KR101168073B1 - Photocuring hard-coating composition and high hardness sheet employing the same - Google Patents

Abstract

PURPOSE: A photo-curable hard coating composition having high hardness is provided to replace existing glass material, to have excellent scratch resistance, and abrasion resistance, and weatherability capable of absorbing/shielding ultra violet rays, to have high hardness and low yellowing property, and not to generate bending flexure. CONSTITUTION: A photo-curable hard coating composition comprises 5-35 weight% of ethoxylated dipentaerythritol hexacrylate in chemical formula 1, 25-60 weight% of aliphatic urethane acrylate oligomer, 20-40 weight% of colloidal inorganic oxide water-dispersible silica sol, 5-10 weight% of a cross-combining silane compound, and 5-25 weight% of glycol ether organic solvent. In chemical formula 1, a-f is an integer of 2-36.

Description

Photocuring hard-coating composition and High hardness sheet employing the same}

The present invention is a photocurable hard coating composition, and a high hardness made by coating the photocurable hard coating composition on all plastic substrates, composite sheets [2 Layer Sheet (PMMA / PC) or 3 Layer Sheet (PMMA / PC / PMMA)] It relates to a sheet, and more particularly, to a photocurable hard coating composition and a high hardness sheet having high hardness, low yellowing, impact resistance, optically transparent, no warpage, and excellent solvent resistance, weather resistance, and wear resistance.

In general, important commercial products, including optically functional products such as windows of various electronics, touch screens for computers, lenses, automotive sunroofs, optical screens, light guide plates and LED faceplates, have been heavily used for glass, but they are heavy and fragile. The defect rate was considerably high when processing the product.

To replace this, thermoplastic and thermosetting polymers are used, which have been used to form various structures characterized by high hardness and high light transmittance.

However, many thermosetting and thermoplastic polymers such as these have excellent stiffness, dimensional stability, transparency and impact resistance, but are poor in abrasion resistance, heat resistance, solvent resistance, and chemical resistance. There is a vulnerability.

Therefore, in order to protect the resin products from physical or mechanical damage, a tempered glass was used or a hard wear layer was coated on the plastic surface. However, when the existing coating composition is applied to the plastic surface, the yellowing is severe and the hardness is excellent. However, it caused various problems such as scratch resistance, discoloration, cracking, low mechanical strength (impact strength, tensile strength, elongation) and fragile defects after coating, which caused defects in product processing.

The present invention has been made to solve the above problems, the object of the present invention is to replace the existing glass material and scratch and wear resistance, excellent weather resistance that can absorb / block ultraviolet rays, high hardness and low yellowing In order to provide a photocurable high hardness hard coat composition and a high hardness sheet that are transparent, do not exhibit warpage, and are excellent in solvent resistance, weather resistance, and wear resistance.

In order to achieve the above object, the present invention provides a photocurable hard coating composition comprising an ethoxylated dipentaerythritol hexaacrylate of the following formula (1).

[Formula 1]

(Wherein a to f are integers from 2 to 36).

In order to achieve another object of the present invention, the present invention is a plastic substrate or composite sheet; And it provides a high hardness sheet comprising a coating layer coated with a photocurable hard coating composition according to the present invention.

The photocurable hard coating composition according to the present invention is photocurable and environmentally friendly and transparent when coated on a plastic substrate such as polymethylmethacrylate (PMMA), polycarbonate (PC), polyethylene terephthalate (PET), and composite sheet (PMMA / PC). It is excellent, there is no warpage and has the same surface hardness as glass, less yellowing after coating and has the advantage of saving energy compared to general heat curing.

Therefore, the composition and the sheet according to the present invention can prevent breakage, which is a disadvantage of the tempered glass, and can achieve a lighter weight of the product, and can be applied to various applications of the existing tempered glass.

For example, when processing window parts of a touch screen product, there is an effect of solving defects and damages. That is, while fully utilizing the advantages of plastic properties such as ultra-light weight, excellent workability, impact resistance, etc., it is possible to prevent breakage and scattering, which is a disadvantage of glass, and to achieve a lighter weight of the product. The weight of the screen products can be considerably reduced, and plastics have much higher processability than glass, which can significantly increase the production yield resulting from defects and breakage.

In addition, the material cost is significantly lower than that of tempered glass, so the replacement cost in case of breakage can be greatly reduced.

In addition, due to the large area of the front glass of the display, the limitation of production yield is drastically lowered, that is, it cannot be applied to more than a certain size and the glass of the large area is very heavy so it is difficult for general consumers to carry it in their daily lives. Can be.

