Stain-resistant and scratch-resistant marbling decorative film and preparation method thereof
By adding specific modifiers to the waterborne polyurethane coating of marble-patterned decorative film, a dense polyurethane network is constructed, which solves the problems of insufficient scratch resistance and stain resistance of marble-patterned decorative film and achieves a high-efficiency improvement in coating performance.
Patent Information
- Application Number
- CN202511956517.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-23
- Publication Date
- 2026-02-17
AI Technical Summary
Existing marble-patterned decorative films have shortcomings in terms of scratch resistance and stain resistance, especially the coating of water-based polyurethane coatings, which is not ideal. Furthermore, traditional preparation methods require high-end equipment and contain harmful diluents.
A waterborne polyurethane coating is used, which combines polyether polyol, castor oil-modified polyol, polydopamine-modified nitrogen-doped titanium dioxide coated with silica and polydopamine-modified trisilyl isobutyl POSS to construct a dense polyurethane network, thereby improving the coating's hardness, hydrophobicity and stain resistance.
It achieves high stain resistance and scratch resistance of marble-patterned decorative film, strong adhesion between coating and substrate, high production efficiency, self-cleaning properties and high scratch resistance.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of decorative materials, in particular to a marble pattern decorative film with stain resistance and scratch resistance and a preparation method thereof. BACKGROUND
[0002] The marble pattern decorative film is a high-performance indoor decorative material that precisely reproduces the texture and color of natural marble on the base film through advanced printing and coating technology. This product avoids the shortcomings of natural marble such as heaviness, fragility, high price, and possible radioactivity, providing a safe, lightweight, and cost-controllable ideal solution for modern interior design. Marble pattern decorative film has been widely used in wall surfaces of homes and commercial spaces.
[0003] For some application areas of marble pattern decorative film, daily contact with friction, collision, and various stains may occur. If it does not have scratch resistance, the surface will have more scratches, looking old and seriously affecting the appearance. Similarly, if it lacks stain resistance, some liquid stains can easily penetrate the material pores, leaving difficult-to-remove stains, not only causing visual defects, but also breeding bacteria.
[0004] Currently, when producing marble pattern decorative film, the surface coating is generally prepared using light-cured polyurethane paint. However, light-cured polyurethane paint requires special ultraviolet equipment, and the flatness of the substrate and the production line cooperation requirements are extremely high. In addition, general light-cured polyurethane paint contains active diluents that may cause skin irritation or allergies. Using water-based polyurethane paint to prepare the surface coating of marble pattern decorative film has lower requirements for equipment and uses water as a diluent, containing almost no volatile organic compounds, making it a more economical and environmentally friendly process. However, the general water-based polyurethane paint prepared surface coating does not have very good stain resistance and scratch resistance, so the raw material formula needs to be researched to obtain marble pattern decorative film with good stain resistance and scratch resistance. SUMMARY
[0005] The purpose of the present application is to provide a marble pattern decorative film with stain resistance and scratch resistance and a preparation method thereof. The surface coating of the marble pattern decorative film is prepared using water-based polyurethane paint, and by using polyether polyol and castor oil modified polyol as polyol monomers, and by using polydopamine modified nitrogen-doped titanium dioxide coated silica and polydopamine modified trisilanol isobutyl POSS, the marble pattern decorative film exhibits excellent stain resistance and scratch resistance.
[0006] To achieve the above purpose, the present application is implemented by the following technical solutions: The anti-stain and scratch-resistant marble pattern decorative film comprises a substrate layer, a marble pattern printing layer and a surface coating layer, and the surface coating layer comprises the following raw materials in parts by weight: polyether polyol 26-37 parts, castor oil modified polyol 7-10 parts, 2,2-dimethylol propionic acid 2-3.5 parts, isophorone diisocyanate 15-20 parts, diphenylmethane-4,4-diisocyanate 5-10 parts, alcohol chain extender 2.5-4 parts, catalyst 1-1.5 parts, polydopamine modified nitrogen-doped titanium dioxide coated silica 2.5-3.5 parts, polydopamine modified trisilanol isobutyl POSS 1.5-3 parts, triethylamine 1.5-2.5 parts, acetone 20-30 parts and water 130-160 parts.
