KR20100037519A - Water dispersion hard coating composition and hard coating film, polarizing plate and display device using the same - Google Patents
Water dispersion hard coating composition and hard coating film, polarizing plate and display device using the same Download PDFInfo
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- KR20100037519A KR20100037519A KR1020080128713A KR20080128713A KR20100037519A KR 20100037519 A KR20100037519 A KR 20100037519A KR 1020080128713 A KR1020080128713 A KR 1020080128713A KR 20080128713 A KR20080128713 A KR 20080128713A KR 20100037519 A KR20100037519 A KR 20100037519A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
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Abstract
The present invention uses an aqueous hard coating composition using water as a solvent and exhibiting excellent coating strength and high hardness, excellent scratch resistance, low curling properties, excellent adhesion, excellent transparency, and excellent coating surface forming ability, and prepared using the same. It relates to a hard coating film, a polarizing plate and a display device having the same.
Water dispersion, hard coating, organic-inorganic hybrid, silica sol
Description
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous hard coating composition, which is environmentally friendly and has high hardness properties. Thus, plastic optical components, various display panels, such as liquid crystal displays (LCDs), plasma displays (PDPs), CRTs, and electronics The present invention relates to an aqueous hard coating composition, a hard coating film, a polarizing plate, and a display device using the same, which can be usefully used for the production of a surface protective hard coating film on a panel such as a light emitting display (EL).
Due to the rapid industrialization, the global environment is rapidly deteriorating such as air and water pollution, ozone depletion and global warming. It's going on.
Particularly, in the air pollution part, an aqueous coating solution that minimizes the use of volatile organic compounds (VOCs) has been applied to many parts. The aqueous coating liquid is applied to the ultraviolet curable coating liquid, and research and development of the ultraviolet curable aqueous coating liquid is actively progressed not only in Korea but also in various countries of the world.
As a representative method for preparing a conventional UV-curable aqueous coating liquid, there is disclosed a method of forcibly dispersing a photocurable resin using a dispersant such as polyvinyl pyrrolidone as in European Patent Publication No. 0012339. The coating liquid prepared by such a forced dispersion method is incompatible with other types of photocurable aqueous dispersions (for example, urethane dispersions or acrylic emulsions), and even after drying, the dispersant contains a considerable amount of water, thereby allowing photocuring. It has a bad effect on the transparency and hardness of the after coating film.
In addition, the photocurable polys disclosed in U.S. Patent Nos. 5,135,963, 6,011,078, 6,207,744, 6,335,397, 6,436,540, German Patent Publication No. 401732, European Patent No. 0753531, 870788, and 0872502. Urethane aqueous products have a relatively large molecular weight for stability in the aqueous phase has a disadvantage of low curing density. That is, the aqueous product has a relatively large molecular weight for water dispersion stability compared to the ultraviolet curable oligomer and the ultraviolet curable monomer, which influences the physical properties of the conventional oil-based photocurable coating liquid, so even if the functional group of the terminal is simply increased to the ultraviolet curable oil-based coating liquid Compared with conventional oil-based photocurable coating solution, it has low curing density after curing, and thus has poor transparency and hardness, and requires properties of coating solution of most optical films such as hydrolysis resistance, base resistance, acid resistance, hot water resistance, scratch resistance, etc. Greatly lacking in
In addition, US Pat. No. 6,521,702 introduces a polyfunctional polyester acrylate in which some hydroxy groups (-OH) and carboxyl groups (-COOH) remain to react two hydroxyl groups with isocyanates and neutralize the carboxyl groups. As a method of dispersing in water, a method of preparing an ultraviolet curable aqueous coating solution was proposed. However, the method is advantageous in terms of physical properties, but the production cost of the polyfunctional polyester acrylate is very high and the process is complicated, so it is difficult to reduce the variation of each product, so the industrial productivity is very low.
In addition, in the case of the conventional aqueous coating liquid has a disadvantage that the coating liquid is composed only of the organic material is unsuitable for high-hardness hard coating applicable to the display device.
The present invention is to solve the above problems, to provide a high hardness aqueous hard coating composition capable of forming a hard coating layer of high hardness, adhesion, scratch resistance, wear resistance, low curling properties on the surface of various substrates There is a purpose.
In another aspect, the present invention is to provide a hard coating film using the aqueous hard coating composition.
In another aspect, the present invention is to provide a polarizing plate using the hard coating film.
Another object of the present invention is to provide a display device having the polarizing plate.
In order to achieve the above object, the present invention provides an aqueous solution comprising water as a polyfunctional urethane (meth) acrylate having a hydrophilic group in a molecule represented by the following formula (1), a (meth) acrylate monomer, a photoinitiator and a solvent. It provides a hard coating composition.
[Formula 1]
(A in Formula 1 is A or O, m is an integer of 1 to 3, X 1 to X 4 is the reaction residue of the starting material used in the synthesis, X 1 is a diiso (thio) cyanate Reaction residue, X 2 is reaction residue of polyol, X 3 is reaction residue of diol having hydrophilic group (sulphone group, carboxyl group or phosphate group), X 4 is reaction of polyfunctional (meth) acrylate having hydroxy group Is a residue)
Furthermore, the present invention is characterized in that the aqueous hard coating composition further comprises water-dispersible organic-inorganic silica particles chemically bonded to the surface hydroxy group of the silica particles with the multifunctional silane compound of formula (2).
