Two-component blending type self-repairing coating as well as preparation method and application thereof

Abstract

The invention relates to a two-component blending type self-repairing coating as well as a preparation method and application thereof. The two-component blending type self-repairing coating comprises the following components in percentage by weight: 50-70% of a main agent A and the balance of a curing agent B, the main agent A is prepared from the following raw material components in percentage by weight: 1 to 10 percent of acrylate, 10 to 15 percent of special modified caprolactone monomer, 1 to 10 percent of hydroxyl acrylic monomer, 0.5 to 1.5 percent of organic silicon modified monomer, 0.5 to 1 percent of chain transfer agent, 0.1 to 0.5 percent of initiator, 5 to 15 percent of solvent type hydroxyl polyurethane prepolymer and the balance of first solvent; the curing agent B comprises the following components in parts by weight: 70-80% of isocyanate and the balance of a second solvent; and adding the curing agent B into the main agent A, and uniformly stirring to obtain the double-component blending type self-repairing coating. The coating provided by the invention has excellent weather resistance and chemical resistance, also has good transparency and glossiness, and is excellent in repairing performance.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of paint, the preparation method of paint and its application, specifically related to a kind of two-component blend type self-repairing paint with excellent self-repairing and flexibility, and with excellent weather resistance, chemical resistance and wear resistance, preparation method and use. BACKGROUND

[0002] At present, domestic film market gradually matures, and the demand for domestic films is gradually increasing. Mobile phones, new energy and conventional gasoline cars are widespread, and in order to make mobile phones and cars more beautiful and longer in use, consumers will generally stick protective films to the products. Under external force, scratches can be repaired by the repair film, and some repair products can even prevent graffiti to ensure that the surface of cars, furniture and mobile phones is clean and new. However, the core technology of repair film is in the hands of developed countries such as the United States, Japan and South Korea, and the product quality is uneven, and the price is high. Due to the huge market potential of repair film, self-repairing coating also has huge market potential, and it is necessary to develop self-repairing to meet the strong demand of the domestic market.

[0003] Now there are many intrinsic self-repairing in China. Intrinsic self-repairing coating refers to the coating material itself containing special chemical bonds or functional groups, which can realize self-repairing through chemical bond recombination, functional group reaction or physical action after damage. Intrinsic self-repairing does not require an external repair system, but the coating material itself contains special chemical bonds or other physical and chemical properties such as reversible covalent bonds, non-covalent bonds, molecular diffusion, etc.

[0004] There are two main types of conventional intrinsic self-repairing. The first type is a system obtained by modifying polyacrylic polyol and reacting with isocyanate. Due to the high crosslinking degree of this reaction system, the three-dimensional network structure of the coating is dense, and the coating obtained has excellent weather resistance and chemical resistance, but the coating hardness is high, easy to break, and not suitable for construction in the automotive and furniture industries, and the repair conditions are harsh and the repair performance is poor. The second type is a system obtained by modifying polyurethane polyol and reacting with isocyanate. The coating obtained from this system has excellent flexibility and wear resistance, and excellent repair performance, and can be repaired at 40-60℃. However, due to the low crosslinking degree of this reaction system, the three-dimensional network structure of the coating is not dense, which makes the coating have relatively weak chemical resistance and weather resistance.

[0005] Therefore, some manufacturers have tried to mix conventional two self-repairing according to different proportions, but the compatibility is poor after mixing, which is not compatible, so that the repair layer obtained is foggy, the surface is rough, there are particles, the transparency and gloss are greatly reduced, and the weather resistance and chemical resistance are also affected, and the disadvantages are much greater than the advantages.

[0006] In addition to good repairability and scratch resistance, outdoor ultraviolet light irradiation and acid rain are currently the two hard indicators that are most concerned about self-repairing coating. Most self-repairing coatings are not resistant to acid rain, which brings great trouble to the user of the repair film. SUMMARY

[0007] In view of the above problems, the main purpose of the present application is to provide a two-component blended self-repairing coating with excellent self-repairing and flexibility, and excellent weather resistance, chemical resistance and wear resistance, a preparation method and use.

