Ultralow free isocyanate monomer aspartic polyurea sealant and preparation method thereof

Abstract

The invention relates to the field of sealant, and particularly discloses an ultralow free isocyanate monomer radix asparagi polyurea sealant and a preparation method thereof. The sealant comprises a component A and a component B. The component A is a polyurea resin component, the component B is an isocyanate component, and the component B is prepared from the following raw materials in parts by weight: 85-95 parts of HDI tripolymer modifier, 0-1 part of a defoaming agent, 5-10 parts of an anti-settling agent and 0-5 parts of a silane coupling agent. The HDI tripolymer modifier is prepared from an HDI tripolymer and an HDI prepolymer; the NCO value of the HDI tripolymer modifier is 16 to 21 percent. No free isocyanate monomer is detected in the sealant, and on the premise that it is ensured that the sealant has the proper construction viscosity, the poison caused by the isocyanate monomer and the allergy condition of constructors are reduced to the maximum extent.

Description

Technical Field

[0001] The present application relates to the field of seam beautifying agents, specifically, to the field of asparagine polyurea seam beautifying agents, and more specifically, to an asparagine polyurea seam beautifying agent with ultra-low free isocyanate monomer and a preparation method thereof. Background Art

[0002] Sealing agent is mainly used in reserved gaps of ceramic tiles, mosaics, stones and other materials during decoration. As an important type of building material for filling gaps and decorating floors and walls, it is significantly better in decorativeness and practicality than cement-based colored seaming agent, solving the problems of unsightly, dirty and black ceramic tile gaps. Traditional seaming agent is applied on the surface of the seaming agent for construction, while the new seaming agent does not require seaming agent as the base layer, and can be directly filled in the gaps after ceramic tiles, mosaics, stones and other materials are bonded, suitable for filling various types of gaps.

[0003] Initially, epoxy caulking agents were the most frequently used in decoration. However, due to its insufficient antioxidant properties, easy yellowing, poor UV resistance, poor water resistance, and limited scope of application, it has been gradually replaced by the rapidly developed asparagus polyurea caulking agents in recent years. Asparagus polyurea caulking agents have the advantages of strong weather resistance, good color stability, wear resistance and corrosion resistance, convenient construction, and environmental safety. They are widely used in the beautification of gaps in materials such as tiles and marble, and can provide long-lasting weather resistance, wear resistance, and chemical resistance.

[0004] The isocyanate component used in the existing asparagus polyurea caulking agent, such as the Chinese patent with publication number CN 114507501 A, is usually obtained by prepolymerization of isocyanate monomer and polyol. The higher the degree of prepolymerization, the greater the viscosity of the caulking agent. However, the greater viscosity is not conducive to on-site construction, and the caulking agent requires 100% solid content, and solvents cannot be added to reduce the viscosity. Therefore, in order to ensure that the product has a suitable construction viscosity, the isocyanate monomer used must be excessive. After the excess isocyanate monomer reacts with the polyol, a certain amount of isocyanate monomer will remain. This part of the excess isocyanate monomer has certain toxic hazards, which leads to the fact that most of the caulking agents on the market are very likely to cause allergies in construction workers and have poor safety. Summary of the invention

[0005] In order to solve the above technical problems, the present application provides an ultra-low free isocyanate monomer aspartame polyurea seam beautifying agent and a preparation method thereof.

[0006] In the first aspect, the present application provides an ultra-low free isocyanate monomer aspartame polyurea seam beautifying agent, which adopts the following technical solution: An ultra-low free isocyanate monomer aspartame polyurea seam beautifying agent comprises a component A and a component B, wherein the component A is a polyurea resin component, the component B is an isocyanate component, and the raw materials used for the component B comprise 85-95 parts of a modified HDI trimer, 0-1 part of a defoamer, 5-10 parts of an anti-settling agent and 0-5 parts of a silane coupling agent by weight; the modified HDI trimer comprises an HDI trimer and an HDI prepolymer; and the NCO value of the modified HDI trimer is 16-21%.

[0007] Specifically, the weight ratio of the HDI trimer to the HDI prepolymer is (70-90):(10-30).