[Formula 2]
(In the above formula (2), n is an integer of 1 to 3, R 1 and R 2 each independently represent an aliphatic or aromatic hydrocarbon having 1 to 10 carbon atoms, R 3 is a carbon number from 1 to 3 containing or not containing a hetero atom) 15 aliphatic or aromatic hydrocarbons, and R 4 and R 5 each represent an aliphatic or aromatic hydrocarbon having 1 to 15 carbon atoms, with or without hydrogen or a hetero atom, wherein R 4 and R 5 are linked to each other and are cyclic. It may form a structure, R 6 is an aliphatic or aromatic hydrocarbon containing or without a hetero atom having 1 to 20 carbon atoms, Y is 7 to 80 carbon atoms containing a (meth) acrylate group having 2 to 10 functional groups Aliphatic or aromatic hydrocarbons with or without hetero atoms)
The polyfunctional silane compound of Chemical Formula 2 is preferably represented by the following Chemical Formula 3.
(3)
(In the above formula (3), n is an integer of 1 to 3, R 1 and R 2 each independently represent an aliphatic or aromatic hydrocarbon having 1 to 10 carbon atoms, R 3 is a carbon number from 1 to 3 containing or without a hetero atom) 15 aliphatic or aromatic hydrocarbons, and R 4 and R 5 each represent an aliphatic or aromatic hydrocarbon having 1 to 15 carbon atoms, with or without hydrogen or a hetero atom, wherein R 4 and R 5 are linked to each other and are cyclic. It may form a structure, R7 is an aliphatic or aromatic hydrocarbon containing or without 1 to 20 carbon atoms, Y is C7-80 hetero atoms containing 2 to 10 (meth) acrylate groups Aliphatic or aromatic hydrocarbons with or without atoms)
The water-dispersible organic-inorganic silica particles may be included in an amount of 5 to 80 parts by weight based on 100 parts by weight of the total aqueous hard coating composition.
The intramolecular urethane bond in Formula 1 provides an aqueous hard coating composition, which is a urea bond.
The polyfunctional urethane (meth) acrylate having a hydrophilic group in the molecule may be included in the range of 5 to 80 parts by weight based on 100 parts by weight of the total aqueous hard coating composition.
The (meth) acrylate monomer may be included 5 to 60 parts by weight based on 100 parts by weight of the total aqueous hard coating composition.
The photoinitiator may be included 0.1 to 10 parts by weight based on 100 parts by weight of the total aqueous hard coating composition.
Water is used as the solvent, and may be included in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the total aqueous hard coating composition.
In order to achieve the other object of the present invention, the present invention provides a hard coating film characterized in that it comprises a high-hardness hard coating layer formed by applying the aqueous hard coating composition on one or both sides of the transparent substrate and then cured.
The transparent substrate may be selected from a triacetyl cellulose film (hereinafter referred to as TAC), a cycloolefin derivative film, a polyethylene terephthalate film (hereinafter referred to as PET), a polycarbonate film (hereinafter referred to as PC), and polymethyl methacrylate (hereinafter referred to as PMMA). Can be.
The hard coating layer has a thickness of 5 to 30 µm and a curling characteristic of 15 mm or less.
The hard coating layer is characterized in that the surface hardness of 4H or more.
In order to achieve another object of the present invention the present invention provides a polarizing plate characterized in that the hard coating film is provided.
In order to achieve another object of the present invention, the present invention provides a display device characterized in that the polarizing plate is provided.
The aqueous hard coating composition according to the present invention is not only environmentally friendly using water as a solvent, but also has excellent high hardness, abrasion resistance, weather resistance and optical high transparency. In addition, according to the present invention, the curing speed is high at the time of manufacture of the coating film, the productivity is excellent, and the cured film hardly occurs after the film is cured. Due to these properties, the coating film of the present invention exhibits excellent physical and optical properties when applied to polarizing plates and display devices.
Hereinafter, the present invention will be described in more detail.
First, an aqueous hard coating composition is described.
An aqueous hard coating composition according to an embodiment of the present invention includes water as a polyfunctional urethane (meth) acrylate, a (meth) acrylate monomer, a photoinitiator and a solvent having a hydrophilic group in a molecule represented by the following Chemical Formula 1.
[Formula 1]
(A in Formula 1 is A or O, m is an integer of 1 to 3, X 1 to X 4 is the reaction residue of the starting material used in the synthesis, X 1 is a diiso (thio) cyanate Reaction residue, X 2 is reaction residue of polyol, X 3 is reaction residue of diol having hydrophilic group (sulphone group, carboxyl group or phosphate group), X 4 is polyfunctional (meth) acrylate having hydroxy group Reaction Remains)
The polyfunctional urethane (meth) acrylate having an intramolecular hydrophilic group represented by the formula (1) is preferably contained 5 to 80 parts by weight, more preferably 10 to 60 parts by weight based on 100 parts by weight of the total aqueous hard coating composition It is good to be included. If the amount of the polyfunctional urethane (meth) acrylate is less than 5 parts by weight, the stability and overall physical properties of the hard coating solution is inhibited. If the amount is more than 80 parts by weight, the surface appearance is deteriorated and workability is poor. .
