KR102239091B1 - Transparent resin laminate, method for preparing thereof and exterior materials for automobiles using the same - Google Patents

Abstract

Including a base layer, a primer layer and a hard coating layer, the primer layer is a cured product of a primer coating composition comprising a (meth)acrylic resin and a sunscreen, and the sunscreen is a mixture of a benzophenone-based compound and a triazine-based compound It provides a transparent resin laminate comprising a.

Description

A transparent resin laminate, a method of manufacturing the same, and an exterior material for automobiles using the same. {TRANSPARENT RESIN LAMINATE, METHOD FOR PREPARING THEREOF AND EXTERIOR MATERIALS FOR AUTOMOBILES USING THE SAME}

It relates to a transparent resin laminate, a method of manufacturing the same, and an exterior material for automobiles using the same.

Recently, the automotive industry is facing problems such as reducing fuel economy, responding to environmental regulations, securing passenger safety, and pressure to reduce costs due to intensifying competition among competitors in the automotive industry. In order to solve such a problem, research has been actively conducted to replace window glass used in window modules or soft steel sheets used in vehicle bodies with lightweight metals, plastics, and carbon composite materials. In particular, plastic materials are used in a wide range of applications due to many advantages including impact resistance, light weight and workability. At present, efforts are being made to further utilize its characteristics. For example, when plastic materials are applied to window panes, a high level of wear resistance and outdoor weather resistance comparable to glass is required.

One embodiment of the present invention provides a transparent resin laminate having excellent long-term weatherability, which maintains excellent surface properties even when exposed to environments such as high heat or ultraviolet rays for a long period of time, and at the same time has excellent peel strength.

Another embodiment of the present invention provides a method of manufacturing the transparent resin laminate.

Another embodiment of the present invention provides an exterior material for automobiles manufactured from the transparent resin laminate.

In one embodiment of the present invention, a base layer, a primer layer, and a hard coating layer are included, and the primer layer is a cured product of a primer coating composition comprising a (meth)acrylic resin and a sunscreen, and the sunscreen is benzope It provides a transparent resin laminate comprising a mixture of a non-based compound and a triazine-based compound.

In another embodiment of the present invention, preparing a primer coating composition comprising a (meth)acrylic resin and a sunscreen; Coating the primer coating composition on a base layer; Forming a primer layer by thermally curing the primer coating composition; And forming a hard coating layer on the primer layer, wherein the sunscreen agent provides a method of manufacturing a transparent resin laminate comprising a mixture of a benzophenone-based compound and a triazine-based compound.

The transparent resin laminate has excellent long-term weather resistance, maintains optical properties such as transparency and high mechanical strength, prevents deterioration of physical properties such as discoloration and discoloration, and at the same time realizes excellent peel strength.

1 is a schematic cross-sectional view of a transparent resin laminate according to an embodiment of the present invention.

Advantages and features of the present invention, and a method of achieving them will become apparent with reference to the embodiments to be described later. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various different forms, However, these embodiments are provided to complete the disclosure of the present invention, and to fully inform the scope of the invention to a person skilled in the art to which the present invention pertains, and the present invention is defined by the scope of the claims. It just becomes.

In the drawings, the thicknesses are enlarged in order to clearly express various layers and regions. In addition, in the drawings, for convenience of description, the thicknesses of some layers and regions are exaggerated. The same reference numerals refer to the same elements throughout the specification.

In addition, in the present specification, when a part such as a layer, a film, a region, or a plate is said to be "on" or "on" another part, it is not only "directly above" another part, but also when another part is in the middle. Also includes. Conversely, when one part is "directly above" another part, it means that there is no other part in the middle. In addition, when a part such as a layer, a film, a region, or a plate is said to be "below" or "under" another part, it is not only "directly below" another part, but also a case where there is another part in the middle. Includes. Conversely, when one part is "right below" another part, it means that there is no other part in the middle.

In one embodiment of the present invention, a base layer, a primer layer, and a hard coating layer are included, and the primer layer is a cured product of a primer coating composition comprising a (meth)acrylic resin and a sunscreen, and the sunscreen is benzope It provides a transparent resin laminate comprising a mixture of a non-based compound and a triazine-based compound.

1 is a schematic cross-sectional view of a transparent resin laminate 10 according to an embodiment of the present invention. Referring to FIG. 1, the transparent resin laminate 10 has a multilayer structure including a base layer 100, a primer layer 300, and a hard coating layer 200 in sequence. Specifically, the base layer 100 is formed on one side of the primer layer 300, and the hard coating layer 200 is formed on the other side of the primer layer 300 in a direction opposite to the side where the base layer 100 contacts. .

