Synthetic resin coating composition and synthetic resin substrate manufacturing method using the same

Abstract

Disclosed is a synthetic resin coating composition that imparts hydrophilic properties to synthetic resins used in scientific and industrial fields, and a method for manufacturing a synthetic resin substrate using the coating composition. In addition, the present invention provides a synthetic resin coating composition comprising a silsesquioxane polymer and a solvent, the silsesquioxane polymer comprising repeating units of Chemical Formula 1 and Chemical Formula 2 described in the specification.

Description

Technical Field

[0001] This invention relates to a synthetic resin coating composition and a method for manufacturing a synthetic resin substrate using the above coating composition, and more particularly to a synthetic resin coating composition for use in the scientific and industrial fields and a method for manufacturing a synthetic resin substrate using the above coating composition. Background Technology

[0002] Recently, the need to develop plastic films and sheets to replace glass has become increasingly important in the scientific and industrial fields. Plastic materials are designed to meet the needs of consumers requiring alternatives with the following properties.

[0003] Depending on the manufacturing method, the synthetic resin used to form the aforementioned plastic can achieve a transparency comparable to that of glass. Furthermore, it is lighter than glass, possesses excellent impact resistance, and offers a wide range of color options. Therefore, it can not only be used to simply replace glass but also be extended to various application areas such as decorative materials. By rationally utilizing the advantages described above, plastic is expected to gradually become a widely used material capable of replacing glass.

[0004] However, transparent materials made from synthetic resins used to form plastics are less likely to achieve surface hydrophilicity compared to glass, thus making it difficult to maintain high levels of surface energy. Due to these drawbacks, plastic materials are subject to the limitations described below in surface (exterior) treatments that determine product value.

[0005] Because the synthetic resins used to form plastics are less likely to achieve surface hydrophilicity compared to glass, their diffusion properties in coating solutions are limited. Therefore, the application of chemical products to impart surface properties such as fingerprint resistance, fingerprint reduction, and improved slipability is very complex and restricted. Furthermore, it is difficult to induce strong adhesion at the interface with coating materials that determine optical properties such as low refractive index, diffuse reflection, and high / low reflectivity, making it difficult to achieve a glass-like appearance. In addition, the applicability of surface coating agents used to enhance physical properties such as hardness and scratch resistance is also limited.

[0006] Therefore, while synthetic resins used to form plastics have many advantages, they are not yet widely applicable as alternatives in all fields where glass is used. Consequently, extensive scientific and technological research is underway to overcome the shortcomings of synthetic resin substrates used to form plastics, as described above.

[0007] In Patent No. 10-2018-0100985, to solve the problems mentioned above, a hydrophilic primer is applied to a plastic substrate after plasma treatment, thereby maintaining its hydrophilic properties for a long time. Furthermore, a fluorine-based coating agent is applied to the substrate to achieve fingerprint resistance and improve sliding properties. In addition, Patent No. 10-2007-0034517 discloses the use of a coating liquid containing a hydrophilic binder to induce hydrophilic properties, thereby producing a substrate with hydrophilic surface properties. The hydrophilic binder contains a photocatalyst and a hydrolyzed organosilicon.

[0008] However, when overcoming the problem using the methods described above, several issues still arise, as described below.

[0009] Incorporating the aforementioned hydrophilic coating agent using a primer requires a highly complex process. Specifically, it necessitates an instantaneous surface hydrophilization treatment on the plastic substrate using a plasma method with a specific gas type, followed by primer application, and then immediate recoating with the target functional coating agent. In this process, the hydrophilic surface formed on the plastic substrate through the instantaneous plasma treatment has an extremely short lifespan, resulting in a reduction to the original surface energy value within minutes to hours. Therefore, primer application must be performed very quickly or continuously, and variations in processing time may compromise the adhesion between the primer layer and the substrate.

[0010] Furthermore, because hydrophilic coatings containing photocatalysts and silicates cannot induce reliable chemical bonding with the adhesives used, it is difficult to ensure glass-like properties (e.g., high surface hardness and scratch resistance), which presents many problems in practical applications. Summary of the Invention

[0011] The problem the invention aims to solve

[0012] Therefore, the object of the present invention is to provide a synthetic resin coating composition that can achieve hydrophilic properties on the surface of a general plastic material for a long period of time without the need for a separate primer or complex continuous processes, and a method for manufacturing a synthetic resin substrate using the above coating composition.

[0013] Another object of the present invention is to provide a synthetic resin coating composition and a method for manufacturing a synthetic resin substrate using the above coating composition, wherein the synthetic resin coating composition can achieve the same level of functional coating currently used on glass surfaces, and can be used in various application areas where glass needs to be replaced.

[0014] means for solving problems

[0015] To achieve the objectives described above, the present invention provides a synthetic resin coating composition comprising a silsesquioxane polymer and a solvent, wherein the silsesquioxane polymer comprises repeating units of the following chemical formulas 1 and 2.

