Matt finish hot melt adhesive erasable film and preparation process thereof

Abstract

The invention relates to the technical field of erasable films, in particular to a matt finish hot melt adhesive erasable film and a preparation process thereof. The matt finish hot melt adhesive erasable film is prepared from the following materials in parts by weight: 40 to 50 parts of ethylene-vinyl acetate copolymer, 20 to 30 parts of polystyrene-butadiene-styrene copolymer, 15 to 20 parts of hydrogenated rosin resin, 10 to 15 parts of terpene resin, 5 to 7 parts of modified polyethylene wax, 3 to 5 parts of microcrystalline wax, 1 to 2 parts of antioxidant and 4 to 6 parts of silicon dioxide modified glass fiber. The matt finish hot melt adhesive erasable film obtained by the preparation process disclosed by the invention not only has excellent matt effect and erasable property, but also has good durability.

Description

Technical Field

[0001] The invention relates to the technical field of erasable films, and in particular to a matte hot-melt adhesive erasable film and a preparation process thereof. Background Art

[0002] Hot melt adhesive film is a kind of adhesive film product that melts the adhesive material and coats it on the surface of the substrate through the hot melt method. It has been widely used in many fields such as packaging, construction, and process manufacturing due to its advantages such as high bonding strength, low cost, and convenient construction. Matt hot melt adhesive erasable film is a special type of hot melt adhesive film. It not only inherits the advantages of traditional hot melt adhesive film, but also has a unique matte effect and erasable function, further broadening its application range.

[0003] Matte hot melt adhesive erasable film is usually composed of resin, adhesive, stabilizer and other additives. These components are processed in a specific ratio and process, so that the film has excellent adhesive properties in the molten state, and can present a matte effect after curing, and has a certain degree of erasability. This feature makes matte hot melt adhesive erasable film particularly suitable for surfaces that need to be repeatedly modified or cleaned, such as whiteboards, note boards, etc.

[0004] Although matte hot melt adhesive erasable film has many advantages, there are still some problems in the prior art. For example, some traditional hot melt adhesive films have a high surface gloss after curing and cannot meet the requirements of matte effect; at the same time, some hot melt adhesive films will have problems such as decreased adhesion and surface damage after repeated erasure, which seriously affects its service life and practicality. Based on this, the present invention proposes a matte hot melt adhesive erasable film and a preparation process thereof. Summary of the invention

[0005] The purpose of the present invention is to provide a matte hot melt adhesive erasable film and a preparation process thereof, so that the prepared matte hot melt adhesive erasable film not only has excellent matte effect and erasability, but also has good durability.

[0006] In a first aspect, the present invention provides a matte hot melt adhesive erasable film, comprising the following materials in parts by weight: 40-50 parts of ethylene-vinyl acetate copolymer, 20-30 parts of polystyrene-butadiene-styrene copolymer, 15-20 parts of hydrogenated rosin resin, 10-15 parts of terpene resin, 5-7 parts of modified polyethylene wax, 3-5 parts of microcrystalline wax, 1-2 parts of antioxidant and 4-6 parts of silica modified glass fiber.

[0007] Furthermore, the preparation method of the modified polyethylene wax comprises: mixing dicumyl peroxide, maleic anhydride and polyethylene wax, and carrying out a grafting reaction under the condition of a stirring speed of 100-120r / min, a reaction temperature of 185-190°C, and a reaction time of 4-5min, then dissolving the polyethylene wax after the grafting reaction in xylene and slowly adding it into acetone, stirring continuously, cooling and filtering, and vacuum drying for 20-22h to obtain the modified polyethylene wax.

[0008] Furthermore, the weight ratio of dicumyl peroxide, maleic anhydride and polyethylene wax is (30-40): (6-8): (5-6).

[0009] Furthermore, the usage ratio of the polyethylene wax, xylene and acetone after the grafting reaction is 1:(4-6):(10-12).

[0010] Furthermore, the preparation method of the silica-modified glass fiber includes: subjecting the glass fiber to calcination, pickling, and pretreatment processes to obtain treated glass fiber, then mixing and stirring with ethanol, water, and ammonia water, dripping ethyl orthosilicate, stirring at a temperature of 28-32°C for 140-160 minutes, filtering, washing, and drying to obtain the obtained glass fiber.

[0011] Furthermore, the steps of calcining, pickling and pretreating the glass fiber include: calcining the glass fiber at a temperature of 350-370°C for 80-100 minutes, soaking it in a sulfuric acid aqueous solution with a mass concentration of 20-24% for 20-22 hours after cooling, and finally repeatedly rinsing it with water until it is neutral, and drying it to obtain the treated glass fiber.

[0012] Furthermore, the dosage ratio of the treated glass fiber, ethanol, water, ammonia water and tetraethyl orthosilicate is (10-12) g: (100-110) mL: (10-12) mL: (6-8) mL: (6-8) mL.

[0013] Furthermore, the antioxidant includes tris(2,4-di-tert-butylphenyl)phosphite and / or bis(2,4-di-tert-butylphenyl)pentaerythritol bisdiphosphite.

