A high-barrier composite hose for cosmetic packaging and its preparation method

Abstract

The present application relates to the technical field of composite hoses for cosmetic packaging, and in particular to a high-barrier composite hose for cosmetic packaging and a method for preparing the same. A high-barrier composite hose for cosmetic packaging, wherein the composite hose comprises, from the outside to the inside, a polyethylene film layer, an adhesive layer, a vacuum sputtered deposited alumina polyethylene film, an adhesive layer, and an antibacterial polyethylene layer; wherein the antibacterial polyethylene layer comprises the following raw materials in parts by mass: high-density polyethylene, low-density polyethylene, metallocene polyethylene, β-cyclodextrin modified titanium dioxide, an antioxidant, an antibacterial agent, and a coupling agent. The high-barrier composite hose for cosmetic packaging of the present application has excellent comprehensive performance, antibacterial performance, and barrier performance, and is also recyclable and reusable, and can provide an efficient, safe, and environmentally friendly packaging solution for the cosmetic packaging industry.

Description

Technical Field

[0001] The present application relates to the technical field of composite hoses for cosmetic packaging, and in particular to a high-barrier composite hose for cosmetic packaging and a preparation method thereof. Background Art

[0002] With the growing popularity of the cosmetics consumer market, the cosmetics packaging industry has also experienced rapid growth. Cosmetics packaging materials are categorized into composite hoses, rigid packaging boxes, and packaging films. Composite hoses, used to contain cosmetics, provide a barrier and preserve the product's quality, directly impacting its storage and quality, making them an essential component of cosmetic packaging. During use, due to repeated external pressure, composite hoses are susceptible to deformation and damage, leading to leakage of the contents. Furthermore, in humid environments, the long-term infiltration of water vapor and oxygen can affect the quality of the contents, and oxygen molecules in the air outside the hose can interpenetrate with the molecules within.

[0003] At present, the commonly used packaging materials in the field of high-barrier packaging include polyolefin (PE, PP) films, EVOH multi-layer co-extruded films, aluminum-plastic composite hoses, etc. Polyolefin (PE, PP) has good chemical stability, does not fall off or degrade into foreign matter, is safe and environmentally friendly, but has poor barrier properties (especially oxygen barrier properties) and no antibacterial properties. For products that are sensitive to water and oxygen, EVOH multi-layer co-extruded film can be used. Its barrier properties are significantly improved compared to polyolefin packaging materials, but its hygroscopicity is weak and its moisture-proof effect is poor, which will lead to a decrease in the shelf life and quality of the packaged products. It is only limited to the packaging of mid- and low-end products and cannot meet the packaging needs of higher-end products.

[0004] Therefore, there is an urgent need to develop a composite hose for cosmetic packaging with excellent comprehensive performance, barrier properties and antibacterial properties. Summary of the Invention

[0005] In response to the deficiencies in the prior art, the present application provides a high-barrier composite hose for cosmetic packaging and a method for preparing the same.

[0006] In the first aspect, the present application provides a high-barrier composite hose for cosmetic packaging using the following technical solutions:

[0007] A high-barrier composite hose for cosmetic packaging, comprising, from the outside to the inside, a polyethylene film layer, an adhesive layer, a vacuum sputtered alumina polyethylene film, an adhesive layer, and an antibacterial polyethylene layer; wherein the antibacterial polyethylene layer comprises the following raw materials in parts by weight: 40-45 parts of high-density polyethylene, 8-10 parts of low-density polyethylene, 18-22 parts of metallocene polyethylene, 20-25 parts of β-cyclodextrin-modified titanium dioxide, 3-5 parts of an antioxidant, 0.5-1 part of an antibacterial agent, and 2-3 parts of a coupling agent.

[0008] By adopting the above technical solution, the polyethylene film layer, serving as the base material of the hose, exhibits excellent transparency and flexibility, protecting the cosmetics inside from the external environment. The adhesive layer is used to tightly bond the various material layers together, enhancing the overall stability of the hose. The vacuum sputtering-deposited alumina polyethylene film forms a dense atomic layer on the surface of the polyethylene film, improving the hose's ability to block oxygen and moisture, preventing the interpenetration of oxygen molecules and cosmetic molecules within the hose. The antibacterial polyethylene layer, a key component of this application, comprises a variety of raw materials and has the following functions: High-density polyethylene and low-density polyethylene increase the flexibility and durability of the polyethylene layer. Metallocene polyethylene strengthens the adhesion between the polyethylene layer and other layers, improving the overall stability of the hose. β-cyclodextrin-modified titanium dioxide improves the compatibility of the composite hose, forming a three-dimensional network structure, increasing steric hindrance, and enhancing the hose's barrier properties. The antioxidant protects the hose material from oxidation and aging, extending the hose's service life. The antibacterial agent imparts antibacterial properties to the hose, effectively inhibiting the growth of bacteria that may be introduced during the cosmetic packaging process. Coupling agent: promotes the synergistic effect of each layer of material and enhances the overall performance of the hose. Through the above multi-layer combination, the cosmetic packaging composite hose of the present application has excellent comprehensive performance, good antibacterial properties and excellent barrier properties, effectively protecting the internal cosmetics from contamination by the external environment and extending the service life.

