KR100670896B1 - Method for manufacturing the hard-coated optical device with high-hardness property and the hard-coated optical device with high-hardness using thereof - Google Patents

Abstract

A high-hardness hard coating optical element manufacturing method and a High-hardness hard coating optical element produced by the same are provided to regulate the thickness of a hard coating layer to be uniform by forming two hard coating layers on a polarizing film by spin-coating. A high-hardness hard coating optical element manufacturing method includes: a first hard coating layer forming step for forming a first hard coating layer(600) by coating a polarizing film attached on an LCD(Liquid Crystal Display) cell(100) with the solution produced by mixing a dispersing agent and a first hard coating composition containing curable resin, a hardening agent of 1~17wt.%, and a leveling agent of 0.5~5wt.%, coating the first hard coating layer by mixing the dispersing agent of 30~150wt.%, to the 100 weight percent of an antistatic coating composition, and then curing the applied materials by heat or ultraviolet, in a continuous rotary coating machine turned at 50~6000RPM(Revolution Per Minute) for 10~600 seconds; and a second hard coating layer forming step for forming a second hard coating layer(700) by coating the upside of the first hard coating layer with the solution produced by mixing the dispersing agent with a second hard coating composition containing curable resin, a hardening agent of 1~17wt.%, a leveling agent of 0.5~5wt.%, and an antimicrobial agent of 0.5~10wt.%, coating the second hard coating layer by mixing the dispersing agent of 30~150wt.%, to the 100 weight percent of an antistatic coating composition, and then hardening the applied materials by heat or ultraviolet, in the continuous rotary coating machine turned at 50~6000RPM for 10~600 seconds.

Description

Method for manufacturing high hardness hard coated optical device and high hardness hard coated optical device using the same {{Method for Manufacturing the Hard-Coated Optical Device with High-Hardness Property and the Hard-Coated Optical Device with High-Hardness using A}

1 is a block diagram of an optical element laminated on a polarizing film attached to a conventional general hard coating film on the LCD cell,

2 is a block diagram of a high-hardness hard coating optical device according to an embodiment of the present invention.

Explanation of symbols on the main parts of the drawings

100: LCD cell 200: adhesive

300, 500: TAC 400: PVA

600: first hard coating layer 700: second hard coating layer

The present invention relates to a method of manufacturing a high hardness hard coating optical device and a high hardness hard coating optical device using the same, in particular, by forming two hard coating layers on a polarizing film by a spin-coating method, The present invention relates to a method of manufacturing a high hardness hard coating optical device having improved thickness, scratch resistance, and abrasion resistance, and a high hardness hard coating optical device using the same.

Currently, hard coating optical films applied to LCD, PDP, etc. require a hard coating layer of a predetermined thickness or more in order to obtain scratch resistance and high hardness. Therefore, conventionally, a general hard coat film was used by laminating it to a polarizing film.

1 is a block diagram of an optical element laminated on a polarizing film attached to a conventional general hard coating film on the LCD cell. As shown, the conventional optical device is a polyvinyl alcohol (hereinafter referred to as 'PVA') (4) and triacetyl cellulose (TAC) (3) by the adhesive (2) on the LCD cell (1) The polarizing film consisting of 5) is attached. And the adhesive 6 is apply | coated on the TAC surface 5 of the said polarizing film, and the general hard-coating film 7 is attached to it.

However, the optical device manufactured by the conventional manufacturing method as described above requires a separate pressure-sensitive adhesive to attach a general hard coating by the pressure-sensitive adhesive, which causes a problem that the cost of the pressure-sensitive adhesive is generated separately and becomes thick.

In addition, the above process has a problem in that the yield is poor because the process is complicated to use the pressure-sensitive adhesive is carried out separately.

Accordingly, the present invention has been proposed to solve the conventional problems as described above, and an object of the present invention is to form a thickness of the hard coating layer by forming two hard coating layers on the polarizing film by a spin-coating method. The present invention provides a method of manufacturing a high-hardness hard-coated optical device which can be constantly adjusted and whose surface hardness is enhanced to improve scratch resistance and abrasion resistance, and a high-hardness hard-coated optical device using the same.

In addition, there is another object to improve the yield by selecting a simple manufacturing process for forming two hard coating layers on a polarizing film using a spin-coating method according to the present invention.

In the method of manufacturing a high hardness hard coating optical device according to the present invention, a first hard coating layer is formed by coating and curing the first hard coating layer by spin-coating on a polarizing film cut and attached to a predetermined size on an LCD cell. And a second hard coat layer forming step of coating and curing a second hard coat layer on the first hard coat layer.

Hereinafter, a method of manufacturing a hard hardness optical coating device according to the present invention will be described in detail for each step.

