Method for preparing high-power mildew-proof dealcoholization type aesthetic edge-sealing adhesive

Abstract

The present invention belongs to the technical field of aesthetic edge-sealing adhesives. Disclosed is a method for preparing a high-power mildew-proof dealcoholization type aesthetic edge-sealing adhesive. The method comprises the preparation of an ultra-fine powder, the preparation of a multi-branched cross-linking accelerant, the preparation of an inorganic mixed mildew inhibitor, and material mixing, wherein the material mixing involves adding hydroxyl-terminated polydimethylsiloxane, dimethicone and the ultra-fine powder to a kneading machine for mixing, dehydration and cooling so as to obtain a base material, adding the obtained base material, the multi-branched cross-linking accelerant, methyltrimethoxysilane, dimethyldimethoxysilane, 3-aminopropyltriethoxysilane, the inorganic mixed mildew inhibitor and dibutyltin dilaurate to a high-speed stirrer, and carrying out high-speed stirring. The high-power mildew-proof dealcoholization type aesthetic edge-sealing adhesive prepared in the present invention has good mildew resistance, high tearing strength, and good oil resistance and puncture resistance, is not prone to generating an oily dialysate, and can also improve the adhesiveness, the deep curing speed and the elasticity of the high-power mildew-proof dealcoholization type aesthetic edge-sealing adhesive and reduce the dependence of the extrudability and thixotropy on temperature.

Description

Preparation method of high-mold-proof dealcoholization type beauty edge adhesive

[0001] This application claims priority to a Chinese patent application filed with the Patent Office of China on July 25, 2023, with application number 202310911995.6 and invention name “A method for preparing a high-fold anti-mildew dealcoholization type beauty edge glue”, the entire contents of which are incorporated herein by reference. Technical Field

[0002] The invention relates to the technical field of beautifying edge finishing adhesives, and in particular to a method for preparing a high-multiple mildew-proof dealcoholization type beautifying edge finishing adhesive. Background Art

[0003] Room temperature vulcanized silicone rubber has excellent electrical properties and chemical inertness, as well as heat resistance, aging resistance, flame resistance, moisture resistance, and breathability. Depending on the chain agent, room temperature vulcanized silicone rubber is divided into many types, such as deacidified type, defatized type, dealcoholized type, deamine type, and deketone type. Among them, dealcoholized room temperature vulcanized silicone rubber refers to a silicone rubber that will produce a dealcoholization reaction during the curing process, volatilizing alcohol substances. Through the dealcoholization reaction, the silicone rubber can be cured to achieve a good sealing effect.

[0004] Dealcoholized room temperature vulcanized silicone rubber was the type that was most researched by major companies in the world in the 1980s and saw the fastest growth in both variety and quantity. Currently, dealcoholized room temperature vulcanized silicone rubber has made great progress in vulcanization speed, storage stability, adhesion and flame retardancy, and has become the main variety and development direction of room temperature vulcanized silicone rubber. Its application range is also becoming increasingly wider, especially as a dealcoholized cosmetic edge finishing adhesive, its application in the construction field is rapidly expanding.

[0005] Compared with other beauty edge trimming adhesive products, dealcoholized beauty edge trimming adhesive has the advantages of strong adhesion, fast curing speed, good elasticity, low dependence of extrusion and thixotropy on temperature, good extrusion and thixotropy in the temperature range of -4°C to 40°C, and excellent aging resistance, UV resistance, and ozone resistance. However, the mildew resistance of dealcoholized beauty edge trimming adhesive is poor, which leads to the easy appearance of black spots and yellowing. In addition, the dealcoholized beauty edge trimming adhesive also has the disadvantages of low tear strength, poor oil resistance, and poor puncture resistance. In addition, since silicone oil needs to be added to the dealcoholized beauty edge trimming adhesive for lubrication, the silicone oil is easy to precipitate, resulting in the dealcoholized beauty edge trimming adhesive easily producing oily exudates after curing.

[0006] In order to overcome the above shortcomings, the most commonly used method at present is to add antifungal agents to the dealcoholized beauty edge finishing adhesive to improve the antifungal properties of the dealcoholized beauty edge finishing adhesive. In addition, modified fillers and cross-linking aids are added to increase the cross-linking density and convert dispersed cross-linking into concentrated cross-linking, thereby improving the tear strength, oil resistance, and puncture resistance of the dealcoholized beauty edge finishing adhesive, and can also avoid the production of oily exudates. However, on the one hand, the addition of antifungal agents will affect the adhesion of the beauty edge finishing adhesive. On the other hand, while increasing the cross-linking density, the time required for cross-linking will also be extended accordingly, resulting in a slower deep curing speed. In addition, it will also affect the elasticity of the dealcoholized beauty edge finishing adhesive, resulting in a greater dependence of extrudability and thixotropy on temperature.

[0007] Chinese patent CN113881393B discloses a silicone adhesive with anti-mildew properties, which is prepared using polydimethylsiloxane as a raw material. A composite anti-mildew agent is added during the preparation of the silicone adhesive with anti-mildew properties; the composite anti-mildew agent comprises nano-zinc oxide and camphor wood powder extract; wherein the weight ratio of the nano-zinc oxide to the camphor wood powder extract is 5-10:1. The prepared silicone adhesive with anti-mildew properties has an inhibitory effect not only on conventional molds and bacteria, but also on methicillin-resistant Staphylococcus aureus. However, the prepared silicone adhesive with anti-mildew properties has low tear strength, poor oil resistance, and is not puncture-resistant.

