CN101585968B - Cationic wax emulsion for leather manufacturing procedure and manufacturing method - Google Patents

Abstract

The invention provides a cationic wax emulsion for leather processing and a preparation method thereof. The wax emulsion uses wax, simethicone, and cetyl alcohol as oily materials, and passes through fatty alcohol polyoxyethylene (3) ether and Span 60 Two kinds of lipophilic emulsifier compound system Fatty alcohol polyoxyethylene (25) ether ether and Tween 60 two kinds of hydrophilic emulsifier compound system, stearic acid and cetyltrimethylammonium chloride cationic surface active Dispersed and emulsified with deionized water, emulsified and dispersed with deionized water, and cooled. The invention has the advantages of good stability, good water emulsification, outstanding performance characteristics and environmental protection, etc. It can increase the moist feeling and softness of leather; When improving the hand feel of leather, adding 0.8% to 1.5% of the total amount of prepared materials by mass percentage can give the leather a moist hand feel.

Description

Cationic wax emulsion for leather processing and preparation method thereof

technical field

The invention belongs to the technical field of leather chemical industry, in particular to a cationic wax emulsion used in leather processing and a preparation method thereof.

Background technique

Emulsifying wax is a commonly used finishing aid in leather processing. This type of product is generally made by emulsifying wax under certain conditions with a suitable emulsifier. According to the type of emulsifier used, wax emulsions are often divided into four types: anionic, nonionic, cationic and zwitterionic. Since the surface of the unpainted leather is usually negatively charged, the cationic wax emulsion can quickly combine with the leather surface during the finishing process to form a thin film, which can effectively prevent the excessive penetration of the finishing material from affecting the leather feel, and make the leather reflect the coating. Good layer fastness, elegant and soft hand feeling. Based on the above advantages, cationic wax emulsion has been more and more favored by researchers and users in recent years. It has been researched and developed abroad for many years, and a series of products with various varieties and excellent performance have been formed. Domestic research and development of wax emulsions, especially cationic wax emulsions, has just started. There are few types of existing products, and most of them have shortcomings such as easy delamination, poor water emulsification, and unremarkable performance characteristics. In addition, in view of the EU's recent regulations restricting the use of APEO (alkylphenol polyoxyethylene ether emulsifiers, OP-10 belongs to APEO products), it has forced the traditional cationic wax emulsion products to be eliminated. Therefore, it is of great significance to develop emulsified cationic wax emulsion products with higher stability, better water emulsifiability, outstanding performance characteristics and environmental protection when used in leather processing.

Contents of the invention

The purpose of the present invention is to overcome the shortcomings and deficiencies of the prior art. The first purpose of the present invention is to provide a cationic wax emulsion with good stability, good water emulsification, outstanding performance characteristics and environmentally friendly leather processing.

The second object of the present invention is to provide a method for preparing cationic wax emulsion used in leather processing.

In order to realize the first object of the present invention, the technical scheme of the present invention is, containing oily material, lipophilic emulsifier compound system, hydrophilic emulsifier compound system, 1631 cationic surfactant, described oily material comprises There are carnauba wax, OP wax, simethicone, cetyl alcohol, and the described lipophilic emulsifier complex system includes fatty alcohol polyoxyethylene (3) ether and sorbitan monooleate, and the described The hydrophilic emulsifier compound system includes fatty alcohol polyoxyethylene (25) ether and polyoxyethylene sorbitan monooleate, and the proportioning ratio of each component is as follows:

(1), oily materials:

Carnauba wax accounts for 85% to 95% of the mass of oily materials;

OP wax accounts for 5% to 15% of the mass percentage of oily materials;

Simethicone oil accounts for 0.5% to 5% of the mass of oily materials;

Cetyl alcohol accounts for 2% to 12% of the mass percentage of oily materials;

(2), the emulsifier material includes lipophilic emulsifier compound system and hydrophilic emulsifier compound system, its total mass accounts for 20%-45% of the oily material mass percentage, wherein

