CN105297449A - Waterborne wear-resistant and scraping-resistant surface treating agent for artificial leather and synthetic leather and preparation method - Google Patents

Abstract

The invention discloses a water-based wear-resistant and scratch-resistant surface treatment agent for artificial leather and synthetic leather. 0.03-0.06 parts of agent, 2-6 parts of matting powder, 0.5-1 part of silicone leveling agent, 1-1.5 parts of silicone coupling agent, 2.0-5.0 parts of hand feeling improver, 0.5-1.0 parts of water-based thickener . The invention is beneficial to the properties of graphene such as lubricity, high transparency, conductivity, antibacterial and mildew resistance, anti-UV, etc., and greatly improves the wear resistance, scratch resistance, antistatic, antiaging and self-cleaning of artificial leather and synthetic leather coatings. Performance, thereby improving the level of artificial leather, synthetic leather and international market competitiveness. In addition, the present invention replaces traditional solvent-based polyurethane with water-based polyurethane, saves organic solvent resources, eliminates organic pollution from the source, eliminates potential safety hazards, and improves the employment environment for laborers. The VOC content in finished leather is less than 5? mg/kg (leather), ecological and environmentally friendly, in line with EU ecological synthetic leather requirements.

Description

Water-based wear-resistant and scratch-resistant surface treatment agent for artificial leather and synthetic leather and its preparation method

technical field

The invention relates to a method for preparing an environment-friendly surface treatment agent for artificial leather and synthetic leather, belonging to the field of fine chemical manufacturing.

Background technique

my country is the largest producer and consumer of synthetic leather in the world. In 2014, my country's artificial leather and synthetic leather production accounted for 76% of the world's total, and the production of artificial leather and synthetic leather by enterprises above designated size reached 3.1426 million tons, totaling 6.28 billion square meters.

In the manufacturing process of artificial leather and synthetic leather, there is a very important process called surface treatment, and the materials used are called surface treatment agents (ie surface treatment agents). The surface treatment agent is generally made of polyurethane and special additives, which mainly endow artificial leather and synthetic leather with special surface effects and trendy effects, such as high gloss, matting, wear resistance, scratch resistance, waterproof, antifouling, etc. Among them, wear resistance and scratch resistance are very important physical properties of artificial leather and synthetic leather. Most artificial leather and synthetic leather include automobile leather, seat leather, sofa leather, bag leather, ball leather, luggage leather, etc. High requirements (Taber wear test method ≥ 5000 times).

In the traditional artificial leather and synthetic leather manufacturing process, in order to improve the wear resistance and scratch resistance of the coating, inorganic fillers such as talcum powder and silicon dioxide, or wax, stearic acid, etc. are usually added to the surface treatment slurry. Organic fillers, or increase the hardness (modulus) of the polyurethane film to improve the wear resistance and scratch resistance of the coating, but the addition of inorganic fillers such as talcum powder and silicon dioxide will make the finished leather thicker and reduce the lightness of the finished leather Adding wax, stearic acid and other organic fillers will cause coating adhesion and gloss changes under hot pressing; increasing the hardness of the polyurethane film will lead to a harder handle of the finished leather and the cold resistance and low temperature of the coating Flexibility decreases, and in severe cases, the coating will crack. Therefore, how to develop high-efficiency wear-resistant and scratch-resistant additives to greatly improve the wear-resistant and scratch-resistant coatings of artificial leather and synthetic leather without reducing other physical properties of the coating is particularly important.

In addition, the traditional synthetic leather industry is also facing severe challenges of environmental pollution. The synthetic leather production line will generate a large amount of organic waste gas. These pollutants mainly come from the disorderly discharge of organic solvents in solvent-based resins. These solvents include dimethylformamide (DMF), toluene, ethyl acetate, butyl acetate, and butyl acetate. Ketones and methylals etc. According to estimates, every synthetic leather production line emits 10.2 tons of DMF (with recycling), 50.8 tons of toluene, 50.80 tons of butanone, and 24.5 tons of acetate solvents per year. Therefore, the artificial leather and synthetic leather industries have long faced the severe challenges of high environmental management costs, serious waste of resources, and environmental pollution. How to develop water-based resins to replace traditional solvent-based resins is the key to maintaining the sustainable development of the artificial leather and synthetic leather industries.

In recent years, with the improvement of people's living standards, people have put forward higher requirements for the ecology of leather products. In developed countries such as Europe and the United States, the requirements of zero formaldehyde, zero azo, and zero heavy metals have been put forward for artificial leather, synthetic leather, especially home interior leather, automotive interior leather, clothing leather, and furniture leather. At the same time, VOC (volatile organic solvent) content ≤ 5mg/Kg (leather). Therefore, the traditional synthetic leather manufacturing technology based on solvent resin cannot meet the requirements of ecological synthetic leather.

