Preparation method of dealcoholized environment-friendly mildew-proof beautifying gel for home decoration

Abstract

The invention relates to a preparation method of a dealcoholization type environment-friendly mildew-proof beauty gel for home decoration, and belongs to the technical field of adhesives, the preparation method of the dealcoholization type environment-friendly mildew-proof beauty gel for home decoration comprises the following four steps: preparation of a modified composite inorganic mildew inhibitor, preparation of modified nano calcium carbonate, preparation of a reaction type tackifier, and mixing to prepare the gel. The surface drying time of the obtained dealcoholization type environment-friendly mildew-proof beautifying glue for home decoration is 9-15 min, the 24-hour curing depth is 5.6-6.8 mm, the bonding strength is 3.5-4.1 MPa, the tensile strength is 4.5-5.9 MPa, the shear strength is 2.6-3.9 MPa, the elongation at break is 375-415%, the shore hardness is 54-60, and the mildew-proof grade is 0 grade in 30 days, 60 days, 120 days, 180 days and 360 days.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of preparation methods of alcohol-removing type environment-friendly mold-proof cosmetic glue for home decoration, belong to adhesive technical field. BACKGROUND

[0002] The cosmetic glue for home decoration is the chemical essence of silicone glue, it has strong weather resistance, good durability, good waterproof sealing performance, strong adhesive force, good appearance and other advantages, has been widely used in the field of home decoration building, according to the different components removed in the use process, can be divided into acid-removing type, ketoxime-removing type, alcohol-removing type, wherein alcohol-removing type cosmetic glue has low corrosion, no odor and is more environmentally friendly, and has good bonding performance to different materials, especially the bonding performance to glass and metal is more excellent, has very large market share in the field of home decoration. But with the increasing high requirements of residential buildings decoration, heating facilities are increasingly improved, and the room sealing performance is continuously strengthened, the water vapor accumulation phenomenon in bathroom and kitchen is also more common. When alcohol-removing type cosmetic glue is used for sealing in these high-humidity areas, mold is easy to breed on the surface, which causes black spots on the surface, affects the appearance and the sealing performance of the glue itself. Therefore, the use of alcohol-removing type cosmetic glue in kitchen and bathroom is also limited accordingly, and the development of alcohol-removing type cosmetic glue with mold-proof function has become the inevitable demand of the market.

[0003] In order to overcome the disadvantage of mildew in high temperature and high humidity environment, the most commonly used method is to add antifungal agent to dealcoholized cosmetic adhesive, so as to improve the antifungal property of dealcoholized cosmetic adhesive, in addition, modified filler and crosslinking aid are also added to improve the crosslinking density, and the dispersed crosslinking is changed into concentrated crosslinking, so as to improve the tensile strength, oil resistance and puncture resistance of dealcoholized cosmetic adhesive, and also avoid the generation of oily exudate, which can also improve the antifungal property. The commonly used antifungal agents in cosmetic adhesive mainly include organic antifungal agents and inorganic antifungal agents. The organic antifungal agents include sodium pentachlorophenol, benzene alkyl acid mercury, phenylmercuric acetate, chlorinated isopeptide nitrile, formaldehyde, phenol and the like. Although the above-mentioned substances have the characteristics of high antifungal efficiency and small addition amount, the organic antifungal agents also have the following obvious disadvantages: poor heat resistance, easy decomposition, poor durability, most of them have certain toxicity, poor environmental protection and easy to cause environmental pollution. The common inorganic antifungal agents include nano metal or nano metal oxide and metal inorganic salt, such as nano copper, silver, zinc, tin and the like, nano titanium dioxide, nano zinc oxide, nano copper oxide, nano zinc borate and the like. The above-mentioned inorganic antifungal agents have the following characteristics: (1) non-toxic or very low toxicity, good environmental protection; (2) high antifungal efficiency, broad-spectrum antifungal property, durability and low concentration high efficiency; (3) good environmental stability and storage stability; (4) strong resistance, strong resistance to ultraviolet, water immersion and heat. However, most of the inorganic antifungal agents are in the form of nano powder, which is easy to agglomerate, and the uniformity of dispersion is a big problem. In addition, the addition of powder generally affects the adhesion of cosmetic adhesive, and in terms of improving crosslinking density, powder is easy to prolong the time required for crosslinking and curing, resulting in slow deep curing speed after sizing. In addition, the addition of powder also affects the elasticity of dealcoholized cosmetic adhesive, resulting in large temperature dependence of extrusion and thixotropy during sizing, and the sizing quality is easy to be affected.

[0004] Chinese patent CN120555009A discloses an anti-mildew cosmetic alcohol-based gel and its preparation process, comprising the following components: 80-100 parts alkoxy-terminated polydimethylsiloxane, 7-20 parts plasticizer, 6-18 parts filler, 0.6-3.5 parts fumed silica, 5-15 parts crosslinking agent, 1.2-2.0 parts anti-mildew agent, and 0.2-2.5 parts catalyst. This patent uses alkoxy-terminated polydimethylsiloxane as the main component, siloxane as the crosslinking agent, and adds plasticizer and filler to prepare the alcohol-based gel. The crosslinking agent can optionally include morpholinosiloxane or ammonium chloride siloxane, and the plasticizer can include quaternized modified silicone oil, which works synergistically with the anti-mildew agent to enable the alcohol-based gel to exert antibacterial and anti-mildew effects, and also exhibits good broad-spectrum, rapid bactericidal properties and thermal stability. This patent uses zinc ions loaded with diatomaceous earth as an anti-mildew functional filler. However, after the surface of the diatomaceous earth is modified, the surface is covered with inorganic materials, which will have a great negative impact on the uniformity of dispersion of diatomaceous earth in the colloidal formulation, thereby affecting the adhesive performance of the colloid and the curing rate inside the colloid layer.

[0005] Chinese patent CN118126673A discloses an ethanol-free environmentally friendly cosmetic adhesive, which is composed of 180-260 parts of α,ω-dihydroxypolydimethylsiloxane, 40-65 parts of modified nano-calcium carbonate, 20-45 parts of modified diatomaceous earth-supported antifungal agent, 2-7 parts of hydrophobic fumed silica, 10-30 parts of composite plasticizer, 0.8-1.5 parts of composite catalyst, 1-5 parts of co-catalyst, 2-5 parts of vinyltriethoxysilane, and 8-19 parts of modified hyperbranched polymer crosslinking agent. The anti-mold properties of the cosmetic gel obtained by this patent mainly rely on the anti-mold agent 3-methyl-4-isopropylphenol loaded with diatomaceous earth to provide a long-lasting anti-mold effect. Although the loading of diatomaceous earth can control the precipitation and loss of the anti-mold agent 3-methyl-4-isopropylphenol, 3-methyl-4-isopropylphenol is still an organic matter and is easily decomposed by environmental influences, eventually losing its anti-mold properties. Moreover, its environmental protection and safety are difficult to match those of inorganic anti-mold agents. In addition, the most significant drawback is the durability of its anti-mold properties, which, theoretically, cannot surpass those of inorganic anti-mold agents.

[0006] As can be seen above, de-alcoholized cosmetic adhesives for home decoration still suffer from poor anti-mold performance and environmental unfriendliness when organic anti-mold agents are added. While adding inorganic anti-mold agents can achieve long-lasting anti-mold performance, it can easily lead to negative effects such as poor adhesive strength and slow deep curing rate. Therefore, there is an urgent need in the market for a de-alcoholized environmentally friendly anti-mold cosmetic adhesive for home decoration that can provide long-lasting anti-mold efficacy, good adhesion, and high deep curing rate. Summary of the Invention

[0007] To address the shortcomings of the existing technology, this invention provides a method for preparing a de-alcoholized environmentally friendly anti-mildew cosmetic adhesive for home decoration, achieving the following objectives: to prepare a de-alcoholized environmentally friendly anti-mildew cosmetic adhesive for home decoration with fast deep curing rate, high bonding strength, high crosslinking strength, and good mechanical properties.

