Stain-resistant and scratch-resistant facing film as well as preparation method and application thereof

Abstract

The invention provides an anti-fouling and scratch-resistant facing film as well as a preparation method and application thereof. The stain-resistant and scratch-resistant facing film comprises a base material and a functional layer coated on the surface of the base material, wherein the functional layer comprises a resin prepolymer, a bifunctional monomer, a fluorine-containing polymer, a photoinitiator, a nano filler, a dispersing agent and a flatting agent. According to the invention, an excimer process is adopted, a functional layer paint vehicle is compounded on a base material, and through the synergistic effect of a resin prepolymer, a bifunctional monomer, a fluorine-containing polymer, a photoinitiator, a nanofiller, a dispersing agent and a flatting agent, the facing film prepared through the excimer process not only has excellent anti-fouling and scratch-resistant performance, but also has excellent anti-fouling and scratch-resistant performance after being worn for a long time; in addition, the environment-friendly anti-fouling plastic also has excellent toughness, and has excellent market competitiveness in home supplies, automotive interiors and packaging materials.

Description

Technical Field

[0001] The invention relates to the technical field of decorative materials, in particular to an anti-fouling and scratch-resistant decorative film and a preparation method and application thereof. Background Art

[0002] As the requirements for surface coating performance in modern industry and consumer goods continue to increase, finishing films are often used as protective and decorative materials in many industries such as furniture, automotive interiors, and packaging materials, and the demand is increasing. At present, the function of finishing films is not only limited to decorative properties, but also needs to protect the surface of the substrate and reduce wear and friction in daily use. However, existing decorative films still face many challenges in terms of anti-fouling and scratch resistance. Especially when used for a long time or exposed to harsh environments, traditional finishing films are easily contaminated, scratched, and worn, resulting in a loss of gloss in appearance, reducing service life and aesthetics.

[0003] Traditional anti-fouling and scratch-resistant finishing films generally improve their surface properties by adding anti-fouling agents or scratch-resistant coatings, but these methods often have the following defects: on the one hand, the anti-fouling performance is usually limited to the simple repulsion of surface attachments and cannot effectively prevent long-term pollution such as oil stains and stains; on the other hand, the improvement of scratch resistance often leads to a decrease in the flexibility and anti-fouling properties of the finishing film, affecting the quality and use effect of the final product.

[0004] Therefore, a finishing film that is both effectively anti-fouling and scratch-resistant and wear-resistant, which still has excellent anti-fouling properties under long-term wear and can meet the economic, environmental protection and processability requirements of practical applications, has become an urgent problem to be solved. Summary of the invention

[0005] 1. Technical issues to be resolved

[0006] In view of the deficiencies in the prior art, the present invention provides an anti-fouling and scratch-resistant finishing film and a preparation method and application thereof, which solve the problems raised in the above-mentioned background technology.

[0007] (II) Technical solution

[0008] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0009] According to a first aspect of the present invention, there is provided an anti-fouling and scratch-resistant finishing film, comprising a substrate and a functional layer coated on the surface of the substrate; wherein the functional layer comprises a resin prepolymer, a bifunctional monomer, a fluorine-containing polymer, a photoinitiator, a nanofiller, a dispersant and a leveling agent.

[0010] The resin prepolymer and the bifunctional monomer in the functional layer of the present invention undergo a cross-linking reaction during the curing process to generate a three-dimensional network structure, which enables the finishing film to have excellent hardness and toughness, and improves the scratch resistance and wear resistance. At the same time, nano-fillers are added therein to fill the three-dimensional network structure, forming a dense micro-tube structure in the finishing film, further increasing the scratch resistance. The added fluorine-containing polymer is cross-linked with the three-dimensional network structure. Due to its low surface energy, the finishing film has excellent hydrophobic and oleophobic properties. When the surface of the finishing film comes into contact with oil stains, etc., they can be removed by simply wiping.

[0011] In the present application, the substrate can be selected from polypropylene substrate, polyethylene substrate, polyester substrate, polyvinyl chloride substrate or textile fabric, etc.

