CN116375396A

CN116375396A - Self-cleaning rock slice real stone paint and preparation method thereof

Info

Publication number: CN116375396A
Application number: CN202310371750.9A
Authority: CN
Inventors: 苏东亮; 朱佰虎; 侯世博
Original assignee: Tianjin Dpv Coating Co ltd
Current assignee: Tianjin Dpv Coating Co ltd
Priority date: 2023-04-10
Filing date: 2023-04-10
Publication date: 2023-07-04

Abstract

The application discloses self-cleaning rock slice true stone paint and a preparation method thereof. The real stone paint comprises white sand, colored sand, rock flakes and a base material, wherein the base material comprises the following components: 340-354 parts of water, 1.2-1.8 parts of bentonite, 2-3 parts of hydroxyethyl cellulose, 0.2-0.8 part of multifunctional auxiliary agent, 0.8-1.2 parts of kathon bactericide, 4-8 parts of antifreezing agent, 100-160 parts of pure acrylic emulsion, 6-12 parts of film forming auxiliary agent, 0.2-0.8 part of defoamer, 2.5-3.5 parts of thickener, 1-1.6 parts of wetting agent, 15-20 parts of potassium silicate, 5-7 parts of lithium silicate and 3-5 parts of 4-5wt% of sodium tetraborate solution. The real stone paint has super-hydrophilic and underwater super-oleophobic properties, can prevent most dirt from adhering to the surface of a coating, can also wash out dirt by using rainwater, realizes the self-cleaning function, and has strong dirt resistance and higher durability.

Description

Self-cleaning rock slice real stone paint and preparation method thereof

Technical Field

The application relates to the field of real stone paint coatings, in particular to self-cleaning rock slice real stone paint and a preparation method thereof.

Background

The stone paint is a paint with decorative effect similar to marble and granite, is mainly prepared from natural stone powder with various colors, has strong decorative effect, has the texture of natural stone, can provide various three-dimensional pattern structures by various wire grid designs, is widely applied to the outer wall of a building, has the stone-like effect, and is the best substitute for the dry-hanging stone of the outer wall. However, the traditional real stone paint has the defects of high specific gravity, high energy consumption, serious resource waste and the like, so that rock slice real stone paint is adopted to replace the traditional real stone paint at present.

The rock slice real stone paint is prepared by mixing natural color sand, water-based polymer resin and rock slices according to a certain proportion. When the natural granite stone is used and blended, the main tone of the imitated natural granite stone is firstly analyzed, the real stone paint blended by the natural color sand close to the main tone is selected, then rock slices are selected according to the color, the size and the proportion of the color particles in the stone, the rock slices are added into the blended real stone paint and are uniformly stirred, and the colorful granite stone effect is obtained by spraying the natural granite stone on the surface of the building outer wall. The rock slice real stone paint has excellent water resistance and weather resistance, is easy to construct, greatly shortens the construction time, saves the construction cost, reduces the construction energy consumption, and is a green, energy-saving and environment-friendly product with excellent performance.

However, since the rock slice stone paint is coated on the surface of the outer wall, the rock slice stone paint can be exposed to the atmosphere for a long time and is polluted by various substances, and pollution sources comprise a large amount of dust, solid mist, smoke and other solid substances, sulfuric acid mist and other liquid substances, sulfur dioxide and other gaseous substances, and in addition, the pollution of microorganisms, rust water sagging and the like can also influence the outer wall surface. On one hand, the pollution of the outer wall can affect the decorative effect and the beautiful appearance of a building, reduce the gloss and the vividness of a coating film and form spots such as gray spots, tear spots and the like; on the other hand, certain pollutants can accelerate ageing and decomposition of the coating film, influence the service life and safety of the building, and increase the cleaning and maintenance cost of the building.

Disclosure of Invention

In order to solve the technical problems, the application provides self-cleaning rock slice true stone paint and a preparation method thereof.

In a first aspect, the application provides a self-cleaning rock slice true stone paint, which adopts the following technical scheme:

a self-cleaning rock slice real stone paint comprises white sand, colored sand, rock slices and base materials with the weight ratio of (350-450): (45-50): (45-55): (480-520); the base material comprises the following components in parts by weight: 340-354 parts of water, 1.2-1.8 parts of bentonite, 2-3 parts of hydroxyethyl cellulose, 0.2-0.8 part of multifunctional auxiliary agent, 0.8-1.2 parts of kathon bactericide, 4-8 parts of antifreezing agent, 100-160 parts of pure acrylic emulsion, 6-12 parts of film forming auxiliary agent, 0.2-0.8 part of defoamer, 2.5-3.5 parts of thickener, 1-1.6 parts of wetting agent, 15-20 parts of potassium silicate, 5-7 parts of lithium silicate and 3-5 parts of 4-5wt% of sodium tetraborate solution.

By adopting the technical scheme, the potassium silicate and the lithium silicate with high surface energy are added into the real stone paint base material, and a plurality of polysilicates or silicon dioxide microspheres which are densely distributed are formed on the surface of the coating by utilizing silicate condensation reaction between the potassium silicate and the lithium silicate. According to the principle of special wettability, the nanoscale roughness is matched with hydrophilic components with high surface energy such as pure acrylic emulsion, so that super-hydrophilic and underwater super-oleophobic performances can be given to the coating, a water film sliding layer formed by combining hydrophilic groups on the surface of the coating with water molecules can prevent most dirt from adhering to the surface of the coating, and dirt can be removed by utilizing the sliding of the water film, so that the real stone paint has a self-cleaning function, and the contamination resistance of the real stone paint is effectively improved. Meanwhile, under the promotion effect of the sodium tetraborate solution, the potassium silicate and the lithium silicate can continuously undergo condensation reaction, and finally a silicon dioxide gel network structure with high crosslinking degree is formed in the real stone paint, so that the adhesive force of the coating is enhanced, and the durability of the real stone paint is improved.

