WO2016032173A1 - Hard coating composition and anti-scattering film using same - Google Patents

Hard coating composition and anti-scattering film using same Download PDF

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Publication number
WO2016032173A1
WO2016032173A1 PCT/KR2015/008765 KR2015008765W WO2016032173A1 WO 2016032173 A1 WO2016032173 A1 WO 2016032173A1 KR 2015008765 W KR2015008765 W KR 2015008765W WO 2016032173 A1 WO2016032173 A1 WO 2016032173A1
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hard coating
coating composition
weight
solvents
film
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PCT/KR2015/008765
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French (fr)
Korean (ko)
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홍주희
조홍관
김장순
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(주)엘지하우시스
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • C09D7/20—Diluents or solvents
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the present invention relates to a hard coating composition and an anti-scattering film having excellent surface hardness and optical properties using the same.
  • the structure of a touch screen panel applied to a mobile phone, etc. has tended to be converted from a conventional multilayer structure to an integrated structure. This is due to the fact that the integrated touch screen panel structure does not have to use a transparent electrode (ITO) film having a high cost ratio.
  • ITO transparent electrode
  • the product can be made slimmer and the visible light transmittance can be increased. In spite of these advantages, the problem that the cover glass on the display surface side is broken by drop impact or the like frequently occurs.
  • a scattering prevention film is inserted between the panel and the cover glass to prevent scattering of the cover glass.
  • Such anti-scattering films generally include a structure of a hard coat layer / substrate / adhesive layer, and the hard coat layer requires surface hardness and optical properties.
  • the present invention is ultraviolet curable acrylate resin; Inorganic nanoparticles; Photoinitiators; And a mixed solvent, wherein the mixed solvent comprises a ketone solvent and an alcohol solvent, and a scattering prevention film having excellent surface hardness and optical properties using the same.
  • the present invention is ultraviolet curable acrylate resin; Inorganic nanoparticles; Photoinitiators; And a mixed solvent, wherein the mixed solvent provides a hard coating composition comprising a ketone solvent and an alcohol solvent.
  • the polarity of the mixed solvent may be 3 to 5.
  • the mixed solvent may further include one or more other solvents selected from the group consisting of amide solvents, hydrocarbon solvents, ester solvents, ether solvents and glycol solvents.
  • the mixed solvent may be characterized in that it comprises a ketone solvent 60-80% by weight, alcohol solvent 15-35% by weight and other solvents 5-10% by weight.
  • the photoinitiator may be 1 to 15 parts by weight.
  • the composition may form a network structure by inorganic nanoparticles.
  • a transparent film In one embodiment of the present invention, a transparent film; And a hard coating layer formed on the transparent film, wherein the hard coating layer is formed of the hard coating composition.
  • the hard coating layer may have a thickness of about 0.1 ⁇ m to about 1 ⁇ m.
  • the pencil hardness of the hard coat layer may be 1H to 9H.
  • the transmittance of the hard coat layer may be 90% to 100%.
  • It may further include a pressure-sensitive adhesive layer formed on the lower portion of the transparent film.
  • It may further include a release film formed on the lower portion of the adhesive layer.
  • Hard coating composition according to the invention is an ultraviolet curable acrylate resin; Inorganic nanoparticles; Photoinitiators; And a mixed solvent, wherein the mixed solvent includes a ketone solvent and an alcohol solvent, and by forming a network structure with inorganic nanoparticles, the hard coating layer formed therefrom may have a thin surface.
  • the scattering prevention film which is excellent in hardness and an optical characteristic can be manufactured.
  • Example 1 is a scanning electron microscope (SEM) photograph of a hard coat layer in the scattering prevention film according to Example 1 and Comparative Example 1 of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing a scattering prevention film according to an embodiment of the present invention.
  • any configuration formed on the “top (or bottom)” of the substrate not only means that any configuration is formed in contact with the top (or bottom) of the substrate, but also on the substrate and the substrate (or It is not limited to not including any other configuration between any of the configurations formed under).
  • the present invention is ultraviolet curable acrylate resin; Inorganic nanoparticles; Photoinitiators; And a mixed solvent, wherein the mixed solvent provides a hard coating composition comprising a ketone solvent and an alcohol solvent.
  • the hard coating composition is to be used for the hard coating layer of the scattering prevention film, UV curable acrylate resin; Inorganic nanoparticles; Photoinitiators; And mixed solvents.
  • the hard coating composition is characterized by forming a network structure by the inorganic nanoparticles due to a certain degree of polarity of the mixed solvent, even if the formed hard coating layer has a thin thickness is excellent in surface hardness.
  • the UV-curable acrylate resin includes at least two or more, preferably 2 to 15 functional groups to contribute to the improvement of hardness and the prevention of wrinkles. At this time, the addition effect may be insufficient when the number of functional groups contained in the ultraviolet curable acrylate resin is less than two, on the other hand, when the number of functional groups exceeds 15, wrinkles may occur.
  • the ultraviolet curable acrylate resin may be added in 10 to 70 parts by weight based on 100 parts by weight of the total composition. At this time, when the ultraviolet curable acrylate resin is less than 10 parts by weight, the addition effect may be insufficient, and when the ultraviolet curable acrylate resin exceeds 70 parts by weight, the functionality of the coating liquid may not be given.
  • the inorganic nanoparticles refer to inorganic particles of nano size, and to secure hardness and curl.
  • the inorganic nanoparticles may be one or more selected from the group consisting of silica, alumina, zirconia, zeolite, titanium oxide, and combinations thereof, more preferably silica in terms of performance and cost, but is not limited thereto.
  • the 50% cumulative mass particle size distribution diameter in the particle distribution in the composition of the inorganic nanoparticles is D50, 5nm ⁇ D50 ⁇ 20nm, the inorganic nanoparticles are not completely dispersed, and the inorganic nanoparticles are dispersed. It is possible to form the network structure in the composition without being nor agglomerated.
  • the inorganic nanoparticles may be added in an amount of 1 to 30 parts by weight based on 100 parts by weight of the total composition. In this case, when the inorganic nanoparticles are less than 1 part by weight, the addition effect may be insufficient, and when the inorganic nanoparticles exceed 30 parts by weight, the coating liquid may not be provided with the functionality.
  • the photoinitiator is excited by ultraviolet rays and serves to initiate photopolymerization.
  • Known photoinitiators can be used as the photoinitiator, benzophenone; Substituted benzophenones; Acetophenone; Substituted acetophenones; Benzoin; Benzoin alkyl esters; Xanthones; Substituted xanthones; Phosphine oxide; Diethoxy-acetophenone; Benzoin methyl ether; Benzoin ethyl ether; Benzoin isopropyl ether; Diethoxyxanthone; Chloro-thio-xanthone; N-methyl diethanol-amine-benzophenone; 2-hydroxy-2-methyl-1-phenyl-propan-1-one; 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone; And it is preferable to use
  • the photoinitiator may be added in 1 to 15 parts by weight based on 100 parts by weight of the total composition. At this time, when the photoinitiator is less than 1 part by weight, there is a problem that the curing reaction time is long, and when the photoinitiator exceeds 15 parts by weight, there is a problem that the unreacted photoinitiator may remain as an impurity.
  • the mixed solvent is characterized in that it comprises a ketone solvent and an alcohol solvent.
  • Ketone solvents include methyl ethyl ketone, methyl isobutyl ketone, 1-methyl-2-pyrrolidinone, cyclohexanone or acetone
  • alcohol solvents include propylene glycol monomethyl ether, methanol, ethanol, and isopropyl. Alcohol or butyl alcohol and the like.