[0008] Chinese patent CN108676544B discloses a high-temperature resistant and mildew-proof silicone sealant and a preparation method thereof. The high-temperature resistant and mildew-proof silicone sealant comprises the following components, calculated by weight: 50-100 parts of α,ω-dihydroxy polysiloxane, 5-20 parts of reinforcing filler, 5-20 parts of methylphenyl silicone oil, 40-100 parts of high-temperature resistant filler, 0.05-0.2 parts of mildew inhibitor, 3-15 parts of cross-linking agent, 0.001-1 parts of catalyst, and 0.2-1 parts of coupling agent. The prepared high-temperature resistant and mildew-proof silicone sealant has good elasticity, high tensile strength and elongation at break, and excellent high-temperature resistance and moisture-heat resistance. However, the deep-layer curing speed is slow, and the extrudability and thixotropy are highly dependent on temperature.

[0009] Chinese patent CN103756630B discloses a one-component, mildew-proof, transparent, dealcoholized silicone sealant and a preparation method. The sealant is prepared by adding a mildew inhibitor to a transparent dealcoholized silicone sealant. The mildew inhibitor is an organic arsenic compound with a polyether polyol as a carrier, and the added mildew inhibitor is 0.1-2 parts by weight based on 100 parts of alkoxyalkyl-terminated polysiloxane. The prepared one-component, mildew-proof, transparent, dealcoholized silicone sealant has the advantages of excellent mildew resistance, low odor, yellowing resistance, and fast deep-cure. However, it has poor oil resistance and is not puncture-resistant.

[0010] Chinese patent CN111793463B discloses a method for preparing an antibacterial and mildew-proof silicone sealant and its product. The preparation method comprises: preparing quaternized polyethyleneimine; blending the silicone sealant and the quaternized polyethyleneimine, wherein the quaternized polyethyleneimine is added in an amount of 1-20 wt %. The prepared antibacterial and mildew-proof silicone sealant has good antibacterial and mildew-proof effects and high mechanical properties, but has weak adhesion and slow deep-layer curing speed.

[0011] Summary of the Invention

[0012] In response to the shortcomings of the existing technology, the present invention provides a method for preparing a high-fold mildew-proof dealcoholization type beauty edge finishing adhesive. The prepared high-fold mildew-proof dealcoholization type beauty edge finishing adhesive has good mildew resistance, high tear strength, good oil resistance and puncture resistance, and is not easy to produce oily exudates. At the same time, it can also improve the adhesion, deep curing speed and elasticity of the high-fold mildew-proof dealcoholization type beauty edge finishing adhesive, and reduce the dependence of extrusion and thixotropy on temperature.

[0013] In order to solve the above technical problems, the technical solutions adopted by the present invention are as follows:

[0014] A method for preparing a high-mold-proof dealcoholized beauty edge adhesive comprises the following steps: preparing ultrafine powder, preparing a multi-branched cross-linking agent, preparing an inorganic mixed mold inhibitor, and mixing the materials;

[0015] The method for preparing ultrafine powder comprises the following steps: adding ultrafine calcium carbonate and deionized water into a high-speed reaction kettle, performing high-speed stirring and ultrasonic oscillation simultaneously, controlling the stirring speed of the high-speed stirring to 800-1000 rpm and the frequency of the ultrasonic oscillation to 20-30 kHz, stopping the high-speed stirring and ultrasonic oscillation after 25-35 minutes, and obtaining an ultrafine calcium carbonate suspension; adding silver nitrate, deionized water, and polyvinylamine into the reaction kettle, controlling the temperature of the reaction kettle to 35-40° C. and the stirring speed to 200-300 rpm, stirring for 30-40 minutes, and then slowly adding the ultrafine calcium carbonate suspension, controlling the addition of the ultrafine calcium carbonate suspension to 100-200 rpm. The mixture was added at a speed of 18-22 g / min, and stirring was continued for 40-50 min after the addition was completed, and then carboxymethyl chitosan and β-glucan were added. While continuing to stir, ultraviolet light was irradiated, and the wavelength of the ultraviolet light was controlled to be 320-380 nm. After 4-5 h, the ultraviolet light irradiation was stopped, and the γ-polyglutamic acid aqueous solution was added, and stirred for 45-55 min. The carboxymethyl chitosan aqueous solution was added, and stirred for 1.5-2 h, and then centrifuged. The speed of the centrifugation was controlled to be 7000-8000 rpm, and the time was 8-10 min. After the centrifugation was completed, the precipitate was placed at 110-120 ° C and dried to obtain an ultrafine powder;

[0016] In the preparation of the ultrafine powder, the mass ratio of ultrafine calcium carbonate to deionized water in the ultrafine calcium carbonate suspension is 3-4:130-140;

[0017] The mass ratio of silver nitrate, deionized water, polyvinylamine, ultrafine calcium carbonate suspension, carboxymethyl chitosan, β-glucan, γ-polyglutamic acid aqueous solution, and carboxymethyl chitosan aqueous solution is 5-5.5:200-220:3-3.5:60-65:0.1-0.12:0.08-0.1:2-3:3-4;

[0018] The mass fraction of the γ-polyglutamic acid aqueous solution is 4-5%;

[0019] The mass fraction of the carboxymethyl chitosan aqueous solution is 3-4%;

[0020] The particle size of the ultrafine calcium carbonate is 0.05-0.08 μm;

[0021] The method for preparing a multi-branched cross-linking agent comprises adding rutile nano-titanium dioxide and deionized water into a closed reactor, controlling the temperature of the closed reactor to 30-35° C., controlling the stirring speed to 180-220 rpm, stirring for 30-40 minutes, adding 3-aminopropyltriethoxysilane and ammonia water, replacing the air in the closed reactor with nitrogen 2-3 times, heating the reactor to 40-45° C., keeping the temperature at 40-45° C. for 4-5 hours, filtering the reactor, washing the reactor with 30-40 mL of anhydrous ethanol and 30-40 mL of deionized water, and drying the reactor at 115-120° C. to obtain amino-titanium dioxide; adding tetrahydrofuran and butanetetracarboxylic acid; The mixture was placed in a closed reactor, the temperature of the closed reactor was controlled to 30-35° C., the stirring speed was controlled to 180-220 rpm, the air in the closed reactor was replaced with nitrogen 2-3 times, and then a tetrahydrofuran solution of N,N'-carbonyldiimidazole was added dropwise at a dropping speed of 3-4 g / min. After the addition was completed, stirring was continued for 4-4.5 hours. Then, amination titanium dioxide was added, and stirring was continued for 5-6 hours. Centrifugation was performed, and the speed of centrifugation was controlled to 7000-8000 rpm for 12-15 minutes. After the centrifugation was completed, the precipitate was washed 2-3 times with deionized water and dried at 110-120° C. to obtain a multi-branched cross-linking agent.

