KR100428639B1 - Multi-layered transparent sheet for exterior - Google Patents

Abstract

The present invention relates to a multi-layer transparent sheet for outdoor use, in particular an outer layer containing a polymethyl methacrylate (PMMA) resin, and methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) methylmethacrylate-acrylonitrile-butadiene The present invention relates to an outdoor multilayer transparent sheet having excellent impact resistance, scratch resistance, weather resistance, and transparency that forms a multilayer of a two-layer structure or a three-layer structure including an inner layer containing a resin.

Description

Outdoor Multi-layer Transparent Sheet {MULTI-LAYERED TRANSPARENT SHEET FOR EXTERIOR}

The present invention relates to an outdoor multilayer transparent sheet, and more particularly, to an outdoor multilayer transparent sheet excellent in impact resistance, scratch resistance, weather resistance, and transparency.

Conventionally, sheet materials that require transparency and impact, such as soundproof walls that require transparency and canopy, which is a building roof material, are mainly composed of polycarbonate and polymethylmethacrylate (PMMA) sheets. Polyethylene terephthalate (PET) sheets and polyvinylchloride (PVC) sheets are also used in small amounts depending on the application.

Polycarbonate sheet is excellent in mechanical properties and is currently used most widely in outdoor environments such as soundproof walls, canopies, etc., but is easily discolored by ultraviolet rays and has a disadvantage in that scratch resistance is weak. To compensate for these disadvantages, polycarbonate with an excessive amount of UV stabilizer is co-extruded with a general polycarbonate to a certain thickness to improve surface weather resistance, and to improve scratch resistance, methyl methacrylate (MMA; methyl methacrylate) compound or The method of strengthening surface hardness by hardening-coating to the thickness of 5-30 micrometers with the raw material which consists of a silicon compound is used.

However, when a certain period of time passes under an external atmosphere, the material is deteriorated by ultraviolet rays contained in sunlight, and the chemical composition of the material changes, thereby deteriorating the adhesion between the polycarbonate material and the surface hardening coating material. In addition to the loss of the scratch-resistant reinforcement function is generated, there is a problem that the appearance quality is reduced to the coating film is separated from the surface. In addition, there is a disadvantage that the manufacturing cost is expensive compared to other transparent materials.

Polymethyl methacrylate sheet has excellent advantages in weather resistance and hardly discolored when used in an outdoor environment, the manufacturing cost is relatively low. However, the impact strength is so low that it is easily broken even by a weak external shock, so it is mainly used for products such as outdoor signboards and low-cost soundproof walls that have little external impact. To supplement the low impact strength of polymethyl methacrylate sheet, there is a high-impact polymethyl methacrylate sheet that has been reinforced with some impact strength by adding acrylic rubber as an impact modifier. There is a problem of high manufacturing cost.

On the other hand, polyethylene terephthalate sheet has a low manufacturing cost, but when the long-term exposure to the outdoors due to deterioration by ultraviolet rays, the physical properties are sharply degraded, the heat deformation temperature is low, the sheet is struck by its own weight or deformed in the high temperature environment in summer have. In addition, polyvinyl chloride sheet has excellent processability and low manufacturing cost, but the use of chlorine compounds, which can cause environmental problems, is spreading in developed countries. There is a problem that occurs.

In addition, Japanese Laid-Open Patent Publication No. 2000-272056 discloses a method for producing a thermoplastic multilayer sheet in combination with a polymethylmethacrylate resin in order to supplement weather resistance of a general acrylonitrile-butadiene-styrene resin. It is limited to opaque products.

The sheet made of transparent acrylonitrile-butadiene-styrene resin alone is excellent in the initial physical balance, but the rubber component in the resin is degraded by ultraviolet rays of the solar light, so the discoloration is severe when long-term exposure in the outdoors, It is rarely used for outdoor use and is used only indoors.

In addition, when the sheet is manufactured by branding methyl methacrylate-acrylonitrile-butadiene-styrene resin and polymethyl methacrylate resin, methyl methacrylate-acrylonitrile-butadiene-styrene resin and polymethyl methacrylate Because of the opacity due to the difference in refractive index of the resin, the desired transparent sheet cannot be obtained. Thus, a technique for producing a transparent sheet using polymethyl methacrylate resin / methyl methacrylate-acrylonitrile-butadiene-styrene resin as a multilayer Was not.