(1) forming the first hard coating layer

1) first hard coating layer coating step

The first hard coating layer coating step comprises mixing a first hard coating composition comprising a curable resin, a curing agent, a leveling agent, and an ultraviolet absorber (used when using an ultraviolet curable resin as the curable resin described below) with a dispersant in the form of a solution. After manufacturing, it is carried out by applying a spin coating method on the polarizing film attached to the LCD cell.

The polarizing film manufactured by the conventional method is used. Polarizing film is mainly used for STN (Super Twisted Nematic), TN (Twisted Nematic), TFT (Thin Film Transitor), OLED (Organic Light Emitting Diode).

The rotation speed and rotation time applied in the spin coating method of the present invention are as follows.

In the present invention, it is preferable to coat a solution obtained by mixing the first hard coating composition with a dispersant at a rotational speed of 50 rpm to 6,000 rpm, more preferably 100 rpm to 4,000 rpm.

If the rotation speed of the spin coating is less than 50 rpm, the desired predetermined thin film may not be obtained, and the first hard coating layer may not be evenly applied to the surface of the polarizing film. In addition, when greater than 6,000rpm, due to the high centrifugal force, a thickness difference occurs in the center portion and the outer portion of the first hard coat layer. In addition, the spin coating apparatus may be difficult to maintain a high rotational speed.

In addition, the rotation time in the spin coating step of the present invention is preferably 10 seconds to 600 seconds, more preferably 30 seconds to 400 seconds. The rotation time may vary depending on the viscosity of the solution in which the first hard coating composition and the dispersant are mixed and the thickness of the first hard coating layer to be coated.

If the rotation time is less than 10 seconds, it is difficult to secure sufficient time to evenly apply the first hard coating layer to the polarizing film, and if it is more than 600 seconds, the economic efficiency is poor.

Looking at the composition of the first hard coating composition consisting of a curable resin, a curing agent, a leveling agent, a UV absorber used in the present invention and a dispersant mixed with the composition are as follows.

① Curable resin

The curable resin used in the present invention uses at least one of a thermosetting resin or a photocurable resin.

Thermosetting resins and photocurable resins generally use known resins. Among the thermosetting resins, polycondensation type resins include phenol resins, urea resins, melamine resins, and the like, and epoxy resins, polyester resins, and the like. In this invention, these can be used individually or in mixture. As the photocurable resin, UV curable resin is generally used. As the photocurable resin, unsaturated polyester resins, polyfunctional acrylate resins, urethane acrylates, epoxy acrylic resins, epoxy acrylate resins and the like can be used alone or in combination. Curable resins usable in the present invention are of course not limited to the resins listed above as long as they exhibit the same effect.

If the curable resin usable in the present invention exhibits the same effect, the range or content is not limited to the listed resins or contents, of course.

In the present invention, the curable resin can be composed of only the thermosetting resin, but the photocurable resin can also be used together. In order to have physical properties such as high hardness and transparency, the photocurable resin used in the present invention is more preferably an ultraviolet curable polyfunctional acrylate resin. In the present invention, the ultraviolet curable polyfunctional group acrylate-based resin is dipentaerythritol hexaacrylte, tetramethylolmethane tetraacrylate, tetramethylolmethane triacrylate, trimethylolmethane triacrylate, or trimethylolmethane triacrylate. Methanolpropane triacrylate, 1,6-hexanediol diacrylate, 1,6-bis (3-acryloyloxy-2-hydroxypropyloxy) hexane [1 Polyfunctional alcohol derivatives such as, 6-bis (3-acryloyloxy-2-hydroxypropyl) hexane], urethane acrylates such as polyethylene glycol diacrylate and pentaerythritol triacrylate , Hexamethylene diisocyanate urethane prepolymer, etc. alone or mixed Use it.

It is preferable to use 10 weight%-90 weight% of said ultraviolet curable polyfunctional acrylate-type resin in 100 weight% of curable resin, More preferably, it is 30 weight%-87 weight%. Even more preferably, 50 to 85% by weight is used.

When the UV-curable polyfunctional acrylate resin is less than 10% by weight in 100% by weight of the curable resin, it is difficult to obtain high hardness due to the combination of functional groups due to the small number of absolute functional groups. There is a downside to falling.

② hardener

The curing agent in the present invention may be appropriately selected or mixed according to the form of the functional group present in the thermosetting resin or photocurable resin, preferably isocyanate compound, epoxy compound, aziridine compound, metal chelate compound, metal alkoxide Metal salts, amine compounds, hydrazine compounds and the like are used alone or in combination.

Isocyanate compounds in the present invention are trimethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane isocyanate, xylene diisocyanate aromatic diisocyanate compounds such as diisocyanate, aliphatic diisocyanate such as hexamethyl diisocyanate, and the like are used alone or in combination.