[0022] In the preparation of the multi-branched cross-linking agent, the mass ratio of rutile nano-titanium dioxide, deionized water, 3-aminopropyltriethoxysilane, and ammonia water is 5-5.3:400-410:10-10.5:2-2.5;

[0023] The mass ratio of tetrahydrofuran, butanetetracarboxylic acid, tetrahydrofuran solution of N,N'-carbonyldiimidazole, and amination titanium dioxide is 32-35:24-26:80-85:11-13;

[0024] The mass fraction of the tetrahydrofuran solution of N,N'-carbonyldiimidazole is 20-25%;

[0025] The particle size of the rutile nano-titanium dioxide is 50-90 nm;

[0026] The mass concentration of the ammonia water is 25-28%;

[0027] The inorganic mixed mildew preventer is prepared by mixing barium metaborate, sodium metaborate, and zinc oxide and then ball milling them, controlling the speed of the ball milling to be 300-400 rpm, the ball-to-material ratio to be 15-20:1, and the time to be 40-50 minutes, then adding 3-aminopropyltriethoxysilane, and continuing the ball milling for 1-1.5 hours to obtain the inorganic mixed mildew preventer;

[0028] In the preparation of the inorganic mixed mildew inhibitor, the mass ratio of barium metaborate, sodium metaborate, zinc oxide, and 3-aminopropyltriethoxysilane is 30-35:20-25:12-15:3-3.5;

[0029] The mixing step comprises adding hydroxyl-terminated polydimethylsiloxane, dimethyl silicone oil, and ultrafine powder into a kneader, mixing and dehydrating at 120-130° C. for 80-90 minutes, and cooling to room temperature to obtain a base material; adding the obtained base material, a multi-branched cross-linking agent, methyltrimethoxysilane, dimethyldimethoxysilane, 3-aminopropyltriethoxysilane, an inorganic mixed mildew inhibitor, and dibutyltin dilaurate into a high-speed mixer for high-speed stirring, controlling the vacuum degree of the high-speed stirring to 0.08-0.09 MPa and the rotation speed to 300-350 rpm, and stirring for 90-100 minutes to obtain a high-strength mildew-proof alcohol-based beauty edge adhesive;

[0030] In the mixture, the mass ratio of hydroxyl-terminated polydimethylsiloxane, dimethyl silicone oil, ultrafine powder, multi-branched cross-linking agent, methyltrimethoxysilane, dimethyldimethoxysilane, 3-aminopropyltriethoxysilane, inorganic mixed mildew inhibitor, and dibutyltin dilaurate is 140-145:14-16:20-22:13-15:6-7:2-3:6-7:1-1.2:0.4-0.5;

[0031] The viscosity of the hydroxyl-terminated polydimethylsiloxane at 25° C. is 50,000-100,000 mPa·s.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] (1) The method for preparing the high-anti-mildew dealcoholized beauty edge glue of the present invention can improve the mildew resistance of the prepared beauty edge glue by adding ultrafine powder to the mixture, and the mildew resistance grade of the prepared beauty edge glue is level 0;

[0034] (2) The preparation method of the high-mold-proof dealcoholized beauty edge glue of the present invention can improve the tear strength of the prepared beauty edge glue by adding ultrafine powder to the mixture. The tear strength of the prepared beauty edge glue is 46-48N / mm;

[0035] (3) The preparation method of the high-anti-mildew dealcoholization type beauty edge glue of the present invention can improve the puncture resistance of the prepared beauty edge glue by adding ultrafine powder to the mixture. The Shore A hardness of the prepared beauty edge glue is 46-49HA;

[0036] (4) The preparation method of the high-mold-proof dealcoholization type beauty edge adhesive of the present invention can improve the adhesion of the prepared beauty edge adhesive by adding a multi-branched cross-linking agent to the mixture. The 100% fixed elongation adhesion of the prepared beauty edge adhesive is not damaged, and the cold drawing and hot pressing ±50% adhesion is not damaged;

[0037] (5) The preparation method of the high-multiple mildew-proof dealcoholization type beauty edge glue of the present invention can improve the deep curing speed of the prepared beauty edge glue by adding a multi-branched cross-linking agent to the mixture. The curing depth of the prepared beauty edge glue is 3.2-3.4 mm after a curing time of 12 hours, and the curing depth is 4.5-4.8 mm after a curing time of 24 hours;

[0038] (6) The preparation method of the high-mold-proof dealcoholized beauty edge glue of the present invention can improve the elasticity of the prepared beauty edge glue by adding a multi-branched cross-linking agent to the mixture. The elastic recovery rate of the prepared beauty edge glue is 87-91%;

[0039] (7) The preparation method of the high-multiple mildew-proof dealcoholization type beauty edge glue of the present invention can improve the oil resistance of the prepared beauty edge glue by adding a multi-branched cross-linking agent to the mixture. The prepared beauty edge glue has a tensile strength of 3.1-3.4 MPa and an elongation at break of 527-535%. After being completely immersed in 10w-30 motor oil at 120°C for 7 days, the tensile strength is 3.1-3.3 MPa and the elongation at break is 522-531%;

