KR101768277B1 - Primer composition and plastic glazing using the same - Google Patents

Abstract

The primer composition of the present invention is characterized by including a (meth) acrylic polymer comprising the repeating unit represented by the formula (1), the repeating unit represented by the formula (2), and the repeating unit represented by the formula (3). The primer layer formed from the primer composition has excellent adhesion to both the upper and lower layers.

Description

TECHNICAL FIELD [0001] The present invention relates to a primer composition and a plastic glaze using the primer composition.

The present invention relates to a primer composition and plastic glazing using the primer composition. More specifically, the present invention relates to a primer composition for forming a primer layer having excellent adhesion with both the upper and lower layers, and polycarbonate glazing comprising the primer layer.

Plastic materials are relatively lightweight compared to other materials, have flexibility in product design, and are economical in that they can be processed to suit their application. Particularly, efforts have been made to develop a plastic sheet having excellent light transmittance, surface properties, and hardness as a glass substitute, and the results are showing. Examples of such plastic sheets are building glazing, greenhouse windows, transparent soundproof walls, canopies such as fighter planes, canopies of two-wheeled electric trains, etc. Especially applicable to front and rear window and triangular windows of vehicles such as sports cars, .

As an automobile part, when plastic glazing is applied, the specific gravity is smaller than that of automobile glass, and there is no fear of breakage during transportation, and it is possible to lighten about 30% of the total weight of the vehicle-mounted glass. Accordingly, not only the fuel efficiency of the vehicle can be improved through the miniaturization of the driving motor and the lightening of the door module, but also the design of the door module is easy, and the curved surface molding and coloring are easy, thereby achieving the aesthetic and aerodynamic shape of the vehicle It is easy to improve the economical efficiency. Also, from the viewpoint of safety, it is anticipated that the passenger will be prevented from being separated from the vehicle in the event of a collision or rollover, thereby reducing the mortality rate and preventing the breakage of the windshield and theft of the vehicle.

For example, plastic materials such as polycarbonate (PC), polymethylmethacrylate (PMMA) and the like have been developed for the above applications. Among them, the polycarbonate is a colorless transparent material having a specific gravity of 1.2 g / cm ³ and a refractive index of about 1.585. The specific gravity of the polycarbonate is half the glass specific gravity, and the refractive index is similar to that of glass. In terms of physical properties, it has a strength (impact resistance) of about 250 times of a glass plate and about 50 times or more of an acrylate in view of physical properties, and has a high melting point of 220 to 250 DEG C, a glass transition temperature of about 145 DEG C, It has a deformation temperature and is excellent in mechanical strength, water resistance and the like. In addition, it has excellent self-extinguishing property and electrical insulating property, and is excellent in workability, flexibility, transportability, and price. In particular, the flexibility of the design enables the ultra-slim door design to be applied to a modular design, facilitates curved surface molding and coloring, and can further enhance the indoor and outdoor sensibility of the vehicle.

Due to these advantages, polycarbonate is considered to be most suitable as a substitute material for glass, in particular, as a substitute material for automobile glass, but has a disadvantage that it is weaker in abrasion resistance and weather resistance than glass. In order to solve this problem, a hard coat layer containing a weather-resistant additive or the like is formed on polycarbonate to overcome weak abrasion resistance, weather resistance, and the like. However, the hard coating layer may have poor adhesion to polycarbonate, and attempts have been made to improve the interlayer adhesion between the polycarbonate and the hard coat layer by introducing a primer layer.

Japanese Patent Application Laid-Open No. 2000-318106

An object of the present invention is to provide a primer composition for forming a primer layer having excellent adhesion to both the upper and lower layers.

Another object of the present invention is to provide a polycarbonate glazing having excellent abrasion resistance, weather resistance and interlaminar adhesion including the primer layer and a method for producing the same.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the present invention relates to a primer composition. The primer composition is characterized by comprising a (meth) acrylic polymer comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3)

[Chemical Formula 1]

In Formula 1, R ₁ is a hydrogen atom or a methyl group, and R ₂ is an alkyl group having 1 to 5 carbon atoms;

(2)

In Formula 2, R ₃ is a hydrogen atom or a methyl group, and R ₄ is an alkylene group having 1 to 2 carbon atoms;

(3)

In Formula 3, R ₅ is a hydrogen atom or a methyl group, and R ₆ is an alkylene group having 3 to 10 carbon atoms.

