A kind of water-based plastic replacement oil and preparation method thereof

Abstract

The present application relates to the technical field of plastic replacement oils, and specifically discloses an aqueous plastic replacement oil and a preparation method thereof. An aqueous plastic replacement oil comprises the following raw materials in parts by weight: 60‑80 parts of aqueous polyurethane composite emulsion, 10‑20 parts of aqueous acrylic emulsion, 2‑4 parts of wax powder, 2‑4 parts of matting powder, 0.5‑2 parts of silicone, and 20‑40 parts of water; the aqueous polyurethane composite emulsion comprises the following raw materials in parts by weight: 40‑50 parts of aqueous isocyanate-terminated polyurethane prepolymer, 10‑20 parts of silica sol, and 1‑3 parts of chain extender. An aqueous plastic replacement oil of the present application adds an appropriate amount of silica sol to the polyurethane prepolymer to promote good compatibility between the silica sol and the polymer in the plastic replacement oil, thereby improving the strength and wear resistance of the aqueous plastic replacement oil.

Description

Technical Field

[0001] The present application relates to the technical field of plastic replacement oil, and more specifically, to an aqueous plastic replacement oil and a preparation method thereof. Background Art

[0002] Water-based plastic replacement oil is a mature thermoplastic water-based polyurethane new environmentally friendly material that has emerged in response to the global plastic restriction order. It has excellent high tension, high tensile strength, folding and riot resistance, waterproof, aging resistance, and environmental protection. After oiling, it has good glossiness and good yellowing resistance on the film surface. It is widely used in medical, electronic equipment, cosmetics, education and other packaging cardboard coating fields.

[0003] However, water-based plastic replacement oils are prone to softening, scratching, and wearing during use, which in turn affects the durability of the coating and shortens the service life of the water-based plastic replacement oils. Summary of the invention

[0004] In order to improve the hardness and wear resistance of water-based plastic replacement oil, the present application provides a water-based plastic replacement oil and a preparation method thereof.

[0005] In the first aspect, the present application provides an aqueous plastic replacement oil, which adopts the following technical solution:

[0006] A water-based plastic replacement oil comprises the following raw materials in parts by weight: 60-80 parts of water-based polyurethane composite emulsion, 10-20 parts of water-based acrylic emulsion, 2-4 parts of wax powder, 2-4 parts of matting powder, 0.5-2 parts of organic silicon, and 20-40 parts of water; the water-based polyurethane composite emulsion comprises the following raw materials in parts by weight: 40-50 parts of water-based isocyanate-terminated polyurethane prepolymer, 10-20 parts of silica sol, and 1-3 parts of chain extender.

[0007] By adopting the above technical solution, the silica sol surface has abundant silanol bonds that can react with isocyanate on polyurethane, thereby improving the hardness and wear resistance of water-based plastic replacement oil. At the same time, the silicon oxygen bonds of the silica sol have a film-forming effect, which can improve the film-forming performance of water-based plastic replacement oil. The use of isocyanate-terminated polyurethane prepolymer mixed with silica sol can promote more reactions between the active groups of the polyurethane prepolymer and the silica sol, thereby improving the compatibility of the organic phase and the inorganic phase.

[0008] Preferably, the organosilicon is a silane coupling agent.

[0009] By adopting the above technical solution, the silane group in the silane coupling agent is chemically bonded with the surface of the substrate during the formation of the water-based plastic oil coating, thereby enhancing the adhesion between the coating and the substrate. At the same time, the silane coupling agent can form a layer of inorganic silicon oxygen network structure on the surface of the coating, thereby improving the weather resistance and anti-pollution performance of the coating.

[0010] Preferably, the wax powder has a particle size of 1-5 μm.

[0011] By adopting the above technical solution and selecting wax powder with a smaller particle size, the dispersibility and uniform distribution of the wax powder in the water-based plastic replacement oil system can be improved. At the same time, the smaller wax powder can improve the transparency of the water-based plastic replacement oil, reduce the scattering and reflection of light, and thus make the coating film more transparent.

[0012] Preferably, the wax powder is coated with silicon dioxide.

