Acrylic emulsion with core-shell structure, high wine resistance and rheological property, preparation method and application of acrylic emulsion in water-based wine bottle paint

Abstract

The invention relates to a high-alcohol-resistance and thixotropy acrylic emulsion with a core-shell structure, a preparation method of the acrylic emulsion and application of the acrylic emulsion in water-based wine bottle paint, and the acrylic emulsion is prepared by taking an inner-layer core structure as a main component and containing a cross-linking monomer and taking an outer-layer shell structure as a main component under the action of an initiator and an emulsifier. The hydrophobic monomer is formed by compounding styrene, butyl acrylate, methyl methacrylate and hydroxyethyl methylacrylate; the hydrophilic monomer is formed by compounding methacrylic acid, butyl acrylate, methyl methacrylate and hydroxyethyl methylacrylate; and the cross-linking monomer is one or more of allyl methacrylate, diallyl phthalate and N-hydroxymethyl acrylamide. When the silver powder is applied to the water-based wine bottle paint, the obtained water-based wine bottle paint not only has good wine resistance but also has very good long-term storage stability while having good silver powder arrangement characteristics, and a serious post-thickening phenomenon is avoided.

Description

Technical Field

[0001] The present application relates to acrylic emulsions and their preparation methods, and in particular to an acrylic emulsion with a core-shell structure having high wine resistance and rheological properties, a preparation method thereof, and an application in water-based wine bottle paints. Background Art

[0002] As an important functional coating material, acrylic emulsions are widely used in fields such as construction and industrial protection, and play a key role especially in water-based coating systems. With the increasingly strict environmental protection regulations and the growing concern of consumers about health and safety, traditional oil-based paints are gradually being replaced, and water-based paints have become the mainstream trend in the market due to their environmentally friendly characteristics.

[0003] The arrangement of effect pigments has always been a headache for paint engineers, especially in water-based coating systems. There is no CAB (cellulose acetate butyrate) fast-drying solvent in the oil-based system that can make the arrangement effect of aluminum powder significant. However, it is currently recognized that in the water-based system, it is achieved by adjusting the rheology of the system and having a low solids and high viscosity. Although the method of adding thickeners can also improve the arrangement of effect pigments, the impact on the emulsion performance is very large. Most of the existing rheological acrylic emulsions are not satisfactory in terms of thixotropy, storage stability, and wine resistance. Especially in the field of water-based wine bottle paints, it is difficult to simultaneously achieve excellent thixotropy, i.e., good aluminum powder arrangement, and good wine resistance. That is, it is difficult to balance good aluminum powder arrangement characteristics and excellent wine resistance. Especially during long-term storage, serious post-thickening phenomena are likely to occur, which seriously affects the convenience of construction of rheological acrylic emulsions in water-based wine bottle paints and the final film quality. Summary of the Invention

[0004] One of the purposes of the present application is to solve the above technical problems that it is difficult for acrylic emulsions to balance good aluminum powder arrangement characteristics and excellent wine resistance, and serious post-thickening phenomena are likely to occur during long-term storage. An acrylic emulsion with a core-shell structure having high wine resistance and rheological properties is provided. When this acrylic emulsion is applied in water-based wine bottle paints, it not only has good aluminum powder arrangement characteristics and excellent wine resistance, but also no post-thickening phenomenon occurs after 30 days of storage.

[0005] The second purpose of the present application is to provide a preparation method of the above acrylic emulsion with a core-shell structure having high wine resistance and rheological properties.

[0006] The third purpose of the present application is to provide a water-based wine bottle paint containing the above acrylic emulsion with a core-shell structure having high wine resistance and rheological properties. This water-based wine bottle paint has good properties such as resistance to white wine and boiling water.

[0007] Technical Solution of the Present Application In the first aspect of the present application, an acrylic emulsion with a core-shell structure and high wine resistance and rheological properties is provided, and the technical solution is as follows: An acrylic emulsion with a core-shell structure and high wine resistance and rheological properties, whose inner core structure is mainly composed of hydrophobic monomers and contains crosslinking monomers, and the outer shell structure is mainly composed of hydrophilic monomers, is prepared under the action of an initiator and an emulsifier.

[0008] By adopting the above technical solution, for an acrylic emulsion with a core-shell structure and high wine resistance and rheological properties, through the core-shell structure design of the inner layer and the outer layer, with the inner layer mainly composed of hydrophobic monomers and the outer layer mainly composed of hydrophilic monomers, the thixotropy of the acrylic emulsion with a core-shell structure and high wine resistance and rheological properties can be adjusted, so that it can have better silver powder arrangement performance during its later application.

[0009] Preferably, the hydrophobic monomers are composed of a composite of styrene, butyl acrylate, methyl methacrylate and 2-hydroxyethyl methacrylate; The hydrophilic monomers are composed of a composite of methacrylic acid, butyl acrylate, methyl methacrylate and 2-hydroxyethyl methacrylate; the crosslinking monomers are one or more of allyl methacrylate, diallyl phthalate and N-methylolacrylamide; The initiator is any one of ammonium persulfate, potassium persulfate and sodium persulfate, and is diluted with deionized water in the raw materials used for preparing the acrylic emulsion with a core-shell structure and high wine resistance and rheological properties before use to a concentration of 5 wt% of the initiator; in this application, only ammonium persulfate is taken as an example for illustration, which does not affect the use of potassium persulfate and sodium persulfate in this application; The emulsifier is an anionic emulsifier, and the anionic emulsifier is one or several of K-12, SR-10, HS-10, ES073 and LPAS830A, etc.