The base layer included in the transparent resin laminate is polycarbonate, polystyrene, polyester, acrylic resin, modified acrylic resin, urethane resin, thiourethane resin, condensate of halogenated bisphenol A and ethylene glycol, acrylic urethane resin, halogenated acrylic- It may include one selected from the group consisting of a containing acrylic resin, a sulfur-containing resin, a modified polycarbonate, and combinations thereof. The modified polycarbonate is a polycarbonate/acrylonitrile butadiene styrene composite (PC/ABS). It may be a polycarbonate/polyethyl terephthalate composite (PC/PET), a polycarbonate/polybutylene terephthalate composite (PC/PBT), and the like. For example, the base layer may include polycarbonate, and a transparent resin laminate including the same may have excellent mechanical strength and electrical insulation, be transparent like glass, and have strong heat resistance at a softening temperature of around 140°C. have.

The primer layer is positioned between the substrate layer and the hard coating layer to improve adhesion between the substrate layer and the hard coating layer, relieve stress between the substrate layer and the hard coating layer, and may have an excellent crack prevention effect. The primer layer is a cured product of the primer coating composition, and may be specifically a thermosetting product. The primer coating composition includes a (meth)acrylic resin and a sunscreen agent, and provides a sunscreen effect with excellent adhesion, thereby imparting long-term weather resistance to the transparent resin laminate.

In general, sunscreens include benzophenone, oxalanilide, benzotriazole, triazine, cyanoacrylate and benzylidene malonate.

The primer layer contains a mixture of a benzophenone-based compound and a triazine-based compound as a UV blocking agent, suppressing photolysis of the substrate layer due to ultraviolet rays, and has excellent long-term weather resistance, maintaining optical properties such as transparency, and high mechanical strength. And, it is possible to prevent deterioration of physical properties such as discoloration and fading, prevent cracks from occurring at the same time, and implement excellent peel strength. The benzophenone compound can block ultraviolet rays of about 320 nm-about 400 nm wavelength, and has excellent compatibility with the (meth)acrylic resin included in the primer layer, so that it will not deteriorate physical properties despite excessive use. I can. The triazine-based compound can block ultraviolet rays having a wavelength of about 280 nm to about 320 nm, and has a long lifetime. In addition, the triazine-based compound is used together with the benzophenone-based compound so that the primer coating composition may include a high content of a sunscreen. In addition, the primer layer, which is a cured product of the primer coating composition, is included in the laminate together with the base layer and the hard coating layer, so that excellent physical properties can be imparted with improved long-term weatherability.

The sunscreen agent, including a mixture of a benzophenone-based compound and a triazine-based compound, blocks all ultraviolet rays of the wavelength, suppressing photolysis of the substrate layer, and has excellent long-term weatherability, and optical properties such as transparency, high It maintains mechanical strength, prevents deterioration of physical properties such as discoloration and discoloration, prevents cracks from occurring at the same time, and realizes excellent peel strength. For example, when polycarbonate is included in the base layer, the polycarbonate may be photodecomposed by ultraviolet rays having a wavelength of about 280 nm-about 310 nm and ultraviolet rays having a wavelength of about 330 nm-about 360 nm. The primer layer laminated on the base layer is a mixture of the benzophenone compound and the triazine compound to block all ultraviolet rays in the above range, thereby protecting the base layer from ultraviolet rays and preventing damage to the physical properties of the base layer. have.

The primer layer may contain the benzophenone-based compound to the triazine-based compound in a weight ratio of about 7:1 to about 5:1, thereby inhibiting photolysis of the base layer. And, by improving the compatibility with the (meth)acrylic resin contained in the primer layer, it is possible to exhibit excellent long-term weather resistance. Therefore, the transparent resin laminate including the primer layer maintains optical properties such as transparency and high mechanical strength, prevents deterioration of physical properties such as discoloration and discoloration, and at the same time prevents cracks from occurring, and provides excellent peel strength. Can be implemented.

Specifically, when the content of the benzophenone-based compound is less than the above range, there may be a problem of deteriorating physical properties such as easily yellowing and cracking, and when it exceeds the above range, additives and (meth)acrylic resin and There may be a problem of poor transparency due to poor compatibility.

