Preparation process of oleophylic adhesion-resistant film layer of perfume glass bottle

Abstract

The invention provides a preparation process of an oleophylic adhesion-resistant film layer of a perfume glass bottle. The preparation process sequentially comprises the steps of ultrasonic cleaning, surface activation, polymer solution spin coating and low-temperature cross-linking curing. The method comprises the following steps: firstly, sequentially adding a water-based decontamination solution, ethanol and deionized water into a glass bottle, and treating in an ultrasonic field of 30-45kHz, so that pollutants on the surface of the inner wall are separated; according to the invention, the low-temperature cross-linked solvent-resistant polymer film layer is formed on the inner wall of the glass, so that the film layer constructs a compact extraction-resistant network structure at 60-90 DEG C, and the permeation rate of ethanol and essential oil to the film layer can be reduced, so that the thickness stability of the film layer is kept for a long time in a closed and high-volatility perfume system; the anti-fingerprint film does not have swelling, softening or demolding phenomena, and is soaked in 85% ethanol and limonene essential oil for 72 hours, the thickness change rate of the film can be controlled below 5%, and the problem that a traditional anti-fingerprint film is easy to lose efficacy in a perfume bottle environment is effectively solved.

Description

A process for preparing an oleophilic barrier film for perfume glass bottles Technical Field

[0001] This invention relates to the field of glass bottle processing technology, and in particular to a process for preparing an oleophilic barrier film for perfume glass bottles. Background Technology

[0002] Anti-fingerprint coating technology is widely used in products such as touchscreen covers, mobile terminal casings, optical glass, and metal fittings. Its basic principle is to form a low surface energy material layer on the substrate surface, reducing the spreadability of grease and thus mitigating fingerprint residue. Existing anti-fingerprint films typically use inorganic silicon-oxygen structures, organic fluorine-modified materials, or a composite system of both as main components, and are formed through methods such as magnetron sputtering, plasma deposition, and spray curing. These films exhibit good oleophobicity and stain resistance under everyday use conditions, and are therefore widely used in electronic displays and consumer electronics.

[0003] However, the application environment of perfume glass bottles differs from that of electronic products. Perfume formulas generally contain high concentrations of ethanol, essential oils, and various volatile organic solvents. These components have strong solubility and permeability, which can significantly affect the film material, binder phase, or interfacial bonding. The inner wall of the bottle will be continuously exposed to this chemical environment during perfume filling, storage, and long-term static placement. The film needs to remain stable under a closed, long-term, and highly volatile wetting condition. This is completely different from the usage conditions of anti-fingerprint films for touch screens, which are used in open environments, with short contact times and a single source of contamination.

[0004] To address this, a process for preparing an oleophilic barrier film for perfume glass bottles is proposed. Summary of the Invention

[0005] In view of this, the present invention provides a process for preparing an oleophilic barrier film layer for perfume glass bottles, so as to solve or alleviate the technical problems existing in the prior art, and at least provide a beneficial alternative.

[0006] The technical solution of this invention is achieved as follows: a process for preparing an oleophilic barrier film layer for perfume glass bottles, comprising the following steps:

[0007] S1. Add water-based detergent, 95% ethanol and deionized water to the perfume glass bottle in sequence, and act on it in an ultrasonic field of 30-45kHz for 1-3 minutes to remove oil, particles and previous residues from the inner wall of the bottle from the glass surface.

[0008] S2. Place the cleaned perfume glass bottle into the activation chamber and treat it with oxygen plasma at a radio frequency power of 80-150W for 10-40 seconds to generate surface-active hydroxyl groups on the inner wall of the glass that can undergo subsequent cross-linking reactions.

[0009] S3. Inject a low-temperature cross-linking solvent inhibitor polymer solution into the activated glass bottle, fix the glass bottle on a rotating clamp and rotate it at a speed of 300-900 rpm for 10-30 seconds to form a continuous and uniform liquid film of polymer solution on the inner wall of the bottle.

[0010] S4. Place the coated glass bottle into a constant temperature curing chamber and keep it at 60-90℃ for 15-40 minutes. The liquid film is cured through a low-temperature crosslinking reaction to form a dense oleophilic and adhesive barrier film.