The compound represented by Chemical Formula 1 may be prepared by reacting a polyol, a polyol having a hydrophilic group, a diiso (thio) cyanate, and a polyfunctional (meth) acrylate having a hydroxyl group.
Although the polyol does not limit the molecular weight, the number average molecular weight is preferably 500 to 5,000, and more preferably 1,000 to 2,000. If the number average molecular weight is less than 500, it is difficult to form micelles during water dispersion, so that the liquid stability is poor. If the number average molecular weight is more than 5,000, the viscosity is high, so that it is difficult to control the reaction and the curing density is low, and thus the physical properties of the desired hard coating liquid after hardening are difficult to be realized.
In addition, the polyol may be a polyester-type polyol, carbonate polyol, caprolactone-based polyol, etc. In more detail, the polyester-type polyol can be generally used commercially available products, condensation reaction of di-acid or acid anhydride and glycol Obtained. Diacids can be used either saturated or unsaturated alkyl or cyclic alkyl and phenyl. Examples include phthalic acid, hydrozinnate phthalic acid, isoplic acid, tellaflic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sublic acid, azeratic acid, sebacic acid, formic acid, succinic anhydride , Phthalic anhydride, maleic anhydride, hydrozinnate phthalic anhydride and the like. Alkyl glycols are generally used as glycols. Examples thereof include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, methyl propane glycol, neopentyl glycol, butylethyl flopane glycol, butanediol, hexane diol and the like. In the case of carbonate polyols, commercially available PCDLs from Asahi Kasai can be used. In the case of caprolactone-based polyols, epsilon caplolactone-modified products can be used, and the commercialized lactone polyol Placcel 200 series of Daicel can be optionally used.
Diol having a hydrophilic group is added to increase the hydrophilicity so that the dispersion stability of the hard coating composition can be maintained well. Wherein the hydrophilic group comprises a sulfone group, a carboxyl group and a phosphate group, and the diol comprising the hydrophilic group includes dimethylolpropanoic acid (DMPA), dihydroxysulfonic acid and dihydroxyphosphonic acid, 2,3-dihydroxypropanephosphate You can use the selected one from phonesan.
As the diiso (thio) cyanate, most of the commercially available diisocyanates or diisothiocyanates can be used, but it is preferable to use a bifunctional isocyanate having no sulfur modification. Examples of the sulfur-free bifunctional isocyanate include xylene diisocyanate, tetramethyl xylene diisocyanate, isophorone diisocyanate, hexane diisocyanate, trimethylhexamethylene diisocyanate, dicyclomethane diisocyanate, and the like. Isophorone diisothiocyanate, hexanediisothiocyanate, toluene diisothiocyanate, etc. can be used as a nate.
The (meth) acrylate having a hydroxy group used in the synthesis of the compound represented by the formula (1) is used to increase the hydrophilicity and to increase the hydrophilicity while providing photocurability. The (meth) acrylate which has the said hydroxyl group is pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, 1, 3- butanediol di (meth) acrylate, 1, 4- butanediol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate and the like may be used, and in addition to the monomer structure mentioned above, monomers prepared by modifying ethylene oxide, propylene oxide, epsilon kaflolactone, etc. Can also be used.
The aqueous hard coating composition according to the present invention includes a (meth) acrylate monomer. For example, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, (meth) acrylic Ester, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, propylene Glycol (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, neo Pentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxy) Isoethyl) isocyanurate di (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, iso At least one compound can be selected and used from the group consisting of dexyl (meth) acrylate, stearyl (meth) acrylate, tetrahydroperfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like. .
The amount of the (meth) acrylate monomer is not limited, but is preferably included 5 to 60 parts by weight, more preferably 5 to 40 parts by weight based on 100 parts by weight of the total aqueous hard coating composition. If the addition amount of the (meth) acrylate monomer is less than 5 parts by weight, the effect of dilution is inferior, and if the addition amount is more than 60 parts by weight, there is a problem that the dispersing force is lowered.
The aqueous hard coating composition according to the present invention includes a photoinitiator. Photoinitiators are, for example, 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1, diphenylketone benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenyl- 1-one, 4-hydroxy cyclophenyl ketone, dimethoxy-2-phenylatetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-knoloacetophenone, 4, At least one selected from the group consisting of 4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone and the like can be used. The photoinitiator may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total aqueous coating composition. If the content of the photoinitiator is less than 0.1 parts by weight, the curing speed is slow and more than 10 parts by weight is uneconomical. The solvent of the aqueous hard coating composition according to the present invention uses water, and in particular, an alcohol-based solvent may be used for the purpose of improving workability. As one example, methanol, ethanol, isopropanol, butanol, methylcellussorb, ethylsolsorb and the like can be used. Water may be added in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the aqueous hard coating composition. If less than 0.1 parts by weight, the coating properties are lowered, if greater than 50 parts by weight it is difficult to raise the desired coating thickness.
