to desired product is introduced a small amount of dimethyl silicone oil in the oiliness material, the introducing of dimethyl silicone oil can make cationic wax emulsion reduce foam in emulsion process, dimethyl silicone oil consumption too conference brings certain degree of difficulty to emulsification, therefore dimethyl silicone oil shared mass percent in the oiliness material is 0.5%～5%, be preferably 1%～2.5%, and the kinematic viscosity selected of dimethyl silicone oil (25 ℃ is 350 ± 18 mm4/s).
When the present invention prepares cationic wax emulsion, in the oiliness material, introduce a small amount of hexadecanol and stearic acid according to the performance requriements of desired product.The introducing of hexadecanol can make the cationic wax emulsion package stability increase, and its shared oiliness quality of material per-cent is 2%～12%, is preferably 3%～8%; Stearic introducing can make the cationic wax emulsion color shoal, easier of water-dispersion in leather processing procedure, since stearic acid in water after the ionization institute electrically charged opposite with cationic emulsifier, consumption too much can cause the cationic wax emulsion stability decreases, therefore to account for oiliness quality of material per-cent be 0%～10% to stearic acid, is preferably 0.1%～3%.
When the present invention prepares cationic wax emulsion, all adopt two kinds of dissimilar emulsifying agents to form the compound emulsifying agent system to lipophilic emulsifier system and hydrophilic emulsifier system, this method helps to improve emulsifying effectiveness, makes the higher cationic wax emulsion of stability;
When the present invention prepares cationic wax emulsion,, require the temperature of deionized water not to be lower than 80 ℃, make emulsifying effectiveness better when emulsification system adds deionized water;
When the present invention prepares cationic wax emulsion, emulsification (stirring) time outbalance, especially after in the oiliness material, adding lipophilicity compound emulsifying agent and wetting ability compound emulsifying agent, all need certain emulsification (stirring) time, but oversize meeting of time increases energy consumption and reduces production efficiency, take all factors into consideration, all need emulsification (stirring) emulsification (stirring) 30～90min after adding lipophilicity compound emulsifying agent and wetting ability compound emulsifying agent, be preferably 40～70min; After the oiliness material is by lipophilicity compound emulsifying agent and hydrophilic emulsifier emulsification, add emulsifying water (stirring) the dispersive time again can lack slightly, emulsification (stirring) 50～90min can obtain good effect, is preferably 50～80min;
When the present invention prepared cationic wax emulsion, stirring velocity was not a key factor, but unsuitable too fast, requirement can evenly get final product the material dispersed with stirring.Behind emulsification post drop to 35 ℃, stirring velocity must reduce, otherwise, have more foam in the product, influence its outward appearance even performance;
The cationic wax emulsion that provides and prepare used in leather processing procedure of the present invention, outward appearance are the milk sap of milky white band blue light, and working substance content is 12.0%～18.0%, pH value (10% water miscible liquid) is 6.0～8.0, room temperature deposit 6 months not stratified, do not have precipitation, emulsifying water is easy.
The invention provides and prepare the cationic wax emulsion of used in leather processing procedure, have satisfactory stability, very easily emulsification, good dispersity.Electrolyte-resistant, anti-hard water, acid and alkali-resistance ability are strong, and the pH value scope that is suitable for is wide; When being used for the covering with paint of leather bottom, can comparatively fast combine and form thin film, prevent that material from too much permeating, play the back cover effect with leather surface; When being used to cover with paint, lacquer, colour wash, etc. back cover, add 5.0%～8.0% of the material total amount of preparing by mass percentage, can realize effective back cover, and bonding firm; Also can be used for moisture regain in the leather in addition, its consumption adds 0.8%～1.0% of the material total amount of preparing by mass percentage, can make leather increase wetness sensation and pliability; When being used to improve leather hand feeling, add 0.8%～1.5% of the material total amount of preparing by mass percentage, can give the feel that leather moistens.
Cationic wax emulsion of the present invention does not contain the APEO (polyoxyethylene nonylphenol ether and polyoxyethylene octylphenol ether) that European Union limits the use of, and the production process three-waste free discharge belongs to the clearer production technology category.
