KR20150041404A - Polycarbonate glazing and the method for preparing the same - Google Patents

Abstract

The present invention relates to a polycarbonate glazing, comprising a polycarbonate based substrate; a buffer layer formed on the substrate; and a silicon based hard coating layer formed on the buffer layer, whose difference of haze is not more than 4.0 between a previous process and a post process of abrasion when a CS-10 F abrasion wheel is rubbed at least 500 times under 500 g load by using a Taber Abraser, and a manufacturing method thereof. The polycarbonate glazing of the present invention has good abrasion resistance, weather resistance, transparency and flexibility, thereby having an outstanding effect of preventing crack, and the manufacturing method thereof is allowed to perform a non-vacuum wet coating by using a wetting process, thereby reducing a manufacturing time and having a good process.

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, attempts have been made to form a silica film with a hard coating layer on a substrate by plasma enhanced chemical vapor deposition (PECVD), CVD, sputtering 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 cumbersome.

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 having excellent weather resistance.

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

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

One aspect of the present invention relates to a polycarbonate based substrate; A buffer layer formed on the substrate; And a silicon hard coating layer formed on the buffer layer. The haze difference (DELTA haze) before and after the abrasion at 500 times of abrasion with a CS-10F abrasion wheel and a load of 500 g was measured using a Taber Abraser 0.0 > 4.0 < / RTI >

Another aspect of the present invention relates to a polycarbonate glazing comprising a buffer layer formed on one surface of a polycarbonate base material and then forming a silicone hard coating layer on the buffer layer with a coating solution containing hydrogenated polysilazane or hydrogenated polysiloxazane And a manufacturing method thereof.

The polycarbonate glazing of the present invention is excellent in abrasion resistance, weather resistance and transparency, excellent in flexibility and excellent in crack prevention effect.

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 an embodiment of the present invention.
2 is a cross-sectional view of a polycarbonate glazing according to another embodiment of the present invention.
3 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.

1 shows a cross-sectional view of a polycarbonate glazing according to an embodiment of the present invention. Referring to FIG. 1, a polycarbonate glazing 100 according to an embodiment of the present invention includes a polycarbonate-based substrate 110; A buffer layer 120 formed on the polycarbonate-based substrate 110; And a silicon-based hard coating layer 140 formed on the buffer layer 120. The polycarbonate glazing according to the present embodiment includes a silicon hard coating layer derived from polysilazane or polysiloxazane and has excellent abrasion resistance as well as adhesion strength and wear resistance to the lower substrate due to the buffer layer.

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. 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 example, the polycarbonate may be prepared by using an ester interchange reaction of a carbonate precursor such as a dihydroxy phenolic compound and diphenyl carbonate. 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 50 mm, for example, 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 buffer layer 120 may be formed on the polycarbonate-based substrate 110. The buffer layer 120 improves the bonding force between the polycarbonate-based substrate 110 and another layer (e.g., a silicon-based hard coat layer) or relaxes the stress between the polycarbonate substrate and the silicon-based hard coat layer, have.

The buffer layer 120 may include at least one selected from a silicone resin, an acrylic resin, an epoxy resin, a urethane resin, an ester resin, or a copolymer thereof, but is not limited thereto. Specifically, the buffer layer 120 may be formed of an acrylic resin such as polymethylmethacrylate (PMMA), and the acrylic resin is excellent in adhesion to the polycarbonate base material 110. Further, the buffer layer 120 may be a silicon-based coating layer containing silica particles formed of a coating solution containing alkoxysilane and colloidal silica. In the case of the silicon-based coating layer containing the silica particles, the wear resistance of the polycarbonate glazing can be improved. The thickness of the buffer layer 120 may be 1 탆 to 50 탆, specifically 1 탆 to 10 탆. In this range, the stress between the polycarbonate substrate and the other layers such as the hard coat layer and the like is relieved to be effective in crack prevention, and the adhesion force between the polycarbonate substrate and the other layer can be increased. In addition, wear resistance can be improved.

The silicon hard coating layer 140 may be formed on the buffer layer 120. The silicone hard coat layer 140 may be derived from polysiloxazane or polysilazane. Specifically, the silicone hard coat layer 140 is formed by coating a surface of the buffer layer 120 with a coating solution containing hydrogenated polysiloxazane or polysilazane, and an organic solvent, and forming a coating layer containing silicon oxide (SiOx) .

The thickness of the silicone hard coat layer 140 may be 0.1 탆 to 2 탆, specifically 0.1 탆 to 0.7 탆. Sufficient wear resistance can be ensured in the above thickness range, and occurrence of cracks can be minimized.