[0008] To achieve the above-mentioned objectives, the present invention adopts the following technical solution: A method for preparing a de-alcoholized environmentally friendly anti-mildew cosmetic adhesive for home decoration includes four steps: preparation of a modified composite inorganic anti-mildew agent, preparation of modified nano-calcium carbonate, preparation of a reactive tackifier, and mixing to form the adhesive. The following are further improvements to the above technical solution: Step 1: Preparation of modified composite inorganic antifungal agent After the composite inorganic antifungal agent is thoroughly dried, it is added to a dispersion reactor along with polyethylene glycol dioleate and methyl ethyl ketone. After being vigorously stirred and dispersed evenly, the temperature is raised and kept constant to the reaction temperature. Under the condition of uniform stirring and reflux, an amino-containing silane coupling agent is added. After the reaction is complete, terminal epoxy silicone oil is added, and stirring is continued until the reaction is complete. After cooling to room temperature, the mixture is centrifuged and separated. The separated solid is then washed and dried to obtain the modified composite inorganic antifungal agent. The composite inorganic antifungal agent is a mixture of nano-zirconium phosphate loaded with copper, nano-zirconium phosphate loaded with silver, nano-zirconium oxide, and nano-zinc borate. The composite inorganic antifungal agent is thoroughly dried at a temperature of 80-95°C for 15-26 hours. The particle size of the copper-loaded zirconium phosphate nanoparticles is 10~100nm; The particle size of the nano-zirconium phosphate loaded with silver is 10~100nm; The particle size of the nano zinc oxide is 10~100nm; The particle size of the nano-zinc borate is 10~100nm; The mass ratio of the nano-zirconium phosphate loaded with copper, nano-zirconium phosphate loaded with silver, nano-zinc oxide, and nano-zinc borate is (6~19):(1~4):(40~90):(20~70). The amine-containing silane coupling agent is one or a mixture of two or more of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N,N-diethyl-3-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-diethylaminomethyltriethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, and 3-(2-aminoethyl)-aminopropyltriethoxysilane in any mass ratio; The epoxy value of the terminal epoxy group silicone oil is 0.3~1.1, and the viscosity at 25°C is 50~900 mPa·s; The mass ratio of the composite inorganic antifungal agent, polyethylene glycol dioleate, methyl ethyl ketone, amine-containing silane coupling agent, and terminal epoxy silicone oil is (80~200):(4~12):(240~900):(8~30):(20~80). The high-intensity stirring and dispersion is carried out at a stirring and dispersion rate of 8000~13000 rpm for 5~10 hours. The reaction temperature is 60~75℃; The uniform stirring is carried out at a speed of 1000~2000 rpm. After the reaction is complete, the reaction time is 6 to 10 hours; The reaction time is 8-13 hours until the reaction is complete. The washing process involves washing with anhydrous ethanol 3 to 5 times, with the mass of anhydrous ethanol used in each wash being equal to the mass of the solid being washed. The drying process involves a drying temperature of 60-80℃ and a drying time of 12-20 hours.

[0009] Step 2: Preparation of modified nano-calcium carbonate The dried nano-calcium carbonate, polyethylene glycol dioleate, and ethyl acetate were added to a dispersion reactor and vigorously stirred to disperse them evenly. The temperature was then raised and kept constant at the reaction temperature. The mixture was stirred at a uniform speed and kept under reflux. A silane coupling agent containing isocyanate groups was added. After the reaction was complete, hydrogenated rosin alcohol was added. The mixture was stirred until the reaction was complete. The mixture was then cooled to room temperature and centrifuged. The separated solid was washed and dried to obtain modified nano-calcium carbonate. The particle size of the nano-calcium carbonate is 10~100nm; The dried nano-calcium carbonate is specifically dried at 90~110℃ for 10~20 hours. The isocyanate-containing silane coupling agent is one of 3-isocyanate-propyltrimethoxysilane and 3-isocyanate-propyltriethoxysilane; The mass ratio of the nano-calcium carbonate, polyethylene glycol dioleate, ethyl acetate, isocyanate-containing silane coupling agent, and hydrogenated rosin alcohol is (60~130):(4~10):(340~800):(6~15):(20~60). The high-intensity stirring and dispersion is carried out at a stirring and dispersion rate of 9000~15000 rpm for 6~13 hours. The reaction temperature is 50~70℃; The uniform stirring is carried out at a speed of 1300~2500 rpm. After the reaction is complete, the reaction time is 8 to 12 hours; The reaction time is 9-14 hours until the reaction is complete. The washing process involves washing with anhydrous ethanol 3 to 5 times, with the mass of anhydrous ethanol used in each wash being equal to the mass of the solid being washed. The drying process involves a drying temperature of 60-80℃ and a drying time of 12-24 hours.

[0010] Step 3: Preparation of reactive tackifier Hydroxyl-terminated vinyl silicone oil, α-diimide nickel, and acetone were placed in a reaction vessel and stirred until completely dissolved. The mixture was stirred at a constant speed and kept under reflux, and the temperature was raised to the reaction temperature. Then, unsaturated amide was added, and the mixture was stirred at a constant temperature until the reaction was complete. The mixture was then transferred to a rotary evaporator and vacuum evaporated to remove acetone, resulting in a viscous reactive thickener. The hydroxyl-terminated vinyl silicone oil has a hydroxyl content of 3-7 wt%, a vinyl content of 4-8 wt%, and a viscosity of 10-120 mPa·s at 25°C. The unsaturated amide is one or a mixture of two or more of fumarate, crotonamide, hydroxymethylacrylamide, N-hydroxymethylacrylamide, and N-(3-hydroxypropyl)acrylamide in any mass ratio; The mass ratio of the terminal hydroxyl vinyl silicone oil, α-diimide nickel, acetone, and unsaturated amide is (40~100):(0.5~1):(260~600):(10~30). The uniform stirring is carried out at a speed of 800-1300 rpm. The reaction temperature is 50~65℃; After the constant temperature stirring reaction is complete, the reaction time is 9 to 15 hours; The vacuum rotary evaporation is performed under the following conditions: vacuum negative pressure of -100 to -96 kPa, rotary evaporation speed of 60 to 95 rpm, rotary evaporation time of 5 to 11 hours, and rotary evaporation temperature of 40 to 55°C.

[0011] Step 4: Mixing and preparing adhesive According to the specific formula of the de-alcoholized environmentally friendly anti-mildew beauty adhesive for home decoration, by weight, α,ω-dihydroxypolydimethylsiloxane, modified nano calcium carbonate, hydrophobic fumed silica, dimethyl silicone oil, and methyltriethoxysilane are placed in a dry double planetary mixer and stirred and dispersed under vacuum for 10-15 hours. Then, modified composite inorganic anti-mildew agent, tetrabutyl titanate, co-catalyst, and reactive tackifier are added. After stirring and dispersing for another 8-13 hours, a viscous adhesive is obtained. After continuous vacuum degassing, the adhesive is discharged and the bubble-free adhesive is filled into a dry packaging container, protected with nitrogen and sealed to obtain the de-alcoholized environmentally friendly anti-mildew beauty adhesive for home decoration. The specific formula of the de-alcoholized environmentally friendly anti-mildew cosmetic adhesive for home decoration is as follows, by weight: 330-500 parts α,ω-dihydroxypolydimethylsiloxane, 25-65 parts modified composite inorganic anti-mildew agent, 65-120 parts modified nano calcium carbonate, 1-8 parts hydrophobic fumed silica, 8-25 parts reactive tackifier, 60-100 parts dimethyl silicone oil, 1-2.5 parts tetrabutyl titanate, 2-6 parts co-catalyst, and 20-60 parts methyltriethoxysilane; The average particle size of the hydrophobic fumed silica is 5~100nm; The co-catalyst is one or a mixture of two or more of N,N-disilyl-silaneamine, bis(trimethylsilylmethyl)amine, 3-dimethylaminoethylsilane, diisopropylamine silane, bis(methyldiethoxysilylpropyl)amine, 3-(4-ureaamino)propyltriethoxysilane, O-(trimethylsilyl)hydroxylamine, tri(trimethylsilyl)amine, bis[3-(triethoxysilyl)propyl]amine, 3-aminopropyltrimethylsilane, bis(tert-butylamino)silane, dimethylsilyldiethylamine, and tri(diethylamino)silane in any mass ratio; The stirring and dispersion under vacuum negative pressure is described, with a negative pressure of -100 to -98 kPa, a stirring rate of 150 to 400 rpm, and a dispersion rate of 8000 to 14000 rpm.

