KR20200082946A - Synthetic resin coating composition and method of manufacturing synthetic resin substrate using the same - Google Patents

Abstract

The present invention relates to a synthetic resin coating composition and a method of manufacturing a synthetic resin substrate by using the same, capable of implementing hydrophilic properties on a surface of conventional plastic materials for a long time. According to the present invention, the synthetic resin coating composition includes: silsesquioxane polymer including a repeating unit represented by Chemical formula 1 and Chemical formula 2; and a solvent.

Description

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

The present invention relates to a synthetic resin coating composition and a method for manufacturing a synthetic resin substrate using the same, and more particularly, to a synthetic resin coating composition used in the scientific and industrial fields and a method for manufacturing a synthetic resin substrate using the same.

Recently, the need for the development of plastic films and sheets for glass replacement in the scientific and industrial fields is gradually emerging. The plastic material originates from the demand for alternative development by consumers who want to use the following characteristics.

The synthetic resin forming the plastic can be transparent to a level comparable to glass according to the manufacturing method, and is very light compared to glass and has excellent strength characteristics to withstand impact, and the implementation of color is free compared to glass, so from simple glass replacement It can have scalability to various application fields from interior materials. If the advantage of such a plastic material is properly used, it can be actively used as a material for gradually replacing glass.

However, the transparent materials of synthetic resins forming plastics have a disadvantage that it is difficult to induce the surface energy to a high level because the surface is more hydrophilic than glass. Due to these shortcomings, plastic materials have the following limitations on the surface (external) treatment that determines the value of the product. (Hydrophilization = improvement of spreading property of coating solution = improvement of adhesion of substrate and reduction of coating defect)

Since the synthetic resin forming the plastic has a limitation in the spreading properties of the silver coating solution, the application of chemical products used for imparting surface properties such as fingerprint, fingerprint reduction, and improved slip properties is very complicated and limited, low refractive index, diffuse reflection , It is difficult to achieve high level of appearance (vitrification) because coating materials that determine optical properties such as high/low reflection cannot induce strong adhesion at the interface. In addition, the application of surface coating agents that enhance physical properties such as hardness and scratches is limited.

For this reason, the synthetic resin forming the plastic has excellent advantages, but has not been actively utilized as a substitute in various fields where glass is applied. Therefore, many scientific/technical approaches have been made to overcome the disadvantages of the synthetic resin base forming these plastics.

According to Patent Publication No. 10-2018-0100985, after the plasma treatment on the plastic substrate in order to solve the above problems, a primer coating agent having hydrophilicity was treated to maintain the hydrophilic properties for a long time, and a fluorine-based coating agent was applied to the upper portion to prevent fingerprints. It was made possible to express an improvement in properties and slip properties. In addition, according to Patent Publication No. 10-2007-0034517, a coating solution capable of inducing hydrophilic properties can be prepared with a coating solution comprising a hydrophilic binder comprising a photocatalytic material and a hydrolyzed organosilicate to produce a substrate having hydrophilic properties. Showed.

However, there are some problems to overcome the problems through the above methods.

The introduction of the hydrophilic coating layer using the primer suggests a complicated process of applying a plasma method selected as a specific gas type to the plastic substrate, and then immediately surface hydrophilizing treatment, then proceeding with the primer coating and immediately coating the desired functional coating agent again. In the above process, the hydrophilic surface made of instantaneous plasma treatment on the plastic substrate has a very short holding time, and is expected to be restored to its original surface energy value within minutes to hours. Therefore, it is necessary to treat the primer coating very quickly or continuously, and when the treatment time is changed, the adhesion between the primer layer and the substrate may not be secured.

In addition, a hydrophilic coating agent including a photocatalyst and a silicate cannot induce a positive chemical bond with a binder to be used, and thus it is difficult to secure a high surface hardness such as glass, scratch resistance, and the like, and thus many problems are expected in practical application.

Accordingly, it is an object of the present invention to provide a synthetic resin coating composition capable of realizing hydrophilic properties for a long time on the surface of ordinary plastic materials without a separate primer or cumbersome continuous process and a method of manufacturing a synthetic resin substrate using the same.

Another object of the present invention is to provide a synthetic resin coating composition and a synthetic resin substrate manufacturing method using the same, which can implement the functional coating layer used on the surface of the existing glass to the same level and can be utilized in various applications to replace the glass. will be.

In order to achieve the above object, the present invention provides a synthetic resin coating composition comprising a silsesquioxane polymer and a solvent comprising repeating units represented by the following Chemical Formulas 1 and 2.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2, R1 is each independently hydrogen, deuterium, halogen, amine group, epoxy group, cyclohexyl epoxy group, (meth)acrylic group, hydroxy group, silol group, isocyanate group, nitrile group, nitro group, Alkyl group having 1 to 40 carbon atoms, alkenyl group having 2 to 40 carbon atoms, alkoxy group having 1 to 40 carbon atoms, cycloalkyl group having 3 to 40 carbon atoms, heterocycloalkyl group having 3 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, carbon number 3 To 40 heteroaryl group, 3 to 40 aralkyl group, 3 to 40 aryloxy group, or 3 to 40 arylthio group, R2 are each independently hydrogen, deuterium, halogen, isocyanate group, Alkyl group having 1 to 40 carbon atoms, alkenyl group having 2 to 40 carbon atoms, cycloalkyl group having 3 to 40 carbon atoms, heterocycloalkyl group having 3 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, heteroaryl group having 3 to 40 carbon atoms, carbon number It is an aralkyl group of 3 to 40 or an epoxy group of 2 to 40 carbon atoms, n and m are each independently an integer of 1 to 100,000, and n/m is 0.1 to 10.

