A glass storage bottle and a method of making the same

Abstract

The application relates to a glass storage bottle and a preparation method thereof, and is characterized in that: (1) brown glass bottles are cleaned by using water, an alkaline cleaning solution and an acidic cleaning solution, and then dried for standby use; (2) a layer of titanium dioxide film is plated on the inner surface and the outer surface of the brown glass bottles by using a dipping method / spraying method, and then dried at 80-120 DEG C; (3) a layer of silicon dioxide film is continuously plated on the titanium dioxide film layer by using the dipping method, and then dried at 80-120 DEG C; (4) the brown glass bottles plated with the film layers are solidified at 350-550 DEG C for 5-20 min, cooled and cleaned; the application has the beneficial effects that the preparation method is simple, the conditions are mild, the quality of the prepared film layers is relatively stable, the bonding force and the thickness of the film layers are improved, and the application is suitable for deep processing of the glass bottles.

Description

Technical Field

[0001] This invention belongs to the field of glass deep processing and surface modification technology, and relates to a glass storage bottle and its preparation method. Background Technology

[0002] Currently, some adhesive products on the market are highly sensitive to light and temperature, prone to aging, and even minute impurities can alter their properties, making packaging and storage requirements extremely stringent. Existing storage materials typically include 1-gallon (3.75-liter) amber glass bottles and 4-liter Nowpack plastic bottles (products of Intergol Corporation). However, Nowpack plastic bottles are made of high-density polyethylene, and their inner liner contains components prohibited by the EU environmental directives PFOS / PFOA. Glass, on the other hand, possesses excellent optical, mechanical, thermal, and chemical stability properties, making it a superior material for adhesive storage packaging.

[0003] Common methods for treating the inner surface of glass storage bottles include frosting (alkali removal) and siliconization. However, due to increasingly stringent requirements for controlling ion precipitation in glass storage bottles, traditional processes can no longer meet the requirements for the precipitation of metal ions and other impurities on the inner surface of glass storage bottles. Furthermore, frosting requires high-temperature heating, resulting in high energy consumption. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a glass storage bottle and its preparation method.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] A glass storage bottle, comprising a brown glass bottle, characterized in that: a composite barrier film layer is provided on both the inner and outer surfaces of the brown glass bottle, wherein the composite barrier film layer is composed of alternating combinations of 1 to 4 layers of titanium dioxide film and 1 to 4 layers of silicon dioxide film.

[0007] A method for preparing a glass storage bottle, characterized by comprising the following steps:

[0008] (1) Clean the brown glass bottle with water, alkaline cleaning solution and acidic cleaning solution, and then dry it for later use.

[0009] (2) A layer of titanium dioxide film is deposited on the inner and outer surfaces of the brown glass bottle by immersion / spraying method, and then dried at low temperature (80~120℃) (5~30min).

[0010] (3) Subsequently, a silicon dioxide film was deposited on the titanium dioxide film by immersion method and dried at low temperature (80~120℃) (5~30min).

[0011] (4) The brown glass bottle coated with the film is then cured at high temperature (350~550℃) for 5~20 minutes, cooled, and cleaned to obtain a glass storage bottle.

[0012] Furthermore, the main components of the alkaline cleaning solution are: potassium hydroxide, ethylenediaminetetraacetic acid, surfactant, and deionized water (50-60℃), wherein the molar mass concentration ratio of each substance is 1:0.3~0.5:0.1~0.8:8~15, and the surfactant is one of stearic acid, alkylbenzene sulfonate, alkyl sulfonate salt, polysiloxane, fatty alcohol sulfate, naphthenate, alkylphenol sulfonate, etc.

[0013] Furthermore, the main components of the acidic cleaning solution are: potassium hydroxide, glycerol, citric acid, nonionic surfactant, and deionized water (30-40℃), wherein the molar mass concentration ratio of each substance is: 1:0.3~0.5:2~8:0.2~1:16~24, and the nonionic surfactant is one of the following: fatty acid glycerides, fatty acid sorbitan, polysorbate, alkylolamide, polyol monofatty acid ester, alkylamine oxide, etc.