Contents of the invention

The object of the present invention is to provide a water-based wear-resistant and scratch-resistant surface treatment agent for artificial leather and synthetic leather and a preparation method for the deficiencies of the prior art. One of its characteristics is that it is beneficial to graphene's lubricity, high transparency, conductivity, antibacterial and mildew resistance, anti-UV and other characteristics, and greatly improves the wear resistance, scratch resistance, antistatic, antiaging and anti-aging properties of artificial leather and synthetic leather coatings. Self-cleaning and other properties, thereby improving the grade and international market competitiveness of artificial leather and synthetic leather; the second is to use water-based polyurethane instead of traditional solvent-based polyurethane as the surface resin to eliminate organic solvent pollution from the source, save organic solvent resources, and eliminate safety. hidden dangers, improve the working environment of employees, and enhance the ecological grade and international market competitiveness of synthetic leather.

The object of the present invention is achieved by the following technical measures, wherein the parts of raw materials are all parts by weight unless otherwise specified.

A water-based wear-resistant and scratch-resistant surface treatment agent for artificial leather and synthetic leather and its preparation method include the following steps:

(1) Pretreatment of graphene or graphene oxide wear-resistant agent:

① Moisten the graphene with propylene glycol methyl ether acetate, add a wetting agent of 1% by weight of the graphene, disperse it by ultrasonic wave for 1-2 hours, and set aside;

②Wet the graphene oxide with dimethylformamide, add a modifier of 5% by weight of graphene oxide, disperse it by ultrasonic wave for 1-2h, and set aside;

(2) Preparation of water-based surface treatment agent:

Take 50-60 parts of water-based polyurethane by weight, 30-40 parts of water, 0.03-0.06 parts of pretreated graphene or graphene oxide wear agent (solid parts), 0-6 parts of matting powder, silicone leveling 0.5-1.0 parts of water-based crosslinking agent, 1.0-1.5 parts of water-based cross-linking agent, 2.0-5.0 parts of hand feeling improver, 0.5-1.0 parts of water-based thickener, mix well, and react at 20-30 ° C for 2-3 hours, and the viscosity is 1000 -2000mPa.s slurry, grind and filter to obtain water-based surface treatment agent.

The surface water-based polyurethane is at least one of aliphatic and/or aromatic polyurethanes of high-gloss type, medium-gloss type, and/or matte type, with a modulus of 50-80Mpa and a solid content of 30-35%.

The anti-wear agent is a kind of in graphene or graphene oxide.

The graphene wetting agent is at least one of isopropanol and OP-10; the graphene oxide modifier is at least one of KH560 and KH550.

The water-based crosslinking agent is at least one of polycarbodiimide, polyethylenimide and/or blocked water-based isocyanate.

The water-based thickener is at least one of a nonionic polyurethane thickener and an acrylic polymer thickener.

The hand feel modifier is at least one of water-based silicone polymer, oil/wax compound and/or organic fluorine polymer.

The surface treatment agent provided by the invention is suitable for the manufacture of many varieties of artificial leather and synthetic leather, including garment leather, luggage leather, shoe upper leather, sofa leather, home interior leather and or automobile leather. The handle and gloss of the finished leather can be adjusted. Wear-resistant and scratch-resistant, the VOC content in leather is less than 5mg/kg (leather), and it also has good antibacterial and mildew resistance, aging resistance, antistatic and other properties, and other properties meet or exceed industry standards.

The present invention has the following innovations:

(1) The present invention is beneficial to the properties of graphene or graphene oxide such as lubricity, high transparency, conductivity, antibacterial and mildew resistance, anti-UV, etc., and greatly improves the wear resistance, scratch resistance and anti-corrosion properties of artificial leather and synthetic leather coatings. Static electricity, anti-aging and self-cleaning properties, using new materials such as graphene to transform traditional industries, greatly improving the physical properties of artificial leather and synthetic leather, its innovation is obvious;

(2) Use solvent to wet graphene or graphene oxide, and control the particle size of graphene and graphene oxide through ultrasonic dispersion to ensure that the two are uniformly dispersed in the water-based polyurethane system; graphene oxide is treated with a modifier (KH550, KH560 ) after the modification, active siloxane groups are introduced, and the hydroxyl groups produced by siloxane hydrolysis can interact with the post-crosslinking agent to realize the grafting of graphene and polyurethane. The process technology is novel;

(3) The addition amount of graphene or graphene oxide in the present invention is between 0.03-0.06% (total amount of surface treatment agent), the addition amount is very small, and will not cause negative effects on other physical properties of the coating such as gloss and cold resistance impact, but at the same time greatly improve the wear resistance and scratch resistance, and give the coating better antibacterial and mildew resistance, electrical conductivity, anti-adhesive and aging resistance, etc.

