CN100390582C - Optical film having adhesive and image display apparatus - Google Patents
Optical film having adhesive and image display apparatus Download PDFInfo
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- CN100390582C CN100390582C CNB2005800006168A CN200580000616A CN100390582C CN 100390582 C CN100390582 C CN 100390582C CN B2005800006168 A CNB2005800006168 A CN B2005800006168A CN 200580000616 A CN200580000616 A CN 200580000616A CN 100390582 C CN100390582 C CN 100390582C
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- thin film
- optical thin
- film
- polaroid
- bonding agent
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Classifications
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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
- G02B5/3083—Birefringent or phase retarding 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
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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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
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
Abstract
An optical film having a pressure-sensitive adhesive layer on at least one surface thereof, characterized in that the pressure-sensitive adhesive layer has a Tg of -35 DEG C or lower. The above optical film with a pressure-sensitive adhesive exhibits such durability that the curvature thereof can be inhibited even when exposed to a low temperature circumstance of room temperature or lower.
Description
Technical field
The present invention relates to a kind of optical thin film that at least one face of optical thin film, has the band bonding agent of adhesive phase.And then, the present invention relates to use the image display device such as liquid crystal indicator, organic EL display, PDP of the optical thin film of above-mentioned band bonding agent.The optical thin film of band bonding agent of the present invention is fit to contain oriented film as optical thin film, for example, can enumerate polaroid, polarizer, optical compensating film, brightness improving film, and then enumerates stacked they and film of obtaining etc.
Background technology
Liquid crystal indicator is used to desk top computer, also is used to clock and watch or TV, monitor etc.These products are to be used in various environment and under various conditions, so require to have various permanance.In addition, in liquid crystal indicator, can use various optical thin films such as polaroid, polarizer.These optical thin films are because of being used with the optical thin film of various optical member adherings as the band bonding agent.Thereby, also require to have permanance for the optical thin film of being with bonding agent.
In order to improve the permanance of the optical thin film of being with bonding agent, adhesive phase various researchs have been carried out.For example, the molecular weight that improves the base polymer be used for bonding agent or at the monomer of the high Tg of base polymer copolymerization or improve the method for degree of crosslinking is arranged.As above-mentioned bonding agent, like using acrylic adhesive (with reference to patent documentation 1) in order to have its outstanding cementability, the transparency etc.But, when the optical thin film that makes the band bonding agent by these methods has permanance, the residual mechanical stress grow of adhesive phase.Its result, this stress produces warpage in optical thin film on optical thin film, if damage the display quality of liquid crystal indicator, will cause significant problem.
Patent documentation 1: the spy opens flat 11-52349 communique
In addition, about the optical thin film permanance of band bonding agent, mainly carry out the improvement of the permanance under high temperature and the hot and humid condition.In recent years, as the purposes of liquid crystal indicator, TV or purposes such as vehicle-mounted begin to increase.Accompany with it, in the optical thin film of band bonding agent, much less under high temperature and hot and humid condition, even also require permanance under the cryogenic conditions of-30 ℃ of grades.But, with regard to having used the optical thin film of the band bonding agent of the acrylic adhesive in the past polaroid of adhesive phase (for example with), even can satisfy the permanance under high temperature and the hot and humid condition, but the durability not insufficient under the cryogenic conditions below the room temperature (23 ℃) is abundant, the optical thin film of band bonding agent produces big warpage when being exposed to cryogenic conditions under the state that is being attached at glass plate etc.
Summary of the invention
The objective of the invention is to, even a kind of optical thin film that also has the band bonding agent of the permanance that can suppress the warpage of optical thin film under the following low temperature environment of room temperature that is placed on is provided.
In addition, the present invention also aims to, a kind of image display device that uses the optical thin film of described band bonding agent is provided.
The inventor etc. concentrate on studies in order to solve above-mentioned problem, found that optical thin film by following band bonding agent etc. can achieve the above object, thereby have finished the present invention.
That is, the present invention relates to a kind of optical thin film with bonding agent, is the optical thin film that has the band bonding agent of adhesive phase at least one face of optical thin film, wherein,
Adhesive phase Tg is below-35 ℃.
Usually bonding agent has the following Tg of room temperature.Near the Tg temperature province is the transitional region of vitreousness and rubbery state, surpass Tg and become vitreousness, accompany with it, the elastic modulus that bonding agent had sharply rises, consequently can't fully follow the tracks of the little change in size of thermal shrinkage degree of optical thin film, produce big warpage.
On the other hand, warpage under the low-temperature region is different with the warpage of testing usually under heating or humidification state, it is characterized in that, becoming with tensile axis to produce strong warpage on 90 ℃ the direction in optical thin film (particularly oriented film), warpage disappears and is back to original state when returning room temperature.This be because, optical thin film particularly polaroid become the thermal expansivity on 90 ℃ the direction bigger than tensile axis direction with tensile axis, the internal force of generation also is to become bigger on 90 ℃ the direction with tensile axis.The phenomenon that warpage disappears when returning room temperature represents that the warpage under the low-temperature region only depends on the thermal stress of optical thin film mostly.
Therefore, in the present invention, by use Tg be member below-35 ℃ as adhesive phase, be suppressed at the caused warpage of the stress by the change in size of following member of optical thin film in the low-temperature region etc.The optical thin film of the band bonding agent that not only also has good durability in high-temperature area but also in low-temperature region can be provided thus.The Tg of adhesive phase is preferably below-40 ℃, more preferably-50 ℃ below.Wherein, if Tg is low excessively, the permanance under hot conditions reduces, so preferred more than-120 ℃, further preferred more than-100 ℃.
With regard to the optical thin film of above-mentioned band bonding agent, be made as at the internal force (F) that causes by thermal stress with above-mentioned optical thin film
F＝α·ΔT·E·l·h
(wherein, α is the thermal expansivity under-60～23 ℃, Δ T is the temperature difference when being benchmark with 23 ℃, E is an elastic modulus, l is a width, h is a thickness) time, for optical thin film have oriented film and under 0 ℃, to become the internal force (F) that produces on 90 ℃ the direction be effective with the tensile axis of above-mentioned oriented film for the film more than the 50N.
Described internal force (F) can be fit to use the optical thin film of band bonding agent of the present invention for the above optical thin film of 50N is easy to generate warpage at low temperatures.When the described internal force (F) of optical thin film is more than the 70N and then is 100N when above, the optical thin film of band bonding agent of the present invention is fit to.
With regard to the optical thin film of above-mentioned band bonding agent, optical thin film can be advantageously applied in the member that contains polaroid and/or polarizer.Use the film of oriented film, be easy to generate warpage at low temperatures, can use the optical thin film of band bonding agent of the present invention well as the inscape of polaroid and/or polarizer.
In addition, the present invention relates to a kind of image display device, use the optical thin film of an above-mentioned band bonding agent at least.
Embodiment
The optical thin film of band bonding agent of the present invention has adhesive phase in the one side of optical thin film.Adhesive phase is to be formed by the member with the low Tg below-35 ℃, can use suitable adhesive in the formation of this adhesive phase, and its kind is not particularly limited.As bonding agent, can enumerate rubber and be bonding agent, acrylic adhesive, silicone-based adhesive, carbamate and be bonding agent, vinyl alkyl ethers and be bonding agent, polyethenol series bonding agent, polyvinylpyrrolidone is that bonding agent, polyacrylamide are bonding agent, cellulose-based bonding agent etc.