[0008] Specifically, the HDI prepolymer is obtained by reacting an HDI trimer and a hydroxy compound in a weight ratio of (15-35):(65-85).

[0009] Specifically, the hydroxy compound is one of polyester polyol, polyether polyol, polycaprolactone polyol, polytetramethylene ether polyol, polycarbonate polyol and polysiloxane polyol.

[0010] More specifically, the defoaming agent may be a defoaming agent commonly used in the field of seam beautifying agents, such as BYK-085 from Germany's BYK.

[0011] More specifically, the anti-settling agent may be an anti-settling agent commonly used in the field of seam beautifying agents, such as hydrophobic fumed silica, brand name Wacker H-18.

[0012] More specifically, the silane coupling agent can be selected from the silane coupling agent commonly used in the field of seam beautifying agents, such as γ-glycidyloxypropyltrimethoxysilane, with the brand name Chenguang KH-560.

[0013] Through the above technical solution, the present application directly adopts the modified HDI trimer as the main component of the B component of the caulking agent, so that the final caulking agent is free of free isocyanate monomers such as HDI, IPDI, and HMDI. Under the premise of ensuring that the caulking agent has a suitable construction viscosity, the occurrence of poisoning caused by isocyanate monomers and allergies of construction workers is reduced to the greatest extent. In addition, the present application optimizes the ratio between the HDI trimer and the hydroxyl compound, so that the final isocyanate component has a higher NCO value, thereby improving the hardness, strength and scratch resistance of the caulking agent.

[0014] Preferably, by weight, the raw materials used for component A include 80-90 parts of aspartic acid ester resin mixture A0, 0-1 part of dispersant, 0-1 part of defoamer, 5-10 parts of anti-settling agent and 5-10 parts of titanium dioxide.

[0015] Specifically, the dispersant may be a dispersant commonly used in the field of seam beautifying agents, such as BYK-163 from Germany's BYK.

[0016] Preferably, in parts by weight, the aspartic acid ester resin mixture A0 comprises 40-60 parts of aspartic acid ester resin A1, 30-50 parts of aspartic acid ester resin A2 and 0-20 parts of aspartic acid ester resin A3; The structural formula of the aspartic acid ester resin A1 is The amino equivalent weight is 290-350, wherein R is the residue after the terminal hydroxyl group of the polyol is removed, and R1 is ethyl; The structural formula of the aspartic acid ester resin A2 is The amino equivalent is 680-800, wherein R is the residue after the terminal hydroxyl group of the polyol is removed, and R2 is an ethyl group; The structural formula of the aspartic acid ester resin A3 is

[0017] Specifically, the aspartic acid ester resin A1 is obtained by transesterification of aspartic acid resin F520 with polyol; the structural formula of the aspartic acid resin F520 is

[0018] Specifically, the aspartic acid ester resin A2 is obtained by transesterification reaction of aspartic acid resin F420 and polyol; the structural formula of the aspartic acid resin F420 is

[0019] Through the above technical scheme, the present application selects the aspartic acid resin A1 obtained by modifying the low-reactivity aspartic acid resin F520 as the main body, and mixes the aspartic acid resin A2 and the aspartic acid resin A3 according to a certain ratio, so that the prepared seam beautifying agent has a suitable gel time and drying speed, which not only ensures that the workers have a longer time for construction, but also allows the site to be put into use quickly. In addition, the viscosity of the resin raw materials used in the present application is relatively low, which can make the seam beautifying agent have good construction performance, good extrudability, and easy glue operation.

[0020] At the same time, the aspartic acid resin A1 and aspartic acid resin A2 of the present application are respectively obtained by ester exchange reaction of aspartic acid resin F520 and aspartic acid resin F420 with polyols. The ester exchange reaction process increases the number of functional groups of aspartic acid resin F520 and aspartic acid resin F420, so that the adhesive strip formed by the caulking agent has a higher cross-linking density, thereby enhancing the hardness and heat resistance of the adhesive strip. At the same time, the long-chain R group in aspartic acid resin A1 and aspartic acid resin A2 provides good flexibility, which significantly improves the problem of large edge brittleness of the caulking agent after 24 hours of construction and curing in a low-temperature environment.

