WO2015009114A1

WO2015009114A1 - Polycarbonate glazing and method for producing same

Info

Publication number: WO2015009114A1
Application number: PCT/KR2014/006570
Authority: WO
Inventors: 김병수; 강세영; 김중인; 이대규; 최우석
Original assignee: 삼성에스디아이 주식회사
Priority date: 2013-07-19
Filing date: 2014-07-18
Publication date: 2015-01-22

Abstract

The present invention relates to polycarbonate glazing and a method for producing same, the polycarbonate glazing comprising: a polycarbonate-based substrate; and a silicon-based hard coating layer formed on one side of the substrate, wherein the hard coating layer is derived from polysilazanes or polysiloxazanes and, when subjected to abrasion for 500 cycles using a Taber abraser with a CS-10F abrasion wheel under a load of 500 g, has a difference in haze (△haze) before and after the abrasion of at most about 6.0 and a transmittance difference (△transmittance) of at most about 0.8. The polycarbonate glazing has superior abrasion resistance and transparency, superior adhesion between the polycarbonate-based substrate and the hard coating layer even without a separate primer layer, excellent gas barrier properties due to low moisture permeability, and superior fouling resistance. In addition, the method for producing polycarbonate glazing according to the present invention allows non-vacuum wet coating in a wet process and thus has reduced production time and superior processability.

Description

Polycarbonate Glazing and Manufacturing Method Thereof

The present invention relates to a polycarbonate glazing and a method of manufacturing the same.

Recently, the automobile industry is facing problems such as fuel economy reduction, responding to environmental regulations, securing passenger safety, and pressure on cost reduction due to intensifying competition among automakers. In order to solve this problem, studies are being actively conducted to replace soft steel sheets used for window modules or car bodies with lightweight metals, plastics, or carbon composite materials.

In particular, plastic materials have contributed to the weight reduction of automobiles, improving design and design freedom, granting new functions, and reducing costs. It is preferred as an alternative material for parts that have been difficult to resinize.

For example, plastic materials such as polycarbonate (PC) and polymethyl methacrylate (PMMA), etc., have excellent impact resistance, transparency and formability, and are currently used in various automotive parts and parts such as B-pillars and headlamps and sunroofs. It is used for manufacture. Automotive window modules offer new uses for the plastic materials due to various advantages in areas such as styling / design, weight reduction, stability / safety and the like. In particular, plastic materials not only differentiate the vehicle from competing vehicles by increasing the overall design and shape complexity, but also provide the automobile manufacturer with the ability to reduce the complexity of the window assembly by integrating functional parts into molded plastic modules. The use of lightweight plastic window modules promotes the vehicle's low center of gravity and fuel economy. In addition, the plastic window module can increase the overall stability of the vehicle by strengthening the occupant's support in a rollover accident.

However, plastic materials such as polycarbonate have a problem in that scratch resistance and abrasion resistance are weak. In order to improve such scratch resistance or abrasion resistance, there have been attempts to form a silica film as a hard coating layer on a substrate by plasma enhanced chemical vapor deposition (PECVD), CVD, sputtering, sol-gel, or the like. . However, the PECVD method, the CVD method, and the sputtering method have a problem that the apparatus is expensive and the control for forming a high quality coating film is troublesome. In the sol-gel method, the required firing temperature is higher than 500 ° C., which makes the process difficult. There is a problem.

The problem to be solved by the present invention is to provide a polycarbonate glazing excellent in wear resistance.

Another problem to be solved by the present invention is to provide a polycarbonate glazing excellent transparency.

Another object of the present invention is to provide a polycarbonate glazing excellent in adhesion between the polycarbonate-based substrate and the hard coating layer.

Another object of the present invention is to provide a polycarbonate glazing having low water permeability and excellent gas barrier properties.

Another problem to be solved by the present invention is to provide a polycarbonate glazing excellent in pollution resistance.

Another problem to be solved by the present invention is to provide a polycarbonate glazing with excellent flexibility to prevent cracking.

Another object of the present invention is to provide a method for producing a polycarbonate glazing having a short manufacturing time and excellent processability by enabling non-vacuum wet coating.

One aspect of the invention is a polycarbonate-based substrate; And a hard coating layer formed on one surface of the substrate, wherein the hard coating layer is an organic-inorganic mixed layer derived from polysilazane or polysiloxane, and 500 g of CS-10F wear wheel using a taper abraser. It is related to polycarbonate glazing in which the haze difference (ΔHaze) before and after abrasion is about 6.0 or less and the permeability difference (ΔTransmittance) is about 0.8 or less at 500 wear under load conditions.