[0007] Preferably, the polyether polyol is a trifunctional polyether polyol; and the castor oil modified polyol is a trifunctional castor oil modified polyol.
[0008] Preferably, the preparation method of the polydopamine modified nitrogen-doped titanium dioxide coated silica comprises the following steps: Silica is added to ethanol, then ultrasonic dispersion is performed, deionized water and ethylenediamine are added, the pH value of the system is adjusted to 3-4 by using dilute nitric acid, then titanium tetrabutoxide is slowly added while stirring, after the addition is completed, the temperature is raised to 50-60 DEG C, stirring reaction is performed for 3-5 h, then centrifugation, washing, vacuum drying are performed, and the nitrogen-doped titanium dioxide coated silica is obtained by calcining at 400-450 DEG C for 2-3 h under a nitrogen atmosphere and cooling to room temperature. Dopamine hydrochloride is added to a Tris-HCl buffer solution with a pH value of 8.5-9, stirring is performed, then the nitrogen-doped titanium dioxide coated silica is added, ultrasonic treatment is performed while stirring for 4-6 h, then centrifugation, water washing and vacuum drying are performed, and the polydopamine modified nitrogen-doped titanium dioxide coated silica is obtained.
[0009] Preferably, the mass ratio of the silica, titanium tetrabutoxide and ethylenediamine is 1:0.8-1.3:0.1-0.2; the mass ratio of the deionized water and titanium tetrabutoxide is 1:2-3; and the particle size of the silica is 200-300 nm.
[0010] Preferably, the mass ratio of the nitrogen-doped titanium dioxide coated silica and dopamine hydrochloride is 1:0.2-0.4.
[0011] Preferably, the preparation method of the polydopamine modified trisilanol isobutyl POSS comprises the following steps: Dopamine hydrochloride is added into Tris-HCl buffer solution with pH value of 8.5-9, after stirring and mixing, tri-silanol isobutyl POSS is added, then ultrasonic treatment is carried out for 3-5.5 hours under stirring, centrifugation, water washing and vacuum drying are carried out, and polydopamine modified tri-silanol isobutyl POSS is obtained.
[0012] Preferably, the mass ratio of the tri-silanol isobutyl POSS and dopamine hydrochloride is 1:0.35-0.6.
[0013] Preferably, the alcohol chain extender is at least one of 1,2-propanediol and 1,4-butanediol; and the catalyst is dibutyltin dilaurate.
[0014] As a general inventive concept, the application further provides a preparation method of a stain-resistant and scratch-resistant marble decorative film, comprising the following steps: S1: preparing water-based polyurethane coating for surface coating by using polyether polyol, castor oil modified polyol, 2,2-dimethylol propionic acid, isophorone diisocyanate, diphenylmethane-4,4-diisocyanate, alcohol chain extender, catalyst, polydopamine modified nitrogen-doped titanium dioxide coated silica, polydopamine modified tri-silanol isobutyl POSS, triethylamine, acetone and water; S2: performing ink printing on the substrate layer to form a marble printing layer on the substrate layer, and obtaining a composite film layer; S3: roll coating the water-based polyurethane coating for surface coating on the composite film layer, and then performing drying to obtain a marble decorative film.
[0015] Preferably, step S1 specifically comprises the following steps: Polyether polyol, castor oil modified polyol and 2,2-dimethylol propionic acid are added into a reactor, acetone is added under nitrogen protection, the temperature is raised to 50-60℃, isophorone diisocyanate and diphenylmethane-4,4-diisocyanate are added, the temperature is raised to 70-75℃, stirring reaction is carried out for 1.5-3 hours, the temperature is cooled to 55-60℃, alcohol chain extender is added, stirring reaction is carried out for 1.5-2 hours, the temperature is cooled to below 50℃, triethylamine is added, stirring is continued for 0.5-1 hour, and water is added for emulsification to obtain a dispersion emulsion; Polydopamine modified nitrogen-doped titanium dioxide coated silica and polydopamine modified tri-silanol isobutyl POSS are added into the dispersion emulsion, after stirring and mixing, acetone is removed by distillation under reduced pressure, and water-based polyurethane coating for surface coating is obtained.
