Wear-resistant and scratch-resistant auxiliary agent, preparation method thereof and application of wear-resistant and scratch-resistant auxiliary agent in water-based industrial paint

Abstract

The invention provides a wear-resistant and scratch-resistant auxiliary agent, a preparation method thereof and application of the wear-resistant and scratch-resistant auxiliary agent in water-based industrial paint, and belongs to the technical field of water-based industrial paint. The wear-resistant and scratch-resistant auxiliary agent comprises the following components in parts by mass: 20-40 parts of silicon paste, 2-4 parts of a reactive emulsifier, 3-6 parts of a nonionic surfactant and 50-75 parts of water. The stable nanoscale oil-in-water system prepared from the reactive emulsifier containing active hydroxyl groups at two ends can be crosslinked into a homogeneous system after being mixed with the water-based resin mother liquor, so that the coating is endowed with durable wear resistance and scratch resistance, meanwhile, the problem that oil spots and bright spots are generated due to precipitation of silicone oil is solved, and the qualification rate of products is increased.

Description

Technical Field

[0001] The invention relates to the technical field of water-based industrial paints, and in particular to a wear-resistant and scratch-resistant additive, a preparation method thereof, and application in water-based industrial paints. Background Art

[0002] As an environmentally friendly coating, water-based industrial paint is widely used in the field of industrial coatings due to its advantages such as low VOC emissions, easy construction and cleaning. However, as consumers' requirements for product durability and appearance retention continue to increase, the market demand for wear-resistant and scratch-resistant additives continues to grow. This demand is not only reflected in traditional coatings, inks and other fields, but also extends to emerging fields such as new energy vehicles, aerospace, etc. These fields are particularly urgent for high-performance and high-durability materials, but traditional water-based industrial paints still need to be improved in terms of wear and scratch resistance. Especially in high-wear and high-scratch industrial environments, the coating is easily damaged, affecting the service life and aesthetics of the product. Therefore, it is particularly important to develop an additive that can effectively improve the wear and scratch resistance of water-based industrial paints. Summary of the invention

[0003] The purpose of the present invention is to provide a wear-resistant and scratch-resistant additive and a preparation method thereof and application in water-based industrial paint, so as to solve the technical problems that the existing water-based industrial paint has poor durability and wear resistance, and conventional wear-resistant and scratch-resistant additives are not compatible with industrial paint and are prone to pitting.

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0005] The present invention provides a wear-resistant and scratch-resistant additive, comprising the following components in parts by weight:

[0006] 20-40 parts of silicone paste;

[0007] Reactive emulsifier 2 to 4;

[0008] 3-6 parts of nonionic surfactant;

[0009] 50-75 parts of water;

[0010] The silicone paste is obtained by reacting nano silicon dioxide, dimethyl silicone oil and / or hydroxy silicone oil;

[0011] The reactive emulsifier is obtained by silicon-hydrogen reaction of terminal hydrogen-containing silicone oil and allyl polyether.

[0012] Furthermore, the preparation method of the silicone paste is:

[0013] The nano-silicon dioxide, dimethyl silicone oil and / or hydroxy silicone oil are mixed and reacted to obtain a silicone paste;

[0014] The reaction temperature is 110-140° C., and the reaction time is 4-5 hours. The nano silicon dioxide accounts for 9-12% of the total mass of the silicone paste, and the dimethyl silicone oil and / or hydroxy silicone oil accounts for 88-91% of the total mass of the silicone paste.

[0015] Furthermore, the viscosity of the dimethyl silicone oil is 50,000 to 500,000 cps; the viscosity of the hydroxy silicone oil is 100,000 to 850,000 cps.

[0016] Furthermore, the preparation method of the reactive emulsifier is:

[0017] After the end-hydrogenated silicone oil and allyl polyether are mixed, the reaction is carried out under the catalytic action of chloroplatinic acid. After the reaction liquid turns transparent, the reaction is continued for 2 to 6 hours. After cooling, a colorless or light yellow transparent liquid is obtained, which is a reactive emulsifier;

[0018] The reaction molar ratio of the terminal hydrogen-containing silicone oil and the allyl polyether is 1.0:1.0-2.2, and the amount of the chloroplatinic acid used is 0.002-0.004% of the total mass of the terminal hydrogen-containing silicone oil and the allyl polyether.

[0019] Furthermore, the mixing temperature is 40-60°C, and the mixing speed is 200-600r / min;

[0020] The reaction temperature is 100-140° C., and the reaction time is 2-6 hours.

