High adhesion polypropylene aluminized film and preparation method thereof

Abstract

The application discloses a kind of high adhesion polypropylene aluminized film and preparation method thereof, belong to packaging material production technical field.The application discloses a kind of high adhesion polypropylene aluminized film and preparation method thereof, belong to packaging material production technical field.The application discloses a kind of high adhesion polypropylene aluminized film and preparation method thereof, belong to packaging material production technical field.The application discloses a kind of high adhesion polypropylene aluminized film and preparation method thereof, belong to packaging material production technical field.The application discloses a kind of high adhesion polypropylene aluminized film and preparation method thereof, belong to packaging material production technical field.The application discloses a kind of high adhesion polypropylene aluminized film and preparation method thereof, belong to packaging material production technical field.The application discloses a kind of high adhesion polypropylene aluminized film and preparation method thereof, belong to packaging material production technical field.The application discloses a kind of high adhesion polypropylene aluminized film and preparation method thereof, belong to packaging material production technical field.The application discloses a kind of high adhesion polypropylene aluminized film and preparation method thereof, belong to packaging material production technical field.The application discloses a kind of high adhesion polypropylene aluminized film and preparation method thereof, belong to packaging material production technical field.The application discloses a kind of high adhesion polypropylene aluminized film and preparation method thereof, belong to packaging material production technical field.The application discloses a kind of high adhesion polypropylene aluminized film and preparation method thereof, belong to packaging material production technical field.The application discloses a kind of high adhesion polypropylene aluminized film and preparation method thereof, belong to packaging material production technical field.The application discloses a kind of high adhesion poly

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of packaging material production, and particularly relates to a high-attachment polypropylene aluminum-plated film and a preparation method thereof. BACKGROUND

[0002] The cast polypropylene aluminum-plated film is widely used in the packaging field of various products including clothes, cosmetics, food, books, paper towels, etc. In order to improve the lubricating effect, an amide type slip agent is often added in the heat sealing layer. However, with the passage of time or the change of temperature, the amide type slip agent added in the heat sealing layer may slowly precipitate, which may cause the adhesion between the aluminum-plated layer and the base film to decrease due to the migration of the precipitate of the slip agent. SUMMARY

[0003] The application aims to provide a high-attachment polypropylene aluminum-plated film and a preparation method thereof, which can inhibit the decrease of the adhesion between the aluminum-plated layer and the base film caused by the migration of the precipitate of the slip agent.

[0004] The application can be achieved by the following technical scheme.

[0005] A high-attachment polypropylene aluminum-plated film, comprising a corona layer material, a core layer material and a heat sealing layer material.

[0006] The heat sealing layer material comprises a multi-component copolymerized polypropylene, a slip agent, an antioxidant, an anti-blocking master batch, an antistatic agent and a stabilizer.

[0007] The stabilizer is prepared by grafting carboxylated titanium dioxide on an amino-silica coating.

[0008] The coating is nano calcium carbonate.

[0009] As a preferred technical scheme of the application, the corona layer material comprises a homopolymerized polypropylene, a linear low-density polyethylene, a permeability-improving master batch and an anti-blocking master batch.

[0010] As a preferred technical scheme of the application, the core layer material comprises a homopolymerized polypropylene.

[0011] As a preferred technical scheme of the application, the mass ratio of the multi-component copolymerized polypropylene, the slip agent, the antioxidant, the anti-blocking master batch, the antistatic agent and the stabilizer is 35-55:0.1-0.2:0.1-0.2:0.2-0.3:0.1-0.2:0.1-0.2.

[0012] As a preferred technical scheme of the present application, the mass ratio of the homopolypropylene, the linear low-density polyethylene, the anti-adhesion master batch and the anti-adhesion master batch is 50-70:15-25:0.2-0.3:0.1-0.2.

[0013] As a preferred technical scheme of the present application, the mass fraction of the homopolypropylene is 65-75.

[0014] As a preferred technical scheme of the present application, the slip agent comprises at least one of oleic acid amide and erucic acid amide.

[0015] The preparation method of the high-adhesion polypropylene aluminum-plated film comprises the following steps:

[0016] S1, batching: preparing corona layer material, core layer material and heat-sealing layer material;

[0017] S2, after the corona layer material, the core layer material and the heat-sealing layer material are respectively blended, they are put into a three-layer co-extrusion flow casting machine, melted and extruded, and vacuum flow casted to obtain a flow-cast polypropylene base film;

[0018] S3, corona treatment, and spraying high-purity aluminum molecules to obtain an aluminum-plated flow-cast polypropylene film.

[0019] The present application has the following beneficial effects:

[0020] (1) The high-adhesion polypropylene aluminum-plated film and the preparation method thereof disclosed in the present application can inhibit the migration of the amide slip agent to the corona-treated surface layer of the film by introducing a stabilizer, thereby avoiding the rapid attenuation of the surface tension of the film and maintaining the adhesion of the aluminum layer.

[0021] (2) The high-adhesion polypropylene aluminum-plated film and the preparation method thereof disclosed in the present application can have strong adsorption to small molecule amide slip agents by introducing high-dispersibility nano calcium carbonate and nano titanium dioxide for synergistic effect, thereby inhibiting the migration of the slip agent.

