One-step formed recyclable packaging tube material and process for making the same

Abstract

The application relates to the technical field of cosmetic packaging tube material research and development, and discloses a one-step forming recyclable packaging tube material and a preparation process thereof, which comprises the following steps: designing the product structure of the one-step forming recyclable packaging tube material; synthesizing ultraviolet blocking type carboxyl modified monomers; performing surface modification treatment on magnesium-aluminum hydrotalcite by using the ultraviolet blocking type carboxyl modified monomers, and then performing complex action on the magnesium-aluminum hydrotalcite, ethylene-vinyl alcohol copolymer resin and low-density polyethylene resin to prepare an organic-inorganic composite barrier composition; and the organic-inorganic composite barrier composition is introduced into a single PE material, and an eleven-layer co-extrusion blow molding film process is adopted to prepare the one-step forming recyclable packaging tube material. The material has very excellent barrier properties and mechanical properties, is made of single PE material, is suitable for recycling, and can be used for manufacturing cosmetic packaging tube material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of cosmetic packaging tube material research and development, in particular to a one-step formed recyclable packaging tube material and a preparation process thereof. BACKGROUND

[0002] The one-step forming process is a method for making plastic products into various shapes by heating the plastic into a viscous flow state, flowing, forming and hardening by cooling. It includes extrusion molding, injection molding, mold pressing and calendering. Among them, the multilayer co-extrusion molding avoids the traditional composite and coating post-processing process, which can effectively reduce the production cost. The prepared multilayer composite material has excellent performance of multiple polymers and is widely used in manufacturing industry.

[0003] The common cosmetic packaging materials on the market include plastic bottles, glass bottles and hoses. Among them, plastic packaging hoses are the most widely used in the cosmetic packaging industry because of their good sealing property, which can isolate external air and prevent the contents from leaking. Most cosmetics are sensitive to light. This is because the photosensitive components in cosmetics are oxidized by ultraviolet light, which may not only lose activity and lose efficacy, but also may produce sensitization and toxicity. For example, ascorbic acid and ferulic acid are easily photolyzed and oxidized, and retinol and its derivatives, furanocoumarin have photosensitivity and phototoxicity. In order to avoid the photolytic oxidation of such components by ultraviolet light, the packaging material must be treated to block ultraviolet light. SUMMARY

[0004] Based on the unique interlayer formula design, a one-step formed recyclable packaging tube material is developed by using single PE material. The material has very excellent barrier property and mechanical property, and can be used to manufacture cosmetic packaging tube material.

[0005] A one-step formed recyclable packaging tube material, the product structure of the one-step formed recyclable packaging tube material is:

[0006] The first PE layer, the formula of the layer is 100wt% low density polyethylene resin, the amount of the layer is 5-15 parts by weight;

[0007] The second PE layer, the formula of the layer is 100wt% high density polyethylene resin, the amount of the layer is 5-15 parts by weight;

[0008] The third PE layer, the formula of the layer is 100wt% low density polyethylene resin, the amount of the layer is 5-15 parts by weight;

[0009] The first adhesive layer, the formula of the layer is 100wt% maleic anhydride grafted polyethylene resin, the amount of the layer is 3-8 parts by weight;

[0010] The first barrier layer has a formulation of 95-99 wt% low-density polyethylene resin and 1-5 wt% ethylene-vinyl alcohol copolymer resin, and the amount of the layer is 5-15 parts by weight;

[0011] The second barrier layer has a formulation of 60-80 wt% low-density polyethylene resin and 20-40 wt% organic-inorganic composite barrier composition, and the amount of the layer is 5-15 parts by weight;

[0012] The organic-inorganic composite barrier composition has a formulation of 65-75 wt% low-density polyethylene resin, 15-25 wt% ethylene-vinyl alcohol copolymer resin, 5-15 wt% ultraviolet barrier modified magnesium-aluminum hydrotalcite, and 0.5-3 wt% liquid paraffin;

[0013] The ultraviolet barrier modified magnesium-aluminum hydrotalcite is prepared by surface modification treatment of magnesium-aluminum hydrotalcite with ultraviolet barrier carboxylated modified monomers based on esterification reaction mechanism;