In addition, the present invention provides a synthetic resin coating composition comprising a silsesquioxane polymer including a repeating unit represented by Formula 1 and Formula 2, a synthetic resin, and a solvent.

In addition, the present invention provides a synthetic resin base material comprising a synthetic resin coating composition comprising a silsesquioxane polymer comprising a repeating unit represented by Formula 1 and Formula 2 and a synthetic resin.

In addition, the present invention is a synthetic resin substrate and a silsesquioxane polymer and a repeating unit represented by the following Chemical Formula 1 and Chemical Formula 2 containing a repeating unit represented by Chemical Formula 1 and Chemical Formula 2 on one or more surfaces of the synthetic resin substrate. It provides a synthetic resin substrate comprising a coating layer cured synthetic resin coating composition comprising a silsesquioxane polymer, a synthetic resin and a solvent comprising a.

The synthetic resin coating composition according to the present invention and the method of manufacturing a synthetic resin substrate using the same can realize long-term hydrophilic properties on the surfaces of ordinary plastic materials without a separate primer or cumbersome continuous process, and the same functional coating layer used on the surface of existing glass Can be implemented at a level.

1 is a cross-sectional view of a synthetic resin molded article according to an embodiment of the present invention.
Figure 2 is a cross-sectional view of a synthetic resin molded article according to another embodiment of the present invention.
3 is a cross-sectional view of a synthetic resin molded article having hydrophilicity according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail.

As an embodiment of the synthetic resin coating composition according to the present invention, it includes a silsesquioxane polymer and a solvent including repeating units represented by the following Chemical Formulas 1 and 2.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2, R1 is each independently hydrogen, deuterium, halogen, amine group, epoxy group, cyclohexyl epoxy group, (meth)acrylic group, hydroxy group, silol group, isocyanate group, nitrile group, nitro group, Alkyl group having 1 to 40 carbon atoms, alkenyl group having 2 to 40 carbon atoms, alkoxy group having 1 to 40 carbon atoms, cycloalkyl group having 3 to 40 carbon atoms, heterocycloalkyl group having 3 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, carbon number 3 It is a heteroaryl group of 40 to 40, an aralkyl group of 3 to 40 carbon atoms, an aryloxy group of 3 to 40 carbon atoms or an arylcyol group of 3 to 40 carbon atoms, and R2 are each independently hydrogen, deuterium, halogen, isocyanate group, carbon number Alkyl group of 1 to 40, alkenyl group of 2 to 40 carbon atoms, cycloalkyl group of 3 to 40 carbon atoms, heterocycloalkyl group of 3 to 40 carbon atoms, aryl group of 6 to 40 carbon atoms, heteroaryl group of 3 to 40 carbon atoms, carbon number 3 It is an aralkyl group of 40 to 40 or an epoxy group of 2 to 40 carbon atoms, n and m are each independently an integer of 1 to 100,000, and n/m is 0.1 to 10. If the value of n/m is less than 0.1, it is oily and peels off from the substrate (for example, a plastic substrate), and if it exceeds 10, it is difficult to use by brittle.

In Chemical Formulas 1 and 2, the alkyl group having 1 to 40 carbon atoms may specifically be a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, pentyl group, hexyl group, or the like. , The aryl group may be a phenyl group. In Chemical Formula 2, R2 may be hydrogen, a methyl group, an ethyl group, or a propyl group, and -OR2 includes oxygen to control the solubility, dispersibility, and compatibility of the silsesquioxane polymer.

If necessary, the R1 and R2 may be substituted with substituents such as deuterium, halogen, amino group, vinyl group, (meth)acrylic group, cyol group, isocyanate group, nitrile group, nitro group, and the like. Specifically, R1 may have a reactive substituent such as an amino group, a (meth)acrylic group, a hydroxy group, a silol group, or a reactive group such as a vinyl group or an epoxy group, and may be, for example, an alkyl group having the reactive substituent or functional group. , By this reactive substituent or functional group, the silsesquioxane polymer of the present invention can be crosslinked. Examples of R1 having the reactive substituent or functional group include (meth)acryloxypropyl group, 2-(3,4-epoxycyclohexyl)ethyl group, and the like.

When the silsesquioxane polymer of the present invention has a reactive substituent or a reactive functional group, the ratio of R1 having a reactive substituent or a reactive functional group with respect to total R1 is, for example, 10 to 100%, specifically 50 to 100% to be. If the content of the reactive substituent or functional group is too small, there is a problem in that the crosslinking power of the silsesquioxane polymer is low, the hardness of the coating film to be finally formed decreases, or the crosslinking of the silsesquioxane polymer takes a long time.

The silsesquioxane polymer may include a polymer represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3, R1, R2, n and m are as defined in Chemical Formulas 1 and 2.

The silsesquioxane polymer represented by Chemical Formula 3 has a random structure, and both R ₁ and OR ₂ may be the same organic functional group, and in some cases, they may be substituted with different kinds, and the silsesqui The weight average molecular weight of the oxane polymer is 2,000 To 100,000.

In Formula 3, the compatibility of the synthetic resin can be controlled by adjusting the amount of introduction of the OR ₂ group. The Si-O-Si group included in Chemical Formula 3 is induced to Si-OH or Si-O when treated in plasma, corona, strong salt or strong acid, and the OR ₂ groups are C-OH and carboxyl grup (eg For example, CC=O, etc.), and the like, so that hydrophilic properties can be maintained for a long time in the same way as glass. Therefore, it is possible to manufacture a plastic sheet and/or film having a long-term hydrophilicity similar to glass.