In the specific examples, the content of the repeating unit represented by the formula (1) in the (meth) acrylic polymer is 60 to 99 mol%, the content of the repeating unit represented by the formula (2) is 0.5 to 30 mol% The content of the repeating unit represented by 3 may be 0.5 to 30 mol%.

In an embodiment, the repeating unit represented by the formula (1) may be a repeating unit represented by the following formula (1a), a repeating unit represented by the following formula (1b), or a combination thereof.

[Formula 1a]

[Chemical Formula 1b]

In the above formulas (1a) and (1b), R ₂ is as defined in the above formula (1).

In an embodiment, the weight average molecular weight of the (meth) acrylic polymer may be 50,000 to 1,000,000 g / mol.

In an embodiment, the primer composition may further comprise an organic solvent.

In an embodiment, the primer composition may further comprise an additive comprising at least one of an ultraviolet stabilizer, an antioxidant, a heat stabilizer and a leveling agent.

Another aspect of the invention relates to polycarbonate glazing. The polycarbonate glazing comprises a polycarbonate substrate; A primer layer formed on at least one side of the polycarbonate substrate; And a hard coating layer formed on a surface of the primer layer, wherein the primer layer is formed from the primer composition.

In an embodiment, the thickness of the polycarbonate substrate is 1 to 50 mm, the thickness of the primer layer is 0.1 to 20 탆, and the thickness of the hard coating layer is 1 to 100 탆.

In an embodiment, the hard coating layer comprises a binder comprising at least one of an organopolysiloxane resin, an acrylic resin, a polyester resin, and an acryl-polyester blend resin; ≪ / RTI > and a catalyst.

In an embodiment, the polycarbonate glazing may have a haze difference (ΔHaze) of between 0.1 and 5 before and after the abrasion at 500 abrasions with a CS-10F abrasion wheel and a 500 g load condition using a Taber Abraser .

Another aspect of the invention relates to a method of making polycarbonate glazing. Wherein the primer composition is applied to at least one surface of a polycarbonate substrate and dried to form a primer layer; And coating and hardening the hard coating liquid composition on the surface of the primer layer to form a hard coating layer.

In an embodiment, the drying of the primer composition may be by heating to a temperature of 80 to 200 ° C.

The present invention provides a polycarbonate glazing having excellent abrasion resistance, weather resistance, and interlayer adhesion, including a primer layer for forming a primer layer having excellent adhesion with both the upper layer and the lower layer, and a primer layer formed from the primer composition, and a method for producing the same. .

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

Hereinafter, the present invention will be described in detail.

The primer composition according to the present invention is characterized by comprising a (meth) acrylic polymer comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3).

[Chemical Formula 1]

In the above formula (1), R ₁ is a hydrogen atom or a methyl group, and R ₂ is an alkyl group having 1 to 5 carbon atoms.

(2)

In Formula 2, R ₃ is a hydrogen atom or a methyl group, and R ₄ is an alkylene group having 1 to 2 carbon atoms.

(3)

In Formula 3, R ₅ is a hydrogen atom or a methyl group, and R ₆ is an alkylene group having 3 to 10 carbon atoms.

The (meth) acrylic polymer is a copolymer of three or more members including the repeating units of the above formulas (1), (2) and (3), and the (meth) acrylate monomer having a hydroxy group .

"(Meth) acrylic" means "acrylic" and "methacrylic" are both possible unless otherwise specified herein. For example, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible.

In the specific examples, the repeating unit represented by the formula (1) may be a repeating unit represented by the following formula (1a), a repeating unit represented by the following formula (1b), or a combination thereof.

[Formula 1a]

[Chemical Formula 1b]

In the above formulas (1a) and (1b), R ₂ is as defined in the above formula (1).

Examples of the alkyl (meth) acrylate monomer capable of forming the repeating unit represented by Formula 1 include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ) Acrylate, pentyl (meth) acrylate, etc. These may be used alone or in admixture of two or more. For example, methyl acrylate and / or methyl methacrylate, methyl (meth) acrylate, and / or ethyl (meth) acrylate may be used, but the present invention is not limited thereto. Specifically, methyl acrylate and / or methyl methacrylate can be used.

In a specific example, the (meth) acrylate monomer having a hydroxy group capable of forming the repeating unit represented by the formula (2) includes hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) And mixtures thereof.

In a specific example, the (meth) acrylate monomer having a hydroxy group capable of forming the repeating unit represented by the formula (3) includes hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (Meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyhexyl (meth) acrylate, A mixture thereof, and the like. For example, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the like, but are not limited thereto.