[0021] Specifically, the polyol is one of polyester polyol, polyether polyol, polycaprolactone polyol, polytetramethylene ether polyol, polycarbonate polyol and polysiloxane polyol.

[0022] Preferably, the molecular weight of the polyol is 500-2000.

[0023] Through the above technical scheme, the present application selects low molecular weight polyols, so that the viscosity of the prepared aspartic acid ester resin A1 and aspartic acid ester resin A2 will not increase much due to the ester exchange reaction, ensuring that the seam beautifying agent can have good construction performance, good extrusion properties, and easy gluing operation.

[0024] Preferably, the polyol is one of polycaprolactone polyol, polytetramethylene ether polyol and polycarbonate polyol.

[0025] Through the above technical scheme, compared with conventional polyester polyols, conventional polyether polyols and polysiloxane polyols, aspartic acid ester resin A1 and aspartic acid ester resin A2 prepared by using one of polycaprolactone polyol, polytetramethylene ether polyol and polycarbonate polyol can further improve the hardness, heat resistance and chemical resistance of the seam beautifying agent.

[0026] In the second aspect, the present application provides a method for preparing an ultra-low free isocyanate monomer aspartame polyurea seam beautifying agent, which adopts the following technical scheme: A method for preparing an ultra-low free isocyanate monomer aspartame polyurea seam beautifying agent comprises the following steps: uniformly mixing all raw materials used for component A, and packaging after vacuum degassing; uniformly mixing all raw materials used for component B, and packaging after vacuum degassing; the volume ratio of component A to component B is 2:1.

[0027] Through the above technical scheme, the present application mixes all the raw materials used in component A evenly, and after vacuum degassing, encapsulates them into the thicker side of the 2:1 two-component caulking agent hose, and mixes all the raw materials used in component B evenly, and after vacuum degassing, encapsulates them into the thinner side of the 2:1 two-component caulking agent hose.

[0028] In summary, this application has the following beneficial technical effects: 1. This application directly uses HDI trimer as the main body, which can make the final caulking agent free of free HDI, IPDI, HMDI and other isocyanate monomers. On the premise of ensuring that the caulking agent has a suitable construction viscosity, the occurrence of toxicity caused by isocyanate monomers and allergies of construction workers is reduced to the greatest extent; 2. The present application uses a certain ratio of aspartic acid resin A1, aspartic acid resin A2 and aspartic acid resin A3 as a resin component and isocyanate component for curing, so that the prepared seam beautifying agent has a suitable gel time and drying speed, which not only ensures that workers have a longer time for construction, but also allows the site to be put into use quickly; 3. The viscosity of the resin raw materials used in the present application is relatively low, and the prepared seam beautifying agent has good construction performance, good extrusion performance, and easy gluing operation; 4. The paint film formed by the seam beautifying agent of the present application after curing has good hardness, strength, scratch resistance, heat resistance and chemical resistance, and also has good flexibility, which can meet the requirements of on-site use. DETAILED DESCRIPTION

[0029] The present application is further described in detail below with reference to the embodiments.

[0030] Unless otherwise specified, the raw materials used in this application are all commercially available products, including: HDI trimer, purchased from Asahi Kasei Corporation, model TPA-100, NCO content 23%; Defoamer, purchased from BYK, Germany, model BYK-085; Dispersant, purchased from BYK, Germany, model BYK-163; Hydrophobic fumed silica, purchased from Wacker, model H-18; γ-Glycidyloxypropyltrimethoxysilane, purchased from Chenguang, model KH-560; Aspartic acid ester resin F520, aspartic acid resin F420 and aspartic acid resin A3 were all purchased from Shenzhen Feiyang Junyan New Materials Co., Ltd., where the model of aspartic acid resin A3 was F241, and the structural formulas of aspartic acid ester resin F520, aspartic acid resin F420 and aspartic acid resin F241 were: Wherein R1 and R2 are both ethyl groups; Polyether diol, purchased from Green Union (Jining) Chemical Technology Co., Ltd., with a molecular weight of 2000; Polyester diol, purchased from Green Union (Jining) Chemical Technology Co., Ltd., model 7362, molecular weight 2000; Polycarbonate diol, purchased from Ube, Japan, model UH-CARB50, molecular weight 500; Polycaprolactone diol, purchased from Wuhan Huaxiang Kejie Biotechnology Co., Ltd., with a molecular weight of 2000; Polytetrahydrofuran diol, purchased from Hyosung Chemical (Jiaxing) Co., Ltd., molecular weight 1000; Dimethicone copolyol, purchased from Kangdisi Chemical (Hubei) Co., Ltd., molecular formula is C6H 18 OSi2.

