KR102071292B1 - Protective film for curved display screen and Method of preparing the same - Google Patents

Abstract

The present invention relates to a display protecting film attached to a display having a curved edge unit. The display protecting film comprises: an upper protecting layer which includes polyethylene terephthalate; an upper silicon adhesive layer which is provided in a lower part of the upper protecting layer; a hard coating layer which is provided in a lower part of the upper silicon adhesive layer, is detachably attached to the upper silicon adhesive layer, and sequentially includes a first coating unit, a second coating unit, a third coating unit, and a polymer resin unit; a substrate layer which is provided in a lower part of the hard coating layer and includes the polyethylene terephthalate; a complex functional resin layer which is provided in a lower part of the substrate layer; a lower protecting layer which is provided in a lower part of the complex functional resin layer and includes the polyethylene terephthalate; a lower silicon adhesive layer which is provided in a lower part of the lower protecting layer; and a fluorine release film layer which is provided in a lower part of the lower silicon adhesive layer and is detachable attached to the lower silicon adhesive layer. The protecting film performs first hardening by applying heat to an upper part of the upper protecting layer, is mounted on the display having a curved edge unit, and performs second hardening since UV is irradiated by a UV lamp in the upper part of the upper protecting layer. Accordingly, the present invention can provide a protecting film for display with improved durability, which can be used for a long time without damage in spite of several times of friction.

Description

Protective film for display attached to a display having a curved edge portion and a method for manufacturing the same {Protective film for curved display screen and Method of preparing the same}

The present invention relates to a protective film for a display attached to a display having a curved edge portion and a method for manufacturing the same, and more particularly, it is not detachable by the curved portion of the display, durability is improved, and long-term use is possible. The present invention relates to a display protective film attached to a display having an improved curved edge portion and a method of manufacturing the same.

Recently, as the demand for smartphones gradually increases, smartphones having various functions and appearances are being released, and among them, smartphones having a curved edge formed on the outer region of the liquid crystal have been released. In the case of the front display unit having such a curved edge portion, when a conventional general protective film is attached, the protective film is not completely adhered to the curved edge portion, and thus a lifting phenomenon occurs. Since it is only released in a form that is cut and attached to a size corresponding to the flat portion, there is a problem in that the entire front display portion, that is, the curved edge portion is not completely protected.

In order to solve this problem, there is a method of forming by heating and pressing so that the edge portion of the flat protective film corresponds to the curved portion, but the foamed shape may be formed for a long time even if the protective film of general synthetic resin is formed. There is a disadvantage that the edge of the protective film is not easy to fall off the curved edge portion is not maintained. Or in the case of a synthetic resin film, there is a problem that the durability, such as the curved surface portion is increased during foaming, bubbles are also easily generated.

In order to solve this problem, a protective film using tempered glass is used. For example, Korean Patent No. 10-1483672 is provided with an air wall portion and a support portion to prevent the lifting phenomenon by preventing a gap generated between the curved surface of the tempered glass and the display. However, when the support portion of Korean Patent No. 10-1483672 is tempered glass, the process of attaching it to the outer edge part is not easy, and if the radius of curvature of the produced display is not the same, it is difficult to control the thickness of the support part, so that a gap occurs due to the support part. The problem has been raised that air is still present in the air wall part, so that air can be introduced into the gap between the PET layer and the silicon layer. In addition, Korean Patent No. 10-1483672 shows a difference in refractive index of light due to different layers forming the liquid crystal protection plate protecting the display front part and the curved edge part. You may feel visual discomfort.

(Prior patent)

Korean Patent Registration No. 10-1483672

SUMMARY OF THE INVENTION An object of the present invention is to provide a display protective film for improved durability that can stably protect the display and can be used for a long time without being damaged by a plurality of frictions by covering the display having a curved edge portion without lifting. .

In addition, another object of the present invention is composed of a plurality of layers made of different materials, the optical properties are improved by controlling the refractive index between the materials constituting each layer, so as not to reduce the recognition ability of the fingerprint, iris, etc. This is to provide a protective film for display.

In addition, another object of the present invention is to produce a protective film for a display that is manufactured using a novel structure and manufacturing method, the scratch resistance, wear resistance, and chemical resistance is improved, and evenly attached to the round-shaped curved display as a whole To provide.

According to one aspect of the present invention, embodiments of the present invention are directed to a display protective film attached to a display having a curved edge portion, the protective film, the upper portion containing polyethylene terephthalate (polyethylene terephthalate, PET) Protective layer; An upper silicon adhesive layer provided below the upper protective layer; A hard coating layer provided below the upper silicon adhesive layer and detachably attached to the upper silicon adhesive layer and sequentially formed of a first coating part, a second coating part, and a third coating part and a polymer resin part; A base layer provided below the hard coating layer and comprising polyethylene terephthalate; A composite functional resin layer provided below the base layer; A lower protective layer provided below the composite functional resin layer and comprising polyethylene terephthalate; A lower silicon adhesive layer provided under the lower protective layer; And a fluorine release film layer provided below the lower silicon adhesive layer and detachably provided with respect to the lower silicon adhesive layer.

After the protective film is subjected to the first curing by applying heat on the upper portion of the upper protective layer, the protective film is placed on the display having a curved edge portion, and then UV is applied by the UV lamp on the upper portion of the upper protective layer. Can be irradiated to perform a second curing.

The first curing is performed by passing the first chamber, the second chamber, the third chamber, the fourth chamber, and the fifth fifth chamber sequentially provided at a speed of 8 m / min to 12 m / min, and the first chamber Is 75 ° C to 85 ° C, the second chamber is 95 ° C to 105 ° C, the third chamber is 115 ° C to 125 ° C, the fourth chamber is 130 ° C to 140 ° C, and the fifth chamber is 75 ° C. ℃ to 85 ℃, the first to the fifth chamber may be provided with the same length of 4m each.

The second curing may be performed by irradiating UV at 10000mJ / cm 2 for 20 seconds at 500 nmW / cm 2 at 365 nm for UV irradiation by a UV lamp.

The thickness of the upper protective layer is 25㎛ to 100㎛, the thickness of the upper silicon adhesive layer is 5㎛ to 20㎛, the thickness of the hard coating layer is 0.5㎛ to 3㎛, the thickness of the composite functional resin layer 10 μm to 50 μm, the thickness of the base layer may be 12 μm to 50 μm, the thickness of the lower silicon adhesive layer may be 5 μm to 50 μm, and the thickness of the lower protective layer may be 25 μm to 100 μm. .

UV blocking layers may be further provided on the upper portion of the upper protective layer and the lower portion of the fluorine release film layer, respectively.

The UV blocking layer has a thickness of 1 μm to 50 μm, and may be provided as a film in which polyvinyl alcohol resin is used as a matrix, and composite nanoparticles of zinc oxide and titanium oxide are dispersed in the polyvinyl alcohol resin.

The UV blocking layer is prepared by using a sol-gel (zinc) powder (sol-gel), by using anatase method (anatase) to prepare a titanium dioxide powder, using the zinc oxide powder and the titanium dioxide powder The composite nanoparticles were prepared, 10 g of polyvinyl alcohol was added to 90 g of distilled water, and then dissolved by stirring at 70 ° C. for 1 hour. The composite nanoparticles were added at 5 wt% and cast in the form of a film. Can be prepared by drying.

The zinc oxide powder is prepared by reacting 0.05 M acetate zinc (M) and 0.5 L absolute ethanol at 80 ° C. in an evaporator for 3 hours to dissolve, and 0.3 L of the reactant is discharged by condensation. 0.3L Absolute Ethanol and 0.07M Lithium Hydroxide (LiOH) were added to the remaining 0.2L reactant and stirred at room temperature for about 1 hour, followed by dispersion and washing with an Ultrasonic Bath. To remove dust and insoluble lithium hydroxide using a 0.1 μm glass filter, obtain a colloidal form, and dry the colloidal form in a 70 ° C. hot air dryer to produce zinc oxide powder. Can be.

The titanium dioxide powder, 5 ml of titanium isopropoxide (TTIP) and 15 ml of isopropanol (Isopropanol) was stirred at room temperature for 1 hour, 250 ml of distilled water was added and stirred for 10 minutes, followed by hydrochloric acid (HCl) The pH is adjusted to 7 using 7, stirred for 20 hours using a magnetic bar (Magnetic Bar) at 70 ℃, washed with distilled water and vacuum dried at 100 ℃ for 1 hour using a vacuum dryer After the vacuum drying, a titanium dioxide powder (TiO 2 Powder) may be manufactured by calcination at 600 ° C. for 2 hours.

The composite nanoparticles, after adding 1 g of zinc oxide powder to 50 ml of absolute ethanol, stirred for 1 hour at room temperature with a magnetic bar, and then dispersed for 1 hour using an ultrasonic bath, and added hydrochloric acid thereto After adjusting to pH 6 to prepare a zinc oxide colloid, 0.2 g of polyvinyl acetate (Poly (vinyl acetate)) was added to 50 ml of ethanol, and then stirred at room temperature with a magnetic bar for 1 hour, followed by titanium isopropoxide. After adding 2ml of side and 2ml of distilled water, the mixture was stirred for 1 hour at room temperature with a magnetic bar to prepare a titanium oxide colloid, and the zinc oxide colloid was added to the titanium oxide colloid and adjusted to pH 7. By reacting for 24 hours at ℃ can be prepared composite nanoparticles.

The display protective film has a transmittance (measured by JIS-K 7361) of 89% to 93%, a surface resistance (measured by TREK 152) of 1.0x10 ⁵ Ω to 9.9x10 ¹¹ Ω, and haze (ASTM D 5946). May be 0.1% to 1%.

The fluorine release film layer may have a peel adhesion (measured by ASTM D 3330 SUS) of 400 gf / 25 mm to 800 gf / 25 mm.

The display protective film is the hardness (measured by ASTMD 2240, JISK 7215) after performing only the first curing before performing the second curing is 40H to 45H, 60H to 65H days after performing the second curing Can be.

The upper protective layer, the first layer made of polyethylene terephthalate, is provided on top of the first layer, and coated with a composite composition made of a water adsorbent and phenoxy, epoxy and imidazole And a second layer formed on the second layer and made of polyethylene terephthalate, wherein the moisture adsorbent is calcium oxide (CaO), silicon oxide (SiO 2), and magnesium oxide. (Magnesium oxide, MgO) and aluminum oxide (Aluminum oxide, Al2O3) may be any one or more.