[0012] Compared with the prior art, the present invention achieves the following beneficial effects: 1. The inorganic antifungal agent added in this invention is a mixture of nano-zirconium phosphate loaded with copper, nano-zirconium phosphate loaded with silver, nano-zinc oxide, and nano-zinc borate. This is mainly to avoid the shortcomings of a single antifungal agent, which does not have broad-spectrum antifungal properties. The combined use of multiple inorganic antifungal agents gives the cosmetic adhesive a good antifungal effect against various molds. The above-mentioned nano-scale inorganic antifungal agents have a large specific surface area, are prone to agglomeration, and have relatively strong surface polarity, making it difficult to achieve uniform dispersion in non-polar silicone adhesive formulations. Therefore, this invention first uses an amino-containing silane coupling agent to modify the surface of these nano-scale inorganic antifungal agents. After modification, the surface of these nano-scale inorganic antifungal agents is covered with amino groups, and then coated with terminal epoxy-containing silicone oil to further reduce the surface polarity of these inorganic antifungal agents. The performance test data of the cosmetic adhesive in the last part of the specification also shows that the modification with an amino-containing silane coupling agent and the surface coating with terminal epoxy-containing silicone oil are very effective in promoting the uniform dispersion of inorganic antifungal agents. 2. In order to enhance the mechanical properties of the de-alcoholized environmentally friendly anti-mildew cosmetic adhesive, this invention uses conventional filler nano-calcium carbonate to strengthen the colloid. However, in order to ensure the uniform dispersion of nano-calcium carbonate, this invention first uses a silane coupling agent containing isocyanate groups to react with the hydroxyl groups on the surface of nano-calcium carbonate. After the reaction, the surface of nano-calcium carbonate is covered with isocyanate functional groups. Then, by utilizing the reaction between the isocyanate functional groups and the hydroxyl groups, and through the reaction between the terminal hydroxyl groups of added hydrogenated rosin alcohol and the isocyanate groups, the surface of nano-calcium carbonate is coated with the molecular structure of hydrogenated rosin alcohol. Hydrogenated rosin alcohol can reduce the surface polarity of nano-calcium carbonate and promote the uniform dispersion of nano-calcium carbonate in the de-alcoholized environmentally friendly anti-mildew cosmetic adhesive formulation. In addition, hydrogenated rosin alcohol plays a very important role in improving the adhesive strength after the colloid is cured, and can also greatly improve the anti-mildew performance of the cosmetic adhesive. 3. This invention uses hydroxyl-terminated vinyl silicone oil and unsaturated amide as raw materials and α-diimide nickel as a catalyst to synthesize a reactive tackifier. The reaction mechanism is roughly as follows: the ethylene double bond in the hydroxyl-terminated vinyl silicone oil and the carbon-carbon double bond in the unsaturated amide undergo an addition polymerization reaction under the catalysis of α-diimide nickel. The side chains of the hydroxyl-terminated vinyl silicone oil molecular chain after the reaction have polar functional groups such as amine and hydroxyl groups, and both ends have reactive hydroxyl-terminated active functional groups. The reactivity of these hydroxyl-terminated groups is similar to that of α,ω-dihydroxypolydimethylsiloxane. The hydroxyl groups contained in the alkane are the same. The above-mentioned polar functional groups such as amino groups and hydroxyl groups can not only greatly improve the wettability and adhesion of the adhesive to the substrate during application, thereby greatly improving the bonding strength, but the amino groups contained therein also have a very strong catalytic effect on the cross-linking and curing of the adhesive. Therefore, reactive tackifiers can also improve the deep curing speed and have a certain effect on improving the cross-linking density. By improving the cross-linking density, the overall water vapor and moisture penetration performance of the cured adhesive can be greatly improved, thus also having a certain effect on improving the anti-mildew performance of cosmetic adhesives. 4. The co-catalyst added in this invention is a silane substance containing amine groups. This type of substance has very high hydrolytic activity. Under the action of the main catalyst tetrabutyl titanate, it is easier to undergo hydrolysis reaction. Therefore, in the formulation of cosmetic adhesive, it can work synergistically with the main catalyst to promote the hydrolysis reaction and related cross-linking reaction of the main material α,ω-dihydroxypolydimethylsiloxane, the cross-linking agent methyltriethoxysilane, and other highly hydrolytically active raw materials. Ultimately, it can accelerate the surface drying time, improve the deep curing rate, and enhance the overall mechanical properties and anti-mildew properties of the cured adhesive. 5. The de-alcoholized environmentally friendly anti-mildew cosmetic adhesive for home decoration obtained by this invention has a surface drying time of 9-15 minutes, a curing depth of 5.6-6.8 mm after 24 hours, an adhesive strength of 3.5-4.1 MPa, a tensile strength of 4.5-5.9 MPa, a shear strength of 2.6-3.9 MPa, an elongation at break of 375-415%, a Shore hardness of 54-60, and an anti-mildew rating of 0 for 30 days, 60 days, 120 days, 180 days, and 360 days. Detailed Implementation

[0013] The preferred embodiments of the present invention are described below. It should be understood that the preferred embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0014] Example 1: A method for preparing a de-alcoholized, environmentally friendly, mildew-resistant cosmetic adhesive for home decoration. Step 1: Preparation of modified composite inorganic antifungal agent After the composite inorganic antifungal agent is thoroughly dried, it is added to a dispersion reactor along with polyethylene glycol dioleate and methyl ethyl ketone. After being vigorously stirred and dispersed evenly, the temperature is raised and kept constant to the reaction temperature. Under the condition of uniform stirring and reflux, an amino-containing silane coupling agent is added. After the reaction is complete, terminal epoxy silicone oil is added, and stirring is continued until the reaction is complete. After cooling to room temperature, the mixture is centrifuged and separated. The separated solid is then washed and dried to obtain the modified composite inorganic antifungal agent. The composite inorganic antifungal agent is a mixture of nano-zirconium phosphate loaded with copper, nano-zirconium phosphate loaded with silver, nano-zirconium oxide, and nano-zinc borate. The composite inorganic antifungal agent is thoroughly dried at a temperature of 90°C for 20 hours. The copper-loaded zirconium phosphate nanoparticles have a particle size of 50 nm. The particle size of the silver-loaded zirconium phosphate nanoparticles is 50 nm. The particle size of the nano zinc oxide is 50 nm; The particle size of the nano zinc borate is 50 nm; The mass ratio of the nano-zirconium phosphate loaded with copper, the nano-zirconium phosphate loaded with silver, the nano-zirconium oxide, and the nano-zinc borate is 11:3:60:50. The amine-containing silane coupling agent is γ-aminopropyltriethoxysilane; The epoxy value of the terminal epoxy silicone oil is 0.9, and the viscosity at 25°C is 400 mPa·s. The mass ratio of the composite inorganic antifungal agent, polyethylene glycol dioleate, methyl ethyl ketone, amine-containing silane coupling agent, and terminal epoxy silicone oil is 120:10:600:23:55. The high-intensity stirring and dispersion is carried out at a stirring and dispersion rate of 10,000 rpm for 8 hours. The reaction temperature is 70°C; The uniform stirring is carried out at a speed of 1600 rpm. The reaction time is 9 hours after the reaction is complete. The reaction time is 11 hours until the reaction is complete. The washing process involves washing four times with anhydrous ethanol, with the mass of anhydrous ethanol used in each wash being equal to the mass of the solid being washed. The drying process is carried out at a temperature of 75°C for 18 hours.