Another aspect of the present invention relates to a method for producing a polycarbonate glazing comprising forming a hard coating layer with a coating liquid containing polysilazane or polysiloxane on one side of a polycarbonate-based substrate.

Polycarbonate glazing of the present invention is excellent in wear resistance and transparency, excellent adhesion between the polycarbonate-based substrate and the hard coating layer without a separate primer layer, excellent water barrier properties, low gas permeability, and excellent pollution resistance. In addition, the polycarbonate glazing manufacturing method of the present invention is non-vacuum wet coating by a wet process, the manufacturing time is short and excellent processability.

1 is a cross-sectional view of a polycarbonate glazing in accordance with one embodiment of the present invention.

2 is a cross-sectional view of a polycarbonate glazing in accordance with another embodiment of the present invention.

Hereinafter, with reference to the accompanying drawings, it will be described embodiments of the present application in more detail. However, the technology disclosed in the present application is not limited to the embodiments described herein and may be embodied in other forms. It is merely to be understood that the embodiments introduced herein are provided so that the disclosure can be made thorough and complete, and that the spirit of the present application can be fully conveyed to those skilled in the art. In the drawings, the width, thickness, and the like of the components are enlarged in order to clearly express the components of each device. In addition, although only a part of the components are shown for convenience of description, those skilled in the art will be able to easily understand the rest of the components. When described in the drawings as a whole, at the point of view of the observer, when one element is referred to as being positioned on top of another, this means that one element may be placed directly on top of another or that additional elements may be interposed between them. Include. In addition, one of ordinary skill in the art may implement the spirit of the present application in various other forms without departing from the technical spirit of the present application. In addition, in the drawings, the same reference numerals refer to substantially the same elements.

폴리카보네이트 글래이징 (Polycarbonate Glazing)Polycarbonate Glazing

One aspect of the invention relates to polycarbonate glazing. In the present invention, the polycarbonate glazing may include a substrate including polycarbonate and at least one coating layer laminated on the substrate.

1 illustrates a cross-sectional view of a polycarbonate glazing in accordance with one embodiment of the present invention. Referring to Figure 1, the polycarbonate glazing 100 is a polycarbonate-based substrate 110; And it may include a hard coating layer 120 formed on one surface of the polycarbonate-based substrate 110.

The polycarbonate-based substrate 110 includes a polycarbonate-based resin, and the polycarbonate-based resin may be used without limitation within a range capable of achieving the object of the present invention. For example, polycarbonate, polycarbonate copolymer or polycarbonate blending resin may be used, and the blending resin may be polyamide, thermoplastic polyurethane (TPU), acrylonitrile-styrene-acrylonitrile, polymethyl methacrylate. A blended polycarbonate with at least one polymer resin selected from the group consisting of polyester and acrylonitrile-butadiene-styrene may be used, but is not limited thereto. Moreover, 2 or more types can be mixed and used. The polycarbonate may be prepared by reacting a dihydric phenol compound with phosgene in the presence of a molecular weight modifier and a catalyst according to a conventional production method. In another embodiment, the polycarbonate may be prepared using an ester interchange reaction of a dihydric phenol compound and a carbonate precursor such as diphenyl carbonate. In the method for producing the polycarbonate, a bisphenol compound may be used as the dihydric phenol compound, and for example, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) may be used. In this case, the bisphenol A may be partially or wholly replaced by another type of dihydric phenol compound.

Specifically, in view of the safety and transparency required as a substrate for polycarbonate glazing, the polycarbonate resin has a tensile strength of about 60 MPa or more, a tensile modulus of about 1.5 GPa or more, a Vicat softening point of about 120 ° C. or more, and a total light transmittance. This may be at least about 80%.

The thickness of the polycarbonate-based substrate 110 may be about 1 mm to 10 mm. Within this range, mechanical strength, flexibility, transparency, and the like may be excellent as a substrate of the polycarbonate glazing.

The hard coating layer 120 may be formed on the polycarbonate-based substrate 110. The hard coat layer 120 may be derived from polysiloxane or polysilazane. Specifically, the hard coating layer 110 is coated with a hydrogenated polysiloxane or polysilazane, and a coating solution containing an organic solvent on one side of the polycarbonate-based substrate 120, the hydrogenated polysilazane or included in the coating solution through a modification process A siloxane compound, such as hydrogenated polysiloxane, may be ceramicized to be converted into silicon dioxide (SiO ₂ ) to form a coating layer containing silicon oxide (SiO x).

