Solvent-free polyaspartic acid ester polyurea floor coating and preparation method thereof

Abstract

The invention provides a solvent-free polyaspartic acid ester polyurea floor coating and a preparation method thereof, the coating comprises a main agent and a curing agent, the main agent comprises polyaspartic acid ester resin, a functional auxiliary agent and a pigment filler; the functional auxiliary agent comprises a dispersing agent, a defoaming agent, a flatting agent, a water absorbent and a coupling agent, and the pigment filler comprises pigment and filler; the curing agent comprises a hydroxyl cyclic ketone compound modified polyisocyanate composition. By optimizing and modifying the components in the radix asparagi polyurea coating, a terrace material can be endowed with excellent properties in the aspects of rapid curing, high-humidity constructability, performance retention rate after curing, leveling wettability, good adhesive force with various coating substrates, high and low temperature resistance, high strength and the like, and the comprehensive performance is excellent; the method is suitable for different terrace application fields.

Description

Technical Field

[0001] This invention belongs to the field of floor coating technology, specifically relating to a solvent-free polyaspartic acid ester polyurea floor coating and its preparation method. Background Technology

[0002] With the continuous development of modern industrial production and commercial and civil buildings, the requirements for floor coatings in various industries and fields are increasing, including aspects such as wear resistance, heavy load resistance, weather resistance, and chemical resistance. In particular, with the renovation of old buildings and the technological upgrading of factories in various industries, there is a need for green and environmentally friendly floor coating systems that can cure quickly in various environments, are easy to apply, and minimize construction and delivery time, thereby reducing losses caused by business or factory shutdowns.

[0003] Common epoxy flooring cures significantly slower in winter or at low temperatures (below 10 degrees Celsius), sometimes taking weeks to reach its designed strength. While polyurethane flooring can achieve normal curing at low temperatures by using driers, its high sensitivity to air humidity and moisture means that in humid environments (such as the plum rain season in southern China or the rainy season in southwestern China), the coating is prone to foaming, leading to decreased strength or poor film quality. Furthermore, outdoor flooring coatings are increasingly used in municipal construction projects. Whether it's colored adhesive stone, colored pavement, or outdoor parking lots, there's a need for flooring coating systems that can resist UV rays, prevent yellowing, and maintain strength even in high summer temperatures.

[0004] Polyaspartic acid ester polyurea coating (aspartic polyurea coating) is a coating made by mixing and reacting polyaspartic acid ester (aspartic resin) with isocyanate and other components. Compared with other materials, aspartic polyurea coating has excellent construction characteristics such as rapid curing and low moisture sensitivity. The cured paint film has good abrasion resistance, weather resistance, aging resistance, UV resistance, impact resistance, and waterproof and corrosion resistance. It can be used indoors or directly exposed outdoors for a long time without aging or chalking.

[0005] However, due to limitations in material properties, common aspartic polyurea coatings exhibit poor wetting and leveling properties, poor resistance to high and low temperatures, and relatively poor adhesion to general-purpose substrates, failing to meet the requirements of many application scenarios. Therefore, to improve its applicability in various flooring applications, it is necessary to develop an aspartic polyurea flooring coating with excellent leveling and wetting properties, good adhesion to various coating substrates, good high and low temperature resistance, and high strength, thereby improving its overall performance. Summary of the Invention

[0006] To overcome the shortcomings of existing technologies, this invention provides a solvent-free polyaspartic acid ester polyurea floor coating and its preparation method. By optimizing and modifying the components in the aspartic polyurea coating, the floor material can be endowed with excellent performance in many aspects, such as improving the leveling properties of the paint film, having good adhesion to various coating substrates, maintaining good high and low temperature resistance, and high strength. It has excellent comprehensive performance and is suitable for different floor application fields.

[0007] The technical solution provided by this invention is as follows:

[0008] A solvent-free polyaspartic acid ester polyurea floor coating includes a base agent and a curing agent, wherein:

[0009] The main components include polyaspartic acid ester resin, functional additives, pigments and fillers; the curing agent includes a modified polyisocyanate composition, which is a polyisocyanate composition modified with hydroxycyclic ketone compounds.

[0010] The present invention is further configured such that the weight parts of each component in the main agent of the solvent-free polyaspartic ester polyurea floor coating are:

[0011] 70-75 parts of polyaspartic acid ester resin;

[0012] Functional additives, 2-4 parts;

[0013] 16-26 parts of pigments and fillers;

[0014] The weight parts of each component in the curing agent are as follows:

[0015] The modified polyisocyanate composition comprises 60-90 parts, preferably 80-90 parts.