In addition, there is a problem that the glass is not easy to bond because the material is different from the outer case or the outer frame, and when the seam is not perfect, dust or foreign matter penetrates into the gap, which may cause abnormalities on the screen or the device. According to the present invention, since a plastic substrate can be used, homogeneous plastics are very simple to bond and are also permanent in contact with each other so that the sealed joint portion is not lifted, broken or opened even upon impact.

In addition, since the present invention does not use any additives such as N, N-dimethylacrylamide (DMA) and dimethylformamide (DMF), which are conventionally used, strong toxicity that is harmful to a human body can be eliminated, and printability, etc. The price competitiveness, mechanical and physical properties are superior to existing products because it can lower the cost and lower the economic cost.

1 is a cross-sectional view of a high hardness sheet coated with a photocurable coating composition on a composite sheet substrate according to an embodiment of the present invention.
2 is a cross-sectional view of a high hardness sheet coated with a photocurable coating composition on a plastic substrate according to an embodiment of the present invention.
3 is a cross-sectional view of a high hardness sheet manufactured according to an embodiment of the present invention applied to a touch screen panel unit.
4 is a cross-sectional view of a high hardness sheet manufactured according to an embodiment of the present invention applied to an on-cell touch panel unit.
5 is a cross-sectional view of a sheet manufactured according to an embodiment of the present invention to a touch screen panel or a window integrated touch screen panel of a direct patterned window (DPW) type.

Hereinafter, the present invention will be described in detail with reference to examples of the present invention. These examples are only presented by way of example only to more specifically describe the present invention, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples. .

The photocurable hard coating composition according to the present invention comprises the ethoxylated dipentaerythritol hexaacrylate of the following formula (1).

[Formula 1]

(Wherein a to f are integers from 2 to 36).

According to one embodiment of the present invention, 5% by weight to 35% by weight of the ethoxylated dipentaerythritol hexaacrylate of the general formula (1), and 25 to 60% by weight of an aliphatic urethane acrylate oligomer having a 3 to 15 functional aliphatic urethane acrylate. Photocurable hard coating comprising 20 wt% to 40 wt% of colloidal inorganic oxide water-dispersed silica sol, 5 wt% to 10 wt% of crosslinkable silane compound, and 5 wt% to 25 wt% of glycol ether organic solvent To provide a composition.

According to one embodiment of the present invention, the ethoxy of the ethoxylated dipentaerythritol hexaacrylate of formula 1 is preferably 2 Mol ~ 36 Mol, preferably 12Mol added product, which is Harder ethoxylated acrylates with less than 2 Mol are hard to crack and crack during ball drop testing, making it difficult to manufacture tempered glass alternatives, and cracks and ball drops with ethoxylated acrylates greater than 36 Mol Excellent but hardness and adhesion can be a problem.

The acrylic monomers such as the ethoxylated dipentaerythritol hexaacrylate monomers include BPA4EODA (Ethoxylated (4) bisphenol A diacrylate ) , BPA10EODA (Ethoxylated (10) bisphenol A diacrylate), BPA10EODMA (Ethoxylated (10) bisphenol A dimethacrylate), HD2EODA (Ethoxylated (2) 1.6hexanediol diacrylate), TMP3EOTA (Ethoxylated (3) Trimethylolpropane triacrylate), TMP6EOTA (Ethoxylated (6) Trimethylolpropane triacrylate), TMP9EOTA (Ethoxylated (9) Trimethylolpropoxylatacrylate It can be applied to all ethoxylated acrylates, such as trimethylolpropane triacrylate) and PPTTA (Ethoxylated (5) Pentaerythritoltetraacrylate).

According to one embodiment of the present invention, the aliphatic urethane acrylate oligomer is preferably used 3 to 15 functional, which is difficult to prepare a high hardness product when the aliphatic urethane acrylate oligomer of less than trifunctional, 15 functional In the case of more aliphatic urethane acrylate oligomers, the hardness is excellent, but the viscosity rises rapidly, and the synthesis is unstable, resulting in gelation of the resin and foreign substances during coating. The aliphatic urethane acrylate oligomers of 3 to 15 functional groups include aliphatic trifunctional urethane acrylates, aliphatic tetrafunctional urethane acrylates, and aliphatic 5-functional urethane acrylates. It is characterized in that at least one of aliphatic hexafunctional urethane acrylate (Aliphatic hexafunctional urethane acrylate), aliphatic 6 or more polyfunctional urethane acrylate (Aliphatic multifunctional urethane acrylate).

According to one embodiment of the present invention, the colloidal inorganic oxide water dispersion silica sol or organic solvent dispersion silica sol can be prepared by a method well known in the art, suitable sol may use a commercially available product have. Colloidal silica dispersed as a sol in aqueous solution may be commercially available under the trade names 'LUDOX' (available from Aldrich Chemical Company, Milwaukee, Wisconsin, USA). Examples include Ludox HS-40, HS-30, TM, SM, AM, LS, AS, CL-X, SK, TMA, PG, CL, CL-P, DM, FM, etc. Nano organic solvent type silica SS-SOL (halosilica size 5 ~ 500 nm).

