A high-toughness, stain-resistant and mildew-resistant decorative film and its preparation method

Abstract

The present invention discloses a high-toughness, stain-resistant and mildew-resistant decorative film and a preparation method thereof, belonging to the technical field of decorative films. The film is composed of a polyvinyl chloride (PVC)-based film and a stain-resistant coating, wherein the PVC-based film is composed of the following components in parts by mass: 77-89 parts of polyvinyl chloride resin, 21-29 parts of chlorinated polyethylene resin, 4-12 parts of a toughening mildew inhibitor, and 4-8 parts of an additive. The chlorinated polyethylene resin can improve the impact resistance of the base film; the toughening mildew inhibitor molecule contains multiple functional groups, which can improve the mildew resistance and impact resistance of the decorative film; the stain-resistant coating has super-hydrophobicity, can achieve self-cleaning, and reduces the difficulty of daily cleaning; in summary, the decorative film prepared by the present invention has significantly improved impact resistance, mildew resistance and stain resistance, solves the problems of traditional PVC decorative films, is particularly suitable for places such as kitchens and bathrooms that require frequent cleaning or may be subject to accidental impact, and has important application value in the field of decorative film technology.

Description

Technical Field

[0001] The present invention belongs to the technical field of decorative films, and in particular relates to a high-toughness, stain-resistant and mildew-resistant decorative film and a preparation method thereof. Background Art

[0002] With the rapid development of the modern architectural decoration industry, performance requirements for interior decorative materials are increasing. Decorative film is a functional material widely used in architecture, furniture, and home appliances, primarily providing protection, aesthetics, and special features to the substrate. Currently, common decorative films on the market are based on substrates such as polyvinyl chloride (PVC), polypropylene (PP), or polyester (PET). PVC is the most widely used decorative film due to its low color, ease of processing, low price, and stable chemical properties.

[0003] While traditional PVC decorative films meet certain aesthetic and basic protective requirements, they still have numerous shortcomings in practical use. For example, PVC is brittle and prone to cracking and tearing due to external impact or prolonged use. This low toughness makes PVC decorative films susceptible to damage during transportation, installation, and daily use, reducing their overall service life. This problem is particularly prominent in areas that require frequent cleaning or are subject to accidental impact, such as kitchens and bathrooms. Stain resistance is another key performance indicator for decorative films. Traditional PVC decorative films are easily contaminated by oil, dust, and other contaminants during daily use, resulting in a poor appearance and increasing cleaning difficulty. Finally, mold resistance is crucial for decorative films, especially in high-humidity environments such as bathrooms and basements. Mold growth not only damages the appearance of the decorative film but also releases harmful substances, posing a health risk to occupants.

[0004] The above problems limit the application scope of polyvinyl chloride decorative film in humid environments or highly polluted areas. Therefore, there is an urgent need to develop a polyvinyl chloride decorative film with high toughness, stain resistance and mildew resistance to meet the higher application requirements in the field of decorative film technology. Summary of the Invention

[0005] The purpose of the present invention is to overcome the defects of the prior art and provide a high-toughness, stain-resistant and mildew-resistant decorative film and a preparation method thereof.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A high-toughness, stain-resistant and mildew-resistant decorative film consists of a polyvinyl chloride-based film and a stain-resistant coating. The polyvinyl chloride-based film consists of the following components in parts by mass: 77-89 parts of polyvinyl chloride resin, 21-29 parts of chlorinated polyethylene resin, 4-12 parts of a toughening and mildew-proofing agent, and 4-8 parts of an additive.

[0008] Furthermore, the additive consists of an antioxidant and a lubricant in a mass ratio of 1:3.

[0009] Furthermore, the antioxidant is a hindered phenol antioxidant.

[0010] Furthermore, the lubricant is one of oleamide, butyl stearate and stearic acid.

[0011] Chlorinated polyethylene is added to the raw materials. It has good compatibility with polyvinyl chloride and can be evenly dispersed in the polyvinyl chloride matrix to form an "island structure" to absorb impact energy and improve the toughness of the base film.