[0010] By adopting the above technical solution For an acrylic emulsion with a core-shell structure and high wine resistance and rheological properties, the addition of crosslinking monomers increases the molecular weight of the acrylic emulsion itself and stabilizes the core-shell structure at the same time. When the acrylic emulsion with a core-shell structure and high wine resistance and rheological properties is applied to waterborne wine bottle paint, while taking into account good silver powder arrangement characteristics, it not only improves the normal temperature water resistance, 100 °C boiling water resistance and wine resistance performance, but also has very good storage (50 °C, 30 days) stability, avoiding serious post-thickening phenomenon.

[0011] Preferably, the crosslinking monomer is N-methylolacrylamide, or is composed of a composite of allyl methacrylate and N-methylacrylamide, and more preferably N-methylolacrylamide.

[0012] By adopting the above technical solution The invention discloses an acrylic emulsion with a core-shell structure, high alcohol resistance and rheological properties. When N-hydroxymethyl acrylamide is used as a crosslinking monomer, its molecule contains hydroxymethyl (—CH2OH) and carbon-carbon double bonds (C=C). During the crosslinking process, on the one hand, its carbon-carbon double bonds can participate in free radical polymerization reaction. For example, under the action of an initiator, the double bonds contained in it are opened to carry out chain growth polymerization with other double-bond-containing monomers (such as acrylic esters) to form polymer chains. On the other hand, the hydroxymethyl groups contained in it can undergo condensation reaction under certain conditions (such as heating, the presence of an acidic catalyst, etc.), and the hydroxymethyl groups or other active hydrogen-containing groups (such as hydroxyl groups and amino groups on the polymer chain) remove water molecules to form a covalent bond crosslinking structure, so that the acrylic emulsion molecules are transformed from a linear structure to a three-dimensional network structure, thereby enhancing the hardness and alcohol resistance of the paint film of the acrylic emulsion with a core-shell structure, high alcohol resistance and rheological properties after being used as a water-based wine bottle paint.

[0013] Preferably, the above-mentioned acrylic emulsion with a core-shell structure and high alcohol resistance and rheological properties, the raw material composition and content used in its preparation, calculated by weight, include the following: It also includes N, N-dimethylethanolamine, and its usage amount is based on adjusting the pH value of the final acrylic emulsion system to 5-7 when preparing the acrylic emulsion with core-shell structure, high alcohol resistance and rheological properties.

[0014] By adopting the above technical solution The present application discloses an acrylic emulsion with a core-shell structure, high alcohol resistance and rheological properties, which is applied to water-based wine bottle paint and has good thixotropy, alcohol resistance and storage stability.

[0015] Preferably, the anionic emulsifier is reactive emulsifier SR10 or HS10.

[0016] By adopting the above technical solution The emulsifier is a reactive emulsifier SR10 or HS10, and the resulting acrylic emulsion with a core-shell structure, high alcohol resistance and rheological properties, is applied to water-based wine bottle paint. While ensuring alcohol resistance, it also has good thixotropy, resistance to normal temperature water and resistance to boiling water. The reason for this may be that the reactive emulsifiers SR-10 and HS-10 can polymerize with the monomers, evenly anchoring the hydrophilic groups in the molecular chains of the acrylic esters, thus avoiding the effects on the performance of the paint film caused by the free emulsifiers in the water phase in the later stage.

[0017] Preferably, the composition and content of the raw materials used in the preparation of the acrylic emulsion with a core-shell structure and high alcohol resistance and rheological properties, calculated by weight, include the following: The crosslinking monomer described above is N-methylolacrylamide.

[0018] By adopting the above technical solution, an acrylic emulsion with a core-shell structure, high wine resistance and rheological properties of the present application, when applied to water-based wine bottle paint, has better thixotropy, wine resistance and storage stability.

[0019] Preferably, the dosage of the above reactive anionic emulsifier is 0.5-2.0% of the total mass of the raw materials of the acrylic emulsion. In the examples of the present application, only the dosage of 0.8% is taken as an example for illustration, but it does not limit the dosage within the scope of protection.

[0020] By adopting the above technical solution, the thixotropy of the obtained acrylic emulsion with a core-shell structure, high wine resistance and rheological properties is better.