[0022] (3) The high-adhesion polypropylene aluminum-plated film and the preparation method thereof disclosed in the present application can further inhibit the migration of the slip agent by the adsorption between the amide bond generated by the amidation reaction of the carboxylated nano titanium dioxide and the amino-silica dioxide and the amide slip agent. DETAILED DESCRIPTION

[0023] In order to further illustrate the technical means and effects adopted by the present application to achieve the predetermined application purposes, the specific embodiments, structures, features and effects according to the present application are described in detail as follows in combination with the embodiments. Embodiment 1

[0024] A preparation method of a high-adhesion polypropylene aluminum-plated film comprises the following steps:

[0025] S1, batching: preparing the corona layer material, the core layer material and the heat-seal layer material;

[0026] S2, after the corona layer material, the core layer material and the heat-seal layer material are respectively blended, they are put into a three-layer co-extrusion casting machine, the three-layer co-extrusion casting machine is heated in sections, the temperature of the first section is 165℃, the temperature of the second section is 180℃, the temperature of the third section is 210℃, the temperature of the die head is 225℃, the extruded material flows through the same die head lip, the temperature of the casting roller is set to 30℃, the extruded material is rapidly cooled and formed under the condition that the vacuum pressure is 1mbar, and a cast polypropylene base film is obtained;

[0027] S3, on the corona treatment surface of the cast polypropylene base film that has undergone surface corona treatment, a layer of high-purity aluminum molecules with a thickness of 0.05μm is sprayed under high-vacuum conditions (1×10 -6 Mbar), and an aluminum-coated cast polypropylene film is obtained; wherein the thickness of the corona layer is 5μm, the thickness of the core layer is 15μm, and the thickness of the heat-seal layer is 5μm.

[0028] The corona layer material includes 50 parts by mass of homopolymer polypropylene, 15 parts by mass of linear low-density polyethylene, 0.2 parts by mass of a transmittance-improving master batch, and 0.1 parts by mass of an anti-blocking master batch; the homopolymer polypropylene is of the type PPH-MN12 (ZHP12J) from the Shanghai Caojing Business Department of Sinopec Chemical Sales Co., Ltd.; the linear low-density polyethylene is of the type Lunicene M4040 from Shanghai Lingding Trading Co., Ltd.; the transmittance-improving master batch is of the type NA605B-JL from Shantou Best Technology Co., Ltd.; and the anti-blocking master batch is of the type 928 from Shantou Best Technology Co., Ltd.

[0029] The core layer material includes 65 parts by mass of homopolymer polypropylene, which is composed of 30 parts by mass of HP510M-Z (from Zhuhai Shell Petrochemical Co., Ltd.) and 35 parts by mass of PPH-MN12 (ZHP12J).

[0030] The heat-seal layer material includes 35 parts by mass of multi-component copolymer polypropylene (of the type LH-F6908 from Lihezhixin New Material Technology Co., Ltd.), 0.1 parts by mass of a slip agent (composed of oleic acid amide and erucic acid amide at a mass ratio of 1:3), 0.1 parts by mass of antioxidant 626, 0.2 parts by mass of anti-blocking master batch AB6018PPR (from Suzhou Constap Engineering Plastics Co., Ltd.), 0.1 parts by mass of antistatic agent HDC-103, and 0.1 parts by mass of a stabilizer.

[0031] The preparation method of the stabilizer includes the following steps:

[0032] A1, take polypropylene glycol-polyethylene glycol-polypropylene glycol triblock copolymer, 37% mass fraction hydrochloric acid solution, deionized water, n-butyl alcohol mixed, stirring at 35℃ for 1h, add tetraethyl orthosilicate, continue to stir for 24h, transfer to Teflon stainless steel autoclave, at 100℃ for 24h, filter the solid phase, washing, drying, calcining at 500℃ for 6h, grinding, get mesoporous silica; the polypropylene glycol-polyethylene glycol-polypropylene glycol triblock copolymer, hydrochloric acid solution, deionized water, n-butyl alcohol, tetraethyl orthosilicate ratio is 6g: 18mL: 200mL: 7g: 12.8g;

[0033] A2, take 100g of quicklime, 90℃ deionized water 500mL mixed, stirring 1h, stand overnight, through 200 mesh screen, take liquid phase into 1g barium chloride, at 10℃ stirring carbon dioxide-nitrogen mixed gas to pH to 6.5, aging 12h, remove supernatant, get calcium carbonate slurry; the carbon dioxide-nitrogen mixed gas in the volume content of carbon dioxide is kept at 20%;

[0034] A3, take the calcium carbonate slurry into deionized water mixed dilution, get 100g of calcium carbonate mass fraction of 8% calcium carbonate slurry, ultrasonic dispersion 1h, add 8g of L-lysine, heating at 50℃ water bath stirring 1h, get modified nano calcium carbonate slurry;

[0035] A4, take the mesoporous silica, modified nano calcium carbonate slurry mixed, ice bath ultrasonic treatment 30min, after treatment transfer to vacuum drying oven at 0.1MPa vacuum conditions for 30min, centrifugal mixture, collect solid phase washing, drying, get mesoporous silica coating; the mesoporous silica, modified nano calcium carbonate slurry ratio is 1g: 14mL;