  • the polarity index (Polarity Index) of the mixed solvent may be 3 to 5. At this time, when the polarity of the mixed solvent is less than 3, there is a problem that the polarity is too low to completely disperse the inorganic nanoparticles to form a network structure by the inorganic nanoparticles, when the polarity of the mixed solvent exceeds 5, The polarity is too high, there is a problem that the inorganic nanoparticles are not dispersed and agglomerated.
  • the mixed solvent may further include one or more other solvents selected from the group consisting of amide solvents, hydrocarbon solvents, ester solvents, ether solvents and glycol solvents.
  • Amide solvents include N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or formamide
  • hydrocarbon solvents include aliphatic hydrocarbons such as hexane or heptane.
  • Solvents and aromatic hydrocarbon solvents such as anisole, mesitylene or xylene, and ester solvents include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -valerolactone, or ⁇ -caprolactone, and the like, and ether solvents include tetrahydrofuran, 2-methyltetrahydrofuran or dibutyl ether.
  • the mixed solvent includes a ketone solvent, an alcohol solvent, and other solvents
  • the mixed solvent includes 60 to 80 wt% of the ketone solvent, 15 to 35 wt% of the alcohol solvent, and 5 to 10 wt% of the other solvent.
  • the mixed solvent may have a certain degree of polarity to induce proper dispersion of the inorganic nanoparticles, thereby forming a network structure in the hard coating composition.
  • the hard coating composition may further add additives as long as it can maintain hard coating properties for use as a hard coating layer in the anti-scattering film, for example, dyes, fillers, reinforcing agents, flame retardants, Plasticizers, lubricants, stabilizers (antioxidants, UV absorbers, heat stabilizers, etc.), release agents, antistatic agents, surfactants, dispersants, flow regulators, leveling agents, antifoaming agents, surface modifiers, low stress agents (silicone oil ), Silicone rubber, various plastic powders, etc.), heat resistance improving agent, etc. can be added further.
  • additives for example, dyes, fillers, reinforcing agents, flame retardants, Plasticizers, lubricants, stabilizers (antioxidants, UV absorbers, heat stabilizers, etc.), release agents, antistatic agents, surfactants, dispersants, flow regulators, leveling agents, antifoaming agents, surface modifiers, low stress agents (silicone oil ), Silicone rubber, various plastic
  • the present invention is a transparent film; And a hard coating layer formed on the transparent film, wherein the hard coating layer is formed of the hard coating composition.
  • FIG. 2 is a cross-sectional view schematically showing a scattering prevention film according to an embodiment of the present invention.
  • the anti-scattering film includes a hard coating layer 120 and a transparent film 110 formed from above, and an adhesive layer 130 which is sequentially formed below the transparent film 110. And a release film 140 may be further included.
  • the transparent film 110 is excellent in strength so as to prevent the scattering of glass, such as tempered glass of the touch screen panel, and transmittance is at least 90% or more, preferably so as not to impair optical characteristics. It may be a film having excellent transparency of 90 to 100%.
  • polyethylene terephthalate PET
  • polyethylene naphthalate PEN
  • polyethersulfone PE
  • PC polycarbonate
  • polyethylene polyethylene
  • PE polyethylene
  • PP polypropylene
  • the hard coating layer 120 is formed on the transparent film 110, characterized in that formed with the hard coating composition. At this time, the hard coating composition is as described above.
  • the anti-scattering film composition forms a network structure by inorganic nanoparticles, so that the hard coating layer 120 formed therefrom is excellent in surface hardness and optical properties even though it has a thin thickness.
  • the hard coating layer 120 is formed by coating the hard coating composition on the upper surface of the transparent film.
  • a coating method a spin coating method, a spray coating method, a cast method, a bar coating method may be used. (bar coating) method, roll to roll coating method, gravure coating method, dipping method and the like.
  • the roll-to-roll coating method is most preferred in terms of productivity, but is not limited thereto.
  • the hard coating layer 120 preferably has a thickness of 0.1 ⁇ m to 1 ⁇ m, more preferably 0.1 ⁇ m to 0.8 ⁇ m, and even more preferably 0.1 ⁇ m to 0.7 ⁇ m, but is not limited thereto. Even if the hard coating layer 120 has a thin thickness as described above, the hard coating layer 120 can secure the surface hardness and optical properties due to the network structure by the inorganic nanoparticles. In this case, when the thickness of the hard coating layer 120 is too thin, there is a problem in hard coating properties, when the thickness of the hard coating layer 120 is too thick, there is a problem of a cost increase due to hard coating.
  • the pencil hardness of the hard coat layer 120 may be 1H to 9H.
  • the hard coating layer 120 may implement excellent wear resistance by having a pencil hardness in the above range.
  • the transmittance of the hard coat layer 120 may be 90% to 100%. Since the hard coating layer 120 has a transmittance in the above range, it is possible to implement high optical properties by maintaining a high level of transparency.
  • the adhesive layer 120 may be formed under the transparent film 110, and the adhesive layer 120 may be further formed to be attached to a touch screen panel, which is an adhered surface.
  • the adhesive layer 130 is formed by coating directly on the lower surface of the transparent film 110, or the adhesive layer 130 is coated on the upper surface of the release film 140 in advance, then the transparent film ( It may be formed by laminating the release film 140 on the lower surface of the (110).
  • the pressure-sensitive adhesive layer 130 may use any known pressure-sensitive adhesive such as an acrylic pressure sensitive adhesive, a silicone pressure sensitive adhesive, and an acid-free hydroxyl-containing pressure sensitive adhesive.
  • the adhesive layer 130 may include at least one selected from these.
  • the acid-free hydroxyl-containing pressure sensitive adhesive may include known photoinitiators such as 2-ethylhexyl acrylate, hydroxyethyl acrylate, and benzophenone, and may include additives. It may further include.
  • the additive is for improving the physical properties of the pressure-sensitive adhesive, and known curing accelerators, plasticizers, dispersants, surfactants, antistatic agents, antifoaming agents, leveling agents and the like can be used without limitation.
  • the release film 140 may be formed under the adhesive layer 130, and is to protect the adhesive layer 130.
  • release film 140 various films such as polyethylene terephthalate (PET) film may be used, and it is preferable to use a release PET film having a release force of about 10 g / in so as to easily release the film. It is not limited to this.
  • PET polyethylene terephthalate
  • a mixed solvent containing 50 parts by weight of methyl ethyl ketone (MEK) as a ketone solvent, 45 parts by weight of propylene glycol monomethyl ether (PGME) as an alcohol solvent and 5 parts by weight of N, N-dimethylacetamide as an amide solvent is prepared. It was.
  • a hard coating composition was formed to form a network structure, including 30 parts by weight of an ultraviolet curable acrylate resin, 20 parts by weight of silica having a size of about 10 nm, and 10 parts by weight of benzophenone, based on the prepared mixed solvent and 100 parts by weight of the total composition. .
  • Example 1 Except for using methyl isobutyl ketone (MIBK) alone as a ketone solvent instead of a mixed solvent in the same manner as in Example 1 was prepared a shatterproof film comprising a hard coating composition and a hard coating layer of about 1.5 ⁇ m thickness ( See FIG. 1 (b)).
  • MIBK methyl isobutyl ketone
  • Example 1 Except for using methyl isobutyl ketone (MIBK) alone as a ketone solvent instead of a mixed solvent in the same manner as in Example 1 was prepared a shatterproof film comprising a hard coating composition and a hard coating layer of about 500nm thickness.