[0008] The present application solves the above technical problems by the following technical scheme: a two-component blended self-repairing coating, the two-component blended self-repairing coating comprises the following components in weight content: main agent A: 50-70%, and the rest is curing agent B.

[0009] The raw materials for preparing the main agent A comprise the following components in weight content:

[0010]

[0011]

[0012] The rest is the first solvent;

[0013] The curing agent B comprises the following components in weight content:

[0014] Isocyanate 70-80%

[0015] The rest is the second solvent.

[0016] In use, the curing agent B is added to the main agent A and stirred uniformly to obtain the two-component blended self-repairing coating.

[0017] In specific embodiments of the present application, the solid content of the self-repairing coating is 38-48%, and the curing agent B accounts for 1 / 3-1 / 2 of the mass of the main agent A.

[0018] In specific embodiments of the present application, the acrylate is selected from one or a mixture of several of isooctyl acrylate, butyl acrylate, ethyl acrylate, methyl acrylate, methyl methacrylate, and butyl methacrylate.

[0019] In specific embodiments of the present application, the first solvent and the second solvent are each independently selected from one or a combination of the two of ethyl acetate and butyl acetate.

[0020] In specific embodiments of the present application, the chain transfer agent is selected from the group consisting of a combination of one or more of alpha-methyl styrene linear dimer, ethanol, isopropyl alcohol, dodecyl mercaptan, beta-naphthalene thiol, thioglycolate, carbon tetrachloride, cumene, isooctyl mercaptoacetate, toluene, chloroform, the initiator is selected from the group consisting of a combination of one or more of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptanitrile.

[0021] In specific embodiments of the present application, the hydroxyl acrylate monomer is selected from the group consisting of a combination of one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate.

[0022] In specific embodiments of the present application, the special modified caprolactone monomer is selected from the group consisting of a combination of one or more of PCL-HA2, PCL-HA3, PCL-HA4, PCL-HAM3.

[0023] In specific embodiments of the present application, the solvent type hydroxyl polyurethane prepolymer is selected from the group consisting of polycarbon aliphatic polyurethane prepolymer. The polycarbon aliphatic polyurethane prepolymer is selected from the group consisting of Runan PU-OH-2.

[0024] In specific embodiments of the present application, the silicone modified monomer is selected from the group consisting of monofunctional silicone modified monomer.

[0025] In specific embodiments of the present application, the isocyanate is selected from the group consisting of a combination of one or more of HDI, IPDI, HDI trimer, and IPDI trimer.

[0026] A preparation method of a two-component blended self-repairing coating, the preparation method comprising the following steps:

[0027] (1) heating the solvent to 40-50°C, adding the initiator, stirring for 5-15 min, to prepare an initiator solution;

[0028] (2) stirring the acrylate, special modified caprolactone monomer, hydroxyl acrylate monomer, silicone modified monomer, and chain transfer agent solution uniformly to obtain a first mixed solution;

[0029] (3) adding the first mixed solution dropwise to the initiator solution, slowly adding for 1-2 h;

[0030] (4) after the addition is completed, heating the mixed solution to 64-70°C, and reacting for 3-5 h;

[0031] (5) after the reaction is completed, cooling to 35°C, adding the solvent type hydroxyl polyurethane prepolymer, stirring uniformly, and then filtering the product to obtain a main agent A;

[0032] (6) dissolving the isocyanate in a second solvent and stirring uniformly to obtain a curing agent B component,

[0033] Wherein step (6) has no sequence with steps (1) to (5).

[0034] Use of a two-component blended self-repairing coating, including use in the preparation of protective film coatings for cars, furniture and mobile phones, and anticorrosion coatings.

[0035] The positive progress effect of the present application is that the two-component blended self-repairing coating, the preparation method and the use thereof provided by the present application have the following advantages:

[0036] 1. The present application provides a two-component blended self-repairing coating, which has excellent weather resistance and chemical resistance, and at the same time has good transparency and gloss, excellent repair performance, greatly improved flexibility, greatly improved acid rain resistance and ultraviolet light resistance, so that the self-repairing can meet more and more extensive application range.