In addition, the epoxy compound in the present invention is a polyethylene glycol diglycidyl ether (diglycidyl ether), diglycidyl ether (diglycidyl ether), trimethylol propane triglycidyl ether (trimethylol propane triglycidyl ether) and the like alone Or mixed.

It is preferable to use 1 to 17 weight% of 100% by weight of the hardening | curing agent in this invention, More preferably, it is 3 to 10 weight%. Even more preferably 5% to 7% by weight.

In the present invention, the curing agent is an additive used to control the molecular weight or the chain structure of the first hard coating composition. When the curing agent is used in the above-described range, the effect of suppressing phase separation and the like is prominent. When the content of the curing agent is less than 1% by weight, it is difficult to expect the function of the curing agent, and when the content of the curing agent is greater than 17% by weight, the content of the curable resin is relatively low, making it difficult to increase the hardness.

③ Leveling agent

In the present invention, a leveling agent is used to even the surface of the first hard coat layer. The leveling agent can be used by mixing a ketone or an ester solvent with a silicone resin. As a leveling agent by this invention, it is preferable to use a silicone diacrylate and a silicone polyacrylate compound individually or in mixture.

The content of the leveling agent is preferably 0.5% by weight to 5% by weight, more preferably 1% by weight to 1.5% by weight, based on 100% by weight of the first hard coating layer composition. When the leveling agent is less than 0.5% by weight, it is difficult to expect the leveling effect, and when it is larger than 5% by weight, the hardness may be weakened.

④ UV absorber

When the photocurable resin is used as the curable resin for ultraviolet curing in the present invention, it is preferable to use a ultraviolet absorber to prevent deterioration generated during ultraviolet curing and to improve durability of the first hard coating layer.

The ultraviolet absorber used in the present invention is preferably used alone or mixed with a salicylate ultraviolet absorber, a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a cyanoacrylate ultraviolet absorber, and a benzoate ultraviolet absorber. Do.

More specifically, the ultraviolet absorber is phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy- 4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4 -Hydroxy-5-benzoylphenyl) methane, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5- Chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5-di -tert-amylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxy Yl) benzotriazole, 2- (2'-hydroxy-3 '-(3', 4 ', 5', 6'-tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole, 2,2 '-Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazolyl-2-yl) phenol], 2- (2'-hydroxy-5'-meta Krilloxyphenyl) -2H-benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol ], And 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl 2-cyano-3,3'-diphenyl acrylate or the like is used alone or in combination.

In the present invention, the content of the ultraviolet absorbent is preferably 1% by weight to 10% by weight, more preferably 3% by weight to 8% by weight, based on 100% by weight of the first hard coating composition.

When the content of the ultraviolet absorber is 1% by weight or less, the effect of adding the ultraviolet absorber may not be realized properly, and when the content of the ultraviolet absorber is 10% by weight or more, the physical properties of the first hard coat layer may be affected.

⑤ dispersant

In the present invention, an organic solvent which is a dispersant is used to apply the first hard coating layer to the polarizing film. In the present invention, it is preferable to use an organic solvent in which the first hard coating composition can be evenly dispersed.

The organic solvent is selected in consideration of the coating property of the first hard coating layer, the adhesion with the polarizing film, and the enhancement of the surface hardness enhancement function.

The organic solvent used in the present invention is a C1-8 saturated hydrocarbon alcohol such as methanol, isopropanol, butanol, t-butanol, isobutanol and the like, acetone, methyl ethyl ketone, methyl isobutyl ketone and the like of ketones. Saturated hydrocarbon-based diketones having 1 to 8 carbon atoms, such as 1 to 8 saturated hydrocarbon ketones and acetyl acetone, ethyl acetate of esters, ethyl hydrocarbons of 1 to 8 carbon atoms such as butyl acetate, and ethyl alcohols of ether alcohols. Solves, methyl cellosolves, butyl cellosolves, 1-methoxy-2-propanol, and N-methyl pyrrolidone, ethyl cellosolve acetate, diacetone alcohol, and the like are used alone or in combination. Moreover, benzene, toluene, xylene, ethylbenzene, etc. which correspond to an aromatic hydrocarbon can also be used individually or in mixture.

The organic solvent is preferably 30 parts by weight to 150 parts by weight with respect to 100 parts by weight of the first hard coating composition to be applied, and more preferably 50 parts by weight to 80 parts by weight. When the content of the organic solvent is less than 30 parts by weight with respect to 100 parts by weight of the first hard coating composition, the viscosity is low, so that the coating property and adhesion with the polarizing film are inferior, and when the content of the organic solvent is greater than 150 parts by weight, it is higher than that of the first hard coating composition. Profitability is inferior by using too many organic solvents.