Preferably, the base material comprises, in parts by weight: water 347 parts, bentonite 1.5 parts, hydroxyethyl cellulose 2.5 parts, a multifunctional auxiliary agent 0.5 part, a kathon bactericide 1 part, an antifreezing agent 6 parts, a pure acrylic emulsion 130 parts, a film forming auxiliary agent 8 parts, a defoaming agent 0.5 part, a thickening agent 3 parts, a wetting agent 1.3 parts, potassium silicate 18 parts, lithium silicate 6 parts and 4-5wt% of a sodium tetraborate solution 4 parts.

Through adopting above-mentioned technical scheme, this application has further controlled the quantity of using of the raw materials that true mineral varnish used, can further improve true mineral varnish's anti-staining ability and durability.

Preferably, the base material also comprises 7-10 parts by weight of nano zinc oxide and 8-10 parts by weight of nano aluminum oxide.

Through adopting above-mentioned technical scheme, this application still will have high surface energy's nanometer zinc oxide and nanometer aluminium oxide embedding in the interior network structure of real mineral varnish, increased the quantity of coating surface nanoparticle, improved the compactness of coating surface nanoparticle to the contamination resistance and the durability of real mineral varnish have further been improved.

Preferably, the pure acrylic emulsion is prepared by the following method:

(1) Dissolving 4.5-5.0 parts by weight of an emulsifier in 15-16 parts by weight of water, then adding 28-30 parts by weight of methyl methacrylate, 59-61 parts by weight of butyl acrylate, 2-3 parts by weight of acrylic acid, 6-7 parts by weight of diethylene glycol diacrylate and 3-4 parts by weight of hydroxyethyl acrylate, and continuing stirring for 30-40min until a milky pre-emulsion is obtained; dissolving 0.4-0.5 weight parts of potassium persulfate in water to obtain a potassium persulfate solution;

(2) 2-3 parts by weight of NaHCO ₃ Dissolving in water, heating to 45-50deg.C, adding pre-emulsion and potassium persulfate solution, heating to 75-80deg.C, maintaining the temperature, and stirring for 30-40min; the dosage of the pre-emulsion is 10-12% of the total amount of the pre-emulsion prepared in the step (1), and the dosage of the potassium persulfate solution is 45-50% of the total amount of the potassium persulfate solution prepared in the step (1);

(3) And (3) dropwise adding the residual pre-emulsion and the potassium persulfate solution into the obtained product in the step (2) within 1-1.5h at the temperature of 75-80 ℃, then heating to 85-90 ℃, carrying out heat preservation reaction for 1-1.2h, cooling to room temperature, filtering, and regulating the pH value to 8-9 by using ammonia water to obtain the pure acrylic emulsion.

Because this application is in order to improve the hiding power of real mineral varnish, the white sand and the various sand that use are mostly about 200 mesh fine powder, and white sand and the various sand of this kind of fineness are extremely easy to be brought to real mineral varnish surface by the rainwater slowly over time and form exudative pollution. Therefore, through adopting above-mentioned technical scheme, this application adopts semicontinuous pre-emulsification technology to methyl methacrylate is hard monomer, and butyl acrylate is soft monomer, mixes collocation as functional monomer and crosslinking monomer with acrylic acid, diethylene glycol diacrylate, hydroxyethyl acrylate, has made the pure acrylic emulsion that has stronger film forming ability, stability, water resistance, wearability, hardness, tensile strength, adhesive force, solvent resistance and oil resistance, can form good parcel to white sand, color sand and rock flake, has reduced the possibility that exudative pollution appears to the resistant contaminated ability of true mineral varnish has been improved.

Preferably, the emulsifier comprises anionic emulsifier and nonionic emulsifier in the weight ratio of (5-6): 1-2; the anionic emulsifier is sodium alkyl sulfosuccinate, and the nonionic emulsifier is nonionic emulsifier S90.

Through adopting above-mentioned technical scheme, the application adopts anion emulsifier to mix the collocation with nonionic emulsifier and uses to adopt sulfosuccinic acid alkyl alcohol ether ester sodium salt as anion emulsifier, nonionic emulsifier S90 is nonionic emulsifier, the synergism of both fully gives full play to, has further improved pure acrylic emulsion ' S hydrophilicity, has strengthened real mineral varnish ' S wettability for the spot that adheres to real mineral varnish surface is carried away by the water more easily, thereby has further improved real mineral varnish ' S resistant dirt ability.

Preferably, in the step (3), 1.8 to 2.0 parts by weight of gelatinized oxidized starch is further added before cooling, and the heat preservation reaction is continued for 1 to 1.2 hours.

Through adopting above-mentioned technical scheme, this application heats oxidized starch in water to the whole collapse of micelle structure, and the starch molecule forms the monomolecular to for water surrounds and becomes solution state back, adds in pure acrylic emulsion, utilizes oxidized starch to provide more crosslinking points for pure acrylic emulsion, has strengthened the inside crosslinking degree of pure acrylic emulsion, and oxidized starch particle can also fill the space between the polyacrylate chain, has improved pure acrylic emulsion network structure's compactness, thereby has further improved the stain resistance and the durability of real mineral varnish.

Preferably, the film forming aid comprises 1 (1.2-1.5) of furfuryl alcohol ester of vegetable oleic acid and ethylene glycol monoester of ricinoleic acid in a weight ratio.

Through adopting above-mentioned technical scheme, this application adopts vegetable oil acid furfuryl alcohol ester and ricinoleic acid ethylene glycol monoester to mix the collocation and use as the film-forming auxiliary agent, can give full play to the synergistic effect between the two, improves the film-forming effect of real mineral varnish to improve the compactness of real mineral varnish, reduced the inside possibility of pollutant infiltration real mineral varnish, and then improved the ability of preventing stains of real mineral varnish.

Preferably, the furfuryl alcohol vegetable oleate is prepared by the following method:

mixing vegetable oleic acid, furfuryl alcohol, cyclohexane, ionic liquid catalyst and sodium hydrosulfite, heating to 80-90 ℃, reacting for 3-3.5h under heat preservation, cooling to room temperature, filtering, and adopting NaHCO 5-7wt% ₃ Regulating pH value of the solution to 6-7, standing for layering, and decompressing and desolventizing an upper oil layer to obtain the plant furfuryl alcohol oleate; n (vegetable oleic acid) is 1 (1.2-1.25), and the weight ratio of cyclohexane, ionic liquid catalyst, sodium hydrosulfite and vegetable oleic acid is (2.8-3.0) (0.01-0.02) 1.

