阅读说明：本技术 一种皮革护理剂及其制备方法 (Leather care agent and preparation method thereof ) 是由 刘山明 于 2019-10-24 设计创作，主要内容包括：本发明提供了一种皮革护理剂,其特征在于,由如下重量份的各组分制成：单端羟丙基硅油改性超支化聚氨酯15-25份、芦荟新甙D/油酸/芥子碱/聚乙二醇单烯丙基醚共聚物10-20份、季铵盐15离子化改性N,N-双(2-羟乙基)-2-氨基乙磺酸1-5份、植物油2-5份、纳米氧化铈0.5-1.5份、助溶剂3-7份、乳化剂4-8份、香精0.1-0.4份、去离子水70-80份。本发明还公开了所述皮革护理剂的制备方法。本发明公开的皮革护理剂具有良好的软化皮质、提高手感的效果,同时能充分保护皮质,使其不易老化、不掉色,恢复光亮、柔软如新,并可清除有害物质、除尘、防霉、防水,使用绿色安全环保。(The invention provides a leather care agent which is characterized by being prepared from the following components in parts by weight: 15-25 parts of single-ended hydroxypropyl silicone oil modified hyperbranched polyurethane, 10-20 parts of barbaloin D/oleic acid/sinapine/polyethylene glycol monoallyl ether copolymer, 1-5 parts of quaternary ammonium salt 15 ionized modified N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, 2-5 parts of vegetable oil, 0.5-1.5 parts of nano cerium oxide, 3-7 parts of cosolvent, 4-8 parts of emulsifier, 0.1-0.4 part of essence and 70-80 parts of deionized water. The invention also discloses a preparation method of the leather care agent. The leather care agent disclosed by the invention has good effects of softening leather and improving hand feeling, can fully protect leather, is not easy to age, does not fade, recovers brightness and softness as new, can remove harmful substances, removes dust, prevents mildew and prevents water, and is green, safe and environment-friendly to use.)

1. The leather care agent is characterized by being prepared from the following components in parts by weight: 15-25 parts of single-ended hydroxypropyl silicone oil modified hyperbranched polyurethane, 10-20 parts of barbaloin D/oleic acid/sinapine/polyethylene glycol monoallyl ether copolymer, 1-5 parts of quaternary ammonium salt 15 ionized modified N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, 2-5 parts of vegetable oil, 0.5-1.5 parts of nano cerium oxide, 3-7 parts of cosolvent, 4-8 parts of emulsifier, 0.1-0.4 part of essence and 70-80 parts of deionized water.

2. The leather care agent of claim 1, wherein the emulsifier is at least one of cetyl alcohol polyoxyethylene ether dimethyl octane ammonium chloride, lauryl alcohol polyoxyethylene ether trimethyl ammonium chloride, imidazoline quaternary ammonium salt, sorbitol monolaurate, and polyoxyethylene alkyl ether; the cosolvent is at least one of ethanol, propylene glycol, isopropanol and glycerol; the vegetable oil is at least one of peanut oil, soybean oil, linseed oil, castor oil and rapeseed oil.

3. The leather care agent according to claim 1, wherein the nano cerium oxide has an average particle size of 10 to 40 nm.

4. The leather care agent as claimed in claim 1, wherein the preparation method of the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified by ionization of the quaternary ammonium salt 15 comprises the following steps: adding quaternary ammonium salt 15 and N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid into tetrahydrofuran, stirring and reacting for 5-8 hours at 25-40 ℃, then performing rotary evaporation to remove tetrahydrofuran, washing the product with diethyl ether for 3-5 times, and then performing rotary evaporation to remove diethyl ether to obtain the quaternary ammonium salt 15 ionized modified N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid.

5. The leather care agent according to claim 4, wherein the mass ratio of the quaternary ammonium salt 15 to the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid to the tetrahydrofuran is 1.18:1 (6-10).