The solvent is an organic solvent, which helps uniform mixing of the synthetic resin and the silsesquioxane polymer according to the present invention, for example, water (distilled water), methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, etc. Alcohols, acetone, ketones such as methyl (isobutyl) ethyl ketone, glycols such as ethylene glycol, and furan systems such as tetrahydrofuran, dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone. As well as polar solvents, hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acrylonitrile, methylene chloride, octadecylamine, Various solvents such as aniline, dimethyl sulfoxide, and benzyl alcohol may be used, but the present invention is not limited thereto. The content of the solvent includes the rest except for the content of the silicone-based composition.

The silsesquioxane polymer represented by Chemical Formula 3 can be obtained by synthesizing and introducing a repeating unit n and m structure to synthesize a precursor by synthesizing a solvent mixed with distilled water and an alcohol solvent and a chlorosilane monomer. have.

As another embodiment of the synthetic resin coating composition according to the present invention, it includes a silsesquioxane polymer, a synthetic resin and a solvent. The silsesquioxane polymer and solvent are the same as described above.

The synthetic resin is a resin forming a plastic, and may include a commercially available organic polymer. For example, polymethylmethacrylate (PMMA), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (polyethylene terephthalate, PET, PET), poly Polyamides (PA, nylon), polyester (PES), polyvinyl chloride (PVC), polyurethane (polyurethanes, PU), polycarbonate (PC), high hardness polycarbonate (high hardness) PC), polyvinylidene chloride (PVDC), polytetrafluoroethylene (PTFE), polyetheretherketone (polyetheretherketone, PEEK) and polyetherimide (polyetherimide, PEI), and the like. The synthetic resin may be present in the form of chips (pellets).

The silsesquioxane polymer comprising the synthetic resin forming the plastic and the repeating units represented by Formula 1 and Formula 2, specifically, the silsesquioxane polymer represented by Formula 3 is 1:9 to 9:1 It is preferred to be mixed at a ratio of, and when the ratio is satisfied, there is a property that the durability of the surface hydrophilicity of the synthetic resin (for example, plastic, etc.) is long lasting.

The present invention includes a synthetic resin substrate whose hydrophilicity is maintained for a long time. 1 is a cross-sectional view of a synthetic resin substrate (eg, plastic film and resin) according to an embodiment of the present invention. The synthetic resin substrate according to FIG. 1 is specifically cured by a synthetic resin coating composition comprising a synthetic resin 20 and a silsesquioxane polymer 10 comprising repeating units represented by Chemical Formulas 1 and 2 A synthetic resin substrate may be formed, and more specifically, a synthetic resin 20 and a silsesquioxane polymer 10 containing repeating units represented by Chemical Formulas 1 and 2 may be mixed and then extruded to form. Can.

2 is a cross-sectional view of a synthetic resin substrate (eg, plastic film and resin) according to another embodiment. The synthetic resin substrate according to FIG. 2, specifically, may form a synthetic resin substrate by forming a coating layer with the synthetic resin coating composition 10 on one or more surfaces of the synthetic resin 20 substrate, and more specifically, synthetic resin (20) A synthetic resin substrate is formed by including a coating layer using the silsesquioxane polymer or the synthetic resin coating composition 10 containing the synthetic resin and the silsesquioxane polymer on one or more surfaces of the substrate and the synthetic resin substrate. can do.

The synthetic resin may be a known plastic material, for example, polyethylene terephthalate (PET) resin, polycarbonate-based (PC) resin, poly (meth) acrylic resin (for example, poly (methyl methacrylate)) Resin (PMMA)), ethylene vinyl acetate (EVA) resin, polyester resin, polyamide resin, polyimide resin, polyamide imide resin, polyarylphthalate resin, silicone resin, polysulfone resin, Polyphenylene sulfide resin, polyether sulfone resin, polyurethane resin, acetal resin, cellulose resin (for example, triacetyl cellulose (TAC) resin), acrylonitrile-styrene copolymer (AS resin), Acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, and the like.

The coating layer is formed by curing the synthetic resin coating composition according to the present invention. The synthetic resin coating composition is a silsesquioxane polymer and a solvent containing a repeating unit represented by Formula 1 and Formula 2 or a silsesquioxane polymer comprising a repeating unit represented by Formula 1 and Formula 2, a synthetic resin And solvents.

Plasma or corona treatment on the surface of the synthetic resin substrate according to the present invention, or strong acid wet. When a strong base treatment is performed, the adhesion of the synthetic resin and the silsesquioxane polymer including the repeating units represented by Chemical Formulas 1 and 2 can be enhanced, and Si-O- of the silsesquioxane polymer is increased. Since the Si structure is derived from Si-OH or Si-O, or the OR ₂ group is derived from a hydrophilic functional group such as C-OH and carboxyl grup (for example, CC=O, etc.), it may have the same hydrophilicity as glass. . For this reason, the functional coating layer used on the surface of the existing glass can be implemented at the same level, and can be utilized in various applications to replace the glass.

If necessary, the synthetic resin substrate may further include a fluorine-based coating layer. By forming the fluorine-based coating layer, water repellency can be maintained for a longer period, and the fluorine-based coating layer is trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxy. Silane, nonafluorobutylethyltrimethoxysilane, nonafluorobutylethyltriethoxysilane, nonafluorhexyltrimethoxysilane, nonafluorhexyltriethoxysilane, heptadecafluordecyltrimethoxy silane, heptadecafluordecyltri Ethoxysilane, heptatecafluordecyl triisopropylsilane, 3-trimethoxysilylpropylpentadecafluoroctate, 3-triethoxysilylpropylpentadecafluoroctate, 3-trimethoxysilylpropylpentadecafluorooctic Amide, 3-triethoxysilylpropylpentadecafluorooctamide, 2-trimethoxysilylethylpentadecafluordecylsulfide, 2-triethoxysilylethylpentadecafluordecylsulfide, pentafluorophenyltrimethoxysilane , Pentafluorphenyltriethoxysilane, 4-(perfluorotoryl)trimethoxysilane, 4-(perfluorotoryl)triethoxysilane, dimethoxybis(pentafluorophenyl)silane, diethoxybis(4-penta Fluoratoryl)silane and the like.

