KR20150010540A - Polycarbonate glazing and the method for preparing the same - Google Patents

Abstract

The present invention relates to a polycarbonate glazing and a method for producing the same. The polycarbonate glazing includes: a polycarbonate base material; and a silicon-based hard-coating layer formed on one surface of the base material. The hard-coating layer is derived from polysilazane or polysiloxane. When abrasion is performed five hundred times under a CS-10F abrasion wheel and a load of 500 g using the Taber Abraser, a difference in haze (ΔHaze) before and after abrasion is 6.0 or less and a difference in transmittance (ΔTransmittance) is 0.8 or less. The polycarbonate glazing has excellent abrasion resistance and transparency. Without a separate primer layer, a polycarbonate-based base material and a hard-coating layer can be excellently adhered, and moisture transmittance is low so that gas barrier properties and pollution resistance are excellent. Moreover, the method for producing a polycarbonate glazing of the present invention can perform non-vacuum wet-coating so that production time is short and processibility is excellent.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a polycarbonate glazing,

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

Recently, the automobile industry is faced with problems such as reducing fuel consumption, responding to environmental regulations, ensuring safety of passengers, and pressure on cost reduction due to intensified competition among automakers. In order to solve such a problem, studies have been actively carried out to replace a soft steel plate used for a window glass module or the like with a lightweight metal, plastic, or carbon composite material.

In particular, plastic materials have contributed to the weight reduction of automobiles, the freedom of design and design, the provision of new functions, and the cost reduction. As a new challenge, the development of technology to cope with environmental problems, It is preferred as a substitute material for components which are difficult to be resinized.

For example, since plastic materials such as polycarbonate (PC) and polymethylmethacrylate (PMMA) have excellent impact resistance, transparency and moldability, they are currently used in various automobile parts and parts such as B- Has been used in manufacturing. Automotive window modules offer new uses for the plastic materials due to their various advantages in areas such as styling / design, weight reduction, stability / safety, and the like. In particular, plastic materials increase the overall design and geometry complexity, which not only differentiates vehicles from competing vehicles, but also provides automakers with the ability to reduce the complexity of window assemblies by integrating functional components 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 enhance the overall stability of the vehicle by enhancing the support of the occupant in a rollover accident.

However, plastic materials such as polycarbonate have a problem that scratch resistance and abrasion resistance are poor. In order to improve the scratch resistance or abrasion resistance, an attempt has been made to form a silica film with a hard coating layer on a substrate by plasma enhanced chemical vapor deposition (PECVD), CVD, sputtering, sol-gel method or the like . However, the PECVD method, the CVD method, and the sputtering method have problems in that the apparatus is expensive and the control for forming a high quality coating film is troublesome. In the sol-gel method, the sintering temperature required is as high as 500 deg. There is a problem.

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

Another object of the present invention is to provide a polycarbonate glazing having excellent transparency.

Another object of the present invention is to provide a polycarbonate glazing excellent in adhesion between a polycarbonate base material and a 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 object of the present invention is to provide a polycarbonate glazing having excellent stain resistance.

Another object of the present invention is to provide polycarbonate glazing having excellent flexibility and excellent crack resistance.

Another object of the present invention is to provide a process for producing polycarbonate glazing which can be non-vacuum-coated and has a short manufacturing time and excellent processability.

One aspect of the present invention relates to a polycarbonate based substrate; And a hard coating layer formed on one surface of the substrate, wherein the hard coating layer is a organic-inorganic mixed layer derived from polysilazane or polysiloxazane, and is formed by using a Taber Abraser, a CS-10F abrasive wheel and 500 g The haze difference (DELTA haze) before and after the abrasion is 6.0 or less and the transmittance difference (DELTA Transmittance) is 0.8 or less at 500 times of abrasion under load conditions.

Another aspect of the present invention relates to a method for producing a polycarbonate glazing comprising forming a hard coat layer with a coating liquid containing a polysilazane or polysiloxazane on one side of a polycarbonate base material.

