Waterproof and wear-resistant carton for transportation and preparation method of waterproof and wear-resistant carton

Abstract

The invention discloses a waterproof and wear-resistant carton for transportation and a preparation method thereof, and relates to the technical field of packaging materials. The invention discloses a preparation method of a waterproof and wear-resistant carton for transportation, which comprises the following steps: coating the surface of the carton with gloss oil, and drying to obtain the waterproof and wear-resistant carton for transportation, the glazing oil is prepared from the following raw materials in percentage by weight: 70 to 85 percent of organic silicon modified water-soluble acrylic emulsion, 3 to 6 percent of functional additive, 1 to 3 percent of wax emulsion and 10 to 40 percent of solvent, the sum of the percentages of the raw materials is 100%; the preparation method of the organic silicon modified water-soluble acrylic emulsion comprises the following step: polymerizing an acrylate monomer, styrene, water-soluble acrylic resin and organic silicon molecules under the action of an initiator to obtain the organic silicon modified water-soluble acrylic emulsion. The prepared organic silicon modified water-soluble acrylic emulsion is used as a resin matrix of the glazing oil, and the surface of a carton is coated with the prepared glazing oil, so that the carton is endowed with excellent waterproof and wear-resistant properties.

Description

Technical Field

[0001] The invention relates to the technical field of packaging materials, and in particular to a waterproof and wear-resistant transportation carton and a preparation method thereof. Background Art

[0002] Cardboard is the main raw material for the production of corrugated boxes, cartons and other products. Its performance directly or indirectly affects the intrinsic quality and performance of the products. For packaging products such as corrugated boxes and cartons, it has the basic quality requirements of wear resistance, waterproof and moisture resistance, high strength and good air tightness. Paper-based packaging materials have been developed to the present day and are suitable for the storage and transportation of almost all kinds of items. However, due to the lack of wood pulp in my country, grass fibers have been mainly used as the raw materials of paper-based materials for a long time. Ordinary cardboard produced by paper mills often does not have good wear resistance, waterproof and moisture resistance, etc., and is easily damaged and broken when subjected to external mechanical forces. Therefore, in order to improve the performance of cartons and cartons, it is necessary to carry out some necessary process technology processing on the surface of cardboard to improve the performance and appearance quality of cardboard. Glazing is a common process for post-printing processing of packaging products. After the surface of the product is coated with glazing, the water resistance and friction resistance of the printed product can be improved.

[0003] Water-based varnish, also known as water-based varnish coating, is a water-dispersible coating. After varnish coating, leveling, drying and other process flows, a thin and uniform transparent film is formed on the surface of the printed matter. The paper material obtained in this way has anti-fouling, anti-wear and waterproof properties. At present, the most widely used type of varnish at home and abroad is water-based varnish, because it has the advantages of non-toxic, pollution-free, and free of organic volatiles, and has good environmental protection performance. Water-based varnish is made of water-based varnish emulsion as the main raw material, and the corresponding functional additives are added and mixed. Styrene-acrylic varnish emulsion is obtained by copolymerization of acrylate and styrene, and has excellent film-forming properties. The film after film formation has excellent weather resistance, light transmittance and adhesion. However, acrylate polymer is a thermoplastic resin, and there is a lack of cross-linking points on the linear molecules, making it difficult to form a spatial network molecular structure. Therefore, after the varnish is coated on the surface of the paper base, its water resistance and wear resistance are poor, and it is easy to become brittle at low temperatures and sticky at high temperatures, which seriously limits its application in paper packaging materials. Summary of the invention

[0004] The purpose of the present invention is to provide a waterproof and wear-resistant transport carton and a preparation method thereof, so as to solve the following technical problems:

[0005] Existing water-based varnish uses styrene acrylic varnish emulsion as the base material, which has poor water resistance and wear resistance, and is prone to become brittle at low temperatures and sticky at high temperatures, which seriously limits its application in paper packaging materials.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A method for preparing a waterproof and wear-resistant transport carton, comprising the following steps: coating varnish on the surface of the carton, and drying to obtain a waterproof and wear-resistant transport carton;

[0008] The varnish comprises the following raw materials in percentage by weight: 70-85% of organic silicon modified water-soluble acrylic emulsion, 3-6% of functional additive, 1-3% of wax emulsion, and 10-40% of solvent; the sum of the percentages of the raw materials is 100%;

[0009] The preparation method of the silicone-modified water-soluble acrylic emulsion comprises the following steps:

[0010] Add part of the deionized water, part of the ammonium persulfate, an emulsifier, and a water-soluble acrylic resin into a reactor, control the temperature at 80-85°C, react until blue light appears, add methyl methacrylate, butyl acrylate, styrene, the remaining deionized water, and the remaining ammonium persulfate, keep the temperature for 2-4 hours, add the organosilicon molecules, keep the temperature for 1-2 hours, filter, and obtain an organosilicon-modified water-soluble acrylic emulsion.