[0016] [Chemical Formula 1]

[0017]

[0018] [Chemical Formula 2]

[0019]

[0020] In both Chemical Formula 1 and Chemical Formula 2, R1 is independently hydrogen, deuterium, halogen, amino group, epoxy group, cyclohexylepoxy group, (meth)acryloyl group, hydroxyl group, thiol group, isocyanate group, nitrile group, nitro group, alkyl group with 1 to 40 carbon atoms, alkenyl group with 2 to 40 carbon atoms, alkoxy group with 1 to 40 carbon atoms, cycloalkyl group with 3 to 40 carbon atoms, heterocycloalkyl group with 3 to 40 carbon atoms, aryl group with 6 to 40 carbon atoms, heteroaryl group with 3 to 40 carbon atoms, aralkyl group with 3 to 40 carbon atoms, and carbon atom The R2 group consists of 3 to 40 aryloxy groups or arylthiol groups with 3 to 40 carbon atoms, where R2 is independently hydrogen, deuterium, halogen, isocyanate group, alkyl group with 1 to 40 carbon atoms, alkenyl group with 2 to 40 carbon atoms, cycloalkyl group with 3 to 40 carbon atoms, heterocycloalkyl group with 3 to 40 carbon atoms, aryl group with 6 to 40 carbon atoms, heteroaryl group with 3 to 40 carbon atoms, aryl group with 3 to 40 carbon atoms, or epoxy group with 2 to 40 carbon atoms, where n and m are independently integers from 1 to 100,000, and n / m is from 0.1 to 10.

[0021] Furthermore, the present invention provides a synthetic resin coating composition comprising a silsesquioxane polymer, a synthetic resin, and a solvent, wherein the silsesquioxane polymer comprises repeating units of the above-mentioned chemical formulas 1 and 2.

[0022] Furthermore, the present invention provides a synthetic resin substrate comprising a synthetic resin coating composition comprising a silsesquioxane polymer, a synthetic resin, and a solvent, wherein the silsesquioxane polymer comprises repeating units of the aforementioned chemical formulas 1 and 2.

[0023] Furthermore, the present invention provides a synthetic resin substrate, comprising a synthetic resin substrate and a coating layer formed on one or more sides of the synthetic resin substrate and cured with a synthetic resin coating composition. The synthetic resin coating composition comprises a silsesquioxane polymer and a solvent, or comprises a silsesquioxane polymer, a synthetic resin, and a solvent. The silsesquioxane polymer comprises repeating units of chemical formulas 1 and 2.

[0024] The effects of the invention

[0025] The synthetic resin coating composition applicable to the present invention and the method for manufacturing a synthetic resin substrate using the above coating composition can achieve hydrophilic properties on the surface of ordinary plastic materials for a long time without the use of additional primers or complex continuous processes, and can also achieve the same level of functional coatings currently used on glass surfaces. Attached Figure Description

[0026] Figure 1 This is a cross-sectional view of a synthetic resin substrate to which an embodiment of the present invention is applicable.

[0027] Figure 2 This is a cross-sectional view of a synthetic resin substrate to which another embodiment of the present invention applies.

[0028] Figure 3 This is a cross-sectional view of a hydrophilic synthetic resin substrate to which an embodiment of the present invention is applicable. Detailed Implementation

[0029] The present invention will then be described in more detail.

[0030] As an example of a synthetic resin coating composition to which the present invention is applicable, it comprises a silsesquioxane polymer and a solvent, wherein the silsesquioxane polymer comprises repeating units of the following chemical formulas 1 and 2.

[0031] [Chemical Formula 1]

[0032]

[0033] [Chemical Formula 2]

[0034]

[0035] In both Chemical Formula 1 and Chemical Formula 2 above, R1 is independently hydrogen; deuterium; halogen; amino group; epoxy group; cyclohexylepoxy group; (meth)acryloyl group; hydroxyl group; thiol group; isocyanate group; nitrile group; nitro group; alkyl group with 1 to 40 carbon atoms; alkenyl group with 2 to 40 carbon atoms; alkoxy group with 1 to 40 carbon atoms; cycloalkyl group with 3 to 40 carbon atoms; heterocycloalkyl group with 3 to 40 carbon atoms; aryl group with 6 to 40 carbon atoms; heteroaryl group with 3 to 40 carbon atoms; aralkyl group with 3 to 40 carbon atoms, specifically aralkyl group with 7 to 40 carbon atoms; aroxy group with 3 to 40 carbon atoms, specifically aroxy group with 6 to 40 carbon atoms; or arylthiol group with 3 to 40 carbon atoms, specifically arylthiol group with 6 to 40 carbon atoms. R2 is independently hydrogen; deuterium; halogen; isocyanate group; alkyl group with 1 to 40 carbon atoms; alkenyl group with 2 to 40 carbon atoms; cycloalkyl group with 3 to 40 carbon atoms; heterocycloalkyl group with 3 to 40 carbon atoms; aryl group with 6 to 40 carbon atoms; heteroaryl group with 3 to 40 carbon atoms; aralkyl group with 3 to 40 carbon atoms, specifically aralkyl group with 7 to 40 carbon atoms; or epoxy group with 2 to 40 carbon atoms. Furthermore, n and m are independently integers from 1 to 100,000, and n / m is from 0.1 to 10. When the n / m value is less than 0.1, peeling from the substrate (e.g., plastic substrate) may occur due to oiliness, while when it exceeds 10, difficulties in use may occur due to brittleness.

