WO2015064928A1 - High hardness multi-layer sheet - Google Patents

High hardness multi-layer sheet Download PDF

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Publication number
WO2015064928A1
WO2015064928A1 PCT/KR2014/009543 KR2014009543W WO2015064928A1 WO 2015064928 A1 WO2015064928 A1 WO 2015064928A1 KR 2014009543 W KR2014009543 W KR 2014009543W WO 2015064928 A1 WO2015064928 A1 WO 2015064928A1
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Prior art keywords
weight
parts
layer
high hardness
multilayer sheet
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PCT/KR2014/009543
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French (fr)
Korean (ko)
Inventor
박환석
황덕율
권동주
이종훈
신창학
예성훈
송예리
유다영
남해림
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(주)엘지하우시스
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Priority to JP2016527358A priority Critical patent/JP6524077B2/en
Priority to CN201480058941.9A priority patent/CN105705332B/en
Publication of WO2015064928A1 publication Critical patent/WO2015064928A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays

Definitions

  • It relates to a high hardness multilayer sheet.
  • a liquid crystal window containing polymethyl methacrylate (PMMA) resin as a main raw material has excellent weather resistance and scratch resistance, but has a low impact resistance.
  • PMMA polymethyl methacrylate
  • the popularity of ultra-slim mobile devices and large LCD Along with the diffusion, disadvantages of the existing polymethyl methacrylate (PMMA) resins are highlighted.
  • various attempts are being made to reinforce the weakened impact resistance while reducing the thickness of the mobile device window to about 0.5 mm, which is about half of the existing one, and removing various protective films to reduce the overall module thickness.
  • One embodiment of the present invention provides a high hardness multilayer sheet including a laminated structure of a polymethyl methacrylate layer and a polycarbonate layer.
  • Another embodiment of the present invention provides a high hardness multi-layer sheet that is optimized by constituting the components of the polymethyl methacrylate layer and the polycarbonate layer, and is produced by an extrusion process exhibiting excellent physical properties.
  • about 75 parts to about 88 parts by weight of the (meth) acrylic acid ester monomer, about 2 parts to about 5 parts by weight of the styrene monomer and about 10 parts to about 20 parts by weight of the N-substituted maleimide monomer Polymethyl methacrylate layer containing an acrylic copolymer formed in parts by weight; And it provides a high hardness multilayer sheet which is a laminated structure of a polycarbonate layer comprising a polycarbonate copolymer.
  • the polymethyl methacrylate layer may have a thickness of about 40 um to about 70 um.
  • the glass transition temperature of the acrylic copolymer may be about 130 ° C to about 140 ° C.
  • the weight average molecular weight of the acrylic copolymer may be about 100,000 to about 150,000.
  • the polymethyl methacrylate layer may further include about 0.1 parts by weight to about 1.5 parts by weight of antioxidant and about 0.5 parts by weight to about 3.0 parts by weight of UV stabilizer based on 100 parts by weight of the acrylic copolymer.
  • the thickness of the polycarbonate layer may be about 900um to about 950um.
  • the glass transition temperature of the polycarbonate copolymer may be about 140 ° C to about 150 ° C.
  • the melt index of the polycarbonate copolymer may be about 3 to about 22.
  • the amount of the polycarbonate copolymer may further include about 0.3 parts by weight to about 2.0 parts by weight of antioxidant and about 0.5 parts by weight to about 3.0 parts by weight of UV stabilizer.
  • the polymethyl methacrylate layer and the polycarbonate layer may be formed by coextrusion.
  • a hard coating layer may be further included on the polymethyl methacrylate layer or below the polycarbonate layer.
  • the pencil hardness of the high hardness multilayer sheet may be about 4H or more.
  • the warpage of the high hardness multilayer sheet may be about 0.1 mm or less.
  • the high hardness multilayer sheet may have excellent scratch resistance while ensuring excellent dimensional stability.
  • the high hardness multilayer sheet is excellent in bending characteristics under high temperature and high humidity conditions and can be easily applied to various electronic products.
  • Figure 1 shows a cross section of a high hardness multilayer sheet which is an embodiment of the present invention.
  • Figure 2 shows a cross section of a high hardness multilayer sheet which is another embodiment of the present invention.
  • Figure 3 shows a cross section of a high hardness multilayer sheet which is another embodiment of the present invention.
  • Tempered glass is typically applied to most mobile devices such as smartphones or tablet product windows.
  • plastic cover is advantageous in various aspects such as cracking characteristics, price, and process yield compared to tempered glass, the demand for plastic cover is continuously increasing.
  • components exhibiting optical properties similar to tempered glass may be polymethylmethacrylate (hereinafter referred to as PMMA), polycarbonate (hereinafter referred to as PC), or the like.
  • PMMA polymethylmethacrylate
  • PC polycarbonate
  • the PMMA has high scratch resistance and excellent optical properties, but has a limitation in impact resistance.
  • the PC has excellent impact properties but shows a limited scratch resistance.
  • the present invention 75 to 88 parts by weight of the (meth) acrylic acid ester monomer, 2 to 5 parts by weight of styrene monomer and 10 parts by weight of N-substituted maleimide monomer Polymethyl methacrylate layer containing an acrylic copolymer formed by 20 parts by weight; And it provides a high hardness multilayer sheet which is a laminated structure of a polycarbonate layer comprising a polycarbonate copolymer.
  • the high hardness multilayer sheet is optimized by constituting the polymethyl methacrylate layer and the polycarbonate layer, and is manufactured by an extrusion process to ensure excellent dimensional stability and may have excellent scratch resistance.
  • the high hardness multilayer sheet is excellent in bending characteristics under high temperature and high humidity conditions and can be easily applied to various electronic products.
  • the polymethyl methacrylate layer (hereinafter referred to as PMMA layer) may include 75 to 88 parts by weight of (meth) acrylic acid ester monomer, 2 to 5 parts by weight of styrene monomer, and 10 to 20 parts by weight of N-substituted maleimide monomer. It may include an acrylic copolymer formed in parts by weight.
  • the acrylic copolymer may include a (meth) acrylic acid ester monomer, a styrene monomer, and an N-substituted maleimide monomer at the same time to ensure excellent heat resistance, thereby ensuring excellent bending characteristics at high temperature and high humidity.
  • the (meth) acrylic acid ester monomer when included outside the above range it may not ensure the durability of the acrylic copolymer.
  • the N-substituted maleimide monomer when included outside the above range, a glass transition temperature of the acrylic copolymer may be lowered, thereby causing problems such as warpage deformation due to lower heat resistance.
  • the PMMA layer may not secure physical properties such as scratch resistance and durability.
  • the (meth) acrylic acid ester monomer is methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate , t-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylic At least one selected from the group consisting of latex, 2-ethylbutyl (meth) acrylate, and combinations thereof.
  • the N-substituted maleimide monomer is N-phenyl maleimide, maleimide, N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-isopropyl maleimide, N-butyl maleimide, N- Isobutyl maleimide, Nt-butyl maleimide, N-cyclohexyl maleimide, N-chlorophenyl maleimide, N-methylphenyl maleimide, N-bromophenyl maleimide, N-naphthyl maleimide, N-la Uryl maleimide, N-hydroxyphenyl maleimide, N-methoxy phenylmaleimide, N-carboxy phenylmaleimide, N-nitrophenyl maleimide and N-benzyl maleimide.
  • the thickness of the PMMA layer may be about 40um to about 70um.
  • the thickness of the PMMA layer can be controlled by the extrusion amount of the PMMA layer resin composition introduced into the feed block from the extruder, so that the amount of the PMMA layer resin composition introduced is always uniformly maintained in order to maintain the thickness of the PMMA layer accurately. It may be necessary to introduce a precise adjustment of the extrusion amount.
  • the thickness of the PMMA layer When the thickness of the PMMA layer is increased, scratch properties are improved, but impact physical properties are reduced. In addition, when the thickness of the PMMA layer is reduced, the stretch characteristics are reduced but the impact properties are improved. Both of them are usually in a trade-off relationship. Therefore, by adjusting the thickness of the PMMA layer in the range of about 40um to about 70um, it is possible to optimize the balance of physical properties with the polycarbonate layer by simultaneously securing a desired level of scratch and impact properties.
  • the glass transition temperature of the acrylic copolymer may be about 130 ° C to about 140 ° C. If the glass transition temperature of the acrylic copolymer is less than about 130 ° C there is a risk of showing a limit to durability at high temperature, high humidity conditions, when exceeding about 140 ° C color discoloration is severe and the polymethyl methacrylate layer is easily broken Problems may arise.
  • the weight average molecular weight of the acrylic copolymer may be about 100,000 to about 150,000.
  • the weight average molecular weight means an average molecular weight obtained by averaging the molecular weights of the component molecular species of a polymer compound having a molecular weight distribution in a weight fraction, whereby the weight average molecular weight of the acryl-based copolymer maintains the above range, thereby providing mechanical strength and polycarbonate.
  • the polymethyl methacrylate layer may further include about 0.1 parts by weight to about 1.5 parts by weight of antioxidant and about 0.5 parts by weight to about 3.0 parts by weight of UV stabilizer based on 100 parts by weight of the acrylic copolymer.
  • the antioxidant prevents crosslinking of the polymer that may occur during discoloration and processing, and maintains the long-term physical properties of the PMMA layer, and also serves to prevent discoloration.