In the specific examples, the content of the repeating unit represented by the formula (1) in the (meth) acrylic polymer may be 60 to 99 mol%, for example 70 to 99 mol%, specifically 80 to 95 mol% The content of the repeating unit represented by the general formula (2) may be 0.5 to 30 mol%, for example, 0.5 to 20 mol%, specifically 1 to 15 mol%, and the content of the repeating unit represented by the general formula (3) Mol%, for example, 0.5 to 20 mol%, specifically 1 to 15 mol%. In the above range, a primer layer having excellent adhesion with both the upper and lower layers can be formed, the shrinkage of the primer layer can be prevented from occurring when the hard coat layer is formed, and the weather resistance can be excellent.

In an embodiment, the (meth) acrylic polymer may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 50,000 to 1,000,000 g / mol, for example, 200,000 to 600,000 g / mol. In the above range, a primer layer having excellent adhesion with both the upper and lower layers can be formed.

The primer composition of the present invention may further comprise an organic solvent. The organic solvent may be any solvent that is not reactive with the (meth) acrylic polymer and can dissolve the (meth) acrylic polymer. The organic solvent may be selected in consideration of the solubility of the (meth) acrylic polymer, the evaporation rate of the solvent, etc., and a plurality of solvents may be used in combination. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diacetone alcohol, ethers such as tetrahydrofuran, 1,4-dioxane and 1,2-dimethoxyethane, Esters such as ethyl acetate and ethoxyethyl acetate, alcohols such as methanol, ethanol, propanol, butanol, 2-methyl-1-propanol, , 2-butoxyethanol and the like, hydrocarbons such as hexane, heptane, octane, benzene, toluene, xylene, gasoline, light oil and kerosene, acetonitrile and the like. These may be used alone or in combination of two or more. Diacetone alcohol, 1-methoxy-2-propanol, a mixture thereof, and the like can be used.

The content of the organic solvent is not particularly limited as far as it can dissolve the (meth) acrylic polymer and evaporate after coating the coating liquid. For example, 100 to 2,000 parts by weight, specifically 150 to 1,200 parts by weight, based on 100 parts by weight of the (meth) acrylic polymer may be used. In such a range, solid components such as the (meth) acrylic polymer of the primer composition can be well dissolved or dispersed, and the solvent can be easily evaporated after application of the primer composition, so that the coating property can be excellent.

In addition, the primer composition of the present invention may further comprise an additive including an ultraviolet stabilizer, an antioxidant, a heat stabilizer, a leveling agent, a mixture thereof and the like.

In a specific example, the ultraviolet stabilizer is for improving the weather resistance of the primer layer, and ultraviolet stabilizer used in ordinary primer composition can be used without limitation. For example, 2,4-dihydroxybenzophenone, 4,6-dibenzoyl resorcinol, Tinuvin-123 (BASF), Tinuvin-292 (BASF), Tinuvin- 152 (BASF), and Tinuvin-5151 (BASF) can be used.

Examples of the antioxidant include a primary antioxidant and a peroxide releasing function as a radical scavenger that reacts with radicals generated in the resin constituting the primer layer to stabilize the resin, A secondary antioxidant that is considered to serve as an auxiliary antioxidant may be used. As the primary antioxidant, a phenol compound aromatic amine compound such as 2-6-di-t-butyl-4-methylphenol (BHT) can be used. As the secondary antioxidant, a phosphite compound, sulfur Compounds, and the like may be used, but the present invention is not limited thereto. In addition, as the prophylactic antioxidant, a metal deactivator may be used.

The heat stabilizer serves to prevent the polymer constituting the primer composition (primer layer) from being destroyed from the heat during the production or use of the primer layer. Examples of the heat stabilizer include an organosilicate compound, a carboxylic acid metal salt compound, Based thermal stabilizer such as a metal-based heat stabilizer, an epoxy compound, and an organic phosphorous acid-based compound typified by triphenyl phosphite can be used, but the present invention is not limited thereto.

The leveling agent is used for improving the appearance of the coating film (primer layer) by improving the flowability of the polymer resin upon formation of the primer layer, and a conventional leveling agent can be used without limitation.

When the additive is used, the content of the additive may be 0.01 to 10 parts by weight based on 100 parts by weight of the (meth) acrylic polymer, but is not limited thereto.

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 can 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.

1 shows a cross-sectional view of a polycarbonate glazing according to an embodiment of the present invention. 1, a polycarbonate glazing 100 according to the present invention comprises a polycarbonate substrate 110; And a primer layer (120) formed on at least one side of the substrate (110); And a hard coating layer 130 formed on the surface of the primer layer 120. Here, the primer layer 120 is formed from the primer composition.