[0011] The low-temperature crosslinking solvent inhibitor polymer is a material that can form a crosslinking network within the curing temperature range and does not swell under ethanol and essential oil immersion conditions. Its number-average molecular weight is 5,000 to 50,000, and the thickness change rate of its cured film layer after immersion in 85% ethanol or limonene essential oil for 72 hours is not higher than 5%.

[0012] The material is selected from at least one of perfluoropolyether modified polyurethane, fluorinated polysilsesquioxane and swelling-resistant polyaryl ether, and the solid content of the solvent-resistant polymer solution is 1 to 10 wt%.

[0013] More preferably, the crosslinking structure of the solvent-inhibiting polymer contains -CF2-, -CF3, -Si-O-Si-, or -NH-CO- bonds, and the thickness of the film layer formed after curing on the inner wall of the glass is 20-150 nm.

[0014] In a further preferred embodiment, the acceleration of the bottle in step S3 is set to 50-200 rpm / s.

[0015] Further preferably, after cleaning the inner wall, the bottle is purged with nitrogen at 0.1–0.3 MPa for 5–10 seconds to reduce the residual moisture content on the inner wall to no more than 50 ppm.

[0016] More preferably, after step S2, a 0.05-0.5 wt% silane undercoat is sprayed to form an initiation layer on the glass surface that can react with the solvent-inhibiting polymer.

[0017] In a further preferred embodiment, the inner diameter of the perfume glass bottle opening is 8–25 mm, the bottle depth is 30–120 mm, and the clamping end of the rotating clamp can extend into the bottle opening by 5–20 mm, so that the coating process can achieve uniform spreading in the deep cavity environment.

[0018] In a further preferred embodiment, the low-temperature cross-linking curing process employs infrared heating or hot air circulation to ensure that the temperature gradient inside the bottle does not exceed ±3℃.

[0019] Further preferably, the obtained oleophilic adhesion barrier film layer has a fragrance adsorption amount of no more than 0.1 μg / cm² after being soaked in fragrance oil for 24 hours, and the fragrance residue adhesion rate is reduced to less than 5%.

[0020] More preferably, the solvent of the solvent-inhibiting polymer solution is composed of at least one of ethyl acetate, methyl isobutyl ketone, and ethylene glycol ethyl ether, with a boiling point range of 78–145°C, used to control the flow rate and evaporation rate of the liquid film.

[0021] More preferably, the internal pressure of the cavity during the surface activation treatment is 20-80 Pa.

[0022] The embodiments of the present invention have the following advantages due to the adoption of the above technical solutions:

[0023] I. This invention forms a low-temperature cross-linked solvent-resistant polymer film on the inner wall of glass, enabling the film to construct a dense, extraction-resistant network structure at 60–90°C. This reduces the permeation rate of ethanol and essential oils into the film, thus maintaining the film thickness stability in a closed, highly volatile perfume system for a long time without swelling, softening, or delamination. After soaking in 85% ethanol and limonene essential oil for 72 hours, the film thickness change rate can be controlled below 5%, effectively solving the problem of traditional anti-fingerprint films easily failing in perfume bottle environments.

[0024] Second, this invention employs a combination of ultrasonic deep cavity cleaning, plasma activation, and constant-speed rotary coating to form a continuous and uniform nanoscale liquid film of the solvent-inhibiting polymer on the inner wall of the bottle. After low-temperature curing, a stable film structure with high adhesion is obtained, avoiding the common problems of film redistribution, sagging, or local thinning in deep cavity containers. This allows the film to maintain its bonding force with the glass interface under long-term immersion conditions, improving the adhesion and retention of essential oils on the inner wall of the glass bottle.

[0025] The above overview is for illustrative purposes only and is not intended to be limiting in any way. In addition to the illustrative aspects, embodiments, and features described above, further aspects, embodiments, and features of the invention will become readily apparent from the accompanying drawings and the following detailed description. Attached Figure Description

[0026] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0027] Figure 1 is a process flow diagram of the present invention. Detailed Implementation

[0028] In the following description, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments can be modified in various ways without departing from the spirit or scope of the invention. Therefore, the drawings and description are considered to be exemplary in nature and not restrictive.

[0029] The embodiments of the present invention will now be described in detail with reference to the accompanying drawings.

