Rigid surface treatment and method of making same and associated coatings, coatings and protective materials

Abstract

The present application belongs to the field of coating, and particularly relates to a rigid surface treatment agent, a preparation method thereof and associated coating, coating layer and protective material, wherein the preparation steps of the rigid surface treatment agent are as follows: polymerizing aminosiloxane to obtain a polyaminosiloxane sol; then performing a first-stage grafting reaction with formula 1 to obtain a modified polysiloxane grafted with formula 1; and performing a second-stage grafting reaction on the modified polysiloxane, formula 2 and an isocyanate crosslinking agent to modify formula 2 on the modified polysiloxane, thereby obtaining the rigid surface treatment agent. The present application modifies formula 1 in advance in the polyaminosiloxane sol, and then modifies formula 2, thereby obtaining a network-like polyaminosiloxane surface treatment agent with excellent rigidity, which greatly enhances the adhesion and mechanical strength of the coating layer, effectively improves the wear resistance, and has excellent light transmittance.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of surface treatment agent, and particularly relates to a rigid surface treatment agent. BACKGROUND

[0002] The fluorosilicon coating is widely applied to special coating fields such as aerospace, electronic industry, textile industry and mechanical industry due to its excellent heat resistance, weather resistance, low friction coefficient and good hydrophobic and oleophobic self-cleaning function. However, the glass coating of high-speed running vehicles such as trains and airplanes requires high hardness, high light transmittance, low friction coefficient and hydrophobic and oleophobic antifouling performance to reduce friction resistance, prevent visual interference and ensure the running safety.

[0003] The traditional fluorosilicon coating and paint mainly include fluorosilicon water-based paint and silicone-modified polyester resin. For example, the fluorosilicon water-based paint mainly uses a water dispersion of a silicon-containing polymer and a water dispersion of a fluorine-containing polymer as a film-forming material, and is widely applied to exterior wall paint, especially latex paint. The silicone-modified polyester resin is a thermosetting resin formed by condensation of dihydric alcohol (or polyhydric alcohol) and diacid (or polyacid, acid anhydride) and then modification by silicone.

[0004] For example, the patent document with the publication number CN105350317A discloses an environmentally friendly super-hydrophobic oil-repellent surface treatment agent for textiles, which is mainly composed of the following raw materials in parts by weight: 1-15 parts of fluorine-containing compound, 1-5 parts of silicon-containing compound, 1-15 parts of fluorosilicon copolymer, 0.5-5 parts of silane coupling agent and 50-95 parts of solvent, the reaction temperature is 5-45℃, and the reaction time is 0.5-3h.

[0005] For another example, the patent document with the publication number CN104530851A discloses a surface treatment agent, which is made of the following substances in weight percentage: 5%-50% of film-forming material, 5%-15% of nano-oxide, 0.5%-20% of auxiliary agent and 15%-89.5% of deionized water.

[0006] In summary, although the existing technology reports some fluorosilicon coating schemes and good effects are achieved, it is still difficult to simultaneously realize high hardness, high hydrophobicity and long-term wear resistance of the coating, so it is difficult to meet the use requirements of the protective coating under extreme conditions. SUMMARY

[0007] In view of the defects of the prior art, the first object of the present application is to provide a preparation method of a surface treatment agent with strong rigidity, so as to prepare a surface treatment agent with excellent high light transmittance, hydrophobic antifouling, high wear resistance and high mechanical strength.

[0008] The second object of the present application is to provide the rigid surface treatment agent prepared by the preparation method.

[0009] The third object of the present application is to provide the coating containing the rigid surface treatment agent and the associated coating and protective material.

[0010] A preparation method of a rigid surface treatment agent, comprising the steps of:

[0011] Step 1:

[0012] polymerizing the aminosiloxane to obtain a polyaminosiloxane sol; and then performing a first-stage grafting reaction with Formula 1 to obtain a modified polysiloxane grafted with Formula 1;

[0013] Formula 1;

[0014] In Formula 1, m and n are integers between 0 and 30, and m and n are not 0 at the same time.

[0015] Step 2:

[0016] performing a second-stage grafting reaction on the modified polysiloxane with Formula 2 and an isocyanate crosslinking agent to modify Formula 2 on the modified polysiloxane, thereby obtaining the rigid surface treatment agent;

[0017] Formula 2;

[0018] In Formula 2, R1 is H, a C1-C8 alkyl group, a C3-C8 cycloalkyl group or a phenyl group; 10 10

[0019] R2 is a substituent containing a substituent a with a carbon number of less than 10, wherein the substituent a contains at least one of a hydroxyl group, an amino group, a halogen and a mercapto group.