  • MIBK methyl isobutyl ketone
  • Pencil hardness and visible light transmittance optical properties and measurement results of the scattering prevention film prepared according to Example 1 and Comparative Examples 1 and 2 are shown in Table 1 below.
  • Pencil hardness was measured using a 750 g weight in accordance with JIS K5600-5-4, and visible light transmittance was measured using a spectrophotometer (Konica Minolta, CM-5) in accordance with JIS K7361-1.
  • the hard coating composition according to Example 1 forms a network structure by the inorganic nanoparticles due to the mixed solvent, even though the hard coating layer formed therein has a significantly thinner thickness than Comparative Example 1, the pencil hardness It was confirmed that the excellent light transmittance was maintained while the equivalent level. On the other hand, in the case of the comparative example 2, pencil hardness fell and it was confirmed that it is not suitable as a scattering prevention film.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

The present invention relates to a hard coating composition and an anti-scattering film using same, the hard coating composition comprising: a UV-curable acrylate resin; inorganic nanoparticles; a photoinitiator; and a mixed solvent, wherein the mixed solvent includes a ketone-based solvent and an alcohol-based solvent.

Description

하드코팅 조성물 및 이를 이용한 비산 방지 필름Hard Coating Composition and Shatter Proof Film Using the Same
본 발명은 하드코팅 조성물 및 이를 이용한 표면 경도 및 광학적 특성이 우수한 비산 방지 필름에 관한 것이다. The present invention relates to a hard coating composition and an anti-scattering film having excellent surface hardness and optical properties using the same.
휴대폰 등에 적용되는 터치 스크린 패널의 구조는 종래 다층형 구조에서 일체형 구조로 전환되는 추세에 있다. 이는 일체형 터치스크린 패널 구조는 원가 비중이 높은 투명전극(ITO) 필름을 사용하지 않아도 되는 점에 기인한다.BACKGROUND OF THE INVENTION The structure of a touch screen panel applied to a mobile phone, etc., has tended to be converted from a conventional multilayer structure to an integrated structure. This is due to the fact that the integrated touch screen panel structure does not have to use a transparent electrode (ITO) film having a high cost ratio.
일체형 터치스크린 패널 구조를 통하여, 제품의 슬림화가 가능하며 가시광선 투과율을 높일 수 있다. 이 같은 장점에도 불구하고 낙하 충격 등에 의해 표시면측의 커버 유리가 깨지는 문제가 빈번히 발생하고 있다.Through the integrated touch screen panel structure, the product can be made slimmer and the visible light transmittance can be increased. In spite of these advantages, the problem that the cover glass on the display surface side is broken by drop impact or the like frequently occurs.
이에 따라, 휴대기기의 유리 파손시 발생하는 파편에 대한 안정성을 강화하기 위하여, 패널과 커버 유리 사이에 비산 방지 필름을 삽입하여 커버 유리의 비산을 방지하고 있다.Accordingly, in order to enhance stability to fragments generated when glass breakage occurs in the portable device, a scattering prevention film is inserted between the panel and the cover glass to prevent scattering of the cover glass.
이러한 비산 방지 필름은 하드코팅층/기재/점착층의 구조를 포함하는 것이 일반적이며, 그 특성상 하드코팅층에 표면 경도 및 광학적 특성이 요구된다.Such anti-scattering films generally include a structure of a hard coat layer / substrate / adhesive layer, and the hard coat layer requires surface hardness and optical properties.
본 발명은 자외선 경화형 아크릴레이트 수지; 무기 나노입자; 광개시제; 및 혼합 용제를 포함하고, 상기 혼합 용제는 케톤계 용제 및 알코올계 용제를 포함하는 것을 특징으로 하는 하드코팅 조성물 및 이를 이용한 표면 경도 및 광학적 특성이 우수한 비산 방지 필름을 제공하고자 한다.The present invention is ultraviolet curable acrylate resin; Inorganic nanoparticles; Photoinitiators; And a mixed solvent, wherein the mixed solvent comprises a ketone solvent and an alcohol solvent, and a scattering prevention film having excellent surface hardness and optical properties using the same.
그러나, 본 발명이 이루고자 하는 기술적 과제는 이상에서 언급한 과제에 제한되지 않으며, 언급되지 않은 또 다른 과제들은 아래의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.However, the technical problem to be achieved by the present invention is not limited to the above-mentioned problem, another task that is not mentioned will be clearly understood by those skilled in the art from the following description.
본 발명은 자외선 경화형 아크릴레이트 수지; 무기 나노입자; 광개시제; 및 혼합 용제를 포함하고, 상기 혼합 용제는 케톤계 용제 및 알코올계 용제를 포함하는 것을 특징으로 하는 하드코팅 조성물을 제공한다.The present invention is ultraviolet curable acrylate resin; Inorganic nanoparticles; Photoinitiators; And a mixed solvent, wherein the mixed solvent provides a hard coating composition comprising a ketone solvent and an alcohol solvent.
상기 혼합 용제의 극성도는 3 내지 5일 수 있다.The polarity of the mixed solvent may be 3 to 5.
상기 혼합 용제는 아마이드계 용제, 탄화수소계 용제, 에스테르계 용제, 에테르계 용제 및 글리콜계 용제로 이루어진 군으로부터 선택된 하나 이상의 기타 용제를 더 포함하는 것을 특징으로 할 수 있다.The mixed solvent may further include one or more other solvents selected from the group consisting of amide solvents, hydrocarbon solvents, ester solvents, ether solvents and glycol solvents.
상기 혼합 용제는 케톤계 용제 60~80 중량%, 알코올계 용제 15~35 중량% 및 기타 용제 5~10 중량%를 포함하는 것을 특징으로 할 수 있다.The mixed solvent may be characterized in that it comprises a ketone solvent 60-80% by weight, alcohol solvent 15-35% by weight and other solvents 5-10% by weight.
상기 무기 나노입자의, 50% 누적질량 입자크기 분포 직경을 D50이라 할 때, 5nm<D50<20nm일 수 있다.When the 50% cumulative mass particle size distribution diameter of the inorganic nanoparticles is D50, 5nm <D50 <20nm.
상기 조성물 총 100 중량부에 대하여, 자외선 경화형 아크릴레이트 수지 10~70 중량부; 무기 나노입자 1~30 중량부; 광개시제 1~15 중량부일 수 있다.10 to 70 parts by weight of the ultraviolet curable acrylate resin based on 100 parts by weight of the composition; 1 to 30 parts by weight of inorganic nanoparticles; The photoinitiator may be 1 to 15 parts by weight.
상기 조성물은 무기 나노입자에 의한 네트워크 구조를 형성할 수 있다.The composition may form a network structure by inorganic nanoparticles.
본 발명의 일 구현예로, 투명 필름; 및 상기 투명 필름의 상부에 형성된 하드코팅층을 포함하고, 상기 하드코팅층은 상기 하드코팅 조성물로 형성된 것인 비산 방지 필름을 제공한다.In one embodiment of the present invention, a transparent film; And a hard coating layer formed on the transparent film, wherein the hard coating layer is formed of the hard coating composition.
상기 하드코팅층의 두께는 0.1㎛ 내지 1㎛일 수 있다.The hard coating layer may have a thickness of about 0.1 μm to about 1 μm.
상기 하드코팅층의 연필 경도는 1H 내지 9H일 수 있다.The pencil hardness of the hard coat layer may be 1H to 9H.
상기 하드코팅층의 투과율은 90% 내지 100%일 수 있다.The transmittance of the hard coat layer may be 90% to 100%.
상기 투명 필름의 하부에 형성된 점착층을 더 포함할 수 있다.It may further include a pressure-sensitive adhesive layer formed on the lower portion of the transparent film.