In general, since the sunscreen prevents cracking and peeling of the coating layer from occurring due to ultraviolet rays, it may be good to increase the content of the sunscreen for long-term weather resistance. However, when the content of the sunscreen agent is increased, compatibility with the resin decreases, adhesion with the hard coating layer laminated thereon, and the like decrease, so that long-term weather resistance decreases, and rather, the physical properties of the transparent resin layered body are deteriorated.

The primer layer contains the benzophenone-based compound and the triazine-based compound in a weight ratio of about 7:1 to about 5:1, and contains a high content of a sunscreen comprising a mixture of the benzophenone-based compound and the triazine-based compound Can be included as. That is, the primer layer may include a high content of a sunscreen agent, thereby exhibiting improved long-term weather resistance and at the same time excellent physical properties.

Specifically, the primer layer may include about 35 parts by weight to about 60 parts by weight based on 100 parts by weight of the (meth)acrylic resin. The sunscreen agent maintains excellent compatibility with the (meth)acrylic resin despite the high content in the above range, and the transparent resin laminate including it can exhibit excellent physical properties such as maintaining excellent transparency, and curing It is possible to prevent the precipitation of the sunscreen agent in the.

Specifically, the benzophenone-based compound is 2-hydroxy-benzophenone, 2,4-dihydroxybenzophenone; 2,4,2',4'-tetrahydroxybenzophenone; 2-hydroxy-4-ene-octoxybenzophenone, 4-[gamma-(trimethoxysilyl)propoxy]-2-hydroxybenzophenone, 4-[ Gamma-(triethoxysilyl)propoxy]-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (2,2'-Dihydroxy-4,4'- dimethoxybenzophenone), 2-(trifluoromethyl)benzophenone (2-(Trifluoromethyl)benzophenone), 2-hydroxy-4-methoxy-4'-methylbenzophenone (2-HYDROXY-4-METHOXY-4'-) METHYLBENZOPHENONE), 2-hydroxy-4-methoxybenzophenone (2-Hydroxy-4-methoxybenzophenone), 4-dodecyloxy-2-hydroxybenzophenone (4-DODECYLOXY-2-HYDROXYBENZOPHENONE) and combinations thereof It may contain one compound selected from the group consisting of .

For example, the benzophenone-based compound may be 2-hydroxy-4-ene-octocybenzophenone. Benzophenone-based compounds generally do not dissolve well in organic solvents, but the benzophenone-based compounds have excellent compatibility with (meth)acrylic resins, and thus solubility may increase. Accordingly, it is possible to exhibit a remarkably improved UV blocking effect compared to the content of the benzophenone-based compound, and can impart excellent long-term weatherability.

The triazine-based compound is a hydroxyphenyltriazine-based compound (Hydroxyphenyl-triazine), 2-hydroxyphenyl-s-triazine-based (2-hydroxyphenyl-s-triazine), bisresorcinyl triazine (bis (resorcinyl) triazine) )-Based compounds and tris(resorcinyl)triazines). E.g [4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5- Triazine, 2-(2-hydroxyphenyl)-1,3,5-triazine, 2-[4-[4,6-bis([1,1'-biphenyl]-4-yl)-1 ,3,5-triazin-2-yl]-3-hydroxyphenoxy]propanoic acid 6-methylheptylester (2-[4-[4,6-Bis(1,1'-biphenyl-4 -yl)-1,3,5-triazine-2-yl]-3-hydroxyphenoxy]propanoic acid 6-methylheptyl ester), 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy] -2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine(2-[4-[(2-Hydroxy-3-dodecyloxypropyl)oxy]-2 -hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine) and a combination thereof may include one compound selected from the group consisting of. For example, the triazine-based compound is particularly 2-[4-[4,6-bis([1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl] -3-hydroxyphenoxy]propanoic acid 6-methylheptylester (2-(4-(4,6-bis((1,1'-biphenyl)-4-yl)-1,3,5- triazin-2-yl)-3-hydroxyphenoxy)-, isooctyl ester). Although the triazine-based compound is very difficult to dissolve in an organic solvent due to its molecular structure, the triazine-based compound has excellent compatibility with a (meth)acrylic resin, and solubility may be increased. Accordingly, it is possible to exhibit a remarkably improved UV blocking effect compared to the content of the triazine-based compound, and can impart excellent long-term weather resistance.