[0020] The present application modifies Formula 1 in advance in the polyaminosiloxane sol, and then modifies Formula 2, thereby obtaining a network-like polyaminosiloxane surface treatment agent with excellent rigidity, which can greatly enhance the adhesion and mechanical strength of the coating, and effectively improve the wear resistance and light transmittance.

[0021] In the present application, the aminosiloxane has the structural formula of Formula 3;

[0022] Formula 3;

[0023] wherein R3 is a C1-C8 alkylene group or -X1-NH-X2, and X1 and X2 are C1-C8 alkylene groups;

[0024] R4 is a C1-C8 alkyl group.

[0025] ​​R5 is at least one of a hydrogen atom, a C1-C8 alkyl group, and a C1-C8 alkoxy group.

[0026] In the present application, the solvent in the polymerization process of formula 3 can be an alcohol aqueous solvent, wherein the alcohol can be a C1-C4 alcohol, and further can be methanol, ethanol, etc. The acid in the polymerization process can be hydrochloric acid, sulfuric acid, etc. The temperature in the polymerization process can be above 50℃, for example, can be 50-80℃. The polymerization time can be 1-5h.

[0027] Further, in the polymerization process, the amount of raw materials can be reasonably adjusted according to the needs, for example, the molar ratio of aminosiloxane (molar mass is calculated based on the amino group), alcohol, acid, water is 0.5-2:20-50:0.002-0.005:0.5-1.5; further preferably 1-1.2:35-50:0.003-0.004:1-1.2.

[0028] In the present application, formula 1 is obtained by reacting formula 4 and formula 5;

[0029] Formula 4;

[0030] m and n in formula 4 are the same as formula 1;

[0031] Formula 5;

[0032] X is halogen, for example, can be Cl.

[0033] In the present application, m can be 4-12. n can be 2-12.

[0034] In the present application, the molar ratio of the hydroxyl group in formula 4 to formula 5 can be 1:0.8-1.2; further can be 1:1.1-1.2.

[0035] In the present application, a catalyst can be added in the reaction process of formula 4 and formula 5, and the catalyst can be at least one of sodium hydroxide and potassium hydroxide. Further, the amount of catalyst is 1.0-3.0wt% of the weight of formula 4; further can be 1.1-2wt%.

[0036] In the present application, the molar ratio of polyaminosiloxane sol (calculated based on the amino group therein) to formula 1 is 0.9-1.2:1; further can be 0.95-1.15:1.

[0037] The reaction is carried out under heating conditions to reflux, the temperature is 35-45℃, and the reaction time is 3-5h.

[0038] In the present application, in formula 2, R1 is C1-C8 alkyl, and further can be C2-C5 alkyl. R2 is a group with a substituent a on a C1-C8 straight carbon chain, an oxygen-containing straight carbon chain, or a five- or six-membered saturated carbon ring. Further, the substituent a is a hydroxyl group. Studies have shown that the use of this preferred functionalized formula 2, in combination with the process of the present application, can further enhance the wear resistance of the prepared treatment agent.

[0039] In the present application, the isocyanate crosslinking agent can be at least one of hexamethylene diisocyanate (HDI), 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, p- and m-tetramethylxylylene diisocyanate, hydrogenated MDI (methylene bis(4-cyclohexyl diisocyanate)), methylene-4,4'-diphenyl diisocyanate, p-m-xylylene diisocyanate, 2,4- and / or 2,6-toluene diisocyanate (TDI) and its adducts, and isophorone diisocyanate (IPDI), and the like; further preferably, the polyisocyanate is isophorone diisocyanate, hexamethylene diisocyanate.

[0040] In the present application, the molar ratio of formula 2, isocyanate crosslinking agent, to formula 1 is 0.3-1.4:0.8-1.2:1; further can be 0.95-1.15:1-1.1:1.

[0041] In step 2 of the present application, an organic Sn catalyst is also added, which can be at least one of dibutyltin diacetate, dibutyltin dilaurate, and bis(dodecylthio)dibutyltin. The amount of organic Sn catalyst is 2.0-4.0 wt% based on the weight of formula 1.