In the middle of these bonding agents, preferably use optical transparence outstanding and demonstrate the adhesion characteristic and the outstanding bonding agents such as against weather or thermotolerance of suitable wetting state, coherency and cementability.As the bonding agent that demonstrates such feature, preferably use acrylic adhesive.
Acrylic adhesive is being that the acrylic acid series polymeric compounds of main framing is as base polymer with the monomeric unit of (methyl) alkyl acrylate.Wherein, (methyl) alkyl acrylate is meant alkyl acrylate and/or alkyl methacrylate, with the identical meaning of (methyl) of the present invention expression.As (methyl) alkyl acrylate of the main framing that constitutes acrylic acid series polymeric compounds, can illustration straight chain shape or the carbon number of the alkyl of a chain be 2～18 Arrcostab.For example, can illustration (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, the different myristin of (methyl) acrylic acid, (methyl) lauryl acrylate etc.As (methyl) alkyl acrylate, the alkyl acrylate with alkyl of branch-like is particularly suitable for.For example, can be fit to use acrylic acid-2-ethyl caproite, Isooctyl acrylate monomer, acrylic acid ester in the different ninth of the ten Heavenly Stems, the different myristin of acrylic acid etc.
In described acrylic acid series polymeric compounds, be purpose to improve cementability or thermotolerance, can import comonomer more than a kind by copolymerization.As the concrete example of such comonomer, for example can enumerate (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) acrylic acid-2-hydroxypropyl acrylate, (methyl) acrylic acid-4-hydroxy butyl ester, (methyl) acrylic acid-own ester of 6-hydroxyl, (methyl) acrylic acid-8-hydroxyl monooctyl ester, (methyl) acrylic acid-10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) acrylic acid-12-hydroxyl lauryl, (4-methylol cyclohexyl)-hydroxyl monomers such as methyl acrylate; (methyl) acrylic acid, (methyl) acrylic acid carboxylic ethyl ester, (methyl) acrylic acid carboxylic pentyl ester, itaconic acid, maleic acid, fumaric acid, crotonic acid etc. contain carboxylic monomer; Maleic anhydride, clothing health acid anhydride etc. contain the anhydride group monomer; Acrylic acid caprolactone addition product; Styrene sulfonic acid, allyl sulphonic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic acid, (methyl) acrylamide propane sulfonic acid, sulfo group propyl group (methyl) acrylate, (methyl) acryloyl group chomene sulfonic acid etc. contain the sulfonic group monomer; Phosphorous acidic group monomers such as 2-hydroxyethyl acryloyl phosphate etc.
In addition, as examples of monomers, can enumerate (methyl) acrylamide, N, (N-replacement) acid amides such as N-dimethyl (methyl) acrylamide, N-butyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxymethyl-propane (methyl) acrylamide are monomer; (methyl) acrylic acid ammonia ethyl ester, (methyl) acrylic acid N, (methyl) acrylic acid alkyl aminoalkyl esters such as N-dimethylamino ethyl ester, (methyl) acrylic acid tert-butyl group amino ethyl ester are monomer; (methyl) alkoxyalkyl acrylates such as (methyl) acrylic acid methoxyl ethyl ester, (methyl) acrylic acid ethoxy ethyl ester are monomer; Succinimides such as N-(methyl) acryloyl oxymethylene succinimide, N-(methyl) acryloyl group-6-oxygen base hexa-methylene succinimide, N-(methyl) acryloyl group-8-oxygen base eight methylene succinimides, N-acryloyl morpholine are monomer etc.
In addition, as modified monomer, can also use ethene base system monomers such as vinyl acetate, propionate, N-vinyl pyrrolidone, methyl ethylene pyrrolidone, vinylpyridine, vinyl piperidones, vinyl pyrimidine, vinyl piperazine, vinylpyrazine, vinyl pyrrole, vinyl imidazole, second alkene base oxazole, vinyl morpholine, N-vinyl carboxylic acid amide-type, styrene, α-Jia Jibenyixi, N-caprolactam; Cyanoacrylate such as vinyl cyanide, methacrylonitrile is a monomer; (methyl) glycidyl acrylate etc. contains the epoxy radicals acrylic monomer; Glycol such as (methyl) polyalkylene glycol acrylate ester, (methyl) acrylic acid polypropylene glycol ester, (methyl) acrylic acid methoxyl glycol ester, (methyl) acrylic acid methoxyl polypropylene glycol ester are acrylate monomer; Acrylic ester monomers such as (methyl) tetrahydrofurfuryl acrylate, fluorine (methyl) acrylate, silicone (methyl) acrylate, acrylic acid 2-methoxyl ethyl ester etc.
Wherein, as the optical thin film purposes,, preferably use the hydroxyl monomer, contain carboxylic monomer to the cementability of liquid crystal cells, the viewpoint of permanance.These monomers become the reflecting point with crosslinking chemical.
Ratio to the described comonomer in the acrylic acid series polymeric compounds is not particularly limited, and is preferably about 0～30% further preferred about 0～15% in the weight rate that all constitutes monomer.
Mean molecular weight to acrylic acid series polymeric compounds is not particularly limited, but weight-average molecular weight is preferably about 300,000～2,500,000.The manufacturing of described acrylic acid series polymeric compounds can be carried out with various known method, for example can suitably select radical polymerizations such as mass polymerization, solution polymerization process, suspension polymerization.As radical polymerization initiator, can use various known materials such as azo system, peroxidating system, temperature of reaction is generally about about 50～80 ℃, and the reaction time is 1～8 hour.In addition, in described manufacture method, the preferred solution polymerization as the solvent of acrylic acid series polymeric compounds, is used ethyl acetate, toluene etc. usually.Solution concentration is about about 20～80 weight % usually.
As rubber is the base polymer of bonding agent, can be exemplified as natural rubber, isoprene rubber, styrene-butadiene and be rubber, reclaimed rubber, polyisobutylene is rubber, and then can also to enumerate styrene-isoprene-phenylethene be that rubber, s-B-S are rubber etc.As the base polymer of silicone-based adhesive, can be exemplified as dimethyl polysiloxane, diphenyl polysiloxane etc., these base polymers also can use the polymkeric substance that has imported functional groups such as carboxyl.
In addition, above-mentioned bonding agent is preferably the adhesive composition that contains crosslinking chemical.As the multi-functional compounds that can in bonding agent, cooperate, can enumerate organic system crosslinking chemical or multi-functional metallo-chelate.As the organic system crosslinking chemical, can enumerate epoxy and be crosslinking chemical, isocyanate-based crosslinking chemical, imines is crosslinking chemical, peroxidating system crosslinking chemical etc.These crosslinking chemicals can use a kind, or make up more than 2 kinds and use.As the organic system crosslinking chemical, preferred isocyanate is a crosslinking chemical.The multi-functional metallo-chelate compound that to be polyvalent metal combine by covalent bond or coordination bond with organic compound.As polyvalent metal atom, can enumerate Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti etc.As the atom in the organic compound that forms covalent bond or coordination bond, can enumerate oxygen atom etc., as organic compound, can enumerate Arrcostab, alcoholic compound, carboxylic acid compound, ether compound, ketonic compound etc.
There is no particular limitation to the ratio that cooperates of base polymers such as acrylic acid series polymeric compounds and crosslinking chemical, usually with respect to base polymer (solid constituent) 100 weight portions, preferred crosslinking chemical (solid constituent) is about 0.001～20 weight portion, more preferably about 0.01～15 weight portion.