[0013] By adopting the above technical solution, the wax powder is coated with silicon dioxide, which can reduce the problem of wax powder easily agglomerating and agglomerating in water-based plastic replacement oil, and reduce the uneven coating phenomenon. At the same time, silicon dioxide can prolong the release rate of wax powder, prompting the wax powder to be gradually released to the surface of plastic replacement oil, which helps to form a uniformly distributed wax powder effect after the coating is dried or solidified, forming a smooth and soft paint film.

[0014] Preferably, the aqueous plastic replacement oil raw material further comprises 1-3 parts of polyvinyl alcohol and 0.1-0.3 parts of sodium hydroxide.

[0015] By adopting the above technical solution, polyvinyl alcohol has good adhesion, which can improve the bonding performance and adhesion of water-based plastic replacement oil, and promote better combination between plastic replacement oil and substrate. Sodium hydroxide can have a certain etching effect on matting powder, which makes the surface of matting powder have more fine concave-convex structures, which can scatter incident light and enhance the matting effect of the coating.

[0016] At the same time, polyvinyl alcohol is coated on the surface of the matting powder, which can promote the matting powder to be evenly dispersed in the water-based plastic replacement oil, reduce the attraction between the matting powder particles, and enhance the anti-precipitation property of the water-based plastic replacement oil system.

[0017] In a second aspect, the present application provides a method for preparing an aqueous plastic replacement oil, using the following technical solution:

[0018] A method for preparing a water-based plastic replacement oil comprises the following specific steps: pre-mixing and dispersing silica sol with water-based isocyanate-terminated polyurethane prepolymer, and then adding a chain extender for mixed reaction to form a water-based polyurethane composite emulsion;

[0019] The water-based polyurethane composite emulsion is evenly mixed with the water-based acrylic emulsion, wax powder, matting powder, silicone and water to form a water-based plastic replacement oil.

[0020] By adopting the above technical solution, the prepared water-based plastic replacement oil has strong hardness and wear resistance under the synergistic effect of various components, and the inorganic phase and the organic phase in the water-based plastic replacement oil have good compatibility.

[0021] Preferably, the wax powder is pre-mixed with the silica sol and dispersed evenly to form a wax powder-silicon dioxide composite, and then the wax powder-silicon dioxide composite is dried and solidified to form a silica-coated wax powder, and then the silica-coated wax powder is evenly mixed with an aqueous polyurethane composite emulsion, an aqueous acrylic emulsion, a matting powder, silicone, and water to form an aqueous plastic replacement oil.

[0022] Preferably, after sodium hydroxide and matting powder are mixed and etched in advance, the matting powder is taken out and washed with water, and then polyvinyl alcohol is mixed with a solvent to form a polyvinyl alcohol solution, and then the etched matting powder is suspended in the polyvinyl alcohol solution and stirred evenly to form a matting powder composite; then the matting powder composite is evenly mixed with an aqueous polyurethane composite emulsion, an aqueous acrylic emulsion, wax powder, silicone, and water to form an aqueous plastic replacement oil.

[0023] By adopting the above technical scheme, the matting powder is etched with an appropriate amount of sodium hydroxide in advance to form a fine rough structure on the surface of the matting powder, and then polyvinyl alcohol is used to perform surface film modification on the surface of the matting powder, thereby improving the uniform distribution of the matting powder in the aqueous plastic replacement oil system and enhancing the uniform matting effect of the aqueous plastic replacement oil.

[0024] In summary, this application has the following beneficial effects:

[0025] 1. Since the present application adopts the combination of silica sol and isocyanate-terminated polyurethane prepolymer, the silica sol can be evenly distributed in the water-based plastic replacement oil system, thereby improving the strength and wear resistance of the water-based plastic replacement oil.

[0026] 2. In the present application, sodium hydroxide is used to etch the matting powder, and then polyvinyl alcohol is used to form a film to coat the matting powder, so as to form a fine concave-convex structure on the surface of the matting powder and improve the matting effect of the matting powder. At the same time, polyvinyl alcohol is used to increase the dispersibility of the matting powder in the aqueous plastic replacement oil system and reduce the aggregation and precipitation of the matting powder in the aqueous plastic replacement oil. DETAILED DESCRIPTION

[0027] The present application is further described in detail below with reference to the embodiments.