The upper protective layer, after washing the polyethylene terephthalate film having a thickness of 50㎛ with acetone and vacuum-dried, put in a plasma reactor of 5mTorr pressure and purged with argon gas, and treated with argon plasma for 3 minutes at 40W, 240mTorr After exhausting the pressure of the plasma reactor to 20 mTorr, acrylic acid vapor is introduced into the plasma reactor to prepare a first layer of a polyethylene terephthalate film to which acrylic acid is adsorbed, to prepare the composite composition, and to prepare the composite composition at room temperature. Coating the composite composition on the upper surface of the layer using a bar coater with a thickness of 5 μm to 7 μm to provide a second layer, and a third layer of polyethylene terephthalate film on the second layer. After attaching, it can be prepared by drying in a 120 ℃ oven for 30 to 40 minutes.

The composite composition was prepared by mixing 3 g of calcium powder with 97 g of methyl ethyl ketone and ball milling for 24 hours to prepare a particle solution, and 125 g of phenoxy to methyl ethyl ketone while maintaining 150 g of methyl ethyl ketone at 60 ° C. After stirring for 30 minutes to dissolve completely to prepare a first solution, and 150 g of methyl ethyl ketone was maintained at a temperature of 35 ℃, while dissolving 125 g of epoxy for 30 minutes to completely dissolve the methyl ethyl ketone. A second solution was prepared by stirring, and the second solution was added to the first solution at a temperature of 60 ° C., followed by stirring with nitrogen purge for 1 hour, and 100 g of the particle solution and 2 g of imidazole were added while purging with nitrogen. Can be mixed.

 In the hard coating layer, the first coating part includes fluorine in a thickness of 200 nm to 300 nm, the second coating part includes a polymer solution in a thickness of 200 nm to 300 nm, and the third coating part covers a surface of the polymer resin part. Corona discharge is formed, and the polymer resin is coated with the polymer solution after the corona discharge to form a second coating, after the first coating is formed by gravure coating, the first to third coating is inline Can be formed.

The polymer resin part is mixed with 100g of isopropoxide (titanium isopropoxide, TTIP, 97%) and 400g of acetylacetone (acetyl, acetone, AA, 99%) until homogenized at room temperature to stir the first mixed solution. 4 mol of a silane coupling agent, 3-glycidoxypropyl-trimethoxysilane, (GPTMS, 98%), 400 g of ethanol, 400 g of distilled water, and 0.001 mol of hydrochloric acid were added. Stirring for a time to prepare a second mixed solution, the first mixed solution and the second mixed solution was stirred for 24 hours at room temperature to prepare a third mixed solution, the third mixed solution using a spin coater 3,500 coating on substrate for 1 minute at rpm, first drying at 90 ° C. for 30 minutes after coating is complete, second drying at 120 ° C. for 2 hours after the first drying is complete, and then holding at room temperature for 24 hours Can be prepared.

The third coating part may be formed by corona discharge at a voltage of 13000 V and a frequency of 20000 Hz on an outer surface of the polymer resin part while maintaining the polymer resin part at a speed of 100 m / min.

The second coating part may be formed by mixing 50 g of a urethane resin emulsion, 111 g of polyvinyl alcohol aqueous solution, and 0.5 g of colloidal silica, coating the third coating part, and drying at 100 ° C. for 5 minutes.

The first coating part is a fluorine-based polymer mixed with 10 g of polyvinylidene fluoride or polyvinylidene difluoride (PVDF) with 28 g of an organic solvent isophorone to prepare a fluorine-based coating composition having a solid content of 20% by weight. The coating composition may be formed by coating on the second coating part and drying at 100 ° C. for 5 minutes.

The composite functional resin layer, based on 200 parts by weight of the composite functional resin layer, 100 parts by weight of adhesive, 75 parts by weight of UV curable resin, 12.5 parts by weight of thermosetting agent, 0.5 parts by weight of thermosetting accelerator, 6.5 parts by weight of photoinitiator and antioxidant 2.0 parts by weight, the adhesive is a urethane adhesive or an acrylic adhesive, the UV curable resin is composed of a 5- or 6-functional monomer, the thermosetting agent is an isocyanate, and the thermosetting accelerator is dibutyltin dilaurate (Dibutyltin dilaurate), the photoinitiator is 1-hydroxycyclohexyl phenyl ketone or 2-hydroxy-2-methylpropiophenone (2-Hydroxy-2-methylpropiophenone), the antioxidant Triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (Triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl can be propionate) All.

The composite functional resin layer, 100 parts by weight of the adhesive is put into the first reactor, the first stirring for 20 minutes at 80 rpm at 35 ℃ to 40 ℃, and after the first stirring is completed UV curing resin 75 in the first reactor After adding the parts by weight, the second stirring was performed at 35 ° C. for 80 minutes at 80 rpm, and after the second stirring was completed, the mixture was cooled to 15 ° C. with a third stirring at 50 rpm, and after the cooling was completed, 12.5 parts by weight of a thermosetting agent and a thermosetting accelerator 0.5 parts by weight, 6.5 parts by weight of photoinitiator and 2.0 parts by weight of antioxidant are added, and the fourth stirring is performed at 80 rpm for 1 hour. After the fourth stirring is completed, the stirring may be performed at 80 rpm while heating.

The lower protective layer, after washing the polyethylene terephthalate film of 25㎛ in acetone, ethanol, primary distilled water for 10 minutes each, dried at room temperature, and after the drying is completed, put the polyethylene terephthalate film in a fluorination reactor, After raising the temperature of the fluorination reactor to 100 ° C., purging twice with 99.8% purity fluorine gas, evacuating to 1.0x10 ^-3 torr, and injecting fluorine gas having purity 99.8% purity for 6 minutes to 75 torr. Direct fluorination is carried out by maintaining for 10 minutes, and the direct fluorinated polyethylene terephthalate film is placed in a container containing distilled water and reacted at 40 kHz for 10 minutes at room temperature with an ultrasonic generator, followed by drying at room temperature.

According to another aspect of the present invention, in one embodiment of the present invention, in the method for manufacturing a protective film for display attached to a display having a curved edge portion, preparing a substrate layer for preparing a substrate layer comprising polyethylene terephthalate Making; Sequentially preparing a hard coating layer comprising a first coating part, a second coating part, a third coating part, and a polymer resin part, and an upper part including polyethylene terephthalate (PET) on the upper silicon adhesive layer. Preparing a first film part by providing a protective layer; A composite functional resin layer is prepared, the composite functional resin layer is provided on an upper portion of a lower protective layer including polyethylene terephthalate, a lower silicon adhesive layer is applied to a lower portion of the lower protective layer, and the lower silicone adhesive layer Preparing a second film part by providing a fluorine-releasing film layer at a lower portion thereof; The first film part is provided on the upper part of the base layer, and the second film part is provided on the lower part of the base material layer, and then passed through a pair of pressure rolls to sequentially stack the first film part, the base layer, and the second film part. Preparing a protective film for a display; Performing a first curing by applying heat at an upper portion of the upper protective layer; And after the first curing is performed, placing the protective film for display on a display having a curved edge portion, and then irradiating UV with a UV lamp on the upper protective layer to perform second curing. It includes a method of manufacturing a protective film for a display.

In the preparing of the first film part, the upper protective layer is provided on the first layer made of polyethylene terephthalate, the first layer, the moisture adsorbent, phenoxy, epoxy and already A second layer formed by coating a composite composition consisting of imidazole, and a third layer provided on the second layer and made of polyethylene terephthalate, wherein the moisture adsorbent is calcium oxide (CaO), oxide Silicon oxide (SiO 2), magnesium oxide (Magnesium oxide, MgO) and aluminum oxide (Aluminum oxide, Al 2 O 3) may be one or more.

The upper protective layer, after washing the polyethylene terephthalate film having a thickness of 50㎛ with acetone and vacuum-dried, put in a plasma reactor of 5mTorr pressure and purged with argon gas, and treated with argon plasma for 3 minutes at 40W, 240mTorr After exhausting the pressure of the plasma reactor to 20 mTorr, acrylic acid vapor is introduced into the plasma reactor to prepare a first layer of a polyethylene terephthalate film to which acrylic acid is adsorbed, to prepare the composite composition, and to prepare the composite composition at room temperature. Coating the composite composition on the upper surface of the layer using a bar coater with a thickness of 5 μm to 7 μm to provide a second layer, and a third layer of polyethylene terephthalate film on the second layer. After attaching, it can be prepared by drying in a 120 ℃ oven for 30 to 40 minutes.

The composite composition was prepared by mixing 3 g of calcium powder with 97 g of methyl ethyl ketone and ball milling for 24 hours to prepare a particle solution, and 125 g of phenoxy to methyl ethyl ketone while maintaining 150 g of methyl ethyl ketone at 60 ° C. After stirring for 30 minutes to dissolve completely to prepare a first solution, and 150 g of methyl ethyl ketone was maintained at a temperature of 35 ℃, while dissolving 125 g of epoxy for 30 minutes to completely dissolve the methyl ethyl ketone. A second solution was prepared by stirring, and the second solution was added to the first solution at a temperature of 60 ° C., followed by stirring with nitrogen purge for 1 hour, and 100 g of the particle solution and 2 g of imidazole were added while purging with nitrogen. Can be prepared by mixing.

In the preparing of the first film portion, the hard coating layer, the first coating portion includes fluorine in a thickness of 200nm to 300nm, the second coating portion includes a polymer solution in a thickness of 200nm to 300nm, 3, the coating part is formed by corona discharge on the surface of the polymer resin part, and the polymer resin part is coated with the polymer solution after the corona discharge, and after the second coating part is formed, a third coating part is formed by gravure coating. The first to third coating parts may be formed inline.

The polymer resin part is mixed with 100g of isopropoxide (titanium isopropoxide, TTIP, 97%) and 400g of acetylacetone (acetyl, acetone, AA, 99%) until homogenized at room temperature to stir the first mixed solution. 4 mol of a silane coupling agent, 3-glycidoxypropyl-trimethoxysilane, (GPTMS, 98%), 400 g of ethanol, 400 g of distilled water, and 0.001 mol of hydrochloric acid were added. Stirring for a time to prepare a second mixed solution, the first mixed solution and the second mixed solution was stirred for 24 hours at room temperature to prepare a third mixed solution, the mixed solution at 3,500 rpm using a spin coater It is prepared by coating on a substrate for 1 minute, first drying at 90 ° C. for 30 minutes after the coating is completed, second drying at 120 ° C. for 2 hours after the first drying is completed, and then keeping at room temperature for 24 hours. Can be.

The third coating part may be formed by corona discharge at a voltage of 13000 V and a frequency of 20000 Hz on an outer surface of the polymer resin part while maintaining the polymer resin part at a speed of 100 m / min.

The second coating part may be formed by mixing 50 g of a urethane resin emulsion, 111 g of polyvinyl alcohol aqueous solution, and 0.5 g of colloidal silica, coating the third coating part, and drying at 100 ° C. for 5 minutes.

