Water-based sand-containing multi-color stone-like paint and preparation method thereof

Abstract

The present application relates to the technical field of water-sand multi-color paint, and particularly discloses a water-based sand-containing multi-color stone-imitating paint and a preparation method thereof. The base paint and the granulation liquid of specific raw material components are matched in the present application. In the drying process of the coating film, the water continuously volatilizes, the neutralizing agent in the paint system continuously volatilizes to cause the pH to drop, the latex particles start to deform, the amino group of hydrazide-modified magnesium lithium silicate and the ketone carbonyl group of functionalized acrylic emulsion undergo crosslinking reaction to quickly form a crosslinking network structure, and the compactness and water resistance of the multi-color paint film are improved. The hydrazide-modified magnesium lithium silicate plays an "anchoring point" role in the network structure, so that the base paint color points can be closely connected together, crosslinked and formed into a film, the continuous phase component is omitted, the post-thickening problem of the multi-color stone-imitating paint is improved, the overall compactness, water white resistance and film hardness of the coating film are improved, and the durability and protection of the paint film after reducing the continuous phase are also improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of water-based sand multi-color paint, in particular to a water-based sand multi-color imitation stone paint and a preparation method thereof. BACKGROUND

[0002] The water-based sand multi-color paint has the characteristics of rich color and adjustable color, and can realize a high degree of simulation stone effect by matching a special shape, simulate the texture, color and texture of natural stone, and thus avoid further consumption of natural heavy material resources. In addition, the water-based sand multi-color paint is simple to construct, has strong designability, is light in quality and safe, low in carbon and environmentally friendly, and relatively low in cost, has the advantages of resisting erosion, waterproofing, stain resistance and the like, and is expected to gradually replace traditional real stone paint in recent years. The existing water-based sand multi-color paint is generally composed of three parts, namely, a sand-containing base paint, a granulation liquid and a continuous phase. After the sand-containing base paint is adjusted in color by a color paste, the sand-containing base paint is mixed with the granulation liquid, the sand-containing base paint and the granulation liquid mixed liquid having different color dot sizes and colors are formed by mechanical cutting and granulation, and then the mixed liquid is mixed with the continuous phase to thicken, so that the water-based sand multi-color paint is formed.

[0003] However, the stability of the protective glue system in the existing water-based sand multi-color paint is poor, the compatibility with the emulsion system is poor, and the emulsion and cellulose in the paint are prone to post-thickening, which leads to problems such as poor viscosity stability of the paint product, poor water whitening resistance and poor particle stability. In order to improve the above problems, the existing technology uses inert emulsion in the continuous phase emulsion, or cancels the continuous phase and only retains the base paint and the granulation liquid. Although these operations can alleviate the post-thickening problem to some extent, they do not fundamentally solve the problem of poor stability of the protective glue system, and at the same time, due to the reduction of the protective effect of the continuous phase film formation, the durability and protection performance of the paint in the later stage are also lost to some extent. SUMMARY

[0004] In view of the above problems, the present application provides a water-based sand multi-color imitation stone paint and a preparation method thereof, which improves the stability of the viscosity of the paint, improves the post-thickening problem of the system, and improves the overall compactness, water whitening resistance and paint film hardness of the paint film, and improves the durability and protection performance of the paint film.

[0005] To solve the above technical problems, the technical scheme provided by the present application is as follows:

[0006] In a first aspect, the present application provides a water-based sand multi-color imitation stone paint composed of a base paint and a granulation liquid.

[0007] The base paint comprises a functionalized acrylic emulsion containing a ketone carbonyl and a carboxyl group and a hydrazide modified magnesium lithium silicate containing an amino group; and the granulation liquid comprises the hydrazide modified magnesium lithium silicate.

[0008] The components of the functionalized acrylic emulsion include a structural formula as shown in Formula 1:

[0009]

[0010] Formula 1;

[0011] In the formula, R is selected from or ;

[0012] R' is selected from -H or -CH3;

[0013] j, t, s and q independently represent positive integers.

[0014] Compared with the prior art, the water-based sand-containing multi-color stone-like paint provided by the application uses a base paint and a granulation liquid of specific raw material components to be matched, and the continuous phase part in the traditional multi-color stone-like paint is omitted, which can effectively improve the post-thickening problem of the multi-color stone-like paint and reduce the complexity of the preparation process; the hydrazide-modified magnesium lithium silicate as the protective glue system of the base paint and the granulation liquid can undergo cross-linking reaction with the functionalized acrylic emulsion in the base paint during the drying process of the coating film, which not only improves the overall compactness, water whitening resistance and film hardness of the coating film, but also makes up for the shortcomings of the durability and protection of the coating film after reducing the continuous phase.

[0015] The application uses the functionalized acrylic emulsion and the hydrazide-modified magnesium lithium silicate as the film-forming material, the hydrazide-modified magnesium lithium silicate is obtained by organic modification of magnesium lithium silicate (a schematic diagram thereof is shown in Figure 1 ), the spacing between the crystal layers of the magnesium lithium silicate is increased, which is more prone to reaction with the latex molecules, and under the action of the carboxyl groups of the functionalized acrylic emulsion, it is also easier to form a card house structure. With the volatilization of water and the decrease of pH, the amino group of the hydrazide-modified magnesium lithium silicate and the keto carbonyl group of the functionalized acrylic emulsion can undergo dehydration condensation reaction and cross-linking at room temperature, therefore, during the drying process of the coating film, water is continuously volatilized, and the ammonia water (neutralizing agent) in the coating system is also continuously volatilized, resulting in a decrease in pH, and the latex particles begin to deform, and at the same time, the cross-linking reaction occurs, so that the hydrazide-modified magnesium lithium silicate in the base paint and the granulation liquid can quickly form a cross-linked network structure with the functionalized acrylic emulsion in the base paint, and a reaction schematic diagram is shown in Figure 2 The generation of the cross-linked structure improves the compactness and water resistance of the multi-color coating film, and the hydrazide-modified magnesium lithium silicate plays the role of an "anchoring point" in the network structure, so that the color points of the base paint can be closely connected together, not only bearing the function of the color points, but also realizing the cross-linking film-forming effect, and omitting the traditional continuous phase component. The surface structure of the base paint of the application can promote the formation of the protective glue "card house" structure to a certain extent, and maintain the viscosity of the finished product, but will not adversely affect the post-thickening viscosity of the overall system.