Since the colloidal inorganic oxide is well distributed in the curable bonding precursor which is an organic substance when the nano-sized fine particles are used in the glycol ether organic solvent, it is excellent in dispersibility without causing entanglement and is optically transparent and curling phenomenon is excellent. It is not generated, and is environmentally friendly, economical, and has excellent mechanical properties such as wear resistance, so that it can be usefully used as a hard coat layer for glass replacement and plastic reinforced products of various plastic substrates.

In addition, the colloidal inorganic oxide of the colloidal inorganic oxide water dispersion or organic solvent dispersed silica sol is preferably particles having an average particle diameter of 5nm to 200nm, if the particle diameter of the colloidal inorganic oxide is less than 5nm is too fine This is because the workability is poor, the dispersion is poor, it is difficult to exhibit the desired physical properties, and when it exceeds 200 nm, the particles are difficult to disperse in the hard coat composition, entanglement may occur, optical smoothness may be poor, and a transparent surface may not be obtained. .

Silica may be used as the colloidal inorganic oxide, and colloidal zinc oxide, colloidal titania, colloidal alumina, colloidal antimony oxide, colloidal tin oxide, colloidal zirconia, colloidal vanadia, colloidal croa Mia, colloidal iron oxide, or mixtures thereof can be used.

According to one embodiment of the present invention, the crosslinkable silane compound contains a hydrolyzable silane moiety and a polymerizable moiety other than the silane moiety, and the silane compound is hydrogensilane, vinyl silane, aminosilane, hydroxy silane, Epoxy silane, methacryloxysilane, carboxy silane, etc. belong to this, Specifically, acryloxyalkyl trimethoxysilane, methacryloxyalkyl trimethoxysilane, (meth) acryloxyalkyl triethoxysilane, (meth) acryl Oxyalkyl trichlorosilane, phenyl trichlorosilane, phenyl trimethoxysilane, phenyl triethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl trichlorosilane, methyl trimethoxysilane, methyltriethoxy Silane, propyl trimethoxysilane, propyl triethoxysilane, glycidoxyalkyl trimethoxysilane, glycidoxyalkyltriethoxysilane, glyc It is preferred that it is at least one component selected from seedoxyalkyl trichlorosilane, perfluoroalkyl trialkoxysilane, perfluoromethyl alkyl trialkoxysilane and perfluoroalkyl trichlorosilane.

It is preferable to use 5% by weight to 10% by weight of the cross-linking silane compound. If the content is less than 5% by weight, the dispersibility of colloidal silica and adhesion to the plastic substrate are reduced, resulting in problems in transparency or quality. If it exceeds 10% by weight, the life-time of the coating composition is shortened, and the hard coat layer to which the coating composition is applied has a problem of deterioration in physical properties due to wear resistance and whitening of the surface.

According to one embodiment of the present invention, in order to stably disperse the colloidal inorganic oxide, an organic solvent may be used in the synthesis. Among the organic solvents, it is preferable that the organic solvent is glycol ethers in consideration of compatibility with a plastic substrate. Representative glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. ether), ethylene glycol monobutyl ether, and di ethylene glycol monobutyl ether. Among them, in consideration of compatibility, specifically, ethylene glycol monoethyl ether Or ethylene glycol mono butyl ether (Ethylene glycol mono butyl ether) is most preferably used.

The organic solvent may further use an organic solvent having a boiling point of 120 ° C. or higher as a ketone, an alcohol, an acetate, or an aromatic solvent. In addition, it is preferable to use the content of the organic solvent 5% by weight to 25% by weight, if the content is less than 5% by weight, the viscosity of the product at the time of synthesis can be gelled off the stability of colloidal silica due to high viscosity, 25% If it exceeds%, it is easy to synthesize, but its effect is insignificant compared to the content and is unnecessary in consideration of cost. However, when the conductive polymer (PEDOT) product is added and used as an antistatic hard coating paint, when the dispersion of the conductive polymer (PEDOT) is poor due to the high viscosity of the antistatic product, glycol ether is considered in consideration of the use of the conductive polymer (PEDOT). It can also be used as a diluted product by adding more than 25% by weight.