2) curing step

The curing step according to the present invention uses a conventional curing method.

Since the first hard coating composition according to the present invention includes a thermosetting resin or a photocurable resin, the curing step is performed by thermosetting or UV curing. Thermal curing and UV curing may proceed sequentially, but may also proceed simultaneously. In addition, it is a matter of course that the components or content of the curing agent and the leveling agent may vary depending on the curing method.

It is preferable that the thickness of the 1st hard coat layer formed through the said step is 1 micrometer-15 micrometers, More preferably, they are 3 micrometers-10 micrometers. The thickness of the first hard coat layer is preferably adjusted in consideration of the thickness of the second hard coat layer to be described later. When the thickness is smaller than 1 μm, the thickness is too thin, so scratch resistance and abrasion resistance are lowered. When the thickness is larger than 15 μm, economical efficiency is lowered during spin coating.

(2) forming a second hard coating layer

1) second hard coating layer coating step

The second hard coating layer coating step may be performed by mixing a second hard coating composition comprising a curable resin, a curing agent, a leveling agent, an ultraviolet absorber (used when using an ultraviolet curable resin as the curable resin described below), and an antibacterial agent with a dispersant. After manufacturing in the form, it is carried out by applying on the first hard coat layer using a spin coating method.

The rotation speed and rotation time applied in the spin coating method of the present invention are as follows.

In the present invention, it is preferable to coat a solution obtained by mixing the second hard coating composition with a dispersant at a rotational speed of 50 rpm to 6,000 rpm, and more preferably 100 rpm to 4,000 rpm.

If the rotation speed of the spin coating is less than 50 rpm, the desired predetermined thin film may not be obtained, and the second hard coating layer may not be evenly applied to the surface of the polarizing film. In addition, when greater than 6,000 rpm, the difference in thickness occurs in the center and the outer portion of the second hard coating layer due to the high centrifugal force. In addition, in order to maintain a high rotational speed can be difficult to spin coating apparatus and may affect the durability of the high-hardness hard-coated optical element itself.

In addition, the rotation time in the spin coating step of the present invention is preferably 10 seconds to 600 seconds, more preferably 30 seconds to 400 seconds. The rotation time may vary depending on the viscosity of the solution in which the second hard coating composition and the dispersant are mixed and the thickness of the second hard coating layer to be coated.

If the rotation time is less than 10 seconds, it is difficult to secure sufficient time to evenly apply the second hard coating layer to the first hard coating layer, and if it is more than 600 seconds, the economy is inferior.

Hereinafter, the composition of the second hard coating composition composed of the curable resin, the curing agent, the leveling agent, the ultraviolet absorbent, and the antimicrobial agent used in the present invention and the dispersant mixed with the composition will be described as follows.

① Curable resin

The curable resin used in the present invention uses at least one of a thermosetting resin or a photocurable resin.

Thermosetting resins and photocurable resins generally use known resins. Among the thermosetting resins, polycondensation type resins include phenol resins, urea resins, melamine resins, and the like, and epoxy resins, polyester resins, and the like. In this invention, these can be used individually or in mixture. As the photocurable resin, UV curable resin is generally used. As the photocurable resin, unsaturated polyester resins, polyfunctional acrylate resins, urethane acrylates, epoxy acrylic resins, epoxy acrylate resins and the like can be used alone or in combination. Curable resins usable in the present invention are, of course, not limited to the resins listed above as long as they exhibit the same effect.

If the curable resin usable in the present invention exhibits the same effect, the range or content is not limited to the listed resins or contents, of course.

In the present invention, the curable resin can be composed of only the thermosetting resin, but the photocurable resin can also be used together. In order to have physical properties such as high hardness and transparency, the photocurable resin used in the present invention is more preferably an ultraviolet curable polyfunctional acrylate resin. In the present invention, the ultraviolet curable polyfunctional acrylate-based resin is dipentaerythritol hexaacrylte, tetramethylolmethane tetraacrylate, tetramethylolmethane triacrylate, trimethanol Propane triacrylate, 1,6-hexanediol diacrylate, 1,6-bis (3-acryloyloxy-2-hydroxypropyloxy) hexane [1, Polyfunctional alcohol derivatives such as 6-bis (3-acryloyloxy-2-hydroxypropyl) hexane], urethane acrylates such as polyethylene glycol diacrylate and pentaerythritol triacrylate, Hexamethylene diisocyanate urethane prepolymer or the like alone or mixed Use open.

It is preferable to use 10 weight%-90 weight% of said ultraviolet curable polyfunctional acrylate-type resin in 100 weight% of curable resin, More preferably, it is 30 weight%-87 weight%. Even more preferably, 50 to 85% by weight is used.