[0016] The present invention is further configured such that, in the main component of the solvent-free polyaspartic acid ester polyurea floor coating, the weight proportions of each component in the functional additives are as follows:

[0017] Dispersant 0.1–0.5 parts;

[0018] Defoamer 0.2 to 1 part;

[0019] Leveling agent 0.1-0.2 parts;

[0020] 0.5 to 1 part water absorbent;

[0021] 1 to 1.5 parts of coupling agent;

[0022] The weight percentages of each component in the pigments and fillers are as follows:

[0023] 3-6 parts pigment;

[0024] 13-20 parts of filler.

[0025] The present invention is further configured such that the mass ratio of the main agent to the curing agent is 1:0.6 to 0.9, preferably 1:0.8 to 0.9;

[0026] The molar ratio of -NCO in the curing agent to -NH in the main agent, -NCO / -NH, is 1 to 1.5, preferably 1.2 to 1.4, and more preferably 1.3.

[0027] The present invention is further configured such that the hydroxycyclic ketone compound is selected from one or more of 3-hydroxycyclobutanone, 3-hydroxycyclopentanone, and 4-hydroxycyclohexanone, preferably 3-hydroxycyclobutanone.

[0028] The present invention is further configured such that the polyisocyanate composition is obtained by polymerizing an aliphatic diisocyanate monomer, wherein the aliphatic diisocyanate monomer is selected from one or more of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and lysine diisocyanate, preferably hexamethylene diisocyanate.

[0029] The polyisocyanate composition is preferably one or more of HDI trimer and HDI biuret.

[0030] The present invention is further configured such that the polyaspartic ester resin is selected from one or more of PAE0760 and W420, preferably PAE0760.

[0031] The present invention is further configured such that the polyaspartic acid ester resin PAE0760 contains a variety of active ingredients having secondary amine functional groups (-NH-), including at least the components shown in Formula 1 and Formula 2:

[0032]

[0033] The present invention further specifies that the preparation method of polyaspartic acid ester resin PAE0760 includes:

[0034] 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and polyetheramine were mixed and stirred, and the mixture was heated to 50-70°C. The molar ratio of 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane to polyetheramine was 1:(7-10), and the mixture was kept at this temperature for at least 20 minutes to homogenize the system. Diethyl maleate was then added dropwise, with the molar ratio of diethyl maleate to 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane being (5-7):1. The mixture was then reacted at 50-70°C for 20-30 hours, and nitrogen gas was introduced to prevent side reactions. After the reaction was completed, the mixture was cooled to room temperature to obtain the prepared polyaspartic acid ester resin PAE0760.

[0035] This invention also provides a method for preparing a solvent-free polyaspartic acid ester polyurea floor coating, comprising the following steps:

[0036] (1) Mix and disperse the specified amount of polyaspartic acid ester resin, functional additives, pigments and fillers evenly as the main agent;

[0037] (2) The polyisocyanate composition is mixed and reacted with hydroxycyclic ketone compounds to prepare a modified polyisocyanate composition, which is used as a curing agent;

[0038] (3) When using, mix the main agent and the curing agent evenly to obtain solvent-free polyaspartic acid ester polyurea floor coating.

[0039] Compared with the prior art, the beneficial effects of the present invention are:

[0040] This invention optimizes the composition of polyaspartic ester resin and modifies the isocyanate curing agent to obtain a solvent-free polyaspartic ester polyurea floor coating. This coating exhibits excellent high and low temperature strength retention, high strength, leveling properties, and good adhesion to various coating substrates. It is suitable for flooring materials in different application fields, especially in various renovation and refurbishment projects for indoor and outdoor floors, as well as colored pavements, and has broad application prospects. Detailed Implementation

[0041] The following detailed description, in conjunction with specific embodiments of the present invention, is provided. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0042] All raw materials used in this invention can be purchased through conventional commercial channels.

[0043] The solvent-free polyaspartic acid ester polyurea floor coating of the present invention comprises a main agent (component A) and a curing agent (component B), wherein:

[0044] Component A includes polyaspartic acid ester resin PAE0760, dispersant, defoamer, leveling agent, water absorbent, coupling agent, pigment, and filler;

[0045] Component B includes a modified polyisocyanate composition, which is a polyisocyanate composition modified with hydroxycyclic ketone compounds.

[0046] The preparation method of the solvent-free polyaspartic acid ester polyurea floor coating of the present invention includes the following steps: preparation of component A, preparation of component B, and mixing of components A and B.