[0030] As shown in Figure 1, this embodiment of the invention provides a process for preparing an oleophilic adhesion-resistant film layer on the inner wall of a perfume glass bottle, including the following steps:

[0031] S1. Inner wall cleaning steps

[0032] Add water-based detergent, 95% ethanol and deionized water to the perfume glass bottle in sequence, and act on it in an ultrasonic field of 30-45kHz for 1-3 minutes to remove oil stains, particles and previous residues from the inner wall of the glass from the glass surface, thereby obtaining a clean substrate.

[0033] After cleaning, nitrogen gas is used to purge the surface of the bottle inner wall for 5 to 10 seconds at a pressure of 0.1 to 0.3 MPa to reduce the residual moisture content to no more than 50 ppm, so as to avoid moisture affecting subsequent surface activation and cross-linking curing.

[0034] The following are the suitable applications for perfume glass bottles:

[0035] Bottle mouth inner diameter: 8-25mm; bottle body depth: 30-120mm; this structure is prone to forming a "deep cavity", so ordinary spraying cannot achieve uniform film formation. The process of this invention can overcome this problem.

[0036] S2, Surface activation step

[0037] The cleaned glass bottle is placed in an activation chamber, maintaining the pressure within the chamber at 20–80 Pa. Oxygen plasma is used to treat the glass surface with 80–150 W radio frequency power for 10–40 seconds, generating a large number of active hydroxyl groups capable of participating in chemical cross-linking reactions. After surface activation, a 0.05–0.5 wt% silane undercoat can be sprayed onto the glass to introduce an initiating layer that can further react, thereby improving the adhesion and durability of the subsequent solvent-resistant polymer film.

[0038] S3, Solvent-inhibiting polymer coating step

[0039] A low-temperature cross-linking solvent-inhibiting polymer solution is injected into the activated glass bottle to cover the bottom and part of the inner wall. The glass bottle is then fixed on a rotating fixture with the clamping end extending 5–20 mm into the bottle opening to suppress splashing and maintain spin coating stability.

[0040] During the coating process, the bottle is rotated at a speed of 300-900 rpm and the acceleration is set to 50-200 rpm / s, so that the polymer solution is evenly spread to the bottle wall under the action of centrifugal force to form a continuous liquid film.

[0041] The solvent-inhibiting polymer solution consists of the following:

[0042] Low-temperature crosslinking solvent-inhibiting polymers (solid content 1-10 wt%): one or more of perfluoropolyether modified polyurethane, fluorinated polysilsesquioxane, and swelling-inhibiting polyaryl ether;

[0043] Solvent: one or more of ethyl acetate, methyl isobutyl ketone and ethylene glycol ethyl ether, with a boiling point of 78–145 °C;

[0044] The number average molecular weight of the solvent polymer is 5,000 to 50,000. The evaporation rate and flow properties of the solution meet the requirements of deep cavity spin coating. The thickness of the wet film is controlled by the solid content and the rotation speed. After curing, the film thickness is stable at 20 to 150 nm.

[0045] S4, Low-temperature crosslinking and curing step

[0046] The spin-coated glass bottle is placed in a constant-temperature curing device. Infrared low-temperature heating or hot air circulation is used to maintain the inner wall temperature of the bottle within the range of 60–90°C for 15–40 minutes. A temperature control system maintains the temperature gradient within ±3°C on the inner wall of the bottle. At this temperature, the solvent-inhibiting polymer undergoes a cross-linking reaction, forming a stable network structure, which includes:

[0047] —CF2— and —CF3— structures provide oleophobicity and adhesion resistance;

[0048] —Si—O—Si— structure, forming an inorganic network and swelling resistance;

[0049] —NH—CO—, polyurethane cross-linked structure;

[0050] After the cured film was immersed in 85% ethanol or limonene essential oil for 72 hours, the film thickness change was no more than 5%, indicating that it has excellent resistance to swelling and chemical stability.

[0051] The final oleophilic barrier film layer had an adsorption capacity of no more than 0.1 μg / cm² after being soaked in essential oil for 24 hours, and the fragrance residue rate on the inner wall of the glass was reduced to below 5%.

