CN111565928B - Polarizing plate and image display device comprising same - Google Patents
Polarizing plate and image display device comprising same Download PDFInfo
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- CN111565928B CN111565928B CN201880085129.3A CN201880085129A CN111565928B CN 111565928 B CN111565928 B CN 111565928B CN 201880085129 A CN201880085129 A CN 201880085129A CN 111565928 B CN111565928 B CN 111565928B
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- polarizing plate
- barrier layer
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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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/02—Homopolymers or copolymers of unsaturated alcohols
- C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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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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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7246—Water vapor barrier
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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
- B32B2551/00—Optical elements
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- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polarising Elements (AREA)
Abstract
An embodiment of the present invention provides a polarizing plate including a polarizing plate and a protective substrate formed on at least one surface of the polarizing plate, wherein the protective substrate includes a laminate of a protective film and a barrier layer, and the barrier layer includes a specific repeating unit. This can significantly prevent the polarizer from being bent under normal temperature, high humidity, or high temperature, high humidity conditions, and thus can effectively prevent light leakage.
Description
Technical Field
The present invention relates to a polarizing plate and an image display device including the same.
Background
The image display device may include a display panel and polarizing plates respectively formed on both surfaces of the display panel. The polarizing plate may include a polarizer and protective films respectively formed on both sides of the polarizer.
In the polarizing plate, as external moisture permeates into the inside of the polarizer at high temperature and high humidity, durability of the polarizing plate may be reduced, and scratch resistance of the polarizer may be reduced.
On the other hand, with the recent trend toward thinner display devices, a single-sided polarizing plate having a protective film on one surface of a polarizing plate and an adhesive layer directly formed on the opposite surface without the protective film has been developed in order to reduce the thickness of the polarizing plate. However, in the case of a single-sided polarizing plate in which an adhesive layer is formed directly on a polarizing plate as described above, if a transparent conductive film electrode such as an ITO film is attached to a panel of a display device after treatment, the moisture permeability is high, iodine or the like attached to the polarizing plate is eluted, and the transparent conductive film electrode such as an ITO film is corroded, and in this case, a problem of visible unevenness on the panel is caused.
Korean laid-open patent No. 2010-0018462 discloses a polarizing plate and an optical display device including the same, but there is still a limitation in solving the above problems.
Disclosure of Invention
Technical subject
The polarizing plate according to the embodiment of the present invention includes a protective film including a barrier layer having a specific repeating unit formed on a polarizer, so that moisture permeability toward the polarizer is low, and the polarizing plate can be significantly prevented from being bent under normal temperature, high humidity, or high temperature, high humidity conditions, thereby preventing light leakage from occurring.
In addition, the polarizing plate according to the embodiment of the present invention has a small change in retardation, and can significantly reduce the occurrence of moire fringes.
Means for solving the problems
1. A polarizing plate comprising a polarizing plate and a protective substrate formed on at least one surface of the polarizing plate, wherein the protective substrate comprises a laminate of a protective film and a barrier layer, the barrier layer comprises a repeating unit represented by the following chemical formula 1,
[ chemical formula 1]
(in the formula, R1And R2Each independently hydrogen or an alkyl group of 1 to 6 carbon atoms, and n is an integer of 10 to 1,000,000).
2. The polarizing plate according to claim 1, wherein the barrier layer has a storage modulus at 80 ℃ of 500 to 2,000 MPa.
3. The polarizing plate according to claim 1, wherein the protective film has a moisture permeability of 5 to 50g/m measured at a relative humidity of 90% and a temperature of 40 ℃ after 24 hours2Day.
4. The polarizing plate according to claim 1, wherein the barrier layer has a thickness of 0.05nm to 5 μm.
5. The polarizing plate according to claim 1, wherein the protective film is disposed so that the barrier layer faces the polarizing plate, and an adhesive layer is further interposed between the polarizing plate and the barrier layer.
6. A polarizing plate comprising a polarizing plate, and a first protective film and a second protective film formed on both surfaces of the polarizing plate, respectively, wherein the first protective film is disposed on a visible side and has a barrier layer adhered to one surface thereof, the barrier layer comprising a repeating unit represented by the following chemical formula 1,
[ chemical formula 1]
(in the formula, R1And R2Each independently hydrogen or an alkyl group of 1 to 6 carbon atoms, and n is an integer of 10 to 1,000,000).
7. The polarizing plate according to claim 6, wherein the barrier layer has a storage modulus at 80 ℃ of 500 to 2,000 MPa.
8. The polarizing plate according to claim 6, further comprising a first adhesive layer interposed between the polarizer and the first protective film, and a second adhesive layer interposed between the polarizer and the second protective film.
9. In the polarizing plate according to claim 8, the barrier layer is disposed so as to face the polarizer, and the first adhesive layer is interposed between the polarizer and the barrier layer.
10. In the polarizing plate according to claim 8, the first adhesive layer is formed from a first adhesive composition containing an acetoacetyl-modified polyvinyl alcohol resin, a glyoxal-based crosslinking agent, and a water-soluble salt of two or more polyvalent metal ions, and the second adhesive layer is formed from a second adhesive composition containing an acetoacetyl-modified polyvinyl alcohol resin and an aziridine crosslinking agent.
11. An image display device comprising the polarizing plate of any one of 1 to 10 above.
Effects of the invention
The polarizing plate according to the embodiment of the present invention includes a barrier layer having a specific repeating unit, so that the moisture permeability to the polarizer is low, and the polarizing plate can be significantly prevented from being bent under normal temperature, high humidity, or high temperature, high humidity conditions, thereby preventing light leakage.
In addition, the polarizing plate according to the embodiment of the present invention has a small change in retardation, and can significantly reduce the occurrence of moire fringes.
Drawings
Fig. 1 is a schematic cross-sectional view for explaining a polarizing plate of an exemplary embodiment.
Fig. 2 is a schematic cross-sectional view for explaining a polarizing plate of an exemplary embodiment.
Detailed Description
An embodiment of the present invention provides a polarizing plate including a polarizing plate and a protective substrate formed on at least one surface of the polarizing plate, wherein the protective substrate includes a laminate of a protective film and a barrier layer, and the barrier layer includes a specific repeating unit. This can significantly prevent the polarizer from being bent under normal temperature, high humidity, or high temperature, high humidity conditions, and thus can effectively prevent light leakage.
Hereinafter, embodiments of the present invention will be described in more detail with reference to the accompanying drawings. However, the following drawings attached to the present specification illustrate preferred embodiments of the present invention and serve to further understand the technical idea of the present invention together with the above-described contents of the invention, and therefore the present invention should not be construed as being limited to the matters described in the drawings.
On the other hand, with respect to reference symbols attached to components of respective drawings, the same or similar reference symbols are used for substantially the same components even if they are shown in different drawings. In describing the present invention, detailed descriptions of related known configurations or functions will be omitted if it is considered that the gist of the present invention may be confused.