[0021] Furthermore, the molecular weight of the hydrogen-terminated silicone oil is 2000-6000; the molecular weight of the allyl polyether is 200-5000.

[0022] Furthermore, the nonionic surfactant comprises isomeric alcohol polyoxyethylene ether and / or fatty alcohol polyoxyethylene ether.

[0023] The present invention also provides a method for preparing a wear-resistant and scratch-resistant additive, which is characterized by comprising the following steps:

[0024] The silicone paste, reactive emulsifier and nonionic surfactant are mechanically mixed, and then water is added for phase inversion to obtain the wear-resistant and anti-scratch additive.

[0025] Furthermore, the rotation speed of the mechanical mixing is 600 to 2000 r / min, and the time of the mechanical mixing is 30 to 120 min.

[0026] The invention provides application of a wear-resistant and scratch-resistant additive in water-based industrial paint.

[0027] Beneficial effects of the present invention:

[0028] The invention forms a stable nano-scale oil-in-water emulsion by selecting a suitable type of emulsifier and strictly controlling the content of each material.

[0029] The present invention utilizes a reactive emulsifier containing active hydroxyl groups at both ends to prepare a stable nano-scale water-in-oil system, which can be cross-linked into a homogeneous system after being mixed with an aqueous resin mother solution, thereby giving the coating long-lasting wear and scratch resistance, while overcoming the problem of oil spots and bright spots caused by the precipitation of silicone oil, thereby improving the qualified rate of products. DETAILED DESCRIPTION

[0030] The present invention provides a wear-resistant and scratch-resistant additive, comprising the following components in parts by weight:

[0031]

[0032] The silicone paste is obtained by reacting nano silicon dioxide, dimethyl silicone oil and / or hydroxy silicone oil;

[0033] The reactive emulsifier is obtained by silicon-hydrogen reaction of terminal hydrogen-containing silicone oil and allyl polyether.

[0034] In the present invention, the amount of the silicone paste is preferably 25 to 35 parts by mass, and more preferably 28 to 32 parts by mass.

[0035] In the present invention, the amount of the reactive emulsifier is preferably 2.2 to 3.8 parts by weight, and more preferably 2.4 to 3.5 parts by weight.

[0036] In the present invention, the amount of the nonionic surfactant is preferably 4 to 5 parts by mass, more preferably 4.5 parts.

[0037] In the present invention, the amount of water used is 55 to 70 parts by mass, and more preferably 60 to 65 parts by mass.

[0038] In the present invention, the preparation method of the silicone paste is:

[0039] The nano-silicon dioxide, dimethyl silicone oil and / or hydroxy silicone oil are mixed and reacted to obtain a silicone paste;

[0040] The reaction temperature is 110-140°C, preferably 120-130°C, and more preferably 125°C; the reaction time is 4-5h, preferably 4.5h; the nano-silicon dioxide accounts for 9-12% of the total mass of the silicone paste, preferably 10-11%; the dimethyl silicone oil and / or hydroxy silicone oil accounts for 88-91% of the total mass of the silicone paste, preferably 89-90%.

[0041] In the present invention, the viscosity of the dimethyl silicone oil is 50,000 to 500,000 cps, preferably 60,000 to 400,000 cps, and more preferably 100,000 to 300,000 cps; the viscosity of the hydroxy silicone oil is 100,000 to 850,000 cps, preferably 200,000 to 650,000 cps, and more preferably 300,000 to 450,000 cps.

[0042] In the present invention, the preparation method of the reactive emulsifier is:

[0043] After the end-hydrogenated silicone oil and allyl polyether are mixed, the reaction is carried out under the catalytic action of chloroplatinic acid. After the reaction liquid turns transparent, the reaction is continued for 2 to 6 hours. After cooling, a colorless or light yellow transparent liquid is obtained, which is a reactive emulsifier;

[0044] The reaction molar ratio of the terminal hydrogen-containing silicone oil and the allyl polyether is 1.0:1.0-2.2, preferably 1.0:1.2-2.0, and more preferably 1.0:1.5-1.8; the amount of chloroplatinic acid used is 0.002-0.004% of the total mass of the terminal hydrogen-containing silicone oil and the allyl polyether, preferably 0.002-0.003%.

[0045] In the present invention, the mixing temperature is 40-60°C, preferably 45-55°C, and more preferably 50°C; the mixing speed is 200-600r / min, preferably 300-500r / min, and more preferably 400-450r / min;

[0046] The reaction temperature is 100-140° C., preferably 110-130° C., and more preferably 120° C.; the reaction time is 2-6 h, preferably 3-5 h, and more preferably 4 h.