In order to achieve the high hardness of the desired physical properties in the present invention, the aqueous hard coating composition according to the present invention further comprises water-dispersible organic-inorganic silica particles chemically bonded to the surface hydroxy group of the silica particles with the polyfunctional silane compound of formula (2). do.
[Formula 2]
(In Formula 2, n is an integer of 1 to 3, R 1 and R 2 each independently represent an aliphatic or aromatic hydrocarbon having 1 to 10 carbon atoms, R 3 is a carbon atom containing 1 to 15 or without a hetero atom Aliphatic or aromatic hydrocarbons, R 4 and R 5 each represent an aliphatic or aromatic hydrocarbon having 1 to 15 carbon atoms, with or without hydrogen or a hetero atom, wherein R 4 and R 5 are linked to each other to form a cyclic structure. R 6 may be an aliphatic or aromatic hydrocarbon having 1 to 20 carbon atoms, including or without a hetero atom, and Y is 7 to 80 carbon atoms including a (meth) acrylate group having 2 to 10 functional groups. Aliphatic or aromatic hydrocarbons with or without hetero atoms)
More preferably, the polyfunctional silane compound of Chemical Formula 2 is represented by the following Chemical Formula 3.
(3)
(In the above formula (3), n is an integer of 1 to 3, R 1 and R 2 each independently represent an aliphatic or aromatic hydrocarbon having 1 to 10 carbon atoms, R 3 is a carbon number from 1 to 3 containing or without a hetero atom) 15 aliphatic or aromatic hydrocarbons, and R 4 and R 5 each represent an aliphatic or aromatic hydrocarbon having 1 to 15 carbon atoms, with or without hydrogen or a hetero atom, wherein R 4 and R 5 are linked to each other and are cyclic. It may form a structure, R7 is an aliphatic or aromatic hydrocarbon containing or without 1 to 20 carbon atoms, Y is C7-80 hetero atoms containing 2 to 10 (meth) acrylate groups Aliphatic or aromatic hydrocarbons with or without atoms)
Although not limited, it will be described in more detail by way of example R 1 and R 2 may be a methyl group, ethyl group, isopropyl group, propyl group, butyl group, phenyl group and the like, R 3 is a methyl group, ethyl group, isopropyl group, propyl group , A butyl group, a pentyl group, or a structure in which a hetero atom such as an ether bond is present in the combination thereof. R 4 and R 5 may be a hydrogen group, a methyl group, an ethyl group, a propyl group, a cyclohexyl group, or the like. R 6 and R 7 may be an alkyl group derived from succinic acid, a phthalic acid derivative, an aromatic group, an aromatic group containing an alkyl group, and the like, and Y may have 7 to 80 carbon atoms including 2 to 10 (meth) acrylate groups. Aliphatic or aromatic hydrocarbons with or without hetero atoms. Although not limited, Y preferably selects a polyfunctional (meth) acrylate which can be reacted with a hydroxyl group present. Examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylic Acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acrylonyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexaneadiol mono (meth ) Acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate and dipentaerythritol penta ( Meta) acrylates and the like are possible.
The compound of Formula 2 is synthesized by a ring-opening reaction with a silane coupling agent containing a (meth) acrylate containing a carboxylic acid group and an oxirane. At this time, the organic compound containing a carboxylic acid group can be synthesized on a simple condition by reacting the organic anhydride in the presence of a tertiary amine to the (meth) atylate containing a hydroxy group.
(Meth) acrylate containing the said hydroxy, for example, dipentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylol propane tri (meth) acrylate, (meth) acrylic Ester, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, propylene Glycol (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, neopentyl glycoldi (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanu Rate di (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, iso-decyl (meth) acrylic Rate and the like can be used.
The above-mentioned (meth) acrylate containing hydroxy can react with organic anhydride to introduce carboxylic acid. For example, succinic anhydride, methyl succinic anhydride, 2,2-dimethyl succinic anhydride, isobutenyl succinic anhydride, 2-octen-1-ylsuccinic anhydride, octadekenyl succinic anhydride, 2-oxabicyclo [3,1,0 ] Hexane-2,4-dione, cis-1,2-cyclohexanedicarboxylic anhydride, trans-1,2-cyclohexanedicarboxylic anhydride, hexahydro-4-methylphthal anhydride, itagonal anhydride, 2-dodecene-1-ylsuccinic anhydride, cis-1,2,3,6-tetrahydropthalic anhydride, Cis-5-norbornene-endo-2,3-dicarboxylic acid anhydride, endo-bicyclo [ 2,2,2] oct-5-ene-2,3-dicarboxylic anhydride, cantharidin, methyl-5-norbornene-2,3-dicarboxylic anhydride, exo-3,6-epoxy-1, 2,3,6-tetrahydrophthalic anhydride, S-acetylmercaptosuccinic anhydride, maleic anhydride, citragonic anhydride, 2,3-dimethylmaleic anhydride, 1-cyclopentene-1,2-dicarboxylic acid Anhydride, 3,4,5,6, tetrahydrophthalic anhydride, bromine Momaleic anhydride, dichromaleic anhydride, glutaric anhydride, 3-methylglutal acid anhydride, 2,2-dimethylglutal acid anhydride, 3,3-dimethylglutal acid anhydride, 3-ethyl-3-methylglutal acid Anhydride, 3,3-tetramethylene glutaric anhydride, hexafluoroglutarate anhydride, diglycolic acid anhydride, phenylsuccinic anhydride, phenylmaleic anhydride, 2,3-diphenylmaleic anhydride, 2-phenylglutalic anhydride, homo Phthalic anhydride, phthalic anhydride, 4-methylphthalic anhydride, 3,6-difluorophthalic anhydride, 3,6-dichlorophthalic anhydride, 4,5-dichlorophthalic anhydride, tetrafluorophthalic anhydride, tetrachlorophthalic anhydride, tetra Bromophthalic anhydride, 3-hydroxyphthalic anhydride, 1,2,4-benzenetricarboxylic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, diphenyl acid anhydride, 1,8-naphthalic anhydride, 4 -Chloro-1,8-naphthalic acid free Water, 4-bromo-1,8-naphthalic anhydride, 4-amino-1,8-naphthalic anhydride, 3-nitro-1,8-naphthalic anhydride, 4-nitro-1,8-naphthalic anhydride And succinic anhydride and phthalic anhydride are the most preferred reaction compounds.