[0036] A5, take the silica coated calcium carbonate ultrasonic dispersion in toluene, add KH-550, at 80℃ reflux stirring 10h, filter the solid phase washing, vacuum drying, get aminosilica coated; the silica coated calcium carbonate, toluene, KH-550 ratio is 0.3g: 50mL: 0.2g;

[0037] A6, take nano titanium dioxide, deionized water mixed, magnetic stirring 1h, ultrasonic treatment 20min, add sodium chloroacetate, with 0.1mol / L sodium hydroxide solution to adjust pH to 11, at 110℃ oil bath heating 3h, filter, take solid phase washing to neutral, vacuum drying 10h, get carboxylated titanium dioxide; the nano titanium dioxide, deionized water, sodium chloroacetate ratio is 3.4g: 500mL: 3.4g;

[0038] A7, the amino-silica coating, toluene, ultrasonic treatment for 20 min, stirring at 45℃ for 15 min, adding carboxylated titanium dioxide, continue stirring for 10 h, filtration, washing, drying, the solid phase, the stabilizer is obtained; the amino-silica coating, toluene, carboxylated titanium dioxide, the amount ratio is 0.18g: 50ml: 0.2g. Example 2

[0039] A preparation method of a high-attachment polypropylene aluminum-plated film, comprising the following steps:

[0040] S1, batching: preparing corona layer material, core layer material and heat sealing layer material;

[0041] S2, the corona layer material, the core layer material and the heat sealing layer material are respectively blended and then put into a three-layer co-extrusion casting machine, the three-layer co-extrusion casting machine is heated in sections, the temperature of the first section is 165℃, the temperature of the second section is 180℃, the temperature of the third section is 210℃, and the temperature of the die head is 225℃; the extruded material is rapidly cooled and formed under the condition of vacuum pressure of 1mbar after flowing through the same die head lip, to obtain a cast polypropylene base film;

[0042] S3, a layer of high-purity aluminum molecules with a thickness of 0.05μm is sprayed on the corona treatment surface of the cast polypropylene base film which has been subjected to surface corona treatment under high vacuum state (1×10 -6 Mbar) to obtain an aluminum-plated cast polypropylene film; wherein the thickness of the corona layer is 5μm, the thickness of the core layer is 15μm, and the thickness of the heat sealing layer is 5μm.

[0043] The corona layer material comprises 60 parts by mass of homopolymer polypropylene, 20 parts by mass of linear low-density polyethylene, 0.25 parts by mass of anti-reflection master batch and 0.15 parts by mass of anti-blocking master batch; the homopolymer polypropylene is of type PPH-MN12 (ZHP12J) from Sinopec Shanghai Caojing Business Department; the linear low-density polyethylene is of type Lunicene M4040 from Shanghai Lingding Trading Co., Ltd.; the anti-reflection master batch is of type NA605B-JL from Shantou Best Technology Co., Ltd.; and the anti-blocking master batch is of type 928 from Shantou Best Technology Co., Ltd.

[0044] The core layer material comprises 70 parts by mass of homopolymer polypropylene, which is composed of 35 parts by mass of HP510M-Z (from Zhonghai Shell Petrochemical Co., Ltd.) and 35 parts by mass of PPH-MN12 (ZHP12J).

[0045] The heat-sealing layer material comprises 45 parts by mass of a multi-copolymerized polypropylene (model LH-F6908 from Lihezhixin New Material Technology Co., Ltd.), 0.15 parts by mass of a slip agent (consisting of oleic acid amide and erucic acid amide at a mass ratio of 1:3), 0.15 parts by mass of an antioxidant 626, 0.25 parts by mass of an anti-blocking masterbatch AB6018PPR (from Suzhou Constap Engineering Plastics Co., Ltd.), 0.15 parts by mass of an antistatic agent HDC-103, and 0.15 parts by mass of a stabilizer.

[0046] The preparation method of the stabilizer comprises the following steps:

[0047] A1, mix polypropylene glycol-polyethylene glycol-polypropylene glycol triblock copolymer, 37% hydrochloric acid solution, deionized water, n-butanol, stir at 35℃ for 1.5h, add tetraethyl orthosilicate, continue to stir for 24h, transfer to a Teflon stainless steel autoclave, stand at 100℃ for 24h, filter the solid phase, wash, dry, calcine at 525℃ for 5h, grind to obtain mesoporous silica; the dosing ratio of the polypropylene glycol-polyethylene glycol-polypropylene glycol triblock copolymer, hydrochloric acid solution, deionized water, n-butanol, tetraethyl orthosilicate is 6.5g:19mL:200mL:7.5g:13.1g;

[0048] A2, mix 100g of quicklime and 500mL of deionized water at 90℃, stir for 1.5h, stand overnight, pass through a 200-mesh screen, add 1g of barium chloride to the liquid phase, stir while passing in carbon dioxide-nitrogen mixed gas to pH 6.5 at 15℃, age for 12h, remove the supernatant to obtain a calcium carbonate slurry; the volume content of carbon dioxide in the carbon dioxide-nitrogen mixed gas is kept at 30%;