The present invention includes a method for producing a synthetic resin substrate that maintains hydrophilicity for a long time. The method of manufacturing the synthetic resin substrate can realize long-term hydrophilicity on the surface of ordinary plastic materials without a separate primer or cumbersome continuous process, and the synthetic resin substrate includes, for example, plastic sheet, plastic film, plastic substrate, and extrusion. Alternatively, injection molding or the like may include plastic molded products manufactured by various methods.

3 is a cross-sectional view of a synthetic resin substrate having hydrophilicity according to an embodiment of the present invention, specifically, plasma or corona treatment or strong salts to the plastic films and resins according to FIGS. 1 and 2. It is a cross-sectional view of a plastic film and a resin having hydrophilicity 30 by treating the surface with wet water in a strong acid.

Specifically, a base material (formed body) is prepared by adding silsesquioxane having heat resistance to an organic polymer that is a base material of the synthetic resin base material (formed body), and simple plasma, corona, or wet treatment is performed on the base material (formed body). It includes a method of manufacturing a synthetic resin substrate that maintains hydrophilicity over a long period of time, such as glass. More specifically, after mixing a synthetic resin and a synthetic resin coating composition comprising a silsesquioxane polymer (10) comprising a repeating unit represented by Chemical Formulas 1 and 2, extruded and cured, the synthetic resin substrate And manufacturing a synthetic resin substrate having hydrophilicity by irradiating plasma or corona on the surface of the synthetic resin substrate, or treating a strong acid or a strong base with wet.

The thickness of the formed synthetic resin substrate (eg, plastic sheet or film) may vary depending on the processing method, and performance is not particularly limited depending on the thickness. The method of manufacturing the synthetic resin substrate may have hydrophilicity on its own surface of the synthetic resin substrate (molded product) by mixing and extruding the synthetic resin coating composition without a coating process.

According to another embodiment of the method for manufacturing a synthetic resin substrate having long-term hydrophilicity according to the present invention, the synthetic resin coating comprising a silsesquioxane polymer comprising the repeating units represented by Chemical Formulas 1 and 2 on a synthetic resin substrate Coating with a composition and treating the plasma or corona with the coated synthetic resin substrate, or wet acid. The method further includes forming a synthetic resin substrate having hydrophilicity by treating the strong base. Specifically, a coating layer may be formed by spraying or applying a synthetic resin coating composition comprising a silsesquioxane polymer including the repeating units represented by Chemical Formulas 1 and 2 and an organic solvent on the synthetic resin substrate, and the coating layer It may further include the step of removing the organic solvent through a high temperature heat treatment.

In addition, the silsesquioxane polymer containing the repeating units represented by Chemical Formula 1 and Chemical Formula 2 can be used as a coating composition by mixing with a conventional coating agent, and if necessary, may further include a photoinitiator.

The coating can sufficiently impart high hardness, scratch resistance and hydrophilicity to the plastic surface even once. The thickness of the coating layer is 50nm to 100um. When the thickness of the coating layer is less than 50 μm, when the corona/plasma process, which is a post-coating process, may weaken the adhesion interface between the substrate and the coating surface, a coating surface may be cracked when the coating thickness is greater than 100 μm.

In the method of imparting hydrophilicity to the synthetic resin substrate, the synthetic resin molded article is treated with plasma or corona, or wetted with strong acid. When a strong base treatment is performed, the adhesion of the synthetic resin and the silsesquioxane polymer including the repeating units represented by Chemical Formulas 1 and 2 can be enhanced, and Si-O- of the silsesquioxane polymer is increased. Since the Si structure is derived from Si-OH or Si-O, or the OR ₂ group is derived from a hydrophilic functional group such as C-OH and carboxyl grup (for example, CC=O, etc.), it may have the same hydrophilicity as glass. . For this reason, the functional coating layer used on the surface of the existing glass can be implemented at the same level, and can be utilized in various applications to replace the glass. If necessary, water repellency can be maintained for a longer period of time by applying a fluorine-based coating agent to the synthetic resin substrate having hydrophilicity.

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited by the following examples.

[Synthesis Example 1] Preparation of silsesquioxane polymer

In a dried flask equipped with a cooling tube and a stirrer, 12 g of distilled water and 50 g of methanol were prepared by mixing, and 200 g of 3-(Trichlorosilyl)propyl methacrylate was slowly added dropwise over 10 minutes. At this time, the temperature was maintained at -4 degrees. After stirring for 20 minutes, 500 g of toluene was additionally added dropwise, and the temperature was raised to room temperature to further agitate for 10 minutes. While the reaction was being prepared, Na ₂ CO ₃ A 20% by weight aqueous solution was separately prepared, and 5 g was added dropwise to the above reactor at once. Subsequently, the temperature was increased to 50 degrees to conduct a condensation reaction for 1 day.

The obtained structure and solvent mixture represented by the formula (1) were obtained by removing the toluene layer under vacuum and depressurizing to obtain a toluene layer after performing layer separation and purification of water and toluene twice and confirming that the pH was neutral.