The first coating part is a fluorine-based polymer mixed with 10 g of polyvinylidene fluoride or polyvinylidene difluoride (PVDF) with 28 g of an organic solvent isophorone to prepare a fluorine-based coating composition having a solid content of 20% by weight, The coating composition may be formed by coating on the second coating part and drying at 100 ° C. for 5 minutes.

In the preparing of the second film portion, the composite functional resin layer, 100 parts by weight of the adhesive is put into the first reactor, the first stirring for 20 minutes at 80 rpm at 35 ℃ to 40 ℃, the first stirring is completed After adding 75 parts by weight of the UV curable resin to the first reactor, and then stirred for 2 minutes at 35 ° C 80 rpm for 40 minutes, and after the second stirring is completed, cooled to 15 ° C with a third stirring at 50 rpm, the cooling is completed After the 12.5 parts by weight of the thermosetting agent, 0.5 parts by weight of the thermosetting accelerator, 6.5 parts by weight of the photoinitiator and 2.0 parts by weight of antioxidant was added and the fourth stirring at 80rpm for 1 hour, the fourth stirring was completed and then stirred at 80rpm while heating Can be.

In the preparing of the second film part, the lower protective layer is washed with a polyethylene terephthalate film of 25㎛ in order of acetone, ethanol, primary distilled water for 10 minutes each, dried at room temperature, and after the drying is complete the polyethylene The terephthalate film was placed in a fluorination reactor, the temperature of the fluorination reactor was raised to 100 ° C, purged twice with fluorine gas with a purity of 99.8%, and then evacuated to 1.0x10 ^-3 torr, and then with a purity of 99.8 in the fluorination reactor. % Fluorine gas was injected for 6 minutes and maintained at 75torr for 10 minutes to carry out direct fluorination.The polyethylene terephthalate film having the direct fluorination was placed in a container containing distilled water and reacted at 40 kHz for 10 minutes with an ultrasonic generator. Can be dried at room temperature.

The first curing is performed by passing the first chamber, the second chamber, the third chamber, the fourth chamber, and the fifth fifth chamber sequentially provided at a speed of 8 m / min to 12 m / min, and the first chamber Is 75 ° C to 85 ° C, the second chamber is 95 ° C to 105 ° C, the third chamber is 115 ° C to 125 ° C, the fourth chamber is 130 ° C to 140 ° C, and the fifth chamber is 75 ° C. ℃ to 85 ℃, the first to fifth chambers are each provided with the same length of 4m, the second curing UV irradiation by UV lamp is 500mW / ㎠ at 365nm for 20 seconds, 10000mJ / ㎠ It can be carried out by irradiation with UV.

The display protective film is the hardness (measured by ASTMD 2240, JISK 7215) after performing only the first curing before performing the second curing is 40H to 45H, 60H to 65H days after performing the second curing Can be.

According to the present invention as described above, by covering the display having a curved edge without lifting, it is possible to stably protect the display, and to improve the display protective film for durability that can be used for a long time without damage by a plurality of friction Can provide.

In addition, according to the present invention is made of a plurality of layers made of different materials, by controlling the refractive index between the materials constituting each layer, such as optical properties are improved to reduce the recognition performance of fingerprints, iris, etc. A protective film can be provided.

In addition, according to the present invention can be provided using a novel structure and manufacturing method, the scratch resistance, wear resistance, and chemical resistance is improved, it is possible to provide a display protective film for uniformly attached to the round shape curved display as a whole. have.

1 is a view showing a cross section of the protective film for a display according to an embodiment of the present invention.
2 is a view schematically showing a state of the second curing the protective film for display according to an embodiment of the present invention.
Figure 3 is a flow chart showing a manufacturing method of a protective film for a display according to another embodiment of the present invention.
4 is a view schematically showing an apparatus for manufacturing a protective film by pressing the first film portion, the base layer, and the second film portion.
FIG. 5 is a view schematically showing an LED device for UV curing used in Example 1. FIG.
Figure 6 is a photograph of the protective film of Example 1.
7 is a Charpy impact tester for measuring impact resistance.

Specific details of other embodiments are included in the detailed description and the drawings.

Advantages and features of the present invention, and methods for achieving them will be apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be embodied in various different forms, and unless stated otherwise in the following description, the present invention expresses components, reaction conditions, and contents of components. All numbers, values and / or expressions are to be understood as being modified in all cases by the term "about" since these numbers are essentially approximations reflecting the various uncertainties in the measurement that occur among others. . Also, where numerical ranges are disclosed herein, these ranges are continuous and include all values from the minimum to the maximum including the maximum, unless otherwise indicated. Furthermore, where such ranges refer to integers, all integers are included, including the minimum to the maximum including the maximum unless otherwise indicated.

In addition, where a range is described for a variable in the present invention, it will be understood that the variable includes all values within the described range including the listed endpoints of the range. For example, the range "5 to 10" includes any subrange such as 6 to 10, 7 to 10, 6 to 9, 7 to 9, as well as values of 5, 6, 7, 8, 9, and 10. And any value between integers that fall within the scope of the described ranges such as 5.5, 6.5, 7.5, 5.5-8.5, 6.5-9, and the like. For example, the range "10% to 30%" may include 10%, 11%, 12%, 13%, etc. and all integers including up to 30%, as well as 10% to 15%, 12% to 18%. It will be understood to include any subranges such as%, 20% to 30%, etc., and to include any value between reasonable integers within the range of the stated range, such as 10.5%, 15.5%, 25.5% and the like.

1 is a view showing a cross-sectional view of a protective film for a display according to an embodiment of the present invention, Figure 2 is a view schematically showing a state of the second curing the protective film for display according to an embodiment of the present invention.

In the display protective film 100 attached to the display 10 having a curved edge portion according to an embodiment of the present invention, the protective film 100, polyethylene terephthalate (polyethylene terephthalate, PET) Upper protective layer 110; An upper silicon adhesive layer 120 provided below the upper protective layer 110; It is provided below the upper silicon adhesive layer 120, detachably provided with respect to the upper silicon adhesive layer 120 and sequentially the first coating portion 131, the second coating portion 132, the third coating A hard coating layer 130 formed of a portion 133 and a polymer resin portion 134; A base layer 140 provided below the hard coating layer 130 and comprising polyethylene terephthalate; A composite functional resin layer 150 provided below the base layer 140; A lower protective layer 160 provided below the composite functional resin layer 150 and comprising polyethylene terephthalate; A lower silicon adhesive layer 170 provided below the lower protective layer 160; And a fluorine release film layer 180 provided below the lower silicon adhesive layer 170 and detachably provided to the lower silicon adhesive layer 170.

The protective film 100 is subjected to the first curing by applying heat from the upper portion of the upper protective layer 110, the protective film 110 is seated on the display 10 having a curved edge portion and then UV is irradiated by the UV lamp in the second curing can be performed.

The display protective film 100 according to the present exemplary embodiment may be cured through two steps of first and second curing to increase the hardness step by step. For example, after the first protective film 100 is cured, the display film is provided on the outer surface of the display 10 having a curved edge portion to cover the curved edge portion, and then irradiated with UV using a UV lamp. 2 can be cured.

The display protective film 100 is the hardness (measured by ASTMD 2240, JISK 7215) 40H to 45H after performing only the first curing before performing the second curing, 60H after performing the second curing To 65H.

Before the display protective film 100 according to the present embodiment performs only the first curing before attaching to the display, removing the fluorine release film layer 180 and the front surface of the display 100 having the curved edge portion It can be attached to. The display protective film 100 is exposed to the lower silicon adhesive layer 170 after the fluorine release film layer 180 is removed, the lower silicon adhesive layer 170 is attached to the front of the display 10. .

In this case, since the display protective film 100 has a hardness of 40H to 45H, it may be attached to the curved edge of the display without lifting. Subsequently, the upper protective layer 110 and the upper silicon adhesive layer 120 are desorbed, and then the composite functional resin layer 150 is cured in the display protective film 100 by irradiating UV with a UV lamp. The hardness of the protective film 100 for display can be improved. As a result, the display protective film 100 is firmly fixed on both sides of the curved edge portion of the display 10, and thus, may be stably attached to the display 10 without lifting.

In the present embodiment, the display protective film 100 may be molded to be stably attached to rounded portions of the curved edge portion and both ends of the display 10 through the first curing, and then through the second curing. Lifting of the curved edge portion that may occur due to the restoring force of the display protective film 100 can be prevented.

The first curing in the display protective film 100, the upper protective layer 110, the upper silicon adhesive layer 120, the hard coating layer 130, the base layer 140, the lower layer of the composite functional resin layer 150 The layer 160, the lower silicon adhesive layer 170, and the fluorine release layer 180 may be sequentially provided, and the second curing may be performed by removing the fluorine release layer 180 and the display 10. After attaching the display protective film 100 to the, after removing the upper protective layer 110 and the upper silicon adhesive layer 120, it is performed by irradiating a UV lamp on the exposed top of the hard coating layer 130 Can be.

The first curing may be performed by passing through the first chamber, the second chamber, the third chamber, the fourth chamber, and the fifth fifth chamber sequentially provided at a speed of 8 m / min to 12 m / min. For example, the first chamber is 75 ℃ to 85 ℃, the second chamber is 95 ℃ to 105 ℃, the third chamber is 115 ℃ to 125 ℃, the fourth chamber is 130 ℃ to 140 ℃, The fifth chamber may be 75 ° C to 85 ° C, the first to fifth chambers are each provided with the same length of 4m,

Preferably, the first chamber may be 80 ° C., the second chamber may be 100 ° C., the third chamber may be 135 ° C., and the fourth chamber may be 80 ° C.

In the first to fifth chambers, the temperature may sequentially increase from the first chamber to the fourth chamber, and in the fifth chamber, the temperature may be the same as that of the first chamber. Heat may be uniformly transmitted to the inside of the protective film 100 for display while sequentially increasing the temperature of the first to fourth chambers.

In addition, both ends of the first chamber and the fifth chamber may be provided at the same temperature of 80 ℃, by being provided at the above-mentioned temperature in the first chamber and the fifth chamber, it is introduced into the first chamber at room temperature The display protective film 100 by the temperature difference between the display protective film 100 and the first chamber, and the display protective film 100 and the room temperature difference discharged to the room temperature from the fifth chamber ( The physical property of 100) can be prevented from falling.

The display protective film 100 according to the present embodiment is formed by stacking different materials having different melting and breaking points, and the heat transferred therebetween is not uniform or a sudden temperature change occurs. In this case, there may be a problem that the bonding force between the interface is reduced, in this embodiment, by performing the first curing by the above-described method, to improve the interface bonding force between each layer of the protective film for display 100 more Can be.

The second curing may be performed by irradiating UV at 10000mJ / cm 2 for 20 seconds at 500 nmW / cm 2 at 365 nm for UV irradiation by a UV lamp.