[0052] Example 1: Film preparation process based on perfluoropolyether modified polyurethane (PFPE-PU)

[0053] I. Test Materials and Bottle Parameters

[0054] Solvent-inhibiting polymer: perfluoropolyether modified polyurethane (Mn = 12,000); solvent: ethyl acetate; solid content: 5 wt%; perfume glass bottle: 12 mm mouth, 60 mm depth;

[0055] II. Preparation process steps:

[0056] S1. Cleaning treatment

[0057] The bottle was rinsed sequentially with water-based detergent, 95% ethanol, and deionized water, and then subjected to ultrasonic treatment at 40 kHz for 2 minutes. After that, it was purged with nitrogen gas at 0.2 MPa for 8 seconds. The residual moisture in the bottle was measured to be approximately 30 ppm.

[0058] S2, Surface activation

[0059] The bottle is placed in a plasma chamber with a chamber pressure of 30 Pa and an oxygen plasma power of 120 W for 20 seconds, resulting in the formation of a uniform hydroxyl layer on the glass surface.

[0060] S3, Inner wall coating

[0061] Add the polymer solution into the bottle so that droplets form a coating at the bottom. Fix the glass bottle to the rotating fixture, with the clamping end extending 10mm into the bottle opening. Rotation parameters: acceleration 120rpm / s → 600rpm, spin coating for 15s to form a uniform wet film.

[0062] S4, low temperature curing

[0063] The spin-coated bottle was placed in a 70°C curing oven and kept for 30 minutes. The thickness of the cured film was measured to be approximately 65 nm using a thin film interferometer.

[0064] III. Film Characterization and Performance Testing

[0065] Immersion in 85% ethanol for 72 h: film thickness change 2.1%; immersion in limonene for 72 h: film thickness change 3.4%; fragrance adsorption (immersion for 24 h): 0.06 μg / cm²; residual fragrance adhesion rate: approximately 4.8%.

[0066] IV. Results Analysis

[0067] After being formed by PFPE-PU, the film exhibits significantly stable resistance to ethanol and essential oils, enhanced oleophobicity, and a substantial reduction in the adsorption of essential oils onto the inner wall of the glass, making it suitable for use in perfume packaging bottles with high solvent systems.

[0068] Example 2: Film preparation process based on fluorinated polysilsesquioxane (F-POSS)

[0069] I. Test Materials and Bottle Parameters

[0070] Polymer: Fluorinated polysilsesquioxane (Mn = 8,000); Solid content: 3wt%; Solvent: Methyl isobutyl ketone (MIBK); Perfume glass bottle: 15mm opening, 80mm depth.

[0071] II. Preparation Process Steps

[0072] S1. Cleaning treatment

[0073] Using the same steps as in Example 1, the final remaining moisture content was approximately 35 ppm.

[0074] S2, Activation Treatment

[0075] Plasma conditions: 100W, 35s, cavity pressure 45Pa.

[0076] S3, Inner wall coating

[0077] The rotating clamp extends 12mm into the bottle opening; spin coating parameters: acceleration 200rpm / s→900rpm20s, forming a uniform film.

[0078] S4, low temperature curing

[0079] The film was cured at 80°C for 20 minutes using hot air circulation; the thickness of the cured film was measured to be approximately 40 nm.

[0080] III. Film Characterization and Performance Testing

[0081] Immersion in 85% ethanol for 72 hours: film thickness change 1.5%; immersion in limonene for 72 hours: change 2.7%; fragrance adsorption: 0.04 μg / cm²; surface energy test (Owens-Wendt method): decrease of approximately 23%.

[0082] IV. Results Analysis

[0083] Thanks to the Si–O–Si inorganic network structure of F-POSS, the swelling resistance of the film is improved, and the film remains stable in the fragrance oil environment.

[0084] Example 3: Reinforced swelling-resistant film layer based on swelling-resistant polyarylene ether (PAE)

[0085] I. Test Materials and Bottle Parameters

[0086] Polymer: polyarylene ether (Mn = 25,000); solid content: 8 wt%; solvent: ethylene glycol ethyl ether; bottle body: 10 mm mouth, deep cavity structure, 100 mm depth;

[0087] II. Preparation Process Steps

[0088] S1. Cleaning treatment

[0089] Ultrasonic cleaning at 30kHz for 2 minutes; nitrogen purging at 0.3MPa for 10 seconds, reducing moisture content to 25ppm.