6. The leather care agent of claim 1, wherein the preparation method of the barbaloin D/oleic acid/sinapine/polyethylene glycol monoallyl ether copolymer comprises the following steps: adding barbaloin D, oleic acid, sinapine, polyethylene glycol monoallyl ether and initiator into high boiling point solvent, stirring and reacting at 70-80 deg.C under nitrogen or inert gas atmosphere for 3-5 hr, and removing solvent by rotary evaporation to obtain barbaloin D/oleic acid/sinapine/polyethylene glycol monoallyl ether copolymer.

7. The leather care agent as claimed in claim 6, wherein the mass ratio of the barbaloin D, the oleic acid, the sinapine, the polyethylene glycol monoallyl ether, the initiator and the high boiling point solvent is 1:0.4:0.3:1 (0.02-0.04): (9-12); the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is one of helium, neon and argon.

8. The leather care agent according to claim 1, wherein the preparation method of the single-ended hydroxypropyl silicone oil modified hyperbranched polyurethane comprises the following steps: stirring and dehydrating the single-end hydroxypropyl silicone oil for 3-5 hours at the vacuum degree of 0.1-0.2MPa and the temperature of 115-125 ℃, then adding the single-end hydroxypropyl silicone oil, the hyperbranched polyurethane and the catalyst into tetrahydrofuran, stirring and reacting for 12-18 hours at the temperature of 70-80 ℃ in the nitrogen atmosphere, then carrying out rotary evaporation to remove the tetrahydrofuran, and drying in a vacuum drying oven at the temperature of 80-90 ℃ to constant weight to obtain the single-end hydroxypropyl silicone oil modified hyperbranched polyurethane.

9. The leather care agent as claimed in claim 8, wherein the mass ratio of the single-ended hydroxypropyl silicone oil, the hyperbranched polyurethane, the catalyst and the tetrahydrofuran is 1 (3-5): 0.3-0.5): 20-30; the catalyst is at least one of isopropyl titanate, zinc octoate and dibutyltin dilaurate.

10. A leather care agent according to any one of claims 1 to 9, wherein the preparation method of the leather care agent comprises the following steps: the components are mixed according to the proportion, stirred for 2-4h at the temperature of 75-85 ℃, and then cooled to room temperature to obtain the leather care agent.

Technical Field

The invention relates to the technical field of cleaning and nursing, in particular to a leather nursing agent and a preparation method thereof.

Background

With the development of economy and the continuous improvement of living standard of people, more and more people like to use leather products, and leather products such as leather shoes, leather clothes, leather bags and the like become popular consumer goods. After thousands of years of leather technology development, today's leather products are not just defensive articles used for keeping out cold or wrapping feet so as to avoid injury, but are symbolized by life attitude, fashion taste and identity, and are more noble. Now that leather products play such an important role in our daily lives, careful care and care is needed. The leather care agent is indispensable in leather care, and is a key factor for determining the leather care effect. Therefore, it is important to develop a leather care agent with good performance.

The leather care agent is used for caring leather products such as leather clothing, leather sofas, leather bags, leather chairs, leather shoes and the like, and enables the leather to recover bright and soft as a new product. At present, most of leather care agents are prepared by using petrochemical grease, solvents, acid-proof agents, synthetic pigments and the like as raw materials, the application range is single, the leather care agents can only be applied to the care of single products, most of the existing leather care agents can not prevent water and protect leather, the care agents are poor in stability, toxic and pungent smells, certain damage is caused to skin and leather, certain pollution is caused to the environment, the leather is denatured and hardened after multiple use, the hand feeling is poor, and the service life of the leather is influenced. The existing leather care agents on the market have good effects on softening leather and hand feeling, but have great damage to leather and are easy to discolor the leather.

The Chinese invention patent with application publication number CN 109576421A discloses a leather care agent, which is prepared by compounding the following raw materials in parts by weight: 1-3 parts of ethylene bis stearamide, 20-30 parts of epoxy resin, 3-9 parts of palm wax, 5-10 parts of silicone oil, 3-5 parts of methyl benzoate, 1-2 parts of sodium bisulfite, 5-15 parts of animal fatty acid, 1-4 parts of plant essential oil, 8-12 parts of polyether siloxane, 3-5 parts of a mildew-proof bactericide, 1-3 parts of sodium stearate, 3-5 parts of sulfated castor oil, 2-3 parts of a lubricant, 1-3 parts of PMMA, 8-10 parts of a softener, 1-2 parts of a brightener and 30-50 parts of deionized water. The invention has low cost, good effects of softening leather and improving hand feeling, but has complex components and poor stability, is easy to cause secondary damage to skin and leather, and the waterproof performance needs to be further improved.