상기 점착층의 하부에 형성된 이형 필름을 더 포함할 수 있다.It may further include a release film formed on the lower portion of the adhesive layer.
본 발명에 따른 하드코팅 조성물은 자외선 경화형 아크릴레이트 수지; 무기 나노입자; 광개시제; 및 혼합 용제를 포함하고, 상기 혼합 용제는 케톤계 용제 및 알코올계 용제를 포함하는 것을 특징으로 하는바, 무기 나노입자에 의한 네트워크 구조를 형성함으로써, 이로 형성된 하드코팅층은 얇은 두께를 가지더라도, 표면 경도 및 광학적 특성이 우수한 비산 방지 필름을 제조할 수 있다.Hard coating composition according to the invention is an ultraviolet curable acrylate resin; Inorganic nanoparticles; Photoinitiators; And a mixed solvent, wherein the mixed solvent includes a ketone solvent and an alcohol solvent, and by forming a network structure with inorganic nanoparticles, the hard coating layer formed therefrom may have a thin surface. The scattering prevention film which is excellent in hardness and an optical characteristic can be manufactured.
도 1은 본 발명의 실시예 1 및 비교예 1에 따른 비산 방지 필름에서 하드코팅층의 주사전자현미경(SEM) 사진이다.1 is a scanning electron microscope (SEM) photograph of a hard coat layer in the scattering prevention film according to Example 1 and Comparative Example 1 of the present invention.
도 2는 본 발명의 일 구현예에 따른 비산 방지 필름을 개략적으로 나타낸 단면도이다.2 is a cross-sectional view schematically showing a scattering prevention film according to an embodiment of the present invention.
이하, 첨부한 도면을 참고로 하여 본 발명의 실시예에 대하여 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 상세히 설명한다. 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.
본 발명을 명확하게 설명하기 위해서 설명과 관계없는 부분은 생략하였으며, 명세서 전체를 통하여 동일 또는 유사한 구성요소에 대해서는 동일한 참조 부호를 붙이도록 한다.In order to clearly describe the present invention, parts irrelevant to the description are omitted, and like reference numerals designate like elements throughout the specification.
도면에서 여러 층 및 영역을 명확하게 표현하기 위하여 두께를 확대하여 나타내었다. 그리고 도면에서, 설명의 편의를 위해, 일부 층 및 영역의 두께를 과장되게 나타내었다.In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. In the drawings, the thicknesses of layers and regions are exaggerated for clarity.
이하에서 기재의 “상부 (또는 하부)”에 임의의 구성이 형성된다는 것은, 임의의 구성이 상기 기재의 상면 (또는 하면)에 접하여 형성되는 것을 의미할 뿐만 아니라, 상기 기재와 기재 상에 (또는 하에) 형성된 임의의 구성 사이에 다른 구성을 포함하지 않는 것으로 한정하는 것은 아니다.In the following, any configuration formed on the “top (or bottom)” of the substrate not only means that any configuration is formed in contact with the top (or bottom) of the substrate, but also on the substrate and the substrate (or It is not limited to not including any other configuration between any of the configurations formed under).
하드코팅 조성물Hard Coating Composition
본 발명은 자외선 경화형 아크릴레이트 수지; 무기 나노입자; 광개시제; 및 혼합 용제를 포함하고, 상기 혼합 용제는 케톤계 용제 및 알코올계 용제를 포함하는 것을 특징으로 하는 하드코팅 조성물을 제공한다.The present invention is ultraviolet curable acrylate resin; Inorganic nanoparticles; Photoinitiators; And a mixed solvent, wherein the mixed solvent provides a hard coating composition comprising a ketone solvent and an alcohol solvent.
즉, 상기 하드코팅 조성물은 비산 방지 필름의 하드코팅층에 이용되기 위한 것으로, 자외선 경화형 아크릴레이트 수지; 무기 나노입자; 광개시제; 및 혼합 용제를 포함한다.That is, the hard coating composition is to be used for the hard coating layer of the scattering prevention film, UV curable acrylate resin; Inorganic nanoparticles; Photoinitiators; And mixed solvents.
상기 하드코팅 조성물은 혼합 용제의 일정 극성도로 인하여 무기 나노입자에 의한 네트워크 구조를 형성하는 것을 특징으로 하는바, 이로 형성된 하드코팅층이 얇은 두께를 가지더라도 표면 경도가 우수하다. The hard coating composition is characterized by forming a network structure by the inorganic nanoparticles due to a certain degree of polarity of the mixed solvent, even if the formed hard coating layer has a thin thickness is excellent in surface hardness.
상기 자외선 경화형 아크릴레이트 수지는 적어도 2개 이상, 바람직하게 2~15개의 관능기를 포함하여 경도 향상 및 주름(Curl) 방지에 기여한다. 이때, 자외선 경화형 아크릴레이트 수지에 포함된 관능기의 수가 2개 미만이면 그 첨가 효과가 불충분할 수 있고, 반면에, 관능기의 수가 15개를 초과하면 주름 발생을 초래할 수 있다.The UV-curable acrylate resin includes at least two or more, preferably 2 to 15 functional groups to contribute to the improvement of hardness and the prevention of wrinkles. At this time, the addition effect may be insufficient when the number of functional groups contained in the ultraviolet curable acrylate resin is less than two, on the other hand, when the number of functional groups exceeds 15, wrinkles may occur.
또한, 상기 자외선 경화형 아크릴레이트 수지는 조성물 총 100 중량부에 대하여 10~70 중량부로 첨가될 수 있다. 이때, 자외선 경화형 아크릴레이트 수지가 10 중량부 미만일 경우, 그 첨가 효과가 불충분할 수 있고, 자외선 경화형 아크릴레이트 수지가 70 중량부를 초과하는 경우, 코팅액이 가진 기능성이 부여되지 않을 수 있다.In addition, the ultraviolet curable acrylate resin may be added in 10 to 70 parts by weight based on 100 parts by weight of the total composition. At this time, when the ultraviolet curable acrylate resin is less than 10 parts by weight, the addition effect may be insufficient, and when the ultraviolet curable acrylate resin exceeds 70 parts by weight, the functionality of the coating liquid may not be given.
상기 무기 나노입자는 나노 크기의 무기 입자를 의미하는 것으로, 경도 및 주름(Curl)을 확보하기 위한 것이다. 상기 무기 나노입자는 실리카, 알루미나, 지르코니아, 제올라이트, 티타늄 산화물 및 이들의 조합으로 이루어진 군으로부터 선택된 하나 이상일 수 있고, 이 중 성능 및 비용적인 측면에서 실리카인 것이 더욱 바람직하나, 이에 한정되지 않는다. The inorganic nanoparticles refer to inorganic particles of nano size, and to secure hardness and curl. The inorganic nanoparticles may be one or more selected from the group consisting of silica, alumina, zirconia, zeolite, titanium oxide, and combinations thereof, more preferably silica in terms of performance and cost, but is not limited thereto.
상기 무기 나노입자의, 상기 조성물 내 입자 분포에서 50% 누적질량 입자크기 분포 직경을 D50이라 할 때, 5nm<D50<20nm 일 수 있어, 무기 나노입자가 완전히 분산되지도 않고, 무기 나노입자가 분산되지 못하고 뭉치게 되지도 않는 채, 상기 조성물 내 네트워크 구조를 형성할 수 있다.When the 50% cumulative mass particle size distribution diameter in the particle distribution in the composition of the inorganic nanoparticles is D50, 5nm <D50 <20nm, the inorganic nanoparticles are not completely dispersed, and the inorganic nanoparticles are dispersed. It is possible to form the network structure in the composition without being nor agglomerated.