[0028] In this specific embodiment, without other special circumstances, the components used are as follows:

[0029] The solid content of the silica sol is 40%, the average particle size is 70-90 nm, and the hydroxyl content is 0.402 mmol / g.

[0030] The viscosity of the aqueous acrylic emulsion is 300 mPa.s at 25° C., and the solid content of the aqueous acrylic emulsion is 35 wt %.

[0031] The aqueous isocyanate-terminated polyurethane prepolymer has a viscosity of 200 mPa.s at 25° C. and a solid content of 38 wt %.

[0032] The degree of polymerization of polyethylene wax powder is 200.

[0033] The molecular weight of polyvinyl alcohol is 120,000.

[0034] Preparation example of waterborne polyurethane composite emulsion

[0035] Preparation Example 1

[0036] The waterborne polyurethane composite emulsion comprises the following raw materials in parts by weight: 45 kg of waterborne isocyanate-terminated polyurethane prepolymer, 15 kg of silica sol, and 2 kg of chain extender, wherein the chain extender is ethylenediamine.

[0037] The preparation method of the aqueous polyurethane composite emulsion comprises the following specific steps:

[0038] Water and silica sol are mixed in advance with a mass ratio of silica sol to water of 1:1.1 to form a silica sol solution, and then the silica sol solution is mixed with a water-based isocyanate-terminated polyurethane prepolymer, stirred at a speed of 150 r / min for 5 minutes, and then a chain extender is added, and stirring is continued for 30 minutes to form a water-based polyurethane composite emulsion.

[0039] Preparation Example 2

[0040] The difference between Preparation Example 2 and Preparation Example 1 is that the amount of aqueous isocyanate-terminated polyurethane prepolymer used as the raw material of the aqueous polyurethane composite emulsion is 40 kg, the amount of silica sol used is 20 kg, and the amount of chain extender used is 1 kg.

[0041] Preparation Example 3

[0042] The difference between Preparation Example 3 and Preparation Example 1 is that the amount of the aqueous isocyanate-terminated polyurethane prepolymer used as the raw material of the aqueous polyurethane composite emulsion is 50 kg, the amount of silica sol used is 10 kg, and the amount of the chain extender used is 3 kg.

[0043] Example

[0044] Example 1

[0045] This embodiment provides an aqueous plastic replacement oil, comprising the following raw materials in parts by weight: 70 kg of aqueous polyurethane composite emulsion, 15 kg of aqueous acrylic emulsion, 3 kg of wax powder, 3 kg of matting powder, 1.3 kg of organic silicon, and 30 kg of water. The aqueous polyurethane composite emulsion is from Preparation Example 1, the organic silicon is KH-560, the wax powder is polyethylene wax powder, and the average particle size of the wax powder is 1-5 μm.

[0046] The preparation method of the water-based plastic replacement oil comprises the following specific steps:

[0047] The water-based polyurethane composite emulsion is evenly mixed with the water-based acrylic emulsion, wax powder, matting powder, silicone and water to form a water-based plastic replacement oil.

[0048] Example 2

[0049] The difference between Example 2 and Example 1 is that the amount of aqueous polyurethane composite emulsion used in the aqueous plastic replacement oil raw material is 60 kg, the amount of aqueous acrylic emulsion used is 20 kg, the amount of wax powder used is 4 kg, the amount of matting powder used is 2 kg, the amount of silicone used is 0.5 kg, and the amount of water used is 20 kg.

[0050] Example 3

[0051] The difference between Example 3 and Example 1 is that the amount of aqueous polyurethane composite emulsion used in the aqueous plastic replacement oil raw material is 80 kg, the amount of aqueous acrylic emulsion used is 10 kg, the amount of wax powder used is 2 kg, the amount of matting powder used is 4 kg, the amount of silicone used is 2 kg, and the amount of water used is 40 kg.

[0052] Example 4

[0053] The difference between Example 4 and Example 1 is that the aqueous polyurethane composite emulsion in the aqueous plastic replacement oil raw material comes from Preparation Example 2.