[0016] The application has the following beneficial effects: 1、The surface coating prepared by the present application adopts water-based polyurethane paint, and polyether polyol and castor oil modified polyol are used as polyol monomers, wherein the castor oil modified polyol structure contains long fatty chains and rigid molecular structure, the long fatty chains can improve the hydrophobic and oleophobic properties of the coating, the rigid molecular structure can improve the strength and hardness of the coating, and thus the anti-stain performance and scratch resistance of the coating can be effectively improved. Further, the three-functional polyether polyol and the three-functional castor oil modified polyol are used in combination, and the two three-functional polyols jointly build a more compact and more solid polyurethane network, thereby making the surface coating have higher scratch resistance and anti-stain performance.
[0017] 2、The present application adds polydopamine modified nitrogen-doped titanium dioxide coated silica to the water-based polyurethane paint used in the surface coating, and uses nanosilica as the material core, which can effectively improve the hardness, density and strength of the coating. By coating nitrogen-doped titanium dioxide on the surface of the silica, the nitrogen-doped titanium dioxide has high photocatalytic effect, so that the coating has self-cleaning performance, thereby improving the anti-stain performance. The use of polydopamine modification can improve the compatibility and dispersibility of the nitrogen-doped titanium dioxide coated silica in the paint, and make the nitrogen-doped titanium dioxide coated silica firmly embedded in the coating, fully exerting its performance. In addition, polydopamine has certain hydrophobicity, which can further improve the hydrophobicity of the coating and make it have higher anti-stain performance. In addition, the present application adds polydopamine modified trisilanol isobutyl POSS to the water-based polyurethane paint used in the surface coating. Trisilanol isobutyl POSS, as an inorganic silica skeleton, can effectively improve the hardness and hydrophobic and oleophobic properties of the coating. Trisilanol isobutyl POSS has three silanol groups that can react with isocyanate groups, thereby improving the cross-linking density of the coating. The use of polydopamine modification can improve the dispersibility of trisilanol isobutyl POSS in the paint and improve the hydrophobic and oleophobic properties of the coating. Therefore, polydopamine modified trisilanol isobutyl POSS can effectively improve the scratch and stain resistance of the coating. The polydopamine modified nitrogen-doped titanium dioxide coated silica and the polydopamine modified trisilanol isobutyl POSS in the present application cooperate to build surface roughness on the surface of the coating and improve the hydrophobicity of the coating surface.
[0018] 3、The present application uses water-based polyurethane paint to prepare the surface coating, which can give the marble pattern decorative film high anti-stain and scratch resistance, and strong adhesion between the substrate and the printing layer, and high coating firmness. The marble pattern of the marble pattern decorative film is realized by printing, and the water-based polyurethane coating can be directly coated online after printing, which has high production efficiency. DETAILED DESCRIPTION
[0019] In order to make the purposes, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application.
[0020] In the following embodiments of the present application, the polyether polyol used is polyether polyol 330N, which is purchased from Jinsheng New Material Co., Ltd. in Jinan; the castor oil modified polyol is castor oil modified polyol YC-CY-250, with a functional group number of 3, which is purchased from Wuhan Shur Biological Technology Co., Ltd.
[0021] Embodiment 1 A stain-resistant and scratch-resistant marble pattern decorative film comprises a PVC substrate layer, a marble pattern printing layer and a surface coating layer. The surface coating layer comprises the following raw materials in parts by weight: 35 parts of polyether polyol, 8 parts of castor oil modified polyol, 3 parts of 2,2-dimethylol propionic acid, 20 parts of isophorone diisocyanate, 5 parts of diphenylmethane-4,4-diisocyanate, 2.5 parts of 1,4-butanediol, 1.2 parts of dibutyltin dilaurate, 2.5 parts of polydopamine modified nitrogen-doped titanium dioxide coated silica, 3 parts of polydopamine modified trisilanol isobutyl POSS, 2 parts of triethylamine, 20 parts of acetone and 150 parts of water.