[0009] Preferably, the polyethylene film layer is blow-molded from a polyethylene material, has a thickness of 50-130 μm, and has a peel strength after heat sealing of more than 43 N / 15 mm.

[0010] Preferably, the method for preparing the vacuum sputtering deposition aluminum oxide polyethylene film comprises the following steps:

[0011] S31, send the polyethylene film to the continuous vacuum sputtering equipment, when the vacuum degree reaches 5×10 -2 When the plasma is modified, the plasma power is 10 kW, the bias voltage is 200 V, the duty cycle is 40%, the argon flow rate is 200 SCCM, the oxygen flow rate is 500 SCCM, and the time is 0.5-1 min;

[0012] S32, sputtering the plasma modified polyethylene film to deposit aluminum oxide, to obtain an aluminum oxide polyethylene film, the process conditions are: when the vacuum degree reaches 8×10 -3 The sputtering power is 20KW, the deposition time is 5-10min, the bias voltage is 40V, the duty cycle is 60%, the argon flow rate is 20SCCM, the oxygen flow rate is 300SCCM, and the sputtering target is 99.99% pure aluminum target.

[0013] Preferably, the thickness of the vacuum sputtering deposited aluminum oxide polyethylene film is 50-100 μm, and the oxygen permeability is ≤0.4 cm 3 / (m 2 *24h), water vapor transmission rate ≤0.4cm 3 / (m 2 *24h), the effective resistance to the rubbing test is 50 times.

[0014] By adopting the above-mentioned technical solution, the role and synergistic effect of the vacuum sputtering deposited aluminum oxide polyethylene film in this application are as follows: Blocking oxygen and moisture: The dense atomic layer formed by vacuum sputtering deposited aluminum oxide effectively blocks the penetration of oxygen and moisture, thereby protecting cosmetics from oxidation and moisture damage. Improving rub resistance: The vacuum sputtering deposited aluminum oxide polyethylene film can effectively resist 50 rub tests and maintain the integrity and stability of the hose. Through the above characteristics, the vacuum sputtering deposited aluminum oxide polyethylene film plays an important role in the composite hose. It can significantly improve the barrier performance of the hose and prevent the mutual penetration between the molecules of the media inside and outside the hose, thereby maintaining the quality and stability of the cosmetics. At the same time, the vacuum sputtering deposited aluminum oxide polyethylene film also has the property of anti-rub, which improves the service life of the hose, making the composite hose have more advantages in cosmetic packaging.

[0015] Preferably, the adhesive layer is made of polyethylene as dry base and ethyl acetate as solvent with a solid content of 50% adhesive, which is cured, has a thickness of 3-4 μm and a coating amount of 6-7 g / m 2 The dry basis weight of the adhesive is 3-3.2g / m 2 .

[0016] Preferably, the preparation method of the β-cyclodextrin modified titanium dioxide comprises the following steps:

[0017] S61. In 400 mL of toluene, 8 g of titanium dioxide and 8 mL of γ-methacryloxypropyltrimethoxysilane were added. Under nitrogen protection, the mixture was refluxed at 130° C. with stirring for 10 h. The mixture was cooled, filtered, washed with acetone and methanol three times, and then dried in vacuo at 110° C. for 10 h to obtain substance A.

[0018] S62. Add 1 g of β-cyclodextrin and 0.2 g of sodium hydroxide to 200 mL of dimethylformamide, stir for 1 hour, and then filter. Add 4 g of substance A to the filtrate. Under nitrogen protection, reflux and stir at 118°C for 28 hours, cool and filter. The obtained solid material is washed three times with acetone and methanol in sequence, and then vacuum dried at 100°C for 10 hours to obtain β-cyclodextrin-modified titanium dioxide.