[0047] (1) The preparation method of component A includes the following steps:

[0048] A certain mass fraction of polyaspartic acid ester resin PAE0760 is added to a vacuum-cooled paint can. The equipment is controlled at a medium-low speed of stirring, with a rotation speed of 500-800 r / min. A certain mass fraction of dispersant, defoamer, leveling agent, water absorbent, coupling agent, pigment, and filler are added sequentially. After a vacuum degassing and dehydration process, high-speed dispersion ensures uniform mixing. After passing quality inspection, component A of the coating is obtained.

[0049] (2) Prepare a modified polyisocyanate composition to obtain coating component B.

[0050] (3) When ready for use, mix component A and component B at a mass ratio of 1:0.6 to 0.9 and stir evenly before application.

[0051] The preparation method of polyaspartic acid ester resin PAE0760 in component A includes the following steps:

[0052] 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (DMDC) and polyetheramine JEFFAMINE EDR-148 were added sequentially at a molar ratio of 1:(7-10). The mixture was stirred and heated to 50-70°C and maintained for at least 20 minutes to homogenize the system. Diethyl maleate (DEM) was then added dropwise at a molar ratio of (5-7):1 to 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (DMDC). The reaction was then carried out at 50-70°C for 20-30 hours, with nitrogen gas purging to prevent side reactions. After the reaction was completed, the mixture was cooled to room temperature to obtain the prepared polyaspartic acid ester resin. The solid content of this polyaspartic acid ester resin was approximately 97%, the equivalent weight was 260 (equivalent weight being secondary amino equivalent), and the viscosity was 100-200 mPa·s.

[0053] The modified polyisocyanate composition in component B can be prepared using the preparation method described in CN118290704A, including the following steps:

[0054] The HDI trimer was reacted with 3-hydroxycyclobutanone at a temperature of 65–90 °C. The molar ratio of HDI trimer to 3-hydroxycyclobutanone, calculated as the molar ratio of NCO functional groups to 3-hydroxycyclobutanone, was (5–15):1. The NCO content was monitored during the reaction using the di-n-butylamine method. The reaction was stopped when the NCO mass no longer decreased. After the reaction was complete, a portion of HDI biuret was added. The amount of HDI biuret added was 3%–10% based on the mass of the modified polyisocyanate composition.

[0055] The technical solution of the present invention will be described in detail below with reference to specific embodiments.

[0056] Example 1

[0057] A solvent-free polyaspartic acid ester polyurea floor coating comprises component A and component B, wherein, by weight parts, component A comprises:

[0058] 72 parts of polyaspartic acid ester resin (PAE0760, self-made)

[0059] Dispersant (Afcona Polymers, Inc., Afcona 4011) 0.3 parts,

[0060] Defoamer 1 (Byk088, Germany) 0.2 parts

[0061] Defoamer II (Byk054, Germany) 0.2 parts

[0062] Leveling agent (Afcona Polymers, Inc., Afcona 3034) 0.1 parts,

[0063] Water absorbent (Shanghai Deyude Trading Co., Ltd., dehydrating agent OF) 0.5 parts,

[0064] 1 part of coupling agent (Dow Corning 6011),

[0065] Pigment (Chemours, USA, titanium dioxide R902) 5 parts

[0066] 20 parts of filler (Sibico, USA, 800 mesh silica powder).

[0067] Component B includes:

[0068] 80 parts of a modified polyisocyanate composition (self-made).

[0069] The mass ratio of component A to component B is 1:0.8, and the molar ratio of -NCO / -NH in component B and component A is 1.3 under this ratio.

[0070] The preparation method of polyaspartic acid ester resin PAE0760 includes the following steps:

[0071] 83.41 g of 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (DMDC) (0.35 mol, Complex High-Tech Materials (Shanghai) Co., Ltd.) and 103.60 g of polyetheramine (JEFFAMINE EDR-148, 2.79 mol, Huntsman Corporation, USA) were added sequentially. The initial stirring speed was set to 100 rpm, and the temperature was raised to 60 °C and maintained for 30 minutes to homogenize the system.

[0072] 361.58 g of diethyl maleate (DEM) (Shenzhen Feiyang Special Chemical New Materials Co., Ltd., 2.10 mol) was added dropwise at a flow rate of 1.5 mL / min. After the addition was complete, the reaction was continued at 60 °C for 24 hours, with nitrogen gas purging to prevent side reactions. After the reaction was completed, the mixture was cooled to room temperature to obtain the prepared polyaspartic acid ester resin. PAE0760 had a solid content of 97 ± 2%, an equivalent of 260 (secondary amine equivalent), and a viscosity of 100–200 mPa·s.