[0016] Preferably, the functional acrylic emulsion is polymerized from a ketone carbonyl-containing acrylic monomer, methyl methacrylate, methacrylic acid and butyl acrylate;

[0017] The ketone carbonyl-containing acrylic monomer is selected from at least one of diacetone acrylamide or acryloyl acetoacetoxyethyl methacrylate.

[0018] The present application uses diacetone acrylamide (DAAM) and / or acryloyl acetoacetoxyethyl methacrylate (AAEM) as the main functional monomer, and methyl methacrylate (MMA), methacrylic acid (MAA) and butyl acrylate (BA) as the main polymerization monomer. After polymerization, ketone carbonyl and carboxyl groups can be introduced into the functional acrylic emulsion. The ketone carbonyl can undergo dehydration condensation reaction with the amino group of hydrazide-modified lithium magnesium silicate to crosslink, thereby replacing the traditional continuous phase component and improving the compactness and water resistance of the paint film. The methacrylic acid contains carboxyl groups, which can be modified on the surface of the functional acrylic emulsion after polymerization. The carboxyl groups in the finished emulsion molecules can promote the swelling of the protective glue molecules (including hydrazide-modified lithium magnesium silicate) in the system and the formation of the card house structure.

[0019] Preferably, the raw materials of the functional acrylic emulsion include the following components in mass fraction: ketone carbonyl-containing acrylic monomer 4-5.2 parts, methyl methacrylate 17.5-19 parts, methacrylic acid 0.5-0.8 parts, butyl acrylate 9.5-11 parts, emulsifier 1.28-1.58 parts, buffer 0.12-0.15 parts, initiator 0.1-0.12 parts and water 61-68 parts.

[0020] The present application has found through a large number of experiments that the Tg (glass transition temperature) of homopolymerized polymethyl methacrylate (PMMA) is about 100℃, the Tg of homopolymerized polymethacrylic acid (PMAA) is about 105℃, the Tg of homopolymerized polybutyl acrylate (PBA) is about -55℃, and the Tg of homopolymerized ketone carbonyl-containing acrylic acid is about 80℃-120℃. By limiting the amount ratio of the main polymerization monomers, the Tg of the functional acrylic emulsion is about 5℃-10℃, which can ensure the film-forming performance of the finished paint film, thereby further balancing the flexibility and water whitening resistance of the multi-color stone-like coating, and improving the comprehensive performance of the multi-color stone-like coating.

[0021] In addition, the functionalized acrylic emulsion is modified by a specific amount of methacrylic acid, and the introduced carboxyl can synergistically thicken the protective glue system without causing the problem of post-thickening of the system. Through a large number of experiments, it is found that when the carboxyl concentration exceeds the limited range of the application, the promotion effect on the protective glue is too strong, which can cause the post-thickening of the system to rise sharply; when the carboxyl is lower than the limited range of the application, the viscosity of the system cannot be well maintained, which can cause the paint to separate.

[0022] Preferably, the raw material components of the functionalized acrylic emulsion further comprise a neutralizing agent, and the pH of the functionalized acrylic emulsion is 8-9.

[0023] In the application, the weak alkaline environment is more conducive to maintaining the stability of the anionic emulsifier. In addition, the initiation of (persulfate) can cause the pH of the system to decrease, and the alkaline environment can maintain the stability of the polymerization reaction, so that the polymerization reaction can be more complete.

[0024] Further preferably, the emulsifier is selected from anionic reactive emulsifiers. More preferably, the emulsifier is SR-10.

[0025] In the application, the preferred emulsifier can reduce the surface tension of the functionalized acrylic emulsion, emulsify the monomers into small droplets, and further form micelles, which is conducive to the occurrence and progress of the subsequent polymerization reaction. The reactive emulsifier contains a polymerizable double bond, which can also participate in the copolymerization reaction of acrylic monomers during the polymerization reaction, thereby improving the stability of the latex particles. In addition, the migration of emulsifier molecules can be reduced during the drying process of the paint film, thereby improving the water whitening resistance of the paint film.

[0026] Further preferably, the buffer is sodium bicarbonate.

[0027] Further preferably, the initiator is ammonium persulfate.

[0028] Further preferably, the neutralizing agent is ammonia.

[0029] In the application, ammonia is used as a neutralizing agent. During the drying process of the paint film, ammonia will continuously evaporate to reduce the pH of the system, so that the hydrazide modified magnesium lithium silicate in the base paint and the prilling liquid can quickly form a crosslinked network structure with the functionalized acrylic emulsion.

[0030] Preferably, the preparation method of the functionalized acrylic emulsion comprises the following steps:

[0031] Sa, the raw material components are weighed according to the designed ratio, the acrylic monomer containing ketone carbonyl, methyl methacrylate, methacrylic acid, butyl acrylate, the first part of the emulsifier and the first part of the water are uniformly mixed to obtain a pre-emulsion;

[0032] Sb, the remaining part of the emulsifier, the buffer and the remaining part of the water are mixed uniformly, the pre-emulsion and the initiator are added at 80℃~85℃, a polymerization reaction is carried out, the pH of the obtained reaction liquid is adjusted to 8~9, and a functional acrylic emulsion is obtained.

[0033] Further preferably, the mass ratio of the first part of the emulsifier to the remaining part of the emulsifier is 0.9:1~1.1:1.

[0034] Further preferably, the mass ratio of the first part of the water to the remaining part of the water is (27~30):(34~38).

[0035] For example, the pre-emulsion and the initiator are added in the form of dropwise addition, and the dropwise addition time is 2h~3h.

[0036] Further preferably, the temperature of the polymerization reaction is 80℃~85℃, and the holding reaction time is 1.5h~2h.

[0037] Preferably, the preparation method of the hydrazide modified lithium magnesium silicate includes the following steps:

[0038] S1, lithium magnesium silicate and a silane coupling agent are added to a first solvent, heated to reflux, and a substitution reaction is carried out to obtain silane modified lithium magnesium silicate;

[0039] S2, under the conditions of a protective atmosphere and light shielding, the silane modified lithium magnesium silicate and methyl acrylate are added to a second solvent, and a Michael addition reaction is carried out to obtain methyl acrylate capped lithium magnesium silicate;

[0040] S3, the methyl acrylate capped lithium magnesium silicate is added to hydrazine hydrate, and a condensation reaction is carried out under a protective atmosphere at 75℃~78℃ to obtain hydrazide modified lithium magnesium silicate.