<Polarizing plate>
Fig. 1 is a schematic cross-sectional view for explaining a polarizing plate of an exemplary embodiment.
Referring to fig. 1, the polarizing plate of the example includes a polarizer 10 and a protective substrate 20.
< polarizing plate >
In one embodiment of the present invention, the polarizing plate 10 is formed by adsorbing and orienting a dichroic dye on a polyvinyl alcohol film.
The polyvinyl alcohol resin constituting the polarizing plate 10 can be obtained by saponifying a polyvinyl acetate resin. Examples of the polyvinyl acetate resin include polyvinyl acetate which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith. Examples of the other monomer copolymerizable with vinyl acetate include unsaturated carboxylic acid-based, unsaturated sulfonic acid-based, olefin-based, vinyl ether-based, and acrylamide-based monomers having an ammonium group. The polyvinyl alcohol resin may be a modified resin, and for example, polyvinyl formal, polyvinyl acetal, or the like modified with aldehydes may be used.
The saponification degree of the polyvinyl alcohol resin is usually 85 to 100 mol%, preferably 98 mol% or more. Further, the polymerization degree of the polyvinyl alcohol-based resin is usually 1,000 to 10,000, preferably 1,500 to 5,000.
The polyvinyl alcohol resin can be used as an original film of a polarizing plate after being formed into a film. The method for forming the film of the polyvinyl alcohol resin is not particularly limited, and a known method can be used. The film thickness of the polyvinyl alcohol-based raw film is not particularly limited, and may be, for example, 10 to 150 μm.
The polarizing plate 10 is generally manufactured through the following steps: a step of uniaxially stretching the polyvinyl alcohol film; a step of staining the substrate with a dichroic dye to adsorb the dye; a step of treating with an aqueous boric acid solution; and washing and drying.
The step of uniaxially stretching the polyvinyl alcohol film may be performed before dyeing, simultaneously with dyeing, or after dyeing. When uniaxial stretching is performed after dyeing, the stretching may be performed before boric acid treatment or may be performed during boric acid treatment. Of course, uniaxial stretching may also be carried out in these multiple steps. In the uniaxial stretching, rolls or hot rolls having different peripheral speeds may be used. The uniaxial stretching may be dry stretching in which stretching is performed in the air, or wet stretching in which stretching is performed in a state where the stretching is swollen with a solvent. The draw ratio is usually 3 to 8 times. The step of dyeing the stretched polyvinyl alcohol film with a dichroic dye can be carried out, for example, by immersing the polyvinyl alcohol film in an aqueous solution containing a dichroic dye. Iodine or a dichroic dye is used as the dichroic pigment. The polyvinyl alcohol film is preferably swollen by being immersed in water before dyeing.
When iodine is used as the dichroic dye, a method of immersing the polyvinyl alcohol film in an aqueous dyeing solution containing iodine and potassium iodide to dye the film can be generally used. Generally, the content of iodine in the aqueous solution for dyeing is 0.01 to 1 part by weight relative to 100 parts by weight of water (distilled water), and the content of potassium iodide is 0.5 to 20 parts by weight relative to 100 parts by weight of water. The temperature of the aqueous solution for dyeing is usually 20 to 40 ℃ and the dipping time (dyeing time) is usually 20 to 1,800 seconds.
On the other hand, when a dichroic organic dye is used as the dichroic pigment, a method of immersing the polyvinyl alcohol film in an aqueous dyeing solution containing a water-soluble dichroic organic dye to perform dyeing can be generally used. The content of the dichroic organic dye in the aqueous solution for dyeing is usually 1X 10 relative to 100 parts by weight of water-4To 10 parts by weight, preferably 1X 10-3To 1 part by weight. The aqueous solution for dyeing may further contain an inorganic salt such as sodium sulfate as a dyeing assistant. The temperature of the aqueous dyeing solution is generally from 20 to 80 ℃ and the impregnation is carried outThe time (dyeing time) is usually 10 to 1,800 seconds.
The step of subjecting the dyed polyvinyl alcohol film to a boric acid treatment can be performed by immersing the film in an aqueous solution containing boric acid. Generally, the content of boric acid in the aqueous solution containing boric acid is 2 to 15 parts by weight, preferably 5 to 12 parts by weight, relative to 100 parts by weight of water. In the case of using iodine as the dichroic pigment, the boric acid-containing aqueous solution preferably contains potassium iodide in an amount of usually 0.1 to 15 parts by weight, preferably 5 to 12 parts by weight, relative to 100 parts by weight of water. The temperature of the aqueous solution containing boric acid is usually 50 ℃ or more, preferably 50 to 85 ℃, more preferably 60 to 80 ℃, and the immersion time is usually 60 to 1,200 seconds, preferably 150 to 600 seconds, more preferably 200 to 400 seconds. After the treatment with boric acid, the polyvinyl alcohol film is usually washed with water and dried. The water washing treatment can be performed by immersing the polyvinyl alcohol film after the boric acid treatment in water. The temperature of the water for the water washing treatment is usually 5 to 40 ℃ and the immersion time is usually 1 to 120 seconds. The polarizing plate can be obtained by washing with water and then drying. The drying treatment is generally carried out using a hot air dryer or a far infrared heater. The drying treatment temperature is usually 30 to 100 ℃, preferably 50 to 80 ℃, and the drying time is usually 60 to 600 seconds, preferably 120 to 600 seconds.
The details of the polarizing plate 10 of the embodiment of the present invention can be applied to korean laid-open patent No. 10-2016-.
< protective substrate >
The protective substrate 20 is formed on at least one surface of the polarizing plate 10, and may include a laminate including a protective film 21 and a barrier layer 22, as shown in fig. 1, for example.
Protective film
In some examples of the present invention, the protective film 21 may be a film excellent in transparency, mechanical strength, thermal stability, water resistance, isotropy, and the like, and specific examples thereof include polyester-based films such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, and polybutylene terephthalate; cellulose films such as diacetylcellulose and triacetylcellulose; acrylic films such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; styrene-based films such as polystyrene and acrylonitrile-styrene copolymer; a polycarbonate-based film; polyolefin-based films such as polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, and ethylene-propylene copolymers; a vinyl chloride film; amide films such as nylon and aromatic polyamide; an imide-based film; a polyethersulfone membrane; a sulfone-based membrane; a polyether ether ketone film; a polyphenylene sulfide-based film; a vinyl alcohol-based film; a vinylidene chloride film; a polyoxymethylene film; epoxy-based films, and the like. Preferably, a polyester film, a cellulose film, an acrylic film, or a polyolefin film can be used.
In some embodiments, the thickness of the protective film 21 is generally 20 to 500 μm.