According to one embodiment of the present invention, the curable hard coat composition may include a photocuring agent (polymerization initiator) to aid in curing. Examples of preferred photocuring agents include organic peroxides, azo compounds, quinones, nitroso compounds, acyl halides, hydrazones, mercapto compounds, pyryllium compounds, imidazoles, chlorotriazines, benzoin, benzoin alkyl ethers, diketones, Phenones, and mixtures thereof. Substituted benzoin ethers such as benzoin ethers such as benzoin methyl ether and benzoin isopropyl ether, anisole methyl ether, 2,2-diethoxy acetophenone, 2,2-dimethoxy-2-phenylacetophenone and the like Aromatic sulfonyl chlorides, such as substituted α-ketols such as substituted acetophenone, 1-hydroxycyclohexyl-phenyl-ketone, and 2-methyl-2-hydroxypropiophenone, and 2-naphthalenesulfonyl chloride Optically active oximes such as phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime and the like can be used. Further examples of suitable photoinitiators are disclosed in US Pat. No. 4,735,632, which is incorporated herein by reference.

In addition, the photocurable hard coating composition according to the present invention may further include an ultraviolet stabilizer or ultraviolet absorber, which improves the weather resistance of the coated optical plastic sheet and reduces the occurrence of yellowing over time. Because. An example of the UV stabilizer is Clariant, which is commercially available under the trademark, and the UV absorber is Clariant " Hostavin PR-25, PR-31 (Reactive HALS) or Sanduvor * 3206 " Some are commercially available. In addition, when the coating film is exposed to the external environment, oxidation is continuously performed, and discoloration or change of physical properties may be started. An antioxidant may be added to prevent the coating film. Antioxidants are commercially available under the trademark Clariant "O3". Such UV stabilizers, antioxidants or UV absorbers are preferably about 10% by weight or less, more preferably about 0.01 to about 5% by weight, based on the total weight of the photocurable organic-inorganic hybrid hard coating composition, excluding the solvent. It includes. In some cases, various ultraviolet stabilizers and ultraviolet absorbers may be used in combination.

The present invention also provides a method of microgravure coating, curtain coating, silk screen coating, roll coating, bar coating, dip coating, flow coating, spray coating, slot die coating, flat coating, spin coating, ink jet coating, etc. on various plastic substrates. By coating the photocurable hard coating composition according to the present invention, it is possible to provide a high hardness sheet.

According to one embodiment of the invention, the plastic substrate includes all plastic substrates (PC, PMMA, PET, MS, TAC, etc.), but in particular a composite sheet (2Layer Sheet (PMMA / PC) and casting or extrusion method of Products containing PMMA are preferred.

According to one embodiment of the present invention, the photocurable hard coating composition does not need to be dried when used in a solvent-free form and coated on a plastic substrate and then irradiated with a UV light amount of 350 ~ 1000mJ / ㎠ on the substrate to prepare a sheet have.

According to one embodiment of the present invention, the photocurable hard coating composition is uniformly mixed when added to an organic solvent, then coated on a plastic substrate and dried for 1 to 10 minutes in a temperature range of 40 ~ 70 ℃ within the mixed composition After completely removing the organic solvent, a UV-hardened amount of 350 ~ 900mJ / ㎠ can be irradiated on the substrate to cure the hardened sheet.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings. However, this is for the purpose of understanding, and the scope of the present invention is not limited thereto.

As shown in FIG. 1, the photocurable hard coating composition according to the present invention is coated on both sides of the prepared PMMA 120 and the PC 130 composite sheet and then cured to form a hard coat layer 110.

Alternatively, when the composite sheet has different heat resistances between the sheets, the PMMA 120 and the PC 130 are coated with different curvatures of the coating composition in consideration of thermal warpage, so that both surfaces are coated to form the hard coating 110. can do.

As shown in FIG. 2, the photocurable hard coating composition according to the present invention is coated on the prepared casting PMMA 220 and then cured to form a hard coating layer 210.

In this case, the hard coating layers 110 and 210 may be formed using various coating methods described above, and the thickness of the coating layer is not limited in the present invention.

According to one embodiment of the present invention, the thickness of the coating layer may be 3 ~ 30㎛.

When the coating thickness of the hard coating layers 110 and 210 of FIGS. 1 and 2 is less than 3 μm, a hard coating layer having a desired high hardness may not be obtained. When the coating layer is 30 μm or more, cracks may be generated on the surface during thermal shock and high temperature and high humidity test. Can be.

FIG. 3 is a cross-sectional view illustrating a structure in which the hard coating film and the sheet shown in FIGS. 1 and 2 are applied to a touch panel unit.

As shown in FIG. 3, the ITO sensor line pattern 330 is coated on the upper and lower portions of the insulating layer glass 340, which is a basic structure of the touch panel, and the tempered glass window is replaced with an optical clean adhesive (OCA) film 320. One hard coating film or sheet 310 may be attached and the polarization film 350, which is the upper part of the display module, may be attached to the touch panels 330 and 340 to be commercialized.