[0014] The third barrier layer has a formulation of 95-99 wt% low-density polyethylene resin and 1-5 wt% ethylene-vinyl alcohol copolymer resin, and the amount of the layer is 5-15 parts by weight;

[0015] The second adhesive layer has a formulation of 100 wt% maleic anhydride grafted polyethylene resin, and the amount of the layer is 3-8 parts by weight;

[0016] The fourth PE layer has a formulation of 100 wt% low-density polyethylene resin, and the amount of the layer is 5-15 parts by weight;

[0017] The fifth PE layer has a formulation of 100 wt% high-density polyethylene resin, and the amount of the layer is 5-15 parts by weight;

[0018] The sixth PE layer has a formulation of 100 wt% low-density polyethylene resin, and the amount of the layer is 5-15 parts by weight.

[0019] Preferably, the preparation method of the ultraviolet barrier carboxylated modified monomer is as follows:

[0020] Under the action of the acid-binding agent, the -NH2 functional group of 2,2,6,6-tetramethylpiperidine amine and the chlorine functional group of 2-(2'-hydroxy-4'-benzoyloxyphenyl)-5-chlorobenzotriazole undergo nucleophilic substitution reaction, and the molar ratio of 2,2,6,6-tetramethylpiperidine amine and 2-(2'-hydroxy-4'-benzoyloxyphenyl)-5-chlorobenzotriazole is controlled to be (1.01-1.05):1, to generate the ultraviolet barrier monomer;

[0021] The amine-ene addition reaction of the -NH- functional group of the ultraviolet blocking monomer and the alkene functional group of beta-(acryloyloxy)propionic acid is catalyzed by an alkaline catalyst, and the molar ratio of the ultraviolet blocking monomer and beta-(acryloyloxy)propionic acid is controlled to be (1.01-1.05):1, to generate the ultraviolet blocking carboxylated modified monomer.

[0022] Preferably, the acid-binding agent is one of sodium carbonate, potassium carbonate, and sodium acetate.

[0023] Preferably, the alkaline catalyst is one of sodium ethoxide, sodium hydride, potassium tert-butoxide, triethylamine, triethylenediamine, 4-dimethylaminopyridine, and 1,8-diazabicycloundec-7-ene.

[0024] Preferably, the mass ratio of the ultraviolet blocking carboxylated modified monomer and the magnesium-aluminum hydrotalcite in the ultraviolet blocking modified magnesium-aluminum hydrotalcite is 1:(1-5).

[0025] Preferably, the magnesium-aluminum hydrotalcite has a flake diameter of 1-3 µm and a thickness of 8-10 nm.

[0026] A preparation process of a one-time molded recyclable packaging tube material, comprising the following steps:

[0027] Step one, preparing an organic-inorganic composite barrier composition: according to the formula of the organic-inorganic composite barrier composition, the formula raw materials are added to a high-speed mixer for uniform mixing, and then extruded and granulated by a double-screw extruder to prepare the organic-inorganic composite barrier composition;

[0028] Step two, preparing a one-time molded recyclable packaging tube material: according to the formula of the one-time molded recyclable packaging tube material, the raw materials of each layer are respectively put into the hoppers of the eleven screw extruders of an eleven-layer co-extrusion film blowing machine set, and after stirring and mixing, the molten resins are converged at the die head by a flow divider, extruded and blown by the die, and the blowing ratio is controlled at 2.4-2.9, and then cooled and rolled to prepare the one-time molded recyclable packaging tube material with a thickness of 250-300 µm.

[0029] Advantages:

[0030] The ultraviolet blocking carboxylated modified monomer is designed and synthesized, the magnesium-aluminum hydrotalcite is surface modified by the ultraviolet blocking carboxylated modified monomer, and then the organic-inorganic composite barrier composition is prepared by the complex action of the ultraviolet blocking carboxylated modified monomer, ethylene-vinyl alcohol copolymer resin and low-density polyethylene resin, and finally the organic-inorganic composite barrier composition is introduced into the single PE material to co-extrude and blow the film by an eleven-layer co-extrusion film blowing machine set to obtain the one-time molded recyclable packaging tube material with excellent barrier properties (blocking oxygen, water vapor and ultraviolet rays). BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 Performance test results of the once-formed recyclable packaging tube material;