[0054] Example 5

[0055] The difference between Example 5 and Example 1 is that the aqueous polyurethane composite emulsion in the aqueous plastic replacement oil raw material comes from Preparation Example 3.

[0056] Example 6

[0057] The difference between Example 6 and Example 1 is that the wax powder in the aqueous plastic replacement oil raw material is coated with silicon dioxide.

[0058] The preparation method of the water-based plastic replacement oil comprises the following specific steps:

[0059] S1: The wax powder is suspended in silica sol, the average particle size of the silica sol is 70-90nm, the mass ratio of silica sol to wax powder is 2:1, ultrasonic dispersion, the ultrasonic frequency is 80kHz, and then stirred at a speed of 300r / min for 24h, and then dried and solidified to form silica-coated wax powder.

[0060] S2: Evenly mix the water-based polyurethane composite emulsion with the water-based acrylic emulsion, the silicon dioxide-coated wax powder, the matting powder, the silicone and water to form a water-based plastic replacement oil.

[0061] Example 7

[0062] The difference between Example 7 and Example 6 is that the aqueous plastic replacement oil raw material further includes 2 kg of polyvinyl alcohol.

[0063] The preparation method of the water-based plastic replacement oil comprises the following specific steps:

[0064] S1: The wax powder is suspended in silica sol, the mass ratio of silica sol to wax powder is 2:1, ultrasonic dispersion is performed, the ultrasonic frequency is 80kHz, and then stirred at a speed of 300r / min for 24h, and then dried and solidified to form silica-coated wax powder.

[0065] S2: Polyvinyl alcohol and water are heated to 70°C to dissolve, and the mass ratio of polyvinyl alcohol to water is 1:1.3 to form a polyvinyl alcohol solution. Then, the matting powder is added to the polyvinyl alcohol solution, stirred at a speed of 300r / min for 24h, and then allowed to stand for 2h, the solid is filtered out, washed with water, and vacuum dried to form a polyvinyl alcohol composite matting powder.

[0066] S3: Evenly mix the water-based polyurethane composite emulsion with the water-based acrylic emulsion, the silicon dioxide-coated wax powder, the polyvinyl alcohol composite matting powder, the silicone and water to form a water-based plastic replacement oil.

[0067] Example 8

[0068] The difference between Example 8 and Example 7 is that the aqueous plastic replacement oil raw material further includes 0.2 kg of sodium hydroxide.

[0069] The preparation method of the water-based plastic replacement oil comprises the following specific steps:

[0070] S1: The wax powder is suspended in silica sol, the mass ratio of silica sol to wax powder is 2:1, ultrasonic dispersion is performed, the ultrasonic frequency is 80kHz, and then stirred at a speed of 300r / min for 24h, and then dried and solidified to form silica-coated wax powder.

[0071] S2: Mix sodium hydroxide and water in advance to form a sodium hydroxide solution with a sodium hydroxide mass fraction of 5%, then add the matting powder to the sodium hydroxide solution, stir at a speed of 300 r / min for 5 minutes, then filter, take out the matting powder, wash with water, and dry to form an etched matting powder; heat polyvinyl alcohol and water to 70°C to dissolve, the mass ratio of polyvinyl alcohol to water is 1:1.3, to form a polyvinyl alcohol solution, then add the etched matting powder to the polyvinyl alcohol solution, stir at a speed of 300 r / min for 24 hours, then let it stand for 2 hours, filter out the solid, wash with water, and vacuum dry to form a matting powder complex.

[0072] S3: Evenly mix the water-based polyurethane composite emulsion with the water-based acrylic emulsion, the silicon dioxide-coated wax powder, the matting powder composite, the silicone and water to form a water-based plastic replacement oil.

[0073] Example 9

[0074] The difference between Example 9 and Example 8 is that the amount of polyvinyl alcohol used in the aqueous plastic replacement oil raw material is 1 kg, and the amount of sodium hydroxide used is 0.1 kg.

[0075] Example 10

[0076] The difference between Example 10 and Example 8 is that the amount of polyvinyl alcohol used in the aqueous plastic replacement oil raw material is 3 kg, and the amount of sodium hydroxide used is 0.3 kg.