[0022] In this embodiment, the preparation method of the polydopamine modified nitrogen-doped titanium dioxide coated silica comprises the following steps: 10 g of silica with a particle size of 200-300 nm is added to 100 mL of ethanol, and then ultrasonic dispersion is performed for 1 h at an ultrasonic power of 200 W; then 30 mL of deionized water and 2 g of ethylenediamine are added, and the pH value of the system is adjusted to 4 using dilute nitric acid, and then 10 g of tetrabutyl titanate is slowly added while stirring, after the addition is completed, the temperature is raised to 60°C, and stirring is performed for 5 h, then centrifugation, washing, vacuum drying and placement in a nitrogen atmosphere are performed, and calcination is performed at 420°C for 2 h, and then the temperature is cooled to room temperature to obtain nitrogen-doped titanium dioxide coated silica; 4 g of dopamine hydrochloride is added to 300 mL of Tris-HCl buffer solution with a pH value of 9, and then stirring is performed, 10 g of nitrogen-doped titanium dioxide coated silica is added, and then ultrasonic treatment is performed for 6 h while stirring, and then centrifugation, water washing and vacuum drying are performed to obtain polydopamine modified nitrogen-doped titanium dioxide coated silica.
[0023] In this embodiment, the preparation method of the polydopamine modified trisilanol isobutyl POSS comprises the following steps: 6g of dopamine hydrochloride was added to 450mL of Tris-HCl buffer solution with pH 9. After stirring and mixing, 10g of trisilyl isobutyl POSS was added. The mixture was then sonicated for 5.5h while stirring, followed by centrifugation, washing with water, and vacuum drying to obtain polydopamine-modified trisilyl isobutyl POSS.
[0024] The method for preparing the stain-resistant and scratch-resistant marble-patterned decorative film in this embodiment includes the following steps: S1: Polyether polyol, castor oil-modified polyol, and 2,2-dimethylolpropionic acid are added to a reactor. Acetone is added under nitrogen protection, and the temperature is raised to 50°C. Isophorone diisocyanate, diphenylmethane-4,4-diisocyanate, and dibutyltin dilaurate are added. The temperature is raised to 70°C, and the mixture is stirred for 1.5 hours. The mixture is then cooled to 60°C, and 1,4-butanediol is added. The mixture is stirred for 2 hours, and the temperature is lowered to below 50°C. Triethylamine is added, and the mixture is stirred for another 0.5 hours. Water is added for emulsification to obtain a dispersed emulsion. Polydopamine-modified nitrogen-doped titanium dioxide coated with silica and polydopamine-modified trisilyl isobutyl POSS were added to the dispersion emulsion. After stirring and mixing, acetone was removed by vacuum distillation to obtain a waterborne polyurethane coating for the surface coating.
[0025] S2: Ink printing is performed on the PVC substrate layer to form a marble pattern printing layer on the PVC substrate layer, resulting in a composite film layer. S3: A water-based polyurethane coating is rolled onto the composite film layer, and then dried to obtain a marble-patterned decorative film.
[0026] Example 2: A stain-resistant and scratch-resistant marble-patterned decorative film includes a PVC substrate layer, a marble-patterned printing layer, and a surface coating. The surface coating comprises the following raw materials in parts by weight: 29 parts polyether polyol, 10 parts castor oil-modified polyol, 2 parts 2,2-dimethylolpropionic acid, 15 parts isophorone diisocyanate, 7 parts diphenylmethane-4,4-diisocyanate, 3 parts 1,4-butanediol, 1 part dibutyltin dilaurate, 3 parts polydopamine-modified nitrogen-doped titanium dioxide coated silica, 2 parts polydopamine-modified trisilyl isobutyl POSS, 1.5 parts triethylamine, 20 parts acetone, and 130 parts water.