In addition, in described bonding agent, as required and in the scope that does not depart from purpose of the present invention, can also suitably use various adjuvants such as filling agent that tackifier, plastifier, glass fibre, beaded glass, metal powder and other inorganic powder etc. constitute, pigment, colorant, filling agent, antioxidant, ultraviolet light absorber, silane coupling agent.In addition, can also be as containing the diffusible adhesive phase of particulate display light etc.
As adjuvant, silane coupling agent is more suitable, with respect to base polymer (solid constituent) 100 weight portions, preferably cooperates about silane coupling agent (solid constituent) 0.001～10 weight portion, further preferred the cooperation about 0.005～5 weight portion.As silane coupling agent, can use known in the past coupling agent with having no particular limits.For example, can illustration 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyldiethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc. contain the epoxy radicals silicone hydride coupling agent; 3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl butylidene) propyl group amine etc. contain amino silane coupling agent; 3-acryloxy propyl trimethoxy silicane, 3-methacryloxypropyl triethoxysilane etc. contain the organosilane coupling agent of (methyl) acrylic; 3-isocyanates propyl-triethoxysilicane etc. contains the silane coupling agent of isocyanate group etc.
As employed optical thin film in the optical thin film of band bonding agent of the present invention, can use the optical thin film that in the formation of image display devices such as liquid crystal indicator, uses, its kind is not particularly limited, as optical thin film, be preferably applied to have polaroid, the member of oriented film such as polarizer.
Polaroid can use polariscopic one or both sides to have the polaroid of transparent protective film usually.Polariscope is not particularly limited, can uses various polariscopes.As polariscope, can be exemplified as on the hydrophilic macromolecule films such as dividing the saponification film at polyvinyl alcohol film, part dimethoxym ethane polyvinyl alcohol film, ethylene-vinyl acetate copolymer pastern the material of unilateral stretching after the dichroic substance of absorption iodine or dichroic dye; Polyenes such as the desalination acid treatment thing of the processed thing of polyvinyl alcohol (PVA) or Polyvinylchloride are oriented film etc.Wherein, the polariscope of preferably forming by dichroic substance such as polyvinyl alcohol film and iodine.There is no particular limitation to these polariscopic thickness, but be generally about about 5～80 μ m.
With polyvinyl alcohol film with iodine staining after the polariscope that unilateral stretching forms for example, after can dyeing by the aqueous solution that polyvinyl alcohol (PVA) be impregnated in iodine, make for 3 to 7 times that are stretched to raw footage.As required, but also can impregnated in the aqueous solution of potassium iodide etc. of boronic acid containing or zinc sulfate, zinc chloride etc.In addition, as required, also can be before dyeing polyvinyl alcohol film be impregnated in the water and wash.By the washing polyvinyl alcohol film, except can the lip-deep dirt of flush away polyvinyl alcohol film and anti blocking agent, can also prevent non-uniform phenomenons such as stain by making the polyvinyl alcohol film swelling.Stretch and both can after with iodine staining, carry out,, perhaps also can after stretching, dye with iodine on one side also can stretch by an Edge Coloring.Also can or stretch in the water-bath in the aqueous solution of boric acid or potassium iodide etc.
Be arranged on the material of the transparent protective film of described polariscopic one or both sides, the preferably material that has good character at aspects such as the transparency, physical strength, thermal stability, moisture shielding, isotropy as formation.For example, can be exemplified as polyester based polymers such as polyethylene terephthalate or PEN; Cellulose-based polymkeric substance such as diacetyl cellulose or triacetyl cellulose; Acrylic acid series polymeric compounds such as polymethylmethacrylate; Polystyrene or acrylonitritrile-styrene resin styrenics such as (AS resins); Polycarbonate based polymer etc.In addition, as the example of the polymkeric substance that forms described transparent protective film, the polyolefin that can also be exemplified as tygon, polypropylene, have ring system or norborene structure, the polyolefin polymkeric substance of ethylene-propylene copolymer and so on; Vinyl chloride-based polymer; Acid amides such as nylon or aromatic polyamide based polymer; The imide series polymkeric substance; The sulfone based polymer; The polyethersulfone based polymer; The polyetheretherketone based polymer; The polyphenylene sulfide based polymer; The vinyl alcohol based polymer, the vinylidene chloride based polymer; The polyvinyl butyral based polymer; Aromatic ester (ア リ レ one ト) based polymer; The polyoxymethylene based polymer; The epoxy based polymer; Perhaps described mixture of polymers etc.Transparent protective film can also form the cured layer of Thermocurables such as acrylic acid series, carbamate system, propenyl carbamate system, epoxy system, silicone-based, uv curing resin.
In addition, open in the 2001-343529 communique (WO 01/37007) thin polymer film of record the spy, can be exemplified as comprise (A) side chain have replace and/or not substituted imido thermoplastic resin and (B) have the resin combination of the thermoplastic resin of replacement and/or unsubstituted phenyl and itrile group at side chain.As concrete example, can be exemplified as and contain by the contract film of resin combination of alternating copolymer that imines forms and acrylonitritrile-styrene resin of isobutylene and N-methyl maleic anhydride.As film, the film that can use mixing extruded product by resin combination etc. to constitute.
The thickness of protective film can suitably determine, from viewpoints such as operability, film such as intensity or the property handled, is generally about 1～500 μ m.Be preferably 5～200 μ m especially.
In addition, protective film had better not be painted.Therefore; the preferred Rth=[(nx+ny that uses)/and 2-nz] d is (wherein; nx and ny are the principal refractive indexs in the thin film planar, and nz is the refractive index of film thickness direction, and d is a film thickness) phase difference value of the film thickness direction of expression for-90nm～+ protective film of 75nm.Phase difference value (Rth) by using this thickness direction for-90nm～+ protective film of 75nm, can roughly eliminate painted (optical clouration) of the polaroid that causes by protective film.Thickness direction phase difference value (Rth) more preferably-80nm～+ 60nm, preferred especially-70nm～+ 45nm.
As protective film, from viewpoints such as polarization property and permanance, cellulose-based polymkeric substance such as preferred triacetyl cellulose.Preferred especially triacetylcellulose film.In addition, when protective film being set, both can use the protective film that constitutes by the same polymer material at its pros and cons, also can use the protective film that constitutes by different polymeric material etc. in polariscopic both sides.Described polariscope and protective film are usually by the water system adhesive bond.As the water system tackifier, can be illustrated as isocyanate-based tackifier, polyethenol series tackifier, gelatin is tackifier, ethene base system latex system, water system polycarbamate, water system polyester etc.
Not having on bonding polariscopic of described transparent protective film, can also carry out that hard conating or antireflection are handled, anti is handled, with diffusion or anti-dazzle be the processing of purpose.
The purpose of implementing to be coated with firmly processing is the surface distress etc. that prevents polaroid, and mode that for example can be by the curing tunicle that the additional hardness that is made of suitable uv curing resin such as acrylic acid series, silicone-based, sliding properties etc. are good on the surface of transparent protective film etc. forms.Implementing the purpose that antireflection handles is the outer reflection of light that prevents on the polaroid surface, can finish by forming to wait based in the past antireflection film.In addition, the purpose of enforcement anti processing is the adhesion that prevents other member and adjacent layer.