[0015] Step 2: Preparation of modified nano-calcium carbonate The dried nano-calcium carbonate, polyethylene glycol dioleate, and ethyl acetate were added to a dispersion reactor and vigorously stirred to disperse them evenly. The temperature was then raised and kept constant at the reaction temperature. The mixture was stirred at a uniform speed and kept under reflux. A silane coupling agent containing isocyanate groups was added. After the reaction was complete, hydrogenated rosin alcohol was added. The mixture was stirred until the reaction was complete. The mixture was then cooled to room temperature and centrifuged. The separated solid was washed and dried to obtain modified nano-calcium carbonate. The particle size of the nano-calcium carbonate is 40 nm; The dried nano-calcium carbonate was specifically dried at 105°C for 17 hours. The isocyanate-containing silane coupling agent is 3-isocyanate-propyltrimethoxysilane; The mass ratio of the nano-calcium carbonate, polyethylene glycol dioleate, ethyl acetate, isocyanate-containing silane coupling agent, and hydrogenated rosin alcohol is 100:7:550:11:45. The high-intensity stirring and dispersion is carried out at a stirring and dispersion rate of 11,000 rpm for 11 hours. The reaction temperature is 58°C; The uniform stirring speed is 1800 rpm; The reaction time is 11 hours after the reaction is complete. The reaction time is 13 hours until the reaction is complete. The washing process involves washing four times with anhydrous ethanol, with the mass of anhydrous ethanol used in each wash being equal to the mass of the solid being washed. The drying process was carried out at a temperature of 66°C for 22 hours.

[0016] Step 3: Preparation of reactive tackifier Hydroxyl-terminated vinyl silicone oil, α-diimide nickel, and acetone were placed in a reaction vessel and stirred until completely dissolved. The mixture was stirred at a constant speed and kept under reflux, and the temperature was raised to the reaction temperature. Then, unsaturated amide was added, and the mixture was stirred at a constant temperature until the reaction was complete. The mixture was then transferred to a rotary evaporator and vacuum evaporated to remove acetone, resulting in a viscous reactive thickener. The hydroxyl-terminated vinyl silicone oil has a hydroxyl content of 5 wt%, a vinyl content of 6 wt%, and a viscosity of 80 mPa·s at 25°C. The unsaturated amide is fumarate; The mass ratio of the hydroxyl-terminated vinyl silicone oil, α-diimide nickel, acetone, and unsaturated amide is 70:0.7:430:23. The uniform stirring speed is 1100 rpm; The reaction temperature is 60°C; After the constant temperature stirring reaction is complete, the reaction time is 11 hours; The vacuum rotary evaporation was carried out under the following conditions: a vacuum negative pressure of -99 kPa, a rotary evaporation speed of 85 rpm, a rotary evaporation time of 9 hours, and a rotary evaporation temperature of 50°C.

[0017] Step 4: Mixing and preparing adhesive According to the specific formula of the de-alcoholized environmentally friendly anti-mildew beauty adhesive for home decoration, α,ω-dihydroxypolydimethylsiloxane, modified nano calcium carbonate, hydrophobic fumed silica, dimethyl silicone oil, and methyltriethoxysilane are placed in a dry double planetary mixer and stirred and dispersed under vacuum for 13 hours. Then, modified composite inorganic anti-mildew agent, tetrabutyl titanate, co-catalyst, and reactive tackifier are added. After stirring and dispersing for another 11 hours, a viscous adhesive is obtained. After continuous vacuum degassing, the adhesive is discharged and the bubble-free adhesive is filled into a dry packaging container, protected with nitrogen and sealed to obtain the de-alcoholized environmentally friendly anti-mildew beauty adhesive for home decoration. The specific formula of the de-alcoholized environmentally friendly anti-mildew beauty adhesive for home decoration is as follows, by weight: 430 parts α,ω-dihydroxypolydimethylsiloxane, 40 parts modified composite inorganic anti-mildew agent, 95 parts modified nano calcium carbonate, 2 parts hydrophobic fumed silica, 15 parts reactive tackifier, 80 parts dimethyl silicone oil, 2 parts tetrabutyl titanate, 5 parts co-catalyst, and 35 parts methyltriethoxysilane. The average particle size of the hydrophobic fumed silica is 50 nm. The cocatalyst is N,N-disilyl-silaneamine; The stirring and dispersion is carried out under vacuum negative pressure, with a negative pressure of -99 kPa, a stirring rate of 250 rpm, and a dispersion rate of 13000 rpm.

[0018] Example 2: A method for preparing a de-alcoholized, environmentally friendly, mildew-resistant cosmetic adhesive for home decoration. Step 1: Preparation of modified composite inorganic antifungal agent After the composite inorganic antifungal agent is thoroughly dried, it is added to a dispersion reactor along with polyethylene glycol dioleate and methyl ethyl ketone. After being vigorously stirred and dispersed evenly, the temperature is raised and kept constant to the reaction temperature. Under the condition of uniform stirring and reflux, an amino-containing silane coupling agent is added. After the reaction is complete, terminal epoxy silicone oil is added, and stirring is continued until the reaction is complete. After cooling to room temperature, the mixture is centrifuged and separated. The separated solid is then washed and dried to obtain the modified composite inorganic antifungal agent. The composite inorganic antifungal agent is a mixture of nano-zirconium phosphate loaded with copper, nano-zirconium phosphate loaded with silver, nano-zirconium oxide, and nano-zinc borate. The composite inorganic antifungal agent is thoroughly dried at a temperature of 80°C for 15 hours. The copper-loaded zirconium phosphate nanoparticles have a particle size of 10 nm. The particle size of the silver-loaded zirconium phosphate nanoparticles is 10 nm. The particle size of the nano zinc oxide is 10 nm; The particle size of the nano zinc borate is 10 nm; The mass ratio of the nano-zirconium phosphate loaded with copper, the nano-zirconium phosphate loaded with silver, the nano-zirconium oxide, and the nano-zinc borate is 6:1:40:20. The amine-containing silane coupling agent is γ-aminopropyltrimethoxysilane; The epoxy value of the terminal epoxy silicone oil is 0.3, and the viscosity at 25°C is 50 mPa·s. The mass ratio of the composite inorganic antifungal agent, polyethylene glycol dioleate, methyl ethyl ketone, amine-containing silane coupling agent, and terminal epoxy silicone oil is 80:4:240:8:20. The high-intensity stirring and dispersion is carried out at a stirring and dispersion rate of 8000 rpm for 5 hours. The reaction temperature is 60°C; The uniform stirring speed is 1000 rpm; The reaction time is 6 hours after the reaction is complete. The reaction time is 8 hours until the reaction is complete; The washing process involves washing three times with anhydrous ethanol, with the mass of anhydrous ethanol used in each wash being equal to the mass of the solid being washed. The drying process involves a drying temperature of 60°C and a drying time of 12 hours.

[0019] Step 2: Preparation of modified nano-calcium carbonate The dried nano-calcium carbonate, polyethylene glycol dioleate, and ethyl acetate were added to a dispersion reactor and vigorously stirred to disperse them evenly. The temperature was then raised and kept constant at the reaction temperature. The mixture was stirred at a uniform speed and kept under reflux. A silane coupling agent containing isocyanate groups was added. After the reaction was complete, hydrogenated rosin alcohol was added. The mixture was stirred until the reaction was complete. The mixture was then cooled to room temperature and centrifuged. The separated solid was washed and dried to obtain modified nano-calcium carbonate. The particle size of the nano-calcium carbonate is 10 nm; The dried nano-calcium carbonate was specifically dried at 90°C for 10 hours. The isocyanate-containing silane coupling agent is 3-isocyanate-propyltriethoxysilane; The mass ratio of the nano-calcium carbonate, polyethylene glycol dioleate, ethyl acetate, isocyanate-containing silane coupling agent, and hydrogenated rosin alcohol is 60:4:340:6:20. The high-intensity stirring and dispersion is carried out at a stirring and dispersion rate of 9000 rpm for 6 hours. The reaction temperature is 50°C; The uniform stirring speed is 1300 rpm; The reaction time is 8 hours after the reaction is complete. The reaction time is 9 hours until the reaction is complete; The washing process involves washing three times with anhydrous ethanol, with the mass of anhydrous ethanol used in each wash being equal to the mass of the solid being washed. The drying process involves a drying temperature of 60°C and a drying time of 12 hours.