[0014] In a second aspect, the present invention provides a process for preparing a matte hot melt adhesive erasable film, the steps comprising: mixing the formulated raw materials and adding them into a twin-screw extruder, melt-extruding, granulating, and then molding by a molding machine.

[0015] Furthermore, the temperature of the first section of the twin-screw extruder is 170-180°C, the temperature of the second section is 200-210°C, the temperature of the third section is 240-250°C, and the screw speed is 80-100r / min; the pressure during compression molding is 7-9MPa and the temperature is 195-205°C.

[0016] The beneficial effects of the present invention are:

[0017] The present invention relates to a matte hot-melt adhesive erasable film, which uses materials such as ethylene-vinyl acetate copolymer and polystyrene-butadiene-styrene copolymer. These materials can form a uniform and delicate microstructure during the melt extrusion process, thereby giving the film material an excellent matte effect. The matte effect not only improves the aesthetics of the product, but also reduces light reflection and glare, thereby improving visual comfort.

[0018] The modified polyethylene wax of the present invention introduces polar groups (such as carboxyl groups) into the polyethylene wax molecular chain through the grafting reaction of dicumyl peroxide, maleic anhydride and polyethylene wax. The presence of these polar groups significantly improves the compatibility between the modified polyethylene wax and other components containing polar groups (such as hydrogenated rosin resin, terpene resin, etc.); the interaction between the polar groups (such as hydrogen bonding, dipole-dipole interaction, etc.) enhances the binding force between molecules and helps to form a dense protective film. The protective film can prevent the erosion and damage of the film material by external factors, and also can make the film material less likely to be scratched or worn when being wiped.

[0019] The introduction of modified polyethylene wax also helps to achieve the matte effect of matte hot melt adhesive erasable film. On the one hand, the polar groups in the modified polyethylene wax can interact with other components to form a complex molecular network structure, which can scatter light and reduce the gloss of the film material; on the other hand, during the modification process, some parts of the polyethylene wax molecular chain may be affected by chemical reactions and break or cross-link, forming smaller molecular fragments or cross-linked networks. These smaller molecular fragments or cross-linked networks may exist in the form of fine particles, and these particle structures can scatter light and enhance the matte effect. Therefore, in the preparation of matte hot melt adhesive erasable film, the introduction of modified polyethylene wax is one of the key factors to achieve the matte effect.

[0020] In the present invention, silica-modified glass fiber is used as an additive to prepare a matte hot-melt adhesive erasable film. The glass fiber that has been pre-treated by high-temperature calcination and pickling has a purer surface and enhanced activity, which is conducive to the hydrolysis and polycondensation reaction of ethyl orthosilicate on its surface, forming a uniform silica coating, and its fine particle structure can scatter light, reduce the glossiness of the film material, and thus enhance the matte effect. This scattering effect causes the light to be reflected and refracted multiple times on the film surface, reducing the amount of directly reflected light, so that the film material presents a soft, uniform matte texture. The presence of this silica coating also increases the surface roughness of the film material, further enhancing the matte effect. The rough surface can more effectively scatter light, reduce glossiness, and provide a better visual touch, so this modified glass fiber gives the film a certain matte effect.

[0021] In addition, the addition of silica-modified glass fiber may also improve the flexibility of the membrane material. The polar groups such as hydroxyl groups in the silica-modified glass fiber can interact with other polar groups in the membrane material (such as polar groups in hydrogenated rosin resin, terpene resin, etc.) to form a strong bonding method such as chemical bonds or hydrogen bonds. When this kind of membrane material with good flexibility is subjected to external forces (such as wiping), it can better maintain its integrity and stability when subjected to external forces, reducing scratches or wear caused by friction, thereby extending the service life of the membrane material.

[0022] Hydrogenated rosin resin is a hydrogenated rosin derivative with low acid value and high stability. Its molecular structure contains a large number of polar groups, such as hydroxyl and carboxyl groups. These polar groups can interact with polar groups in other components to form strong intermolecular forces, thereby improving the adhesion and cohesion of the membrane material. Terpene resin is a natural or synthetic resin with a unique molecular structure and chemical properties. Its molecules contain a large number of unsaturated bonds and polar groups, which can also interact with other components to enhance the overall performance of the membrane material.

[0023] The present invention utilizes the compounding of hydrogenated rosin resin and terpene resin to improve the durability, matte effect and erasability of the film, because the polar groups between the two can complement and synergize each other to form a more complex and stable intermolecular network structure. This structure not only improves the adhesion and cohesion of the film material, but also enables the film material to better disperse and withstand stress when subjected to external forces, thereby improving the durability of the film. In addition, since the molecular structures of hydrogenated rosin resin and terpene resin contain a large number of unsaturated bonds and polar groups, these groups can deform and displace when subjected to external forces, thereby absorbing and dispersing stress. This characteristic enables the film material to better maintain its integrity and stability when subjected to external forces such as stretching, compression, bending, and the mutual intermolecular forces are strong, and they can form a dense protective film on the surface of the film material, which can not only prevent external factors from eroding and destroying the film material, but also enable the film material to be less likely to produce scratches or wear when subjected to friction or wiping, thereby maintaining its good erasability. DETAILED DESCRIPTION

[0024] The technical solution of the present invention is described clearly and completely below. 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.