FIG. 4 is a cross-sectional view illustrating a structure in which the hard coat film and sheet shown in FIGS. 1 and 2 are applied to an on-cell touch panel unit.

4 is a thin film on the outside of the upper glass substrate of the LCD or OLED 440, and the polarizing film 420 is attached to the upper part of the formed touch panel 430, and the upper surface of the polarizing film 420. An optically clean adhesive (OCA) film or a UV adhesive 410 may be used to attach and commercialize a hard coat film or sheet 310 replacing the tempered glass window.

FIG. 5 is a cross-sectional view illustrating a structure in which the hard coating film and sheet shown in FIGS. 1 and 2 are applied to a touch screen panel or a window integrated touch screen panel of a DPW (Direct Patterned Window) type.

FIG. 5 is a cell coating 540 with an OCA (Optical clean adhesive) film or UV adhesive 510 after modularizing by thin coating a touch sensor using a multi-coating directly onto the hard coating film or sheet 310 replacing the tempered glass window. ), The upper glass 530, the polarizing film 520 and the display unit can be attached to be commercialized.

As shown in the cross-sectional view of FIGS. 3, 4 and 5, the tempered glass window 310 is a hard coat layer using the composition synthesized according to the present invention on the PMMA 120, PC 130 composite sheet illustrated in FIG. The high hardness sheet manufactured by forming the hard coating layer 210 using the composition synthesized according to the present invention on the PMMA 220 illustrated in FIG. 2 or replaced by the high hardness sheet manufactured by forming the 110. Can be replaced by

Hereinafter, the configuration and effects of the present invention will be described in more detail with reference to Examples and Comparative Examples. However, this embodiment is intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.

Example  One

50 weight% of aliphatic urethane acrylate oligomer (Nippon Synthetic Chemical Industry Co., Ltd) and 10 weight product of ethoxy group (EO) 12 ethoxy group (EO) 12% of ethoxylated dipentaerythritol hexaacrylate (DPE-126, Hannong Chemicals, Inc.) %, Inorganic dispersion water dispersion silica sol (LUDOX AS-40, GRACE CO.) 25% by weight, silane compound 3-methacryloxy propyltrimethoxysilane (OFS-6030, Dow Corning Co.) 5% by weight and stabilization A mixture of 10 wt% of ethylene glycol mono ethyl ether, zein ethylene glycol, was stirred in a 5 L flask at about 50 ° C. for 30 minutes and vacuum-reduced at about 60 ° C. to remove water, methanol and ethylene glycol. While completing the reaction to prepare a photocurable hard coating composition.

After the completion of the dehydration reaction, the photocurable hard coating composition was diluted with methyl isobutyl ketone (MIBK) to a solid content of 50%. About 3 weight% of Irgakur 184 (IRGACURE 184, Shiba Gaiji Co., Ltd.) was added here as a photocuring agent.

The photocurable hard coating composition was coated on a composite sheet (PMMA / PC, substrate product name: AW-10U, Shine Techno.Co. Ltd) based plastic by flow coating method, and then heat dried at 60 ° C. for 2 minutes to form a coating composition. After removing the solvent in the coating composition was applied to a thickness of 3 ~ 15㎛ and the coating was cured on the conveyor belt of the ultraviolet light processor using a high-pressure mercury lamp (Ritzen Co., Ltd.). At this time, a high hardness sheet was manufactured by irradiating 700 mJ / cm 3 of ultraviolet light.

Example  2 to Example  6, and Comparative example  One

A high hardness sheet was manufactured in the same manner as in Example 1, except that the hard coating composition was prepared in the composition of Table 1.

(Unit weight%) A B C D E1 E2 E3 Example 1 50 10 25 5 10 Example 2 40 20 25 5 10 Example 3 30 30 25 5 10 Example 4 - 60 25 5 10 Example 5 30 30 25 5 10 Example 6 30 30 25 5 10 Comparative Example 1 60 25 5 10

A: aliphatic urethane acrylate oligomer (Nippon Synthetic Chemical Industry Co., Ltd)

B: ethoxylated dipentaerythritol hexaacrylate (DPE-126, Hannong Chemicals, Inc) [12 mol addition product of the ethoxy group]

C: Inorganic Oxide Water Disperse Silica Sol (LUDOX AS-40, GRACE CO.)

D: 3-methacryloxy propyltrimethoxysilane (OFS-6030, Dow Corning) as a silane compound.