[0027] In this embodiment, the preparation method of polydopamine-modified nitrogen-doped titanium dioxide coated with silicon dioxide includes the following steps: 10g of silica with a particle size of 200-300nm was added to 100mL of ethanol and then ultrasonically dispersed for 1h at an ultrasonic power of 200W. 20mL of deionized water and 1g of ethylenediamine were then added, and the pH of the system was adjusted to 3 using dilute nitric acid. 8g of tetrabutyl titanate was then slowly added dropwise while stirring. After the addition was complete, the temperature was raised to 60℃ and the reaction was stirred for 3h. The mixture was then centrifuged, washed, vacuum dried, and calcined at 400℃ for 3h under a nitrogen atmosphere. After cooling to room temperature, nitrogen-doped titanium dioxide coated silica was obtained. 3g of dopamine hydrochloride was added to 300mL of Tris-HCl buffer solution with a pH of 8.5. After stirring and mixing, 10g of nitrogen-doped titanium dioxide was added to coat the silica. The mixture was then sonicated for 6h while stirring, followed by centrifugation, washing with water, and vacuum drying to obtain polydopamine-modified nitrogen-doped titanium dioxide coated silica.
[0028] The preparation method of polydopamine-modified trisilyl isobutyl POSS in this embodiment includes the following steps: 5g of dopamine hydrochloride was added to 450mL of Tris-HCl buffer solution with pH 9. After stirring and mixing, 10g of trisilyl isobutyl POSS was added. The mixture was then sonicated while stirring for 4.5h, followed by centrifugation, washing with water, and vacuum drying to obtain polydopamine-modified trisilyl isobutyl POSS.
[0029] The method for preparing the stain-resistant and scratch-resistant marble-patterned decorative film in this embodiment includes the following steps: S1: Polyether polyol, castor oil-modified polyol, and 2,2-dimethylolpropionic acid are added to the reactor. Acetone is added under nitrogen protection, and the temperature is raised to 60°C. Isophorone diisocyanate, diphenylmethane-4,4-diisocyanate, and dibutyltin dilaurate are added. The temperature is raised to 75°C, and the reaction is stirred for 3 hours. The temperature is then cooled to 55°C, and 1,4-butanediol is added. The reaction is stirred for 1.5 hours, and the temperature is then lowered to below 50°C. Triethylamine is added, and the reaction is stirred for another 1 hour. Water is added for emulsification to obtain a dispersed emulsion. Polydopamine-modified nitrogen-doped titanium dioxide coated with silica and polydopamine-modified trisilyl isobutyl POSS were added to the dispersion emulsion. After stirring and mixing, acetone was removed by vacuum distillation to obtain a waterborne polyurethane coating for the surface coating.
[0030] S2: Ink printing is performed on the PVC substrate layer to form a marble pattern printing layer on the PVC substrate layer, resulting in a composite film layer. S3: A water-based polyurethane coating is rolled onto the composite film layer, and then dried to obtain a marble-patterned decorative film.
[0031] Example 3: A stain-resistant and scratch-resistant marble-patterned decorative film includes a PVC substrate layer, a marble-patterned printing layer, and a surface coating. The surface coating comprises the following raw materials in parts by weight: 37 parts polyether polyol, 9 parts castor oil-modified polyol, 3.5 parts 2,2-dimethylolpropionic acid, 18 parts isophorone diisocyanate, 10 parts diphenylmethane-4,4-diisocyanate, 3 parts 1,4-butanediol, 1.5 parts dibutyltin dilaurate, 3.5 parts polydopamine-modified nitrogen-doped titanium dioxide coated silica, 1.5 parts polydopamine-modified trisilyl isobutyl POSS, 2.5 parts triethylamine, 30 parts acetone, and 160 parts water.
[0032] In this embodiment, the preparation method of polydopamine-modified nitrogen-doped titanium dioxide coated with silicon dioxide includes the following steps: 10g of silica with a particle size of 200-300nm was added to 100mL of ethanol and then ultrasonically dispersed for 1h at an ultrasonic power of 200W. 25mL of deionized water and 1.5g of ethylenediamine were then added, and the pH of the system was adjusted to 4 using dilute nitric acid. 13g of tetrabutyl titanate was then slowly added dropwise while stirring. After the addition was complete, the temperature was raised to 50℃ and the reaction was stirred for 5h. The mixture was then centrifuged, washed, vacuum dried, and calcined at 450℃ for 2h under a nitrogen atmosphere. After cooling to room temperature, nitrogen-doped titanium dioxide coated silica was obtained. 2g of dopamine hydrochloride was added to 300mL of Tris-HCl buffer solution with pH 9. After stirring and mixing, 10g of nitrogen-doped titanium dioxide was added to coat the silica. The mixture was then sonicated while stirring for 4h, followed by centrifugation, washing with water, and vacuum drying to obtain polydopamine-modified nitrogen-doped titanium dioxide coated silica.