[0073] The preparation method of the modified polyisocyanate composition includes the following steps:

[0074] 100g of HDI trimer curing agent (WANNATE HT-100, Wanhua Chemical Group Co., Ltd.) was heated to 65℃, and 5.6g of 3-hydroxycyclobutanone was slowly added in batches with constant stirring. After 50 minutes, the NCO mass fraction of the functional group was monitored throughout using the di-n-butylamine method. The reaction was stopped when the NCO mass fraction reached approximately 18.3%. Subsequently, 6g of HDI biuret (WANNATE HB-100, Wanhua Chemical Group Co., Ltd.) was added, finally yielding a modified polyisocyanate composition with an NCO mass fraction of 18.4%. Temperature fluctuations during the preparation process were controlled within ±0.5℃, and the stirring rate was maintained at approximately 300 r / min throughout.

[0075] The preparation method of polyaspartic acid ester polyurea floor coating specifically includes the steps of preparing component A, preparing component B, and mixing components A and B:

[0076] (1) The preparation method of component A includes the following steps: Add the above-mentioned mass proportions of polyaspartic acid ester resin PAE0760 to a vacuum-sealed paint can. The equipment is controlled at a medium-low speed stirring, with a rotation speed of 500–800 r / min. Then, add the above-mentioned mass proportions of dispersant, defoamer, leveling agent, water absorbent, coupling agent, pigment, and filler sequentially. After a vacuum degassing and dehydration process, disperse at high speed for 30 minutes to ensure uniform mixing and dispersion. Take samples for observation. After passing quality inspection (controlling the fineness to be no greater than 40 micrometers and the viscosity to be 600–1000 mPa·s), component A of the coating is obtained. The polyaspartic acid ester resin PAE0760 is designated as R4.

[0077] (2) A modified polyisocyanate composition was prepared according to the above preparation method to obtain coating component B. The modified polyisocyanate composition is labeled as H2.

[0078] (3) When ready for use, mix component A and component B at a mass ratio of 1:0.8 and stir evenly. If the coating is applied, it will be marked as R4-H2.

[0079] Example 2

[0080] Similar to Example 1, the selection and preparation methods of each component remain unchanged. The difference is that component A, by weight, comprises:

[0081] 75 parts of polyaspartic acid ester resin,

[0082] 0.1 parts dispersant

[0083] Defoamer 0.1 parts

[0084] Defoamer 20.1 parts

[0085] 0.1 parts leveling agent

[0086] 0.5 parts water-absorbing agent

[0087] 1 part of coupling agent

[0088] 5 parts pigment

[0089] 18 parts of filler.

[0090] Component B includes:

[0091] 80 parts of modified polyisocyanate composition.

[0092] The mass ratio of component A to component B is 1:0.8, and the molar ratio of -NCO / -NH in component B and component A is 1.2 under this ratio.

[0093] Example 3

[0094] Similar to Example 1, the selection and preparation methods of each component remain unchanged. The difference is that component A, by weight, comprises:

[0095] 70 parts of polyaspartic acid ester resin,

[0096] 0.5 parts dispersant

[0097] Defoamer 0.5 parts

[0098] Defoamer 20.5 parts

[0099] 0.2 parts leveling agent

[0100] 1 part absorbent

[0101] 1.5 parts coupling agent

[0102] 6 parts pigment

[0103] 20 parts of filler.

[0104] Component B includes:

[0105] 86 parts of modified polyisocyanate composition.

[0106] The mass ratio of component A to component B is 1:0.86, and the molar ratio of -NCO / -NH in component B and component A is 1.4 under this ratio.

[0107] Comparative Example 1

[0108] Same as in Example 1, except that: the polyaspartic acid ester resin in component A is W420 (Yantai Wanshun New Material Co., Ltd.), the solid content of W420 is 97±2%, the equivalent is 277 (secondary amine equivalent), and it is labeled as R1.

[0109] To maintain the -NCO / -NH molar ratio in the coating at 1.3, the weight of W420 is adjusted to 75 parts, while other parameters remain unchanged. The coating is then labeled as R1-H2.

[0110] Comparative Example 2

[0111] Same as in Example 1, except that: the polyaspartic acid ester resin in component A is W520 (Yantai Wanshun New Material Co., Ltd.), the solid content of W520 is 97±2%, the equivalent is 290, and it is labeled as R2.