  • octadecyl-3- (3,5-di-talt-butyl-4-hydroxyphenyl) propionate tris (2,4-di-talt-butylphenyl) phosphite, tetrakis [methylene -3- (3,5-di-talt-butyl-4-hydroxyphenyl) propionate] methane, 4,4'-thiobis (6-talt-butyl-m-cresol), pentaerythritol Tetrakis (3-laurylthiopropionate) and the like.
  • the antioxidant may include from about 0.1 parts by weight to about 1.5 parts by weight with respect to 100 parts by weight of the acrylic copolymer, by maintaining the above range can inhibit decomposition due to processing can maintain stable physical properties.
  • the UV stabilizer serves to prevent aging phenomenon such as cracking and discoloration caused by ultraviolet rays when the plastic is exposed to sunlight for a long time.
  • examples of the UV stabilizer include benzophenone, benzotriazole, and HALS.
  • Known materials such as systems may be used mainly, but are not limited thereto.
  • the UV stabilizer may include about 0.5 parts by weight to about 3.0 parts by weight with respect to 100 parts by weight of the acrylic copolymer, it is possible to effectively suppress discoloration by UV by maintaining the above range.
  • the polycarbonate layer (hereinafter, referred to as a PC layer) may include a polycarbonate copolymer.
  • the polycarbonate copolymer has no particular structural limitation and may be formed by interfacial polymerization or melt polymerization.
  • LUPOY PC1201-08 (LG Chem) or LUPOY PC 1300-30 (LG Chem) may be used as the polycarbonate copolymer.
  • the thickness of the PC layer may be about 900um to about 950um.
  • the thickness control of the PC layer can be controlled by the extrusion amount of the PC layer resin composition introduced into the feed block from the extruder, so that the amount of the PC layer resin composition introduced is always maintained in order to maintain the thickness of the PC layer resin composition accurately. It may be necessary to introduce uniformly to precisely control the amount of extrusion.
  • the glass transition temperature of the polycarbonate copolymer may be about 140 ° C to about 150 ° C. If the glass transition temperature of the polycarbonate copolymer is less than about 140 ° C there is a risk that the physical properties at high temperature, high humidity conditions may be lowered, and when the glass transition temperature exceeds about 150 ° C may cause a problem that the processing temperature increases.
  • the melt index of the polycarbonate copolymer may be about 3 to about 22.
  • Melt Index (MI) refers to the melt flow index, which refers to the weight of resin flowing through a capillary tube for 10 minutes at a constant load and temperature.
  • melt index of the polycarbonate copolymer is less than 3, it is necessary to control the temperature high during the extrusion operation due to the fluidity of the polycarbonate copolymer, and the difference between the upper layer PMMA layer and the deep layer may be a problem of layer thickness and uniformity have. In addition, when the melt index exceeds 22, there may be a problem that sheet workability worsens in the T-die during extrusion of the polycarbonate copolymer.
  • the amount of the polycarbonate copolymer may further include about 0.3 parts by weight to about 2.0 parts by weight of antioxidant and about 0.5 parts by weight to about 3.0 parts by weight of UV stabilizer. Matters regarding the antioxidant and UV stabilizer are as described above.
  • the polymethyl methacrylate layer and the polycarbonate layer may be formed by coextrusion.
  • Coextrusion refers to a method of making a coating film and a sheet by adding one or more layers during extrusion coating, film or sheet production using one or more extruders.
  • the coextrusion process is not particularly limited and may form the PMMA layer and the PC layer by a general coextrusion process.
  • the coextrusion process is suitable for realizing the properties to be implemented by the high hardness multilayer sheet of the PMMA layer / PC layer structure, the PMMA layer implements excellent scratch and appearance properties, the PC layer is excellent (toughness) characteristics and heat resistance can be implemented, it is possible to control the physical properties of the high-hardness sheet as a whole.
  • a hard coating layer may be further included on the polymethyl methacrylate layer or below the polycarbonate layer.
  • the hard coating layer is to increase the hardness of the multi-layer sheet, and to prevent problems causing secondary appearance defects. Referring to Figures 2 and 3, the high-hardness multilayer sheet 100 is from the top, the hard coating layer ( 30), the PMMA layer 10 and the PC layer 20 or the hard coating layer 30, the PMMA layer 10, the PC layer 20 and the hard coating layer 30 may be included.
  • a urethane acrylate copolymer series may be used as a component of the hard coating layer.
  • the urethane acrylate copolymer-based hard coating resin is a resin prepared by copolymerization of an acryl-based monomer having a hydroxy group, a urethane-based polyol and isocyanate, polyether polyol, polyester polyol, polycaprolactone polyol, polybaconate polyol
  • Polyol components such as polybutadiene polyol, aromatic isocyanates such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) or isophorone diisocyanate (IPDI; Isophorone diisocyanate), hexamethylene diisocyanate
  • Aliphatic isocyanates such as (HMDI; Hexamethylene diisocyanate) can be reacted to select an appropriate raw material having elasticity capable of three-dimensional molding and scratch
  • the thickness of the hard coating layer may be about 5um to about 30um.
  • the thickness of the hard coating layer is less than 5um, there is a problem that a glossiness change of the film may occur, and when the thickness of about 30um is exceeded, cracks may occur in the hard coating layer.
  • An additive may be further included in the hard coating layer, and the additive may include a silicone-based additive (reactive monomer / oligomer having a silicone group), a fluorine-based additive (reactive monomer / oligomer having a fluorine group), a resin having a silicone group or a fluorine group, a surfactant, One or more selected from the group consisting of oil can be used.
  • a silicone-based additive reactive monomer / oligomer having a silicone group
  • a fluorine-based additive reactive monomer / oligomer having a fluorine group
  • a resin having a silicone group or a fluorine group a surfactant
  • One or more selected from the group consisting of oil can be used.
  • a photoinitiator may be further included in the hard coating layer, and the photoinitiator may include benzyl ketals, benzoin ethers, acetophenone derivatives, ketoxime ethers, benzophenone, (amino) benzoate, and benzyl as photoinitiators for UV curing.
  • At least one free radical initiator selected from dimethyl ketal compounds and at least one cationic initiator selected from onium salts, ferrocenium salts and diazonium salts, or the free radical initiator and the cation Sex initiator mixtures can be used.
  • the pencil hardness of the high hardness multilayer sheet may be about 4H or more.
  • Pencil hardness is the hardness of a certain material compared with the hardness of the pencil lead, it can be represented by the symbols such as H, F, B for each hardness and concentration.
  • Pencil hardness of the high hardness multilayer sheet is measured using ASTM D3363-05 (Mitsubishi pencil, 1kg load), by maintaining a hardness of about 4H or more can implement a superior hardness than a conventional multilayer sheet.
  • the plastic window material to which the high hardness multilayer sheet is applied is warped under high temperature and high humidity conditions, and the warp may cause problems in operation of the touch panel. Therefore, if a certain level of warpage occurs under high temperature and high humidity conditions, the window cover for the touch panel cannot be applied.
  • the curvature of the high hardness multilayer sheet may be about 0.1 mm after being left for 72 hours at a temperature of 85 ° C. and a humidity of 85%.
  • MMA methyl methacrylate
  • styrene 2 parts by weight of styrene, 15 parts by weight of N-cyclohexylmaleimide, 0.2 parts by weight of n-octyl mercaptan as a chain transfer agent and azobisiso-butyronitrile (AIBN as a polymerization initiator)
  • AIBN azobisiso-butyronitrile
  • PMMA-2 was prepared by the same method as PMMA-1 except for changing n-cyclohexylmaleimide to phenylmaleimide in the method for preparing PMMA-1.
  • the molecular weight of the PMMA-2 was 120,000 and the Tg was 133 ° C.
  • HP202 (LG MMA Co., Ltd.) having a molecular weight of 120,000 and a Tg of 104 ° C was used.
  • PC-1 polycarbonate copolymer
  • PC-2 Polycarbonate Copolymer
  • Phenolic antioxidant Irganox1010
  • UV stabilizer Hostavin B-CAP
  • Pencil Hardness The hardness of the Examples and Comparative Examples was measured using ASTM D3363-05 (Mitsubishi Pencil, 1 kg load).
  • Comparative Examples 1 to 4 have a higher hardness and excellent bending characteristics than Comparative Examples 1 to 4.
  • Comparative Examples 1 and 3 are PC layers containing a polycarbonate copolymer having a melt index of 22 or more
  • Comparative Examples 2 and 4 include a PMMA layer including an acrylic copolymer having a glass transition temperature of less than 130 ° C.
  • Example 1 to 4 which is a multilayered structure of a PMMA layer comprising an acrylic copolymer having a glass transition temperature of 130 ° C. to 140 ° C. and a PC layer including a polycarbonate copolymer having a melt index of 3 to 22. Compared with the hardness, the hardness and the bending property were also lower.
  • the thickness of the PC layer was set to 900um or less, and the bending property was lowered due to the relative increase in the thickness of the PMMA layer.
  • the thickness of the PMMA layer was set to 70um or more. Only the hardness is maintained, the bending property is reduced, it was confirmed that only the high hardness multilayer sheet of Examples 1 to 4 can implement the bending property and the scratch resistance at the same time.

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Abstract

The present invention provides a high hardness multi-layer sheet of polycarbonate multilayer structure comprising: a polymethyl methacrylate layer having an acrylic copolymer formed from 75 parts by weight to 88 parts by weight of (meth)acrylic acid ester monomer, 2 parts by weight to 5 parts by weight of styrene monomer, and 10 parts by weight to 20 parts by weight of N-substituted maleimide monomer; and a polycarbonate copolymer.