[0020] Step 3: Preparation of reactive tackifier Hydroxyl-terminated vinyl silicone oil, α-diimide nickel, and acetone were placed in a reaction vessel and stirred until completely dissolved. The mixture was stirred at a constant speed and kept under reflux, and the temperature was raised to the reaction temperature. Then, unsaturated amide was added, and the mixture was stirred at a constant temperature until the reaction was complete. The mixture was then transferred to a rotary evaporator and vacuum evaporated to remove acetone, resulting in a viscous reactive thickener. The hydroxyl-terminated vinyl silicone oil has a hydroxyl content of 3 wt%, a vinyl content of 4 wt%, and a viscosity of 10 mPa·s at 25°C. The unsaturated amide is crotonamide; The mass ratio of the hydroxyl-terminated vinyl silicone oil, α-diimide nickel, acetone, and unsaturated amide is 40:0.5:260:10. The uniform stirring speed is 800 rpm; The reaction temperature is 50°C; After the constant temperature stirring reaction is complete, the reaction time is 9 hours; The vacuum rotary evaporation was carried out under the following conditions: a vacuum negative pressure of -100 kPa, a rotary evaporation speed of 60 rpm, a rotary evaporation time of 5 hours, and a rotary evaporation temperature of 40°C.

[0021] Step 4: Mixing and preparing adhesive According to the specific formula of the de-alcoholized environmentally friendly anti-mildew beauty adhesive for home decoration, α,ω-dihydroxypolydimethylsiloxane, modified nano calcium carbonate, hydrophobic fumed silica, dimethyl silicone oil, and methyltriethoxysilane are placed in a dry double planetary mixer and stirred and dispersed under vacuum for 10 hours. Then, modified composite inorganic anti-mildew agent, tetrabutyl titanate, co-catalyst, and reactive tackifier are added. After stirring and dispersing for another 8 hours, a viscous adhesive is obtained. After continuous vacuum degassing, the adhesive is discharged and the bubble-free adhesive is filled into a dry packaging container, protected with nitrogen and sealed to obtain the de-alcoholized environmentally friendly anti-mildew beauty adhesive for home decoration. The specific formula of the home decoration de-alcoholized environmentally friendly anti-mildew beauty adhesive is as follows, by weight: 330 parts α,ω-dihydroxypolydimethylsiloxane, 25 parts modified composite inorganic anti-mildew agent, 65 parts modified nano calcium carbonate, 1 part hydrophobic fumed silica, 8 parts reactive tackifier, 60 parts dimethyl silicone oil, 1 part tetrabutyl titanate, 2 parts co-catalyst, and 20 parts methyltriethoxysilane. The average particle size of the hydrophobic fumed silica is 5 nm. The co-catalyst is bis(trimethylsilylmethyl)amine; The stirring and dispersion are carried out under vacuum negative pressure, with a negative pressure of -100 kPa, a stirring rate of 150 rpm, and a dispersion rate of 8000 rpm.

[0022] Example 3: A method for preparing a de-alcoholized, environmentally friendly, mildew-resistant cosmetic adhesive for home decoration. Step 1: Preparation of modified composite inorganic antifungal agent After the composite inorganic antifungal agent is thoroughly dried, it is added to a dispersion reactor along with polyethylene glycol dioleate and methyl ethyl ketone. After being vigorously stirred and dispersed evenly, the temperature is raised and kept constant to the reaction temperature. Under the condition of uniform stirring and reflux, an amino-containing silane coupling agent is added. After the reaction is complete, terminal epoxy silicone oil is added, and stirring is continued until the reaction is complete. After cooling to room temperature, the mixture is centrifuged and separated. The separated solid is then washed and dried to obtain the modified composite inorganic antifungal agent. The composite inorganic antifungal agent is a mixture of nano-zirconium phosphate loaded with copper, nano-zirconium phosphate loaded with silver, nano-zirconium oxide, and nano-zinc borate. The composite inorganic antifungal agent was thoroughly dried at a temperature of 95°C for 26 hours. The copper-loaded zirconium phosphate nanoparticles have a particle size of 100 nm. The particle size of the silver-loaded zirconium phosphate nanoparticles is 100 nm. The particle size of the nano zinc oxide is 100 nm; The particle size of the nano zinc borate is 100 nm; The mass ratio of the nano-zirconium phosphate loaded with copper, the nano-zirconium phosphate loaded with silver, the nano-zirconium oxide, and the nano-zinc borate is 19:4:90:70. The amine-containing silane coupling agent is N,N-diethyl-3-aminopropyltrimethoxysilane; The epoxy value of the terminal epoxy silicone oil is 1.1, and the viscosity at 25°C is 900 mPa·s. The mass ratio of the composite inorganic antifungal agent, polyethylene glycol dioleate, methyl ethyl ketone, amine-containing silane coupling agent, and terminal epoxy silicone oil is 200:12:900:30:80. The high-intensity stirring and dispersion is carried out at a stirring and dispersion rate of 13,000 rpm for 10 hours. The reaction temperature is 75°C; The uniform stirring is carried out at a stirring speed of 2000 rpm. The reaction time is 10 hours after the reaction is complete. The reaction time is 13 hours until the reaction is complete. The washing process involves washing five times with anhydrous ethanol, with the mass of anhydrous ethanol used in each wash being equal to the mass of the solid being washed. The drying process involves a drying temperature of 80°C and a drying time of 20 hours.

[0023] Step 2: Preparation of modified nano-calcium carbonate The dried nano-calcium carbonate, polyethylene glycol dioleate, and ethyl acetate were added to a dispersion reactor and vigorously stirred to disperse them evenly. The temperature was then raised and kept constant at the reaction temperature. The mixture was stirred at a uniform speed and kept under reflux. A silane coupling agent containing isocyanate groups was added. After the reaction was complete, hydrogenated rosin alcohol was added. The mixture was stirred until the reaction was complete. The mixture was then cooled to room temperature and centrifuged. The separated solid was washed and dried to obtain modified nano-calcium carbonate. The particle size of the nano-calcium carbonate is 100 nm; The dried nano-calcium carbonate was specifically dried at 110°C for 20 hours. The isocyanate-containing silane coupling agent is 3-isocyanate-propyltriethoxysilane; The mass ratio of the nano-calcium carbonate, polyethylene glycol dioleate, ethyl acetate, isocyanate-containing silane coupling agent, and hydrogenated rosin alcohol is 130:10:800:15:60. The high-intensity stirring and dispersion is carried out at a stirring and dispersion rate of 15,000 rpm for 13 hours. The reaction temperature is 70°C; The uniform stirring is carried out at a speed of 2500 rpm. The reaction time is 12 hours after the reaction is complete. The reaction time is 14 hours until the reaction is complete. The washing process involves washing five times with anhydrous ethanol, with the mass of anhydrous ethanol used in each wash being equal to the mass of the solid being washed. The drying process involves a drying temperature of 80°C and a drying time of 24 hours.