[0040] (8) The method for preparing the high-multiple mildew-proof dealcoholization type beauty edge glue of the present invention is to add a multi-branched cross-linking agent to the mixture, so that the prepared beauty edge glue is not easy to produce oily dialysis products. After the prepared beauty edge glue is left to stand in an environment with a temperature of 40°C and a humidity of 60% for 100 days, no oily dialysis products are found on the surface;

[0041] (9) The preparation method of the high-multiple mildew-proof dealcoholization type beauty edge glue of the present invention can reduce the dependence of extrudability and thixotropy on temperature by adding ultrafine powder and multi-branched cross-linking agent to the mixture. The prepared beauty edge glue has an extrudability of 250-280 mL / min at -4°C, an extrudability of 260-280 mL / min at 23°C, and an extrudability of 260-280 mL / min at 40°C. The thixotropic index at -4°C is 5.0-5.2, the thixotropic index at 23°C is 5.1-5.4, and the thixotropic index at 40°C is 5.1-5.5. DETAILED DESCRIPTION

[0042] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

[0043] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

[0044] Example 1

[0045] A preparation method of a high-mold-proof dealcoholization type beauty edge adhesive, specifically comprising:

[0046] 1. Preparation of ultrafine powder: 3g ultrafine calcium carbonate and 130g deionized water were added to a high-speed reactor, and ultrasonic oscillation was performed while stirring at high speed. The stirring speed of the high-speed stirring was controlled to 800rpm and the frequency of the ultrasonic oscillation was 20kHz. After 25min, the high-speed stirring and ultrasonic oscillation were stopped to obtain an ultrafine calcium carbonate suspension. 5g silver nitrate, 200g deionized water and 3g polyvinylamine were added to the reactor, the temperature of the reactor was controlled to 35°C, the stirring speed was controlled to 200rpm, and after stirring for 30min, 60g ultrafine calcium carbonate suspension was slowly added, and the addition speed of the ultrafine calcium carbonate suspension was controlled to 100%. The mixture was stirred at a speed of 18 g / min, and stirring was continued for 40 min after the addition was completed. Then, 0.1 g of carboxymethyl chitosan and 0.08 g of β-glucan were added, and ultraviolet irradiation was performed while continuing to stir. The wavelength of the ultraviolet irradiation was controlled to be 320 nm. After 4 h, the ultraviolet irradiation was stopped, 2 g of a 4% aqueous solution of gamma-polyglutamic acid by mass was added, and stirring was continued for 45 min. 3 g of a 3% aqueous solution of carboxymethyl chitosan by mass was added, and stirring was continued for 1.5 h. The mixture was centrifuged, and the speed of the centrifugation was controlled to be 7000 rpm for 8 min. After the centrifugation was completed, the precipitate was dried at 110° C. to obtain an ultrafine powder.

[0047] The particle size of the ultrafine calcium carbonate is 0.05 μm;

[0048] 2. Preparation of a multi-branched cross-linking agent: 5 g of rutile nano-titanium dioxide and 400 g of deionized water were added to a closed reactor, the temperature of the closed reactor was controlled to 30 ° C, the stirring speed was controlled to 180 rpm, and after stirring for 30 min, 10 g of 3-aminopropyltriethoxysilane and 2 g of ammonia water were added. After replacing the air in the closed reactor with nitrogen twice, the temperature was raised to 40 ° C, kept at 40 ° C for 4 h, and then filtered. The mixture was washed with 30 mL of anhydrous ethanol and 30 mL of deionized water, respectively, and then dried at 115 ° C to obtain amino titanium dioxide; 32 g of tetrahydrofuran and 24 g of butanetetracarboxylic acid were added to a closed reactor, the temperature of the closed reactor was controlled to 30 ° C, the stirring speed was controlled to 180 rpm, and nitrogen was used. The air in the closed reactor was replaced twice, and then 80 g of a 20% by mass solution of N,N'-carbonyldiimidazole in tetrahydrofuran was added dropwise at a rate of 3 g / min. After the addition was completed, stirring was continued for 4 h. Then, 11 g of amino titanium dioxide was added, and stirring was continued for 5 h. The mixture was centrifuged at a speed of 7000 rpm for 12 min. After the centrifugation was completed, the precipitate was washed twice with deionized water and dried at 110°C to obtain a multi-branched cross-linking agent.

[0049] The particle size of the rutile nano-titanium dioxide is 50 nm;

[0050] The mass concentration of the ammonia water is 25%;

[0051] 3. Preparation of an inorganic mixed mildew inhibitor: 30 g of barium metaborate, 20 g of sodium metaborate, and 12 g of zinc oxide were mixed and ball-milled at a speed of 300 rpm, a ball-to-material ratio of 15:1, and a milling time of 40 min. Then, 3 g of 3-aminopropyltriethoxysilane was added and ball-milling was continued for 1 h to obtain an inorganic mixed mildew inhibitor.

[0052] 4. Mixing: Add 140g of hydroxyl-terminated polydimethylsiloxane, 14g of dimethyl silicone oil, and 20g of ultrafine powder to a kneader, mix and dehydrate at 120°C for 80min, and cool to room temperature to obtain a base material; add the obtained base material, 13g of a multi-branched cross-linking agent, 6g of methyltrimethoxysilane, 2g of dimethyldimethoxysilane, 6g of 3-aminopropyltriethoxysilane, 1g of an inorganic mixed mildew inhibitor, and 0.4g of dibutyltin dilaurate to a high-speed blender and stir at high speed. Control the vacuum degree of high-speed stirring at 0.08MPa and the speed at 300rpm. Stir for 90min to obtain a high-strength mildew-proof alcohol-based beauty edge adhesive;

[0053] The viscosity of the hydroxyl-terminated polydimethylsiloxane at 25° C. is 50,000 mPa·s.