[0032] Figure 2 Synthesis route of the ultraviolet blocking type carboxyl-modified monomer. DETAILED DESCRIPTION

[0033] Example 1:

[0034] A once-formed recyclable packaging tube material, the product structure of which is in turn:

[0035] A first PE layer, the formulation of which is 100wt% low-density polyethylene resin (purchased from Jiangsu Rantai Plastic Co., Ltd., with the brand LD 150DW), and the amount of which is 10 parts by weight;

[0036] A second PE layer, the formulation of which is 100wt% high-density polyethylene resin (purchased from Dongguan Longhang Plastic Raw Material Co., Ltd., with the brand FB5600), and the amount of which is 10 parts by weight;

[0037] A third PE layer, the formulation of which is 100wt% low-density polyethylene resin, and the amount of which is 10 parts by weight;

[0038] A first adhesive layer, the formulation of which is 100wt% maleic anhydride grafted polyethylene resin (purchased from Dongguan Taota Plastic Raw Material Co., Ltd., with the brand 4288), and the amount of which is 5 parts by weight;

[0039] A first barrier layer, the formulation of which is 97wt% low-density polyethylene resin and 3wt% ethylene-vinyl alcohol copolymer resin (purchased from Guangzhou Best New Material Technology Co., Ltd., with the brand ET3803RB), and the amount of which is 10 parts by weight;

[0040] A second barrier layer, the formulation of which is 70wt% low-density polyethylene resin and 30wt% organic-inorganic composite barrier composition, and the amount of which is 10 parts by weight;

[0041] The formulation of the organic-inorganic composite barrier composition is: 68wt% low-density polyethylene resin, 20wt% ethylene-vinyl alcohol copolymer resin, 10wt% ultraviolet blocking modified magnesium-aluminum hydrotalcite, and 2wt% liquid paraffin;

[0042] The preparation method of the ultraviolet blocking modified magnesium-aluminum hydrotalcite is described in the experimental example;

[0043] A third barrier layer, the formulation of which is 97wt% low-density polyethylene resin and 3wt% ethylene-vinyl alcohol copolymer resin, and the amount of which is 10 parts by weight;

[0044] a second adhesive layer, the formulation of the layer being 100wt% maleic anhydride grafted polyethylene resin, the amount of the layer being 5 parts by weight;

[0045] a fourth PE layer, the formulation of the layer being 100wt% low density polyethylene resin, the amount of the layer being 10 parts by weight;

[0046] a fifth PE layer, the formulation of the layer being 100wt% high density polyethylene resin, the amount of the layer being 10 parts by weight;

[0047] a sixth PE layer, the formulation of the layer being 100wt% low density polyethylene resin, the amount of the layer being 10 parts by weight.

[0048] Example 2:

[0049] A preparation process of a one-step formed recyclable packaging tube material, comprising the following steps:

[0050] Step one, preparing an organic-inorganic composite barrier composition: according to the formulation of the organic-inorganic composite barrier composition, the raw materials are mixed uniformly in a high-speed mixer, and then extruded and granulated by a double-screw extruder to obtain the organic-inorganic composite barrier composition;

[0051] The process parameters of the double-screw extruder are set as follows: the temperatures of zones 1-6 are 160℃, 165℃, 170℃, 175℃, 175℃ and 180℃ respectively, and the rotation speed is 200r / min;

[0052] Step two, preparing a one-step formed recyclable packaging tube material: according to the formulation of the one-step formed recyclable packaging tube material, the raw materials of each layer are respectively put into the hoppers of the eleven screw extruders of an eleven-layer co-extrusion film blowing machine set, and then stirred and mixed, after that, the molten resins are converged at the die head by a flow divider, extruded and blown through the die, the blowing ratio is controlled at 2.8, and then cooled and rolled to obtain a one-step formed recyclable packaging tube material with a thickness of 280μm;

[0053] The process parameters of the screw extruder corresponding to the PE layer are set as follows: the temperatures of zones 1-3 are 120℃, 150℃ and 170℃ respectively, the flow channel temperature is 165℃, and the rotation speed is 30r / min;

[0054] The process parameters of the screw extruder corresponding to the adhesive layer are set as follows: the temperatures of zones 1-3 are 115℃, 145℃ and 160℃ respectively, the flow channel temperature is 150℃, and the rotation speed is 15r / min;

[0055] The process parameters of the screw extruder corresponding to the barrier layer are set as follows: the temperatures of zones 1-3 are 130 DEG C, 160 DEG C and 190 DEG C respectively, the flow channel temperature is 180 DEG C, and the rotation speed is 50 r / min.