[0041] In the present application, the hydrazide modification of the hydrazide modified lithium magnesium silicate and the ketone carbonyl of the functional acrylic emulsion can be room temperature crosslinked, which improves the compactness of the paint film, and makes the originally separated basic color points tightly crosslinked, and the structure of the hydrazide modified lithium magnesium silicate plays a role of "anchoring point" therein. The reaction equation in the preparation process of the hydrazide modified lithium magnesium silicate of the present application can be seen in Figure 3 .

[0042] Further preferably, in S1, the silane coupling agent is aminopropyltrimethoxysilane.

[0043] Further preferably, in S1, the first solvent is toluene.

[0044] Further preferably, in S1, a mass-volume ratio of the lithium magnesium silicate, the silane coupling agent and the first solvent is (4.8-5.2) g:(10.2-12.8) mL:(150-180) mL.

[0045] Further preferably, in S1, the substitution reaction is performed for 7-8 hours.

[0046] In an example, after the substitution reaction, the obtained reaction solution is continuously stirred at room temperature for 12-14 hours, filtered, and the filter cake is washed with a Soxhlet extractor for 16-18 hours, and dried to obtain the silane-modified lithium magnesium silicate. The drying method can be vacuum freeze-drying.

[0047] In the present application, the silane coupling agent can be substituted with the lithium magnesium silicate to graft the amino group onto the lithium magnesium silicate, and by limiting the amount of the silane coupling agent and the lithium magnesium silicate and the reaction conditions, it is beneficial for subsequent end-capping of the lithium magnesium silicate with corresponding substances. In addition, the preferred silane coupling agent contains an amino group, which has strong activity and aggressiveness, and can directly perform the subsequent Michael addition reaction without adding alkali.

[0048] Further preferably, in S2, the second solvent is selected from methanol, ethanol or N,N-dimethylformamide.

[0049] Further preferably, in S2, a mass-volume ratio of the silane-modified lithium magnesium silicate, the methyl acrylate and the second solvent is (5.2-5.7) g:(4.2-4.8) mL:(48-55) mL.

[0050] Further preferably, in S2, the Michael addition reaction is performed at a temperature of 10-40℃ for 48-56 hours.

[0051] In an example, after the Michael addition reaction, the obtained reaction solution is subjected to vacuum distillation to remove the second solvent.

[0052] In an example, the protective atmosphere is a nitrogen atmosphere.

[0053] Further preferably, in S3, the volume concentration of the hydrazine hydrate is 70-80%.

[0054] Further preferably, in S3, a mass-volume ratio of the methyl acrylate end-capped lithium magnesium silicate and the hydrazine hydrate is (6-6.5) g:(18-21) mL.

[0055] Further preferably, in S3, the condensation reaction is performed for 22-24 hours.

[0056] In the example, in S3, after the condensation reaction is completed, the obtained reaction solution is concentrated, diluted with a third solvent (selected from chloroform, benzene or toluene), washed with brine, dried with anhydrous sodium sulfate, and then concentrated under reduced pressure to remove the third solvent to obtain the hydrazide-modified lithium magnesium silicate.

[0057] The present application sequentially reacts methyl acrylate and hydrazine hydrate with the silane-modified lithium magnesium silicate to expand the number of hydrazide amino groups that can react with the ketone carbonyl group, and controls the amount of each reactant and the reaction conditions to obtain the hydrazide-modified lithium magnesium silicate that can optimally crosslink with the ketone carbonyl group of the functionalized acrylic emulsion.

[0058] Preferably, the base paint and the granulation liquid both comprise lithium magnesium silicate.

[0059] Compared with lithium magnesium silicate, the hydrazide-modified lithium magnesium silicate has reduced hydrophilicity, and the addition of lithium magnesium silicate can promote the dispersion and swelling of the hydrazide-modified lithium magnesium silicate in the aqueous phase, and also more easily form a card house structure under the action of the carboxyl group of the functionalized acrylic emulsion. During the drying process of the coating film, the protective colloid system of lithium magnesium silicate and hydrazide-modified lithium magnesium silicate can crosslink with the functionalized acrylic emulsion in the base paint, not only improving the overall compactness, water whitening resistance and film hardness of the coating film, but also compensating for the poor durability and protective properties of the coating film after reducing the continuous phase.

[0060] Preferably, the mass ratio of the base paint to the granulation liquid is 7:3 to 8:2.

[0061] Preferably, the base paint comprises the following components in the following mass percentages: functionalized acrylic emulsion 22% to 25%, lithium magnesium silicate 0.38% to 0.42%, hydrazide-modified lithium magnesium silicate 0.19% to 0.21%, cellulose 0.6% to 1%, dispersant 0.08% to 0.12%, defoaming agent 0.2% to 0.4%, antifreeze 0.7% to 1.2%, film-forming aid 1.2% to 1.8%, bactericide 0.3% to 0.6%, pigment and filler 4.5% to 5.8%, neutralizing agent 0.08% to 0.12%, quartz sand 32% to 38%, color paste 0 to 2%, and water 25% to 30%.

[0062] Preferably, the granulation liquid comprises the following mass percentage of components: magnesium lithium silicate 2%~3.5%, hydrazide modified magnesium lithium silicate 2.2%~3.5%, anti-settling agent 0.35%~0.5%, bactericide 0.3%~0.5%, and water 92%~95%. Further preferably, the granulation liquid comprises the following mass percentage of raw material components: magnesium lithium silicate 2.2%~3.5%, hydrazide modified magnesium lithium silicate 2.2%~3.5%, anti-settling agent 0.36%~0.42%, bactericide 0.32%~0.42%, and water 92.5%~94.5%.