[0049] A3, dilute the calcium carbonate slurry by mixing with deionized water to obtain 100g of a calcium carbonate slurry with a mass fraction of 9% calcium carbonate, ultrasonic dispersion for 1.5h, add 9g of L-lysine, heat and stir at 50℃ water bath for 1.5h to obtain a modified nano calcium carbonate slurry;

[0050] A4, mix the mesoporous silica and the modified nano calcium carbonate slurry, ice-bath ultrasonic treatment for 35min, after treatment, transfer to a vacuum drying oven under vacuum condition of 0.1MPa for 35min, centrifuge the mixture, collect the solid phase, wash, dry to obtain a mesoporous silica coating; the dosing ratio of the mesoporous silica and the modified nano calcium carbonate slurry is 1.5g:16mL;

[0051] A5, the silica-coated calcium carbonate is ultrasonically dispersed in toluene, KH-550 is added, reflux stirring is carried out at 80 DEG C for 15h, the solid phase is filtered, washing, vacuum drying, and the amino-silica-coated material is obtained;The silica-coated calcium carbonate, toluene, KH-550 are 0.38g: 50ml: 0.25g in the ratio of the amount of preparation.

[0052] A6, the nano-titanium dioxide is mixed with deionized water, magnetic stirring is carried out for 1.5h, ultrasonic treatment is carried out for 25min, sodium chloroacetate is added, 0.1mol / L sodium hydroxide solution is used to adjust pH to 12, oil bath heating is carried out at 110 DEG C for 3.5h, filtration is carried out, the solid phase is washed until pH is neutral, vacuum drying is carried out for 11h, and the carboxylated titanium dioxide is obtained;The nano-titanium dioxide, deionized water, sodium chloroacetate are 3.8g: 500ml: 3.6g in the ratio of the amount of preparation.

[0053] A7, the amino-silica-coated material is mixed with toluene, ultrasonic treatment is carried out for 25min, stirring is carried out at 45 DEG C for 20min, the carboxylated titanium dioxide is added, and continues to stir for 12h, filtration is carried out, the solid phase is washed, and drying is carried out, and the stabilizer is obtained;The amino-silica-coated material, toluene, carboxylated titanium dioxide are 0.21g: 50ml: 0.23g in the ratio of the amount of preparation. Example 3

[0054] A kind of preparation method of high-attached polypropylene aluminized film, comprising the following steps:

[0055] S1, ingredient: prepare corona layer material, core layer material and heat seal layer material;

[0056] S2, the corona layer material, core layer material and heat seal layer material are respectively blended and then put into three-layer co-extrusion casting machine, the three-layer co-extrusion casting machine is heated in sections, the temperature of one section is 165 DEG C, the temperature of two sections is 180 DEG C, the temperature of three sections is 210 DEG C, the die temperature is 225 DEG C;The extrusion is carried out through the same die lip, the temperature of casting roller is set to 30 DEG C, under the condition that the vacuum pressure is 1mbar, the extrusion material is rapidly cooled and formed, and the casting polypropylene base film is obtained;

[0057] S3, on the corona treatment surface of the casting polypropylene base film treated by surface corona, a layer of high-purity aluminum molecules with a thickness of 0.05 μm is sprayed under high vacuum state (1x10 -6 Mbar), and an aluminized casting polypropylene film is obtained;The thickness of the corona layer is 5 μm, the thickness of the core layer is 15 μm, and the thickness of the heat seal layer is 5 μm.

[0058] The corona layer material comprises 70 parts by mass of homopolymer polypropylene, 25 parts by mass of linear low-density polyethylene, 0.3 parts by mass of a transmittance-improving master batch, and 0.2 parts by mass of an anti-blocking master batch; the homopolymer polypropylene is of the type PPH-MN12 (ZHP12J) from the Shanghai Caojing Business Department of Sinopec Chemical Sales Co., Ltd.; the linear low-density polyethylene is of the type Lunicene M4040 from Shanghai Lingding Trading Co., Ltd.; the transmittance-improving master batch is of the type NA605B-JL from Shantou Best Technology Co., Ltd.; and the anti-blocking master batch is of the type 928 from Shantou Best Technology Co., Ltd.

[0059] The core layer material comprises 75 parts by mass of homopolymer polypropylene, which is composed of 38 parts by mass of HP510M-Z (from Zhuhai Shell Petrochemical Co., Ltd.) and 37 parts by mass of PPH-MN12 (ZHP12J).

[0060] The heat-sealing layer material comprises 55 parts by mass of multi-component copolymer polypropylene (of the type LH-F6908 from Lihezhixin New Material Technology Co., Ltd.), 0.2 parts by mass of a slip agent (composed of oleic acid amide and erucic acid amide at a mass ratio of 1:3), 0.2 parts by mass of antioxidant 626, 0.3 parts by mass of anti-blocking master batch AB6018PPR (from Suzhou Constap Engineering Plastics Co., Ltd.), 0.2 parts by mass of antistatic agent HDC-103, and 0.2 parts by mass of a stabilizer.