[0056] Comparative Example:

[0057] Preparation of conventional packaging tube material: the difference between the one-step formed recyclable packaging tube material and the conventional packaging tube material is only that the organic-inorganic composite barrier composition is not used.

[0058] Performance test:

[0059] (1) Oxygen barrier performance: the oxygen barrier performance of the sample was tested according to GB / T 1038-2000 using a Y110 oxygen transmission tester, and the oxygen transmission amount of the sample was recorded;

[0060] (2) Water vapor barrier performance: the water vapor barrier performance of the sample was tested according to GB / T 1037-2021 using a TC-03 water vapor transmission tester, and the water vapor transmission amount of the sample was recorded;

[0061] (3) Ultraviolet barrier performance: the light transmittance of the sample was tested according to GB / T 2410-2008 using a Lambda 950 ultraviolet-visible spectrophotometer, the wavelength range was 250-800 nm, and the light transmittance of the sample at 380 nm was recorded;

[0062] (4) Mechanical property test: the tensile property of the sample was tested according to GB / T 1040-2006 using an Instron 5565 universal tensile testing machine, and the tensile strength of the sample was recorded; wherein, the test speed is 5 mm / min;

[0063] The above experimental results are shown in Table 1 and Figure 1 .

[0064] Table 1 Performance test results of one-step formed recyclable packaging tube material

[0065]

[0066] Through comprehensive analysis of the above experimental results, the following conclusions can be drawn:

[0067] The organic-inorganic composite barrier composition independently developed by the application significantly improves the barrier performance (oxygen, water vapor and ultraviolet) and mechanical properties of the one-step formed recyclable packaging tube material.

[0068] Experimental example:

[0069] Preparation of ultraviolet blocking modified magnesium-aluminum hydrotalcite: based on the esterification reaction mechanism, the surface of magnesium-aluminum hydrotalcite is modified by using ultraviolet blocking carboxylated modified monomer to prepare ultraviolet blocking modified magnesium-aluminum hydrotalcite. The specific preparation steps are as follows: 2 g of ultraviolet blocking carboxylated modified monomer, 5 g of hydrophilic nano magnesium-aluminum hydrotalcite powder (purchased from Hunan Xiongnian New Material Technology Co., Ltd., with a flake diameter of 1-3 μm and a thickness of 8-10 nm) and 50 mL of N,N-dimethylformamide are added to a three-necked flask. Under the action of mechanical stirring, 2 mL of concentrated sulfuric acid is slowly added to the three-necked flask, and the temperature is raised to 80°C for 5h. Deionized water is used for washing, rotary evaporation and drying to obtain ultraviolet blocking modified magnesium-aluminum hydrotalcite;

[0070] The synthesis route of the ultraviolet blocking carboxylated modified monomer is shown in Figure 2 The preparation process is as follows:

[0071] (1) Preparation of ultraviolet blocking monomer: under the action of an acid-binding agent, nucleophilic substitution reaction occurs between the -NH2 functional group of 2,2,6,6-tetramethylpiperidine amine and the chlorine functional group of 2-(2'-hydroxy-4'-benzoyloxyphenyl)-5-chlorobenzotriazole (ultraviolet absorber UV-366), and the molar ratio of 2,2,6,6-tetramethylpiperidine amine and 2-(2'-hydroxy-4'-benzoyloxyphenyl)-5-chlorobenzotriazole is controlled at 1.02:1 to generate ultraviolet blocking monomer. The specific experimental steps are as follows: 3.6 g of 2-(2'-hydroxy-4'-benzoyloxyphenyl)-5-chlorobenzotriazole and 40 mL of acetone are added to a three-necked flask, and stirred at room temperature until completely dissolved. Then 10 mL of acetone solution containing 1.6 g of 2,2,6,6-tetramethylpiperidine amine and 1.5 mL of 20 wt% sodium carbonate aqueous solution are added to the three-necked flask in turn. After mixing, the temperature is raised to 50°C for stirring reaction for 4h. The solvent is removed by rotary evaporation, and then washed with saturated sodium chloride aqueous solution and deionized water in turn. Vacuum drying is performed to obtain ultraviolet blocking monomer;