The hard coating layer 120 may have a thickness of about 50 to 3,000 nm, specifically about 100 to 1,000 nm. It is possible to secure sufficient wear resistance in the thickness range, it is possible to minimize the occurrence of cracks. In addition, since the hard coating layer 120 is formed by a wet process, it is possible to secure sufficient adhesion or adhesion without forming a separate primer layer on the polycarbonate-based substrate. Therefore, it may be formed directly on the polycarbonate-based substrate 110.

Polycarbonate glazing according to an embodiment of the present invention may be excellent in wear resistance by having a hard coating layer derived from polysiloxane or polysilazane. Specifically, the polycarbonate glazing has a haze difference (ΔHaze) of about 6.0 or less after wear and wear 500 times under a CS-10F wear wheel and 500 g load condition using a taper abraser. , The transmittance difference (ΔTransmittance) may be about 0.8 or less.

In addition, the polycarbonate glazing according to an embodiment of the present invention has a modulus of about 45 to 60 GPa, thereby minimizing the crack of the hard coating layer and ensuring sufficient strength, and has excellent wear resistance. In the present invention, "modulus" means a value measured at room temperature using a nanoindenter Ti 750 Ubi (manufactured by Hysitron). In the present invention, room temperature means 25 ° C ± 3 ° C unless otherwise specified.

In addition, the polycarbonate glazing according to an embodiment of the present invention has a water permeability (WVTR) (g / m ² / day) is measured using the Aquatran Model 1 (Mocon Co., Ltd.) according to ASTM F-1249 standard ( 1.0) g / (m ² · day) or less, excellent barrier property against gas and impurities.

In addition, the polycarbonate glazing according to an embodiment of the present invention may have a surface roughness (Ra) of about 1 to 50nm, it is possible to obtain a polycarbonate glazing improved surface flatness due to the hard coating layer.

Hereinafter, a polycarbonate glazing according to another embodiment of the present invention will be described with reference to FIG. 2. Figure 2 shows a cross-sectional view of a polycarbonate glazing in accordance with another embodiment of the present invention. The polycarbonate glazing according to another embodiment of the present invention is substantially the same as the polycarbonate glazing according to the embodiment of the present invention except that an intermediate layer is further laminated between the polycarbonate-based substrate and the hard coating layer. The explanation will focus on the middle layer.

Referring to FIG. 2, the intermediate layer 130 may be a laminate structure of a bonding layer, a functional layer or a bonding layer, and a functional layer, and may be a laminate structure of at least one layer. The functional layer may be, for example, an ultraviolet blocking layer, a buffer layer, an abrasion resistant layer, a barrier layer, or the like, and may be a plurality of layers in combination thereof.

In one embodiment, the intermediate layer 130 may improve the bonding force between the polycarbonate-based substrate 110 and other layers, and selected from amide resin, acrylic resin, urethane resin, siloxane resin, silicone resin or copolymer thereof It may include, but is not limited to, a substance. Specifically, aliphatic polyether thermoplastic polyurethanes, polyester / polyether thermoplastic polyurethanes, anionic fatty polyester based polyurethanes, anionic fatty polyester / polyether polyurethanes, aqueous polyurethanes, polyamides, and polyester acrylics And the like.

In one embodiment, the intermediate layer 130 may include a material that absorbs light having a wavelength of about 200 to 340 nm, which is an ultraviolet region, as an ultraviolet absorber to protect the polycarbonate-based substrate from ultraviolet rays to improve weather resistance. The ultraviolet absorber may include metal oxide fine particles, an organic compound, and the like, and specifically, may include metal oxide. In one embodiment, the metal oxide used as the ultraviolet absorber is a fine particle having an average particle diameter of about 1 to 100 nm, for example, about 5 to 25 nm, selected from the group consisting of zinc oxide, titanium oxide, cerium oxide, iron oxide, and the like. It may comprise one or more fine particles. In another embodiment, the organic compound used as the ultraviolet absorber may include a benzotriazole, triazine, or the like. In addition, the ultraviolet absorber may include a HALS agent having an antioxidant function, for example, a hindered amine compound may be used as the HALS agent. In this case, the intermediate layer 130 may include a binder resin, and the binder resin may include an acrylate monomer, an acrylate oligomer, a siloxane monomer, a siloxane polymer, a silicone monomer, a silicone polymer, an acrylic resin, or a uritan based resin. Resins and the like can be used.

In one embodiment, the intermediate layer 130 is a silicon-based having a silica network structure formed by condensation reaction of a hydrolyzed alkoxy silane by a colloidal silica sol by sol-gel synthesis It may be a buffer layer. As said alkoxy silane, a trivalent or tetravalent alkoxy silane can be used. Examples of the alkoxy silane include vinyltrimethoxysilane, propyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane and the like. May be used alone or in combination.

