阅读说明：本技术 一种阳离子皮革加脂剂及其制备方法 (Cationic leather fatting agent and preparation method thereof ) 是由 万祥祥 张文 周中平 于 2021-05-24 设计创作，主要内容包括：本发明涉及一种加脂剂的制备方法,特别涉及一种阳离子皮革加脂剂及其制备方法,属于制革技术领域。一种阳离子皮革加脂剂,该阳离子皮革加脂剂以重量份计的原料是：阳离子乳化剂10-20份、中性油10-15份、脂肪酸甘油酯衍生物5-15份、助乳化剂5-10份、助溶剂1-3份、粘度调节剂2-4份、有机酸水溶液47-68份。本发明所述的阳离子皮革加脂剂可作为皮革主加脂的二次表面加油,具有极好的耐光性,能够改善皮革粒面的油润感,对染色有一定的增深作用；同时可以用于皮革主鞣的油预鞣处理,不仅可以增强鞣剂的渗透能力,而且有助于改善皮革鞣制材料在皮革纤维中的分布、吸收以及结合状况。(The invention relates to a preparation method of a fatting agent, in particular to a cationic leather fatting agent and a preparation method thereof, belonging to the technical field of leather making. The cation leather fatting agent comprises the following raw materials in parts by weight: 10-20 parts of cationic emulsifier, 10-15 parts of neutral oil, 5-15 parts of fatty glyceride derivative, 5-10 parts of co-emulsifier, 1-3 parts of cosolvent, 2-4 parts of viscosity regulator and 47-68 parts of organic acid aqueous solution. The cationic leather fatting agent can be used as a secondary surface of leather main fatting for oiling, has excellent light resistance, can improve the oil-moist feeling of the grain surface of the leather, and has a certain deepening effect on dyeing; meanwhile, the method can be used for oil pretanning treatment of leather main tanning, can enhance the penetrating capability of a tanning agent, and is beneficial to improving the distribution, absorption and combination conditions of leather tanning materials in leather fibers.)

1. The cation leather fatting agent is characterized by comprising the following raw materials in parts by weight:

10-20 parts of cationic emulsifier,

10-15 parts of neutral oil,

5-15 parts of fatty glyceride derivative,

5-10 parts of auxiliary emulsifier,

1-3 parts of cosolvent,

2-4 parts of viscosity regulator,

47-68 parts of an organic acid aqueous solution;

wherein the cationic emulsifier is fatty acid bis-hydroxyethyl aminoethyl ester, and the molecular structural formula is as follows:

wherein R is the fatty alkane carbon chain structure of palmitic acid or stearic acid.

2. Cationic leather fatliquor according to claim 1, characterized in that: the solid content of the cationic leather fatliquor is 45-55%, and the pH of 10% mass concentration emulsion of the cationic leather fatliquor is 3.5-4.5.

3. Cationic leather fatliquor according to claim 1, characterized in that: the neutral oil is one or two of No. 32 white mineral oil or No. 36 white mineral oil.

4. Cationic leather fatliquor according to claim 1, characterized in that: the fatty glyceride derivative is one or more of monoglyceride palmitate, diglyceride palmitate, monoglyceride stearate and diglyceride stearate.

5. Cationic leather fatliquor according to claim 1, characterized in that: the auxiliary emulsifier is one or a mixture of more than two of emulsifier O-5 and softening agent SG-6.

6. Cationic leather fatliquor according to claim 1, characterized in that: the cosolvent is one or more of propylene glycol monoethyl ether and propylene glycol monobutyl ether.

7. Cationic leather fatliquor according to claim 1, characterized in that: the viscosity regulator is one or more of peregal O-30 and AS-80(C16-18 alcohol adduct 80EO product).

8. Cationic leather fatliquor according to claim 1, characterized in that: the organic acid is formic acid or acetic acid, and the mass concentration is 3-7%.

9. A method of preparing the cationic leather fatliquor according to claim 1, characterized in that the method comprises the following steps:

s1, mixing the cationic emulsifier, neutral oil, fatty glyceride derivative, co-emulsifier and cosolvent in the formula uniformly according to the proportion, heating to 65-75 ℃, slowly adding organic acid aqueous solution at 70-80 ℃ within 60-90 minutes,

s2, continuously stirring the mixed solution obtained in the step S1 at the temperature of 70-80 ℃ for 60 +/-5 minutes, adding a viscosity regulator when the temperature is reduced to 60-70 ℃, keeping the temperature and stirring for 60 +/-5 minutes,

and S3, dispersing the mixed solution obtained in the step S2 at the temperature of 60-70 ℃ for 30-60 minutes at the speed of 1000 +/-100 r/min to obtain the emulsion type cationic leather fatliquor.