[0011] As a further scheme of the present invention: in the preparation process of the organosilicon-modified water-soluble acrylic emulsion, the addition ratio of deionized water, ammonium persulfate, emulsifier, water-soluble acrylic resin, methyl methacrylate, butyl acrylate, styrene, and organosilicon molecules is 40-50 mL: 0.6-1 g: 0.5-1 g: 10-20 g: 9-12 g: 15 g: 1-1.5 g: 5-10 g.

[0012] As a further solution of the present invention: the emulsifier is obtained by mixing alkylphenol polyoxyethylene ether and sodium dodecyl sulfate in a mass ratio of 1:2-2.5; the mass ratio of ammonium persulfate added twice before and after in the preparation process of the organosilicon-modified water-soluble acrylic emulsion is 3-4:1; the mass ratio of deionized water added twice before and after in the preparation process of the organosilicon-modified water-soluble acrylic emulsion is 3-5:1.

[0013] As a further embodiment of the present invention: the method for preparing the organosilicon molecule comprises the following steps:

[0014] A1: add isopropanol, tetramethylammonium hydroxide and deionized water into a reaction kettle and disperse them evenly, add γ-methacryloxypropyltrimethoxysilane, react at room temperature for 9-15 hours under stirring, remove isopropanol by vacuum distillation, add toluene and reflux for 6-9 hours, filter, adjust the pH to neutral, and remove toluene by vacuum distillation to obtain component 1;

[0015] A2: In a nitrogen atmosphere, add component 1 and chloroform into a reaction bottle, add thioglycolic acid and triethylamine, control the temperature at 60-70°C, keep the reaction for 6-9 hours, wash and dry to obtain component 2;

[0016] A3: Add component 2, amino-modified mesoporous silica and N,N-dimethylformamide into the reaction kettle and disperse them evenly. Control the temperature at 50-60°C, keep the reaction warm for 1-3 hours, centrifuge, wash and dry to obtain organosilicon molecules.

[0017] As a further embodiment of the present invention, the addition ratio of isopropanol, tetramethylammonium hydroxide, deionized water, γ-methacryloxypropyltrimethoxysilane and toluene in A1 is 350-450 mL: 2-3 g: 20-30 mL: 100 g: 300-400 mL.

[0018] As a further solution of the present invention: the addition ratio of component 1, chloroform, thioglycolic acid and triethylamine in A2 is 10g:100-300mL:1-2g:1-2mL.

[0019] As a further solution of the present invention: the addition ratio of component 2, amino-modified mesoporous silica, and N,N-dimethylformamide in A3 is 10 g: 3-5 g: 100-200 mL.

[0020] As a further scheme of the present invention: The preparation method of amino mesoporous silica includes the following steps: adding P123, hydrochloric acid solution, and tetraethyl orthosilicate into a reaction bottle and mixing, controlling the temperature at 35-45°C, keeping the temperature for reaction for 2-4 hours, adding aminopropyltriethoxysilane, keeping the temperature for reaction for 18-24 hours, controlling the temperature at 100-105°C, crystallizing for 18-24 hours, filtering, washing, and drying to obtain amino mesoporous silica.

[0021] As a further solution of the present invention: the hydrochloric acid solution in the preparation process of amino mesoporous silica is a 2 mol / L hydrochloric acid aqueous solution; the addition ratio of P123, hydrochloric acid solution, tetraethyl orthosilicate, and aminopropyltriethoxysilane is 4-6g:140-180g:10g:0.5-1.5g.

[0022] As a further solution of the present invention: the solvent includes water and a cosolvent; the cosolvent is ethanol; the cosolvent accounts for 5-10% of the total mass of the glazing oil. The present application adopts a mixture of water and anhydrous ethanol as a solvent to improve the drying performance of the aqueous solvent and improve the processing difficulty of the aqueous glazing oil.

[0023] As a further solution of the present invention, the functional additives include defoamers, dispersants and film-forming agents; the defoamers account for 0.05-0.1% of the total mass of the glazing oil; the dispersants account for 0.5-1% of the total mass of the glazing oil; and the film-forming agents account for 1-5% of the total mass of the glazing oil.

[0024] As a further solution of the present invention: the dispersant is a sodium acrylate aqueous dispersant; the dispersant can improve the dispersion performance of the resin, prevent sticking and improve the wear resistance.