[0047] In the present invention, the molecular weight of the hydrogen-terminated silicone oil is 2000-6000, preferably 3000-5000, and more preferably 4000; the molecular weight of the allyl polyether is 200-5000, preferably 1000-4000, and more preferably 1500-3000.

[0048] In the present invention, the allyl polyether is preferably polyether F6 / F10 produced by Jiangsu Zhongshan Chemical Co., Ltd., Yangzhou Chenhua New Materials Co., Ltd., Liaoning Kelong Fine Chemical Co., Ltd., etc., and more preferably F6 / F10 produced by Jiangsu Zhongshan Chemical Co., Ltd.

[0049] In the present invention, the nonionic surfactant comprises isomeric alcohol polyoxyethylene ether and / or fatty alcohol polyoxyethylene ether, and the fatty alcohol polyoxyethylene ether preferably comprises linear alkyl alcohol polyoxyethylene ether AEO series products, and the AEO series products preferably come from BASF AG, Shell Group, and Sanjiang Chemical Co., Ltd., and the linear alkyl alcohol polyoxyethylene ether is preferably BASF AEO-9.

[0050] In the present invention, the isomeric alcohol polyoxyethylene ether preferably includes isomeric tridecanol polyoxyethylene ether; the isomeric tridecanol polyoxyethylene ether preferably comes from BASF AG or Sasol Chemical Co., Ltd. In a specific embodiment of the present invention, the isomeric tridecanol polyoxyethylene ether is specifically Sasol 1370 isomeric tridecanol polyoxyethylene ether.

[0051] The present invention also provides a method for preparing a wear-resistant and scratch-resistant additive, comprising the following steps:

[0052] The silicone paste, reactive emulsifier and nonionic surfactant are mechanically mixed, and then water is added for phase inversion to obtain the wear-resistant and anti-scratch additive.

[0053] In the present invention, the rotation speed of the mechanical mixing is 600-2000 r / min, 1000-2000 r / min, and more preferably 1000-1500 r / min; the time of the mechanical mixing is 30-120 min, preferably 60-100 min, and more preferably 90 min.

[0054] In the present invention, the mechanical mixing is preferably to first mechanically stir the silicone paste and the reactive emulsifier for 0.5 to 1 hour, then add the nonionic surfactant, and continue to mechanically stir for 0.5 to 1 hour.

[0055] In the present invention, the water is added dropwise, and the time of the dropwise addition is preferably 2.5 to 3 hours.

[0056] The invention provides application of a wear-resistant and scratch-resistant additive in water-based industrial paint.

[0057] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0058] Example 1

[0059] Preparation of silicone paste:

[0060] Add 435g of dimethyl silicone oil with a viscosity of 300000cps and 165g of hydroxy silicone oil with a viscosity of 600000cps into a four-necked flask and heat to 140°C. Then start stirring and slowly add 75g of nano-silicon dioxide. After adding, keep warm and stir for 4 hours, then cool to room temperature to obtain a turbid paste, which is silicone paste.

[0061] Preparation of reactive emulsifier:

[0062] Add end-hydrogenated silicone oil with a molecular weight of 3000 and allyl polyether with a molecular weight of 160 (Polyether F6 from Jiangsu Zhongshan Chemical Co., Ltd.) into a four-necked flask and start stirring. Raise the temperature to 50°C at a speed of 500r / min, add catalyst chloroplatinic acid, and continue to raise the temperature to 140°C. After the reaction liquid turns transparent, continue to keep the temperature for 4 hours, and cool to room temperature to obtain a colorless to light yellow transparent liquid, which is a reactive emulsifier.

[0063] The reaction molar ratio of the terminal hydrogen-containing silicone oil to the allyl polyether is 1.0:2.2.

[0064] Preparation of wear-resistant and scratch-resistant additives:

[0065] Add 2 parts of reactive emulsifier and 20 parts of silicone paste into the emulsifier, turn on the power of the emulsifier, rotate at 800r / min, stir mechanically for 0.5h, then add 4 parts of non-ionic surfactant AE0-9 while stirring, continue stirring for 0.5h, and slowly add 74 parts of deionized water within 2h to obtain the wear-resistant and anti-scratch additive.