Therefore, how to develop the leather care agent which is green, environment-friendly, waterproof and wide in application range has very important practical significance.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention aims to provide the leather care agent and the preparation method thereof, and the preparation method has the advantages of simple process, reasonable raw material selection and low cost; the prepared leather care agent has good effects of softening leather and improving hand feeling, can fully protect leather, enables the leather not to be aged easily, not to fade, to recover brightness and softness as new, can remove harmful substances, removes dust, prevents mildew and prevents water, and is green, safe and environment-friendly to use.

The invention is realized by the following technical scheme: the leather care agent is characterized by being prepared from the following components in parts by weight: 15-25 parts of single-ended hydroxypropyl silicone oil modified hyperbranched polyurethane, 10-20 parts of barbaloin D/oleic acid/sinapine/polyethylene glycol monoallyl ether copolymer, 1-5 parts of quaternary ammonium salt 15 ionized modified N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, 2-5 parts of vegetable oil, 0.5-1.5 parts of nano cerium oxide, 3-7 parts of cosolvent, 4-8 parts of emulsifier, 0.1-0.4 part of essence and 70-80 parts of deionized water.

Further, the emulsifier is at least one of cetyl alcohol polyoxyethylene ether dimethyl octane ammonium chloride, lauryl alcohol polyoxyethylene ether trimethyl ammonium chloride, imidazoline quaternary ammonium salt, sorbitol monolaurate and polyoxyethylene alkyl ether.

Further, the cosolvent is at least one of ethanol, propylene glycol, isopropanol and glycerol.

Further, the average particle size of the nano cerium oxide is 10-40 nm.

Further, the vegetable oil is at least one of peanut oil, soybean oil, linseed oil, castor oil and rapeseed oil.

Further, the preparation method of the quaternary ammonium salt 15 ionized modified N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid comprises the following steps: adding quaternary ammonium salt 15 and N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid into tetrahydrofuran, stirring and reacting for 5-8 hours at 25-40 ℃, then performing rotary evaporation to remove tetrahydrofuran, washing the product with diethyl ether for 3-5 times, and then performing rotary evaporation to remove diethyl ether to obtain the quaternary ammonium salt 15 ionized modified N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid.

Preferably, the mass ratio of the quaternary ammonium salt 15, the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid and the tetrahydrofuran is 1.18:1 (6-10).

Further, the preparation method of the barbaloin D/oleic acid/sinapine/polyethylene glycol monoallyl ether copolymer comprises the following steps: adding barbaloin D, oleic acid, sinapine, polyethylene glycol monoallyl ether and initiator into high boiling point solvent, stirring and reacting at 70-80 deg.C under nitrogen or inert gas atmosphere for 3-5 hr, and removing solvent by rotary evaporation to obtain barbaloin D/oleic acid/sinapine/polyethylene glycol monoallyl ether copolymer.

Preferably, the mass ratio of the barbaloin D, the oleic acid, the sinapine, the polyethylene glycol monoallyl ether, the initiator and the high-boiling point solvent is 1:0.4:0.3:1 (0.02-0.04) to (9-12).

Preferably, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is one of helium, neon and argon.

Further, the preparation method of the single-ended hydroxypropyl silicone oil modified hyperbranched polyurethane comprises the following steps: stirring and dehydrating the single-end hydroxypropyl silicone oil for 3-5 hours at the vacuum degree of 0.1-0.2MPa and the temperature of 115-125 ℃, then adding the single-end hydroxypropyl silicone oil, the hyperbranched polyurethane and the catalyst into tetrahydrofuran, stirring and reacting for 12-18 hours at the temperature of 70-80 ℃ in the nitrogen atmosphere, then carrying out rotary evaporation to remove the tetrahydrofuran, and drying in a vacuum drying oven at the temperature of 80-90 ℃ to constant weight to obtain the single-end hydroxypropyl silicone oil modified hyperbranched polyurethane.