[0031] In the preparation process of HDI prepolymer, since there is no significant difference in the effect of conventional polyester polyols, conventional polyether polyols, polycaprolactone polyols, polytetramethylene ether polyols, polycarbonate polyols and polysiloxane polyols as hydroxyl compounds, in the specific embodiments of the present application, polyether diols in conventional polyether polyols are used as examples for illustration, and since the reaction between HDI trimer and hydroxyl compound is a conventional reaction method well known to those skilled in the art, it is not described in detail in the present application.

[0032] Preparation Example 1.1 Aspartic acid ester resin A1 was prepared by the following method: At a temperature of 110° C., aspartic acid resin F520 and polyester diol (Mn=2000, hydroxyl value of 50±3.5 mgKOH / g) were subjected to an ester exchange reaction to obtain aspartic acid ester resin A1 with an amino equivalent of 290.

[0033] Preparation Example 1.2 Aspartic acid ester resin A1 was prepared by the following method: At a temperature of 110° C., aspartic acid resin F520 and polydimethylsiloxane copolyol were subjected to an ester exchange reaction to obtain aspartic acid ester resin A1 having an amino equivalent of 320.

[0034] Preparation Example 1.3 Aspartic acid ester resin A1 was prepared by the following method: At a temperature of 110° C., aspartic acid resin F520 and polyether diol (Mn=2000, hydroxyl value of 56±1.5 mgKOH / g) were subjected to an ester exchange reaction to obtain aspartic acid ester resin A1 with an amino equivalent of 310.

[0035] Preparation Example 1.4 Aspartic acid ester resin A1 was prepared by the following method: At a temperature of 110° C., aspartic acid resin F520 and polycarbonate diol (Mn=500, hydroxyl value of 224±20 mgKOH / g) were subjected to an ester exchange reaction to obtain aspartic acid ester resin A1 with an amino equivalent of 350.

[0036] Preparation Example 1.5 Aspartic acid ester resin A1 was prepared by the following method: At a temperature of 110° C., aspartic acid resin F520 and polycaprolactone diol (Mn=2000, hydroxyl value of 56±5 mgKOH / g) were subjected to an ester exchange reaction to obtain aspartic acid ester resin A1 with an amino equivalent of 300.

[0037] Preparation Example 1.6 Aspartic acid ester resin A1 was prepared by the following method: At a temperature of 110° C., aspartic acid resin F520 and polytetrahydrofuran diol (Mn=1000, hydroxyl value of 110±10 mgKOH / g) were subjected to an ester exchange reaction to obtain aspartic acid ester resin A1 with an amino equivalent of 340.

[0038] Preparation Example 2.1 Aspartic acid ester resin A2 was prepared by the following method: At a temperature of 110° C., aspartic acid resin F420 and polycarbonate diol (Mn=500, hydroxyl value of 224±20 mgKOH / g) were subjected to an ester exchange reaction to obtain aspartic acid ester resin A2 with an amino equivalent of 800.

[0039] Preparation Example 2.2 Aspartic acid ester resin A2 was prepared by the following method: At a temperature of 110° C., aspartic acid resin F420 and polycaprolactone diol (Mn=2000, hydroxyl value of 56±5 mgKOH / g) were subjected to an ester exchange reaction to obtain aspartic acid ester resin A2 with an amino equivalent of 680.