In one embodiment, the intermediate layer 130 may be an acrylic wear resistant layer including a photocurable resin and silica nanoparticles. The photocurable resin may be formed by curing an ultraviolet curable compound having an acrylate functional group. The ultraviolet curable compound may be a polyfunctional (meth) acrylate compound and the like. For example, as the polyfunctional acrylate compound, ethylene glycol diacrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, trimethylolpropane tri (meth) acrylate, di Obtained by esterifying pentaerythritol hexa (meth) acrylate, polyol poly (meth) acrylate, di (meth) acrylate of bisphenol A-diglycidyl ether, polyhydric alcohol and polyhydric carboxylic acid, and its anhydride and acrylic acid Ester (meth) acrylate, a siloxane compound containing an acrylate functional group, urethane (meth) acrylate, pentaerythritol tetramethacrylate, glycerin trimethacrylate, and the like may be used, but is not limited thereto.

The silica nanoparticles may have an average particle diameter (D50) of about 100 nm or less, for example, about 10 to 50 nm, and about 50 wt% or less, for example, about 5 to 40 wt% of the acrylic wear resistant layer. When silica nanoparticles are included in the above range, the hardness may be increased to further improve wear resistance.

Hereinafter, the composition of the coating liquid for forming the hard coating layer according to the embodiments of the present invention will be described in detail.

하드코팅층 코팅액Hard Coating Layer Coating Solution

The coating solution for forming a hard coat layer may be hydrogenated polysiloxane, hydrogenated polysilazane or a mixture thereof; And solvents. Referring to each component constituting the coating solution is as follows.

(A) 수소화 폴리실록사잔 또는 수소화 폴리실라잔(A) hydrogenated polysiloxane or hydrogenated polysilazane

The coating solution of the present invention may include a hydrogenated polysiloxane, hydrogenated polysilazane or a mixture thereof as a composition for forming a silicon oxide layer.

The hydrogenated polysiloxane or hydrogenated polysilazane may be converted to a silicon oxide material by heating and oxidation, and a hard coating layer having excellent wear resistance may be obtained.

The hydrogenated polysiloxane may include silicon-oxygen-silicon (Si-O-Si) bonding units in addition to silicon-nitrogen (Si-N) bonding units in the structure. Such silicon-oxygen-silicon (Si-O-Si) bonding units can alleviate stress upon curing to reduce shrinkage.

Hydrogenated polysilazanes have a basic backbone in the structure including silicon-hydrogen (Si-H), nitrogen-hydrogen (N-H) coupling units in addition to silicon-nitrogen (Si-N) coupling units.

After both the hydrogenated polysiloxane and hydrogenated polysilazane have been baked or cured, the (Si-N) bond may be substituted with a (Si-O) bond.

In embodiments, the hydrogenated polysiloxane may have a unit represented by Formula 1, a unit represented by Formula 2, and a terminal portion represented by Formula 3 below:

[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 and 2, R ₁ to R ₇ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 Aryl group, substituted or unsubstituted C3 to C30 arylalkyl group, substituted or unsubstituted C3 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 heterocyclic alkyl group, substituted or unsubstituted C3 to C30 alkene It means a niyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxy group or a combination thereof.

In the present invention, "substituted" means hydrogen, halogen atom, hydroxyl group, nitro group, cyano group, amino group, azido group, amidino group, hydrazino group, carbonyl group, carbamyl group, thiol group, ester group, Carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphate groups or salts thereof, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and carbon atoms An aryl group having -30, an aryloxy group having 6-30 carbon atoms, a cycloalkyl group having 3-30 carbon atoms, a cycloalkenyl group having 3-30 carbon atoms, a cycloalkynyl group having 3-30 carbon atoms, or a combination thereof is meant.

The hydrogenated polysiloxane or hydrogenated polysilazane may have an oxygen content of about 0.2% to 3% by weight. When it is contained in the above range, the stress relaxation by the silicon-oxygen-silicon (Si-O-Si) bond in the structure is sufficient to prevent shrinkage during heat treatment and thus prevent the occurrence of cracks in the formed hard coating layer. have. For example, the oxygen content of the hydrogenated polysiloxane or hydrogenated polysilazane may be about 0.2 to 3% by weight, specifically about 0.5 to 2% by weight.

In addition, the hydrogenated polysiloxane or polysilazane has a structure in which the terminal portion is capped with hydrogen, and the terminal group represented by Formula 3 is about 15 with respect to the total content of Si—H bonds in the hydrogenated polysiloxaneoxane or hydrogenated polysilazane structure. To 35% by weight. When included in the above range, the oxidation reaction occurs during curing, but the SiH ₃ portion during curing prevents from being scattered by SiH ₄ to prevent shrinkage and the hard coating layer formed therefrom may prevent cracks from occurring. For example, the terminal group of Formula 3 may be included in about 20 to 30% by weight relative to the total content of Si-H bonds in the hydrogenated polysiloxane or hydrogenated polysilazane structure.