Preferably, the mass ratio of the single-ended hydroxypropyl silicone oil to the hyperbranched polyurethane to the catalyst to the tetrahydrofuran is 1 (3-5) to (0.3-0.5) to (20-30).

Preferably, the catalyst is at least one of isopropyl titanate, zinc octoate and dibutyltin dilaurate.

The invention also aims to provide a preparation method of the leather care agent, which is characterized by comprising the following steps: the components are mixed according to the proportion, stirred for 2-4h at the temperature of 75-85 ℃, and then cooled to room temperature to obtain the leather care agent.

Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:

(1) the leather care agent provided by the invention has the advantages of simple preparation method, reasonable raw material selection, low cost, convenience in operation, high preparation efficiency and finished product qualification rate, and obvious economic value, social value and ecological value.

(2) The leather care agent provided by the invention overcomes the defects that the traditional leather care agent has a single application range, can only be applied to the care of a single product, cannot prevent water and protect leather, has poor stability, toxic and pungent odor, has certain damage to skin and leather, has certain pollution to the environment, can denaturize and harden the leather after being used for many times, has poor hand feeling and influences the service life of the leather, has good effects of softening the leather and improving the hand feeling, can fully protect the leather, is not easy to age and fade, can recover brightness and softness as new, can remove harmful substances, removes dust, prevents mildew and prevents water, and is green, safe and environment-friendly in use.

(3) The leather care agent provided by the invention has the advantages that the added single-ended hydroxypropyl silicone oil modified hyperbranched polyurethane combines the advantages of polysiloxane and a polyurethane material, the polyurethane material has good adhesion with a leather substrate and good compatibility, a film is easily formed on the surface of leather, the performances such as water resistance, weather resistance, stain resistance and the like are achieved, the leather care effect is further improved, the leather can be endowed with excellent toughness due to the introduction of a polysiloxane structure, and the brightening effect can be achieved, so that the surface of the leather is smooth and bright; due to the introduction of the hyperbranched structure, the substance with a unique branched structure has no entanglement among molecules and contains a large amount of terminal isocyanate groups, thereby showing high solubility, low viscosity and high chemical reactivity and providing a reaction site for graft modification.

(4) According to the leather care agent provided by the invention, the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified by the ionization of the quaternary ammonium salt 15 not only can improve the emulsion stability, but also introduces the quaternary ammonium salt structure to improve the antibacterial property and the adhesive force with the leather surface; the introduction of the barbaloin D/oleic acid/sinapine/polyethylene glycol monoallyl ether copolymer can play the roles of oxidation resistance and mildew resistance due to the introduction of the barbaloin D and sinapine structures; the oleic acid can improve the emulsification effect and the performance stability; the copolymer and the single-end hydroxypropyl silicone oil modified hyperbranched polyurethane have synergistic effect, so that the surface brightness of the leather can be improved, the drying speed and the hardness of a coating are improved, the leather can be polished and repaired easily, the formed coating film is bright, and the nursing effect of the leather can be improved; the added vegetable oil permeates into the inner layer of the leather, so that the surface of the leather is smooth and bright; the nano cerium oxide forms a certain contact angle on the surface of the leather, so that the adsorption of tiny water drops can be prevented, the water resistance is enhanced, the tanning property can be improved, and the leather has air permeability, corrosion resistance, tear resistance and flexing resistance.

Detailed Description

In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.

The raw materials used in the following examples of the present invention were all purchased commercially; the CAS of polyethylene glycol monoallyl ether is 27274-31-3, which is purchased from Shanghai Michelle chemical technology Co., Ltd, and has the product number: GEL-ENEA 0261; the single-ended hydroxypropyl silicone oil is single-ended hydroxypropyl silicone oil IOTA2050, has a weight average molecular weight of 5000 and is purchased from Aiyuta silicone oil Co.Ltd in Anhui; the hyperbranched polyurethane is prepared in advance, and the preparation method refers to the following steps: synthesis of hyperbranched polyurethanes, porifen, university of zhongshan, master's academic paper, 2008.