[0040] Preparation Example 2.3 Aspartic acid ester resin A2 was prepared by the following method: At a temperature of 110° C., aspartic acid resin F420 and polytetrahydrofuran diol (Mn=1000, hydroxyl value of 110±10 mgKOH / g) were subjected to an ester exchange reaction to obtain aspartic acid ester resin A2 with an amino equivalent of 720.

[0041] Example 1.1 A method for preparing an ultra-low free isocyanate monomer aspartame polyurea seam beautifying agent comprises the following steps: S1. Preparation of component A: 8 kg of aspartic acid ester resin mixture A0, 0.1 kg of dispersant BYK-163, 1 kg of hydrophobic fumed silica and 0.5 kg of titanium dioxide were stirred at a speed of 1000 r / min for 15 minutes, and a vacuum pump was turned on to maintain the vacuum degree at -0.095 MPa for 30 minutes to obtain component A; Wherein, the aspartic acid ester resin mixture A0 includes 3.2 kg of aspartic acid ester resin A1 prepared in Preparation Example 1.1, 4 kg of aspartic acid ester resin A2 prepared in Preparation Example 2.1 and 0.8 kg of aspartic acid ester resin F241; S2, preparation of component B: 8.5 kg of HDI trimer modified product, 0.1 kg of defoamer BYK-085, 0.5 kg of hydrophobic fumed silica and 0.5 kg of silane coupling agent KH-560 were stirred at a speed of 1000 r / min for 20 minutes, and the vacuum pump was turned on to maintain the vacuum degree at -0.097 MPa for 30 minutes to obtain component B; The HDI trimer modified product includes 5.95 kg HDI trimer and 2.55 kg HDI prepolymer (prepared by reacting HDI trimer and polyether diol in a weight ratio of 15:85), and the NCO value of the HDI trimer modified product is 16%; S3, respectively loading component A and component B into a 2:1 two-component seam beautifying agent hose to obtain a finished seam beautifying agent.

[0042] Example 1.2 A method for preparing an ultra-low free isocyanate monomer aspartame polyurea seam beautifying agent comprises the following steps: S1. Preparation of component A: 9 kg of aspartic acid ester resin mixture A0, 0.1 kg of defoamer BYK-085, 0.5 kg of hydrophobic fumed silica and 1 kg of titanium dioxide were stirred at a speed of 1000 r / min for 15 minutes, and a vacuum pump was turned on to maintain the vacuum degree at -0.095 MPa for 30 minutes to obtain component A; Wherein, the aspartic acid resin mixture A0 includes 4.5 kg of aspartic acid resin A1 prepared in Preparation Example 1.2, 2.7 kg of aspartic acid resin A2 prepared in Preparation Example 2.2 and 1.8 kg of aspartic acid resin F241; S2. Preparation of component B: 9.5 kg of HDI trimer modified product and 1 kg of hydrophobic fumed silica were stirred at a speed of 1000 r / min for 20 minutes, and the vacuum pump was turned on to maintain the vacuum degree at -0.097 MPa for 30 minutes to obtain component B; The HDI trimer modified product includes 8.55 kg HDI trimer and 0.95 kg HDI prepolymer (prepared by reacting HDI trimer and polyether diol in a weight ratio of 35:65), and the NCO value of the HDI trimer modified product is 21%; S3, respectively loading component A and component B into a 2:1 two-component seam beautifying agent hose to obtain a finished seam beautifying agent.