When the UV-curable polyfunctional acrylate resin is less than 10% by weight in 100% by weight of the curable resin, it is difficult to obtain high hardness due to the combination of functional groups due to the small number of absolute functional groups. There is a downside to falling.

② hardener

The curing agent in the present invention may be appropriately selected or mixed according to the form of the functional group present in the thermosetting resin or photocurable resin, preferably isocyanate compound, epoxy compound, aziridine compound, metal chelate compound, metal alkoxide Metal salts, amine compounds, hydrazine compounds and the like are used alone or in combination.

Isocyanate compounds in the present invention are trimethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane isocyanate, xylene diisocyanate aromatic diisocyanate compounds such as diisocyanate, aliphatic diisocyanate such as hexamethyl diisocyanate, and the like are used alone or in combination.

In addition, the epoxy compound in the present invention is a polyethylene glycol diglycidyl ether (diglycidyl ether), diglycidyl ether (diglycidyl ether), trimethylol propane triglycidyl ether (trimethylol propane triglycidyl ether) and the like alone Or mixed.

It is preferable to use 1 to 17 weight% of the hardening | curing agent in 100 weight% of 2nd hard coat compositions, More preferably, it is 3 to 10 weight%. Even more preferably 5% to 7% by weight.

In the present invention, the curing agent is an additive used to control the molecular weight or the chain structure of the second hard coating composition. When the curing agent is used in the above-described range, the effect of suppressing phase separation and the like is prominent. When the content of the curing agent is less than 1% by weight, it is difficult to expect the function of the curing agent, and when the content of the curing agent is greater than 17% by weight, the content of the curable resin is relatively low, making it difficult to increase the hardness.

③ Leveling agent

In the present invention, a leveling agent is used to even the surface of the second hard coat layer. The leveling agent can be used by mixing a ketone or an ester solvent with a silicone resin. As a leveling agent by this invention, it is preferable to use a silicone diacrylate and a silicone polyacrylate compound individually or in mixture.

The content of the leveling agent is preferably 0.5% by weight to 5% by weight, more preferably 1% by weight to 1.5% by weight, based on 100% by weight of the second hard coat layer composition. When the leveling agent is less than 0.5% by weight, it is difficult to expect the leveling effect, and when it is larger than 5% by weight, the hardness may be weakened.

④ UV absorber

When the photocurable resin is used as the curable resin for ultraviolet curing in the present invention, it is preferable to use a ultraviolet absorber to prevent deterioration generated during ultraviolet curing and to improve durability of the second hard coating layer.

The ultraviolet absorber used in the present invention is preferably used alone or mixed with a salicylate ultraviolet absorber, a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a cyanoacrylate ultraviolet absorber, and a benzoate ultraviolet absorber. Do.

More specifically, the ultraviolet absorber is phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy- 4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4 -Hydroxy-5-benzoylphenyl) methane, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5- Chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5- Di-tert-amylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxy Phenyl) benzotriazole, 2- (2'-hydroxy-3 '-(3', 4 ', 5', 6'-tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole, 2,2 '-Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazolyl-2-yl) phenol], 2- (2'-hydroxy-5'-meta Krilloxyphenyl) -2H-benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol ], And 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl 2-cyano-3,3'-diphenyl acrylate or the like is used alone or in combination.

In the present invention, the content of the ultraviolet absorber is preferably 1% by weight to 10% by weight, more preferably 3% by weight to 8% by weight, based on 100% by weight of the second hard coating composition.

When the content of the ultraviolet absorber is 1% by weight or less, the effect of adding the ultraviolet absorber may not be realized properly, and when the content of the ultraviolet absorber is 10% by weight or more, the physical properties of the second hard coat layer may be affected.

⑤ antibacterial

In the present invention, it is preferable to use an antimicrobial agent for the removal effect or antimicrobial effect of foreign matter adhering to the surface. As an antimicrobial agent, silver inorganic antimicrobial agents, such as a silver inorganic antimicrobial agent carrying a zirconium phosphate, a silver inorganic antimicrobial agent carrying a zeolite, a silver inorganic antimicrobial agent carrying a calcium phosphate, and a silver inorganic antimicrobial agent carrying a silica gel, Various antibacterial agents, such as an organic antimicrobial agent which mix | blends an amino acid compound and the organic antimicrobial agent which mix | blends a nitrogen-containing sulfur type compound, etc. which can be used can be used.

The amount of the antimicrobial agent is controlled according to the type of antimicrobial agent used, the antimicrobial activity required, its holding time, etc., but the content thereof is usually 0.5 wt% to 10 wt% in 100 wt% of the second hard coating composition. It is preferable to use, More preferably, it is 1 to 5 weight%. When the content of the antimicrobial agent is 0.5% by weight or less, the antimicrobial effect is hard to be realized, and when the content is 10% by weight or more, economic efficiency is low.