[0014] Furthermore, in step (2), the titanium dioxide film is prepared from a titanium dioxide nanoparticle dispersion, which is made from the following raw materials: nano-titanium dioxide particles, halogen acids (such as hydrochloric acid, hydrogen bromide, etc.), dispersants (isopropanol, sodium dodecyl sulfate, methylpentanol), and deionized water, with a molar mass concentration ratio of 1:0.03~0.08:0.01~0.08:30~80, and the titanium dioxide nanoparticles have a particle size of 15~50 nm.

[0015] Furthermore, the specific preparation method of the titanium dioxide nanoparticle dispersion is as follows: first, mix the nano-titanium dioxide particles, dispersant and water in proportion and then slowly add halogen acid, and stir to homogenize for 30~120 min.

[0016] Furthermore, in step (3), the silica film is prepared by acidic silica sol, wherein the acidic silica sol is prepared by the following steps: water and alcohol are mixed evenly in a molar mass concentration ratio of 1.0~1.8:1.0~5.0, and under stirring, the pH value of the system is adjusted to between 4 and 5 with concentrated hydrochloric acid, stirred and homogenized, and then tetraethyl orthosilicate is slowly added dropwise, stirred and homogenized for 2~6 hours, and then allowed to stand and age for 12-36 hours to form a sol, wherein the molar mass concentration ratio of silica and alcohol in the sol is 0.2~0.4:1.0~5.0.

[0017] Furthermore, steps (2) and (3) are repeated 1-3 times.

[0018] This invention utilizes acidic silica sol, which possesses a Si-O-Si network structure. The silica particles in the film are densely packed, exhibiting good strength and quality. In the composite structure, the titanium dioxide film and silica sol form multiple active sites on the film surface, resulting in cross-linking and a dense network structure. Simultaneously, stress is released using the silica film, further enhancing the adhesion and thickness of the composite film and optimizing its corrosion resistance and stability. By repeatedly depositing titanium dioxide and silica films and utilizing intermediate layers to release stress, the adhesion and final thickness of the films are improved.

[0019] The beneficial effects of the present invention are: the method of the present invention is simple, the conditions are mild, the quality of the obtained film is relatively stable, the adhesion and thickness of the film are improved, and it is suitable for the deep processing of glass bottles. Detailed Implementation

[0020] A method for preparing a glass storage bottle, the specific implementation steps of which are as follows: Example

[0021] (1) Clean the glass bottle: Rinse with high-pressure water, then place it in an alkaline cleaning solution (the main components are potassium hydroxide, ethylenediaminetetraacetic acid, stearic acid, and deionized water, with a molar mass concentration ratio of 1:0.3:0.2:9) and immerse the bottle in the solution at 50°C to fill it with liquid. Clean it with ultrasonic (100KHZ) for 15 minutes. Rinse with high-pressure water again, then place it in an acidic cleaning solution (the main components are potassium hydroxide, glycerol, citric acid, fatty acid glycerides, and deionized water, with a molar mass concentration ratio of 1:0.3:3:0.4:18) and immerse the bottle in the solution at 30°C to fill it with liquid. Clean it with ultrasonic (80KHZ) for 15 minutes. Finally, rinse with high-pressure water and dry it for later use.

[0022] (2) Mix 80g of titanium dioxide particles with a particle size of 20nm, 2.88g of sodium dodecyl sulfate and 720mL of water evenly, then slowly add 3mL of 36% hydrochloric acid, stir and homogenize for 30min to obtain a titanium dioxide nanoparticle dispersion; deposit a titanium dioxide film on the inner and outer walls of the glass bottle by immersion method, and dry at a low temperature of 80℃ for 25min;

[0023] (3) After mixing 30 mL of water and 270 mL of ethanol evenly, the pH of the system was adjusted to 4 with concentrated hydrochloric acid under stirring. After stirring and homogenizing, 40 mL of tetraethyl orthosilicate was slowly added dropwise and stirred and homogenized for 3 h. Then, the mixture was allowed to stand and age for 24 h to form an acidic silica sol. The brown glass bottle coated with titanium dioxide film was immersed in the acidic silica sol and then taken out and dried at a low temperature of 80 °C for 15 min.

