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KR-102963998-B1 - Improved Scratch-resistance and Fouling resistance Polymethylmethacrylate film

KR102963998B1KR 102963998 B1KR102963998 B1KR 102963998B1KR-102963998-B1

Abstract

The present invention provides a polymethyl methacrylate film with improved scratch resistance and stain resistance, and a method for manufacturing the same. The polymethyl methacrylate film is a film comprising a crosslinkable polymer and a crosslinkable functional additive containing a functional group, wherein the film may have excellent transmittance and transparency by preventing haze through the functional group, while the scratch resistance and stain resistance are improved.

Inventors

  • 강홍규
  • 김상조
  • 우한영
  • 손재훈

Assignees

  • 광주과학기술원
  • 고려대학교 산학협력단

Dates

Publication Date
20260512
Application Date
20231110

Claims (14)

  1. A first monomer that is a methacrylate-based compound; A second monomer which is a compound containing a diazo group; and A third monomer that is a functional additive of a siloxane-based compound; comprising A crosslinkable functional additive, wherein the first monomer, the second monomer, and the third monomer are copolymerized.
  2. In paragraph 1, The first monomer is a crosslinkable functional additive, wherein the first monomer is one or more methacrylate-based compounds selected from the group consisting of methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate (n-BMA), isobutyl methacrylate (i-BMA), allyl methacrylate (AMA), phenyl methacrylate (PMA), and ethoxyethyl methacrylate (ETMA).
  3. In paragraph 1, The above-mentioned second monomer is a crosslinkable functional additive comprising 2-(2-diazo-2-phenylacetoxy)ethyl methacrylate (PEDAz) and 4-azido-2,3,5,6-tetrafluorobenzyl methacrylate (ABMA).
  4. In paragraph 1, The above-mentioned third monomer is a crosslinkable functional additive, which is one or more siloxane-based compounds selected from the group consisting of 3-(dimethoxy(methyl)silyl)propyl methacrylate, 3-(trimethoxysilyl)propyl methacrylate (TMOPMA), 3-(triethoxysilyl)propyl methacrylate (TESPMA), and dimethylsiloxane methacrylate.
  5. In paragraph 1, The above-mentioned crosslinkable functional additive is a crosslinkable functional additive represented by the following chemical formula 3: [Chemical Formula 3] . In the above formula, m + n + l is 1, m is 0.5 to 0.9, n is 0.05 to 0.2, and l is 0.05 to 0.3.
  6. A step of preparing a mixed solution comprising a first monomer which is a methacrylate-based compound, a second monomer which is a compound containing a diazo group, and a third monomer which is a functional additive of a siloxane-based compound; and A method for manufacturing a crosslinkable functional additive, comprising the step of copolymerizing the above-mentioned mixed solution to produce a crosslinkable functional additive.
  7. In paragraph 6, A method for manufacturing a crosslinkable functional additive, further comprising the step of precipitating, after copolymerizing the above-mentioned mixed solution, in one or more precipitation solvents selected from the group consisting of water, methanol, ethanol, acetone, ether, chloroform, ethyl acetate, isopropyl alcohol, hexane, benzene, toluene, and mixtures thereof.
  8. In paragraph 6, A method for manufacturing a crosslinkable functional additive, wherein the above-mentioned mixed solution has a molar ratio of the first monomer, the second monomer, and the third monomer of 30:1:4 to 4:1:4.
  9. In paragraph 6, A method for preparing a crosslinkable functional additive, wherein the first monomer is one or more methacrylate-based compounds selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, allyl methacrylate, phenyl methacrylate, and ethoxyethyl methacrylate; the second monomer is a compound containing a diazo group, such as 2-(2-diazo-2-phenylacetoxy)ethyl methacrylate and 4-azido-2,3,5,6-tetrafluorobenzenyl methacrylate; and the third monomer is one or more siloxane-based compounds selected from the group consisting of 3-(dimethoxy(methyl)silyl)propyl methacrylate, 3-(trimethoxysilyl)propyl methacrylate, 3-(triethoxysilyl)propyl methacrylate, and dimethylsiloxane methacrylate.
  10. Polymethyl methacrylate; and A crosslinkable functional additive that crosslinks with the above-mentioned polymethyl methacrylate; comprising, The above-mentioned crosslinkable functional additive comprises a first monomer which is a methacrylate-based compound, a second monomer which is a compound containing a diazo group, and a third monomer which is a functional additive of a siloxane-based compound, and is a copolymer formed by copolymerizing the first monomer, the second monomer, and the third monomer. Polymethyl methacrylate film in which hardness is increased and the surface has hydrophobicity due to the above-mentioned crosslinkable functional additive, thereby improving scratch resistance and stain resistance.
  11. delete
  12. In Paragraph 10, The above film is a polymethyl methacrylate film having transparency, wherein the phase separation of the polymethyl methacrylate and the third monomer, which is a functional additive of the siloxane-based compound, is prevented by the crosslinkable functional additive.
  13. In Paragraph 10, The first monomer is one or more methacrylate compounds selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, allyl methacrylate, phenyl methacrylate, and ethoxyethyl methacrylate; the second monomer is a compound containing a diazo group, such as 2-(2-diazo-2-phenylacetoxy)ethyl methacrylate and 4-azido-2,3,5,6-tetrafluorobenzyl methacrylate (ABMA); and the third monomer is one or more siloxane compounds selected from the group consisting of 3-(dimethoxy(methyl)silyl)propyl methacrylate, 3-(trimethoxysilyl)propyl methacrylate, 3-(triethoxysilyl)propyl methacrylate, and dimethylsiloxane methacrylate. Polymethyl methacrylate film, which is a compound.
  14. In Paragraph 10, The above film is a polymethyl methacrylate film comprising 80 wt% to 99 wt% of polymethyl methacrylate and 1 wt% to 20 wt% of a crosslinkable functional additive.

