WO2020004835A1 - Ultraviolet blocking film - Google Patents

Ultraviolet blocking film Download PDF

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Publication number
WO2020004835A1
WO2020004835A1 PCT/KR2019/007093 KR2019007093W WO2020004835A1 WO 2020004835 A1 WO2020004835 A1 WO 2020004835A1 KR 2019007093 W KR2019007093 W KR 2019007093W WO 2020004835 A1 WO2020004835 A1 WO 2020004835A1
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WO
WIPO (PCT)
Prior art keywords
acrylate
ultraviolet
meth
blocking
blocking film
Prior art date
Application number
PCT/KR2019/007093
Other languages
French (fr)
Korean (ko)
Inventor
서광석
김헌
변진석
장영래
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020190068578A external-priority patent/KR102131995B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP19816186.1A priority Critical patent/EP3627196B1/en
Priority to US16/631,525 priority patent/US11549025B2/en
Priority to CN201980003073.7A priority patent/CN110876273B/en
Priority to JP2020500825A priority patent/JP6966148B2/en
Publication of WO2020004835A1 publication Critical patent/WO2020004835A1/en

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/41—Organic pigments; Organic dyes

Definitions

  • the present invention relates to an ultraviolet ray blocking film suitable for the protection of an organic light emitting device, such as excellent light resistance and low haze value.
  • Ultraviolet rays which correspond to wavelengths of about 10 to 400 11111 in sunlight, have greater energy than visible or infrared rays and have energy that can excite or cleave molecular bonds such as organic compounds.
  • the organic light emitting device (01 high 1), which is widely used as a display material in recent years, may cause damage to organic compounds such as blue light emitting materials present in the organic layer when exposed to ultraviolet rays and blue light of 405 ⁇ or less, and Contraction or outgassing of the diaphragm The phenomenon may occur, and the device may eventually lose its function.
  • An object of the present invention is to provide a UV protection film that can stably exhibit UV protection performance even under prolonged UV exposure, and has a low haze value and is suitable for application to display devices such as 01 and 0 display devices.
  • the present invention to solve the above problems,
  • a polymer substrate An undercoat layer comprising an ultraviolet absorbing organic dye and a photocurable binder resin; And an ultraviolet blocking film sequentially laminated with an overcoat layer comprising ultraviolet blocking inorganic particles and a photocurable binder resin,
  • the ultraviolet ray blocking film having a transmittance after the light resistance test was three times or less the transmittance before the light resistance test was provided.
  • the UV blocking film may have a transmittance of 60% or more at a wavelength of 430 1 ⁇ 1 measured using the UV-VIS-NIR spectrophotometer before the light resistance test.
  • the UV blocking film may have a haze value of 1.5 or less measured according to the 118 K 7136 method.
  • the ultraviolet absorbing organic dye may be at least one selected from the group consisting of a benzotriazole compound, a triazine compound, an ester compound, an indole compound, and a pyrimidine compound.
  • the ultraviolet absorbing organic dye may be included in 1 to 10% by weight of the total weight of the undercoat layer.
  • the refractive index of the UV blocking inorganic particles may range from 1.8 to 2.1.
  • the average particle diameter of the UV blocking inorganic particles may range from 20 to 200 111 ⁇ 1.
  • the ultraviolet blocking inorganic particles may be zinc oxide. 2020/004835 1 »(: 1 ⁇ 1 ⁇ 2019/007093
  • the sunscreen inorganic particles may be included in 10 to 50% by weight of the total weight of the overcoat layer.
  • the photocurable binder resin is a reactive acrylate oligomer group consisting of urethane acrylate oligomer, epoxide acrylate oligomer, polyester acrylate and polyether acrylate;
  • Trimethylolpropane tri (meth) acrylate pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate , Polyfunctional (meth) acrylate consisting of dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol nucleated sand (meth) acrylate, and glycerin propoxylated triacrylate It may be a polymer of at least one photopolymerizable compound selected from the group monomer group.
  • the undercoat layer may have a thickness of 1 to 10 III.
  • the thickness of the overcoat layer may be 1 to 5 !!!
  • the UV blocking film of the present invention has excellent light resistance properties and maintains stable UV blocking ability even when exposed to ultraviolet rays for a long time, and has a low haze value and thus shows high transparency, and thus can be suitably used as a protective film for 01 Yu display devices. have.
  • the present invention may be variously modified and may have various forms. 2020/004835 1 »(: 1 ⁇ 1 ⁇ 2019/007093
  • the present invention is a polymer substrate; An undercoat layer comprising an ultraviolet absorbing organic dye and a photocurable binder resin; And an ultraviolet blocking film sequentially laminated with an overcoat layer comprising ultraviolet blocking inorganic particles and a photocurable binder resin,
  • the ultraviolet ray blocking film having a transmittance after the light resistance test is three times or less than the transmittance before the light test.
  • Temperature 50X , irradiance 0.55 2 , wavelength 290 to 400
  • the UV blocking film includes ultraviolet blocking inorganic particles so as to prevent decomposition of the additive dye, thereby significantly improving the light resistance characteristics, and thus the change in transmittance is small even when exposed to ultraviolet rays for a long time.
  • the UV blocking film may have a transmittance of 405 wavelength after the light resistance test of 2.5 times or less, or 2.3 times or less, or 2.2 times or less of the transmittance before the light resistance test.
  • the UV blocking film preferably has a transmittance of 60% or more or 63% or more of the wavelength of 430 ⁇ measured using the 11 ⁇ ⁇ 18-18 spectrophotometer before the light resistance test. .
  • UV protection film for high device protection should be secured in the ultraviolet region and blue light blocking ability of less than 405 1 ⁇ 11, and at the same time should be transparent so as not to impair the color expressed from the device. Accordingly, although the transmittance is low and the transmittance of 430 11111 wavelength is high for wavelengths of 405 0X1 or less, the UV blocking film of the present invention exhibits the above-described transmittance characteristics by satisfying a predetermined configuration.
  • the UV blocking film has a haze value measured according to the 7136 method. 2020/004835 1 »(: 1 ⁇ 1 ⁇ 2019/007093
  • the UV blocking film of the present invention has a low haze value, excellent transmittance characteristics and light resistance characteristics, and can be suitably used for protective film applications such as 01 silk devices, and may contribute to the life characteristics of 01 high devices. .
  • the UV blocking film is a polymer substrate; An undercoat layer comprising an ultraviolet absorbing organic dye; And an overcoat layer including UV-blocking inorganic particles may be sequentially stacked.
  • the surface of the polymer substrate is in contact with one surface of the device, the surface of the overcoat layer is exposed to ultraviolet rays. Accordingly, the ultraviolet absorbing organic dye of the undercoat layer can be protected from ultraviolet exposure by the ultraviolet blocking inorganic particles of the overcoat layer. Therefore, the decomposition rate of the organic dye is significantly slower than the case of using only the UV absorbing organic dye without the UV blocking inorganic particles, and the UV blocking ability of the film may be maintained even when exposed to UV light for a long time.
  • the UV blocking film when used as the 01 and device protection film, not only the organic material of the 01 Yu 0 device can be sufficiently protected by the UV absorbing organic dye of the undercoat layer and the UV blocking inorganic particles of the overcoat layer, but also for a long time. Even when exposed to ultraviolet light, the ultraviolet ray blocking ability of the film is small, so that the effective protection of the 01Oul device for a long time, the life characteristics of the device can be significantly improved.
  • the polymer substrate used in the UV blocking film is advantageously a substrate having a low transmittance in the wavelength range of 380 ⁇ or less, a high transmittance for the 430 11111 wavelength, and a haze of less than 2.5.
  • the material of the substrate may be triacetyl cellulose, cycloolefin polymer, polyacrylate, polycarbonate, polyethylene terephthalate, etc., preferably triacetyl cellulose or polyethylene terephthalate, more preferably 380 Triacetyl cellulose having a very low wavelength transmittance below and low haze may be used.
  • the thickness of the base film may be 10 to 300 III in consideration of productivity, but is not limited thereto.
  • At least one of a triazine compound, an ester compound, and an indole (urine 1 (101 ′ compound and pyrimidine> ⁇ 111 ⁇ (3 ⁇ 411 ⁇ 2)) compound may be preferably used. These compounds have a low transmittance at a wavelength near 400 ⁇ , which can more effectively protect the 01k0 device from ultraviolet and blue light.
  • benzophenone 0 ⁇ ! 01) 11 ⁇ 2110116) based compound Compounds such as oxalanilide (0 votes ⁇ 11 (16) -based compounds) are also known as ultraviolet absorbing organic dyes, but in the case of these dyes, there is a problem of high transmittance at a wavelength near 400 11111. Not suitable for application to protective sunscreen films. Therefore, in order to secure the effect of the present invention, it is preferable to use at least one of the benzotriazole-based, triazine-based, ester-based, indole-based and pyrimidine-based compounds.
  • the benzotriazole-based, triazine-based, ester-based, indole-based, and pyrimidine-based compounds each have a benzotriazole, triazine, ester, indole, pyrimidine moiety (1110, 50, and the above-described compounds) If not particularly limited, specifically as the compound 384
  • the amount of the ultraviolet absorbing organic dye is not particularly limited, but is preferably included in 1 to 10% by weight of the total weight of the solid content of the undercoat layer,
  • the content of the ultraviolet absorbing organic dye is less than 1% by weight of the total weight of the undercoat layer solid, it may not be able to sufficiently secure the UV blocking ability in the wavelength range of 405. If the content is more than 10% by weight, the transmittance around 430 ⁇ is very low. Since there may be a problem of precipitation into white spots, it is preferable to satisfy the above range.
  • the ultraviolet blocking inorganic particles are added to prevent the ultraviolet absorbing organic dye from being decomposed by ultraviolet rays.
  • the UV blocking inorganic particles are preferably included in the overcoat layer laminated on the undercoat layer containing the ultraviolet absorbing organic dye.
  • UV protection film for device protection should ensure transparency 2020/004835 1 »(: 1 ⁇ 1 ⁇ 2019/007093