[0043] Example 1.3 A method for preparing an ultra-low free isocyanate monomer aspartame polyurea seam beautifying agent comprises the following steps: S1. Preparation of component A: 8.5 kg of aspartic acid ester resin mixture A0, 0.05 kg of dispersant BYK-163, 0.05 kg of defoamer BYK-085, 0.75 kg of hydrophobic fumed silica and 0.75 kg of titanium dioxide were stirred at a speed of 1000 r / min for 15 minutes, and a vacuum pump was turned on to maintain the vacuum degree at -0.095 MPa for 30 minutes to obtain component A; Wherein, the aspartic acid ester resin mixture A0 includes 5.1 kg of the aspartic acid ester resin A1 prepared in Preparation Example 1.3 and 3.4 kg of the aspartic acid ester resin A2 prepared in Preparation Example 2.2; S2, preparation of component B: 9 kg of HDI trimer modified product, 0.05 kg of defoamer BYK-085, 0.75 kg of hydrophobic fumed silica and 0.25 kg of silane coupling agent KH-560 were stirred at a speed of 1000 r / min for 20 minutes, and the vacuum pump was turned on to maintain the vacuum degree at -0.097 MPa for 30 minutes to obtain component B; The HDI trimer modified product includes 7.2 kg HDI trimer and 1.8 kg HDI prepolymer (prepared by reacting HDI trimer and polyether diol in a weight ratio of 20:80), and the NCO value of the HDI trimer modified product is 20%; S3, respectively loading component A and component B into a 2:1 two-component seam beautifying agent hose to obtain a finished seam beautifying agent.

[0044] Examples 2.1-2.3 A method for preparing an ultra-low free isocyanate monomer aspartic acid polyurea caulking agent, which is different from Example 1.3 in that: in step S1, the aspartic acid resin A1 prepared in Preparation Example 1.3 is replaced by the aspartic acid resin A1 prepared in Preparation Examples 1.4-1.6 respectively, and the rest is the same as Example 1.3.

[0045] Comparative Example 1 The difference from Example 1.3 is that in step S2, the modified HDI trimer in component B is replaced with polyether diol, HDI monomer and HDI trimer in a weight ratio of 22:35:50, and the rest is the same as Example 1.3.

[0046] Comparative Example 2 The difference from Example 1.3 is that in step S3, the volume ratio of component A to component B is 1:1, and the rest is the same as Example 1.3.

[0047] Comparative Example 3 The difference from Example 1.3 is that in step S3, the volume ratio of component A to component B is 1.2:1, and the rest is the same as Example 1.3.

[0048] Comparative Example 4 The difference from Example 1.3 is that in component A in step S1, only 8.5 kg of aspartic acid ester resin A1 prepared in Preparation Example 1.3 is mixed with dispersant, defoamer, hydrophobic fumed silica and titanium dioxide, and the rest is the same as Example 1.3.

[0049] Comparative Example 5 The difference from Example 1.3 is that in component A in step S1, only 8.5 kg of aspartic acid ester resin A2 prepared in Preparation Example 2.2 is mixed with dispersant, defoamer, hydrophobic fumed silica and titanium dioxide, and the rest is the same as Example 1.3.

[0050] Comparative Example 6 The difference from Example 1.3 is that in component A in step S1, the weight ratio of aspartic acid resin A1, aspartic acid resin A2 and aspartic acid resin F241 is 8:1:1, the amount of aspartic acid resin A1 is 6.8 kg, the amount of aspartic acid resin A2 is 0.85 kg, the amount of aspartic acid resin F241 is 0.85 kg, and the rest is the same as Example 1.3.

[0051] Comparative Example 7 The difference from Example 1.3 is that in component A in step S1, the weight ratio of aspartic acid ester resin A1, aspartic acid ester resin A2 and aspartic acid ester resin F241 is 1:2:7, the amount of aspartic acid ester resin A1 is 0.85 kg, the amount of aspartic acid ester resin A2 is 1.7 kg, the amount of aspartic acid ester resin F241 is 5.95 kg, and the rest is the same as Example 1.3.

[0052] Comparative Example 8 The difference from Example 1.3 is that in component A in step S1, aspartic acid ester resin A1 is replaced by aspartic acid ester resin F520, and the rest is the same as Example 1.3.

[0053] Comparative Example 9 The difference from Example 1.3 is that in component A in step S1, aspartic acid ester resin A2 is replaced by aspartic acid ester resin F420, and the rest is the same as Example 1.3.