Therefore, research on a multi-layered transparent sheet that can be used for outdoor use due to its excellent impact resistance, scratch resistance, weather resistance, and transparency is needed.

In order to solve the above problems, an object of the present invention is to provide a multi-layered transparent sheet for outdoor use having a low manufacturing cost as well as transparency and impact resistance and significantly improved scratch resistance and weather resistance compared to polycarbonate sheet. .

In order to achieve the above object, the present invention

a) containing polymethyl methacrylate (PMMA)

The outer layer; And

b) methylmethacrylate-acrylonitrile-butadiene-styrene (MABS;

containing methylmethacrylate-acrylonitrile-butadiene-styrene)

Inner layer

It provides a multilayer transparent sheet comprising a.

Hereinafter, the present invention will be described in detail.

MEANS TO SOLVE THE PROBLEM The present inventors heat-melt a polymethylmethacrylate resin and a methylmethacrylate-acrylonitrile- butadiene-styrene resin, while researching the outdoor transparent sheet which has transparency, impact resistance, and excellent scratch resistance and weatherability. By co-extrusion, the polymethyl methacrylate resin is introduced into the outer layer to obtain excellent weather resistance and scratch resistance, and the methyl methacrylate-acrylonitrile-butadiene-styrene resin is introduced into the inner layer to obtain excellent impact resistance. In addition, it was confirmed that there is an excellent effect that can simultaneously satisfy the weather resistance, scratch resistance, impact resistance, and transparency that could not be expected in the case of using each of these single resin, and completed the present invention based on this.

The outdoor multilayer transparent sheet of the present invention comprises two layers of an outer layer-inner layer including an outer layer containing polymethyl methacrylate resin and an inner layer containing methyl methacrylate-acrylonitrile-butadiene-styrene resin. Structure, or an outer layer-inner layer-outer layer.

The polymethyl methacrylate resin of a) used in the present invention is a polymer of methyl methacrylate, which polymerizes methyl methacrylate alone, or other acrylic such as methyl methacrylate, styrene, cyclohexyl maleimide, etc. It can be manufactured by copolymerizing a rate monomer by methods, such as block polymerization, suspension polymerization, or solution polymerization.

Polymethylmethacrylate resins are generally pure polymethylmethacrylate resins, or methyl methacrylates, which do not contain acrylic acid alkyl ester rubbers when the final transparent sheet is not stressed by external forces or its own weight. You may use the copolymer which copolymerized other acrylate monomers, such as styrene and a cyclohexyl maleimide.

However, when it is required to install in the form of curved surface or if a lot of external force or self stress is applied after installation, fine surface cracks may occur due to stress, so that the alkyl acrylate ester rubber is reinforced to absorb the stress. It is preferable to use the prepared polymethyl methacrylate resin.

The polymethyl methacrylate resin may be grafted with acrylic acid alkyl ester-based rubber as a reinforcing agent for impact reinforcement. The acrylic acid alkyl ester-based rubber content is preferably included up to 60 parts by weight based on 100 parts by weight of the total polymethyl methacrylate resin.

The acrylic acid alkyl ester rubber used as the reinforcing agent is a compound containing at least one acrylic acid alkyl ester polymer having a glass transition temperature (Tg) of 0 ° C. or lower, and preferably butyl acrylate. In addition, rubber reinforcement copolymers copolymerized with other monomers such as butyl acrylate rubber, methyl acrylate, methyl methacrylate, or styrene may be used as necessary.

Rubber-reinforced acrylate resin is prepared by copolymerizing methyl methacrylate, styrene, cyclohexyl maleimide and the like in the presence of 10-60 wt% acrylic acid alkyl ester rubber.

When the rubber content of the rubber-reinforced polymethyl methacrylate resin is less than 10 parts by weight, the rubber reinforcement effect cannot be sufficiently achieved. When the rubber content of the rubber-reinforced polymethyl methacrylate resin is less than 10 parts by weight, it is difficult to extrude during extrusion, and the transparency of the product is reduced. There is a problem that the manufacturing cost is high due to rising costs.