As a result of measuring the molecular weight, it was confirmed that silsesquioxane having a linear structure such as the structure represented by Chemical Formula 1 has a molecular weight in terms of 3,000 styrene, and it was confirmed that no unreacted monomer exists.

As a result of measuring the decomposition temperature through TGA analysis, the residual ratio of alkoxy was 1 wt%, and as a result of measurement through 1H-NMR, it was confirmed that the ratio of n/m had a value of 0.5.

[Synthesis Example 2] Preparation of silsesquioxane polymer

50 g of the material obtained in Synthesis Example 1 was placed in a dried flask equipped with a cooling tube and a stirrer, and replaced with a nitrogen atmosphere for 1 hour, and then 100 g of toluene was slowly added. Then, 50 g of hydrochloric acid aqueous solution was added and the temperature was raised to 50 degrees, followed by stirring very strongly for 3 days.

Subsequently, the layer-separated purification of water and toluene was performed 5 times, and after confirming that the pH was neutral, a toluene layer was obtained to remove all of the toluene under vacuum pressure. As a result of measuring the molecular weight, it was confirmed that the silsesquioxane having a linear structure in which the alkoxy portion was removed from the structure represented by Chemical Formula 1 has a molecular weight in terms of 2,500 styrene, and the alkoxy was used as a method for measuring the decomposition temperature through TGA analysis. It was confirmed that it does not exist and changed to Si-OH. As a result of measurement through 1H-NMR, it was confirmed that the ratio of n/m was not changed at a ratio of 0.5.

[Synthesis Example 3] Preparation of silsesquioxane polymer

To a dried flask equipped with a cooling tube and a stirrer, 5 g of distilled water and 100 g of methanol were prepared by mixing, and 261.61 g of 3-(Trichlorosilyl)propyl methacrylate was slowly added dropwise over 10 minutes. At this time, the temperature was maintained at -4 degrees. After stirring for 50 minutes, 500 g of toluene was additionally added dropwise, and the temperature was raised to room temperature to further agitate for 10 minutes. While the reaction was being prepared, a 20% by weight aqueous solution of KOH was separately prepared, and 5 g was added dropwise to the reactor at once. Thereafter, the condensation reaction was slowly performed at room temperature for 7 days.

The obtained structure and solvent mixture represented by Chemical Formula 1, the layer separation and purification of water and toluene were performed twice, and after confirming that the pH was neutral, a toluene layer was obtained to remove all of the toluene under vacuum pressure. .

As a result of measuring the molecular weight, it was confirmed that it has a molecular weight equivalent to 20,000 styrene, and it was confirmed that no monomer in an unreacted state was present.

As a method for measuring the decomposition temperature through TGA analysis, alkoxy was not present, and it was confirmed that the ratio of n/m was 15 through 1H-NMR and 29Si-NMR analysis.

[Synthesis Example 4] Preparation of silsesquioxane polymer

To a dried flask equipped with a cooling tube and a stirrer, 0.1 g of distilled water and 100 g of methanol were prepared by mixing, and 261.61 g of 3-(Trichlorosilyl)propyl methacrylate was slowly added dropwise over 10 minutes. At this time, the temperature was maintained at -4 degrees. After stirring for 50 minutes, 500 g of toluene was additionally added dropwise, and the temperature was raised to room temperature to further agitate for 10 minutes. While the reaction was being prepared, a 20% by weight aqueous solution of KOH was prepared separately, and 10 g was added dropwise to the reactor at once. Thereafter, the condensation reaction was slowly performed at room temperature for 3 days.

The obtained structure and solvent mixture represented by Chemical Formula 1, the layer separation and purification of water and toluene were performed twice, and after confirming that the pH was neutral, a toluene layer was obtained to remove all of the toluene under vacuum pressure. .

As a result of measuring the molecular weight, it was confirmed that it had a molecular weight equivalent to 30,000 styrene, and it was confirmed that no monomer in an unreacted state was present.

As a result of measuring the decomposition temperature through TGA analysis, the residual rate of alkoxy was 10 wt%, and as a result of measurement through 1H-NMR, it was confirmed that the ratio of n/m had a value of 0.05.

[Example 1 and Comparative Examples 1 to 3] Preparation of hydrophilic plastic film

A plastic film was prepared by mixing the Synthesis Example 1 and a polymethyl methacrylate (PMMA) resin (Example 1), and instead of Synthesis Example 1, Synthesis Examples 2 to 4 were polymethyl methacrylate resins. And mixed to prepare a plastic film (Comparative Examples 1 to 3).

The PMMA is LG IH830, and was prepared by dissolving in toluene at 50 wt%. The prepared PMMA toluene mixed solution and the materials obtained in Synthesis Examples 1 to 4 were mixed and stirred at 50 wt%, respectively. After stirring for 3 hours, the mixed solution was poured into a flat glass, and after the doctor blade coating, specimens of 50 um, 500 um, and 2 mm thickness were prepared. Corona treatment was performed on the prepared plastic film surface (3DT company multidyne, DC24V).

At this time, Comparative Example 2 using the Synthesis Example 3 did not form a film, and Comparative Examples 1 and 3 using the Synthesis Examples 2 and 4 were not fixed and had a flowing property, so that a film was not formed. .