(4) Use water-based polyurethane instead of solvent-based polyurethane to eliminate environmental pollution caused by organic solvents from the source, save a large amount of organic solvent resources, eliminate fire hazards, significantly improve the employment environment of laborers, and reduce VOC content in finished leather, which is conducive to the sustainable development of the industry. Continuous development.

detailed description

The present invention is specifically described below by way of examples. It is necessary to point out that this embodiment is only used to further illustrate the present invention, and should not be construed as limiting the protection scope of the present invention. Those skilled in the art can make some non-essential improvements and adjustments according to the content of the above invention.

In addition, it is also worth noting that the parts used in the following examples are all parts by weight.

Example 1

(1) Pretreatment of graphene wear-resistant agent:

Wet the graphene with propylene glycol methyl ether acetate, add 1% isopropanol by weight of the graphene, ultrasonically disperse for 1-2h, and set aside;

(2) Preparation of water-based surface treatment agent:

Take 50 parts of aliphatic matting water-based polyurethane with a modulus of 50Mpa and a solid content of 30% by weight fraction, 40 parts of water, 0.03 parts of graphene wear-resistant agent pretreated according to (1) (solid parts), 2.0 parts of matting powder, Mix 0.5 parts of silicone leveling agent, 1.0 parts of aziridine crosslinking agent, 2.0 parts of silicone handle improver, and 0.5 parts of water-based polyurethane thickener, react at 20-30 ° C for 2 hours, and adjust the viscosity to 1000 mPa.s Left and right, after grinding and filtering, the water-based surface treatment agent is obtained.

The surface treatment agent uses aliphatic water-based polyurethane with a low modulus, and the amount of modified graphene is relatively low. The coating feels soft, has good wear resistance, scratch resistance, antibacterial and mildew resistance, and high Anti-yellowing and matte effect, VOC content is less than 5mg/kg (leather), suitable for surface treatment of clothing, sofas, sole leather, etc.

Example 2

(1) Pretreatment of graphene oxide wear-resistant agent:

Wet the graphene oxide with dimethylformamide, add KH560 with 5% by weight of graphene oxide, ultrasonically disperse for 1-2h, and set aside;

(2) Preparation of water-based surface treatment agent:

Take 60 parts of matting aromatic water-based polyurethane with a modulus of 80Mpa and a solid content of 35% by weight, 40 parts of water, 0.06 parts of graphene oxide wear-resistant agent pretreated by (1) (solid parts), and 6 parts of matting powder , 1.0 parts of silicone leveling agent, 1.5 parts of blocked water-based isocyanate crosslinking agent, 5.0 parts of hand feel improver, mixed evenly, 0.6 part of water-based polyurethane thickener, 0.4 part of water-based acrylic polymer thickener, mixed evenly, at 20 React at -30°C for 3 hours, adjust the viscosity to 2000mPa.s slurry, grind and filter to obtain a water-based surface treatment agent.

The surface treatment agent is made of aromatic extinction water-based polyurethane with high modulus, and the amount of modified graphene is relatively high. The coating has good wear resistance, scratch resistance and high matte (delustering) effect, and has low VOC content. 5mg/kg (leather), suitable for the surface treatment of artificial leather and synthetic leather that require high wear resistance, scratch resistance and haze, such as automobile leather, seat leather and sofa leather.

Example 3

(1) Pretreatment of graphene and graphene oxide wear agents:

Wet the graphene with propylene glycol methyl ether acetate, add OP-10 of 1% by weight of graphene, ultrasonically disperse for 1-2h, and set aside; wet the graphene oxide with dimethylformamide, add graphene oxide weight Part of 5% KH550, ultrasonic dispersion for 1-2h, spare;

(2) Preparation of water-based surface treatment agent:

Take 55 parts of aliphatic medium-gloss water-based polyurethane with a modulus of 60Mpa and a solid content of 35% by weight fraction, 35 parts of water, 0.02 parts of graphene oxide wear-resistant agent pretreated by (1), and 0.3 parts of graphene (calculated by solid parts) ), 0.7 parts of silicone leveling agent, 1.2 parts of carbodiimide crosslinking agent, 3 parts of oil wax handle improver, 0.6 parts of water-based polyurethane thickener, mix well, react at 20-30 °C for 2-3 hours, adjust Viscosity to 1500mPa.s slurry, after grinding, filtering, to obtain water-based surface treatment agent.

The surface resin adopts medium modulus resin without adding silicone matting powder, which can endow the coating with good wear resistance, scratch resistance, softness, antibacterial and mildew resistance, natural gloss, and VOC content below 5mg/kg (Leather), suitable for shoe upper leather, boot shaft leather, etc.