[0042] In step 2 of the present application, the solvent for the second-stage grafting reaction can be at least one of acetone, ethyl acetate, n-butyl acetate, tetrahydrofuran, and hydrofluoroether.

[0043] In the present application, the atmosphere for the second-stage grafting reaction can be at least one of nitrogen, argon, and helium.

[0044] In the present application, the temperature for the second-stage grafting reaction can be 30-50°C, and the time can be 2-5 h.

[0045] The present application also includes the rigid surface treatment agent prepared by the preparation method.

[0046] The present application also provides a coating material comprising the rigid surface treatment agent prepared by the preparation method of the present application, and further comprising at least one of a diluent and an auxiliary agent.

[0047] In the present application, the coating comprises the rigid surface treatment agent as described in the present application, and other components can be known, and the content of the components can be known.

[0048] For example, the coating comprises a diluent, which can be a conventional fluorinated diluent, further can be a hydrofluoroether, further can be 3M 7200.

[0049] In the coating of the present application, the solid content of the rigid surface treatment agent can be 5% to 50%, further preferably 20% to 30%.

[0050] The present application also provides a coating layer obtained by coating and drying the coating of the present application.

[0051] The present application also provides a protective material comprising a substrate to be protected and a coating layer compounded on the surface thereof, wherein the coating layer is the coating layer of the present application.

[0052] The substrate is a glass screen, windshield, lens, plastic plate, etc.

[0053] Advantages

[0054] 1) The present application provides a preparation method of a rigid surface treatment agent, which forms a polyamino siloxane sol in advance, and then performs first-stage grafting using Formula 1, and second-stage grafting using a functionalized Formula 2, which can realize synergy, optimize the network structure and active group content of the treatment agent, effectively solve the phase separation caused by the nanometer size effect of the components, and greatly enhance the adhesion and mechanical strength of the coating layer, effectively improve the wear resistance, and has excellent light transmittance.

[0055] 2) The preparation method of the surface treatment agent with strong rigidity provided by the present application has the advantages of simple operation steps and mild reaction conditions, and provides a new idea for the preparation of a new type of high-stability strong-wear-resistant surface treatment agent. BRIEF DESCRIPTION OF DRAWINGS

[0056] Figure 1 SEM spectrum of the coating layer prepared from Example 1;

[0057] Figure 2 SEM spectrum of the coating layer prepared from Comparative Example 4. DETAILED DESCRIPTION

[0058] The technical solutions of the present application will be further described below in combination with specific embodiments of the present application. It should be noted that the described embodiments are only a part of the embodiments of the present application, not all the embodiments; these embodiments are only for better understanding of the present application, not to limit the scope of the present application.

[0059] Unless otherwise specified, all reagents and raw materials used in the present application are commercially available or can be prepared by known methods.

[0060] The room temperature in the examples and comparative examples of the present application is 25°C.

[0061] Example 1

[0062] The present example provides a surface treatment agent with strong rigidity, and the specific preparation method comprises the following preparation steps:

[0063] 1) 3-aminopropyltrimethoxysilane is weighed and dissolved in ethanol, then hydrochloric acid and deionized water are added (molar ratio is 1:36:0.0035:1.1), and after being uniformly mixed in a three-necked flask, it is heated to 60°C and refluxed for 2h to obtain a polyamino silicone sol;

[0064] 2) Formula 4 (m=12, n=12) and epichlorohydrin with a molar ratio of 1:1.2 are added to acetone, sodium hydroxide (1.15 wt% of the weight of formula 4) is added, and heated to 65°C for 3h to prepare a product with the structure of formula 1 (wherein m and n are both 12);

[0065] 3) The formula 1 product obtained from step (2) is added to the polyamino silicone sol obtained from step (1) (the molar ratio of the amino group in the polyamino silicone sol to formula 1 is 1:1), and stirring is carried out at 40°C, and heating reflux is carried out for 4h to carry out ring-opening reaction, and after purification, a modified polysiloxane grafted with formula 1 is obtained;

[0066] 4) Hexamethylene diisocyanate and formula 2A (m=12, n=12) are weighed and added to the formula 1 grafted modified polysiloxane obtained from step (3) (the molar amount is calculated based on the grafted formula 1) (the molar ratio is 1.1:1:1), the solvent is acetone, and dibutyl tin diacetate is added (the amount is 3 wt% of the weight of formula I in step 3), and the reaction is carried out at 45°C for 3h under a nitrogen atmosphere, and after separation and purification, a composite sol is obtained;

[0067] The above prepared composite sol is compounded with hydrofluoroether 3M 7200 to control the solid content to 25% to obtain a surface treatment agent with strong rigidity.