[0063] The present application can better exert the synergistic effect of each component by limiting the components and their contents of the base paint and the granulation liquid, effectively control the cross-linking degree of the protective glue system and the functional acrylic emulsion during the drying process of the coating film, ensure that the water-based sand-containing multi-color stone-like coating has stable viscosity, water whitening resistance and hardness, and does not adversely affect the post-thickening viscosity of the overall system, so that the comprehensive performance of the water-based sand-containing multi-color stone-like coating reaches the best state.

[0064] Preferably, the cellulose is hydroxyethyl cellulose.

[0065] Further preferably, the hydroxyethyl cellulose is selected from at least one of 250HBR, 250HHBR or HE-10K.

[0066] Preferably, the pigment filler is selected from at least one of calcined kaolin or rutile titanium dioxide.

[0067] Preferably, the dispersant is a polycarboxylic acid sodium salt type dispersant.

[0068] Further preferably, the dispersant is SN-5040.

[0069] Preferably, the defoaming agent is a mineral oil type defoaming agent.

[0070] Further preferably, the defoaming agent is NXZ.

[0071] Preferably, the antifreeze is selected from at least one of ethylene glycol or propylene glycol.

[0072] Preferably, the film-forming aid is alcohol ester twelve.

[0073] Preferably, the bactericide is an isothiazolinone type bactericide.

[0074] Further preferably, the bactericide is selected from at least one of CMIT (5-chloro-2-methyl-4-isothiazolin-3-one), MIT (2-methyl-4-isothiazolin-3-one) or BIT (1,2-benzisothiazolin-3-one).

[0075] Preferably, the anti-settling agent is xanthan gum.

[0076] Preferably, the color paste is selected from at least one of iron red, iron yellow or carbon black.

[0077] The present application can further improve the comprehensive performance of the water-based sand-containing multi-color stone-like paint by limiting the corresponding auxiliary materials in the base paint and the granulation liquid.

[0078] In a second aspect, the present application provides a preparation method of a water-based sand-containing multi-color stone-like paint, comprising the following steps:

[0079] SI, preparing a base paint:

[0080] According to the designed ratio, each raw material component is weighed and taken, the cellulose, the dispersing agent, the first portion of the defoaming agent and the first portion of water are uniformly mixed, the pigments and fillers and the neutralizing agent are added and uniformly mixed, the antifreezing agent, the film-forming aid, the functionalized acrylic emulsion, the remaining portion of the defoaming agent and the bactericide are added and uniformly mixed to obtain a mixed system;

[0081] The magnesium lithium silicate and the hydrazide-modified magnesium lithium silicate are added into the remaining portion of water to obtain a protective glue solution;

[0082] The protective glue solution is added into the mixed system, and the quartz sand and the color paste are added to obtain the base paint;

[0083] SII, preparing a granulation liquid:

[0084] The magnesium lithium silicate, the hydrazide-modified magnesium lithium silicate, the anti-settling agent, the bactericide and water are uniformly mixed to obtain the granulation liquid;

[0085] SIII, preparing a water-based sand-containing multi-color stone-like paint:

[0086] The base paint is added into the granulation liquid, and granulation is mixed to obtain the water-based sand-containing multi-color stone-like paint.

[0087] The preparation method of the water-based sand-containing multi-color stone-like paint provided by the present application is simple and easy to operate, suitable for large-scale production, and has high market application value. It should be noted that the present application does not limit the order of SI and SII.

[0088] Further preferably, in SI, the mass ratio of the first portion of the defoaming agent to the remaining portion of the defoaming agent is 0.9:1~1.1:1.

[0089] Preferably, in SI, the mass ratio of the first portion of water to the remaining portion of water is (20~23):(5~7). BRIEF DESCRIPTION OF DRAWINGS

[0090] Figure 1 It is a schematic diagram of the charge structure of the magnesium lithium silicate in the present application;

[0091] Figure 2 A schematic diagram of a dehydration condensation reaction between a hydrazine amino group of hydrazine modified magnesium lithium silicate and a ketone carbonyl group of a functionalized acrylic emulsion in the present application;

[0092] Figure 3 A schematic diagram of a reaction equation in the preparation process of hydrazine modified magnesium lithium silicate in the present application;

[0093] wherein k, m, n and p respectively represent positive integers, and R represents methyl or ethyl. DETAILED DESCRIPTION

[0094] In order to make the purpose, technical scheme and advantages of the present application more clear and explicit, the present application will be further described in detail below in combination with examples. It should be understood that the specific examples described herein are only used to explain the present application, and are not used to limit the present application.

[0095] Example 1

[0096] The present embodiment provides a water-based sand-containing multi-color stone-like paint, which is composed of a base paint and a granulation liquid in a mass ratio of 8:2, and the specific raw material composition and ratio are shown in Tables 1-2.

[0097] The preparation method of the above water-based sand-containing multi-color stone-like paint comprises the following steps:

[0098] S1, preparing a functionalized acrylic emulsion:

[0099] S1-1, weighing each raw material component according to the designed ratio, and uniformly mixing the acrylic monomer containing a ketone carbonyl group, methyl methacrylate, methyl methacrylate, butyl acrylate, 0.75 parts of emulsifier and 30 parts of water to obtain a pre-emulsion.

[0100] S1-2, uniformly mixing 0.83 parts of emulsifier, buffer and 35 parts of water, and adding the pre-emulsion and initiator dropwise at 83℃, and continuing the polymerization reaction at 83℃ for 2.5h after the dropping is completed, and then keeping the temperature for 1.8h; adjusting the pH of the obtained reaction solution to 8.5 with a neutralizing agent to obtain a functionalized acrylic emulsion.

[0101] S2, preparing hydrazine modified magnesium lithium silicate:

[0102] S2-1, adding 5g of magnesium lithium silicate and 11mL of KH-540 into 160mL of toluene, heating to reflux, and performing substitution reaction for 7.5h; after the reaction is completed, continuing to stir the obtained reaction solution at room temperature for 13h, filtering, washing the filter cake with a Soxhlet extractor for 17h, and vacuum freeze-drying to obtain silane modified magnesium lithium silicate.

[0103] S2-2, 5.5 g of silane-modified magnesium lithium silicate and 52 mL of methanol were mixed and stirred under N2 flow for 35 min~40 min to remove oxygen, then 4.5 mL of methyl acrylate was added, and a Michael addition reaction was carried out at room temperature in the dark for 52 h; after the reaction was completed, the obtained reaction liquid was subjected to vacuum distillation to remove methanol, and magnesium lithium silicate capped with methyl acrylate was obtained.