[0061] The preparation method of the stabilizer comprises the following steps:

[0062] A1, mix polypropylene glycol-polyethylene glycol-polypropylene glycol triblock copolymer, 37% hydrochloric acid solution, deionized water, and n-butanol, stir at 35°C for 2h, add tetraethyl orthosilicate, continue to stir for 24h, transfer to a Teflon stainless steel autoclave, stand at 100°C for 24h, filter the solid phase, wash, dry, calcine at 550°C for 4h, grind, and obtain mesoporous silica; the polypropylene glycol-polyethylene glycol-polypropylene glycol triblock copolymer, hydrochloric acid solution, deionized water, n-butanol, and tetraethyl orthosilicate are in a ratio of 7g:20mL:200mL:8g:13.5g;

[0063] A2, mix 100g of quicklime and 500mL of deionized water at 90°C, stir for 2h, stand overnight, pass through a 200-mesh sieve, take the liquid phase, add 1g of barium chloride, stir at 20°C, and pass in carbon dioxide-nitrogen mixed gas until the pH reaches 6.5, age for 12h, remove the supernatant, and obtain a calcium carbonate slurry; the volume content of carbon dioxide in the carbon dioxide-nitrogen mixed gas is kept at 40%;

[0064] A3, the calcium carbonate slurry is added to deionized water to dilute, to obtain 100 g of calcium carbonate slurry with a mass fraction of 10% of calcium carbonate, ultrasonic dispersion for 2 h, 10 g of L-lysine is added, heated in a water bath at 50℃ and stirred for 2 h, to obtain modified nano calcium carbonate slurry;

[0065] A4, the mesoporous silica and the modified nano calcium carbonate slurry are mixed, and ice bath ultrasonic treatment is performed for 40 min, then the mixture is transferred to a vacuum drying box and kept under a vacuum condition of 0.1 MPa for 40 min, and the mixture is centrifuged, the solid phase is collected, washed and dried to obtain a mesoporous silica coating; the amount ratio of the mesoporous silica and the modified nano calcium carbonate slurry is 2 g:18 mL;

[0066] A5, the silica-coated calcium carbonate is ultrasonically dispersed in toluene, KH-550 is added, refluxed and stirred at 80℃ for 20 h, the solid phase is collected by filtration, washed and vacuum dried to obtain an aminosilica coating; the amount ratio of the silica-coated calcium carbonate, toluene and KH-550 is 0.45 g:50 mL:0.3 g;

[0067] A6, the nano titanium dioxide and deionized water are mixed, magnetically stirred for 2 h, ultrasonically treated for 30 min, sodium chloroacetate is added, the pH is adjusted to 13 with 0.1 mol / L sodium hydroxide solution, heated in an oil bath at 110℃ for 4 h, filtered, the solid phase is collected, washed to neutral pH and vacuum dried for 12 h to obtain carboxylated titanium dioxide; the amount ratio of the nano titanium dioxide, deionized water and sodium chloroacetate is 4.2 g:500 mL:3.8 g;

[0068] A7, the aminosilica coating and toluene are mixed, ultrasonically treated for 30 min, stirred at 45℃ for 25 min, the carboxylated titanium dioxide is added, and the stirring is continued for 15 h, the solid phase is collected by filtration, washed and dried to obtain the stabilizer; the amount ratio of the aminosilica coating, toluene and carboxylated titanium dioxide is 0.24 g:50 mL:0.25 g.

[0069] Comparative Example 1

[0070] The difference from Example 2 is that no stabilizer is added to the heat-sealing layer material.

[0071] Comparative Example 2

[0072] The difference from Example 2 is that the preparation method of the stabilizer comprises the following steps:

[0073] A1, take polypropylene glycol-polyethylene glycol-polypropylene glycol triblock copolymer, 37% mass fraction of hydrochloric acid solution, deionized water, n-butanol mixed, stirring at 35℃ for 1.5h, add tetraethyl orthosilicate, continue to stir for 24h, transfer to Teflon stainless steel autoclave, at 100℃ for 24h, filter to get solid phase, washing, drying, calcining at 525℃ for 5h, grinding, get mesoporous silica; the polypropylene glycol-polyethylene glycol-polypropylene glycol triblock copolymer, hydrochloric acid solution, deionized water, n-butanol, tetraethyl orthosilicate ratio is 6.5g: 19ml: 200ml: 7.5g: 13.1g;

[0074] A2, take the mesoporous silica dispersed in toluene, add KH-550, reflux stirring at 80℃ for 15h, filter to get solid phase washing, vacuum drying, get aminosilica; the mesoporous silica, toluene, KH-550 ratio is 0.38g: 50ml: 0.25g;

[0075] A3, take nano titanium dioxide, deionized water mixed, magnetic stirring for 1.5h, ultrasonic treatment for 25min, add sodium chloroacetate, with 0.1mol / L of sodium hydroxide solution to adjust pH to 12, oil bath heating at 110℃ for 3.5h, filter, get solid phase washing to pH neutral, vacuum drying for 11h, get carboxylated titanium dioxide; the nano titanium dioxide, deionized water, sodium chloroacetate ratio is 3.8g: 500ml: 3.6g;

[0076] A7, take the aminosilica, toluene mixed, ultrasonic treatment for 25min, stirring at 45℃ for 20min, add carboxylated titanium dioxide, continue to stir for 12h, filter, get solid phase washing, drying, get the stabilizer; the aminosilica coating, toluene, carboxylated titanium dioxide ratio is 0.21g: 50ml: 0.23g.