[0072] The acid-binding agent is one of sodium carbonate, potassium carbonate and sodium acetate. In this experimental example, potassium carbonate is used;

[0073] (2) Preparation of the ultraviolet blocking carboxyl-modified monomer: the amine-ene addition reaction of the -NH- functional group of the ultraviolet blocking monomer and the olefinic functional group of the β-(acryloyloxy)propionic acid is catalyzed by a basic catalyst, and the molar ratio of the ultraviolet blocking monomer and the β-(acryloyloxy)propionic acid is controlled to be 1.04:1, to generate the ultraviolet blocking carboxyl-modified monomer, and the specific experimental steps are as follows: 2.4 g of the ultraviolet blocking monomer and 30 mL of acetone are added to a three-necked flask, stirred at room temperature until completely dissolved, then 10 mL of the acetone solution containing 0.7 g of the β-(acryloyloxy)propionic acid is added dropwise to the three-necked flask, stirred at room temperature for 30 min, 1.3 mL of 1,8-diazabicycloundec-7-ene is added dropwise to the three-necked flask, heated to 45°C and stirred for 5 h, the solvent is removed by rotary evaporation, washed with saturated sodium chloride solution and deionized water, and vacuum dried to obtain the ultraviolet blocking carboxyl-modified monomer;

[0074] wherein the basic catalyst is one of sodium ethoxide, sodium hydride, potassium tert-butoxide, triethylamine, triethylenediamine, 4-dimethylaminopyridine, and 1,8-diazabicycloundec-7-ene; and in this experimental example, 1,8-diazabicycloundec-7-ene is used;

[0075] The ultraviolet blocking carboxyl-modified monomer is characterized by nuclear magnetic resonance hydrogen spectrum as follows: 1 H NMR (CDCl3, 400 MHz) δ: 1.20 (s, 6H), 1.25 (s, 6H), 1.81-1.83 (d, 4H), 2.58-2.61 (t, 2H), 2.74-2.77 (t, 2H), 3.71-3.75 (t, 2H), 3.97-4.04 (m, 1H), 4.47-4.51 (t, 2H), 6.80-8.15 (m, 11H).

Claims

1. A one-trip recyclable packaging tube material characterized in that, The product structure of the one-time formed recyclable packaging tube material is: The first PE layer, the formula of the layer is 100wt% low density polyethylene resin, the amount of the layer is 5-15 parts by weight; The second PE layer, the formula of the layer is 100wt% high density polyethylene resin, the amount of the layer is 5-15 parts by weight; The third PE layer, the formula of the layer is 100wt% low density polyethylene resin, the amount of the layer is 5-15 parts by weight; The first adhesive layer, the formula of the layer is 100wt% maleic anhydride grafted polyethylene resin, the amount of the layer is 3-8 parts by weight; The first barrier layer, the formula of the layer is 95-99wt% low density polyethylene resin and 1-5wt% ethylene-vinyl alcohol copolymer resin, the amount of the layer is 5-15 parts by weight; The second barrier layer, the formula of the layer is 60-80wt% low density polyethylene resin and 20-40wt% organic-inorganic composite barrier composition, the amount of the layer is 5-15 parts by weight; The formula of the organic-inorganic composite barrier composition is: 65-75wt% low density polyethylene resin, 15-25wt% ethylene-vinyl alcohol copolymer resin, 5-15wt% ultraviolet barrier modified magnesium-aluminum hydrotalcite and 0.5-3wt% liquid paraffin; The preparation method of the ultraviolet barrier modified magnesium-aluminum hydrotalcite is: based on the esterification reaction mechanism, the surface of the magnesium-aluminum hydrotalcite is modified by using the ultraviolet barrier carboxylated modified monomer to obtain the ultraviolet barrier modified magnesium-aluminum hydrotalcite; The chemical structural formula of the ultraviolet barrier carboxylated modified monomer is: ； The third barrier layer, the formula of the layer is 95-99wt% low density polyethylene resin and 1-5wt% ethylene-vinyl alcohol copolymer resin, the amount of the layer is 5-15 parts by weight; The second adhesive layer, the formula of the layer is 100wt% maleic anhydride grafted polyethylene resin, the amount of the layer is 3-8 parts by weight; The fourth PE layer, the formula of the layer is 100wt% low density polyethylene resin, the amount of the layer is 5-15 parts by weight; The fifth PE layer, the formula of the layer is 100wt% high density polyethylene resin, the amount of the layer is 5-15 parts by weight; The sixth PE layer, the formula of the layer is 100wt% low density polyethylene resin, the amount of the layer is 5-15 parts by weight.