The polycarbonate glazing according to the present invention is excellent in abrasion resistance and transparency, has excellent adhesion between a polycarbonate base material and a hard coating layer without a separate primer layer, has excellent gas barrier property and excellent stain resistance due to low water permeability. In addition, the method of producing polycarbonate glazing according to the present invention can be wet-coated by a wet process, shortening the manufacturing time and being excellent in processability.

1 is a cross-sectional view of a polycarbonate glazing according to one embodiment of the present invention.
2 is a cross-sectional view of a polycarbonate glazing according to another embodiment of the present invention.

Embodiments of the present application will now be described in more detail with reference to the accompanying drawings. However, the techniques disclosed in the present application are not limited to the embodiments described herein but may be embodied in other forms. It should be understood, however, that the embodiments disclosed herein are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the drawings, the width, thickness, and the like of the components are enlarged in order to clearly illustrate the components of each device. In addition, although only a part of the components is shown for convenience of explanation, those skilled in the art will be able to easily grasp the rest of the components. It is to be understood that when an element is described as being located on another element, it is meant that the element is directly on top of the other element or that additional elements can be interposed between the elements . It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention. In the drawings, the same reference numerals denote substantially the same elements.

Polycarbonate Glazing

One aspect of the invention relates to polycarbonate glazing. The polycarbonate glazing in the present invention may include a substrate comprising a polycarbonate and at least one coating layer laminated on the substrate.

1 shows a cross-sectional view of a polycarbonate glazing according to one embodiment of the present invention. Referring to FIG. 1, a polycarbonate glazing 100 includes a polycarbonate-based substrate 110; And a hard coating layer 120 formed on one side of the polycarbonate-based substrate 110.

The polycarbonate-based substrate 110 includes a polycarbonate-based resin, and the polycarbonate-based resin can be used without limitation within a range that can achieve the object of the present invention. For example, a polycarbonate, a polycarbonate copolymer or a polycarbonate blending resin may be used, and as the blending resin, polyamide, thermoplastic polyurethane (TPU), acrylonitrile-styrene-acrylonitrile, polymethyl methacrylate , Polyesters, and acrylonitrile-butadiene-styrene may be used, but the present invention is not limited thereto. Two or more of them may be used in combination. The polycarbonate can be produced by reacting phosgene with a dihydric phenol compound in the presence of a molecular weight modifier and a catalyst according to a conventional production method. Further, as another embodiment, the polycarbonate may be prepared by using an ester interchange reaction of a carbonate precursor such as a diphenyl carbonate and a dihydric phenol compound. In the process for producing such a polycarbonate, the dihydric phenol compound may be a bisphenol compound. For example, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) may be used. At this time, the bisphenol A may be partially or wholly replaced by other dihydric phenol compounds.

Specifically, from the viewpoints of safety and transparency required as substrates for polycarbonate glazing, the polycarbonate resin preferably has a tensile strength of 60 MPa or more, a tensile elastic modulus of 1.5 GPa or more, a Vicat softening point of 120 캜 or more, a total light transmittance of 80% Or more.

The thickness of the polycarbonate-based substrate 110 may be 1 mm to 10 mm. Within the above range, mechanical strength, flexibility, transparency and the like can be excellent as a base material for 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 polysiloxazane or polysilazane. Specifically, the hard coating layer 110 is formed by applying a coating solution containing a hydrogenated polysiloxazane or polysilazane and an organic solvent to one side of the polycarbonate base material 120, and then performing a modification process to the hydrogenated polysilazane or a siloxane compound such as hydrogenated polysiloxazane made upset ceramic is turned into silicon dioxide (SiO ₂₎ may be formed as a coating layer containing silicon oxide (SiOx).

The thickness of the hard coat layer 120 may be 50 to 3,000 nm, specifically 100 to 1,000 nm. Sufficient wear resistance can be ensured in the above thickness range, and occurrence of cracks can be minimized. Further, since the hard coating layer 120 is formed by a wet process, sufficient adhesion or adhesion can be ensured without forming a separate primer layer on the polycarbonate base material. Therefore, it can be formed directly on the polycarbonate-based substrate 110.