[0025] Example 1

[0026] The present embodiment provides a matte hot melt adhesive erasable film, comprising the following materials in parts by weight: 45 parts of ethylene-vinyl acetate copolymer, 25 parts of polystyrene-butadiene-styrene copolymer, 17.5 parts of hydrogenated rosin resin, 12.5 parts of terpene resin, 6 parts of modified polyethylene wax, 4 parts of microcrystalline wax, 1.5 parts of antioxidant and 5 parts of silica-modified glass fiber; the antioxidant is tris(2,4-di-tert-butylphenyl)phosphite;

[0027] The preparation method of the modified polyethylene wax comprises: mixing dicumyl peroxide, maleic anhydride and polyethylene wax, carrying out grafting reaction under the condition of stirring speed of 110r / min, reaction temperature of 187°C, reaction time of 4.5min, then dissolving the polyethylene wax after grafting reaction in xylene and slowly adding it into acetone, stirring continuously, cooling and filtering, and vacuum drying for 21h to obtain the modified polyethylene wax; the weight ratio of dicumyl peroxide, maleic anhydride and polyethylene wax is 35:7:5.5; the amount ratio of polyethylene wax after grafting reaction, xylene and acetone is 1:5:11;

[0028] The preparation method of silica-modified glass fiber includes: calcining the glass fiber at a temperature of 360°C for 90 minutes, soaking it in a sulfuric acid aqueous solution with a mass concentration of 22% for 21 hours after cooling, and finally repeatedly rinsing it with water until it is neutral, and drying it to obtain the treated glass fiber; mixing the treated glass fiber with ethanol, water and ammonia water, dropping tetraethyl orthosilicate into it, stirring it at a temperature of 30°C for 150 minutes, filtering it, washing it, and drying it to obtain the glass fiber; the amount ratio of the treated glass fiber, ethanol, water, ammonia water and tetraethyl orthosilicate is 11g:105mL:11mL:7mL:7mL;

[0029] The preparation process of this matte hot melt adhesive erasable film includes the following steps: mixing the raw materials in a formula amount and adding them into a twin-screw extruder, melt-extruding, granulating, and then compression molding by a molding machine; the temperature of the first section of the twin-screw extruder is 175°C, the temperature of the second section is 205°C, the temperature of the third section is 245°C, and the screw speed is 90r / min; the pressure during compression molding is 8MPa and the temperature is 200°C.

[0030] Example 2

[0031] The present embodiment provides a matte hot melt adhesive erasable film, comprising the following materials in parts by weight: 40 parts of ethylene-vinyl acetate copolymer, 30 parts of polystyrene-butadiene-styrene copolymer, 15 parts of hydrogenated rosin resin, 15 parts of terpene resin, 5 parts of modified polyethylene wax, 5 parts of microcrystalline wax, 1 part of antioxidant and 6 parts of silica-modified glass fiber; the antioxidant is tris(2,4-di-tert-butylphenyl)phosphite;

[0032] The preparation method of the modified polyethylene wax comprises: mixing dicumyl peroxide, maleic anhydride and polyethylene wax, carrying out grafting reaction under the condition of stirring speed of 120r / min, reaction temperature of 185°C, reaction time of 5min, then dissolving the polyethylene wax after grafting reaction in xylene and slowly adding it into acetone, stirring continuously, cooling and filtering, and vacuum drying for 20h to obtain the modified polyethylene wax; the weight ratio of dicumyl peroxide, maleic anhydride and polyethylene wax is 40:6:6; the amount ratio of polyethylene wax, xylene and acetone after grafting reaction is 1:4:12;

[0033] The preparation method of silica-modified glass fiber includes: calcining the glass fiber at a temperature of 370°C for 80 minutes, soaking it in a sulfuric acid aqueous solution with a mass concentration of 24% for 20 hours after cooling, and finally repeatedly rinsing it with water until it is neutral, and drying it to obtain the treated glass fiber; mixing the treated glass fiber with ethanol, water and ammonia water, dropping tetraethyl orthosilicate into it, stirring it at a temperature of 32°C for 140 minutes, filtering, washing and drying it to obtain the glass fiber; the amount ratio of the treated glass fiber, ethanol, water, ammonia water and tetraethyl orthosilicate is 12g:100mL:12mL:6mL:8mL;

[0034] The preparation process of this matte hot melt adhesive erasable film includes the following steps: mixing the raw materials in a formula amount and adding them into a twin-screw extruder, melt-extruding, granulating, and then compression molding by a molding machine; the temperature of the first section of the twin-screw extruder is 170°C, the temperature of the second section is 210°C, the temperature of the third section is 240°C, and the screw speed is 100r / min; the pressure during compression molding is 7MPa and the temperature is 205°C.