[0012] Furthermore, the toughening mildew inhibitor is prepared by the following steps:

[0013] Step A1, 2-aminothiazole and 3,5-dihydroxybenzoic acid were weighed as reaction raw materials, and added to a 300 mL three-necked flask equipped with a magnetic stirrer together with N,N-dimethylformamide. After magnetic stirring, 1-ethyl-(3-dimethylaminopropyl)carbodiimide was added to the system. The reaction was stirred at room temperature for 8 hours. After the reaction was completed, the mixture was filtered, and part of the solvent was distilled off under reduced pressure. The mixture was purified by column chromatography to obtain reaction product 1;

[0014] The reaction principle of step A1 is: under the catalysis of 1-ethyl-(3-dimethylaminopropyl)carbodiimide (EDC), the amino group in the 2-aminothiazole molecule undergoes an amidation reaction with the carboxyl group on 3,5-dihydroxybenzoic acid; the reaction formula is as follows:

[0015]

[0016] Step A2, pyridine and 1,10-dichlorodecane were weighed as reaction raw materials, added to a 300 mL three-necked flask equipped with a thermometer, a condenser, and a magnetic stirrer, and after magnetic stirring, the device was heated until the temperature stabilized at 70°C, and the reaction was stirred at this temperature for 6 hours. After the reaction was complete, the mixture was filtered, and part of the solvent was distilled off under reduced pressure, and purified by column chromatography to obtain reaction product 2;

[0017] The reaction principle of step A2 is as follows: This reaction is a solvent-free reaction. The nitrogen atom of pyridine acts as a strong nucleophile and undergoes a nucleophilic substitution reaction (SN2) with 1,10-dichlorodecane. The molar ratio of the two is controlled at 1:1, and a slight excess of 1,10-dichlorodecane is used to reduce side reactions. The reaction formula is as follows:

[0018]

[0019] Step A3, weighing reaction product 1 and reaction product 2 as reaction raw materials, and adding them to 300 mL of a three-necked flask equipped with a thermometer, a constant pressure dropping funnel, a condenser, and a magnetic stirrer with anhydrous toluene. At room temperature, under stirring, slowly add sodium hydroxide solution (mass fraction 20%) through the constant pressure dropping funnel. After the addition is completed, the apparatus is heated until the temperature stabilizes at 75°C, and the reaction is stirred at this temperature for 5 hours. After the reaction is completed, the mixture is filtered, and some of the solvent is removed by distillation under reduced pressure. The mixture is purified by column chromatography and dried in vacuo to obtain a toughening mildew inhibitor;

[0020] The reaction principle of step A3 is as follows: sodium hydroxide can react with the hydroxyl group in the reaction product 1 molecule to form a more nucleophilic sodium phenolate, which reacts with the chlorine group in the reaction product 2 molecule; the molar ratio of the two is controlled at 1:2, and the reaction product 2 is slightly excessive to reduce side reactions.

[0021] Furthermore, in step A1, the ratio of 2-aminothiazole, 3,5-dihydroxybenzoic acid, N,N-dimethylformamide, and 1-ethyl-(3-dimethylaminopropyl)carbodiimide is 9.9 g:15.4 g:100 mL:15.5 g.

[0022] Furthermore, in step A2, the ratio of pyridine to 1,10-dichlorodecane is 7.9 g:23.7 g.

[0023] Furthermore, in step A3, the ratio of the amount of reaction product 1, reaction product 2, anhydrous toluene, and sodium hydroxide solution is 23.6 g:52.3 g:150 mL:40 mL.