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. Referring to FIG. 2, a polycarbonate glazing 200 according to another embodiment of the present invention includes a polycarbonate-based substrate 110; A first buffer layer 221 formed on one surface of the polycarbonate-based substrate 110; A second buffer layer 222 formed on the first buffer layer 221; And a silicon-based hard coating layer 140 formed on the second buffer layer 222. This embodiment includes substantially the same components as the polycarbonate glazing according to an embodiment of the present invention except that the buffer layer is formed by a multilayer structure of the first buffer layer 221 and the second buffer layer 222 Here, the buffer layers 221 and 222 will be mainly described.

The first buffer layer 221 may be formed of an acrylic resin. For example, a coating liquid containing an acrylic resin such as polymethylmethacrylate (PMMA) and a solvent and a solvent, but is not limited thereto. The first buffer layer 221 may further include an ultraviolet absorber.

The second buffer layer 222 may be a silicon layer including inorganic particles, and may be an organic-inorganic hybrid silicon-based coating layer containing, for example, silica particles. Specifically, the second buffer layer 222 may be formed by sol-gel reaction of alkoxysilane and colloidal silica, and may include a silica network structure. As the alkoxysilane, a trivalent or tetravalent alkoxysilane may be used. Examples include vinyl trimethoxysilane, propyl trimethoxysilane,? -Glycidoxy propyl trimethoxysilane, methyl trimethoxysilane, methyl trimethoxysilane, May be used singly or in combination, but the present invention is not limited thereto. The second buffer layer 222 formed by the sol-gel synthesis method has high chemical uniformity and is excellent in weather resistance and thick film coating property and is excellent in flexibility and relieves the stress between the polycarbonate substrate and the silicone hard coat layer, Prevention effect can be obtained.

The size of the inorganic particles may be 1 nm to 100 nm, which is uniformly dispersible in water or an organic solvent. Specifically, the inorganic particles may be at least one selected from the group consisting of Al, Si, B, Mg, Ca, Sr, Ba, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Zr, Hf, A metal, a nonmetal, an oxide, a nitride, or a carbide thereof selected from the group consisting of W, La, Ce, Sn, As, Sb, Y, Pb, Bi, Gd, Ho, Ag, Au and C . Since the inorganic particles must be uniformly dispersed in water or an organic solvent, they are preferably used in the form of a stable colloidal dispersion in consideration of PZC (Point of Zero Charge) or IEP (Isoelectric Point). For example, the inorganic particles may be uniformly dispersed in water or an organic solvent in an amount of 5 to 70% by weight. The inorganic particles may be contained in an amount of 0.01 to 80% by weight in the buffer layer. If it is contained in an amount exceeding 80% by weight, transparency and coating properties may be deteriorated.

When the buffer layers 221 and 222 are formed in a multi-layer structure as shown in FIG. 2, the thickness of the first buffer layer 221 may be 1 to 3 μm and the thickness of the second buffer layer 222 may be 4 to 10 μm .

Hereinafter, polycarbonate glazing according to another embodiment of the present invention will be described with reference to FIG. Figure 3 shows a cross-sectional view of a polycarbonate glazing according to another embodiment of the present invention. Referring to FIG. 3, a polycarbonate glazing 300 according to another embodiment of the present invention includes a polycarbonate-based substrate 110; A buffer layer 320 formed on one surface of the polycarbonate-based substrate 110; And a silicon hard coating layer 140 formed on the buffer layer 320. The polycarbonate glazing 300 of the present embodiment is substantially similar to the polycarbonate glazing 100 according to one embodiment of the present invention except that the buffer layer 320 may be an ultraviolet barrier layer, The buffer layer 320 will be mainly described below.

The buffer layer 320 may comprise an ultraviolet absorber. When the ultraviolet absorbent is included, the weather resistance can be further improved without forming a separate ultraviolet barrier layer. Although only a case where the buffer layer 320 is formed as a single layer is illustrated in the drawing, when the buffer layer 320 has a multi-layer structure, the ultraviolet absorbing agent may be included in at least one layer.

The ultraviolet absorber may include metal oxide fine particles, organic compounds and the like, and may specifically include a metal oxide. In one embodiment, the metal oxide used as the ultraviolet absorber is fine particles having an average particle diameter (D50) of 1 to 100 nm, for example, 5 to 25 nm, such as zinc oxide, titanium oxide, cerium oxide, And at least one kind of fine particles selected from the group consisting of In another embodiment, the organic compound used as the ultraviolet absorber may be benzotriazole-based, triazine-based, or hindered amine-based compounds. For example, there can be mentioned 2-hydroxy-benzophenone, 2- (2-hydroxyphenyl) benzotriazole, 2- (2-hydroxyphenyl) And oxalanilide, but the present invention is not limited thereto.