The polycarbonate glazing according to an embodiment of the present invention may include a hard coating layer derived from polysiloxazane or polysilazane, so that the abrasion resistance can be excellent. Specifically, the polycarbonate glazing had a Haze difference (ΔHaze) of 6.0 or less before and after abrasion at 500 times of abrasion with a CS-10F abrasive wheel under a 500 g load condition using a Taber Abraser, The difference (Transmittance) may be less than or equal to 0.8.

In addition, the polycarbonate glazing according to an embodiment of the present invention has a modulus of 45 to 60 GPa, minimizes cracks in the hard coating layer, can secure sufficient strength, and is excellent in wear resistance. 'Modulus' in the present invention means a value measured at room temperature using a nanoindenter Ti 750 Ubi (manufactured by Hysitron). In the present invention, room temperature means 25 캜 3 캜 unless otherwise specified.

The polycarbonate glazing according to one embodiment of the present invention is characterized in that when the water permeability (WVTR) (g / m ² / day) is measured according to ASTM F-1249 standard (1.0 ) g / (m ² .day) or less, and is excellent in the 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 1 to 50 nm, and polycarbonate glazing having improved surface flatness due to the hard coat layer can be obtained.

Hereinafter, polycarbonate glazing according to another embodiment of the present invention will be described with reference to FIG. Figure 2 shows a cross-sectional view of a polycarbonate glazing according to 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 base material and the hard coat layer, We will focus on the middle layer.

Referring to FIG. 2, the intermediate layer 130 may be a laminated structure of a bonding layer, a functional layer or a bonding layer and a functional layer, and may have a laminated structure of at least one layer. The functional layer may be, for example, an ultraviolet barrier layer, a buffer layer, an abrasion layer or a barrier layer, or the like, and may be a plurality of layers combined with each other.

 In one embodiment, the intermediate layer 130 can improve the bonding force between the polycarbonate base material 110 and the other layer, and can be selected from amide resins, acrylic resins, urethane resins, siloxane resins, silicone resins, But are not limited thereto. Specific examples thereof include polyolefins such as an aliphatic polyether thermoplastic polyurethane, a polyester / polyether thermoplastic polyurethane, an anionic lipophilic polyester polyurethane, an anionic fatty polyester / polyether polyurethane, an aqueous polyurethane, a polyamide, And the like.

In one embodiment, the intermediate layer 130 may include a material that absorbs light having a wavelength of 200 to 340 nm, which is an ultraviolet ray region, as an ultraviolet absorber, thereby protecting the polycarbonate base material from ultraviolet rays to improve weatherability. The ultraviolet absorber may include a metal oxide fine particle, an organic compound, and the like. Specifically, a metal oxide may be included. In one embodiment, the metal oxide used as the ultraviolet absorber is a fine particle having an average particle diameter of 1 to 100 nm, for example, 5 to 25 nm, and may be one kind selected from the group consisting of zinc oxide, titanium oxide, cerium oxide, Or more fine particles. In another embodiment, the organic compound used as the ultraviolet absorber may include a benzotriazole system, a triazine system, and 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. Examples of the binder resin include an acrylate-based monomer, an acrylate-based oligomer, a siloxane-based monomer, a siloxane-based polymer, a silicone-based monomer, a silicone- Resin or the like can be used.

In one embodiment, the intermediate layer 130 may be formed by a sol-gel synthesis method in which the hydrolyzed alkoxysilane is condensed with a colloidal silica sol to form a silicone system having a silica network structure Buffer layer. As the alkoxysilane, a trivalent or tetravalent alkoxysilane may be used. Examples of the alkoxysilane include vinyltrimethoxysilane, propyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, and the like. May be used singly or in combination.

In one embodiment, the intermediate layer 130 may be an acrylic abrasion layer comprising a photo-curable resin and silica nanoparticles. The photo-curing resin can be formed by curing an ultraviolet curing compound having an acrylate-based functional group. The ultraviolet ray curable compound may be a polyfunctional (meth) acrylate compound or the like. For example, the polyfunctional acrylate compound may be at least one selected from the group consisting of ethylene glycol diacrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, trimethylolpropane tri (meth) Di (meth) acrylates of bisphenol A-diglycidyl ether, polyhydric alcohols and polycarboxylic acids, and anhydrides thereof with acrylic acid to obtain a poly (meth) acrylate (Meth) acrylate, acrylate functional group-containing siloxane compound, urethane (meth) acrylate, pentaerythritol tetramethacrylate, glycerin trimethacrylate, and the like.