[0104] S2-3, 6.3 g of magnesium lithium silicate capped with methyl acrylate and 20 mL of 75% volume concentration of hydrazine hydrate were mixed and stirred under N2 flow for 35 min~40 min to remove oxygen, then a condensation reaction was carried out at 76℃ for 23 h; after the reaction was completed, the obtained reaction liquid was concentrated, diluted with chloroform, washed with salt water, dried with anhydrous sodium sulfate, and then concentrated under reduced pressure to remove chloroform, and hydrazide-modified magnesium lithium silicate was obtained.

[0105] S3, preparation of base paint:

[0106] According to the designed ratio, each component was weighed, the cellulose, the dispersing agent, half of the amount of the defoaming agent and the first part of water were uniformly mixed, the pigment and filler and the neutralizing agent were added and uniformly mixed, then the antifreezing agent, the film-forming aid, the functionalized acrylic emulsion, the remaining amount of the defoaming agent and the bactericide were added and uniformly mixed, and a mixed system was obtained.

[0107] The magnesium lithium silicate and the hydrazide-modified magnesium lithium silicate were added into the remaining part of water to obtain a protective glue solution. The mass ratio of the first part of water to the remaining part of water was 4:1.

[0108] The protective glue solution was added into the mixed system, and then the quartz sand and the color paste were added to obtain the base paint.

[0109] S4, preparation of granulation liquid:

[0110] According to the designed ratio, each component was weighed, the magnesium lithium silicate, the hydrazide-modified magnesium lithium silicate, the anti-settling agent, the bactericide and water were uniformly mixed to obtain a granulation liquid.

[0111] S5, preparation of water-based sand-containing multi-color stone-like coating:

[0112] The base paint was added into the granulation liquid, and granulation was carried out to obtain the water-based sand-containing multi-color stone-like coating.

[0113] It should be noted that the present application does not limit the order of S1 and S2, nor the order of S3 and S4.

[0114] Example 2

[0115] The present embodiment provides a water-based sand-containing multi-color stone-like coating, which is composed of a base paint and a granulation liquid in a mass ratio of 7:3, and the specific raw material composition and ratio are shown in Tables 1~2.

[0116] The preparation method of the water-based sand-containing multi-color stone-like coating comprises the following steps:

[0117] S1, preparing functionalized acrylic emulsion:

[0118] S1-1, each raw material component was weighed according to the design ratio, the ketone carbonyl-containing acrylic monomer, methyl methacrylate, methacrylic acid, butyl acrylate, 0.64 parts of emulsifier and 29 parts of water were uniformly mixed to obtain a pre-emulsion.

[0119] S1-2, 0.64 parts of emulsifier, buffer and 34 parts of water were uniformly mixed, the pre-emulsion and initiator were added dropwise at 80℃, after 3h of dropping, the polymerization reaction was continued at 80℃ for 2h; the pH of the obtained reaction solution was adjusted to 8 by a neutralizing agent to obtain a functionalized acrylic emulsion.

[0120] S2, preparing hydrazide-modified lithium magnesium silicate:

[0121] S2-1, 4.8g of lithium magnesium silicate and 10.2mL of KH-540 were added to 150mL of toluene, heated to reflux, and substitution reaction was carried out for 7h; after the reaction was completed, the obtained reaction solution was continuously stirred at room temperature for 14h, filtered, the filter cake was washed with a Soxhlet extractor for 16h, and vacuum freeze-dried to obtain silane-modified lithium magnesium silicate.

[0122] S2-2, 5.2g of silane-modified lithium magnesium silicate and 48mL of ethanol were mixed and stirred for 35min~40min under N2flow to deoxidize, then 4.2mL of methyl acrylate was added, and the Michael addition reaction was carried out at room temperature in the dark for 48h; after the reaction was completed, the obtained reaction solution was distilled under reduced pressure to remove ethanol to obtain methyl acrylate-terminated lithium magnesium silicate.

[0123] S2-3, 6g of methyl acrylate-terminated lithium magnesium silicate and 18mL of 80% volume concentration of hydrazine hydrate were mixed and stirred for 35min~40min under N2flow to deoxidize, then condensation reaction was carried out at 75℃ for 24h; after the reaction was completed, the obtained reaction solution was concentrated, diluted with benzene, washed with salt water, dried with anhydrous sodium sulfate, and then concentrated under reduced pressure to remove benzene to obtain hydrazide-modified lithium magnesium silicate.

[0124] S3, preparing base paint:

[0125] Each component was weighed according to the design ratio, the cellulose, dispersant, half amount of defoamer and first part of water were uniformly mixed, the pigment and filler and neutralizing agent were added and uniformly mixed, then the antifreeze agent, film-forming aid, functionalized acrylic emulsion, remaining amount of defoamer and bactericide were added and uniformly mixed to obtain a mixed system.

[0126] The lithium magnesium silicate and hydrazide-modified lithium magnesium silicate were added to the remaining part of water to obtain a protective glue solution. The mass ratio of the first part of water to the remaining part of water was 23:5.

[0127] The protective glue solution is added into the mixed system, then the quartz sand and the color paste are added, and the base paint is obtained.

[0128] S4, preparing a granulation liquid:

[0129] The components are weighed according to the design ratio, and the magnesium lithium silicate, hydrazide-modified magnesium lithium silicate, anti-settling agent, bactericide and water are uniformly mixed to obtain a granulation liquid.

[0130] S5, preparing a water-based sand-containing multi-color stone-like paint:

[0131] The base paint is added into the granulation liquid, and granulation is mixed to obtain the water-based sand-containing multi-color stone-like paint.

[0132] It should be noted that the present application does not limit the order of S1 and S2, nor the order of S3 and S4.

[0133] Example 3

[0134] The present embodiment provides a water-based sand-containing multi-color stone-like paint, which is composed of a base paint and a granulation liquid in a mass ratio of 7:3, and the specific raw material composition and ratio are shown in Tables 1-2.

[0135] The preparation method of the above water-based sand-containing multi-color stone-like paint comprises the following steps:

[0136] S1, preparing a functionalized acrylic emulsion:

[0137] S1-1, the components are weighed according to the design ratio, and the components are uniformly mixed to obtain a pre-emulsion liquid.