Example 4

(1) Pretreatment of graphene oxide wear-resistant agent:

Wet the graphene oxide with dimethylformamide, add KH560 with 5% by weight of graphene oxide, ultrasonically disperse for 1-2h, and set aside;

(2) Preparation of water-based surface treatment agent:

Take 55 parts of aliphatic high-gloss water-based polyurethane with a modulus of 70Mpa and a solid content of 35% by weight, 35 parts of water, 0.05 parts of graphene oxide wear agent pretreated by (1) (solid parts), silicone leveling 1.0 parts of aziridine crosslinking agent, 1.5 parts of aziridine crosslinking agent, 4.0 parts of organic fluorine hand feel improver, mixed evenly, 0.8 parts of water-based polyurethane thickener, mixed evenly, reacted at 20-30°C for 2.5h, and adjusted the viscosity to 1500mPa.s The slurry is ground and filtered to obtain a water-based surface treatment agent.

The surface treatment agent is made of aliphatic water-based polyurethane and organic fluorine with high gloss and high modulus. The amount of modified graphene is relatively high. The coating has excellent wear resistance, scratch resistance, yellowing resistance, waterproof and antifouling. Good quality and high gloss, VOC content is less than 5mg/kg (leather), suitable for surface treatment of high-gloss luggage leather, shoe upper leather, seat leather, home interior leather, etc.

Claims (8)

1. A water-based wear-resistant and scratch-resistant surface treatment agent for artificial leather and synthetic leather and a preparation method, is characterized in that it comprises the following steps: (1) Pretreatment of graphene or graphene oxide wear-resistant agent: ① Moisten the graphene with propylene glycol methyl ether acetate, add a wetting agent of 1% by weight of the graphene, disperse it by ultrasonic wave for 1-2 hours, and set aside; ②Wet the graphene oxide with dimethylformamide, add a modifier of 1% by weight of graphene oxide, disperse it by ultrasonic wave for 1-2h, and set aside; (2) Preparation of water-based surface treatment agent: Take 50-60 parts of water-based polyurethane by weight, 30-40 parts of water, 0.03-0.06 parts of pretreated graphene or graphene oxide wear agent (solid parts), 0-6 parts of matting powder, silicone leveling 0.5-1.0 parts of water-based cross-linking agent, 1.0-1.5 parts of water-based cross-linking agent, 2-5 parts of hand feeling improver, 0.5-1.0 parts of water-based thickener, mix well, and react at 20-30°C for 2-3 hours, and the viscosity is 1000 -2000mPa.s slurry, grind and filter to obtain water-based surface treatment agent. 2. A kind of artificial leather, synthetic leather water-based wear-resistant and scratch-resistant surface treatment agent and preparation method as claimed in claim 1, it is characterized in that the surface treatment water-based polyurethane is high-gloss type, medium-gloss type and/or extinction type, modulus At least one of aliphatic and/or aromatic polyurethanes with 50-80Mpa and 30-35% solid content. 3. a kind of artificial leather, synthetic leather water-based wear-resistant and scratch-resistant surface treatment agent and preparation method as claimed in claim 1, it is characterized in that the wear-resistant agent is a kind of in graphene or graphene oxide. 4. a kind of artificial leather as claimed in claim 1, synthetic leather water-based wear-resistant and scratch-resistant surface treatment agent and preparation method, it is characterized in that the wetting agent of graphene is at least one in Virahol and OP-10; The graphene modifier is at least one of KH560 (γ-glycidoxypropyltrimethoxysilane) and KH550 (γ-aminopropyltriethoxysilane). 5. a kind of artificial leather as claimed in claim 1, synthetic leather water-based wear-resistant and scratch-resistant surface treatment agent and preparation method are characterized in that water-based cross-linking agent is polycarbodiimide, polyaziridine, epoxy resin and/or Or at least one of blocked water-based isocyanates. 6. A kind of artificial leather as claimed in claim 1, synthetic leather water-based wear-resistant and scratch-resistant surface treatment agent and preparation method are characterized in that water-based thickener is nonionic polyurethane thickener and acrylic acid polymer thickener at least one. 7. A kind of water-based wear-resistant and scratch-resistant surface treatment agent for artificial leather and synthetic leather as claimed in claim 1, and its preparation method is characterized in that the hand feel modifier is water-based organic silicon polymer, oil/wax compound and/or organic fluorine At least one of the class polymers. 8. a kind of artificial leather as claimed in claim 1, synthetic leather water-based wear-resistant and scratch-resistant surface treatment agent and preparation method, it is characterized in that described artificial leather, synthetic leather comprise clothing leather, bag leather, shoe upper leather, sofa leather , home decoration leather and or car leather and other varieties.