[0068] The SEM image of Figure 1 It can be seen from the SEM image of the above surface treatment agent that the coating formed by the surface treatment agent has a smooth surface and no crystals of formula 2A exist, which confirms the excellent performance of the technical scheme.

[0069] Example 2

[0070] ​The embodiment provides a surface treatment agent with strong rigidity, and a specific preparation method comprises the following preparation steps.

[0071] 1) N-[3-(trimethoxysilyl)propyl]ethylenediamine is weighed and dissolved in ethanol, then hydrochloric acid and deionized water are added (the molar ratios are 1:40:0.004:1.1 respectively), the mixture is uniformly mixed in a three-necked flask, heated to 65 DEG C, and refluxed for 2h to obtain a polyamino silicone sol;

[0072] 2) Formula 4 (m=12, n=12) and epichlorohydrin with a molar ratio of 1:1.15 are added to acetone, sodium hydroxide (1.5 wt% of the weight of formula 4) is added, heated to 70 DEG C, and reacted for 3.5h to prepare a product with the structure of formula 1 (wherein m and n are both 12);

[0073] 3) The formula 1 product obtained in step (2) is added to the polyamino silicone sol obtained in step (1) (the molar ratio of the amino group in the polyamino silicone sol to formula 1 is 1.05:1), stirring is performed at 43 DEG C, ring-opening reaction is performed by heating and refluxing for 4h, and after purification, a modified polysiloxane grafted with formula 1 is obtained;

[0074] 4) Isophorone diisocyanate and formula 2B (m=4, n=2) are weighed and added to the formula 1 grafted modified polysiloxane obtained in step (3) (the molar amount is calculated based on the grafted formula 1) (the molar ratio is 1.02:0.6:1), acetone is used as a solvent, dibutyltin diacetate (the amount is 3 wt% of the weight of formula 1 in step 3) is added, reaction is performed at 40 DEG C for 4h under a nitrogen atmosphere, and after separation and purification, a composite sol is obtained;

[0075] The composite sol prepared above is compounded with hydrofluoroether 3M 7200, the solid content is adjusted to 25%, and a surface treatment agent with strong rigidity is obtained.

[0076] Embodiment 3

[0077] The embodiment provides a surface treatment agent with strong rigidity, and a specific preparation method comprises the following preparation steps:

[0078] 1) 3-aminopropyltriethoxysilane is weighed and dissolved in ethanol, then hydrochloric acid and deionized water are added (the molar ratios are 1:50:0.0025:0.8 respectively), the mixture is uniformly mixed in a three-necked flask, heated to 70 DEG C, and refluxed for 1.5h to obtain a precursor sol;

[0079] 2) Formula 4 (m=4, n=2) and epichlorohydrin with a molar ratio of 1:1.1 are added to acetone, sodium hydroxide (2 wt% of the weight of formula 4) is added, heated to 65 DEG C, and reacted for 4h to prepare a product with the structure of formula 1 (m=4, n=2);​

[0080] 3) The product of formula 1 obtained from step (2) is added to the polyaminosiloxane sol obtained from step (1) (molar ratio of amino groups in the polyaminosiloxane sol to formula 1 is 0.95:1), stirring is carried out at 45°C, ring-opening reaction is carried out by heating to reflux for 4h, and the modified polysiloxane grafted with formula 1 is obtained after purification;

[0081] 4) Methylene-4,4'-diphenyl diisocyanate, formula 2C ) is added to the modified polysiloxane grafted with formula 1 obtained from step (3) (molar ratio is 1.05:1.1:1, respectively), the solvent is acetone, dibutyl tin dilaurate is added (its amount is 2.5 wt% of the weight of formula 1 in step 3), the reaction is carried out at 40°C for 3h under a nitrogen atmosphere, and the composite sol is obtained after separation and purification;

[0082] The composite sol prepared above is compounded with hydrofluoroether 3M 7100 to obtain a surface treatment agent with strong rigidity with a solid content of 26%.