[0138] S1-2, 0.67 parts of emulsifier, buffer and 35 parts of water are uniformly mixed, and the pre-emulsion liquid and initiator are added dropwise at 85℃, and after 2h of dropping, the polymerization reaction is continued at 85℃ for 1.5h; the pH of the obtained reaction liquid is adjusted to 9 by a neutralizing agent, and a functionalized acrylic emulsion is obtained.

[0139] S2, preparing hydrazide-modified magnesium lithium silicate:

[0140] S2-1, 5.2g of magnesium lithium silicate and 12.8mL of KH-540 are added to 180mL of toluene, heated to reflux, and subjected to substitution reaction for 8h; after the reaction is completed, the obtained reaction liquid is continuously stirred at room temperature for 12h, filtered, and the filter cake is washed with a Soxhlet extractor for 18h, and vacuum freeze-dried to obtain silane-modified magnesium lithium silicate.

[0141] S2-2, 5.7 g of silane-modified magnesium lithium silicate and 55 mL of N,N-dimethylformamide were mixed and stirred under N2 flow for 35 min~40 min to remove oxygen, then 4.8 mL of methyl acrylate was added, and a Michael addition reaction was carried out at room temperature in the dark for 56 h; after the reaction was completed, the obtained reaction liquid was subjected to reduced pressure distillation to remove N,N-dimethylformamide, and methyl acrylate-terminated magnesium lithium silicate was obtained.

[0142] S2-3, 6.5 g of methyl acrylate-terminated magnesium lithium silicate and 21 mL of 70% volume concentration of hydrazine hydrate were mixed and stirred under N2 flow for 35 min~40 min to remove oxygen, then a condensation reaction was carried out at 78℃ for 22 h; after the reaction was completed, the obtained reaction liquid was concentrated, diluted with toluene, washed with salt water, dried with anhydrous sodium sulfate, and then toluene was removed by reduced pressure concentration, and hydrazide-modified magnesium lithium silicate was obtained.

[0143] S3, preparation of base paint:

[0144] According to the designed ratio, each component was weighed, the cellulose, the dispersing agent, half of the amount of the defoaming agent and the first part of water were uniformly mixed, the pigment and filler and the neutralizing agent were added and uniformly mixed, then the antifreezing agent, the film-forming aid, the functionalized acrylic emulsion, the remaining amount of the defoaming agent and the bactericide were added and uniformly mixed, and a mixed system was obtained.

[0145] The magnesium lithium silicate and the hydrazide-modified magnesium lithium silicate were added into the remaining part of water to obtain a protective glue solution. The mass ratio of the first part of water to the remaining part of water was 23:7.

[0146] The protective glue solution was added into the mixed system, and then the quartz sand was added to obtain the base paint.

[0147] S4, preparation of granulation liquid:

[0148] According to the designed ratio, each component was weighed, the magnesium lithium silicate, the hydrazide-modified magnesium lithium silicate, the anti-settling agent, the bactericide and water were uniformly mixed to obtain a granulation liquid.

[0149] S5, preparation of water-based sand-containing multi-color stone-like coating:

[0150] The base paint was added into the granulation liquid, and granulation was carried out to obtain the water-based sand-containing multi-color stone-like coating.

[0151] It should be noted that the present application does not limit the order of S1 and S2, and does not limit the order of S3 and S4.

[0152] Example 4

[0153] The present embodiment provides a water-based sand-containing multi-color stone-like coating, which is composed of a base paint and a granulation liquid with a mass ratio of 75:25, and the specific raw material composition and ratio are shown in Tables 1~2.

[0154] The preparation method of the above-mentioned water-based sand-containing multi-color stone-like paint is the same as that of Example 1 (the mass ratio of the emulsifier in S1-1 and the emulsifier in S1-2 is 1:1, and the mass ratio of the water in S1-1 and the water in S1-2 is 27:34), and details are not repeated.

[0155] Example 5

[0156] The present embodiment provides a water-based sand-containing multi-color stone-like paint, which is composed of a base paint and a granulation liquid in a mass ratio of 75:25, and the specific raw material composition and ratio are shown in Tables 1-2.

[0157] The preparation method of the above-mentioned water-based sand-containing multi-color stone-like paint is the same as that of Example 1 (the mass ratio of the emulsifier in S1-1 and the emulsifier in S1-2 is 1:1, and the mass ratio of the water in S1-1 and the water in S1-2 is 30:38), and details are not repeated.

[0158] Table 1 Raw material components and ratios (%) of the water-based sand-containing multi-color stone-like paint of Examples 1-5

[0159]

[0160] Table 2 Raw material components and ratios (parts) of the functionalized acrylic emulsion of Examples 1-5

[0161]

[0162] Example 6

[0163] The present embodiment provides a water-based sand-containing multi-color stone-like paint, which is composed of a base paint and a granulation liquid in a mass ratio of 75:25, and the specific raw material composition and ratio are shown in Tables 1-2.

[0164] The preparation method of the above-mentioned water-based sand-containing multi-color stone-like paint is the same as that of Example 4, and details are not repeated.

[0165] Comparative Example 1

[0166] The present comparative example provides a water-based sand-containing multi-color stone-like paint, which is composed of a base paint, a granulation liquid and a continuous phase in a mass ratio of 8:2:2.

[0167] The raw material components and ratios of the base paint and the granulation liquid are similar to those of Example 1, except that the functionalized acrylic emulsion in the base paint is replaced by the same mass of commercially available acrylic emulsion Bardu RS-2788, and the hydrazide-modified lithium magnesium silicate in the base paint and the granulation liquid is replaced by the same mass of lithium magnesium silicate. The remaining raw material components and ratios are the same as those of Example 1, and details are not repeated.

[0168] The continuous phase is composed of the following raw material components in percentage: acrylic emulsion (Parchem RS-3799) 60%, anti-freezing solution (Run Tai Chemical) 2%, Run Tai Chemical C-12 3%, Sancure NXZ 0.3%, Hofmann CMIT / MIT (1:1) 0.4%, ammonia (Jingxin Hongrun) 0.4%, thickening agent (Dow Chemical TT-935) 1%, and deionized water 32.9%.