[0077] Comparative example 3

[0078] The difference between example 2 is that the preparation method of the stabilizer comprises the following steps:

[0079] A1, take polypropylene glycol-polyethylene glycol-polypropylene glycol triblock copolymer, 37% mass fraction of hydrochloric acid solution, deionized water, n-butanol mixed, stirring at 35℃ for 1.5h, add tetraethyl orthosilicate, continue to stir for 24h, transfer to Teflon stainless steel autoclave, at 100℃ for 24h, filter to get solid phase, washing, drying, calcining at 525℃ for 5h, grinding, get mesoporous silica; the polypropylene glycol-polyethylene glycol-polypropylene glycol triblock copolymer, hydrochloric acid solution, deionized water, n-butanol, tetraethyl orthosilicate ratio is 6.5g: 19ml: 200ml: 7.5g: 13.1g;

[0080] A2, take 100 g of quicklime, 90 ℃ deionized water 500 mL mixed, stirring 1.5 h, stand overnight, through 200 mesh screen, take the liquid phase to add 1 g of barium chloride, at 15 ℃ stirring into carbon dioxide-nitrogen mixed gas to pH to 6.5, aging 12 h, remove the supernatant, to get calcium carbonate slurry; the volume content of carbon dioxide in the carbon dioxide-nitrogen mixed gas is kept at 30%;

[0081] A3, take the calcium carbonate slurry added deionized water mixed dilution, to get 100 g of calcium carbonate mass fraction of 9% calcium carbonate slurry, ultrasonic dispersion 1.5 h, add 9 g of L-lysine, in 50 ℃ water bath heating stirring 1.5 h, to get modified nano calcium carbonate slurry;

[0082] A4, take the mesoporous silica, modified nano calcium carbonate slurry mixed, ice bath ultrasonic treatment 35 min, after treatment to transfer to vacuum drying oven in 0.1 MPa vacuum conditions for 35 min, the mixture material centrifugation, collection of solid phase washing, drying, to get mesoporous silica coated material; the mesoporous silica, modified nano calcium carbonate slurry of the amount ratio is 1.5 g:16 mL;

[0083] A5, take the silica coated calcium carbonate ultrasonic dispersion in toluene, add KH-550, at 80 ℃ reflux stirring 15 h, filter to solid phase washing, vacuum drying, to get the stabilizer; the silica coated calcium carbonate, toluene, KH-550 of the amount ratio is 0.38 g:50 mL:0.25 g.

[0084] Comparative example 4

[0085] The difference between example 2 is that the preparation method of the stabilizer comprises the following steps:

[0086] A1, take polypropylene glycol-polyethylene glycol-polypropylene glycol triblock copolymer, mass fraction of 37% hydrochloric acid solution, deionized water, n-butanol mixed, stirring at 35 ℃ 1.5 h, add tetraethyl orthosilicate, continue stirring 24 h, transfer to Teflon stainless steel autoclave, at 100 ℃ stand 24 h, filter to solid phase, washing, drying, at 525 ℃ calcination 5 h, grinding, to get mesoporous silica; the polypropylene glycol-polyethylene glycol-polypropylene glycol triblock copolymer, hydrochloric acid solution, deionized water, n-butanol, tetraethyl orthosilicate of the amount ratio is 6.5 g:19 mL:200 mL:7.5 g:13.1 g;

[0087] A2, take 100g of quicklime, 90℃ of deionized water 500mL mixed, stirring 1.5h, stand overnight, through 200 mesh screen, take the liquid phase to add 1g of barium chloride, at 15℃ stirring into carbon dioxide-nitrogen mixed gas to pH to 6.5, aging 12h, remove the supernatant, get calcium carbonate slurry; the volume content of carbon dioxide in the carbon dioxide-nitrogen mixed gas is kept at 30%;

[0088] A3, take the calcium carbonate slurry added deionized water mixed dilution, ultrasonic dispersion 1.5h get 100g of calcium carbonate mass fraction of 9% calcium carbonate slurry;

[0089] A4, take the mesoporous silica, calcium carbonate slurry mixed, ice bath ultrasonic treatment 35min, after treatment to the vacuum drying oven under the condition of 0.1MPa vacuum pressure 35min, centrifugal collection of solid phase washing, drying, get mesoporous silica coated material; the amount of the mesoporous silica, calcium carbonate slurry is 1.5g: 16mL;

[0090] A5, take the silica coated calcium carbonate ultrasonic dispersion in toluene, add KH-550, at 80℃ reflux stirring 15h, filter, take the solid phase washing, vacuum drying, get aminosilica coated material; the amount of the silica coated calcium carbonate, toluene, KH-550 is 0.38g: 50mL: 0.25g;

[0091] A6, take nano titanium dioxide, deionized water mixed, magnetic stirring 1.5h, ultrasonic treatment 25min, add sodium chloroacetate, with 0.1mol / L of sodium hydroxide solution to adjust pH to 12, at 110℃ oil bath heating 3.5h, filtration, take the solid phase washing to pH neutral, vacuum drying 11h, get carboxylated titanium dioxide; the amount of the nano titanium dioxide, deionized water, sodium chloroacetate is 3.8g: 500mL: 3.6g;

[0092] A7, take the aminosilica coated material, toluene mixed, ultrasonic treatment 25min, at 45℃ stirring 20min, add carboxylated titanium dioxide, continue stirring 12h, filtration, take the solid phase washing, drying, get the stabilizer; the amount of the aminosilica coated material, toluene, carboxylated titanium dioxide is 0.21g: 50mL: 0.23g.