[0019] By adopting the above technical solution, the preparation method of β-cyclodextrin-modified titanium dioxide prepares β-cyclodextrin-modified titanium dioxide through the reaction of β-cyclodextrin and titanium dioxide. This modified titanium dioxide has the following effects and synergistic effects: Improving the compatibility of the system: Due to the reaction between β-cyclodextrin and titanium dioxide, titanium dioxide is dispersed in the β-cyclodextrin molecules, increasing the compatibility of the system and preventing the agglomeration of titanium dioxide particles. Forming a three-dimensional network structure: Due to the presence of β-cyclodextrin, titanium dioxide forms a three-dimensional network structure during the formation process, increasing steric hindrance and giving the modified titanium dioxide a more stable and dense structure. Improving the barrier properties of the hose: The introduction of β-cyclodextrin-modified titanium dioxide significantly improves the barrier properties of the hose. It can effectively prevent the mutual penetration between oxygen molecules in the air outside the hose and the molecules inside the hose, thereby protecting the quality of the cosmetics. Providing antimicrobial properties: The antimicrobial agent added to the antimicrobial polyethylene layer interacts with β-cyclodextrin-modified titanium dioxide, imparting excellent antimicrobial properties to the cosmetics packaging composite hose, effectively inhibiting bacterial growth. In summary, the introduction of β-cyclodextrin-modified titanium dioxide enhances the barrier and antimicrobial properties of the composite hose, ensuring the quality and stability of cosmetics. Furthermore, this modified titanium dioxide synergizes with the other layered materials to enhance the overall performance of the composite hose.

[0020] Preferably, the antioxidant is selected from a composition of antioxidant 1010 and butylated hydroxyanisole in a mass ratio of 5:1-3.

[0021] Preferably, the coupling agent is selected from a composition of isopropyl tristearate titanate and γ-methacryloxypropyl trimethoxysilane in a mass ratio of 4:1-2.

[0022] By adopting the above technical solution, the coupling agent is selected from a composition of isopropyl tristearate titanate and γ-methacryloxypropyl trimethoxysilane in a mass ratio of 4:1-2. This coupling agent plays the following roles and synergistic effects in high-barrier composite hoses for cosmetic packaging: It promotes bonding between raw materials: As a component of the adhesive layer, the coupling agent promotes bonding between raw materials, improving the overall performance of the composite hose. It also improves the bond strength of the composite material: Due to the presence of the coupling agent, it can strengthen the bond strength between different film layers, increasing the stability and durability of the composite hose. It also improves the barrier properties of the hose: The coupling agent works together with other ingredients to enhance the barrier properties of the composite hose. For example, the introduction of the coupling agent can improve the interfacial bonding strength between the polyethylene film and other layers, preventing the penetration of oxygen and moisture, thereby improving the barrier properties of the hose.

[0023] Preferably, the antibacterial agent is Dongguan Mingyuan antibacterial agent KP-J67.

[0024] In a second aspect, the present application provides a method for preparing a high-barrier composite hose for cosmetic packaging, using the following technical solution:

[0025] A method for preparing a high-barrier composite hose for cosmetic packaging, using the raw materials of the above-mentioned high-barrier composite hose for cosmetic packaging, the preparation method comprises the following steps:

[0026] S101, preparation of antibacterial polyethylene layer: high-density polyethylene, low-density polyethylene, metallocene polyethylene, β-cyclodextrin-modified titanium dioxide, antioxidant, antibacterial agent and coupling agent are mixed uniformly at 132° C., followed by extrusion granulation and blow molding into a film to obtain an antibacterial polyethylene layer with a thickness of 50-100 μm;

[0027] S102, preparing a vacuum sputtering-deposited aluminum oxide polyethylene film: using a polyethylene film as a substrate, depositing aluminum oxide on the surface of the polyethylene film by a plasma-enhanced sputtering deposition method to form a thin film layer, thereby obtaining a vacuum sputtering-deposited aluminum oxide polyethylene film;

[0028] S103, compounding: applying a polyethylene adhesive between the polyethylene film layer and the vacuum sputtering deposited aluminum oxide polyethylene film prepared in step S102, and between the vacuum sputtering deposited aluminum oxide polyethylene film prepared in step S102 and the antibacterial polyethylene layer prepared in step S101, respectively, to form adhesive layers; and compounding the polyethylene film layer, the vacuum sputtering deposited aluminum oxide polyethylene film, and the antibacterial polyethylene layer into a composite film roll through the bonding effect of the cured adhesive layers to obtain a composite film roll;

[0029] S104, rolling the composite film into a composite hose for cosmetic packaging required by the customer.

[0030] In summary, this application includes at least one of the following beneficial technical effects:

[0031] 1. Excellent comprehensive performance: The cosmetic packaging composite hose has a reasonable structural design and the selection and proportion of the materials of each layer are properly matched, so that the hose has excellent comprehensive performance, including high barrier performance, antibacterial performance and anti-permeation performance.

[0032] 2. Excellent antibacterial properties: By adding antibacterial agents and β-cyclodextrin-modified titanium dioxide and other raw materials, the antibacterial polyethylene layer has excellent antibacterial properties, which can effectively inhibit the growth and reproduction of bacteria and protect the quality and safety of cosmetics.