[0090] S2, Activation Treatment

[0091] Power 90W, 15s, cavity pressure 50Pa; surface hydroxyl density significantly increased.

[0092] S3, Deep Cavity Spin Coating

[0093] A two-stage spin coating method is adopted:

[0094] First stage: 300 rpm (5 s) → Initial spreading of the liquid film;

[0095] Second stage: 700rpm (20s) → Achieve homogenization of deep cavity;

[0096] Clamp extension: 20mm.

[0097] S4, low temperature curing

[0098] After curing at 90°C for 40 minutes, the film thickness after cooling is approximately 120 nm.

[0099] III. Film Characterization and Performance Testing

[0100] Immersion in 85% ethanol for 72 hours: film thickness change 4.3%; immersion in limonene for 72 hours: change 4.8%; film thickness uniformity (deep cavity detection): ±6%; odor residue detection: reduced to below 30% of the control group;

[0101] IV. Results Analysis

[0102] Polyarylene ether films are thick and dense, providing excellent flowability in deep-cavity bottles. They are suitable for highly extractable essential oils and fragrance products with higher requirements for swelling resistance.

[0103] Example 4: Composite process using silane undercoat to enhance adhesion

[0104] I. Test Materials and Bottle Parameters

[0105] Primer: 0.2wt% silane coupling agent solution (ethanol system); Main coating: PFPE-PU system (same as Example 1); Bottle body: 14mm at the top, 70mm in depth;

[0106] II. Preparation Process Steps

[0107] S1–S2 were cleaned according to Example 1 → plasma treatment (110W, 25s), followed immediately by spraying a silane primer to form an initiation layer of about 5–10 nm on the bottle wall.

[0108] S3, Rotary Coating

[0109] The spin coating parameters are similar to those in Example 1: 500 rpm × 15 s, acceleration 100 rpm / s.

[0110] S4, low temperature curing

[0111] Curing at 70°C for 25 minutes yielded a film thickness of approximately 55 nm.

[0112] III. Performance Testing

[0113] The test items included adhesion with and without primer (100 peel cycles of 3M 610 tape). Approximately 20% of the area showed no peeling. After 24 hours of ethanol soaking, no significant peeling was observed in the peel test. Residual fragrance adhesion rates were 3.9% and 6.8%. surface

[0114] IV. Results Analysis

[0115] The silane primer forms a chemical bond with the solvent-inhibiting polymer, which significantly improves the adhesion, immersion resistance and long-term stability of the film.

[0116] Comparative Example 1: Using a traditional fluorosilane anti-fingerprint coating (non-crosslinked type)

[0117] I. Test Materials and Bottle Parameters

[0118] Coating material: Commercial fluorosilane anti-fingerprint agent (without low-temperature cross-linking structure); Solvent: Isopropanol; Glass bottle: 12mm mouth, 60mm depth;

[0119] II. Comparison of process steps (following the conventional anti-fingerprint film process)

[0120] S1, Cleaning

[0121] The cleaning was performed using 40kHz ultrasound for 2 minutes, and the cleaning method was the same as in Example 1.

[0122] S2, Activation

[0123] No plasma or silane primer was applied; only hot air drying was used.

[0124] S3, Coating

[0125] The initial thin layer is formed on the bottle wall using a drop-coating method, and the bottle is manually rotated to spread the liquid film.

[0126] S4, Curing

[0127] Cured at 120℃ for 10 minutes.

[0128] The resulting film thickness is approximately 30 nm.

[0129] III. Performance Testing

[0130] 1. Resistant to ethanol immersion (85% ethanol, 72h):

[0131] Film thickness change rate: 38%; whitening and film delamination occurred in some areas;

[0132] 2. Fragrance-resistant essential oil infusion (limonene, 72h):

[0133] The film surface showed obvious swelling; the localized detachment area was approximately 15–30%.

[0134] 3. Fragrance adsorption capacity:

[0135] Adsorption capacity after 24 hours: 0.52 μg / cm²; Fragrance residue adhesion rate: 27%.