또한, 상기 무기 나노입자는 조성물 총 100 중량부에 대하여 1~30 중량부로 첨가될 수 있다. 이때, 무기 나노입자가 1 중량부 미만일 경우, 그 첨가 효과가 불충분할 수 있고, 무기 나노입자가 30 중량부를 초과하는 경우, 코팅액이 가진 기능성이 부여되지 않을 수 있다.In addition, the inorganic nanoparticles may be added in an amount of 1 to 30 parts by weight based on 100 parts by weight of the total composition. In this case, when the inorganic nanoparticles are less than 1 part by weight, the addition effect may be insufficient, and when the inorganic nanoparticles exceed 30 parts by weight, the coating liquid may not be provided with the functionality.
상기 광개시제는 자외선에 의해 여기되어 광중합을 개시하는 역할을 한다. 상기 광개시제로 공지의 광개시제를 사용할 수 있고, 벤조페논; 치환된 벤조페논; 아세토페논; 치환된 아세토페논; 벤조인; 벤조인 알킬 에스테르; 크산톤; 치환된 크산톤; 포스핀 옥시드; 디에톡시-아세토페논; 벤조인 메틸 에테르; 벤조인 에틸 에테르; 벤조인 이소프로필 에테르; 디에톡시크산톤; 클로로-티오-크산톤; N-메틸 디에탄올-아민-벤조페논; 2-히드록시-2-메틸-1-페닐-프로판-1-온; 2-벤질-2-(디메틸아미노)-1-[4-(4-모르폴리닐)페닐]-1-부탄온; 및 이들의 조합으로 이루어진 군으로부터 선택된 하나 이상을 사용하는 것이 바람직하나, 이에 한정되지 않는다.The photoinitiator is excited by ultraviolet rays and serves to initiate photopolymerization. Known photoinitiators can be used as the photoinitiator, benzophenone; Substituted benzophenones; Acetophenone; Substituted acetophenones; Benzoin; Benzoin alkyl esters; Xanthones; Substituted xanthones; Phosphine oxide; Diethoxy-acetophenone; Benzoin methyl ether; Benzoin ethyl ether; Benzoin isopropyl ether; Diethoxyxanthone; Chloro-thio-xanthone; N-methyl diethanol-amine-benzophenone; 2-hydroxy-2-methyl-1-phenyl-propan-1-one; 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone; And it is preferable to use one or more selected from the group consisting of, but is not limited thereto.
또한, 상기 광개시제는 조성물 총 100 중량부에 대하여 1~15 중량부로 첨가될 수 있다. 이때, 광개시제가 1 중량부 미만일 경우, 경화 반응 시간이 길어지는 문제점이 있고, 광개시제가 15 중량부를 초과하는 경우, 미반응 광개시제가 불순물로 잔존할 수 있는 문제점이 있다.In addition, the photoinitiator may be added in 1 to 15 parts by weight based on 100 parts by weight of the total composition. At this time, when the photoinitiator is less than 1 part by weight, there is a problem that the curing reaction time is long, and when the photoinitiator exceeds 15 parts by weight, there is a problem that the unreacted photoinitiator may remain as an impurity.
상기 혼합 용제는 케톤계 용제 및 알코올계 용제를 포함하는 것을 특징으로 한다. 케톤계 용제로는 메틸에틸케톤, 메틸이소부틸케톤, 1-메틸-2-피롤리디논, 시클로헥사논 또는 아세톤 등이 있고, 알코올계 용제로는 프로필렌글리콜모노메틸에테르, 메탄올, 에탄올, 이소프로필알코올 또는 부틸알코올 등이 있다.The mixed solvent is characterized in that it comprises a ketone solvent and an alcohol solvent. Ketone solvents include methyl ethyl ketone, methyl isobutyl ketone, 1-methyl-2-pyrrolidinone, cyclohexanone or acetone, and alcohol solvents include propylene glycol monomethyl ether, methanol, ethanol, and isopropyl. Alcohol or butyl alcohol and the like.
상기 혼합 용제의 극성도(Polarity Index)는 3~5일 수 있다. 이때, 혼합 용제의 극성도가 3 미만인 경우, 극성이 너무 낮아 무기 나노입자가 완전히 분산되어 무기 나노입자에 의한 네트워크 구조를 형성하지 못하는 문제점이 있고, 혼합 용제의 극성도가 5를 초과하는 경우, 극성이 너무 높아 무기 나노입자가 분산되지 못하고 뭉치게 되는 문제점이 있다. The polarity index (Polarity Index) of the mixed solvent may be 3 to 5. At this time, when the polarity of the mixed solvent is less than 3, there is a problem that the polarity is too low to completely disperse the inorganic nanoparticles to form a network structure by the inorganic nanoparticles, when the polarity of the mixed solvent exceeds 5, The polarity is too high, there is a problem that the inorganic nanoparticles are not dispersed and agglomerated.
상기 혼합 용제는 아마이드계 용제, 탄화수소계 용제, 에스테르계 용제, 에테르계 용제 및 글리콜계 용제로 이루어진 군으로부터 선택된 하나 이상의 기타 용제를 더 포함할 수 있다. 아마이드계 용제로는 N,N-디메틸아세트아마이드, N,N-디메틸포름아마이드, 디메틸설폭사이드, N-메틸피롤리돈 또는 포름아마이드 등이 잇고, 탄화수소계 용제로는 헥산 또는 헵탄 등과 같은 지방족 탄화수소계 용제 및 아니솔, 메시틸렌 또는 자일렌 등과 같은 방향족 탄화수소계 용제가 있고, 에스테르계 용제로는 메틸 아세테이트, 에틸 아세테이트, 프로필 아세테이트, 메틸프로피오네이트, 에틸 프로피오네이트, γ-부티로락톤, γ-발레로락톤, γ-카프로락톤, δ-발레로락톤 또는 ε-카프로락톤 등이 있으며, 에테르계 용제로는 테트라하이드로퓨란, 2-메틸테트라하이드로퓨란 또는 디부틸에테르 등이 있다.The mixed solvent may further include one or more other solvents selected from the group consisting of amide solvents, hydrocarbon solvents, ester solvents, ether solvents and glycol solvents. Amide solvents include N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or formamide, and hydrocarbon solvents include aliphatic hydrocarbons such as hexane or heptane. Solvents and aromatic hydrocarbon solvents such as anisole, mesitylene or xylene, and ester solvents include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, γ-valerolactone, γ-caprolactone, δ-valerolactone, or ε-caprolactone, and the like, and ether solvents include tetrahydrofuran, 2-methyltetrahydrofuran or dibutyl ether.
상기 혼합 용제가 케톤계 용제, 알코올계 용제 및 기타 용제를 포함하는 경우, 상기 혼합 용제는 케톤계 용제 60~80 중량%, 알코올계 용제 15~35 중량% 및 기타 용제 5~10 중량%를 포함하는 것이 바람직하나, 이에 한정되지 않는다. 이와 같은 중량비를 유지함으로써, 상기 혼합 용제는 일정 극성도를 가짐으로써 무기 나노입자의 적절한 분산을 유도하여, 하드코팅 조성물 내 네트워크 구조를 형성할 수 있다.When the mixed solvent includes a ketone solvent, an alcohol solvent, and other solvents, the mixed solvent includes 60 to 80 wt% of the ketone solvent, 15 to 35 wt% of the alcohol solvent, and 5 to 10 wt% of the other solvent. Preferably, but not limited to. By maintaining such a weight ratio, the mixed solvent may have a certain degree of polarity to induce proper dispersion of the inorganic nanoparticles, thereby forming a network structure in the hard coating composition.