  • the haze value is at a low level, that is, 1.5 or less.
  • the UV blocking inorganic particles preferably have a refractive index in the range of 1.8 to 2.1, or 1.85 to 2.05. If the refractive index of the inorganic particles is too high exceeding 2.1, the haze value of the UV blocking film is high, and if it is too low below 1.8, there is a problem that the UV blocking efficiency may be low.
  • the average particle diameter of an ultraviolet-ray inorganic particle is preferably in the range of 20-200 11111, or 30-150. If the average particle diameter of the particles exceeds 200 ps, the haze value becomes high, and if the particle size is less than 20 11111, there may be a problem that the UV blocking efficiency is lowered, thus satisfying the above range.
  • the UV blocking inorganic particles may be inorganic particles having UV blocking ability known in the art, but it is preferable to use zinc oxide (3 ⁇ 410) particles to control the haze of the UV blocking film.
  • zinc oxide 3 ⁇ 410 particles
  • the haze value of the UV blocking film is lower than 50%, 01 It is more desirable to be applied to the film for protection.
  • the content of the UV blocking inorganic particles may be, for example, 10 to 50% by weight of the total weight of the solid content of the overcoat layer, or may be 20 to 50% by weight. If the content of the sunscreen inorganic particles is too small, less than 10% by weight of the overcoat layer, the protective effect of the sunscreen organic dyes present in the undercoat layer may not be sufficiently exhibited. Since the haze value of may be high, it is preferable to satisfy the above range.
  • the undercoat layer and the overcoat layer each include a binder resin, wherein the binder resin may be suitably used as a photocurable binder resin.
  • the binder resin may be suitably used as a photocurable binder resin.
  • a plastic resin such as PMMA or polyvinyl butyral
  • the heat and moisture resistance of the UV blocking film may be deteriorated.
  • fluorine-based plastic resin is used, the haze is high, and thus it is not suitable to be applied as a film for protection of 01 Yu.
  • the photocurable binder resin undergoes a polymerization reaction when light such as ultraviolet rays is irradiated. 2020/004835 1 »(: 1 ⁇ 1 ⁇ 2019/007093
  • a polymer of a photopolymerizable compound that can be produced it may be one commonly used in the art to which the present invention pertains.
  • a reactive acrylate oligomer group As the photopolymerizable compound, a reactive acrylate oligomer group; And one or more selected from the group of polyfunctional (meth) acrylate monomers may be used.
  • the reactive acrylate oligomer may be at least one selected from the group consisting of urethane acrylate oligomers, epoxide acrylate oligomers, polyester acrylates and polyether acrylates.
  • the singular polyfunctional (meth) acrylate monomer may be a 2 to 6 functional (meth) acrylate monomer.
  • the said (meth) acrylate is the meaning containing both an acrylate () and a methacrylate (] ⁇ 1: 113 ( ⁇ 16).
  • said polyfunctional (meth) acrylate type monomer is not limited to this, For example, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) Acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol It may be at least one selected from the group consisting of nucleated (meth) acrylate and glycerin propoxylated triacrylate.
  • the photocurable binder resin used for an undercoat layer and an overcoat layer does not need to be the same.
  • the undercoat layer is urethane acrylate oligomer, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, in order to ensure compatibility with the ultraviolet absorbing organic dye and mechanical properties of the coating layer.
  • a polymer of at least one photopolymerizable compound selected from the group consisting of dipentaerythritol nuxaacrylate may be used as a binder, and the overcoat layer may be compatible with UV-blocking inorganic particles and adhesion with an undercoat layer.
  • the undercoat layer and the overcoat layer may each include one or more additives.
  • the additive is used to form a uniform coating layer, a material that does not affect particle aggregation and has a good leveling property may be preferably used.
  • fluorine-based and silicone-based additives having good compatibility with acrylic binders may be used.
  • 553 (£) 10, ⁇ 11 (010), 1210 0 ⁇ and 1410 ⁇ 0 or more) can be used one or more additives selected from the group consisting of.
  • Such additives may be included in the range of 0.1 to 0.5% by weight in the undercoat and overcoat layers, respectively, so as to secure the above-described purpose, so as not to impair the transmittance and haze characteristics of the sunscreen.
  • the thickness of the undercoat layer is not particularly limited, but in order to secure optical and mechanical properties simultaneously, 1 to 10 To 8 11 1 ⁇ 1 may be preferred. In addition, it is preferable that the thickness of the overcoat layer is in the range of 1 to 5 111, or 1 to 4 !! ⁇ !, or 1 to 2 11 111 when considering the total thickness of the substrate including the coating layer.
  • the undercoat layer may be obtained by applying a photopolymerizable coating composition comprising a photocurable binder resin, a photopolymerization initiator, and an ultraviolet absorbing organic dye on a polymer substrate, and photopolymerizing the applied result.
  • the overcoat layer may be obtained by applying a photopolymerizable coating composition comprising a photocurable binder resin, a photopolymerization initiator and an ultraviolet blocking inorganic particle on the prepared undercoat layer, and photopolymerizing the applied resultant.
  • the photopolymerizable coating composition may further include the additives described above.
  • the photopolymerization initiator may be used without particular limitation as long as it is a compound known to be used in the photocurable coating composition, and specifically, a benzophenone compound, acetophenone compound, biimidazole compound, triazine compound, oxime compound or Mixtures of two or more thereof can be used.
  • the photopolymerization initiator may be used in an amount of 1 to 100 parts by weight, 1 to 50 parts by weight or 1 to 20 parts by weight.
  • the content of the photopolymerization initiator in the photocurable coating composition is The solid content of the photocurable coating composition may be adjusted to 0.1 wt% to 15 wt% or 1 wt% to 10 wt%.
  • the amount of the photopolymerization initiator is too small, an uncured material remaining in the photocuring step of the photocurable coating composition may occur. If the amount of the photopolymerization initiator is too large, the unreacted initiator may remain as an impurity or have a low crosslinking density, thereby lowering mechanical properties or significantly increasing reflectance of the film.
  • the photocurable coating composition may further include an organic solvent.
  • the organic solvent include ketones, alcohols, acetates and ethers, or mixtures of two or more thereof.
  • Specific examples of such organic solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetylacetone or isobutyl ketone; Alcohols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, or t-butanol; Acetates such as ethyl acetate, iso-propyl acetate, or polyethylene glycol monomethyl ether acetate; Ethers such as tetrahydrofuran or propylene glycol monomethyl ether; Or mixtures of two or more thereof.
  • the method and apparatus conventionally used to apply the photopolymerizable coating composition may be used without particular limitation, for example, a bar coating method such as Mayer bar coating, gravure coating method, 2 roll reverse coating method, vacuum slot die Coating method or 2 roll coating method can be used.
  • a bar coating method such as Mayer bar coating, gravure coating method, 2 roll reverse coating method, vacuum slot die Coating method or 2 roll coating method can be used.
  • the exposure amount is preferably 100 to 4,000 mJ / cin 2 when irradiated.
  • Exposure time is not specifically limited, either, It can change suitably according to the wavelength of an exposure apparatus used, irradiation light, or exposure amount.
  • nitrogen purging may be performed to apply nitrogen atmospheric conditions.
  • TMPTA trimethylolpropane triacrylate
  • Polyvinylidene fluoride (size- 3 ⁇ 4 1 (3 ⁇ 4 ⁇ , Weight average molecular weight: 30,000)
  • an undercoat composition having the composition of Table 1 below, it was 60 acetyl triacetyl cellulose On one side of the film After coating, it was dried at 60 ° 0 for 2 minutes. The dried material was irradiated with ultraviolet light of 100 1/011 2 to prepare an undercoat layer having a thickness of 4].
  • Example 4 The overcoat compositions of Example 4 and Comparative Example 5 were prepared with the compositions shown in Table 5 below.
  • Each overcoat composition was put on the undercoat layer manufactured by said (1). Coated with Dried for 2 minutes. The dried material was irradiated with ultraviolet light of 200/1/01 2 to prepare an overcoat layer having a thickness of 3 to 4!.
  • Each of the undercoat compositions was coated with # 80 11 61 ⁇ 31 ⁇ on one surface of a 60-thick triacetylcellulose show (:) film, and then dried at 60 ⁇ : for 5 minutes to prepare an undercoat layer having a thickness of It was. This was set as Comparative Example 6.
  • Each ultraviolet-ray blocking film obtained by the said manufacture example was made into temperature 50 degrees 0, and the irradiance is 0.55. Exposed. 2. Transmittance Measurement
  • the transmittance of the UV blocking film before and after the light test was immediately determined by the following method.
  • the transmission spectrum of the entire film including the under and overcoating layers was examined using a UV-VIS-NIR spectrophotometer (Model name: Solidspec-3700, manufacturer: Shimadzu) with the film free as the baseline.
  • the haze value of each ultraviolet ray blocking film was measured according to JIS K 7136 standard.
  • the total light transmittance of each ultraviolet ray blocking film was measured according to the JIS K 7361 standard.
  • Comparative Example 4 without the overcoat layer, or the UV blocking film of Comparative Examples 1 and 5 in which the overcoat layer does not contain UV-blocking inorganic particles the transmittance is significantly increased after the light resistance test, it can be confirmed that the UV blocking effect is not maintained.
  • the content of zinc oxide contained in the overcoat layer should be 10% by weight or more in order to secure the effect of the present invention.
  • titanium oxide when comparing Comparative Examples 2 and 3, titanium oxide also exhibits a UV blocking effect at a level similar to zinc oxide, but the haze value is more than two times, it is found that it is not suitable for use as a protective purpose of the 01 ⁇ 0 device.
  • Comparative Examples 6 to 9 using fluorine-based plastic resins other than photocurable binders as binders of the undercoat layer and the overcoat layer the haze value was very high, which was unsuitable for the protection of the 01 HU0 device.
  • Comparative Examples 6 and 7 using a binder the coating property was poor.