[0024] The toughened mildew preventer is prepared by a three-step reaction. The experimental principle is simple, the raw materials are clear, and the operation is clear. The toughened mildew preventer molecule contains two long-chain alkyl structures. This structure has high flexibility, can increase the free volume of the molecular chain, and reduce the packing density between molecular chains. In addition, the long-chain alkyl can be embedded in the polymer macromolecule, absorb energy and disperse stress when the matrix is ​​subjected to external force, prevent local stress concentration, improve the impact resistance of the polyvinyl chloride matrix, and also improve the migration resistance of the toughened mildew preventer and improve the stability of the small molecule toughened mildew preventer. In addition, the toughened mildew preventer also contains pyridinium quaternary ammonium salt and thiazole group, among which N +It can strongly bind to the negatively charged surface of the mold cell membrane (such as the phosphate group of the phospholipid head group and the carboxyl group of the protein), destroying the cell structure of the mold, and has a long-lasting and fast-acting effect, thereby improving the anti-mildew performance of the matrix; the thiazole group is a sulfur-containing group that can bind to the key enzymes of the mold (such as sulfhydryl enzymes) and inhibit their activity, thereby interfering with the metabolic process of the mold and further improving the anti-mildew performance of the matrix; it should be emphasized that the anti-mildew mechanisms of pyridinium quaternary ammonium salt and thiazole group are different, therefore, the two can play a synergistic role, greatly improving the anti-mildew performance of the matrix.

[0025] Furthermore, the anti-fouling coating is prepared by the following steps:

[0026] Add hydrophobic silica to anhydrous ethanol, ultrasonically disperse for 15-30 minutes, then mix with methyltrimethoxysilane, tridecafluorooctyltriethoxysilane and ethyl orthosilicate, stir evenly, then slowly add hydrochloric acid solution and continue stirring to promote the hydrolysis reaction of siloxane. After stirring for 2-3 hours, stop stirring to obtain a stain-resistant coating.

[0027] Furthermore, the ratio of the amount of the hydrophobic silica, anhydrous ethanol, methyltrimethoxysilane, tridecafluorooctyltriethoxysilane, ethyl orthosilicate and hydrochloric acid solution is 8.7g:100mL:56.2g:3.6g:5.1g:5mL.

[0028] The introduction of fluorine-containing groups into the coating significantly reduces the surface energy and improves the hydrophobicity. The addition of hydrophobic silica makes the coating rougher, increases the contact angle between the water droplet and the coating, and further improves the hydrophobicity. Therefore, the coating obtained is a super-hydrophobic coating. The lotus leaf structure on the surface removes dust and other pollutants, has a self-cleaning effect, and can improve the stain resistance of the decorative film.

[0029] The present invention also provides a method for preparing a high-toughness, stain-resistant and mildew-resistant decorative film, comprising the following steps:

[0030] A layer of anti-fouling paint is applied on the surface of the polyvinyl chloride film using a gravure printing roller, and then placed in an oven at 100-120°C for drying and curing. After being taken out, a high-toughness, anti-fouling and anti-mildew decorative film is obtained.

[0031] Beneficial effects of the present invention:

[0032] The decorative film prepared by the present invention is composed of a polyvinyl chloride-based film and a stain-resistant coating;

[0033] 1. Adding chlorinated polyethylene resin to the base film can effectively absorb impact energy, improve the impact resistance of the base film, and solve the problem of easy brittle cracking of traditional PVC decorative film;

[0034] 2. A toughening antifungal agent is prepared through a three-step reaction. The toughening antifungal agent molecules contain multiple functional groups, which can improve the mildew resistance and impact resistance of the decorative film;

[0035] 3. Introducing hydrophobic silica and fluorinated silane into the anti-fouling coating creates a super-hydrophobic surface, greatly reducing surface energy. The "lotus effect" on the coating surface enables self-cleaning, reduces the adhesion of pollutants such as oil stains and dust, and reduces the difficulty of daily cleaning.