[0024] Step 3: Preparation of reactive tackifier Hydroxyl-terminated vinyl silicone oil, α-diimide nickel, and acetone were placed in a reaction vessel and stirred until completely dissolved. The mixture was stirred at a constant speed and kept under reflux, and the temperature was raised to the reaction temperature. Then, unsaturated amide was added, and the mixture was stirred at a constant temperature until the reaction was complete. The mixture was then transferred to a rotary evaporator and vacuum evaporated to remove acetone, resulting in a viscous reactive thickener. The hydroxyl-terminated vinyl silicone oil has a hydroxyl content of 7 wt%, a vinyl content of 8 wt%, and a viscosity of 120 mPa·s at 25°C. The unsaturated amide is hydroxymethylacrylamide; The mass ratio of the hydroxyl-terminated vinyl silicone oil, α-diimide nickel, acetone, and unsaturated amide is 100:1:600:30; The uniform stirring speed is 1300 rpm; The reaction temperature is 65°C; After the constant temperature stirring reaction is complete, the reaction time is 15 hours; The vacuum rotary evaporation was carried out under the following conditions: vacuum negative pressure of -96 kPa, rotary evaporation speed of 95 rpm, rotary evaporation time of 11 hours, and rotary evaporation temperature of 55°C.

[0025] Step 4: Mixing and preparing adhesive According to the specific formula of the de-alcoholized environmentally friendly anti-mildew beauty adhesive for home decoration, α,ω-dihydroxypolydimethylsiloxane, modified nano calcium carbonate, hydrophobic fumed silica, dimethyl silicone oil, and methyltriethoxysilane are placed in a dry double planetary mixer and stirred and dispersed under vacuum for 15 hours. Then, modified composite inorganic anti-mildew agent, tetrabutyl titanate, co-catalyst, and reactive tackifier are added. After stirring and dispersing for another 13 hours, a viscous adhesive is obtained. After continuous vacuum degassing, the adhesive is discharged and the bubble-free adhesive is filled into a dry packaging container, protected with nitrogen and sealed to obtain the de-alcoholized environmentally friendly anti-mildew beauty adhesive for home decoration. The specific formula of the de-alcoholized environmentally friendly anti-mildew beauty adhesive for home decoration is as follows, by weight: 500 parts α,ω-dihydroxypolydimethylsiloxane, 65 parts modified composite inorganic anti-mildew agent, 120 parts modified nano calcium carbonate, 8 parts hydrophobic fumed silica, 25 parts reactive tackifier, 100 parts dimethyl silicone oil, 2.5 parts tetrabutyl titanate, 6 parts co-catalyst, and 60 parts methyltriethoxysilane; The average particle size of the hydrophobic fumed silica is 100 nm. The cocatalyst is 3-dimethylaminoethylsilane; The stirring and dispersion is carried out under vacuum negative pressure, with a negative pressure of -98 kPa, a stirring rate of 400 rpm, and a dispersion rate of 14,000 rpm.

[0026] Example 4: Preparation method of a de-alcoholized environmentally friendly anti-mildew cosmetic adhesive for home decoration Step 1: Preparation of modified composite inorganic antifungal agent The amine-containing silane coupling agent is N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane; Other operations are the same as in Example 1.

[0027] Step 2 is the same as in Example 1.

[0028] Step 3: Preparation of reactive tackifier The unsaturated amide is N-hydroxymethylmethacrylamide; Other operations are the same as in Example 1.

[0029] Step 4: Mixing and preparing adhesive The co-catalyst is diisopropylamine silane; Other operations are the same as in Example 1.

[0030] Example 5: A method for preparing a de-alcoholized, environmentally friendly, mildew-resistant cosmetic adhesive for home decoration. Step 1: Preparation of modified composite inorganic antifungal agent The amine-containing silane coupling agent is γ-diethylaminomethyltriethoxysilane; Other operations are the same as in Example 1.

[0031] Step 2 is the same as in Example 1.

[0032] Step 3: Preparation of reactive tackifier The unsaturated amide is N-(3-hydroxypropyl)acrylamide; Other operations are the same as in Example 1.

[0033] Step 4: Mixing and preparing adhesive The co-catalyst is bis(methyldiethoxysilylpropyl)amine; Other operations are the same as in Example 1.

[0034] Example 6: A method for preparing a de-alcoholized, environmentally friendly, mildew-resistant cosmetic adhesive for home decoration. Step 1: Preparation of modified composite inorganic antifungal agent The amine-containing silane coupling agent is 4-amino-3,3-dimethylbutyltrimethoxysilane; Other operations are the same as in Example 1.

[0035] Steps 2 and 3 are the same as in Example 1.

[0036] Step 4: Mixing and preparing adhesive The cocatalyst is 3-(4-ureaamino)propyltriethoxysilane; Other operations are the same as in Example 1.

[0037] Example 7: A method for preparing a de-alcoholized, environmentally friendly, mildew-resistant cosmetic adhesive for home decoration. Step 1: Preparation of modified composite inorganic antifungal agent The amine-containing silane coupling agent is 3-(2-aminoethyl)-aminopropyltriethoxysilane; Other operations are the same as in Example 1.

[0038] Steps 2 and 3 are the same as in Example 1.

[0039] Step 4: Mixing and preparing adhesive The cocatalyst is O-(trimethylsilyl)hydroxylamine; Other operations are the same as in Example 1.

[0040] Example 8: A method for preparing a de-alcoholized, environmentally friendly, mildew-resistant cosmetic adhesive for home decoration. Steps 1, 2, and 3 are the same as in Example 1.

[0041] Step 4: Mixing and preparing adhesive The co-catalyst is tris(trimethylsilyl)amine; Other operations are the same as in Example 1.

[0042] Example 9: A method for preparing a de-alcoholized, environmentally friendly, mildew-resistant cosmetic adhesive for home decoration. Steps 1, 2, and 3 are the same as in Example 1.

[0043] Step 4: Mixing and preparing adhesive The co-catalyst is bis[3-(triethoxysilyl)propyl]amine; Other operations are the same as in Example 1.

[0044] Example 10: A method for preparing a de-alcoholized, environmentally friendly, mildew-resistant cosmetic adhesive for home decoration. Steps 1, 2, and 3 are the same as in Example 1.

[0045] Step 4: Mixing and preparing adhesive The cocatalyst is 3-aminopropyltrimethylsilane; Other operations are the same as in Example 1.

[0046] Example 11: Preparation method of a de-alcoholized environmentally friendly anti-mildew cosmetic adhesive for home decoration Steps 1, 2, and 3 are the same as in Example 1.

[0047] Step 4: Mixing and preparing adhesive The co-catalyst is bis(tert-butylamino)silane; Other operations are the same as in Example 1.

[0048] Example 12: Preparation method of a de-alcoholized environmentally friendly anti-mildew cosmetic adhesive for home decoration Steps 1, 2, and 3 are the same as in Example 1.

[0049] Step 4: Mixing and preparing adhesive The co-catalyst is dimethylsilyldiethylamine; Other operations are the same as in Example 1.

[0050] Example 13: Preparation method of a de-alcoholized environmentally friendly anti-mildew cosmetic adhesive for home decoration Steps 1, 2, and 3 are the same as in Example 1.

[0051] Step 4: Mixing and preparing adhesive The cocatalyst is tris(diethylamino)silane; Other operations are the same as in Example 1.

[0052] Comparative Example 1: Based on Example 1, step 1, the preparation of the modified composite inorganic mildew inhibitor, was omitted. In step 4, the mixing and adhesive preparation, 40 parts of the modified composite inorganic mildew inhibitor were replaced with 40 parts of a composite inorganic mildew inhibitor. The specific operation is as follows: Step 1, the preparation of the modified composite inorganic antifungal agent, is not performed; Steps 2 and 3 are the same as in Example 1; Step 4: Mixing and preparing adhesive Based on Example 1, 40 parts of modified composite inorganic antifungal agent were replaced with 40 parts of composite inorganic antifungal agent in equal amounts, and other operations were the same as in Example 1; The composite inorganic antifungal agent is a mixture of nano-zirconium phosphate loaded with copper, nano-zirconium phosphate loaded with silver, nano-zirconium oxide, and nano-zinc borate. The mass ratio of the nano-zirconium phosphate loaded with copper, the nano-zirconium phosphate loaded with silver, the nano-zinc oxide, and the nano-zinc borate is 11:3:60:50.