[0036] In the aforementioned chemical formulas 1 and 2, the alkyl groups having 1 to 40 carbon atoms can specifically be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, hexyl, etc., while the aryl groups can be phenyl, etc. In the aforementioned chemical formula 2, R2 can be hydrogen, methyl, ethyl, or propyl, and the -OR2 group can adjust the solubility, dispersibility, and compatibility of sesquioxane polymers by including oxygen.

[0037] As needed, R1 and R2 can be substituted with substituents such as deuterium, halogen, amino, vinyl, (meth)acryloyl, thiol, isocyanate, nitrile, nitro, etc. Specifically, R1 can have reactive substituents such as amino, (meth)acryloyl, hydroxyl, thiol, or reactive functional groups such as vinyl or epoxy. For example, it can be an alkyl group having the above-mentioned reactive substituents or functional groups. With the aid of the reactive substituents or functional groups described above, the silsesquioxane polymer of the present invention can be cross-linked. Examples of R1 having the above-mentioned reactive substituents or functional groups include (meth)acryloyloxypropyl and 2-(3,4-epoxycyclohexyl)ethyl.

[0038] In the case where the silsesquioxane polymer of the present invention has reactive substituents or reactive functional groups, the proportion of R1 having reactive substituents or reactive functional groups relative to the total R1 can be, for example, 10% to 100%, specifically 50% to 100%. If the content of the aforementioned reactive substituents or functional groups is too low, the cross-linking bonding force of the silsesquioxane polymer may be too low, leading to a decrease in the hardness of the final coated film or a longer cross-linking bonding time for the silsesquioxane polymer.

[0039] The aforementioned silsesquioxane polymers may include polymers with the following chemical formula 3.

[0040] [Chemical Formula 3]

[0041]

[0042] In the above chemical formula 3, the definitions of R1, R2, n and m are the same as those in chemical formula 1 and chemical formula 2.

[0043] The silsesquioxane polymer of the above chemical formula 3 has a random structure. R1 and -OR2 can be the same organic functional group, and can be replaced by other types depending on the situation. The weight average molecular weight of the above silsesquioxane polymer can be from 2,000 to 100,000.

[0044] In the above chemical formula 3, the compatibility of the synthetic resin can be adjusted by regulating the amount of OR2 groups introduced. The Si-O-Si groups contained in the above chemical formula 3 are induced to Si-OH or Si-O· upon treatment with plasma, corona, strong alkali, or strong acid, while the aforementioned OR2 groups are induced to hydrophilic functional groups such as C-OH and carboxyl groups (e.g., CC=O), thus maintaining the same long-term hydrophilic properties as glass. Therefore, plastic sheets and / or films with the same long-term hydrophilicity as glass can be manufactured.

[0045] The solvents mentioned above are organic solvents, which help to uniformly mix the synthetic resin and the silsesquioxane polymer applicable to this invention. For example, not only polar solvents (such as water (distilled water); alcohols such as methanol, ethanol, isopropanol, butanol, etc.; ketones such as acetone, methyl (isobutyl) ethyl ketone, etc.; diols such as ethylene glycol, etc.; furans such as tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, etc.) can be used, but they are not limited to these.

[0046] The silsesquioxane polymer of the above chemical formula 3 can be obtained by first synthesizing a precursor with a chlorosilane monomer in a solvent of mixed distilled water and ethanol, followed by polycondensation to introduce repeating units n and m, and then purification.

[0047] As another embodiment of the synthetic resin coating composition to which the present invention is applicable, it comprises a silsesquioxane polymer, a synthetic resin, and a solvent. The silsesquioxane polymer and solvent described above are the same as those described above.

[0048] The aforementioned synthetic resins are resins used to form plastics and may contain commercially available organic polymers. For example, they may contain polymethyl methacrylate (PMMA), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET), polyamides (PA), polyester (PES), polyvinyl chloride (PVC), polyurethanes (PU), polycarbonate (PC), high-hardness polycarbonate (high-hardness PC), polyvinylidene chloride (PVDC), polytetrafluoroethylene (PTFE), polyetheretherketone (PEEK), and polyetherimide (PEI), etc. These synthetic resins may be used in fragment (granular) form.

[0049] The synthetic resin and the silsesquioxane polymer containing repeating units of chemical formula 1 and chemical formula 2 are preferably mixed in a weight ratio of 1:9 to 9:1. When the above weight ratio is satisfied, the surface hydrophilicity of the formed synthetic resin substrate is maintained for a long time.

[0050] The present invention includes a synthetic resin substrate that can maintain hydrophilicity over a long period of time. Figure 1 This is a cross-sectional view of a synthetic resin substrate (e.g., a plastic film and resin) to which embodiments of the present invention are applicable. The above... Figure 1 The synthetic resin substrate shown can be formed by curing a synthetic resin coating composition comprising synthetic resin 20 and silsesquioxane polymer 10 and, as needed, a solvent capable of dissolving the synthetic resin 20 and silsesquioxane polymer 10. More specifically, it can be formed by extrusion molding after mixing synthetic resin 20 and silsesquioxane polymer 10. The silsesquioxane polymer 10 comprises repeating units of the above chemical formulas 1 and 2.