[0012] Preferably, the functional layer comprises, by mass fraction, 30-70wt% of resin prepolymer, 5-50wt% of bifunctional monomer, 5-20wt% of fluorine-containing polymer, 0.5-5wt% of photoinitiator, 0-5wt% of nanofiller, 0.5-3wt% of dispersant and 0.1-1wt% of leveling agent.

[0013] Further preferably, the functional layer comprises, by weight, 50-65 wt% of a resin prepolymer, 10-30 wt% of a bifunctional monomer, 10-20 wt% of a fluorine-containing polymer, 1-2 wt% of a photoinitiator, 2-4 wt% of a nanofiller, 1-2 wt% of a dispersant and 0.1-1 wt% of a leveling agent.

[0014] Preferably, the resin prepolymer is selected from at least one of polyurethane acrylate, polyester acrylate and epoxy acrylate.

[0015] Preferably, the bifunctional monomer is selected from at least one of ethylene glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, diglycidyl ether bisphenol A, glycidyl ether acrylate, tripropylene glycol diacrylate, and adipic acid diacrylate.

[0016] Preferably, the fluorine-containing polymer is selected from perfluoroalkyl compounds or fluorinated carbon nanotubes.

[0017] Specifically, the perfluoroalkyl compound is selected from at least one of perfluorooctane sulfonic acid, perfluorooctanoic acid, perfluorohexadecane, perfluoroalkyl alcohol, perfluoroalkyl polymer, perfluoroalkyl silane, perfluoroalkyl amine, and perfluoroalkyl salt.

[0018] Preferably, the photoinitiator is selected from at least one of benzoin photoinitiator, acetophenone derivative photoinitiator and benzil ketal derivative photoinitiator.

[0019] Preferably, the nanofiller is selected from nano silicon dioxide or nano titanium dioxide;

[0020] The dispersant is selected from at least one of sodium lauryl sulfate, sodium stearate, polyvinyl alcohol, polyvinyl acid, vegetable oil derivatives, and rosin derivatives;

[0021] The leveling agent is selected from any one of BKY051, BKY052, BYK065, BYK065, BYK085, and BYK088.

[0022] According to a second aspect of the present invention, a method for preparing an anti-fouling and scratch-resistant finishing film is provided, comprising the following steps: S1, firstly mixing a resin prepolymer, a bifunctional monomer, a fluorine-containing polymer and a nanofiller, and then adding a dispersant, a leveling agent and a photoinitiator and mixing them evenly to obtain a functional layer paint;

[0023] S2. Apply the functional layer paint onto a substrate, pre-cure it with an LED, and then cure it with an excimer lamp to obtain the anti-fouling and scratch-resistant finishing film.

[0024] Preferably, the curing energy of the LED pre-curing is 200-500 mj / cm 2 , the LED pre-curing time is 10 to 30 seconds;

[0025] The curing energy of the excimer lamp radiation curing is 1300-1500 mj / cm 2 The time of the excimer radiation curing is 10 to 20 seconds.

[0026] According to a third aspect of the present invention, there is provided a scratch-resistant and stain-resistant finishing film for use in household products, automobile interiors, and packaging materials.

[0027] (III) Beneficial effects

[0028] The present invention provides an anti-fouling and scratch-resistant finishing film and a preparation method and application thereof, which has the following beneficial effects:

[0029] (1) The present invention provides an anti-fouling and scratch-resistant finishing film, which is prepared by a quasi-molecular process through the synergistic effect of resin prepolymers, bifunctional monomers and fluorine-containing polymers with photoinitiators, nanofillers, dispersants and leveling agents. The finishing film not only has excellent anti-fouling and scratch-resistant properties, but also has excellent toughness and excellent market competitiveness in household products, automotive interiors and packaging materials.