[0033] 3. Good barrier performance: By adding alumina polyethylene film obtained by vacuum sputtering deposition of alumina and antibacterial polyethylene layer obtained by adding β-cyclodextrin modified titanium dioxide, the barrier performance of the hose can be significantly improved, preventing the penetration of external substances such as oxygen molecules and moisture, and protecting the stability and quality of cosmetics.

[0034] 4. Recyclable and reusable: By using vacuum sputtering deposition of alumina to replace aluminum foil, the problem of aluminum foil recycling is solved, so that the composite hose can be recycled and reused repeatedly, extending the service life, reducing costs, and also meeting environmental protection requirements. DETAILED DESCRIPTION

[0035] The embodiments of the present application will be described in detail below with reference to the examples, but it will be appreciated by those skilled in the art that the following examples are merely illustrative of the present application and should not be construed as limiting the scope of the present application. Specific conditions not specified in the examples are carried out according to conventional conditions or manufacturer recommendations. The reagents used or the instruments not specified in the manufacturer's specifications are conventional products that can be purchased commercially. Metallocene polyethylene is the metallocene polyethylene produced by Pu Ruiman, antioxidant 1010 is the antioxidant 1010 of BASF, and antibacterial agent is the antibacterial agent KP-J67 of Dongguan Mingyuan Company.

[0036] Preparation Example 1: Preparation of β-cyclodextrin modified titanium dioxide

[0037] The preparation method of β-cyclodextrin modified titanium dioxide comprises the following steps:

[0038] S61. In 400 mL of toluene, 8 g of titanium dioxide and 8 mL of γ-methacryloxypropyltrimethoxysilane were added. Under nitrogen protection, the mixture was refluxed at 130° C. with stirring for 10 h. The mixture was cooled, filtered, washed with acetone and methanol three times, and then dried in vacuo at 110° C. for 10 h to obtain substance A.

[0039] S62. Add 1 g of β-cyclodextrin and 0.2 g of sodium hydroxide to 200 mL of dimethylformamide, stir for 1 hour, and then filter. Add 4 g of substance A to the filtrate. Under nitrogen protection, reflux and stir at 118°C for 28 hours, cool and filter. The obtained solid material is washed three times with acetone and methanol in sequence, and then vacuum dried at 100°C for 10 hours to obtain β-cyclodextrin-modified titanium dioxide.

[0040] Preparation Example 2: Preparation of vacuum sputtering deposited aluminum oxide polyethylene film

[0041] The method for preparing a vacuum sputtering deposition aluminum oxide polyethylene film comprises the following steps:

[0042] S31, send the polyethylene film to the continuous vacuum sputtering equipment, when the vacuum degree reaches 5×10 -2 When the plasma modification was carried out, the plasma power was 10 kW, the bias voltage was 200 V, the duty cycle was 40%, the argon flow rate was 200 SCCM, the oxygen flow rate was 500 SCCM, and the time was 0.5 min;

[0043] S32, sputtering the plasma modified polyethylene film to deposit aluminum oxide, to obtain an aluminum oxide polyethylene film, the process conditions are: when the vacuum degree reaches 8×10 -3 The sputtering power was 20KW, the deposition time was 5min, the bias voltage was 40V, the duty cycle was 60%, the argon flow rate was 20SCCM, the oxygen flow rate was 300SCCM, and the sputtering target was 99.99% pure aluminum. The thickness of the vacuum sputtering deposited aluminum oxide polyethylene film was 50μm and the oxygen permeability was 0.32cm 3 / (m 2 *24h), water vapor transmission rate is 0.31cm 3 / (m 2 *24h), the effective resistance to the rubbing test is 50 times.

[0044] Preparation Example 3: Preparation of vacuum sputtering deposited aluminum oxide polyethylene film

[0045] The method for preparing a vacuum sputtering deposition aluminum oxide polyethylene film comprises the following steps:

[0046] S31, send the polyethylene film to the continuous vacuum sputtering equipment, when the vacuum degree reaches 5×10 -2 When the plasma modification was carried out, the plasma power was 10 kW, the bias voltage was 200 V, the duty cycle was 40%, the argon flow rate was 200 SCCM, the oxygen flow rate was 500 SCCM, and the time was 1 min;

[0047] S32, sputtering the plasma modified polyethylene film to deposit aluminum oxide, to obtain an aluminum oxide polyethylene film, the process conditions are: when the vacuum degree reaches 8×10 -3 The sputtering power is 20KW, the deposition time is 10min, the bias voltage is 40V, the duty cycle is 60%, the argon flow rate is 20SCCM, the oxygen flow rate is 300SCCM, and the sputtering target is 99.99% pure aluminum. The thickness of the vacuum sputtering deposited aluminum oxide polyethylene film is 100μm and the oxygen permeability is 0.25cm 3 / (m 2 *24h), water vapor transmission rate is 0.28cm 3 / (m 2 *24h), the effective resistance to the rubbing test is 50 times.