Technical Field

The invention relates to a preparation method of a fatting agent, in particular to a cationic leather fatting agent and a preparation method thereof, belonging to the technical field of leather making.

Background

The fatting is a vital procedure in the leather-making process, and the fatting agent permeates into the collagen fiber network to play a role in lubricating fibers and play a key role in the properties of hand feeling and the like. The majority of fatting agents used in leather making are anionic fatting agents, and exist in leather collagen fibers mainly in the forms of electrovalence bonds, physical adsorption or hydrogen bonds. However, because a large amount of anionic retanning filling materials are used in the earlier processing process of leather fibers, the surfaces of the leather fibers show strong anionic electrical characteristics, so that the binding sites of later anionic fatliquoring agent materials are insufficient, and as a result, the fatliquoring agent and leather collagen are bonded insecurely, so that the risk of low absorption rate sometimes occurs, and finally, the softness of the fatliquoring leather is poor and the surface oil-wet feeling is poor. In order to improve the above-mentioned greasing defect, the secondary greasing method (also called surface greasing) of cationic greasing agent is mainly adopted in the main greasing process at present, and by adding cationic oil again into the main greasing bath, on one hand, the combined absorption of anionic grease material in the bath liquid is promoted, the defect of insufficient surface oiliness is improved, and simultaneously, the secondary greasing method can have the effect of promoting dyeing and combining deepening to anionic dye in the greasing bath. Besides the surface secondary oiling in the main oiling, the cation fatting agent can be used in the pickling and tanning process, and is helpful to improve the distribution, absorption and combination conditions of leather tanning materials in leather fibers and implement the effect of multi-process oiling.

According to analysis in published data at home and abroad, the preparation methods of the cationic fatliquor have two conventional methods: firstly, natural oil is used as a main raw material, cationization modification is carried out on the natural oil, and cationic groups are introduced while the hydrophilicity of oil molecules is increased, so that the product has a self-emulsifying characteristic; the other is a product which takes a cationic surfactant as a main component and forms an external emulsification type emulsion shape by emulsifying neutral oil. The quality of leather blanks produced by leather making is further improved due to the improvement of the quality requirement of leather terminal products, the quality requirements of the leather blanks such as appearance, hand feeling, yellowing resistance, smell and the like are increasingly strict besides the physical and mechanical properties of the leather blanks, and the use of the fatting agent has great influence on the hand feeling, yellowing resistance, smell and the like of the leather. The use of fatliquoring agents therefore increasingly requires synthetic oils as the main, wherein the same is true for cationic fatliquoring. The traditional external emulsification type cationic fatting is mainly prepared by mainly using a cationic emulsifier 1631 and adding solid paraffin and the like for emulsification and dispersion, has single component, has insufficient soft hand feeling effect due to the limitation of the emulsifier structure except emulsification, mainly uses neutral oil as solid paraffin, and has unobvious moistening feeling.

Disclosure of Invention

The invention aims to provide a preparation method of a cationic leather fatting agent, which takes fatty acid bis-hydroxyethyl aminoethyl, neutral oil, fatty glyceride derivatives and various assistants as raw materials, and adopts a phase inversion method to carry out compound emulsification to prepare the emulsion type cationic fatting agent with composite characteristics of material components.

The technical scheme adopted by the invention for solving the technical problems is as follows:

the cation leather fatting agent comprises the following raw materials in parts by weight:

10-20 parts of cationic emulsifier,

10-15 parts of neutral oil,

5-15 parts of fatty glyceride derivative,

5-10 parts of auxiliary emulsifier,

1-3 parts of cosolvent,

2-4 parts of viscosity regulator,

47-68 parts of an organic acid aqueous solution;

wherein the cationic emulsifier is fatty acid bis-hydroxyethyl aminoethyl ester, and the molecular structural formula is as follows:

wherein R is the fatty alkane carbon chain structure of palmitic acid or stearic acid.