The silica nanoparticles may have an average particle size (D50) of 100 nm or less, for example, 10 to 50 nm, and 50% by weight or less, for example, 5 to 40% by weight of the acrylic abrasion-resistant layer. When the silica nanoparticles are contained in the above range, the hardness can be increased to further improve the abrasion 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.

Hard coat layer coating liquid

The coating liquid for forming the hard coat layer may be a hydrogenated polysiloxazane, a hydrogenated polysilazane, or a mixture thereof; And a solvent. The components constituting the coating liquid will be described as follows.

(A) hydrogenated polysiloxazane or hydrogenated polysilazane

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

The hydrogenated polysiloxazane or hydrogenated polysilazane can be converted into a silicon oxide material by heating and oxidation reaction, and a hard coat layer having excellent abrasion resistance can be obtained.

The hydrogenated polysiloxazane contains a silicon-oxygen-silicon (Si-O-Si) bonding unit in addition to a silicon-nitrogen (Si-N) bonding unit in the structure. Such silicon-oxygen-silicon (Si-O-Si) bonding units can reduce shrinkage by relaxing stress during curing.

The hydrogenated polysilazane contains silicon-hydrogen (Si-H) and nitrogen-hydrogen (N-H) bonding units in addition to the silicon-nitrogen (Si-N) bonding unit in the basic skeleton in the structure.

After the hydrogenated polysiloxazane or the hydrogenated polysilazane is subjected to the baking process or the curing process, the (Si-N) bond may be replaced with the (Si-O) bond.

In an embodiment, the hydrogenated polysiloxazane has a unit represented by the following formula (1), a unit represented by the following formula (2), and a terminal represented by the following formula (3)

[Chemical Formula 1]

(2)

(3)

In the general formulas (1) and (2), R1 to R7 each independently represent 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 , A substituted or unsubstituted C3 to C30 arylalkyl group, a substituted or unsubstituted C3 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 heterocycle alkyl group, a substituted or unsubstituted C3 to C30 alkenyl group, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxy group, or a combination thereof.

The term "substituted" in the present invention means hydrogen, halogen atom, hydroxyl group, nitro group, cyano group, amino group, azido group, amidino group, hydrazino group, carbonyl group, carbamyl group, A carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphate group or a salt thereof, an alkyl group having 1-20 carbon atoms, an alkenyl group having 2-20 carbon atoms, an alkynyl group having 2-20 carbon atoms, an alkoxy group having 1-20 carbon atoms, An aryloxy group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a cycloalkenyl group having 3 to 30 carbon atoms, a cycloalkynyl group having 3 to 30 carbon atoms, or a combination thereof.

The hydrogenated polysiloxazane or hydrogenated polysilazane may have an oxygen content of 0.2% to 3% by weight. When it is contained in the above range, the stress relaxation due to the silicon-oxygen-silicon (Si-O-Si) bond in the structure is sufficient to prevent shrinkage during heat treatment, have. For example, the oxygen content of the hydrogenated polysiloxazane or the hydrogenated polysilazane may be 0.2 to 3 wt%, specifically 0.5 to 2 wt%.

Also, the hydrogenated polysiloxazane or polysilazane is a structure in which the terminal portion is capped with hydrogen, and the terminal group represented by the above-mentioned general formula (3) is in the range of from 15 to 100 parts by mass relative to the total content of Si-H bonds in the hydrogenated polysiloxazane or hydrogenated polysilazane structure. 35% by weight. When it is included in the above range, the oxidation reaction occurs sufficiently during curing, and the SiH ₃ part is prevented from being scattered due to SiH ₄ during curing, thereby preventing shrinkage and preventing cracks from being formed in the hard coating layer formed therefrom. For example, the terminal group of Formula 3 may be included in the hydrogenated polysiloxazane or the hydrogenated polysilazane structure in an amount of 20 to 30% by weight based on the total amount of Si-H bonds.