[0025] As a further solution of the present invention, the defoaming agent is a silicone defoaming agent; the defoaming agent improves the quality defects such as fish eyes and pinholes that appear during the use of the glazing oil.

[0026] As a further embodiment of the present invention: the film-forming aid is ethylene glycol butyl ether, propylene glycol phenyl ether or dipropylene glycol monomethyl ether.

[0027] As a further solution of the present invention: the functional additive further comprises a neutralizer; the neutralizer is ammonia water; the ammonia water is used to adjust the pH value of the glazing oil to 7-8.

[0028] As a further scheme of the present invention: a method for preparing a water-soluble acrylic resin comprises the following steps: adding isopropanol and part of the monomers into a reaction kettle and dispersing them uniformly, heating and refluxing, adding part of the initiator, controlling the temperature at 80-85°C, adding the remaining monomers and the remaining initiator, keeping the temperature for reaction for 3-6 hours, controlling the temperature at 50-60°C, and dropping ammonia water to adjust the pH to 8-9 to obtain a water-soluble acrylic resin; the monomers are obtained by mixing methyl methacrylate, butyl acrylate, and acrylic acid in a mass ratio of 15-30:18-22:1-2.

[0029] As a further solution of the present invention: during the preparation of the water-soluble acrylic resin, the weight ratio of the monomer added twice is 1:2; the monomer accounts for 50-60% of the total weight of the acrylic resin.

[0030] As a further solution of the present invention: during the preparation of the water-soluble acrylic resin, the initiator is added twice in a ratio of 1:3; the initiator is azobisisobutyronitrile, and the azobisisobutyronitrile accounts for 0.7-1% of the total mass of the acrylic resin.

[0031] A waterproof and wear-resistant transport carton, made by any one of the above-mentioned preparation methods.

[0032] Beneficial effects of the present invention:

[0033] (1) The present application firstly hydrolyzes methacryloxypropyltrimethoxysilane under alkaline conditions to obtain component one; and utilizes the thiol group of thioglycolic acid to react with the double bond of component one to obtain component two. Component two prepared in the present application is an octahedral silsesquioxane having an acryloyloxy group and a carboxyl group; then, using tetraethyl orthosilicate and aminopropyltriethoxysilane as raw materials, a mesoporous silica having an amino group on the surface is prepared, i.e., amino-modified mesoporous silica; finally, the amino group of the amino-modified mesoporous silica is amidated with the carboxyl group of component two to obtain an organosilicon molecule.

[0034] The present application modifies the conventional aqueous acrylic emulsion used in aqueous varnishes, and uses organic silicon molecules to chemically crosslink water-soluble acrylic resins to obtain organic silicon-modified aqueous acrylic emulsions; organic silicon molecules are composed of silicon atoms and oxygen atoms alternately forming a stable skeleton, which gives the material excellent water resistance, wear resistance and temperature resistance, and organic silicon-modified acrylic emulsions introduce mesoporous silica with siloxane molecular chains into its polymer main chain to obtain highly anti-adhesive aqueous varnishes; the organic silicon-modified acrylic emulsions obtained in the present application have high storage stability and are not prone to phase separation. Mesoporous silica, as a rigid inorganic particle, can be added to the resin to improve the mechanical properties of the material, such as hardness, and the mesoporous silica and the water-soluble acrylic resin are crosslinked through the organic silicon molecular chain, which not only modifies the compatibility between silica and the matrix, but also plays a role in strengthening and toughening.

[0035] (2) The present application utilizes a mixture of soft and hard acrylate monomers and copolymerizes them with styrene to obtain a core-shell styrene-acrylic emulsion, and adds a water-soluble acrylic resin and an organosilicon molecule to improve the waterproofness of the water-based varnish. The soft emulsion ensures low-temperature film formation, and the hard emulsion gives the coating hardness and anti-adhesion properties. The present application adds organosilicon molecules, and the vinyl groups on the organosilicon molecules react chemically with the functional groups on the water-based acrylic resin to form chemical bonds, so that the material has excellent weather resistance and water resistance as well as low surface tension. The defect of water-based coatings that most of the solvent is water and the water resistance of water-based coatings after film formation is effectively improved. The organosilicon molecules have hydrophobic properties. During the coating process, the silanol groups in the siloxane will undergo condensation and cross-linking reactions, and the coating will exhibit excellent anti-pollution properties. In the present application, wax emulsion is added to the glazing oil. As the flux evaporates, some wax particles migrate to the surface of the film, forming a "floating effect" and forming a wax protective layer on the surface of the coating, which is not conducive to water adhesion. The water-soluble resin solution can fill the gaps between the emulsions and improve the density of the coating.