The polycarbonate glazing according to the embodiments of the present invention may have excellent abrasion resistance by having a silicone hard coat layer derived from polysiloxazane or polysilazane. Specifically, the polycarbonate glazing according to the embodiments of the present invention was evaluated for haze difference (?) Between before and after abrasion at 500 times of abrasion with a CS-10F abrasion wheel and a load of 500 g using a Taber Abraser Haze) may be 4.0 or less.

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

Silicone hard coat layer coating liquid

The composition for the silicone 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 hydrogenated polysiloxazane or hydrogenated polysilazane can be converted into a dense silicon oxide material by heating and oxidation reaction, and a silicon-based hard coat layer excellent in 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.

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 the 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. If 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 in the heat treatment and to prevent cracks from being generated in the silicone hard coating layer . 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-mentioned range, oxidation reaction occurs sufficiently during curing, and SiH ₄ part is prevented from being scattered due to SiH ₄ during curing, thereby preventing shrinkage and preventing cracks from being formed in the silicone 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, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers, and alicyclic ethers. Specific examples thereof include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and tallow, halogenated hydrocarbons such as methylene chloride and trichloroethane, ethers such as dibutyl ether, dioxane and tetra- . The solubility of the siloxane-based compound, the evaporation rate of the solvent, and the like may be suitably selected and mixed with a plurality of solvents.

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 examples thereof include 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 a polycarbonate glazing according to an embodiment of the present invention comprises forming a buffer layer on one surface of a polycarbonate base material and then forming a silicone hard coating layer on the buffer layer with a coating solution containing hydrogenated polysilazane or hydrogenated polysiloxazane . ≪ / RTI > Specifically, the coating liquid may be applied and then modified to form a silicone hard coat layer.

First, a buffer layer is formed on one surface of a polycarbonate substrate. Specifically, a composition for forming a buffer layer may be applied on the polycarbonate substrate, followed by drying or heat treatment. For example, when the composition for forming a buffer layer is an acrylic composition, a coating solution for forming a buffer layer containing an acrylic resin such as polymethylmethacrylate (PMMA) and a solvent is applied on the polycarbonate substrate, can do. When the composition for forming a buffer layer is a silicon buffer layer, a coating solution for forming a buffer layer containing alkoxysilane and colloidal silica may be coated and then heat-treated to form a mesh structure including colloidal silica by a sol-gel synthesis method. As an example, the heat treatment may be performed for 1 to 100 minutes at a temperature of 80 to 150 DEG C and a relative humidity of 10 to 90%.

Then, a silicon hard coating layer is formed on the buffer layer.

Specifically, a coating liquid containing polysilazane or polysiloxazane is applied. 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. After the application of the coating liquid, it may be dried for 1 to 100 minutes at 50 to 100 DEG C and 40 to 90% relative humidity.

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

In one embodiment of the present invention, ultraviolet irradiation or ceramization under high temperature and high humidity may be employed 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 another embodiment of the present invention, in order to further increase the conversion to silica after the ultraviolet ray irradiation, for example, 40 to 100% at 80 to 150 ° C and a relative humidity of 10 to 90%, specifically 40 to 90% Lt; RTI ID = 0.0 > minutes. ≪ / RTI >

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: 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 mu m to prepare a 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: Coating solution II

105.63 g of isopropyl alcohol, 3.41 g of acetic acid and 116.34 g of colloidal silica (Ludox TMA) were sequentially added to a 1 L three-necked flask, and then, while maintaining the temperature at 25 ° C, Glycidoxypropyltrimethoxysilane and 74.26 g of methyltrimethoxysilane were added dropwise over about 30 minutes and the mixture was stirred at 50 ° C for about 2 hours. 68.15 g of n-butyl alcohol was added to the mixture, followed by addition of an ultraviolet absorber (Tinuvin ™ 479 , BASF), and the mixture was stirred at room temperature for about 1 hour to prepare a coating solution. The weight average molecular weight of the coating liquid measured by gel permeation chromatography was 2,100 g / mol.

Production Example 3: Coating solution III

9.59 g of polymethylmethacrylate (Aldrich, molecular weight 120 k), 19.18 g of diacetone alcohol, and 67.13 g of 1-methoxy-2-propanol were placed in a 250 ml three-necked flask The mixture was stirred at 50 ° C for about 4 hours, 4.10 g of an ultraviolet absorber (Tinuvin ™ 479 BASF) was added thereto at room temperature, and the mixture was stirred for about 1 hour to prepare a coating solution.