[0021] In the second aspect of the present application, a preparation method of the above acrylic emulsion with a core-shell structure, high wine resistance and rheological properties is provided, including the following steps (in the following preparation process, the initiator is diluted with deionized water to 5wt% before use, and then a 5wt% initiator aqueous solution is obtained and used): (1) Preparation of the core layer pre-emulsion Add 15-20% of the total mass of deionized water to container I (this 15-20% of the total mass of deionized water, that is, 15-20% of the total mass of deionized water used in the preparation of the acrylic emulsion with a core-shell structure, high wine resistance and rheological properties). Under stirring conditions, add 5 / 8 of the total mass of the emulsifier (this 5 / 8 of the total mass of the emulsifier accounts for 5 / 8 of the total mass of the emulsifier used in the preparation of the acrylic emulsion with a core-shell structure, high wine resistance and rheological properties) and disperse evenly. Then, under stirring conditions, add all of the styrene, 80% of the total mass of butyl acrylate, 75% of the total mass of methyl methacrylate, 80% of the total mass of 2-hydroxyethyl methacrylate and all of the crosslinking monomer in sequence, and continue to stir and disperse evenly to obtain the core layer pre-emulsion; (2) Monomer polymerization reaction of the core layer Under stirring conditions, add 70-75% of the total mass of deionized water and 2 / 8 of the total mass of the emulsifier to the reaction kettle, heat up to 80-85°C, and then add 5% of the total volume of the core layer pre-emulsion obtained in step (1) and 50% of the total mass of the initiator to react for 15-25 minutes to obtain the core layer seed liquid; Then, synchronously and uniformly add 30% of the total mass of the core layer pre-emulsion and initiator obtained in the remaining step (1) to the core layer seed solution, and control the addition to be completed within 2.5 - 3.5 h. After the addition, control the temperature at 80 - 85 °C and carry out the core layer monomer polymerization reaction for 0.5 h; (3) Preparation of the shell layer pre-emulsion Under stirring conditions, sequentially add the remaining butyl acrylate, the remaining methyl methacrylate, the remaining 2-hydroxyethyl methacrylate, the remaining emulsifier (1 / 8 of the total mass of the emulsifier), and all methacrylic acid to container II, stir and mix evenly to obtain the shell layer pre-emulsion; (4) Monomer polymerization reaction in the shell layer After the core layer monomer polymerization reaction in step (2) ends, synchronously and uniformly add the shell layer pre-emulsion prepared in step (3) and the remaining initiator (20% of the total mass of the initiator), and control the addition to be completed within 20 - 40 min. After the addition, control the temperature at 80 - 85 °C and carry out the shell layer monomer polymerization reaction for 0.5 - 1.5 h; During the above-mentioned shell layer monomer polymerization reaction process, it also includes the reaction of a small amount of core layer monomers in the core layer in step (2) that did not have time to react completely, further forming a stable core-shell structure; (5) After the monomer polymerization reaction of the shell layer in step (4) ends, cool down to 40 - 50 °C, add the remaining deionized water, and then add N,N-dimethylethanolamine to adjust the pH of the system to 5 - 7 to obtain an acrylic emulsion with a core-shell structure, high wine resistance, and rheological properties.

[0022] Adopting the above technical solution, a preparation method of an acrylic emulsion with a core-shell structure, high wine resistance, and rheological properties, by controlling the distribution amounts of butyl acrylate, methyl methacrylate, and 2-hydroxyethyl methacrylate in the core and shell, and assisted by controlling the corresponding feeding sequence, feeding time, and corresponding control parameters during the preparation process, finally obtains an acrylic emulsion with a core-shell structure, high wine resistance, and rheological properties that has good thixotropy, wine resistance, and storage stability. Its solid content is about 26.2 - 27.0 wt%, it is applied to water-based wine bottle paints, the glass adhesion (cross-cut method) is grade 0, the viscosity cp / 25 °C (6r / 60r) is 14490 / 2103 - 29640 / 4039, the resistance to 52-degree white wine is 1 - 3 h, and there is no abnormality during storage at 50 °C for 30 days.

[0023] In the third aspect of the present application, there is provided a water-based wine bottle paint containing the above-mentioned acrylic emulsion with a core-shell structure, high wine resistance, and rheological properties, and the amount of the acrylic emulsion with a core-shell structure, high wine resistance, and rheological properties in the water-based wine bottle paint is 42.5 - 43.5 wt%.

[0024] Preferably, for the raw materials used in the preparation of the above-mentioned water-based wine bottle paint, calculated by weight percentage, the raw material composition and content are as follows: The pH regulator is an aqueous solution of DMEA with a mass percentage concentration of 30%; For the above-mentioned prefabricated silver paste, calculated by weight percentage according to the raw materials used in its preparation, the raw material composition and content are as follows:

[0025] Adopting the above technical solution A water-based wine bottle paint, due to containing the above-mentioned acrylic emulsion with core-shell structure, high wine resistance and rheological properties, the finally obtained water-based wine bottle paint has excellent silver powder arrangement, excellent boiling water resistance, wine resistance and long-term storage stability.

[0026] The preparation method of the above-mentioned water-based wine bottle paint is specifically as follows: First, according to the raw materials used in the preparation of the prefabricated silver paste, add ethylene glycol monobutyl ether and deionized water to container I first, and then add dispersant SN-1792 and water-based silver paste 7012 in turn under stirring conditions, and continue to stir until there are no obvious particles and then stop stirring to obtain the prefabricated silver paste; preferably, the rotation speed during the stirring process is controlled at 550-650 r / min; Then, according to the raw materials used in the preparation of the water-based wine bottle paint, add the acrylic emulsion with core-shell structure, high wine resistance and rheological properties to container II first, and slowly add 50% of the total amount of pH regulator DMEA under stirring conditions (preferably controlling the rotation speed at 250-350 r / min), and then add 30% of the total mass of deionized water, ethylene glycol monobutyl ether, and alcohol ester 12 in turn and stir evenly, then add amino resin KW-8225 and stir evenly, then add substrate wetting agent SN-4727, defoaming agent SN-6788 and the remaining deionized water in turn, continue to stir evenly and then add the above-mentioned obtained prefabricated silver paste, control the stirring rotation speed at 750-850 r / min and stir until there are no obvious particles, and then slowly add the remaining pH regulator DMEA (at this time, the pH value of the water-based wine bottle paint detected is about 9), and continue to stir for 10-15 min and then stop stirring to obtain the water-based wine bottle paint.