The silane coupling agent containing an oxirane is, for example, (beta)-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, [(3-methyloxetan-3-yl) -methyloxypropyl] -trie Methoxysilane, [(3-methyloxetan-3-yl) -methyloxypropyl] -trimethoxysilane, [(3-methyloxetan-3-yl) -propyloxypropyl] -methyltrimethoxysilane, [(3-Methyloxetan-3-yl) -propyloxypropyl] -methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glyci Doxybutyltrimethoxysilane, γ-glycidoxy butyltriethoxysilane, γ-glycidoxypropyldimethoxyethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyldimethylethoxy Silane, 3,4-epoxybutyltrimethoxysilane The most preferred compounds are [(3-methyloxetan-3-yl) -methyloxypropyl] -triethoxysilane, β- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, γ -Glycidoxypropyltrimethoxysilane and the like can be used.
The water-dispersible organic-inorganic silica particles according to the present invention are prepared by chemically bonding a multifunctional silane compound including the polyfunctional (meth) acrylate of the formula (2) to a silica particle surface hydroxy group.
In this case, the water-dispersible organic-inorganic silica particles are not limited, but may be included in an amount of 5 to 80 parts by weight based on 100 parts by weight of the aqueous hard coating composition. If the content of the water-dispersible organic-inorganic silica particles is less than 5 parts by weight, it is difficult to produce sufficient hardness, and curling may occur when the content exceeds 80 parts by weight.
The silica particles used in the preparation of the water-dispersible organic-inorganic silica particles are not limited, but it is preferable to use a water-dispersible colloidal silica sol. Specific examples of commercially available dispersion colloidal silica sol include PURISOL-O series (manufactured by Gamatek, average particle size of 5-40 nm, silica content of 20-40%), and CATALOID-S series (catalyst, average particle size 5 ~). 80 nm, silica content 20-48%), YGS-series (Youngilization agent, particle average size 10-80 nm, silica content 20-40%), etc. are mentioned. Any one or more of these can be used.
In addition, the average particle diameter of the colloidal silica particles is not limited, but may be used in the range of 10nm ~ 100nm and when used in the cured transparent film is preferably 10nm ~ 50nm. When the particle diameter of the number average particle exceeds 100 nm, transparency may fall or coating surface state may be unsatisfactory. In addition, when the particle diameter is less than 10 nm, it can be found that the hard hardness of the coating is deteriorated. In addition, various surfactants and amines may be added to improve the dispersibility of the particles.
The aqueous hard coating composition according to the present invention may further include a photostimulating agent. Examples of photostimulants include triethylamine, diethylamine, methyldiethanolamine, ethanolamine, 4-dimenylamino-benzoic acid, isoamyl-4-dimethylaminobenzoate, secondary or tertiary amines and Commercially available amine modified acrylate oligomers and the like can be used.
In addition to the above materials, antioxidants, UV absorbers, light stabilizers, thermal polymerisation inhibitors, leveling agents, surfactants, lubricants, antifouling agents and the like may be used in the aqueous hard coating composition.
The present invention also provides a hard coating film using the above-mentioned aqueous hard coating composition.
The hard coating film according to the present invention includes a hard coating layer formed by applying the above-mentioned aqueous hard coating composition to one or both surfaces of a transparent substrate and then curing.
Since the cured hard coating layer contains a large number of polyfunctional silane compounds of Chemical Formula 2, the hard coating film according to the present invention has improved slip properties, has high hardness by silicon inorganic materials, and physical properties such as peeling and curling. Will be excellent. In addition, the hydroxy group of Formula 2 is capable of hydrogen bonding with a transparent substrate such as triacetyl cellulose (hereinafter referred to as TAC) film, and thus more excellent bonding force, it is possible to further prevent curling phenomenon.