Examples 1 to 3 and Comparative Examples 1 to 3

Example 1

The coating solution II was coated on one side of a 3 mm-thick polycarbonate substrate (LEXAN, GE) using a Meyer bar, leveled at room temperature for 20 minutes, thermally cured in convection oven at 130 占 폚 for 1 hour, a silicon-based buffer layer having a thickness of 7.5 mu m was formed by a sol-gel method.

The buffer layer and the silicon-based coating solution by spin coating I above and dried at 80 ℃ convection oven for 3 minutes, and the UV irradiation exposure for 214 seconds with illumination intensity 14mW / cm ² at the (SMT社CR403) to 4,000mJ / cm ² After UV irradiation, the film was allowed to stand at room temperature for 24 hours to form a silicone hard coat layer with a thickness of 500 nm.

The physical properties of the polycarbonate glazing manufactured by the above method are shown in Table 1 below.

Example 2

The coating solution III was coated on one side of a 3 mm-thick polycarbonate substrate (LEXAN, GE) using a Meyer bar, leveled at room temperature for 20 minutes, and dried in a convection oven at 125 캜 for 20 minutes to obtain a An acrylic buffer layer was formed.

The coating solution I was applied onto the acrylic buffer layer by spin coating, dried in a convection oven at 80 ° C for 3 minutes, exposed at 214 mW / cm ² at an irradiation intensity of 14 mW / cm ² in a UV irradiator (SMT CR403) at 4,000 mJ / cm ² After UV irradiation, the film was allowed to stand at room temperature for 24 hours to form a 0.5-μm-thick silicon hard coating layer.

The physical properties of the polycarbonate glazing manufactured by the above method are shown in Table 1 below.

Example 3

Coating solution III was coated on one side of a 3 mm-thick polycarbonate substrate (LEXAN, GE) using a Meyer bar, leveled at room temperature for 20 minutes, and dried in a convection oven at 125 ° C for 20 minutes to form an acrylic buffer layer . The coating solution II was coated on the acrylic buffer layer using a Meyer bar, leveled at room temperature for 20 minutes, and heat treated in convection oven at 130 占 폚 for 1 hour to form a silicon buffer layer 6 占 퐉 thick by sol-gel method.

Applying a coating liquid I by spin coating over the silicon-based buffer layer, and dried at 80 ℃ convection oven for 3 minutes, and UV irradiation as (SMT社CR403) intensity 14mW / cm ² with exposure to 4,000 mJ / cm ² for 214 seconds After UV irradiation, the film was allowed to stand at room temperature for 24 hours to form a 0.5 占 퐉 -thick silicon hard coating layer.

The physical properties of the polycarbonate glazing manufactured by the above method are shown in Table 1 below.

Comparative Example 1

Coating solution II was coated on one side of a 3 mm-thick polycarbonate substrate (LEXAN, GE) using a Meyer bar, leveled for 20 minutes at room temperature, and heat-treated for 1 hour in a convection oven at 130 ° C, a silicon-based buffer layer having a thickness of 8 占 퐉 was formed by a sol-gel method.

The physical properties of the polycarbonate glazing manufactured by the above method are shown in Table 1 below.

Comparative Example 2

The coating solution III was coated on one side of a 3 mm-thick polycarbonate substrate (LEXAN, GE) using a Meyer bar, leveled at room temperature for 20 minutes, and dried in a convection oven at 125 ° C for 20 minutes to form an acrylic- .

The physical properties of the polycarbonate glazing manufactured by the above method are shown in Table 1 below.

Comparative Example 3

The coating solution III was coated on one side of a 3 mm-thick polycarbonate substrate (LEXAN, GE) using a Meyer bar, leveled at room temperature for 20 minutes, and dried in a convection oven at 125 캜 for 20 minutes to form an acrylic- . The coating solution II was coated on the acrylic buffer layer using a Meyer bar and then leveled at room temperature for 20 minutes and heat treated in convection oven at 130 占 폚 for 1 hour to form a silicon buffer layer having a thickness of 6.5 占 퐉 by sol-gel method.

The physical properties of the polycarbonate glazing manufactured by the above method are shown in Table 1 below.

Property evaluation method

(1) Abrasion resistance: Haze (before and after wear) with a haze meter (NHD 2000N, Nippon Denshoku) when using a CS-10F abrasive wheel and a 500 g load condition with a Taber Abraser Respectively.