The hydrogenated polysiloxane or hydrogenated polysilazane of the present invention may have a weight average molecular weight (Mw) of about 1,000 to 5,000 g / mol. In the above range, it is possible to form a dense organic-inorganic mixed layer with a thin film coating while reducing components to evaporate during heat treatment. For example, the weight average molecular weight (Mw) may be about 1,500 to 3,500 g / mol.

The hydrogenated polysiloxane, hydrogenated polysilazane or a mixture thereof may be included in an amount of about 0.1 to 50% by weight based on the total content of the coating solution. When included in the above range can maintain a suitable viscosity and can be formed flat and evenly without bubbles and voids (Void).

(B) 용매(B) solvent

The solvent may be used as long as it is a solvent which can dissolve them without being reactive with hydrogenated polysiloxane or hydrogenated polysilazane. However, when OH is contained, a solvent containing no -OH group is preferable because it is reactive with the siloxane compound. For example, ethers, such as hydrocarbon solvents, such as aliphatic hydrocarbon, alicyclic hydrocarbon, and aromatic hydrocarbon, halogenated hydrocarbon solvent, aliphatic ether, alicyclic ether, can be used. Specifically, hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, sorbetso, and taben, halogen hydrocarbons such as methylene chloride and tricholoethane, dibutyl ether, dioxane, tetra hybrido furan and the like Ryu. The solubility of a siloxane compound, the evaporation rate of a solvent, etc. may be selected suitably, and a some solvent may be mixed.

The coating liquid of the present invention may further include a thermal acid generator (TAG). The thermal acid generator is an additive for improving the developability of the hydride polysiloxane and the contamination by uncuring, so that the hydride polysiloxane may be developed at a relatively low temperature. The thermal acid generator is not particularly limited as long as it is a compound capable of generating an acid (H +) by heat, but may be selected to have low volatility by being activated at about 90 ° C. or higher to generate sufficient acid. Such thermal acid generators can be selected, for example, from nitrobenzyl tosylate, nitrobenzyl benzenesulfonate, phenol sulfonate and combinations thereof. The thermal acid generator may be included in about 25% by weight or less, for example about 0.01 to 20% by weight based on the total content of the coating liquid. When included in the above range, the siloxane compound may be developed at a relatively low temperature.

The coating liquid of the present invention may further include a surfactant. The said surfactant is not specifically limited, For example, polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene ether, polyoxyethylene rail ether, polyoxyethylene nonyl phenol ether, etc. Polyoxyethylene sorbitan such as polyoxyethylene alkyl allyl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate Nonionic surfactants such as fatty acid esters, F-top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), Megapack F171, F173 (manufactured by Dainippon Ink, Inc.). Fluorine-based surfactants such as Prorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Saffron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahigara Corporation), or Kano siloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.), etc., etc. are mentioned. The surfactant may be included in about 10% by weight or less, for example, about 0.001 to 5% by weight based on the total content of the coating liquid.

폴리카보네이트 글래이징의 제조방법Method of Making Polycarbonate Glazing

Method for producing a polycarbonate glazing according to an embodiment of the present invention may include forming a hard coating layer with a coating liquid containing a hydrogenated polysilazane or a hydrogenated polysiloxane to one side of the substrate. Specifically, it may include forming a hard coat layer by applying a coating solution and then modifying it.

First, a coating liquid containing polysilazane or polysiloxazane is applied onto the polycarbonate-based substrate. The coating solution may be applied by roll coating, spin coating, bar coating, dip coating, flow coating, spray coating, or the like, but is not limited thereto. Do not. For example, the spin coating may be applied to the coating solution for about 10 to 60 seconds at about 500 to 4,000rpm, the coating may be repeated one or more times.

The coating thickness of the coating solution may be about 50 to 3,000 nm, and after coating the coating solution may be dried for about 1 to 100 minutes at about 50 to 100 ℃ and relative humidity about 40 to 90%.

The modification to form the hard coat layer refers to a process of converting a siloxane compound such as hydrogenated polysiloxane or hydrogenated polysilazane into silicon dioxide to ceramic.

In one embodiment of the present invention, in order to increase the conversion rate of the silazane or polysiloxane compound to silicon dioxide, it may be ceramicized under ultraviolet irradiation or high temperature, high humidity.