[0054] Example 2

[0055] A preparation method of a high-mold-proof dealcoholization type beauty edge adhesive, specifically comprising:

[0056] 1. Preparation of ultrafine powder: 3.5 g ultrafine calcium carbonate and 135 g deionized water were added to a high-speed reactor, and ultrasonic oscillation was performed while stirring at high speed. The stirring speed of the high-speed stirring was controlled at 900 rpm and the frequency of the ultrasonic oscillation was 25 kHz. After 30 minutes, the high-speed stirring and ultrasonic oscillation were stopped to obtain an ultrafine calcium carbonate suspension. 5.2 g silver nitrate, 210 g deionized water, and 3.2 g polyvinylamine were added to the reactor. The temperature of the reactor was controlled to 38 ° C. The stirring speed was controlled to 250 rpm. After stirring for 35 minutes, 62 g ultrafine calcium carbonate suspension was slowly added. The addition speed of the ultrafine calcium carbonate suspension was controlled to 2. 0g / min, stirring was continued for 45min after the addition was completed, and then 0.11g carboxymethyl chitosan and 0.09g β-glucan were added, and ultraviolet irradiation was performed while continuing to stir, and the wavelength of the ultraviolet irradiation was controlled to be 350nm. After 4.5h, the ultraviolet irradiation was stopped, 2.5g of a 4.5% aqueous solution of gamma-polyglutamic acid by mass was added, and stirred for 50min. 3.5g of a 3.5% aqueous solution of carboxymethyl chitosan by mass was added, and stirred for 1.8h, and then centrifuged, and the speed during centrifugation was controlled to be 7500rpm for 9min. After the centrifugation was completed, the precipitate was placed at 115°C for drying to obtain an ultrafine powder;

[0057] The particle size of the ultrafine calcium carbonate is 0.06 μm;

[0058] 2. Preparation of a multi-branched cross-linking agent: 5.2 g of rutile nano-titanium dioxide and 405 g of deionized water were added to a closed reactor, the temperature of the closed reactor was controlled to 32 ° C, the stirring speed was controlled to 200 rpm, and after stirring for 35 min, 10.2 g of 3-aminopropyltriethoxysilane and 2.2 g of ammonia water were added, and the air in the closed reactor was replaced with nitrogen twice, and then the temperature was raised to 42 ° C, kept warm at 42 ° C for 4.5 h, and then filtered, and washed with 35 mL of anhydrous ethanol and 35 mL of deionized water, respectively, and then dried at 118 ° C to obtain amino titanium dioxide; 34 g of tetrahydrofuran and 25 g of butanetetracarboxylic acid were added to a closed reactor, the temperature of the closed reactor was controlled to 32 ° C, the stirring speed was controlled to 200 rpm, and nitrogen was used to replace the air in the closed reactor. The air in the closed reactor was replaced three times, and then 82 g of a 22% by mass solution of N,N'-carbonyldiimidazole in tetrahydrofuran was added dropwise at a rate of 3.5 g / min. After the addition was completed, stirring was continued for 4.2 h. Then, 12 g of amino titanium dioxide was added, and stirring was continued for 5.5 h. The mixture was centrifuged at a speed of 7500 rpm for 14 min. After the centrifugation was completed, the precipitate was washed twice with deionized water and dried at 115°C to obtain a multi-branched cross-linking agent.

[0059] The particle size of the rutile nano-titanium dioxide is 80 nm;

[0060] The mass concentration of the ammonia water is 26%;

[0061] 3. Preparation of an inorganic mixed mildew inhibitor: 32 g of barium metaborate, 22 g of sodium metaborate, and 14 g of zinc oxide were mixed and ball-milled at a speed of 350 rpm, a ball-to-material ratio of 18:1, and a milling time of 45 min. Then, 3.2 g of 3-aminopropyltriethoxysilane was added and ball-milling was continued for 1.2 h to obtain an inorganic mixed mildew inhibitor.

[0062] 4. Mixing: Add 142g of hydroxyl-terminated polydimethylsiloxane, 15g of dimethyl silicone oil, and 21g of ultrafine powder to a kneader, mix and dehydrate at 125°C for 85min, and cool to room temperature to obtain a base material; add the obtained base material, 14g of a multi-branched cross-linking agent, 6.5g of methyltrimethoxysilane, 2.5g of dimethyldimethoxysilane, 6.5g of 3-aminopropyltriethoxysilane, 1.1g of an inorganic mixed mildew inhibitor, and 0.4g of dibutyltin dilaurate to a high-speed blender and stir at high speed. Control the vacuum degree of high-speed stirring at 0.085MPa and the speed at 320rpm. Stir for 95min to obtain a high-strength mildew-proof alcohol-based beauty edge adhesive;

[0063] The viscosity of the hydroxyl-terminated polydimethylsiloxane at 25° C. is 80,000 mPa·s.