The primer layer may include a (meth)acrylic resin, together with the sunscreen agent, to improve adhesion to the base layer and the hard coating layer. The (meth)acrylic resin has a high glass transition temperature, so that excellent heat resistance can be imparted, and it is organically combined with the sunscreen to prevent cracks from occurring in relation to the hard coating layer attached to the top of the laminate. have. Accordingly, it may be suitable for use as an exterior material for automobiles that are exposed to the outside.

The (meth)acrylic resin may have a glass transition temperature of about 90°C to about 120°C. The (meth)acrylic resin may exhibit excellent coating workability and heat resistance by organically bonding with the sunscreen agent by having a glass transition temperature within the above range. In addition, the primer layer is located between the base layer and the hard coating layer, and the primer layer includes the (meth)acrylic resin having a glass transition temperature in the range, so that the primer layer is prevented from slumping and peeling during the curing process. It can, and it is possible to prevent the occurrence of cracks in the upper hard coating layer. In addition, in the process of using the transparent resin laminate, for example, in the process of using it as an exterior material for automobiles that are exposed a lot to the outside with severe environmental changes, it is located between the base layer and the hard coating layer having different expansion coefficients. It is possible to prevent the occurrence of cracks in the layer.

Specifically, if it is less than the range of the glass transition temperature, there may be a problem that cracks may occur due to deterioration in heat resistance, and if it exceeds the above range, the heat resistance is excellent, but other additives must be used to increase the glass transition temperature. However, due to the other additives used in this way, there may be a problem in that aging is further accelerated.

The (meth)acrylic resin may have a weight average molecular weight (Mw) of about 100,000 g/mol to about 2 million g/mol. Specifically, the weight average molecular weight (Mw) of the (meth)acrylic resin may be from about 300,000 g/mol to about 1 million g/mol, and more specifically, from about 300,000 g/mol to about 600,000 g/ may be mol.

The (meth)acrylic resin may exhibit excellent compatibility by organically bonding with the sunscreen agent by having a weight average molecular weight in the above range. In addition, by imparting excellent long-term weather resistance to the transparent resin laminate including the same, it is possible to prevent the occurrence of white cloudiness or deterioration of adhesion.

Specifically, when the weight average molecular weight (Mw) of the (meth)acrylic resin is less than the above range, interlayer adhesion is weakened due to weak bonding strength in the resin, and a migration phenomenon in which additives escape to the outside of the primer layer in a high temperature environment is caused. There may be a problem that occurs and loses transparency. In addition, when it exceeds the above range, there may be a problem in that the coating property is deteriorated, the surface stiffness becomes severe, or the coating thickness is not uniform.

The (meth)acrylic resin is polymethyl methacrylate, polybutyl acrylate, polyauryl acrylate, polystearyl acrylate, polyglycidyl acrylate, polyglycidyl methacrylate, polyacrylonitrile, poly It may include one selected from the group consisting of acrylamide, polyacrylonitrile-polyalkylacrylate, and combinations thereof. Specifically, the (meth)acrylic resin may be polymethyl methacrylate, which is a single polymer of methyl methacrylate as a monomer, through which it forms an excellent chemical cross-linking with the upper hard coating layer to improve adhesion between each layer. I can. In addition, the (meth)acrylic resin exhibits excellent compatibility with a sunscreen agent, which is a mixture of the benzophenone compound and the triazine compound, and may exhibit excellent effects even in long-term weather resistance.

The primer coating composition may further include one additive selected from the group consisting of an ultraviolet stabilizer, a leveling agent, an antioxidant, and a combination thereof. The primer coating composition may include about 0.001% by weight to about 1% by weight of the additive.

The UV stabilizer may be a Halse (Hindered Amine Light Stabilizers) compound, and may further improve the heat resistance and life time of the UV blocker to further improve long-term weather resistance. When the content of the ultraviolet stabilizer exceeds the above range, the compatibility with the (meth)acrylic resin decreases, and the haze may increase rapidly due to poor water resistance.

The leveling agent may include one selected from the group consisting of a polyester-modified silicone surface additive, a hydroxy functional silicone surface additive, and a combination thereof. The leveling agent may improve the smoothness of the primer coating composition. When the above range is exceeded, the leveling agent forms a thin layer on the surface of the coating layer, thereby preventing chemical bonding between the primer layer and the hand coating layer. Thus, there may be a problem of lowering the adhesion between each layer.