[0136] IV. Comparative Explanation

[0137] Because existing fluorosilane films lack a cross-linked network, their chain segments are prone to swelling and dissolution in strong solvent environments, leading to:

[0138] The membrane thickness is unstable; solvent extraction leads to membrane stripping; and the adsorption of essential oils is significantly higher than in this invention.

[0139] Comparative Example 2: Using a conventional silicone resin antifouling coating (thermosetting type)

[0140] I. Test Materials and Bottle Parameters

[0141] Coating material: silicone resin (Mn≈3,000, non-swellable type); solid content: 8wt%; curing temperature: 150℃; glass bottle: 15mm mouth, 80mm depth;

[0142] II. Comparison of process steps

[0143] S1, Cleaning

[0144] The method is the same as in Example 2.

[0145] S2, Activation

[0146] (Plasma treatment was not used.)

[0147] S3, Coating

[0148] The dip-coating method is used, where the bottle is slowly tilted to form a liquid film.

[0149] S4, Curing

[0150] Curing at 150℃ for 20 minutes yields a film thickness of approximately 100 nm.

[0151] III. Performance Testing

[0152] Soak in 1.85% ethanol for 72 hours:

[0153] Film thickness change rate: 22%; the film layer softens and becomes more viscous;

[0154] 2. Soak in limonene for 72 hours:

[0155] Swelling rate: >30%; fluid redistribution occurs in the membrane layer at the bottom of the deep cavity; localized peeling area is approximately 10–18%;

[0156] 3. Fragrance adsorption capacity:

[0157] After 24 hours: 0.31 μg / cm²; Adhesion rate: approximately 18%;

[0158] IV. Comparative Explanation

[0159] While conventional silicone coatings possess some oleophobic properties, however:

[0160] The resin has a soft structure and low cross-linking density; its molecular chain segments are highly polar and easily penetrated by ethanol or terpene solvents; and its coating uniformity is poor in deep-cavity bottles.

[0161] This results in the inability to form a stable and resistant adhesive layer on the inner wall of the perfume bottle, and the film stability and swelling resistance are significantly weaker than the low-temperature cross-linked solvent-resistant polymer of the present invention.

[0162] The comparative structures of Examples 1-4 and Comparative Examples 1-2 are shown in the table below:

[0163] Test Item Comparative Example 1 (Traditional Fluorosilane Membrane) Comparative Example 2 (Conventional Organosilicon Resin Membrane) This Invention (Low-Temperature Crosslinking Inhibitor Polymer Membrane) Membrane Thickness Change Rate (85% Ethanol, 72h) 38% 22% ≤5% Limonene Essential Oil Swelling (72h) Severe Swelling, Local Desquamation Obvious Swelling, Membrane Softening No Obvious Swelling, Stable Structure Fragrance Adsorption (μg / cm², 24h Wetting) 0.5 20.3 1 ≤0.1 Fragrance Residue Adhesion Rate 27% 18% ≤5% Membrane Adhesion Easily Desorbed After Ethanol Extraction Deep Cavity Bottom Peeling Stable Adhesion, No Delamination Coating Uniformity (Deep Cavity Bottle) Poor, Easily Forms Sagging Membrane Redistribution Uniformity ±6% surface

[0164] As can be seen from the above comparison, both the traditional fluorosilane film (Comparative Example 1) and the conventional organosilicon resin film (Comparative Example 2) showed obvious swelling, thinning and local peeling failure under long-term immersion in ethanol and essential oils. Their fragrance adsorption and residual adhesion rate were also significantly higher than those of the system of the present invention, making it difficult to meet the usage requirements of the inner wall of perfume glass bottles.

[0165] In contrast, the low-temperature cross-linking solvent-inhibiting polymer used in this invention can form a dense cross-linking network at lower temperatures, enabling the film to remain stable in strong solvent environments without swelling or detachment, and significantly reducing fragrance adsorption and residue. This indicates that the film of this invention is significantly superior to existing technologies in terms of solvent resistance, adhesion, and anti-adhesion performance, and can effectively solve the problem of traditional films easily failing under long-term immersion conditions in perfume bottles.