[0064] Example 3

[0065] A preparation method of a high-mold-proof dealcoholization type beauty edge adhesive, specifically comprising:

[0066] 1. Preparation of ultrafine powder: 4g ultrafine calcium carbonate and 140g deionized water were added to a high-speed reactor, and ultrasonic oscillation was performed while stirring at high speed. The stirring speed of the high-speed stirring was controlled to 1000rpm and the frequency of the ultrasonic oscillation was 30kHz. After 35min, the high-speed stirring and ultrasonic vibration were stopped to obtain an ultrafine calcium carbonate suspension. 5.5g silver nitrate, 220g deionized water and 3.5g polyvinylamine were added to the reactor, the temperature of the reactor was controlled to 40°C, the stirring speed was controlled to 300rpm, and after stirring for 40min, 65g ultrafine calcium carbonate suspension was slowly added. The ultrafine calcium carbonate suspension was controlled to The addition rate was 22 g / min, and stirring was continued for 50 min after the addition was completed. Then, 0.12 g of carboxymethyl chitosan and 0.1 g of β-glucan were added, and ultraviolet irradiation was performed while continuing to stir, and the wavelength of the ultraviolet irradiation was controlled to be 380 nm. After 5 h, the ultraviolet irradiation was stopped, 3 g of a 5% aqueous solution of γ-polyglutamic acid by mass was added, and stirred for 55 min. 4 g of a 4% aqueous solution of carboxymethyl chitosan by mass was added, and stirred for 2 h. The mixture was centrifuged, and the speed during centrifugation was controlled to be 8000 rpm for 10 min. After the centrifugation was completed, the precipitate was dried at 120° C. to obtain an ultrafine powder.

[0067] The particle size of the ultrafine calcium carbonate is 0.08 μm;

[0068] 2. Preparation of a multi-branched cross-linking agent: 5.3 g of rutile nano-titanium dioxide and 410 g of deionized water were added to a closed reactor, the temperature of the closed reactor was controlled to 35 ° C, the stirring speed was controlled to 220 rpm, and after stirring for 40 min, 10.5 g of 3-aminopropyltriethoxysilane and 2.5 g of ammonia water were added, and the air in the closed reactor was replaced with nitrogen three times, and then the temperature was raised to 45 ° C, kept at 45 ° C for 5 h, and then filtered, and washed with 40 mL of anhydrous ethanol and 40 mL of deionized water respectively, and then dried at 120 ° C to obtain amino titanium dioxide; 35 g of tetrahydrofuran and 26 g of butanetetracarboxylic acid were added to a closed reactor, the temperature of the closed reactor was controlled to 35 ° C, the stirring speed was controlled to 220 rpm, and nitrogen was used. The air in the closed reactor was replaced three times, and then 85 g of a 25% by mass solution of N,N'-carbonyldiimidazole in tetrahydrofuran was added dropwise at a rate of 4 g / min. After the addition was completed, stirring was continued for 4.5 h. Then, 13 g of amino titanium dioxide was added, and stirring was continued for 6 h. The mixture was centrifuged at a speed of 8000 rpm for 15 min. After the centrifugation was completed, the precipitate was washed three times with deionized water and dried at 120°C to obtain a multi-branched cross-linking agent.

[0069] The particle size of the rutile nano-titanium dioxide is 90 nm;

[0070] The mass concentration of the ammonia water is 28%;

[0071] 3. Preparation of an inorganic mixed mildew inhibitor: 35 g of barium metaborate, 25 g of sodium metaborate, and 15 g of zinc oxide were mixed and ball-milled at a speed of 400 rpm, a ball-to-material ratio of 20:1, and a milling time of 50 min. Then, 3.5 g of 3-aminopropyltriethoxysilane was added and ball-milling was continued for 1.5 h to obtain an inorganic mixed mildew inhibitor.

[0072] 4. Mixing: Add 145g of hydroxyl-terminated polydimethylsiloxane, 16g of dimethyl silicone oil, and 22g of ultrafine powder to a kneader, mix and dehydrate at 130°C for 90 minutes, and cool to room temperature to obtain a base material; add the obtained base material, 15g of a multi-branched cross-linking agent, 7g of methyltrimethoxysilane, 3g of dimethyldimethoxysilane, 7g of 3-aminopropyltriethoxysilane, 1.2g of an inorganic mixed mildew inhibitor, and 0.5g of dibutyltin dilaurate to a high-speed blender and stir at high speed. Control the vacuum degree of high-speed stirring at 0.09MPa and the speed at 350rpm. After stirring for 100 minutes, a high-strength mildew-proof alcohol-based beauty edge adhesive is obtained;

[0073] The viscosity of the hydroxyl-terminated polydimethylsiloxane at 25° C. is 100,000 mPa·s.

[0074] Comparative Example 1

[0075] The method for preparing the high-mold-proof dealcoholization type beauty edge finishing glue described in Example 2 is adopted, except that the first step of preparing ultrafine powder is omitted, and 21g of ultrafine calcium carbonate with a particle size of 0.06μm is used instead of 21g of ultrafine powder in the mixing step 3.

[0076] Comparative Example 2

[0077] The method for preparing the high-mold-proof dealcoholization type beauty edge finishing adhesive described in Example 2 is adopted, except that the second step of preparing the multi-branched cross-linking agent is omitted, and the addition of the multi-branched cross-linking agent is omitted in the third step of mixing.

[0078] Test Example 1

[0079] The mildew resistance grade, tear strength, tensile strength, elongation at break, Shore hardness, 100% fixed stretch adhesion, cold drawing and hot pressing ±50% adhesion, curing depth, and elastic recovery rate of the high-mold-proof dealcoholized cosmetic edge adhesive prepared in Examples 1-3 and Comparative Examples 1-2 were tested. The test results are as follows:

[0080] From the above results, it can be seen that the addition of ultrafine powder can improve mildew resistance, tear strength, tensile strength, elongation at break, and Shore hardness, and the multi-branched cross-linking agent can improve adhesion, deep curing speed, and elasticity;

[0081] The preparation of ultrafine powder is mainly through loading silver on the surface of ultrafine calcium carbonate and then coating and modifying it with γ-polyglutamic acid and carboxymethyl chitosan aqueous solution. When carboxymethyl chitosan and β-glucan are added together, they mainly play a role in reducing silver ions. β-glucan can play a role in synergistically reducing silver ions. After reduction, silver ions become nano-silver, which can play a role as an auxiliary anti-fungal agent and improve the anti-fungal property of beauty edge glue. If nano-silver is added alone, it can also play an auxiliary anti-fungal role, but nano-silver is easy to agglomerate, and the agglomerated nano-silver Silver nanoparticles can affect the cross-linking of the adhesive, causing a decrease in the tear strength, tensile strength, elongation at break, and Shore hardness of the adhesive. Loading nanosilver onto ultrafine calcium carbonate and then coating and modifying it with an aqueous solution of γ-polyglutamic acid and carboxymethyl chitosan can improve the compatibility of the loaded ultrafine calcium carbonate with the adhesive, facilitate the dispersion of the ultrafine calcium carbonate in the adhesive, and prevent the agglomeration of nanosilver, thereby better enhancing the mechanical strength, elongation, and hardness of the adhesive.