상기 하드코팅 조성물은 비산 방지 필름에서 하드코팅층으로 사용되기 위해 하드코팅성을 유지할 수 있는한, 첨가제를 더 추가할 수 있는데, 예를 들면, 염료, 충전제(필러(filler)), 보강제, 난연제, 가소제, 윤활제, 안정제(산화방지제, 자외선 흡수제, 열안정제 등), 이형제, 대전방지제, 계면활성제, 분산제, 유동 조정제, 레벨링(leveling)제, 소포제, 표면개질제, 저응력화제(실리콘 오일(silicone oil), 실리콘고무, 각종 플라스틱 분말 등), 내열성 개량제 등을 더 추가할 수 있다.The hard coating composition may further add additives as long as it can maintain hard coating properties for use as a hard coating layer in the anti-scattering film, for example, dyes, fillers, reinforcing agents, flame retardants, Plasticizers, lubricants, stabilizers (antioxidants, UV absorbers, heat stabilizers, etc.), release agents, antistatic agents, surfactants, dispersants, flow regulators, leveling agents, antifoaming agents, surface modifiers, low stress agents (silicone oil ), Silicone rubber, various plastic powders, etc.), heat resistance improving agent, etc. can be added further.
비산 방지 필름Shatterproof film
본 발명은 투명 필름; 및 상기 투명 필름의 상부에 형성된 하드코팅층을 포함하고, 상기 하드코팅층은 상기 하드코팅 조성물로 형성된 것인 비산 방지 필름을 제공한다.The present invention is a transparent film; And a hard coating layer formed on the transparent film, wherein the hard coating layer is formed of the hard coating composition.
도 2는 본 발명의 일 구현예에 따른 비산 방지 필름을 개략적으로 나타낸 단면도이다.2 is a cross-sectional view schematically showing a scattering prevention film according to an embodiment of the present invention.
도 2를 참조하면, 본 발명의 일 구현예에 따른 비산 방지 필름은 위로부터 형성된 하드코팅층(120) 및 투명 필름(110)을 포함하고, 상기 투명 필름(110) 하부에 차례로 형성된 점착층(130) 및 이형 필름(140)을 더 포함할 수 있다.Referring to FIG. 2, the anti-scattering film according to the embodiment of the present invention includes a hard coating layer 120 and a transparent film 110 formed from above, and an adhesive layer 130 which is sequentially formed below the transparent film 110. And a release film 140 may be further included.
상기 투명 필름(110)은 터치 스크린 패널(touch screen panel)의 강화유리와 같은 유리의 비산을 방지할 수 있도록 강도가 우수하고, 아울러 광학적 특성을 저해하지 않도록 투과율이 적어도 90% 이상, 바람직하게는 90~100%인 투명성이 우수한 필름일 수 있다.The transparent film 110 is excellent in strength so as to prevent the scattering of glass, such as tempered glass of the touch screen panel, and transmittance is at least 90% or more, preferably so as not to impair optical characteristics. It may be a film having excellent transparency of 90 to 100%.
이러한 투명 필름(110)으로, 폴리에틸렌 테레프탈레이트(polyethylene terephthalate; PET), 폴리에틸렌 나프탈레이트(polyethylene naphthalate; PEN), 폴리에테르설폰(polyethersulfone; PES), 폴리 카보네이트(Poly carbonate; PC), 폴리에틸렌(polyethylene; PE), 폴리 프로필렌(poly propylene; PP) 또는 이들의 조합으로 이루어진 군으로부터 선택된 하나 이상을 사용하는 것이 바람직하고, 가시광선 투과율이 92%인 광학용 PET 필름을 사용하는 것이 보다 바람직하나, 이에 한정되지 않는다.As the transparent film 110, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polycarbonate (PC), polyethylene (polyethylene); It is preferable to use one or more selected from the group consisting of PE), poly propylene (PP) or a combination thereof, and more preferably to use an optical PET film having a visible light transmittance of 92%. It doesn't work.
상기 하드코팅층(120)은 상기 투명 필름(110)의 상부에 형성된 것으로, 상기 하드코팅 조성물로 형성된 것을 특징으로 한다. 이때, 하드코팅 조성물에 대해서는 전술한 바와 같다.The hard coating layer 120 is formed on the transparent film 110, characterized in that formed with the hard coating composition. At this time, the hard coating composition is as described above.
즉, 상기 비산 방지 필름 조성물은 무기 나노입자에 의한 네트워크 구조를 형성함으로써, 이로 형성된 하드코팅층(120)은 얇은 두께를 가지더라도, 표면 경도 및 광학적 특성이 우수하다.That is, the anti-scattering film composition forms a network structure by inorganic nanoparticles, so that the hard coating layer 120 formed therefrom is excellent in surface hardness and optical properties even though it has a thin thickness.
상기 하드코팅층(120)은 상기 하드코팅 조성물을 투명 필름 상부면에 코팅하여 형성하는데, 코팅 방법으로는 스핀 코팅(spin coating)법, 스프레이 코팅(spray coating)법, 캐스트(cast)법, 바 코팅(bar coating)법, 롤투롤 코팅(roll to roll coating)법, 그라비아 코팅(gravure coating)법, 디핑(dipping)법 등을 들 수 있다. 이들 방법 중 생산성 측면에서 롤투롤 코팅 법이 가장 바람직하나, 이에 한정되지 않는다.The hard coating layer 120 is formed by coating the hard coating composition on the upper surface of the transparent film. As a coating method, a spin coating method, a spray coating method, a cast method, a bar coating method may be used. (bar coating) method, roll to roll coating method, gravure coating method, dipping method and the like. Among these methods, the roll-to-roll coating method is most preferred in terms of productivity, but is not limited thereto.
상기 하드코팅층(120)의 두께는 0.1㎛ 내지 1㎛인 것이 바람직하고, 0.1㎛ 내지 0.8㎛인 것이 보다 바람직하고, 0.1㎛ 내지 0.7㎛인 것이 보다 더 바람직하나, 이에 한정되지 않는다. 상기 하드코팅층(120)은 상기와 같이 얇은 두께를 가지더라도, 무기 나노입자에 의한 네트워크 구조로 인하여 표면 경도 및 광학적 특성을 확보할 수 있다. 이때, 상기 하드코팅층(120)의 두께가 너무 얇은 경우, 하드코팅성에 문제점이 있고, 상기 하드코팅층(120)의 두께가 너무 두꺼운 경우, 하드코팅으로 인한 비용 상승의 문제점이 있다. The hard coating layer 120 preferably has a thickness of 0.1 μm to 1 μm, more preferably 0.1 μm to 0.8 μm, and even more preferably 0.1 μm to 0.7 μm, but is not limited thereto. Even if the hard coating layer 120 has a thin thickness as described above, the hard coating layer 120 can secure the surface hardness and optical properties due to the network structure by the inorganic nanoparticles. In this case, when the thickness of the hard coating layer 120 is too thin, there is a problem in hard coating properties, when the thickness of the hard coating layer 120 is too thick, there is a problem of a cost increase due to hard coating.
상기 하드코팅층(120)의 연필 경도는 1H 내지 9H인 것일 수 있다. 상기 하드코팅층(120)이 상기 범위의 연필 경도를 가짐으로써 우수한 내마모성을 구현할 수 있다.The pencil hardness of the hard coat layer 120 may be 1H to 9H. The hard coating layer 120 may implement excellent wear resistance by having a pencil hardness in the above range.