[0169] The preparation method of the above-mentioned water-based sand-containing multi-color stone-like paint comprises the following steps:

[0170] S1~S2, except that the functionalized acrylic emulsion is replaced by Parchem RS-2788 and the hydrazide-modified lithium magnesium silicate is replaced by lithium magnesium silicate, the remaining steps are the same as S3~S4 of Example 1, and will not be repeated.

[0171] S3, mix Parchem RS-3799, anti-freezing solution, Run Tai Chemical C-12, Sancure NXZ, Hofmann CMIT / MIT (1:1), ammonia, thickening agent, and deionized water uniformly to obtain a continuous phase.

[0172] S4, mix the base paint and the granulation liquid uniformly, add the continuous phase, mix and granulate to obtain a water-based sand-containing multi-color stone-like paint.

[0173] It should be noted that there is no sequence between S1~S3.

[0174] Comparative Example 2

[0175] This comparative example provides a water-based sand-containing multi-color stone-like paint, the raw material components and the proportioning are similar to Example 2, the difference is that the functionalized acrylic emulsion in the base paint is replaced by the same mass of commercially available acrylic emulsion Parchem RS-2788, and the hydrazide-modified lithium magnesium silicate in the base paint and the granulation liquid is replaced by the same mass of lithium magnesium silicate. The remaining raw material components and the proportioning are the same as Example 2, and will not be repeated.

[0176] The preparation method of the above-mentioned water-based sand-containing multi-color stone-like paint comprises the following steps:

[0177] S1~S2, the same as S1~S2 of Comparative Example 1, and will not be repeated.

[0178] S3, the same as S5 of Example 2, and will not be repeated.

[0179] Comparative Example 3

[0180] This comparative example provides a water-based sand-containing multi-color stone-like paint, the raw material components and the proportioning are similar to Example 3, the difference is that the hydrazide-modified lithium magnesium silicate in the base paint and the granulation liquid is replaced by the same mass of lithium magnesium silicate. The remaining raw material components and the proportioning are the same as Example 3, and will not be repeated.

[0181] The preparation method of the water-based sand-containing multi-color stone-like paint comprises the following steps:

[0182] S1, same as S1 of Example 3, and will not be repeated.

[0183] S2-S3, except that the hydrazide-modified magnesium lithium silicate is replaced by magnesium lithium silicate, the remaining steps are the same as S3-S4 of Example 3, and will not be repeated.

[0184] S4, same as S5 of Example 3, and will not be repeated.

[0185] Comparative Example 4

[0186] This comparative example provides a water-based sand-containing multi-color stone-like paint, the raw material components and the ratio thereof are similar to those of Example 1, the difference is that the functionalized acrylic emulsion in the base paint is replaced by the same mass of commercially available acrylic emulsion Bardu RS-2788. The remaining raw material components and the ratio thereof are the same as those of Example 1, and will not be repeated.

[0187] The preparation method of the water-based sand-containing multi-color stone-like paint comprises the following steps:

[0188] S1, same as S2 of Example 1, and will not be repeated.

[0189] S2, except that the functionalized acrylic emulsion is replaced by Bardu RS-2788, the remaining steps are the same as S3 of Example 1, and will not be repeated.

[0190] S3-S4, same as S4-S5 of Example 1, and will not be repeated.

[0191] Comparative Example 5

[0192] This comparative example provides a water-based sand-containing multi-color stone-like paint, the raw material components and the ratio thereof are similar to those of Example 4, the difference is that the MAA in the functionalized acrylic emulsion is omitted. The remaining raw material components and the ratio thereof are the same as those of Example 4, and will not be repeated.

[0193] Except for the above differences, the preparation method of the water-based sand-containing multi-color stone-like paint is the same as Example 4, and will not be repeated.

[0194] Comparative Example 6

[0195] This comparative example provides a water-based sand-containing multi-color stone-like paint, the raw material components and the ratio thereof are similar to those of Example 5, the difference is that the ketone carbonyl-containing acrylic monomer in the functionalized acrylic emulsion is omitted. The remaining raw material components and the ratio thereof are the same as those of Example 5, and will not be repeated.

[0196] Except for the above differences, the preparation method of the water-based sand-containing multi-color stone-like paint is the same as Example 5, and will not be repeated.

[0197] Performance test

[0198] The water-based sand-containing multi-color stone-like coating provided by the examples 1-6 and the comparative examples 1-5 of the present application were tested for performance according to HG / T 4343-2012 Water-based multi-color architectural coating, and the composite coating was tested as transparent primer + water-based sand-containing multi-color stone-like coating + matt finish paint. The test results are shown in Table 3 (the state in the container is normal).

[0199] The post-thickening phenomenon test conditions include:

[0200] Initial viscosity: The viscosity of the coating prepared within 2h was tested at 23℃±0.5℃, and was recorded as the initial viscosity;

[0201] Thermal storage viscosity: After being taken out from the oven at 50℃±5℃ for 3d, the coating was tested for viscosity after being kept at 23℃±0.5℃, and was recorded as the thermal storage viscosity;

[0202] Post-thickening viscosity = thermal storage viscosity - initial viscosity.

[0203] Table 3 Comprehensive performance test results of the water-based sand-containing multi-color stone-like coating of the examples and the comparative examples

[0204]

[0205] The above description is only the preferred embodiments of the present application, and is not intended to limit the present application. Any modification, equivalent replacement or improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. An aqueous, sand-containing, multi-color, faux stone paint, characterized in that, The base paint and the granulation liquid are composed of; The base paint comprises a functionalized acrylic emulsion containing a ketone carbonyl and a carboxyl group and a hydrazide modified magnesium lithium silicate containing an amino group; and the granulation liquid comprises the hydrazide modified magnesium lithium silicate; The component of the functionalized acrylic emulsion comprises a structural formula as shown in Formula 1: Formula 1 wherein R is selected from or ; wherein, represents a point of attachment to the backbone; R' is selected from -H or -CH3; j, t, s and q independently represent positive integers; The preparation method of the hydrazide modified magnesium lithium silicate comprises the following steps: S1, the silane coupling agent is added to the first solvent, heated to reflux, and the substitution reaction is carried out to obtain the silane modified magnesium lithium silicate; S2, the silane modified magnesium lithium silicate and methyl acrylate are added to the second solvent under the condition of protective atmosphere and light protection, and the Michael addition reaction is carried out to obtain the methyl acrylate capped magnesium lithium silicate; S3, the methyl acrylate capped magnesium lithium silicate is added to the hydrazine hydrate, and the condensation reaction is carried out under the protective atmosphere to obtain the hydrazide modified magnesium lithium silicate.