[0035] Example 3

[0036] The present embodiment provides a matte hot melt adhesive erasable film, comprising the following materials in parts by weight: 50 parts of ethylene-vinyl acetate copolymer, 20 parts of polystyrene-butadiene-styrene copolymer, 20 parts of hydrogenated rosin resin, 10 parts of terpene resin, 7 parts of modified polyethylene wax, 3 parts of microcrystalline wax, 2 parts of antioxidant and 4 parts of silica-modified glass fiber; the antioxidant is bis(2,4-di-tert-butylphenyl)pentaerythritol bisdiphosphite;

[0037] The preparation method of the modified polyethylene wax comprises: mixing dicumyl peroxide, maleic anhydride and polyethylene wax, carrying out grafting reaction under the condition of stirring speed of 120r / min, reaction temperature of 185°C, reaction time of 5min, then dissolving the polyethylene wax after grafting reaction in xylene and slowly adding it into acetone, stirring continuously, cooling and filtering, and vacuum drying for 20h to obtain the modified polyethylene wax; the weight ratio of dicumyl peroxide, maleic anhydride and polyethylene wax is 40:6:6; the amount ratio of polyethylene wax, xylene and acetone after grafting reaction is 1:4:12;

[0038] The preparation method of silica-modified glass fiber includes: calcining the glass fiber at a temperature of 350°C for 100 minutes, soaking it in a sulfuric acid aqueous solution with a mass concentration of 20% for 22 hours after cooling, and finally repeatedly rinsing it with water until it is neutral, and drying it to obtain the treated glass fiber; mixing the treated glass fiber with ethanol, water and ammonia water, dropping tetraethyl orthosilicate into it, stirring it at a temperature of 28°C for 160 minutes, filtering, washing and drying it to obtain the glass fiber; the amount ratio of the treated glass fiber, ethanol, water, ammonia water and tetraethyl orthosilicate is 10g:110mL:10mL:8mL:6mL;

[0039] The preparation process of this matte hot melt adhesive erasable film includes the following steps: mixing the raw materials in a formula amount and adding them into a twin-screw extruder, melt-extruding, granulating, and then compression molding by a molding machine; the temperature of the first section of the twin-screw extruder is 180°C, the temperature of the second section is 200°C, the temperature of the third section is 250°C, and the screw speed is 80r / min; the pressure during compression molding is 9MPa and the temperature is 195°C.

[0040] Example 4

[0041] The present embodiment provides a matte hot melt adhesive erasable film, comprising the following materials in parts by weight: 40 parts of ethylene-vinyl acetate copolymer, 20 parts of polystyrene-butadiene-styrene copolymer, 15 parts of hydrogenated rosin resin, 10 parts of terpene resin, 5 parts of modified polyethylene wax, 3 parts of microcrystalline wax, 1 part of antioxidant and 4 parts of silica-modified glass fiber; the antioxidant is bis(2,4-di-tert-butylphenyl)pentaerythritol bisdiphosphite;

[0042] The preparation method of the modified polyethylene wax comprises: mixing dicumyl peroxide, maleic anhydride and polyethylene wax, carrying out grafting reaction under the condition of stirring speed of 120r / min, reaction temperature of 190°C, reaction time of 5min, then dissolving the polyethylene wax after grafting reaction in xylene and slowly adding it into acetone, stirring continuously, cooling and filtering, and vacuum drying for 22h to obtain the modified polyethylene wax; the weight ratio of dicumyl peroxide, maleic anhydride and polyethylene wax is 40:8:6; the amount ratio of polyethylene wax after grafting reaction, xylene and acetone is 1:6:12;

[0043] The preparation method of silica-modified glass fiber includes: calcining the glass fiber at a temperature of 370°C for 100 minutes, soaking it in a sulfuric acid aqueous solution with a mass concentration of 24% for 22 hours after cooling, and finally repeatedly rinsing it with water until it is neutral, and drying it to obtain the treated glass fiber; mixing the treated glass fiber with ethanol, water and ammonia water, dropping tetraethyl orthosilicate into it, stirring it at a temperature of 32°C for 160 minutes, filtering, washing and drying it to obtain the glass fiber; the amount ratio of the treated glass fiber, ethanol, water, ammonia water and tetraethyl orthosilicate is 12g:110mL:12mL:8mL:8mL;

[0044] The preparation process of this matte hot melt adhesive erasable film includes the following steps: mixing the raw materials in a formula amount and adding them into a twin-screw extruder, melt-extruding, granulating, and then compression molding by a molding machine; the temperature of the first section of the twin-screw extruder is 180°C, the temperature of the second section is 210°C, the temperature of the third section is 250°C, and the screw speed is 100r / min; the pressure during compression molding is 9MPa and the temperature is 205°C.