[0051] Figure 2 This is a cross-sectional view of a synthetic resin substrate (e.g., a plastic film and resin) applicable to another embodiment. The above... Figure 2 The synthetic resin substrate shown can be formed by forming a coating layer on one side or more of the synthetic resin 20 substrate using the synthetic resin coating composition 10. More specifically, the synthetic resin substrate can be formed by including the synthetic resin 20 substrate and a coating layer formed on one side or more of the synthetic resin substrate using the synthetic resin coating composition 10. The synthetic resin coating composition 10 contains the silsesquioxane polymer or contains the synthetic resin and the silsesquioxane polymer.

[0052] The aforementioned synthetic resins may use known plastic materials, such as polyethylene terephthalate (PET) resin, polycarbonate (PC) resin, poly(meth)acrylic acid resin (e.g., poly(methyl methacrylate) resin (PMMA), etc.), ethylene vinyl acetate (EVA) resin, polyester resin, polyamide resin, polyimide resin, polyamide-imide resin, polyallyl phthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, acetal resin, cellulose resin (e.g., cellulose triacetate (TAC) resin), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, etc.

[0053] The coating layer described above can be formed by curing the synthetic resin coating composition to which the present invention is applicable. The synthetic resin coating composition described above may contain a silsesquioxane polymer and a solvent, or may contain a silsesquioxane polymer, a synthetic resin, and a solvent, wherein the silsesquioxane polymer contains repeating units of the above-described chemical formulas 1 and 2.

[0054] By subjecting the synthetic resin substrate formed according to the present invention to plasma or corona treatment, or to wet treatment with strong acid or strong alkali, the surface energy is increased. This enhances the adhesion between the synthetic resin and the silsesquioxane polymer containing repeating units of Formula 1 and Formula 2. Furthermore, because the Si-O-Si structure of the silsesquioxane polymer is induced to Si-OH or Si-O·, or the OR2 group is induced to C-OH, carboxyl groups (e.g., CC=O), or other hydrophilic functional groups, it can possess the same hydrophilicity as glass. Therefore, functional coatings currently used on glass surfaces can be achieved at the same level, and it can be used in various application areas where glass replacement is required.

[0055] The aforementioned synthetic resin substrate may also include a fluorinated coating layer as needed. By forming a fluorinated coating layer, water repellency can be maintained for a longer period. The fluorinated coating layer may use materials such as trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, nonafluorobutylethyltrimethoxysilane, nonafluorobutylethyltriethoxysilane, nonafluorohexyltrimethoxysilane, nonafluorohexyltriethoxysilane, heptadecanyltrimethoxysilane, heptadecanyltriethoxysilane, heptadecanyltriisopropylsilane, 3-trimethoxysilylpropylpentadecanylfluorooctanoate, 3-trimethoxysilylpropyltridecylfluorooctanoate, etc. Compounds such as oxysilylpropylpentadecanooctanoate, 3-trimethoxysilylpropylpentadecanooctanoamide, 3-triethoxysilylpropylpentadecanooctanoamide, 2-trimethoxysilylethylpentadecanofluorodidecyl sulfide, 2-triethoxysilylethylpentadecanofluorodidecyl sulfide, pentafluorophenyltrimethoxysilane, pentafluorophenyltriethoxysilane, 4-(perfluorotolyl)trimethoxysilane, 4-(perfluorotolyl)triethoxysilane, dimethoxybis(pentafluorophenyl)silane, and diethoxybis(pentafluorotolyl)silane are formed.

[0056] This invention includes a method for manufacturing a synthetic resin substrate that can maintain hydrophilicity over a long period. The method for manufacturing the synthetic resin substrate achieves long-term hydrophilicity on the surface of common plastic materials without the need for additional primers or complex continuous processes. The synthetic resin substrate may include plastic sheets, plastic films, plastic substrates, and plastic molded articles manufactured by methods such as extrusion or injection molding.

[0057] Figure 3 This is a cross-sectional view of a hydrophilic synthetic resin substrate to which embodiments of the present invention are applicable. Specifically, it is a cross-sectional view of the following... Figure 1 or Figure 2 A cross-sectional view of a synthetic resin substrate with hydrophilicity 30, formed by plasma or corona treatment, or by wet surface treatment in a strong alkali or strong acid.

[0058] Specifically, the method includes a method for manufacturing a synthetic resin substrate with long-term hydrophilicity similar to glass. This method involves adding a heat-resistant silsesquioxane polymer to the base material of the synthetic resin substrate (molded body), namely an organic polymer, to create the substrate (molded body). The substrate (molded body) is then subjected to simple plasma, corona, or wet treatment. More specifically, the method includes: firstly, forming a synthetic resin coating composition comprising a synthetic resin and a silsesquioxane polymer 10; then, manufacturing a synthetic resin substrate by extrusion molding and curing, wherein the silsesquioxane polymer 10 comprises repeating units of chemical formulas 1 and 2; and finally, manufacturing a hydrophilic synthetic resin substrate by irradiating the surface of the synthetic resin substrate with plasma or corona, or by wet treatment with a strong acid or strong alkali.