⑤ dispersant

In the present invention, an organic solvent that is a dispersant is used to apply the second hard coat layer to the first hard coat layer. In the present invention, it is preferable to use an organic solvent in which the second hard coating composition can be evenly dispersed.

The organic solvent is selected in consideration of the coating property of the second hard coating layer, the adhesion with the polarizing film, and the enhancement of the surface hardness enhancement function.

The organic solvent used in the present invention is a C1-8 saturated hydrocarbon alcohol such as methanol, isopropanol, butanol, t-butanol, isobutanol and the like, acetone, methyl ethyl ketone, methyl isobutyl ketone and the like of ketones. Saturated hydrocarbon-based diketones having 1 to 8 carbon atoms, such as saturated hydrocarbon ketones of 1 to 8 and acetyl acetone, ethyl acetate of esters, and ethyl ethers of ether alcohols having 1 to 8 carbon atoms, such as butyl acetate. Cellosolve, methyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, and other N-methyl pyrrolidone, ethyl cellosolve acetate, diacetone alcohol and the like are used alone or in combination. Moreover, benzene, toluene, xylene, ethylbenzene, etc. which correspond to an aromatic hydrocarbon can also be used individually or in mixture.

The organic solvent is preferably used in an amount of 30 parts by weight to 150 parts by weight based on 100 parts by weight of the second hard coating layer composition to be applied, and more preferably 50 parts by weight to 80 parts by weight. When the content of the organic solvent is less than 30 parts by weight with respect to 100 parts by weight of the second hard coating composition, the viscosity is low, so that the coating property and adhesion with the polarizing film are inferior, and when the content of the organic solvent is greater than 150 parts by weight, it is higher than that of the second hard coating composition. Profitability is inferior by using too many organic solvents.

2) curing step

The curing step according to the present invention uses a conventional curing method.

Since the second hard coating composition according to the present invention includes a thermosetting resin or a photocurable resin, the curing step is performed by thermosetting or UV curing. Thermal curing and UV curing may proceed sequentially, but may also proceed simultaneously. In addition, it is a matter of course that the components or content of the curing agent and the leveling agent may vary depending on the curing method.

It is preferable that the thickness of the 2nd hard coating layer formed through the said step is 1 micrometer-15 micrometers, More preferably, they are 3 micrometers-10 micrometers. The thickness of the second hard coat layer is adjustable in consideration of the thickness of the first hard coat layer described above. When the thickness is smaller than 1 μm, the thickness is too thin, so scratch resistance and abrasion resistance are lowered. When the thickness is larger than 15 μm, economical efficiency is lowered during spin coating.

Therefore, the total thickness (thickness of the first hard coat layer and the second hard coat layer) is preferably 2 μm to 15 μm.

A high hardness hard coating optical device manufactured through the above process (first hard coating layer forming step and second hard coating layer forming step) is illustrated in FIG. 2. As shown, the high-hardness hard-coating optical device is a polyvinyl alcohol (hereinafter referred to as 'PVA') 400 and triacetyl cellulose (TAC) by the adhesive 200 on the LCD cell 100 ( 300, 500) is attached to the polarizing film. The first hard coating layer 600 is coated on the TAC surface 500 of the polarizing film, and the second hard coating layer 700 is coated on the first hard coating layer 600 to be laminated.

Of course, the high-hardness hard-coated optical device manufactured by the method of manufacturing a high-hardness hard-coated optical device according to the present invention is also included in the scope of the present invention. In addition, the high hardness hard coating optical element manufactured by the high hardness hard coating optical element manufacturing method according to the present invention is a cathode ray tube (CRT), a liquid crystal display (LCD) as an image display device. The present invention is also applicable to at least one image display device among a group consisting of a plasma display panel (PDP) and an organic light emitting diode (OLED).

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings, preferred embodiments of the present invention and comparative examples.

Example 1

After manufacturing a polarizing film in a conventional method, cut to 500mm horizontally and vertically, and then attach the polarizing film to the LCD cell using a pressure-sensitive adhesive in a continuous rotary coating machine. The first hard coating composition comprising a polyfunctional acrylate-based resin as a curable resin on the TAC side of the polarizing film, comprising 3% by weight of a curing agent, 1% by weight of a leveling agent, and 3% by weight of phenyl salicylate, After dissolving in the form of a solution, the solution was coated on the TAC surface of the polarizing film at a rotational speed of 200 rpm for 20 seconds. After drying for 1 minute at a rotational speed of 500 rpm at 60 ° C., ultraviolet curing was performed to form a first hard coating layer having a thickness of 5 μm. After the first hard coat layer was formed, a multifunctional acrylate-based resin was used as the curable resin in the first hard coat layer in a continuous rotary coating machine, and 3 wt% of a curing agent, 1 wt% of a leveling agent, and phenyl salicyl as an ultraviolet absorber. After preparing a second hard coating composition comprising 3% by weight of a silver-based inorganic antimicrobial agent containing 3% by weight of silver and a zirconium phosphate as an antimicrobial agent in xylene, the solution was prepared in the form of a solution. The hard coating layer was coated for 20 seconds at a rotation speed of 200 rpm. After drying for 1 minute at a rotational speed of 500 rpm at 60 ° C., UV curing was performed to form a second hard coating layer having a thickness of 5 μm. The xylene was mixed in a ratio of 70 parts by weight based on 100 parts by weight of the first hard coating composition and 100 parts by weight of the second hard coating composition.