As the transparent base film, any film can be used as long as it is a transparent plastic film. For example, a cycloolefin derivative having a unit of a monomer containing a cycloolefin, such as norbornene or a polycyclic norbornene monomer. field; Cellulose selected from diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, isobutyl ester cellulose, ethylene-vinyl acetate copolymer, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose and the like; Or polyester, polystyrene, polyamide, polyetherimide, polyacryl, polyimide, polyethersulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, poly Selected from thermoplastic polymers such as vinyl acetal, polyether ketone, polyether ether ketone, polyether sulfone, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyurethane and epoxy It can be used, and an unoriented uniaxial or biaxially oriented film can be used. Among them, preferably a uniaxial or biaxially stretched polyester film having excellent transparency and heat resistance, but a triacetyl cellulose film may be suitably used in view of transparency and optically anisotropy.
The thickness of a transparent base film is about 8-1000 micrometers, Preferably 40-100 micrometers is used.
Application of the coating film in the present invention may be applied in a suitable manner selected from the die coater, air knife, reverse roll, spray, blade, casting, gravure and spin coating.
Coating thickness is 0.1-200 micrometers normally, Preferably it is 5-30 micrometers, More preferably, it is 10-25 micrometers. After applying the aqueous hard coating composition is 30 ~ 150? Drying is carried out by evaporation of the volatiles for 1 second to 2 hours, preferably 10 seconds to 1 hour at the temperature.
UV irradiation for curing reaction. UV irradiation is preferably used a high-pressure mercury-type, metal halide-type lamp and the irradiation amount of UV light is about 0.01 ~ 10J / cm 2 , preferably 0.1 ~ 2J / cm 2 .
Although the thickness of the hard coating layer formed through the curing reaction is not limited, it is preferably in the range of 5 to 30 μm, more preferably in the range of 10 to 25 μm, through which a coating film having an adjustable curling property of 15 mm or less can be obtained. have. In addition, the surface hardness of the hard coating layer is 4H or more in pencil hardness.
The present invention provides a polarizing plate having excellent physical properties formed by laminating the aforementioned hard coat film on at least one surface.
The polarizing plate is not particularly limited, but various kinds may be used. As a polarizing plate, the film polyvinyl which uniaxially stretched by adsorb | sucking dichroic substances, such as iodine and a dichroic dye, to hydrophilic polymer films, such as a polyvinyl alcohol-type film and an ethylene-vinyl acetate copolymerization partial saponification film, for example. And polyene-based alignment films such as alcohol dehydration products and polyvinyl chloride dehydrochlorination products. Among these, the polarizing plate which consists of dichroic substances, such as a polyvinyl alcohol-type film and iodine, is preferable. Although the thickness of these polarizing plates is not specifically limited, Generally, it is about 5-80 micrometers.
The present invention also provides a display device including a polarizing plate to which the above-described hard coating film is applied. For example, by incorporating the polarizing plate having the hard coat film of the present invention into a display device, various display devices of the present invention having excellent visibility can be manufactured. In addition, the hard coat film of the present invention may be attached to the window of the display device. The hard coat film of the present invention can be preferably used in reflective, transmissive, transflective LCD or LCD of various driving methods such as TN type, STN type, OCB type, HAN type, VA type, IPS type, and the like. In addition, the hard coat film of the present invention can be preferably used for various display devices such as plasma displays, field emission displays, organic EL displays, inorganic EL displays, electronic papers, and the like.
The present invention will be further illustrated by the following examples, which are only specific examples of the present invention, and are not intended to limit or limit the protection scope of the present invention.
Synthesis Example 1 Synthesis of Carbonic Acid Polyfunctional (Meta) acrylate
4.76 parts by weight of succinic anhydride (Aldrich) was slowly added to 100 parts by weight of dipentaerythritol penta / hexaacrylate (Nipon Kayaku Co., KAYARAD DPHA) and 1.5 parts by weight of triethylamine (Aldrich) at room temperature for one hour. After the addition, the temperature was raised to 80 degrees and stirred for six hours.
The infrared spectral absorption peak of the product can confirm that carbonyl 1810 Cm- 1 of succinic anhydride disappears and 1710 Cm- 1 , which is the carbonyl absorption peak of carboxylic acid. The carboxylic acid value is 26.5 mg KOH / g.
Synthesis Example 2
It carried out similarly to the synthesis example 1 except using pentaerythritol tri / tetra acrylate (Miwon Corporation, M340) as a polyfunctional (meth) acrylate.
The infrared spectral absorption peak of the product can confirm that carbonyl 1810 Cm- 1 of succinic anhydride disappears and 1710 Cm- 1 , which is the carbonyl absorption peak of carboxylic acid. The carboxylic acid value is 26.4 mg KOH / g.
Synthesis Example 3 Synthesis of Polyfunctional Silane Compound Containing Polyfunctional (meth) acrylate
100 parts by weight of the organic compound prepared in Synthesis Example 1, 11.16 parts by weight of 3-glycidylpropyltrimethoxysilane (Shin-Etsu Corp., KBM-503), 1.67 parts by weight Tetrabutylammonium bromide (Aldrich), 1.1 parts by weight 4 Mix methoxyphenol (Eastman) and raise the temperature to 85 degrees and stir for 9 hours. The infrared spectral absorption peak of the product can confirm that the epoxy 910 Cm -1 disappears. The carboxylic acid value is 0.05 mg KOH / g.