[0048] Preparation Example 4: Preparation of vacuum sputtering deposited aluminum oxide polyethylene film

[0049] The method for preparing a vacuum sputtering deposition aluminum oxide polyethylene film comprises the following steps:

[0050] S31, send the polyethylene film to the continuous vacuum sputtering equipment, when the vacuum degree reaches 5×10 -2 When the plasma modification was carried out, the plasma power was 10 kW, the bias voltage was 200 V, the duty cycle was 40%, the argon flow rate was 200 SCCM, the oxygen flow rate was 500 SCCM, and the time was 0.8 min;

[0051] S32, sputtering the plasma modified polyethylene film to deposit aluminum oxide, to obtain an aluminum oxide polyethylene film, the process conditions are: when the vacuum degree reaches 8×10 -3 The sputtering power was 20KW, the deposition time was 8min, the bias voltage was 40V, the duty cycle was 60%, the argon flow rate was 20SCCM, the oxygen flow rate was 300SCCM, and the sputtering target was 99.99% pure aluminum. The thickness of the vacuum sputtering deposited aluminum oxide polyethylene film was 80μm and the oxygen permeability was 0.3cm 3 / (m 2 *24h), water vapor transmission rate is 0.3cm 3 / (m 2 *24h), the effective resistance to the rubbing test is 50 times.

[0052] Example 1

[0053] A high-barrier composite hose for cosmetic packaging, comprising, from the outside to the inside, a polyethylene film layer, an adhesive layer, a vacuum sputtered alumina polyethylene film, an adhesive layer, and an antibacterial polyethylene layer; wherein the antibacterial polyethylene layer comprises the following raw materials in parts by weight: 40 parts high-density polyethylene, 8 parts low-density polyethylene, 18 parts metallocene polyethylene, 20 parts β-cyclodextrin-modified titanium dioxide, 3 parts antioxidant, and antibacterial agent KP-J67. 0.5 parts, 2 parts of coupling agent, the antioxidant is selected from a composition of antioxidant 1010 and butylated hydroxyanisole in a mass ratio of 5:1; the coupling agent is selected from a composition of isopropyl tristearate titanate and γ-methacryloxypropyltrimethoxysilane in a mass ratio of 4:1; the polyethylene film layer is blown by polyethylene material, with a thickness of 50 μm and a peel strength of 60N / 15mm after heat sealing; the adhesive layer is made of an adhesive with a solid content of 50% of polyethylene as a dry basis and ethyl acetate as a solvent, and is matured, with a thickness of 3 μm and a coating amount of 6g / m 2 The dry basis weight of the adhesive is 3g / m 2 .

[0054] A method for preparing a high-barrier composite hose for cosmetic packaging, using the raw materials of the high-barrier composite hose for cosmetic packaging, the preparation method comprises the following steps:

[0055] S101. Preparation of an antibacterial polyethylene layer: High-density polyethylene, low-density polyethylene, metallocene polyethylene, β-cyclodextrin-modified titanium dioxide, an antioxidant, an antibacterial agent KP-J67, and a coupling agent were mixed uniformly at 132° C., followed by extrusion granulation and film blowing to obtain an antibacterial polyethylene layer with a thickness of 100 μm.

[0056] S102, vacuum sputtering deposition of aluminum oxide polyethylene film prepared in Preparation Example 2;

[0057] S103, compounding: applying a polyethylene adhesive between the polyethylene film layer and the vacuum sputtering deposited aluminum oxide polyethylene film prepared in step S102, and between the vacuum sputtering deposited aluminum oxide polyethylene film prepared in step S102 and the antibacterial polyethylene layer prepared in step S101, respectively, to form adhesive layers; and compounding the polyethylene film layer, the vacuum sputtering deposited aluminum oxide polyethylene film, and the antibacterial polyethylene layer into a composite film roll through the bonding effect of the cured adhesive layers to obtain a composite film roll;

[0058] S104, rolling the composite film into a composite hose for cosmetic packaging required by the customer.