Description

고경도 다층시트High Hardness Multilayer Sheet
고경도 다층시트에 관한 것이다.It relates to a high hardness multilayer sheet.
최근 다양한 모바일 기기가 대중화되어 있으며, 현재 일반적으로 모바일 기기에 사용되는 재료는 내후성, 외부자극의 긁힘에 대해 견딜 수 있는 내스크레치성, 외부충격에 대한 내충격성 및 가공성 등의 특성이 우수하여야 한다. Recently, various mobile devices have been popularized, and materials generally used in mobile devices should have excellent characteristics such as weather resistance, scratch resistance to withstand scratches of external stimuli, impact resistance against external impact, and workability.
종래 모바일 기기에 사용되는 원료로서 폴리메틸메타크릴레이트(PMMA) 수지를 주원료로 하는 액정창은 내후성 및 내스크레치성이 우수한 반면 내충격성이 약한 문제가 있고, 최근 초슬림 모바일 기기의 인기와 대형 LCD의 확산과 함께 기존 폴리메틸메타크릴레이트(PMMA) 수지의 단점이 부각되고 있다. 초슬림 모바일 기기 생산을 위해 모바일 기기창의 두께가 기존의 절반 정도인 0.5mm 정도로 줄어들고 전체 모듈 두께 감소를 위해 각종 보호필름을 제거하면서 약해진 내충격성을 보강하기 위해 다양한 시도가 증가하고 있다.As a raw material used in conventional mobile devices, a liquid crystal window containing polymethyl methacrylate (PMMA) resin as a main raw material has excellent weather resistance and scratch resistance, but has a low impact resistance. Recently, the popularity of ultra-slim mobile devices and large LCD Along with the diffusion, disadvantages of the existing polymethyl methacrylate (PMMA) resins are highlighted. In order to produce ultra-slim mobile devices, various attempts are being made to reinforce the weakened impact resistance while reducing the thickness of the mobile device window to about 0.5 mm, which is about half of the existing one, and removing various protective films to reduce the overall module thickness.
본 발명의 일 구현예는 폴리메틸메타크릴레이트층 및 폴리카보네이트층의 적층구조를 포함하는 고경도 다층시트를 제공한다.One embodiment of the present invention provides a high hardness multilayer sheet including a laminated structure of a polymethyl methacrylate layer and a polycarbonate layer.
본 발명의 다른 구현예는 폴리메틸메타크릴레이트층 및 폴리카보네이트층의 구성성분을 최적화하고, 압출공정에 의해 제조되어 우수한 물성을 나타내는 고경도 다층시트를 제공한다. Another embodiment of the present invention provides a high hardness multi-layer sheet that is optimized by constituting the components of the polymethyl methacrylate layer and the polycarbonate layer, and is produced by an extrusion process exhibiting excellent physical properties.
본 발명의 일 구현예에서, (메타)아크릴산 에스테르계 단량체 약 75중량부 내지 약 88중량부, 스틸렌 단량체 약 2중량부 내지 약 5중량부 및 N-치환말레이미드 단량체 약 10중량부 내지 약 20중량부로 형성된 아크릴계 공중합체를 포함하는 폴리메틸메타크릴레이트층; 및 폴리카보네이트 공중합체를 포함하는 폴리카보네이트층의 적층구조인 고경도 다층시트를 제공한다.In one embodiment of the invention, about 75 parts to about 88 parts by weight of the (meth) acrylic acid ester monomer, about 2 parts to about 5 parts by weight of the styrene monomer and about 10 parts to about 20 parts by weight of the N-substituted maleimide monomer Polymethyl methacrylate layer containing an acrylic copolymer formed in parts by weight; And it provides a high hardness multilayer sheet which is a laminated structure of a polycarbonate layer comprising a polycarbonate copolymer.
상기 폴리메틸메타크릴레이트층의 두께는 약 40um 내지 약 70um일 수 있다. The polymethyl methacrylate layer may have a thickness of about 40 um to about 70 um.
상기 아크릴계 공중합체의 유리전이온도는 약 130°C 내지 약 140°C일 수 있다.The glass transition temperature of the acrylic copolymer may be about 130 ° C to about 140 ° C.
상기 아크릴계 공중합체의 중량평균 분자량은 약 10만 내지 약 15만일 수 있다. The weight average molecular weight of the acrylic copolymer may be about 100,000 to about 150,000.
상기 폴리메틸메타크릴레이트층은 아크릴계 공중합체 100중량부에 대해서 산화방지제 약 0.1중량부 내지 약 1.5중량부 및 UV안정제 약 0.5중량부 내지 약 3.0중량부를 더 포함할 수 있다. The polymethyl methacrylate layer may further include about 0.1 parts by weight to about 1.5 parts by weight of antioxidant and about 0.5 parts by weight to about 3.0 parts by weight of UV stabilizer based on 100 parts by weight of the acrylic copolymer.
상기 폴리카보네이트층의 두께는 약 900um 내지 약 950um일 수 있다. The thickness of the polycarbonate layer may be about 900um to about 950um.
상기 폴리카보네이트 공중합체의 유리전이온도는 약 140°C 내지 약 150°C일 수 있다. The glass transition temperature of the polycarbonate copolymer may be about 140 ° C to about 150 ° C.
상기 폴리카보네이트 공중합체의 용융지수는 약 3 내지 약 22일 수 있다.The melt index of the polycarbonate copolymer may be about 3 to about 22.
상기 폴리카보네이트 공중합체 100중량부에 대해서 산화방지제 약 0.3중량부 내지 약 2.0중량부 및 UV안정제 약 0.5중량부 내지 약 3.0중량부를 더 포함할 수 있다. The amount of the polycarbonate copolymer may further include about 0.3 parts by weight to about 2.0 parts by weight of antioxidant and about 0.5 parts by weight to about 3.0 parts by weight of UV stabilizer.
상기 폴리메틸메타크릴레이트층과 상기 폴리카보네이트층이 공압출되어 형성될 수 있다. The polymethyl methacrylate layer and the polycarbonate layer may be formed by coextrusion.
상기 폴리메틸메타크릴레이트층 상부 또는 상기 폴리카보네이트층 하부에 하드코팅층을 더 포함할 수 있다. A hard coating layer may be further included on the polymethyl methacrylate layer or below the polycarbonate layer.
상기 고경도 다층시트의 연필경도가 약 4H이상일 수 있다. The pencil hardness of the high hardness multilayer sheet may be about 4H or more.
온도 85°C, 습도 85%의 조건에서 72시간 동안 방치한 후에 상기 고경도 다층시트의 휨이 약 0.1mm이하일 수 있다. After leaving for 72 hours at a temperature of 85 ° C. and a humidity of 85%, the warpage of the high hardness multilayer sheet may be about 0.1 mm or less.
상기 고경도 다층시트는 우수한 치수안정성을 확보하는 동시에 우수한 내스크래치 특성을 가질 수 있다. The high hardness multilayer sheet may have excellent scratch resistance while ensuring excellent dimensional stability.
또한, 상기 고경도 다층시트는 고온고습 조건에서의 휨특성이 우수하여 각종 전자제품에 쉽게 적용될 수 있다. In addition, the high hardness multilayer sheet is excellent in bending characteristics under high temperature and high humidity conditions and can be easily applied to various electronic products.
도 1은 본 발명의 일실시예인 고경도 다층시트의 단면을 나타낸 것이다.Figure 1 shows a cross section of a high hardness multilayer sheet which is an embodiment of the present invention.
도 2는 본 발명의 다른 실시예인 고경도 다층시트의 단면을 나타낸 것이다.Figure 2 shows a cross section of a high hardness multilayer sheet which is another embodiment of the present invention.
도 3은 본 발명의 또다른 실시예인 고경도 다층시트의 단면을 나타낸 것이다.Figure 3 shows a cross section of a high hardness multilayer sheet which is another embodiment of the present invention.
이하, 본 발명의 구현예를 상세히 설명하기로 한다. 다만, 이는 예시로서 제시되는 것으로, 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구항의 범주에 의해 정의될 뿐이다. Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.
통상적으로 대부분의 모바일 기기인 스마트폰이나 테블릿 제품 윈도우에는 강화 유리가 적용되고 있다. 그러나, 강화유리의 장점에도 불구하고, 플라스틱 커버는 강화유리와 대비하여 깨짐특성, 가격, 공정수율 등 여러가지 면에서 유리하기 때문에, 지속적으로 플라스틱 커버에 대한 요구가 증가하고 있다.Tempered glass is typically applied to most mobile devices such as smartphones or tablet product windows. However, in spite of the advantages of tempered glass, since plastic cover is advantageous in various aspects such as cracking characteristics, price, and process yield compared to tempered glass, the demand for plastic cover is continuously increasing.
상기 플라스틱 커버 재료에 있어서, 강화유리와 유사한 광학적 특성을 보이는 성분은 폴리메틸메타크릴레이트(이하, PMMA), 폴리카보네이트(이하, PC) 등이 될 수 있다. 일반적으로 상기 PMMA는 높은 내스크래치성 및 우수한 광학적 특성을 가지고 있으나, 내충격 특성에 있어서 한계가 있다. 반면, 상기 PC는 우수한 충격 물성을 지니고 있지만 스크래치성에 한계를 보인다. In the plastic cover material, components exhibiting optical properties similar to tempered glass may be polymethylmethacrylate (hereinafter referred to as PMMA), polycarbonate (hereinafter referred to as PC), or the like. In general, the PMMA has high scratch resistance and excellent optical properties, but has a limitation in impact resistance. On the other hand, the PC has excellent impact properties but shows a limited scratch resistance.