또한, 상기 하드코팅층(120)의 투과율은 90% 내지 100%인 것일 수 있다. 상기 하드코팅층(120)이 상기 범위의 투과율을 가짐으로써 높은 수준의 투명성을 유지하여 우수한 광학적 특성을 구현할 수 있다.In addition, the transmittance of the hard coat layer 120 may be 90% to 100%. Since the hard coating layer 120 has a transmittance in the above range, it is possible to implement high optical properties by maintaining a high level of transparency.
상기 점착층(120)은 상기 투명 필름(110)의 하부에 형성될 수 있는 것으로, 상기 점착층(120)은 피착면인 터치 스크린 패널 등에 부착을 위하여 추가로 형성될 수 있다.The adhesive layer 120 may be formed under the transparent film 110, and the adhesive layer 120 may be further formed to be attached to a touch screen panel, which is an adhered surface.
구체적으로, 상기 점착층(130)은 상기 투명 필름(110)의 하부면에 직접 코팅되어 형성되거나, 상기 점착층(130)은 상기 이형 필름(140)의 상부면에 미리 코팅된 후 투명 필름(110)의 하부면에 이형 필름(140)을 합지함으로써 형성될 수 있다.Specifically, the adhesive layer 130 is formed by coating directly on the lower surface of the transparent film 110, or the adhesive layer 130 is coated on the upper surface of the release film 140 in advance, then the transparent film ( It may be formed by laminating the release film 140 on the lower surface of the (110).
이러한 점착층(130)은 아크릴계 점착제, 실리콘계 점착제, 무산(acid-free) 타입의 히드록실(hydroxyl) 함유 점착제 등 공지의 점착제를 제한없이 이용할 수 있다. 점착층(130)은 이들 중 선택된 1종 이상을 포함할 수 있다. 예를 들어, 무산 타입의 히드록실 함유 점착제는 2-에틸헥실아크릴레이트(2-ethylhexyl acrylate), 하이드록시에틸 아크릴레이트(Hydroxyethyl acrylate) 및 벤조페논 등의 공지된 광개시제를 포함할 수 있고, 첨가제를 더 포함할 수 있다. 첨가제는 점착제의 물성 향상을 위한 것으로, 공지의 경화 촉진제, 가소제, 분산제, 계면활성제, 대전 방지제, 소포제, 레벨링제 등을 제한없이 이용할 수 있다.The pressure-sensitive adhesive layer 130 may use any known pressure-sensitive adhesive such as an acrylic pressure sensitive adhesive, a silicone pressure sensitive adhesive, and an acid-free hydroxyl-containing pressure sensitive adhesive. The adhesive layer 130 may include at least one selected from these. For example, the acid-free hydroxyl-containing pressure sensitive adhesive may include known photoinitiators such as 2-ethylhexyl acrylate, hydroxyethyl acrylate, and benzophenone, and may include additives. It may further include. The additive is for improving the physical properties of the pressure-sensitive adhesive, and known curing accelerators, plasticizers, dispersants, surfactants, antistatic agents, antifoaming agents, leveling agents and the like can be used without limitation.
상기 이형 필름(140)은 상기 점착층(130)의 하부에 형성될 수 있는 것으로, 상기 점착층(130)을 보호하기 위한 것이다.The release film 140 may be formed under the adhesive layer 130, and is to protect the adhesive layer 130.
이러한 이형 필름(140)으로는 폴리에틸렌테레프탈레이트(Polyethylene terephthalate; PET) 필름 등 다양한 필름을 사용할 수 있고, 이형을 쉽게 할 수 있도록 이형력이 10g/in 정도인 이형용 PET 필름을 사용하는 것이 바람직하나, 이에 한정되지 않는다.As the release film 140, various films such as polyethylene terephthalate (PET) film may be used, and it is preferable to use a release PET film having a release force of about 10 g / in so as to easily release the film. It is not limited to this.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 하기 실시예에 의해 본 발명의 내용이 한정되는 것은 아니다.Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited by the following examples.
[실시예]EXAMPLE
실시예 1Example 1
케톤계 용제로서 메틸에틸케톤(MEK) 50 중량부, 알코올계 용제로서 프로필렌글리콜모노메틸에테르(PGME) 45 중량부 및 아마이드계 용제로서 N,N-디메틸아세트아마이드 5 중량부를 포함하는 혼합 용제를 준비하였다. 준비된 혼합 용제와, 조성물 총 100 중량부에 대하여, 자외선 경화형 아크릴레이트 수지 30 중량부, 약 10nm 크기의 실리카 20 중량부 및 벤조페논 10 중량부를 포함하여, 네트워크 구조를 형성하는 하드코팅 조성물을 제조하였다. 제조된 하드코팅 조성물을 롤투롤 코팅을 통해 PET 투명 필름 상부에 도포한 후, 건조 및 UV 경화하여 약 537.7~646.1nm 두께의 하드코팅층을 제조함으로써 비산 방지 필름을 제조하였다(도 1(a) 참조).A mixed solvent containing 50 parts by weight of methyl ethyl ketone (MEK) as a ketone solvent, 45 parts by weight of propylene glycol monomethyl ether (PGME) as an alcohol solvent and 5 parts by weight of N, N-dimethylacetamide as an amide solvent is prepared. It was. A hard coating composition was formed to form a network structure, including 30 parts by weight of an ultraviolet curable acrylate resin, 20 parts by weight of silica having a size of about 10 nm, and 10 parts by weight of benzophenone, based on the prepared mixed solvent and 100 parts by weight of the total composition. . After applying the prepared hard coating composition on the PET transparent film through a roll-to-roll coating, and dried and UV cured to prepare a hard coating layer having a thickness of about 537.7 ~ 646.1nm to prepare a scatter-proof film (see Fig. 1 (a)). ).
비교예 1Comparative Example 1
혼합 용제 대신 케톤계 용제로서 메틸이소부틸케톤(MIBK)을 단독으로 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드코팅 조성물 및 약 1.5㎛ 두께의 하드코팅층을 포함하는 비산 방지 필름을 제조하였다(도 1(b) 참조).Except for using methyl isobutyl ketone (MIBK) alone as a ketone solvent instead of a mixed solvent in the same manner as in Example 1 was prepared a shatterproof film comprising a hard coating composition and a hard coating layer of about 1.5㎛ thickness ( See FIG. 1 (b)).
비교예 2Comparative Example 2
혼합 용제 대신 케톤계 용제로서 메틸이소부틸케톤(MIBK)을 단독으로 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드코팅 조성물 및 약 500nm 두께의 하드코팅층을 포함하는 비산 방지 필름을 제조하였다.Except for using methyl isobutyl ketone (MIBK) alone as a ketone solvent instead of a mixed solvent in the same manner as in Example 1 was prepared a shatterproof film comprising a hard coating composition and a hard coating layer of about 500nm thickness.
실험예: 물성 평가Experimental Example: Evaluation of Properties
실시예 1 및 비교예 1~2에 따라 제조된 비산 방지 필름의 연필 경도 및 가시광선 투과율 광학적 특성 및 측정 결과는 하기 표 1에 나타내었다. Pencil hardness and visible light transmittance optical properties and measurement results of the scattering prevention film prepared according to Example 1 and Comparative Examples 1 and 2 are shown in Table 1 below.
연필 경도는 JIS K5600-5-4에 의거하여 750g의 추를 사용하여 측정하였고, 가시광선 투과율은 JIS K7361-1에 의거하여 분광광도계(Konica Minolta社, CM-5)를 사용하여 측정하였다.Pencil hardness was measured using a 750 g weight in accordance with JIS K5600-5-4, and visible light transmittance was measured using a spectrophotometer (Konica Minolta, CM-5) in accordance with JIS K7361-1.