[0093] Comparative example 5

[0094] The difference from example 2 is that the preparation method of the stabilizer comprises the following steps:

[0095] A1, taking polypropylene glycol-polyethylene glycol-polypropylene glycol triblock copolymer, 37% hydrochloric acid solution, deionized water, n-butyl alcohol, stirring at 35°C for 1.5h, adding tetraethyl orthosilicate, continuing to stir for 24h, transferring to a Teflon stainless steel autoclave, standing at 100°C for 24h, filtering to take the solid phase, washing, drying, calcining at 525°C for 5h, grinding, to obtain mesoporous silica; the polypropylene glycol-polyethylene glycol-polypropylene glycol triblock copolymer, hydrochloric acid solution, deionized water, n-butyl alcohol, tetraethyl orthosilicate are in a ratio of 6.5g:19mL:200mL:7.5g:13.1g;

[0096] A2, taking 100g of quicklime, mixing with 500mL of deionized water at 90°C, stirring for 1.5h, standing overnight, passing through a 200 mesh screen, taking the liquid phase adding 1g of barium chloride, stirring while passing in carbon dioxide-nitrogen mixed gas to pH 6.5 at 15°C, aging for 12h, removing the supernatant to obtain a calcium carbonate slurry; the volume content of carbon dioxide in the carbon dioxide-nitrogen mixed gas is kept at 30%;

[0097] A3, taking the calcium carbonate slurry adding deionized water to dilute, to obtain 100g of calcium carbonate slurry with a mass fraction of 9% calcium carbonate, ultrasonic dispersion for 1.5h, adding 9g of L-lysine, heating in a water bath at 50°C and stirring for 1.5h to obtain a modified nano calcium carbonate slurry;

[0098] A4, taking the mesoporous silica, modified nano calcium carbonate slurry, ice bath ultrasonic treatment for 35min, after treatment, transferring to a vacuum drying oven under vacuum conditions of 0.1MPa for 35min, centrifuging the mixture, collecting the solid phase, washing, drying, to obtain a mesoporous silica coating; the mesoporous silica, modified nano calcium carbonate slurry are in a ratio of 1.5g:16mL;

[0099] A5, taking the silica-coated calcium carbonate, nano titanium dioxide, ultrasonic dispersion in toluene, ultrasonic treatment for 25min, filtering, washing, drying, to obtain the stabilizer; the silica-coated calcium carbonate, toluene, carboxylated titanium dioxide are in a ratio of 0.21g:50mL:0.23g.

[0100] Performance test

[0101] The mass of the slip agent exuded from the inner surface of the polypropylene film after the polypropylene aluminum-plated film prepared in Examples 1-3 and Comparative Examples 1-5 was placed at room temperature for 7 days and 14 days, and the results are shown in Table 1 below. The mass of the slip agent was tested using liquid chromatography, and the unit is mg / m 2 and the peeling strength, and the test results are shown in Table 1.

[0102] Table 1

[0103]

[0104] As shown in Table 1, the polypropylene aluminum film prepared in Examples 1-3 has good adhesion and migration inhibition performance; in Comparative Example 1, no stabilizer is added, resulting in a decrease in peel strength and an increase in migration amount; in Comparative Example 2, no nano calcium carbonate is added, resulting in a decrease in peel strength and an increase in migration amount; in Comparative Example 3, no nano titanium dioxide is added, resulting in a decrease in peel strength and an increase in migration amount; in Comparative Example 4, the nano calcium carbonate is not surface treated, resulting in agglomeration, a decrease in peel strength, and an increase in migration amount; in Comparative Example 5, no amidation modification is performed, resulting in a decrease in peel strength and an increase in migration amount.

[0105] The above description is only the preferred embodiment of the present application, and is not intended to limit the present application in any form. Although the present application has been disclosed as above with the preferred embodiment, it is not intended to limit the present application. Any person skilled in the art can make some changes or modifications to the above disclosed technical content without departing from the scope of the technical solution of the present application, and any equivalent embodiments with equivalent changes are equivalent to the above embodiments. Any modification, change, and modification of the above embodiments according to the technical essence of the present application are still within the scope of the technical solution of the present application.