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Abstract

The present invention relates to an ultraviolet blocking film, which has excellent light resistance characteristics and thus exhibits stable ultraviolet blocking ability for a long time, and has a low haze value and thus is suitable to protect an organic light emitting element or the like from an external light source.

Description

2020/004835 1»（：1^1{2019/007093  2020/004835 1 »（： 1 ^ 1 {2019/007093
【발명의 명칭】 [Name of invention]
자외선 차단 필름  Uv protection film
【기술분야】 Technical Field
관련 출원（들）과의 상호 인용  Cross Citation with Related Application (s)
본 출원은 2018년 6월 29일자 한국 특허 출원 제 10-2018-0075903호 및 2019년 6월 11일자 한국 특허 출원 제 10-2019-0068578호에 기초한 우선권의 이익을 주장하며， 해당 한국 특허 출원의 문헌에 개시된 모든 내용을 본 명세서의 일부로서 포함한다.  This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0075903 dated June 29, 2018 and Korean Patent Application No. 10-2019-0068578 dated June 11, 2019. All content disclosed in the literature is included as part of this specification.
본 발명은 내광 특성이 우수하고 헤이즈 값이 낮아 유기발광소자 등의 보호에 적합한자외선 차단필름에 관한 것이다.  The present invention relates to an ultraviolet ray blocking film suitable for the protection of an organic light emitting device, such as excellent light resistance and low haze value.
【배경기술】 Background Art
태양광 중 파장 약 10 내지 400 11111 영역에 해당하는 자외선은 가시광선이나 적외선보다 에너지가 커서 유기 화합물 등의 분자 결합을 여기하거나 절단할수 있는수준의 에너지를 지니고 있다.  Ultraviolet rays, which correspond to wavelengths of about 10 to 400 11111 in sunlight, have greater energy than visible or infrared rays and have energy that can excite or cleave molecular bonds such as organic compounds.
특히, 최근 디스플레이 재료로 널리 사용되고 있는 유기 발광 소자（01고1））는 자외선 및 405 ^ 이하의 청색광에 노출될 경우 유기물 층에 존재하는 청색 발광 물질과 같은 유기 화합물의 손상이 발생할 수 있고， 픽셀 격막의 수축이나 아웃개싱
Figure imgf000002_0001
현상이 발생할 수 있으며, 결국 소자의 기능을 잃게 되는문제가 있다. In particular, the organic light emitting device (01 high 1), which is widely used as a display material in recent years, may cause damage to organic compounds such as blue light emitting materials present in the organic layer when exposed to ultraviolet rays and blue light of 405 ^ or less, and Contraction or outgassing of the diaphragm
Figure imgf000002_0001
The phenomenon may occur, and the device may eventually lose its function.
이에， 01玉0 소자를 자외선으로부터 보호하기 위하여, 자외선 흡수가 가능한 유기 염료를 포함하는 코팅층을 01玉0 소자 상에 도입하는 기술이 제시되었다. 그러나 상기 유기 염료는 자외선에 장시간 노출될 경우 분해가 일어나 자외선 흡수 특성을 점차 잃게 되는 바， 최초의 자외선 차단 성능을 유지하지 못하여 결국 01고0 제품수명의 저하를초래하게 되는문제가 있다. 따라서， 01고0 소자를 외부 광으로부터 효과적으로 보호할 수 있는， 내광특성이 우수한자외선 차단 필름의 개발이 필요한실정이다. 【발명의 상세한설명】 2020/004835 1»（：1^1{2019/007093 Accordingly, in order to protect the 01 Chuo device from ultraviolet rays, a technique of introducing a coating layer containing an organic dye capable of absorbing UV light onto the 01 Chuo device has been proposed. However, when the organic dye is exposed to ultraviolet light for a long time, decomposition occurs and gradually loses UV absorbing properties. Therefore, the organic dye does not maintain the original UV blocking performance, resulting in a deterioration of product life. Therefore, there is a need for the development of an ultraviolet ray blocking film having excellent light resistance characteristics, which can effectively protect the 01 high-zero device from external light. Detailed Description of the Invention 2020/004835 1 »（： 1 ^ 1 {2019/007093
【기술적 과제】 [Technical problem]
본 발명은 장시간 자외선 노출에도 안정적으로 자외선 차단 성능을 나타낼 수 있으며, 헤이즈 값이 낮아 01고0 디스플레이 소자 등에 적용되기에 적합한 자외선 차단 필름을 제공하는 것을 목적으로 한다.  An object of the present invention is to provide a UV protection film that can stably exhibit UV protection performance even under prolonged UV exposure, and has a low haze value and is suitable for application to display devices such as 01 and 0 display devices.
【기술적 해결방법】 Technical Solution
상기 과제를 해결하기 위하여 본 발명은，  The present invention to solve the above problems,
고분자 기재; 자외선 흡수 유기 염료 및 광경화성 바인더 수지를 포함하는 언더코트층; 및 자외선 차단 무기 입자 및 광경화성 바인더 수지를 포함하는 오버코트층이 순차로 적층된 자외선 차단 필름으로서,  A polymer substrate; An undercoat layer comprising an ultraviolet absorbing organic dye and a photocurable binder resin; And an ultraviolet blocking film sequentially laminated with an overcoat layer comprising ultraviolet blocking inorganic particles and a photocurable binder resin,
하기의 내광 테스트 실시 전과 후에
Figure imgf000003_0001
미터를 이용하여 405 11111 파장의 투과율을 측정하였을 때, 내광 테스트 후의 투과율이 내광 테스트 전의 투과율의 3배 이하인， 자외선 차단 필름을 제공한다. Before and after the following light test
Figure imgf000003_0001
When the transmittance of 405 11111 wavelength was measured using a meter, the ultraviolet ray blocking film having a transmittance after the light resistance test was three times or less the transmittance before the light resistance test was provided.
［내광 테스트 방법］  [Light resistance test method]
온도 50 V, 복사 조도 0.55 2, 파장 290 내지 400
Figure imgf000003_0002
Temperature 50 V, irradiance 0.55 2 , wavelength 290 to 400
Figure imgf000003_0002
하에서 48 시간 동안 노출시킴. Exposure under 48 hours.
상기 자외선 차단 필름은 상기 내광 테스트 전， 상기 UV-VIS - NIR 스펙트로포토미터를 이용하여 측정한 430 1^1 파장의 투과율이 60% 이상일 수 있다.  The UV blocking film may have a transmittance of 60% or more at a wavelength of 430 1 ^ 1 measured using the UV-VIS-NIR spectrophotometer before the light resistance test.
또한, 상기 자외선 차단 필름은 118 K 7136법에 따라 측정된 헤이즈 값이 1.5 이하일 수 있다.  In addition, the UV blocking film may have a haze value of 1.5 or less measured according to the 118 K 7136 method.
상기 자외선 흡수 유기 염료는 벤조트리아졸계 화합물, 트라이아진계 화합물, 에스터계 화합물, 인돌계 화합물 및 피리미딘계 화합물로 이루어지는 군에서 선택되는 1종 이상일 수 있다.  The ultraviolet absorbing organic dye may be at least one selected from the group consisting of a benzotriazole compound, a triazine compound, an ester compound, an indole compound, and a pyrimidine compound.
상기 자외선 흡수 유기 염료는 언더코트층 총 중량의 1 내지 10 중량%로 포함될 수 있다.  The ultraviolet absorbing organic dye may be included in 1 to 10% by weight of the total weight of the undercoat layer.
상기 자외선 차단 무기 입자의 굴절률은 1.8 내지 2.1 범위일 수 있다. 상기 자외선 차단 무기 입자의 평균 입경은 20 내지 200 111X1 범위일 수 있다.  The refractive index of the UV blocking inorganic particles may range from 1.8 to 2.1. The average particle diameter of the UV blocking inorganic particles may range from 20 to 200 111 × 1.
상기 자외선 차단 무기 입자는 산화아연일 수 있다. 2020/004835 1»（：1^1{2019/007093 The ultraviolet blocking inorganic particles may be zinc oxide. 2020/004835 1 »（： 1 ^ 1 {2019/007093
상기 자외선 차단 무기 입자는 오버코트층 총 중량의 10 내지 50 중량%로 포함될 수 있다. The sunscreen inorganic particles may be included in 10 to 50% by weight of the total weight of the overcoat layer.
상기 광경화성 바인더 수지는 우레탄 아크릴레이트 올리고머, 에폭사이드 아크릴레이트 올리고머, 폴리에스테르 아크릴레이트 및 폴리에테르 아크릴레이트로 이루어진 반응성 아크릴레이트 올리고머 군; 및  The photocurable binder resin is a reactive acrylate oligomer group consisting of urethane acrylate oligomer, epoxide acrylate oligomer, polyester acrylate and polyether acrylate; And
트리메틸올프로판 트리（메타）아크릴레이트, 펜타에리트리톨 디（메타）아크릴레이트, 펜타에리트리톨 트리（메타）아크릴레이트， 펜타에리트리톨 테트라（메타）아크릴레이트, 디펜타에리트리톨 트리（메타）아크릴레이트, 디펜타에리트리톨 테트라（메타）아크릴레이트, 디펜타에리트리톨 펜타（메타）아크릴레이트, 디펜타에리트리톨 핵사（메타）아크릴레이트 및 글리세린 프로폭실화 트리아크릴레이트로 이루어진 다관능성 （메트）아크릴레이트계 모노머 군;에서 선택된 1종 이상의 광중합성 화합물의 중합체일 수 있다.  Trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate , Polyfunctional (meth) acrylate consisting of dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol nucleated sand (meth) acrylate, and glycerin propoxylated triacrylate It may be a polymer of at least one photopolymerizable compound selected from the group monomer group.
상기 언더코트층의 두께는 1 내지 10 III일 수 있다.  The undercoat layer may have a thickness of 1 to 10 III.
상기 오버코트층의 두께는 1 내지 5 !!!일 수 있다.  The thickness of the overcoat layer may be 1 to 5 !!!
【발명의 효과】 【Effects of the Invention】
본 발명의 자외선 차단 필름은 내광 특성이 우수하여 장시간 자외선에 노출되는 경우에도 안정적인 자외선 차단능을 유지하며, 헤이즈 값이 낮아 고투명도를 나타내는 바, 01玉0 디스플레이 소자의 보호용 필름으로서 적합하게 사용될 수 있다.  The UV blocking film of the present invention has excellent light resistance properties and maintains stable UV blocking ability even when exposed to ultraviolet rays for a long time, and has a low haze value and thus shows high transparency, and thus can be suitably used as a protective film for 01 Yu display devices. have.
【발명의 실시를 위한 형태】 [Form for implementation of invention]
본 명세서에서 사용되는 용어는 단지 예시적인 실시예들을 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도는 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 명세서에서， "포함하다"， "구비하다" 또는 "가지다” 등의 용어는 실시된 특징, 단계, 구성 요소 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 단계， 구성 요소, 또는 이들을 조합한 것들의 존재 또는 부가가능성을 미리 배제하지 않는 것으로 이해되어야 한다.  The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. As used herein, the terms "comprise", "comprise" or "have" are intended to indicate that there is a feature, step, component, or combination thereof, and one or more other features or steps, It is to be understood that the present invention does not exclude the existence or addition of components, or combinations thereof.
본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는 2020/004835 1»（：1^1{2019/007093 The present invention may be variously modified and may have various forms. 2020/004835 1 »（： 1 ^ 1 {2019/007093