[0112] To maintain the -NCO / -NH molar ratio in the coating at 1.3, the weight of W520 was adjusted to 79 parts, while other parameters remained unchanged. The coating was then labeled as R2-H2.

[0113] Comparative Example 3

[0114] Same as in Example 1, except that: the polyaspartic acid ester resin in component A is F2580 (Zhuhai Feiyang New Materials Co., Ltd.), the solid content of F2580 is 97±2%, the equivalent is 290, and it is labeled as R3.

[0115] To maintain the -NCO / -NH molar ratio in the coating at 1.3, the weight of F2580 is adjusted to 79 parts, while other parameters remain unchanged. The coating is then labeled as R3-H2.

[0116] Comparative Example 4

[0117] Same as in Example 1, except that the polyaspartic acid ester resin in component A is replaced with castor oil polyol A4105 (Shanghai Jingri New Materials Co., Ltd.), with a hydroxyl value of 315 mgKOH / g, and the weight of A4105 is 70 parts, labeled as R5.

[0118] The weight parts of the modified polyisocyanate composition are adjusted to 110 parts, the mass ratio of component A to component B is 1:1.1, the molar ratio of -NCO / -OH in the coating is 1.23, and other parameters remain unchanged. Then the coating is labeled as R5-H2.

[0119] Comparative Example 5

[0120] Same as Example 1, except that: the modified polyisocyanate composition in component B is unmodified HDI trimer WANNATE HT-100 (Wanhua Chemical Group Co., Ltd.), with an NCO content of 21.8 wt%, labeled as H1.

[0121] To maintain the -NCO / -NH molar ratio in the coating at 1.3, the weight of the modified polyisocyanate composition was adjusted to 69 parts, while other parameters remained unchanged. The coating was then labeled R4-H1.

[0122] Comparative Example 6

[0123] Similar to Comparative Example 1, except that the modified polyisocyanate composition in component B is unmodified HDI trimer WANNATE HT-100 (Wanhua Chemical Group Co., Ltd.), with an NCO content of 21.8 wt%, labeled as H1.

[0124] To maintain the -NCO / -NH molar ratio in the coating at 1.3, the weight of the modified polyisocyanate composition was adjusted to 68 parts, while other parameters remained unchanged. The coating was then labeled R1-H1.

[0125] Comparative Example 7

[0126] Similar to Comparative Example 2, except that the modified polyisocyanate composition in component B is unmodified HDI trimer WANNATE HT-100 (Wanhua Chemical Group Co., Ltd.), with an NCO content of 21.8 wt%, labeled as H1.

[0127] To maintain the -NCO / -NH molar ratio in the coating at 1.3, the weight of the modified polyisocyanate composition was adjusted to 68 parts, while other parameters remained unchanged. The coating was then labeled R2-H1.

[0128] Comparative Example 8

[0129] Similar to Comparative Example 3, except that the modified polyisocyanate composition in component B is unmodified HDI trimer WANNATE HT-100 (Wanhua Chemical Group Co., Ltd.), with an NCO content of 21.8 wt%, labeled as H1.

[0130] To maintain the -NCO / -NH molar ratio in the coating at 1.3, the weight of the modified polyisocyanate composition was adjusted to 68 parts, while other parameters remained unchanged. The coating was then labeled R3-H1.

[0131] Comparative Example 9

[0132] Similar to Comparative Example 4, except that the modified polyisocyanate composition in component B is unmodified HDI trimer WANNATE HT-100 (Wanhua Chemical Group Co., Ltd.), with an NCO content of 21.8 wt%, labeled as H1.

[0133] To maintain the -NCO / -OH molar ratio in the coating at 1.23, the weight of the modified polyisocyanate composition was adjusted to 93 parts, while other parameters remained unchanged. The coating was then labeled R5-H1.

[0134] Test case

[0135] High and low temperature resistance test

[0136] Solvent-free floor coatings typically form a film thickness greater than 300 micrometers in a single application, and can even reach 1000-2000 micrometers. Therefore, pencil hardness is unsuitable for evaluating the strength of this type of coating film; Shore D hardness is used instead. Considering that floor coatings are used in environments ranging from -20°C (e.g., cold storage) to 50-60°C (e.g., outdoor parking lots in summer), resistance to temperature changes is an important evaluation indicator.