[0030] (2) This scheme provides a method for preparing an anti-fouling and scratch-resistant finishing film, which first pre-cures the film layer through an LED lamp to stabilize the surface structure of the film layer, providing a good foundation for radiation curing. Then, combined with excimer radiation curing, the polymer in the film layer undergoes a cross-linking reaction to obtain a finishing film that is anti-fouling, wear-resistant and has good toughness. DETAILED DESCRIPTION

[0031] In order to make the purpose, technical solution and advantages of the embodiment of the present invention clearer, the technical solution of the embodiment of the present invention will be clearly and completely described in combination with the embodiment of the present invention. Obviously, the described embodiment is a part of the embodiment of the present invention, not all the embodiments. Based on the described embodiment of the present invention, all other embodiments obtained by ordinary technicians in this field belong to the scope of protection of the present invention.

[0032] Example 1

[0033] Preparation of functional layer paint: first, by mass percentage, 50wt% of polyurethane acrylate, 35.9wt% of ethylene glycol diacrylate, 10wt% of perfluorooctane sulfonic acid and 2wt% of nano-silica were mixed, and then 1wt% of benzoin photoinitiator, 1wt% of sodium lauryl sulfate and 0.1wt% of BKY051 were added and mixed evenly to obtain a functional layer coating;

[0034] Preparation of decorative film: The prepared functional coating was coated on a polypropylene substrate and first cured with a curing energy of 200 mj / cm 2 The LED light was used for pre-curing for 10 seconds, and then the curing energy was 1300mj / cm 2 The excimer isotropic radiation was cured for 10 seconds to obtain a finishing film.

[0035] Example 2

[0036] Preparation of functional layer paint: first, by mass percentage, 60wt% of polyester acrylate, 29.4wt% of 1,6-hexanediol diacrylate, 15wt% of perfluorooctane sulfonic acid and 3wt% of nano-silica were mixed, and then 1.5wt% of benzoin photoinitiator, 1wt% of sodium dodecyl sulfate and 0.1wt% of BKY051 were added and mixed evenly to obtain a functional layer coating;

[0037] Preparation of decorative film: The prepared functional coating was coated on a polypropylene substrate and first cured with a curing energy of 300 mj / cm 2 The LED light was used for pre-curing for 15 seconds, and then the curing energy was 1400mj / cm 2 The excimer isotropic radiation was cured for 10 seconds to obtain a finishing film.

[0038] Example 3

[0039] Preparation of functional layer paint: first, by mass percentage, 65wt% of epoxy acrylate, 16wt% of diethylene glycol diacrylate, 10wt% of fluorinated carbon nanotubes and 4wt% of nano titanium dioxide are mixed, and then 2wt% of acetophenone derivative photoinitiator, 2wt% of sodium stearate and 1wt% of BKY052 are added and mixed evenly to obtain a functional layer coating;

[0040] Preparation of decorative film: The prepared functional coating was coated on a polypropylene substrate and first cured with a curing energy of 300 mj / cm 2 The LED light was used for pre-curing for 15 seconds, and then the curing energy was 1400mj / cm 2 The excimer isotropic radiation was cured for 10 seconds to obtain a finishing film.

[0041] Example 4

[0042] Preparation of functional layer paint: first, by mass percentage, 35wt% of polyurethane acrylate, 45.4wt% of ethylene glycol diacrylate, 15wt% of perfluorooctane sulfonic acid and 3wt% of nano-silica were mixed, and then 1wt% of benzoin photoinitiator, 0.5wt% of sodium lauryl sulfate and 0.1wt% of BKY051 were added and mixed evenly to obtain a functional layer coating;

[0043] Preparation of decorative film: The prepared functional coating was coated on a polypropylene substrate and first cured with a curing energy of 200 mj / cm 2 The LED light was used for pre-curing for 10 seconds, and then the curing energy was 1300mj / cm 2 The excimer isotropic radiation was cured for 10 seconds to obtain a finishing film.

[0044] Example 5

[0045] Preparation of functional layer coating: first, by weight percentage, 50 wt % of polyurethane acrylate, 37.9 wt % of ethylene glycol diacrylate and 10 wt % of perfluorooctane sulfonic acid were mixed, and then 1 wt % of benzoin photoinitiator, 1 wt % of sodium lauryl sulfate and 0.1 wt % of BKY051 were added and mixed evenly to obtain a functional layer coating;

[0046] Preparation of decorative film: The prepared functional coating was coated on a polypropylene substrate and first cured with a curing energy of 200 mj / cm 2 The LED light was used for pre-curing for 10 seconds, and then the curing energy was 1300mj / cm 2 The excimer isotropic radiation was cured for 10 seconds to obtain a finishing film.