[0037] 2. Compared with the existing single type of self-repairing coating, the present application adopts the way of synthesizing modified polyacrylic polyol first, then adding hydroxyl-containing polycarbon aliphatic polyurethane prepolymer, and then crosslinking by HDI trimer and IPDI trimer reaction, so that the self-repairing can meet more and more extensive application range, and make up for the problems of single type of self-repairing, such as insufficient performance and narrow application range. DETAILED DESCRIPTION

[0038] The preferred embodiments of the present application are given below to explain the technical solutions of the present application in detail.

[0039] The present application provides a two-component blended self-repairing coating. The self-repairing coating adopts the way of synthesizing modified polyacrylic polyol first, then adding hydroxyl-containing polycarbon aliphatic polyurethane prepolymer, and then crosslinking by HDI trimer and IPDI trimer reaction, which solves the existing self-repairing problem. The self-repairing can be used for the protective film of mobile phones, cars, furniture and outdoor products, and has excellent weather resistance and chemical resistance, and at the same time has good transparency and gloss, excellent repair performance, greatly improved flexibility, greatly improved acid rain resistance and ultraviolet light resistance.

[0040] The two-component blended self-repairing coating of the present application comprises the following components by weight: 50-70% of main agent A, 30-50% of curing agent B, wherein the raw materials for preparing the main agent A comprise the following components by weight: 1-10% of acrylate, 1-10% of hydroxy acrylate monomer, 0.5-1.5% of silicone modified monomer, 10-15% of special modified caprolactone monomer, 0.1-0.5% of initiator, 0.5-1% of chain transfer agent, 60-70% of first solvent, and 5-15% of solvent type hydroxyl polyurethane prepolymer; wherein the component of the curing agent B comprises the following components by weight: 70-80% of isocyanate and 20-30% of second solvent; in use, the curing agent B is added into the main agent A to be stirred uniformly to obtain the two-component blended self-repairing coating.

[0041] In the two-component blended self-repairing of the present application, the role of the acrylate is to improve the cohesion and hardness of the self-repairing coating. The acrylate that can be used in the present application includes but is not limited to isooctyl acrylate, butyl acrylate, ethyl acrylate, methyl acrylate, methyl methacrylate, and butyl methacrylate.

[0042] In the two-component blended self-repairing of the present application, the first solvent and the second solvent that can be used in the present application can be the same or different, and include but are not limited to ethyl acetate and butyl acetate.

[0043] In the two-component blended self-repairing of the present application, the role of the hydroxy acrylate monomer is to provide a reaction group that can be crosslinked with isocyanate. The hydroxy acrylate monomer that can be used in the present application includes but is not limited to hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.

[0044] In the two-component blended self-repairing of the present application, the role of the special modified caprolactone monomer is to modify the polyacrylic resin, so as to achieve the purpose of mutual compatibility with the solvent type hydroxyl polyurethane prepolymer, and to provide a reaction group that can be crosslinked with isocyanate. The hydroxy acrylate monomer that can be used in the present application includes but is not limited to PCL-HA2, PCL-HA3, PCL-HA4, and PCL-HAM3.

[0045] In the two-component blended self-repairing coating of the present application, the role of the silicone modified monomer is to improve the anti-graffiti ability and slipperiness of the self-repairing coating. The silicone modified monomer that can be used in the present application includes but is not limited to monofunctional silicone modified monomer.

[0046] The solvent type hydroxyl polyurethane prepolymer in the two-component blended self-repairing coating of the present application can improve the repair performance and flexibility of the self-repairing coating and provide reactive groups to crosslink with isocyanate.

[0047] The chain transfer agent in the two-component blended self-repairing coating of the present application can control the relative molecular mass / polymerization degree / viscosity of the modified polyacrylic polyol.

[0048] The initiator in the two-component blended self-repairing coating of the present application can generate free radicals and react with the acrylate, the special modified caprolactone monomer, the hydroxyl acrylate monomer and the silicone modified monomer to synthesize a polymer with a certain molecular weight.

[0049] The isocyanate in the two-component blended self-repairing coating of the present application can crosslink with the modified polyacrylic polyol and the solvent type hydroxyl polyurethane prepolymer to solve the drawbacks of the current self-repairing.