[0045] Comparative Example 1

[0046] The comparative example provides a matte hot melt adhesive erasable film, comprising the following materials in parts by weight: 45 parts of ethylene-vinyl acetate copolymer, 25 parts of polystyrene-butadiene-styrene copolymer, 17.5 parts of hydrogenated rosin resin, 12.5 parts of terpene resin, 6 parts of polyethylene wax, 4 parts of microcrystalline wax, 1.5 parts of antioxidant and 5 parts of silica-modified glass fiber; the antioxidant is tris(2,4-di-tert-butylphenyl)phosphite;

[0047] The preparation method of silica-modified glass fiber includes: calcining the glass fiber at a temperature of 360°C for 90 minutes, soaking it in a sulfuric acid aqueous solution with a mass concentration of 22% for 21 hours after cooling, and finally repeatedly rinsing it with water until it is neutral, and drying it to obtain the treated glass fiber; mixing the treated glass fiber with ethanol, water and ammonia water, dropping tetraethyl orthosilicate into it, stirring it at a temperature of 30°C for 150 minutes, filtering it, washing it, and drying it to obtain the glass fiber; the amount ratio of the treated glass fiber, ethanol, water, ammonia water and tetraethyl orthosilicate is 11g:105mL:11mL:7mL:7mL;

[0048] The preparation process of this matte hot melt adhesive erasable film includes the following steps: mixing the raw materials in a formula amount and adding them into a twin-screw extruder, melt-extruding, granulating, and then compression molding by a molding machine; the temperature of the first section of the twin-screw extruder is 175°C, the temperature of the second section is 205°C, the temperature of the third section is 245°C, and the screw speed is 90r / min; the pressure during compression molding is 8MPa and the temperature is 200°C.

[0049] Comparative Example 2

[0050] The present comparative example provides a matte hot melt adhesive erasable film, comprising the following materials in parts by weight: 45 parts of ethylene-vinyl acetate copolymer, 25 parts of polystyrene-butadiene-styrene copolymer, 17.5 parts of hydrogenated rosin resin, 12.5 parts of terpene resin, 10 parts of modified polyethylene wax, 1.5 parts of antioxidant and 5 parts of silica-modified glass fiber; the antioxidant is tris(2,4-di-tert-butylphenyl)phosphite;

[0051] The preparation method of the modified polyethylene wax comprises: mixing dicumyl peroxide, maleic anhydride and polyethylene wax, carrying out grafting reaction under the condition of stirring speed of 110r / min, reaction temperature of 187°C, reaction time of 4.5min, then dissolving the polyethylene wax after grafting reaction in xylene and slowly adding it into acetone, stirring continuously, cooling and filtering, and vacuum drying for 21h to obtain the modified polyethylene wax; the weight ratio of dicumyl peroxide, maleic anhydride and polyethylene wax is 35:7:5.5; the amount ratio of polyethylene wax after grafting reaction, xylene and acetone is 1:5:11;

[0052] The preparation method of silica-modified glass fiber includes: calcining the glass fiber at a temperature of 360°C for 90 minutes, soaking it in a sulfuric acid aqueous solution with a mass concentration of 22% for 21 hours after cooling, and finally repeatedly rinsing it with water until it is neutral, and drying it to obtain the treated glass fiber; mixing the treated glass fiber with ethanol, water and ammonia water, dropping tetraethyl orthosilicate into it, stirring it at a temperature of 30°C for 150 minutes, filtering it, washing it, and drying it to obtain the glass fiber; the amount ratio of the treated glass fiber, ethanol, water, ammonia water and tetraethyl orthosilicate is 11g:105mL:11mL:7mL:7mL;

[0053] The preparation process of this matte hot melt adhesive erasable film includes the following steps: mixing the raw materials in a formula amount and adding them into a twin-screw extruder, melt-extruding, granulating, and then compression molding by a molding machine; the temperature of the first section of the twin-screw extruder is 175°C, the temperature of the second section is 205°C, the temperature of the third section is 245°C, and the screw speed is 90r / min; the pressure during compression molding is 8MPa and the temperature is 200°C.

[0054] Comparative Example 3

[0055] The comparative example provides a matte hot melt adhesive erasable film, comprising the following materials in parts by weight: 45 parts of ethylene-vinyl acetate copolymer, 25 parts of polystyrene-butadiene-styrene copolymer, 17.5 parts of hydrogenated rosin resin, 12.5 parts of terpene resin, 6 parts of modified polyethylene wax, 4 parts of microcrystalline wax, 1.5 parts of antioxidant and 5 parts of silica-modified glass fiber; the antioxidant is tris(2,4-di-tert-butylphenyl)phosphite;

[0056] The preparation method of the modified polyethylene wax comprises: mixing dicumyl peroxide, maleic anhydride and polyethylene wax, carrying out grafting reaction under the condition of stirring speed of 110r / min, reaction temperature of 187°C, reaction time of 4.5min, then dissolving the polyethylene wax after grafting reaction in xylene and slowly adding it into acetone, stirring continuously, cooling and filtering, and vacuum drying for 21h to obtain the modified polyethylene wax; the weight ratio of dicumyl peroxide, maleic anhydride and polyethylene wax is 35:7:5.5; the amount ratio of polyethylene wax after grafting reaction, xylene and acetone is 1:5:11;

[0057] The preparation method of silica-modified glass fiber includes: soaking the glass fiber in a sulfuric acid aqueous solution with a mass concentration of 22% for 21 hours, and finally repeatedly washing with water until neutral, and drying to obtain the treated glass fiber; mixing the treated glass fiber with ethanol, water and ammonia water, dropping ethyl orthosilicate, stirring at a temperature of 30°C for 150 minutes, filtering, washing, and drying to obtain the glass fiber; the amount ratio of the treated glass fiber, ethanol, water, ammonia water and ethyl orthosilicate is 11g:105mL:11mL:7mL:7mL;

[0058] The preparation process of this matte hot melt adhesive erasable film includes the following steps: mixing the raw materials in a formula amount and adding them into a twin-screw extruder, melt-extruding, granulating, and then compression molding by a molding machine; the temperature of the first section of the twin-screw extruder is 175°C, the temperature of the second section is 205°C, the temperature of the third section is 245°C, and the screw speed is 90r / min; the pressure during compression molding is 8MPa and the temperature is 200°C.