[0033] The preparation method of polydopamine-modified trisilyl isobutyl POSS in this embodiment includes the following steps: 3.5 g of dopamine hydrochloride was added to 450 mL of Tris-HCl buffer solution with a pH of 8.5. After stirring and mixing, 10 g of trisilyl isobutyl POSS was added. The mixture was then sonicated while stirring for 3 h. After centrifugation, washing with water and vacuum drying, polydopamine-modified trisilyl isobutyl POSS was obtained.
[0034] In this embodiment, the method for preparing the stain-resistant and scratch-resistant marble-patterned decorative film is the same as in Embodiment 2.
[0035] Example 4: A stain-resistant and scratch-resistant marble-patterned decorative film includes a PVC substrate layer, a marble-patterned printing layer, and a surface coating. The surface coating comprises the following raw materials in parts by weight: 26 parts polyether polyol, 7 parts castor oil-modified polyol, 2.5 parts 2,2-dimethylolpropionic acid, 15 parts isophorone diisocyanate, 5 parts diphenylmethane-4,4-diisocyanate, 3 parts 1,4-butanediol, 1.2 parts dibutyltin dilaurate, 2.7 parts polydopamine-modified nitrogen-doped titanium dioxide coated silica, 1.5 parts polydopamine-modified trisilyl isobutyl POSS, 2 parts triethylamine, 25 parts acetone, and 135 parts water.
[0036] In this embodiment, the preparation of polydopamine-modified nitrogen-doped titanium dioxide coated with silicon dioxide and polydopamine-modified trisilyl isobutyl POSS are both the same as in Example 1.
[0037] In this embodiment, the method for preparing the stain-resistant and scratch-resistant marble-patterned decorative film is the same as in Embodiment 1.
[0038] Comparative Example 1: Unlike Example 2, the surface coating comprises the following raw materials in parts by weight: 29 parts polyether polyol, 2 parts 2,2-dimethylolpropionic acid, 15 parts isophorone diisocyanate, 7 parts diphenylmethane-4,4-diisocyanate, 3 parts 1,4-butanediol, 1 part dibutyltin dilaurate, 3 parts polydopamine-modified nitrogen-doped titanium dioxide coated silica, 2 parts polydopamine-modified trisilyl isobutyl POSS, 1.5 parts triethylamine, 20 parts acetone, and 130 parts water.
[0039] Comparative Example 2: Unlike Example 2, the polydopamine-modified nitrogen-doped titanium dioxide coated silica was replaced with silica with a particle size of 200-300 nm; and the polydopamine-modified trisilyl isobutyl POSS was replaced with trisilyl isobutyl POSS.
[0040] Comparative Example 3: The difference from Example 2 is that the polydopamine-modified trisilyl isobutyl POSS is replaced with polydopamine-modified octaamino POSS; The preparation method of polydopamine-modified octaaminoPOSS includes the following steps: 5g of dopamine hydrochloride was added to 450mL of Tris-HCl buffer solution with a pH of 9. After stirring and mixing, 10g of octaaminoPOSS was added. The mixture was then sonicated while stirring for 4.5h, followed by centrifugation, washing with water, and vacuum drying to obtain polydopamine-modified octaaminoPOSS.
[0041] Performance testing: 1. For the marble-patterned decorative films in Examples 1-4 and Comparative Examples 1-3, scratch resistance tests were conducted according to GB / T 17657-2022 "Test Methods for Physical and Chemical Properties of Wood-based Panels and Decorative Wood-based Panels". During the scratch resistance test, the load was 5N, and scratches were classified into 5 levels: Level 1: No continuous visible scratches on the surface; Level 2: Slight continuous scratches, but the scratched surface did not show significant changes; Level 3: Continuous scratches, and slight changes appeared at the scratched area; Level 4: Continuous scratches, and significant changes appeared at the scratched area, but the scratch boundaries were not easily distinguishable; Level 5: Continuous scratches, and severe changes appeared at the scratched area, with clearly visible scratch boundaries. Specific test results are shown in Table 1.