The upper protective layer 110 may have a thickness of 25 μm to 100 μm. The upper protective layer 110 is a portion which is removed after attaching the display protective film 100 to the display. When the thickness of the upper protective layer 110 is less than 25 μm, the inner layers may be formed by moisture, oxygen, or the like. It is difficult to protect, and if it is more than 100㎛ it is difficult to transfer heat uniformly inside the first curing process is a problem.

The upper silicon adhesive layer 120 may have a thickness of about 5 μm to 20 μm, and the upper silicon adhesive layer 120 is removed together with the upper protective layer 110, and then to the outside of the hard coating layer 130. May be exposed. If the thickness of the upper silicon adhesive layer 120 is less than 5㎛, it is difficult to fix the upper protective layer 110, if the thickness exceeds 20㎛ it is difficult to maintain a uniform thickness.

The hard coating layer 130 may have a thickness of about 0.5 μm to about 3 μm. The hard coating layer 130 is a portion which is attached to the front of the display 10, the display protective film 100, the upper protective layer 110 and the upper silicon adhesive layer 120 is exposed to the outside. If the hard coating layer 130 is less than 0.5㎛ problem is low durability against friction, if it exceeds 3㎛ problem by increasing the overall thickness of the display protective film 100.

The base layer 140 may have a thickness of 12 μm to 50 μm, and the base layer 140 may be located at a central portion of the base layer 140 in the process of manufacturing the display protective film 100. It may function to support the layers provided on each of the upper and lower portions of the. When the thickness of the base layer 140 is less than 12㎛, the strength of the base layer 140 is low, the supportability is a problem, and if it is more than 50㎛ may reduce the flexible characteristics of the display protective film 100 have.

The composite functional resin layer 150 may have a thickness of 10 μm to 50 μm. The composite functional resin layer 150 is cured by the second curing, thereby maintaining the shape of the display protective film 100. If the thickness of the composite functional resin layer 150 is less than 10㎛ UV curing ability is a problem, if it is more than 50㎛ may reduce the strength of the display protective film 100.

The lower protective layer 160 may have a thickness of 12 μm to 50 μm. The lower protective layer 160 may support the composite functional resin layer 150 together with the base layer 140. The lower protective layer 160 may be provided with a thickness in the above-described range, so that the composite functional resin layer 150 may be stably supported, and at the same time, the manufacturing process of the protective film 100 for display may be efficiently performed. .

The lower silicon adhesive layer 170 may have a thickness of about 5 μm to about 50 μm. The lower silicon adhesive layer 170 is provided between the lower protective layer 160 and the fluorine release film layer 180, and then removes the fluorine release film layer 180 and the lower silicon adhesive layer 170. As a result, the display protective film 100 may be stably attached to the front surface of the display 10. If the thickness of the lower silicon adhesive layer 170 is less than 5 μm, the adhesion performance is deteriorated. If the thickness of the lower silicon adhesive layer 170 is greater than 50 μm, the fluorine release film layer 180 is partially removed when the fluorine release film layer 180 is removed. It can be detached and is a problem.

The fluorine release film layer 180 may have a thickness of 25 μm to 100 μm. The fluorine release film layer 180 protects the display protective film 100, and when the display protective film 100 is attached to the display 10, is detached and removed. If the thickness of the fluorine release film layer 180 is less than 25㎛, it is difficult to protect the protective film for display 100, if the thickness of more than 100㎛ lowers the flexible capability of the display protective film 100 is a problem.

The display protective film 100 has a transmittance (measured by JIS-K 7361) of 89% to 93%, a surface resistance (measured by TREK 152) of 1.0x10 ⁵ Ω to 9.9x10 ¹¹ Ω, and haze (ASTM). D 5946) may be 0.1% to 1%. In addition, the fluorine release film layer 180, the peel adhesion (measured by the ASTM D 3330 SUS) may be 400gf / 25mm to 800gf / 25mm, thereby stable in the lower silicon adhesive layer 170 Can be detached.

The upper protective layer 110 may be formed of first to third layers, which are provided on the silicon adhesive layer 120, and are provided on the first layer of polyethylene terephthalate and on the first layer. , A second layer formed by coating a composite composition of a moisture adsorbent with phenoxy, epoxy and imidazole, and a third layer provided on the second layer and made of polyethylene terephthalate. Can be.

The moisture adsorbent may be one or more of calcium oxide (CaO), silicon oxide (Silicon oxide, SiO 2), magnesium oxide (Magnesium oxide, MgO), and aluminum oxide (Aluminum oxide, Al 2 O 3).

The upper protective layer 110 may be formed of first to third layers, and may be provided on the outermost surface of the display protective film 100 to effectively prevent oxygen and moisture from penetrating into the inside.

When oxygen and moisture penetrate into the display protective film 100, the moldability of the display protective film 100 may be lowered, which may cause a problem in attaching to the curved edge portion of the display. In addition, when the oxygen and moisture penetrate, the composite functional resin layer 150 may be deteriorated, and after the attachment of the protective film 100 for display 100, recognition performance of a fingerprint or the like may be degraded. The upper protective layer 110 may protect the display protective film 100 so that physical properties can be easily maintained even in a high temperature and high humidity environment in the process of transporting and storing the display protective film 100 for a long time.

The upper protective layer 110, after washing a polyethylene terephthalate film having a thickness of 50㎛ with acetone and vacuum-dried, put it in a plasma reactor of 5mTorr pressure and purged with argon gas and argon for 3 minutes at 40W, 240mTorr After plasma treatment, the pressure of the plasma reactor is evacuated to 20 mTorr, and acrylic acid vapor is introduced into the plasma reactor to prepare a first layer made of an acrylic acid adsorbed polyethylene terephthalate film. Subsequently, the composite composition is prepared, and the composite composition is coated on the upper surface of the first layer at a room temperature with a bar coater having a thickness of 5 μm to 7 μm to provide a second layer. After attaching a third layer, which is a polyethylene terephthalate film, on top of the second layer, it may be prepared by drying in a 120 ° C. oven for 30 to 40 minutes.

In the upper protective layer 110, the first layer may be made of a polyethylene terephthalate film, the first layer may be washed with acetone, and then put into a plasma reactor to perform a plasma treatment using acrylic acid vapor. . The first layer is acrylic acid is adsorbed on the surface of the polyethylene terephthalate film by the plasma treatment, the first layer is polarized on the surface by the acrylic acid. The first layer having polarity by the acrylic acid can thereby be firmly attached to the second layer uniformly.

A second layer may be provided on the first layer, and the second layer may be formed by coating a composite composition including a moisture absorbent.

The composite composition may be prepared by preparing a particle solution, a first solution, and a second solution, and mixing the first solution and the second solution. The particle solution is mixed with 3g calcium powder to 97g methyl ethyl ketone and ball milled for 24 hours to prepare a methyl ethyl ketone solution in which the calcium powder is uniformly dispersed.

The first solution may be prepared by stirring 150 g of methyl ethyl ketone at a temperature of 60 ° C., stirring 125 g of phenoxy (YP-50) for 30 minutes in methyl methyl ketone, and then dissolving it completely.

The second solution may be prepared by stirring 150 g of methyl ethyl ketone at a temperature of 35 ° C., stirring 125 g of epoxy (KSR-50) for 30 minutes, and then dissolving it completely.

Subsequently, after mixing the first solution at a temperature of 60 ° C., the second solution was added thereto, followed by stirring with nitrogen purge for 1 hour, and 100 g of the particle solution and 2 g of imidazole were mixed while purging with nitrogen. By doing so, the composite composition can be produced.

The composite composition may be formed using a calcium powder, which is a moisture absorbent, formed of a polymer resin as a matrix, and may be coated on the first layer, and may prevent external moisture from being introduced into the inside by the moisture absorbent.

In addition, the upper protective layer 120 is composed of a first layer made of a polyethylene terephthalate film, a second layer formed by coating a composite composition containing a moisture adsorbent, and a third layer formed of a polyethylene terephthalate film, sequentially Since polymer resins having different densities are formed by stacking, flow paths, which are flows of gases that can flow in from the outside, are not formed in a straight line due to different characteristics of each layer, but are formed in a curved manner, thereby increasing the flow path of the gas. The gas can be prevented from entering inside.

The hard coating layer 130 may include a first coating part 131, a second coating part 132 provided under the first coating part 131, and a lower coating part 132 provided under the second coating part 132. The three coating part 133 and the polymer resin part 134 provided below the third coating part 133 may be sequentially provided.

The first coating part 131 includes fluorine in a thickness of 200 nm to 300 nm, the second coating part 132 includes a polymer solution in a thickness of 200 nm to 300 nm, and the third coating part 133 The surface of the polymer resin 134 may be formed by corona discharge.

The hard coating layer 130 forms a third coating part 133 by performing a corona discharge on the surface of the polymer resin part 134, and a polymer solution is coated on the third coating part 133. After the second coating part 132 is formed, the first coating part 131 is formed by gravure coating, from the polymer resin part 134 to the first to third coating parts 131, 132, and 133. ) May be formed in-line.

The polymer resin unit 134 may be homogenized at room temperature by mixing 100 g of isopropoxide (TTIP, 97%, Aldrich Chemical) and 400 g of acetylacetone (AA, 99%, Aldrich Chemical). The mixture was stirred until the first solution was prepared, and 4 mol of 3-glycidoxypropyl-trimethoxysilane [(3-glycidoxypropyl) -trimethoxysilane, GPTMS, 98%, Aldrich Chemical], a silane coupling agent, 400 g of ethanol, and distilled water 400 g and 0.001 mol of hydrochloric acid as a catalyst were added thereto, followed by stirring for 1 hour to prepare a second mixed solution. The first mixed solution and the second mixed solution were stirred at room temperature for 24 hours to prepare a third mixed solution.

After coating the third mixed solution on the substrate for 1 minute at 3,500 rpm using a spin coater (Spin 1200, Midas), and after the coating is completed, the first drying at 90 ℃ 30 minutes, after the first drying is completed After the second drying for 2 hours at 120 ℃, it can be maintained at room temperature for 24 hours to prepare the polymer resin portion 134.

The third coating part 133, while transferring the polymer resin portion 134 in the form of a film wound and transported in a roll at a speed of 100 m / min, a voltage of 13000 V and 20000 Hz on the outer surface of the polymer resin portion It can be formed by a corona discharge at a frequency of. Subsequently, it may be formed by coating a primer composition made of a polymer resin on the third coating part 133. The primer composition is 50g of a urethane resin emulsion (CK-PUD-F (10% emulsion solids), polyvinyl alcohol aqueous solution (Japan Synthetic Chemical Z200, solid content 4.5% aqueous solution) 111g, colloidal silica (Ranco Co., Ltd.) It is formed by mixing 0.5g of a solid content 20% aqueous solution), it can be formed by coating the primer composition on the third coating and dried at 100 ℃ for 5 minutes.