E1: Ethylene glycol mono ethyl ether, a stabilizer of ethylene glycol

E2: Ethylene glycol mono butyl ether as ethylene glycol

E3: Methyl isobutyl ketone as stabilizer

Example  7 to 9

A hard coat sheet was manufactured in the same manner as in Example 3 except that the photocurable hard coat composition prepared in the same manner as in Example 3 was coated on the substrate of Table 2 below.

materials Coating composition Example 7 Casting PMMA (HS Chemicals, Inc.) Example 3 Composition Example 8 PC (I components, Co. Ltd) Example 3 Composition Example 9 PET (SKC, SH-40) Example 3 Composition

Comparative example  2

Pentaerythritol triacrylate (PETA) 50% by weight, silica 32% by weight (Nalco 2327, Nalco Corporation), 3-methacryloxy propyltrimethoxysilane (A-174, Union Carbide Co., Ltd.) is a silane compound %, A mixture of 10% by weight of acrylomorphrin (ACMO) was stirred for 30 minutes at about 50 ℃ in a 5L flask, and then vacuum and reduced pressure at about 60 ℃ to complete the reaction while removing water and methanol photocurable hard coating composition Except for preparing a hard coat coating sheet was prepared in the same manner as in Example 1.

Comparative example  3 to 5

A coating sheet was prepared in the same manner as in Comparative Example 1 except that the photocurable high hardness hard coating composition was coated on the substrate of Table 3 below.

materials Coating Composition Comparative Example 3 Casting PMMA (HS Chemicals, Inc.) Comparative Example 2 Composition Comparative Example 4 PC (I components, Co. Ltd) Comparative Example 2 Composition Comparative Example 5 PET (SKC, SH-40) Comparative Example 2 Composition

Comparative example  6

As Comparative Example 5, tempered glass product GLASS (US Corning Gorilla Glass) which was not coated with a photocurable high hardness hard coating composition was used.

[ Experimental Example ]

Experimental Example  1: light transmittance test

Samples of the glass substrates of the sheets prepared in Examples 1 to 9 and Comparative Examples 1 to 5 and Comparative Example 6 were prepared, and the transmittance was measured at a wavelength band of 550 nm using a spectrophotometer MINOLTA CM-3600D. And in Table 5.

Experimental Example  2: pencil hardness test

Prepare specimens of Examples 1 to 9 and Comparative Examples 1 to 6 and polish the tip of the shim to be flat and angled in a state where the hardness meter Mitsumi Shisa pencil core was exposed to a cylindrical shape for about 3 mm, and then at the coating surface. The pencil core was touched at an angle of about 45 ° and subjected to 10 mm five times at a uniform speed under a 1 kg load. The results are shown in Tables 4 and 5.

Experimental Example 3: Adhesive Strength Test

Prepare specimens of Examples 1 to 9 and Comparative Examples 1 to 6, cut the coating surface at 1 mm intervals, and then attach a 3M Scotch tape having a width of about 2 cm to the coating surface (this is 90 ° to the surface). I leave it to some extent). After standing for 1 minute, the remaining portion was pulled vertically and the extent of the coating surface remained on the polyester film was observed.

Experimental Example 4: Content Test

The specimens of Examples 1 to 9 and Comparative Examples 1 to 6 were prepared and immersed in methanol, ethanol or isopropyl alcohol at room temperature for 24 hours, and evaluated according to the change of physical properties of the coating film.

Experimental Example  5: Yellowing test

Prepare the specimens of Examples 1 to 9 and Comparative Examples 1 to 6, and cover 15W, UV-B wavelength with half of black tape and the test specimen 20cm away from Lamp 15W, UV-B wavelength. After leaving for 72 hours at 4 hours after discoloration was confirmed and the results are shown in Table 4 and Table 5.

Experimental Example 6: Steel Ball Drop Test

Steel ball (about 20.7mm in diameter and about 36g in weight) is offset by 5mm from the outline of the mobile phone folder window and draw a diagonal line connecting each corner to the line. Draw a horizontal and vertical line based on the point where the diagonal lines intersect. Fall once every time the line intersects.

The specimens of Examples 1 to 9 and Comparative Examples 1 to 6 Evaluation as described above is shown in Table 4 and Table 5 below.

Experimental Example 7: BENDING TEST

The specimens of Examples and Comparative Examples were fabricated as 150 mm X 150 mm specimens, and were determined to be "poor" when bent at 91 or more, "normal" when bent at 89 to 61, and "good" when bent at 60 or less.

Experimental Example 8: Appearance Test

The specimens of Examples and Comparative Examples were visually checked at an angle of 30 ° and a distance of 45 cm at three wavelengths to check for troubles, orange peel, cracking, pinholes, and the like. Otherwise, the result is shown as "0K" (pinhole to 450mm x 550mm PMMA size, "OK" to 0.25mm size 3EA, "NG" above and above (except 0.25mm and above).

Experimental Example 9 ANTI-SCRATCH Test

Using steel wool # 000, the surface of the specimens of the examples and the comparative examples was rubbed in ten units under a weight of 175 g and the results are shown in Tables 4 and 5.