[0066] Example 2

[0067] Preparation of silicone paste:

[0068] Add 435g of dimethyl silicone oil with a viscosity of 200000cpscps and 165g of hydroxy silicone oil with a viscosity of 650000cps into a four-necked flask and heat to 140°C. Then start stirring and slowly add 75g of nano-silicon dioxide. After adding, keep warm and stir for 4 hours, then cool to room temperature to obtain a turbid paste, which is silicone paste.

[0069] Preparation of reactive emulsifier:

[0070] Add end-hydrogenated silicone oil with a molecular weight of 4000 and allyl polyether with a molecular weight of 660 (Polyether F10 of Jiangsu Zhongshan Chemical Co., Ltd.) into a four-necked flask and start stirring. Raise the temperature to 60°C at a speed of 600r / min, add catalyst chloroplatinic acid, and continue to raise the temperature to 130°C. After the reaction liquid turns transparent, continue to keep warm for 3 hours, and cool to room temperature to obtain a colorless to light yellow transparent liquid, which is a reactive emulsifier.

[0071] The reaction molar ratio of the terminal hydrogen-containing silicone oil to the allyl polyether is 1.0:2.2.

[0072] Preparation of wear-resistant and scratch-resistant additives:

[0073] Add 3 parts of reactive emulsifier and 20 parts of silicone paste into the emulsifier, turn on the power of the emulsifier, rotate at 800r / min, stir mechanically for 0.5h, then add 4 parts of non-ionic surfactant AE0-9 while stirring, continue stirring for 0.5h, and slowly add 73 parts of deionized water within 2.5h to obtain the wear-resistant and anti-scratch additive.

[0074] Example 3

[0075] Preparation of silicone paste:

[0076] Add 365g of dimethyl silicone oil with a viscosity of 180000cps and 185g of hydroxy silicone oil with a viscosity of 500000cps into a four-necked flask and heat to 140°C. Then start stirring and slowly add 75g of nano-silicon dioxide. After adding, keep warm and stir for 5 hours, then cool to room temperature to obtain a turbid paste, which is silicone paste.

[0077] Preparation of reactive emulsifier:

[0078] Add end-hydrogenated silicone oil with a molecular weight of 4000 and allyl polyether with a molecular weight of 160 (Polyether F6 from Jiangsu Zhongshan Chemical Co., Ltd.) into a four-necked flask and start stirring. Raise the temperature to 40°C at a speed of 400r / min, add catalyst chloroplatinic acid, and continue to raise the temperature to 110°C. After the reaction liquid turns transparent, continue to keep the temperature for 6 hours, and cool to room temperature to obtain a colorless to light yellow transparent liquid, which is a reactive emulsifier.

[0079] The reaction molar ratio of the terminal hydrogen-containing silicone oil to the allyl polyether is 1.0:2.2.

[0080] Preparation of wear-resistant and scratch-resistant additives:

[0081] Add 4 parts of reactive emulsifier and 20 parts of silicone paste into the emulsifier, turn on the power of the emulsifier, rotate at 800r / min, stir mechanically for 0.5h, then add 4 parts of non-ionic surfactant 1370 while stirring, continue stirring for 0.5h, and slowly add 72 parts of non-ionic water within 3h to obtain the wear-resistant and anti-scratch additive.

[0082] Comparative Example 1

[0083] The preparation method of the wear-resistant and scratch-resistant additive is the same as that of Example 1, except that conventional emulsifier Tween 20 is used instead of the reactive emulsifier.

[0084] Comparative Example 2

[0085] The preparation method of the wear-resistant and scratch-resistant additive is the same as that of Example 1; the difference is that 435 g of dimethyl silicone oil with a viscosity of 300,000 cps and 165 g of hydroxy silicone oil with a viscosity of 600,000 cps are used instead of the silicone paste.

[0086] The effect of the wear-resistant and anti-scratch additive of the water-based industrial paint prepared in the above embodiment was tested by the following method:

[0087] Prepare the base liquid:

[0088] In a 2L measuring cup, add 800g of aqueous blank resin, 88g of deionized water, 30g of co-solvent dipropylene glycol methyl ether, 30g of dipropylene glycol butyl ether, 4g of RHEOBYK-H750VF, 4g of TEGO TWIN 4100, 2g of TEGO FOAMEX 902W, 3g of TEGOGLDE 450, and 20g of SYLOID AQ800 at a dispersion speed of 800rpm and stir for 30 minutes to obtain a base liquid with a viscosity of 500-600CPS, a solid content of 35%, and a gloss (60°) of 25-30%.