[0082] The added multi-branched cross-linking agent is polycarboxyl titanium dioxide. The polycarboxyl structure can improve the compatibility between titanium dioxide and other components of the beauty edge trimming glue, which is beneficial to the dispersion of titanium dioxide in the beauty edge trimming glue. In addition, since polycarboxyl titanium dioxide has high reactivity, it can also promote cross-linking during the curing process of the beauty edge trimming glue, thereby increasing the cross-linking speed and cross-linking density of the beauty edge trimming glue, thereby improving the adhesion, deep curing speed and elasticity of the beauty edge trimming glue.

[0083] Test Example 2

[0084] The high-mold-proof dealcoholization type beauty edge adhesive test samples prepared in Examples 1-3 and Comparative Examples 1-2 were completely immersed in 10w-30 motor oil at 120°C for 7 days. The tensile strength and elongation at break of the test samples were tested. The test results are as follows:

[0085] From the above results, it can be seen that the multi-branched cross-linking agent can improve the oil resistance of the cosmetic edge adhesive;

[0086] The added multi-branched cross-linking agent is polycarboxyl titanium dioxide, which can not only increase the cross-linking density inside the beauty edge trimming glue, but also increase the cross-linking density on the surface of the beauty edge trimming glue, thereby preventing the oil from penetrating into the beauty edge trimming glue and damaging the interior of the beauty edge trimming glue.

[0087] Test Example 3

[0088] The high-mold-proof dealcoholization type beauty edge adhesive test samples prepared in Examples 1-3 and Comparative Examples 1-2 were placed in an environment with a temperature of 40°C and a humidity of 60% for 100 days. The surfaces of the test samples were then observed for the presence of oily exudates. The observation results are as follows:

[0089] From the above results, it can be seen that the multi-branched cross-linking agent can prevent the production of oily exudates in the cosmetic edge glue;

[0090] The added multi-branched cross-linking agent is polycarboxyl titanium dioxide, which can, on the one hand, improve the cross-linking density of the surface of the beauty edge glue, and on the other hand, can also play a certain lubricating role in the preparation of the beauty edge glue, thereby reducing the amount of dimethyl silicone oil added and avoiding the precipitation of dimethyl silicone oil.

[0091] Test Example 4

[0092] The extrudability and thixotropic index of the high-mold-proof dealcoholization-type cosmetic edge adhesive prepared in Examples 1-3 and Comparative Examples 1-2 at -4°C, 23°C, and 40°C were tested in accordance with GB / T 16776-2005. The test results are as follows:

[0093] The thixotropic index is tested by using a Bolifei viscometer with a T-E95 rotor, measuring the viscosity value V2 at a rotation speed of 2 rpm and the viscosity value V20 at a rotation speed of 20 rpm, and then calculating V2 / V20 as the thixotropic index.

[0094] From the above results, it can be seen that the addition of ultrafine powder and multi-branched cross-linking agent can reduce the dependence of the extrudability and thixotropy of the cosmetic edge adhesive on temperature;

[0095] The particle sizes of the added calcium carbonate and titanium dioxide are both small. The addition of small-particle additives can improve the extrudability and thixotropy of the beauty edge glue. However, the smaller the particle size, the easier it is to agglomerate and difficult to disperse, and the lower the temperature, the more difficult it is for calcium carbonate and titanium dioxide to disperse in the beauty edge glue, which leads to a greater dependence of extrudability and thixotropy on temperature. By modifying ultrafine calcium carbonate to make ultrafine powder and modifying titanium dioxide to make a multi-branched cross-linking agent, the compatibility of ultrafine calcium carbonate and titanium dioxide with the beauty edge glue is improved, thereby achieving the purpose of improving the dispersion uniformity inside the beauty edge glue. The addition of evenly dispersed small-particle additives can improve the fluidity of the beauty edge glue during extrusion and stirring and the consistency when standing, thereby improving the extrudability and thixotropy of the beauty edge glue while reducing the dependence of extrudability and thixotropy on temperature.

[0096] Unless otherwise specified, all percentages used in the present invention are by mass.

[0097] The above embodiments are only intended to help understand the method and core concept of the present invention. It should be noted that, without departing from the principles of the present invention, a number of improvements and modifications may be made to the present invention by those skilled in the art, and such improvements and modifications also fall within the scope of protection of the claims of the present invention.