바， 특정 실시예들을 예시하고 하기에서 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. The specific embodiments are exemplified and described in detail below. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.
이하，본 발명을상세히 설명한다. 본 발명은 고분자 기재; 자외선 흡수 유기 염료 및 광경화성 바인더 수지를 포함하는 언더코트층; 및 자외선 차단 무기 입자 및 광경화성 바인더 수지를포함하는오버코트층이 순차로 적층된 자외선 차단필름으로서,  Hereinafter, the present invention will be described in detail. The present invention is a polymer substrate; An undercoat layer comprising an ultraviolet absorbing organic dye and a photocurable binder resin; And an ultraviolet blocking film sequentially laminated with an overcoat layer comprising ultraviolet blocking inorganic particles and a photocurable binder resin,
하기의 내광 테스트 실시 전과 후에
Figure imgf000005_0001
미터를 이용하여 405 ^ 파장의 투과율을 측정하였을 때, 내광 테스트 후의 투과율이 내광 테스트 전의 투과율의 3배 이하인,자외선 차단필름을 제공한다. Before and after the following light test
Figure imgf000005_0001
When the transmittance of 405 ^ wavelength is measured using a meter, the ultraviolet ray blocking film having a transmittance after the light resistance test is three times or less than the transmittance before the light test.
［내광 테스트 방법］  [Light resistance test method]
온도 50 X :, 복사 조도 0.55 2, 파장 290 내지 400
Figure imgf000005_0002
Temperature 50X :, irradiance 0.55 2 , wavelength 290 to 400
Figure imgf000005_0002
하에서 48 시간동안노출시킴. Exposure for 48 hours.
상기 자외선 차단 필름은 자외선 흡수 유기 염료 외에， 상가 염료의 분해를 방지할수 있도록자외선 차단무기 입자를포함함에 따라 내광특성이 현저히 향상되어 장시간 자외선에 노출될 경우에도 투과율의 변화가 적다. 바람직하기로, 상기 자외선 차단 필름은 상기 의 내광 테스트 실시 후의 405 파장의 투과율이 내광 테스트 전 투과율의 2.5배 이하, 또는 2.3배 이하, 또는 2.2배 이하일 수 있다.  In addition to the UV absorbing organic dye, the UV blocking film includes ultraviolet blocking inorganic particles so as to prevent decomposition of the additive dye, thereby significantly improving the light resistance characteristics, and thus the change in transmittance is small even when exposed to ultraviolet rays for a long time. Preferably, the UV blocking film may have a transmittance of 405 wavelength after the light resistance test of 2.5 times or less, or 2.3 times or less, or 2.2 times or less of the transmittance before the light resistance test.
또한， 상기 자외선 차단 필름은 투명도 확보를 위하여， 상기 내광 테스트 전, 상기 11\ ^18 - 汉 스팩트로포토미터를 이용하여 측정한 430 ^ 파장의 투과율이 60% 이상,또는 63% 이상인 것이 바람직하다.  In addition, in order to ensure transparency, the UV blocking film preferably has a transmittance of 60% or more or 63% or more of the wavelength of 430 ^ measured using the 11 \ ^ 18-18 spectrophotometer before the light resistance test. .
01고0 소자 보호를 위한 자외선 차단 필름은 자외선 영역 및 405 1^11 이하의 청색광 차단능이 확보되어야 하며， 동시에 소자로부터 발현되는 색감을 저해하지 않도록 투명해야 한다. 이에， 405 0X1 이하의 파장에 대해서는 투과율이 낮고, 430 11111파장의 투과율은높아야하는데,본 발명의 자외선 차단 필름은소정의 구성을 만족함으로써 상기와같은투과율특성을나타낸다.  01 UV protection film for high device protection should be secured in the ultraviolet region and blue light blocking ability of less than 405 1 ^ 11, and at the same time should be transparent so as not to impair the color expressed from the device. Accordingly, although the transmittance is low and the transmittance of 430 11111 wavelength is high for wavelengths of 405 0X1 or less, the UV blocking film of the present invention exhibits the above-described transmittance characteristics by satisfying a predetermined configuration.
또한，상기 자외선 차단필름은 7136법에 따라측정된 헤이즈 값이 2020/004835 1»（：1^1{2019/007093 In addition, the UV blocking film has a haze value measured according to the 7136 method. 2020/004835 1 »（： 1 ^ 1 {2019/007093
1.5 이하일 수 있으며, 1.2 이하, 또는 1 이하인 것이 보다 바람직하다. 본 발명의 자외선 차단 필름은 이와 같이 헤이즈 값이 낮고, 투과율 특성 및 내광 특성이 우수하여， 01正0 소자 등의 보호 필름 용도로 적합하게 사용될 수 있으며, 01고0소자의 수명 특성에 기여할수 있다. It may be 1.5 or less, more preferably 1.2 or less, or 1 or less. Thus, the UV blocking film of the present invention has a low haze value, excellent transmittance characteristics and light resistance characteristics, and can be suitably used for protective film applications such as 01 silk devices, and may contribute to the life characteristics of 01 high devices. .
본 발명의 일 실시예에 따르면, 상기 자외선 차단 필름은 고분자 기재; 자외선 흡수 유기 염료를 포함하는 언더코트층; 및 자외선 차단 무기 입자를 포함하는오버코트층이 순차로 적층된 것일 수 있다.  According to an embodiment of the present invention, the UV blocking film is a polymer substrate; An undercoat layer comprising an ultraviolet absorbing organic dye; And an overcoat layer including UV-blocking inorganic particles may be sequentially stacked.
이때, 상기 고분자 기재 면이 01^0 소자의 일면에 접하는 면이 되며, 오버코트층이 자외선에 노출되는 면이 된다. 이에 따라, 언더코트층의 자외선 흡수 유기 염료가 오버코트층의 자외선 차단 무기 입자에 의하여 자외선 노출로부터 보호될 수 있다. 따라서, 자외선 차단 무기 입자 없이 자외선 흡수 유기 염료만을 사용하는 경우에 비하여 상기 유기 염료의 분해 속도가 현저히 더뎌지며, 장시간 자외선에 노출되는 경우에도 필름의 자외선 차단능이 유지될 수 있다.  In this case, the surface of the polymer substrate is in contact with one surface of the device, the surface of the overcoat layer is exposed to ultraviolet rays. Accordingly, the ultraviolet absorbing organic dye of the undercoat layer can be protected from ultraviolet exposure by the ultraviolet blocking inorganic particles of the overcoat layer. Therefore, the decomposition rate of the organic dye is significantly slower than the case of using only the UV absorbing organic dye without the UV blocking inorganic particles, and the UV blocking ability of the film may be maintained even when exposed to UV light for a long time.
따라서, 상기 자외선 차단 필름을 01고 소자 보호용 필름으로 사용할 경우 01玉0 소자의 유기 물질이 언더코트층의 자외선 흡수 유기 염료 및 오버코트층의 자외선 차단 무기 입자에 의하여 충분히 보호될 수 있을 뿐만 아니라, 장시간 자외선에 노출될 경우에도 필름의 자외선 차단능 저하가 적어 01玉0소자를 장기간동안효과적으로 보호할수 았는 바, 소자의 수명 특성이 현저히 향상될 수 있다.  Therefore, when the UV blocking film is used as the 01 and device protection film, not only the organic material of the 01 Yu 0 device can be sufficiently protected by the UV absorbing organic dye of the undercoat layer and the UV blocking inorganic particles of the overcoat layer, but also for a long time. Even when exposed to ultraviolet light, the ultraviolet ray blocking ability of the film is small, so that the effective protection of the 01Oul device for a long time, the life characteristics of the device can be significantly improved.
상기 자외선 차단 필름에 사용되는 고분자 기재는 380 ^ 이하의 파장 영역의 투과율이 낮은 기재가 유리하며, 430 11111 파장에 대한 투과율은 높고, 헤이즈는 2.5 미만인 것이 바람직하게 사용될 수 있다. 예를 들어, 상기 기재의 소재는 트리아세틸셀룰로오스, 사이클로올레핀중합체, 폴리아크릴레이트， 폴리카보네이트， 폴리에틸렌테레프탈레이트 등일 수 있고， 바람직하게는 트리아세틸셀룰로오스 또는 폴리에틸렌테레프탈레이트일 수 있으며， 보다 바람직하게는 380 이하의 파장 투과율이 매우 낮고, 헤이즈가 낮은 트리아세틸셀룰로오스일 수 있다. 또한, 상기 기재 필름의 두께는 생산성 등을 고려하여 10내지 300 III일 수 있으나, 이에 한정하는 것은 아니다.  The polymer substrate used in the UV blocking film is advantageously a substrate having a low transmittance in the wavelength range of 380 ^ or less, a high transmittance for the 430 11111 wavelength, and a haze of less than 2.5. For example, the material of the substrate may be triacetyl cellulose, cycloolefin polymer, polyacrylate, polycarbonate, polyethylene terephthalate, etc., preferably triacetyl cellulose or polyethylene terephthalate, more preferably 380 Triacetyl cellulose having a very low wavelength transmittance below and low haze may be used. In addition, the thickness of the base film may be 10 to 300 III in consideration of productivity, but is not limited thereto.
상기 자외선 흡수 유기 염료로는 벤조트리아졸 0^112야1 201이계 화합물, 2020/004835 1»（：1^1{2019/007093 As the ultraviolet absorbing organic dye, benzotriazole 0 ^ 112ya1 201 double compound, 2020/004835 1 »（： 1 ^ 1 {2019/007093
트라이아진（仕 ）계 화합물， 에스터 ）계 화합물， 인돌（뇨1（101句계 화합물 및 피리미딘 ＞^111^（¾1½）계 화합물 중 1종 이상이 바람직하게 사용될 수 있다. 이들 화합물은 400 ^부근의 파장에서 투과율이 낮아서， 자외선 및 청색광으로부터 01止0 소자를 더욱 효과적으로 보호할 수 있다. 반면, 벤조페논 0^! 01）1½110116）계 화합물,
Figure imgf000007_0001
옥살아닐라이드（0표^11 （16）계 화합물과 같은 화합물 역시 자외선 흡수 유기 염료로 알려져 있기는 하나, 이들 염료의 경우， 400 11111 부근의 파장에서 투과도가 높은 문제점이 문제가 있으므로 01玉。 소자 보호용 자외선 차단 필름에 적용되기에는 부적합하다. 따라서, 본 발명의 효과를 확보하기 위해서는 상기 벤조트리아졸계， 트라이아진계, 에스터계， 인돌계 및 피리미딘계 화합물 중 1종 이상을 사용함이 바람직하다. At least one of a triazine compound, an ester compound, and an indole (urine 1 (101 ′ compound and pyrimidine> ^ 111 ^ (¾1½)) compound may be preferably used. These compounds have a low transmittance at a wavelength near 400 ^, which can more effectively protect the 01k0 device from ultraviolet and blue light. On the other hand, benzophenone 0 ^! 01） 1½110116） based compound,
Figure imgf000007_0001
Compounds such as oxalanilide (0 votes ^ 11 (16) -based compounds) are also known as ultraviolet absorbing organic dyes, but in the case of these dyes, there is a problem of high transmittance at a wavelength near 400 11111. Not suitable for application to protective sunscreen films. Therefore, in order to secure the effect of the present invention, it is preferable to use at least one of the benzotriazole-based, triazine-based, ester-based, indole-based and pyrimidine-based compounds.
상기 벤조트리아졸계, 트라이아진계, 에스터계, 인돌계 및 피리미딘계 화합물은 각각 벤조트리아졸, 트라이아진, 에스터， 인돌, 피리미딘 모이어티（1110治50를 가지고 있으며, 상술한 효과를 나타내는 화합물이면 특별히 제한되지 않으나， 구체적으로 상기 화합물로는 상품명
Figure imgf000007_0002
384The benzotriazole-based, triazine-based, ester-based, indole-based, and pyrimidine-based compounds each have a benzotriazole, triazine, ester, indole, pyrimidine moiety (1110, 50, and the above-described compounds) If not particularly limited, specifically as the compound
Figure imgf000007_0002
384
（벤조트리아졸계）, 1¾111' 11®
Figure imgf000007_0003
（벤조트리아졸계）,
Figure imgf000007_0004
Figure imgf000007_0005