The cationic leather fatting agent can be used as a secondary surface of leather main fatting for oiling, has excellent light resistance, can improve the oil-moist feeling of the grain surface of the leather, and has a certain deepening effect on dyeing; meanwhile, the method can be used for oil pretanning treatment of leather main tanning, can enhance the penetrating capability of a tanning agent, and is beneficial to improving the distribution, absorption and combination conditions of leather tanning materials in leather fibers. The leather cationic fatting agent has excellent emulsifying dispersivity, acid resistance, alkali resistance, electrolyte resistance and other performances, and the fatted crust leather is yellowing-resistant, free of special bad smell and good in surface moistening feeling.

Preferably, the solid content of the cationic leather fatliquor is 45-55%, and the pH of the 10% mass concentration emulsion of the cationic leather fatliquor is 3.5-4.5.

Preferably, the neutral oil is one or two of No. 32 white mineral oil or No. 36 white mineral oil.

Preferably, the fatty acid glyceride derivative is one or a mixture of two or more of monoglycerol palmitate, diglycol palmitate, and diglycol stearate.

Preferably, the auxiliary emulsifier is one or a mixture of more than two of emulsifier O-5 and softening agent SG-6.

Preferably, the cosolvent is one or a mixture of more than two of propylene glycol monoethyl ether and propylene glycol monobutyl ether.

Preferably, the viscosity regulator is one or a mixture of more than two of peregal O-30 and AS-80 (a product of C16-18 alcohol plus 80 EO).

Preferably, the organic acid is formic acid or acetic acid, and the mass concentration is 3-7%.

The preparation method of the cationic leather fatliquor comprises the following steps:

s1, mixing the cationic emulsifier, neutral oil, fatty glyceride derivative, co-emulsifier and cosolvent in the formula uniformly according to the proportion, heating to 65-75 ℃, slowly adding organic acid aqueous solution at 70-80 ℃ within 60-90 minutes,

s2, continuously stirring the mixed solution obtained in the step S1 at the temperature of 70-80 ℃ for 60 +/-5 minutes, adding a viscosity regulator when the temperature is reduced to 60-70 ℃, keeping the temperature and stirring for 60 +/-5 minutes,

and S3, dispersing the mixed solution obtained in the step S2 at the temperature of 60-70 ℃ for 30-60 minutes at the speed of 1000 +/-100 r/min to obtain the emulsion type cationic leather fatliquor.

Compared with the existing products, the invention has the beneficial effects that:

1. the cationic emulsifier is fatty acid bis-hydroxyethyl aminoethyl, the hydrophobic alkane in the molecule is a natural saturated fatty acid chain, except cationic amino, the structure contains ester bond and hydroxyl, and the hydrophilicity and the softness lubricity of the cationic emulsifier are superior to 1631;

2. the neutral oil is added with monoglyceride and diglyceride of saturated fatty acid similar to the neutral oil, and nonionic oily auxiliary emulsifying agents O-5 (C1618 alcohol adds 5 EO) and SG-6 (stearic acid adds 6 EO) besides the neutral oil (white oil or paraffin) component of the traditional scheme, the addition of the two materials further highlights the oil-moist feeling and the wax feeling of the material component, and the material has excellent yellowing resistance and simultaneously enhances excellent acid resistance and electrolyte resistance;

2. the traditional production process of the emulsion type cationic fatting agent adopts an emulsification mode of heating and mixing water and materials together, and the obtained emulsion of the cationic fatting agent has thicker particles and wide particle size distribution. The method adopts a phase inversion emulsification mode and combines a high-speed homogenizer, the obtained product emulsion particles are fine, the particle size distribution is narrow, and the obtained cationic fatting agent product has good stability and excellent fat penetration performance.

Detailed Description

The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.

In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.

Viscosity modifier AS-80, available from Saxol (China) chemical Co., Ltd;

the cationic emulsifier, bis-hydroxyethyl-aminoethyl palmitate, was purchased from Haian petrochemical plant, Jiangsu province.