[0036] Therefore, the present invention significantly improves the impact resistance, mildew resistance and stain resistance of the decorative film by modifying chlorinated polyethylene, preparing a stain-resistant coating and introducing a toughening mildew inhibitor, thereby solving the problems of traditional PVC decorative film. The film is particularly suitable for places such as kitchens and bathrooms that require frequent cleaning or may be subject to accidental impact. DETAILED DESCRIPTION

[0037] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0038] Example 1: Preparation of toughened mildew inhibitor:

[0039] Step A1: 9.9 g of 2-aminothiazole and 15.4 g of 3,5-dihydroxybenzoic acid were weighed as reaction raw materials and added to a 300 mL three-necked flask equipped with a magnetic stirrer together with 100 mL of N,N-dimethylformamide. After magnetic stirring, 15.5 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide was added to the system. The mixture was stirred at room temperature for 8 h. After the reaction was complete, the mixture was filtered, and the solvent was partially removed by distillation under reduced pressure. The mixture was purified by column chromatography (eluent: petroleum ether and ethyl acetate, volume ratio: 3:1), and the eluent was removed by rotary evaporation to obtain reaction product 1.

[0040] Step A2, weighing 7.9 g of pyridine and 23.7 g of 1,10-dichlorodecane as reaction raw materials, adding them to a 300 mL three-necked flask equipped with a thermometer, a condenser, and a magnetic stirrer, and after magnetic stirring, heating the apparatus until the temperature stabilizes at 70°C, stirring at this temperature for 6 hours. After the reaction is complete, filtering, partially distilling to remove the solvent under reduced pressure, and purifying by column chromatography (eluent: petroleum ether and ethyl acetate, the volume ratio of the two is 5:1), and removing the eluent by rotary evaporation to obtain reaction product 2;

[0041] Step A3, weigh 23.6g of reaction product 1, 52.3g of reaction product 2 and 150mL of anhydrous toluene as reaction raw materials, add them into a 300mL three-necked flask equipped with a thermometer, a constant pressure dropping funnel, a condenser and a magnetic stirrer, and slowly add 40mL of sodium hydroxide solution (mass fraction 20%) through a constant pressure dropping funnel at room temperature under stirring. After the addition is completed, the apparatus is heated until the temperature stabilizes at 75°C, stirred at this temperature for 5h, the reaction is completed, filtered, and part of the solvent is removed by distillation under reduced pressure. The mixture is purified by column chromatography (the eluent is petroleum ether and ethyl acetate, and the volume ratio of the two is 10:1). The eluent is removed by rotary evaporation and vacuum drying to obtain a toughened mildew inhibitor.

[0042] Example 2: Preparation of anti-fouling coating:

[0043] 8.7 g of hydrophobic silica (1 g of nano-silica produced by Hangzhou Hengge Nanotechnology Co., Ltd., model HN-SP15) was mixed with 100 mL of ethanol aqueous solution and added to a magnetic stirring device. A magnet was added and stirring was started. The mixture was dispersed for 30 min to uniformly disperse the nano-silica in the ethanol aqueous solution. The device was evacuated and N2 gas was introduced. 7.3 g of KH-560 was added and oil bath heating was started. The temperature was set to 50 ° C. The condensation water was turned on and the reaction temperature was set to 80 ° C for 4 h. The mixture was evacuated. The obtained mixture was filtered, washed with ethanol, and dried in a vacuum drying oven for 2 h to obtain hydrophobic nano-silica. The mixture was added to 100 mL of anhydrous ethanol and ultrasonically dispersed for 30 min. The mixture was then mixed with 56.2 g of methyltrimethoxysilane, 3.6 g of tridecafluorooctyltriethoxysilane, and 5.1 g of ethyl orthosilicate. After stirring evenly, 5 mL of hydrochloric acid solution (mass fraction 12%) was slowly added dropwise while stirring continuously to promote the hydrolysis reaction of siloxane. After stirring for 3 h, the stirring was stopped to obtain a stain-resistant coating.

[0044] Example 3: Preparation of polyvinyl chloride film:

[0045] 77 g of polyvinyl chloride resin (produced by Xinjiang Zhongtai Chemical Co., Ltd., model SG-3), 21 g of chlorinated polyethylene resin (produced by Weifang Yaxing Chemical Co., Ltd., model CPE 135A), 4 g of the toughening mildew inhibitor prepared in Example 1, and 4 g of additives (consisting of 1 g of antioxidant 1076 and 3 g of oleamide) were added to a mixer, and the materials were mixed at 1200 r / min. After stirring for 5 minutes, the mixed raw materials were added to an extruder, melt-blended, extruded, and cast onto a cooling roller. A film with a thickness of 50 μm was formed by cooling and setting, and the film was wound up to obtain a polyvinyl chloride based film.

