Recoverable packaging pipe material formed at one time and preparation process of recoverable packaging pipe material

Abstract

The invention relates to the technical field of cosmetic packaging tube material research and development, and discloses a one-time-formed recoverable packaging tube material and a preparation technology thereof.The preparation technology comprises the steps that the product structure of the one-time-formed recoverable packaging tube material is designed; synthesizing an ultraviolet blocking type carboxylation modified monomer; the preparation method comprises the following steps: carrying out surface modification treatment on magnesium-aluminum hydrotalcite by using an ultraviolet blocking type carboxylation modified monomer, and compounding with ethylene-vinyl alcohol copolymer resin and low-density polyethylene resin to prepare the organic-inorganic composite blocking composition. An organic-inorganic composite barrier composition is introduced into a single PE material, an eleven-layer co-extrusion blow molding film forming technology is adopted, the one-time-formed recyclable packaging pipe material is prepared, and the material has very excellent barrier performance and mechanical performance, is made of the single PE material, is suitable for recycling and can be used for manufacturing cosmetic packaging pipe materials.

Description

Technical Field

[0001] The invention relates to the technical field of research and development of cosmetic packaging tube materials, and in particular to a one-time formed recyclable packaging tube material and a preparation process thereof. Background Art

[0002] The one-shot molding process is a method of making plastics into products of various shapes by heating them to make them viscous and fluid, and then flowing, molding, and cooling and hardening them. It includes extrusion molding, injection molding, compression molding, and calendaring molding. Among them, multi-layer co-extrusion molding avoids traditional post-processing processes such as compounding and coating, which can effectively reduce production costs. The prepared multi-layer composite materials have the excellent properties of multiple polymers and are widely used in the manufacturing industry.

[0003] Common cosmetic packaging materials on the market include plastic bottles, glass bottles, and hoses. Plastic packaging hoses are the most widely used in the cosmetic packaging industry because they have good airtightness, can isolate the outside air, and prevent the contents from leaking out. Most cosmetics are sensitive to light. This is because the photosensitive ingredients in cosmetics may lose their activity and efficacy after being oxidized by ultraviolet rays, and may even cause allergy and toxicity. For example, ascorbic acid and ferulic acid are easily photolytically oxidized, and retinol and its derivatives, and furanocoumarins are photosensitive and phototoxic. In order to prevent these ingredients from being photolytically oxidized by ultraviolet rays, the packaging materials must be treated to block ultraviolet rays. Summary of the invention

[0004] The present invention is based on a unique interlayer formula design and adopts a single PE material to develop a one-time molded recyclable packaging tube material. The material has very excellent barrier properties and mechanical properties and can be used to manufacture cosmetic packaging tube materials.

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

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

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

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

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

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

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

[0012] 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;

[0013] The preparation method of the ultraviolet-shielding modified magnesium-aluminum hydrotalcite is as follows: based on the esterification reaction mechanism, the surface of the magnesium-aluminum hydrotalcite is modified by using an ultraviolet-shielding carboxyl modified monomer;

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

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

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

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

[0018] The sixth PE layer has a formula of 100 wt% low-density polyethylene resin and a usage of 5-15 parts by weight.

[0019] Preferably, the preparation method of the ultraviolet blocking carboxyl modified monomer is:

[0020] Under the action of an acid-binding agent, a 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 to 2-(2'-hydroxy-4'-benzoyloxyphenyl)-5-chlorobenzotriazole is controlled to be (1.01-1.05):1, thereby generating a UV-blocking monomer;

[0021] The -NH-functional group of the UV-blocking monomer and the alkenyl functional group of β-(acryloyloxy)propionic acid are catalyzed by an alkaline catalyst to undergo an amine-ene addition reaction, and the molar ratio of the UV-blocking monomer to β-(acryloyloxy)propionic acid is controlled to be (1.01-1.05):1 to generate a UV-blocking carboxyl 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-shielding carboxyl modified monomer to the magnesium-aluminum hydrotalcite in the ultraviolet-shielding modified magnesium-aluminum hydrotalcite is 1:(1-5).