[0059] Example 2

[0060] A high-barrier composite hose for cosmetic packaging, comprising, from the outside to the inside, a polyethylene film layer, an adhesive layer, a vacuum sputtered alumina polyethylene film, an adhesive layer, and an antibacterial polyethylene layer; wherein the antibacterial polyethylene layer comprises the following raw materials in parts by weight: 45 parts high-density polyethylene, 10 parts low-density polyethylene, 22 parts metallocene polyethylene, 25 parts β-cyclodextrin-modified titanium dioxide, 5 parts antioxidant, and antibacterial agent KP-J67. 1 part, 3 parts of coupling agent, the antioxidant is selected from a composition of antioxidant 1010 and butylated hydroxyanisole in a mass ratio of 5:3; the coupling agent is selected from a composition of isopropyl tristearate titanate and γ-methacryloxypropyltrimethoxysilane in a mass ratio of 4:2; the polyethylene film layer is blown by polyethylene material, with a thickness of 130 μm and a peel strength of 75N / 15mm after heat sealing; the adhesive layer is made of an adhesive with a solid content of 50% of polyethylene as a dry basis and ethyl acetate as a solvent, and is matured, with a thickness of 4 μm and a coating amount of 7g / m 2 The dry basis weight of the adhesive is 3.2g / m 2 .

[0061] A method for preparing a high-barrier composite hose for cosmetic packaging, using the raw materials of the high-barrier composite hose for cosmetic packaging, the preparation method comprises the following steps:

[0062] S101. Preparation of an antibacterial polyethylene layer: High-density polyethylene, low-density polyethylene, metallocene polyethylene, β-cyclodextrin-modified titanium dioxide, an antioxidant, an antibacterial agent KP-J67, and a coupling agent were mixed uniformly at 132° C., followed by extrusion granulation and film blowing to obtain an antibacterial polyethylene layer with a thickness of 50 μm.

[0063] S102, vacuum sputtering deposition of aluminum oxide polyethylene film prepared in Preparation Example 3;

[0064] S103, compounding: applying a polyethylene adhesive between the polyethylene film layer and the vacuum sputtering deposited aluminum oxide polyethylene film prepared in step S102, and between the vacuum sputtering deposited aluminum oxide polyethylene film prepared in step S102 and the antibacterial polyethylene layer prepared in step S101, respectively, to form adhesive layers; and compounding the polyethylene film layer, the vacuum sputtering deposited aluminum oxide polyethylene film, and the antibacterial polyethylene layer into a composite film roll through the bonding effect of the cured adhesive layers to obtain a composite film roll;

[0065] S104, rolling the composite film into a composite hose for cosmetic packaging required by the customer.

[0066] Example 3

[0067] A high-barrier composite hose for cosmetic packaging, comprising, from the outside to the inside, a polyethylene film layer, an adhesive layer, a vacuum sputtered alumina polyethylene film, an adhesive layer, and an antibacterial polyethylene layer; wherein the antibacterial polyethylene layer comprises the following raw materials in parts by weight: 43 parts high-density polyethylene, 9 parts low-density polyethylene, 20 parts metallocene polyethylene, 22 parts β-cyclodextrin modified titanium dioxide, 4 parts antioxidant, and antibacterial agent KP-J67. 0.8 parts, 2.5 parts of coupling agent, the antioxidant is selected from a composition of antioxidant 1010 and butylated hydroxyanisole in a mass ratio of 5:2; the coupling agent is selected from a composition of isopropyl tristearate titanate and γ-methacryloxypropyltrimethoxysilane in a mass ratio of 4:1.5; the polyethylene film layer is blown by polyethylene material, with a thickness of 90 μm and a peel strength after heat sealing of 58N / 15mm; the adhesive layer is made of an adhesive with a solid content of 50% of polyethylene as a dry basis and ethyl acetate as a solvent, and is matured, with a thickness of 3.5 μm and a coating amount of 6.6 g / m 2 The dry basis weight of the adhesive is 3.1g / m 2 .

[0068] A method for preparing a high-barrier composite hose for cosmetic packaging, using the raw materials of the high-barrier composite hose for cosmetic packaging, the preparation method comprises the following steps:

[0069] S101. Preparation of an antibacterial polyethylene layer: High-density polyethylene, low-density polyethylene, metallocene polyethylene, β-cyclodextrin-modified titanium dioxide, an antioxidant, an antibacterial agent KP-J67, and a coupling agent were mixed uniformly at 132° C., followed by extrusion granulation and film blowing to obtain an antibacterial polyethylene layer with a thickness of 85 μm.

[0070] S102, vacuum sputtering deposition of aluminum oxide polyethylene film prepared in Preparation Example 4;

[0071] S103, compounding: applying a polyethylene adhesive between the polyethylene film layer and the vacuum sputtering deposited aluminum oxide polyethylene film prepared in step S102, and between the vacuum sputtering deposited aluminum oxide polyethylene film prepared in step S102 and the antibacterial polyethylene layer prepared in step S101, respectively, to form adhesive layers; and compounding the polyethylene film layer, the vacuum sputtering deposited aluminum oxide polyethylene film, and the antibacterial polyethylene layer into a composite film roll through the bonding effect of the cured adhesive layers to obtain a composite film roll;

[0072] S104, rolling the composite film into a composite hose for cosmetic packaging required by the customer.