The polymer resin part 134 has a surface modified by the third coating part 133 to form a hydrophilic functional group on the surface, thereby improving adhesion to the second coating part 132 made of the primer composition.

The first coating part 131 is a fluorine-based polymer, and 10 g of polyvinylidene fluoride (polyvinylidene fluoride or polyvinylidene difluoride, PVDF, Alfa Aesar) is mixed with 28 g of an organic solvent isophorone (isophorone, Sigma-Aldrich) 20 wt% of the fluorine-based coating composition may be prepared, and the fluorine-based coating composition may be formed by coating the second coating part 131 and then drying at 100 ° C. for 5 minutes.

The first coating part 131 is a part exposed to the outside after removing the upper protective layer 110 and the upper silicon adhesive layer 120 after attaching the display protective film 100 to the display 10, The first coating part 131 may be formed using the fluorine-based coating composition to improve wear resistance and chemical resistance of the user's skin and hands.

The base layer 140, the composite functional resin layer 150 has a UV blocking ability, it is possible to prevent the UV transmitted to the inside of the protective film 10 for a display. In addition, the composite functional resin layer 150 may be cured in the process of performing the second curing to maintain the display protective film 10 in a predetermined form.

The composite functional resin layer 150 connects the base layer 140 and the lower protective layer 160 to each other, and at the same time gives the strength of the protective film for display 10 by the second curing with UV blocking ability. It may be to maintain the curved surface of the protective film 10 for a display.

The composite functional resin layer 150 is based on 200 parts by weight of the composite functional resin layer 150, 100 parts by weight of adhesive, 75 parts by weight of UV curable resin, 12.5 parts by weight of thermosetting agent, 0.5 parts by weight of thermosetting accelerator, photoinitiator It may consist of 6.5 parts by weight and 2.0 parts by weight of antioxidant.

In the composite functional resin layer 150, the adhesive and the UV curable resin are included in the above-described range, so that the display protective film 100 has a predetermined strength by first curing in the display protective film 100. The display may be molded to be uniformly attached to the entire surface of the display, and the strength may be further improved by the second curing so that the surface of the display may be stably fixed without lifting or the like at the curved edge portion of the display.

The adhesive may be a urethane adhesive or an acrylic adhesive.

The urethane adhesive is composed of a polyol, a diisocyanate, a chain extender, and a component of a catalyst, and the polyol is prepared using adipic acid and 1,6-hexanediol to have a molecular weight of 2,500 to 4,000, and 1 mole of a polyol. Diisocyanate may be used at a ratio of 1.5 to 3.0 moles per mole.

The UV curable resin is composed of a 5- or 6-functional monomer, the thermosetting agent is an isocyanate, the thermosetting accelerator is dibutyltin dilaurate, and the photoinitiator is 1-hydroxycyclolexyl phenyl Ketone (1-hydroxycyclohexyl phenyl ketone) or 2-hydroxy-2-methylpropiophenone, and the antioxidant is triethylene glycol-bis-3- (3-tert-butyl- 4-hydroxy-5-methylphenyl) propionate (Triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate).

The composite functional resin layer 150, 100 parts by weight of the adhesive is put into the first reactor, the first stirring for 20 minutes at 80 rpm at 35 ℃ to 40 ℃, and after the first stirring is complete UV in the first reactor After adding 75 parts by weight of the cured resin, a second stirring was performed at 35 ° C. at 80 rpm for 40 minutes, and the second stirring was completed, followed by cooling to 15 ° C. with a third stirring at 50 rpm. Subsequently, after cooling is completed, 12.5 parts by weight of a thermosetting agent, 0.5 parts by weight of a thermosetting accelerator, 6.5 parts by weight of a photoinitiator, and 2.0 parts by weight of an antioxidant are added thereto, and the fourth stirring is performed at 80 rpm for 1 hour, and the heating is performed after the fourth stirring is completed. After stirring at 80 rpm, it may be prepared by coating on the lower surface of the base layer 140.

In the composite functional resin layer 150, the adhesive and the UV curable resin may be first mixed and heated to uniformly mix the adhesive and the UV curable resin. Subsequently, after cooling to 15 ° C., a thermosetting agent, a thermosetting accelerator, a photoinitiator, and an antioxidant are added to prevent the reaction from occurring before the thermosetting agent, the thermosetting accelerator, and the photoinitiator are uniformly mixed in the adhesive and the UV curing resin. do. The thermosetting agent, the thermosetting accelerator, the photoinitiator and the antioxidant are heated to 35 DEG C to 40 DEG C again by sufficiently mixing the thermosetting agent, the thermosetting accelerator and the photoinitiator with the adhesive and the UV curing resin at a low temperature of 15 DEG C. It can make it react uniformly to cured resin as a whole.

The lower protective layer 160 may be provided below the composite functional resin layer 150. The lower protective layer 160, after washing the polyethylene terephthalate film of 25㎛ in acetone, ethanol, primary distilled water for 10 minutes each, dried at room temperature, and after drying is complete the polyethylene terephthalate film in a fluorination reactor After raising the temperature of the fluorination reactor to 100 ° C., purging twice with 99.8% purity fluorine gas, evacuating to 1.0 × 10 ⁻³ torr, and fluorine gas having purity 99.8% purity to the fluorination reactor for 6 minutes. Injected and maintained at 75torr for 10 minutes to perform direct fluorination, the direct fluorinated polyethylene terephthalate film is placed in a container containing distilled water can be prepared by reacting at 40kHz, room temperature for 10 minutes with an ultrasonic generator and dried at room temperature have.

The lower protective layer 160 has a surface etching phenomenon caused by the fluorine gas to smooth the surface, and then promote the decomposition or synthesis of carbon chains of the polyethylene terephthalate during the ultrasonic scanning process. Thus, C-HF, CC , The bond of CH is broken, and more stable and high hydrophilic C-OH, C-OOH bond is formed. As a result, a hydrophilic functional group is introduced into the polyethylene terephthalate film to form the composite functional resin layer 150 and the lower protective layer 160 provided on the lower protective layer 160 and the lower protective layer 160. Cohesion with the lower silicon adhesive layer 170 provided in the can be improved.

In addition, the bonding force between the lower protective layer 160 and the lower silicon adhesive layer 170 is increased, so that the display protective film 100 is attached to the front surface of the display 100 to the fluorine-releasing film layer ( In the process of removing 180, the lower silicon adhesive layer 170 is not detached by the fluorine release film layer 180, so that a feeling of stickiness of the fluorine release film layer 180 does not remain, and the lower silicon adhesion layer is retained. By keeping the flat 170, the display protective film 100 may be firmly attached to the display.

In the present embodiment, the display protective film 100 is sequentially from the top, the upper protective layer 110, the upper silicon adhesive layer 120, the hard coating layer 130, the base layer 140, the composite functional water It is composed of a ground layer 150, a lower protective layer 160, a lower silicon adhesive layer 170 and a fluorine release film layer 180, the display protective film 100 is the upper protective layer 110 and the upper silicon. After removing the adhesive layer 120 and the fluorine release film layer 180 is attached to the display.

The display protective film 100 is attached to the display to protect the display by friction, chemicals, moisture, etc., to prevent contamination such as fingerprints left on the surface or to prevent scratches, etc., at the same time The display device may be provided so as not to interfere with the optical characteristics of the display, ultrasonic waves such as fingerprint recognition, face recognition, and the like.

Thus, the display protective film 100 according to the present embodiment is the polyethylene terephthalate provided in the upper protective layer 110, the base layer 140 and the lower protective layer 160 is provided with a refractive index of 1.5 to 1.6 It may be provided in a range approximately similar to the refractive index between the other layers. The display protective film 100 may be provided with a refractive index similar to each other as a whole, thereby minimizing interference by the display protective film 100 during ultrasonic and optical recognition.

Hereinafter, another embodiment of the present invention will be described with reference to FIG. 3. Except for the content to be described later, since it is similar to the content described in the embodiment described in Figures 1 and 2 will not be described in detail.

Alternatively, the display protective film may be further provided with a UV blocking layer, respectively, on the upper portion of the upper protective layer and the lower portion of the fluorine release film layer. The UV blocking layer may be provided on the outermost surface of the protective film for display, respectively, and may be provided to block UV that may be introduced from the outside. The UV blocking layer may be provided with a thickness of 1㎛ to 50㎛, if the thickness is less than 1㎛ problem of low UV blocking ability, if it exceeds 50㎛ problem by increasing the thickness of the display protective film unnecessarily.

 The UV blocking layer may be a polyvinyl alcohol resin as a matrix, and may be provided in the form of a film in which composite nanoparticles of zinc oxide and titanium oxide are dispersed in the polyvinyl alcohol resin.

The UV blocking layer is prepared by using a sol-gel (zinc) powder (sol-gel), by using anatase method (anatase) to prepare a titanium dioxide powder, using the zinc oxide powder and the titanium dioxide powder The composite nanoparticles were prepared, 10 g of polyvinyl alcohol was added to 90 g of distilled water, and then dissolved by stirring at 70 ° C. for 1 hour. The composite nanoparticles were added at 5 wt% and cast in the form of a film. Can be prepared by drying.

The zinc oxide powder is prepared by reacting 0.05 M acetate zinc (M) and 0.5 L absolute ethanol at 80 ° C. in an evaporator for 3 hours to dissolve, and 0.3 L of the reactant is discharged by condensation. To the remaining 0.2 L reactant, 0.3 L absolute ethanol and 0.07 M lithium hydroxide (Lithium Hydroxide, LiOH) were added and stirred at room temperature for about 1 hour. Subsequently, after dispersing and washing with an ultrasonic bath, a dust filter and lithium hydroxide are removed using a 0.1 μm glass filter to obtain a colloidal form. Zinc oxide powder (Zinc Oxide Powder) may be prepared by drying in a 70 ° C. hot air dryer.

The titanium dioxide powder, 5 ml of titanium isopropoxide (TTIP) and 15 ml of isopropanol (Isopropanol) was stirred at room temperature for 1 hour, 250 ml of distilled water was added and stirred for 10 minutes, followed by hydrochloric acid (HCl) Adjust the pH to 7 using. Subsequently, the mixture was stirred at 70 ° C. for 20 hours using a magnetic bar, washed with distilled water, and then vacuum dried at 100 ° C. for 1 hour using a vacuum dryer, and dried at 600 ° C. after the vacuum drying. Titanium dioxide powder (TiO 2 Powder) can be prepared by a calcination process for 2 hours.