[0059] The thickness of the synthetic resin substrate (e.g., plastic sheet or film) formed as described above may vary depending on the processing method, but its properties are not limited by the thickness. The method for manufacturing the synthetic resin substrate described above can impart hydrophilicity to the surface of the synthetic resin substrate (molded article) by mixing the aforementioned synthetic resin coating composition and extruding it without performing a coating process.

[0060] Another embodiment of the method for manufacturing a synthetic resin substrate that can maintain hydrophilicity for a long period of time, applicable to the present invention, includes: a step of coating a synthetic resin substrate with the aforementioned synthetic resin coating composition comprising a silsesquioxane polymer, wherein the silsesquioxane polymer comprises repeating units of the aforementioned chemical formulas 1 and 2; and a step of forming a hydrophilic synthetic resin substrate by subjecting the coated synthetic resin substrate to plasma or corona treatment or by wet treatment with a strong acid or strong alkali. Specifically, a coating layer can be formed by spraying or coating the synthetic resin substrate with a synthetic resin coating composition comprising a silsesquioxane polymer and an organic solvent, wherein the silsesquioxane polymer comprises repeating units of the aforementioned chemical formulas 1 and 2, and may further include a step of removing the organic solvent by subjecting the coating layer to high-temperature heat treatment.

[0061] Furthermore, silsesquioxane polymers containing repeating units of the above-mentioned chemical formulas 1 and 2 can be used as coating compositions by mixing with general coating agents, and can also contain photoinitiators as needed.

[0062] The above coating process only needs to be performed once to sufficiently impart high hardness, scratch resistance, and hydrophilicity to the plastic surface. The thickness of the coating layer is 50 nm to 100 μm. On films with a coating layer thickness of less than 50 nm, the adhesion interface between the substrate and the coating layer may be weakened during subsequent processes such as plasma or corona treatment. In thicker coating layers exceeding 100 μm, coating layer cracking may occur.

[0063] Regarding the method of imparting hydrophilicity to the aforementioned synthetic resin substrate, the surface energy can be increased by subjecting the synthetic resin molded article to plasma or corona treatment, or by wet treatment with strong acids or alkalis. This enhances the adhesion between the synthetic resin and the silsesquioxane polymer containing repeating units of the aforementioned chemical formulas 1 and 2. Furthermore, because the Si-O-Si structure of the aforementioned silsesquioxane polymer is induced to form Si-OH or Si-O·, or the aforementioned OR2 groups are induced to form hydrophilic functional groups such as C-OH or carboxyl groups (e.g., CC=O), it can possess the same hydrophilicity as glass. Therefore, functional coatings currently used on glass surfaces can be replicated at the same level, allowing for use in various applications where glass replacement is required. Fluorine coatings can also be applied to the aforementioned hydrophilic synthetic resin substrate as needed, thereby maintaining water repellency for an even longer period. Specific Implementation

[0065] The present invention will then be described in more detail with reference to the embodiments, but the present invention is not limited to the following embodiments.

[0066] [Synthesis example 1] Manufacturing of silsesquioxane polymers

[0067] In a dry flask equipped with a cooling tube and a stirrer, 12 g of distilled water and 50 g of methanol were mixed. Then, 200 g of 3-(trichlorosilyl)propyl methacrylate was slowly added dropwise over 10 minutes. The temperature was maintained at -4°C. Next, after stirring for 20 minutes, 500 g of toluene was slowly added dropwise, and the temperature was raised to room temperature while stirring continued for 10 minutes. During the preparation of the above reaction, an additional 20 wt% Na₂CO₃ aqueous solution was prepared, and 5 g of the prepared 20 wt% Na₂CO₃ was added dropwise to the reactor. The temperature was then raised to 50°C and the polycondensation reaction was carried out for 1 day.

[0068] The mixture of the chemical formula 3 obtained by the above polycondensation reaction and the solvent was purified by two layers of water and toluene separation. After confirming that the pH was neutral, the toluene layer was obtained, and all toluene was removed by vacuum decompression to obtain the final product.

[0069] The molecular weight determination results confirm that the linear sesquioxane polymer with the structure shown in chemical formula 3 has a styrene equivalent molecular weight of 3000, and it can also be confirmed that there are no unreacted monomers.

[0070] Thermogravimetric analysis (TGA) confirmed that the residual alkoxy group was 1 wt%, while 1H nuclear magnetic resonance (1H-NMR) analysis confirmed that the n / m ratio was 0.5.

[0071] [Synthesis example 2] Manufacturing of silsesquioxane polymers

[0072] 50 g of the substance obtained by Synthesis Example 1 above was added to a dry flask equipped with a cooling tube and a stirrer, and after substitution under nitrogen for 1 hour, 100 g of toluene was slowly added. Then, 50 g of hydrochloric acid aqueous solution was added, and the temperature was raised to 50°C and stirred vigorously for 3 days.