[0073] Example 4

[0074] The same as Example 3, except that an equal amount of isopropyl tristearate titanate is used instead of the coupling agent selected from a composition of isopropyl tristearate titanate and γ-methacryloxypropyltrimethoxysilane in a mass ratio of 4:1.5.

[0075] Example 5

[0076] The same as Example 3, except that an equal amount of γ-methacryloxypropyltrimethoxysilane is used instead of the coupling agent, and the coupling agent is selected from a composition of isopropyl tristearate titanate and γ-methacryloxypropyltrimethoxysilane in a mass ratio of 4:1.5.

[0077] Comparative Example 1

[0078] The same as Example 3, except that a polyethylene film of the same thickness and mass is used instead of the vacuum sputtering deposited aluminum oxide polyethylene film prepared in this application.

[0079] Comparative Example 2

[0080] The same as Example 3, except that: in the antibacterial polyethylene layer, an equal amount of titanium dioxide is used instead of the β-cyclodextrin modified titanium dioxide prepared in this application.

[0081] Performance testing

[0082] The cosmetic packaging composite hoses prepared in Examples 1-5 and Comparative Examples 1-2 were sampled and tested. The test results are shown in Table 1.

[0083] Barrier performance: According to the standard of GB / T1038.2-2022 Test method for gas permeability of plastic film and sheet - Part 2: Isobaric method, the oxygen permeability of cosmetic packaging hose is tested (cm 3 / m 2 ·24h·0.1Mpa);

[0084] Water vapor transmission rate (g / m 2 24h): Test the water vapor transmission rate of cosmetic packaging hose according to the standard "GB / T Plastic film and sheeting water vapor transmission rate determination - humidity sensor method" (g / m 2 24 hours);

[0085] Table 1

[0086]

[0087] Table 1 shows that the composite hoses for cosmetic packaging prepared in Examples 1-3 exhibit low oxygen and water vapor transmission rates, demonstrating excellent barrier properties. In particular, a comparative analysis of the performance of Examples 3 and 4-5 reveals that the use of a coupling agent selected from a combination of isopropyl tristearate titanate and γ-methacryloxypropyl trimethoxysilane in a mass ratio of 4:1.5 further enhances the barrier properties of the cosmetic hose by leveraging the synergistic effect between the two.

[0088] As can be seen from Table 1, a comparative analysis of Example 3 and Comparative Example 1 shows that the vacuum sputtering-deposited aluminum oxide polyethylene film prepared by the present application can significantly improve the barrier performance.

[0089] As can be seen from Table 1, a comparative analysis of Example 3 and Comparative Example 2 shows that the β-cyclodextrin-modified titanium dioxide prepared in the present application makes the titanium dioxide molecules more dispersed and less likely to agglomerate, making the spatial network structure more stable and improving the barrier performance.

[0090] Antibacterial performance test

[0091] The cosmetic packaging composite hoses prepared in Examples 1-5 were sampled and subjected to antibacterial testing according to JIS Z2801:2000. The test results are shown in Table 2.

[0092] Table 2

[0093]

[0094] From Table 2, it can be seen that the antibacterial rates of Staphylococcus aureus and Escherichia coli of the cosmetic packaging composite hoses prepared in Examples 1-5 are all greater than 99.90%, showing excellent antibacterial effects.

[0095] The above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the same. Although the above embodiments provide a detailed description of the present invention, relevant technical personnel should understand that the specific implementation methods of the present invention can still be modified or replaced by equivalents. Any modifications and equivalent replacements 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 high-barrier composite hose for cosmetic packaging, characterized in that: The cosmetic packaging composite hose comprises, from the outside to the inside, a polyethylene film layer, an adhesive layer, a vacuum sputtered deposited alumina polyethylene film, an adhesive layer and an antibacterial polyethylene layer; wherein the antibacterial polyethylene layer comprises the following raw materials in parts by mass: 40-45 parts of high-density polyethylene, 8-10 parts of low-density polyethylene, 18-22 parts of metallocene polyethylene, 20-25 parts of β-cyclodextrin-modified titanium dioxide, 3-5 parts of an antioxidant, 0.5-1 part of an antibacterial agent, and 2-3 parts of a coupling agent, wherein the coupling agent is selected from a composition of isopropyl tristearate titanate and γ-methacryloxypropyltrimethoxysilane in a mass ratio of 4:1-2.

2. The high-barrier composite hose for cosmetic packaging according to claim 1, characterized in that: The polyethylene film layer is blown from polyethylene material, has a thickness of 50-130 μm, and has a peel strength of more than 43 N / 15 mm after heat sealing.