[0046] Example 4: Preparation of polyvinyl chloride film:

[0047] 83 g of polyvinyl chloride resin (produced by Xinjiang Zhongtai Chemical Co., Ltd., model SG-3), 25 g of chlorinated polyethylene resin (produced by Weifang Yaxing Chemical Co., Ltd., model CPE 135A), 8 g of the toughening mildew inhibitor prepared in Example 1, and 6 g of additives (consisting of 1.5 g of antioxidant 1076 and 4.5 g of butyl stearate) were added to a mixer, and the materials were mixed at 1200 r / min. After stirring for 5 minutes, the mixed raw materials were added to an extruder, melt-blended, extruded, and cast onto a cooling roller. A film with a thickness of 50 μm was formed by cooling and setting, and the film was wound up to obtain a polyvinyl chloride based film.

[0048] Example 5: Preparation of polyvinyl chloride film:

[0049] 89 g of polyvinyl chloride resin (produced by Xinjiang Zhongtai Chemical Co., Ltd., model SG-3), 29 g of chlorinated polyethylene resin (produced by Weifang Yaxing Chemical Co., Ltd., model CPE 135A), 12 g of the toughening mildew inhibitor prepared in Example 1, and 8 g of additives (consisting of 2 g of antioxidant 1076 and 6 g of stearic acid) were added to a mixer, and the mixture was mixed at 1200 r / min. After stirring for 5 minutes, the mixed raw materials were added to an extruder, melt-blended, extruded, and cast onto a cooling roller. A film with a thickness of 50 μm was formed by cooling and setting, and the film was wound up to obtain a polyvinyl chloride based film.

[0050] Example 6: The polyvinyl chloride film prepared in Example 5 was coated with the anti-fouling coating prepared in Example 2 using a gravure printing roller. The film was then dried and cured in a 100°C oven. After removal, a highly tough, anti-fouling, and anti-mildew decorative film was obtained. The contact angle of the coating in Example 6 was measured using a contact angle meter to be 157.3°. A coating greater than 150° is considered super-hydrophobic, and this coating imparts excellent anti-fouling properties to the decorative film.

[0051] Comparative Example 1: During the preparation process of Example 5, only the toughening mildew preventer was replaced with an equal amount of octylisothiazolinone mildew preventer, while other conditions remained unchanged, to obtain a base film.

[0052] Comparative Example 2: A commercially available toughened polyvinyl chloride material (produced by Shanghai Chlor-Alkali Chemical Co., Ltd., model SC-800T) was used to prepare a film with a thickness of 50 μm using a casting method.

[0053] Comparative Example 3: During the preparation process of Example 5, chlorinated polyethylene resin was not added, and the remaining steps were the same as those of Example 5.

[0054] Examples 3, 4, and 5, and comparative examples 1, 2, and 3 were made into corresponding shapes according to different test standards, and the following performance tests were performed:

[0055] GB / T 9639-2008 “Plastic film and sheeting test method for impact resistance – Free-fall dart method” was used to measure the impact resistance.

[0056] The mold resistance test is carried out according to the ASTM E1428-2015 standard, and the grades are divided according to ISO 846-2019 "Evaluation of Plastics under the Action of Fungi and Bacteria"; the mold resistance grade is 0-4, Grade 0: No growth (no visible mold on the surface); Grade 1: Slight growth (mold coverage area <10%); Grade 2: Moderate growth (mold coverage area 10%-30%); Grade 3: Significant growth (mold coverage area 30%-60%); Grade 4: Severe growth (mold coverage area >60%).