[0036] After the glazing oil prepared in the present application is coated on the surface of the corrugated paper, it combines with the paper fibers and forms a dense and continuous coating film on the surface; the carton is processed by polishing oil and calendering to form a bright protective layer on the surface of the product, and at the same time, the surface of the product has the characteristics of being waterproof, anti-fouling, wear-resistant, beautiful and durable. DETAILED DESCRIPTION

[0037] The following will be described clearly and completely in conjunction with the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0038] Example 1 The method for preparing an organosilicon molecule comprises the following steps:

[0039] A1: 4 g P123, 150 g 2 mol / L hydrochloric acid aqueous solution, and 10 g tetraethyl orthosilicate were added to a reaction bottle and mixed, the temperature was controlled at 40°C, and the reaction was kept warm for 3 h. 1.5 g aminopropyltriethoxysilane was added, and the reaction was kept warm for 18 h. The temperature was controlled at 100°C, and the crystallization treatment was performed for 18 h. The mixture was filtered, washed, and dried to obtain amino mesoporous silica.

[0040] A2: 350 mL of isopropanol, 2 g of tetramethylammonium hydroxide and 20 mL of deionized water were added to a reaction kettle and dispersed evenly, 100 g of γ-methacryloxypropyltrimethoxysilane was added, and the mixture was reacted at room temperature for 9 h under stirring conditions, and the isopropanol was removed by vacuum distillation, and 300 mL of toluene was added and refluxed for 6 h, filtered, and the pH was adjusted to neutral, and the toluene was removed by vacuum distillation to obtain component 1;

[0041] A3: In a nitrogen atmosphere, add 10g of component 1 and 100mL of chloroform into a reaction bottle, add 1g of thioglycolic acid and 1mL of triethylamine, control the temperature at 60°C, keep the reaction for 6h, wash and dry to obtain component 2;

[0042] A4: Add 10g of component 2, 3g of amino-modified mesoporous silica and 100mL of N,N-dimethylformamide into a reaction kettle and disperse them evenly. Control the temperature at 50°C and keep the reaction for 1h. Centrifuge, wash and dry to obtain organosilicon molecules.

[0043] Example 2 The method for preparing an organosilicon molecule comprises the following steps:

[0044] A1: 4 g P123, 150 g 2 mol / L hydrochloric acid aqueous solution, and 10 g tetraethyl orthosilicate were added to a reaction bottle and mixed, the temperature was controlled at 40°C, and the reaction was kept warm for 3 h. 1.5 g aminopropyltriethoxysilane was added, and the reaction was kept warm for 18 h. The temperature was controlled at 100°C, and the crystallization treatment was performed for 18 h. The mixture was filtered, washed, and dried to obtain amino mesoporous silica.

[0045] A2: 400 mL of isopropanol, 2.5 g of tetramethylammonium hydroxide and 25 mL of deionized water were added to a reaction kettle and dispersed evenly, 100 g of γ-methacryloxypropyltrimethoxysilane was added, and the mixture was reacted at room temperature for 12 h under stirring conditions, and the isopropanol was removed by vacuum distillation, and 350 mL of toluene was added and refluxed for 7 h, filtered, and the pH was adjusted to neutral, and the toluene was removed by vacuum distillation to obtain component 1;

[0046] A3: In a nitrogen atmosphere, add 10g of component 1 and 200mL of chloroform into a reaction bottle, add 1.5g of thioglycolic acid and 1.5mL of triethylamine, control the temperature at 65°C, keep the reaction for 7h, wash and dry to obtain component 2;

[0047] A4: Add 10g of component 2, 4g of amino-modified mesoporous silica and 150mL of N,N-dimethylformamide into a reaction kettle and disperse them evenly. Control the temperature at 55°C and keep the reaction for 2h. Centrifuge, wash and dry to obtain organosilicon molecules.

[0048] Example 3 The method for preparing an organosilicon molecule comprises the following steps:

[0049] A1: 4 g P123, 150 g 2 mol / L hydrochloric acid aqueous solution, and 10 g tetraethyl orthosilicate were added to a reaction bottle and mixed, the temperature was controlled at 40°C, and the reaction was kept warm for 3 h. 1.5 g aminopropyltriethoxysilane was added, and the reaction was kept warm for 18 h. The temperature was controlled at 100°C, and the crystallization treatment was performed for 18 h. The mixture was filtered, washed, and dried to obtain amino mesoporous silica.