The polycarbonate substrate 110 used in the present invention may comprise a conventional polycarbonate resin. For example, polycarbonate, polycarbonate copolymer or polycarbonate blending resin may be used. As the blending resin, a polymer resin such as polyamide, thermoplastic polyurethane (TPU), acrylonitrile-styrene-acrylonitrile, polymethyl methacrylate, polyester, acrylonitrile-butadiene-styrene, Polycarbonate may be blended, but the present invention is not limited thereto. The polycarbonate may be produced by reacting a dihydric phenol compound with phosgene in the presence of a molecular weight modifier and a catalyst or by esterifying a carbonate precursor such as a dihydric phenol compound with diphenyl carbonate, / ≪ / RTI > or an ester exchange reaction. 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" . At this time, the bisphenol A may be partially or wholly replaced by other dihydric phenol compounds.

In a specific example, 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 (VST) of 120 ° C or more, The total light transmittance may be 80% or more, but is not limited thereto.

In an embodiment, the thickness of the polycarbonate substrate 110 may be between 1 and 50 mm, for example between 1 and 20 mm. In the above range, the glazing base material may have excellent mechanical strength, flexibility, transparency and the like.

The primer layer 120 used in the present invention is formed from the primer composition and plays a role of coupling between the substrate 110 and the hard coat layer 130 , It is possible to reduce cracks in polycarbonate glazing and to improve long-term reliability.

In an embodiment, the thickness of the primer layer 120 is 0.1 to 20 탆, for example, 0.5 to 10 탆. In this range, the interlaminar adhesive strength with the substrate 110 and the hard coat layer 130 is excellent, and (long-term) reliability can be obtained and more effective for abrasion resistance, stress relaxation, and crack prevention of polycarbonate glazing.

The hard coating layer 130 used in the present invention is prepared by applying a conventional hard coating liquid composition onto the surface of the primer layer 120 and curing the coating. The curing of the hard coating liquid composition can be performed by a conventional curing method using heat and / or ultraviolet rays. Generally, when the hard coating liquid composition is cured, cross-linking occurs in the binder matrix to increase the degree of curing, thereby forming a network structure.

In an embodiment, the hard coating liquid composition may comprise (a) a binder, and (b) a catalyst.

As the binder (a), a binder used in a conventional hard coating liquid composition may be used. For example, at least one of an organopolysiloxane resin, an acrylic resin, a polyester resin, and an acryl-polyester blend resin may be used . Preferably, an organopolysiloxane-based resin can be used.

In one embodiment, the organopolysiloxane-based resin may include colloidal silica and a hydrolysis and condensation product of a trialkoxysilane compound (including RSiO _3/2 repeating units, wherein R represents an alkyl group) It does not.

As the colloidal silica, silica fine particles having a diameter of 5 to 200 nm, for example, 5 to 40 nm, dispersed in water or an organic solvent in a colloidal form, may be used. Specifically, silica fine particles dispersed in an acidic aqueous solution may be used, but the present invention is not limited thereto.

The content of the colloidal silica (solid content) may be, for example, 1 to 40% by weight, for example, 5 to 25% by weight based on the total organopolysiloxane resin, but is not limited thereto.

The hydrolysis-condensation product of the trialkoxysilane compound may be at least one selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane ,? -methacryloxypropyltrimethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? -glycidoxypropyltrimethoxysilane,? -aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane, N -? - (aminoethyl) -? - aminopropyltrimethoxysilane, N -? - (aminoethyl) -? - aminopropyltriethoxysilane, Hydrolysis condensation reaction of an alkoxysilane compound.

The content of the hydrolyzed condensate of the trialkoxysilane compound may be, for example, from 60 to 99% by weight, for example, from 85 to 95% by weight based on the total organopolysiloxane resin, but is not limited thereto.

In an embodiment, the organopolysiloxane-based resin can be produced by subjecting the colloidal silica and the trialkoxysilane compound to a hydrolysis condensation reaction under acidic conditions. Under these conditions, the acid is used as a hydrolyzate, and the acid includes inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; Organic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid and paratoluenesulfonic acid; Etc. may be used. From the viewpoint of ease of pH control, organic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid and maleic acid are preferable, and acetic acid is particularly preferable.

In the hydrolysis and condensation reaction under acidic conditions, the content of the acid may be 0.1 to 50 parts by weight, for example, 1 to 30 parts by weight, based on 100 parts by weight of the trialkoxysilane compound, but is not limited thereto.