In addition; the purpose of implementing non-glare treated is to prevent that outer light from disturbing the identification of polaroid transmitted light etc. in the polaroid surface reflection; for example; can give the micro concavo-convex structure to the transparent protective film surface and form by mode of slightly coming to the surface that adopts sandblast mode or embossing processing mode or the suitable modes such as mode that cooperate transparent particulate.As the particulate that in the formation of described surperficial micro concavo-convex structure, contains, for example, can use mean grain size is the inorganic organic system particulate transparent particulates of being made up of silicon dioxide, aluminium oxide, titanium dioxide, zirconia, tin oxide, indium oxide, cadmium oxide, antimony oxide etc. such as (containing globule (beads)) that is particulate, is made up of crosslinked or uncrosslinked polymkeric substance etc. that often has electric conductivity of 0.5～50 μ m.When forming surperficial micro concavo-convex structure, the use amount of particulate forms the transparent resin of surperficial micro concavo-convex structure with respect to 100 weight portions, is typically about 2～50 weight portions, preferred 5～25 weight portions.Antiglare layer also can be held concurrently to work as and be used for the polaroid transmitted light is spread and the diffusion layer (visual angle expanded functionality etc.) at expansion visual angle etc.
Also have, described anti-reflection layer, antiblocking layers, diffusion layer or antiglare layer etc. can also be as other optical layers and transparent protective film separate configuration except being arranged on transparent protective film from one's body.
In addition, as optical thin film, can be exemplified as reflecting plate or half transmitting plate, polarizer (comprise 1/2,1/4 etc. wavelength plate), viewing angle compensation film, brightness improving film etc. become the optical layers of using in the formation of liquid crystal indicator etc. film.They can be used alone as optical thin film, in addition, and can be when reality is used stacked on the described polaroid and can use more than 1 layer or 2 layers.
Particularly preferred polaroid is reflection type polarizer or the semi-transmission type polaroid that further stacked reflecting plate or semi-penetration plate form on polaroid; Further laminated phase-difference plate forms on polaroid ellipsoidal polarizing plate or circular polarizing disk; The wide visual angle polaroid that further stacked viewing angle compensation film forms on polaroid; Perhaps further stacked brightness improving film and the polaroid that forms on polaroid.
Reflection type polarizer is provided with the reflection horizon and forms on polaroid, can be used for forming the liquid crystal indicator of the type that reflection shows from the incident light of identification side (demonstration side) incident etc., and can omit the built-in of light sources such as backlight, thereby have advantages such as being easy to make the liquid crystal indicator slimming.When forming reflection type polarizer, can be undertaken by the suitable modes such as mode of setting up the reflection horizon that constitutes by metal etc. by protective clear layer etc. in the one side of polaroid as required.
As the object lesson of reflection type polarizer, can be exemplified as required on the one side of the transparent protective film of handling through delustring, set up the paper tinsel that constitutes by reflective metal such as aluminium or vapor-deposited film and form the polaroid etc. in reflection horizon.In addition, can also enumerate and make described transparent protective film contain particulate and form surperficial micro concavo-convex structure, and have the reflection type polarizer etc. in the reflection horizon of micro concavo-convex structure thereon.The reflection horizon of described micro concavo-convex structure makes incident light diffusion by diffuse reflection, prevents that thus directionality or outward appearance are shinny, has the advantage that can suppress the light and shade inequality etc.In addition, the transparent protective film that contains particulate also has when incident light and reflected light thereof see through it the advantage etc. that can further suppress the light and shade inequality by diffusion.The formation in reflection horizon of the micro concavo-convex structure of the surperficial micro concavo-convex structure of reflection transparent protective film, method that for example can be by directly setting up metal on the surface of protective clear layer with suitable mode such as vacuum evaporation mode, ion plating mode, sputter mode or plating mode etc. is carried out.
Instead reflecting plate directly is attached to the mode on the transparent protective film of described polaroid, the reflection horizon can also be set on the suitable film that with this transparent membrane is benchmark forms reflector plate etc. and then use.Also have; because the reflection horizon is made up of metal usually; so from the decline of the reflectivity that prevents to cause, and then keep the viewpoint of initial reflectance for a long time and the viewpoint avoiding establishing protective seam in addition waits, preferably cover the type of service of its reflecting surface with transparent protective film or polaroid etc. owing to oxidation.
Also have, in above-mentioned, the semi-transmission type polaroid can come the catoptrical reflection horizon of the semi-transmission types such as semi-transparent semi-reflecting lens of light transmission that makes simultaneously to obtain by making with the reflection horizon.The semi-transmission type polaroid is located at the rear side of liquid crystal cells usually, can form the liquid crystal indicator of following type etc., promptly, in brighter environment, use under the situation of liquid crystal indicator etc., reflection comes from the incident light of identification side (demonstration side) and display image, in darker environment, use the built-in powers such as backlight at the back side that is built in the semi-transmission type polaroid to come display image.Promptly, the semi-transmission type polaroid is useful in the formation of liquid crystal indicator of following type etc., that is, under bright environment, can save the energy that uses light sources such as backlight, under darker environment, also can use in the formation of liquid crystal indicator etc. of type of built-in power very useful.
Ellipsoidal polarizing plate or the circular polarizing disk that further laminated phase-difference plate on the polaroid is constituted describes below.Rectilinearly polarized light being changed into elliptically polarized light or circularly polarized light, perhaps elliptically polarized light or circularly polarized light are changed into rectilinearly polarized light, perhaps change under the situation of polarization direction of rectilinearly polarized light, can use polarizer etc.Particularly, as rectilinearly polarized light being changed into circularly polarized light or circularly polarized light being changed into the polarizer of rectilinearly polarized light, can use so-called 1/4 wavelength plate (be also referred to as λ/4 slice).1/2 wavelength plate (be also referred to as λ/2 slice) is generally used for changing the situation of the polarization direction of rectilinearly polarized light.
Ellipsoidal polarizing plate can be used for following situation etc. effectively, i.e. compensation (preventing) supertwist nematic phase (STN) type liquid crystal indicator painted (blue or yellow) that produce because of the birefringence of liquid crystal layer, thus carry out the described painted white black situation about showing etc. that do not have.In addition, it is painted that the polaroid of control three-dimensional refractive index produces in the time of can also compensating (preventing) from the picture of oblique observation liquid crystal indicator, thereby preferred.Circular polarizing disk for example can be used for effectively to situation about adjusting with the tone of the image of the reflection-type liquid-crystal display device of color display image etc., but also has the function of reflecting of preventing.
As polarizer, can enumerate to macromolecular material carry out that unidirectional or two-way stretch is handled and the oriented film of the birefringent film that forms, liquid crystal polymer, with the member of the oriented layer of film support liquid crystal polymer etc.Thickness to polarizer also is not particularly limited, and generally is about 20～150 μ m.
As macromolecular material, for example can enumerate polyvinyl alcohol (PVA), polyvinyl butyral, poly-ethylene methacrylic ether, Poly(Hydroxyethyl Methacrylate), hydroxyethyl cellulose, hydroxypropyl cellulose, methylcellulose, polycarbonate, polyarylate, polysulfones, polyethylene terephthalate, PEN, polyethersulfone, polyphenylene sulfide, polyphenylene oxide, polyene propyl group (ア リ Le) sulfone, polyamide, polyimide, polyolefin, Polyvinylchloride, cellulose-based polymkeric substance, norbornene resin or their two metaclass, the various multipolymers of three metaclass, graft copolymer, potpourri etc.These macromolecular materials can wait by stretching becomes orientation thing (oriented film).