The methyl methacrylate-acrylonitrile-butadiene-styrene resin of b) used in the present invention is an aromatic vinyl compound 15-30 parts by weight, 15 parts by weight or less of vinyl cyan compound, 8 parts by weight of a rubbery polymer, and acrylic acid. A method of copolymerizing 40 to 60 parts by weight of an alkyl ester,

Graft methylmethacrylate-acrylo having a high rubber content obtained by polymerizing 10 to 15 parts by weight of an aromatic vinyl compound, 5 parts by weight or less of a vinyl cyan compound, and 20 to 40 parts by weight of an acrylic acid alkyl ester to 30 to 60 parts by weight of a rubbery polymer. Graft methylmethacrylate-acrylonitrile-butadiene-styrene resin having high rubber content by using nitrile-butadiene-styrene polymer, aromatic vinyl compound, vinyl cyan compound, acrylic acid alkyl ester, and phenyl maleimide It can be manufactured by the method of branding the polymerized polymer by adjusting so that refractive index may match.

The rubbery polymer generally has a higher impact strength as the particle size increases. However, when the rubbery polymer is too large, the rubber polymer in the final methylmethacrylate-acrylonitrile-butadiene-styrene resin produced is difficult to transmit light, thereby rapidly decreasing transparency. Will be. Conversely, the smaller the particles, the higher the transparency, but no satisfactory impact strength. Therefore, the particle size of the rubbery polymer used for the production of methyl methacrylate-acrylonitrile-butadiene-styrene resin is preferably in the range of 0.2 to 0.4 m, more preferably in the range of 0.25 to 0.35 m.

The component of the rubbery polymer is preferably polybutadiene or polybutadiene-styrene copolymer, and the monomer copolymerized with polybutadiene is not necessarily limited, but the refractive index of the rubbery polymer produced is preferably in the range of 1.50 to 1.55.

The monomers used in the preparation of the graft methyl methacrylate-acrylonitrile-butadiene-styrene resin are not necessarily limited, but the aromatic vinyl compound is styrene, the vinyl cyan compound is acrylonitrile, and the acrylic acid alkyl ester is methyl methacrylate, And phenyl maleimide is preferably N-phenyl maleimide.

In the preparation of methyl methacrylate-acrylonitrile-butadiene-styrene resin, it is very important to design such that the refractive index between the rubbery polymer and the matrix polymer is similar, and since the refractive indexes of the monomers constituting the matrix have an absolute effect, Good adjustment of the combination ratio, such that the refractive index is similar to the rubbery polymer, improves the transparency.

In the outdoor multilayer transparent sheet of the present invention, a rubber-reinforced polymethyl methacrylate resin, or a general polymethyl methacrylate resin is located in the upper and lower layers, and the methyl methacrylate-acrylonitrile-butadiene-styrene resin is located in the intermediate layer. The co-extrusion method of the sheet | seat which consists of a two-layered structure which is a 3-layered structure to be made, or an outer surface is a polymethylmethacrylate resin layer, and an inner surface is a methylmethacrylate-acrylonitrile-butadiene-styrene resin layer. Manufacture by The total thickness of the outdoor multilayer transparent sheet is preferably in the range of 0.8 to 15 mm, and the thickness of each polymethyl methacrylate resin layer is preferably in the range of 0.1 to 1.5 mm in the total sheet thickness. When the thickness of each polymethyl methacrylate resin layer is less than 0.1 mm, sufficient weather resistance cannot be exhibited. When the thickness of each polymethyl methacrylate resin layer is greater than 2 mm, the weatherability is improved, but the manufacturing cost increases and the impact strength is lowered economically. There is this.