The protective film 21 can be produced by a method generally used in the art, and is preferably produced by extrusion molding by a melt extrusion method such as T-die method or inflation, casting by a melt kneading method, or rolling. Extrusion molding does not require a step of drying and scattering an organic solvent in an adhesive used in processing, as in the dry (dry) lamination method, and is excellent in terms of productivity. Specifically, there is a method in which a (meth) acrylate resin composition as a raw material is fed to an extruder connected to a T-die, melt-kneaded and extruded, and then water-cooled and drawn to form a film. The screw type of the extruder may be uniaxial or biaxial, and additives such as a plasticizer and an antioxidant may be added. The extrusion molding temperature may be appropriately adjusted, and is preferably 80 to 180 ℃ higher, more preferably 100 to 150 ℃ higher than the glass transition temperature (Tg) of the resin that becomes the raw material of the protective film. If the extrusion molding temperature is too low, the flowability of the resin is insufficient and the moldability is poor, and if the temperature is too high, the viscosity of the resin becomes low and there is a possibility that the production stability is lowered such as the thickness of the finally molded film becomes uneven.
A surface treatment layer such as a hard coat layer, an antireflection layer, an antiglare layer, and an antistatic layer may be further laminated on the protective film 10 as necessary.
The detailed contents of the protective film 10 can be applied to korean laid-open patent No. 10-2016-.
Barrier layer
The barrier layer 22 may be provided to protect the polarizing plate 10 and to prevent external moisture from penetrating into the polarizing plate 10, thereby improving durability under normal temperature/high humidity or high temperature/high humidity conditions.
In an embodiment, the barrier layer 22 may include a repeating unit represented by the following chemical formula 1.
[ chemical formula 1]
(in the formula, R1And R2Each independently hydrogen or an alkyl group of 1 to 6 carbon atoms, and n is an integer of 10 to 1,000,000).
The barrier layer 22 of the example includes the repeating unit represented by the above chemical formula 1, and thus has an excellent water-repellent effect on the polarizer 10, can improve the quality of the polarizing plate, and can significantly reduce the occurrence of defects such as light leakage of the polarizing plate under normal temperature/high humidity conditions and damage or breakage of the panel due to bending.
In some embodiments, the barrier layer 22 may be formed from a barrier layer forming composition containing a silicone (Si) based compound, a photocurable resin, a polymerization initiator, and a solvent.
The organosilicon (Si) compound may include, for example, perhydropolysilazane (PHPS).
In some examples, the organosilicon (Si) -based compound may further contain a compound having a polysiloxane structure in addition to the perhydropolysilazane. Examples of the compound having a polysiloxane structure include reactive silicones, polysiloxanes having silanol groups at both ends, and the like.
The compound having a polysiloxane structure can be obtained by, for example, curing a silane coupling agent and/or a fluorine-containing silane coupling agent by a condensation reaction in the presence of a catalyst. Specific examples of the silane coupling agent and/or the fluorine-containing silane coupling agent include those selected from the group consisting of methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β -methoxyethoxy) silane, 3,3, 3-trifluoropropyltrimethoxysilane, methyl-3, 3, 3-trifluoropropyldimethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, γ -glycidoxymethyltrimethoxysilane, γ -glycidoxymethyltriethoxysilane, gamma-glycidoxymethyl-triethoxysilane, fluorine-containing silane coupling agents, fluorine-containing silanes, and mixtures thereof, Gamma-glycidoxyethyltrimethoxysilane, gamma-glycidoxyethyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma- (beta-glycidoxymethyl) propyltrimethoxysilane, gamma- (meth) acryloyloxymethyltrimethoxysilane, gamma- (meth) acryloyloxymethyltriethoxysilane, gamma- (meth) acryloyloxyethyltrimethoxysilane, gamma- (meth) acryloyloxyethyltriethoxysilane, gamma- (meth) acryloyloxypropyltrimethoxysilane, butyltrimethoxysilane, or a mixture of a cyclic compound, Isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, 3-ureidoisopropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, N-beta (aminoethyl) gamma-aminopropylmethyldimethoxysilane, N-beta (aminoethyl) gamma-aminopropyltrimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane.
In some examples, the content of the silicone compound may be 5 to 55 wt% based on 100 wt% of the barrier layer forming composition.
The polymerization initiator is preferably a photopolymerization initiator, and examples of the photopolymerization initiator include acetophenones, benzophenones, benzoins, phosphineoxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2, 3-dialkyldiketone compounds, disulfide compounds, fluoroamine compounds, aromatic sulfonium compounds, powderine dimers, triphenylamine compounds, and mixtures thereof,
Salts, borates, active esters, active halogens, inorganic complexes, and coumarin polymerization initiators, and two or more of these polymerization initiators may be used in combination.
Examples of commercially available photopolymerization initiators include "IRGAC URE 651", "IRGACURE 184", "IRGACURE 819", "IRGACURE 907", "IRGACURE 1870" (CGI-403/IRGACURE184 mixed initiator 7/3), "IRGACURE 500", "IRGACURE 369", "IRGACURE 1173", "IRGACURE 2959", "IRGACURE 4265", "IRGACURE 4263", "IRGACURE 127" and "OXE01" manufactured by yama seminifera; "KAYACURE DETX-S", "KAYACURE BP-100", "KAYACURE BDMK", "KAYACURE CTX", "KAYACURE BMS", "KAYACURE 2-EAQ", "KAYACURE ABQ", "KAYACURE CPTX", "KAYACURE EPD", "KAYACURE ITX", "KAYACURE QTX", "KAYACURE BTC", "KAYACURE MCA" and the like, manufactured by Kayaku Kagaku Kaishi; "Esacure (KIP100F, KB1, EB3, BP, X33, KTO46, KT37, KIP150, TZT)" manufactured by sandomar corporation, and the like, and they may be used alone or in combination of two or more kinds.
In some examples, the content of the polymerization initiator may be 0.5 to 7% by weight, preferably 1 to 5% by weight, relative to 100% by weight of the barrier layer forming composition.
The photocurable resin may be, for example, a photocurable (meth) acrylate oligomer or a polymer of a photocurable monomer.
The photocurable (meth) acrylate oligomer may contain, for example, an epoxy (meth) acrylate or a urethane (meth) acrylate, and preferably may contain a urethane (meth) acrylate.
The urethane (meth) acrylate can be produced, for example, by polymerizing a polyfunctional (meth) acrylate having a hydroxyl group in the molecule and a compound having an isocyanate group in the presence of a catalyst.
The (meth) acrylate having a hydroxyl group in the molecule may be at least one selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxyisopropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone ring-opening hydroxy acrylate, pentaerythritol tri/tetra (meth) acrylate mixture, and dipentaerythritol penta/hexa (meth) acrylate mixture, for example.