[0027] The beneficial technical effects of this application A kind of acrylic emulsion with core-shell structure, high alcohol resistance and thixotropy of the present application, due to the synergistic effect among the raw materials used in the preparation (special core-shell structure raw materials, special cross-linking monomers and their dosage ratios), when applied in water-based wine bottle paint, the obtained water-based wine bottle paint not only has good silver powder arrangement characteristics, but also has excellent wine resistance, and at the same time has good water resistance (normal temperature water and boiling water at 100 °C).

[0028] A preparation method of a kind of acrylic emulsion with core-shell structure, high alcohol resistance and thixotropy of the present application. Due to the different synergistic effects of the distribution amounts of butyl acrylate, methyl methacrylate and hydroxyethyl methacrylate in the core and shell during the preparation process, the corresponding feeding sequence, feeding time and corresponding control parameters, etc., finally an acrylic emulsion with core-shell structure, high alcohol resistance and thixotropy is obtained. When it is applied in water-based wine bottle paint, the obtained water-based wine bottle paint not only has good silver powder arrangement characteristics, but also has excellent wine resistance, and at the same time has good water resistance (normal temperature water and boiling water at 100 °C). Its preparation process is simple and the operation is convenient.

[0029] Furthermore, when a kind of acrylic emulsion with core-shell structure, high alcohol resistance and thixotropy of the present application is applied in water-based wine bottle paint, in the obtained water-based wine bottle paint, when the usage amount is about 43 wt%, it has better thixotropy, wine resistance and storage stability (no post-thickening phenomenon after storing for 30 days at 50 °C). Specific embodiments

[0030] The technical solutions of the present application will be described in detail below in conjunction with the embodiments, but the present application is not limited thereto.

[0031] For the raw materials used in the embodiments of the present application, except for those commercially available, the information of other specific raw material names, specifications and manufacturers is as follows (it can be listed one by one or given in the form of a list): Raw material name Specification Manufacturer SR-10 Industrial grade, 98% Adeka Japan HS-10 Industrial grade, 98% Daiichi Sankyo Japan LPAS830A Industrial grade, 29% Lianhong New Materials ES073 Industrial grade, 30% Shanghai Zhongcheng K12 Industrial grade, 92% Shandong Jinyueyuan Ammonium persulfate Industrial grade, 98% Shanghai Hongshun Biotechnology Methyl methacrylate Industrial grade, 99% Wanhua Chemical Butyl acrylate Industrial grade, 99% Wanhua Chemical 2-Hydroxyethyl methacrylate Industrial grade, 98% Wanhua Chemical Styrene Industrial grade, 99% Shandong Lihuayi Allyl methacrylate Industrial grade, 99.5% Evonik Industries Methacrylic acid Industrial grade, 99% Wanhua Chemical Diallyl phthalate Industrial grade, 99.5% Daicel Japan N-Hydroxymethyl acrylamide Industrial grade, 98% Guangzhou Zhongye Chemical N,N-Dimethylethanolamine Industrial grade, over 99% Yangzi BASF Petrochemical The detection methods for the performance indexes of the acrylic emulsion with core-shell structure, high wine resistance and rheological properties obtained in the embodiments of the present application and the water-based wine bottle paint prepared by using the emulsion are as follows: Detection method for solid content: It is determined according to the method in GB / T20263-2006 for reference; Detection method for viscosity: At 25 °C, according to the standard of GB / T9751-2008, the viscosity values at 6r and 60r are respectively measured by using an NDJ-5S intelligent touch viscosity meter (Shanghai Nirun Intelligent Technology Co., Ltd.); Glass adhesion: It is determined according to the cross-cut method; Test of water resistance at room temperature: spray water-based wine bottle paint on glass wine bottles at room temperature of 25℃, bake at 180℃ for 20 minutes, take out and cool, soak in 25℃ water, observe the changes of the paint film, and calculate the number of days without pathological changes such as blistering, shedding, decreased adhesion (cannot be removed by hand), which is the water resistance at room temperature; Test of resistance to 52-degree liquor: spray water-based wine bottle paint on a glass wine bottle, bake it at 180℃ for 20 minutes, take it out and cool it, then soak it in 52-degree liquor at 25℃, observe the changes in the paint film, and calculate the number of hours without showing any pathological changes such as blistering, shedding, decreased adhesion (cannot be removed by hand), which is the resistance to 52-degree liquor; Test of resistance to 100℃ boiling water: spray water-based wine bottle paint on glass wine bottles, bake at 180℃ for 20 minutes, take out and cool, then soak in 100℃ boiling water, observe the changes of the paint film, and calculate the number of hours without pathological changes such as blistering, shedding, reduced adhesion (cannot be removed by hand), which is the resistance to 100℃ boiling water; Storage stability (30 days) test: Store at 50°C for 30 days and observe whether the product has any abnormality in form, such as very slight thickening, slight thickening, gelling, etc.

[0032] The present invention discloses a method for applying a core-shell structured acrylic emulsion with high alcohol resistance and thixotropy in a water-based wine bottle paint, which includes two steps of preparing a prefabricated silver paste and preparing a water-based wine bottle paint. The composition and content of raw materials used in the preparation of the prefabricated silver paste and the preparation of the water-based wine bottle paint (including the signal of the raw materials and the information of the manufacturer), and the preparation sequence are shown in the following table: Example 1 An acrylic emulsion with a core-shell structure, high alcohol resistance and rheological properties, the raw materials used in its preparation are calculated by weight (kg), and its composition and content are as follows: It also includes an appropriate amount of N,N-dimethylethanolamine for adjusting the pH of the acrylic emulsion system to 6; The anionic emulsifier is a reactive emulsifier, and the reactive emulsifier is SR-10; The cross-linking monomer is allyl methacrylate; The initiator is ammonium persulfate, which is diluted with deionized water in the raw materials used for preparation to a mass percentage concentration of 5% before use (0.1 kg of initiator is diluted with 1.9 kg of deionized water to obtain 2 kg of an initiator aqueous solution with a concentration of 5 wt%).