Experimental Example 10 Constant Temperature and Humidity Test

The specimens of Examples 1 to 9 and Comparative Examples 1 to 6 were prepared, and after being left for 72 hours in a chamber (constant temperature and humidity chamber) at 85 ° C. and 85% humidity, after 4 hours at room temperature, cracks were generated in Tables 4 and 5. Indicated.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 SHEET Composite sheet Composite sheet Composite sheet Composite sheet Composite sheet Composite sheet PMMA P.C PET Light transmittance
(T%) 91.6 92.1 92.4 92.3 92.2 91.8 92.1 91.2 92.8 Haze (%) 0.52 0.36 0.34 0.32 0.41 0.57 0.42 0.2 0.4 On coating coating
According to pencil hardness
PMMA side 5㎛ 5H 4H 4H 2H 4H 4H 6H - 2H 10 탆 6H 5H 5H 3H 5H 5H 7H - 3H 15 μm 7H 6H 6H 4H 6H 6H 8H - 3H 20 탆 7H 6H 6H 4H 6H 6H 8H - 3H 25 μm 7H 6H 6H 5H 6H 6H 8H - 3H 30 μm 7H 7H 7H 5H 7H 7H 9H - 3H Pencil hardness
PC cotton H H H H H H - H - Coating film 10㎛
Adhesive strength 100/100 100/100 100/100 90/100 100/100 100/100 100/100 100/100 100/100 Solvent resistance clear clear clear clear clear clear clear clear clear Cosmetic resistance clear clear clear clear clear clear clear clear clear Yellowing OK OK OK OK OK OK OK OK OK Coating 10㎛ breaking strength
Ball drop 15 cm 25 cm  35 cm 60 cm  35 cm 35 cm 25 cm 120 cm - Coating film 10㎛
BENDING TEST Good
60 usually
90 Good
60 Good
50 Good
60 Good
60 usually
80 Good Good Exterior OK OK OK OK OK NG OK OK OK Scratch resistance 2000 OK 1800 OK 1800 OK 1000 times
OK 1800 OK 1800 OK 2000 OK 500
OK 500
OK Constant temperature and humidity
(85 ℃ / 85%) 5㎛ No crack No crack No crack No crack No crack No crack No crack No crack No crack 10 탆 No crack No crack No crack No crack No crack No crack No crack No crack No crack 15 μm Cracking No crack No crack No crack No crack No crack No crack No crack No crack 20 탆 Cracking No crack No crack No crack No crack No crack Cracking No crack No crack 25 μm Cracking Cracking No crack No crack No crack No crack Cracking No crack No crack 30 μm Cracking Cracking Cracking Cracking Cracking Cracking Cracking Cracking Cracking

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 SHEET Composite sheet Composite sheet PMMA P.C PET tempered glass Light transmittance
(T%) 90.8 91.2 91.8 90.2 91.3 91 Haze (%) 0.58 0.6 1.2 0.5 0.8 - By paint
Pencil hardness
PMMA side 5㎛ 6H 4H 5H - 2H 9H
(tempered glass) 10 탆 7H 5H 6H - 2H 15 μm 8H 5H 6H - 3H 20 탆 8H 5H 6H - 3H 25 μm 8H 5H 6H - 3H 30 μm 8H 6H 7H - 3H Pencil hardness
PC side H HB - HB Adhesive strength 100/100 80/100 70/100 75/100 80/100 - Solvent resistance clear Peeling Peeling clear clear clear Cosmetic resistance clear Uplifting clear Discoloration and lifting clear clear Yellowing OK NG NG NG NG - Breaking strength
Ball DROP 10 cm 10 cm  15 cm 80 cm - 10 cm BENDING TEST Bad
120 usually Bad Bad Bad Bad Exterior OK NG NG OK OK - Scratch resistance 2000 OK 1000 times
NG 1000 times
OK 200 times
OK 200 times
OK - Constant temperature and humidity
(85 ℃ / 85%) 5㎛ No crack No crack No crack No crack No crack - 10 탆 Cracking No crack Cracking No crack No crack 15 μm Cracking Cracking Cracking No crack No crack 20 탆 Cracking Cracking Cracking Cracking No crack 25 μm Cracking Cracking Cracking Cracking No crack 30 μm Cracking Cracking Cracking Cracking Cracking

Sheets made of a photocurable hard coating composition comprising the ethoxylated dipentaerythritol hexaacrylate of the formula (1) as in Examples 1 to 9 from Table 4 are products having high hardness, low yellowing and excellent impact resistance, and light weight It can be seen that the optically transparent, warpage does not occur, and excellent sheets such as wear resistance can be produced.