Examples of the compound having an isocyanate group include compounds selected from the group consisting of 1, 4-diisocyanatobutane, 1, 6-diisocyanatohexane, 1, 8-diisocyanatooctane, 1, 12-diisocyanatododecane, 1, 5-diisocyanato-2-methylpentane, trimethyl-1, 6-diisocyanatohexane, 1, 3-bis (isocyanatomethyl) cyclohexane, trans-1, 4-cyclohexene diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, xylene-1, 4-diisocyanate, tetramethylxylene-1, 3-diisocyanate, mixtures thereof, and the like, 1-chloromethyl-2, 4-diisocyanate, 4 '-methylenebis (2, 6-dimethylphenyl isocyanate), 4' -oxybis (phenyl isocyanate), a 3-functional isocyanate derived from hexamethylene diisocyanate, and trimethylolpropane-added toluene diisocyanate.
The photocurable monomer may contain, for example, an unsaturated group such as a (meth) acryloyl group, vinyl group, styryl group, or allyl group as a photocurable functional group. Preferably, a (meth) acryloyl group may be contained.
Examples of the (meth) acryloyl group-containing photocurable monomer include those selected from the group consisting of neopentyl glycol acrylate, 1, 6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2, 4-cyclohexane tetra (meth) acrylate, pentaglycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, polypropylene glycol di (meth) acrylate, and the like, Dipentaerythritol hexa (meth) acrylate, tripentaerythritol tri (meth) acrylate, tripentaerythritol hexa tri (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, and isobornyl (meth) acrylate.
The photocurable (meth) acrylate oligomer and the photocurable monomer may be used each alone or in a mixture of two or more.
In some examples, the photocurable resin may be contained in an amount of 1 to 80 wt% based on 100 wt% of the barrier layer-forming composition. Within the above range, the barrier layer is excellent in hardness and adhesion, and can suppress the occurrence of Haze (Haze) and curling.
Examples of the solvent include ketone solvents selected from the group consisting of acetone, 2-octanone, 2-pentanone, 2-hexanone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, methylcyclohexanone, 1, 2-diacetoxy acetone, acetylacetone, diacetone alcohol, methyl acetoacetate, and ethyl acetoacetate; acetic acid ester solvents such as ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, methyl 2-methoxyacetate, methyl 2-ethoxyacetate and ethyl 2-ethoxyacetate; and at least one of amide solvents such as dimethylformamide and dimethylacetamide. Preferably, the solvent may be at least one of a ketone solvent and an acetate solvent, and more preferably, butyl acetate and methyl ethyl ketone may be used.
The solvent can swell the surface of the barrier layer to improve the adhesion between the barrier layer and the polarizing plate.
In some examples, the solvent may be contained in an amount of 10 to 95% by weight, based on 100% by weight of the barrier layer forming composition. Preferably, it may be 20 to 80% by weight.
Within the above range, the viscosity of the composition for forming a barrier layer can be adjusted to further improve the adhesion between the barrier layer and the polarizing plate. When the content of the solvent is more than 95% by weight, the barrier layer may be damaged to cause Haze (Haze), and when the content is less than 10% by weight, the surface of the barrier layer may not be sufficiently swelled to reduce adhesion between the polarizing plate and the barrier layer.
In some examples, the solvent may include 20 to 35 wt% of an acetate-based solvent and 50 to 65 wt% of a ketone-based solvent, and preferably may include 20 to 30 wt% of an acetate-based solvent and 55 to 65 wt% of a ketone-based solvent, based on 100 wt% of the barrier layer-forming composition.
Within the above-mentioned range of the solvent content, the barrier layer-forming composition is excellent in appearance, and the formed barrier layer is excellent in cutter (cutter) evaluation, bending evaluation and 180 ° peel force. In addition, the thickness of the coating layer can be easily adjusted, and the generation of haze can be easily prevented.
In some embodiments, the solvent may further include a solvent having excellent compatibility with the mixture.
The solvent may further comprise a solvent selected from the group consisting of dibutyl ether, dimethoxyethane, diethoxyethane, propylene oxide, and 1, 4-bis
Alkane, 1, 3-dioxolane, 1,3, 5-tris
Alkane, tetrahydroFuran, anisole, phenetole, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethyl formate, propyl formate, pentyl formate, methyl acetate, methyl propionate, ethyl propionate, γ -butyrolactone, ethyl 2-ethoxypropionate, 2-methoxyethanol, 2-propoxyethanol, 2-butoxyethanol, methanol, ethanol, isopropanol, n-butanol, cyclohexanol, benzyl alcohol, ethylene glycol ethyl ether, ethylene glycol isopropyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, ethyl carbitol, butyl carbitol, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, benzene, toluene, xylene, and propylene glycol monomethyl ether.
In some embodiments, the composition for forming a barrier layer may contain a solvent in a part or the balance other than the silicone compound and the polymerization initiator.
The term "remainder or balance" used herein means a variable amount including the amounts excluding the silicone compound, the polymerization initiator, and the additives when other additives are included.
In some examples, the barrier layer-forming composition may further contain an additive to provide an additional function within a range not impairing the effects of the silicone compound, the polymerization initiator, and the solvent. For example, the additive may include one or more of light-transmitting particles, fluorine-containing compounds, UV absorbers, reaction inhibitors, adhesion improvers, conductivity-imparting agents, stabilizers, antistatic agents, antioxidants, and leveling agents, but is not limited thereto.
In some embodiments, barrier layer 22 may have a storage modulus at 80 ℃ of 500 to 2,000MPa, and preferably may be 1,000 to 1,500 MPa. The storage modulus can be used as an index indicating the bending property, the degree of curing, and the like of the barrier layer 22.
In some examples, the barrier layer 22 has a storage modulus at 80 ℃ adjusted to the above range, and thus, the barrier layer 22 or a polarizing plate including the same can be prevented from swelling, deformation, or bending due to heat, moisture, or the like not only under normal temperature and high humidity conditions but also under high temperature and high humidity conditions, and occurrence of defects such as light leakage, damage or breakage due to bending, or the like of the polarizing plate can be significantly reduced. In addition, the polarizing plate including the barrier layer 22 having the storage modulus in the above range can reduce the moisture permeability toward the polarizer 10, and can maintain high quality.
In addition, the barrier layer 22 of the embodiment having the storage modulus in the above range can reduce the change in retardation of the polarizing plate by, for example, laminating it on the polarizing plate 10, thereby preventing the occurrence of moire that may occur in the polarizing plate.
If the storage modulus of the barrier layer 22 at 80 ℃ is less than 500MPa, the water-blocking effect of the barrier layer cannot be sufficiently achieved, and the bending phenomenon of the panel under normal temperature and high humidity conditions cannot be sufficiently prevented to fear light leakage, and if it is more than 2,000MPa, a defect of the polarizing plate may occur due to damage of the barrier layer under high temperature and high humidity conditions.
The storage modulus of the barrier layer 22 in the above range can be realized by appropriately adjusting the components, content, and the like of the composition for forming a barrier layer.