2. A one-trip formable recyclable packaging tube material according to claim 1, characterized in that, The preparation method of the ultraviolet barrier carboxylated modified monomer is: Under the action of the acid binding agent, the nucleophilic substitution reaction occurs between the -NH2 functional group of 2,2,6,6-tetramethylpiperidinamine and the chlorine functional group of 2-(2'-hydroxy-4'-benzoyloxyphenyl)-5-chlorobenzotriazole, and the molar ratio of 2,2,6,6-tetramethylpiperidinamine and 2-(2'-hydroxy-4'-benzoyloxyphenyl)-5-chlorobenzotriazole is controlled to be (1.01-1.05):1, and the ultraviolet barrier monomer is generated; The amine-ene addition reaction of the -NH- functional group of the ultraviolet blocking monomer and the olefinic functional group of the β-(acryloyloxy)propionic acid is catalyzed by a basic catalyst, and the molar ratio of the ultraviolet blocking monomer and the β-(acryloyloxy)propionic acid is controlled to be (1.01-1.05):1, to generate the ultraviolet blocking carboxyl-modified monomer.

3. A one-trip formable recyclable packaging tube material according to claim 2, characterized in that, The acid-binding agent is one of sodium carbonate, potassium carbonate, and sodium acetate.

4. A one-trip formable recyclable packaging tube material according to claim 2, wherein, The basic catalyst is one of sodium ethoxide, sodium hydride, potassium tert-butoxide, triethylamine, triethylenediamine, 4-dimethylaminopyridine, and 1,8-diazabicycloundec-7-ene.

5. A one-trip formable recyclable packaging tube material according to claim 1, wherein, The mass ratio of the ultraviolet blocking carboxyl-modified monomer and the magnesium-aluminum hydrotalcite in the ultraviolet blocking modified magnesium-aluminum hydrotalcite is 1:(1-5).

6. A one-trip formable recyclable packaging tube material according to claim 5, wherein, The magnesium-aluminum hydrotalcite has a flake diameter of 1-3 μm and a thickness of 8-10 nm.

7. A process for the production of a one-trip recyclable packaging tube material according to any one of claims 1-6, characterized in that, The method comprises the following steps: Step one, preparation of the organic-inorganic composite barrier composition: ingredients are prepared according to the formula of the organic-inorganic composite barrier composition, the formula raw materials are added into a high-speed mixer for uniform mixing, and the organic-inorganic composite barrier composition is prepared by extruding and granulating through a double-screw extruder. Step two, preparation of the one-step formed recyclable packaging tube material: ingredients are prepared according to the formula of the one-step formed recyclable packaging tube material, the raw materials of each layer are respectively put into the hoppers of the eleven screw extruders of the eleven-layer co-extrusion film blowing machine set, and after stirring and mixing, the molten resins are converged at the die head through a flow divider, extruded and blown through the die, the blowing ratio is controlled to be 2.4-2.9, and the one-step formed recyclable packaging tube material with a thickness of 250-300 μm is prepared after cooling and winding.

8. Application of the one-step formed recyclable packaging tube material according to any one of claims 1-6 in the field of cosmetic packaging tube materials.

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