[0089] The prepared base liquid was divided into 5 parts on average, and then the wear-resistant and scratch-resistant additives of the above three embodiments, the imported brand DC-51 and the domestic company CG-51 were added to each part, with 5% of the total mass of the base liquid as the wear-resistant and scratch-resistant additives, the dispersion speed was 1200rpm, and the mixture was stirred for 15 minutes. Then, the mixture was sprayed onto the wooden board by conventional process, and the wear-resistant effect was tested by using an aber wear tester after drying, and the scratch-resistant effect was tested by using a pencil hardness test method. The test results are shown in Table 1 below:

[0090] Table 1 Test results

[0091]

[0092] Remark:

[0093] Compatibility: A means slight stratification, B means basic compatibility, C means complete compatibility

[0094] Feel level: 1 (poor), 2 (average), 3 (good), 4 (very good)

[0095] Wear and scratch resistance: The higher the level, the better

[0096] Storage stability: indicated by excellent and good

[0097] It can be seen from the above examples that the present invention provides a wear-resistant and scratch-resistant additive and a preparation method thereof and an application in water-based industrial paints. It can be seen from the above test data that the comprehensive performance of the wear-resistant and scratch-resistant additive of Example 2 is good, such as compatibility, feel, wear resistance, scratch resistance and product storage stability are relatively excellent, and its wear-resistant and scratch-resistant performance is on par with foreign competing products, but the advantage of Example 2 is that it has better compatibility, is priced lower than foreign competing products, and has a high cost-effectiveness.

[0098] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A wear-resistant and scratch-resistant additive, characterized in that: Contains the following components in parts by weight: The silicone paste is obtained by reacting nano silicon dioxide, dimethyl silicone oil and / or hydroxy silicone oil; The reactive emulsifier is obtained by silicon-hydrogen reaction of terminal hydrogen-containing silicone oil and allyl polyether.

2. The wear-resistant and scratch-resistant additive according to claim 1, characterized in that: The preparation method of the silicone paste is: The nano-silicon dioxide, dimethyl silicone oil and / or hydroxy silicone oil are mixed and reacted to obtain a silicone paste; The reaction temperature is 110-140° C., and the reaction time is 4-5 hours. The nano silicon dioxide accounts for 9-12% of the total mass of the silicone paste, and the dimethyl silicone oil and / or hydroxy silicone oil accounts for 88-91% of the total mass of the silicone paste.

3. The wear-resistant and scratch-resistant additive according to claim 2, characterized in that: The viscosity of the dimethyl silicone oil is 50,000 to 500,000 cps; the viscosity of the hydroxy silicone oil is 100,000 to 850,000 cps.

4. The wear-resistant and scratch-resistant additive according to claim 1, characterized in that: The preparation method of the reactive emulsifier is: After the end-hydrogenated silicone oil and allyl polyether are mixed, the reaction is carried out under the catalytic action of chloroplatinic acid. After the reaction liquid turns transparent, the reaction is continued for 2 to 6 hours. After cooling, a colorless or light yellow transparent liquid is obtained, which is a reactive emulsifier; The reaction molar ratio of the terminal hydrogen-containing silicone oil and the allyl polyether is 1.0:1.0-2.2, and the amount of the chloroplatinic acid used is 0.002-0.004% of the total mass of the terminal hydrogen-containing silicone oil and the allyl polyether.

5. The wear-resistant and scratch-resistant additive according to claim 4, characterized in that: The mixing temperature is 40-60°C, and the mixing speed is 200-600r / min; The reaction temperature is 100-140° C., and the reaction time is 2-6 hours.

6. The wear-resistant and scratch-resistant additive according to claim 4 or 5, characterized in that: The molecular weight of the hydrogen-terminated silicone oil is 2000-6000; the molecular weight of the allyl polyether is 200-5000.

7. The wear-resistant and scratch-resistant additive according to claim 1, 3 or 4, characterized in that: The nonionic surfactant comprises isomeric alcohol polyoxyethylene ether and / or fatty alcohol polyoxyethylene ether.

8. The method for preparing the wear-resistant and scratch-resistant additive according to any one of claims 1 to 7, characterized in that: The following steps are involved: The silicone paste, reactive emulsifier and nonionic surfactant are mechanically mixed, and then water is added for phase inversion to obtain the wear-resistant and anti-scratch additive.

9. The preparation method according to claim 8, characterized in that: The rotation speed of the mechanical mixing is 600-2000 r / min, and the time of the mechanical mixing is 30-120 min.

10. Use of the wear-resistant and scratch-resistant additive according to any one of claims 1 to 7 in water-based industrial paints.

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