[0024] (4) Repeat steps (2) and (3) twice more;

[0025] (5) Place the dried brown glass bottle at a high temperature of 450°C for 15 minutes to cure. After curing, cool and clean to obtain the glass storage bottle. Example

[0026] (1) Clean the glass bottle: Rinse with high pressure water, then place it in an alkaline cleaning solution (the main components are potassium hydroxide, ethylenediaminetetraacetic acid, stearic acid, and deionized water, with a molar mass concentration ratio of 1:0.4:0.5:12) and immerse the bottle in the solution at 55°C to fill it with liquid. Clean with ultrasonic (60KHZ) for 20 minutes. Rinse with high pressure water again, then place the bottle in an acidic cleaning solution (the main components are potassium hydroxide, glycerol, citric acid, fatty acid glycerides, and deionized water, with a molar mass concentration ratio of 1:0.4:5:0.6:20) and immerse the bottle in the solution at 35°C to fill it with liquid. Clean with ultrasonic (60KHZ) for 20 minutes. Finally, rinse with high pressure water and dry the bottle for later use.

[0027] (2) Mix 80g of titanium dioxide particles with a particle size of 30nm, 10mL of methylpentanol and 1080mL of water evenly, then slowly add 5mL of 36% hydrochloric acid, stir and homogenize for 60min to obtain a titanium dioxide nanoparticle dispersion; deposit a titanium dioxide film on the inner and outer walls of the glass bottle by immersion method, and dry at 100℃ for 10min.

[0028] (3) After mixing 20 mL of water and 180 mL of ethanol evenly, the pH of the system was adjusted to 4 with concentrated hydrochloric acid under stirring. After stirring and homogenizing, 80 mL of tetraethyl orthosilicate was slowly added dropwise and stirred and homogenized for 5 h. Then, the mixture was allowed to stand and age for 30 h to form an acidic silica sol. The brown glass bottle coated with titanium dioxide film was immersed in the acidic silica sol and then taken out and dried at 100 °C for 10 min.

[0029] (4) Repeat steps (2) and (3) once more;

[0030] (5) Place the dried brown glass bottle at a high temperature of 500℃ for 10 minutes to cure. After curing, cool and clean to obtain the glass storage bottle. Example

[0031] (1) Clean the glass bottle: Rinse with high pressure water, then place it in an alkaline cleaning solution (the main components are potassium hydroxide, ethylenediaminetetraacetic acid, sodium dodecylbenzenesulfonate, and deionized water, with a molar mass concentration ratio of 1:0.5:0.6:14) and immerse the bottle in the solution at 50°C to fill it with liquid. Clean with ultrasonic (40KHZ) for 25 minutes. Rinse with high pressure water again, then place the bottle in an acidic cleaning solution (the main components are potassium hydroxide, glycerin, citric acid, polysorbate, and deionized water, with a molar mass concentration ratio of 1:0.5:7:0.8:22) and immerse the bottle in the solution at 30°C to fill it with liquid. Clean with ultrasonic (40KHZ) for 25 minutes. Finally, rinse with high pressure water and dry the bottle for later use.

[0032] (2) Mix 80g of titanium dioxide particles with a particle size of 45nm, 17.2g of sodium dodecyl sulfate and 1440mL of water evenly, then slowly add 8mL of 36% hydrochloric acid, stir and homogenize for 90min to obtain a titanium dioxide nanoparticle dispersion; deposit a titanium dioxide film on the inner and outer walls of the glass bottle by immersion method, and dry at a low temperature of 120℃ for 5min;

[0033] (3) After mixing 36 mL of water and 80 mL of ethanol evenly, the pH of the system was adjusted to 5 with concentrated hydrochloric acid under stirring. After stirring and homogenizing, 20 mL of tetraethyl orthosilicate was slowly added dropwise and stirred and homogenized for 2 hours. Then, the mixture was allowed to stand and age for 14 hours to form an acidic silica sol. The brown glass bottle coated with titanium dioxide film was immersed in the acidic silica sol and then taken out and dried at a low temperature of 120°C for 5 minutes.