The hydrogenated polysiloxazane or hydrogenated polysilazane of the present invention may have a weight average molecular weight (Mw) of 1,000 to 5,000 g / mol. In the case of the above range, a dense organic-inorganic mixed layer can be formed by a thin film coating while reducing a component to be evaporated during heat treatment. For example, the weight average molecular weight (Mw) may be 1,500 to 3,500 g / mol.

The hydrogenated polysiloxazane, hydrogenated polysilazane, or a mixture thereof may be contained in an amount of 0.1 to 50% by weight based on the total amount of the coating liquid. When it is included in the above-mentioned range, it can maintain an appropriate viscosity and can be formed flat and even without bubbles and voids.

(B) Solvent

The solvent may be any solvent which is not reactive with hydrogenated polysiloxazane or hydrogenated polysilazane but is capable of dissolving them. However, when OH is contained, a solvent containing no -OH group is preferable because it is reactive with the siloxane-based compound. For example, hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, alcohols such as aliphatic ethers and alicyclic ethers can be used. Specific examples thereof include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and tallow, halogen hydrocarbons such as methylene chloride and tricholoroethane, ethers such as dibutyl ether, dioxane and tetra- And so on. The solubility of the siloxane-based compound, the evaporation rate of the solvent, and the like may be suitably selected and a plurality of solvents may be mixed.

The coating solution 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 hydrogenated polysiloxazane and the stain due to uncured silicone resin so that the hydrogenated polysiloxazane can 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 it can be activated at about 90 캜 or higher to generate sufficient acid to have low volatility. Such thermal acid generators may be selected from, for example, nitrobenzyl tosylate, nitrobenzyl benzene sulfonate, phenol sulfonate, and combinations thereof. The thermal acid generator may be contained in an amount of 25% by weight or less, for example, 0.01 to 20% by weight based on the total amount of the coating liquid. When included in the above range, the siloxane-based compound can be developed at a relatively low temperature.

The coating liquid of the present invention may further comprise a surfactant. The surfactant is not particularly limited and includes, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene ether, and polyoxyethylene rail ether, polyoxyethylene nonylphenol ether Polyoxyethylene sorbitan esters such as polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, and the like; And nonionic surfactants such as fatty acid esters such as EFTOP EF301, EF303 and EF352 (manufactured by TOKEM PRODUCTS CO., LTD.), Megapac F171 and F173 (manufactured by Dainippon Ink and Chemicals, Inc.). Fluorinated surfactants such as Prorad FC430 and FC431 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Chaplon S-382, SC101, SC102, SC103, SC104, SC105 and SC106 (manufactured by Asahi Glass Co., A siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and other silicone surfactants. The surfactant may be contained in an amount of 10% by weight or less, for example, 0.001 to 5% by weight based on the total amount of the coating liquid.

Manufacturing method of polycarbonate glazing

A method of manufacturing polycarbonate glazing according to an embodiment of the present invention may include forming a hard coating layer on a surface of a substrate with a coating liquid containing a hydrogenated polysilazane or a hydrogenated polysiloxazane. Specifically, the coating liquid may be applied and then modified to form a hard coat layer.

First, a coating liquid containing a polysilazane or polysiloxazane is coated on a polycarbonate base material. The application of the coating liquid may be applied by roll coating, spin coating, bar coating, dip coating, flow coating, spray coating, Do not. For example, the spin coating may be performed at 500 to 4,000 rpm for 10 to 60 seconds, and the coating may be repeated one or more times.

The coating thickness of the coating liquid may be 50 to 3,000 nm, and the coated liquid may be dried for 1 to 100 minutes at 50 to 100 ° C and 40 to 90% relative to the coating liquid.

The modification to form the hard coating layer means a process of converting a siloxane compound such as hydrogenated polysiloxazane or hydrogenated polysilazane into silicon dioxide to ceramize it.

As one embodiment of the present invention, ultraviolet irradiation or ceramization under high temperature and high humidity may be performed to increase the conversion rate of the silazane or polysiloxazane compound to silicon dioxide.