It is to be understood that the present invention is not limited to the above embodiments and various changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims (14)

To include ethoxylated dipentaerythritol hexaacrylate of the formula (1),
5 wt% to 35 wt% of the photocurable hard coating composition of the ethoxylated dipentaerythritol hexaacrylate of Chemical Formula 1; 25 to 60 weight% of a 3-15 functional aliphatic urethane acrylate oligomer as a curable bonding precursor; 20% to 40% by weight of colloidal inorganic oxide water-dispersed silica sol; 5 wt% to 10 wt% of the crosslinkable silane compound; And 5 wt% to 25 wt% of a glycol ether organic solvent.
[Formula 1]

(Wherein a to f are integers from 2 to 36). delete The method of claim 1,
The aliphatic urethane acrylate oligomers of 3 to 15 functional groups include aliphatic trifunctional urethane acrylates, aliphatic tetrafunctional urethane acrylates, and aliphatic 5-functional urethane acrylates. Aliphatic hexafunctional urethane acrylate (Aliphatic hexafunctional urethane acrylate), Photo-curable hard coating composition of at least one of aliphatic six or more functional polyfunctional urethane acrylate (Aliphatic multifunctional urethane acrylate). The method of claim 1,
The photocurable hard coating composition, characterized in that the average particle diameter of the colloidal inorganic oxide is 5nm to 200nm particles. The method of claim 4, wherein
The inorganic oxide is at least one inorganic oxide selected from the group consisting of silica, titania, alumina, antimony oxide and tin oxide, zinc oxide, lithium oxide, colloidal vanadia, colloidal chromia and colloidal iron oxide. Photocurable hard coating composition. The method of claim 1,
The crosslinkable silane compound may be acryloxyalkyl trimethoxysilane, methacryloxyalkyl trimethoxysilane, (meth) acryloxyalkyl triethoxysilane, (meth) acryloxyalkyl trichlorosilane, γ-methacryloxy Propyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiisooxysilane, acryloxypropyltrimethoxysilane, acryloxypropylmethyldimethoxysilane, γ-methacryloxy Carbitoltrimethoxysilane, phenyl trichlorosilane, phenyl trimethoxysilane, phenyl triethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl trichlorosilane, methyl trimethoxysilane, methyltrie Methoxysilane, propyl trimethoxysilane, propyl triethoxysilane, glycidoxyalkyl trimethoxysilane, glycidoxyalkyltriethoxysilane, glycidoxyal At least one silane selected from the group consisting of trichlorosilane, melamine-based trimethoxy silane, acrylic trimethoxy silane, perfluoroalkyl trialkoxysilane, perfluoromethyl alkyl trialkoxysilane and perfluoroalkyl trichlorosilane Photocurable high hardness hard coating composition, characterized in that the compound. The method of claim 1,
The glycol ether organic solvent may be ethylene glycol mono methyl ether, ethylene glycol mono ethyl ether, ethylene glycol mono butyl ether, diethylene glycol mono Photo-curable hard coating composition, characterized in that at least one glycol ether selected from the group consisting of butyl ether (Di Ethylene glycol mono butyl ether), and ethylene glycol mono ethyl ether (Ethylene glycol mono ethyl ether). The method of claim 1,
2-hydroxyethylacrylate, 2-Hydroxyethyl methacrylate, Tetrahydrofurfury Acrylate, Trimethylolpropane triacrylate, Pentaerythritol Pentaerythritol triacrylate, Dipentaerythritol hexaacrylate, Ethoxylated (5) pentaerythritol tetraacrylate and Acryloyl morpholine Photocurable hard coating composition further comprises at least one monomer selected from the group consisting of two or more. Base material containing at least 1 sort (s) of polymethylacrylate and polycarbonate; And
At least one surface of the substrate includes a coating layer coated with a photocurable hard coating composition,
The high hardness sheet, characterized in that the photocurable hard coating composition is a photocurable hard coating composition of any one of claims 1, 3 or 7. 10. The method of claim 9,
The high hardness sheet, wherein the substrate comprises at least two layers containing polymethyl methacrylate and polycarbonate. 10. The method of claim 9,
High hardness sheet, characterized in that the thickness of the single-side coating of the coating layer is 3 ~ 30㎛. Glass substrate,
A touch panel attached to at least one surface of the glass substrate,
OCA (Optical clean adhesive) film attached to the touch panel, and
A high hardness sheet attached to the OCA film,
The high hardness sheet is a high hardness sheet of claim 9, wherein the display panel. An optical plastic substrate, a film, a composite sheet, or a cast PMMA is a product for replacing plastic tempered glass, wherein the photocurable hard coating composition of any one of claims 1 or 3 to 8. The method of claim 13,
The plastic tempered glass replacement product is selected from the group consisting of a mobile phone and smartphone window, a touch screen panel unit, a clean room and a soundproof wall.

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