[0137] The above-described embodiments and comparative examples of coating samples underwent room temperature curing in accordance with GB / T22374-2018 standard, and Shore D hardness data (HD) were recorded. The temperature change resistance test method was performed according to section 6.2 of JG / T25-2017, "Test Method for Temperature Change Resistance of Architectural Coatings." The low-temperature chamber temperature was set to -20±2℃, and the constant-temperature chamber temperature was set to 80±2℃. Three cycles were performed according to steps 6.2.1-6.2.3 to test the basic hardness change trend of the material and record the Shore D hardness data.

[0138] normal temperature After heat resistance Example 1 R4-H2 76 76 Example 2 R4-H2 75 74 Example 3 R4-H2 77 77 Comparative Example 1 R1-H2 75 74 Comparative Example 2 R2-H2 63 59 Comparative Example 3 R3-H2 42 31 Comparative Example 5 R4-H1 75 70 Comparative Example 6 R1-H1 74 69 Comparative Example 7 R2-H1 64 55 Comparative Example 8 R3-H1 43 20

[0139] The data in the table above shows that the combination of modified isocyanate curing agent and aspartic resin can significantly improve the high and low temperature resistance of aspartic polyurea coatings. In particular, the aspartic polyurea coatings obtained by combining aspartic resins PAE0760 and W420 with the modified isocyanate curing agent show almost no change in film strength after temperature resistance testing, exhibiting excellent high and low temperature resistance. Furthermore, the coating using PAE0760 aspartic resin has a higher hardness level.

[0140] Tear strength test

[0141] Tear strength refers to a material's ability to resist tearing. The tear strength data of the coating samples from the above examples and comparative examples were tested according to Method A in GB / T529-2008, as shown in the table below, with units of kN / m.

[0142]

[0143]

[0144] The data in the table above shows that the modified isocyanate curing agent combined with aspartic resin can significantly improve the tear strength of aspartic polyurea coatings. In particular, the aspartic resin PAE0760, when combined with the modified isocyanate curing agent, produces aspartic polyurea coatings with the highest tear strength, superior to similar aspartic polyurea coatings.

[0145] Intercoating adhesion test

[0146] Interlayer adhesion refers to the ability of different coating layers in a coating system to adhere to each other, and is an important indicator of the overall performance and service life of the coating. Aspartic polyurea floor coatings are commonly used in various new or renovated flooring projects, and need to be applied to various types of floor coatings or old floor coatings. It requires that the polyaspartic ester polyurea topcoat have good interlayer adhesion with various common old floor coatings.

[0147] The coatings described in the examples and comparative examples were applied to various types of floor coatings, and interlayer adhesion was tested. The cross-cut adhesion test was used for evaluation, based on ISO 2409:2020 standards, with a cut-off spacing of 2 mm. Test results were graded from 0 to 5, with grade 0 indicating the strongest adhesion and grade 5 indicating the weakest adhesion.

[0148]

[0149] According to the data in the table above, the combination of modified isocyanate curing agent and aspartic resin can improve the adhesion of aspartic polyurea coatings on some floor coatings. The aspartic polyurea coatings obtained by combining aspartic resin PAE0760 with the modified isocyanate curing agent have significantly improved adhesion on different floor coatings. Except for hardener floor coatings, they all reach the best level of adhesion test.

[0150] Through the comparison of the above three tests, the results of Comparative Examples 2, 3, 7, and 8 show that the coatings formed by using R2 and R3 aspartic resins, whether combined with unmodified curing agent H1 or modified curing agent H2, cannot meet the requirements of high-strength, all-weather, indoor and outdoor floor coatings. Next, we will further compare and test the leveling data of the aspartic polyurea floor coatings in Examples 1, 2, and 3, as well as Comparative Examples 1, 5, and 6.

[0151] Leveling test

[0152] Coating leveling property refers to the ability of liquid coating to spread and eliminate surface irregularities during the drying process. This characteristic is crucial and affects the final quality of the floor coating film. Poor leveling property can easily lead to defects such as orange peel and brush marks, severely impacting appearance and protective performance. Good leveling property results in a uniform and smooth coating film, enhancing protection of the substrate and extending service life. Furthermore, the compatibility between the resin and curing agent in the main agent can, to some extent, correlate with the coating film leveling property. Testing the leveling property of the coating can also reflect the degree of compatibility between different film-forming substances in the coating composition.

[0153] Tested according to ASTM D4062-24 standard: Using a leveling tester, observe the degree of disappearance of streaks after application. Determine the leveling grade by referring to the leveling grade chart; grade 10 indicates the best leveling performance, and grade 0 indicates the worst leveling performance. The experimental results are shown in the table below.