Below in conjunction with embodiment of the present invention group is further introduced.
Embodiment
Below provide the embodiment that the present invention specifically prepares the used in leather processing procedure cationic wax emulsion, only the present invention will be further described for its process parameter.
Embodiment 1
In the there-necked flask that agitator, prolong are housed, add 18.0g carnauba wax, 2.0gOP wax, 0.2g dimethyl silicone oil, 2.0g hexadecanol and 0.2g stearic acid, open and stir and open water of condensation, add 2.0g aliphatic alcohol polyethenoxy (3) ether and 60 two kinds of hydrophilic emulsifiers of 4.4g Span, be warming up to 105 ℃ and pick up counting, at 105 ℃ of following emulsifications (stirring) 30min.Add 1.2g aliphatic alcohol polyethenoxy (25) ether and 60 two kinds of hydrophilic emulsifiers of 9.0gTween and 0.2g1631 cationic emulsifier, at 105 ℃ of following emulsifications (stirring) 45min, then deionized water more than 80 ℃ is divided into 5 addings, each deionized water quality that adds is 59.0g, behind deionized water of every adding at 105 ℃ of following emulsifications (stirring) 15min, be cooled to then below 35 ℃, continue emulsification (stirring) 30min, obtain the cationic wax emulsion finished product, outward appearance is the milk sap of milky white band blue light, working substance content＞10.0%.
Embodiment 2
In the there-necked flask that agitator, prolong are housed, add 36.0g carnauba wax, 4.0gOP wax, 0.4g dimethyl silicone oil, 4.0g hexadecanol and 0.5g stearic acid, open and stir and open water of condensation, add 3.2g aliphatic alcohol polyethenoxy (3) ether and 60 two kinds of hydrophilic emulsifiers of 7.2g Span, be warming up to 115 ℃ and pick up counting, at 115 ℃ of following emulsifications (stirring) 45min.Add 0.8g aliphatic alcohol polyethenoxy (25) ether and 60 two kinds of hydrophilic emulsifiers of 24gTween and 1.6g1631 cationic emulsifier, at 115 ℃ of following emulsifications (stirring) 45min, then deionized water more than 80 ℃ is divided into 5 addings, each deionized water quality that adds is 115.0g, behind deionized water of every adding at 115 ℃ of following emulsifications (stirring) 15min, be cooled to then below 35 ℃, continue emulsification (stirring) 30min, obtain the cationic wax emulsion finished product, outward appearance is the milk sap of milky white band blue light, working substance content＞12.0%.
Embodiment 3
In the there-necked flask that agitator, prolong are housed, add 27.0g carnauba wax, 3.0gOP wax, 0.3g dimethyl silicone oil, 2.4g hexadecanol and 0.3g stearic acid, open and stir and open water of condensation, add 2.1g aliphatic alcohol polyethenoxy (3) ether and 60 two kinds of hydrophilic emulsifiers of 7.2g Span, be warming up to 110 ℃ and pick up counting, at 110 ℃ of following emulsifications (stirring) 30min.Add 1.8g aliphatic alcohol polyethenoxy (25) ether and 60 two kinds of hydrophilic emulsifiers of 12gTween and 1.5g1631 cationic emulsifier, at 110 ℃ of following emulsifications (stirring) 30min, then deionized water more than 80 ℃ is divided into 5 addings, each deionized water quality that adds is 85.0g, behind deionized water of every adding at 110 ℃ of following emulsifications (stirring) 30min, be cooled to then below 35 ℃, continue emulsification (stirring) 30min, obtain the cationic wax emulsion finished product, outward appearance is the milk sap of milky white band blue light, working substance content＞12.0%.