표 1
구 분 연필 경도 가시광선투과율(%)
실시예 1 H 92
비교예 1 H 92
비교예 2 F 92
Table 1
division Pencil hardness Visible light transmittance (%)
Example 1 H 92
Comparative Example 1 H 92
Comparative Example 2 F 92
상기 표 1에서 보듯이, 실시예 1에 따른 하드코팅 조성물은 혼합 용제로 인하여 무기 나노입자에 의한 네트워크 구조를 형성함으로써, 이로 형성된 하드코팅층은 비교예 1에 비해 현저히 얇은 두께를 가지더라도, 연필 경도가 동등한 수준을 유지하면서도 가시광선 투과율이 우수함을 확인할 수 있었다. 한편, 비교예 2의 경우 연필 경도가 저하되어 비산 방지 필름으로서 적합하지 못함을 확인할 수 있었다.As shown in Table 1, the hard coating composition according to Example 1 forms a network structure by the inorganic nanoparticles due to the mixed solvent, even though the hard coating layer formed therein has a significantly thinner thickness than Comparative Example 1, the pencil hardness It was confirmed that the excellent light transmittance was maintained while the equivalent level. On the other hand, in the case of the comparative example 2, pencil hardness fell and it was confirmed that it is not suitable as a scattering prevention film.
전술한 본 발명의 설명은 예시를 위한 것이며, 본 발명이 속하는 기술분야의 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 쉽게 변형이 가능하다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다.The foregoing description of the present invention is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims (13)

  1. 자외선 경화형 아크릴레이트 수지; 무기 나노입자; 광개시제; 및 혼합 용제를 포함하고,Ultraviolet curable acrylate resins; Inorganic nanoparticles; Photoinitiators; And mixed solvents,
    상기 혼합 용제는 케톤계 용제 및 알코올계 용제를 포함하는 것을 특징으로 하는The mixed solvent comprises a ketone solvent and an alcohol solvent
    하드코팅 조성물.Hard coating composition.
  2. 제1항에 있어서,The method of claim 1,
    상기 혼합 용제의 극성도는 3 내지 5인 The polarity of the mixed solvent is 3 to 5
    하드코팅 조성물.Hard coating composition.
  3. 제1항에 있어서,The method of claim 1,
    상기 혼합 용제는 아마이드계 용제, 탄화수소계 용제, 에스테르계 용제, 에테르계 용제 및 글리콜계 용제로 이루어진 군으로부터 선택된 하나 이상의 기타 용제를 더 포함하는 것을 특징으로 하는 The mixed solvent further comprises one or more other solvents selected from the group consisting of amide solvents, hydrocarbon solvents, ester solvents, ether solvents and glycol solvents.
    하드코팅 조성물.Hard coating composition.
  4. 제3항에 있어서,The method of claim 3,
    상기 혼합 용제는 케톤계 용제 60~80 중량%, 알코올계 용제 15~35 중량% 및 기타 용제 5~10 중량%를 포함하는 것을 특징으로 하는 The mixed solvent is characterized in that it comprises a ketone solvent 60-80% by weight, alcohol solvent 15-35% by weight and other solvents 5-10% by weight
    하드코팅 조성물.Hard coating composition.
  5. 제1항에 있어서,The method of claim 1,
    상기 무기 나노입자의, 50% 누적질량 입자크기 분포 직경을 D50이라 할 때, 5nm<D50<20nm인When the 50% cumulative mass particle size distribution diameter of the inorganic nanoparticles is D50, 5nm <D50 <20nm
    하드코팅 조성물.Hard coating composition.
  6. 제1항에 있어서,The method of claim 1,
    상기 조성물 총 100 중량부에 대하여, 자외선 경화형 아크릴레이트 수지 1~70 중량부; 무기 나노입자 1~30 중량부; 광개시제 1~15 중량부인100 parts by weight of the total composition, 1 to 70 parts by weight of an ultraviolet curable acrylate resin; 1 to 30 parts by weight of inorganic nanoparticles; 1 to 15 parts by weight of photoinitiator
    하드코팅 조성물.Hard coating composition.
  7. 제1항에 있어서,The method of claim 1,
    상기 조성물은 무기 나노입자에 의한 네트워크 구조를 형성하는 The composition forms a network structure by inorganic nanoparticles
    하드코팅 조성물.Hard coating composition.
  8. 투명 필름; 및Transparent film; And
    상기 투명 필름의 상부에 형성된 하드코팅층을 포함하고,It includes a hard coating layer formed on the transparent film,
    상기 하드코팅층은 제1항 내지 제7항 중 어느 한 항에 따른 하드코팅 조성물로 형성된 것인The hard coating layer is formed of a hard coating composition according to any one of claims 1 to 7.
    비산 방지 필름.Shatterproof film.
  9. 제8항에 있어서,The method of claim 8,
    상기 하드코팅층의 두께는 0.1㎛ 내지 1㎛인The hard coating layer has a thickness of 0.1 μm to 1 μm.
    비산 방지 필름.Shatterproof film.
  10. 제8항에 있어서,The method of claim 8,
    상기 하드코팅층의 연필 경도는 1H 내지 9H인The pencil hardness of the hard coating layer is 1H to 9H
    비산 방지 필름.Shatterproof film.
  11. 제8항에 있어서,The method of claim 8,
    상기 하드코팅층의 투과율은 90% 내지 100%인The transmittance of the hard coat layer is 90% to 100%
    비산 방지 필름.Shatterproof film.
  12. 제8항에 있어서,The method of claim 8,
    상기 투명 필름의 하부에 형성된 점착층을 더 포함하는 Further comprising a pressure-sensitive adhesive layer formed on the lower portion of the transparent film
    비산 방지 필름.Shatterproof film.
  13. 제12항에 있어서,The method of claim 12,
    상기 점착층의 하부에 형성된 이형 필름을 더 포함하는 Further comprising a release film formed on the lower portion of the adhesive layer
    비산 방지 필름.Shatterproof film.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110043444A (en) * 2009-10-20 2011-04-27 닛뽄 가야쿠 가부시키가이샤 Uv curable resin composition for hard coat, and hard coated film and hard coated moldings using the same
KR101168073B1 (en) * 2011-09-28 2012-07-24 이성권 Photocuring hard-coating composition and high hardness sheet employing the same
KR101184448B1 (en) * 2008-12-29 2012-09-20 제일모직주식회사 Uv curing hard coating composition, polarizing film having anti-smudge using the composition and method of manufacturing hard coating layer
KR20130013881A (en) * 2011-07-29 2013-02-06 도레이첨단소재 주식회사 Cover film for electronic paper
KR101385031B1 (en) * 2010-12-30 2014-04-14 제일모직주식회사 Hard coating film

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101184448B1 (en) * 2008-12-29 2012-09-20 제일모직주식회사 Uv curing hard coating composition, polarizing film having anti-smudge using the composition and method of manufacturing hard coating layer
KR20110043444A (en) * 2009-10-20 2011-04-27 닛뽄 가야쿠 가부시키가이샤 Uv curable resin composition for hard coat, and hard coated film and hard coated moldings using the same
KR101385031B1 (en) * 2010-12-30 2014-04-14 제일모직주식회사 Hard coating film
KR20130013881A (en) * 2011-07-29 2013-02-06 도레이첨단소재 주식회사 Cover film for electronic paper
KR101168073B1 (en) * 2011-09-28 2012-07-24 이성권 Photocuring hard-coating composition and high hardness sheet employing the same

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