①. Lipophilic emulsifier compound system: it is composed of fatty alcohol polyoxyethylene (3) ether and sorbitan monooleate, the total amount of which accounts for 20% to 45% of the mass percentage of the emulsifier material. In the lipophilic emulsifier compound system, the fatty alcohol polyoxyethylene (3) ether accounts for 20% to 40% by mass, and the sorbitan monooleate accounts for 60% to 80% by mass;

②. Hydrophilic emulsifier compound system: compounded with fatty alcohol polyoxyethylene (25) ether and polyoxyethylene sorbitan monooleate, the total amount of which accounts for 55% to 50% by mass of the emulsifier material 80%, the mass percentage of fatty alcohol polyoxyethylene (25) ether in the hydrophilic emulsifier compound system is 5% to 25%, and the mass percentage of polyoxyethylene sorbitan monooleate is 75% to 95%;

(3), 1631 cationic surfactant accounts for 0.5% to 10% of the oily material by mass;

The rest is water, and the solid content of the cationic wax emulsion can be adjusted between 8.0% and 22% according to the requirement of performance.

It is further set that stearic acid is also included, and its added amount accounts for 0%-10% of the mass percentage of the oily material.

It is further provided that the cationic surfactant is cetyltrimethylammonium chloride cationic surfactant.

Further settings are that the carnauba wax grade is 3#, the melting point is 82-83°C, the acid value is 9.3-9.6mg KOH/g, and the saponification value is 86.0-87.8mg KOH/g.

It is further provided that the OP wax is white particles in appearance, with a density of 0.95-0.96 g/cm ³ and an acid value of 20-24 mg KOH/g.

For realizing the second purpose of the present invention, technical scheme of the present invention is, comprises the following steps:

(1), each raw material described in claim 1 is melted and mixed by each raw material ratio value described in claim 1, and oily material, fatty alcohol polyoxyethylene (3) ether, sorbitan are mixed in proportion Mix monooleate and heat to 100-130°C and stir for at least 30 minutes, then add fatty alcohol polyoxyethylene (25) ether, polyoxyethylene sorbitan monooleate and 1631 cationic emulsifier in proportion and keep 100- Stir at 130°C for at least 50 minutes and mix well;

(2) Water injection emulsification, add deionized water above 80°C in 4 to 5 times in equal amounts, and emulsify and stir for at least 30 minutes after adding deionized water each time;

(3) The finished product is obtained by cooling and emulsifying, the temperature is lowered to below 35° C., the stirring speed is slowed down, and the emulsifying and stirring is continued for at least 30 minutes to obtain the finished product of cationic wax emulsion for leather processing.

The further setting is that in the described step (1), stearic acid and oily material, fatty alcohol polyoxyethylene (3) ether, sorbitan mono-oil, which account for 0% to 10% by mass of the oily material will be added. The acid esters are heated and melted together in proportion and mixed.

When the present invention prepares the cationic wax emulsion, a small amount of simethicone is introduced into the oily material according to the performance requirements of the desired product. The introduction of the simethicone can reduce the foam of the cationic wax emulsion in the emulsification process, and the amount of simethicone is too large. The conference brings certain difficulties to emulsification, so the mass percentage of simethicone in the oily material is 0.5% to 5%, preferably 1% to 2.5%, and the selected kinematic viscosity of simethicone (25°C, mm4/s) is 350±18.

When the present invention prepares the cationic wax emulsion, a small amount of cetyl alcohol and stearic acid are introduced into the oily material according to the performance requirements of the desired product. The introduction of cetyl alcohol can increase the storage stability of the cationic wax emulsion, and its mass percentage of the oily material is 2% to 12%, preferably 3% to 8%; the introduction of stearic acid can make the color of the cationic wax emulsion lighter , it is easier to be dispersed by water in the process of leather processing. Since the charge of stearic acid after ionization in water is opposite to that of cationic emulsifiers, excessive dosage will cause the stability of cationic wax emulsion to decrease. Therefore, stearic acid accounts for the mass percentage of oily materials It is 0% to 10%, preferably 0.1% to 3%.