Embodiment 4
In the there-necked flask that agitator, prolong are housed, add 18.0g carnauba wax, 2.0gOP wax, 0.25g dimethyl silicone oil, 1.2g hexadecanol and 0.15g stearic acid, open and stir and open water of condensation, add 1.6g aliphatic alcohol polyethenoxy (3) ether and 60 two kinds of hydrophilic emulsifiers of 4.8g Span, be warming up to 120 ℃ and pick up counting, at 120 ℃ of following emulsifications (stirring) 30min.Add 0.8g aliphatic alcohol polyethenoxy (25) ether and 60 two kinds of hydrophilic emulsifiers of 11.0gTween and 0.2g1631 cationic emulsifier, at 120 ℃ of following emulsifications (stirring) 30min, then deionized water more than 80 ℃ is divided into 5 addings, each deionized water quality that adds is 45.0g, behind deionized water of every adding at 120 ℃ of following emulsifications (stirring) 15min, be cooled to then below 35 ℃, continue emulsification (stirring) 30min, obtain the cationic wax emulsion finished product, outward appearance is the milk sap of milky white band blue light, working substance content＞16.0%.
Embodiment 5
In the there-necked flask that agitator, prolong are housed, add 54.0g carnauba wax, 6.0gOP wax, 0.5g dimethyl silicone oil, 2.4g hexadecanol and 0.9g stearic acid, open and stir and open water of condensation, add 6.0g aliphatic alcohol polyethenoxy (3) ether and 60 two kinds of hydrophilic emulsifiers of 9.6g Span, be warming up to 118 ℃ and pick up counting, at 118 ℃ of following emulsifications (stirring) 30min.Add 2.4g aliphatic alcohol polyethenoxy (25) ether and 60 two kinds of hydrophilic emulsifiers of 30.0gTween and 2.4g1631 cationic emulsifier, at 118 ℃ of following emulsifications (stirring) 30min, then deionized water more than 80 ℃ is divided into 5 addings, each deionized water quality that adds is 120.0g, behind deionized water of every adding at 118 ℃ of following emulsifications (stirring) 30min, be cooled to then below 35 ℃, continue emulsification (stirring) 30min, obtain the cationic wax emulsion finished product, outward appearance is the milk sap of milky white band blue light, working substance content＞18.0%.
Claims (7)
1. the cationic wax emulsion of a used in leather processing procedure, it is characterized in that: contain the oiliness material, the lipophilic emulsifier compound system, the hydrophilic emulsifier compound system, 1631 cats products, described oiliness material includes carnauba wax, OP wax, dimethyl silicone oil, hexadecanol, described lipophilic emulsifier compound system includes aliphatic alcohol polyethenoxy (3) ether and sorbitan monooleate, described hydrophilic emulsifier compound system includes aliphatic alcohol polyethenoxy (25) ether and polyoxyethylene 20 sorbitan monooleate, and the proportioning of each component is as follows:
(1), oiliness material:
It is 85%～95% that carnauba wax accounts for oiliness quality of material per-cent;
It is 5%～15% that OP wax accounts for oiliness quality of material per-cent;
It is 0.5%～5% that dimethyl silicone oil accounts for oiliness quality of material per-cent;
It is 2%～12% that hexadecanol accounts for oiliness quality of material per-cent;
The mass percent summation of all components is 100% in the above-mentioned oiliness material;
(2), the emulsifying agent material includes lipophilic emulsifier compound system and hydrophilic emulsifier compound system, it is 20%-45% that its total mass accounts for oiliness quality of material per-cent, wherein
1., lipophilic emulsifier compound system: by aliphatic alcohol polyethenoxy (3) ether with sorbitan monooleate is composite forms, it is 20%～45% that its total amount accounts for emulsifying agent quality of material per-cent, in this lipophilic emulsifier compound system, the shared mass percent of aliphatic alcohol polyethenoxy (3) ether is 20%～40%, and the shared mass percent of sorbitan monooleate is 60%～80%;
2., hydrophilic emulsifier compound system: by aliphatic alcohol polyethenoxy (25) ether with polyoxyethylene 20 sorbitan monooleate is composite forms, it is 55%～80% that its total amount accounts for emulsifying agent quality of material per-cent, in this hydrophilic emulsifier compound system, the shared mass percent of aliphatic alcohol polyethenoxy (25) ether is 5%～25%, and the shared mass percent of polyoxyethylene 20 sorbitan monooleate is 75%～95%;
(3), to account for oiliness quality of material per-cent be 0.5%～10% to 1631 cats products;
All the other are water, and described cationic wax emulsion is according to the requirement of use properties, and solid content can be regulated between 8.0～22%.