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

[0026] A preparation process of a one-step formed recyclable packaging tube material comprises the following steps:

[0027] Step 1, preparing an organic-inorganic composite barrier composition: preparing ingredients according to the formula of the organic-inorganic composite barrier composition, adding the formula raw materials into a high-speed mixer and mixing them evenly, and extruding and granulating them through a twin-screw extruder to prepare an organic-inorganic composite barrier composition;

[0028] Step 2, preparing a one-time formed recyclable packaging tube material: according to the formula of the one-time formed recyclable packaging tube material, the ingredients are prepared, and the raw materials of each layer are respectively put into the hoppers of the eleven screw extruders of the eleven-layer co-extrusion film blow molding unit. After stirring and mixing, the molten resin is converged at the head of the machine through a diverter, and is extruded and blow-molded through a die head. The blow ratio is controlled at 2.4-2.9, cooled and rolled, and a one-time formed recyclable packaging tube material with a thickness of 250-300μm is prepared.

[0029] Beneficial effects:

[0030] The invention designs and synthesizes a UV-blocking carboxyl modified monomer, firstly performs surface modification treatment on magnesium aluminum hydrotalcite with the UV-blocking carboxyl modified monomer, then performs compounding with ethylene-vinyl alcohol copolymer resin and low-density polyethylene resin to prepare an organic-inorganic composite barrier composition, finally introduces the organic-inorganic composite barrier composition into a single PE material, and uses an eleven-layer co-extrusion film blowing unit to co-extrude and blow film to produce a one-time molded recyclable packaging tube material with excellent barrier properties (barrier to oxygen, water vapor and UV rays). BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The performance test results of the one-time molded recyclable packaging tube material;

[0032] Figure 2 It is a synthetic route for UV-blocking carboxyl-modified monomers. DETAILED DESCRIPTION

[0033] Embodiment 1:

[0034] A one-time formed recyclable packaging tube material, the product structure of which is as follows:

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

[0036] The second PE layer, the formula of this layer is 100wt% high-density polyethylene resin (purchased from Dongguan Longhuang Plastic Raw Materials Co., Ltd., brand FB5600), the amount of this layer is 10 parts by weight;

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

[0038] The first adhesive layer, the formula of this layer is 100wt% maleic anhydride grafted polyethylene resin (purchased from Dongguan Taotao Plastic Raw Materials Co., Ltd., brand 4288), the amount of this layer is 5 parts by weight;

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

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

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

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

[0043] The third barrier layer has a formula of 97 wt% low-density polyethylene resin and 3 wt% ethylene-vinyl alcohol copolymer resin, and the amount of this layer is 10 parts by weight;

[0044] A second adhesive layer, the formula of which is 100 wt% maleic anhydride grafted polyethylene resin, and the amount of which is 5 parts by weight;

[0045] The fourth PE layer, the formula of this layer is 100wt% low-density polyethylene resin, and the amount of this layer is 10 parts by weight;

[0046] The fifth PE layer, the formula of this layer is 100wt% high-density polyethylene resin, and the amount of this layer is 10 parts by weight;

[0047] The sixth PE layer has a formula of 100 wt% low-density polyethylene resin and a usage of 10 parts by weight.

[0048] Embodiment 2:

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

[0050] Step 1, preparing an organic-inorganic composite barrier composition: preparing ingredients according to the formula of the organic-inorganic composite barrier composition, adding the formula raw materials into a high-speed mixer and mixing them evenly, and extruding and granulating them through a twin-screw extruder to prepare an organic-inorganic composite barrier composition;

[0051] The process parameters of the twin-screw extruder were set as follows: the temperatures of zones 1-6 were 160°C, 165°C, 170°C, 175°C, 175°C, and 180°C, respectively, and the rotation speed was 200 r / min;

[0052] Step 2, preparing a one-time formed recyclable packaging tube material: according to the formula of the one-time formed recyclable packaging tube material, the ingredients are prepared, and the raw materials of each layer are respectively put into the hoppers of eleven screw extruders of the eleven-layer co-extrusion film blow molding unit, after stirring and mixing, the molten resin is merged at the head of the machine through the diverter, and is extruded and blow-molded through the die head, the blow-up ratio is controlled at 2.8, cooled, and rolled up to prepare a one-time formed recyclable packaging tube material with a thickness of 280 μm;

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

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

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

[0056] Comparative Example:

[0057] Preparation of conventional packaging tube materials: Compared with the one-time molded recyclable packaging tube materials, the only difference is that no organic-inorganic composite barrier composition is used.