[0033] The preparation method of the above acrylic emulsion with a core-shell structure, high alcohol resistance and thixotropy includes the following steps: (1) Preparation of the core layer pre-emulsion Add 12.5 kg of deionized water (17.08% of the total mass of deionized water) to container I. Under stirring conditions, add 0.5 kg of anionic emulsifier (5 / 8 of the total mass of anionic emulsifier), then control the rotation speed at 600 r / min for dispersion for 30 min. Then, under stirring conditions, add 5 kg of styrene, 4 kg of butyl acrylate (80% of the total mass of butyl acrylate used in the preparation), 9 kg of methyl methacrylate (75% of the total mass of methyl methacrylate used in the preparation), 2 kg of 2-hydroxyethyl methacrylate (80% of the total mass of 2-hydroxyethyl methacrylate used in the preparation) and all 0.2 kg of crosslinking monomer in sequence, and control the rotation speed at 1000 / min for dispersion for 30 min to obtain the core layer pre-emulsion; (2) Monomer polymerization reaction of the core layer Under stirring conditions, add 53.8 kg of deionized water (73.50% of the total mass of deionized water) and 0.2 kg of anionic emulsifier (2 / 8 of the total amount of anionic emulsifier) to the reaction kettle, heat up to 80 - 85 °C, then add 1.4 kg of the core layer pre-emulsion obtained in step (1) (the addition amount is 5% of the total mass of the core layer pre-emulsion obtained in step (1)) and 1.0 kg of an initiator aqueous solution with a concentration of 5 wt% (the dosage of the initiator is 0.05 kg, 50% of the total mass of the initiator used in the preparation) for reaction for 20 min to obtain the core layer seed liquid; After the above reaction ends, under the condition of constant temperature at 80 - 85 °C, the remaining core layer pre-emulsion obtained in step (1) and 0.6 kg of an initiator aqueous solution with a concentration of 5 wt% (the dosage of the initiator is 0.05 kg, 30% of the total mass of the initiator used in the preparation) are synchronously and uniformly added to the core layer seed liquid, and it is controlled to be added within 3 h. After adding, control the temperature at 80 - 85 °C for the core layer monomer polymerization reaction for 0.5 h; (3) Preparation of the shell layer pre-emulsion Under stirring conditions, add 1 kg of the remaining butyl acrylate, 3 kg of the remaining methyl methacrylate, 0.5 kg of the remaining 2-hydroxyethyl methacrylate, 1 kg of all methacrylic acid and the remaining 0.1 kg (1 / 8 of the total amount of anionic emulsifier) to container II in sequence, and stir and mix for 10 min to prepare the shell layer pre-emulsion; (4) Shell monomer polymerization reaction After the polymerization reaction of the core layer monomer in step (2) is completed, the shell layer pre-emulsion prepared in step (3) and the remaining 0.40 kg of a 5 wt% initiator aqueous solution (the amount of initiator used is 0.02 kg, which is 20% of the total mass of the initiator used in the preparation) are added simultaneously and uniformly, and the addition is controlled to be completed within 30 minutes. After the addition is completed, the temperature is continued to be controlled at 80-85° C. to carry out the polymerization reaction of the shell layer monomer for 1 hour; (5) After the polymerization reaction of the shell layer monomer in step (4) is completed, the temperature is lowered to 45° C., the remaining deionized water (5 kg) is added and mixed, and then N, N-dimethylethanolamine is slowly added to adjust the pH of the system to 6, and stirring is continued for 30 minutes to obtain an acrylic emulsion with high alcohol resistance and rheological properties having a core-shell structure.

[0034] Example 2-3 An acrylic emulsion with a core-shell structure and high alcohol resistance and rheological properties, except that propyl phthalate and N-hydroxymethyl acrylamide are used as crosslinking monomers instead of allyl methacrylate in Example 1, and the composition and content of other raw materials used in the preparation are calculated by weight (kg) and are the same as those in Example 1.

[0035] The above-mentioned method for preparing an acrylic emulsion with a core-shell structure and high alcohol resistance and rheological properties is different from the above-mentioned method in that in the preparation process of the core layer pre-emulsion in the preparation step (1), the cross-linking monomer allyl methacrylate is replaced by propyl phthalate and N-hydroxymethyl acrylamide, respectively. The other preparation methods are the same as those in Example 1, and finally an acrylic emulsion with a core-shell structure and high alcohol resistance and rheological properties is obtained.

[0036] The acrylic emulsion with core-shell structure, high alcohol resistance and rheological properties obtained in the above Examples 1-3 was used in an amount of 43% by mass to prepare water-based wine bottle paint.

[0037] The viscosity, glass adhesion, room temperature water resistance, 52-degree liquor resistance, 100°C boiling resistance and storage stability of the water-based wine bottle paint prepared from the acrylic emulsion obtained in Examples 1-3 were measured, and the results are shown in Table 1 below: Table 1: Viscosity, glass adhesion, room temperature water resistance, 52 degree liquor resistance, 100°C boiling resistance and storage stability of water-based wine bottle paint prepared from acrylic emulsions obtained in Examples 1-3

[0038] It can be seen from Table 1 above that when the composition and content of the raw materials used in the preparation are the same, when N-hydroxymethyl acrylamide is preferably used as the cross-linking monomer, while ensuring the thixotropy, the acrylic emulsion with high alcohol resistance and rheological properties with a core-shell structure can be enhanced (room temperature water resistance, 100°C boiling resistance) and alcohol resistance after being used as a water-based wine bottle paint.