[0166] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any person skilled in the art can easily conceive of various variations or substitutions within the technical scope disclosed in the present invention, and these should all be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A process for preparing an oleophilic barrier film for perfume glass bottles, characterized in that, Includes the following steps: S1. Add water-based detergent, 95% ethanol, and deionized water sequentially to the perfume glass bottle, and treat it in an ultrasonic field of 30-45 kHz for 1-3 minutes to remove oil, particles, and previous residues from the inner wall of the bottle. S2. Place the cleaned perfume glass bottle into the activation chamber and treat it with oxygen plasma at a radio frequency power of 80-150 W for 10-40 seconds to generate surface-active hydroxyl groups on the inner wall of the glass that can undergo subsequent cross-linking reactions. S3. Inject a low-temperature cross-linking solvent-inhibiting polymer solution into the activated glass bottle, fix the glass bottle on a rotating clamp, and rotate it at a speed of 300-900 rpm for 10-30 seconds to form a continuous and uniform liquid on the inner wall of the bottle. S4. Place the coated glass bottle into a constant temperature curing chamber and maintain it at 60-90℃ for 15-40 minutes to solidify the liquid film through a low-temperature crosslinking reaction to form a dense oleophilic anti-adhesion film layer; wherein, the low-temperature crosslinking type solvent inhibitor polymer is a material that can form a crosslinking network within the curing temperature range and does not swell under ethanol and essential oil immersion conditions, with a number average molecular weight of 5,000-50,000, and the thickness change rate of the cured film layer after immersion in 85% ethanol or limonene essential oil for 72 hours is not higher than 5%; the material is selected from at least one of perfluoropolyether modified polyurethane, fluorinated polysilsesquioxane, and anti-swelling polyaryl ether, and the solid content of the solvent inhibitor polymer solution is 1-10 wt%.

2. The process for preparing the oleophilic barrier film layer for perfume glass bottles according to claim 1, characterized in that: The cross-linked structure of the solvent-inhibiting polymer contains -CF2-, -CF3, -Si-O-Si-, or -NH-CO- bonds, and the thickness of the film layer formed after curing on the inner wall of the glass is 20-150 nm.

3. The process for preparing the oleophilic barrier film layer for perfume glass bottles according to claim 1, characterized in that: In step S3, the acceleration of the bottle is set to 50-200 rpm / s.

4. The process for preparing the oleophilic barrier film layer for perfume glass bottles according to claim 1, characterized in that: After cleaning the inner wall, purge with nitrogen at 0.1–0.3 MPa for 5–10 seconds to reduce the residual moisture content on the inner wall of the bottle to no more than 50 ppm.

5. The process for preparing the oleophilic barrier film layer for perfume glass bottles according to claim 1, characterized in that: After step S2, a 0.05-0.5 wt% silane undercoat is sprayed to form an initiation layer on the glass surface that can react with the solvent-inhibiting polymer.

6. The process for preparing the oleophilic barrier film layer for perfume glass bottles according to claim 1, characterized in that: The inner diameter of the perfume glass bottle opening is 8-25mm, and the bottle depth is 30-120mm. The clamping end of the rotating fixture can extend into the bottle opening by 5-20mm, so that the coating process can achieve uniform spreading in the deep cavity environment.

7. The process for preparing the oleophilic barrier film layer for perfume glass bottles according to claim 1, characterized in that: The low-temperature cross-linking and curing process uses infrared heating or hot air circulation to ensure that the temperature gradient inside the bottle does not exceed ±3℃.

8. The process for preparing the oleophilic barrier film layer for perfume glass bottles according to claim 1, characterized in that: The resulting oleophilic adhesion barrier film layer exhibits a fragrance adsorption amount of no more than 0.1 μg / cm² after being soaked in essential oil for 24 hours, and the fragrance residue adhesion rate is reduced to below 5%.

9. The process for preparing the oleophilic barrier film layer for perfume glass bottles according to claim 1, characterized in that: The solvent of the solvent-inhibiting polymer solution is composed of at least one of ethyl acetate, methyl isobutyl ketone, and ethylene glycol ethyl ether, with a boiling point range of 78–145°C, and is used to control the flow rate and evaporation rate of the liquid film.

10. The process for preparing the oleophilic barrier film layer for perfume glass bottles according to claim 1, characterized in that: The internal pressure of the cavity during the surface activation treatment is 20-80 Pa.

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