In an embodiment, the hydrolysis and condensation reaction may be carried out at 20 to 100 DEG C for 1 to 72 hours, but is not limited thereto.

In an embodiment, the organopolysiloxane resin may be a branched, ladder, network, mixed structure thereof, or the like. The weight average molecular weight measured by gel permeation chromatography (GPC) For example from 800 to 100,000 g / mol, for example from 1,000 to 50,000 g / mol. In the above range, the coating property of the hard coating liquid composition can be excellent, and the hard coating layer can be excellent in abrasion resistance and reliability.

In an embodiment, the binder may contain, in addition to the organopolysiloxane-based resin, an epoxy resin, an amide resin, an acrylic resin, a urethane-based resin, a silicone-based resin, And a resin for a common binder such as a polymer. When the resin for a binder other than the organopolysiloxane-based resin is used, its content may be 0.1 to 100 parts by weight based on 100 parts by weight of the organopolysiloxane-based resin, but is not limited thereto.

The binder may be used as a solution (solution) in which a solid content of the organopolysiloxane-based resin or the like is dissolved in a solvent, but is not limited thereto. The solvent may be any solvent which is not reactive with the solid component (such as organopolysiloxane resin) of the binder and can dissolve the solid content. Examples of the solvent include hydrocarbon solvents such as alcohols having 1 to 15 carbon atoms, aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, alcohols such as aliphatic ethers and alicyclic ethers, and mixtures thereof have. When the binder is in a solution state, the amount of the solvent is not limited as long as it can dissolve the solid content. For example, the amount of the solvent may be 0.1 to 900 parts by weight based on 100 parts by weight of the binder solid.

The catalyst (b) is a curing catalyst for forming a hard coating layer, and a catalyst used in a conventional hard coating liquid composition can be used. Examples of the catalyst include, but are not limited to, tetrabutylammonium acetate, triphenylphosphine, titanium butoxide, and the like.

The catalyst may be used in a state in which it is dissolved in a solvent. Examples of the solvent include hydrocarbon solvents such as alcohols having 1 to 15 carbon atoms, aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, alcohols such as aliphatic ethers and alicyclic ethers, and mixtures thereof . When the catalyst is in a solution state, the content of the solvent may be, for example, 0.1 to 900 parts by weight based on 100 parts by weight of the catalyst, but is not limited thereto.

The content of the catalyst (based on solid content) may be 0.01 to 25 parts by weight, for example, 1 to 10 parts by weight, based on 100 parts by weight of the binder (solid basis). When the hard coat layer is formed in the above range, the degree of curing can be excellent.

The hard coating liquid composition may contain additives used in a conventional hard coating liquid composition such as an ultraviolet (UV) stabilizer, a Hindered Amine Light Stabilizer (HALS), an activity reducing agent, an antioxidant, A filler, an inorganic filler, a mixture thereof, and the like. Among the above additives, ultraviolet stabilizers, HALS, activity reducing agents, antioxidants, and the like may be added to further improve the weather resistance of the hard coat layer, and the leveling agent may be added to improve coatability, , Inorganic fillers, hardeners, etc. may be added to improve the abrasion resistance and / or scratch resistance of the coating layer.

Specific examples of the additive include 2-hydroxy-4- (3-triethoxysilyl-propoxy) -diphenylketone, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, Tinuvin-400 (BASF), Tinuvin- Tinuvin-123 (BASF), ADK STAB 1413 (Adeka), LA-31 (Adeka), 4,6-dibenzoyl resorcinol, Tinuvin-123 Irganox 1125 (BASF), Irganox 1135 (BASF), Irganox 3114 (BASF), Irgafos (registered trademark of BASF), Tinuvin-152 (BASF), Tinuvin-5151 (BASF), hydroquinone, methoxyhydroquinone, Irganox 245 168 (BASF), and the like, but the present invention is not limited thereto. When the additive is used, the content of the additive may be 0.01 to 80 parts by weight based on 100 parts by weight of the binder (solid basis), but is not limited thereto.

The hard coating liquid composition may further include the solvent. The amount of the solid content of the binder, catalyst and the like can be dissolved and evaporated after application of the hard coating liquid composition. For example, it may be 100 to 2,000 parts by weight based on 100 parts by weight of the binder (solid basis), but is not limited thereto.

The hard coating liquid composition may be prepared, for example, by simply mixing and stirring the above components, or by polymerizing the binder in the presence of the additive, and then mixing and stirring the remaining components such as a catalyst.