3. The high-barrier composite hose for cosmetic packaging according to claim 1, characterized in that: The method for preparing the vacuum sputtering deposition aluminum oxide polyethylene film comprises the following steps: S31, send the polyethylene film to the continuous vacuum sputtering equipment, when the vacuum degree reaches 5×10 -2 When the plasma is modified, the plasma power is 10 kW, the bias voltage is 200 V, the duty cycle is 40%, the argon flow rate is 200 SCCM, the oxygen flow rate is 500 SCCM, and the time is 0.5-1 min; S32, sputtering the plasma modified polyethylene film to deposit aluminum oxide, to obtain an aluminum oxide polyethylene film, the process conditions are: when the vacuum degree reaches 8×10 -3 The sputtering power is 20KW, the deposition time is 5-10min, the bias voltage is 40V, the duty cycle is 60%, the argon flow rate is 20SCCM, the oxygen flow rate is 300SCCM, and the sputtering target is 99.99% pure aluminum target.

4. The high-barrier composite hose for cosmetic packaging according to claim 1, characterized in that: The thickness of the vacuum sputtering deposited aluminum oxide polyethylene film is 50-100 μm, and the oxygen permeability is ≤0.4 cm 3 / (m 2 *24h), water vapor transmission rate ≤0.4cm 3 / (m 2 *24h), the effective resistance to the rubbing test is 50 times.

5. The high-barrier composite hose for cosmetic packaging according to claim 1, characterized in that: The adhesive layer is made of polyethylene as dry base and ethyl acetate as solvent with a solid content of 50% adhesive, which is matured. Its thickness is 34μm and its coating amount is 67g / m 2 The dry basis weight of the adhesive is 3-3.2g / m 2 .

6. The high-barrier composite hose for cosmetic packaging according to claim 1, characterized in that: The preparation method of the β-cyclodextrin modified titanium dioxide comprises the following steps: S61. In 400 mL of toluene, 8 g of titanium dioxide and 8 mL of γ-methacryloxypropyltrimethoxysilane were added. Under nitrogen protection, the mixture was refluxed at 130° C. with stirring for 10 h. The mixture was cooled, filtered, washed with acetone and methanol three times, and then dried in vacuo at 110° C. for 10 h to obtain substance A. S62. Add 1 g of β-cyclodextrin and 0.2 g of sodium hydroxide to 200 mL of dimethylformamide, stir for 1 hour, and then filter. Add 4 g of substance A to the filtrate. Under nitrogen protection, reflux and stir at 118°C for 28 hours, cool and filter. The obtained solid material is washed three times with acetone and methanol in sequence, and then vacuum dried at 100°C for 10 hours to obtain β-cyclodextrin-modified titanium dioxide.

7. The high-barrier composite hose for cosmetic packaging according to claim 1, characterized in that: The antioxidant is selected from a composition of antioxidant 1010 and butylated hydroxyanisole in a mass ratio of 5:1-3.

8. The high-barrier composite hose for cosmetic packaging according to claim 1, characterized in that: The antibacterial agent is antibacterial agent KP-J67.

9. A method for preparing a high-barrier composite hose for cosmetic packaging, characterized in that: The raw material of the high-barrier composite hose for cosmetic packaging according to any one of claims 1 to 8 is used, and the preparation method thereof comprises the following steps: S101, preparation of antibacterial polyethylene layer: high-density polyethylene, low-density polyethylene, metallocene polyethylene, β-cyclodextrin-modified titanium dioxide, antioxidant, antibacterial agent and coupling agent are mixed uniformly at 132° C., followed by extrusion granulation and blow molding into a film to obtain an antibacterial polyethylene layer with a thickness of 50-100 μm; S102, preparing a vacuum sputtering-deposited aluminum oxide polyethylene film: using a polyethylene film as a substrate, depositing aluminum oxide on the surface of the polyethylene film by a plasma-enhanced sputtering deposition method to form a thin film layer, thereby obtaining a vacuum sputtering-deposited aluminum oxide polyethylene film; S103, compounding: applying a polyethylene adhesive between the polyethylene film layer and the vacuum sputtering deposited aluminum oxide polyethylene film prepared in step S102, and between the vacuum sputtering deposited aluminum oxide polyethylene film prepared in step S102 and the antibacterial polyethylene layer prepared in step S101, respectively, to form adhesive layers; and compounding the polyethylene film layer, the vacuum sputtering deposited aluminum oxide polyethylene film, and the antibacterial polyethylene layer into a composite film roll through the bonding effect of the cured adhesive layers to obtain a composite film roll; S104, rolling the composite film into a composite hose for cosmetic packaging required by the customer.

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