Using the zinc oxide powder and titanium dioxide powder prepared as described above, zinc oxide colloids and titanium oxide colloids may be prepared, respectively, and may be prepared as composite nanoparticles.

The zinc oxide colloid, after adding 1 g of the zinc oxide powder to 50 ml of absolute ethanol, stirred for 1 hour with a magnetic bar at room temperature, and then dispersed for 1 hour using an ultrasonic bath, hydrochloric acid was added thereto It can be prepared by adjusting to pH 6.

The titanium oxide colloid was added 0.2 g of polyvinyl acetate (Poly (vinyl acetate)) to 50 ml of ethanol, and then stirred at room temperature with a magnetic bar for 1 hour, and then 2 ml of titanium isopropoxide and 2 ml of distilled water were added thereto. After stirring at room temperature with a magnetic bar can be prepared for 1 hour.

Subsequently, the zinc oxide colloid is added to the titanium oxide colloid and adjusted to pH 7, followed by reaction at 250 ° C. for 24 hours through a hydrothermal synthesizer to prepare composite nanoparticles.

The UV blocking layer may further include composite nanoparticles, wherein the composite nanoparticles may be prepared by zinc oxide powder prepared by the sol-gel method and titanium dioxide powder prepared by the atanase method. The composite nanoparticles may be provided as nano-sized particles and uniformly dispersed in a matrix composed of the polyvinyl alcohol column. The composite nanoparticles constituting the UV blocking layer has a linear relationship with the surface area and the UV absorbance of the composite nanoparticles, thereby absorbing the UV irradiated by the protective film for the display to allow UV to penetrate between the UV blocking layers. Can be effectively prevented. In addition, the UV blocking layer may be respectively provided on the upper surface of the upper protective layer, the lower surface of the fluorine release film layer may be detached before performing the second curing.

Figure 3 is a flow chart showing a manufacturing method of a protective film for a display according to another embodiment of the present invention.

According to another aspect of the present invention, an embodiment of the present invention may include a method of manufacturing a protective film for display.

The manufacturing method of the protective film for a display, which is attached to a display having a curved edge portion, preparing a base layer for preparing a base layer comprising a polyethylene terephthalate; Sequentially preparing a hard coating layer consisting of a first coating part, a second coating part, a third coating part, and a polymer resin part, applying an upper silicon adhesive layer on top of the hard coating layer, and an upper part of the upper silicon adhesive layer Preparing a first film part by including an upper protective layer including polyethylene terephthalate (PET); A composite functional resin layer is prepared, the composite functional resin layer is provided on an upper portion of a lower protective layer including polyethylene terephthalate, a lower silicon adhesive layer is applied to a lower portion of the lower protective layer, and the lower silicone adhesive layer Preparing a second film part by providing a fluorine-releasing film layer at a lower portion thereof; The first film part is provided on the upper part of the base layer, and the second film part is provided on the lower part of the base material layer, and then passed through a pair of pressure rolls to sequentially stack the first film part, the base layer, and the second film part. Preparing a protective film for a display; Performing a first curing by applying heat at an upper portion of the upper protective layer; And after the first curing is performed, mounting the protective film for display on a display having a curved edge portion, and then irradiating UV with a UV lamp on the upper protective layer to perform second curing. It may include.

The protective film for display according to the present embodiment has a first film part composed of a plurality of layers on the upper part of the substrate layer, and a second film part composed of a plurality of layers on the lower part of the substrate layer. The first film portion, the base layer and the second film portion are sequentially laminated, and the first curing is performed so that the hardness (as measured by ASTMD 2240, JISK 7215) is 40H to 45H, and then the second curing It can be performed so that the hardness (measured by ASTMD 2240, JISK 7215) is 60H to 65H.

In the method of manufacturing a display protective film according to the present embodiment, the display protective film may be provided with a hardness of 40H to 45H by performing a first curing before attaching to the display.

By maintaining the hardness of the display protective film to 40H to 45H by the first curing, the predetermined shape of the display protective film is maintained and the protective film for display is attached to the front surface of the display and then curved It can be attached to the branch without lifting. Subsequently, the display film is cured by the second hardening, thereby preventing the lifting phenomenon in the curved edge portion due to the bending restoring force.

In the preparing of the first film part, the upper protective layer is provided on the first layer made of polyethylene terephthalate, the first layer, the moisture adsorbent, phenoxy, epoxy and already A second layer formed by coating a composite composition consisting of imidazole, and a third layer provided on the second layer and made of polyethylene terephthalate, wherein the moisture adsorbent is calcium oxide (CaO), oxide Silicon oxide (SiO 2), magnesium oxide (Magnesium oxide, MgO) and aluminum oxide (Aluminum oxide, Al 2 O 3) may be one or more.

The upper protective layer may be formed of a first layer to a third layer. First, a first layer disposed at the bottom may be prepared first, and a second layer may be formed by coating a composite composition on the first layer. It may be prepared by laminating a third layer on top of the second layer.

The first layer was a polyethylene terephthalate film having a thickness of 50㎛ washed with acetone and vacuum dried, put into a plasma reactor of 5mTorr pressure and purged with argon gas, and treated with argon plasma for 3 minutes at 40W, 240mTorr, After exhausting the pressure of the plasma reactor to 20mTorr may be prepared by introducing acrylic acid vapor into the plasma reactor, the first layer may be made of polyethylene terephthalate film adsorbed acrylic acid.

The second layer may be provided by manufacturing the composite composition and coating the composite composition on a top surface of the first layer at a room temperature using a bar coater with a thickness of 5 μm to 7 μm.

The third layer may be formed by attaching a third layer, which is a polyethylene terephthalate film, on top of the second layer, and then sequentially preparing the first layer, the second layer, and the third layer in a 120 ° C. oven. The top protective layer may be prepared by drying for 30 to 40 minutes.

The composite composition constituting the second layer may be prepared by preparing a particle solution, a first solution, and a second solution, respectively, and mixing the particle solution, the first solution, and the second solution.

The particle solution may be prepared by mixing 3 g of calcium powder with 97 g of methyl ethyl ketone and ball milling for 24 hours. Subsequently, in preparing the first solution, the first solution was prepared by dividing 125 g of phenoxy (YP-50) into the methyl ethyl ketone for 30 minutes while maintaining 150 g of methyl ethyl ketone at 60 ° C. It can be prepared by stirring to dissolve completely. The second solution may be prepared by stirring 150 g of methyl ethyl ketone at a temperature of 35 ° C., stirring 125 g of epoxy (KSR-50) for 30 minutes, and then dissolving it completely.

After the second solution was added to the first solution at a temperature of 60 ° C., the mixture was stirred while purging with nitrogen for 1 hour, and 100 g of the particle solution and 2 g of imidazole were mixed while nitrogen purging to prepare the composite composition. Can be.

In the preparing of the first film portion, the hard coating layer, the first coating portion is provided with a thickness of 200nm to 300nm, including fluorine, the second coating portion includes a polymer solution in a thickness of 200nm to 300nm, The third coating part is formed by corona discharge on the surface of the polymer resin part, and the polymer resin part is coated with the polymer solution after the corona discharge, and then a second coating part is formed. The first to third coating parts may be formed inline.

The hard coating layer may first prepare a polymer resin part, and the polymer resin part may be provided in a roll in a film form.

The polymer resin part is mixed with 100 g of isopropoxide (titanium isopropoxide, TTIP, 97%, Aldrich Chemical) and 400 g of acetylacetone (acetyl acetone, AA, 99%, Aldrich Chemical) until it is homogenized at room temperature. To prepare a first solution. Next, 4 mol of 3-glycidoxypropyl-trimethoxysilane [(3-glycidoxypropyl) -trimethoxysilane, GPTMS, 98%, Aldrich Chemical], a silane coupling agent, 400 g of ethanol, 400 g of distilled water, and 0.001 mol of hydrochloric acid as a catalyst were added thereto. To stir for 1 hour to prepare a second solution.

The first solution and the second solution were stirred at room temperature for 24 hours to prepare a mixed solution, and the mixed solution was coated on the substrate for 1 minute at 3,500 rpm using a spin coater (Spin 1200, Midas), and coated. After the completion of the first drying at 90 ℃ for 30 minutes, and after the first drying is completed, the second drying at 120 ℃ for 2 hours, it can be prepared by maintaining at room temperature for 24 hours.

A third coating part may be provided on the upper part of the polymer resin part, wherein the third coating part proceeds at a speed of 100 m / min in the polymer resin part wound on the roll, and a voltage of 13000 V and 20000 Hz on the outer surface of the polymer resin part. It can be formed by a corona discharge at a frequency of.

A hydrophilic group is formed on the surface of the polymer resin part by the third coating part to improve the coupling of the polymer coating part with the second coating part provided on the third coating part.

The second coating part, 50g urethane resin emulsion (CK-PUD-F (10% emulsion solids), polyvinyl alcohol aqueous solution (Japan Synthetic Chemical Z200, 4.5% solids aqueous solution) 111g, colloidal silica ( Ranco, 20% solids 20% aqueous solution) After mixing, it can be formed by coating on the third coating and dried at 100 ℃ for 5 minutes.

The first coating part is a fluorine-based polymer mixed with 10 g of polyvinylidene fluoride (polyvinylidene difluoride, PVDF, Alfa Aesar) and 28 g of an organic solvent isophorone (isophorone, Sigma-Aldrich) to a solid content of 20% by weight. The fluorine-based coating composition may be prepared, and the fluorine-based coating composition may be coated on the second coating part and then dried at 100 ° C. for 5 minutes.

In the preparing of the second film portion, the composite functional resin layer, 100 parts by weight of the adhesive is put into the first reactor, the first stirring for 20 minutes at 80 rpm at 35 ℃ to 40 ℃, the first stirring is completed After adding 75 parts by weight of the UV curable resin to the first reactor, and then stirred for 2 minutes at 35 ° C 80 rpm for 40 minutes, and after the second stirring is completed, cooled to 15 ° C with a third stirring at 50 rpm, the cooling is completed After the 12.5 parts by weight of the thermosetting agent, 0.5 parts by weight of the thermosetting accelerator, 6.5 parts by weight of the photoinitiator and 2.0 parts by weight of antioxidant was added and the fourth stirring at 80rpm for 1 hour, the fourth stirring was completed and then stirred at 80rpm while heating Can be.

The composite functional resin layer provides adhesiveness and UV blocking ability, and at the same time provides different hardness by the first curing and the second curing of the protective film for display, so that the protective film for display is made by the composite functional resin layer. In order to prevent deterioration during distribution and storage, and to attach the protective film for display to the front surface of the display, it is possible to be molded to adhere well without bubbles or the like on the curved edges, and then by performing the second curing. As the display yaw protection film is stably fixed to the display, it is possible to prevent a defect such as a spring back of the display protection film from the curved edge portion.