When the present invention prepares the cationic wax emulsion, two different types of emulsifiers are used to form a composite emulsifier system for both the lipophilic emulsifier system and the hydrophilic emulsifier system. This method helps to improve the emulsification effect and obtain higher stability cationic wax emulsion;

When the cationic wax emulsion is prepared in the present invention, when deionized water is added to the emulsification system, the temperature of the deionized water is required not to be lower than 80°C, so that the emulsification effect is better;

When the present invention prepares cationic wax emulsion, emulsification (stirring) time is comparatively important, especially all needs certain emulsification (stirring) time after adding lipophilic compound emulsifier and hydrophilic compound emulsifier in oily material, but the time is too long Long time will increase energy consumption and reduce production efficiency. Comprehensive consideration, after adding lipophilic compound emulsifier and hydrophilic compound emulsifier, emulsification (stirring) emulsification (stirring) is required for 30-90 minutes, preferably 40-70 minutes; when oily materials After being emulsified by lipophilic compound emulsifier and hydrophilic emulsifier, the time for adding water to emulsify (stir) and disperse can be slightly shorter, emulsify (stir) for 50-90 minutes to obtain good results, preferably 50-80 minutes;

When the cationic wax emulsion is prepared in the present invention, the stirring speed is not a key factor, but it should not be too fast, and it is required to be able to stir and disperse the materials evenly. After cooling down to 35°C in the late stage of emulsification, the stirring speed must be reduced, otherwise, there will be more foam in the product, which will affect its appearance and even performance;

The present invention provides and prepares the cationic wax emulsion used in the leather processing process, the appearance is a milky white emulsion with blue light, the active substance content is 12.0% to 18.0%, the pH value (10% water emulsion) is 6.0 to 8.0, and it is stored at room temperature for 6 No delamination, no precipitation, easy water emulsification within one month.

The invention provides and prepares cationic wax emulsion for leather processing, which has good stability, easy emulsification and good dispersibility. It is resistant to electrolytes, hard water, acid and alkali, and is applicable to a wide range of pH values; when used for leather bottom coating, it can quickly combine with the leather surface and form a thin film to prevent excessive penetration of materials and play a role in back sealing; When it is used for coating the back cover, add 5.0%~8.0% of the total amount of the prepared materials according to the mass percentage, which can realize the effective back cover and make the adhesion firm; in addition, it can also be used for the moisture regain of the leather, and the dosage is added according to the mass percentage to the prepared materials 0.8% to 1.0% of the total amount can increase the wetness and softness of the leather; when used to improve the leather feel, adding 0.8% to 1.5% of the total amount of the prepared materials can give the leather a moist feel.

The cationic wax emulsion of the present invention does not contain APEO (nonylphenol polyoxyethylene ether and octylphenol polyoxyethylene ether) restricted by the European Union, does not discharge three wastes in the production process, and belongs to the category of clean production technology.

The present invention will be further introduced below in conjunction with specific embodiments.

Detailed ways

The following is an example of the present invention specifically preparing cationic wax emulsion for leather processing, and its process parameters only further illustrate the present invention.

Example 1

In a three-necked flask equipped with a stirrer and a condenser, add 18.0g of carnauba wax, 2.0g of OP wax, 0.2g of simethicone, 2.0g of cetyl alcohol and 0.2g of stearic acid, start stirring and turn on condensed water, add 2.0g fatty alcohol polyoxyethylene (3) ether and 4.4g Span 60 two hydrophilic emulsifiers, start timing when the temperature is raised to 105°C, and emulsify (stir) at 105°C for 30min. Add 1.2g of fatty alcohol polyoxyethylene (25) ether and 9.0g of Tween 60 two hydrophilic emulsifiers and 0.2g of 1631 cationic emulsifier, emulsify (stir) at 105°C for 45min, and then divide the deionized water above 80°C into 5 Each addition, the mass of deionized water added each time is 59.0g, after each addition of deionized water, emulsify (stir) at 105°C for 15min, then cool down to below 35°C, and continue to emulsify (stirrer) for 30min to obtain cationic wax The finished emulsion is a milky white emulsion with blue light in appearance, and the active matter content is >10.0%.