In an embodiment, the hard coating layer 130 may have a single-layer structure or a laminated structure of two or more layers.

The hard coating layer 130 may have a thickness of 0.1 to 100 μm, for example, 1 to 30 μm. The abrasion resistance, scratch resistance, etc. of the polycarbonate glazing 100 can be excellent in the above range.

The polycarbonate glazing 100 of the present invention is formed by applying and drying the primer composition on at least one side of a polycarbonate substrate 110 to form a primer layer 120; And then coating and hardening the hard coating liquid composition on the surface of the primer layer 120 to form a hard coating layer 130.

In embodiments, the application of the primer composition may be accomplished by conventional application such as bar coating, roll coating, spin coating, dip coating, flow coating, spray coating, Method. ≪ / RTI >

The drying (curing) of the primer composition may be performed at a temperature of 80 to 200 ° C, for example, 100 to 150 ° C for 1 to 180 minutes. In this range, a primer layer having an excellent interlayer adhesion can be formed.

In an embodiment, the coating of the hard coating liquid composition is applied by a coating method such as bar coating, roll coating, spin coating, dip coating, flow coating, spray coating, But is not limited thereto.

In addition, the curing of the hard coating liquid composition can be thermally cured or ultraviolet cured, and ultraviolet curing is advantageous in a small size. However, recently, as the size of a molded product increases, a tendency to adopt a thermosetting method is increasing. In embodiments, the curing may be a thermal curing that is heat treated (heated) at a temperature of 100 to 200 占 폚, for example 120 to 140 占 폚, for example, for 1 to 180 minutes. A hard coat layer having excellent abrasion resistance can be formed in the above temperature range.

In an embodiment, the polycarbonate glazing of the present invention has a haze difference (DELTA Haze) of between 500 and 500 g under 500 g loading condition with a CS-10F abrasive wheel using a Taber Abraser between 0.1 and 5 days . Polycarbonate glazing having excellent abrasion resistance in the above range can be obtained.

The plastic glaze according to the present invention includes a primer layer 120 formed from the primer composition and is excellent in interlaminar adhesion with the substrate 110 and the hard coat layer 130 and has excellent abrasion resistance, scratch resistance, And the like are suitable for vehicle glazing, particularly for automotive windows.

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.

Example

Production Example 1: Preparation of (meth) acrylic polymer

89 mol% of methyl methacrylate, 1 mol% of methyl acrylate, 5 mol% of 2-hydroxyethyl methacrylate and 5 mol of 4-hydroxybutyl acrylate (% By mass) was subjected to conventional suspension polymerization to prepare a (meth) acrylic polymer. After the polymerized latex was sieved, the obtained polymer product was washed with water several times and then dried at 60 ° C for 3 days. This was reprecipitated and purified to prepare a white powdery (meth) acrylic polymer (weight average molecular weight: 357,500 g / mol).

Production Example 2: Preparation of (meth) acrylic polymer

89 mol% of methyl methacrylate, 1 mol% of methyl acrylate, and 10 mol% of 2-hydroxyethyl methacrylate were added, and then the same procedure as in Production Example 1 (Weight average molecular weight: 339,000 g / mol) in the form of a white powder.

Production Example 3: Preparation of organopolysiloxane resin solution

A 1 L three-necked flask was charged with 138.2 g of methyltrimethoxysilane, 112.0 g of colloidal silica solution (trade name: MA-ST, manufactured by Nissan chemical Co., Ltd., silica content: 30% by weight) And acetic acid (5.0 g) were added, the mixture was heated to 70 to 75 ° C, stirred for 6 hours, and then cooled to room temperature. Then, 50.0 g of n-butyl alcohol was added and stirred at room temperature for 24 hours to prepare an organopolysiloxane resin solution. As a result of GPC measurement, the weight average molecular weight of the organopolysiloxane resin produced was about 2,200 g / mol.

Production Example 4: Preparation of catalyst solution

10.0 g of tetrabutylammonium acetate as a catalyst and 90.0 g of isopropyl alcohol as a solvent were added to a 100 ml single-necked flask and stirred until all the catalyst was dissolved to prepare a catalyst solution.

Production Example 5: Preparation of hard coating liquid composition

30.0 g of the organopolysiloxane resin solution of Preparation Example 3, 0.3 g of the catalyst solution of Preparation Example 4, and 2 g of 2-hydroxy-4- (3-triethoxysilyl-propoxy) 0.5 g of 2-hydroxy-4- (3-triethoxysilyl-propoxy) -diphenylketone as a solvent and 10.0 g of isopropyl alcohol as a solvent were added and stirred at room temperature for 1 hour to prepare a hard coating liquid composition .