[0058] Performance Testing:

[0059] (1) Oxygen barrier performance: Use a Y110 oxygen permeability tester to test the oxygen barrier performance of the sample in accordance with GB / T 1038-2000, and record the oxygen permeability of the sample;

[0060] (2) Water vapor barrier performance: Use TC-03 water vapor transmission meter to test the water barrier performance of the sample in accordance with GB / T 1037-2021, and record the water vapor transmission rate of the sample;

[0061] (3) Ultraviolet blocking performance: Lambda 950 UV-visible spectrophotometer was used to test the transmittance of the samples in accordance with GB / T2410-2008. The test wavelength range was 250-800 nm, and the transmittance of the samples at 380 nm was recorded.

[0062] (4) Mechanical properties test: The tensile properties of the samples were tested using an Instron 5565 universal tensile testing machine in accordance with GB / T 1040-2006, and the tensile strength of the samples was recorded; the test speed was 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 molded recyclable packaging tube materials

[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 present invention significantly improves the barrier properties (barrier to oxygen, water vapor and ultraviolet rays) and mechanical properties of the one-time molded 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 ultraviolet-blocking carboxyl modified monomer to prepare ultraviolet-blocking modified magnesium aluminum hydrotalcite. The specific preparation steps are as follows: 2g of ultraviolet-blocking carboxyl modified monomer, 5g of hydrophilic nano magnesium aluminum hydrotalcite powder (purchased from Hunan Xiong Innovation Materials Technology Co., Ltd., with a flake diameter of 1-3μm and a thickness of 8-10nm) and 50mL of N,N-dimethylformamide are added to a three-necked flask, and 2mL of concentrated sulfuric acid is slowly added to the three-necked flask under mechanical stirring, and the temperature is raised to 80°C for reaction for 5h, and the ultraviolet-blocking modified magnesium aluminum hydrotalcite is obtained by washing with deionized water, rotary evaporation and drying.

[0070] Among them, the synthetic route of UV-blocking carboxyl-modified monomers is as follows: Figure 2 As shown, the preparation process is as follows:

[0071] (1) Preparation of UV-blocking monomers: Under the action of an acid-binding agent, a nucleophilic substitution reaction is carried out between the -NH2 functional group of 2,2,6,6-tetramethylpiperidinamine and the chlorine functional group of 2-(2'-hydroxy-4'-benzoyloxyphenyl)-5-chlorobenzotriazole (UV absorber UV-366), and the molar ratio of 2,2,6,6-tetramethylpiperidinamine to 2-(2'-hydroxy-4'-benzoyloxyphenyl)-5-chlorobenzotriazole is controlled to be 1.02:1 to generate UV-blocking monomers. The specific experimental steps are as follows: The method comprises the following steps: adding 3.6 g of 2-(2'-hydroxy-4'-benzoyloxyphenyl)-5-chlorobenzotriazole and 40 mL of acetone into a three-necked flask, stirring at room temperature until all dissolved, then sequentially adding 10 mL of an acetone solution containing 1.6 g of 2,2,6,6-tetramethylpiperidinamine and 1.5 mL of a 20 wt% sodium carbonate aqueous solution into the three-necked flask, mixing evenly, heating to 50° C., stirring and reacting for 4 h, rotary evaporation to remove the solvent, sequentially washing with a saturated sodium chloride aqueous solution and deionized water, and vacuum drying to obtain a UV-blocking monomer;