[0083] Example 4

[0084] The present embodiment provides a surface treatment agent with strong rigidity, and the specific preparation method comprises the following preparation steps:

[0085] 1) 3-Aminopropyltrimethoxysilane is weighed and dissolved in ethanol, then hydrochloric acid and deionized water are added (molar ratio is 1:30:0.004:1.2, respectively), the mixture is uniformly mixed in a three-necked flask, heated to 65°C, and refluxed for 3h to obtain a precursor sol;

[0086] 2) Formula 4 (m=8, n=7) and epichlorohydrin with a molar ratio of 1:1.1 are added to acetone, sodium hydroxide (1.5 wt% of the weight of formula 4) is added, heated to 70°C, and reacted for 4h to prepare a product with the structure of formula 1 (wherein m and n are 8 and 7, respectively);

[0087] 3) The product obtained from step (2) is added to the polyaminosiloxane sol obtained from step (1) (molar ratio of amino groups in the polyaminosiloxane sol to formula 1 is 1:1), stirring is carried out at 40°C, ring-opening reaction is carried out by heating to reflux for 4h, and the modified polysiloxane grafted with formula 1 is obtained after purification;

[0088] 4) M-xylene diisocyanate, formula 2D ) to the modified polysiloxane of formula 1 obtained in step (3) (molar ratio of 1.09:0.95:1, respectively) with acetone as solvent, and adding di(dodecylthio) dibutyl tin (its amount is 3.5 wt% of the weight of formula 1 in step 3), under nitrogen atmosphere, at 45°C for 4h, and after separation and purification, a composite sol is obtained;

[0089] The composite sol prepared above is compounded with hydrofluoroether 3M 7300 to regulate the solid content to 30%, and a surface treatment agent with strong rigidity is obtained.

[0090] Example 5

[0091] Compared with Example 1, the only difference is that formula 2A is replaced by formula 2E (R1 is , and R2 is of formula 2), and the rest of the preparation steps and conditions are the same.

[0092] Comparative Example 1

[0093] Compared with Example 1, the only difference is that step (1) is not performed, but amino propyl trimethoxy silane is directly reacted with the product obtained in step (2), and the rest of the preparation steps and conditions are the same.

[0094] Comparative Example 2

[0095] Compared with Example 1, the only difference is that step (2) is not performed, and in step 3, comparative formula A ( , m and n are both 12) is used to replace formula 1, and the rest of the preparation steps and conditions are the same.

[0096] Comparative Example 3

[0097] Compared with Example 1, the only difference is that step (4) is not performed, but formula 2A is directly added to the product of step (3), and the rest of the preparation steps and conditions are the same.

[0098] Comparative Example 4

[0099] Compared with Example 1, the only difference is that in step (4), formula 2A is replaced by comparative formula B (R1 and R2 are both of formula 2), and the rest of the preparation steps and conditions are the same.

[0100] Comparative Example 5

[0101] Compared with Example 1, the only difference is that the silica sol is first modified by formula 2, and then modified by formula 1, specifically, after step 1, the product is directly subjected to step 4 treatment, and then steps 2 and 3 are performed in sequence, and the other operations and parameters are the same as Example 1.

[0102] Comparative Example 6

[0103] Comparative Example 6 is the same as Example 1 except that steps 2 and 3 are not performed, and step 4 is performed directly after step 1. The other operations and parameters are the same as those of Example 1.

[0104] The surface treatment agent prepared by Example 1-5 and Comparative Example 1-6 is uniformly and precisely coated on the surface of the substrate by spraying, and then cured at 40℃ for 2h.

[0105] The adhesion, initial water contact angle, steel wool rubbing, and water contact angle after alkali immersion of the coating on the surface of the substrate are tested to verify the stability, hydrophobic antifouling, abrasion resistance, corrosion resistance, and other properties of the surface treatment agent obtained in each example or comparative example. The test results are shown in Table 1 below.

[0106] Transmittance test method: The transmittance is measured by a TH-110 type transmittance and haze meter. Place the coated substrate on the test platform, press the HOLD key of the instrument, and the instrument will start testing after self-calibration. Record the test results.

[0107] Pencil hardness: Referring to GB / T 6739-2022 "Paint and Varnish - Pencil Method for Testing Film Hardness": the hardness of the coating is determined by pencil method.

[0108] Adhesion: 3M 600 tape is used to test 3 times.

[0109] Water contact angle test method: The static contact angle of the coating is measured by a JGW-360a type contact angle meter. The test liquid volume is 2 microliters, the test environment is 24 ± 1℃, and the relative humidity is 45 ± 1%. The water contact angle is measured for 5 points, and the average value is taken.