The antioxidant is from the group consisting of phosphate antioxidants, phenolic antioxidants, metal deactivators, trioester antioxidants, and combinations thereof. It may contain a selected one. Specifically, triethylene glycol-bis-3-(3-tert-bu?K-4-hydroxy-5-methylphenyl)-propionate (Triethylene-glycol-bis-3-(3-tert-butyl-4) -hydroxy-5-methylphenyl)Propionate) and Tetrax (2,4-di-tert-butylphenyl)[1.1-biphenyl]-4,4'-dinylbisphosphonit-(Tetrakis(2,4 -di-tert-butyphenyl)[1.1-biphenyl]-4,4'-diylbisphosphonite), and combinations thereof. The primer coating composition may further improve long-term weather resistance by including the antioxidant. On the other hand, since the antioxidant is less compatible with the (meth)acrylic resin than the sunscreen agent, when it is included in excess of the above range, it may be separated from the (meth)acrylic resin to significantly reduce physical properties. Thus, it may cause defects in the molded article including the same.

The thickness of the primer layer may be about 1 μm to about 6 μm. Since the primer layer has a thickness within the above range, it has excellent long-term weatherability even when exposed to high heat or ultraviolet rays for a long period of time, and maintains optical properties such as transparency and high mechanical strength, and physical properties such as discoloration and discoloration. It is possible to prevent deterioration and at the same time realize excellent peel strength.

The hard coating layer may be a cured product of a hard coating composition including at least one compound selected from the group consisting of an acrylic compound, an epoxy compound, a silicon compound, a silicone compound, and a combination thereof. Specifically, the hard coating layer may be a cured product of a hard coating composition including a silicone-based compound, and more specifically, may include an organic-inorganic silicone-based compound. The hard coating layer includes an organic-inorganic silicone-based compound, is formed on one surface of the primer layer, and is organically combined with the primer coating composition to impart high hardness and damage resistance such as scratch resistance or abrasion resistance. In addition, the hard coating layer may exhibit excellent gloss with excellent abrasion resistance.

The thickness of the hard coating layer may be about 3 μm to about 20 μm. By having a thickness within the above range, the hard coating layer can maintain excellent light transmittance of the substrate layer, high hardness and damage resistance, and excellent weather resistance without excessively increasing the thickness of the transparent resin laminate.

In another embodiment of the present invention, preparing a primer coating composition comprising a (meth)acrylic resin and a sunscreen; Coating the primer coating composition on a base layer; Forming a primer layer by thermally curing the primer coating composition; And forming a hard coating layer on the primer layer, wherein the sunscreen agent provides a method of manufacturing a transparent resin laminate comprising a mixture of a benzophenone-based compound and a triazine-based compound.

The transparent resin laminate may be manufactured as described above through the method of manufacturing the transparent resin laminate, and a detailed description of the transparent resin laminate is as described above.

The transparent resin laminate prepared through the method of manufacturing the transparent resin laminate may contain a benzophenone-based compound and a triazine-based compound in a weight ratio of about 7:1 to about 5:1 even when exposed to high heat or ultraviolet rays for a long period of time. By including a mixed sunscreen agent, photodecomposition of the substrate layer can be suppressed, and compatibility with the above-described (meth)acrylic resin is improved, and excellent long-term weather resistance is obtained, and optical properties such as transparency, and high mechanical strength are maintained. And, it is possible to prevent deterioration of physical properties such as discoloration and fading, prevent cracks from occurring at the same time, and implement excellent peel strength.

In addition, the primer coating composition may be thermally cured at a temperature of about 90 °C to about 130 °C. The primer coating composition is thermally cured to prevent damage to the substrate layer during the curing process, and increase reliability in long-term weather resistance.

In addition, the primer coating composition is thermally cured in the above temperature range, so that even a substrate having a curved surface can be coated with a uniform thickness, and can be coated without chemical change of the substrate during curing.

In another embodiment of the present invention, it provides an exterior material for a vehicle manufactured from the transparent resin laminate. Automotive exterior materials refer to various materials used for various parts outside the vehicle, for example, door trim, dash outer, hood silence, headliner, and rear package. It can be used for a tray (rear package tray) or the like.

Detailed description of the transparent resin laminate is as described above. The transparent resin laminate is manufactured as an exterior material that replaces the use of exterior materials for automobiles, for example, glass for automobiles through cutting processing.

Hereinafter, specific embodiments of the present invention are presented. However, the examples described below are only for illustrating or explaining the present invention in detail, and the present invention is not limited thereto.