[0054] Performance Testing 1. Referring to the method in GB / T 18446-2009, the total content (%) of free isocyanate monomers in the seam beautifying agents prepared in the above examples and comparative examples was detected; 2. Referring to the method in GB / T 36797-2008, the extrudability (kN) of the seam beautifying agents prepared in the above embodiments and comparative examples was tested; 3. The operable time (min) of the seam beautifying agents prepared in the above embodiments and comparative examples was calculated according to the gun stop interval, and the actual drying time (h) was recorded; 4. Referring to the method in GB / T 531.1-2008, the hardness (Shore D) and heat aging hardness (Shore D) of the seam beautifiers prepared in the above examples and comparative examples were tested, wherein the heat aging hardness was tested by curing for 6 days under standard test conditions, then curing in a blast drying oven at (60±2)°C for 7 days, and then taking out and cooling to room temperature before testing; 5. Chemical resistance: With reference to Method A (immersion method) in GB / T 9274-1998, the seam beautifying agents prepared in the above embodiments and comparative examples were respectively applied on the surface of the steel plate to obtain a coating with a thickness of (200±25) μm. The size of the steel plate was 120 mm×50 mm×(0.45-0.55) mm. The coated steel plate was immersed in a 5wt% sodium hydroxide solution for 10 days, and the occurrence of blistering, rusting, cracking, peeling and other coating pathological phenomena was recorded; The above performance test results are recorded in Table 1.

[0055] Table 1 Performance test results Data Analysis: As can be seen from Table 1, the caulking agent prepared in Examples 1.1-2.3 of the present application does not contain isocyanate monomers and has good extrudability, which means that the present application can greatly reduce the possibility of workers experiencing allergic reactions during production and use while ensuring that the caulking agent has a suitable construction viscosity, and is extremely safe. In addition, the caulking agent prepared in the present application also has a suitable operable time and a shoveling time, which not only ensures that workers have a longer construction time, but also enables the site to be put into use quickly. In addition, the caulking agent prepared in the present application also has good hardness, heat resistance, and chemical resistance, and can meet the requirements for on-site use.

[0056] The difference between Examples 2.1-2.3 and Example 1.3 is that different polyols are used in the preparation of aspartic acid ester resin A1. As can be seen from Table 1, the hardness and heat aging hardness of Examples 2.1-2.3 are slightly higher than those of Example 1.3. Experimental data show that compared with other polyols, a modified resin prepared by using one of polycarbonate polyol, polycaprolactone polyol and polytetramethylene glycol can further improve the hardness and heat resistance of the paint film.

[0057] As can be seen from Table 1, isocyanate monomers were detected in the caulking agent prepared in Comparative Example 1, which indicates that the free isocyanate monomers in the traditional caulking agent can easily cause allergies and the like in personnel during production and use, and the safety is relatively low.

[0058] The difference between Comparative Example 2-3 and Example 1.3 is that the ratio of component A and component B is different. It can be seen from Table 1 that the hardness and strength of Comparative Example 2-3 are lower than those of Example 1.3. The experimental data show that the present application optimizes the ratio between component A and component B to improve the hardness and strength of the seam beautifying agent.

[0059] The difference between Comparative Examples 4-5 and Example 1.3 is that the resin in component A is only aspartic acid resin A1 or only aspartic acid resin A2. It can be seen from Table 1 that when only aspartic acid resin A1 is used, the operable time of the caulking agent is up to 330 minutes, and the time for scraping glue is up to 12 hours; when only aspartic acid resin A2 is used, the operable time of the caulking agent is only 10 minutes, and the time for scraping glue is 1.25 hours; and when aspartic acid resin A1, aspartic acid resin A2 and aspartic acid resin F241 are mixed and used in a certain ratio in Example 1.3, the caulking agent has a suitable operable time and a time for scraping glue. And according to the data comparison between Comparative Examples 6-7 and Example 1.3, it can also be seen that the present application can further balance the operable time and the time for scraping glue by optimizing the ratio between the three resins.