[0047] Example 6

[0048] Preparation of functional layer paint: first, by mass percentage, 49.5wt% of polyurethane acrylate, 30wt% of ethylene glycol diacrylate, 10wt% of perfluorooctane sulfonic acid and 5wt% of nano titanium dioxide are mixed, and then 1.2wt% of benzoin photoinitiator, 3.5wt% of sodium lauryl sulfate and 0.8wt% of BKY051 are added and mixed evenly to obtain a functional layer coating;

[0049] Preparation of decorative film: The prepared functional coating was coated on a polypropylene substrate and first cured with a curing energy of 200 mj / cm 2 The LED light was used for pre-curing for 10 seconds, and then the curing energy was 1300mj / cm 2 The excimer isotropic radiation was cured for 10 seconds to obtain a finishing film.

[0050] Comparative Example 1

[0051] Preparation of functional layer paint: first, by mass percentage, 20wt% of polyurethane acrylate, 62.9wt% of ethylene glycol diacrylate, 10wt% of perfluorooctane sulfonic acid and 2wt% of nano-silica were mixed, and then 1wt% of benzoin photoinitiator, 1wt% of sodium lauryl sulfate and 0.1wt% of BKY051 were added and mixed evenly to obtain a functional layer coating;

[0052] Preparation of decorative film: The prepared functional coating was coated on a polypropylene substrate and first cured with a curing energy of 200 mj / cm 2 The LED light was used for pre-curing for 10 seconds, and then the curing energy was 1300mj / cm 2 The excimer isotropic radiation was cured for 10 seconds to obtain a finishing film.

[0053] Comparative Example 2

[0054] Preparation of functional layer paint: first, by mass percentage, 85.9wt% of polyurethane acrylate, 10wt% of perfluorooctane sulfonic acid and 2wt% of nano-silica were mixed, and then 1wt% of benzoin photoinitiator, 1wt% of sodium dodecyl sulfate and 0.1wt% of BKY051 were added and mixed evenly to obtain a functional layer coating;

[0055] Preparation of decorative film: The prepared functional coating was coated on a polypropylene substrate and first cured with a curing energy of 200 mj / cm 2 The LED light was used for pre-curing for 10 seconds, and then the curing energy was 1300mj / cm 2 The excimer isotropic radiation was cured for 10 seconds to obtain a finishing film.

[0056] Comparative Example 3

[0057] Preparation of functional layer paint: first, by mass percentage, 85.9wt% of ethylene glycol diacrylate, 10wt% of perfluorooctane sulfonic acid and 2wt% of nano-silica were mixed, and then 1wt% of benzoin photoinitiator, 1wt% of sodium dodecyl sulfate and 0.1wt% of BKY051 were added and mixed evenly to obtain a functional layer coating;

[0058] Preparation of decorative film: The prepared functional coating was coated on a polypropylene substrate and first cured with a curing energy of 200 mj / cm 2 The LED light was used for pre-curing for 10 seconds, and then the curing energy was 1300mj / cm 2 The excimer isotropic radiation was cured for 10 seconds to obtain a finishing film.

[0059] Comparative Example 4

[0060] Preparation of functional layer paint: first, by mass percentage, 56.4wt% of polyurethane acrylate, 35.9wt% of ethylene glycol diacrylate and 2wt% of nano-silica were mixed, and then 1wt% of benzoin photoinitiator, 1wt% of sodium lauryl sulfate and 0.1wt% of BKY051 were added and mixed evenly to obtain a functional layer coating;

[0061] Preparation of decorative film: The prepared functional coating was coated on a polypropylene substrate and first cured with a curing energy of 200 mj / cm 2 The LED light was used for pre-curing for 10 seconds, and then the curing energy was 1300mj / cm 2 The excimer isotropic radiation was cured for 10 seconds to obtain a finishing film.