< Example And Comparative example >

Example One

Poly(methyl methacrylate), PMMA, which is a polymer of methylmethacrylate having a weight average molecular weight of 380,000 g/mol and a glass transition temperature of 95°C; 2-hydroxy-4-n-octoxybenzophenone, a benzophenone-based compound, versus 2-[4-[4,6-bis([1,1], a triazine-based compound) '-Biphenyl]-4-yl)-1,3,5-triazin-2-yl]-3-hydroxyphenoxy]propanoic acid 6-methylheptylester (2-[4-[4, A sunscreen comprising 6-Bis(1,1'-biphenyl-4-yl)-1,3,5-triazine-2-yl]-3-hydroxyphenoxy]propanoic acid 6-methylheptyl ester) in a ratio of 7:1; And a leveling agent (BYK3700), which is an additive for a hydroxy functional silicone surface, to prepare a primer coating composition.

At this time, the primer coating composition included the PMMA resin in an amount of about 3% to 10% by weight, and the sunscreen agent was included in an amount of about 50 parts by weight relative to 100 parts by weight of the PMMA resin. And, after flow coating the primer coating composition to a thickness of about 1 ~ 4㎛ on the top of the polycarbonate base layer of about 3 mm thick, and then heat cured at a temperature of about 130 ℃ for 15 minutes to form a primer layer. I did.

A transparent resin laminate was prepared by thermally curing a hard coating composition containing polysilsesquioxane, an organic-inorganic silicone compound, on the primer layer at a temperature of about 130° C. for 45 minutes to form a hard coating layer. I did.

Example 2

As for the sunscreen, a transparent resin laminate was prepared in the same manner as in Example 1, except that the benzophenone-based compound versus the triazine-based compound was mixed at a ratio of 6:1.

Example 3

As for the sunscreen, a transparent resin laminate was prepared in the same manner as in Example 1, except that a benzophenone-based compound versus a triazine-based compound was mixed at a ratio of 5:1.

Example 4

A transparent resin in the same manner as in Example 3, except that a copolymer of methylmethacrylate and methacrylate having a weight average molecular weight of 90,000 g/mol and a glass transition temperature of 95°C was included. A laminate was prepared.

Comparative example One

Poly(methyl methacrylate, PMMA), a polymer of methylmethacrylate having a weight average molecular weight of 380,000 g/mol and a glass transition temperature of 95° C.; A primer coating composition comprising a benzophenone-based compound, 2-hydroxy-4-n-octoxybenzophenone, and a leveling agent for a hydroxy functional silicone surface (BYK3700). Was prepared. Other than that, a transparent resin laminate was prepared in the same manner as in Example 1.

Comparative example 2

Triazine-based compound 2-[4-[4,6-bis([1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl]-3-hydroxyphenoxy Si] propanoic acid 6-methylheptyl ester (2-[4-[4,6-Bis(1,1'-biphenyl-4-yl)-1,3,5-triazine-2-yl]-3 -hydroxyphenoxy]propanoic acid 6-methylheptyl ester) and 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4- Dimethylphenyl)-1,3,5-triazine 2-[4-[(2-Hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1, 3,5-triazine) was prepared as a transparent resin laminate in the same manner as in Comparative Example 1, except that 1:1 was used as a sunscreen.

<Evaluation>

Experimental example 1: Weather resistance

The transparent resin laminates of the above Examples and Comparative Examples were prepared as test specimens having a size of 100 mm X 100 mm X 3 mm, and weather resistance was investigated under the following xenon arc furnace conditions specified in ASTM G-155 mod. Specifically, the change in haze of the specimen, cracks, and abnormalities in adhesion were evaluated.

(Xenon arc furnace setting conditions)

Irradiance Wavelength: 295~2500 nm

BLACK PNL temperature- 70±2℃ (LIGHT) irradiation (40±5%RH)

Cycle-102 minutes irradiation, 18 minutes irradiation + surface spray

Irradiance-0.75±0.02W/(㎡ㆍnm) [340nm]

At this time, the weather resistance was evaluated at 1,000 hour intervals up to 4,000 hours, and is shown in Table 1 below. The evaluation criteria were as follows.

Specifically, for haze, measure the amount of change in haze with a hazemeter according to the ASTM D1003 method, for cracks, measure the length of cracks generated in the specimen, and for peeling/attachment, the peeling area generated on the specimen is measured as a% of the total area of the specimen I did.