[0050] A2: 450 mL of isopropanol, 3 g of tetramethylammonium hydroxide and 30 mL of deionized water were added to a reaction kettle and dispersed evenly, 100 g of γ-methacryloxypropyltrimethoxysilane was added, and the mixture was reacted at room temperature for 15 h under stirring conditions, and the isopropanol was removed by vacuum distillation, and 400 mL of toluene was added and refluxed for 9 h, filtered, and the pH was adjusted to neutral, and the toluene was removed by vacuum distillation to obtain component 1;

[0051] A3: In a nitrogen atmosphere, add 10g of component 1 and 300mL of chloroform into a reaction bottle, add 2g of thioglycolic acid and 2mL of triethylamine, control the temperature to 70°C, keep the reaction for 9h, wash and dry to obtain component 2;

[0052] A4: Add 10g of component 2, 5g of amino-modified mesoporous silica and 200mL of N,N-dimethylformamide into a reaction kettle and disperse them evenly. Control the temperature at 60°C and keep the reaction for 3h. Centrifuge, wash and dry to obtain organosilicon molecules.

[0053] Embodiment 4 A method for preparing a waterproof and wear-resistant transport carton comprises the following steps:

[0054] S1: 45 g of isopropanol and 18 g of the monomer mixture were added to a reaction kettle and dispersed evenly, the temperature was raised to reflux, 0.25 g of azobisisobutyronitrile was added, the temperature was controlled at 80°C, 36 g of the monomer mixture and 0.75 g of azobisisobutyronitrile were added, the temperature was kept at 50°C for 6 hours, ammonia water was added dropwise to adjust the pH to 8, and a water-soluble acrylic resin was obtained;

[0055] S2: 40 mL of deionized water, 0.8 g of ammonium persulfate, 0.3 g of alkylphenol polyoxyethylene ether (OP-21), 0.6 g of sodium dodecyl sulfate (SDS), and 20 g of water-soluble acrylic resin were added to a reactor, the temperature was controlled at 80°C, and the reaction was carried out until blue light appeared, 12 g of methyl methacrylate, 15 g of butyl acrylate, 1.2 g of styrene, 10 mL of deionized water, and 0.2 g of ammonium persulfate were added, and the reaction was kept warm for 4 h, 10 g of the organosilicon molecules prepared in Example 1 were added, the reaction was kept warm for 2 h, and 300 mesh was filtered to obtain an organosilicon-modified water-soluble acrylic emulsion;

[0056] S3: 80 g of silicone-modified water-soluble acrylic emulsion, 0.1 g of defoamer YCK-700, 0.9 g of dispersant Alcosperse 602N, 3 g of ethylene glycol butyl ether, 2 g of wax emulsion MD-2000, 9 g of water, and 5 g of ethanol were mixed, and ammonia water was added to adjust the pH to 8 to obtain a varnish;

[0057] S4: Apply varnish on the surface of the carton and dry it to obtain a waterproof and wear-resistant transportation carton.

[0058] Embodiment 5 A method for preparing a waterproof and wear-resistant transport carton comprises the following steps:

[0059] S1: 45 g of isopropanol and 18 g of the monomer mixture were added to a reaction kettle and dispersed evenly, the temperature was raised to reflux, 0.25 g of azobisisobutyronitrile was added, the temperature was controlled at 80°C, 36 g of the monomer mixture and 0.75 g of azobisisobutyronitrile were added, the temperature was kept at 50°C for 6 hours, ammonia water was added dropwise to adjust the pH to 8, and a water-soluble acrylic resin was obtained;

[0060] S2: 40 mL of deionized water, 0.8 g of ammonium persulfate, 0.3 g of alkylphenol polyoxyethylene ether (OP-21), 0.6 g of sodium dodecyl sulfate (SDS), and 20 g of water-soluble acrylic resin were added to a reactor, the temperature was controlled at 80°C, and the reaction was carried out until blue light appeared, 12 g of methyl methacrylate, 15 g of butyl acrylate, 1.2 g of styrene, 10 mL of deionized water, and 0.2 g of ammonium persulfate were added, and the reaction was kept warm for 4 h, 10 g of the organosilicon molecules prepared in Example 2 were added, the reaction was kept warm for 2 h, and 300 mesh was filtered to obtain an organosilicon-modified water-soluble acrylic emulsion;

[0061] S3: 80 g of silicone-modified water-soluble acrylic emulsion, 0.1 g of defoamer YCK-700, 0.9 g of dispersant Alcosperse 602N, 3 g of ethylene glycol butyl ether, 2 g of wax emulsion MD-2000, 9 g of water, and 5 g of ethanol were mixed, and ammonia water was added to adjust the pH to 8 to obtain a varnish;

[0062] S4: Apply varnish on the surface of the carton and dry it to obtain a waterproof and wear-resistant transportation carton.