As liquid crystal polymer, for example can enumerate the backbone chain type of the linearity atomic group (mesogene) that on the main chain of polymkeric substance or side chain, has imported the conjugacy of giving liquid crystal aligning or the various polymkeric substance of side chain type etc.Concrete example as main chain liquid crystalline polymer, can enumerate and have the polymkeric substance that combines the structure of linearity atomic group on the spacer portion of bendability giving, for example the polyester to the row orientation is liquid-crystalline polymer, discoid polymkeric substance or cholesteric polymers etc.Concrete example as side chain liquid crystalline polymer, can enumerate following compound etc., promptly, with polysiloxane, polyacrylate, polymethacrylate or poly-malonate as main chain backbone, the spacer portion that constitutes across atomic group as side chain and have compound of the straight line atom regiment headquarters that constitutes by the para-oriented ring shape compound unit of giving to the row orientation etc. by conjugacy.These liquid crystal polymers are for example handled by the following method, promptly, material after friction treatment is carried out on the surface that is formed on films such as polyimide on the glass plate or polyvinyl alcohol (PVA), oblique evaporation on the orientation process face of oxide materials etc., heat-treat after sprawling the solution of liquid-crystalline polymer.
Polarizer can be that for example various wavelength plates or be used to material of compensating painted or visual angle that the birefringence by liquid crystal layer causes etc. etc. has the material corresponding to the suitable phase differential of application target, also can be stacked more than 2 kinds polarizer and controlled material of optical characteristics such as phase differential etc.
In addition, described ellipsoidal polarizing plate or reflection-type ellipsoidal polarizing plate are by suitably combination and laminated polarizing sheet or reflection type polarizer and polarizer form.These class ellipsoidal polarizing plates etc. also can form by independent successively stacked (reflection-type) polaroid and polarizer in the manufacture process of liquid crystal indicator, to constitute the combination of (reflection-type) polaroid and polarizer, and as mentioned above, under situation about being pre-formed to optical thin films such as ellipsoidal polarizing plates, because outstanding, therefore has the advantage of the manufacturing efficient that can improve liquid crystal indicator etc. at aspects such as quality of stability or lamination operation.
The viewing angle compensation film is also to make image seem more clearly, be used to enlarge the film of field angle under the situation of the picture of observing liquid crystal indicator from the direction that tilts a little that is not orthogonal to picture.As this kind viewing angle compensation polarizer, for example by the oriented film of polarizer, liquid crystal polymer etc. or transparent base upper support the material etc. of oriented layer such as liquid crystal polymer constitute.As common polarizer, that uses has been implemented unilateral stretching, has had birefringent thin polymer film along its face direction, relative therewith, as the polarizer that is used as the viewing angle compensation film, can use along its face direction be implemented the birefringent thin polymer film of having of two-way stretch, biaxially oriented film refractive index and that have birefringent polymkeric substance or tilted alignment film and so on of the may command thickness direction that also has been stretched by unidirectional stretching and along its thickness direction along its face direction etc.As the tilted alignment film, for example can enumerate behind the bonding heat shrink films on the thin polymer film under effect because of the convergent force that adds thermosetting, thin polymer film has been carried out stretch processing or/and the material of shrink process, make material that the liquid crystal polymer tilted alignment forms etc.Starting material polymkeric substance as polarizer, can use the polymer phase that illustrates in the polarizer with the front with polymkeric substance, can use with the painted grade that variation was brought at the identification angle that prevents to form or enlarge the suitable polymkeric substance as purpose such as the good field angle of identification based on the phase differential that causes by liquid crystal cells.
In addition, from the viewpoint that realizes the wide visual field angle that identification is good etc., can preferably use the optical compensation polarizer that supports the optical anisotropic layer that the tilted alignment layer by the oriented layer of liquid crystal polymer, particularly discoid liquid crystal polymer constitutes with triacetylcellulose film.
With polaroid and the film adhered polaroid that forms of brightness improving together, be located at the back side one side of liquid crystal cells usually and use.The brightness improving film is the film that shows below characteristic, promptly, when because of the backlight of liquid crystal indicator etc. or from reflection of rear side etc., when natural light incident is arranged, the rectilinearly polarized light of reflection regulation polarizing axis or the circularly polarized light of prescribed direction, and make other light transmissions, therefore brightness improving film and the stacked polaroid that forms of polaroid can be made light incident from light sources such as backlights, and the light that sees through of polarized light state is stipulated in acquisition, simultaneously, light beyond the described regulation polarized light state can not see through, and is reflected.Be reversed in the light that reflects on this brightness improving pellicular front once more by reflection horizon of being located at its rear side etc., make it to incide once more on the brightness improving film, make its part or all light transmission as the regulation polarized light state, thereby increase the light that sees through the brightness improving film, simultaneously provide the polarized light that is difficult to absorb to polariscope, can be thereby increase in the light quantity of utilization in the image demonstration of liquid crystal display etc., and can improve brightness thus.Promptly, pass polariscope and make under the situation of light incident from the rear side of liquid crystal cells with backlight etc. not using the brightness improving film, have light with the inconsistent polarization direction of polariscopic polarizing axis and be polarized mirror basically and absorb, thereby can't see through polariscope.That is, though can be different because of employed polariscopic characteristic, about 50% light can be polarized mirror and sponge, and therefore, the light quantity that can utilize in the liquid crystal image demonstration etc. will reduce, and cause the image deepening.Because the brightness improving film carries out following operation repeatedly, promptly, making the light with the polarization direction that can be polarized the mirror absorption is not to incide on the polariscope, but such light is reflected on the brightness improving film, and then finish counter-rotating by reflection horizon of being located at its rear side etc., light is incided on the brightness improving film once more, like this, the brightness improving film only makes in the light of the two reflection and counter-rotating, its polarization direction becomes and can see through by the polarized light of polariscopic polarization direction, provide it to polariscope simultaneously, therefore can in the demonstration of the image of liquid crystal indicator, use the light of backlight etc. effectively, thereby can make picture bright.
Also can between brightness improving film and described reflection horizon etc., diffuser plate be set.Towards described reflection horizon etc., set diffuser plate can spread the light that passes through equably by the light of the polarized light state of brightness improving film reflection, eliminates polarized light state simultaneously and becomes the nonpolarized light state.Carry out following operation repeatedly, that is, and with light directive reflection horizon of natural light state etc., after being reflected by reflection horizon etc., once more by diffuser plate and incide on the brightness improving film.So make polarized light return to the diffuser plate of original natural light state by between brightness improving film and described reflection horizon etc., being provided with, can be in the brightness of keeping display frame, reduce the inequality of the brightness of display frame, thereby even and bright picture can be provided.By this diffuser plate is set, thinking suitably to increase the repeated reflection number of times of first incident light, and utilizes the diffusion function of diffuser plate, and bright uniformly display frame can be provided.
As described brightness improving film, for example can use: the demonstration of thin-film multilayer duplexer that dielectric multilayer film or refractive index anisotropy are different and so on send as an envoy to the rectilinearly polarized light of regulation polarizing axis see through and reflect the characteristic of other light film, cholesteric liquid crystal polymer oriented film or in the film substrate upper support the demonstrating of film and so on of this aligned liquid-crystal layer will any circularly polarized light in left-handed or the dextrorotation reflect and make the suitable films such as film of the characteristic of other light transmissions.