[0073] Subsequently, five layers of water and toluene were separated and purified. After confirming that the pH was neutral, a toluene layer was obtained. All toluene was then removed by vacuum decompression to obtain the silsesquioxane polymer. Molecular weight determination confirmed that the linear silsesquioxane polymer with the alkoxy group removed from the structure of the above chemical formula 3 has a styrene equivalent molecular weight of 2500. Thermogravimetric analysis (TGA) confirmed the absence of alkoxy groups and the conversion of the Si-O-Si structure to Si-OH. 1H nuclear magnetic resonance (1H-NMR) measurements confirmed that the n / m ratio was 0.5, indicating no change in the ratio.

[0074] [Synthesis example 3] Manufacturing of silsesquioxane polymers

[0075] In a dry flask equipped with a cooling tube and a stirrer, 5 g of distilled water and 100 g of methanol were mixed. Then, 261.61 g of 3-(trichlorosilyl)propyl methacrylate was slowly added dropwise over 10 minutes. The temperature was maintained at -4°C. Next, after stirring for 50 minutes, 500 g of toluene was slowly added dropwise, and the temperature was raised to room temperature while stirring continued for 10 minutes. During the preparation of the above reaction, an additional 20% by weight KOH aqueous solution was prepared, and 5 g of the prepared 20% by weight KOH was added dropwise to the reactor at once. The polycondensation reaction was then carried out slowly at room temperature for 7 days.

[0076] The mixture of the chemical formula 3 structure obtained through the above process and the solvent is purified by two layers of water and toluene separation. After confirming that the pH is neutral, the toluene layer is obtained, and all toluene is removed by vacuum decompression to obtain the final product.

[0077] The molecular weight determination results confirm that it has a styrene equivalent molecular weight of 20,000, and that there are no unreacted monomers.

[0078] The presence of no alkoxy groups was confirmed by thermogravimetric analysis (TGA) to determine the decomposition temperature, while the n / m ratio of 15 was confirmed by 1H nuclear magnetic resonance (1H-NMR) and 29Si nuclear magnetic resonance (29Si-NMR) analysis.

[0079] [Synthesis Example 4] Manufacturing of silsesquioxane polymers

[0080] In a dry flask equipped with a cooling tube and a stirrer, 0.1 g of distilled water and 100 g of methanol were mixed. Then, 261.61 g of 3-(trichlorosilyl)propyl methacrylate was slowly added dropwise over 10 minutes. The temperature was maintained at -4°C. Next, after stirring for 50 minutes, 500 g of toluene was slowly added dropwise, and the temperature was raised to room temperature while stirring continued for 10 minutes. During the preparation of the above reaction, an additional 20% by weight KOH aqueous solution was prepared, and 10 g of the prepared 20% by weight KOH was added dropwise to the reactor at once. The polycondensation reaction was then carried out slowly at room temperature for 3 days.

[0081] The mixture of the chemical formula 3 structure obtained through the above process and the solvent is purified by two layers of water and toluene separation. After confirming that the pH is neutral, the toluene layer is obtained, and all toluene is removed by vacuum decompression to obtain the final product.

[0082] The molecular weight determination results confirm that it has a styrene equivalent molecular weight of 30,000, and that there are no unreacted monomers.

[0083] Thermogravimetric analysis (TGA) confirmed that the residual alkoxy group was 10 wt%, while 1H nuclear magnetic resonance (1H-NMR) analysis confirmed that the n / m ratio was 0.05.

[0084] [Example 1 and Comparative Examples 1 to 3] Manufacturing of hydrophilic plastic films

[0085] Plastic films were manufactured by mixing the above-described Synthetic Example 1 with polymethyl methacrylate (PMMA) resin (Example 1), and plastic films were manufactured by mixing Synthetic Examples 2 to 4 (i.e., using Synthetic Examples 2 to 4 instead of Synthetic Example 1) with polymethyl methacrylate resin (Comparative Examples 1 to 3).

[0086] The aforementioned polymethyl methacrylate (PMMA) resin was LG IH830, prepared by dissolving it in toluene at 50 wt%. The prepared PMMA resin-toluene mixture was then mixed with the substances obtained in Synthesis Examples 1 to 4 at 50 wt% each. After stirring for 3 hours, the mixture was poured onto a flat glass plate and coated with a doctor blade to produce test pieces with thicknesses of 50 μm, 500 μm, and 2 mm. The surface of the plastic films produced was subjected to corona treatment (3DT Multidyne, DC 24V).

[0087] At this time, in Comparative Example 2 using Synthesis Example 3, no film was formed due to breakage, and in Comparative Examples 1 and 3 using Synthesis Example 2 and Synthesis Example 4, no film was formed because it was not fixed and thus had flow characteristics.