[0053] Comparative Example 2: Based on Example 1, in step 1, the preparation of the modified composite inorganic antifungal agent, no terminal epoxy-based silicone oil was added; only an amine-containing silane coupling agent was added for modification. The specific operation is as follows: Step 1: Preparation of modified composite inorganic antifungal agent After the composite inorganic antifungal agent is thoroughly dried, it is added to a dispersion reaction vessel along with polyethylene glycol dioleate and methyl ethyl ketone. After being vigorously stirred and dispersed evenly, the temperature is raised and kept constant to the reaction temperature. While stirring at a uniform speed and maintaining a reflux state, an amine-containing silane coupling agent is added. After the reaction is complete, the temperature is lowered to room temperature and centrifuged. The separated solid is then washed and dried to obtain the modified composite inorganic antifungal agent. Other operations are the same as in Example 1; Steps 2, 3, and 4 are the same as in Example 1.

[0054] Comparative Example 3: Based on Example 1, in step 2, the preparation of modified nano-calcium carbonate, hydrogenated rosin alcohol was not added; instead, a silane coupling agent containing isocyanate groups was added for modification. The specific operation is as follows: Step 1 is the same as in Example 1; Step 2: Preparation of modified nano-calcium carbonate The dried nano-calcium carbonate, polyethylene glycol dioleate, and ethyl acetate were added to a dispersion reactor and stirred vigorously to disperse them evenly. The mixture was then heated and kept at the reaction temperature. The mixture was stirred at a constant speed and kept under reflux. A silane coupling agent containing isocyanate groups was added. After the reaction was complete, the mixture was cooled to room temperature and centrifuged. The separated solid was then washed and dried to obtain modified nano-calcium carbonate. Other operations are the same as in Example 1; Steps 3 and 4 are the same as in Example 1.

[0055] Comparative Example 4: Based on Example 1, step 3, the preparation of the reactive tackifier, was omitted. In step 4, the mixing and adhesive preparation, 15 parts of the reactive tackifier were replaced with 15 parts of α,ω-dihydroxypolydimethylsiloxane. The specific operation is as follows: Steps 1 and 2 are the same as in Example 1; Step 3, the preparation of reactive thickeners, is not performed; Step 4: Mixing and preparing adhesive Replace 15 parts of reactive tackifier with 15 parts of α,ω-dihydroxypolydimethylsiloxane, and perform the other operations as in Example 1.

[0056] Comparative Example 5: Based on Example 1, in step 4, mixing and preparing the adhesive, no co-catalyst was added. Instead, 5 parts of the co-catalyst were replaced with 5 parts of α,ω-dihydroxypolydimethylsiloxane. The specific operation is as follows: Steps 1, 2, and 3 are the same as in Example 1; Step 4: Mixing and preparing adhesive Replace 5 parts of the co-catalyst with 5 parts of α,ω-dihydroxypolydimethylsiloxane, and perform the other operations as in Example 1.

[0057] Performance testing: For the environmentally friendly anti-mildew cosmetic adhesives for home decoration obtained in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 and Comparative Examples 1, 2, 3, 4, 5, the surface drying time, 24-hour curing depth, bond strength, tensile strength, shear strength, Shore hardness, and elongation at break were tested according to GB / T13477.3-2017, GB / T11211-2009, GB / T528-2009, and GB / T531.1-2008. The anti-mildew rating was tested at 30°C and 60% relative humidity according to JC / T885-2016 and GB / T 1741-2020. The specific test results are shown in Table 1: Table 1

[0058] As shown in Table 1, the surface drying time of Examples 1-13 was within 15 minutes, the curing depth after 24 hours was above 5.6 mm, the bond strength was greater than 3.5 MPa, and the measured values ​​of tensile strength, shear strength, elongation at break, and Shore hardness were all relatively high. The anti-mold rating was 0 throughout the 360-day testing period. This indicates that the anti-mold cosmetic adhesive prepared by this invention has the advantages of fast deep curing rate, high bond strength, high crosslinking strength, and good mechanical properties. Furthermore, the anti-mold agents incorporated into the cosmetic adhesive formulation of this invention are all inorganic anti-mold agents. Therefore, the de-alcoholized cosmetic adhesive obtained by this invention has long-lasting anti-mold efficacy and is environmentally friendly and safe. In Comparative Example 1, a composite inorganic anti-mold agent, namely inorganic anti-mold agent sodium, was directly added. Without surface modification, the surface drying time of the rice powder in the comparative example increased to 36 minutes, and the curing depth after 24 hours decreased to 1.4 mm. Mechanical properties such as bond strength, tensile strength, shear strength, elongation at break, and Shore hardness all decreased drastically, and the anti-mold rating also dropped significantly. This indicates that inorganic anti-mold agents without surface modification are very prone to agglomeration, and excessively large agglomerated particles significantly affect the curing and mechanical properties of the colloid, making it difficult to exert anti-mold effects. In Comparative Example 2, the inorganic anti-mold agent was modified only with an amine-containing silane coupling agent without further surface coating with terminal epoxy-based silicone oil. Compared to Comparative Example 1, Comparative Example 2 had a relatively shorter surface drying time of 22 minutes and a greater curing depth after 24 hours. The thickness reached 3.7 mm. Mechanical properties such as bond strength, tensile strength, shear strength, elongation at break, and Shore hardness were significantly better than in Comparative Example 1, but still much lower than in Example 1. This indicates that the inorganic antifungal agent, modified only with an amine-containing silane coupling agent, still has relatively strong polarity when its surface is ultimately covered with amine groups. This presents a certain obstacle to its compatibility with the siloxane-based cosmetic adhesive formulation, resulting in a less than ideal dispersion effect. Test data shows that the performance indicators of Comparative Example 2 are significantly worse than those of Example 1. This strongly suggests that modification with an amine-containing silane coupling agent followed by surface coating with terminal epoxy-based silicone oil is highly effective in promoting the uniform dispersion of the inorganic antifungal agent. Furthermore, Comparative Example 2... Compared to Example 1, the anti-mildew performance of Comparative Example 2 was significantly reduced, indicating that the dispersion uniformity of the inorganic anti-mildew agent in Comparative Example 2 was significantly worse than that in Example 1. In the preparation of modified nano-calcium carbonate, Comparative Example 3 did not add hydrogenated rosin alcohol, but only added a silane coupling agent containing isocyanate groups for modification. Compared with Example 1, the surface drying time of Comparative Example 3 was slightly prolonged, and the curing depth after 24 hours was almost unchanged. However, the mechanical properties of Comparative Example 3, such as adhesive strength, tensile strength, shear strength, and elongation at break, were significantly reduced, while the Shore hardness did not change much. This indicates that after the surface of the modified nano-calcium carbonate is coated with hydrogenated rosin alcohol, the mechanical properties of the cosmetic adhesive can be effectively improved, especially the adhesive strength. The adhesive strength of Comparative Example 3 decreased to 2.The pressure of the anti-mold agent in Comparative Example 3 was 1 MPa, much lower than that in Example 1. Furthermore, the anti-mold rating of Comparative Example 3 decreased from level 0 to level 1 after 360 days. This may be due to the relatively strong anti-mold properties of the hydrogenated rosin alcohol structure and the relatively large amount of nano-calcium carbonate added, resulting in the hydrogenated rosin alcohol-coated nano-calcium carbonate contributing significantly to the anti-mold performance. In Comparative Example 4, no reactive tackifier was prepared, and no reactive tackifier was added to the colloid formulation. The surface drying time of Comparative Example 4 remained unchanged, but the curing depth after 24 hours significantly decreased to 3.2 mm. The bond strength dropped drastically, as low as 2.0 MPa. Tensile strength, shear strength, and Shore hardness also decreased to varying degrees. The anti-mold rating also decreased significantly after 360 days. This indicates that the reactive tackifier plays a crucial role in improving the bond strength and deep curing speed of the cosmetic adhesive. This may be because the reactive tackifier has many amides containing amino and hydroxyl polar groups grafted onto its side chains. These groups can significantly improve the bond strength and deep curing speed of the adhesive. High application rates of the adhesive significantly improve its wettability and adhesion to the substrate, thus greatly enhancing bond strength. The amino groups within the adhesive strongly catalyze cross-linking and curing, allowing reactive tackifiers to accelerate deep curing and increase cross-linking density. This increased density significantly improves the overall water and moisture resistance of the cured adhesive, contributing to its anti-mold properties. Comparative Example 5, without a co-catalyst in its formulation, showed an increased surface drying time of 27 minutes and a decreased curing depth to 2.0 mm after 24 hours. Mechanical properties such as bond strength, tensile strength, shear strength, elongation at break, and Shore hardness also decreased to varying degrees. The anti-mold rating also dropped to level 1 after 360 days. This demonstrates that the co-catalyst plays a crucial role in accelerating surface drying time, increasing deep curing rate, and enhancing the overall mechanical and anti-mold properties of the cured adhesive.