In the preparing of the second film part, the lower protective layer is washed with a polyethylene terephthalate film of 25㎛ in order of acetone, ethanol, primary distilled water for 10 minutes each, dried at room temperature, and after the drying is complete the polyethylene The terephthalate film was placed in a fluorination reactor, the temperature of the fluorination reactor was raised to 100 ° C, purged twice with fluorine gas with a purity of 99.8%, and then evacuated to 1.0x10 ^-3 torr, and then with a purity of 99.8 in the fluorination reactor. % Fluorine gas was injected for 6 minutes and maintained at 75torr for 10 minutes to carry out direct fluorination.The polyethylene terephthalate film having the direct fluorination was placed in a container containing distilled water and reacted at 40 kHz for 10 minutes with an ultrasonic generator. It may be prepared by drying at room temperature.

The lower protective layer may be provided with a composite functional resin layer on an upper portion of the lower protective layer, and a lower silicon adhesive layer on a lower portion of the lower protective layer. Both sides of the composite functional resin layer and the lower silicone adhesive is provided with a state of viscosity, thereby increasing the adhesive strength of the upper and lower portions of the lower protective layer, it is also important to use the protective film for the display later Only the fluorine release film layer is removed in the process and the lower silicon adhesive layer should be attached to the lower protective layer. By performing the surface treatment of the lower protective layer as described above, the lower protective layer may be such that the composite functional resin layer and the lower silicon adhesive layer is well maintained.

The method for manufacturing a protective film for display according to the present embodiment may include a first curing using heat, and a second curing using UV.

The first curing may be performed by passing through the first chamber, the second chamber, the third chamber, the fourth chamber, and the fifth fifth chamber sequentially provided at a speed of 8 m / min to 12 m / min. The first chamber is 75 ℃ to 85 ℃, the second chamber is 95 ℃ to 105 ℃, the third chamber is 115 ℃ to 125 ℃, the fourth chamber is 130 ℃ to 140 ℃, the first The five chambers may be between 75 ° C and 85 ° C. The first to fifth chambers may be provided with the same length of 4m, respectively.

Preferably, the first chamber may be 80 ° C, the second chamber may be 100 ° C, the third chamber may be 120 ° C, the fourth chamber may be 135 ° C, and the fifth chamber may be 80 ° C.

The second curing may be performed by irradiating UV at 10000mJ / cm 2 for 20 seconds at 500 nmW / cm 2 at 365 nm for UV irradiation by a UV lamp.

Hereinafter, examples and comparative examples of the present invention are described. However, the following examples are only one preferred embodiment of the present invention and the scope of the present invention is not limited by the following examples.

1. Preparation of Examples and Comparative Examples

Preparation Example 1 (Preparation of Hard Coating Layer)

100 g of isopropoxide (TTIP, 97%, Aldrich Chemical) and 400 g of acetyl acetone (AA, 99%, Aldrich Chemical) are mixed and stirred until homogenized at room temperature to prepare the first mixed solution. 4 mol of silane coupling agent, 3-glycidoxypropyl-trimethoxysilane, (GPTMS, 98%, Aldrich Chemical), 400 g of ethanol, 400 g of distilled water, and 0.001 mol of hydrochloric acid as a catalyst were prepared. After the addition, the mixture was stirred for 1 hour to prepare a second mixed solution, and the first mixed solution and the second mixed solution were stirred at room temperature for 24 hours to prepare a third mixed solution. Subsequently, the third mixed solution is coated on the substrate for 1 minute at 3,500 rpm using a spin coater (Spin 1200, Midas), and after the coating is completed, firstly dried at 90 ° C. for 30 minutes, and the first drying is completed. After the second drying for 2 hours at 120 ℃, and maintained at room temperature for 24 hours to prepare a polymer resin in the form of a film. The polymer resin prepared in the form of a film was wound on a roll and formed by corona discharge at a voltage of 13000 V and a frequency of 20000 Hz while transferring at a speed of 100 m / min to form a corona coating layer having a thickness of 5 nm. 50 g of urethane resin emulsion (CK-PUD-F (Chokwang-poly urethane dispersion) solid content 10% emulsion) and polyvinyl alcohol aqueous solution (Japan synthetic chemicals Z200, 4.5% solid content aqueous solution) 111 g, colloidal 0.5 g of silica (Ranco, 20% solids aqueous solution) was mixed until homogenized at room temperature to prepare a primer composition, and the primer composition was formed by coating the prepared primer composition on a corona coating layer at a thickness of 300 nm. 10 g of polyvinylidene fluoride (polyvinylidene fluoride, PVDF, Alfa Aesar) was mixed with 28 g of an organic solvent isophorone (isophorone, Sigma-Aldrich) to prepare a fluorine-based coating composition having a solid content of 20% by weight. The coating composition was coated on a primer layer transported at a speed of 100 m / min, and then dried at 100 ° C. for 5 minutes to form a fluorine coating layer. The thickness of the fluorine coating layer, primer layer, corona coating layer, and polymer resin part was sequentially A 1.5 micrometer hard coat layer was prepared.

Example 1

The polyethylene terephthalate film having a thickness of 25 μm was washed with acetone and dried in vacuo to prepare a substrate layer.

After coating 7657 (manufactured by Dow Corning), a silicone adhesive, to a thickness of 10 μm on top of the 1.5 μm hard coating layer prepared in Preparation Example 1, drying at 25 ° C. for 30 minutes to prepare an upper silicone adhesive layer, A first film part was prepared by providing an upper protective layer made of a polyethylene terephthalate film having a thickness of 50 μm on the upper silicon adhesive layer.

As shown in Table 1 below, 100 g of the adhesive was put in a first reactor, stirred at 80 ° C. for 20 minutes at 35 ° C., and 75 g of a UV curable resin was added to the first reactor, followed by a second stirring at 80 ° C. at 35 ° C. for 40 minutes. . Then, the stirring speed was slowed to 50 rpm, cooled to 15 DEG C with a third stirring, and the stirring was maintained for 30 minutes while adding 12.5 g of a thermosetting agent, 0.5 g of a thermosetting accelerator, 6.5 g of a photoinitiator, and 2.0 g of an antioxidant, followed by 1 at 80 rpm. After the fourth stirring for 4 hours, the mixture was stirred at 80 rpm while heating to room temperature after the fourth stirring was completed, and stirred at room temperature for 1 hour to prepare a resin mixture. The resin mixture was applied on the polyethylene terephthalate film (lower protective layer) having a thickness of 50 μm to form a composite functional resin layer having a thickness of 25 μm. The upper part of the lower protective layer formed with a composite functional resin layer was coated with a silicon adhesive 7657 (manufactured by Dow Corning) so as to have a thickness of 10㎛, and dried at 25 ℃ for 30 minutes to prepare a lower silicone adhesive layer, A second film part was prepared by providing a fluorine-releasing film layer under the lower silicon adhesive layer. By arranging the first film portion on the upper portion of the base layer so that the second film portion is provided on the lower portion of the base layer, a protective film in which the first film portion, the base layer, and the second film portion are sequentially laminated using the apparatus as shown in FIG. 6 is manufactured. It was. 4 is a view schematically showing an apparatus for manufacturing a protective film by pressing the first film portion, the base layer, and the second film portion.

Subsequently, the prepared protective film was passed through four chambers each having a length of 4 m at a speed of 8 m / min. At this time, the temperature of the four chambers are sequentially 80 ℃, 100 ℃, 135 ℃ and 80 ℃, and passed through the four chambers for the protective film for display and maintained at room temperature for 24 hours. Subsequently, after the protective film is etched to fit the shape of the display, it is attached to the top of the display and using a jig as shown in FIG. 4 using a UV LED lamp at 500 mW / cm 2 for 20 sec (at 365 nm, 10000 mJ / cm2) was irradiated with UV for 5 seconds to perform a second curing to prepare a protective film of the form as shown in FIG. 5 is a view schematically showing an LED device for UV curing used in Example 1, Figure 6 is a photograph of the protective film of Example 1.

Amount (g)
Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 glue urethane 100 100 100 100 100 100 100 UV Curing Resin 2- or 4-functional monomer 75 5-functional monomer 75 6 functional monomer 75 75 6-functional oligomer 75 9-functional oligomer 75 No addition Thermosetting agent Isocyanate Thermosetting accelerator Dibutyltin dilaurate Antioxidant Triethylene Glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate 2 2 2 2 2 0 2 Photoinitiator 1-hydroxycyclolexyl phenyl ketone 6.5 6.5 6.5 6.5 6.5 6.5 No addition

Example 2

Prepared as in Example 1, the resin mixture to form a composite functional resin layer was mixed in the composition shown in Table 1 to prepare a protective film.

Comparative Example 1

Prepared as in Example 1, the resin mixture to form a composite functional resin layer was mixed in the composition shown in Table 1 to prepare a protective film.

Comparative Example 2

Prepared as in Example 1, the resin mixture to form a composite functional resin layer was mixed in the composition shown in Table 1 to prepare a protective film.

Comparative Example 3

Prepared as in Example 1, the resin mixture to form a composite functional resin layer was mixed in the composition shown in Table 1 to prepare a protective film.

Comparative Example 4

Prepared as in Example 1, the resin mixture to form a composite functional resin layer was mixed in the composition shown in Table 1 to prepare a protective film.

Comparative Example 5

Prepared as in Example 1, the resin mixture to form a composite functional resin layer was mixed in the composition shown in Table 1 to prepare a protective film.

2. Evaluation of Examples and Comparative Examples

Visual test

Table 2 below is a result of visually confirming the transparency of the Examples 1, 2 and Comparative Examples 1 to 5, the yellowing and the occurrence of lifting of the edge portion.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Transparency O O O X X O O Yellowing (X: Occurrence) O O O O △ X O Edge Lifted (X: Lifted) △ O X O O O X

In Table 2, transparency and yellowing were confirmed by visual inspection, and the occurrence of lifting of the curved edges was maintained for 5 minutes after attaching the protective film according to the Examples and Comparative Examples to the display having the curved edges. It was confirmed whether or not it occurs.

As shown in Table 2, Example 1 and Example 2 was excellent in transparency, yellowing did not occur, it was confirmed that the lifting does not occur in the curved edge portion. On the other hand, Comparative Example 1 and Comparative Example 5 was confirmed that the lifting occurs in the curved edge portion. This is because Comparative Example 1 was not sufficiently cured UV curing resin in the process of performing the second curing, Comparative Example 2 does not include the UV curing resin does not adhere well to the curved edge of the display during the first curing It seems to have occurred. In the case of Example 1 and Example 2, it was not hard after only the first curing was progressed, so that it adhered well to the curved edge of the display, and then, after the second curing was performed, no lift was generated on the curved edge of the display. It could be confirmed that it is attached well. Comparative Examples 2, 3, and 4 were not suitable because they were not transparent to the naked eye.