(Benzotriazole), 1¾111 '11®
Figure imgf000007_0003
(Benzotriazole type),
Figure imgf000007_0004
Figure imgf000007_0005
009（피리미딘계）로 이루어지는 군에서 선택되는 1종 이상을 사용할 수 있다. 상기 자외선 흡수 유기 염료의 사용량은 특별히 제한되는 것은 아니나， 언더코트층의 고형분 총 중량의 1 내지 10 중량%로 포함되는 것이 바람직하고， 1 or more types chosen from the group which consists of 009 (pyrimidine system) can be used. The amount of the ultraviolet absorbing organic dye is not particularly limited, but is preferably included in 1 to 10% by weight of the total weight of the solid content of the undercoat layer,
2 내지 8 중량%, 또는 3 내지 6 중량%가 보다 바람직하다. 만일 자외선 흡수 유기 염료의 함량이 언더코트층 고형분 총 중량의 1 중량% 미만이면 파장 405 범위의 자외선 차단능을 충분히 확보하지 못할 수 있고, 10 중량%를 초과하면 430 ^ 부근의 투과율이 매우 낮으며 백색의 반점으로 석출되는 문제가 있을 수 있으므로, 상기 범위를 만족함이 바람직하다. 2-8 weight%, or 3-6 weight% is more preferable. If the content of the ultraviolet absorbing organic dye is less than 1% by weight of the total weight of the undercoat layer solid, it may not be able to sufficiently secure the UV blocking ability in the wavelength range of 405. If the content is more than 10% by weight, the transmittance around 430 ^ is very low. Since there may be a problem of precipitation into white spots, it is preferable to satisfy the above range.
상기 자외선 차단 무기 입자는 자외선 흡수 유기 염료가 자외선에 의하여 분해되는 것을 방지하기 위하여 투입된다. 상기 효과를 확보하기 위하여， 자외선 차단 무기 입자는 자외선 흡수 유기 염료가 포함된 언더코트층 위에 적층되는 오버코트층에 포함되는 것이 바람직하다.  The ultraviolet blocking inorganic particles are added to prevent the ultraviolet absorbing organic dye from being decomposed by ultraviolet rays. In order to secure the above effect, the UV blocking inorganic particles are preferably included in the overcoat layer laminated on the undercoat layer containing the ultraviolet absorbing organic dye.
01제） 소자 보호용 자외선 차단 필름은 투명성이 확보되어야 하기 2020/004835 1»（：1^1{2019/007093 01) UV protection film for device protection should ensure transparency 2020/004835 1 »（： 1 ^ 1 {2019/007093
때문에, 헤이즈 값이 낮은 수준， 즉 1.5 이하인 것이 바람직하다. 이에, 본 발명에서 상기 자외선 차단무기 입자는 굴절률이 1.8 내지 2.1 범위,또는 1.85 내지 2.05인 것이 바람직하다. 만일 무기 입자의 굴절률이 2.1을 초과하여 너무 높으면， 자외선 차단 필름의 헤이즈 값이 높아지게 되고, 1.8 미만으로 너무 낮으면 자외선 차단효율이 낮을수 있는문제가 있다. Therefore, it is desirable that the haze value is at a low level, that is, 1.5 or less. Thus, in the present invention, the UV blocking inorganic particles preferably have a refractive index in the range of 1.8 to 2.1, or 1.85 to 2.05. If the refractive index of the inorganic particles is too high exceeding 2.1, the haze value of the UV blocking film is high, and if it is too low below 1.8, there is a problem that the UV blocking efficiency may be low.
또한， 상기 헤이즈 값을 확보하기 위해서, 자외선 차단 무기 입자의 평균 입경은 20 내지 200 11111, 또는 30 내지 150 범위인 것아바람직하다. 만일 입자의 평균 입경이 200삐를초과하면 헤이즈 값이 높아지게 되고, 20 11111 미만인 경우 자외선 차단 효율이 저하되는 문제가 있을 수 있으므로, 상기 범위를 만족함이 바람직하다.  In addition, in order to ensure the said haze value, the average particle diameter of an ultraviolet-ray inorganic particle is preferably in the range of 20-200 11111, or 30-150. If the average particle diameter of the particles exceeds 200 ps, the haze value becomes high, and if the particle size is less than 20 11111, there may be a problem that the UV blocking efficiency is lowered, thus satisfying the above range.
상기 자외선 차단 무기 입자는 당 업계에 알려진 자외선 차단능을 가지는 무기 입자가 사용 가능하나, 자외선 차단 필름의 헤이즈를 제어하기 위하여 산화아연 (¾10) 입자를 사용하는 것이 바람직하다. 후술하는 본원 발명의 실험예에서 확인할 수 있듯이, 널리 알려진 자외선 차단 무기 입자인 산화티타늄 ( 02)에 비하여 산화아연 입자를 사용하는 경우에 자외선 차단 필름의 헤이즈 값이 50 % 이상 낮게 나타나므로, 01玉0 소자 보호용 필름에 적용되기에 보다바람직하다. The UV blocking inorganic particles may be inorganic particles having UV blocking ability known in the art, but it is preferable to use zinc oxide (¾10) particles to control the haze of the UV blocking film. As can be seen in the experimental example of the present invention to be described later, when the zinc oxide particles are used compared to the titanium oxide (0 2 ) which is a well-known UV blocking inorganic particles, the haze value of the UV blocking film is lower than 50%, 01 It is more desirable to be applied to the film for protection.
상기 자외선 차단 무기 입자의 함량은 일례로 오버코트층의 고형분 총 중량의 10 내지 50중량%일 수 있고， 또는 20내지 50 중량%일 수 있다. 만일 자외선 차단 무기 입자의 함량이 오버코트층의 10 중량% 미만으로 너무 적으면 언더코트층에 존재하는 자외선 차단 유기 염료의 보호 효과를 충분히 나타낼 수 없고, 50 중량%를 초과하여 지나치게 많이 포함되면 오버코트층의 헤이즈 값이 높아질 수 있으므로,상기 범위를 만족함이 바람직하다.  The content of the UV blocking inorganic particles may be, for example, 10 to 50% by weight of the total weight of the solid content of the overcoat layer, or may be 20 to 50% by weight. If the content of the sunscreen inorganic particles is too small, less than 10% by weight of the overcoat layer, the protective effect of the sunscreen organic dyes present in the undercoat layer may not be sufficiently exhibited. Since the haze value of may be high, it is preferable to satisfy the above range.
한편, 상기 언더코트층 및 오버코트층은 각각 바인더 수지를 포함하며, 이때 바인더 수지는 광경화성 바인더 수지가 적합하게 사용될 수 있다. 만일 PMMA, 폴리비닐부티랄 등의 가소성 수지가 사용될 경우 자외선 차단 필름의 내습열 특성이 떨어질 수 있고,
Figure imgf000008_0001
불소계 가소성 수지를 사용할 경우 헤이즈가 높게 나타나 01玉0 보호용 필름으로서 적용되기에 부적합하다. Meanwhile, the undercoat layer and the overcoat layer each include a binder resin, wherein the binder resin may be suitably used as a photocurable binder resin. If a plastic resin such as PMMA or polyvinyl butyral is used, the heat and moisture resistance of the UV blocking film may be deteriorated.
Figure imgf000008_0001
When fluorine-based plastic resin is used, the haze is high, and thus it is not suitable to be applied as a film for protection of 01 Yu.
상기 광경화성 바인더 수지는 자외선 등의 광이 조사되면 중합 반응을 2020/004835 1»（：1^1{2019/007093 The photocurable binder resin undergoes a polymerization reaction when light such as ultraviolet rays is irradiated. 2020/004835 1 »（： 1 ^ 1 {2019/007093
일으킬 수 있는 광중합성 화합물의 중합체로서， 본 발명이 속한 기술분야에서 통상적으로 사용되는 것일 수 있다. 상기 광중합성 화합물로는 반응성 아크릴레이트 올리고머 군; 및 다관능성 （메트）아크릴레이트계 모노머 군에서 선택되는 1종 이상이 사용될 수 있다. As a polymer of a photopolymerizable compound that can be produced, it may be one commonly used in the art to which the present invention pertains. As the photopolymerizable compound, a reactive acrylate oligomer group; And one or more selected from the group of polyfunctional (meth) acrylate monomers may be used.
상기 반응성 아크릴레이트 올리고머는 우레탄 아크릴레이트 올리고머, 에폭사이드 아크릴레이트 올리고머, 폴리에스테르 아크릴레이트 및 폴리에테르 아크릴레이트로 이루어진 군에서 선택된 1종 이상일 수 있다.  The reactive acrylate oligomer may be at least one selected from the group consisting of urethane acrylate oligomers, epoxide acrylate oligomers, polyester acrylates and polyether acrylates.
싱기 다관능성 （메트）아크릴레이트계 모노머는 2 내지 6 관능성 （메트）아크릴레이트계 모노머일 수 있다. 이때， 상기 （메타）아크릴레이트는 아크릴레이트（ ） 및 메타크릴레이트（］^1：113（^1 6） 양쪽 모두를 포함하는 의미이다.  The singular polyfunctional (meth) acrylate monomer may be a 2 to 6 functional (meth) acrylate monomer. At this time, the said (meth) acrylate is the meaning containing both an acrylate () and a methacrylate (] ^ 1: 113 (^ 16).
상기 다관능성 （메트）아크릴레이트계 모노머의 종류는 이로써 한정하는 것은 아니나, 예를 들어, 트리메틸올프로판 트리（메타）아크릴레이트， 펜타에리트리톨 디（메타）아크릴레이트， 펜타에리트리톨 트리（메타）아크릴레이트， 펜타에리트리톨 테트라（메타）아크릴레이트, 디펜타에리트리톨 트리（메타）아크릴레이트, 디펜타에리트리톨 테트라（메타）아크릴레이트, 디펜타에리트리톨 펜타（메타）아크릴레이트, 디펜타에리트리톨 핵사（메타）아크릴레이트 및 글리세린 프로폭실화 트리아크릴레이트로 이루어진 군에서 선택된 1종 이상일 수 있다.  Although the kind of said polyfunctional (meth) acrylate type monomer is not limited to this, For example, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) Acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol It may be at least one selected from the group consisting of nucleated (meth) acrylate and glycerin propoxylated triacrylate.
이때, 언더코트층 및 오버코트층에 사용되는 광경화성 바인더 수지는 동일할 필요는 없다. 바람직하기로, 언더코트층은 자외선 흡수 유기 염료와의 상용성 및 코팅층의 기계적 물성을 확보하기 위하여, 우레탄 아크릴레이트 올리고머 , 트리메틸올프로판 트리（메타）아크릴레이트, 펜타에리트리톨 트리（메타）아크릴레이트， 및 디펜타에리트리톨 핵사아크릴레이트로 이루어지는 군에서 선택되는 1종 이상의 광중합성 화합물의 _중합체를 바인더로 사용할 수 있고， 오버코트층은 자외선 차단 무기 입자와의 상용성 및 언더코팅층과의 부착성을 확보하기 위하여 펜타에리트리톨 트리（메타）아크릴레이트, 글리세린 프로폭실화 트리아크릴레이트作 시, 디펜타에리트리톨
Figure imgf000009_0001
및 디펜타에리트리톨 핵사（메타）아크릴레이트로 이루어지는 군에서 선택되는 _1종 이상의 광중합성 화합물의 중합체를 바인더로 2020/004835 1»（：1^1{2019/007093 At this time, the photocurable binder resin used for an undercoat layer and an overcoat layer does not need to be the same. Preferably, the undercoat layer is urethane acrylate oligomer, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, in order to ensure compatibility with the ultraviolet absorbing organic dye and mechanical properties of the coating layer. And a polymer of at least one photopolymerizable compound selected from the group consisting of dipentaerythritol nuxaacrylate may be used as a binder, and the overcoat layer may be compatible with UV-blocking inorganic particles and adhesion with an undercoat layer. In order to ensure pentaerythritol tri (meth) acrylate, glycerin propoxylated triacrylate, dipentaerythritol
Figure imgf000009_0001
And polymers of _1 or more photopolymerizable compounds selected from the group consisting of dipentaerythritol nucleated (meth) acrylates as binders 2020/004835 1 »（： 1 ^ 1 {2019/007093
사용할수 있다. Can be used