(Evaluation standard)

O: Haze: less than 1%, crack: no occurrence, peeling/attachment: no occurrence,

△: Haze: 1 to 2%, crack: less than 1 cm, peeling/adhering: less than 10% of specimen area

X: Haze: more than 2%, crack : 1 cm or more, peeling/adhering: specimen area 10% or more

Experimental example 2: heat resistance cycle test

In order to evaluate the reliability of the above Examples and Comparative Examples, the change in haze of the specimen and the degree of adhesion were evaluated after the specimens were allowed to stand for 8 hours in harsh conditions in a 100°C constant temperature water bath, respectively. The degree of adhesion was repeatedly tested 5 times under the cross cut conditions specified in ISO 2409, and the amount of peeling by the tape was quantified.

The evaluation results are shown in Table 2 below. The evaluation criteria were as follows.

O: Haze: 1% or less, Adhesion: Class 0,1

△: Haze: 1~2%, Adhesion: Class 2,3

X: Haze: 2% or more, Adhesion: Class 4,5

(ISO class evaluation criteria)

1. Class 0 grade: The peeling area is 0% of the area of the specimen to be evaluated;

2. Class 1 grade: The peeling area is more than 0% and less than 5% of the area of the specimen to be evaluated;

3. Class 2 grade: The peeling area is more than 5% and less than 15% of the area of the specimen to be evaluated;

4. Class 3 grade: The peeling area is more than 15% and less than 35% of the area of the specimen to be evaluated;

5. Class 4 grade: The peeling area is more than 35% and less than 65% of the specimen area to be evaluated;

6. Class 5 grade: The peeling area exceeds 65% of the area of the specimen to be evaluated.

Example Comparative example Time(h) Experiment One 2 3 4 One 2 0 Haze O O O O O △ Exfoliation O O O O O O crack O O O O O O 1000 Haze O O O O O △ Exfoliation O O O O O O crack O O O O O O 2000 Haze O O O O O △ Exfoliation O O O O O O crack O O O O O O 3000 Haze O O O O O △ Exfoliation O O O O O O crack O O O O O △ 4000 Haze O O O O O △ Exfoliation O O O △ △ O crack O O O O △ X

Haze Interlayer adhesion Early 100℃ Early 100℃ Example One O O O O Example 2 O O O O Example 3 O O O O Example 4 O △ O △ Comparative example One O O O △ Comparative example 2 △ X △ X

Experimental Example 1 was to measure the physical properties of each of the Examples and Comparative Examples under conditions similar to the actual environment. In the case of automotive exterior materials, weather resistance of 10 years or more is required, which corresponds to a weather resistance test of about 8000 hours or more, and the experiment is not easy. Experimental Example 2 is a measurement of a rapid change in physical properties by promoting aging in the harsh conditions of a 100° C. constant temperature water bath, and can replace the long-term weatherability evaluation of about 8000 hours.

As shown in Table 1, it can be seen that the laminate of the embodiment exhibits excellent weather resistance, such as continuously maintaining excellent effects in haze, peelability, and crack generation. On the other hand, in Comparative Examples 1 and 2, when only a single additive is used, UV protection is not completely blocked, resulting in a problem of peeling and adhesion degradation, and Comparative Example 2 contains a high content of UV protection agent, resulting in poor compatibility with resin, It can be seen that the transparency of the laminate is poor, and the haze increases from the beginning.

And, as shown in Table 2, unlike the Example, Comparative Example 1 containing only a benzophenone-based compound, it can be seen that the adhesion is lowered in only 8 hours under the harsh conditions of a 100 ℃ constant temperature water bath. Accordingly, it can be seen that the peeling force in Comparative Example 1 is significantly lower in long-term weather resistance.

Therefore, it can be seen that the transparent resin laminate of the embodiment having improved long-term weather resistance is suitable for automotive exterior materials requiring weather resistance of 10 years or more.

10: transparent resin laminate
100: base layer
200: hard coating layer
300: primer layer

Claims (14)