[0059] Comparative Example 4

[0060] The comparative example provides a matte hot melt adhesive erasable film, comprising the following materials in parts by weight: 45 parts of ethylene-vinyl acetate copolymer, 25 parts of polystyrene-butadiene-styrene copolymer, 17.5 parts of hydrogenated rosin resin, 12.5 parts of terpene resin, 6 parts of modified polyethylene wax, 4 parts of microcrystalline wax, 1.5 parts of antioxidant and 5 parts of silica-modified glass fiber; the antioxidant is tris(2,4-di-tert-butylphenyl)phosphite;

[0061] The preparation method of the modified polyethylene wax comprises: mixing dicumyl peroxide, maleic anhydride and polyethylene wax, carrying out grafting reaction under the condition of stirring speed of 110r / min, reaction temperature of 187°C, reaction time of 4.5min, then dissolving the polyethylene wax after grafting reaction in xylene and slowly adding it into acetone, stirring continuously, cooling and filtering, and vacuum drying for 21h to obtain the modified polyethylene wax; the weight ratio of dicumyl peroxide, maleic anhydride and polyethylene wax is 35:7:5.5; the amount ratio of polyethylene wax after grafting reaction, xylene and acetone is 1:5:11;

[0062] The preparation method of silica-modified glass fiber includes: calcining the glass fiber at a temperature of 360° C. for 90 minutes, and cooling to obtain the treated glass fiber; mixing the treated glass fiber with ethanol, water and ammonia water, dropping ethyl orthosilicate, stirring at a temperature of 30° C. for 150 minutes, filtering, washing and drying to obtain the glass fiber; the amount ratio of the treated glass fiber, ethanol, water, ammonia water and ethyl orthosilicate is 11 g: 105 mL: 11 mL: 7 mL: 7 mL;

[0063] The preparation process of this matte hot melt adhesive erasable film includes the following steps: mixing the raw materials in a formula amount and adding them into a twin-screw extruder, melt-extruding, granulating, and then compression molding by a molding machine; the temperature of the first section of the twin-screw extruder is 175°C, the temperature of the second section is 205°C, the temperature of the third section is 245°C, and the screw speed is 90r / min; the pressure during compression molding is 8MPa and the temperature is 200°C.

[0064] Comparative Example 5

[0065] The comparative example provides a matte hot melt adhesive erasable film, comprising the following materials in parts by weight: 45 parts of ethylene-vinyl acetate copolymer, 25 parts of polystyrene-butadiene-styrene copolymer, 17.5 parts of hydrogenated rosin resin, 12.5 parts of terpene resin, 6 parts of modified polyethylene wax, 4 parts of microcrystalline wax, 1.5 parts of antioxidant and 5 parts of glass fiber; the antioxidant is tris (2,4-di-tert-butylphenyl) phosphite;

[0066] The preparation method of the modified polyethylene wax comprises: mixing dicumyl peroxide, maleic anhydride and polyethylene wax, carrying out grafting reaction under the condition of stirring speed of 110r / min, reaction temperature of 187°C, reaction time of 4.5min, then dissolving the polyethylene wax after grafting reaction in xylene and slowly adding it into acetone, stirring continuously, cooling and filtering, and vacuum drying for 21h to obtain the modified polyethylene wax; the weight ratio of dicumyl peroxide, maleic anhydride and polyethylene wax is 35:7:5.5; the amount ratio of polyethylene wax after grafting reaction, xylene and acetone is 1:5:11;

[0067] The preparation process of this matte hot melt adhesive erasable film includes the following steps: mixing the raw materials in a formula amount and adding them into a twin-screw extruder, melt-extruding, granulating, and then compression molding by a molding machine; the temperature of the first section of the twin-screw extruder is 175°C, the temperature of the second section is 205°C, the temperature of the third section is 245°C, and the screw speed is 90r / min; the pressure during compression molding is 8MPa and the temperature is 200°C.