[0042] Table 1: As shown in Table 1, the marble-patterned decorative films in the embodiments of the present invention all possess excellent scratch resistance.
[0043] As can be seen from the comparison between Example 2 and Comparative Example 1, the scratch resistance will decrease if castor oil-modified polyol is not added.
[0044] As can be seen from the comparison between Example 2 and Comparative Example 2, if silica and trisilyl isobutyl POSS are not modified, the scratch resistance will decrease significantly. Unmodified silica and trisilyl isobutyl POSS have poor dispersibility and compatibility in coatings, causing the agglomeration of nanoparticles, which in turn significantly reduces the scratch resistance.
[0045] As can be seen from the comparison between Example 2 and Comparative Example 3, if the polydopamine-modified trisilyl isobutyl POSS is replaced with polydopamine-modified octaamino POSS, the scratch resistance performance decreases. It can be seen that the trisilyl isobutyl POSS used in this invention has a better effect than other POSSes.
[0046] 2. The water contact angle of the marble-patterned decorative films in Examples 1-4 and Comparative Examples 1-3 was tested. The anti-mold performance of the marble-patterned decorative films was tested using ASTM E1428-15, "Standard Test Method for Determining the Resistance of Materials to Mold by Laboratory Mold Colony Method." The rating was based on the percentage of the sample surface covered by mold, according to the rating table in the standard. The rating standards are as follows: Grade 0: No growth (0%), Grade 1: Trace growth (<10%), Grade 2: Slight growth (10-30%), Grade 3: Moderate growth (30-60%), Grade 4: Severe growth (60-100%). Specific test results are shown in Table 2. As shown in Table 2, the marble-patterned decorative film in the embodiments of the present invention has a high water contact angle, a hydrophobic surface, good anti-fouling performance, and excellent anti-mildew performance.
[0047] As can be seen from the comparison between Example 2 and Comparative Example 1, the water contact angle will decrease significantly if castor oil-modified polyol is not added. This shows that in the present invention, castor oil-modified polyol is very important for improving the hydrophobic properties of marble-patterned decorative film.
[0048] As can be seen from the comparison between Example 2 and Comparative Example 2, if the silica and trisilyl isobutyl POSS are not modified, the water contact angle will decrease and the anti-mildew performance will be significantly reduced.
[0049] As can be seen from the comparison between Example 2 and Comparative Example 3, when polydopamine-modified trisilyl isobutyl POSS is replaced with polydopamine-modified octaamino POSS, the water contact angle will decrease slightly.
[0050] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. A stain-resistant and scratch-resistant marble-patterned decorative film, comprising a substrate layer, a marble-patterned printing layer, and a surface coating, characterized in that, The surface coating comprises the following raw materials in parts by weight: 26-37 parts of polyether polyol, 7-10 parts of castor oil-modified polyol, 2-3.5 parts of 2,2-dimethylolpropionic acid, 15-20 parts of isophorone diisocyanate, 5-10 parts of diphenylmethane-4,4-diisocyanate, 2.5-4 parts of alcohol chain extender, 1-1.5 parts of catalyst, 2.5-3.5 parts of polydopamine-modified nitrogen-doped titanium dioxide coated silica, 1.5-3 parts of polydopamine-modified trisilyl isobutyl POSS, 1.5-2.5 parts of triethylamine, 20-30 parts of acetone, and 130-160 parts of water.
2. The stain-resistant and scratch-resistant marble-patterned decorative film according to claim 1, characterized in that, The polyether polyol is a trifunctional polyether polyol; the castor oil modified polyol is a trifunctional castor oil modified polyol.