그러므로, 표면층에 PMMA층을 생성하고, 코어에는 PC층을 도입하여 스크래치 특성과 내충격 특성을 동시에 확보하고자 하는 여러 시도들이 있었으나, 다른 종류의 수지로 이루어진 시트는 내스크래치 특성, 내충격 특성, 휨 특성이 서로 맞물려 있어 각층의 두께, 구성성분의 함량에 따른 물성 편차가 매우 심하여 품질 안정화가 쉽지 않은 문제점이 있었다. Therefore, various attempts have been made to simultaneously secure scratch and impact resistance by creating a PMMA layer on the surface layer and introducing a PC layer on the core. However, the sheet made of different resins has scratch resistance, impact resistance, and warpage characteristics. Due to interlocking with each other, there is a problem that quality stabilization is not easy due to the serious variation in physical properties depending on the thickness of each layer and the content of components.
상기 문제점을 해결하기 위해, 본 발명의 일 구현예에서, (메타)아크릴산 에스테르계 단량체 75중량부 내지 88중량부, 스틸렌 단량체 2중량부 내지 5중량부 및 N-치환말레이미드 단량체 10중량부 내지 20중량부로 형성된 아크릴계 공중합체를 포함하는 폴리메틸메타크릴레이트층; 및 폴리카보네이트 공중합체를 포함하는 폴리카보네이트층의 적층구조인 고경도 다층시트를 제공한다.In order to solve the above problems, in one embodiment of the present invention, 75 to 88 parts by weight of the (meth) acrylic acid ester monomer, 2 to 5 parts by weight of styrene monomer and 10 parts by weight of N-substituted maleimide monomer Polymethyl methacrylate layer containing an acrylic copolymer formed by 20 parts by weight; And it provides a high hardness multilayer sheet which is a laminated structure of a polycarbonate layer comprising a polycarbonate copolymer.
상기 고경도 다층시트는 폴리메틸메타크릴레이트층 및 폴리카보네이트층의 구성성분을 최적화하고, 압출공정에 의해 제조되어 우수한 치수안정성을 확보하는 동시에 우수한 내스트래치 특성을 가질 수 있다. 또한, 상기 고경도 다층시트는 고온고습 조건에서의 휨특성이 우수하여 각종 전자제품에 쉽게 적용될 수 있다. The high hardness multilayer sheet is optimized by constituting the polymethyl methacrylate layer and the polycarbonate layer, and is manufactured by an extrusion process to ensure excellent dimensional stability and may have excellent scratch resistance. In addition, the high hardness multilayer sheet is excellent in bending characteristics under high temperature and high humidity conditions and can be easily applied to various electronic products.
폴리메틸메타크릴레이트층Polymethyl methacrylate layer
상기 폴리메틸메타크릴레이트층(이하, PMMA층)은 (메타)아크릴산 에스테르계 단량체 75중량부 내지 88중량부, 스틸렌 단량체 2중량부 내지 5중량부 및 N-치환말레이미드 단량체 10중량부 내지 20중량부로 형성된 아크릴계 공중합체를 포함할 수 있다. The polymethyl methacrylate layer (hereinafter referred to as PMMA layer) may include 75 to 88 parts by weight of (meth) acrylic acid ester monomer, 2 to 5 parts by weight of styrene monomer, and 10 to 20 parts by weight of N-substituted maleimide monomer. It may include an acrylic copolymer formed in parts by weight.
상기 아크릴계 공중합체는 (메타)아크릴산 에스테르계 단량체, 스틸렌 단량체 및 N-치환말레이미드 단량체를 일정함량 동시에 포함함으로써 우수한 내열성을 확보하여 고온, 고습에서의 우수한 휨특성을 확보할 수 있다. The acrylic copolymer may include a (meth) acrylic acid ester monomer, a styrene monomer, and an N-substituted maleimide monomer at the same time to ensure excellent heat resistance, thereby ensuring excellent bending characteristics at high temperature and high humidity.
구체적으로, 상기 (메타)아크릴산 에스테르계 단량체가 상기 범위를 벗어나 포함되는 경우 아크릴계 공중합체의 내구성을 확보할 수 없다. 또한, 상기 N-치환말레이미드 단량체가 상기 범위를 벗어나 포함되는 경우 아크릴계 공중합체의 유리전이 온도가 낮아져 내열성 저하로 인한 휨 변형 등의 문제가 발생할 수 있다. Specifically, when the (meth) acrylic acid ester monomer is included outside the above range it may not ensure the durability of the acrylic copolymer. In addition, when the N-substituted maleimide monomer is included outside the above range, a glass transition temperature of the acrylic copolymer may be lowered, thereby causing problems such as warpage deformation due to lower heat resistance.
상기 스틸렌 단량체가 상기 범위를 벗어나 포함되는 경우, PMMA층이 내스크래치성, 내구성 등의 물리적 특성을 확보할 수 없다.When the styrene monomer is included outside the above range, the PMMA layer may not secure physical properties such as scratch resistance and durability.
보다 구체적으로, 상기 (메타)아크릴산 에스테르계 단량체는 메틸 (메타)아크릴레이트, 에틸 (메타)아크릴레이트, n-프로필 (메타)아크릴레이트, 이소프로필 (메타)아크릴레이트, 부틸 (메타)아크릴레이트, t-부틸 (메타)아크릴레이트, 펜틸 (메타)아크릴레이트, 2-에틸헥실 (메타)아크릴레이트, n-옥틸 (메타)아크릴레이트, 이소옥틸 (메타)아크릴레이트, 이소노닐 (메타)아크릴레이트, 2-에틸부틸 (메타)아크릴레이트 및 이들의 조합으로 이루어진 군으로부터 선택된 하나 이상일 수 있다. More specifically, the (meth) acrylic acid ester monomer is methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate , t-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylic At least one selected from the group consisting of latex, 2-ethylbutyl (meth) acrylate, and combinations thereof.
상기 N-치환 말레이미드 단량체는 N-페닐 말레이미드, 말레이미드, N-메틸 말레이미드, N-에틸 말레이미드, N-프로필 말레이미드, N-이소프로필 말레이미드, N-부틸 말레이미드, N-이소부틸 말레이미드, N-t-부틸 말레이미드, N-시클로헥실 말레미미드, N-클로로페닐 말레이미드, N-메틸페닐 말레이미드, N-브로모페닐 말레이미드, N-나프틸 말레이미드, N-라우릴 말레이미드, N-히드록시페닐 말레이미드, N-메톡시 페닐말레이미드, N-카르복시 페닐말레이미드, N-니트로페닐 말레이미드 및 N-벤질 말레이미드로 이루어진 군에서 선택된 하나 이상일 수 있다. The N-substituted maleimide monomer is N-phenyl maleimide, maleimide, N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-isopropyl maleimide, N-butyl maleimide, N- Isobutyl maleimide, Nt-butyl maleimide, N-cyclohexyl maleimide, N-chlorophenyl maleimide, N-methylphenyl maleimide, N-bromophenyl maleimide, N-naphthyl maleimide, N-la Uryl maleimide, N-hydroxyphenyl maleimide, N-methoxy phenylmaleimide, N-carboxy phenylmaleimide, N-nitrophenyl maleimide and N-benzyl maleimide.
상기 PMMA층의 두께는 약 40um 내지 약 70um일 수 있다. 상기 PMMA층의 두께조절은 압출기로부터 피드블럭에 유입되는 PMMA층 수지 조성물의 압출량에 의하여 조절할 수 있음으로, 상기 PMMA층의 두께를 정확하게 유지하기 위해서는 도입되는 PMMA층 수지 조성물의 양을 항상 균일하게 도입하여 압출량을 정확하게 조절해야 할 수 있다.The thickness of the PMMA layer may be about 40um to about 70um. The thickness of the PMMA layer can be controlled by the extrusion amount of the PMMA layer resin composition introduced into the feed block from the extruder, so that the amount of the PMMA layer resin composition introduced is always uniformly maintained in order to maintain the thickness of the PMMA layer accurately. It may be necessary to introduce a precise adjustment of the extrusion amount.
상기 PMMA층의 두께를 두껍게 하는 경우 스크래치 특성을 향상하나, 충격물성은 감소한다. 또한, 상기 PMMA층의 두께를 얇게 하는 경우 스트래치 특성은 감소하나 충격물성을 향상되는바, 양자는 트레이드오프(trade off) 관계에 있는 것이 보통이다. 그러므로, 상기 PMMA층의 두께를 약 40um 내지 약 70um의 범위로 조절함으로써 원하는 수준의 스크래치 특성과 충격 물성을 동시에 확보하여 폴리카보네이트층과의 물성 균형을 최적화할 수 있다.When the thickness of the PMMA layer is increased, scratch properties are improved, but impact physical properties are reduced. In addition, when the thickness of the PMMA layer is reduced, the stretch characteristics are reduced but the impact properties are improved. Both of them are usually in a trade-off relationship. Therefore, by adjusting the thickness of the PMMA layer in the range of about 40um to about 70um, it is possible to optimize the balance of physical properties with the polycarbonate layer by simultaneously securing a desired level of scratch and impact properties.