Shock test

Table 3 below shows the results of experiments of the impact resistance tests for the examples and the comparative examples. Impact resistance test was repeated 5 times the sample to confirm the average value after 10 repeated tests, using a Charpy impact tester as shown in Figure 7, the higher the value means that the higher the shock absorbed.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Shock test
(Scale value) 500 mJ 520mJ 400 mJ 420mJ 380mJ 400 mJ 200 mJ

Referring to Table 3, it was confirmed that Example 1 and Example 2 exhibit a relatively high value compared to Comparative Examples 1 to 5. Among Comparative Examples 1 to 5, Comparative Example 5 exhibited the lowest value, which is considered to have a relatively low value since no UV curable resin was added.

Blue Light Block Rate Test by Wavelength

Using the protective film according to Example 1 was confirmed the fluorite blocking rate for each wavelength band, it is shown in Table 4 and FIG.

Wavelength band (nm) 380-500 430-450 450-470 430-470 Real black 54.9 35.2 35.8 35.5 Real orange 50.2 30.9 31.1 30.9 Yellow 31.7 36.8 34.1 35.2 UV400 31.8 0.7 2.8 1.8

Referring to Table 4 and Figure 8, Example 1 was confirmed that the excellent blue light cut performance.

Shore-A Hardness Test

Shore-A hardness was measured and shown in Table 5 for Examples and Comparative Examples. Fig. 6 is a hardness measuring device (product name: HT-6510, measuring range: 10 to 90H (A)), and measurement standards were measured using ASTMD 2240 and JISK 7215.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Before UV irradiation 43 40 43 55 38 40 50 After UV irradiation 60 61 55 71 55 65 52

As shown in Table 5, in Examples 1 and 2, the hardness was low before UV irradiation, and thus the moldability was favorable, and after UV irradiation, the hardness was increased to adhere to the curved edge of the display. On the other hand, in Comparative Example 1, the hardness was too high after UV irradiation, and the lifting phenomenon occurred. In Comparative Example 5, since the hardness was high even before UV irradiation, it was difficult to adhere to the curved edges.

Those skilled in the art will appreciate that the present invention can be embodied in other specific forms without changing the technical spirit or essential features of the present invention. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. The scope of the present invention is indicated by the scope of the following claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and the equivalent concept are included in the scope of the present invention. Should be interpreted.

100: protective film for display
110: upper protective layer
120: upper silicon adhesive layer
130: hard coating layer
140: substrate layer
150: composite functional resin layer
160: lower protective layer
170: lower silicon adhesive layer
180: fluorine release film layer

Claims (25)

delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete In the manufacturing method of the protective film for display attached to the display having a curved edge portion,
Preparing a base layer for preparing a base layer including polyethylene terephthalate;
Sequentially preparing a hard coating layer consisting of a first coating part, a second coating part, a third coating part, and a polymer resin part, and including polyethylene terephthalate (PET) having an upper silicon adhesive layer at a lower part thereof. Stacking an upper protective layer on the hard coating layer to prepare a first film part;
A composite functional resin layer is prepared, the composite functional resin layer is provided on an upper portion of a lower protective layer including polyethylene terephthalate, a lower silicon adhesive layer is applied to a lower portion of the lower protective layer, and the lower silicone adhesive layer Preparing a second film part by providing a fluorine-releasing film layer at a lower portion thereof;
The first film part is provided on the upper part of the base layer, and the second film part is provided on the lower part of the base material layer, and then passed through a pair of pressure rolls to sequentially stack the first film part, the base layer and the second film part. Preparing a protective film for a display;
Applying heat to the upper protective layer to perform first curing; And
And after the first curing is performed, placing the protective film for display on a display having a curved edge portion, and then performing a second curing by irradiating UV with a UV lamp.
In the preparing of the first film portion, the hard coating layer,
The first coating portion contains fluorine in a thickness of 200nm to 300nm,
The second coating part comprises a polymer solution in a thickness of 200nm to 300nm,
The third coating portion is formed by corona discharge on the surface of the polymer resin portion,
The polymer resin is coated with the polymer solution after the corona discharge to form a second coating, after the third coating is formed by gravure coating, the first to third coating is formed inline,
The polymer resin portion,
100 g of isopropoxide (TTIP) and 400 g of acetyl acetone (AA) were mixed and stirred until homogenized at room temperature to prepare a first solution.
4 mol of 3-glycidoxypropyl-trimethoxysilane (GPTMS), a silane coupling agent, 400 g of ethanol, 400 g of distilled water, and 0.001 mol of hydrochloric acid as a catalyst were added thereto, followed by stirring for 2 hours. To prepare a solution,
Preparing a mixed solution by stirring the first solution and the second solution at room temperature for 24 hours,
The mixed solution is coated on the substrate for 1 minute at 3,500 rpm using a spin coater,
After the coating is completed, the first drying at 90 ℃ 30 minutes,
After the first drying is completed, after the second drying for 2 hours at 120 ℃,
Prepared by keeping at room temperature for 24 hours,
The third coating unit,
While maintaining the polymer resin part at a speed of 100 m / min, the polymer resin part is formed by corona discharge at a voltage of 13000 V and a frequency of 20000 Hz,
The second coating part,
50 g of a urethane resin emulsion, 111 g of polyvinyl alcohol aqueous solution, and 0.5 g of colloidal silica are mixed, and then coated on the third coating part and dried at 100 ° C. for 5 minutes,
The first coating unit,
10 g of polyvinylidene fluoride or polyvinylidene difluoride (PVDF) is mixed with 28 g of an organic solvent isophorone to prepare a fluorine-based coating composition having a solid content of 20% by weight, and the fluorine-based coating composition is used as the fluorine-based polymer. Method of manufacturing a protective film for a display is formed by coating on the coating portion and then dried for 5 minutes at 100 ℃.
The method of claim 18,
In the preparing of the first film portion, the upper protective layer,
A first layer made of polyethylene terephthalate, a second layer provided on top of the first layer and formed by coating a composite composition made of a moisture adsorbent and phenoxy, epoxy and imidazole, The third layer is provided on the second layer and made of polyethylene terephthalate, wherein the moisture adsorbent is calcium oxide (CaO), silicon oxide (SiO ₂ ), magnesium oxide (Magnesium oxide, MgO). ) And aluminum oxide (Aluminum oxide, Al ₂ O ₃ ),
The upper protective layer,
After washing the polyethylene terephthalate film having a thickness of 50㎛ with acetone and vacuum drying, put into a plasma reactor with a pressure of 5mTorr and purged with argon gas, and treated with argon plasma for 3 minutes at 40W, 240mTorr, the pressure of the plasma reactor After exhausting to 20mTorr acrylic acid vapor is introduced into the plasma reactor to prepare a first layer consisting of a polyethylene terephthalate film adsorbed acrylic acid,
Preparing the composite composition, and coating the composite composition on the upper surface of the first layer at a room temperature with a thickness of 5 μm to 7 μm using a bar coater to provide a second layer,
After attaching a third layer of a polyethylene terephthalate film on top of the second layer, and then dried for 30 to 40 minutes in a 120 ℃ oven manufacturing method of a protective film for a display.
The method of claim 19,
The composite composition,
3 g of calcium powder was mixed with 97 g of methyl ethyl ketone and ball milled for 24 hours to prepare a particle solution.
150 g of methyl ethyl ketone was maintained at a temperature of 60 ° C., and 125 g of phenoxy was added to the methyl ethyl ketone for 30 minutes while stirring to dissolve completely to prepare a first solution.
150 g of methyl ethyl ketone was maintained at a temperature of 35 ° C., and 125 g of epoxy was split into the methyl ethyl ketone for 30 minutes and stirred to dissolve completely to prepare a second solution.
After the second solution was added to the first solution at a temperature of 60 ° C., the mixture was stirred while purging with nitrogen for 1 hour,
A method of manufacturing a protective film for display, which is prepared by mixing 100 g of the particle solution and 2 g of imidazole while purging with nitrogen.
delete The method of claim 18,
In the preparing of the second film portion, the composite functional resin layer,
100 parts by weight of the adhesive was placed in a first reactor, first stirred at 80 rpm at 35 ° C. to 40 ° C. for 20 minutes,
After the first stirring is completed, 75 parts by weight of the UV curable resin is added to the first reactor, and the second stirring is performed at 35 ° C. for 80 minutes at 80 rpm,
After the second stirring is completed and cooled to 15 ℃ with a third stirring at 50 rpm,
After the cooling was completed, 12.5 parts by weight of the thermosetting agent, 0.5 parts by weight of the thermosetting accelerator, 6.5 parts by weight of the photoinitiator and 2.0 parts by weight of antioxidant were added and stirred for 4 hours at 80 rpm for 1 hour,
Method of manufacturing a protective film for a display is prepared by stirring at 80 rpm while heating after the fourth stirring is completed.
The method of claim 18,
In the preparing of the second film portion, the lower protective layer,
After washing the polyethylene terephthalate film of 25㎛ each for 10 minutes in acetone, ethanol, primary distilled water and dried at room temperature,
After drying is complete, the polyethylene terephthalate film is placed in a fluorination reactor, the temperature of the fluorination reactor is raised to 100 ° C, purged twice with fluorine gas with a purity of 99.8%, and then exhausted to 1.0x10 ^-3 torr,
Injecting fluorine gas with a purity of 99.8% for 6 minutes into the fluorination reactor for 10 minutes at 75torr to perform direct fluorination,
The method of manufacturing a protective film for display, which the fluorinated polyethylene terephthalate film is placed in a container containing distilled water and reacted at 40 kHz for 10 minutes at room temperature with an ultrasonic generator, followed by drying at room temperature.
The method of claim 18,
The first curing is performed by passing through the first chamber, the second chamber, the third chamber, the fourth chamber and the fifth fifth chamber sequentially provided at a speed of 8 m / min to 12 m / min,
The first chamber is 75 ℃ to 85 ℃,
The second chamber is 95 ℃ to 105 ℃,
The third chamber is 115 ° C to 125 ° C,
The fourth chamber is 130 ℃ to 140 ℃,
The fifth chamber is 75 ℃ to 85 ℃,
The first to fifth chambers are each provided with the same length of 4m,
The second curing is a method of manufacturing a protective film for a display is carried out by UV irradiation by UV lamp for 20 seconds at 500mW / ㎠ at 365nm, UV at 10000mJ / ㎠.
The method of claim 18,
The display protective film is the hardness (measured by ASTMD 2240, JISK 7215) after performing only the first curing before performing the second curing is 40H to 45H, after performing the second curing is 60H to 65H Method of manufacturing protective film for display.

Images