Example 1

A preparation method of a cation leather fatting agent specifically comprises the following steps: adding 12g of bis-hydroxyethyl palmitate, 10g of No. 32 white mineral oil, 15g of diglyceride palmitate, 58g of emulsifier O and 2.5g of propylene glycol monoethyl ether into a 250ml three-neck flask with a stirrer, mixing, heating to 65 ℃, uniformly stirring, slowly adding 70 ℃ acetic acid aqueous solution (mixed solution of 50g of water and 2.5g of acetic acid) under the conditions of 65 ℃ and 60 minutes of a system, continuously stirring for 60 minutes at 70 ℃ after adding, adding a viscosity regulator AS-802 g after cooling to 60 ℃, stirring for 60 minutes at a constant temperature, and dispersing for 30 minutes by a high-speed homogenizer at 60 ℃ to obtain the emulsion type cationic fatting agent, wherein the solid content of the emulsion type cationic fatting agent is 51%, and the pH of 10% emulsion is 3.9.

Example 2

A preparation method of a cation leather fatting agent specifically comprises the following steps: adding 15g of bis-hydroxyethyl palmitate, 12g of No. 36 white mineral oil, 10g of monoglyceride palmitate, 510 g of emulsifier O-and 2.0g of propylene glycol monobutyl ether into a 250ml three-neck flask with a stirrer, mixing, heating to 70 ℃, uniformly stirring, slowly adding 75 ℃ formic acid aqueous solution (mixed solution of 46g of water and 2.0g of formic acid) at the temperature of 70 ℃ and within 80 minutes of a system, continuously stirring at 75 ℃ for 60 minutes after the addition is finished, adding a viscosity regulator AS-802 g when the temperature is reduced to 70 ℃, stirring for 60 minutes at a constant temperature, and dispersing for 45 minutes by a high-speed homogenizer at 70 ℃ to obtain the emulsion type cationic fatting agent with the solid content of 53 percent and the pH value of 10 percent emulsion of 4.2.

Example 3

A preparation method of a cation leather fatting agent specifically comprises the following steps: adding 20g of stearic acid bis-hydroxyethyl aminoethyl ester, 10g of No. 32 white mineral oil, 15g of stearic acid diglyceride, 65g of softener SG, 1g of propylene glycol monoethyl ether and 0.5g of propylene glycol monobutyl ether into a 250ml three-neck flask with stirring, mixing and heating to 75 ℃, uniformly stirring, slowly adding 80 ℃ formic acid aqueous solution (a mixed solution of 65g of water and 3.0g of formic acid) under the conditions of 75 ℃ and 90 minutes of a system, continuously stirring for 60 minutes at 75 ℃, adding a viscosity regulator after cooling to 70 ℃, flatly adding O-304 g of the viscosity regulator, keeping the temperature and stirring for 60 minutes, and dispersing for 60 minutes by a high-speed homogenizer at 70 ℃ to obtain an emulsion type cationic fatting agent with the solid content of 46% and the pH of 10% emulsion of 3.6.

Example 4

A preparation method of a cation leather fatting agent specifically comprises the following steps: adding 10g of stearic acid bis-hydroxyethyl aminoethyl ester, 10g of No. 36 white mineral oil, 10g of palmitic acid diglyceride, 5g of palmitic acid monoglyceride, O-53 g of emulsifier, 66 g of SG-66 g and 1g of propylene glycol monobutyl ether into a 250ml three-neck flask with stirring, mixing and heating to 65 ℃ and uniformly stirring, slowly adding 70 ℃ acetic acid aqueous solution (mixed solution of 50g of water and 2.0g of acetic acid) under the conditions of 65 ℃ and 60 minutes of a system, continuously stirring for 60 minutes at 70 ℃, adding a viscosity regulator AS-801 g and a flatly adding O-302g when the temperature is reduced to 60 ℃, preserving heat and stirring for 60 minutes, and dispersing for 60 minutes by a high-speed homogenizer at 60 ℃ to obtain an emulsion type cation fatting agent with the solid content of 49 percent and the pH of 10 percent emulsion of 3.6.

Example 5

A preparation method of a cation leather fatting agent specifically comprises the following steps: adding 15g of stearic acid bis-hydroxyethyl aminoethyl ester, 7g of No. 32 white mineral oil, 8g of No. 36 white mineral oil, 5g of stearic acid diglyceride, 10g of stearic acid monoglyceride, SG-65 g of softening agent and 2.0g of propylene glycol monoethyl ether into a 250ml three-neck flask with stirring, mixing and heating to 70 ℃, uniformly stirring, slowly adding 70 ℃ formic acid aqueous solution (mixed solution of 60g of water and 2.0g of formic acid) at 70 ℃ within 60 minutes of a system, continuously stirring for 60 minutes at 75 ℃ after finishing the addition, adding a viscosity regulator AS-802 g after cooling to 65 ℃, keeping the temperature and stirring for 60 minutes, and dispersing for 30 minutes by a high-speed homogenizer at 65 ℃ to obtain an emulsion type cationic fatting agent with the solid content of 48% and the pH of 10% emulsion of 3.7.