[0057] The measured results are shown in the following table:

[0058]

[0059] As can be seen from the above table, the base film prepared in the embodiment of the present invention has higher impact resistance than the comparative example, which also reflects that the toughness of the embodiment is higher than that of the comparative example. In addition, the base film of the embodiment has good mildew resistance. Using this base film and the anti-fouling coating as raw materials for the decorative film can give the decorative film high toughness and mildew resistance. Therefore, the decorative film prepared in the present invention has important application value in the field of decorative film technology.

[0060] Throughout the specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0061] The above contents are merely examples and explanations of the present invention. Any modifications or additions made by those skilled in the art to the described specific embodiments, or replacements made in a similar manner, shall fall within the scope of protection of the present invention.

Claims

1. A high-toughness, stain-resistant and mildew-resistant decorative film, consisting of a polyvinyl chloride-based film and a stain-resistant coating, characterized in that: The polyvinyl chloride film is composed of the following components in parts by weight: 77-89 parts of polyvinyl chloride resin, 21-29 parts of chlorinated polyethylene resin, 4-12 parts of toughening and mildewproofing agent, and 4-8 parts of additives; Wherein, the toughening mildew inhibitor is prepared by the following steps: Step A1: 2-aminothiazole, 3,5-dihydroxybenzoic acid, and N,N-dimethylformamide were added to a flask, stirred, and then 1-ethyl-(3-dimethylaminopropyl)carbodiimide was added. The mixture was stirred at room temperature for 8 hours. The reaction was completed to obtain reaction product 1. Step A2, pyridine and 1,10-dichlorodecane were added to a flask, stirred, and reacted at 70° C. for 6 h. The reaction was completed to obtain reaction product 2; Step A3: Add reaction product 1, reaction product 2, and anhydrous toluene into a flask, add sodium hydroxide solution dropwise at room temperature with stirring, and stir at 75° C. for 5 h until the reaction is complete to obtain a toughened mildew inhibitor; Among them, the ratio of the amount of 2-aminothiazole, 3,5-dihydroxybenzoic acid, N,N-dimethylformamide, and 1-ethyl-(3-dimethylaminopropyl)carbodiimide used in step A1 is 9.9 g:15.4 g:100 mL:15.5 g; the ratio of the amount of pyridine and 1,10-dichlorodecane used in step A2 is 7.9 g:23.7 g.

2. The high-toughness, stain-resistant and mildew-resistant decorative film according to claim 1, characterized in that: In step A3, the ratio of reaction product 1, reaction product 2, anhydrous toluene, and sodium hydroxide solution is 23.6 g:52.3 g:150 mL:40 mL.

3. The high-toughness, stain-resistant and mildew-resistant decorative film according to claim 1, characterized in that: The additive consists of an antioxidant and a lubricant in a mass ratio of 1:3; the antioxidant is a hindered phenol antioxidant; and the lubricant is one of oleamide, butyl stearate and stearic acid.

4. The high-toughness, stain-resistant and mildew-resistant decorative film according to claim 1, characterized in that: The anti-fouling coating is prepared by the following steps: Add hydrophobic silica to anhydrous ethanol, ultrasonically disperse for 15-30 minutes, then mix with methyltrimethoxysilane, tridecafluorooctyltriethoxysilane and ethyl orthosilicate, stir evenly, then slowly add hydrochloric acid solution and continue stirring for 2-3 hours to obtain a stain-resistant coating.

5. The high-toughness, stain-resistant and mildew-resistant decorative film according to claim 4, characterized in that: The ratio of the amount of the hydrophobic silica, anhydrous ethanol, methyltrimethoxysilane, tridecafluorooctyltriethoxysilane, ethyl orthosilicate and hydrochloric acid solution is 8.7 g:100 mL:56.2 g:3.6 g:5.1 g:5 mL.

6. The method for preparing a high-toughness, stain-resistant and mildew-resistant decorative film according to any one of claims 1 to 5, characterized in that: The following steps are involved: A layer of anti-fouling paint is applied on the surface of the polyvinyl chloride film using a gravure printing roller, and then placed in an oven at 100-120°C for drying and curing. After being taken out, a high-toughness, anti-fouling and anti-mildew decorative film is obtained.

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