Example 2

Under the same conditions as in Example 1, except that the first hard coating layer was coated with a rotational speed of 200 rpm in the coating step and the second hard coating layer was coated with a thickness of 7 μm with a rotational speed of 150 rpm in the second hard coating layer coating step. Prepared.

Example 3

Under the same conditions as in Example 1 except that the first hard coating layer was coated with a rotational speed of 200 rpm in the coating step, and the second hard coating layer was coated with a thickness of 10 μm with a rotational speed of 100 rpm in the second hard coating layer coating step. Prepared.

Example 4

In the first hard coating layer coating step, the rotational speed is 150 rpm, and the first hard coating layer is coated with a thickness of 7 μm. In the second hard coating layer coating step, the second hard coating layer is coated with the thickness of 5 μm. It was manufactured under the same conditions as in Example 1 except for the above.

Example 5

In the first hard coating layer coating step, the rotational speed was 150 rpm, and the first hard coating layer was coated with a thickness of 7 μm. In the second hard coating layer coating step, the second hard coating layer was coated with the thickness of 7 μm. It was manufactured under the same conditions as in Example 1 except for the above.

Example 6

In the first hard coating layer coating step, the rotational speed is 150 rpm, and the first hard coating layer is coated with a thickness of 7 μm. In the second hard coating layer coating step, the second hard coating layer is coated with the thickness of 10 μm. It was manufactured under the same conditions as in Example 1 except for the above.

Example 7

In the first hard coating layer coating step, the rotational speed is 100 rpm, and the first hard coating layer is coated with a thickness of 10 μm. In the second hard coating layer coating step, the second hard coating layer is coated with the thickness of 5 μm at 200 rpm. It was manufactured under the same conditions as in Example 1 except for the above.

Example 8

In the first hard coating layer coating step, the rotational speed is 100 rpm, and the first hard coating layer is coated with a thickness of 10 μm. In the second hard coating layer coating step, the second hard coating layer is coated with the thickness of 7 μm at 150 rpm. It was manufactured under the same conditions as in Example 1 except for the above.

Example 9

In the first hard coating layer coating step, the rotational speed is 100 rpm, and the first hard coating layer is coated with a thickness of 10 μm. In the second hard coating layer coating step, the second hard coating layer is coated with the thickness of 10 μm. It was manufactured under the same conditions as in Example 1 except for the above.

Comparative Example 1

The conventional optical element shown in FIG. 1 was used.

Table 1 shows the results of measuring the adhesion, pencil hardness, wear resistance, and the thickness of the coating layer, which are physical properties of the optical devices obtained in Examples and Comparative Examples.

division Adhesion Pencil hardness Wear resistance Coating thickness (㎛) Overall coating thickness (μm) First hard coating layer 2nd hard coating layer Example 1 100/100 4H ○ 5 5 10 Example 2 100/100 4H ○ 5 7 12 Example 3 100/100 5H ○ 5 10 15 Example 4 100/100 4H ○ 7 5 12 Example 5 100/100 4H ○ 7 7 14 Example 6 100/100 5H ◎ 7 10 17 Example 7 100/100 4H ○ 10 5 15 Example 8 100/100 5H ◎ 10 7 17 Example 9 100/100 6H ◎◎ 10 10 20 Comparative example 100/100 2H X 17 (including thickness of adhesive) 17 (including thickness of adhesive)

The adhesion, pencil hardness, and wear resistance measured in [Table 1] were measured by the following method.

(Adhesiveness)

When the surface of the hard coating layer of the optical element was put in 100 1 mm x 1 mm cross hatching, the cellophane adhesive tape was attached, and the cellophane adhesive tape was removed, the number of eyes remaining on the film substrate was measured. Counted.

(Pencil hardness)

The pencil hardness of the surface of the hard coat layer of the optical device was measured using a conventional pencil scratch tester.

(Wear resistance)

The hard coating layer was rubbed with a steel surface, and the scratches were visually observed.

Observation results were measured as follows.