Description

Improved Scratch-resistance and Fouling resistance Polymethylmethacrylate film The present invention relates to a polymethyl methacrylate film with improved scratch resistance and stain resistance, and more specifically, to a polymethyl methacrylate film having excellent transmittance while having improved scratch resistance and stain resistance by means of a functional additive, an additive for manufacturing the same, a method for manufacturing the additive, and a film using the same. Polymer materials, widely used in various fields such as electrical and electronic, automotive, and medical industries, can easily lose their existing properties due to external physical or chemical stimuli. In particular, protective materials utilizing polymers can easily lose their characteristics due to repetitive external stress, and this loss of properties can lead to scratches or contamination, significantly shortening their durability and lifespan. Polymethyl methacrylate is a synthetic polymer of methyl methacrylate and is a polymer material widely used as a substitute for glass and as a material for polymer optical films due to its excellent optical properties, weather resistance, surface gloss, and transparency. However, polymethyl methacrylate films have low impact resistance compared to other plastic materials, which limits their applications. To address this, methods have been proposed to improve the impact resistance of films by mixing or polymerizing polymethyl methacrylate with additives that can increase flexibility or mechanical properties; however, there is a problem that the strength is insufficient for commercialization. In addition, optical films using polymethyl methacrylate have the disadvantage of being relatively hydrophilic, having high surface energy, and having poor chemical resistance, which can lead to the surface being easily contaminated, thus requiring a method to improve this. A representative method to improve the stain resistance of optical films using polymethyl methacrylate is to coat the surface of the optical film; specifically, this involves coating the surface of the optical film with alkyl chains containing fluorine or silicon, which have low surface energy, so that the surface of the optical film becomes hydrophobic. However, alkyl chains containing fluorine or silicon are not uniformly coated over the entire surface of the polymethyl methacrylate film, so they can easily peel off, and phase separation occurs, resulting in reduced transmittance. Therefore, there is a need for an optical film that can maintain the transmittance of a polymethyl methacrylate film while possessing scratch resistance and stain resistance. Figure 1 is a graph showing the results of analyzing a crosslinkable polymer containing a diazo group of the present invention by 1 H-NMR. Figure 2 is a figure comparing colors based on the content of a compound containing diazo groups included in the crosslinkable polymer of the present invention. Figure 3 is a graph showing the results of analyzing the crosslinkable polymer of the present invention using a thermogravimetric analysis (TGA). Figure 4 is a graph showing the results of analyzing the crosslinkable functional additive of the present invention by TGA. Figure 5 is a graph showing the analysis of a poly(methyl methacrylate), PMMA polymer containing the crosslinkable functional additive of the present invention and a conventional PMMA polymer using a Differential Scanning Calorimeter (DSC). Figure 6 is a graph confirming the transmittance of a film containing the crosslinkable functional additive of the present invention and PMMA, and a figure confirming the haze and yellowness of the film. Figure 7 is a figure comparing and confirming the water contact angle of a film containing the crosslinkable functional additive of the present invention and PMMA. Hereinafter, the present invention will be described in detail with reference to embodiments and drawings so that those skilled in the art to which the present invention pertains can easily implement it. The embodiments of the present invention are provided to more completely explain the present invention to those with average knowledge in the art. Accordingly, the embodiments of the present invention may be modified in various different forms, and the scope of the present invention is not limited to the embodiments described below but may be embodied in other forms. Throughout the specification of the present invention, when a part is described as "comprising" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components. Throughout the specification of the present invention, "steps" or "steps of" do not mean "steps for." Examples The present invention provides a crosslinkable functional additive comprising three or more types of monomers. The crosslinkable functional additive may be a copolymer comprising a first monomer wh