Preferably, the ricinoleic acid glycol monoester is prepared by the following method:

Adding ricinoleic acid and a solid acid catalyst into 100-110 parts by weight of toluene, mixing and stirring for 10-15min, adding ethylene glycol, heating to 87-90 ℃, reacting for 4-5h, cooling to room temperature, and adopting NaHCO with the concentration of 3-4wt% ₃ Regulating pH value of the solution to 6-7, standing for layering, and decompressing and desolventizing an upper oil layer to obtain ricinoleic acid glycol monoester; n (ricinoleic acid) n (ethylene glycol) is 1 (1.2-1.3), and the dosage of the solid acid catalyst is 1.8-2wt% of ricinoleic acid.

In a second aspect, the present application provides a method for preparing a self-cleaning rock fragment stone lacquer, comprising the steps of:

s1, magnetically stirring lithium silicate, a wetting agent and pure acrylic emulsion for 10-15min, then dropwise adding potassium silicate, magnetically stirring for 10-15min, and then mixing and stirring with 4-5wt% of sodium tetraborate solution for 20-30min to obtain a mixed solution;

s2, adding bentonite and hydroxyethyl cellulose into water while stirring, then dispersing at a high speed for 20-30min at a rotating speed of 1300-1400r/min, then reducing the rotating speed to 500-600r/min, adding a multifunctional auxiliary agent, a kasong bactericide, an antifreezing agent, the mixed solution in the step S1, a film-forming auxiliary agent and a defoaming agent, mixing and stirring for 5-10min, adding a thickening agent, and dispersing at a rotating speed of 800-900r/min for 8-10min to obtain a base material;

S3, adding white sand, colored sand and rock flakes into the base material in the step S2 at the rotating speed of 300-310r/min, and uniformly mixing to obtain the self-cleaning rock flake real stone paint.

Through adopting above-mentioned technical scheme, the application adopts step by step to mix for can fully mix between each component in the real mineral varnish, reduce the possibility that the aggregation phenomenon appears in the component in the real mineral varnish, thereby further improved the contamination resistance and the durability of real mineral varnish. In addition, the preparation method is simple, easy to operate, easy to obtain raw materials and suitable for large-scale industrial production.

Preferably, in the step S1, 7-10 parts by weight of nano zinc oxide and 8-10 parts by weight of nano aluminum oxide are also added.

In summary, the present application has the following beneficial technical effects:

1. the real stone paint has super-hydrophilic and underwater super-oleophobic properties, can prevent most dirt from adhering to the surface of the coating, can also remove the dirt adhering to the surface of the coating by utilizing the flushing of rainwater, realizes the self-cleaning function, and has stronger dirt resistance; 2. the real stone paint is different from the common super-hydrophilic self-cleaning real stone paint, has stronger self-cleaning capability and higher durability, can be firmly attached to a substrate, and reduces the possibility of losing super-hydrophilic characteristics due to separation of the real stone paint from the substrate or surface structure change;

3. The preparation method of the real stone paint has the advantages of simple steps, easy operation and easily obtained raw materials, and is suitable for large-scale industrial production.

Detailed Description

The present application is described in further detail below in connection with examples and comparative examples.

In the following preparation examples, examples and comparative examples,

white sand producing area is Cicheng with 80-200 meshes;

the mesh number of the colored sand producing area is 200-300 meshes;

the rock slice is purchased from Sanchen chemical industry Co., ltd., and has a diameter of 1-3mm;

bentonite is available from claiminton, model ZW;

hydroxyethyl cellulose was purchased from Shandong cloud hawk, model BR100000H;

the multifunctional auxiliary agent is purchased from Sorvy, model MP380;

the pinocembrin fungicide is available from toll, model HF;

antifreeze (ethylene glycol) was purchased from Tianjin HaoMing chemical Co., ltd;

defoamer was purchased from sanguinea, japan, model SN154;

thickeners were purchased from dow, usa, model TT615;

wetting agent was purchased from Qingdao Chengshi new materials Co., ltd., model RD9125;

potassium silicate and lithium silicate were purchased from eastern mountain chemical company, ltd;

sodium tetraborate is purchased from gallery dry technology limited;

nano zinc oxide was purchased from \280954, available from new materials technologies, inc;

nanometer alumina is purchased from Dongguandong ultra-new material science and technology Co., ltd;

Methyl methacrylate was purchased from Shanghai Meilin Biochemical technologies Co., ltd;

butyl acrylate was purchased from Shandong Huasheng New Material Co., ltd;

acrylic acid was purchased from atanan chemical industry limited;

diethylene glycol diacrylate was purchased from Guangdong Santa paint New Material Co., ltd;

hydroxyethyl acrylate was purchased from Shandong Yao chemical Co., ltd;

potassium persulfate was purchased from shandong Xup chemical company, inc;

alkyl alcohol ether sulfosuccinate sodium salt was purchased from Shanghai loyalty fine chemical Co., ltd;

nonionic emulsifier S90 (secondary alcohol polyoxyethylene ether) was purchased from saen chemical technologies limited;

oxidized starch was purchased from Jiangsu ryan environmental technologies, inc.;

vegetable oleic acid was purchased from Shunfang chemical industry Co., ltd;

furfuryl alcohol was purchased from Shangheimer pharmaceutical technologies Co., ltd;

ionic liquid catalysts (1-butyl-3-methylimidazole dicyandiamide salt) were purchased from Wohinsm biotechnology Co., ltd; sodium hydrosulfite (sodium hydrosulfite) was purchased from mountain eastern sea boarding new materials limited;

ricinoleic acid was purchased from Shandong Tokyo chemical Co., ltd;

the solid acid catalyst is purchased from Whank Mike biomedical technology Co., ltd., model HND-8;

sodium dodecyl sulfate was purchased from atan Hengteng chemical company, inc.;

Sodium dodecyl sulfonate was purchased from Shandong Ruijiang chemical Co., ltd;

sodium alkyl phenol ether sulfosuccinate was purchased from Shanghai loyalty fine chemical Co., ltd;

the film forming aid TEXANOL was purchased from Guangzhou Hengxi chemical Co.