[0059] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A method for preparing a de-alcoholized, environmentally friendly, mildew-resistant cosmetic adhesive for home decoration, characterized in that: The preparation method of the home decoration de-alcoholized environmentally friendly anti-mildew beauty adhesive includes four steps: preparation of modified composite inorganic anti-mildew agent, preparation of modified nano calcium carbonate, preparation of reactive tackifier, and mixing and adhesive preparation. The modified composite inorganic antifungal agent is prepared by adding the composite inorganic antifungal agent, polyethylene glycol dioleate, and methyl ethyl ketone into a dispersion reaction vessel, stirring vigorously to disperse evenly, adding an amine-containing silane coupling agent, and after the reaction is complete, adding terminal epoxy silicone oil, continuing the reaction until complete, and then centrifuging, washing, and drying to obtain the modified composite inorganic antifungal agent. The composite inorganic antifungal agent is a mixture of nano-zirconium phosphate loaded with copper, nano-zirconium phosphate loaded with silver, nano-zirconium oxide, and nano-zinc borate. The modified nano-calcium carbonate is prepared by adding dried nano-calcium carbonate, polyethylene glycol dioleate, and ethyl acetate into a dispersion reaction vessel, adding a silane coupling agent containing isocyanate groups, and then adding hydrogenated rosin alcohol. After the reaction is complete, the modified nano-calcium carbonate is obtained by centrifugation, washing, and drying. The reactive tackifier is prepared by dissolving hydroxyl-terminated vinyl silicone oil, α-diimide nickel, and acetone by stirring, then adding unsaturated amide, allowing the reaction to complete, and then vacuum rotary evaporating to obtain a viscous reactive tackifier. The unsaturated amide is one or more of fumarate, crotonamide, hydroxymethylacrylamide, N-hydroxymethylacrylamide, and N-(3-hydroxypropyl)acrylamide in any mass ratio.

2. The preparation method of the de-alcoholized environmentally friendly anti-mildew cosmetic adhesive for home decoration according to claim 1, characterized in that: The mixing and preparation of the adhesive involves uniformly dispersing α,ω-dihydroxypolydimethylsiloxane, modified nano-calcium carbonate, hydrophobic fumed silica, dimethyl silicone oil, and methyltriethoxysilane under vacuum negative pressure. Then, a modified composite inorganic antifungal agent, tetrabutyl titanate, a co-catalyst, and a reactive tackifier are added. After further stirring and uniform dispersion, the mixture is degassed and sealed to obtain a de-alcoholized environmentally friendly antifungal beauty adhesive for home decoration. The specific formula of the de-alcoholized environmentally friendly anti-mildew cosmetic adhesive for home decoration is as follows, by weight: 330-500 parts α,ω-dihydroxypolydimethylsiloxane, 25-65 parts modified composite inorganic anti-mildew agent, 65-120 parts modified nano calcium carbonate, 1-8 parts hydrophobic fumed silica, 8-25 parts reactive tackifier, 60-100 parts dimethyl silicone oil, 1-2.5 parts tetrabutyl titanate, 2-6 parts co-catalyst, and 20-60 parts methyltriethoxysilane; The cocatalyst is one or a mixture of two or more of N,N-disilyl-silaneamine, bis(trimethylsilylmethyl)amine, 3-dimethylaminoethylsilane, diisopropylamine silane, bis(methyldiethoxysilylpropyl)amine, 3-(4-ureaamino)propyltriethoxysilane, O-(trimethylsilyl)hydroxylamine, tri(trimethylsilyl)amine, bis[3-(triethoxysilyl)propyl]amine, 3-aminopropyltrimethylsilane, bis(tert-butylamino)silane, dimethylsilyldiethylamine, and tri(diethylamino)silane in any mass ratio.

3. The preparation method of the de-alcoholized environmentally friendly anti-mildew cosmetic adhesive for home decoration according to claim 1, characterized in that: The particle size of the copper-loaded zirconium phosphate nanoparticles is 10~100nm; The particle size of the nano-zirconium phosphate loaded with silver is 10~100nm; The particle size of the nano zinc oxide is 10~100nm; The particle size of the nano-zinc borate is 10~100nm; The mass ratio of the nano-zirconium phosphate loaded with copper, nano-zirconium phosphate loaded with silver, nano-zinc oxide, and nano-zinc borate is (6~19):(1~4):(40~90):(20~70).

4. The preparation method of the de-alcoholized environmentally friendly anti-mildew cosmetic adhesive for home decoration according to claim 1, characterized in that: The amine-containing silane coupling agent is one or a mixture of two or more of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N,N-diethyl-3-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-diethylaminomethyltriethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, and 3-(2-aminoethyl)-aminopropyltriethoxysilane in any mass ratio; The epoxy value of the terminal epoxy group silicone oil is 0.3~1.1, and the viscosity at 25°C is 50~900 mPa·s; The mass ratio of the composite inorganic antifungal agent, polyethylene glycol dioleate, methyl ethyl ketone, amine-containing silane coupling agent, and terminal epoxy silicone oil is (80~200):(4~12):(240~900):(8~30):(20~80).

5. The preparation method of the de-alcoholized environmentally friendly anti-mildew cosmetic adhesive for home decoration according to claim 1, characterized in that: The particle size of the nano-calcium carbonate is 10~100nm; The isocyanate-containing silane coupling agent is one of 3-isocyanate-propyltrimethoxysilane and 3-isocyanate-propyltriethoxysilane; The mass ratio of the nano-calcium carbonate, polyethylene glycol dioleate, ethyl acetate, silane coupling agent containing isocyanate groups, and hydrogenated rosin alcohol is (60~130):(4~10):(340~800):(6~15):(20~60).

6. The preparation method of the de-alcoholized environmentally friendly anti-mildew cosmetic adhesive for home decoration according to claim 1, characterized in that: The hydroxyl-terminated vinyl silicone oil has a hydroxyl content of 3-7 wt%, a vinyl content of 4-8 wt%, and a viscosity of 10-120 mPa·s at 25°C. The unsaturated amide is one or a mixture of two or more of fumarate, crotonamide, hydroxymethylacrylamide, N-hydroxymethylacrylamide, and N-(3-hydroxypropyl)acrylamide in any mass ratio; The mass ratio of the terminal hydroxyl vinyl silicone oil, α-diimide nickel, acetone, and unsaturated amide is (40~100):(0.5~1):(260~600):(10~30).

7. The preparation method of the de-alcoholized environmentally friendly anti-mildew cosmetic adhesive for home decoration according to claim 2, characterized in that: The average particle size of the hydrophobic fumed silica is 5~100nm; The stirring and dispersion under vacuum negative pressure is described, with a negative pressure of -100 to -98 kPa, a stirring rate of 150 to 400 rpm, and a dispersion rate of 8000 to 14000 rpm.

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