상기 아크릴계 공중합체의 유리전이온도는 약 130°C 내지 약 140°C일 수 있다. 상기 아크릴계 공중합체의 유리전이온도가 약 130°C미만인 경우 고온, 고습 조건에서 내구성에 한계를 보일 우려가 있고, 약 140°C를 초과하는 경우 칼라변색이 심하고 폴리메틸메타크릴레이트층이 쉽게 깨지는 문제점이 발생할 수 있다. The glass transition temperature of the acrylic copolymer may be about 130 ° C to about 140 ° C. If the glass transition temperature of the acrylic copolymer is less than about 130 ° C there is a risk of showing a limit to durability at high temperature, high humidity conditions, when exceeding about 140 ° C color discoloration is severe and the polymethyl methacrylate layer is easily broken Problems may arise.
상기 아크릴계 공중합체의 중량평균 분자량은 약 10만 내지 약 15만일 수 있다. 중량평균 분자량은 분자량 분포가 있는 고분자 화합물의 성분 분자종의 분자량을 중량 분율로 평균하여 얻어지는 평균 분자량을 의미하는바, 상기 아크릴계 공중합체의 중량평균 분자량이 상기 범위를 유지함으로써, 기계적 강도와 폴리카보네이트와의 공압출에 적합한 점도를 확보하여 고경도 다층시트의 기계적 강도와 휨특성을 양호하게 구현할 수 있다.The weight average molecular weight of the acrylic copolymer may be about 100,000 to about 150,000. The weight average molecular weight means an average molecular weight obtained by averaging the molecular weights of the component molecular species of a polymer compound having a molecular weight distribution in a weight fraction, whereby the weight average molecular weight of the acryl-based copolymer maintains the above range, thereby providing mechanical strength and polycarbonate. By securing a viscosity suitable for co-extrusion with and can realize a good mechanical strength and bending characteristics of a high hardness multilayer sheet.
상기 폴리메틸메타크릴레이트층은 아크릴계 공중합체 100중량부에 대해서 산화방지제 약 0.1중량부 내지 약 1.5중량부 및 UV안정제 약 0.5중량부 내지 약 3.0중량부를 더 포함할 수 있다. The polymethyl methacrylate layer may further include about 0.1 parts by weight to about 1.5 parts by weight of antioxidant and about 0.5 parts by weight to about 3.0 parts by weight of UV stabilizer based on 100 parts by weight of the acrylic copolymer.
상기 산화방지제는 변색과 가공과정의 진행 중에 발생할 수 있는 고분자의 가교를 막아주고, PMMA층의 장기적 물성을 유지할 뿐만 아니라, 변색을 막아주는 역할을 하고, 이에 대한 종류로는 힌더레드 페놀계(hindered phenol), 락톤계(lacton), 포스파이트계(phosphite), 티오이스터계(thioester) 등이 있으나, 이에 한정되는 것은 아니다. The antioxidant prevents crosslinking of the polymer that may occur during discoloration and processing, and maintains the long-term physical properties of the PMMA layer, and also serves to prevent discoloration. Hindered phenolic (hindered) phenol, lactone, phosphite, thioester, and the like, but is not limited thereto.
예를 들어, 옥타데실-3-(3,5-다이-털트-부틸-4-하이드록시페닐) 프로피오네이트, 트리스(2,4-다이-털트-부틸페닐) 포스파이트, 테트라키스[메틸렌-3-(3,5-다이-털트-부틸-4-하이드록시페닐)프로피오네이트] 메탄, 4,4'-티오비스(6-털트-부틸-m-크레솔), 펜타에리트리틸 테트라키스(3-라우릴티오프로 피오네이트) 등을 포함할 수 있다. For example, octadecyl-3- (3,5-di-talt-butyl-4-hydroxyphenyl) propionate, tris (2,4-di-talt-butylphenyl) phosphite, tetrakis [methylene -3- (3,5-di-talt-butyl-4-hydroxyphenyl) propionate] methane, 4,4'-thiobis (6-talt-butyl-m-cresol), pentaerythritol Tetrakis (3-laurylthiopropionate) and the like.
상기 산화방지제는 아크릴계 공중합체 100중량부에 대해서 약 0.1중량부 내지 약 1.5중량부를 포함할 수 있는바, 상기 범위를 유지함으로써 가공에 따른 분해를 억제하여 안정적인 물성을 유지할 수 있다. The antioxidant may include from about 0.1 parts by weight to about 1.5 parts by weight with respect to 100 parts by weight of the acrylic copolymer, by maintaining the above range can inhibit decomposition due to processing can maintain stable physical properties.
상기 UV안정제는 플라스틱이 햇빛에 장시간 노출시, 자외선에 의해 발생되는 균열 및 탈색 등 노화현상을 방지하는 역할을 하고, 이에 대한 종류로는 벤조페논계(benzophenone), 벤조트리아졸계(benzotriazole), HALS계 등의 공지의 물질이 주로 사용될 수 있으나, 이에 한정되는 것은 아니다. The UV stabilizer serves to prevent aging phenomenon such as cracking and discoloration caused by ultraviolet rays when the plastic is exposed to sunlight for a long time. Examples of the UV stabilizer include benzophenone, benzotriazole, and HALS. Known materials such as systems may be used mainly, but are not limited thereto.
예를 들어, 비스(2,2,6,6-테트라메틸-4-피퍼리디닐) 세바케이트, 폴리[[6-(1,1,3,3-테트라메틸부틸)아미노]-s-트리아진-2,4-다이닐][(2,2,6,6-테트라메틸-4-피퍼리디닐)이미노] 헥사메틸렌[2,2,6,6-테트라메틸-4-피퍼리디닐) 이미노]], 다이메틸 숙시네이트와 4-하이드록시-2,2,6,6,-테트라메틸-1-피퍼리딘 에탄올 등을 포함할 수 있다. For example, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, poly [[6- (1,1,3,3-tetramethylbutyl) amino] -s-tri Azine-2,4-dinyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino] hexamethylene [2,2,6,6-tetramethyl-4-piperidinyl ) Imino]], dimethyl succinate and 4-hydroxy-2,2,6,6, -tetramethyl-1-piperidine ethanol and the like.
상기 UV안정제는 아크릴계 공중합체 100중량부에 대해서 약 0.5중량부 내지 약 3.0중량부를 포함할 수 있는바, 상기 범위를 유지함으로써 UV에 의한 변색을 효과적으로 억제할 수 있다. The UV stabilizer may include about 0.5 parts by weight to about 3.0 parts by weight with respect to 100 parts by weight of the acrylic copolymer, it is possible to effectively suppress discoloration by UV by maintaining the above range.
폴리카보네이트층Polycarbonate layer
상기 폴리카보네이트층(이하, PC층)은 폴리카보네이트 공중합체를 포함할 수 있다. 상기 폴리카보네이트 공중합체는 특별한 구조적 제한을 없으며, 계면중합 또는 용융 중합에 의해 형성될 수 있다. 예를 들어, 상기 폴리카보네이트 공중합체로 LUPOY PC1201-08(LG화학) 또는 LUPOY PC 1300-30(LG화학)을 사용할 수 있다. The polycarbonate layer (hereinafter, referred to as a PC layer) may include a polycarbonate copolymer. The polycarbonate copolymer has no particular structural limitation and may be formed by interfacial polymerization or melt polymerization. For example, LUPOY PC1201-08 (LG Chem) or LUPOY PC 1300-30 (LG Chem) may be used as the polycarbonate copolymer.
상기 PC층의 두께는 약 900um 내지 약 950um일 수 있다. 상기 PC층의 두께조절은 압출기로부터 피드블럭에 유입되는 PC층 수지 조성물의 압출량에 의하여 조절할 수 있음으로, 상기 PC층 수지 조성물의 두께를 정확하게 유지하기 위해서는 도입되는 PC층 수지 조성물의 양을 항상 균일하게 도입하여 압출량을 정확하게 조절해야 할 수 있다.The thickness of the PC layer may be about 900um to about 950um. The thickness control of the PC layer can be controlled by the extrusion amount of the PC layer resin composition introduced into the feed block from the extruder, so that the amount of the PC layer resin composition introduced is always maintained in order to maintain the thickness of the PC layer resin composition accurately. It may be necessary to introduce uniformly to precisely control the amount of extrusion.
상기 PC층의 두께를 상기 범위로 조절함으로써 고경도 다층시트의 기계적 강도를 유지하는데 적합하다.It is suitable to maintain the mechanical strength of the high hardness multilayer sheet by adjusting the thickness of the PC layer in the above range.
상기 폴리카보네이트 공중합체의 유리전이온도는 약 140°C 내지 약 150°C일 수 있다. 상기 폴리카보네이트 공중합체의 유리전이온도가 약 140°C미만인 경우 고온, 고습조건에서의 물성이 저하될 우려가 있고, 약 150°C를 초과하는 경우 가공온도가 높아지는 문제점이 발생할 수 있다.The glass transition temperature of the polycarbonate copolymer may be about 140 ° C to about 150 ° C. If the glass transition temperature of the polycarbonate copolymer is less than about 140 ° C there is a risk that the physical properties at high temperature, high humidity conditions may be lowered, and when the glass transition temperature exceeds about 150 ° C may cause a problem that the processing temperature increases.