Synthesis Example 4
100 parts by weight of the organic compound prepared in Synthesis Example 2, 11.3 parts by weight of 3-glycidylpropyltrimethoxysilane (Shin-Etsu, KBM503), 1.64 parts by weight of tetrabutylammonium bromide (Aldrich), 1.1 parts by weight of 4-methoxy Phenol (Eastman) is mixed and the temperature is raised to 85 degrees and stirred for 9 hours. The infrared spectral absorption peak of the product can confirm that the epoxy 910 Cm -1 disappears. The carboxylic acid value is 0.03 mg KOH / g.
Synthesis Example 5 Water Dispersion Polyfunctional (meth) acrylate Synthesis
An electric stirrer, a cooler, a thermometer, a heating mantle and the like were installed in a four-necked 3L round bottom flask. Here, 460.4 g of a polyester polyol (Aldrich) having a number average molecular weight of 1500 produced by the reaction of neopentyl glycol (Aldrich) and adipic acid (Aldrich), 1-isocyanato-3,3, 136.3 g of 5-trimethyl-5-isocyanatomethyl-cyclohexane (BASF, IPDI), 32.9 g of dimethylolpropionic acid (Aldrich, DMPA) as a substance having two hydroxyl groups which can react with a hydrophilic group and an isocyanate, 250 g of hexanediol diacrylate (Miwon Corporation, M200), 0.4 g of dibutyltin dilaurate (Aldrich, DBTDL) as a catalyst, and 1 g of methoxy hydroquinone (TCI, HQMME) as a radical polymerization inhibitor Stirred. When the reactant was slowly exothermic and the exotherm was terminated at about 60 ° C., the reaction temperature was forced up to 80 ° C. using a heating mantle. After reacting at 80 ° C. for 8 hours, the NCO% by end group analysis was 4.1% except the amount of HDDA.
Lower the temperature of the reactant to 40 ℃ and add 96 g of pentaerythritol tri / tetraacrylate (Mwon Sang, Inc.), 2,260 cm-1 is the isocyanate characteristic peak on Fourier transform ultraviolet spectroscopy (FT-IR) The reaction was carried out at 100 ° C. until complete disappearance. When the reaction was completed, the temperature was lowered to 60 ° C, and 24 g of triethylamine (Aldrich) was slowly dropped using a dropping funnel to neutralize the acid groups of the resin. After neutralization for 1 hour or more and completely neutralized, 1,500 g of distilled water was added while stirring at high speed to prepare a photocurable water-dispersible polyfunctional acrylate having 6 acrylic functional groups at the resin terminal.
Synthesis Example 6
Synthesis was carried out in the same manner as in Synthesis example 5, and instead of pentaerythritol triacrylate (Mwon Sang, M340), dipentaerthol penta / hexa acrylate (Japanese gunpowder, KAYARAD DPHA) was added, and the sight of 10 acrylic functional groups at the end of the resin was added. A fire-dispersible polyfunctional acrylate was prepared.
Preparation Example 1 Preparation of Colloidal Water-Dispersible Organic-Inorganic Silica Particles
10.22 parts by weight of the organic compound prepared in Synthesis Example 3, 107.28 parts by weight of PURISOL-O (manufactured by Gamatek, water dispersion, solid content of 30%), 0.2 parts by weight of methanol (Aldrich) at 80 degrees and nitrogen gas atmosphere for 3 hours do. 1.4 weight part of methyl orthopermate (Aldrich) is added, and it stirred at 80 degree | times and nitrogen gas atmosphere for 1 hour.
[Production Example 2]
It carried out similarly to the manufacture example 1 except using the product manufactured by the synthesis example 4 as a polyfunctional silane compound compound containing a polyfunctional (meth) acrylate.
<Examples 1 to 9 and Comparative Examples 1 to 4>
Each component was mixed at a weight ratio shown in Table 1 to prepare an aqueous hard coating composition.
PURISOL-O: Water Dispersed Silica Sol
UV 2282: Water Dispersed Urethane Acrylate (manufactured by Bayer)
Acrylate monomer: pentaerythritol triacrylate (Miwon Corporation, M340)
Experimental Example
The aqueous hard coating composition according to the above Examples and Comparative Examples was applied by a meyer bar to a thickness of 20㎛ on a transparent substrate film (80㎛, TAC) after stirring for 1 hour, and then dried for 1 minute at 70 ℃, 720 mJ / It was cured to cm 2 to prepare a high hardness hard coat film.
The prepared hard coating film was subjected to the physical property evaluation as shown below and the results are shown in Table 2 below.
(1) surface smoothness
The coated surface of the film is observed in the direction of inclination of 20 to 30 degrees by shining with electric light, and the presence or absence of wrinkles or wrinkles that is thought to be caused by the uniformity (microscopic) of the surface layer or the surface property of the hard coating layer is observed. Confirmed.
A: There is no micro aggregation in the surface layer, and it is uniform, and unevenness | corrugation and a wrinkle are not recognized by a hard coat layer.
B: Although microscopic aggregation is seen in the surface layer, it is very mild and unevenness | corrugation and a wrinkle are not recognized by a hard coat layer.
C: Although micro aggregates are seen in the surface layer, irregularities and wrinkles are not observed in the hard coat layer.