[0088] [Example 2 and Comparative Examples 4 to 6] Manufacturing of hydrophilic plastic films

[0089] Plastic films were manufactured by mixing the above-described Synthetic Example 1 with polycarbonate (PC) resin (Example 2), and plastic films were manufactured by replacing Synthetic Example 1 with Synthetic Examples 2 to 4 (Comparative Examples 4 to 6). The polycarbonate (PC) was PC-1220 from Rakuten Chemical Co., Ltd., which was prepared by dissolving it in toluene at 50 wt%. The prepared polycarbonate (PC) toluene mixture was mixed with the substances obtained by Synthetic Examples 1 to 4 at 50 wt% and stirred. After stirring for 3 hours, the mixture was poured onto a flat glass plate and coated with a doctor blade to produce test pieces with thicknesses of 50 μm, 500 μm, and 2 mm. The surface of the plastic films manufactured above was subjected to corona treatment (3DT Multidyne, DC 24V).

[0090] At this time, in Comparative Example 5 using Synthesis Example 3, no film was formed because of breakage, and in Comparative Examples 4 and 6 using Synthesis Examples 2 and 4, no film was formed because it was not fixed and thus had flow characteristics.

[0091] [Examples 3 to 4] Manufacturing of hydrophilic plastic films

[0092] 50g of the structure of chemical formula 3 obtained by synthesis example 1 above was dissolved in methyl isobutyl ketone at 50wt% to prepare 100g of composition. Then, 5g of ultraviolet (UV) initiator (irgacure-250 (BASF)) was added to the 100g prepared composition and stirred for 10 minutes to prepare a photocurable resin composition. The prepared photocurable resin composition was coated onto 2mm thick polymethyl methacrylate (PMMA) (SPOLYTECH) sheets (Example 3) and polycarbonate (PC) (SPOLYTECH) sheets (Example 4), and after evaporating the solvent in a drying oven at 85°C, it was irradiated with 1J / cm using an ultraviolet (UV) device. 2 The coating film is formed by ultraviolet (UV) light. The coating thickness is 20 μm. The surface of the plastic film manufactured above is then subjected to corona treatment (3DT Multidyne, DC24V).

[0093] [Examples 5 to 8] Manufacturing of hydrophilic plastic films

[0094] Before corona treatment, the sheets and films produced by Examples 1 to 4 were respectively immersed in an ethanol aqueous solution containing 1 kg of KOH, 1 kg of ethanol and 1 kg of distilled water and subjected to surface treatment for 20 minutes. Then, they were washed three times with distilled water and dried in an oven at 100°C for 10 minutes to produce Examples 5 to 8.

[0095] [Experimental Example 1] Changes in water contact angle (comparison of hydrophilicity)

[0096] The changes in the water contact angle of Examples 1 to 8, which underwent corona treatment, were measured over 60 days, and the results are shown in Table 1 below. Changes in ordinary glass (i.e., soda-lime glass), pure polycarbonate (PC), and polymethyl methacrylate (PMMA) resin were also measured simultaneously.

[0097] [Table 1]

[0098]

[0099] Referring to Table 1 above, it can be confirmed that Examples 1 to 8 of the present invention have the same degree of surface hydrophilicity as glass.

[0100] [Test Evaluation] Comparison of physical properties of silsesquioxane polymers with different n / m ratios

[0101] The physical properties of silsesquioxane polymers with different n / m ratios, such as transparency, adhesion, post-coating strength, and flexibility, were compared and evaluated. The results are shown in Table 2 below.

[0102] [Table 2]

[0103]

[0104]

[0105] Referring to Table 2 above, it can be seen that in the tests where the n / m ratio of the above silsesquioxane polymers meets the requirements of 0.1 to 10, the physical properties such as transparency, adhesion, post-coating strength, and flexibility are more excellent.

[0106] [Test Evaluation] The non-reaction of silsesquioxane polymers with polymethyl methacrylate (PMMA) or polycarbonate (PC) Comparison of hydrophilization at the same mixing ratio

[0107] Thin films were prepared by mixing the aforementioned silsesquioxane polymer with polymethyl methacrylate (PMMA) or polycarbonate (PC) in the mixing ratios described in Table 3 below. The degree of hydrophilicity induced by corona treatment was evaluated in the prepared films, and the results are shown in Table 3 below.

[0108] [Table 3]

[0109]

[0110]

[0111]

[0112] Referring to Table 3 above, the mixing ratio of the above silsesquioxane polymer with polymethyl methacrylate (PMMA) or polycarbonate (PC) meets the test requirements of 1:9 to 9:1, resulting in a better degree of hydrophilicity and a longer duration of surface hydrophilicity. Moreover, as can be seen from Table 1 above, it has the same degree of hydrophilicity as glass.