Example 6

A preparation method of a cation leather fatting agent specifically comprises the following steps: adding 15g of stearic acid bis-hydroxyethyl aminoethyl ester, 10g of No. 32 white mineral oil, 12g of stearic acid monoglyceride, 610 g of softener and 3.0g of propylene glycol monoethyl ether into a 250ml three-neck flask with stirring, mixing and heating to 70 ℃, uniformly stirring, slowly adding 75 ℃ acetic acid aqueous solution (mixed solution of 58g of water and 3.0g of acetic acid) under the conditions of 70 ℃ and 60 minutes of a system, continuously stirring for 60 minutes at 75 ℃, adding a viscosity regulator AS-802 g when the temperature is reduced to 65 ℃, stirring for 60 minutes at a constant temperature, and dispersing for 30 minutes by a high-speed homogenizer at 60 ℃ to obtain the emulsion type cationic fatting agent, wherein the solid content of the emulsion type cationic fatting agent is 48%, and the pH value of 10% emulsion is 4.1.

The following experiments illustrate the fatliquoring effect of the cationic fatliquor according to the invention by means of specific applications:

the evenly-cut cowhide upper leather wet-blue leather is weighed in the greasing test (the chemical material dosage is based), and the weighing method comprises the following steps:

rewetting and washing with water: 150% of water, 35 DEG C

0.1 percent of penetrating agent

0.2 percent of the degreasing agent is rotated for 30min, the liquid is discharged,

neutralizing: 150% of water, 35 DEG C

Sodium formate 2.5% for 20min

0.5 percent of baking soda is rotated for 90min, the pH value is 5.5-6.0, liquid is discharged,

washing with water: discharging liquid with 150% water at 30 deg.C for 30min,

dyeing and oiling: 150% water, 55 deg.C

Composite black 2% for 30min

10 percent of the synthetic fat liquor is rotated for 60min,

adding acid for fixation: formic acid (85%) 0.5% (diluted with 10 times of water) and transferred for 15min

Formic acid (85%) 0.5% (diluted with 10 times water and added)

2% of cationic fatting agent (emulsified by 2 times of hot water) is added, and the time is 60min

The pH value is 3.5-3.8. And (5) discharging, standing and controlling water.

After hanging, airing and drying, the drum is softened and then is subjected to toggling, and then, the test is carried out.

Under the same test conditions, the above method is adopted to carry out the fatliquoring experiment on the samples by using the cationic fatliquoring agents of examples 1-6 and comparative examples 1-2 respectively, wherein the ratio of comparative example 1: the 2% cation fatting agent adopts a conventional reagent, and the basic formula of the ion fatting agent is as follows: cationic surfactant 163120%, mineral oil 15%, C_16-182% of fatty alcohol, 10% of paraffin, 803% of span and 50% of water; comparative example 2: yang (Yang)The dosage of the ionic fatliquor is 0 percent. The softness test data and the oily feeling evaluation results are shown in table 1.

Table 1 softness and oil-wet feeling test and evaluation results of greased leather blanks

Oil wet in the table was scored on a 5-point scale, 5 best, 1 worst.

The results of the greasing experiments show that the leather blanks after the 8 groups of experiments are fatliquored have good and nearly consistent absorption of the dyed grease bath liquid; by observation and hand feeling judgment, after the sample series cationic fatting agent and the conventional cationic fatting agent are used for fatting, the surface chromaticity is darker, and the color and luster dry-wet rubbing fastness is improved by 0.5 grade compared with that without the cationic fatting agent; the surface oil-moist feeling of the crust leather is stronger, and in the aspects of the softness and the surface oil-moist feeling of the crust leather, the 8 groups of the comparative experiments adopt the series of cationic fatting agents which are obviously more prominent than those without the cationic fatting agents, but the 6 groups of the sample examples contribute better than the conventional cationic fatting agents to the softness and the surface oil-moist feeling of the crust leather.

The embodiments are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same or similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.

The cationic leather fatting agent and the preparation method thereof provided by the invention are described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.