[0034] (4) Place the dried brown glass bottle at a high temperature of 400℃ for 20 minutes to cure. After curing, cool and clean to obtain the glass storage bottle.

[0035] Table 1. Adhesion strength and thickness of the film layer after the test in the example.

[0036]

[0037] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that those skilled in the art can make several improvements and modifications without departing from the inventive concept of the present invention, and these all fall within the protection scope of the present invention.

Claims

1. A method of making a glass storage bottle, characterized by It comprises the following steps: (1) the brown glass bottle is cleaned with water, alkaline cleaning solution and acid cleaning solution, and then dried for standby; (2) a layer of titanium dioxide film is coated on the inner and outer surfaces of the brown glass bottle by immersion method / spraying method, and then dried at 80-120℃; the titanium dioxide film in step (2) is prepared from a titanium dioxide nanoparticle dispersion liquid, wherein the titanium dioxide nanoparticle dispersion liquid is composed of titanium dioxide nanoparticles, halogen acid, dispersant and deionized water, and the molar mass concentration ratio of the above components is 1:0.03-0.08:0.01-0.08:30-80, and the particle size of the titanium dioxide nanoparticles is 15-50 nm, wherein the halogen acid is hydrochloric acid or hydrogen bromide, and the dispersant is isopropyl alcohol, sodium dodecyl sulfate or methyl amyl alcohol; (3) then a layer of silica film is coated on the titanium dioxide film layer by immersion method, and then dried at 80-120℃; the silica film in step (3) is prepared from an acidic silica sol, wherein the acidic silica sol is prepared by the following steps: first, mix water and alcohol uniformly according to the molar mass concentration ratio of 1.0-1.8:1.0-5.0, then adjust the pH value of the system to 4-5 with concentrated hydrochloric acid under stirring, stir and homogenize, then slowly drop in tetraethyl orthosilicate, stir and homogenize for 2-6 h, then stand and age for 12-36 h to form a sol, wherein the molar mass concentration ratio of silica and alcohol in the sol is 0.2-0.4:1.0-5.0; steps (2) and (3) are repeated 1-3 times; (4) then the brown glass bottle coated with the film layer is solidified at 350-550℃ for 5-20 min, cooled, washed, and a glass storage bottle is obtained.

2. The method of claim 1, wherein the glass storage bottle is prepared by the steps of: The main components of the alkaline cleaning solution are potassium hydroxide, ethylenediaminetetraacetic acid, surfactant and deionized water, and the molar mass concentration ratio of the above components is 1:0.3-0.5:0.1-0.8:8-15, and the surfactant is one of stearic acid, alkyl benzene sulfonate, alkyl sulfonate, polysiloxane, fatty alcohol sulfate, naphthenate and alkyl phenol sulfonate. ​ 3. The method for preparing a glass storage bottle according to claim 1, characterized in that: The main components of the acid cleaning solution are potassium hydroxide, glycerol, citric acid, non-ionic surfactant and deionized water, and the molar mass concentration ratio of the above components is 1:0.3-0.5:2-8:0.2-1:16-24, and the non-ionic surfactant is one of fatty acid glyceride, fatty acid sorbitan, polysorbate, alkyl alcohol amide, polyol monofatty acid ester and alkyl amine oxide.

4. The method for preparing a glass storage bottle according to claim 1, characterized in that: The specific preparation method of the titanium dioxide nanoparticle dispersion liquid is as follows: first, mix the titanium dioxide nanoparticles, dispersant and water uniformly according to the proportion, then slowly drop in the halogen acid, and stir and homogenize for 30-120 min.

5. The glass storage bottle prepared according to the method of any one of claims 1-4, characterized by: The inner and outer surfaces of the brown glass bottle are provided with a composite barrier film layer, wherein the composite barrier film layer is composed of 2-4 layers of titanium dioxide film and 2-4 layers of silica film alternately combined.

Images