[Example 2 and Comparative Examples 4 to 6] Preparation of hydrophilic plastic film

A plastic film was prepared by mixing the Synthesis Example 1 and a polycarbonate (PC, polycarbonate) resin (Example 2), and instead of the Synthesis Example 1, a Synthesis Example 2 to 4 was used to prepare a plastic film (Comparative Example). 4 to 6). The PC is PC-1220 of Lotte Chemical, and was prepared by dissolving in toluene at 50 wt%. The prepared PC toluene mixed solution and the materials obtained in Synthesis Examples 1 to 4 were mixed and stirred at 50 wt%, respectively. After stirring for 3 hours, the mixed solution was poured into a flat glass, and after the doctor blade coating, specimens of 50 um, 500 um, and 2 mm thickness were prepared. Corona treatment was performed on the prepared plastic film surface (3DT company multidyne, DC24V).

At this time, Comparative Example 5 using Synthesis Example 3 did not form a film, and Comparative Examples 4 and 6 using Synthesis Examples 2 and 4 were not fixed and had a flowing property, so that a film was not formed.

[Examples 3 to 4] Preparation of hydrophilic plastic film

50 g of the structure of Formula 1 obtained in Synthesis Example 1 was dissolved in methyl isobutyl ketone at 50 wt% to prepare a composition of 100 g. Thereafter, 5 g of a UV initiator irgacure-250 (BAST) was added to 100 g of the prepared composition and stirred for 10 minutes to prepare a photocurable resin composition. The prepared photocurable resin composition was applied to a 2 mm thick PMMA sheet (Example 3) and a PC sheet (Example 4), and the solvent was evaporated in a drying oven at 85° C., followed by UV The coating film was formed by irradiating UV of 1 J/cm ² using equipment. At this time, the coating thickness was 20 um. Corona treatment was performed on the prepared plastic film surface (3DT company multidyne, DC24V).

[Examples 5 to 8] Preparation of hydrophilic plastic film

The sheets and films prepared in Examples 1 to 4 were taken before corona treatment, respectively, placed in an alcohol aqueous solution containing 1 kg of KOH, 1 kg of ethyl alcohol, and 1 kg of distilled water, and after 20 minutes of surface treatment, washed three times with distilled water and washed in a 100° C. oven. Examples 5 to 8 were prepared by drying for 10 minutes.

[Experimental Example 1] Change in water contact angle (comparison with hydrophilicity)

The changes in the water contact angle of the corona-treated Examples 1 to 8 were measured for 60 days and are shown in Table 1 below. At this time, changes in soda lime glass, which is a general glass, and pure PC and PMMA resin were also measured.

Sample name Water contact angle after corona treatment (°) Before treatment Immediately after treatment 5 days later 10 days later 20 days later 30 days later 40 days later 50 days later 60 days later Example 1
(Formula 1/PMMA mixed film)
+ Corona 90 degrees 10 degrees or less 35 35 35 35 35 35 35 Example 2
(Formula 1/PC mixed film)
+ Corona 85 degrees 10 degrees or less 35 35 35 35 35 35 35 Example 3
(Formula 1/PMMA coating film)
+ Corona 100 degrees 10 degrees or less 35 35 35 35 35 35 35 Example 4
(Formula 1 / PC coating film)
+ Corona 105 degrees 10 degrees or less 35 35 35 35 35 35 35 Example 5
(Formula 1/PMMA mixed film)
+KOH alcohol aqueous solution 90 degrees 10 degrees or less 30 33 35 35 38 38 38 Example 6
(Formula 1/PC mixed film)
+KOH alcohol aqueous solution 85 degrees 10 degrees or less 30 33 35 35 38 38 38 Example 7
(Formula 1/PMMA coating film)
+KOH alcohol aqueous solution 100 degrees 10 degrees or less 30 33 35 35 38 38 38 Example 8
(Formula 1 / PC coating film)
+KOH alcohol aqueous solution 105 degrees 10 degrees or less 30 33 35 35 38 38 38 PMMA 75 degrees 10 degrees or less 67 70 75 75 75 75 75 PC 70 degrees 10 degrees or less 65 70 70 70 70 70 70 Glass 50 degrees 10 degrees or less 30 35 35 35 35 35 35

Referring to Table 1, it was confirmed that Examples 1 to 8 according to the present invention have the same surface hydrophilization as glass.

[Experimental Evaluation] Comparison of physical properties of n-m ratio of silsesquioxane polymer

Physical properties such as transparency, adhesion, strength after coating, and flexibility according to the ratio of n/m of the silsesquioxane polymer were compared and evaluated, and the results are shown in Table 2 below.

shape n/m transparency Adhesion Surface hardness flexibility PMMA/
SSQ single coating 0.1 ○ ○ 8H ○ PMMA/
SSQ single coating One ○ ○ 8H ○ PMMA/
SSQ single coating 5 ○ ○ 9H ○ PMMA/
SSQ single coating 10 ○ ○ 9H △ PC/
SSQ single coating 0.1 ○ ○ 4H ○ PC/SSQ single coating One ○ ○ 4G ○ PC/
SSQ single coating 5 ○ ○ 6 ○ PC/
SSQ single coating 10 ○ ○ 7 △ PMMA/
Synthetic coating 0.1 ○ ○ 6 ○ PMMA/
Synthetic coating One ○ ○ 6 ○ PMMA/
Synthetic coating 5 ○ ○ 7 ○ PMMA/
Synthetic coating 10 ○ ○ 8 ○ PC/synthetic coating 0.1 ○ ○ 4 ○ PC/
Synthetic coating One ○ ○ 5 ○ PC/
Synthetic coating 5 ○ ○ 5 ○ PC/
Synthetic coating 10 ○ ○ 6 ○ PMMA/
SSQ single coating 0.01 ○ X -(Not available) ○ PMMA/SSQ single coating n only △ X -(fracture) X PMMA/
SSQ single coating 11 △ X -(fracture) X PC/
SSQ single coating 0.01 ○ X -(Not available) ○ PC/
SSQ single coating n only △ X -(fracture) X PC/
SSQ single coating 11 △ X -(fracture) X PMMA/
Synthetic coating m only ○ X -(Not available) ○ PMMA/
Synthetic coating n only △ X -(fracture) X PMMA/synthetic coating 11 △ X -(fracture) X PC/
Synthetic coating m only ○ X -(Not available) ○ PC/
Synthetic coating n only △ X -(fracture) X PC/
Synthetic coating 11 △ X -(fracture) X

Referring to Table 2, it can be seen that an experiment in which the ratio of n/m of the silsesquioxane polymer satisfies 0.1 to 10 has good physical properties such as transparency, adhesion, strength after coating, and flexibility.