Therefore, make the brightness improving film of the type that the rectilinearly polarized light of described regulation polarizing axis sees through by utilization, make this see through light and directly incide on the polaroid, can when suppressing the absorption loss that causes by polaroid, light be seen through effectively along the direction consistent with polarizing axis.On the other hand, utilize the brightness improving film that makes the type that circularly polarized light sees through of cholesteric and so on, though light is incided on the polariscope, but, from suppressing the viewpoint of absorption loss, preferably this circularly polarized light carry out rectilinearly polarized lightization, reenter afterwards and be mapped on the polaroid by polarizer.And, by using 1/4 wavelength plate, circularly polarized light can be transformed to rectilinearly polarized light as this polarizer.
In broad wavelength coverages such as visible region, can play the polarizer of 1/4 wavelength plate effect, for example can utilize following mode to obtain, that is, the phase separation layer that will play the polarizer of 1/4 wavelength plate effect with respect to the light luminous energy of wavelength 550nm and show other phase difference characteristics for example can play the overlapping mode of the phase separation layer of 1/2 wavelength plate effect etc.So the polarizer that is disposed between polaroid and the brightness improving film can be made of the phase separation layer more than 1 layer or 2 layers.
Also have, with regard to cholesteric, also can make up the material of different reflection wavelengths, constitute overlapping arrangement more than 2 layers or 3 layers, obtain member thus, thereby can obtain the circularly polarized light that sees through of broad wavelength coverage based on this at the wavelength coverage internal reflection circularly polarized light of broads such as visible region.
In addition, polaroid is as described polarized light divergence type polaroid, can be made of the member of stacked polaroid and the optical layers more than 2 layers or 3 layers.So, also can be to have made up reflection-type ellipsoidal polarizing plate that described reflection type polarizer or semi-transmission type polaroid and polarizer form or semi-transmission type ellipsoidal polarizing plate etc.
The stacked optical thin film of described optical layers on polaroid, can utilize that independent successively stacked mode forms in the manufacture process of liquid crystal indicator etc., but outstanding through being laminated in advance at aspects such as quality of stability or assembly operations to the polaroid of blooming, therefore have the advantage of the manufacturing process that can improve liquid crystal indicator etc.In stacked, can use suitable adhesion means such as adhesive phase.When bonding described polaroid and other optical layers, their optic axis can adopt suitable arrangement angles according to target phase difference characteristic etc.
The manufacturing of the optical thin film of band bonding agent of the present invention is to be undertaken by form adhesive phase on above-mentioned optical thin film.The formation method is not particularly limited, can enumerates the dry method of the laggard row of coat binding agent solution, carry out the method for transfer printing etc. by the release sheet that adhesive phase is set.Thickness to adhesive phase is not particularly limited, can be for about 3～100 μ m, about preferred 10～40 μ m.Wherein, when forming adhesive phase, can after forming antistatic backing, form adhesive phase.
As the constituent material of release sheet, can enumerate paper, film of synthetic resin such as tygon, polypropylene, polyethylene terephthalate, sheet rubber, paper, cloth, nonwoven fabrics, net, foaming thin sheet or metal forming, the thin slice body that their duplexer etc. are suitable etc.In order to improve fissility, can implement the lift-off processing of low cementabilities such as silicone-treated, chain alkyl processing, fluorine processing as required to the surface of release sheet from adhesive phase.
Wherein, on each layers such as the optical thin film of the optical thin film of band bonding agent of the present invention or adhesive phase, also can make it to become member with ultraviolet absorption ability etc. by the modes such as mode of for example using salicylate based compound or benzo phenol (benzophenol) based compound, benzotriazole based compound or ultraviolet light absorbers such as cyanoacrylate based compound, nickel complex salt based compound to handle.
The optical thin film of band bonding agent of the present invention can be preferred for forming various image display devices such as liquid crystal indicator etc.The formation of liquid crystal indicator can be carried out according to mode in the past.Promptly, in general, liquid crystal indicator can be by the component parts such as combination of liquid crystals unit and the optical thin film of band bonding agent and the illuminator that adds as required and the driving circuit of packing into etc. form aptly, in the present invention, except using optical thin film this point of the present invention, be not particularly limited, can carry out according to mode in the past.For liquid crystal cells, for example can use any types such as TN type, STN type, π type.
The one or both sides that can be formed on liquid crystal cells have disposed the liquid crystal indicator of the optical thin film of band bonding agent, used the suitable liquid crystal indicators such as device of backlight or reflecting plate in illuminators.At this moment, optical thin film of the present invention can be arranged on the one or both sides of liquid crystal cells.When optical thin film was arranged on both sides, they both can be identical materials, also can be different materials.In addition, when forming liquid crystal indicator, can go up suitable parts such as for example diffuser plate of configuration more than 1 layer or 2 layers, antiglare layer, antireflection film, fender, prism array, lens arra thin slice, light diffusing sheet, backlight in position.
Then, Organnic electroluminescent device (organic EL display) is described.Optical thin film of the present invention (polaroid etc.) also is suitable in organic EL display.In general, organic EL display is to stack gradually transparency electrode, organic luminous layer and metal electrode and form luminophor (organic electroluminescent body) on transparency carrier.Here, organic luminous layer is the duplexer of various organic films, and known have: for example duplexer of the duplexer of hole injection layer that is made of triphenylamine derivant etc. and the luminescent layer that is made of epipolic organic solids such as anthracenes or this kind luminescent layer and the electron injecting layer that is made of perylene derivant etc. or the various combinations such as duplexer of these hole injection layers, luminescent layer and electron injecting layer.
Organic EL display is to carry out luminous according to following principle, promptly, by on transparency electrode and metal electrode, applying voltage, injected hole and electronics in organic luminous layer, the energy excitation fluorescent material that produces by the compound of these holes and electronics, when the fluorescent material that is excited is got back to ground state, will radiate bright dipping.Middle recombination mechanism is identical with general diode, also can infer thus, and electric current and luminous intensity demonstrate with respect to impressed voltage and follow the stronger non-linear of rectification.
In organic EL display, in order to take out the light that produces in the organic luminous layer, at least one side's electrode must be transparent, will be used as anode by the transparency electrode that tin indium oxide transparent conductive bodies such as (ITO) is made usually.On the other hand, improve luminescence efficiency in order to carry out the injection of electronics easily, it is crucial using the less material of work function in negative electrode, uses metal electrodes such as Mg-Ag, Al-Li usually.
In the organic EL display with this kind formation, organic luminous layer is that film as thin as a wafer about 10nm forms by thickness.So organic luminous layer is also the same with transparency electrode, light is fully seen through basically.Consequently, when not luminous from the surperficial incident of transparency carrier and see through transparency electrode and organic luminous layer and can be once more penetrating to the face side of transparency carrier at the light of metal electrode reflection, therefore, when carrying out identification from the outside, the display surface of organic El device is as minute surface.
In the organic EL display that comprises organic electroluminescent body as described below, can polaroid be set in the face side of transparency electrode, simultaneously between these transparency electrodes and polaroid, polarizer is set, wherein, described organic electroluminescent body is being provided with transparency electrode by applying the face side that voltage carries out luminous organic luminous layer, and the rear side at organic luminous layer is provided with metal electrode simultaneously.