Example 2

In a three-necked flask equipped with a stirrer and a condenser, add 36.0g carnauba wax, 4.0g OP wax, 0.4g simethicone oil, 4.0g cetyl alcohol and 0.5g stearic acid, start stirring and turn on condensed water, add 3.2g fatty alcohol polyoxyethylene (3) ether and 7.2g Span 60 two hydrophilic emulsifiers, start timing when the temperature is raised to 115°C, and emulsify (stir) at 115°C for 45min. Add 0.8g of fatty alcohol polyoxyethylene (25) ether and 24g of Tween 60 two hydrophilic emulsifiers and 1.6g of 1631 cationic emulsifier, emulsify (stir) at 115°C for 45min, and then divide the deionized water above 80°C into 5 times Adding, the quality of deionized water added each time is 115.0g, after adding deionized water once, emulsify (stir) at 115°C for 15min, then lower the temperature to below 35°C, and continue to emulsify (stirrer) for 30min to obtain a cationic wax emulsion The finished product is a milky white emulsion with blue light in appearance, and the active matter content is >12.0%.

Example 3

In a three-necked flask equipped with a stirrer and a condenser, add 27.0g of carnauba wax, 3.0g of OP wax, 0.3g of simethicone, 2.4g of cetyl alcohol and 0.3g of stearic acid, start stirring and turn on condensed water, add 2.1g fatty alcohol polyoxyethylene (3) ether and 7.2g Span 60 two hydrophilic emulsifiers, start timing when the temperature is raised to 110°C, and emulsify (stir) at 110°C for 30min. Add 1.8g of fatty alcohol polyoxyethylene (25) ether and 12g of Tween 60 two hydrophilic emulsifiers and 1.5g of 1631 cationic emulsifier, emulsify (stir) at 110°C for 30min, and then divide the deionized water above 80°C into 5 times Add, the quality of deionized water added each time is 85.0g, emulsify (stir) at 110°C for 30min after each addition of deionized water, then cool down to below 35°C, and continue to emulsify (stirrer) for 30min to obtain a cationic wax emulsion The finished product is a milky white emulsion with blue light in appearance, and the active matter content is >12.0%.

Example 4

In a three-necked flask equipped with a stirrer and a condenser, add 18.0g carnauba wax, 2.0g OP wax, 0.25g simethicone, 1.2g cetyl alcohol and 0.15g stearic acid, start stirring and turn on condensed water, add 1.6g fatty alcohol polyoxyethylene (3) ether and 4.8g Span 60 two hydrophilic emulsifiers, start timing when the temperature is raised to 120°C, and emulsify (stir) at 120°C for 30min. Add 0.8g of fatty alcohol polyoxyethylene (25) ether and 11.0g of Tween 60 two hydrophilic emulsifiers and 0.2g of 1631 cationic emulsifier, emulsify (stir) at 120°C for 30min, and then divide the deionized water above 80°C into 5 Each addition, the mass of deionized water added each time is 45.0g. After each deionized water is added, it is emulsified (stirred) at 120°C for 15min, and then cooled to below 35°C, and emulsified (stirred) for 30min to obtain a cationic wax The finished emulsion is a milky white emulsion with blue light in appearance, and the active matter content is >16.0%.

Example 5

In a three-necked flask equipped with a stirrer and a condenser, add 54.0g of carnauba wax, 6.0g of OP wax, 0.5g of simethicone, 2.4g of cetyl alcohol and 0.9g of stearic acid, start stirring and turn on condensed water, add 6.0g fatty alcohol polyoxyethylene (3) ether and 9.6g Span 60 two hydrophilic emulsifiers, start timing when the temperature is raised to 118°C, and emulsify (stir) at 118°C for 30min. Add 2.4g of fatty alcohol polyoxyethylene (25) ether and 30.0g of Tween 60 two hydrophilic emulsifiers and 2.4g of 1631 cationic emulsifier, emulsify (stir) at 118°C for 30min, and then divide the deionized water above 80°C into 5 Each addition, the mass of deionized water added each time is 120.0g. After each deionized water is added, it is emulsified (stirred) at 118°C for 30min, then cooled to below 35°C, and emulsified (stirred) for 30min to obtain cationic wax The finished emulsion is a milky white emulsion with blue light in appearance, and the active substance content is >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.