The polymethyl methacrylate resin used for the outer layer of the outdoor multilayer transparent sheet is a resin having excellent weather resistance, but blocks a considerable amount of ultraviolet rays, but because it is not completely blocked, methyl methacrylate-acrylonitrile-butadiene of the inner layer When the light stabilizer is added to the styrene resin layer, the light stabilizer added with radicals generated by some ultraviolet rays passing through the polymethylmethacrylate resin layer and reaching the inner surface of the styrene resin layer captures, erases, or absorbs ultraviolet rays to convert them into thermal energy. Therefore, the weather resistance of the sheet can be greatly improved by minimizing discoloration and deterioration of physical properties of the multi-layered sheet, in particular, the intermediate layer methyl methacrylate-acrylonitrile-butadiene-styrene resin. Although the light stabilizer is not limited, it is preferable to select a kind that does not impair the transparency of the sheet and to determine the amount of addition, and in general, methyl methacrylate-acrylonitrile- when the thickness of the polymethyl methacrylate resin layer is 0.2 mm or less. It is preferable to reinforce the light stabilizer in the butadiene-styrene resin layer or the polymethyl methacrylate resin layer.

In addition, antioxidants, heat stabilizers, lubricants, pigments, and the like necessary for processing may be appropriately added in advance in compounding the resin.

In addition, the outdoor multilayer transparent sheet of the present invention has a surface hardness of the polymethyl methacrylate resin by forming the outer surface layer of the polymethyl methacrylate resin, can greatly improve scratch resistance, excellent surface gloss and weather resistance Excellent impact strength and transparency.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Example 1

The coextruder is melted in each individual extruder and immediately after passing through the die end or die of a die divided into three blocks, a polymethylmethacrylate resin sheet layer and a methylmethacrylate-acrylonitrile-butadiene-styrene resin sheet layer It was configured to meet each other. Methyl methacrylate-acrylonitrile-butadiene-styrene resin sheet layers were prepared using a 135Φ single extruder, with temperatures of 235 ° C. (hopper), 240 ° C. (cylinder 1), and 245 ° C. (cylinder 2). , 245 ° C. (cylinder 3), 245 ° C. (cylinder 4), and 250 ° C. (die). The polymethyl methacrylate resin sheet layer used a 55Φ single extruder, wherein the temperature was 245 ℃ (hopper), 255 ℃ (cylinder 1), 260 ℃ (cylinder 2), 260 ℃ (cylinder 3), 260 ℃ (cylinder 4), 260 ℃ (die) was set. In addition, roll temperature was set to 90 degreeC (top), 85 degreeC (middle), and 80 degreeC (bottom).

Using a co-extruder prepared as described above, a polymethyl methacrylate resin (butyl acrylate-methyl methacrylate-styrene copolymer) having a rubber content of 20% was 0.9 mm in the upper and lower layers, respectively. The methyl methacrylate-acrylonitrile-butadiene-styrene resin (methyl methacrylate-acrylonitrile-butadiene-styrene copolymer) having a rubber content of 15% to a thickness of 4.2 mm The polymethyl methacrylate / methyl methacrylate-acrylonitrile-butadiene-styrene multilayer transparent sheet was prepared by adjusting.

Example 2

In Example 1, the polymethyl methacrylate resin (butyl acrylate-methyl methacrylate-styrene copolymer) having a rubber content of 20% was adjusted to have a thickness of 0.45 mm on the upper and lower layers, respectively, and the rubber content was 20 % Methyl methacrylate-acrylonitrile-butadiene-styrene resin (methyl methacrylate-acrylonitrile-butadiene-styrene copolymer) was adjusted to have a thickness of 5.1 mm in the inner layer to the same method as in Example 1 Was carried out.

Example 3

In Example 1, except that the polymethyl methacrylate resin layer having a rubber content of 20% was adjusted to have a thickness of 0.2 mm, respectively.

Example 4

Using a co-extruder prepared in Example 1 to adjust the polymethyl methacrylate resin (butyl acrylate-methyl methacrylate-styrene copolymer) having a rubber content of 20% to the thickness of 0.1 mm in the upper and lower layers, respectively The methyl methacrylate-acrylonitrile-butadiene-styrene resin (methyl methacrylate-acrylonitrile-butadiene-styrene copolymer) having a rubber content of 15% was adjusted to a thickness of 5.8 mm in the inner surface layer of methyl A methacrylate / methyl methacrylate-acrylonitrile-butadiene-styrene multilayer transparent sheet was prepared, wherein the inner layer of methyl methacrylate-acrylonitrile-butadiene-styrene resin layer was coated with Hisorb 327 (LG Chemistry). ) Was carried out in the same manner as in Example 1, except that 0.15 part by weight and 0.15 part by weight of Hisorb 770 (LG Chem) were added.