Including a base layer, a primer layer and a hard coating layer,
The primer layer is a cured product of a primer coating composition comprising a (meth)acrylic resin and a sunscreen,
The sunscreen agent includes a mixture of a benzophenone-based compound and a triazine-based compound,
The weight average molecular weight (Mw) of the (meth)acrylic resin is 300,000 g/mol to 1 million g/mol,
Including 35 parts by weight to 60 parts by weight of the sunscreen based on 100 parts by weight of the (meth)acrylic resin,
The weight ratio of the benzophenone-based compound to the triazine-based compound is 7:1 to 5:1,
The benzophenone-based compound is 2-hydroxy-4-ene-octoxybenzophenone, 4-[gamma-(trimethoxysilyl)propoxy]-2-hydroxy Benzophenone, 4-[gamma-(triethoxysilyl)propoxy]-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (2,2'-Dihydroxy -4,4'-dimethoxybenzophenone), 2-(trifluoromethyl)benzophenone (2-(Trifluoromethyl)benzophenone), 2-hydroxy-4-methoxy-4'-methylbenzophenone (2-HYDROXY-4) -METHOXY-4'-METHYLBENZOPHENONE), 2-hydroxy-4-methoxybenzophenone (2-Hydroxy-4-methoxybenzophenone), 4-dodecyloxy-2-hydroxybenzophenone (4-DODECYLOXY-2-HYDROXYBENZOPHENONE) ) And a combination thereof, including one compound selected from the group consisting of
Transparent resin laminate.
delete delete delete The method of claim 1,
The triazine-based compound is [4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2-hydroxyphenyl)-1,3,5-triazine, 2-[4-[4,6-bis([1,1'-biphenyl]-4 -Yl)-1,3,5-triazin-2-yl]-3-hydroxyphenoxy]propanoic acid 6-methylheptyl ester and a combination thereof, including one compound selected from the group consisting of
Transparent resin laminate.
The method of claim 1,
The primer coating composition further comprises one additive selected from the group consisting of an ultraviolet stabilizer, a leveling agent, an antioxidant, and a combination thereof.
Transparent resin laminate.
The method of claim 1,
The (meth)acrylic resin is polymethyl methacrylate, polybutyl acrylate, polyauryl acrylate, polystearyl acrylate, polyglycidyl acrylate, polyglycidyl methacrylate, polyacrylonitrile, poly Comprising one selected from the group consisting of acrylamide, polyacrylonitrile-polyalkylacrylate, and combinations thereof
Transparent resin laminate
The method of claim 1,
The glass transition temperature of the (meth)acrylic resin is 90 ℃ to 120 ℃
Transparent resin laminate.
delete The method of claim 1,
The base layer is polycarbonate, polystyrene, polyester, acrylic resin, modified acrylic resin, urethane resin, thiourethane resin, condensate of halogenated bisphenol A and ethylene glycol, acrylic urethane resin, halogenated acrylic-containing acrylic resin, sulfur-containing Including one selected from the group consisting of resins, modified polycarbonates, and combinations thereof
Transparent resin laminate.
The method of claim 1,
The hard coating layer is a cured product of a hard coating composition comprising at least one compound selected from the group consisting of an acrylic compound, an epoxy compound, a silicon compound, a silicone compound, and a combination thereof.
Transparent resin laminate
Preparing a primer coating composition comprising a (meth)acrylic resin and a sunscreen agent;
Coating the primer coating composition on a base layer;
Forming a primer layer by thermally curing the primer coating composition; And
Forming a hard coating layer on the primer layer;
Including,
The sunscreen agent includes a mixture of a benzophenone-based compound and a triazine-based compound,
The weight average molecular weight (Mw) of the (meth)acrylic resin is 300,000 g/mol to 1 million g/mol,
Including 35 parts by weight to 60 parts by weight of the sunscreen based on 100 parts by weight of the (meth)acrylic resin,
The weight ratio of the benzophenone-based compound to the triazine-based compound is 7:1 to 5:1,
The benzophenone-based compound is 2-hydroxy-4-ene-octoxybenzophenone, 4-[gamma-(trimethoxysilyl)propoxy]-2-hydroxy Benzophenone, 4-[gamma-(triethoxysilyl)propoxy]-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (2,2'-Dihydroxy -4,4'-dimethoxybenzophenone), 2-(trifluoromethyl)benzophenone (2-(Trifluoromethyl)benzophenone), 2-hydroxy-4-methoxy-4'-methylbenzophenone (2-HYDROXY-4) -METHOXY-4'-METHYLBENZOPHENONE), 2-hydroxy-4-methoxybenzophenone (2-Hydroxy-4-methoxybenzophenone), 4-dodecyloxy-2-hydroxybenzophenone (4-DODECYLOXY-2-HYDROXYBENZOPHENONE) ) And a combination thereof, including one compound selected from the group consisting of
Method for producing a transparent resin laminate.
delete Prepared from the transparent resin laminate according to any one of claims 1, 5 to 8, 10 and 11
Automotive exterior materials.

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