상기 폴리카보네이트 공중합체의 용융지수는 약 3 내지 약 22일 수 있다. 용융지수(Melt Folw Index, MI)는 용융흐름지수를 의미하는바, 일정한 부하와 온도에서 10분동안 모세관을 흐르는 수지의 무게를 일컫는다. The melt index of the polycarbonate copolymer may be about 3 to about 22. Melt Index (MI) refers to the melt flow index, which refers to the weight of resin flowing through a capillary tube for 10 minutes at a constant load and temperature.
상기 폴리카보네이트 공중합체의 용융지수가 3미만인 경우, 폴리카보네이트 공중합체의 유동성 저하로 인해 압출작업시 온도를 높게 조절해야 하고, 상부층인 PMMA층과 유동차이가 심해 층두께 및 균일성이 문제될 수 있다. 또한, 상기 용융지수가 22를 초과하는 경우 상기 폴리카보네이트 공중합체 압출시 티-다이(T-die)에서 시트 작업성이 나빠지는 문제점이 발생할 수 있다. If the melt index of the polycarbonate copolymer is less than 3, it is necessary to control the temperature high during the extrusion operation due to the fluidity of the polycarbonate copolymer, and the difference between the upper layer PMMA layer and the deep layer may be a problem of layer thickness and uniformity have. In addition, when the melt index exceeds 22, there may be a problem that sheet workability worsens in the T-die during extrusion of the polycarbonate copolymer.
상기 폴리카보네이트 공중합체 100중량부에 대해서 산화방지제 약 0.3중량부 내지 약 2.0중량부 및 UV안정제 약 0.5중량부 내지 약 3.0중량부를 더 포함할 수 있다. 상기 산화방지제 및 UV안정제에 관한 사항은 전술한 바와 같다.The amount of the polycarbonate copolymer may further include about 0.3 parts by weight to about 2.0 parts by weight of antioxidant and about 0.5 parts by weight to about 3.0 parts by weight of UV stabilizer. Matters regarding the antioxidant and UV stabilizer are as described above.
고경도 다층시트High Hardness Multilayer Sheet
상기 폴리메틸메타크릴레이트층과 상기 폴리카보네이트층이 공압출되어 형성될 수 있다. 공압출이란 하나 이상의 압출기를 사용하여 압출코팅, 필름 또는 시트 제작시 하나 이상의 층을 더하여 코팅필름 및 시트를 만드는 방법을 일컫는다. 상기 공압출 공정은 특별한 제한을 받지 않으며 일반적인 공압출 공정에 의해 상기 PMMA층 및 상기 PC층을 형성할 수 있다.The polymethyl methacrylate layer and the polycarbonate layer may be formed by coextrusion. Coextrusion refers to a method of making a coating film and a sheet by adding one or more layers during extrusion coating, film or sheet production using one or more extruders. The coextrusion process is not particularly limited and may form the PMMA layer and the PC layer by a general coextrusion process.
그러나, 상기 공압출 공정은 PMMA층/PC층 구조의 고경도 다층시트가 구현하고자 하는 물성을 구현하기에 적합한바, 상기 PMMA층은 우수한 스크래치 특성과 외관 특성을 구현하며, 상기 PC층은 우수한 거침(toughness) 특성과 내열성을 구현할 수 있어, 고경도 시트의 물성을 전체적으로 제어할 수 있다. However, the coextrusion process is suitable for realizing the properties to be implemented by the high hardness multilayer sheet of the PMMA layer / PC layer structure, the PMMA layer implements excellent scratch and appearance properties, the PC layer is excellent (toughness) characteristics and heat resistance can be implemented, it is possible to control the physical properties of the high-hardness sheet as a whole.
상기 폴리메틸메타크릴레이트층 상부 또는 상기 폴리카보네이트층 하부에 하드코팅층을 더 포함할 수 있다. 상기 하드코팅층은 다층시트의 경도를 높이고, 2차적인 외관 불량을 야기시키는 문제를 방지하기 위한 것으로, 도 2 및 도 3을 참고하면, 고경도 다층시트는(100)은 위로부터, 하드코팅층(30), PMMA층(10) 및 PC층(20) 또는 하드코팅층(30), PMMA층(10), PC층(20) 및 하드코팅층(30)을 포함할 수 있다. A hard coating layer may be further included on the polymethyl methacrylate layer or below the polycarbonate layer. The hard coating layer is to increase the hardness of the multi-layer sheet, and to prevent problems causing secondary appearance defects. Referring to Figures 2 and 3, the high-hardness multilayer sheet 100 is from the top, the hard coating layer ( 30), the PMMA layer 10 and the PC layer 20 or the hard coating layer 30, the PMMA layer 10, the PC layer 20 and the hard coating layer 30 may be included.
예를 들어, 상기 하드코팅층의 성분으로 우레탄계 아크릴레이트 공중합체 계열을 이용할 수 있다. 상기 우레탄계 아크릴레이트 공중합체 계열 하드코팅 수지는 하이드록시기를 갖는 아크릴계 모노머와 폴리올과 이소시아네이트를 반응시킨 우레탄계의 공중합으로 제조되는 수지로, 폴리에테르 폴리올, 폴리에스테르 폴리올, 폴리카프로락톤 폴리올, 폴리바코네이트 폴리올, 폴리부타디엔 폴리올 등의 폴리올 성분과 톨루엔 디이소시아네이트(TDI; Toluene diisocyanate), 디페닐메탄 디이소시아네이트(MDI;Diphenylmethane diisocyanate) 등의 방향족 이소시아네이트 또는 이소포론 디이소시아네이트(IPDI;Isophorone diisocyanate), 헥사메틸렌 디이소시아네이트(HMDI;Hexamethylene diisocyanate) 등의 지방족 이소시아네이트를 반응시켜 3차원 성형이 가능한 탄성과 동시에 외부 자극에 견딜 수 있는 내스크레성을 갖는 적합한 원료를 선택하여 사용할 수 있다.For example, a urethane acrylate copolymer series may be used as a component of the hard coating layer. The urethane acrylate copolymer-based hard coating resin is a resin prepared by copolymerization of an acryl-based monomer having a hydroxy group, a urethane-based polyol and isocyanate, polyether polyol, polyester polyol, polycaprolactone polyol, polybaconate polyol Polyol components such as polybutadiene polyol, aromatic isocyanates such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) or isophorone diisocyanate (IPDI; Isophorone diisocyanate), hexamethylene diisocyanate Aliphatic isocyanates such as (HMDI; Hexamethylene diisocyanate) can be reacted to select an appropriate raw material having elasticity capable of three-dimensional molding and scratch resistance that can withstand external stimuli.
또한, 상기 하드코팅층의 두께는 약 5um 내지 약 30um일 수 있다. 상기 하드코팅층의 두께가 5um 미만인 경우에 필름의 광택 변화가 발생할 수 있는 문제점이 있으며, 약 30um 초과하는 경우에 하드코팅층에 크랙이 발생할 수 있다.In addition, the thickness of the hard coating layer may be about 5um to about 30um. When the thickness of the hard coating layer is less than 5um, there is a problem that a glossiness change of the film may occur, and when the thickness of about 30um is exceeded, cracks may occur in the hard coating layer.
상기 하드코팅층에 첨가제가 더 포함될 수 있고, 상기 첨가제로는 실리콘계 첨가제(실리콘기를 가지는 반응성 모노머/올리고머), 불소계 첨가제 (불소기를 가지는 반응성 모노머/올리고머), 실리콘기 또는 불소기를 가지는 수지, 계면활성제 및 오일로 이루어진 군에서 하나이상 선택하여 사용할 수 있다.An additive may be further included in the hard coating layer, and the additive may include a silicone-based additive (reactive monomer / oligomer having a silicone group), a fluorine-based additive (reactive monomer / oligomer having a fluorine group), a resin having a silicone group or a fluorine group, a surfactant, One or more selected from the group consisting of oil can be used.
나아가, 하드코팅층에 광개시제가 더 포함될 수 있고, 상기 광개시제로는 UV 경화를 위한 광개시제로서 벤질 케탈류, 벤조인 에테르류, 아세토페논 유도체, 케톡심 에테르류, 벤조페논, (아미노)벤조에이트, 벤질 디메틸 케탈 화합물 중 선택된 하나이상의 자유라디칼 개시제와 오늄 염(onium salts), 페로세늄 염(ferrocenium salts) 및 디아조늄 염(diazonium salts) 중 선택된 1종 이상의 양이온성 개시제, 또는 상기 자유라디칼 개시제 및 상기 양이온성 개시제 혼합물을 사용할 수 있다. Furthermore, a photoinitiator may be further included in the hard coating layer, and the photoinitiator may include benzyl ketals, benzoin ethers, acetophenone derivatives, ketoxime ethers, benzophenone, (amino) benzoate, and benzyl as photoinitiators for UV curing. At least one free radical initiator selected from dimethyl ketal compounds and at least one cationic initiator selected from onium salts, ferrocenium salts and diazonium salts, or the free radical initiator and the cation Sex initiator mixtures can be used.