Preparation example

Preparation example 1

The preparation method of the pure acrylic emulsion comprises the following steps:

(1) 45g of emulsifier (sodium alkyl sulfosuccinate) is dissolved in 160g of water, 280g of methyl methacrylate, 610g of butyl acrylate, 20g of acrylic acid, 70g of diethylene glycol diacrylate and 30g of hydroxyethyl acrylate are then added, and stirring is continued for 40min until a milky pre-emulsion is obtained; adding 4g of potassium persulfate into water, and shaking uniformly to dissolve to obtain a potassium persulfate solution;

(2) 30g of NaHCO ₃ Dissolving in water, heating to 45deg.C, adding pre-emulsion and potassium persulfate solution, heating to 80deg.C, maintaining the temperature, and stirring for 30min; wherein the dosage of the pre-emulsion is 12% of the total amount of the pre-emulsion prepared in the step (1), and the dosage of the potassium persulfate solution is 45% of the total amount of the potassium persulfate solution prepared in the step (1);

(3) And (3) dropwise adding the residual pre-emulsion and the potassium persulfate solution into the product obtained in the step (2) at the temperature of 80 ℃ within 1h, then heating to 90 ℃, carrying out heat preservation reaction for 1h, cooling to room temperature, filtering, and regulating the pH value to 9 by using ammonia water to obtain the pure acrylic emulsion.

Preparation example 2

(1) 50g of emulsifier (nonionic emulsifier S90) are dissolved in 150g of water, 300g of methyl methacrylate, 590g ofButyl acrylate, 30g of acrylic acid, 60g of diethylene glycol diacrylate and 40g of hydroxyethyl acrylate, and stirring for 30min until a milky pre-emulsion is obtained; adding 5g of potassium persulfate into water, shaking and dissolving uniformly to obtain a potassium persulfate solution; (2) 20g of NaHCO ₃ Dissolving in water, heating to 50deg.C, adding pre-emulsion and potassium persulfate solution, heating to 75deg.C, maintaining the temperature, and stirring for 40min; wherein the dosage of the pre-emulsion is 10% of the total amount of the pre-emulsion prepared in the step (1), and the dosage of the potassium persulfate solution is 50% of the total amount of the potassium persulfate solution prepared in the step (1);

(3) And (3) dropwise adding the residual pre-emulsion and the potassium persulfate solution into the product obtained in the step (2) at the temperature of 75 ℃ within 1.5h, then heating to 85 ℃, carrying out heat preservation reaction for 1.2h, cooling to room temperature, filtering, and regulating the pH value to 8 by using ammonia water to obtain the pure acrylic emulsion.

Preparation example 3

(1) 48g of emulsifier (nonionic emulsifier S90) is dissolved in 155g of water, 290g of methyl methacrylate, 600g of butyl acrylate, 25g of acrylic acid, 65g of diethylene glycol diacrylate and 35g of hydroxyethyl acrylate are then added, and stirring is continued for 35min until a milky pre-emulsion is obtained; adding 4.5g of potassium persulfate into water, shaking and dissolving to obtain a potassium persulfate solution;

(2) 25g of NaHCO ₃ Dissolving in water, heating to 48 ℃, then adding the pre-emulsion and the potassium persulfate solution, continuously heating to 78 ℃, and keeping the temperature and stirring for 35min; wherein the dosage of the pre-emulsion is 10% of the total amount of the pre-emulsion prepared in the step (1), and the dosage of the potassium persulfate solution is 50% of the total amount of the potassium persulfate solution prepared in the step (1);

(3) And (3) dropwise adding the residual pre-emulsion and the potassium persulfate solution into the product obtained in the step (2) at the temperature of 78 ℃ within 1.2h, then heating to 88 ℃, carrying out heat preservation reaction for 1.1h, cooling to room temperature, filtering, and regulating the pH value to 8 by using ammonia water to obtain the pure acrylic emulsion.

Preparation example 4

The difference from preparation example 3 is that: the emulsifier in the step (1) comprises sodium alkyl alcohol ether sulfosuccinate and a nonionic emulsifier S90 in a weight ratio of 5:2, wherein the sodium alkyl alcohol ether sulfosuccinate is 34.3g, and the nonionic emulsifier S90 is 13.7g.

Preparation example 5

The difference from preparation example 3 is that: the emulsifier in the step (1) comprises sodium alkyl sulfosuccinate and a nonionic emulsifier S90 in a weight ratio of 6:1, wherein the sodium alkyl sulfosuccinate is 41.1g, and the nonionic emulsifier S90 is 6.9g.

Preparation example 6

The difference from preparation example 3 is that: the emulsifier in the step (1) comprises sodium alkyl sulfosuccinate and a nonionic emulsifier S90 in a weight ratio of 3:5, wherein the sodium alkyl sulfosuccinate is 18g, and the nonionic emulsifier S90 is 30g.

Preparation example 7

The difference from preparation example 3 is that: the emulsifier in the step (1) comprises sodium alkyl sulfosuccinate and a nonionic emulsifier S90 in a weight ratio of 8:1, wherein the sodium alkyl sulfosuccinate is 42.7g, and the nonionic emulsifier S90 is 5.3g.

Preparation example 8

The difference from preparation example 3 is that: the emulsifier in the step (1) comprises sodium dodecyl sulfate and a nonionic emulsifier S90 in a weight ratio of 5:2, wherein the sodium dodecyl sulfate is 34.3g, and the nonionic emulsifier S90 is 13.7g.

Preparation example 9

The difference from preparation example 3 is that: the emulsifier in the step (1) comprises sodium dodecyl sulfonate and a nonionic emulsifier S90 in a weight ratio of 5:2, wherein the sodium dodecyl sulfonate is 34.3g, and the nonionic emulsifier S90 is 13.7g.