Example 5

In the same manner as in Example 1, except that the pure polymethyl methacrylate resin (methyl methacrylate polymer) layer was adjusted to 0.2 mm in Example 1, respectively.

Example 6

The polymethyl methacrylate resin layer having a rubber content of 20% was adjusted to 0.45 mm on only one side, and methyl methacrylate-acrylonitrile-butadiene-styrene resin (methyl methacrylate-butadiene-styrene copolymer) ) Was carried out in the same manner as in Example 1 except that it was adjusted to a thickness of 5.55 mm.

Example 7

The polymethyl methacrylate resin layer having a rubber content of 20% is adjusted to 0.2 mm on one side only, and the methyl methacrylate-acrylonitrile-butadiene-styrene resin having a rubber content of 15% (methyl methacrylate-acrylic) Ronitrile-butadiene-styrene copolymer) was carried out in the same manner as in Example 1 except that the inner layer was adjusted to have a thickness of 2.8 mm.

Comparative Example 1

The methyl methacrylate-acrylonitrile-butadiene-styrene sheet was adjusted to a thickness of 6 mm through an extrusion machine using only the methyl methacrylate-acrylonitrile-butadiene-styrene resin without the polymethyl methacrylate resin layer. Prepared.

Comparative Example 2

A commercially available 6 mm thick general polycarbonate sheet was used.

Comparative Example 3

A commercially available 6 mm thick UV protected, hard coated polycarbonate sheet was used.

Comparative Example 4

A commercially available 6 mm thick UV protective polycarbonate sheet was used.

Comparative Example 5

A commercially available 6 mm thick pure polymethylmethacrylate sheet was used.

Experimental Example

Using the polymethyl methacrylate / methyl methacrylate-acrylonitrile-butadiene-styrene multilayer transparent sheet prepared in Examples 1 to 7 and the sheets of Comparative Examples 1 to 5 the physical properties of importance in the transparent sound barrier It evaluated using the method and the result is shown in following Table 1 and Table 2.

A) Impact strength-Izo by cutting the sheet and making the specimen according to ASTM D256

IZOD impact strength was measured.

B) Weather resistance-Q-UV Panel equipped with UVB lamp shine 8

hr X Condensation 200 hours consecutively on condition that 4hr is one cycle

After the eye test, the color tone change amount (ΔE) of the sheet before and after the test was measured.

C) Light transmittance-The light transmittance was measured at a visible light wavelength of 600 nm.

D) Scratch resistance-The pencil hardness was measured according to the KSD 3502 method.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 PMMA resin (outer layer) Furtherance BA-MMA-ST BA-MMA-ST BA-MMA-ST BA-MMA-ST MMA BA-MMA-ST BA-MMA-ST Rubber content 20% 20% 20% 20% - 20% 20% Upper layer thickness 0.9 mm 0.45 mm 0.2 mm 0.1 mm 0.2 mm 0.45 mm 0.2 mm Lower layer thickness 0.9 mm 0.45 mm 0.2 mm 0.1 mm 0.2 mm - - Refractive index 1.490 1.490 1.490 1.490 1.490 1.490 1.490 Transparent ABS resin (inner layer) Furtherance MMA-AN-BD-ST MMA-AN-BD-ST MMA-AN-BD-ST MMA-AN-BD-ST MMA-AN-BD-ST MMA-BD-ST MMA-AN-BD-ST Rubber content 15% 22% 15% 15% 15% - 15% Layer thickness 4.2 mm 5.1 mm 5.6 mm 5.8 mm 5.6 mm 5.55 mm 2.8 mm Hisorb 327 - - - 0.15 - - - Hisorb 770 - - - 0.15 - - - Refractive index 1.517 1.516 1.517 1.517 1.517 1.530 1.517 Impact strength 9 12 13 14 12 14 12 Weather resistance 0.6 0.9 1.5 1.6 1.7 0.9 1.4 Transparency 86 85 85 85 85 83 83 Scratch resistance H H H H 2H H H Surface after installation (flat plate) Good Good Good Good Good Good Good Status (surface plate) Good Good Good Good Fine crack Good Good [Note] BA-MMA-ST (butyl acrylate-methyl methacrylate-styrene) copolymer: LGMMA MMA (methyl methacrylate) copolymer: LGMMA MMA-AN-BD-ST (methyl methacrylate- Acrylonitrile-butadiene-styrene copolymer MMA-BD-ST (methyl methacrylate butadiene-styrene) copolymer: Japanese electrochemical transparent ABS resin Light stabilizer: Hisorb 327 (manufactured by LG Chem, benzotriazole light stabilizer) , Hisorb 770 (manufactured by LG Chem, HALS light stabilizer)