In some embodiments, the thickness of the barrier layer 22 may be 0.05nm to 0.5 μm, and preferably may be 100 to 250 nm. Within the above thickness range, the barrier layer 22 can exert the water-repellent effect and the bending prevention effect of the polarizing plate at an excellent level.
In some embodiments, the protective substrate 20 has a moisture transmission of 5 to 50g/m measured after 24 hours at 90% relative humidity and 40 ℃2Day (day), preferably 5 to 40g/m2The waterproof effect of protecting the substrate 20 or the barrier layer 22 contained therein can be more excellent.
In the present specification, the moisture permeability can be defined by dividing the difference between the wet-proof weight and the initial weight of the protective substrate 20 after a specific time at a specific relative humidity and temperature by the value of the moisture-permeable area, and can be calculated, for example, by the following equation 1.
[ mathematical formula 1]
Water permeability (g/m)2Tian) ═ (B-A)/(C×D)
In the above mathematical formula 1, a is the initial weight (g) of the protective substrate 20, B is the post-wet weight (g) of the protective substrate 20 measured after a specific time at a specific relative humidity and temperature, and C is the moisture-permeable area (m)2) And D is a specific time (day).
In some embodiments, the protective substrate 20 may be disposed such that the barrier layer 22 faces the polarizer 10, as shown in fig. 1. For example, as shown in fig. 1, the protective film 21 is disposed so as to be positioned on the visible side or the outer side of the polarizing plate, and the barrier layer 22 is disposed so as to face the polarizing plate 10, whereby the moisture permeation toward the polarizing plate 10 and the occurrence of light leakage due to bending can be effectively prevented. In this case, as shown in fig. 1, an adhesive layer 30 may be further interposed between the polarizing plate 10 and the barrier layer 22, which will be described later.
The polarizing plate of the example includes the protective substrate 20 including the laminate of the protective film 21 and the barrier layer 22, and the barrier layer 22 includes the repeating unit represented by the above chemical formula 1, thereby having excellent water-repellent effect on the polarizing plate 10, being capable of remarkably preventing the bending of the polarizing plate under normal temperature, high humidity or high temperature, high humidity conditions, and preventing the occurrence of light leakage.
< adhesive layer >
In some embodiments, the polarizing plate may further include an adhesive layer 30, and may be provided, for example, for adhering or attaching the protective substrate 20 to the polarizer 10. In some embodiments, an adhesive layer 30, as shown in FIG. 1, is interposed between the barrier layer 22 and the polarizer 10, and may be provided for attaching or bonding the polarizer 10 to the barrier layer 22. For example, after the protective substrate 20 including the protective film 21 and the barrier layer 22 is formed, the barrier layer 22 may be bonded to the polarizing plate 10 via the adhesive layer 30.
The adhesive layer 30 is not particularly limited as long as it is a mechanism capable of adhering the protective base 20 or the barrier layer 22 to the polarizing plate 10, and can be formed using, for example, a water-soluble adhesive such as an isocyanate-based, polyvinyl alcohol-based, melamine-based, gelatin-based, vinyl polymer-based, or water-soluble polyester-based adhesive, and a heat-curable or ultraviolet-curable adhesive such as a urethane-based, epoxy-based, acrylic, or silicone-based adhesive. Among these, a polyvinyl alcohol-based adhesive is mainly used, and the solid content is preferably 0.5 to 10% by weight, more preferably 1.5 to 5.0% by weight.
In some embodiments, adhesive layer 30 may have a thickness of 0.1 to 5 μm.
For the details of the adhesive layer 30, korean laid-open patent No. 10-2010-0134961 may be applied.
Fig. 2 is a schematic cross-sectional view for explaining a polarizing plate of an exemplary embodiment.
Referring to fig. 2, the polarizing plate of the embodiment includes a polarizer 10, and a first protective film 41 and a second protective film 42 respectively formed on both surfaces of the polarizer 10, wherein the first protective film 41 is disposed on the visible side, a barrier layer 50 is attached to one surface of the first protective film 41, and the barrier layer 50 includes a repeating unit represented by the above chemical formula 1.
The first protective film 41 and the second protective film 42 may be formed on both surfaces of the polarizing plate 10, respectively, as shown in fig. 2.
In an embodiment, the first protective film 41 included in the polarizing plate may be disposed on the visible side of the user, and the second protective film 42 may be disposed on the opposite side of the visible side, for example, the light source side of the image display device when the polarizing plate is attached to the image display device.
The first protective film 41 and the second protective film 42 are not particularly limited, and protective films having excellent transparency, mechanical strength, thermal stability, water resistance, isotropy, and the like can be used without limitation, and for example, protective films having the same material and thickness or subjected to the same processing method as the protective film 21 described with reference to fig. 1 can be used as the first protective film 41 and/or the second protective film 42.
In some embodiments, regarding the first protective film 41 and the second protective film 42, for example, the first protective film 41 may be an acrylic film such as poly (methyl) acrylate, poly (ethyl) acrylate, or the like, and preferably may be polymethyl methacrylate (PMMA), and the second protective film 42 may be a polyester film such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene terephthalate, or the like; cellulose films such as diacetylcellulose and triacetylcellulose; and/or acrylic films such as polymethyl (meth) acrylate and polyethyl (meth) acrylate.
The barrier layer 50 may be attached to one surface or both surfaces of the first protective film 41 and/or the second protective film 42, and the attachment position thereof is not particularly limited, and in some embodiments, the barrier layer 50 may be attached to the visible side as shown in fig. 2 or may be attached to one surface of the first protective film 41 in view of preventing moisture from penetrating from the outside.
The barrier layer 50 includes the repeating unit represented by the above chemical formula 1, and thus has an excellent water-repellent effect on the polarizer 10, can improve the quality of the polarizing plate, and can significantly reduce the occurrence of defects such as light leakage of the polarizing plate under normal temperature/high humidity conditions, and damage or breakage of the panel due to bending.
In some examples, the barrier layer 50 may have a storage modulus at 80 ℃ of 500 to 2,000MPa, preferably 1,000 to 1,500MPa, so that expansion, deformation, or bending of the polarizing plate due to heat, moisture, or the like can be significantly prevented not only under normal temperature/high humidity conditions but also under high temperature/high humidity conditions, and occurrence of defects such as light leakage, damage, or breakage due to bending of the polarizing plate can be significantly reduced. In addition, the polarizing plate including the barrier layer 50 having the storage modulus in the above range can reduce the moisture permeability toward the polarizer 10, and thus can maintain high quality.
In addition, the barrier layer 50 of the embodiment having the storage modulus in the above range can reduce the change in retardation of the polarizing plate by, for example, laminating it on the polarizing plate 10, thereby preventing the occurrence of moire that may occur in the polarizing plate.