[0063] Embodiment 6 A method for preparing a waterproof and wear-resistant transport carton comprises the following steps:

[0064] S1: 45 g of isopropanol and 18 g of the monomer mixture were added to a reaction kettle and dispersed evenly, the temperature was raised to reflux, 0.25 g of azobisisobutyronitrile was added, the temperature was controlled at 80°C, 36 g of the monomer mixture and 0.75 g of azobisisobutyronitrile were added, the temperature was kept at 50°C for 6 hours, ammonia water was added dropwise to adjust the pH to 8, and a water-soluble acrylic resin was obtained;

[0065] S2: 40 mL of deionized water, 0.8 g of ammonium persulfate, 0.3 g of alkylphenol polyoxyethylene ether (OP-21), 0.6 g of sodium dodecyl sulfate (SDS), and 20 g of water-soluble acrylic resin were added to a reactor, the temperature was controlled at 80°C, and the reaction was carried out until blue light appeared, 12 g of methyl methacrylate, 15 g of butyl acrylate, 1.2 g of styrene, 10 mL of deionized water, and 0.2 g of ammonium persulfate were added, and the reaction was kept warm for 4 h, 10 g of the organosilicon molecules prepared in Example 3 were added, the reaction was kept warm for 2 h, and 300 mesh was filtered to obtain an organosilicon-modified water-soluble acrylic emulsion;

[0066] S3: 80 g of silicone-modified water-soluble acrylic emulsion, 0.1 g of defoamer YCK-700, 0.9 g of dispersant Alcosperse 602N, 3 g of ethylene glycol butyl ether, 2 g of wax emulsion MD-2000, 9 g of water, and 5 g of ethanol were mixed, and ammonia water was added to adjust the pH to 8 to obtain a varnish;

[0067] S4: Apply varnish on the surface of the carton and dry it to obtain a waterproof and wear-resistant transportation carton.

[0068] Comparative Example 1 The method for preparing an organosilicon molecule comprises the following steps:

[0069] A1: 10 g of nano-silica, 1.5 g of aminopropyltriethoxysilane, 90 mL of anhydrous ethanol and 10 mL of deionized water were mixed, the temperature was controlled at 50°C, the heat treatment was carried out for 18 h, and then filtered, washed and dried to obtain amino-silica;

[0070] A2: 400 mL of isopropanol, 2.5 g of tetramethylammonium hydroxide and 25 mL of deionized water were added to a reaction kettle and dispersed evenly, 100 g of γ-methacryloxypropyltrimethoxysilane was added, and the mixture was reacted at room temperature for 12 h under stirring conditions, and the isopropanol was removed by vacuum distillation, and 350 mL of toluene was added and refluxed for 7 h, filtered, and the pH was adjusted to neutral, and the toluene was removed by vacuum distillation to obtain component 1;

[0071] A3: In a nitrogen atmosphere, add 10g of component 1 and 200mL of chloroform into a reaction bottle, add 1.5g of thioglycolic acid and 1.5mL of triethylamine, control the temperature at 65°C, keep the reaction for 7h, wash and dry to obtain component 2;

[0072] A4: Add 10g of component 2, 4g of amino-silica and 150mL of N,N-dimethylformamide into a reaction kettle and disperse them evenly. Control the temperature at 55°C and keep the reaction for 2h. Centrifuge, wash and dry to obtain organosilicon molecules.

[0073] Comparative Example 2 The method for preparing the organosilicon molecule comprises the following steps:

[0074] A1: In a nitrogen atmosphere, 4 g P123, 150 g 2 mol / L hydrochloric acid aqueous solution, and 10 g tetraethyl orthosilicate were added to a reaction bottle and mixed, the temperature was controlled at 40°C, and the reaction was kept warm for 3 h. 1.5 g γ-mercaptopropyltriethoxysilane was added, and the reaction was kept warm for 18 h. The temperature was controlled at 100°C, and the crystallization treatment was performed for 18 h. The mixture was filtered, washed, and dried to obtain mercaptolated mesoporous silica.

[0075] A2: 400 mL of isopropanol, 2.5 g of tetramethylammonium hydroxide and 25 mL of deionized water were added to a reaction kettle and dispersed evenly, 100 g of γ-methacryloxypropyltrimethoxysilane was added, and the mixture was reacted at room temperature for 12 h under stirring conditions, and the isopropanol was removed by vacuum distillation, and 350 mL of toluene was added and refluxed for 7 h, filtered, and the pH was adjusted to neutral, and the toluene was removed by vacuum distillation to obtain component 1;

[0076] A3: In a nitrogen atmosphere, add 10g of component 1 and 200mL of chloroform into a reaction bottle, add 4g of thiolated mesoporous silica and 1.5mL of triethylamine, control the temperature at 65°C, keep the reaction for 7h, wash and dry to obtain an organosilicon molecule.