Example 1: Preparation of primer composition

2.4 g of the (meth) acrylic polymer of Preparation Example 1, 0.6 g of 2,4-dihydroxybenzophenone as an ultraviolet stabilizer, and 1 g of 1-methoxy-2 21 g of 1-methoxy-2-propanol and 6 g of diacetone alcohol were charged and the temperature was raised to 40 to 50 DEG C to stir the solid until all the solids were dissolved. The mixture was then cooled to room temperature to obtain a primer composition .

Comparative Example 1: Preparation of primer composition

A primer composition was prepared in the same manner as in Example 1, except that the (meth) acrylic polymer of Preparation Example 2 was used in place of the (meth) acrylic polymer of Preparation Example 1 above.

Comparative Example 2: Preparation of primer composition

Except that poly (methyl methacrylate) (manufacturer: Sigma-Aldrich, weight average molecular weight: 350,000 g / mol) was used in place of the (meth) acrylic polymer of Production Example 1, To prepare a primer composition.

Comparative Example 3: Preparation of primer composition

Except that poly (methyl methacrylate) (manufactured by Sigma-Aldrich, weight average molecular weight: 20,000 g / mol) was used in place of the (meth) acrylic polymer of Production Example 1, To prepare a primer composition.

Example 2: Preparation of polycarbonate glazing

The surface of a polycarbonate substrate (thickness: 3 mm, size: 20 cm x 30 cm, product name: Lexan, manufacturer: GE) was washed with isopropyl alcohol. The primer composition of Example 1 was coated on one side of the cleaned substrate using a mayer bar. After the application, it was dried at room temperature for 20 minutes and dried at 125 DEG C for 20 minutes to form a primer layer having a thickness of 1.5 mu m. After cooling the substrate coated with the primer layer to room temperature, the hard coating solution composition of Preparation Example 5 was filtered using a 1.0 탆 syringe filer, and then the surface of the primer layer was coated with a Mayer bar . This was dried at room temperature for 20 minutes and cured at 130 DEG C for 1 hour to form a hard coat layer having a thickness of 7.2 mu m to produce polycarbonate glazing. The physical properties of the produced polycarbonate glaze were measured according to the following physical property measuring method, and the results are shown in Table 1 below.

Comparative Example 4: Preparation of polycarbonate glazing

Polycarbonate glazing was prepared in the same manner as in Example 2 except that the primer composition of Comparative Example 1 was used in place of the primer composition of Example 1. [ The physical properties of the produced polycarbonate glaze were measured according to the following physical property measuring method, and the results are shown in Table 1 below.

Comparative Example 5: Preparation of polycarbonate glazing

Polycarbonate glazing was prepared in the same manner as in Example 2 except that the primer composition of Comparative Example 2 was used in place of the primer composition of Example 1. [ The physical properties of the produced polycarbonate glaze were measured according to the following physical property measuring method, and the results are shown in Table 1 below.

Comparative Example 6: Production of polycarbonate glazing

Polycarbonate glazing was prepared in the same manner as in Example 2 except that the primer composition of Comparative Example 3 was used in place of the primer composition of Example 1. [ The physical properties of the produced polycarbonate glaze were measured according to the following physical property measuring method, and the results are shown in Table 1 below.

How to measure property

1. Thickness measurement: Measured using Filmetrics F-20 (equipment name) equipment. After 5 measurements, mean value was indicated.

2. Evaluation of abrasion resistance: The produced polycarbonate glazing was subjected to 500 times of abrasion with a CS-10F abrasion wheel and a 500 g load condition using a Taber abrasion tester (Gardoco, device name: 5135). The haze difference (ΔHaze, unit:%) before and after the abrasion was measured using a haze meter (manufacturer: Nippon Denshoku Co., Ltd., device name: NDH 5000) to evaluate abrasion resistance.

3. Adhesion Evaluation: The adhesion was evaluated according to ASTM D3359 (Cross-hatch test).

4. Water bath test: Polycarbonate glazing test specimens were taken out at 100 ℃ water bath for 2 hours and dried at room temperature. It was found that the case where the interlayer separation did not occur at all on the surface of the specimen was OK, and the case where the crack occurred a little was found to be crack, and the specimen (surface) was in a cloudy state (cracks which were not visually recognized, Case), it turned out to be Hazy. In addition, the adhesive strength was evaluated by ASTM D3359 (Cross-hatch test) for the specimens subjected to the above treatment.