[Experimental Evaluation] Comparison of hydrophilization according to the mixing ratio of silsesquioxane polymer and PMMA or PC

The mixing ratio of the silsesquioxane polymer and PMMA or PC was mixed at the mixing ratio shown in Table 3 to prepare a film. The prepared film was compared and evaluated for the degree of hydrophilization that induced hydrophilization through corona treatment, and the results are shown in Table 3 below.

Sample Water contact angle after corona treatment (°) Mixing ratio
(Total = 10) Before treatment Immediately after treatment 5 days later 10 days later 20 days later 30 days later 40 days later 50 days later 60 days later SSQ Synthetic resin One PMMA (9) 85 degrees 10 degrees
Below 38 38 38 38 38 38 38 2 PMMA (8) 85 degrees 10 degrees or less 35 35 35 35 35 35 35 3 PMMA (7) 90 degrees 10 degrees or less 35 35 35 35 35 35 35 4 PMMA (6) 90 degrees 10 degrees or less 35 35 35 35 35 35 35 6 PMMA (4) 100 degrees 10 degrees or less 35 35 35 35 35 35 35 7 PMMA (3) 95 degrees 10 degrees or less 35 35 35 35 35 35 35 8 PMMA (2) 100 degrees 10 degrees or less 37 35 35 35 38 38 38 9 PMMA (1) 105 degrees 10 degrees or less 35 35 35 35 35 35 35 One PC (9) 80 degrees 10 degrees or less 30 35 35 35 35 35 35 2 PC (8) 85 degrees 10 degrees or less 30 30 30 30 30 35 35 3 PC (7) 75 degrees 10 degrees
Below 30 35 35 35 35 35 35 4 PC (6) 80 10 degrees
Below 35 35 35 35 35 35 35 6 PC (4) 80 10 degrees or less 38 38 38 38 38 38 38 7 PC (3) 75 10 degrees or less 35 35 35 35 35 35 35 8 PC (2) 80 10 degrees
Below 33 33 33 33 33 33 33 9 PC (1) 85 10 degrees
Below 35 35 35 35 35 35 35 0 PMMA(10) 75 degrees 10 degrees
Below 67 70 75 75 75 75 75 0.5 PMMA(9.5) 80 degrees 10 degrees
Below 35 45 45 45 45 45 45 9.5 PMMA(0.5) 105 degrees 10 degrees
Below 35 35 35 35 35 35 35 0 PC(10) 70 degrees 10 degrees
Below 65 70 70 70 70 70 70 0.5 PC(9.5) 70 degrees 10 degrees
Below 35 35 40 40 45 45 50 9.5 PC(0.5) 85 degrees 10 degrees
Below 35 35 35 35 35 35 35 10 0 105 degrees 10 degrees
Below 33 33 35 35 35 35 35

Referring to Table 3, it can be seen that the experiment in which the mixing ratio of the silsesquioxane polymer and PMMA or PC satisfies 1:9 to 9:1 has a good degree of hydrophilicity, and the persistence of surface hydrophilicity is long. , Referring to Table 1 above, it can be seen that it has the same degree of hydrophilization as glass.

Claims (12)

A silsesquioxane polymer comprising repeating units represented by the following Chemical Formulas 1 and 2; And
Synthetic resin coating composition comprising a solvent.
[Formula 1]

[Formula 2]

In Formula 1 and Formula 2, R1 is each independently hydrogen, deuterium, halogen, amine group, epoxy group, cyclohexyl epoxy group, (meth)acrylic group, hydroxy group, silol group, isocyanate group, nitrile group, nitro group, Alkyl group having 1 to 40 carbon atoms, alkenyl group having 2 to 40 carbon atoms, alkoxy group having 1 to 40 carbon atoms, cycloalkyl group having 3 to 40 carbon atoms, heterocycloalkyl group having 3 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, carbon number 3 To 40 heteroaryl group, 3 to 40 aralkyl group, 3 to 40 aryloxy group, or 3 to 40 arylthio group, R2 are each independently hydrogen, deuterium, halogen, isocyanate group, Alkyl group having 1 to 40 carbon atoms, alkenyl group having 2 to 40 carbon atoms, cycloalkyl group having 3 to 40 carbon atoms, heterocycloalkyl group having 3 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, heteroaryl group having 3 to 40 carbon atoms, carbon number It is an aralkyl group of 3 to 40 or an epoxy group of 2 to 40 carbon atoms, n and m are each independently an integer of 1 to 100,000, and n/m is 0.1 to 10. A silsesquioxane polymer comprising repeating units represented by the following Chemical Formulas 1 and 2;
Synthetic resins; And
Synthetic resin coating composition comprising a solvent.
[Formula 1]

[Formula 2]