Become the effect of polarized light because polarizer and polaroid have to make from outside incident and at the light of metal electrode reflection, therefore have and make the effect that can't pick out the minute surface of metal electrode from the outside by this polarized light effect.Particularly, adopt 1/4 wavelength plate to constitute polarizer, and the angle of the direction of polarized light of polaroid and polarizer is adjusted into π/4 o'clock, can cover the minute surface of metal electrode fully.
That is, the exterior light that incides this organic EL display has only the rectilinearly polarized light composition because of the existence of polaroid and sees through.This rectilinearly polarized light generally can be converted to elliptically polarized light by polarizer, particularly when polarizer be the angle of the direction of polarized light of 1/4 wavelength plate and polaroid and polarizer when being π/4, will become circularly polarized light.
This circularly polarized light sees through transparency carrier, transparency electrode, organic film, reflects on metal electrode, sees through organic film, transparency electrode, transparency carrier afterwards once more, converts rectilinearly polarized light once more to by polarizer.Then, because therefore the direction of polarized light quadrature of this rectilinearly polarized light and polaroid can't see through polaroid.Consequently the minute surface of metal electrode can be covered fully.
Embodiment
Below, according to embodiment the present invention is specifically described, but the present invention is not limited to these embodiment.Also have, part and % in each example are weight basis.
(mensuration of the Tg of adhesive phase)
The Tg of adhesive phase tries to achieve by the DSC method.Tg is temperature to start with.Employed determinator is the DSC6220 type differential scanning calorimeter of セ イ コ one イ Application ス Star Le メ Application Star corporate system.
(mensuration of the internal force (F) that causes by thermal stress of optical thin film)
Try to achieve by F=α Δ TElh (wherein, α is the thermal expansivity under-60～23 ℃, and Δ T is the temperature difference when being benchmark with 23 ℃, and E is an elastic modulus, and l is a width, and h is a thickness).Thermalexpansioncoefficient is tried to achieve according to the TMA method.Employed determinator is the TMA/SS6100 type thermo-mechanical analysis device of セ イ コ one イ Application ス Star Le メ Application Star corporate system.Elastic modulus E is tried to achieve by the tension test of the autoplotter AG-1 of use Shimadzu Seisakusho Ltd. system.Lh is the sectional area of optical thin film.
Embodiment 1
In the reaction vessel that possesses condenser pipe, nitrogen ingress pipe, thermometer and stirring apparatus, add 1.0 parts of 99.9 parts of Isooctyl acrylate monomers, acrylic acid 2-hydroxyl ethyl ester and 2 together with ethyl acetate, 0.3 part of 2 '-azoisobutyronitrile, under stream of nitrogen gas, under 60 ℃, make its reaction 4 hours, in this reactant liquor, add ethyl acetate then, obtain solid component concentration and be 30% acrylic acid series polymeric compounds solution (weight-average molecular weight 1,600,000 of acrylic acid series polymeric compounds).Cooperate 0.15 part trimethylolpropane toluene diisocyanate and 0.01 part 3-glycidoxypropyltrime,hoxysilane for per 100 parts with respect to the solid constituent of this solution, obtain acrylic adhesive.Then, by carrying out the described acrylic adhesive of coating on the separator that the surface-treated mylar constituted with the silicone-based remover,, obtain the adhesive phase that thickness is 20 μ m 150 ℃ of following heat treated 5 minutes.Measure the Tg of above-mentioned adhesive phase, the result is-62 ℃.
This adhesive phase is shifted and be adhered to polaroid, and (day eastern electrician's corporate system on face NPF-SEG5224DU), obtains the optical thin film with bonding agent.Then, use laminating machine that the polaroid of above-mentioned band bonding agent is fitted on the alkali-free glass plate of 280mm * 280mm size, in 50 ℃, 5 atmospheric pressure cookers, placed 15 minutes, carry out sufficient crimping and handle.
Wherein, the tensile axis of relative polaroid becomes thermalexpansioncoefficient=5.3 * 10 of 90 ° of directions
-5(1/ ℃), elastic modulus=3.05 * 10
9Pa, thickness=185 μ m, width=270mm, the caused internal force of thermal shrinkage (F) under calculating 0 ℃, the result is F=186N.
Embodiment 2
Equally with embodiment 1 obtain the adhesive phase that thickness is 20 μ m.This adhesive phase is shifted and be adhered to polaroid, and (day eastern electrician's corporate system, NPF-TEG5465DU) one upwards obtains the optical thin film with bonding agent.Then, use laminating machine that the polaroid of above-mentioned band bonding agent is fitted on the alkali-free glass plate of 280mm * 280mm size, in 50 ℃, 5 atmospheric pressure cookers, placed 15 minutes, carry out sufficient crimping and handle.
Wherein, the tensile axis of relative polaroid becomes thermalexpansioncoefficient=5.3 * 10 of 90 ° of directions
-5(1/ ℃), elastic modulus=3.6 * 10
9Pa, thickness=105 μ m, width=270mm, the caused internal force of thermal shrinkage (F) under calculating 0 ℃, the result is F=124N.
Embodiment 3
In the reaction vessel that possesses condenser pipe, nitrogen ingress pipe, thermometer and stirring apparatus, add 0.1 part of 99.9 parts of 2-EHA, acrylic acid 2-hydroxyl ethyl ester and 2 together with ethyl acetate, 0.3 part of 2 '-azoisobutyronitrile, under stream of nitrogen gas, under 60 ℃, make its reaction 4 hours, add ethyl acetate then in this reactant liquor, obtaining solid component concentration is the acrylic acid series polymeric compounds solution (weight-average molecular weight 1,700,000 of acrylic acid series polymeric compounds) of 30 weight %.Cooperate 0.15 part trimethylolpropane toluene diisocyanate and 0.01 part 3-glycidoxypropyltrime,hoxysilane for per 100 parts with respect to the solid constituent of this solution, obtain acrylic adhesive.Then, by carrying out the described acrylic adhesive of coating on the separator that the surface-treated mylar constituted with the silicone-based remover,, obtain the adhesive phase that thickness is 20 μ m 150 ℃ of following heat treated 5 minutes.Measure the Tg of above-mentioned adhesive phase, the result is-60 ℃.
This adhesive phase is shifted and be adhered to polaroid, and (day eastern electrician's corporate system on face NPF-SEG5224DU), obtains the optical thin film with bonding agent.Then, use laminating machine that the polaroid of above-mentioned band bonding agent is fitted on the alkali-free glass plate of 280mm * 280mm size, in 50 ℃, 5 atmospheric pressure cookers, placed 15 minutes, carry out sufficient crimping and handle.
Embodiment 4
In the reaction vessel that possesses condenser pipe, nitrogen ingress pipe, thermometer and stirring apparatus, add 1 part of 99 parts of butyl acrylate, acrylic acid 4-hydroxyl ethyl ester and 2 together with ethyl acetate, 0.3 part of 2 '-azoisobutyronitrile, under stream of nitrogen gas, under 60 ℃, make its reaction 4 hours, add ethyl acetate then in this reactant liquor, obtaining solid component concentration is the acrylic acid series polymeric compounds solution (weight-average molecular weight 1,650,000 of acrylic acid series polymeric compounds) of 30 weight %.With respect to per 100 parts of dibenzoyl peroxide and 0.02 part trimethylolpropane toluene diisocyanate and 0.2 part the 3-glycidoxypropyltrime,hoxysilane that cooperate 0.3 part of the solid constituent of this solution, obtain acrylic adhesive.Then, by carrying out the described acrylic adhesive of coating on the separator that the surface-treated mylar constituted with the silicone-based remover,, obtain the adhesive phase that thickness is 20 μ m 155 ℃ of following heat treated 3 minutes.Measure the Tg of above-mentioned adhesive phase, the result is-38 ℃.