[0077] Comparative Example 3 The preparation method of the organosilicon molecule comprises the following steps:

[0078] 400 mL of isopropanol, 2.5 g of tetramethylammonium hydroxide and 25 mL of deionized water were added into a reaction kettle and dispersed evenly. 100 g of γ-methacryloxypropyltrimethoxysilane was added and reacted at room temperature for 12 h under stirring conditions. The isopropanol was removed by vacuum distillation. 350 mL of toluene was added and refluxed for 7 h. The reaction was filtered, the pH was adjusted to neutral, and the toluene was removed by vacuum distillation to obtain an organosilicon molecule.

[0079] Compared with Example 4, Comparative Example 4 is that only the organosilicon molecules prepared in Example 1 added in Example 4 are replaced by the organosilicon molecules prepared in Comparative Example 1 in equal amounts, and the remaining components and preparation methods are completely consistent with those of Example 4.

[0080] Compared with Example 4, Comparative Example 5 is that only the organosilicon molecules prepared in Example 1 added in Example 4 are replaced by the organosilicon molecules prepared in Comparative Example 2 in equal amounts, and the remaining components and preparation methods are completely consistent with those of Example 4.

[0081] Compared with Example 4, Comparative Example 6 is that only the organosilicon molecules prepared in Example 1 added in Example 4 are replaced by the organosilicon molecules prepared in Comparative Example 3 in equal amounts, and the remaining components and preparation methods are completely consistent with those of Example 4.

[0082] Performance Testing

[0083] (1) Friction resistance: The glazing oils prepared in Examples 4-6 and Comparative Examples 4-6 were coated on red solid-bottom white board paper and dried, and then rubbed using a friction decolorization tester to record the number of times the bottom of the paper leaked for the first time. The applied force was 4 pounds. The test results are shown in Table 1;

[0084] (2) Water absorption rate: According to the standard HG / T 13856-2006 "Thermosetting Powder Coatings", first, the glazing oil prepared in Examples 4-6 and Comparative Examples 4-6 was coated on the surface of a copper sheet with a weight of m0 and then dried. The copper sheet was weighed with a weight of m1. The copper sheet was immersed in distilled water at 25° C. for 24 h. The surface moisture was wiped off with absorbent paper and weighed with a weight of m2. The water absorption rate η was calculated according to the following formula:

[0085] η=[(m2-m1) / (m1-m0)]×100%

[0086] Wherein, η-water absorption, %; m0-weight of copper plate, mg; m1-weight of copper plate after coating with varnish, mg; m0-weight of copper plate after immersion in water after coating with varnish, mg; the test results are shown in Table 1;

[0087] (3) Water resistance: The glazing oils prepared in Examples 4-6 and Comparative Examples 4-6 were coated on red solid-bottom white board paper, dried, and boiled in a constant-temperature water bath at 50° C. The time for the surface to turn white was recorded. The test results are shown in Table 1.

[0088] Table 1: Statistical table of water and wear resistance test data of Examples 4-6 and Comparative Examples 4-6

[0089]

[0090] As can be seen from Table 1, the silicone molecules prepared in the present application are cross-linked with water-soluble acrylic resin, acrylic monomer and styrene to obtain silicone-modified water-soluble acrylic emulsion. The silicone-modified water-soluble acrylic emulsion prepared in the present application is used as the resin matrix of glazing oil. The prepared glazing oil is coated on the surface of the carton to give the carton excellent waterproof and wear-resistant properties.

[0091] The above is a detailed description of an embodiment of the present invention, but the content is only a preferred embodiment of the present invention and cannot be considered to limit the scope of implementation of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.

Claims

1. A method for preparing a waterproof and wear-resistant transport carton, characterized in that: The method comprises the following steps: applying varnish on the surface of the carton and drying to obtain a waterproof and wear-resistant transport carton; The glazing oil comprises the following raw materials in weight percentage: 70-85% of organic silicon modified water-soluble acrylic emulsion, 3-6% of functional additive, 1-3% of wax emulsion, and 10-40% of solvent; the sum of the raw material percentages is 100%; The preparation method of the organosilicon-modified water-soluble acrylic emulsion comprises the following steps: Add part of the deionized water, part of the ammonium persulfate, an emulsifier, and a water-soluble acrylic resin into a reactor, control the temperature at 80-85°C, react until blue light appears, add methyl methacrylate, butyl acrylate, styrene, the remaining deionized water, and the remaining ammonium persulfate, keep the temperature for 2-4 hours, add the organosilicon molecules, keep the temperature for 1-2 hours, filter, and obtain an organosilicon-modified water-soluble acrylic emulsion.