Claims

1. A high adhesion polypropylene aluminized film, characterized by, The hot-seal layer material comprises a multi-component copolymerized polypropylene, a slip agent, an antioxidant, an anti-blocking master batch, an antistatic agent and a stabilizer; The stabilizer is prepared by grafting carboxylated titanium dioxide onto an amino-silica coating; The coating is nano calcium carbonate; The preparation method of the stabilizer comprises the following steps: A1, mix polypropylene glycol-polyethylene glycol-polypropylene glycol triblock copolymer, hydrochloric acid solution, deionized water and n-butanol, stir uniformly at 35 DEG C, add tetraethyl orthosilicate, continue to stir for 24h, transfer to a Teflon stainless steel autoclave, stand at 100 DEG C for 24h, filter the solid phase, wash, dry, calcine, grind, to obtain mesoporous silica; the polypropylene glycol-polyethylene glycol-polypropylene glycol triblock copolymer, hydrochloric acid solution, deionized water, n-butanol, tetraethyl orthosilicate are in a ratio of 6-7g: 18-20mL: 200mL: 7-8g: 12.8-13.5g; A2, mix 100g of quicklime and 500mL of deionized water at 90 DEG C, stir for 1-2h, stand overnight, pass through a 200 mesh screen, add 1g of barium chloride to the liquid phase, stir while passing carbon dioxide-nitrogen mixed gas at 10-20 DEG C until the pH reaches 6.5, age for 12h, remove the supernatant to obtain a calcium carbonate slurry; the volume content of carbon dioxide in the carbon dioxide-nitrogen mixed gas is maintained at 20-40%; A3, dilute the calcium carbonate slurry with deionized water to obtain a 100mL calcium carbonate slurry with a mass fraction of 8-10%, ultrasonic dispersion, add 8-10g of L-lysine, heat and stir at 50 DEG C water bath for 1-2h to obtain a modified nano calcium carbonate slurry; A4, mix the mesoporous silica and the modified nano calcium carbonate slurry, ice bath ultrasonic treatment, transfer to a vacuum drying oven under a vacuum of 0.1MPa for 30-40min, centrifuge the mixture, collect the solid phase, wash, dry to obtain a mesoporous silica coating; the mesoporous silica and the modified nano calcium carbonate slurry are in a ratio of 1-2g: 14-18mL; A5, ultrasonic dispersion of the silica-coated calcium carbonate in toluene, add KH-550, heat and reflux stirring, filter the solid phase, wash, vacuum drying, to obtain an amino-silica coating; the silica-coated calcium carbonate, toluene, KH-550 are in a ratio of 0.3-0.45g: 50mL: 0.2-0.3g; A6, mix nano titanium dioxide and deionized water, magnetic stirring, ultrasonic treatment, add sodium chloroacetate, adjust the pH to 11-13, oil bath heating, filter, wash the solid phase to neutral pH, vacuum drying, to obtain carboxylated titanium dioxide; the nano titanium dioxide, deionized water, sodium chloroacetate are in a ratio of 3.4-4.2g: 500mL: 3.4-3.8g; ​ A7, the amino-silica coating, toluene mixture, ultrasonic treatment, heating and stirring, adding carboxylated titanium dioxide, continue stirring, filtration, washing, drying, the solid phase, the stabilizer is obtained; the amino-silica coating, toluene, carboxylated titanium dioxide ratio is 0.18-0.24g: 50ml: 0.2-0.25g.

2. The high adhesion polypropylene aluminum clad film according to claim 1, characterized in that, The corona layer material comprises homopolymer polypropylene, linear low density polyethylene, anti-sticking masterbatch and anti-blocking masterbatch.

3. The high adhesion polypropylene aluminum clad film according to claim 1, wherein, The core layer material comprises homopolymer polypropylene.

4. The high-adhesion polypropylene-aluminum laminated film according to claim 1, wherein The mass ratio of the multi-component copolymer polypropylene, the slip agent, the antioxidant, the anti-blocking masterbatch, the antistatic agent and the stabilizer is 35-55: 0.1-0.2: 0.1-0.2: 0.2-0.3: 0.1-0.2: 0.1-0.

2.

5. The high adhesion polypropylene aluminum laminated film according to claim 2, wherein, The mass ratio of the homopolymer polypropylene, the linear low density polyethylene, the anti-sticking masterbatch and the anti-blocking masterbatch is 50-70: 15-25: 0.2-0.3: 0.1-0.

2.

6. The high-adhesion polypropylene-aluminum laminated film according to claim 3, wherein the polypropylene layer is a polypropylene layer having a thickness of 10 to 30 μm. The mass fraction of the homopolymer polypropylene is 65-75.

7. The high-adhesion polypropylene-aluminum laminated film according to claim 1, wherein The slip agent comprises at least one of oleic acid amide and erucic acid amide.

8. A method of producing a high adhesion polypropylene-aluminum laminated film according to any one of claims 1 to 7, characterized by, The method comprises the following steps: S1, batching: preparing the corona layer material, the core layer material and the heat-sealing layer material; S2, the corona layer material, the core layer material and the heat-sealing layer material are respectively blended and then put into a three-layer co-extrusion casting machine, melted and extruded, and vacuum cast to obtain a cast polypropylene base film; the three-layer co-extrusion casting machine is heated in sections, the temperature of the first section is 165℃, the temperature of the second section is 180℃, the temperature of the third section is 210℃, and the temperature of the die head is 225℃; S3, corona treatment, spraying high-purity aluminum molecules to obtain an aluminum-coated cast polypropylene film; wherein the thickness of the corona layer is 5μm, the thickness of the core layer is 15μm, and the thickness of the heat-sealing layer is 5μm.

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