The formation method, thickness, arrangement, etc. of the barrier layer 50 may be the same as the formation method, thickness, and/or arrangement of the barrier layer 22 described with reference to fig. 1.
In some embodiments, as shown in fig. 2, the polarizing plate may further include a first adhesive layer 61 and a second adhesive layer 62, the first adhesive layer 61 may be interposed between the polarizer 10 and the first protective film 41, and the second adhesive layer 62 may be interposed between the polarizer 10 and the second protective film 42.
In one embodiment, the barrier layer 50 is disposed so as to face the polarizer 10 as shown in fig. 2, and a first adhesive layer 61 may be interposed between the polarizer 10 and the barrier layer 50. For example, as shown in fig. 2, the first protective film 41 is disposed so as to be positioned outside the polarizing plate, and the barrier layer 50 is disposed so as to face the polarizing plate 10, thereby effectively preventing moisture from penetrating into the polarizing plate 10 and light from leaking due to bending.
The first adhesive layer 61 and the second adhesive layer 62 are not particularly limited as long as they can adhere to the polarizing plate 10, the protective film 41, the protective film 42, and/or the barrier layer 50.
In some embodiments, the types of adhesives used in the first adhesive layer 61 and the second adhesive layer 62 may be different, and for example, the first adhesive layer 61 may be formed of a first adhesive composition containing an acetoacetyl-modified polyvinyl alcohol resin, a glyoxal-based crosslinking agent, and a water-soluble salt of two or more polyvalent metal ions, and the second adhesive layer 62 may be formed of a second adhesive composition containing an acetoacetyl-modified polyvinyl alcohol resin and an aziridine crosslinking agent, using an adhesive composition different from the first adhesive layer, for example.
<Image display device>
In addition, the present invention provides an image display device comprising the polarizing plate.
The image display device of the present invention may further include a structure known in the art in addition to the polarizing plate.
Hereinafter, preferred embodiments are provided to aid understanding of the present invention, but these embodiments are merely illustrative of the present invention and do not limit the scope of the appended claims, and various changes and modifications of the embodiments within the scope and technical spirit of the present invention, which will be apparent to those skilled in the art, are also included in the scope of the appended claims.
Experimental example 1
Production example 1: production of polarizing plate
A75 μm-thick PVA film (VF-PS, Kramery) having an average polymerization degree of 2,400 and a saponification degree of 99.9% was swollen in a swelling tank filled with deionized water at 25 ℃ and subjected to 1.30-fold stretching. The stretched film was immersed in a 30 ℃ aqueous solution for dyeing containing 100 parts by weight of deionized water, 3.0mM iodine, and 2.5 parts by weight of potassium iodide for 180 seconds to be dyed, and then stretched 1.40 times. Then, sulfuric acid was added to a crosslinking aqueous solution at 53 ℃ containing 100 parts by weight of deionized water, 3.7 parts by weight of boric acid, and 11.5 parts by weight of potassium iodide to adjust the pH to 2.8, and then the resulting solution was immersed for 90 seconds to crosslink and subjected to 3.40-fold stretching, whereby the total stretching ratio was 6.19-fold. If the stretching and crosslinking are completed, the polarizer is manufactured by drying in an oven at 60 ℃ for 4 minutes after washing with deionized water.
Production example 2: production of composition for Forming Barrier layer
The composition for forming a barrier layer was prepared by mixing 10 wt% of perhydropolysilazane as a silicone compound, 5 wt% of a photocurable resin M340(M iwon Specialty Chemical), 60 wt% of methyl ethyl ketone as an organic solvent, 22 wt% of butyl acetate, 2.5 wt% of 2-hydroxy-2-methyl-1-phenyl-1-one as a polymerization initiator, and BYK-35500.5 wt% as an additive.
Production example 3: production of first adhesive composition
Preparation of liquid a composition: an acetoacetyl group-modified polyvinyl alcohol resin (GOHSENOL Z200, japan synthetic chemical industry ltd.) having a saponification degree of 99.2 mol% was dissolved in water (distilled water), thereby producing an aqueous solution having a solid content of 3.8%. To the aqueous solution, 30 parts by weight of a 40% aqueous solution of a glyoxal crosslinking agent (dazuki gold) was added based on 100 parts by weight of the acetoacetyl-modified polyvinyl alcohol resin, followed by mixing to prepare a liquid adhesive a composition.
Preparation of liquid B composition: an acetoacetyl group-modified polyvinyl alcohol resin (GOHSENOL Z200, japan synthetic chemical industry ltd.) having a saponification degree of 99.2 mol% was dissolved in distilled water to prepare an aqueous solution having a solid content of 3.8 wt%. To the aqueous solution, 2 parts by weight of zinc chloride (dahlia gold) and 30 parts by weight of zinc nitrate (dahlia gold), which are water-soluble salts of polyvalent metal ions, were added based on 100 parts by weight of the acetoacetyl-modified polyvinyl alcohol resin, and the mixture was mixed to prepare an adhesive B liquid composition.
The first adhesive composition was prepared by mixing the liquid a composition and the liquid B composition prepared above at room temperature and stirring for about 30 minutes.
Production example 4: production of second adhesive composition
An acetoacetyl group-modified polyvinyl alcohol resin (GOHSENOL Z200, japan synthetic chemical industry, ltd.) having a saponification degree of 99.2 mol% was dissolved in water (distilled water) to prepare an aqueous solution having a solid content of 5 wt%.
A second adhesive composition was produced by mixing 50 parts by weight of trimethylolpropane-tris (2-methyl-1-aziridinepropionate) as an aziridine crosslinking agent with the above acetoacetyl-modified polyvinyl alcohol resin aqueous solution based on 100 parts by weight of the acetoacetyl-modified polyvinyl alcohol resin (based on the solid content).
Example (b): manufacture of polarizing plate
Example 1
As the first protective film, a 60 μm-thick polymethyl methacrylate (PMMA) film was used, and the composition for forming a barrier layer manufactured in production example 2 was applied to one surface of the first protective film, and a barrier layer having a thickness of 102nm was formed under drying conditions of 120 ℃ for 5 minutes and curing conditions of 1,000mJ (UV-a), thereby manufacturing a laminate of the first protective film and the barrier layer.
The first adhesive composition produced in production example 3 was applied to one surface of the polarizing plate produced in production example 1, and the laminate of the first protective film and the barrier layer was attached to the polarizing plate on the surface to which the first adhesive composition was applied so that the barrier layer faced the polarizing plate.
The second adhesive composition produced in production example 4 was applied to the other surface of the polarizer, and a 60 μm thick triacetyl cellulose film was attached to the polarizer as a second protective film, thereby producing a polarizing plate of example 1.