[0110] Steel wool abrasion resistance test method: The steel wool abrasion resistance test is determined by a ZJ-339-GSR type abrasion tester. The coated substrate is fixed on the tester, the rubber type is MUNBANGSAWOO, the pressure is set to 1000g, the stroke is set to 40mm, the speed is 40 cycles / min, and the water contact angle test result of the substrate is recorded after the test is completed.

[0111] The test results of each case are shown in Table 1:

[0112]

[0113] As can be seen from the data of Examples 1-5, the strong rigid surface treatment agent exhibits excellent hydrophobic antifouling and mechanical strength, the initial water contact angle is all > 120°, the adhesion is 5B grade, and after 30k times of steel wool rubbing, the water contact angle is still > 110°, showing excellent rubbing resistance. In addition, it can be found from Examples 1, 2 and Examples 3, 4 that the surface treatment agent containing hydroxyl formula 2 is better than the surface treatment agent containing amino or halogen formula 2 in terms of wear resistance. The data results of Comparative Example 1 show that the self-condensation step of amino siloxane is beneficial to improve the adhesion and mechanical strength of the coating. Comparative Example 2 does not use the formula 1 described in the present application, resulting in a smaller initial water contact angle, poorer hydrophobic antifouling and rubbing resistance. The data results of Comparative Examples 3 and 4 show that the addition of formula 2 compound which cannot be chemically combined cannot effectively improve the rubbing resistance of the coating. Comparative Example 5 swaps the reaction order, resulting in poor hydrophobic and wear resistance. Comparative Example 6 only modifies formula 2, and the hydrophobic performance is poor.

[0114] The above examples are only used to illustrate the technical solutions of the present application, not to limit them: although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that they can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solution deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for preparing a rigid surface treatment agent, characterized in that the steps include... include: Step 1: Aminosiloxanes are polymerized to obtain polyaminosiloxane sol; then, a first-stage grafting reaction is carried out with Formula 1 to obtain modified polysiloxane grafted with Formula 1. Formula 1; In Formula 1, m is 4~12; n is 2~12; The molar ratio of amino groups to Formula 1 in the polyaminosiloxane sol is 0.9~1.2:1; Step 2: The modified polysiloxane, Formula 2, and isocyanate crosslinking agent are subjected to a second-stage grafting reaction to modify Formula 2 on the modified polysiloxane, thereby obtaining the rigid surface treatment agent. Formula 2; In Equation 2, R1 represents H, C1~C 10 Alkyl groups, C3~C 10 cycloalkyl or phenyl; R2 is a substituent containing a substituent a with 10 or fewer carbon atoms, wherein the substituent a comprises at least one of hydroxyl, amino, and mercapto groups; The molar ratio of the isocyanate crosslinking agent in Formula 2 to that in Formula 1 is 0.3~1.4:0.8~1.2:1; In step 2, an organic Sn catalyst is also added, and the amount of organic Sn catalyst is 2.0~4.0 wt% of the weight of Formula 1.

2. The method for preparing the rigid surface treatment agent as described in claim 1, characterized in that, Aminosiloxanes are compounds having the structural formula 3; Formula 3 Wherein, R3 is a C1~C8 alkylene group or -X1-NH-X2-, wherein X1 and X2 are C1~C8 alkylene groups; R4 is a C1-C8 alkyl group; R5 is at least one of a hydrogen atom, a C1-C8 alkyl group, or a C1-C8 alkoxy group.

3. The method for preparing the rigid surface treatment agent as described in claim 1, characterized in that, Equation 1 is obtained by reacting Equations 4 and 5; Equation 4; In Equation 4, m and n are the same as in Equation 1; Formula 5 X is a halogen.

4. The method for preparing the rigid surface treatment agent as described in claim 1, characterized in that, In Formula 2, R1 is a C1-C8 alkyl group; R2 is a group consisting of a straight carbon chain of C1 to C8 with a five- or six-membered saturated carbon ring bearing the substituent a.

5. A rigid surface treatment agent prepared by the preparation method according to any one of claims 1 to 4.

6. A coating, characterized in that, The rigid surface treatment agent prepared by the preparation method according to any one of claims 1 to 4 further comprises at least one of a diluent and an auxiliary agent.

7. A coating, characterized in that, The coating is obtained by applying and drying the coating as described in claim 6.

8. A protective material comprising a substrate to be protected and a coating laminated thereon, characterized in that, The coating is the coating described in claim 7.

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