◎: no scratch

○: almost no scratch

×: scratches

As shown in Table 1, Examples 1 to 9 have better pencil hardness than Comparative Example 1 (2H). This is because Examples 1 to 9 form the hard coating layer in two layers, thereby further strengthening the hardness. In addition, Example 6 and Example 9 is superior to other examples and comparative examples in pencil hardness and wear resistance, because the thickness of the hard coating layer is relatively thick. Therefore, it can be seen that the implementation of two hard coating layers is excellent in terms of hardness and wear resistance.

In the above, this invention was demonstrated in detail with reference to an Example and a comparative example centering on a structure. However, the scope of the present invention is not limited to the above embodiments but may be embodied in various forms of embodiments within the appended claims. Without departing from the gist of the invention as claimed in the claims, any person of ordinary skill in the art is deemed to be within the scope of the claims underlying the present invention to the extent possible for various modifications.

In addition, the preferred range, more preferred range, and even more preferred range limitation in the present invention is to maximize the effect even more, it is possible to obtain a more satisfactory technical effect by narrowing the limited range.

As described above, the manufacturing method of the high-hardness hard-coating optical device and the high-hardness hard-coating optical device using the same have the advantage of obtaining an optical device having improved hardness by forming two hard coating layers.

In addition, the hard coating layer is formed by the spin coating method, so that the manufacturing process is simple and the yield is improved.

Claims (7)

(a) 100% by weight of the first hard coating composition comprising a curable resin, a curing agent, and a leveling agent under rotation conditions of a rotational speed of 50 rpm to 6000 rpm and a rotation time of 10 seconds to 600 seconds in a continuous rotary coating machine. , Iii) 1% to 17% by weight of the curing agent Ii) coating a solution obtained by mixing the first hard coating composition comprising 0.5% by weight to 5% by weight of the leveling agent with a dispersant and coating a solution on a polarizing film attached to an LCD cell, wherein the content of the dispersant is antistatic coating composition 100 A first hard coat layer forming step of coating the first hard coat layer by mixing in a ratio of 30 parts by weight to 150 parts by weight with respect to parts by weight, and thermally or UV curing to form a first hard coat layer; And (b) 100% by weight of the second hard coating composition comprising a curable resin, a curing agent, a leveling agent, and an antimicrobial agent under rotation conditions of a rotational speed of 50 rpm to 6000 rpm and a rotation time of 10 seconds to 600 seconds in the continuous rotation coating machine. To Iii) 1% to 17% by weight of the curing agent Ii) 0.5% to 5% by weight of the leveling agent Iii) the antimicrobial agent is mixed with a dispersant to dissolve the second hard coating composition comprising 0.5% by weight to 10% by weight on the first hard coating layer, the content of the dispersant is 100 parts by weight of the antistatic coating composition Mixing in a ratio of 30 parts by weight to 150 parts by weight with respect to the coating of the second hard coating layer, heat curing or ultraviolet curing to form a second hard coating layer to form a second hard coating layer characterized in that it comprises a high diameter Figure also a method of manufacturing a hard coat optical element. The method of claim 1, Wherein the curable resin is at least one of a thermosetting resin or a photocurable resin. The method of claim 2, When the photocurable resin is included in the curable resin, the first hard coating composition and / or the second hard coating composition may further include an ultraviolet absorber, and the amount of the ultraviolet absorber may be the first hard coating composition or the second hard coating composition. 100% by weight of the hard coating composition, characterized in that from 1% by weight to 10% by weight method for producing a hard coating optical element. The method of claim 3, wherein The ultraviolet absorber is phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydride Hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-meth Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy 5-benzoylphenyl) methane, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- ( 2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotria Sol, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5-di-tert- Amylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzoate Azole, 2- (2'-hydroxy-3 '-(3', 4 ', 5', 6'-tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2'-hydroxy-5'-methacryloxyphenyl) -2H-benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol], 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl-2-cyano At least one of -3,3'-diphenyl acrylate. The method of claim 1, The antimicrobial agent includes a silver inorganic antimicrobial agent containing zirconium phosphate, a silver inorganic antimicrobial agent supporting a zeolite, a silver inorganic antimicrobial agent supporting a calcium phosphate, a silver inorganic antimicrobial agent supporting a silica gel, and an amino acid compound. An organic antimicrobial agent comprising a combination of an organic antimicrobial agent and a nitrogen-containing sulfur compound, or a mixture of the organic antimicrobial agent. The method according to any one of claims 1 to 5, The method of claim 1, wherein the first hard coat layer or the second hard coat layer has a thickness of about 1 μm to about 15 μm. A high hardness hard coating optical element, characterized in that manufactured by the method of manufacturing a high hardness hard coating optical element according to claim 6.

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