[0050] The present application further provides a preparation method of the two-component blended self-repairing coating, which comprises the following steps:

[0051] (1) heating the solvent to 40-50℃, adding the initiator, stirring for 5-15 min to prepare an initiator solution;

[0052] (2) stirring the acrylate, the special modified caprolactone monomer, the hydroxyl acrylate monomer, the silicone modified monomer and the chain transfer agent solution uniformly to obtain a first mixed solution;

[0053] (3) adding the first mixed solution dropwise into the initiator solution, slowly adding for 1-2 h;

[0054] (4) after the addition is completed, heating the mixed solution to 64-70℃, reacting for 3-5 h;

[0055] (5) after the reaction is completed, cooling to 35℃, adding the solvent type hydroxyl polyurethane prepolymer, stirring uniformly and then filtering the product to obtain the main agent A;

[0056] (6) dissolving the isocyanate in the second solvent and stirring uniformly to obtain the curing agent B component,

[0057] Wherein, the step (6) has no sequence with the steps (1) to (5).

[0058] The application also provides the use of the two-component blended self-repairing coating, which includes the use in preparing automobile, furniture and mobile phone protective film coating and anticorrosive coating.

[0059] The application will be further described in conjunction with specific examples. It should be understood that these examples are only used to illustrate the application and not used to limit the scope of the application. The experimental methods in the following examples without specific conditions are usually according to the conventional conditions or according to the conditions suggested by the manufacturers. Unless otherwise specified, the percentages and parts are weight percentages and weight parts. The "parts" mentioned in the following examples refer to "weight parts".

[0060] Example 1

[0061] The two-component blended self-repairing components of the example are shown in Table 1, and the specific preparation process is as follows:

[0062] Step (1): 67.5 grams of butyl acetate is heated to 46℃, 0.5 grams of initiator azobis isonipecotinamide is added, and stirred for 10 min to prepare an initiator solution;

[0063] Step (2): 5 grams of butyl methacrylate, 12 grams of PCL-HA3, 3 grams of hydroxyethyl methacrylate, 1 gram of single-organic silicon modified monomer SLOCO 3811F4 and 1 gram of chain transfer agent α-methyl styrene linear dimer are stirred uniformly to obtain a first mixed solution;

[0064] Step (3): The first mixed solution is added dropwise to the initiator solution, and slowly added for 1-2h;

[0065] Step (4): After the dropwise addition is completed, the mixed solution is heated to 64-70℃, and reacted for 3-5h;

[0066] Step (5): After the reaction is completed, the temperature is lowered to 35℃, 10 grams of solvent type hydroxyl polyurethane prepolymer PU-OH-2 is added, stirred uniformly, and then filtered to obtain the main agent A;

[0067] Step (5): 16.2 grams of N3600 and 10.5 grams of Z4470BA are dissolved in 6.3 grams of ethyl acetate to obtain a 72% solid content curing agent B;

[0068] When used, the curing agent B is added to the main agent A to obtain a two-component blended self-repairing.

[0069] Example 2

[0070] The two-component blended self-repairing components of the example are shown in Table 1, and the specific preparation process is as follows:

[0071] Step (1): 63.5 grams of butyl acetate was heated to 46°C, 0.5 grams of initiator azobisisoheptanenitrile was added, stirred for 10 min to prepare an initiator solution;

[0072] Step (2): 5 grams of butyl methacrylate, 12 grams of PCL-HA3, 3 grams of hydroxyethyl methacrylate, 1 gram of single-organosilicon modified monomer Silo 3811F4 and 1 gram of chain transfer agent α-methyl styrene linear dimer were stirred uniformly to obtain a first mixture;

[0073] Step (3): The first mixture was added dropwise to the initiator solution, and slowly added for 1-2 h;

[0074] Step (4): After the addition was completed, the mixture was heated to 64-70°C, and reacted for 3-5 h;

[0075] Step (5): After the reaction was completed, the temperature was lowered to 35°C, 15 grams of solvent type hydroxyl polyurethane prepolymer PU-OH-2 was added, stirred uniformly, and then filtered to obtain the main agent A;

[0076] Step (5): 19.6 grams of N3600 and 12.7 grams of Z4470BA were dissolved in 7.6 grams of ethyl acetate to obtain a 72% solid content curing agent B;

[0077] When used, the curing agent B was added to the main agent A to obtain a two-component blended self-repairing.