[0068] Comparative Example 6

[0069] The present comparative example provides a matte hot melt adhesive erasable film, comprising the following materials in parts by weight: 45 parts of ethylene-vinyl acetate copolymer, 25 parts of polystyrene-butadiene-styrene copolymer, 17.5 parts of hydrogenated rosin resin, 12.5 parts of terpene resin, 6 parts of modified polyethylene wax, 4 parts of microcrystalline wax, and 1.5 parts of antioxidant; the antioxidant is tris(2,4-di-tert-butylphenyl)phosphite;

[0070] The preparation method of the modified polyethylene wax comprises: mixing dicumyl peroxide, maleic anhydride and polyethylene wax, carrying out grafting reaction under the condition of stirring speed of 110r / min, reaction temperature of 187°C, reaction time of 4.5min, then dissolving the polyethylene wax after grafting reaction in xylene and slowly adding it into acetone, stirring continuously, cooling and filtering, and vacuum drying for 21h to obtain the modified polyethylene wax; the weight ratio of dicumyl peroxide, maleic anhydride and polyethylene wax is 35:7:5.5; the amount ratio of polyethylene wax after grafting reaction, xylene and acetone is 1:5:11;

[0071] The preparation process of this matte hot melt adhesive erasable film includes the following steps: mixing the raw materials in a formula amount and adding them into a twin-screw extruder, melt-extruding, granulating, and then compression molding by a molding machine; the temperature of the first section of the twin-screw extruder is 175°C, the temperature of the second section is 205°C, the temperature of the third section is 245°C, and the screw speed is 90r / min; the pressure during compression molding is 8MPa and the temperature is 200°C.

[0072] Comparative Example 7

[0073] The comparative example provides a matte hot melt adhesive erasable film, comprising the following materials in parts by weight: 45 parts of ethylene-vinyl acetate copolymer, 25 parts of polystyrene-butadiene-styrene copolymer, 17.5 parts of hydrogenated rosin resin, 12.5 parts of terpene resin, 6 parts of modified polyethylene wax, 4 parts of microcrystalline wax, 1.5 parts of antioxidant and 5 parts of silica-modified glass fiber; the antioxidant is tris(2,4-di-tert-butylphenyl)phosphite;

[0074] The preparation method of the modified polyethylene wax comprises: mixing dicumyl peroxide, maleic anhydride and polyethylene wax, carrying out grafting reaction under the condition of stirring speed of 110r / min, reaction temperature of 187°C, reaction time of 4.5min, then dissolving the polyethylene wax after grafting reaction in xylene and slowly adding it into acetone, stirring continuously, cooling and filtering, and vacuum drying for 21h to obtain the modified polyethylene wax; the weight ratio of dicumyl peroxide, maleic anhydride and polyethylene wax is 35:7:5.5; the amount ratio of polyethylene wax after grafting reaction, xylene and acetone is 1:5:11;

[0075] The preparation method of silica-modified glass fiber includes: calcining the glass fiber at a temperature of 360°C for 90 minutes, soaking it in a sulfuric acid aqueous solution with a mass concentration of 22% for 21 hours after cooling, and finally repeatedly rinsing it with water until it is neutral, and drying it to obtain the treated glass fiber; mixing the treated glass fiber with ethanol, water and ammonia water, dropping tetraethyl orthosilicate into it, stirring it at a temperature of 30°C for 150 minutes, filtering it, washing it, and drying it to obtain the glass fiber; the amount ratio of the treated glass fiber, ethanol, water, ammonia water and tetraethyl orthosilicate is 11g:105mL:11mL:7mL:7mL;

[0076] The preparation process of this matte hot melt adhesive erasable film includes the following steps: mixing the raw materials in a formula amount and adding them into a twin-screw extruder, melt-extruding, granulating, and then compression molding by a molding machine; the temperature of the first section of the twin-screw extruder is 175°C, the temperature of the second section is 205°C, the temperature of the third section is 245°C, and the screw speed is 90r / min; the pressure during compression molding is 8MPa and the temperature is 200°C.

[0077] Comparative Example 8

[0078] The comparative example provides a matte hot melt adhesive erasable film, comprising the following materials in parts by weight: 45 parts of ethylene-vinyl acetate copolymer, 25 parts of polystyrene-butadiene-styrene copolymer, 17.5 parts of hydrogenated rosin resin, 12.5 parts of terpene resin, 6 parts of modified polyethylene wax, 4 parts of microcrystalline wax, 1.5 parts of antioxidant and 5 parts of silica-modified glass fiber; the antioxidant is tris(2,4-di-tert-butylphenyl)phosphite;

[0079] The preparation method of the modified polyethylene wax comprises: mixing dicumyl peroxide, maleic anhydride and polyethylene wax, carrying out grafting reaction under the condition of stirring speed of 110r / min, reaction temperature of 187°C, reaction time of 4.5min, then dissolving the polyethylene wax after grafting reaction in xylene and slowly adding it into acetone, stirring continuously, cooling and filtering, and vacuum drying for 21h to obtain the modified polyethylene wax; the weight ratio of dicumyl peroxide, maleic anhydride and polyethylene wax is 35:7:5.5; the amount ratio of polyethylene wax after grafting reaction, xylene and acetone is 1:5:11;

[0080] The preparation method of silica-modified glass fiber includes: calcining the glass fiber at a temperature of 360°C for 90 minutes, soaking it in a sulfuric acid aqueous solution with a mass concentration of 22% for 21 hours after cooling, and finally repeatedly rinsing it with water until it is neutral, and drying it to obtain the treated glass fiber; mixing the treated glass fiber with ethanol, water and ammonia water, dropping tetraethyl orthosilicate into it, stirring it at a temperature of 30°C for 150 minutes, filtering it, washing it, and drying it to obtain the glass fiber; the amount ratio of the treated glass fiber, ethanol, water, ammonia water and tetraethyl orthosilicate is 11g:105mL:11mL:7mL:7mL;

[0081] The preparation process of this matte hot melt adhesive erasable film includes the following steps: mixing the raw materials in a formula amount and adding them into a twin-screw extruder, melt-extruding, granulating, and then compression molding by a molding machine; the temperature of the first section of the twin-screw extruder is 175°C, the temperature of the second section is 205°C, the temperature of the third section is 245°C, and the screw speed is 90r / min; the pressure during compression molding is 8MPa and the temperature is 200°C.