The ultraviolet ray irradiation may be performed using vacuum ultraviolet rays. Specifically, a vacuum ultraviolet ray of about 100 to about 200 nm may be used. The irradiation intensity of the ultraviolet rays and the irradiation amount can be appropriately set. The ultraviolet radiation may be irradiated for about 0.1 to about 5 minutes, for example, at an irradiation intensity of about 10 to about 200 mW / cm 2, and an irradiation dose of about 100 to about 6,000 mJ / cm 2. The dose may be specifically from about 1,000 to about 5,000 mJ / cm < 2 >.

The ceramization under the high temperature and high humidity may be, for example, a heat treatment at 300 to 1,500 占 폚 for 1 to 12 hours.

According to the production method according to another embodiment of the present invention, after the ultraviolet ray irradiation, for example, the ultraviolet ray is irradiated at a temperature of 80 to 150 ° C and a relative humidity of 10 to 90%, specifically 40 to 90% Lt; RTI ID = 0.0 > 40-100 < / RTI > minutes.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. However, the following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited to the following examples. The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

Production Example 1: Hard Coat Layer Coating Solution I

The inside of a 2 L reactor equipped with a stirrer and a temperature controller was replaced with dry nitrogen, 2.0 g of pure water was poured into 1,500 g of dry pyridine, and the mixture was thoroughly mixed. 100 g of dichlorosilane was slowly added thereto over 1 hour, and then 70 g of ammonia was slowly injected over 3 hours while stirring. Next, dry nitrogen was injected for 30 minutes to remove ammonia remaining in the reactor. The resulting white slurry product was filtered through a 1 mu m teflon filter under a dry nitrogen atmosphere to obtain 1,000 g of a filtrate. 1,000 g of dry xylene was added thereto, and the operation of replacing the solvent with xylene in pyridine using a rotary evaporator was repeated three times in total to adjust the solid content concentration to 20%, and finally the pore size And filtered through a Teflon filter of 0.03 占 퐉 to prepare a hard coat layer coating solution I.

The oxygenated content of the obtained hydrogenated polysiloxazane was 0.5%, the SiH ₃ / SiH (total) was 0.20, and the weight average molecular weight was 2,000 g / mol.

Production Example 2: Hard Coat Layer Coating Solution II

25.62 g of tetraethyl silicate (TEOS, Sigma Aldrich) was added to 100 g of distilled water containing 0.3 g of 95% acetic acid, and methyltrimethoxysilane (MTMS, Shin Etsu KBM503) was added thereto while stirring To prepare a resin solution at room temperature. The molar ratio of tetraethyl silicate to methyltrimethoxysilane added was 1: 2. Thereafter, silica particles (SiO ₂ , manufactured by FUSO) were added in an amount of 30 parts by weight based on the resin solid content to prepare hard coating solution II.

Production Example 3: Hard Coat Layer Coating Solution III

28.0 g of a urethane acrylate resin (UNIDIC RC27-947, DIC CORPORATION) was added to 69.0 g of a solvent isopropyl alcohol (IPA, KBM503, manufactured by Samyoung Co., Ltd.) and stirred with Igacure 184 (Ciba) 3 g was further added thereto, followed by stirring at 700 rpm for 20 minutes to prepare a resin solution. Thereafter, silica particles (SiO ₂ , manufactured by FUSO) were added in an amount of 30 parts by weight based on the resin solid content to prepare hard coating solution III.

Production Example 4: Hard Coat Layer Coating Solution IV

10 g of dipentaerythritol hexaacrylate (DPHA, SK Cytec), which is a polyfunctional acrylate monomer, and 10 g of pentaerythritol triacrylate (PETA, Satomer) were dissolved in a first solvent, 2-methoxyethanol (MCS, 3 g of Igacure 184 (Ciba) was added as a photoinitiator, and the mixture was sufficiently stirred at 700 rpm for 20 minutes. Then, a second solvent, isopropyl alcohol (IPA, ) Was added and stirred for 20 minutes. Finally, 0.1 g of polyether-modified polydimethylsiloxane (BYK306) was added as a leveling improving additive and stirred for 10 minutes to prepare a resin solution. Thereafter, silica particles (SiO ₂ , manufactured by FUSO) were added in an amount of 30 parts by weight based on the resin solid content to prepare hard coating solution IV.