[0078] Example 3

[0079] The two-component blended self-repairing components of this example are shown in Table 1, and the specific preparation process is as follows:

[0080] Step (1): 60 grams of butyl acetate was heated to 46°C, 0.5 grams of initiator azobisisoheptanenitrile was added, stirred for 10 min to prepare an initiator solution;

[0081] Step (2): 8 grams of butyl methacrylate, 15 grams of PCL-HA3, 4.5 grams of hydroxyethyl methacrylate, 1 gram of single-organosilicon modified monomer Silo 3811F4 and 1 gram of chain transfer agent α-methyl styrene linear dimer were stirred uniformly to obtain a first mixture;

[0082] Step (3): The first mixture was added dropwise to the initiator solution, and slowly added for 1-2 h;

[0083] Step (4): After the addition was completed, the mixture was heated to 64-70°C, and reacted for 3-5 h;

[0084] Step (5): After the reaction is completed, the temperature is lowered to 35°C, 10 grams of solvent-based hydroxyl polyurethane prepolymer PU-OH-2 is added, and the mixture is stirred uniformly, and then filtered to obtain the main agent A;

[0085] Step (5): 19.6 grams of N3600 and 12.7 grams of Z4470BA are dissolved in 7.6 grams of ethyl acetate to obtain a curing agent B with a solid content of 72%.

[0086] In use, the curing agent B is added to the main agent A to obtain a two-component blended self-repairing agent.

[0087] Example 4

[0088] The two-component blended self-repairing components of the present example are shown in Table 1, and the specific preparation process is as follows:

[0089] Step (1): 55 grams of butyl acetate is heated to 46°C, 0.5 grams of initiator azobisisoheptyl nitrile is added, and the mixture is stirred for 10 minutes to prepare an initiator solution;

[0090] Step (2): 8 grams of butyl methacrylate, 15 grams of PCL-HA3, 4.5 grams of hydroxyethyl methacrylate, 1 gram of single-organic-silicon-modified monomer SLOKOE 3811F4, and 1 gram of chain transfer agent α-methylstyrene linear dimer are stirred uniformly to obtain a first mixture;

[0091] Step (3): The first mixture is added dropwise to the initiator solution, and the dropping is slowly added for 1-2 hours;

[0092] Step (4): After the dropping is completed, the mixture is heated to 64-70°C, and the reaction is carried out for 3-5 hours;

[0093] Step (5): After the reaction is completed, the temperature is lowered to 35°C, 15 grams of solvent-based hydroxyl polyurethane prepolymer PU-OH-2 is added, and the mixture is stirred uniformly, and then filtered to obtain the main agent A;

[0094] Step (5): 22 grams of N3600 and 14.3 grams of Z4470BA are dissolved in 8.6 grams of ethyl acetate to obtain a curing agent B with a solid content of 72%.

[0095] In use, the curing agent B is added to the main agent A to obtain a two-component blended self-repairing agent.

[0096] Table 1. Material components and their addition amounts (weight parts) of Examples 1-4

[0097]

[0098]

[0099] Performance testing

[0100] The self-repairing coating obtained by each embodiment of the present application is scraped by a 20-30 micron wire rod to a film thickness of 5-7 microns, placed in an oven for baking at 110°C / 2-3 min, then subjected to PET film coating treatment, and after coating, subjected to curing, placed in an oven for baking at 40-50°C / 48h. The detailed parameters are shown in Table 2. The performance test of the obtained coating is shown in Table 3, and the standard test method is shown in Table 4.

[0101] Table 2. Test parameters:

[0102] Item Example 1 Example 2 Example 3 Example 4 Substrate TPU film TPU film TPU film TPU film Main agent A 100g 100g 100g 100g Curing agent B 33g 39.9g 39.9g 44.9g Dry film thickness 5-7um 5-7um 5-7um 5-7um Curing temperature 110℃ / 2-3min 110℃ / 2-3min 110℃ / 2-3min 110℃ / 2-3min Curing temperature 40-50℃ / 48h 40-50℃ / 48h 40-50℃ / 48h 40-50℃ / 48h

[0103] Table 3. Performance test results:

[0104]

[0105]

[0106] Table 4. Standard test method:

[0107]

[0108] The basic principles and main features of the present application and the advantages of the present application are shown and described above. It should be understood by those skilled in the art that the present application is not limited by the above embodiments, and the above embodiments and descriptions in the specification are only to illustrate the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the present application. The scope of protection of the present application is defined by the appended claims and their equivalents.