The ultraviolet irradiation may be performed using a vacuum ultraviolet. Specifically, about 100 to 200 nm vacuum ultraviolet light may be used. Irradiation intensity and irradiation amount of ultraviolet ray can be set suitably. For example, the ultraviolet radiation may be irradiated at an irradiation intensity of about 10 to 200 mW / cm 2 and an irradiation amount of about 100 to 6,000 mJ / cm 2 for about 0.1 to 5 minutes. Specifically, the dosage may be about 1,000 to 5,000 mJ / cm 2.

The ceramicization under high temperature and high humidity may be, for example, heat treatment at about 300 to 1,500 ° C. for about 1 to 12 hours.

According to a manufacturing method according to another embodiment of the present invention, after the ultraviolet irradiation, in order to further increase the conversion to silica, for example, about 80 to 150 ℃ and relative humidity about 10 to 90%, specifically about 40 to The heat treatment may further include a heat treatment for about 40 to 100 minutes at 90% of the conditions.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, the following examples are provided to help the understanding of the present invention, and the scope of the present invention is not limited to the following examples. Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

제조예 1: 하드코팅층 코팅액 IPreparation Example 1 Hard Coating Layer Coating Liquid I

The inside of the 2L reactor equipped with the stirrer and the temperature controller was replaced with dry nitrogen, and 2.0 g of pure water was injected into 1,500 g of dry pyridine, followed by sufficient mixing. Here, 100 g of dichlorosilane was slowly injected over 1 hour, and then 70 g of ammonia was slowly injected over 3 hours with stirring. Next, dry nitrogen was injected for 30 minutes and the ammonia remaining in the reactor was removed. The product on the obtained white slurry was filtered using a 1 μm Teflon filter under a dry nitrogen atmosphere to obtain 1,000 g of a filtrate. After adding 1,000 g of dried xylene, the operation of replacing the solvent with pyridine to xylene using a rotary evaporator was repeated three times, adjusting the solid content concentration to 20% and finally pore size. A hard coating layer coating solution I was prepared by filtration with a filter made of 0.03 μm of Teflon filter.

The oxygen content of the obtained hydrogenated polysiloxazane is _{0.5%, SiH 3 / SiH (} total) is 0.20, a weight average molecular weight of 2,000g / mol.

제조예 2: 하드코팅층 코팅액 ⅡPreparation Example 2 Hard Coating Layer Coating Solution II

Add 25.62 g of tetraethyl silicate (TEOS, Sigma-Aldrich Co., Ltd.) to 100 g of distilled water mixed with 0.3 g of 95% acetic acid and add methyltrimethoxysilane (MTMS, Shin Etsu KBM503) while stirring. To prepare a resin solution at room temperature. At this time, the molar ratio of tetraethyl silicate and methyltrimethoxysilane added is 1: 2. Thereafter, silica particles (SiO ₂ , FUSO Co., Ltd.) were added to 30 parts by weight of the resin solids to prepare a hard coating solution II.

제조예 3: 하드코팅층 코팅액 ⅢPreparation Example 3: Hard Coating Layer Coating Solution Ⅲ

28.0 g of urethane acrylate resin (UNIDIC RC27-947, DIC CORPORATION) was added to 69.0 g of solvent isopropyl alcohol (IPA, Samjeon Pure Chemical Co., Ltd., KBM503) and stirred, while stirring, and Igacure 184 (Igacure 184, Ciba Co., Ltd.) as a photoinitiator. After adding 3 g additionally, the resin solution was prepared by stirring at 700 rpm for 20 minutes. Thereafter, silica particles (SiO ₂ , FUSO Co., Ltd.) were added to 30 parts by weight of the resin solids to prepare a hard coating solution III.

제조예 4: 하드코팅층 코팅액 ⅣPreparation Example 4 Hard Coating Layer Coating Solution Ⅳ

10 g of the polyfunctional acrylate monomer dipentaerythritol hexa acrylate (DPHA, SK Cytec) and 10 g pentaerythritol triacrylate (PETA, Satomer) were used as the first solvent, 2-methoxyethanol (MCS, Samjeon Pure Chemical). ) Was added to 20 g and stirred, and 3 g of Igacure 184 (Igacure 184, Ciba) was added as a photoinitiator, followed by stirring at 700 rpm for 20 minutes, and isopropyl alcohol (IPA, Samjeon Pure Chemical Co., Ltd.) KBM503 ) 57.0 g was added and stirred for 20 minutes, and finally, 0.1 g of polyether-modified polydimethyl siloxane (BYK306) was added as a leveling improving additive, followed by stirring for 10 minutes to prepare a resin solution. Thereafter, silica particles (SiO ₂ , FUSO Co., Ltd.) were added at 30 parts by weight based on the resin solid content to prepare a hard coating solution IV.