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 PMMA resin Furtherance - - - - MMA thickness - - - - 6 mm Transparent ABS resin Furtherance MMA-AN-BD-ST - - - - thickness 6 mm - - - - PC resin thickness - 6 mm 6 mm 6 mm - Surface treatment - - UV protection, hard coating UV protective coating - Impact strength 15 18 18 18 1.2 Weather resistance 10 10 1.8 1.8 0.6 Scratch resistance 3B 5B 3H 5B 2H Transparency 76 85 85 85 92 Surface after installation (flat plate) discoloration discoloration Coating layer peeling Good Good Status (surface plate) discoloration discoloration Coating layer peeling Good crack

Through Tables 1 and 2 above, an embodiment comprising an outer layer containing a polymethyl methacrylate resin and an inner layer containing a methyl methacrylate-acrylonitrile-butadiene-styrene resin according to the present invention. Sheets 1 to 7 was found to be excellent in impact strength, weather resistance, scratch resistance, transparency, and surface and state after installation compared to the sheets of Comparative Examples 1 to 5.

As described above, the outdoor multilayer transparent sheet of the present invention not only combines the advantages of the excellent weather resistance of the polymethyl methacrylate resin, and the scratch resistance and the excellent impact resistance of the methyl methacrylate-acrylonitrile-butadiene-styrene resin. In addition, the manufacturing cost is low compared to the polycarbonate sheet, does not require a separate post-process to improve scratch resistance, there is an advantage that the quality of the product does not occur due to changes over time after installation. In addition, it has a much higher impact strength than polymethyl methacrylate resin, so it is suitable for outdoor transparent sheets requiring impact strength, weather resistance and scratch resistance simultaneously. It is suitable for use. In addition, the polymethyl methacrylate resin and the methyl methacrylate-acrylonitrile-butadiene-styrene resin of the multi-layered transparent sheet of the present invention have the same major constituents as methyl methacrylate and have excellent compatibility. There is an effect that can be recycled to acrylonitrile-butadiene-styrene.

Claims (7)

a) containing polymethyl methacrylate (PMMA) The outer layer; And b) methylmethacrylate-acrylonitrile-butadiene-styrene (MABS; containing methylmethacrylate-acrylonitrile-butadiene-styrene) Inner layer Multilayer transparent sheet comprising a. The method of claim 1, The multilayer transparent sheet is a two-layer structure of the outer layer-inner layer, or a three-layer structure of the outer layer-inner layer-outer layer. The method of claim 1, The polymethyl methacrylate resin of a) is methyl methacrylate alone or a copolymer of methyl methacrylate and styrene or cyclohexyl maleimide. The method of claim 1, The polymethyl methacrylate resin is a multi-layer transparent sheet containing up to 60 parts by weight of an acrylic acid alkyl ester rubber having a glass transition temperature (Tg) of up to 0 ℃ as an impact modifier. The method of claim 1, The methyl methacrylate-acrylonitrile-butadiene-styrene resin of b) is 15-30 parts by weight of an aromatic vinyl compound, up to 15 parts by weight of a vinyl cyan compound, and 40-60 alkyl acrylate esters in 8-30 parts by weight of the rubbery polymer. Multilayer transparent sheet copolymerized by weight. The method of claim 5, The multi-layered transparent sheet which is a polybutadiene or polybutadiene-styrene copolymer whose particle diameter of the said rubbery polymer is 0.2-0.4 micrometers, and refractive index is 1.50-1.55. The method of claim 1, The total thickness of the said outdoor multilayer transparent sheet is the range of 0.8-15 mm, and the thickness of each polymethyl methacrylate resin layer is 0.1-1.5 mm in the total sheet thickness.