[0039] Embodiment 4-7 An acrylic emulsion with a core-shell structure and high alcohol resistance and rheological properties, except that the emulsifiers are anionic emulsifiers K-12, HS-10, ES073 and LPAS830A instead of SR-10 in Example 1, and the composition and content of other raw materials used in the preparation are the same as those in Example 1, calculated by weight (kg).

[0040] The above-mentioned method for preparing an acrylic emulsion with high alcohol resistance and rheological properties having a core-shell structure is as follows: the anionic emulsifier SR-10 in the preparation process of the core layer pre-emulsion in the preparation step (1) and the monomer polymerization reaction of the core layer in the step (2) is replaced by K-12, HS-10, ES073 and LPAS830A, respectively, and the rest is the same as the preparation method in Example 1, and finally an acrylic emulsion with high alcohol resistance and rheological properties having a core-shell structure is obtained.

[0041] The viscosity, glass adhesion, room temperature water resistance, 52-degree liquor resistance, 100°C boiling resistance and storage stability of the water-based wine bottle paint prepared from the acrylic emulsion obtained in Examples 4-7 were measured, and the results are shown in Table 2 below: Table 2: Viscosity, glass adhesion, room temperature water resistance, 52 degree liquor resistance, 100°C boiling resistance and storage stability of water-based wine bottle paints prepared from acrylic emulsions obtained in Examples 1, 4-7

[0042] It can be seen from Table 2 above that by using reactive emulsifiers SR-10 and HS-10, the corresponding viscosity (60r / 6r), room temperature water resistance and water boiling resistance are better. The reason may be that reactive emulsifiers SR-10 and HS-10 can be polymerized with monomers to evenly anchor the hydrophilic groups in the molecular chains of acrylates, avoiding them from being free in the water phase, thus affecting the room temperature water resistance and 100°C water boiling resistance of the acrylic emulsion with high alcohol resistance and rheological properties with a core-shell structure after being used in water-based wine bottle paint.

[0043] Embodiment 8-10 An acrylic emulsion with a core-shell structure, high wine resistance and rheological properties, which is different from Example 1. Among the raw materials used in the preparation, except for the different crosslinking monomers and the dosage of the crosslinking monomers (in order to balance the overall solid content of the emulsion system, the change in the dosage of the crosslinking monomers is balanced by the dosage of styrene in the core layer), the composition and content of other raw materials are the same as those in Example 1: The crosslinking monomers used in Examples 8-10 are all composed of allyl methacrylate and N-methylacrylamide. The compounding ratio is 0.2:1.5 by mass ratio of allyl methacrylate to N-methylacrylamide. The dosages of the crosslinking monomers and styrene are as shown in Table 3 below (for performance comparison, Examples 1 and 3 are also listed in the table): Table 3: Dosages of crosslinking monomers and styrene in the acrylic emulsions of Examples 1, 3, 8-10

[0044] The preparation method of the above-mentioned acrylic emulsion with a core-shell structure, high wine resistance and rheological properties is specifically the same as the preparation process of Example 1, and finally an acrylic emulsion with a core-shell structure, high wine resistance and rheological properties is obtained.

[0045] The viscosity, glass adhesion, water resistance at room temperature, resistance to 52-degree white wine, resistance to boiling water at 100 °C and storage stability of the water-based wine bottle paint prepared from the acrylic emulsions obtained in Examples 8-10 were measured. The results are shown in Table 4 below (for performance comparison, Examples 1 and 3 are also listed in the table): Table 4: Viscosity, glass adhesion, water resistance at room temperature, resistance to 52-degree white wine, resistance to boiling water at 100 °C and storage stability of the water-based wine bottle paint prepared from the acrylic emulsions obtained in Examples 1, 3, 8-10

[0046] It can be seen from the comparison of the relevant data of Examples 8-10 in Table 4 above that when using a compounded crosslinking monomer, with the increase of the dosage of the compounded monomer, both water resistance (water resistance at room temperature, resistance to boiling water at 100 °C) and wine resistance are enhanced.

[0047] However, further analysis of the relevant data of Examples 1, 3 and 8 shows that using only N-methylolacrylamide as the crosslinking monomer has a better wine resistance performance than using a compound of allyl methacrylate and N-methylacrylamide.

[0048] Examples 11-12 An acrylic emulsion with a core-shell structure, high alcohol resistance and rheological properties, which is different from Example 1 in that among the raw materials used in the preparation, except for the different crosslinking monomers and the different dosages of the crosslinking monomers (in order to balance the overall solid content of the emulsion system, the change in the dosage of the crosslinking monomer is balanced by the dosage of styrene in the core layer), the composition and content of other raw materials are the same as those in Example 1: The crosslinking monomers, the dosages of the crosslinking monomers and the dosages of styrene used in Examples 11 and 12 are as shown in Table 5 below (for performance comparison, Examples 1 and 3 are also listed in the table): Table 5: Crosslinking monomers, dosages of crosslinking monomers and dosages of styrene in the acrylic emulsions of Examples 1, 3, 11 - 12

[0049] The preparation method of the above acrylic emulsion with a core-shell structure, high alcohol resistance and rheological properties is specifically the same as the preparation process of Example 1, and finally an acrylic emulsion with a core-shell structure, high alcohol resistance and rheological properties is obtained.