In Formula 1 and Formula 2, R1 is each independently hydrogen, deuterium, halogen, amine group, epoxy group, cyclohexyl epoxy group, (meth)acrylic group, hydroxy group, silol group, isocyanate group, nitrile group, nitro group, Alkyl group having 1 to 40 carbon atoms, alkenyl group having 2 to 40 carbon atoms, alkoxy group having 1 to 40 carbon atoms, cycloalkyl group having 3 to 40 carbon atoms, heterocycloalkyl group having 3 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, carbon number 3 To 40 heteroaryl group, 3 to 40 aralkyl group, 3 to 40 aryloxy group, or 3 to 40 arylthio group, R2 are each independently hydrogen, deuterium, halogen, isocyanate group, Alkyl group having 1 to 40 carbon atoms, alkenyl group having 2 to 40 carbon atoms, cycloalkyl group having 3 to 40 carbon atoms, heterocycloalkyl group having 3 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, heteroaryl group having 3 to 40 carbon atoms, carbon number It is an aralkyl group of 3 to 40 or an epoxy group of 2 to 40 carbon atoms, n and m are each independently an integer of 1 to 100,000, and n/m is 0.1 to 10. The synthetic resin coating composition according to claim 1 or 2, wherein the silsesquioxane polymer comprises a polymer represented by the following Chemical Formula 3.
[Formula 3]

In Formula 3, R1, R2, n and m are as defined in Formula 1 and Formula 2. The synthetic resin coating composition of claim 2, wherein the synthetic resin comprises an organic polymer. The synthetic resin coating composition of claim 2, wherein the synthetic resin and the silsesquioxane polymer are mixed in a ratio of 1:9 to 9:1. A synthetic resin base material comprising a synthetic resin coating composition comprising a silsesquioxane polymer comprising a repeating unit represented by the following Chemical Formulas 1 and 2 and a synthetic resin.
[Formula 1]

[Formula 2]

In Formula 1 and Formula 2, R1 is each independently hydrogen, deuterium, halogen, amine group, epoxy group, cyclohexyl epoxy group, (meth)acrylic group, hydroxy group, silol group, isocyanate group, nitrile group, nitro group, carbon number Alkyl group of 1 to 40, alkenyl group of 2 to 40 carbon atoms, alkoxy group of 1 to 40 carbon atoms, cycloalkyl group of 3 to 40 carbon atoms, heterocycloalkyl group of 3 to 40 carbon atoms, aryl group of 6 to 40 carbon atoms, 3 to 3 carbon atoms A heteroaryl group of 40, an aralkyl group of 3 to 40 carbon atoms, an aryloxy group of 3 to 40 carbon atoms, or an arylcyol group of 3 to 40 carbon atoms, and R2 are each independently hydrogen, deuterium, halogen, isocyanate group, carbon number Alkyl group of 1 to 40, alkenyl group of 2 to 40 carbon atoms, cycloalkyl group of 3 to 40 carbon atoms, heterocycloalkyl group of 3 to 40 carbon atoms, aryl group of 6 to 40 carbon atoms, heteroaryl group of 3 to 40 carbon atoms, carbon number 3 It is an aralkyl group of 40 to 40 or an epoxy group of 2 to 40 carbon atoms, n and m are each independently an integer of 1 to 100,000, and n/m is 0.1 to 10. The method of claim 6, wherein the silsesquioxane polymer is a synthetic resin substrate comprising a polymer represented by the formula (3).
[Formula 3]

In Formula 3, R1, R2, n and m are as defined in Formula 1 and Formula 2. The synthetic resin substrate according to claim 6, wherein the synthetic resin comprises an organic polymer. According to claim 6, The synthetic resin and silsesquioxane polymer is a synthetic resin base material mixed in a ratio of 1: 9 to 9: 1. The synthetic resin substrate according to claim 6, further comprising a fluorine-based coating layer on the synthetic resin substrate. Synthetic resin substrates; And
Silsesquioxane polymer comprising a repeating unit represented by the following Chemical Formulas 1 and 2 and a solvent or silsesquioxane polymer comprising a repeating unit represented by the following Chemical Formulas 1 and 2 on one or more surfaces of the synthetic resin substrate, A synthetic resin substrate comprising a coating layer in which a synthetic resin coating composition comprising a synthetic resin and a solvent is cured.
[Formula 1]

[Formula 2]

In Formula 1 and Formula 2, R1 is each independently hydrogen, deuterium, halogen, amine group, epoxy group, cyclohexyl epoxy group, (meth)acrylic group, hydroxy group, silol group, isocyanate group, nitrile group, nitro group, carbon number Alkyl group of 1 to 40, alkenyl group of 2 to 40 carbon atoms, alkoxy group of 1 to 40 carbon atoms, cycloalkyl group of 3 to 40 carbon atoms, heterocycloalkyl group of 3 to 40 carbon atoms, aryl group of 6 to 40 carbon atoms, 3 to 3 carbon atoms A heteroaryl group of 40, an aralkyl group of 3 to 40 carbon atoms, an aryloxy group of 3 to 40 carbon atoms, or an arylcyol group of 3 to 40 carbon atoms, and R2 are each independently hydrogen, deuterium, halogen, isocyanate group, carbon number Alkyl group of 1 to 40, alkenyl group of 2 to 40 carbon atoms, cycloalkyl group of 3 to 40 carbon atoms, heterocycloalkyl group of 3 to 40 carbon atoms, aryl group of 6 to 40 carbon atoms, heteroaryl group of 3 to 40 carbon atoms, carbon number 3 It is an aralkyl group of 40 to 40 or an epoxy group of 2 to 40 carbon atoms, n and m are each independently an integer of 1 to 100,000, and n/m is 0.1 to 10. The synthetic resin substrate of claim 11, further comprising a fluorine-based coating layer on the synthetic resin substrate.

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