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

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

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

[0075] The nuclear magnetic resonance hydrogen spectrum of the UV-blocking carboxyl modified monomer is characterized as follows: 1 H NMR (CDCl3, 400MHz) 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-time molded recyclable packaging tube material, characterized in that: The product structure of the one-step formed recyclable packaging tube material is as follows: The first PE layer, the formula of this layer is 100wt% low-density polyethylene resin, and the amount of this layer is 5-15 parts by weight; The second PE layer, the formula of this layer is 100wt% high-density polyethylene resin, and the amount of this layer is 5-15 parts by weight; The third PE layer, the formula of this layer is 100wt% low-density polyethylene resin, and the amount of this layer is 5-15 parts by weight; The first adhesive layer, the formula of this layer is 100wt% maleic anhydride grafted polyethylene resin, and the amount of this layer is 3-8 parts by weight; The first barrier layer, the formula of this layer is 95-99wt% low-density polyethylene resin and 1-5wt% ethylene-vinyl alcohol copolymer resin, and the amount of this layer is 5-15 parts by weight; The second barrier layer, the formula of which is 60-80wt% low-density polyethylene resin and 20-40wt% organic-inorganic composite barrier composition, and the amount of which 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-shielding modified magnesium-aluminum hydrotalcite is as follows: based on the esterification reaction mechanism, the surface of the magnesium-aluminum hydrotalcite is modified by using an ultraviolet-shielding carboxyl modified monomer; The third barrier layer, the formula of this layer is 95-99wt% low-density polyethylene resin and 1-5wt% ethylene-vinyl alcohol copolymer resin, and the amount of this layer is 5-15 parts by weight; The second adhesive layer, the formula of this layer is 100wt% maleic anhydride grafted polyethylene resin, and the amount of this layer is 3-8 parts by weight; The fourth PE layer, the formula of this layer is 100wt% low-density polyethylene resin, and the amount of this layer is 5-15 parts by weight; The fifth PE layer, the formula of this layer is 100wt% high-density polyethylene resin, and the amount of this layer is 5-15 parts by weight; The sixth PE layer has a formula of 100 wt% low-density polyethylene resin and a usage of 5-15 parts by weight.

2. The one-time molded recyclable packaging tube material according to claim 1, characterized in that: The chemical structural formula of the ultraviolet blocking carboxyl modified monomer is:

3. The one-time molded recyclable packaging tube material according to claim 2, characterized in that: The preparation method of the ultraviolet blocking carboxyl modified monomer is as follows: Under the action of an acid-binding agent, a 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 to 2-(2'-hydroxy-4'-benzoyloxyphenyl)-5-chlorobenzotriazole is controlled to be (1.01-1.05):1, thereby generating a UV-blocking monomer; The -NH-functional group of the UV-blocking monomer and the alkenyl functional group of β-(acryloyloxy)propionic acid are catalyzed by an alkaline catalyst to undergo an amine-ene addition reaction, and the molar ratio of the UV-blocking monomer to β-(acryloyloxy)propionic acid is controlled to be (1.01-1.05):1 to generate a UV-blocking carboxyl modified monomer.

4. The one-time molded recyclable packaging tube material according to claim 3, characterized in that: The acid binding agent is one of sodium carbonate, potassium carbonate and sodium acetate.

5. The one-time molded recyclable packaging tube material according to claim 3, characterized in that: The alkaline catalyst is one of sodium ethoxide, sodium hydride, potassium tert-butoxide, triethylamine, triethylenediamine, 4-dimethylaminopyridine, and 1,8-diazabicycloundec-7-ene.

6. The one-time molded recyclable packaging tube material according to claim 1, characterized in that: The mass ratio of the ultraviolet-shielding carboxyl modified monomer to the magnesium-aluminum hydrotalcite in the ultraviolet-shielding modified magnesium-aluminum hydrotalcite is 1:(1-5).

7. The one-time molded recyclable packaging tube material according to claim 6, characterized in that: The sheet diameter of the magnesium aluminum hydrotalcite is 1-3 μm and the thickness is 8-10 nm.

8. A process for preparing a one-time formed recyclable packaging tube material according to any one of claims 1 to 7, characterized in that: The following steps are involved: Step 1, preparing an organic-inorganic composite barrier composition: preparing ingredients according to the formula of the organic-inorganic composite barrier composition, adding the formula raw materials into a high-speed mixer and mixing them evenly, and extruding and granulating them through a twin-screw extruder to prepare an organic-inorganic composite barrier composition; Step 2, preparing a one-time formed recyclable packaging tube material: according to the formula of the one-time formed recyclable packaging tube material, the ingredients are prepared, and the raw materials of each layer are respectively put into the hoppers of the eleven screw extruders of the eleven-layer co-extrusion film blow molding unit. After stirring and mixing, the molten resin is converged at the head of the machine through a diverter, and is extruded and blow-molded through a die head. The blow ratio is controlled at 2.4-2.9, cooled and rolled, and a one-time formed recyclable packaging tube material with a thickness of 250-300μm is prepared.

9. Application of the one-time molded recyclable packaging tube material according to any one of claims 1 to 7 in the field of cosmetic packaging tube materials.

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