[0154] Leveling grade Example 1 R4-H2 Level 7 Example 2 R4-H2 Level 7 Example 3 R4-H2 Level 7 Comparative Example 1 R1-H2 Level 5 Comparative Example 5 R4-H1 Level 6 Comparative Example 6 R1-H1 Level 4

[0155] The data in the table above shows that the combination of modified isocyanate curing agent and aspartic resin can significantly improve the wetting and leveling properties of aspartic polyurea coatings. In particular, the combination of aspartic resin PAE0760 and the modified isocyanate curing agent results in aspartic polyurea coatings with even better wetting and leveling properties.

[0156] Drying and curing speed test

[0157] According to the testing standard GB / T 22374-2018 -6.3.3, the curing and drying speed of each coating was tested, and the unit is: hours.

[0158] surface dry Practical work Example 1 R4-H2 1.1 3.2 Example 2 R4-H2 1.2 3.5 Example 3 R4-H2 1.0 3.0 Comparative Example 1 R1-H2 1.2 3.3 Comparative Example 2 R2-H2 1.6 4.0 Comparative Example 3 R3-H2 1.9 4.5 Comparative Example 4 R5-H2 4.5 24 Comparative Example 5 R4-H1 1.0 3.0 Comparative Example 6 R1-H1 1.0 3.1 Comparative Example 7 R2-H1 1.5 4.0 Comparative Example 8 R3-H1 1.8 4.4 Comparative Example 9 R5-H1 4 22

[0159] As can be seen from the table above, the curing and drying speed of floor coatings using castor oil polyols is much slower than that using aspartic resins. This is especially important in renovation projects, where the floor coating needs to complete 2-3 application steps within a day and be fully dry within 3-4 hours to allow for pedestrian traffic and facilitate the next step of application. This is crucial to meeting the installation needs of such projects to the greatest extent possible. (Note: While meeting this curing speed requirement, a slightly slower curing speed is preferable, as it improves coating leveling and adhesion.)

[0160] Water vapor sensitivity test

[0161] The application of floor coatings often encounters climatic environments with high air humidity, such as the rainy season. In such cases, the floor coatings are required to have low sensitivity to moisture, and to be able to be applied normally under different relative humidity conditions to obtain an ideal floor coating film.

[0162] The gloss and Shore D hardness of the cured coating film were tested and evaluated using the same temperature (23℃) but different relative humidity conditions (RH: 50% and RH: 85%).

[0163] Surface gloss of the paint film: A 1000-micron thick self-leveling floor paint film was prepared using a wet film preparation device. The film was applied and cured for 7 days under different relative humidity conditions at 23℃. The gloss (in %) at a 60° incident angle was tested according to ISO 2813:2014. The results are listed below:

[0164] RH: 50% RH: 85% Example 1 R4-H2 92 89 Example 2 R4-H2 92 89 Example 3 R4-H2 91 88 Comparative Example 1 R1-H2 90 88 Comparative Example 2 R2-H2 91 85 Comparative Example 3 R3-H2 90 83 Comparative Example 4 R5-H2 82 58 Comparative Example 5 R4-H1 91 86 Comparative Example 6 R1-H1 90 86 Comparative Example 7 R2-H1 91 85 Comparative Example 8 R3-H1 90 80 Comparative Example 9 R5-H1 81 52

[0165] As shown in the table above, under high humidity conditions, the gloss of the floor coating using castor oil polyol combined with isocyanate curing agent decreased significantly. This is because water vapor in the air reacted with the isocyanate curing agent, resulting in numerous pores on the coating surface and causing diffuse reflection, thus reducing the gloss. While modification of the isocyanate curing agent can improve the gloss of the coating film to some extent, significant gloss loss still occurs.

[0166] Floor coatings using aspartic resin combined with isocyanate curing agents exhibit good gloss retention in high humidity environments. Furthermore, the modified isocyanate curing agent can enhance the gloss of the coating film to some extent. In particular, floor coatings using aspartic resin PAE0760, while showing a slight decrease in gloss under high humidity conditions, still maintain a high level of gloss.

[0167] Shore D Hardness: Samples were prepared according to GB / T22374-2018 standard (humidity condition: RH: 50%). A type D Shore hardness tester was used to test the Shore D hardness of the cured paint films of each example and comparative example. Additionally, the Shore D hardness was tested under different humidity conditions (RH: 85%). The results are listed below:

[0168]

[0169]

[0170] As shown in the table above, under high humidity conditions, the Shore hardness of floor coatings using castor oil polyol combined with isocyanate curing agents decreased significantly. This is because water vapor in the air reacted with the isocyanate curing agent, producing carbon dioxide gas that created numerous micropores within the paint film, resulting in a decrease in film hardness. While modified isocyanate curing agents can improve the Shore hardness of the coating film to some extent, it remains relatively low.