또한， 상기 언더코트층 및 오버코트층은 각각 1종 이상의 첨가제를 포함할 수 있다. 상기 첨가제는 균일한 코팅층을 형성하기 위해 사용되는 것으로, 입자 응집에 영향을 주지 않으며 레벨링성이 좋은 물질이 바람직하게 사용될 수 있다. 예를 들어， 상기 첨가제로는 아크릴 바인더와 상용성이 좋은 불소계 및 실리콘계 첨가제들이 사용 가능하며 바람직하기로 ?553 （£）10 社）， ^11（010社）， 1210 0^ 社） 및 1410 ^0社）로 이루어지는군에서 선택되는 1종 이상의 첨가제를사용할수 있다.  In addition, the undercoat layer and the overcoat layer may each include one or more additives. The additive is used to form a uniform coating layer, a material that does not affect particle aggregation and has a good leveling property may be preferably used. For example, as the additive, fluorine-based and silicone-based additives having good compatibility with acrylic binders may be used. Preferably,? 553 (£) 10, ^ 11 (010), 1210 0 ^ and 1410 ^ 0 or more) can be used one or more additives selected from the group consisting of.
이러한 첨가제는 상술한 목적을 확보할 수 있으면서, 자외선 차단 필름의 투과율 및 헤이즈 특성을 저해하지 않도록, 언더코트층 및 오버코트층 각각에 0.1 내지 0.5중량%범위로포함될 수 있다.  Such additives may be included in the range of 0.1 to 0.5% by weight in the undercoat and overcoat layers, respectively, so as to secure the above-described purpose, so as not to impair the transmittance and haze characteristics of the sunscreen.
상기 언더코트층의 두께는 특별히 제한되는 것은 아니나, 광학 물성 및 기계적 물성을 동시에 확보하기 위하여, 1 내지 10
Figure imgf000010_0001
내지 8 11 1x1 범위가 바람직할 수 있다. 또한， 오버코트층의 두께는 1 내지 5 111， 또는 1 내지 4 !!ø!， 또는 1 내지 2 11 111 범위인 것이, 코팅층을 포함한 전체 기재 두께를 고려할 때 바람직할수 있다. The thickness of the undercoat layer is not particularly limited, but in order to secure optical and mechanical properties simultaneously, 1 to 10
Figure imgf000010_0001
To 8 11 1 × 1 may be preferred. In addition, it is preferable that the thickness of the overcoat layer is in the range of 1 to 5 111, or 1 to 4 !! ø !, or 1 to 2 11 111 when considering the total thickness of the substrate including the coating layer.
본 발명의 일 실시예에서， 상기 언더코트층은 광경화성 바인더 수지， 광중합 개시제 및 자외선 흡수 유기 염료를 포함하는 광중합성 코팅 조성물을 고분자 기재 상에 도포하고， 도포된 결과물을 광중합함으로써 얻어질 수 있다. 마찬가지로, 상기 오버코트층은 광경화성 바인더 수지, 광중합 개시제 및 자외선 차단 무기 입자를 포함하는 광중합성 코팅 조성물을 상기 제조된 언더코트층 상에 도포하고, 도포된 결과물을 광중합함으로써 얻어질 수 있다. 상기 각광중합성 코팅 조성물은상술한 첨가제를 더 포함하는 것일 수 있다. 상기 광중합 개시제로는 광경화성 코팅 조성물에 사용될 수 있는 것으로 알려진 화합물이면 특별한 제한 없이 사용 가능하며， 구체적으로 벤조페논계 화합물, 아세토페논계 화합물, 비이미다졸계 화합물, 트리아진계 화합물,옥심계 화합물또는 이들의 2종 이상의 혼합물이 사용될 수 있다.  In one embodiment of the present invention, the undercoat layer may be obtained by applying a photopolymerizable coating composition comprising a photocurable binder resin, a photopolymerization initiator, and an ultraviolet absorbing organic dye on a polymer substrate, and photopolymerizing the applied result. . Similarly, the overcoat layer may be obtained by applying a photopolymerizable coating composition comprising a photocurable binder resin, a photopolymerization initiator and an ultraviolet blocking inorganic particle on the prepared undercoat layer, and photopolymerizing the applied resultant. The photopolymerizable coating composition may further include the additives described above. The photopolymerization initiator may be used without particular limitation as long as it is a compound known to be used in the photocurable coating composition, and specifically, a benzophenone compound, acetophenone compound, biimidazole compound, triazine compound, oxime compound or Mixtures of two or more thereof can be used.
상기 광중합성 화합물 100 중량부에 대하여, 상기 광중합 개시제는 1 내지 100 중량부， 1 내지 50중량부 혹은 1 내지 20중량부의 함량으로사용될 수 있다. 또한, 상기 광경화성 코팅 조성물 중 상기 광중합 개시제의 함량은 상기 광경화성 코팅 조성물의 고형분에 대하여 0.1 중량%내지 15 중량%혹은 1 중량%내지 10중량%로조절될 수 있다. For 100 parts by weight of the photopolymerizable compound, the photopolymerization initiator may be used in an amount of 1 to 100 parts by weight, 1 to 50 parts by weight or 1 to 20 parts by weight. In addition, the content of the photopolymerization initiator in the photocurable coating composition is The solid content of the photocurable coating composition may be adjusted to 0.1 wt% to 15 wt% or 1 wt% to 10 wt%.
상기 광중합 개시제의 양이 너무 적으면, 상기 광경화성 코팅 조성물의 광경화 단계에서 미경화되어 잔류하는 물질이 발생할 수 있다. 상기 광중합 개시제의 양이 너무 많으면， 미반응 개시제가 불순물로 잔류하거나 가교 밀도가 낮아져서 제조되는 필름의 기계적 물성이 저하되거나 반사율이 크게 높아질 수 있다.  If the amount of the photopolymerization initiator is too small, an uncured material remaining in the photocuring step of the photocurable coating composition may occur. If the amount of the photopolymerization initiator is too large, the unreacted initiator may remain as an impurity or have a low crosslinking density, thereby lowering mechanical properties or significantly increasing reflectance of the film.
한편, 상기 광경화성 코팅 조성물은 유기 용매를 더 포함할 수 있다. 상기 유기 용매의 비제한적인 예를 들면 케톤류, 알코올류， 아세테이트류 및 에테르류, 또는 이들의 2종 이상의 혼합물을 들 수 있다. 이러한 유기 용매의 구체적인 예로는， 메틸에틸케톤， 메틸이소부틸케톤, 아세틸아세톤 또는 이소부틸케톤 등의 케톤류; 메탄올， 에탄올, n-프로판올， iso-프로판올, n-부탄올, iso-부탄올，또는 t-부탄올등의 알코올류; 에틸아세테이트, iso-프로필아세테이트， 또는 폴리에틸렌글리콜 모노메틸에테르 아세테이트 등의 아세테이트류; 테트라하이드로퓨란 또는 프로필렌글라이콜 모노메틸에테르 등의 에테르류; 또는 이들의 2종 이상의 혼합물을들수 있다.  Meanwhile, the photocurable coating composition may further include an organic solvent. Non-limiting examples of the organic solvent include ketones, alcohols, acetates and ethers, or mixtures of two or more thereof. Specific examples of such organic solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetylacetone or isobutyl ketone; Alcohols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, or t-butanol; Acetates such as ethyl acetate, iso-propyl acetate, or polyethylene glycol monomethyl ether acetate; Ethers such as tetrahydrofuran or propylene glycol monomethyl ether; Or mixtures of two or more thereof.
상기 광중합성 코팅 조성물을 도포하는데 통상적으로사용되는 방법 및 장치를 별 다른 제한 없이 사용할수 있으며, 예를들어, Mayer bar coating등의 바코팅법 ,그라비아코팅법 , 2 roll reverse코팅법 , vacuum slot die코팅법 , 2 roll 코팅법 등을사용할수 있다.  The method and apparatus conventionally used to apply the photopolymerizable coating composition may be used without particular limitation, for example, a bar coating method such as Mayer bar coating, gravure coating method, 2 roll reverse coating method, vacuum slot die Coating method or 2 roll coating method can be used.
상기 광중합성 코팅 조성물을 광중합 시키는 단계에서는 200~400nm 파장의 자외선 또는 가시 광선을 조사할 수 있고, 조사시 노광량은 100 내지 4,000 mJ/cin2 이 바람직하다. 노광 시간도 특별히 한정되는 것이 아니고, 사용되는 노광 장치, 조사 광선의 파장 또는 노광량에 따라 적절히 변화시킬 수 있다. 또한， 상기 광중합성 코팅 조성물을 광중합 시키는 단계에서는 질소 대기 조건을 적용하기 위하여 질소 퍼징 등을 할수 있다. 이하본 발명의 이해를 돕기 위하여 바람직한실시예를 제시하나， 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 2020/004835 1»（：1^1{2019/007093 In the step of photopolymerizing the photopolymerizable coating composition may be irradiated with ultraviolet rays or visible light having a wavelength of 200 ~ 400nm, the exposure amount is preferably 100 to 4,000 mJ / cin 2 when irradiated. Exposure time is not specifically limited, either, It can change suitably according to the wavelength of an exposure apparatus used, irradiation light, or exposure amount. In addition, in the step of photopolymerizing the photopolymerizable coating composition, nitrogen purging may be performed to apply nitrogen atmospheric conditions. Hereinafter, preferred examples are provided to help the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and various changes and modifications within the scope and spirit of the present invention are apparent to those skilled in the art. 2020/004835 1 »（： 1 ^ 1 {2019/007093
이러한 변경 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다. It is natural that such changes and modifications fall within the scope of the appended claims.
［실시예］ EXAMPLE
이하의 실시예에서， 약어로 표기된 물질명은 다음과 같다.  In the following examples, abbreviated material names are as follows.
＜바인더＞ <Binder>
TMPTA: 트리메틸올프로판트리아크릴레이트  TMPTA: trimethylolpropane triacrylate
11쇼7933: 2관능 우레탄 아크릴레이트 올리고
Figure imgf000012_0001
£^18, 중량평균분자량 3,000） 11 Show 7933: Bifunctional Urethane Acrylate Oligo
Figure imgf000012_0001
£ ^ 18, weight average molecular weight 3,000）
九 펜타에리트리톨 트리아크릴레이
Figure imgf000012_0002
九 pentaerythritol triacrylic
Figure imgf000012_0002
예묘쇼: 디펜타에리트리톨 핵사아크릴레이
Figure imgf000012_0003
Yemyo show: dipentaerythritol nucleated acrylamide
Figure imgf000012_0003
306^ 6관능 우레탄 아크릴레이트 出묘，중량평균분자량 1,000）  306 ^ 6 functional urethane acrylate drawing weight, weight average molecular weight 1,000）
폴리비닐리덴플루오라이드 （ 크 - ¾1（¾此， 중량평균분자량: 30,000）Polyvinylidene fluoride （size- ¾ 1 （¾ 此 ， Weight average molecular weight: 30,000）
Figure imgf000012_0004
덴플루오라이드- ¥ -핵사플루오로프로필렌 （ 切크
Figure imgf000012_0004
Denfluoride- ¥ -Nuclear Fluoropropylene (check)
801 ® 21508） 801 ® 21508）
^흡수유기염료 ñ ^ Absorbing organic dyes ñ
1^-3912:
Figure imgf000012_0005
케미컬 사， 인돌계 유기 염료） 1 ^ -3912:
Figure imgf000012_0005
Chemical Company, Indole Organic Dyes）
Figure imgf000012_0006
Figure imgf000012_0006
＜개시제＞ <Initiator>
1-184: 184（〔¾ 사） ＜용매 ñ 1-184: 184 (¾) <Solvent ñ
九 이소프로필 알코올  소 isopropyl alcohol
Figure imgf000013_0001
실시예 1 내지 3 및 비교예 1 내지 3
Figure imgf000013_0001
Examples 1 to 3 and Comparative Examples 1 to 3
（1） 언더코트층의 제조  (1) Preparation of undercoat layer
하기 표 1의 조성을 갖는 언더코트 조성물을 제조하고, 이를 60 두께의 트리아세틸셀룰로오스
Figure imgf000013_0003
필름의 일 면에
Figure imgf000013_0002
코팅한 다음， 60 °0 에서 2 분간 건조하였다. 상기 건조물에 100 1 /0112의 자외선을 조사하여 4 ］ 두께의 언더코트층을 제조하였다. To prepare an undercoat composition having the composition of Table 1 below, it was 60 acetyl triacetyl cellulose
Figure imgf000013_0003
On one side of the film
Figure imgf000013_0002
After coating, it was dried at 60 ° 0 for 2 minutes. The dried material was irradiated with ultraviolet light of 100 1/011 2 to prepare an undercoat layer having a thickness of 4].