5. Weatherability evaluation: The specimens were stored under standard conditions of SAE J1960 for 1,000 hours using a weatherometer (manufacturer: Atlas Co., Ltd., Ci4000), and then the appearance evaluation and yellow index change (ΔYI) were measured. The appearance evaluation was OK when the interlayer peeling or cracking did not occur at all on the apparent surface of the specimen, and it was found that the crack occurred when a slight degree of cracking occurred. The yellowness index (YI) value of the specimen before and after the light resistance test was measured using a spectrophotometer (manufacturer: Konica-Minolta, device name: CM-3600d), and the yellow index difference before and after the light resistance test was calculated .

Primer layer forming material Abrasion resistance
(ΔHaze) Adhesion
(Cross-hatch) Water bath Weatherability Exterior Adhesion Exterior △ YI Example 2 Example 1 2.4 5B OK 5B OK 0.7 Comparative Example 3 Comparative Example 1 4.7 5B Hazy 4B Crack 1.9 Comparative Example 4 Comparative Example 2 4.3 5B OK 4B Crack 4.1 Comparative Example 5 Comparative Example 3 - 2B Crack - - -

From the above results, it can be seen that the polycarbonate glazing manufactured using the primer composition containing the (meth) acrylic polymer of the present invention is excellent in both abrasion resistance, interlaminar adhesion, and weather resistance.

On the other hand, in the case of the comparative example, the overall physical properties are poor and the weatherability is particularly low.

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 primer composition comprising a (meth) acrylic polymer comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3)
[Chemical Formula 1]

In Formula 1, R ₁ is a hydrogen atom or a methyl group, and R ₂ is an alkyl group having 1 to 5 carbon atoms;
(2)

In Formula 2, R ₃ is a hydrogen atom or a methyl group, and R ₄ is an alkylene group having 1 to 2 carbon atoms;
(3)

In Formula 3, R ₅ is a hydrogen atom or a methyl group, and R ₆ is an alkylene group having 3 to 10 carbon atoms.
[2] The method according to claim 1, wherein the content of the repeating unit represented by the formula (1) is 60 to 99 mol%, the content of the repeating unit represented by the formula (2) is 0.5 to 30 mol% Wherein the content of the repeating unit represented by the formula (3) is 0.5 to 30 mol%.
The primer composition according to claim 1, wherein the repeating unit represented by the formula (1) is a repeating unit represented by the following formula (1a), a repeating unit represented by the following formula (1b)
[Formula 1a]

[Chemical Formula 1b]

In the above formulas (1a) and (1b), R ₂ is as defined in the above formula (1).
The primer composition according to claim 1, wherein the weight average molecular weight of the (meth) acrylic polymer is 50,000 to 1,000,000 g / mol.
The primer composition according to claim 1, wherein the primer composition further comprises an organic solvent.
The primer composition according to claim 1, wherein the primer composition further comprises an additive comprising at least one of an ultraviolet stabilizer, an antioxidant, a heat stabilizer, and a leveling agent.
Polycarbonate substrates;
A primer layer formed on at least one side of the polycarbonate substrate; And
And a hard coat layer formed on the surface of the primer layer,
Wherein the primer layer is formed from the primer composition according to any one of claims 1 to 6.
The polycarbonate glazing according to claim 7, wherein the thickness of the polycarbonate substrate is 1 to 50 mm, the thickness of the primer layer is 0.1 to 20 탆, and the thickness of the hard coating layer is 1 to 100 탆.
8. The optical information recording medium according to claim 7, wherein the hard coating layer comprises a binder comprising at least one of an organopolysiloxane resin, an acrylic resin, a polyester resin, and an acryl-polyester blend resin; And a catalyst. ≪ Desc / Clms Page number 24 >
The polycarbonate glazing according to claim 7, wherein the polycarbonate glazing has a haze difference (DELTA Haze) of from 0.1 to 5 before and after abrading at 500 times of abrasion with a CS-10F abrasive wheel and a load of 500 g using a Taber Abraser Lt; RTI ID = 0.0 > polycarbonate < / RTI >
Applying and drying the primer composition according to any one of claims 1 to 6 on at least one side of the polycarbonate substrate to form a primer layer; And
And coating and hardening the hard coating liquid composition on the surface of the primer layer to form a hard coating layer.
The method of claim 11, wherein the drying of the primer composition is performed at a temperature of 80 to 200 캜.

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