Examples 1 to 3 and Comparative Examples 1 to 3

Example 1

Spin coating was performed with a hard coating layer coating solution I on one side of a 3 mm thick polycarbonate substrate (LEXAN, GE) to form an inorganic layer having a thickness of 500 nm. The coating solution was diluted with DBE (dibutyl ether) to a solid content of 9.5%. Spin coating was performed at 1,000 rpm for 20 seconds, followed by drying in a convection oven at 80 ° C for 3 minutes. CR403) at a light intensity of 14 mW / cm < ² > for 143 seconds and UV irradiation at 2,000 mJ / cm < ² >, then left at room temperature for 24 hours to prepare polycarbonate glazing. Respectively.

Example 2

Spin coating was performed with a hard coating layer coating solution I on one side of a 3 mm polycarbonate substrate (LEXAN, GE) to form an inorganic layer having a thickness of 500 nm. The coating solution was diluted with DBE (dibutyl ether) to a solid content of 9.5%. Spin coating was performed at 1,000 rpm for 20 seconds, followed by drying in a convection oven at 80 ° C for 3 minutes. CR403) at 214 mW / cm < ² > for 214 seconds and UV irradiation at 4,000 mJ / cm < ² >, and left at room temperature for 24 hours to prepare polycarbonate glazing. Respectively.

Example 3

Spin coating was performed on a surface of a 3 mm polycarbonate substrate (LEXAN, GE) with a hard coating layer coating solution I to form an inorganic layer having a thickness of 1,000 nm. At this time, the coating liquid was diluted with DBE (dibutyl ether) so that the solid content was 9.5%. The spin coating was performed at 1,000 rpm for 20 seconds, followed by drying in convection oven at 80 占 폚 for 3 minutes, coating at 1,000 rpm for 20 seconds, and drying at 80 占 폚 in convection oven for 3 minutes.

After spin coating, the substrate was exposed to UV light (SMT CR403) at an irradiation intensity of 14 mW / cm ² for 143 seconds and then irradiated with UV light at 2,000 mJ / cm ² , and then allowed to stand at room temperature for 24 hours to produce polycarbonate glazing. The measured values are shown in Table 1 below.

Comparative Example 1

A coating layer having a thickness of 500 nm was formed on the surface of a 3 mm polycarbonate substrate (LEXAN, GE) by spin coating with a hard coating layer coating solution II. At this time, the spin coating is then coated for 20 seconds to 1,000rpm, was dried at 80 ℃ convection oven for 3 minutes, UV irradiation by exposure for 143 seconds with illumination intensity 14mW / cm2 at (SMT社CR403) 2,000 mJ / cm 2 And then allowed to stand at room temperature for 24 hours to prepare polycarbonate glazing. The measured values after measurement of physical properties are shown in Table 1 below.

Comparative Example 2

A coating layer having a thickness of 1,000 nm was formed on the surface of a 3 mm polycarbonate substrate (LEXAN, GE) by spin coating with a hard coating layer coating solution III. At this time, spin coating was performed for 20 seconds at 1,000 rpm, followed by drying for 3 minutes at 80 ° C. in a convection oven. Polycarbonate glazing was prepared by irradiating ultraviolet ray at 350 mJ / cm light intensity using a high pressure mercury lamp, The measured values are shown in Table 1 below.

Comparative Example 3

A coating layer having a thickness of 1,000 nm was formed on the surface of a 3 mm polycarbonate substrate (LEXAN, GE) by spin coating with a hard coating layer coating liquid IV. At this time, spin coating was performed for 20 seconds at 1,000 rpm, followed by drying for 3 minutes at 80 ° C. in a convection oven. Polycarbonate glazing was prepared by irradiating ultraviolet ray at 350 mJ / cm light intensity using a high pressure mercury lamp, The measured values are shown in Table 1 below.