[0098] The above description of the disclosed embodiments is intended to enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not limited to the embodiments shown herein but is intended to conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a high-multiple mildew-proof dealcoholization type beauty edge adhesive, characterized in that: The method comprises the following steps: preparing ultrafine powder, preparing multi-branched cross-linking agent, preparing inorganic mixed mildew-proof agent, and mixing materials; The method for preparing the ultrafine powder comprises the following steps: adding ultrafine calcium carbonate to deionized water and dispersing the ultrafine calcium carbonate uniformly to obtain an ultrafine calcium carbonate suspension; adding silver nitrate, deionized water and polyvinylamine to a reaction kettle, controlling the temperature of the reaction kettle to 35-40° C., stirring, slowly adding the ultrafine calcium carbonate suspension, continuing to stir after the addition is completed, then adding carboxymethyl chitosan and β-glucan, continuing to stir while irradiating with ultraviolet light, adding a γ-polyglutamic acid aqueous solution, stirring, adding a carboxymethyl chitosan aqueous solution, stirring, centrifuging, and drying to obtain the ultrafine powder; The method for preparing a multi-branched cross-linking accelerator comprises adding rutile nano-titanium dioxide and deionized water into a closed reactor, controlling the temperature of the closed reactor to 30-35° C., stirring, adding 3-aminopropyltriethoxysilane and ammonia water, replacing the air in the closed reactor with nitrogen, heating to 40-45° C., keeping the temperature at 40-45° C. for 4-5 hours, filtering, washing the filter residue, and drying to obtain amination titanium dioxide; adding tetrahydrofuran and butanetetracarboxylic acid into a closed reactor, controlling the temperature of the closed reactor to 30-35° C., stirring, replacing the air in the closed reactor with nitrogen, and then dripping a tetrahydrofuran solution of N,N'-carbonyldiimidazole, continuing to stir after the dripping is completed, and then adding amination titanium dioxide, continuing to stir, centrifuging, washing the precipitate, and drying to obtain a multi-branched cross-linking accelerator; The inorganic mixed mildew preventer is prepared by mixing barium metaborate, sodium metaborate and zinc oxide and then ball milling them, then adding 3-aminopropyltriethoxysilane and continuing ball milling to obtain the inorganic mixed mildew preventer; The mixed material comprises adding hydroxyl-terminated polydimethylsiloxane, dimethyl silicone oil and ultrafine powder into a kneader for mixing and dehydration, and then cooling to room temperature to obtain a base material; adding the obtained base material, multi-branched cross-linking promoter, methyltrimethoxysilane, dimethyldimethoxysilane, 3-aminopropyltriethoxysilane, inorganic mixed mildew preventer and dibutyltin dilaurate into a high-speed mixer and stirring evenly to obtain a high-fold mildew preventer alcohol type beauty edge finishing adhesive.

2. The method for preparing the high-multiple mildew-proof dealcoholization type beauty edge adhesive according to claim 1, characterized in that: In the preparation of the ultrafine powder, the mass ratio of ultrafine calcium carbonate to deionized water in the ultrafine calcium carbonate suspension is 3-4:130-140; Silver nitrate, deionized water, polyvinylamine, ultrafine calcium carbonate suspension, carboxymethyl chitosan, β- The mass ratio of dextran, gamma-polyglutamic acid aqueous solution and carboxymethyl chitosan aqueous solution is 5-5.5:200-220:3-3.5:60-65:0.1-0.12:0.08-0.1:2-3:3-4.

3. The method for preparing the high-multiple mildew-proof dealcoholization type beauty edge adhesive according to claim 1, characterized in that: In the preparation of the ultrafine powder, the mass fraction of the γ-polyglutamic acid aqueous solution is 4-5%; The mass fraction of the carboxymethyl chitosan aqueous solution is 3-4%; The addition rate of the ultrafine calcium carbonate suspension is 18-22 g / min.

4. The method for preparing the high-multiple mildew-proof dealcoholization type beauty edge adhesive according to claim 1, characterized in that: In the preparation of the ultrafine powder, the particle size of the ultrafine calcium carbonate is 0.05-0.08 μm; The wavelength of the ultraviolet light irradiation is 320-380nm and the time is 4-5h.

5. The method for preparing the high-multiple mildew-proof dealcoholization type beauty edge adhesive according to claim 1, characterized in that: In the preparation of the multi-branched cross-linking agent, the mass ratio of rutile nano-titanium dioxide, deionized water, 3-aminopropyltriethoxysilane, and ammonia water is 5-5.3:400-410:10-10.5:2-2.5; The mass ratio of tetrahydrofuran, butanetetracarboxylic acid, tetrahydrofuran solution of N,N'-carbonyldiimidazole and amino titanium dioxide is 32-35:24-26:80-85:11-13.

6. The method for preparing the high-multiple mildew-proof dealcoholization type beauty edge adhesive according to claim 1, characterized in that: In the preparation of the multi-branched cross-linking agent, the mass fraction of the tetrahydrofuran solution of N,N'-carbonyldiimidazole is 20-25%; The dropping speed of the tetrahydrofuran solution of N,N'-carbonyldiimidazole is 3-4 g / min; The particle size of the rutile nano-titanium dioxide is 50-90nm; The mass concentration of the ammonia water is 25-28%.

7. The method for preparing the high-multiple mildew-proof dealcoholization type beauty edge adhesive according to claim 1, characterized in that: In the preparation of the inorganic mixed mildew inhibitor, the mass ratio of barium metaborate, sodium metaborate, zinc oxide and 3-aminopropyltriethoxysilane is 30-35:20-25:12-15:3-3.

5.

8. The method for preparing the high-multiple mildew-proof dealcoholization type beauty edge adhesive according to claim 1, characterized in that: In the mixture, the mass ratio of hydroxyl-terminated polydimethylsiloxane, dimethyl silicone oil, ultrafine powder, multi-branched cross-linking agent, methyltrimethoxysilane, dimethyldimethoxysilane, 3-aminopropyltriethoxysilane, inorganic mixed mildew inhibitor, and dibutyltin dilaurate is 140-145:14-16:20-22:13-15:6-7:2-3:6-7:1-1.2:0.4-0.5; The viscosity of the hydroxyl-terminated polydimethylsiloxane at 25° C. is 50,000-100,000 mPa·s.

9. The method for preparing the high-multiple mildew-proof dealcoholization type beauty edge adhesive according to claim 1, characterized in that: The temperature of the mixing and dehydration is 120-130° C., and the time is 80-90 minutes.

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