【표 1】 Table 1
Figure imgf000013_0004
Figure imgf000013_0004
（2） 오버코트층의 제조 (2) Preparation of overcoat layer
하기 표 2 및 3의 조성（중량부로 표기）으로 비교예 1 내지 3 및 실시예 2020/004835 1»(：1^1{2019/007093 Comparative Examples 1 to 3 and Examples as shown in Tables 2 and 3 (expressed in parts by weight). 2020/004835 1 »(： 1 ^ 1 {2019/007093
1 내지 3의 오버코트 조성물을 제조하였다. One to three overcoat compositions were prepared.
각 오버코트 조성물을, 상기 (1)에서 제조한 언더코트층 상에 코팅한
Figure imgf000014_0001
에서 2분간 건조하였다. 이때， 실시예 3을 제외하고는
Figure imgf000014_0002
Each overcoat composition was coated on the undercoat layer prepared in the above (1).
Figure imgf000014_0001
Dried for 2 minutes. At this time, except Example 3
Figure imgf000014_0002
로 코팅하였으며, 실시예 3은 #8 11 ｝ · 로 코팅하였다. 상기 건조물에 200 /이2의 자외선을 조사하여 1 내지 2 脚 두께 (단, 실시예 3은 3 내지 4 /패)의 오버코트층을 제조하였다. Coated with # 8 11｝. Irradiated with ultraviolet rays of 200/2 on the dry matter of 1 to 2脚thickness (provided that Example 3 was 3 to 4 / L) was prepared in the overcoat layer.
【표 2】 Table 2
Figure imgf000014_0003
Figure imgf000014_0003
【표 3】 Table 3
Figure imgf000014_0004
Figure imgf000015_0002
Figure imgf000014_0004
Figure imgf000015_0002
* 표 2 및 3에서 괄호 안은 용매를 제외한 고형분 중 해당 성분의 중량%를 의미함. 실시예 4 및 비교예 4 내지 5  * In Tables 2 and 3, the parenthesis means the weight percent of the corresponding component in the solid content excluding the solvent. Example 4 and Comparative Examples 4 to 5
（1） 언더코트층의 제조  (1) Preparation of undercoat layer
하기 표 4의 조성을 갖는 언더코트 조성물을 제조하고, 이를 60 _두께의 트리아세틸셀룰로오스（1쇼（：） 필름의 일 면에
Figure imgf000015_0001
코팅한 다음, 60 에서 2 분간 건조하였다. 상기 건조물에 100 / 의 자외선을 조사하여 4 _두께의 언더코트층을 제조하였다. To prepare an undercoat composition having the composition shown in Table 4, and to the one side of a 60-thick triacetyl cellulose (1 show (：) film)
Figure imgf000015_0001
After coating, it was dried at 60 minutes for 2 minutes. The dry matter was irradiated with 100 / ultraviolet rays to prepare an undercoat layer having a thickness of 4 _.
【표 4】 Table 4
Figure imgf000015_0003
2020/004835 1»(：1^1{2019/007093
Figure imgf000015_0003
2020/004835 1 »(： 1 ^ 1 {2019/007093
(2) 오버코트층의 제조 (2) Preparation of Overcoat Layer
하기 표 5의 조성 (중량부로 표기)으로 실시예 4 및 비교예 5의 오버코트 조성물을 제조하였다.  The overcoat compositions of Example 4 and Comparative Example 5 were prepared with the compositions shown in Table 5 below.
각 오버코트 조성물을, 상기 (1)에서 제조한 언더코트층 상에
Figure imgf000016_0001
로 코팅한 다음,
Figure imgf000016_0002
에서 2분간 건조하였다. 상기 건조물에 200 1 /0112의 자외선을 조사하여 3 내지 4 !두께의 오버코트층을 제조하였다. Each overcoat composition was put on the undercoat layer manufactured by said (1).
Figure imgf000016_0001
Coated with
Figure imgf000016_0002
Dried for 2 minutes. The dried material was irradiated with ultraviolet light of 200/1/01 2 to prepare an overcoat layer having a thickness of 3 to 4!.
또， 오버코트층 없이 기재 및 상기 (1)의 언더코트층 만을 포함하는 자외선 차단 필름을 비교예 4로 하였다. 【표 5]  Moreover, the ultraviolet blocking film containing only the base material and the undercoat layer of said (1) without an overcoat layer was made into the comparative example 4. [Table 5]
Figure imgf000016_0003
Figure imgf000016_0003
* 표 5에서 괄호 안은 용매를 제외한 고형분 중 해당 성분의 중량%를 의미함. 비교예 6 내지 9  * In Table 5, parentheses refer to the weight percent of the corresponding component among the solids except for the solvent. Comparative Examples 6 to 9
(1) 언더코트층의 제조 하기 표 6의 조성으로 비교예 6 및 7， 표 7의 조성으로 비교예 8 및 9의 언더코트 조성물을 제조하였다. (1) Preparation of Undercoat Layer The undercoat compositions of Comparative Examples 6 and 7 and Comparative Examples 8 and 9 were prepared using the compositions shown in Table 6 below.
상기 각 언더코트 조성물을 60 _두께의 트리아세틸셀룰로오스 쇼（：） 필름의 일 면에 #80 11 61^31·로 코팅한 다음, 60 X: 에서 5 분간 건조하여 각각 두께의 언더코트층을 제조하였다. 이를 비교예 6으로 하였다.  Each of the undercoat compositions was coated with # 80 11 61 ^ 31 · on one surface of a 60-thick triacetylcellulose show （：） film, and then dried at 60 ×: for 5 minutes to prepare an undercoat layer having a thickness of It was. This was set as Comparative Example 6.
【표 6】 Table 6
Figure imgf000017_0001
Figure imgf000017_0001
【표 7] [Table 7]
Figure imgf000017_0002
Figure imgf000017_0002
（2） 오버코트층의 제조 하기 표 8의 조성 (중량부로 표기)으로 오버코트 조성물을 제조하고, 상기 (1)에서 제조한 언더코트증 상에
Figure imgf000018_0001
코팅한 다음， 60 °0 에서(2) Preparation of overcoat layer To prepare an overcoat composition by the composition of Table 8 (expressed in parts by weight), and on the undercoat prepared in (1)
Figure imgf000018_0001
After coating, at 60 ° 0
2분간 건조하였다. 상기 건조물에 200 ! /0112의 자외선을 조사하여 3 내지 4 두께의 오버코트층을 제조하였다. It was dried for 2 minutes. 200 in the dry matter! Ultraviolet rays of / 011 2 were irradiated to prepare an overcoat layer having a thickness of 3-4.
【표 8】 Table 8
Figure imgf000018_0003
Figure imgf000018_0003
* 표 7에서 괄호 안은 용매를 제외한 고형분 중 해당 성분의 중량%를 의미함. 실험예  * In Table 7, the parenthesis means the weight percentage of the corresponding component among the solids except the solvent. Experimental Example
1.내광테스트  1. Light resistance test
상기 제조예에서 얻어진 각 자외선 차단 필름을 온도 50 °0 , 복사 조도 0.55
Figure imgf000018_0002
노출시켰다. 2.투과율측정 Each ultraviolet-ray blocking film obtained by the said manufacture example was made into temperature 50 degrees 0, and the irradiance is 0.55.
Figure imgf000018_0002
Exposed. 2. Transmittance Measurement
상기 내광테스트 전 및 후의 자외선 차단 필름의 투과율을 다음과 같은 방법으로 즉정하였다. UV-VIS-NIR spectrophotometer (모델명: Solidspec-3700, 제조사: Shimadzu)를 이용하여 필름이 없는 상태를 베이스 라인으로 설정한 상태에서 언더 및 오버코팅층을 포함한 필름 전체의 투과 스펙트럼을 조사하였다.  The transmittance of the UV blocking film before and after the light test was immediately determined by the following method. The transmission spectrum of the entire film including the under and overcoating layers was examined using a UV-VIS-NIR spectrophotometer (Model name: Solidspec-3700, manufacturer: Shimadzu) with the film free as the baseline.
3.헤이즈 (Hz)측정 3.Haze (Hz) measurement
JIS K 7136 규격에 따라 각 자외선 차단 필름의 헤이즈 값을 측정하였다.  The haze value of each ultraviolet ray blocking film was measured according to JIS K 7136 standard.
4.전광선투과율 (Tt)측정 4. Measurement of total light transmittance (Tt)
JIS K 7361 규격에 따라 각 자외선 차단 필름의 전광선 투과율을 측정하였다.  The total light transmittance of each ultraviolet ray blocking film was measured according to the JIS K 7361 standard.
상기 실험 결과를 하기 표 9 내지 1 1에 나타내었다.  The experimental results are shown in Tables 9 to 1 below.
【표 9] [Table 9]
Figure imgf000019_0001
2020/004835 1»(：1/10公019/007093
Figure imgf000020_0001
Figure imgf000019_0001
2020/004835 1 »(： 1/10 公 019/007093
Figure imgf000020_0001
【표 10】
Figure imgf000020_0002
Table 10
Figure imgf000020_0002
【표 11】 Table 11
Figure imgf000020_0003
2020/004835 1»（：1^1{2019/007093
Figure imgf000020_0003
2020/004835 1 » （： 1 ^ 1 {2019/007093
Figure imgf000021_0002
Figure imgf000021_0002
** 405 11111 투과율 변화 비율 = 내광 테스트 후 405 ^ 투과율/내광 테스트 전 405 11111투과율 실험 결과， 실시예 1 내지 4의 자외선 차단 필름은 내광 테스트 후의 405 1따1파장투과율이 내광 테스트 전의 약 3배 미만으로, 내광 테스트후에도 자외선 차단 효과가 높게 유지되는 것을 확인할 수 있다. 또,실시예의 자외선 차단필름은낮은 헤이즈 값을나타내는 것으로 확인되었다.  ** 405 11111 Transmittance change ratio = 405 after light test 405 ^ Transmittance / before light test 405 11111 Transmittance test results, the UV blocking film of Examples 1 to 4 405 1 ~ 1 wavelength transmittance after the light test is about 3 times before the light test Below, it can be confirmed that even after the light test, the UV blocking effect is maintained high. In addition, it was confirmed that the ultraviolet blocking film of the example exhibited a low haze value.
그러나오버코트층이 없는 비교예 4나， 오버코트층에 자외선 차단무기 입자를 포함하지 않는 비교예 1 및 5의 자외선 차단 필름은 내광 테스트 후 투과율이 현저히 높아져, 자외선 차단 효과가유지되지 못하는 것을 확인할 수 있다. 또한， 비교예 3의 결과로부터, 본 발명의 효과 확보를 위해서는 오버코트층에 포함된 산화아연의 함량이 10 중량% 이상이어야 함을 알 수 있다.  However, Comparative Example 4 without the overcoat layer, or the UV blocking film of Comparative Examples 1 and 5 in which the overcoat layer does not contain UV-blocking inorganic particles, the transmittance is significantly increased after the light resistance test, it can be confirmed that the UV blocking effect is not maintained. . In addition, from the results of Comparative Example 3, it can be seen that the content of zinc oxide contained in the overcoat layer should be 10% by weight or more in order to secure the effect of the present invention.
또한, 비교예 2 및 3을 비교하면, 산화티탄 역시 산화아연과 유사한 수준으로 자외선 차단 효과를 나타내지만, 헤이즈 값이 2배 이상 높아 01止0 소자의 보호용도로사용되기에는부적합함을 알수 있다.  In addition, when comparing Comparative Examples 2 and 3, titanium oxide also exhibits a UV blocking effect at a level similar to zinc oxide, but the haze value is more than two times, it is found that it is not suitable for use as a protective purpose of the 01 止 0 device.
한편, 언더코트층 및 오버코트층의 바인더로서 광경화성 바인더가 아닌 불소계 가소성 수지를사용한 비교예 6 내지 9의 경우, 헤이즈 값이 매우 높게 나타나 01玉0 소자 보호 용도로 부적합하였으며,
Figure imgf000021_0001
바인더를 사용한 비교예 6 및 7의 경우코팅성이 불량하게 나타났다. On the other hand, in Comparative Examples 6 to 9 using fluorine-based plastic resins other than photocurable binders as binders of the undercoat layer and the overcoat layer, the haze value was very high, which was unsuitable for the protection of the 01 HU0 device.
Figure imgf000021_0001
In Comparative Examples 6 and 7 using a binder, the coating property was poor.