실시예 1 내지 3 및 비교예 1 내지 3Examples 1 to 3 and Comparative Examples 1 to 3

실시예 1Example 1

The inorganic coating having a thickness of 500 nm was formed by spin coating a hard coating layer coating solution I on one surface of a polycarbonate substrate (LEXAN, GE) having a thickness of 3 mm. At this time, the coating solution was used to dilute the solid content to 9.5% with DBE (dibuthyl ether), spin coating was coated at 1,000rpm for 20 seconds, dried for 3 minutes at 80 ℃ convection oven, UV irradiation (SMT Co., Ltd.) CR403) was exposed to irradiation intensity of 14mW / cm ² for 143 seconds, UV irradiation at 2,000mJ / cm ² , and then left at room temperature for 24 hours to prepare polycarbonate glazing, and the measured values were measured in Table 1 below. Indicated.

실시예 2Example 2

On one surface of a 3 mm polycarbonate substrate (LEXAN, GE, Inc.), an inorganic layer having a thickness of 500 nm was formed by spin coating with a hard coating layer coating solution I. At this time, the coating solution was used to dilute the solid content to 9.5% with DBE (dibuthyl ether), spin coating was coated at 1,000rpm for 20 seconds, dried for 3 minutes at 80 ℃ convection oven, UV irradiation (SMT Co., Ltd.) CR403) was exposed to irradiation intensity of 14 mW / cm ² for 214 seconds, UV irradiation at 4,000 mJ / cm ² , and then left at room temperature for 24 hours to prepare polycarbonate glazing, and the measured values were measured in Table 1 below. Indicated.

실시예 3Example 3

On one surface of a 3 mm polycarbonate substrate (LEXAN, GE, Inc.), an inorganic layer having a thickness of 1,000 nm was formed by spin coating with a hard coating layer coating solution I. At this time, the coating solution was diluted with DBE (dibuthyl ether) so that the solid content was 9.5%. The spin coating was coated for 20 seconds at 1,000 rpm, then dried for 3 minutes in an 80 ° C. convection oven, and again for 20 seconds at 1,000 rpm, followed by drying for 3 minutes in an 80 ° C. convection oven.

After spin coating, UV irradiation was performed at 14mW / cm ² for 143 seconds using UV irradiator (SMT CR403) and UV irradiation at 2,000mJ / cm ² , and then left at room temperature for 24 hours to prepare polycarbonate glazing. The measured values are shown in Table 1 below.

비교예 1Comparative Example 1

On one surface of a 3 mm polycarbonate substrate (LEXAN, GE), a coating layer having a thickness of 500 nm was formed by spin coating with a hard coating layer coating solution II. At this time, the spin coating was coated for 20 seconds at 1,000rpm, dried for 3 minutes at 80 ℃ convection oven, 2,000mJ / cm ² by exposure for 14 minutes at 14mW / cm 2 irradiation intensity in a UV irradiator (CR403) SMT After irradiating with UV, and left at room temperature for 24 hours to prepare a polycarbonate glazing, the measured values are shown in Table 1 after measuring the physical properties.

비교예 2Comparative Example 2

On one surface of a 3 mm polycarbonate substrate (LEXAN, GE), a coating layer having a thickness of 1,000 nm was formed by spin coating the hard coating layer coating solution III. At this time, the spin coating was coated for 20 seconds at 1,000rpm, dried for 3 minutes in an 80 ℃ convection oven, polycarbonate glazing was prepared by UV irradiation at 350mJ / cm light using a high-pressure mercury lamp, measured physical properties The measured values are shown in Table 1 below.

비교예 3Comparative Example 3

On one surface of a 3 mm polycarbonate substrate (LEXAN, GE, Inc.), a coating layer having a thickness of 1,000 nm was formed by spin coating with a hard coating layer coating solution IV. At this time, the spin coating was coated for 20 seconds at 1,000rpm, dried for 3 minutes in an 80 ℃ convection oven, polycarbonate glazing was prepared by UV irradiation at 350mJ / cm light using a high-pressure mercury lamp, measured physical properties The measured values are shown in Table 1 below.

물성 평가 방법 Property evaluation method

(1) Abrasion resistance: Haze before and after abrasion with haze meter (NHD 2000N, Nippon Denshoku) when wear 500 times under CS-10F wear wheel and 500g load condition using Taber Abraser Transmittance was measured respectively.

(2) Cracks: After leaving the polycarbonate glazing prepared in the above Examples and Comparative Examples for 1 hour at room temperature, it was determined by the naked eye.

* Excellent (it represents with "x" mark in a table.): The crack part of a coating layer is not seen.