2. The water-based, sand-containing, multicolor, faux finish paint of claim 1, wherein, The functionalized acrylic emulsion is polymerized by an acrylic monomer containing a ketone carbonyl, methyl methacrylate, methacrylic acid and butyl acrylate; The acrylic monomer containing a ketone carbonyl is selected from at least one of diacetone acrylamide or acryloyl oxyethyl methyl acrylate.

3. The water-based, sand-containing, multicolor, faux finish paint according to claim 1 or 2, wherein, The raw materials of the functionalized acrylic emulsion comprise the following components in mass fraction: the acrylic monomer containing a ketone carbonyl 4-5.2 parts, methyl methacrylate 17.5-19 parts, methacrylic acid 0.5-0.8 parts, butyl acrylate 9.5-11 parts, emulsifier 1.28-1.58 parts, buffer 0.12-0.15 parts, initiator 0.1-0.12 parts and water 61-68 parts. The pH of the functionalized acrylic emulsion is 8-9.

4. The water-based, sand-containing, multicolor faux finish paint of claim 3, wherein, The preparation method of the functionalized acrylic emulsion comprises the following steps: Sa, the components are weighed according to the designed ratio, the acrylic monomer containing a ketone carbonyl, methyl methacrylate, methacrylic acid, butyl acrylate, the first part of the emulsifier and the first part of the water are uniformly mixed to obtain a pre-emulsion; Sb, the remaining part of the emulsifier, the buffer and the remaining part of the water are uniformly mixed, and the pre-emulsion and the initiator are added to the pre-emulsion at 80-85°C to carry out the polymerization reaction for 1.5-2h, and the pH of the obtained reaction solution is adjusted to 8-9 to obtain the functionalized acrylic emulsion.

5. The water-based, sand-containing, multicolor faux finish paint of claim 1, wherein, In the preparation method of the hydrazide modified magnesium lithium silicate, in S3, the condensation reaction is carried out at a temperature of 75-78°C.

6. The water-borne, sand-containing, multicolor, faux finish paint of claim 1, wherein, In the preparation method of the hydrazide modified magnesium lithium silicate, in S1, the silane coupling agent is aminopropyl trimethoxysilane; and / or In S1, the first solvent is toluene; and / or In S1, the mass-volume ratio of the magnesium lithium silicate, the silane coupling agent and the first solvent is (4.8-5.2)g:(10.2-12.8)mL:(150-180)mL; and / or In S2, the second solvent is selected from methanol, ethanol or N,N-dimethylformamide; and / or In S2, the mass-volume ratio of the silane modified magnesium lithium silicate, the methyl acrylate and the second solvent is (5.2-5.7)g:(4.2-4.8)mL:(48-55)mL; and / or In S3, the volume concentration of the hydrazine hydrate is 70% to 80%; and / or In S3, the mass-volume ratio of the methyl acrylate-terminated lithium magnesium silicate and the hydrazine hydrate is (6 to 6.5) g:(18 to 21) mL.

7. The water-borne, sand-containing, multicolor, faux finish paint of claim 1, wherein, In the preparation method of the hydrazide-modified lithium magnesium silicate, in S1, the time of the substitution reaction is 7 h to 8 h; and / or In S2, the temperature of the Michael addition reaction is 10°C to 40°C, and the reaction time is 48 h to 56 h; and / or In S3, the time of the condensation reaction is 22 h to 24 h.

8. The water-borne, sand-containing, multicolor, faux finish paint of claim 1, wherein, The base paint and the granulation liquid both comprise lithium magnesium silicate; and / or The mass ratio of the base paint and the granulation liquid is 7:3 to 8:

2.

9. The water-borne, sand-containing, multicolor, faux finish paint of claim 1 or 8, wherein, The base paint comprises the following components in mass percentage: functionalized acrylic emulsion 22% to 25%, lithium magnesium silicate 0.38% to 0.42%, hydrazide-modified lithium magnesium silicate 0.19% to 0.21%, cellulose 0.6% to 1%, dispersant 0.08% to 0.12%, defoaming agent 0.2% to 0.4%, antifreeze 0.7% to 1.2%, film-forming aid 1.2% to 1.8%, bactericide 0.3% to 0.6%, pigment and filler 4.5% to 5.8%, neutralizing agent 0.08% to 0.12%, quartz sand 32% to 38%, color paste 0 to 2%, and water 25% to 30%; and / or The granulation liquid comprises the following components in mass percentage: lithium magnesium silicate 2% to 3.5%, hydrazide-modified lithium magnesium silicate 2.2% to 3.5%, anti-settling agent 0.35% to 0.5%, bactericide 0.3% to 0.5%, and water 92% to 95%.

10. The method of making an aqueous, sand-containing, multicolor faux finish paint of claim 9, characterized in that, The method comprises the following steps: SI, preparing a base paint: The components are weighed according to the design ratio, the cellulose, dispersant, first portion of defoaming agent, and first portion of water are mixed uniformly, the pigment and filler and neutralizing agent are added and mixed uniformly, the antifreeze, film-forming aid, functionalized acrylic emulsion, remaining portion of defoaming agent, and bactericide are added and mixed uniformly, to obtain a mixed system; The lithium magnesium silicate and hydrazide-modified lithium magnesium silicate are added to the remaining portion of water to obtain a protective glue solution; The protective glue solution is added to the mixed system, and the quartz sand and color paste are added, to obtain the base paint; SII, preparing a granulation liquid: The lithium magnesium silicate, hydrazide-modified lithium magnesium silicate, anti-settling agent, bactericide, and water are mixed uniformly, to obtain the granulation liquid; SIII, preparing a water-based sand-containing multi-color stone-like paint: The base paint is added to the granulation liquid, and granulation is performed, to obtain the water-based sand-containing multi-color stone-like paint.

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