상기 고경도 다층시트의 연필경도가 약 4H이상일 수 있다. 연필경도는 어떠한 물질의 단단함을 연필심의 단단함과 비교한 것으로, 경도 및 농도별로 H, F, B 등의 기호로 나타낼 수 있다. 상기 고경도 다층시트의 연필경도는 ASTM D3363-05(미츠비시 연필, 1kg 하중)을 사용하여 측정되는바, 약 4H이상의 경도를 유지함으로써 통상의 다층시트에 비해 우수한 경도를 구현할 수 있다.The pencil hardness of the high hardness multilayer sheet may be about 4H or more. Pencil hardness is the hardness of a certain material compared with the hardness of the pencil lead, it can be represented by the symbols such as H, F, B for each hardness and concentration. Pencil hardness of the high hardness multilayer sheet is measured using ASTM D3363-05 (Mitsubishi pencil, 1kg load), by maintaining a hardness of about 4H or more can implement a superior hardness than a conventional multilayer sheet.
고경도 다층시트가 적용되는 플라스틱 윈도우 소재는 고온, 고습의 조건에서 휨이 발생하며, 이러한 휨은 터치패널의 작동에 문제를 일으킬 수 있다. 따라서, 고온, 고습의 조건에서 일정수준 이상의 휨이 발생하면 터치 패널용 윈도우 커버로 적용될 수 없다. 예를 들어, 온도 85°C, 습도 85%의 조건에서 72시간 동안 방치한 후에 상기 고경도 다층시트의 휨이 약 0.1mm일 수 있다.The plastic window material to which the high hardness multilayer sheet is applied is warped under high temperature and high humidity conditions, and the warp may cause problems in operation of the touch panel. Therefore, if a certain level of warpage occurs under high temperature and high humidity conditions, the window cover for the touch panel cannot be applied. For example, the curvature of the high hardness multilayer sheet may be about 0.1 mm after being left for 72 hours at a temperature of 85 ° C. and a humidity of 85%.
이하에서는 본 발명의 구체적인 실시예들을 제시한다. 다만, 하기에 기재된 실시예들은 본 발명을 구체적으로 예시하거나 설명하기 위한 것에 불과하며, 이로서 본 발명이 제한되어서는 아니된다.The following presents specific embodiments of the present invention. However, the embodiments described below are merely for illustrating or explaining the present invention in detail, and thus the present invention is not limited thereto.
<제조예><Production example>
PMMA-1(아크릴계 공중합체)PMMA-1 (acrylic copolymer)
메틸메타아크릴레이트(MMA) 83중량부, 스틸렌 2중량부, N-사이클로헥실말레이미드 15중량부, 연쇄이동제로써 n-옥틸메르캅탄 0.2중량부 및 중합개시제로써 아조비스이소-부티로니트릴(AIBN) 0.1중량부의 혼합액을 분산제 수용액(이온교환수 250중량부 + 중합 분산제 2중량부)에 투입하여 80°C에서 4시간 동안 중합하고 110°C에서 2시간 추가 중합하여 잔류 단량체를 제거한 후 건조하여 비드 형태의 PMMA-1(아크릴계 공중합체)를 제조하였다. 상기 PMMA-1의 분자량은 13만이었고, Tg는 132°C였다.83 parts by weight of methyl methacrylate (MMA), 2 parts by weight of styrene, 15 parts by weight of N-cyclohexylmaleimide, 0.2 parts by weight of n-octyl mercaptan as a chain transfer agent and azobisiso-butyronitrile (AIBN as a polymerization initiator) ) 0.1 parts by weight of the mixed solution was added to an aqueous solution of dispersant (250 parts by weight of ion-exchanged water + 2 parts by weight of a polymerization dispersant) and polymerized at 80 ° C. for 4 hours, and further polymerized at 110 ° C. for 2 hours to remove residual monomers and dried. PMMA-1 (acrylic copolymer) in the form of beads was prepared. The molecular weight of the PMMA-1 was 130,000 and the Tg was 132 ° C.
PMMA-2(아크릴계 공중합체)PMMA-2 (acrylic copolymer)
상기 PMMA-1의 제조방법에서 n-사이클로헥실말레이미드를 페닐말레이미드로 변경한 것을 제외하고는 PMMA-1과 동일한 방법으로 PMMA-2를 제조하였다. 상기 PMMA-2의 분자량은 12만이었고, Tg는 133°C였다.PMMA-2 was prepared by the same method as PMMA-1 except for changing n-cyclohexylmaleimide to phenylmaleimide in the method for preparing PMMA-1. The molecular weight of the PMMA-2 was 120,000 and the Tg was 133 ° C.
PMMA-3(아크릴계 공중합체)PMMA-3 (acrylic copolymer)
분자량이 12만이고, Tg가 104°C인 HP202(LG MMA사)를 사용하였다.HP202 (LG MMA Co., Ltd.) having a molecular weight of 120,000 and a Tg of 104 ° C was used.
PC-1(폴리카보네이트 공중합체)PC-1 (polycarbonate copolymer)
용융지수(300°C, 1.2kg)가 8.0이고, Tg가 148°C인 LUPOY PC 1201-08(LG화학)을 사용하였다.Melt index (300 ° C., 1.2 kg) was 8.0, and LUPOY PC 1201-08 (LG Chem) with Tg of 148 ° C. was used.
PC-2(폴리카보네이트 공중합체)PC-2 (Polycarbonate Copolymer)
용융지수(300°C, 1.2kg)가 30이고, Tg가 144°C인 LUPOY PC 1300-30(LG화학)을 사용하였다. Melt index (300 ° C, 1.2kg) was 30, and TUP was used LUPOY PC 1300-30 (LG Chemistry) having 144 ° C.
<실시예 및 비교예><Examples and Comparative Examples>
상기 PMMA-1, PMMA-2 및 PMMA-3에 하기 표 1과 같이 첨가제(산화방지제 및 UV안정제)를 첨가한 후, 275°C에서 이축 압출기를 통해 펠렛 형태로 PMMA층 수지 조성물을 형성하였다. 또한, 상기 PC-1 및 PC-2에 하기 표 1과 같이 첨가제(산화방지제 및 UV안정제)를 첨가한 후, 275°C에서 이축 압출기를 통해 펠렛 형태로 PC층 수지 조성물을 형성하였다. 그 후, 상기 PMMA층 수지 조성물 및 상기 PC층 수지 조성물을 공압출하여 PMMA층 및 PC층을 포함하는 고경도 다층시트를 제조하였다. Scanning Electronic Microscope(SEM)를 사용하여 상기 실시예 및 비교예의 PMMA층, PC층 두께를 측정하였다.After adding the additives (antioxidants and UV stabilizers) as shown in Table 1 to the PMMA-1, PMMA-2 and PMMA-3, to form a PMMA layer resin composition in pellet form through a twin screw extruder at 275 ° C. In addition, after the addition of additives (antioxidants and UV stabilizers) as shown in Table 1 to the PC-1 and PC-2, to form a PC layer resin composition in pellet form through a twin screw extruder at 275 ° C. Thereafter, the PMMA layer resin composition and the PC layer resin composition were coextruded to prepare a high hardness multilayer sheet including the PMMA layer and the PC layer. Scanning Electronic Microscope (SEM) was used to measure the thickness of the PMMA layer and the PC layer in the above Examples and Comparative Examples.
표 1
실시예1 실시예2 실시예3 실시예4 비교예1 비교예2 비교예3 비교예4
PMMA층 PMMA1 100 - 100 - 100 - 100 -
PMMA2 - 100 - 100 - - - -
PMMA3 - - - - - 100 - 100
첨가제 0.3/2.0 0.3/2.0 0.3/2.0 0.3/2.0 0.3/2.0 0.3/2.0 0.3/2.0 0.3/2.0
PC층 PC1 100 100 100 100 - 100 - 100
PC2 - - - - 100 - 100 -
첨가제 0.3/2.0 0.3/2.0 0.3/2.0 0.3/2.0 0.3/2.0 0.3/2.0 0.3/2.0 0.3/2.0
층두께(um)(PMMA층/PC층) 980(50/930) 975(55/920) 980(40/940) 980(60/920) 980(40/940) 980(50/930) 940(50/890) 1000(90/910)
Table 1
Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4
PMMA layer PMMA1 100 - 100 - 100 - 100 -
PMMA2 - 100 - 100 - - - -
PMMA3 - - - - - 100 - 100
additive 0.3 / 2.0 0.3 / 2.0 0.3 / 2.0 0.3 / 2.0 0.3 / 2.0 0.3 / 2.0 0.3 / 2.0 0.3 / 2.0
PC layer PC1 100 100 100 100 - 100 - 100
PC2 - - - - 100 - 100 -
additive 0.3 / 2.0 0.3 / 2.0 0.3 / 2.0 0.3 / 2.0 0.3 / 2.0 0.3 / 2.0 0.3 / 2.0 0.3 / 2.0
Layer thickness (um) (PMMA layer / PC layer) 980 (50/930) 975 (55/920) 980 (40/940) 980 (60/920) 980 (40/940) 980 (50/930) 940 (50/890) 1000 (90/910)
* 첨가제(중량부): 페놀계 산화방지제(Irganox1010)/ UV 안정제(Hostavin B-CAP)* Additive (part by weight): Phenolic antioxidant (Irganox1010) / UV stabilizer (Hostavin B-CAP)
<실험예> - 다층구조의 물성평가Experimental Example-Evaluation of Physical Properties of Multi-layered Structure
1) 연필경도: ASTM D3363-05(미츠비시 연필, 1kg 하중)을 사용하여 상기 실시예 및 비교예의 경도를 측정하였다.1) Pencil Hardness: The hardness of the Examples and Comparative Examples was measured using ASTM D3363-05 (Mitsubishi Pencil, 1 kg load).