[0062] Performance Testing

[0063] The finishing films prepared in Examples 1-6 and Comparative Examples 1-4 were subjected to surface abrasion, and the surfaces of the finishing films were rubbed with the same rough dirt. The water contact angles were measured at 0.5 min, 1 min, 3 min, 10 min, and 30 min, respectively, as shown in Table 1.

[0064]

[0065]

[0066] According to the data comparison in Table 1, it can be seen that through the synergistic effect of the resin prepolymer, the bifunctional monomer and the fluorine-containing polymer, the water contact angle is high and has excellent hydrophobic and anti-fouling properties. Moreover, after long-term wear, the water contact angle changes little and the hydrophobic and anti-fouling properties will not decrease.

[0067] The anti-fouling and scratch-resistant finishing film provided by the present invention still has excellent anti-fouling performance under the condition of long-term wear and tear, and also has excellent toughness, and has excellent market competitiveness in household products, automobile interiors and packaging materials.

[0068] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A stain-resistant and scratch-resistant finishing film, characterized in that: It comprises a substrate and a functional layer coated on the surface of the substrate; wherein the functional layer comprises a resin prepolymer, a bifunctional monomer, a fluorine-containing polymer, a photoinitiator, a nanofiller, a dispersant and a leveling agent.

2. The anti-fouling and scratch-resistant finishing film according to claim 1, characterized in that: The functional layer comprises, by mass fraction, 30-70 wt % of resin prepolymer, 5-50 wt % of bifunctional monomer, 5-20 wt % of fluorine-containing polymer, 0.5-5 wt % of photoinitiator, 0-5 wt % of nano filler, 0.5-3 wt % of dispersant and 0.1-1 wt % of leveling agent.

3. The anti-fouling and scratch-resistant finishing film according to claim 1, characterized in that: The resin prepolymer is selected from at least one of polyurethane acrylate, polyester acrylate and epoxy acrylate.

4. The anti-fouling and scratch-resistant finishing film according to claim 1, characterized in that: The bifunctional monomer is at least one selected from ethylene glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, diglycidyl ether bisphenol A, glycidyl ether acrylate, tripropylene glycol diacrylate, and adipic acid diacrylate.

5. The anti-fouling and scratch-resistant finishing film according to claim 1, characterized in that: The fluorine-containing polymer is selected from perfluoroalkyl compounds or fluorinated carbon nanotubes.

6. The anti-fouling and scratch-resistant finishing film according to claim 1, characterized in that: The photoinitiator is selected from at least one of benzoin photoinitiator, acetophenone derivative photoinitiator and benzil ketal derivative photoinitiator.

7. The anti-fouling and scratch-resistant finishing film according to claim 1, characterized in that: The nano filler is selected from nano silicon dioxide or nano titanium dioxide; The dispersant is selected from at least one of sodium lauryl sulfate, sodium stearate, polyvinyl alcohol, polyvinyl acid, vegetable oil derivatives, and rosin derivatives; The leveling agent is selected from any one of BKY051, BKY052, BYK065, BYK065, BYK085, and BYK088.

8. A method for preparing the anti-fouling and scratch-resistant finishing film according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1. Firstly, a resin prepolymer, a bifunctional monomer, a fluorine-containing polymer and a nanofiller are mixed, and then a dispersant, a leveling agent and a photoinitiator are added and mixed evenly to obtain a functional layer paint; S2. Apply the functional layer paint onto a substrate, pre-cure it with an LED, and then cure it with an excimer lamp to obtain the anti-fouling and scratch-resistant finishing film.

9. The method for preparing an anti-fouling and scratch-resistant finishing film according to claim 8, characterized in that: The curing energy of the LED pre-curing is 200-500 mj / cm 2 , the LED pre-curing time is 10 to 30 seconds; The curing energy of the excimer lamp radiation curing is 1300-1500 mj / cm 2 The time of the excimer radiation curing is 10 to 20 seconds.

10. Use of the anti-fouling and scratch-resistant finishing film according to any one of claims 1 to 7 or the anti-fouling and scratch-resistant finishing film obtained by the preparation method according to claim 8 or 9 in household products, automobile interiors, and packaging materials.

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