Preparation example 10

The difference from preparation example 3 is that: the emulsifier in the step (1) comprises sodium alkyl phenol ether sulfosuccinate and a nonionic emulsifier S90 in a weight ratio of 5:2, wherein the sodium alkyl phenol ether sulfosuccinate is 34.3g, and the nonionic emulsifier S90 is 13.7g.

PREPARATION EXAMPLE 11

The difference from preparation example 3 is that: in the step (3), 18g of gelatinized oxidized starch is also added before cooling, and the heat preservation reaction is continued for 1h.

Preparation example 12

The difference from preparation example 3 is that: in the step (3), 20g of gelatinized oxidized starch is also added before cooling, and the heat preservation reaction is continued for 1.2h.

Preparation example 13

The preparation method of the furfuryl alcohol vegetable oleate comprises the following steps:

20g of vegetable oleic acid, 8.3g of furfuryl alcohol, 56g of cyclohexane, 0.2g of ionic liquid catalyst and 0.2g of sodium hydrosulfite are mixed, heated to 90 ℃, reacted for 3 hours with heat preservation, cooled to room temperature, filtered, and 7wt% of NaHCO is adopted ₃ Regulating pH value of the solution to 6, standing for layering, and decompressing and desolventizing an upper oil layer to obtain the plant furfuryl alcohol oleate.

PREPARATION EXAMPLE 14

20g of vegetable oleic acid, 8.67g of furfuryl alcohol, 60g of cyclohexane, 0.4g of ionic liquid catalyst and 0.4g of sodium hydrosulfite are mixed, heated to 80 ℃, reacted for 3.5h with heat preservation, cooled to room temperature, filtered, and 5wt% of NaHCO is adopted ₃ Regulating pH value of the solution to 7, standing for layering, and decompressing and desolventizing an upper oil layer to obtain the plant furfuryl alcohol oleate.

Preparation example 15

The preparation method of the ricinoleic acid glycol monoester comprises the following steps:

20g of ricinoleic acid and 0.36g of solid acid catalyst are added into 100g of toluene, mixed and stirred for 15min, then 5g of ethylene glycol is added, the temperature is raised to 87 ℃, the reaction is carried out for 5h, then the mixture is cooled to room temperature, and 3wt% of NaHCO is adopted ₃ Regulating pH value of the solution to 7, standing for layering, and decompressing and desolventizing an upper oil layer to obtain the ricinoleic acid glycol monoester.

PREPARATION EXAMPLE 16

20g of ricinoleic acid and 0.4g of solid acid catalyst were added to 110g of tolueneMixing and stirring for 10min, adding 5.4g of ethylene glycol, heating to 90 ℃, reacting for 4h, cooling to room temperature, adopting 4wt% of NaHCO ₃ Regulating pH value of the solution to 6, standing for layering, and decompressing and desolventizing an upper oil layer to obtain the ricinoleic acid glycol monoester.

Examples

Example 1

A preparation method of self-cleaning rock slice real stone paint comprises the following steps:

s1, magnetically stirring 5g of lithium silicate, 1g of wetting agent and 100g of pure acrylic emulsion prepared in preparation example 1 for 10min, then dropwise adding 20g of potassium silicate, magnetically stirring for 15min, and then mixing and stirring with 4wt% of sodium tetraborate solution for 30min to obtain a mixed solution; s2, adding 1.8g of bentonite and 2g of hydroxyethyl cellulose into 340g of water while stirring, then dispersing at a high speed for 30min at a rotation speed of 1300r/min, then reducing the rotation speed to 500r/min, adding 0.8g of multifunctional auxiliary agent, 0.8g of kathon bactericide, 8g of antifreeze, the mixed solution in the step S1, 12g of film forming auxiliary agent TEXANOL and 0.2g of defoaming agent, mixing and stirring for 10min, adding 3.5g of thickening agent, and dispersing at a rotation speed of 800r/min for 10min to obtain a base material;

S3, adding white sand, colored sand and rock flakes into the base material in the step S2 at the rotating speed of 300r/min, and uniformly mixing to obtain the self-cleaning rock flake real stone paint, wherein the weight ratio of the white sand to the colored sand to the rock flakes to the base material is 350:50:45:520.

Example 2

s1, magnetically stirring 5.5g of lithium silicate, 1.2g of wetting agent and 145g of pure acrylic emulsion prepared in preparation example 2 for 13min, then dropwise adding 19g of potassium silicate, magnetically stirring for 12min, and then mixing and stirring with 4.5wt% of sodium tetraborate solution for 25min to obtain a mixed solution;

s2, adding 1.35g of bentonite and 2.7g of hydroxyethyl cellulose into 352g of water while stirring, then dispersing at a high speed for 25min at a rotational speed of 1350r/min, then reducing the rotational speed to 550r/min, adding 0.32g of a multifunctional auxiliary agent, 0.9g of a kathon bactericide, 7g of an antifreezing agent, the mixed solution in the step S1, 7g of a film-forming auxiliary agent TEXANOL and 0.3g of a defoaming agent, mixing and stirring for 8min, adding 3.1g of a thickening agent, and dispersing at a rotational speed of 850r/min for 9min to obtain a base material;

s3, adding white sand, colored sand and rock flakes into the base material in the step S2 at the rotating speed of 305r/min, and uniformly mixing to obtain the self-cleaning rock flake real stone paint, wherein the weight ratio of the white sand to the colored sand to the rock flakes to the base material is 400:50:50:500.

Example 3

s1, magnetically stirring 7g of lithium silicate, 1.6g of wetting agent and 160g of pure acrylic emulsion prepared in preparation example 3 for 15min, then dropwise adding 15g of potassium silicate, magnetically stirring for 10min, and then mixing and stirring with 5wt% of sodium tetraborate solution for 20min to obtain a mixed solution;

s2, adding 1.2g of bentonite and 3g of hydroxyethyl cellulose into 354g of water while stirring, then dispersing at a high speed for 20min at a rotating speed of 1400r/min, then reducing the rotating speed to 600r/min, adding 0.2g of multifunctional auxiliary agent, 1.2g of kathon bactericide, 4g of antifreeze, the mixed solution in the step S1, 6g of film forming auxiliary agent TEXANOL and 0.8g of defoaming agent, mixing and stirring for 5min, adding 2.5g of thickening agent, and dispersing at a rotating speed of 900r/min for 8min to obtain a base material;

s3, adding white sand, colored sand and rock flakes into the base material in the step S2 at the rotating speed of 310r/min, and uniformly mixing to obtain the self-cleaning rock flake real stone paint, wherein the weight ratio of the white sand to the colored sand to the rock flakes to the base material is 450:45:55:480.