3. The stain-resistant and scratch-resistant marble-patterned decorative film according to claim 1, characterized in that, The preparation method of polydopamine-modified nitrogen-doped titanium dioxide coated with silicon dioxide includes the following steps: Silica was added to ethanol and then ultrasonically dispersed. Deionized water and ethylenediamine were then added, and the pH of the system was adjusted to 3-4 using dilute nitric acid. Tetrabutyl titanate was then slowly added dropwise while stirring. After the addition was complete, the temperature was raised to 50-60℃ and the reaction was stirred for 3-5 hours. The mixture was then centrifuged, washed, vacuum dried, and calcined at 400-450℃ for 2-3 hours under a nitrogen atmosphere. After cooling to room temperature, nitrogen-doped titanium dioxide coated with silica was obtained. Dopamine hydrochloride was added to a Tris-HCl buffer solution with a pH of 8.5-9, stirred and mixed, and then nitrogen-doped titanium dioxide was added to coat the silica. The mixture was then sonicated while stirring for 4-6 hours, followed by centrifugation, washing with water, and vacuum drying to obtain polydopamine-modified nitrogen-doped titanium dioxide coated silica.
4. The stain-resistant and scratch-resistant marble-patterned decorative film according to claim 3, characterized in that, The mass ratio of silicon dioxide to tetrabutyl titanate and ethylenediamine is 1:0.8~1.3:0.1~0.2; the mass ratio of deionized water to tetrabutyl titanate is 1:2~3; and the particle size of silicon dioxide is 200~300nm.
5. The stain-resistant and scratch-resistant marble-patterned decorative film according to claim 3, characterized in that, The mass ratio of nitrogen-doped titanium dioxide coated with silicon dioxide to dopamine hydrochloride is 1:0.2~0.
4.
6. The stain-resistant and scratch-resistant marble-patterned decorative film according to claim 1, characterized in that, The preparation method of the polydopamine-modified trisilyl isobutyl POSS includes the following steps: Dopamine hydrochloride was added to a Tris-HCl buffer solution with a pH of 8.5-9 and stirred. Then, trisilyl isobutyl POSS was added and the mixture was sonicated while stirring for 3-5.5 hours. After centrifugation, washing with water, and vacuum drying, polydopamine-modified trisilyl isobutyl POSS was obtained.
7. The stain-resistant and scratch-resistant marble-patterned decorative film according to claim 6, characterized in that, The mass ratio of trisilyl isobutyl POSS to dopamine hydrochloride is 1:0.35~0.
6.
8. The stain-resistant and scratch-resistant marble-patterned decorative film according to claim 1, characterized in that, The alcohol chain extender is at least one of 1,2-propanediol and 1,4-butanediol; the catalyst is dibutyltin dilaurate.
9. A method for preparing a stain-resistant and scratch-resistant marble-patterned decorative film according to any one of claims 1 to 8, characterized in that, Includes the following steps: S1: A waterborne polyurethane coating for surface coating is prepared using polyether polyol, castor oil modified polyol, 2,2-dimethylolpropionic acid, isophorone diisocyanate, diphenylmethane-4,4-diisocyanate, alcohol chain extender, catalyst, polydopamine modified nitrogen-doped titanium dioxide coated silica, polydopamine modified trisilyl isobutyl POSS, triethylamine, acetone, and water. S2: Ink printing is performed on the substrate layer to form a marble pattern printing layer on the substrate layer, resulting in a composite film layer; S3: A water-based polyurethane coating is rolled onto the composite film layer, and then dried to obtain a marble-patterned decorative film.
10. The method for preparing the stain-resistant and scratch-resistant marble-patterned decorative film according to claim 9, characterized in that, Step S1 specifically includes the following steps: Polyether polyol, castor oil-modified polyol, and 2,2-dimethylolpropionic acid were added to a reactor. Acetone was added under nitrogen protection, and the temperature was raised to 50-60°C. Isophorone diisocyanate, diphenylmethane-4,4-diisocyanate, and catalyst were added, and the temperature was raised to 70-75°C. The mixture was stirred for 1.5-3 hours, cooled to 55-60°C, and then an alcohol chain extender was added. The mixture was stirred for 1.5-2 hours, cooled to below 50°C, and then triethylamine was added. The mixture was stirred for another 0.5-1 hour, and then water was added for emulsification to obtain a dispersed emulsion. Polydopamine-modified nitrogen-doped titanium dioxide coated with silica and polydopamine-modified trisilyl isobutyl POSS were added to the dispersion emulsion. After stirring and mixing, acetone was removed by vacuum distillation to obtain a waterborne polyurethane coating for the surface coating.