[0050] The viscosity, glass adhesion, water resistance at room temperature, resistance to 52-degree white liquor, resistance to boiling at 100 °C and storage stability of the water-based wine bottle paint prepared from the acrylic emulsions obtained in Examples 11 - 12 were measured, and the results are shown in Table 6 below (the relevant data of Examples 1 and 3 are also listed in the table): Table 6: Viscosity, glass adhesion, water resistance at room temperature, resistance to 52-degree white liquor, resistance to boiling at 100 °C and storage stability of the water-based wine bottle paint prepared from the acrylic emulsions obtained in Examples 1, 3, 11 - 12

[0051] It can be seen from Table 6 above that on the premise of ensuring that the total dosage of styrene and the crosslinking monomer remains unchanged, as the dosage of the crosslinking monomer N-methylacrylamide increases, the alcohol resistance effect of the water-based wine bottle paint prepared from the obtained acrylic emulsion will be very good.

[0052] Examples 13 - 14 An acrylic emulsion with a core-shell structure, high alcohol resistance and rheological properties, which is different from Example 1 in that the dosages of methacrylic acid are 0.8 parts (0.8 kg) and 1.5 parts (1.5 kg) respectively. The change in the amount of methacrylic acid relative to that in Example 1 is balanced by adjusting the change in the dosage of styrene used in the preparation to balance the total solid content, and the composition and content of other raw materials are the same as those in Example 1.

[0053] The dosages of methacrylic acid and styrene used in Examples 13 and 14 are as shown in Table 7 below (for performance comparison, Examples 1 and 3 are also listed in the table): Table 7: Dosages of methacrylic acid and styrene in the acrylic emulsions of Examples 1, 3, 13 - 14

[0054] The preparation method of an acrylic emulsion with a core - shell structure, high wine resistance and rheological properties is as described above. Specifically, it is the same as the preparation process of Example 1, and finally an acrylic emulsion with a core - shell structure, high wine resistance and rheological properties is obtained.

[0055] The viscosity, glass adhesion, water resistance at room temperature, resistance to 52 - degree white liquor, resistance to boiling at 100 °C and storage stability of the water - based wine bottle paint prepared from the acrylic emulsions obtained in Examples 13 - 14 were measured. The results are shown in Table 8 below (the relevant data of Examples 1 and 3 are also listed in the table): Table 8: Viscosity, glass adhesion, water resistance at room temperature, resistance to 52 - degree white liquor, resistance to boiling at 100 °C and storage stability of the water - based wine bottle paint prepared from the acrylic emulsions obtained in Examples 1, 3, 13 - 14

[0056] As can be seen from Table 8 above, when the dosage of methacrylic acid in the shell layer increases, when the obtained acrylic emulsion is applied in the water - based wine bottle paint, its wine - resistance effect is not affected. However, with the increase of the dosage, although the thixotropy increases, the storage stability becomes worse.

[0057] The acrylic emulsions with a core - shell structure, high wine resistance and rheological properties obtained in the above Examples 1 - 14 were detected to have a solid content of 26.2 - 27.0 wt%.

[0058] In summary, for the acrylic emulsion with a core - shell structure, high wine resistance and rheological properties of the present application, due to the synergistic effect among the raw materials used in the preparation, when it is applied to the preparation of water - based wine bottle paint, especially when the usage amount is about 43 wt% of the total amount of raw materials used in the preparation of water - based wine bottle paint, the obtained water - based wine bottle paint has good thixotropy, thus ensuring good silver powder arrangement properties of the water - based wine bottle paint. At the same time, it also has excellent water resistance (room - temperature water and boiling at 100 °C) and wine - resistance performance, and no serious post - thickening phenomenon occurs during the 50 °C, 30 - day storage test.

[0059] The specific embodiments of the present application are only explanations of the present application, and they do not limit the present application. Those skilled in the art can make modifications without creative contributions to these embodiments according to their needs after reading this specification, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. An acrylic emulsion with a core-shell structure, high alcohol resistance and rheological properties, characterized in that The acrylic emulsion with core-shell structure and high alcohol resistance and rheological properties has an inner core structure mainly composed of hydrophobic monomers and containing crosslinking monomers, and an outer shell structure mainly composed of hydrophilic monomers, and is prepared under the action of an initiator and an emulsifier.

2. The acrylic emulsion with a core-shell structure, high alcohol resistance and rheological properties according to claim 1, wherein The hydrophobic monomer is composed of styrene, butyl acrylate, methyl methacrylate and hydroxyethyl methacrylate; The hydrophilic monomer is composed of methacrylic acid, butyl acrylate, methyl methacrylate and hydroxyethyl methacrylate; The cross-linking monomer is one or more of allyl methacrylate, diallyl phthalate and N-hydroxymethyl acrylamide; The initiator is any one of ammonium persulfate, potassium persulfate and sodium persulfate; The emulsifier is an anionic emulsifier, and the anionic emulsifier is one or more of K-12, SR-10, HS-10, ES073 and LPAS830A.