Example 4

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: the water content is 347g, the bentonite content is 1.5g, the hydroxyethyl cellulose content is 2.5g, the multifunctional auxiliary agent content is 0.5g, the kathon bactericide content is 1g, the antifreeze content is 6g, the pure acrylic emulsion content is 130g, the film forming auxiliary agent TEXANOL content is 8g, the antifoaming agent content is 0.5g, the thickener content is 3g, the wetting agent content is 1.3g, the potassium silicate content is 18g, the lithium silicate content is 6g, and the sodium tetraborate solution content is 4g.

Example 5

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: the amount of wetting agent was 1.3g, the amount of potassium silicate was 18g, the amount of lithium silicate was 6g, and the amount of sodium tetraborate solution was 4g.

Example 6

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: in step S1, 7g of nano zinc oxide and 10g of nano aluminum oxide are also added after the sodium tetraborate solution is added.

Example 7

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: in step S1, 10g of nano zinc oxide and 8g of nano aluminum oxide are also added after the sodium tetraborate solution is added.

Example 8

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: in step S1, 5g of nano zinc oxide and 15g of nano aluminum oxide are also added after the sodium tetraborate solution is added.

Example 9

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: in step S1, 18g of nano zinc oxide and 1g of nano aluminum oxide are also added after the sodium tetraborate solution is added.

Example 10

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: in step S1, 7g of nano zinc oxide and 10g of nano titanium dioxide are also added after the sodium tetraborate solution is added.

Example 11

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: the pure acrylic emulsion prepared in preparation example 4 was used.

Example 12

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: the pure acrylic emulsion prepared in preparation example 5 was used.

Example 13

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: the pure acrylic emulsion prepared in preparation example 6 was used.

Example 14

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: the pure acrylic emulsion prepared in preparation example 7 was used.

Example 15

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: the pure acrylic emulsion prepared in preparation example 8 was used.

Example 16

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: the pure acrylic emulsion prepared in preparation example 9 was used.

Example 17

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: the pure acrylic emulsion prepared in preparation example 10 was used.

Example 18

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: the pure acrylic emulsion prepared in preparation example 11 was used.

Example 19

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: the pure acrylic emulsion prepared in preparation example 12 was used.

Example 20

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: the film forming additive comprises the furfuryl alcohol ester of vegetable oleic acid prepared in preparation example 13 and the ethylene glycol monoester of ricinoleic acid prepared in preparation example 15, wherein the weight ratio of the furfuryl alcohol ester of vegetable oleic acid to the ethylene glycol monoester of ricinoleic acid is 1:1.2, and the weight ratio of the furfuryl alcohol ester of vegetable oleic acid to the ethylene glycol monoester of ricinoleic acid is 3.82g.

Example 21

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: the film forming additive comprises the furfuryl alcohol ester of vegetable oleic acid prepared in preparation example 14 and the ethylene glycol monoester of ricinoleic acid prepared in preparation example 16, wherein the weight ratio of the furfuryl alcohol ester of vegetable oleic acid is 2.8g, and the ethylene glycol monoester of ricinoleic acid is 4.2g.

Example 22

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: the film forming aid comprises TEXANOL and ethylene glycol ricinoleate in a weight ratio of 1:1.5, wherein TEXANOL is 2.8g, and the ethylene glycol ricinoleate is 4.2g.

Example 23

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: the film forming additive comprises a 2:1 weight ratio of furfuryl alcohol ester of vegetable oil acid and a 2.33g monoester of ethylene glycol ricinoleate, wherein the furfuryl alcohol ester of vegetable oil acid is 4.67 g.

Example 24

The preparation method of the self-cleaning rock slice real stone paint is different from the embodiment 2 in that: the film forming additive comprises 1:3 of furfuryl alcohol vegetable oleate and 5.25g of ethylene glycol ricinoleate.

Comparative example

Comparative example 1

The difference from example 2 is that: and (3) removing the step S1, adding pure acrylic emulsion between the antifreezing agent and the film forming auxiliary agent, and the rest is the same.

Comparative example 2

The difference from example 2 is that: the pure acrylic emulsion is produced by Japanese Zhaoya, the model is 4765, and the rest are the same.

Comparative example 3

The difference from example 2 is that: in step S1, potassium silicate is not added, and the rest are the same.

Comparative example 4

The difference from example 2 is that: in step S1, no lithium silicate is added, and the rest are the same.

Comparative example 5

The difference from example 2 is that: the potassium silicate in step S1 is changed to sodium silicate, and the rest are the same.

Comparative example 6

The difference from example 2 is that: the lithium silicate in step S1 is changed to sodium silicate, and the rest are the same.

Comparative example 7

The difference from example 2 is that: methyl methacrylate in the pure acrylic emulsion prepared in preparation example 2 was replaced with methyl acrylate, and the rest were the same.

Comparative example 8

The difference from example 2 is that: the butyl acrylate in the pure acrylic emulsion prepared in preparation example 2 was replaced by ethyl acrylate, and the rest were the same.

Comparative example 9

The difference from example 2 is that: the diethylene glycol diacrylate in the pure acrylic emulsion prepared in preparation example 2 was replaced with diethylene glycol dimethacrylate, and the rest were the same.