2. the cationic wax emulsion of used in leather processing procedure according to claim 1, it is characterized in that: also include stearic acid, it is 0%～10% that its addition accounts for oiliness quality of material per-cent.
3. the cationic wax emulsion of used in leather processing procedure according to claim 1 and 2, it is characterized in that: described cats product is the palmityl trimethyl ammonium chloride cats product.
4. the cationic wax emulsion of used in leather processing procedure according to claim 3, it is characterized in that: the described carnauba wax trade mark is 3#, fusing point is 82～83 ℃, acid number 9.3～9.6mg KOH/g, saponification value 86.0～87.8mg KOH/g.
5. the cationic wax emulsion of used in leather processing procedure according to claim 4, it is characterized in that: described OP wax outward appearance is a white particle, density 0.95～0.96g/cm
3, acid number 20～24mg KOH/g.
6. the preparation method of a used in leather processing procedure cationic wax emulsion is characterized in that may further comprise the steps:
(1), each raw material described in the claim 1 is mixed by each the material rate value thawing described in the claim 1, in proportion oiliness material, aliphatic alcohol polyethenoxy (3) ether, sorbitan monooleate are mixed and be heated to 100-130 ℃ and stir 30min at least, add aliphatic alcohol polyethenoxy (25) ether, polyoxyethylene 20 sorbitan monooleate and 1631 cationic emulsifiers more in proportion and keep 100-130 ℃ to stir 50min at least, mix;
(2) water filling emulsification deionized water more than 80 ℃ is divided into 4～5 equivalent adds, and 30min is at least stirred in emulsification after adding deionized water each time;
(3) cooling emulsification is cooled to below 35 ℃, and the stirring velocity that slows down continues emulsification and stirs 30min at least, makes the cationic wax emulsion finished product of used in leather processing procedure.
7. the preparation method of used in leather processing procedure cationic wax emulsion according to claim 6 is characterized in that: also will be added in the described step (1) and account for oiliness quality of material per-cent be 0%～10% stearic acid with oiliness material, aliphatic alcohol polyethenoxy (3) ether, sorbitan monooleate in proportion heating and melting mix.
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| CN2009101004348A CN101585968B (en) | 2009-06-26 | 2009-06-26 | Cationic wax emulsion for leather manufacturing procedure and manufacturing method |
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| CN2009101004348A CN101585968B (en) | 2009-06-26 | 2009-06-26 | Cationic wax emulsion for leather manufacturing procedure and manufacturing method |
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| CN101585968B true CN101585968B (en) | 2011-05-18 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102226060A (en) * | 2011-05-19 | 2011-10-26 | 江苏力宝建材工业有限公司 | Cloud paraffin |
| CN102553504B (en) * | 2012-01-18 | 2014-12-17 | 朗盛（常州）有限公司 | Preparation method of emulsion, leather care emulsion, and use leather care emulsion |
| CN103059730B (en) * | 2012-11-06 | 2015-06-24 | 海南必凯水性涂料有限公司 | Water-based wax emulsion used for thin film coating and manufacturing method thereof |
| CN106366920A (en) * | 2016-08-29 | 2017-02-01 | 浙江奥王服饰有限公司 | Emulsion used in leather processing process and preparation method thereof |
| CN107675552A (en) * | 2017-10-24 | 2018-02-09 | 苏州丰倍生物科技有限公司 | A kind of plant type paper products water and oil repellent agent capable of washing and preparation method thereof |
| CN109294443A (en) * | 2018-10-12 | 2019-02-01 | 温州大学 | A kind of leather surface protects light type and covers with paint, lacquer, colour wash, etc. wax and preparation method thereof |
| CN110385087B (en) * | 2019-07-16 | 2021-06-15 | 邱越 | Compound surfactant containing quaternary ammonium salt and application thereof |
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Assignee: Decision Chemical Co., Ltd. Assignor: Wenzhou University Contract record no.: 2011510000146 Denomination of invention: Cationic wax emulsion for leather manufacturing procedure and manufacturing method Granted publication date: 20110518 License type: Exclusive License Open date: 20091125 Record date: 20110812 |
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