3. The acrylic emulsion with a core-shell structure, high alcohol resistance and rheological properties as described in claim 2, wherein The raw materials used in the preparation also include deionized water and N,N-dimethylethanolamine for adjusting the pH of the final acrylic emulsion system; The composition and content of the raw materials used in the preparation, calculated by weight, include the following: 70-80 parts of deionized water Emulsifier 0.1-2 parts Butyl acrylate 3-7 parts Methyl methacrylate 10-15 parts 2-3 parts of hydroxyethyl methacrylate Styrene 1-5 parts Methacrylic acid 0.8-1.0 parts Cross-linking monomer 0.2-1.7 parts Initiator 0.1-1 part; The amount of N,N-dimethylethanolamine used in the preparation is based on adjusting the pH of the final acrylic emulsion system with core-shell structure, high alcohol resistance and rheological properties to 5-7.

4. The acrylic emulsion with a core-shell structure and high alcohol resistance and rheological properties as described in claim 3, characterized in that, The composition and content of the raw materials used in the preparation, calculated by weight, include the following: 73.2 parts of deionized water Anionic emulsifier 0.8 parts Butyl acrylate 5 parts 12 parts of methyl methacrylate 2.5 parts of hydroxyethyl methacrylate Styrene 3.3-5.0 parts Methacrylic acid 1.0 part Cross-linking monomer 0.2-1.7 parts Initiator 0.1 part; The cross-linking monomer is N-hydroxymethyl acrylamide; Before using the initiator, dilute it with deionized water in the raw materials used for preparation to a concentration of 5 wt % before use.

5. An acrylic emulsion with a core-shell structure, high alcohol resistance and rheological properties as claimed in claim 4, characterized in that, The anionic emulsifier is SR10 or HS10.

6. The acrylic emulsion with a core-shell structure, high alcohol resistance and rheological properties according to claim 5, characterized in that, The amount of the anionic emulsifier used is 0.5-2.0% of the total raw material mass for preparing the acrylic emulsion with core-shell structure, high alcohol resistance and rheological properties.

7. The preparation method of an acrylic emulsion with a core-shell structure, high alcohol resistance and rheological properties as described in claims 1-6, characterized in that, The steps include: (1) Preparation of nuclear layer pre-emulsion Add 15-20% of the total mass of deionized water to container I, add 5 / 8 of the total mass of emulsifier under stirring and disperse evenly, then add all the styrene, 80% of the total mass of butyl acrylate, 75% of the total mass of methyl methacrylate, 80% of the total mass of hydroxyethyl methacrylate and all the cross-linking monomers in sequence under stirring, and continue to stir and disperse evenly to obtain a core layer pre-emulsion; (2) Monomer polymerization reaction of the core layer Under stirring conditions, add deionized water accounting for 70 - 75% of the total mass and an emulsifier accounting for 2 / 8 of the total mass to the reaction kettle, mix them, and then heat up to 80 - 85°C. Then, add 5% of the total volume of the core layer pre-emulsion obtained in step (1) and 50% of the total mass of the initiator to react for 15 - 25 minutes to obtain the core layer seed liquid; Then, synchronously and uniformly add the remaining core layer pre-emulsion obtained in step (1) and 30% of the total mass of the initiator to the core layer seed liquid, and control to add them within 2.5 - 3.5 hours. After adding, control the temperature at 80 - 85°C to carry out the core layer monomer polymerization reaction for 0.4 - 0.6 hours; (3) Preparation of the shell layer pre-emulsion Under stirring conditions, sequentially add the remaining butyl acrylate, the remaining methyl methacrylate, the remaining 2-hydroxyethyl methacrylate, all of the methacrylic acid, and an emulsifier accounting for 1 / 8 of the total mass to container II, and stir and mix evenly to obtain the shell layer pre-emulsion; (4) Monomer polymerization reaction of the shell layer After the core layer monomer polymerization reaction in step (2) ends, synchronously and uniformly add the shell layer pre-emulsion prepared in step (3) and the remaining initiator, and control to add them within 20 - 40 minutes. After adding, continue to control the temperature at 80 - 85°C to carry out the shell layer monomer polymerization reaction for 0.5 - 1.5 hours; After the monomer polymerization reaction of the shell layer in step (4) ends, cool down to 40 - 50°C, add the remaining deionized water, and then add N,N-dimethylethanolamine to adjust the pH of the system to 5 - 7 to obtain an acrylic emulsion with a core-shell structure, high alcohol resistance, and rheological properties.

8. An aqueous wine bottle paint containing the acrylic emulsion with a core-shell structure, high alcohol resistance, and rheological properties as described in claims 1 - 6.

9. The water-based wine bottle paint according to claim 8, characterized in that, The raw materials used in the preparation of the aqueous wine bottle paint contain 42.5 - 43.5 wt% of the acrylic emulsion with a core-shell structure, high alcohol resistance, and rheological properties.

10. The water-based wine bottle paint according to claim 9, characterized in that, The composition and content of the raw materials used in the preparation are as follows by weight percentage: Acrylic emulsion with a core-shell structure, high alcohol resistance, and rheological properties 43.0% pH regulator 1.0% Deionized water 27.1% Ethylene glycol monobutyl ether 5.0% Alcohol ester 12 3.0% Amino resin KW-8225 2.7% Substrate wetting agent SN-4727 0.2% Defoaming agent SN-6788 2.0% Preformed silver paste 16.0%; The pH regulator is a 30% by mass concentration aqueous solution of DMEA; For the preformed silver paste, the composition and content of the raw materials used in the preparation are as follows by weight percentage: Ethylene glycol monobutyl ether 22.8% Deionized water 25% Dispersant SN-1792 2.2% Aqueous silver paste 7012 50%.

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