Claims

1. A synthetic resin coating composition, characterized in that, Include: Silsesquioxane polymers contain repeating units of the following chemical formula 1 and chemical formula 2; Synthetic resins; and solvent, The above-mentioned silsesquioxane polymers include polymers with the following chemical formula 3. [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] In the above chemical formulas 1 to 3, R1 is independently hydrogen, deuterium, halogen, amino, epoxy, cyclohexylepoxy, (meth)acryloyl, hydroxyl, thiol, isocyanate, nitrile, nitro, alkyl with 1 to 40 carbon atoms, alkenyl with 2 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, cycloalkyl with 3 to 40 carbon atoms, heterocycloalkyl with 3 to 40 carbon atoms, aryl with 6 to 40 carbon atoms, heteroaryl with 3 to 40 carbon atoms, aralkyl with 3 to 40 carbon atoms, aryloxy with 3 to 40 carbon atoms, or arylthiol with 3 to 40 carbon atoms. R2 is independently hydrogen, deuterium, halogen, isocyanate group, alkyl group with 1 to 40 carbon atoms, alkenyl group with 2 to 40 carbon atoms, cycloalkyl group with 3 to 40 carbon atoms, heterocycloalkyl group with 3 to 40 carbon atoms, aryl group with 6 to 40 carbon atoms, heteroaryl group with 3 to 40 carbon atoms, aralkyl group with 3 to 40 carbon atoms, or epoxy group with 2 to 40 carbon atoms. n and m are each independent integers from 1 to 100,000, and n / m is from 0.1 to 10.

2. The synthetic resin coating composition according to claim 1, characterized in that: The aforementioned synthetic resins contain organic polymers.

3. The synthetic resin coating composition according to claim 1, characterized in that: The above-mentioned synthetic resin and silsesquioxane polymer are mixed in a weight ratio of 1:9 to 9:

1.

4. A synthetic resin substrate, characterized in that, Include: Silsesquioxane polymers comprising repeating units of chemical formula 1 and chemical formula 2; and Synthetic resins The above-mentioned silsesquioxane polymers include polymers with the following chemical formula 3, [chemical formula 1]. [Chemical Formula 2] [Chemical Formula 3] In the above chemical formulas 1 to 3, R1 is independently hydrogen, deuterium, halogen, amino, epoxy, cyclohexylepoxy, (meth)acryloyl, hydroxyl, thiol, isocyanate, nitrile, nitro, alkyl with 1 to 40 carbon atoms, alkenyl with 2 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, cycloalkyl with 3 to 40 carbon atoms, heterocycloalkyl with 3 to 40 carbon atoms, aryl with 6 to 40 carbon atoms, heteroaryl with 3 to 40 carbon atoms, aralkyl with 3 to 40 carbon atoms, aryloxy with 3 to 40 carbon atoms, or arylthiol with 3 to 40 carbon atoms. R2 is independently hydrogen, deuterium, halogen, isocyanate group, alkyl group with 1 to 40 carbon atoms, alkenyl group with 2 to 40 carbon atoms, cycloalkyl group with 3 to 40 carbon atoms, heterocycloalkyl group with 3 to 40 carbon atoms, aryl group with 6 to 40 carbon atoms, heteroaryl group with 3 to 40 carbon atoms, aralkyl group with 3 to 40 carbon atoms, or epoxy group with 2 to 40 carbon atoms. n and m are each independent integers from 1 to 100,000, and n / m is from 0.1 to 10.

5. The synthetic resin substrate according to claim 4, characterized in that: The aforementioned synthetic resins contain organic polymers.

6. The synthetic resin substrate according to claim 4, characterized in that: The above-mentioned synthetic resin and silsesquioxane polymer are mixed in a weight ratio of 1:9 to 9:

1.

7. The synthetic resin substrate according to claim 4, characterized in that: The synthetic resin substrate also includes a fluorine coating layer on top.

8. A synthetic resin substrate, characterized in that, include: Synthetic resin substrate; as well as A coating layer formed on one or more sides of the aforementioned synthetic resin substrate and cured with a synthetic resin coating composition, wherein the synthetic resin coating composition comprises a silsesquioxane polymer and a solvent, or comprises a silsesquioxane polymer, a synthetic resin, and a solvent, wherein the silsesquioxane polymer comprises repeating units of the following chemical formulas 1 and 2. The above-mentioned silsesquioxane polymers include polymers with the following chemical formula 3. [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] In the above chemical formulas 1 to 3, R1 is independently hydrogen, deuterium, halogen, amino, epoxy, cyclohexylepoxy, (meth)acryloyl, hydroxyl, thiol, isocyanate, nitrile, nitro, alkyl with 1 to 40 carbon atoms, alkenyl with 2 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, cycloalkyl with 3 to 40 carbon atoms, heterocycloalkyl with 3 to 40 carbon atoms, aryl with 6 to 40 carbon atoms, heteroaryl with 3 to 40 carbon atoms, aralkyl with 3 to 40 carbon atoms, aryloxy with 3 to 40 carbon atoms, or arylthiol with 3 to 40 carbon atoms. R2 is independently hydrogen, deuterium, halogen, isocyanate group, alkyl group with 1 to 40 carbon atoms, alkenyl group with 2 to 40 carbon atoms, cycloalkyl group with 3 to 40 carbon atoms, heterocycloalkyl group with 3 to 40 carbon atoms, aryl group with 6 to 40 carbon atoms, heteroaryl group with 3 to 40 carbon atoms, aralkyl group with 3 to 40 carbon atoms, or epoxy group with 2 to 40 carbon atoms. n and m are each independent integers from 1 to 100,000, and n / m is from 0.1 to 10.

9. The synthetic resin substrate according to claim 8, characterized in that: The synthetic resin substrate also includes a fluorine coating layer on top.

Images