* Defective (marked with "○" in the table.): A cracked part is seen in part or the whole of the coating layer.

(3) Adhesion (number / number): 100 points were made by making a checkerboard scale by drawing lines on the specimen at 2mm intervals. The number of times where peeling did not occur was carried out by tape-taking and pulling once strongly in a vertical direction.

(4) Modulus: Measured at 25 ° C using a nanoindenter Ti 750 Ubi (manufactured by Hysitron).

(5) Moisture Permeability (WVTR) (g / m ² / day): Measured according to ASTM F-1249 standard using Aquatran Model1 (Mocon). Specimen size is 100 * 100mm.

(7) Surface roughness (Ra): Measured using a veeco surface roughness meter NT1100.

Table 1

division			Example 1	Example 2	Example 3	Comparative Example 1	Comparative Example 2	Comparative Example 3
Hard Coating Layer (nm)	Coating solution Ⅰ		500	500	1,000	-	-	-
	Coating solution Ⅱ		-	-	-	500	-	-
	Coating solution Ⅲ		-	-	-	-	1,000	-
	Coating solution Ⅳ		-	-	-	-	-	1,000
Wear resistance	Haze (%)	Pre-wear	0.4	0.4	0.4	0.5	0.4	0.5
		Wear	5.4	4.2	3.8	9.2	27.0	35.4
		△ H	5.0	3.8	3.2	8.8	26.6	29.9
	Permeability (%)	Pre-wear	88.0	88.1	88.1	89.0	88.0	88.0
		Wear	88.4	88.0	88.1	86.1	85.9	85.0
		△ T	0.4	0.1	0.0	0.9	2.1	3.0
crack			X	X	X	O	X	O
Adhesiveness
			100/100	100/100	100/100	0/100	0/100	0/100
Modulus (G)			53	54	58	44	32	30
WVTR (g / m ² / day)			<1.0	<1.0	<1.0	35	44	38
Surface roughness (Ra)			3.9 nm	4.1nm	3.7 nm	11nm	3.7 nm	10.3 nm

As shown in the results of Table 1, the PC glazing of the embodiment including a hard coating layer derived from polysilazane or polysiloxane and formed by a wet process has a haze difference (ΔHaze) and a transmittance difference (ΔTransmittance) before and after wear. ) Is lower than the comparative example, and it can be seen from this that the wear resistance is excellent. In addition, the PC glazing of the embodiment is excellent in adhesion between the substrate and the hard coating layer without having a separate primer layer, low moisture permeability (WVTR), excellent barrier properties, low surface roughness, surface flatness of the hard coating layer It can be seen that it is excellent.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments and can be manufactured in various forms, and a person of ordinary skill in the art to which the present invention pertains has the technical idea of the present invention. However, it will be understood that other specific forms may be practiced without changing the essential features. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims

Polycarbonate-based substrates; And a silicon-based hard coating layer formed on one surface of the substrate,

When wear 500 times under CS-10F wear wheel and 500g load condition using Taber Abraser, haze difference (△ Haze) before and after wear is about 6.0 or less and permeability difference (△ Transmittance) is about Polycarbonate glazing less than 0.8.
The method of claim 1,

Wherein said hard coating layer is derived from polysilazane or polysiloxane.
The method of claim 1,

The polycarbonate-based substrate has a thickness of about 1 mm to 10 mm,

The hard coating layer has a thickness of about 100nm to 1000nm polycarbonate glazing.
The method of claim 1,

Surface roughness (Ra) of the hard coating layer is about 1 to 20nm polycarbonate glazing.
The method of claim 1,

Polycarbonate glazing with a modulus of about 45 to 60 GPa.
The method of claim 1,

The hard coating layer is a polycarbonate glazing having a moisture permeability (WVTR) of about (1.0) g / (m 2 ㆍ day) or less measured according to ASTM F-1249.
The method of claim 1,

The hard coating layer is a polycarbonate glazing formed by coating directly on the polycarbonate-based substrate.
Method for producing a polycarbonate glazing comprising forming a hard coating layer with a coating liquid containing polysilazane or polysiloxane on one side of the polycarbonate-based substrate.
The method of claim 8,

Forming the hard coating layer, the method of manufacturing a polycarbonate glazing comprising applying the coating solution to at least one surface of the polycarbonate-based substrate and converting it into silicon dioxide by irradiation with ultraviolet rays.
The method of claim 9,

The irradiating the ultraviolet rays is a method of producing a polycarbonate glazing comprising irradiating ultraviolet rays with an ultraviolet irradiation intensity of about 10 to 200mW / ㎠ and an irradiation amount of about 100 to 6,000mJ / ㎠.