[0082] The erasable films prepared in Examples 1-4 and Comparative Examples 1-8 were tested:

[0083] 1. Gloss: measured using a 60° angle gloss meter, model MG-60, provided by Shanghai Lichen Bangxi Instrument Technology Co., Ltd.

[0084] 2. Erasability: Refer to the industry standard "QB / T 4153-2010 Writing Whiteboard" and use the A method shown in standard 5.3.2.2 for testing;

[0085] 2. Writing adhesion: refer to the industry standard "QB / T 4153-2010 Writing Whiteboard";

[0086] 3. Wear resistance: Refer to the industry standard "QB / T 4153-2010 Writing Whiteboard".

[0087] The test results are shown in Table 1.

[0088] Table 1 Test results

[0089]

[0090]

[0091]

[0092] Finally, it should be noted that the above embodiments are only used to illustrate the present invention and are not intended to limit the technical solutions described in the present invention. Those skilled in the art should understand that the present invention can still be modified or replaced by equivalents. All technical solutions and improvements that do not depart from the spirit and scope of the present invention should be included in the scope of the claims of the present invention.

Claims

1. A matte hot melt adhesive erasable film, characterized in that: The invention comprises the following materials in parts by weight: 40-50 parts of ethylene-vinyl acetate copolymer, 20-30 parts of polystyrene-butadiene-styrene copolymer, 15-20 parts of hydrogenated rosin resin, 10-15 parts of terpene resin, 5-7 parts of modified polyethylene wax, 3-5 parts of microcrystalline wax, 1-2 parts of antioxidant and 4-6 parts of silica-modified glass fiber.

2. The matte hot melt adhesive erasable film according to claim 1, characterized in that: The preparation method of the modified polyethylene wax comprises: mixing dicumyl peroxide, maleic anhydride and polyethylene wax, carrying out grafting reaction under the condition of stirring speed of 100-120r / min, reaction temperature of 185-190°C, reaction time of 4-5min, then dissolving the polyethylene wax after grafting reaction in xylene and slowly adding it into acetone, stirring continuously, filtering after cooling, and vacuum drying for 20-22h to obtain the modified polyethylene wax.

3. The matte hot melt adhesive erasable film according to claim 2, characterized in that: The weight ratio of dicumyl peroxide, maleic anhydride and polyethylene wax is (30-40): (6-8): (5-6).

4. The matte hot melt adhesive erasable film according to claim 2, characterized in that: The usage ratio of the polyethylene wax, xylene and acetone after the grafting reaction is 1:(4-6):(10-12).

5. The matte hot melt adhesive erasable film according to claim 1, characterized in that: The preparation method of the silica-modified glass fiber comprises: subjecting the glass fiber to calcination, acid washing and pretreatment processes to obtain treated glass fiber, then mixing and stirring with ethanol, water and ammonia water, dropping ethyl orthosilicate, stirring at a temperature of 28-32° C. for 140-160 minutes, filtering, washing and drying to obtain the glass fiber.

6. The matte hot melt adhesive erasable film according to claim 5, characterized in that: The steps of calcining, pickling and pretreating the glass fiber include: calcining the glass fiber at a temperature of 350-370°C for 80-100 minutes, soaking it in a sulfuric acid aqueous solution with a mass concentration of 20-24% for 20-22 hours after cooling, and finally repeatedly rinsing it with water until it is neutral, and drying it to obtain the treated glass fiber.

7. The matte hot melt adhesive erasable film according to claim 5, characterized in that: The dosage ratio of the treated glass fiber, ethanol, water, ammonia water and tetraethyl orthosilicate is (10-12) g: (100-110) mL: (10-12) mL: (6-8) mL: (6-8) mL.

8. The matte hot melt adhesive erasable film according to claim 1, characterized in that: The antioxidant includes tris(2,4-di-tert-butylphenyl)phosphite and / or bis(2,4-di-tert-butylphenyl)pentaerythritol bisdiphosphite.

9. A process for preparing a matte hot melt adhesive erasable film according to any one of claims 1 to 8, characterized in that the steps include: The raw materials in the formula amount are mixed and added into a twin-screw extruder, melt-extruded, granulated, and then molded by a molding machine to obtain the product.

10. The process for preparing a matte hot melt adhesive erasable film according to claim 9, characterized in that: The temperature of the first section of the twin-screw extruder is 170-180°C, the temperature of the second section is 200-210°C, the temperature of the third section is 240-250°C, and the screw speed is 80-100r / min; the pressure during compression molding is 7-9MPa and the temperature is 195-205°C.

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