[0077] Embodiment 11

[0078] The difference between Example 11 and Example 8 is that polyvinyl alcohol is not used in the aqueous plastic replacement oil raw material.

[0079] The preparation method of the water-based plastic replacement oil comprises the following specific steps:

[0080] S1: The wax powder is suspended in silica sol, the mass ratio of silica sol to wax powder is 2:1, ultrasonic dispersion is performed, the ultrasonic frequency is 80kHz, and then stirred at a speed of 300r / min for 24h, and then dried and solidified to form silica-coated wax powder.

[0081] S2: Mix sodium hydroxide and water in advance to form a sodium hydroxide solution with a mass fraction of 5%, then add the matting powder into the sodium hydroxide solution, stir at a speed of 300r / min for 5 minutes, then filter, take out the matting powder, wash it with water, and dry it to form the etched matting powder.

[0082] S3: Evenly mix the water-based polyurethane composite emulsion with the water-based acrylic emulsion, the silicon dioxide-coated wax powder, the etched matting powder, the silicone and water to form a water-based plastic replacement oil.

[0083] Comparative Example

[0084] Comparative Example 1

[0085] The difference between Comparative Example 1 and Example 1 is that an equal amount of aqueous polyurethane emulsion is used in the aqueous plastic replacement oil raw material instead of the aqueous polyurethane composite emulsion.

[0086] Comparative Example 2

[0087] The difference between Comparative Example 2 and Example 1 is that an equal amount of aqueous polyurethane emulsion is used in the aqueous plastic replacement oil raw material instead of the aqueous polyurethane composite emulsion, and silica sol is directly added into the aqueous plastic replacement oil, and the amount of silica sol used is 15 kg.

[0088] The preparation method of the water-based plastic replacement oil comprises the following specific steps:

[0089] The water-based polyurethane emulsion is evenly mixed with the water-based acrylic emulsion, wax powder, matting powder, silicone, silica sol and water to form a water-based plastic replacement oil.

[0090] Performance testing

[0091] The following performance tests were performed on the aqueous plastic replacement oils provided in Examples 1-11 and Comparative Examples 1-2 of the present application. The specific test results are shown in Table 1.

[0092] Detection Methods

[0093] 1. Glossiness

[0094] Use a gloss meter, model DG60 Pro, with a gloss meter measuring angle of 60°. Place the gloss meter on the surface of the plastic oil for testing.

[0095] 2. Wear resistance

[0096] Cut the sample into 230mm×50mm and fix it on the friction table of the equipment; then fix the white paper on a 4-pound load block, place it above the sample, and set the friction number to 1000 times.

[0097] 3. Hardness

[0098] According to the GB / T6739-2006 pencil hardness test, a pencil is pressed downward on the surface of the solidified plastic replacement oil at a 45° angle under a load of 500g.

[0099] Table 1: Performance test data table

[0100] Example Glossiness Wear resistance hardness Example 1 5 No obvious linear scratches 1H Example 2 6 No obvious linear scratches 1H Example 3 7 No obvious linear scratches 1H Example 4 6 No obvious linear scratches 1H Example 5 5 No obvious linear scratches 1H Example 6 4 No obvious linear scratches 2H Example 7 3 No obvious linear scratches 3H Example 8 1 No obvious linear scratches 3H Example 9 2 No obvious linear scratches 3H Example 10 1 No obvious linear scratches 3H Embodiment 11 3 No obvious linear scratches 2H Comparative Example 1 8 There are many scratches and the paint film is easy to fall off B Comparative Example 2 9 There are a few scratches HB

[0101] The performance test results show that the water-based plastic replacement oil prepared in this application has high hardness and wear resistance, while maintaining a good matte effect. In Examples 1-5 of this application, the usage amounts of each component in the water-based plastic replacement oil system are different, and Example 1 has better comprehensive performance.