(2) Pencil hardness: The surface was scratched with a pencil hardness tester (CT-PC2, manufactured by Core Tech Co., Ltd.) under a load of 1 kg and 45 degrees in accordance with ASTM D3363.

(3) Gloss Reduction: Gloss was measured using a gloss meter (UGA-6P, SUGA) at an incident angle of 60 ° and an angle of reflection. Gloss reduction refers to the decrease in gloss after 1000 hours of initial exposure.

(4) YI: The YI (Yellowness Index) was measured using a spectrophotometer (CM-3600d, KONICA-MINOLTA) according to ASTM E313-1996. ? YI means the amount of change in the YI value after 1000 hours elapse from the initial value.

(5) △ E: The color coordinates L *, a * and b * in the CIE Lab color space were measured in accordance with SAE J 1960, and ΔE values were calculated after 1000 hours from the initial value according to the following formula.

△ E = √ ((△ L *) 2 + (△ a *) 2 + (△ b *) 2) = √ ((L * (t = 1000hr) -L * (t = 0)) 2 + (a * (t = 1000hr) -a * (t = 0)) 2 + (b * (t = 1000hr) -b * (t = 0)) 2)

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 nose
Ting
layer Acrylic buffer layer
(Coating liquid / thickness) - Coating liquid III
(7.5 mu m) Coating liquid III
(1.5 탆) - Coating liquid III
(8 탆) Coating liquid III
(1.5 탆) The silicon-
(Coating liquid / thickness) Coating solution II
(7.5 mu m) Coating solution II
(6 탆) Coating solution II
(8 탆) - Coating solution II
(6.5 탆) The silicone-based hard coating layer
(Coating liquid / thickness) Coating solution I
(0.5 탆) Coating solution I
(0.5 탆) Coating solution I
(0.5 탆) - - - Abrasion resistance (DELTA H) 2.20 2.45 2.35 4.5 27.5 4.7 Pencil hardness 3H 3H 3H 2H HB 2H of mine
after
castle Gloss Reduction 1.5 1.6 1.2 1.3 1.6 1.2 △ YI 1.4 1.3 1.0 1.3 1.5 1.4 ΔE 1.5 1.5 1.1 1.5 1.6 1.5

As shown in the results of Table 1, Example 1-3, in which a buffer layer was formed between the polycarbonate base material and the silicone hard coat layer, showed superior abrasion resistance and surface hardness in comparison with Comparative Example 1-3 in which the silicone hard coat layer was not formed. . The weather resistance of each of the buffer layer and the hard coat layer in the above Examples and Comparative Examples was found to be equal to that of the UV absorber.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (12)

A polycarbonate-based substrate;
A buffer layer formed on the substrate; And
Based hard coating layer formed on the buffer layer,
Polycarbonate glazing with CS-10F abrasive wheel using a Taber Abraser and a Haze difference (Haze) of 4.0 or less before and after abrading 500 times under 500g load conditions. The method according to claim 1,
Wherein the silicone-based hard coating layer is derived from polysilazane or polysiloxazane. The method according to claim 1,
Wherein the buffer layer comprises an acrylic resin. The method according to claim 1,
Wherein the buffer layer is a silicon-based organic-inorganic hybrid layer. The method according to claim 1,
Wherein the buffer layer comprises an acrylic first buffer layer and a silicon-based second buffer layer. The method according to claim 1,
Wherein the buffer layer is an ultraviolet blocking layer. The method according to claim 1,
Wherein the buffer layer comprises inorganic particles having a size of 1 nm to 100 nm. The method according to claim 1,
The thickness of the polycarbonate base material is 1 mm to 50 mm,
The thickness of the buffer layer is 1 탆 to 10 탆,
Wherein the silicon hard coating layer has a thickness of 0.1 to 0.7 占 퐉. A method for producing a polycarbonate glazing comprising forming a buffer layer on one surface of a polycarbonate base material and then forming a silicone hard coat layer on the buffer layer with a coating solution containing hydrogenated polysilazane or hydrogenated polysiloxazane. 10. The method of claim 9,
Wherein the buffer layer is an acrylic or silicon buffer layer. The method according to claim 10,
Wherein the silicon-based buffer layer is formed by sol-gel synthesis by applying a coating solution containing alkoxysilane and colloidal silica, followed by heat treatment. Ninthly,
Wherein the silicon based hard coating layer is formed by applying the coating solution for forming a silicon hard coating layer onto one surface of the buffer layer or the buffer layer and then converting the coating solution into silicon dioxide by irradiating ultraviolet rays.

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