Property evaluation method

(1) Abrasion resistance: haze (haze) before and after abrasion with a haze meter (NHD 2000N, Nippon Denshoku) with a CS-10F abrasive wheel using a Taber Abraser and 500 times of wear under a load of 500 g, And transmittance were measured respectively.

(2) Cracks: The polycarbonate glazing produced in the above Examples and Comparative Examples was allowed to stand at room temperature for 1 hour, and then visually observed.

* Excellent (Marked with "x" in the table): The cracked portion of the coating layer is not seen.

* Bad (In the table, marked with " o "): Cracks appear in part or all of the coating layer.

(3) Adhesiveness (number / number): A line was drawn at intervals of 2 mm on a specimen to form a grid-like scale and 100 points were displayed. The tape was bonded and strongly pulled once in the vertical direction to measure the number of peeling not to occur.

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

(5) Water Permeability (WVTR) (g / m ² / day): Measured according to ASTM F-1249 standard using Aquatran Model 1 (Mocon). The size of the specimen is 100 * 100mm.

(6) Surface roughness (Ra): Measured using a surface roughness meter NT1100 manufactured by veeco.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Ha
De
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Ting
layer
(nm) Coating solution I 500 500 1,000 - - - Coating solution II - - - 500 - - Coating liquid III - - - - 1,000 - Coating liquid IV - - - - - 1,000 of mine
hemp
mother
castle He
this
The
(%) Before abrasion 0.4 0.4 0.4 0.5 0.4 0.5 After abrasion 5.4 4.2 3.8 9.2 27.0 35.4 ΔH 5.0 3.8 3.2 8.8 26.6 29.9 form
and
Degree
(%) Before abrasion 88.0 88.1 88.1 89.0 88.0 88.0 After abrasion 88.4 88.0 88.1 86.1 85.9 85.0 ΔT 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 4.1 nm 3.7 nm 11 nm 3.7 nm 10.3 nm

As can be seen from the results of Table 1, the PC glazing of Examples which includes a hard coating layer derived from polysilazane or polysiloxazane and formed by a wet process had haze difference (Δ Haze) before and after abrasion and difference in transmittance ) Is lower than that of the comparative example, and it can be seen from this that the abrasion resistance is excellent. In addition, the PC glazing according to the embodiment has excellent adhesion between the substrate and the hard coating layer without having a separate primer layer, has excellent barrier properties due to low water permeability (WVTR), low surface roughness, It can be seen that it is excellent.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.

Claims (10)

A polycarbonate-based substrate; And a silicone-based hard coating layer formed on one surface of the substrate,
The haze difference (Δ Haze) before and after the abrasion was 6.0 or less and the transmittance difference (Δ Transmittance) was 0.8 or less when the abrasion wheel of CS-10F and the abraded wheel of 500 g were 500 times abraded using a Taber Abraser Polycarbonate glazing.
The method according to claim 1,
Wherein the hard coat layer is derived from polysilazane or polysiloxazane.
The method according to claim 1,
The thickness of the polycarbonate-based substrate is 1 to 10 mm,
The hard coating layer has a thickness of 100 to 1000 nm.
The method according to claim 1,
Wherein the hard coat layer has a surface roughness (Ra) of 1 to 20 nm.
The method according to claim 1,
Polycarbonate glazing with a modulus of 45 to 60 GPa.
The method according to claim 1,
Wherein the hard coat layer has a water permeability (WVTR) measured according to ASTM F-1249 of (1.0) g / (m ² day) or less.
The method according to claim 1,
The hard coating layer is formed by coating directly on the polycarbonate-based substrate.
A method for producing a polycarbonate glazing comprising forming a hard coating layer on a surface of a polycarbonate base material with a coating liquid containing polysilazane or polysiloxazane.
9. The method of claim 8,
The formation of the hard coating layer includes coating the coating liquid on at least one surface of the polycarbonate base material and then converting the coating liquid into silicon dioxide by irradiating ultraviolet rays.
10. The method of claim 9,
And irradiating the ultraviolet rays with ultraviolet rays at an ultraviolet irradiation intensity of 10 to 200 mW / cm 2 and an irradiation dose of 100 to 6,000 mJ / cm 2.

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