[0102] By comparing Example 6 with Example 1, it can be seen that the wax powder in Example 6 is coated with silica. From the performance test results, it can be seen that the comprehensive performance of the aqueous plastic replacement oil prepared in Example 6 is better. At the same time, there is no agglomeration phenomenon during the storage of the aqueous plastic replacement oil, which further illustrates the coating effect of silica on the wax powder, enhances the dispersibility of the wax powder in the aqueous plastic replacement oil, and improves the uniformity of the gloss of the aqueous plastic replacement oil.

[0103] In Examples 7-10, appropriate amounts of polyvinyl alcohol and sodium hydroxide were added to the water-based plastic replacement oil, respectively. From the performance test results, it can be seen that the prepared water-based plastic replacement oil has a better matting effect. At the same time, from the comparison between Example 11 and Example 8, it can be seen that Example 11 does not use polyvinyl alcohol, but only uses sodium hydroxide to etch the matting powder. From the performance test results, it can be seen that the matting effect of the water-based plastic replacement oil will decrease. This may be because after the matting powder is etched with sodium hydroxide, the rough concave-convex structure on the surface is not modified by polyvinyl alcohol, and it is directly added to the water-based plastic replacement oil, resulting in uneven matting effect of the matting powder, which in turn affects the matting uniformity of the water-based plastic replacement oil.

[0104] By comparing Comparative Examples 1 and 2 with Example 1, it can be seen that no silica sol is used in Comparative Example 1, and the silica sol is directly added to the water-based plastic replacement oil in Comparative Example 2. From the performance test results, it can be seen that the comprehensive performance of the water-based plastic replacement oil will decrease, which further illustrates that the existing water-based plastic replacement oil has the problems of being too soft and having poor wear resistance. Although the hardness is increased by directly adding silica sol to the plastic replacement oil, the wear resistance of the plastic replacement paint film is still poor due to the compatibility problem between silica sol and organic polymers.

[0105] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A water-based plastic replacement oil, characterized in that: The waterborne polyurethane composite emulsion comprises the following raw materials in parts by weight: 60-80 parts of waterborne polyurethane composite emulsion, 10-20 parts of waterborne acrylic emulsion, 2-4 parts of wax powder, 2-4 parts of matting powder, 0.5-2 parts of silicone, 20-40 parts of water, 1-3 parts of polyvinyl alcohol, and 0.1-0.3 parts of sodium hydroxide; the waterborne polyurethane composite emulsion comprises the following raw materials in parts by weight: 40-50 parts of waterborne isocyanate-terminated polyurethane prepolymer, 10-20 parts of silica sol, and 1-3 parts of chain extender; The particle size of the wax powder is 1-5 μm. The wax powder is coated with silicon dioxide. In the preparation of the aqueous plastic replacement oil, sodium hydroxide and matting powder are mixed and etched in advance, the matting powder is taken out, washed with water, and then polyvinyl alcohol is mixed with a solvent to form a polyvinyl alcohol solution. The etched matting powder is then suspended in the polyvinyl alcohol solution and stirred evenly to form a matting powder composite.

2. The aqueous plastic replacement oil according to claim 1, characterized in that: The organic silicon is a silane coupling agent.

3. A method for preparing an aqueous plastic replacement oil as claimed in any one of claims 1 to 2, characterized in that: The method comprises the following specific steps: mixing and dispersing silica sol with water-based isocyanate-terminated polyurethane prepolymer in advance, and then adding a chain extender for mixed reaction to form a water-based polyurethane composite emulsion; After etching the sodium hydroxide and the matting powder, the matting powder is taken out and washed with water, and then polyvinyl alcohol is mixed with a solvent to form a polyvinyl alcohol solution, and then the etched matting powder is suspended in the polyvinyl alcohol solution and stirred evenly to form a matting powder composite; then the matting powder composite is evenly mixed with an aqueous polyurethane composite emulsion, an aqueous acrylic emulsion, wax powder, silicone, and water to form an aqueous plastic replacement oil.

4. The method for preparing an aqueous plastic replacement oil according to claim 3, characterized in that: The wax powder and the silica sol are mixed in advance and dispersed evenly to form a wax powder-silicon dioxide composite. The wax powder-silicon dioxide composite is then dried and solidified to form a silicon dioxide-coated wax powder.