On the other hand, the storage modulus of the barrier layer at 80 ℃ was measured using a viscoelasticity measuring apparatus (MCR-301, Anton Paar Co.). Specifically, the barrier layer sample was measured under the conditions of a frequency of 1.0Hz and a strain of 2% in a state where the sample was bonded to a Glass Plate (Glass Plate) with the sample size of 30mm in length × 30mm in width and the tip (tip) for measurement.
Examples 2 to 7
As shown in table 1 below, polarizing plates of examples 2 to 7 were manufactured in the same manner as in example 1, except that the barrier layer forming conditions and thickness, the kind of the first protective film, and the like were different from those of example 1. The polarizing plate includes the same polarizing plate as in example 1, including the polarizing plate, the first adhesive composition, and the second adhesive composition, in terms of type, composition, thickness, and formation method.
Comparative examples 1 to 3
As shown in table 1 below, polarizing plates of comparative examples 1 to 3 were produced in the same manner as in example 1, except that the barrier layer forming conditions, thickness, and the like were different from those of example 1. The polarizing plate includes the same polarizing plate as in example 1, including the polarizing plate, the first adhesive composition, and the second adhesive composition, in terms of type, composition, thickness, and formation method.
[ Table 1]
Experimental example 1
Experimental example 1-1: panel bending measurement under normal temperature and high humidity conditions
The laminate of the first protective film and the barrier layer (the first protective film in the case where no barrier layer is present) of examples and comparative examples was left at a relative humidity of 90% and a temperature of 25 ℃ for 72 hours, then at a relative humidity of 55% and a temperature of 25 ℃ for 1 hour, and then at a relative humidity of 55% and a temperature of 40 ℃ for 24 hours, and then the panel bending was measured by a two-dimensional meter.
Experimental examples 1-2: determination of water permeability
Samples of the laminated body of the first protective film and the barrier layer (the first protective film in the case of no barrier layer) of the examples and the comparative examples were prepared in a size of 10cm × 10 cm. Then, about 7g of calcium chloride was charged into a cup for moisture permeability measurement, the samples were fixed in order on a support table, and the cup was immersed in a paraffin solution so as not to overflow around the support table, and then cooled naturally, and the weight of the cup with the samples fixed thereto was measured by an electronic scale.
Then, the cup was put into an oven at 40 ℃ and 90% relative humidity and allowed to stand for 24 hours. Then, the cup with the sample fixed thereto was taken out, and the moisture permeability was measured according to the following numerical formula 1.
[ mathematical formula 1]
Water permeability (g/m)2Day) ═ (B-a)/(C × D)
(in the mathematical formula 1, A is the initial weight (g) of the protective substrate 20, B is the post-wet weight (g) of the protective substrate 20 measured after a specific time at a specific relative humidity and temperature, and C is the moisture-permeable area (m)2) D is a specific time (day)
Experimental examples 1 to 3: phase difference measurement
The phase difference was measured using a prince-measuring instrument (KOBRA-WPR). Samples of the laminated body of the first protective film and the barrier layer (the first protective film in the case of no barrier layer) of the examples and the comparative examples were prepared in a size of 4cm × 5 cm. In order to saturate the ambient temperature and humidity of the measuring instrument, the prepared sample was left for 12 hours, fixed to the measuring instrument, and the thickness direction phase difference value (Rth) was measured with the incident angle to the slow axis set to 40 °.
Experimental examples 1 to 4: moire fringe evaluation
The polarizing plates of the fabricated examples and comparative examples were laminated on a prism sheet of a backlight unit in which a reflection plate, a light source, a diffusion plate, and a prism sheet were laminated in this order. Next, the intensity of moire fringes caused by the prism sheet was visually observed, and evaluated according to the following criteria.
< reference >
Very good: no moire fringes at all
O: producing little moire
And (delta): partially producing moire fringes
X: apparent generation of moire fringes
[ Table 2]
Referring to table 2, the protective substrate or the polarizing plate of the example includes the barrier layer including the repeating unit represented by the above chemical formula 1, thereby exhibiting excellent panel bending prevention, low moisture transmittance, moir e generation prevention effects, but the comparative example does not.
Experimental example 2: additional physical properties/appearance evaluation depending on changes in composition ingredients for forming barrier layer
The compositions for forming a barrier layer of samples 1 to 8 were prepared by mixing perhydropolysilazane as a silicone compound, a photocurable resin M340(Miwon Specialty Chemical), an organic solvent, 2-hydroxy-2-methyl-1-phenyl-1-one as a polymerization initiator, and BYK-3550 as an additive in the amounts shown in table 3 below.
[ Table 3]
Polarizing plate samples 1 to 8 were produced in the same manner as in example 1, except that the composition for forming a barrier layer produced from samples 1 to 8 was applied to one surface of the first protective film.
Experimental example 2
Experimental example 2-1: resistance deviceEvaluation of appearance of Barrier layer Forming composition
For the compositions for forming a barrier layer of samples 1 to 8, the appearance of the barrier layer was evaluated by evaluating the light transmittance.
[ evaluation standards ]
Very good: the barrier layer-forming composition has a light transmittance of 97% or more
O: the light transmittance of the composition for forming the barrier layer is more than 90% and less than 97%
And (delta): the light transmittance of the composition for forming the barrier layer is more than 80% and less than 90%
A barrier layer-forming composition having a light transmittance of less than 80%
Experimental example 2-2: evaluation of adhesion force (Cutter evaluation)
A Cutter blade (Cutter) was inserted between the first protective films and the barrier layers of the polarizing plate samples 1 to 8 with an inclination of 70 °, and the degree of insertion of the blade into the barrier layers was evaluated. When the insert cannot be inserted, the adhesion force is determined to be excellent.
[ evaluation standards ]
O. the blade cannot be inserted
Delta within 2mm substrate cut after blade insertion
X the blade can be inserted
Experimental examples 2 to 3: adhesion force evaluation (bending evaluation)
The first protective films of the polarizing plate samples 1 to 8 were subjected to surface damage of a depth of 0.5mm or less using a Cutter blade, and the polarizing plate was bent 180 ° with respect to the damage direction to confirm whether or not air bubbles were generated. The less the generation of bubbles, the more excellent the adhesion force can be judged.
[ evaluation standards ]
Very good: haze is less than 3%
O: the haze is more than 3 percent and less than 5 percent
And (delta): the haze is more than 5 percent and less than 7 percent
X: haze of 7% or more
EXAMPLES 2 to4 evaluation of adhesion force (180 ℃ Peel force)
Samples 1 to 8 of the polarizing plate were cut into pieces having a width of 2.5mm and a length of 20cm or more based on the stretching direction of the polarizing plate to prepare samples. The cutting of the respective samples was performed by using a sample precision cutter (TOKO Co., TMC-600). The first protective film having the barrier layer of the polarizing Plate was fixed to a Glass Plate (Glass Plate) with a double-sided tape, and with respect to the polarizing Plate, the measured force was evaluated while peeling the laminate of the first protective film (PMMA) and the barrier layer and the laminate of the second protective film (TAC) and the polarizer at 180 °. The 180 ℃ peel force was measured by using a UTM instrument (Shimadzu CA-210).