[0171] Floor coatings using aspartic resin combined with isocyanate curing agents exhibit good Shore hardness retention in high humidity environments. Floor coatings using aspartic resin PAE0760 combined with isocyanate curing agents show almost no change in Shore hardness in high humidity environments, and are unaffected by high humidity conditions.

Claims

1. A solvent-free polyaspartic acid ester polyurea floor coating, characterized in that, Includes the main agent and the curing agent, wherein: The main component includes polyaspartic acid ester resin, functional additives, pigments and fillers; The curing agent includes a modified polyisocyanate composition, wherein the modified polyisocyanate composition is a polyisocyanate composition modified with hydroxycyclic ketone compounds.

2. The solvent-free polyaspartic acid ester polyurea floor coating according to claim 1, characterized in that, The weight proportions of each component in the main agent are as follows: 70-75 parts of polyaspartic acid ester resin; Functional additives, 2-4 parts; 16-26 parts of pigments and fillers; The weight parts of each component in the curing agent are as follows: 60-90 parts of modified polyisocyanate composition.

3. The solvent-free polyaspartic acid ester polyurea floor coating according to claim 2, characterized in that, In the main agent, the weight proportions of each component in the functional additives are as follows: Dispersant 0.1–0.5 parts; Defoamer 0.2 to 1 part; Leveling agent 0.1-0.2 parts; 0.5 to 1 part water-absorbing agent; 1 to 1.5 parts of coupling agent; The weight percentages of each component in the pigments and fillers are as follows: 3-6 parts pigment; 13-20 parts of filler.

4. The solvent-free polyaspartic acid ester polyurea floor coating according to claim 1, characterized in that, The mass ratio of the main agent to the curing agent is 1:0.6 to 0.9; The molar ratio of -NCO in the curing agent to -NH in the main agent, -NCO / -NH, is 1 to 1.5, preferably 1.2 to 1.

4.

5. The solvent-free polyaspartic acid ester polyurea floor coating according to claim 1, characterized in that, The hydroxycycloketone compound is selected from one or more of 3-hydroxycyclobutanone, 3-hydroxycyclopentanone, and 4-hydroxycyclohexanone, preferably 3-hydroxycyclobutanone.

6. The solvent-free polyaspartic acid ester polyurea floor coating according to claim 5, characterized in that, The polyisocyanate composition is obtained by polymerizing aliphatic diisocyanate monomers, wherein the aliphatic diisocyanate monomers are selected from one or more of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and lysine diisocyanate, preferably hexamethylene diisocyanate. The polyisocyanate composition is preferably one or more of HDI trimer and HDI biuret.

7. The solvent-free polyaspartic acid ester polyurea floor coating according to claim 1, characterized in that, The polyaspartic acid ester resin is selected from one or more of PAE0760 and W420, preferably PAE0760.

8. The solvent-free polyaspartic acid ester polyurea floor coating according to claim 7, characterized in that, The polyaspartic acid ester resin PAE0760 contains a variety of active ingredients with secondary amine functional groups (-NH-), including at least the components shown in Formula 1 and Formula 2:

9. The solvent-free polyaspartic acid ester polyurea floor coating according to claim 7, characterized in that, The preparation method of the polyaspartic acid ester resin PAE0760 includes: 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and polyetheramine were mixed and stirred at a molar ratio of 1:(7-10) and heated to 50-70°C for at least 20 minutes to homogenize the system. Diethyl maleate was added dropwise, with a molar ratio of diethyl maleate to 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane of (5-7):

1. The mixture was then reacted at 50-70°C for 20-30 hours, with nitrogen gas introduced to prevent side reactions. After the reaction was completed, the mixture was cooled to room temperature to obtain the prepared polyaspartic acid ester resin PAE0760.

10. The method for preparing the solvent-free polyaspartic acid ester polyurea floor coating according to any one of claims 1-9, characterized in that, Includes the following steps: (1) Mix and disperse the specified amount of polyaspartic acid ester resin, functional additives, pigments and fillers evenly as the main agent; (2) The polyisocyanate composition is mixed and reacted with hydroxycyclic ketone compounds to prepare a modified polyisocyanate composition, which is used as a curing agent; (3) When using, mix the main agent and the curing agent evenly to obtain solvent-free polyaspartic acid ester polyurea floor coating.

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