Claims

2020/004835 1»（：1 1{2019/007093 【청구의 범위】 2020/004835 1 »（： 1 1 {2019/007093 【Scope of claim】
【청구항 1】  [Claim 1]
고분자기재;  Polymer substrates;
자외선 흡수 유기 염료 및 광경화성 바인더 수지를 포함하는 언더코트층; 및  An undercoat layer comprising an ultraviolet absorbing organic dye and a photocurable binder resin; And
자외선 차단 무가 입자 및 광경화성 바인더 수지를 포함하는 오버코트층이 순차로 적층된 자외선 차단필름으로서,  An ultraviolet blocking film in which an overcoat layer containing ultraviolet ray-free particles and a photocurable binder resin is sequentially laminated,
하기의 내광 테스트 실시 전과 후에 11\^-¥犯 - 11 스펙트로포토미터를 이용하여 405 11111 파장의 투과율을 측정하였을 때, 내광 테스트 후의 투과율이 내광 테스트 전의 투과율의 3배 이하인，자외선 차단필름.  The ultraviolet ray blocking film whose transmittance after the light resistance test is 3 times or less than the transmittance before the light resistance test when the transmittance of 405 11111 wavelength is measured using a 11 \ ^-¥ 犯 -11 spectrophotometer before and after the following light test.
[내광테스트 방법]  [Light resistance test method]
온도 50 °0, 복사 조도 0.55 \¥/1112, 파장 290 내지 400 11111
Figure imgf000022_0001
하에서 48 시간동안노출시킴. Temperature 50 ° 0, radiance roughness 0.55 \ ¥ / 111 2 , wavelength 290 to 400 11111
Figure imgf000022_0001
Exposure for 48 hours.
【청구항 2]  [Claim 2]
제 1항에 있어서,  The method of claim 1,
상기 내광 테스트 전， 상기
Figure imgf000022_0002
미터를 이용하여 측정한 430 !파1파장의 투과율이 60% 이상인,자외선 차단필름. Before the light resistance test
Figure imgf000022_0002
UV-blocking film with a transmittance of 430! Wavelength 1 wavelength of 60% or more, measured using a meter.
【청구항 3】  [Claim 3]
제 1항에 있어서,  The method of claim 1,
_!13 1＜：7136법에 따라측정된 헤이즈 값이 1.5 이하인,자외선 차단 필름. _! 13 The ultraviolet blocking film whose haze value measured by the method of 1 <: 7136 is 1.5 or less.
【청구항 4] [Claim 4]
제 1항에 있어서,  The method of claim 1,
상기 자외선 흡수 유기 염료는 벤조트리아졸계 화합물， 트라이아진계 화합물, 에스터계 화합물, 인돌계 화합물 및 피리미딘계 화합물로 이루어지는 군에서 선택되는 1종 이상인,자외선 차단필름.  The ultraviolet absorbing organic dye is at least one member selected from the group consisting of benzotriazole-based compound, triazine-based compound, ester-based compound, indole-based compound and pyrimidine-based compound, UV blocking film.
【청구항 5]  [Claim 5]
제 1항에 있어서，  The method of claim 1,
상기 자외선 흡수 유기 염료는 언더코트층 총 중량의 1 내지 10 중량%로포함되는,자외선 차단필름.  The ultraviolet absorbing organic dye is included in 1 to 10% by weight of the total weight of the undercoat layer, UV blocking film.
【청구항 6】 2020/004835 1»（：1^1{2019/007093 [Claim 6] 2020/004835 1 »（： 1 ^ 1 {2019/007093
제 1항에 있어서, The method of claim 1,
상기 자외선 차단 무기 입자의 굴절률은 1.8 내지 2.1인, 자외선 차단 필름.  The refractive index of the ultraviolet blocking inorganic particles is 1.8 to 2.1, the UV blocking film.
【청구항 7】  [Claim 7]
제 1항에 있어서,  The method of claim 1,
상기 자외산차단 무기 입자의 평균 입경은 20 내지 200 인, 자외선 차단 필름.  The ultraviolet particle blocking average particle diameter of the ultraviolet-blocking inorganic particles is 20 to 200.
【청구항 8】  [Claim 8]
제 1항에 있어서，  The method of claim 1,
상기 자외선 차단 무기 입자는 산화아연인, 자외선 차단 필름.  The ultraviolet blocking inorganic particles are zinc oxide, UV blocking film.
【청구항 9】  [Claim 9]
제 1항에 있어서,  The method of claim 1,
상기 자외선 차단 무기 입자는 오버코트층 총 중량의 10 내지 50 중량%로 포함되는, 자외선 차단 필름.  The sunscreen inorganic particles are contained in 10 to 50% by weight of the total weight of the overcoat layer, the sunscreen film.
【청구항 10】  [Claim 10]
제 1항에 있어서,  The method of claim 1,
상기 광경화성 바인더 수지는 우레탄 아크릴레이트 올리고머， 에폭사이드 아크릴레이트 올리고머 , 폴리에스테르 아크릴레이트 및 폴리에테르 아크릴레이트로 이루어진 반응성 아크릴레이트 올리고머 군; 및  The photocurable binder resin is a reactive acrylate oligomer group consisting of urethane acrylate oligomer, epoxide acrylate oligomer, polyester acrylate and polyether acrylate; And
트리메틸올프로판 트리（메타）아크릴레이트, 펜타에리트리톨 디（메타）아크릴레이트, 펜타에리트리톨 트리（메타）아크릴레이트, 펜타에리트리톨 테트라（메타）아크릴레이트, 디펜타에리트리톨 트리（메타）아크릴레이트， 디펜타에리트리톨 테트라（메타）아크릴레이트, 디펜타에리트리톨 펜타（메타）아크릴레이트, 디펜타에리트리톨 핵사（메타）아크릴레이트 및 글리세린 프로폭실화 트리아크릴레이트로 이루어진 다관능성 （메트）아크릴레이트계 모노머 군;에서 선택된 1종 이상의 광중합성 화합물의 중합체인, 자외선 차단 필름.  Trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate , Polyfunctional (meth) acrylate consisting of dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol nucleated (meth) acrylate and glycerin propoxylated triacrylate A sunscreen film, which is a polymer of at least one photopolymerizable compound selected from the group of monomers.
【청구항 11】  [Claim 11]
제 1항에 있어서,  The method of claim 1,
상기 언더코트층의 두께는 1 내지 10 111인， 자외선 차단 필를. 2020/004835 1»（：1/10公019/007093 The undercoat layer has a thickness of 1 to 10 111, the sunscreen peel. 2020/004835 1 »（： 1/10 公 019/007093
【청구항 12】 [Claim 12]
제 1항에 있어서，  The method of claim 1,
상기 오버코트층의 두께는 1 내지 5 11111인，자외선 차단 필름.  The thickness of the overcoat layer is 1 to 5 11111, UV blocking film.
PCT/KR2019/007093 2018-06-29 2019-06-12 Ultraviolet blocking film WO2020004835A1 (en)

Priority Applications (4)

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EP19816186.1A EP3627196B1 (en) 2018-06-29 2019-06-12 Ultraviolet blocking film
US16/631,525 US11549025B2 (en) 2018-06-29 2019-06-12 Film for blocking ultraviolet rays
CN201980003073.7A CN110876273B (en) 2018-06-29 2019-06-12 Film for blocking ultraviolet rays
JP2020500825A JP6966148B2 (en) 2018-06-29 2019-06-12 UV blocking film

Applications Claiming Priority (4)

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KR20180075903 2018-06-29
KR10-2018-0075903 2018-06-29
KR1020190068578A KR102131995B1 (en) 2018-06-29 2019-06-11 Uv-cut film
KR10-2019-0068578 2019-06-11

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JP2012234164A (en) * 2011-04-22 2012-11-29 Nitto Denko Corp Optical laminate
KR20170004940A (en) * 2016-12-29 2017-01-11 롯데케미칼 주식회사 Uv-cut coating compostion and uv-cut film using same
JP2017054506A (en) * 2015-09-07 2017-03-16 積水化学工業株式会社 Light-transmitting conductive film
KR20170112554A (en) * 2016-03-31 2017-10-12 주식회사 엘지화학 Ultraviolet blocking film
KR20180031598A (en) * 2016-09-20 2018-03-28 주식회사 엘지화학 Optical film with high slip property and excellent property of blocking UV light, and polarizing plate comprising the same

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JP2012234164A (en) * 2011-04-22 2012-11-29 Nitto Denko Corp Optical laminate
JP2017054506A (en) * 2015-09-07 2017-03-16 積水化学工業株式会社 Light-transmitting conductive film
KR20170112554A (en) * 2016-03-31 2017-10-12 주식회사 엘지화학 Ultraviolet blocking film
KR20180031598A (en) * 2016-09-20 2018-03-28 주식회사 엘지화학 Optical film with high slip property and excellent property of blocking UV light, and polarizing plate comprising the same
KR20170004940A (en) * 2016-12-29 2017-01-11 롯데케미칼 주식회사 Uv-cut coating compostion and uv-cut film using same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111789975A (en) * 2020-07-29 2020-10-20 固安翌光科技有限公司 Disinfection and sterilization device in vehicle

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