D: Microscopic aggregation is remarkable in the surface layer, and irregularities and wrinkles are also seen in the hard coat layer.
(2) transmittance and haze
Total light transmittance and total haze were measured using a spectrophotometer (HZ-1, manufactured by Suga Japan).
(3) pencil hardness
Pencil hardness was measured using a pencil hardness tester (PHT, manufactured by Seokbo Science, Inc.) under a 500g load. The pencil was made 5 times per pencil hardness using Mitsubishi products. If there were two or more gases, it was determined to be defective.
Kiss: 0 OK
Kiss: 1 OK
Ges: 2 or more NG
(4) scratch resistance
The scratch resistance was tested by using a steel wool tester (WT-LCM100, manufactured by Protec Co., Ltd.) for 10 reciprocations at 1 kg / (2 cm × 2 cm).
Steel wool used # 0000.
A: 0 scratches
A ': 1 to 10 scratches
B: 11-20 scratches
C: 21-30 scratches
D: 31 or more scratches
(5) adhesion
Eleven straight lines were drawn on the coated surface of the film at intervals of 1 mm each to make 100 squares, and then a peel test was conducted three times using a tape (CT-24, manufactured by Nichi Nippon Co., Ltd.). Three 100 squares were tested and averaged.
The adhesion was recorded as follows.
Adhesion = n / 100
n: number of rectangles that do not peel out of the entire rectangle
100: total number of squares
Therefore, when none of the peeling was recorded as 100/100.
(6) curling
The sample cut into the square shape of A4 size (29.7 X 21.0 cm) was placed on a flat glass plate with the coated surface of the film facing up, and the distance from the square glass plate was measured at 25? And 50% RH, and then averaged. Was taken as a measured value.
Very good: 0 to 15 mm, good: 15 to 30 mm, poor: 30 to 50 mm, very poor: more than 50 mm.
(7) fingerprint wiping
Fingerprint marks on the coated surface of the film were gently wiped 10 times by ten testers with clean paper (ULTIMA®, Hansong), and the wipeability was visually evaluated.
A: No wipe marks remained. B: A little wipe left. C: Wipe marks remained.
* TAC: triacetylcellulose
As shown in Table 2, the aqueous hard coating composition comprising a polyfunctional urethane (meth) acrylate having a hydrophilic group in the molecule represented by Chemical Formula 1 according to the present invention within a preferred range according to Examples 8 and 9 It can be seen that it exhibits excellent physical properties compared to Comparative Example 4, which is an aqueous hard coating composition. Example 7 can be confirmed that the physical properties of the polyfunctional urethane (meth) acrylate having an intramolecular hydrophilic group represented by the formula (1) is slightly reduced compared to Examples 8 and 9 when the addition of more than the preferred range of the present invention . In addition, in the case of Examples 1 to 6, which further includes the silica particles according to the present invention in a preferred range, it can be confirmed that the overall physical properties including the hardness characteristics are more excellent.
Claims (15)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101127952B1 (en) * | 2011-03-16 | 2012-03-23 | 에스케이씨 주식회사 | Optical hard coating film |
| WO2013180510A1 (en) * | 2012-05-31 | 2013-12-05 | 주식회사 엘지화학 | Method for manufacturing hard coating film |
| US9778398B2 (en) | 2012-05-31 | 2017-10-03 | Lg Chem, Ltd. | Hard coating film and preparation method thereof |
| US9926461B2 (en) | 2012-05-31 | 2018-03-27 | Lg Chem, Ltd. | Hard coating film |
| KR20210131733A (en) | 2020-04-24 | 2021-11-03 | (주)도 은 | Process for preparing non-flammable hard coating composition for spectacle lens |
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2008
- 2008-12-17 KR KR1020080128713A patent/KR20100037519A/en not_active Application Discontinuation
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101127952B1 (en) * | 2011-03-16 | 2012-03-23 | 에스케이씨 주식회사 | Optical hard coating film |
| WO2013180510A1 (en) * | 2012-05-31 | 2013-12-05 | 주식회사 엘지화학 | Method for manufacturing hard coating film |
| US9403991B2 (en) | 2012-05-31 | 2016-08-02 | Lg Chem, Ltd. | Hard coating composition |
| US9701862B2 (en) | 2012-05-31 | 2017-07-11 | Lg Chem, Ltd. | Method of preparing hard coating film |
| US9778398B2 (en) | 2012-05-31 | 2017-10-03 | Lg Chem, Ltd. | Hard coating film and preparation method thereof |
| US9884977B2 (en) | 2012-05-31 | 2018-02-06 | Lg Chem, Ltd. | Hard coating composition |
| US9896597B2 (en) | 2012-05-31 | 2018-02-20 | Lg Chem, Ltd. | Method of preparing hard coating film |
| US9926461B2 (en) | 2012-05-31 | 2018-03-27 | Lg Chem, Ltd. | Hard coating film |
| US10294387B2 (en) | 2012-05-31 | 2019-05-21 | Lg Chem, Ltd. | Hard coating film |
| KR20210131733A (en) | 2020-04-24 | 2021-11-03 | (주)도 은 | Process for preparing non-flammable hard coating composition for spectacle lens |
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