[0060] The difference between Comparative Examples 8-9 and Example 1.3 is that aspartic acid resin F520 is used instead of aspartic acid resin A1, and aspartic acid resin F420 is used instead of aspartic acid resin A2. It can be seen from Table 1 that the heat aging hardness of Example 1.3 is significantly higher than that of Comparative Examples 8-9, and after chemical resistance testing, it is found that Example 1.3 does not have blistering and other phenomena, while Comparative Examples 8-9 have blistering, cracking and other phenomena. Experimental data show that the present application can significantly improve the crosslinking density of the paint film formed by the seam beautifying agent by conducting an ester exchange reaction on aspartic acid resin F520 and aspartic acid resin F520, thereby improving the problems of large brittleness of the paint film, many bubbles, and softening after being placed for a long time.

[0061] The embodiments of this specific implementation method are all preferred embodiments of the present application, and are not intended to limit the protection scope of the present application. Therefore, all equivalent changes made based on the structure, shape, and principle of the present application should be included in the protection scope of the present application.

Claims

1. An ultra-low free isocyanate monomer aspartame polyurea seam beautifying agent, comprising component A and component B, wherein component A is a polyurea resin component, and component B is an isocyanate component, characterized in that: By weight, the raw materials used for the B component include 85-95 parts of HDI trimer modified product, 0-1 part of defoamer, 5-10 parts of anti-settling agent and 0-5 parts of silane coupling agent; the HDI trimer modified product includes HDI trimer and HDI prepolymer; the NCO value of the HDI trimer modified product is 16-21%.

2. The ultra-low free isocyanate monomer aspartame polyurea seam beautifying agent according to claim 1, characterized in that: The weight ratio of the HDI trimer to the HDI prepolymer is (70-90):(10-30).

3. The ultra-low free isocyanate monomer aspartame polyurea seam beautifying agent according to claim 2, characterized in that: The HDI prepolymer is obtained by reacting an HDI trimer and a hydroxy compound in a weight ratio of (15-35):(65-85).

4. The ultra-low free isocyanate monomer aspartame polyurea seam beautifying agent according to claim 3, characterized in that: The hydroxy compound is one of polyester polyol, polyether polyol, polycaprolactone polyol, polytetramethylene ether polyol, polycarbonate polyol and polysiloxane polyol.

5. The ultra-low free isocyanate monomer aspartame polyurea seam beautifying agent according to claim 1, characterized in that: In parts by weight, the raw materials used for the A component include 80-90 parts of aspartic acid ester resin mixture A0, 0-1 part of dispersant, 0-1 part of defoamer, 5-10 parts of anti-settling agent and 5-10 parts of titanium dioxide.

6. The ultra-low free isocyanate monomer aspartame polyurea seam beautifying agent according to claim 5, characterized in that: In parts by weight, the aspartic acid ester resin mixture A0 comprises 40-60 parts of aspartic acid ester resin A1, 30-50 parts of aspartic acid ester resin A2 and 0-20 parts of aspartic acid ester resin A3; The structural formula of the aspartic acid ester resin A1 is The amino equivalent weight is 290-350, wherein R is the residue after the terminal hydroxyl group of the polyol is removed, and R1 is ethyl; The structural formula of the aspartic acid ester resin A2 is The amino equivalent is 680-800, wherein R is the residue after the terminal hydroxyl group of the polyol is removed, and R2 is an ethyl group; The structural formula of the aspartic acid ester resin A3 is 7. The ultra-low free isocyanate monomer aspartame polyurea seam beautifying agent according to claim 6, characterized in that: The polyol is one of polyester polyol, polyether polyol, polycaprolactone polyol, polytetramethylene ether polyol, polycarbonate polyol and polysiloxane polyol.

8. The ultra-low free isocyanate monomer aspartame polyurea seam beautifying agent according to claim 7, characterized in that: The molecular weight of the polyol is 500-2000.

9. The ultra-low free isocyanate monomer aspartame polyurea seam beautifying agent according to claim 7, characterized in that: The polyol is one of polycaprolactone polyol, polytetramethylene ether polyol and polycarbonate polyol.

10. A method for preparing the ultra-low free isocyanate monomer aspartame polyurea seam beautifying agent according to claim 1, characterized in that: The following steps are involved: All the raw materials used for component A are mixed evenly, and then packaged after vacuum degassing; all the raw materials used for component B are mixed evenly, and then packaged after vacuum degassing; the volume ratio of component A to component B is 2:1.

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