Experimental examples 2 to 5: haze of coating film
Haze was evaluated using the faces of the first protective films of the polarizing plate samples 1 to 8. Haze was measured by using a haze meter (MH-150, village).
[ evaluation standards ]
O: free of air bubbles
And (delta): 1mm of air bubbles is less than 2
X: more than 1mm 2 bubbles
[ Table 4]
Referring to table 4, it was confirmed that the composition for forming a barrier layer of the polarizing plate of sample 1 using the composition for forming a barrier layer of sample 1 was excellent in appearance and adhesion force of the barrier layer, the barrier layer did not generate haze, and the thickness of the barrier layer was easily adjusted. In the case of sample 2, the contents of Methyl Ethyl Ketone (MEK) and butyl acetate were adjusted, but a 180 ° peel force decrease could be confirmed. Further, in the case of samples 3 to 8, it was confirmed that the appearance of the coating liquid and the adhesion force were decreased by the kind of the organic solvent and the adjustment of the photocurable resin and the like.
Claims (10)
1. A polarizing plate, comprising:
a polarizing plate; and
a protective substrate formed on at least one surface of the polarizing plate,
the protective base material is composed of a laminate of a protective film and a barrier layer, and has a water permeability of 5 to 50g/m as measured according to the formula 12The number of days is,
mathematical formula 1
Moisture permeability ═ B-a)/(C × D)
In the above mathematical formula 1, A is the initial weight of the protective substrate, B is the post-wet weight of the protective substrate measured after 24 hours at a relative humidity of 90% and 40 ℃, C is the moisture-permeable area, D is 24 hours, wherein the unit of moisture permeability is g/m2Day, initial weight and post-wet weight units are g, and moisture permeable area units are m2，
The barrier layer includes a repeating unit represented by the following chemical formula 1,
[ chemical formula 1]
In the formula, R1And R2Each independently hydrogen or an alkyl group of 1 to 6 carbon atoms, and n is an integer of 10 to 1,000,000.
2. The polarizing plate of claim 1, wherein the barrier layer has a storage modulus of 500 to 2,000MPa at 80 ℃.
3. The polarizing plate of claim 1, wherein the barrier layer has a thickness of 0.05nm to 5 μm.
4. The polarizing plate according to claim 1, wherein the protective film is disposed so that the barrier layer faces the polarizer,
an adhesive layer is further interposed between the polarizer and the barrier layer.
5. A polarizing plate, comprising:
a polarizing plate;
a protective substrate formed on one surface of the polarizing plate and including a first protective film and a barrier layer; and
a second protective film formed on the other surface of the polarizing plate,
the protective substrate has a water permeability of 5 to 50g/m as measured according to the formula 12The number of days is,
mathematical formula 1
Moisture permeability ═ B-a)/(C × D)
In the above mathematical formula 1, A is the initial weight of the protective substrate, B is the post-wet weight of the protective substrate measured after 24 hours at a relative humidity of 90% and 40 ℃, C is the moisture-permeable area, D is 24 hours, wherein the unit of moisture permeability is g/m2Day, initial weight and post-wet weight units are g, and moisture permeable area units are m2，
The first protective film is disposed on the visible side and has the barrier layer attached to one surface thereof,
the barrier layer includes a repeating unit represented by the following chemical formula 1,
[ chemical formula 1]
In the formula, R1And R2Each independently hydrogen or an alkyl group of 1 to 6 carbon atoms, and n is an integer of 10 to 1,000,000.
6. The polarizing plate of claim 5, wherein the barrier layer has a storage modulus of 500 to 2,000MPa at 80 ℃.
7. The polarizing plate according to claim 5, further comprising a first adhesive layer interposed between the polarizer and the first protective film and a second adhesive layer interposed between the polarizer and the second protective film.
8. The polarizing plate according to claim 7, wherein the barrier layer is disposed so as to face the polarizer,
the first adhesive layer is interposed between the polarizing plate and the barrier layer.
9. The polarizing plate according to claim 7, wherein the first adhesive layer is formed from a first adhesive composition comprising an acetoacetyl-modified polyvinyl alcohol resin, a glyoxal cross-linking agent, and a water-soluble salt of two or more polyvalent metal ions,
the second adhesive layer is formed from a second adhesive composition containing an acetoacetyl-modified polyvinyl alcohol resin and an aziridine crosslinking agent.
10. An image display device comprising the polarizing plate of any one of claims 1 to 9.
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| KR20180000191 | 2018-01-02 | ||
| KR10-2018-0000191 | 2018-01-02 | ||
| PCT/KR2018/016672 WO2019135541A1 (en) | 2018-01-02 | 2018-12-26 | Polarizing plate and image display device including same |
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| CN111565928A CN111565928A (en) | 2020-08-21 |
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| KR (1) | KR20190082668A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105467495A (en) * | 2014-09-30 | 2016-04-06 | 住友化学株式会社 | Polarizing plate, polarizing plate with adhesive and liquid crystal display device |
| CN106132695A (en) * | 2014-03-31 | 2016-11-16 | 柯尼卡美能达株式会社 | Gas barrier film and manufacture method thereof and use its electronic equipment and manufacture method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5267920B2 (en) | 2008-08-06 | 2013-08-21 | 住友化学株式会社 | Polarizing plate, method for manufacturing the same, and liquid crystal display device |
| KR101936157B1 (en) * | 2012-06-05 | 2019-01-08 | 엘지디스플레이 주식회사 | Flexible display device |
| KR101783510B1 (en) * | 2014-01-08 | 2017-09-29 | 동우 화인켐 주식회사 | Adhesive Composition and Polarizing Plate Comprising the Same |
| KR101737181B1 (en) * | 2014-09-30 | 2017-05-17 | 삼성에스디아이 주식회사 | Optical film and method for preparing the same |
-
2018
- 2018-12-26 CN CN201880085129.3A patent/CN111565928B/en active Active
- 2018-12-26 WO PCT/KR2018/016672 patent/WO2019135541A1/en active Application Filing
- 2018-12-26 KR KR1020180169891A patent/KR20190082668A/en not_active Application Discontinuation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106132695A (en) * | 2014-03-31 | 2016-11-16 | 柯尼卡美能达株式会社 | Gas barrier film and manufacture method thereof and use its electronic equipment and manufacture method thereof |
| CN105467495A (en) * | 2014-09-30 | 2016-04-06 | 住友化学株式会社 | Polarizing plate, polarizing plate with adhesive and liquid crystal display device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111565928A (en) | 2020-08-21 |
| WO2019135541A1 (en) | 2019-07-11 |
| KR20190082668A (en) | 2019-07-10 |
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