Performance detection

The self-cleaning rock flake real stone paint prepared in examples 1 to 24 and comparative examples 1 to 9 was sprayed on a board according to the method prescribed in JG/T24-2018 "synthetic resin emulsion sand wall building paint", standard condition curing was 14d, and then the following performance tests were performed on the templates of examples 1 to 24 and comparative examples 1 to 9, and the results are shown in Table 1;

1. stain resistance

Referring to a 5.5 dipping method in GB/T9780-2013 "method for testing stain resistance of architectural coating", in order to make test results have data contrast, adopting reflectance reduction rate before and after stain resistance to replace gray card color comparison;

2. Durability of

(1) Artificial climate aging test: referring to an artificial weather aging test A method specified in GB/T1865-2009 "Xe arc radiation filtered by color paint and varnish artificial weather aging and artificial radiation exposure", the stain-resistant effect retention condition of a test board after exposure to sun for 3 months, artificial accelerated aging (Xe-spray aging) for 200h and soaking for 48h is tested;

(2) Adhesive strength: the standard bonding strength and the bonding strength after freeze thawing cycle are measured by referring to the method of 7.17 in JG/T24-2018 synthetic resin emulsion sand wall building paint;

3. water resistance

The test was carried out with reference to the method of 7.13 in JG/T24-2018, "synthetic resin emulsion sand wall building paint" (immersion time: 120 h), and the surface state of each group of 3 test panels was recorded, and if 2 test panels among the 3 test panels were free from occurrence of film-like symptoms such as bulging, cracking, peeling, etc., and the color was allowed to slightly change as compared with the non-immersed portion, it was assessed as "no abnormality". The occurrence of the above-mentioned film-coating pathological phenomena is described in GB/T1766.

Table 1 table of performance test results

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As can be seen from Table 1, the reflectance reduction rate of the self-cleaning rock slice true stone paint prepared by the method is below 13%, the reflectance reduction rate of the self-cleaning rock slice true stone paint before and after pollution resistance is still below 13% after an aging test, the bonding strength can reach more than 1.0MPa and is far higher than the standard requirement (more than or equal to 0.6 MPa), the bonding strength after 5 times of freeze thawing cycle is more than 0.7MPa and is also higher than the standard requirement (more than or equal to 0.4 MPa), and after soaking for 120 hours, the surface is free from abnormality and is higher than 96 hours of the standard requirement, so that the self-cleaning rock slice true stone paint has stronger self-cleaning capability, better pollution resistance, higher durability and water resistance, and lower possibility of losing super-hydrophilic property due to separation from a base material or surface structure change.

The reflectance decrease rate of examples 4-5 and the reflectance decrease rate after aging test are lower than those of example 2, and the bonding strength after 5 times of freeze thawing cycle are higher than those of example 2, which shows that the contamination resistance and durability of the real stone paint can be further improved by further controlling the addition amount of the raw materials used in the real stone paint.

The reflectance decrease rate of examples 6-7 and the reflectance decrease rate after aging test are lower than those of example 2, and the bonding strength after 5 times of freeze thawing cycle are higher than those of example 2, which shows that the contamination resistance and durability of the real stone paint can be further improved by further adding the nano particles with high surface energy into the real stone paint.

The reflectance decrease rate of examples 8-9 and the reflectance decrease rate after aging test are lower than those of example 2, but higher than those of examples 6-7, and the bonding strength after 5 times of freeze thawing cycle are higher than those of example 2, but lower than those of examples 6-7, which shows that the contamination resistance and durability of the real stone paint can be further improved by further controlling the addition amount of the nano particles.

The reflectance decrease rate of the embodiment 10 and the reflectance decrease rate after the aging test are lower than those of the embodiment 2, but higher than those of the embodiments 6-7, and the bonding strength after 5 times of freeze thawing cycle are higher than those of the embodiment 2, but lower than those of the embodiments 6-7, which indicates that the application adopts the mixed and matched use of nano zinc oxide and nano aluminum oxide, can fully play the synergistic effect of the nano zinc oxide and the nano aluminum oxide, and further improves the contamination resistance and durability of the real stone paint.

The reflectance decrease rate of examples 11-12 and the reflectance decrease rate after aging test are lower than those of example 2, and the bonding strength after 5 times of freeze thawing cycle are higher than those of example 2, which shows that the application adopts the mixed and matched use of the anionic emulsifier and the nonionic emulsifier as the emulsifier of the pure acrylic emulsion, so that the hydrophilicity of the pure acrylic emulsion can be improved, and the contamination resistance and the durability of the real stone paint are further improved.

The reflectance decrease rate of examples 13 to 14 and the reflectance decrease rate after aging test are lower than those of example 2, but higher than those of examples 11 to 12, and the bonding strength after 5 times of freeze thawing cycle are higher than those of example 2, but lower than those of examples 11 to 12, which means that the application further controls the weight ratio of the anionic emulsifier to the nonionic emulsifier, and can further improve the hydrophilicity of the pure acrylic emulsion, thereby further improving the stain resistance and durability of the real stone paint.

The reflectance decrease rate of examples 15-17 and the reflectance decrease rate after aging test are lower than those of example 2, but higher than those of examples 11-12, and the bonding strength after 5 times of freeze thawing cycle are higher than those of example 2, but lower than those of examples 11-12, which shows that the application adopts the mixed collocation of sodium alkyl sulfosuccinate and nonionic emulsifier S90, so that the synergistic effect of the sodium alkyl sulfosuccinate and the nonionic emulsifier can be fully exerted, thereby further improving the hydrophilicity of the pure acrylic emulsion, and further improving the contamination resistance and durability of the real stone paint.

The reflectance decrease rate of examples 18-19 and the reflectance decrease rate after aging test are lower than those of example 2, and the bonding strength after 5 times of freeze thawing cycle are higher than those of example 2, which shows that the application can further improve the crosslinking degree and compactness of the internal network structure of the pure acrylic emulsion by further adding gelatinized oxidized starch into the pure acrylic emulsion, thereby further improving the contamination resistance and durability of the real stone paint.

The reflectance decrease rate of examples 20-21 and the reflectance decrease rate after aging test are lower than those of example 2, and the bonding strength after 5 times of freeze thawing cycle are higher than those of example 2, which shows that the application adopts the mixture of the furfuryl alcohol oleate and the ethylene glycol ricinoleate as the film forming auxiliary agent, so that the film forming effect of the real stone paint can be further improved, and the stain resistance and durability of the real stone paint are further improved.