2-1) 초기휨: 상기 실시예 및 비교예의 고경도 다층시트를 가로 60mm, 세로 100mm의 시편으로 제작한 후 모서리와 바닥면의 높이를 측정하여 위로 휜 정도를 간극 계측기(Gap gauge)를 이용하여 분석하였다.2-1) Initial Warp: After fabricating the high hardness multilayer sheets of the above Examples and Comparative Examples into specimens of 60 mm in width and 100 mm in length, the heights of the edges and the bottom surface were measured, and then the gap was measured using a gap gauge. And analyzed.
2-2) 후기휨: 상기 고경도 다층시트의 시편을 온도 85°C, 습도 85%의 조건에서 72시간 동안 방치한 후, 시편의 모서리와 바닥면과의 높이를 측정하여 위로 휜 정도를 간극 계측기(Gap gauge)를 이용하여 분석하였다. 2-2) Lateral warpage: After leaving the specimen of the high hardness multilayer sheet for 72 hours at a temperature of 85 ° C. and a humidity of 85%, measure the height of the edge of the specimen and the bottom surface to raise the gap. The analysis was performed using a gap gauge.
표 2
실시예1 실시예2 실시예3 실시예4 비교예1 비교예2 비교예3 비교예4
연필경도 4H 4H 4H 4H 2H 4H 4H 4H
초기휨(mm) 0.04 0.05 0.05 0.05 0.04 0.08 0.10 0.12
후기휨(mm) 0.09 0.10 0.07 0.09 0.11 0.20 0.18 0.17
TABLE 2
Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4
Pencil hardness 4H 4H 4H 4H 2H 4H 4H 4H
Initial warpage (mm) 0.04 0.05 0.05 0.05 0.04 0.08 0.10 0.12
Late warpage (mm) 0.09 0.10 0.07 0.09 0.11 0.20 0.18 0.17
상기 표 2를 참고하면, 실시예 1 내지 4는 비교예 1 내지 4에 비해 고경도이며 휨특성 또한 우수함을 확인할 수 있다. 구체적으로, 상기 비교예 1, 3은 용융지수가 22이상인 폴리카보네이트 공중합체를 포함하는 PC층, 비교예 2, 4는 유리전이 온도가 130°C 미만인 아크릴계 공중합체를 포함하는 PMMA층을 포함하는 다층시트인바, 유리전이온도가 130°C 내지 140°C인 아크릴계 공중합체를 포함하는 PMMA층과 용융지수가 3 내지 22인 폴리카보네이트 공중합체를 포함하는 PC층의 적층구조인 실시예 1 내지 4에 비하여 경도가 떨어지고, 휨특성 또한 떨어짐을 알 수 있었다.Referring to Table 2, it can be seen that Examples 1 to 4 have a higher hardness and excellent bending characteristics than Comparative Examples 1 to 4. Specifically, Comparative Examples 1 and 3 are PC layers containing a polycarbonate copolymer having a melt index of 22 or more, and Comparative Examples 2 and 4 include a PMMA layer including an acrylic copolymer having a glass transition temperature of less than 130 ° C. Example 1 to 4, which is a multilayered structure of a PMMA layer comprising an acrylic copolymer having a glass transition temperature of 130 ° C. to 140 ° C. and a PC layer including a polycarbonate copolymer having a melt index of 3 to 22. Compared with the hardness, the hardness and the bending property were also lower.
또한, 비교예 3은 PC층의 두께를 900um이하로 하였는바, 상대적인 PMMA층의 두께 상승으로 인해 휨특성이 저하되는 특성을 보였으며, 비교예 4는 PMMA층의 두께를 70um이상으로 하였는바, 경도만 유지될 뿐, 휨특성이 저하되었는바, 실시예 1 내지 4의 고경도 다층시트만이 휨특성과 내스트래치성을 동시에 구현할 수 있음을 확인하였다. In addition, in Comparative Example 3, the thickness of the PC layer was set to 900um or less, and the bending property was lowered due to the relative increase in the thickness of the PMMA layer. In Comparative Example 4, the thickness of the PMMA layer was set to 70um or more. Only the hardness is maintained, the bending property is reduced, it was confirmed that only the high hardness multilayer sheet of Examples 1 to 4 can implement the bending property and the scratch resistance at the same time.
[부호의 설명][Description of the code]
100: 고경도 다층시트100: high hardness multilayer sheet
10: 폴리메틸메타크릴레이트층10: polymethyl methacrylate layer
20: 폴리카보네이트층20: polycarbonate layer
30: 하드코팅층 30: hard coating layer

Claims (13)

  1. (메타)아크릴산 에스테르계 단량체 75중량부 내지 88중량부, 스틸렌 단량체 2중량부 내지 5중량부 및 N-치환말레이미드 단량체 10중량부 내지 20중량부로 형성된 아크릴계 공중합체를 포함하는 폴리메틸메타크릴레이트층; 및 Polymethyl methacrylate comprising an acrylic copolymer formed of 75 to 88 parts by weight of (meth) acrylic acid ester monomer, 2 to 5 parts by weight of styrene monomer, and 10 to 20 parts by weight of N-substituted maleimide monomer. layer; And
    폴리카보네이트 공중합체를 포함하는 폴리카보네이트층의 적층구조인Laminated structure of the polycarbonate layer containing a polycarbonate copolymer
    고경도 다층시트. High hardness multilayer sheet.
  2. 제 1항에 있어서, The method of claim 1,
    상기 폴리메틸메타크릴레이트층의 두께는 40um 내지 70um인The thickness of the polymethyl methacrylate layer is 40um to 70um
    고경도 다층시트. High hardness multilayer sheet.
  3. 제 1항에 있어서,The method of claim 1,
    상기 아크릴계 공중합체의 유리전이온도는 130°C 내지 140°C인The glass transition temperature of the acrylic copolymer is 130 ° C to 140 ° C
    고경도 다층시트. High hardness multilayer sheet.
  4. 제 1항에 있어서,The method of claim 1,
    상기 아크릴계 공중합체의 중량평균 분자량은 10만 내지 15만인The weight average molecular weight of the acrylic copolymer is 100,000 to 150,000
    고경도 다층시트. High hardness multilayer sheet.
  5. 제 1항에 있어서,The method of claim 1,
    상기 폴리메틸메타크릴레이트층은 아크릴계 공중합체 100중량부에 대해서 산화방지제 0.1중량부 내지 1.5중량부 및 UV안정제 0.5중량부 내지 3.0중량부를 더 포함하는 The polymethyl methacrylate layer further comprises 0.1 parts by weight to 1.5 parts by weight of antioxidant and 0.5 parts by weight to 3.0 parts by weight of UV stabilizer based on 100 parts by weight of the acrylic copolymer.
    고경도 다층시트. High hardness multilayer sheet.
  6. 제 1항에 있어서, The method of claim 1,
    상기 폴리카보네이트층의 두께는 900um 내지 950um인The thickness of the polycarbonate layer is 900um to 950um
    고경도 다층시트. High hardness multilayer sheet.
  7. 제 1항에 있어서,The method of claim 1,
    상기 폴리카보네이트 공중합체의 유리전이온도는 140°C 내지 150°C인The glass transition temperature of the polycarbonate copolymer is 140 ° C to 150 ° C
    고경도 다층시트. High hardness multilayer sheet.
  8. 제 1항에 있어서,The method of claim 1,
    상기 폴리카보네이트 공중합체의 용융지수는 3 내지 22인Melt index of the polycarbonate copolymer is 3 to 22
    고경도 다층시트.High hardness multilayer sheet.
  9. 제 1항에 있어서,The method of claim 1,
    상기 폴리카보네이트 공중합체 100중량부에 대해서 산화방지제 0.3중량부 내지 2.0중량부 및 UV안정제 0.5중량부 내지 3.0중량부를 더 포함하는 Further comprising 0.3 parts to 2.0 parts by weight of antioxidant and 0.5 parts to 3.0 parts by weight of UV stabilizer based on 100 parts by weight of the polycarbonate copolymer
    고경도 다층시트. High hardness multilayer sheet.
  10. 제 1항에 있어서,The method of claim 1,
    상기 폴리메틸메타크릴레이트층과 상기 폴리카보네이트층이 공압출되어 형성되는The polymethyl methacrylate layer and the polycarbonate layer is formed by coextrusion
    고경도 다층시트. High hardness multilayer sheet.
  11. 제 1항에 있어서,The method of claim 1,
    상기 폴리메틸메타크릴레이트층 상부 또는 상기 폴리카보네이트층 하부에 하드코팅층을 더 포함하는 Further comprising a hard coating layer on the polymethyl methacrylate layer or the lower polycarbonate layer
    고경도 다층시트. High hardness multilayer sheet.
  12. 제 1항에 있어서,The method of claim 1,
    상기 고경도 다층시트의 연필경도가 4H이상인 The pencil hardness of the high hardness multilayer sheet is 4H or more
    고경도 다층시트. High hardness multilayer sheet.
  13. 제 1항에 있어서,The method of claim 1,
    온도 85°C, 습도 85%의 조건에서 72시간 동안 방치한 후에 상기 고경도 다층시트의 휨이 0.1mm이하인 After leaving for 72 hours at a temperature of 85 ° C. and a humidity of 85%, the warpage of the high hardness multilayer sheet is 0.1 mm or less.
    고경도 다층시트. High hardness multilayer sheet.
PCT/KR2014/009543 2013-10-31 2014-10-10 High hardness multi-layer sheet WO2015064928A1 (en)

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