Claims

1. A two-component blended self-healing coating characterized in that, The two-component blended self-repairing coating comprises the following components by weight: 50-70% of main agent A, and the rest is curing agent B; The raw materials for preparing the main agent A comprise the following components by weight: The rest by weight is the first solvent; The curing agent B comprises the following components by weight: Isocyanate 70-80% The rest by weight is the second solvent; In use, the curing agent B is added to the main agent A to obtain the two-component blended self-repairing coating.

2. The two-component blended self-healing coating according to claim 1 or 2, characterized in that: The solid content of the self-repairing coating is 38-48%, and the curing agent B accounts for 1 / 3-1 / 2 of the mass of the main agent A.

3. The dual component blended self-healing coating according to claim 1, characterized in that: The acrylate is selected from one or a mixture of several of isooctyl acrylate, butyl acrylate, ethyl acrylate, methyl acrylate, methyl methacrylate, and butyl methacrylate.

4. The dual component blended self-healing coating of claim 1, wherein: The first solvent and the second solvent are each independently selected from one or a combination of the two of ethyl acetate and butyl acetate.

5. The dual component blended self-healing coating according to claim 1 or 2, characterized in that: The chain transfer agent is selected from one or a combination of several of α-methyl styrene linear dimers, ethanol, isopropyl alcohol, dodecyl mercaptan, β-naphthalene thiol, thioglycol ester, carbon tetrachloride, cumene, isooctyl mercaptoacetic acid, toluene, and chloroform, and the initiator is selected from one or a combination of several of azobisisobutyronitrile, azobisisovaleronitrile, and azobisisoheptyl nitrile.

6. The dual component blended self-healing coating according to claim 1 or 2, characterized in that: The hydroxy acrylate monomer is selected from one or a combination of several of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.

7. The dual component blended self-healing coating according to claim 1 or 2, characterized in that: The special modified caprolactone monomer is selected from one or a combination of several of PCL-HA2, PCL-HA3, PCL-HA4, and PCL-HAM3.

8. The dual component blended self-healing coating according to claim 1 or 2, characterized in that: The solvent type hydroxyl polyurethane prepolymer is selected from a polycarbon aliphatic polyurethane prepolymer, and the polycarbon aliphatic polyurethane prepolymer is selected from Yunyan PU-OH-2.

9. The dual component blended self-healing coating according to claim 1 or 2, characterized in that: The organosilicon modified monomer is a monofunctional organosilicon modified monomer.

10. The dual component blended self-healing coating according to claim 1 or 2, characterized in that: The isocyanate is selected from one or a combination of several of HDI, IPDI, HDI trimer, and IPDI trimer.

11. A method for preparing the dual-component blended self-repairing coating as claimed in any one of claims 1-10, characterized in that, The preparation method comprises the following steps: (1) heating the solvent to 40-50°C, adding the initiator, and stirring for 5-15 min to prepare an initiator solution; (2) stirring the acrylate, special modified caprolactone monomer, hydroxy acrylate monomer, organosilicon modified monomer, and chain transfer agent solution uniformly to obtain a first mixed solution; (3) adding the first mixed solution dropwise to the initiator solution, and slowly adding for 1-2 h; (4) after the addition is completed, heating the mixed solution to 64-70°C, and reacting for 3-5 h; (5) after the reaction is completed, cooling to 35°C, adding the solvent type hydroxyl polyurethane prepolymer, stirring uniformly, and then filtering the product to obtain the main agent A; (6) dissolving the isocyanate in the second solvent and stirring uniformly to obtain the curing agent B component, There is no sequence between step (6) and steps (1) to (5).

12. Use of the two-component blended self-repairing coating according to claim 1 or 11, characterized in that, The use includes the use in preparing automobile, furniture, and mobile phone protective film coatings, and anticorrosion coatings.

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