The reflectance decrease rate of examples 22-24 and the reflectance decrease rate after aging test are lower than those of example 2, but higher than those of examples 20-21, and the bonding strength after 5 times of freeze thawing cycle are higher than those of example 2, but lower than those of examples 20-21, which shows that the application adopts the mixture collocation of the furfuryl alcohol oleate and the ethylene glycol ricinoleate, and the weight ratio of the furfuryl alcohol oleate and the ethylene glycol ricinoleate is controlled, so that the synergistic effect of the furfuryl alcohol oleate and the ethylene glycol ricinoleate can be fully exerted, thereby further improving the film forming effect of the real stone paint, and further improving the stain resistance and the durability of the real stone paint.

The reflectance reduction rate of comparative example 1 and the reflectance reduction rate after aging test are both significantly higher than those of example 2, the bonding strength and the bonding strength after 5 times of freeze thawing cycle are both significantly lower than those of example 2, and the foaming phenomenon occurs after soaking for 120 hours, the foaming density grade is 2, and the foaming size grade is S3, which indicates that silicate is added into the real stone paint in the application, so that the real stone paint has higher contamination resistance and durability.

The reflectance reduction rate of comparative example 2 and the reflectance reduction rate after aging test are both significantly higher than those of example 2, the bonding strength and the bonding strength after 5 times of freeze thawing cycle are both significantly lower than those of example 2, and the foaming phenomenon occurs after soaking for 120 hours, the foaming density grade is 1, and the foaming size grade is S1, which indicates that the pure acrylic emulsion prepared by the application can enable the real stone paint to have higher contamination resistance and durability compared with the commercial pure acrylic emulsion.

The reflectance reduction rate of comparative examples 3 to 6 and the reflectance reduction rate after aging test are both obviously higher than those of example 2, the bonding strength and the bonding strength after 5 times of freeze thawing cycle are both obviously lower than those of example 2, the foaming phenomenon occurs after soaking for 120 hours, the foaming density grade is 1, and the foaming size grade is S2, which indicates that the application adopts the mixed collocation of potassium silicate and lithium silicate, and the synergistic effect of the potassium silicate and the lithium silicate can be fully exerted, so that the stain resistance and the durability of the real stone paint are further improved.

The reflectance reduction rate of comparative examples 7 to 9 and the reflectance reduction rate after aging test are both significantly higher than those of example 2, the bonding strength and the bonding strength after 5 times of freeze thawing cycle are both significantly lower than those of example 2, and the foaming phenomenon occurs after soaking for 120 hours, the foaming density grade is 1, and the foaming size grade is S1, which indicates that the pure acrylic emulsion of the application adopts specific hard monomer, soft monomer and crosslinking monomer, so that the pure acrylic emulsion of the application has better performance, thereby further improving the contamination resistance and durability of the real stone paint.

The embodiments of the present invention are all preferred embodiments of the present application, and are not intended to limit the scope of the present application in this way, therefore: all equivalent changes in structure, shape and principle of this application should be covered in the protection scope of this application.

Claims

1. The self-cleaning rock slice real stone paint is characterized by comprising white sand, colored sand, rock slices and base materials in a weight ratio of (350-450): (45-50): (45-55): (480-520); the base material comprises the following components in parts by weight: 340-354 parts of water, 1.2-1.8 parts of bentonite, 2-3 parts of hydroxyethyl cellulose, 0.2-0.8 part of multifunctional auxiliary agent, 0.8-1.2 parts of kathon bactericide, 4-8 parts of antifreezing agent, 100-160 parts of pure acrylic emulsion, 6-12 parts of film forming auxiliary agent, 0.2-0.8 part of defoamer, 2.5-3.5 parts of thickener, 1-1.6 parts of wetting agent, 15-20 parts of potassium silicate, 5-7 parts of lithium silicate and 3-5 parts of 4-5wt% of sodium tetraborate solution.

2. The self-cleaning rock fragment stone paint according to claim 1, wherein the base material further comprises 7-10 parts by weight of nano zinc oxide and 8-10 parts by weight of nano aluminum oxide.

3. The self-cleaning rock fragment stone paint according to claim 1, wherein the pure acrylic emulsion is prepared by the following method:

4. A self-cleaning rock fragment real stone paint according to claim 3, wherein the emulsifier comprises an anionic emulsifier and a nonionic emulsifier in a weight ratio of (5-6): (1-2); the anionic emulsifier is sodium alkyl sulfosuccinate, and the nonionic emulsifier is nonionic emulsifier S90.

5. The self-cleaning rock slice real stone paint according to claim 3, wherein 1.8-2.0 parts by weight of gelatinized oxidized starch is added before cooling in the step (3), and the heat preservation reaction is continued for 1-1.2 hours.

6. The self-cleaning rock flake real stone paint according to claim 1, wherein the film forming auxiliary agent comprises (1.2-1.5) of furfuryl alcohol oleate and (1.2-1.5) of ethylene glycol ricinoleate.

7. The self-cleaning rock flake real stone paint according to claim 6, wherein the vegetable oil furfuryl alcohol ester is prepared by the following method:

8. The self-cleaning rock fragment stone paint according to claim 6, wherein the ricinoleic acid glycol monoester is prepared by the following method:

adding ricinoleic acid and a solid acid catalyst into 100-110 parts by weight of toluene, mixing and stirring for 10-15min,then adding glycol and heating to 87-90 ℃, reacting for 4-5h, then cooling to room temperature, adopting NaHCO with 3-4wt% ₃ Regulating pH value of the solution to 6-7, standing for layering, and decompressing and desolventizing an upper oil layer to obtain ricinoleic acid glycol monoester; n (ricinoleic acid) n (ethylene glycol) is 1 (1.2-1.3), and the dosage of the solid acid catalyst is 1.8-2wt% of ricinoleic acid.

9. A method of preparing a self-cleaning rock fragment stone-like lacquer according to any one of claims 1-8, characterized in that it comprises the steps of:

10. The method for preparing the self-cleaning rock fragment stone-like paint according to claim 9, which is characterized in that: in the step S1, 7-10 parts by weight of nano zinc oxide and 8-10 parts by weight of nano aluminum oxide are also added.