2. The method for preparing a waterproof and wear-resistant transport carton according to claim 1, characterized in that: In the preparation process of the silicone-modified water-soluble acrylic emulsion, the addition ratio of deionized water, ammonium persulfate, emulsifier, water-soluble acrylic resin, methyl methacrylate, butyl acrylate, styrene, and silicone molecules is 40-50mL: 0.6-1g: 0.5-1g: 10-20g: 9-12g: 15g: 1-1.5g: 5-10g.

3. The method for preparing a waterproof and wear-resistant transport carton according to claim 1, characterized in that: The emulsifier is obtained by mixing alkylphenol polyoxyethylene ether and sodium dodecyl sulfate in a mass ratio of 1:2-2.5; during the preparation of the organosilicon-modified water-soluble acrylic emulsion, the mass ratio of ammonium persulfate added twice before and after is 3-4:1; during the preparation of the organosilicon-modified water-soluble acrylic emulsion, the mass ratio of deionized water added twice before and after is 3-5:

1.

4. The method for preparing a waterproof and wear-resistant transport carton according to claim 1, characterized in that: The method for preparing the organosilicon molecule comprises the following steps: A1: add isopropanol, tetramethylammonium hydroxide and deionized water into a reaction kettle and disperse them evenly, add γ-methacryloxypropyltrimethoxysilane, react at room temperature for 9-15 hours under stirring, remove isopropanol by vacuum distillation, add toluene and reflux for 6-9 hours, filter, adjust the pH to neutral, and remove toluene by vacuum distillation to obtain component 1; A2: In a nitrogen atmosphere, add component 1 and chloroform into a reaction bottle, add thioglycolic acid and triethylamine, control the temperature at 60-70°C, keep the reaction for 6-9 hours, wash and dry to obtain component 2; A3: Add component 2, amino-modified mesoporous silica and N,N-dimethylformamide into the reaction kettle and disperse them evenly. Control the temperature at 50-60°C, keep the reaction warm for 1-3 hours, centrifuge, wash and dry to obtain organosilicon molecules.

5. The method for preparing a waterproof and wear-resistant transport carton according to claim 1, characterized in that: The preparation method of amino mesoporous silica includes the following steps: adding P123, hydrochloric acid solution and tetraethyl orthosilicate into a reaction bottle and mixing, controlling the temperature at 35-45°C, keeping the temperature for reaction for 2-4 hours, adding aminopropyltriethoxysilane, keeping the temperature for reaction for 18-24 hours, controlling the temperature at 100-105°C, crystallizing for 18-24 hours, filtering, washing and drying to obtain amino mesoporous silica.

6. The method for preparing a waterproof and wear-resistant transport carton according to claim 1, characterized in that: The preparation method of water-soluble acrylic resin comprises the following steps: adding isopropanol and part of monomers into a reaction kettle and dispersing them uniformly, heating and refluxing, adding part of initiator, controlling the temperature at 80-85 DEG C, adding remaining monomers and remaining initiator, keeping the temperature for reaction for 3-6 hours, controlling the temperature at 50-60 DEG C, dropping ammonia water to adjust the pH to 8-9, and obtaining water-soluble acrylic resin; the monomers are obtained by mixing methyl methacrylate, butyl acrylate and acrylic acid in a mass ratio of 15-30:18-22:1-2.

7. The method for preparing a waterproof and wear-resistant transport carton according to claim 1, characterized in that: The solvent includes water and auxiliary solvent; the auxiliary solvent is ethanol; the auxiliary solvent accounts for 5-10% of the total mass of the glazing oil.

8. The method for preparing a waterproof and wear-resistant transport carton according to claim 1, characterized in that: The functional additives include defoamers, dispersants and film-forming agents; the defoamers account for 0.05-0.1% of the total mass of the glazing oil; the dispersants account for 0.5-1% of the total mass of the glazing oil; and the film-forming agents account for 1-5% of the total mass of the glazing oil.

9. The method for preparing a waterproof and wear-resistant transport carton according to claim 8, characterized in that: The functional additive also includes a neutralizer; the neutralizer is ammonia water; the ammonia water is used to adjust the pH value of the glazing oil to 7-8.

10. A waterproof and wear-resistant transport carton, characterized in that: Prepared by the preparation method described in any one of claims 1 to 9.

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