This adhesive phase is shifted and be adhered to polaroid, and (day eastern electrician's corporate system on face NPF-SEG5224DU), obtains the optical thin film with bonding agent.Then, use laminating machine that the polaroid of above-mentioned band bonding agent is fitted on the alkali-free glass plate of 280mm * 280mm size, in 50 ℃, 5 atmospheric pressure cookers, placed 15 minutes, carry out sufficient crimping and handle.
Comparative example 1
In the reaction vessel that possesses condenser pipe, nitrogen ingress pipe, thermometer and stirring apparatus, add 5 parts of 95 parts of butyl acrylates, acrylic acid and 2 together with ethyl acetate, 0.3 part of 2 '-azoisobutyronitrile, under stream of nitrogen gas, under 60 ℃, make its reaction 4 hours, add ethyl acetate then in this reactant liquor, obtaining solid component concentration is the acrylic acid series polymeric compounds solution (weight-average molecular weight 2,000,000 of acrylic acid series polymeric compounds) of 30 weight %.Cooperate 0.6 part trimethylolpropane toluene diisocyanate and 0.075 part 3-glycidoxypropyltrime,hoxysilane for per 100 parts with respect to the solid constituent of this solution, obtain acrylic adhesive.Then, by carrying out the described acrylic adhesive of coating on the separator that the surface-treated mylar constituted with the silicone-based remover,, obtain the adhesive phase that thickness is 20 μ m 150 ℃ of following heat treated 5 minutes.Measure the Tg of above-mentioned adhesive phase, the result is-30 ℃.
This adhesive phase is shifted and be adhered to polaroid, and (day eastern electrician's corporate system on face NPF-SEG5224DU), obtains the optical thin film with bonding agent.Then, use laminating machine that the polaroid of above-mentioned band bonding agent is fitted on the alkali-free glass plate of 280mm * 280mm size, in 50 ℃, 5 atmospheric pressure cookers, placed 15 minutes, carry out sufficient crimping and handle.
Comparative example 2
Equally with comparative example 1 obtain the adhesive phase that thickness is 20 μ m.This adhesive phase is shifted and be adhered to employed polaroid in embodiment 2, and (day eastern electrician's corporate system on face NPF-TEG5465DU), obtains the optical thin film with bonding agent.Then, use laminating machine that the polaroid of above-mentioned band bonding agent is fitted on the alkali-free glass plate of 280mm * 280mm size, in 50 ℃, 5 atmospheric pressure cookers, placed 15 minutes, carry out sufficient crimping and handle.
Optical thin film (being fitted in the sample on the alkali-free glass plate) for the band bonding agent that obtains in embodiment and the comparative example carries out following evaluation.In table 1 display result.
＜amount of warpage 〉
In the low-temperature region below 0 ℃ shown in the table 1 above-mentioned sample is carried out handling in 30 minutes, then under 23 ℃, the atmosphere of 55%RH, be arranged on level and do not have on the rough objective table, the use amount gap gauge is measured the amount of warpage of 4 points in the face.Amount of warpage is this mean value of 4.Metewand is as follows.
Zero: the warpage of glass is less than 0.5mm.
△: the warpage of glass is 0.5～1.0mm.
*: the warpage of glass surpasses 1.0mm.
[table 1]
Utilize possibility on the industry
Optical thin film with adhesive of the present invention is fit to contain the member of oriented film as optically thin The film of film, it is aobvious to be fit to be applied to the images such as liquid crystal indicator, organic EL display, PDP Showing device.
Claims (3)
1. the optical thin film with bonding agent is the optical thin film that the band bonding agent of adhesive phase is arranged at least one mask of optical thin film, it is characterized in that,
The Tg of adhesive phase is below-35 ℃,
Be made as at the internal force F that causes by thermal stress above-mentioned optical thin film
F＝α·ΔT·E·l·h
Optical thin film has oriented film, under 0 ℃ of condition, is more than the 50N become the internal force F that produces on 90 ℃ the direction with the tensile axis of above-mentioned oriented film,
In described formula, α is the thermal expansivity of optical thin film under-60～23 ℃, and Δ T is the temperature difference when being benchmark with 23 ℃, and E is the elastic modulus of optical thin film, and l is the width of optical thin film, and h is the thickness of optical thin film.
2. the optical thin film of band bonding agent according to claim 1 is characterized in that,
Optical thin film contains polaroid and/or polarizer.
3. image display device uses at least one of the optical thin film of claim 1 or 2 described band bonding agents.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP195412/2004 | 2004-07-01 | ||
| JP2004195412 | 2004-07-01 |
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| CN1820217A CN1820217A (en) | 2006-08-16 |
| CN100390582C true CN100390582C (en) | 2008-05-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800006168A Expired - Fee Related CN100390582C (en) | 2004-07-01 | 2005-06-23 | Optical film having adhesive and image display apparatus |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2011017009A (en) |
| KR (1) | KR100724323B1 (en) |
| CN (1) | CN100390582C (en) |
| TW (1) | TWI261125B (en) |
| WO (1) | WO2006003827A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4673344B2 (en) * | 2007-06-07 | 2011-04-20 | 日東電工株式会社 | Method for producing pressure-sensitive adhesive sheet for optical film |
| JP2011203641A (en) * | 2010-03-26 | 2011-10-13 | Sumitomo Chemical Co Ltd | Polarizing plate |
| JP2013001761A (en) * | 2011-06-14 | 2013-01-07 | Nitto Denko Corp | Self-adhesive composition, self-adhesive layer, and self-adhesive sheet |
| KR102032016B1 (en) | 2013-06-19 | 2019-10-14 | 소켄 케미칼 앤드 엔지니어링 캄파니, 리미티드 | Pressure-sensitive adhesive composition for polarization plates, pressure-sensitive adhesive sheet for polarization plates, polarization plate with pressure-sensitive adhesive layer, laminate body and flat panel display |
| CN106707384B (en) * | 2015-11-13 | 2019-05-24 | 宁波长阳科技股份有限公司 | A kind of warpage preventing reflectance coating and preparation method thereof |
| JP6755089B2 (en) | 2015-11-27 | 2020-09-16 | 三星エスディアイ株式会社ＳＡＭＳＵＮＧ ＳＤＩ Ｃｏ．， ＬＴＤ． | Adhesive composition, adhesive layer, adhesive sheet, and image display device |
| CN107229091B (en) * | 2016-03-24 | 2020-10-13 | 深超光电（深圳）有限公司 | Polaroid, display panel and display |
| US9960389B1 (en) | 2017-05-05 | 2018-05-01 | 3M Innovative Properties Company | Polymeric films and display devices containing such films |
| KR102084113B1 (en) | 2017-05-22 | 2020-03-04 | 삼성에스디아이 주식회사 | Adhesive film, optical member comprising the same and optical display apparatus comprising the same |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1264840A (en) * | 1999-01-14 | 2000-08-30 | 住友化学工业株式会社 | Anti-reflection membrane |
| JP2002275296A (en) * | 2001-01-11 | 2002-09-25 | Teijin Ltd | Laminated polyester film for surface-protected film and surface-protected film |
| JP2003154616A (en) * | 2001-11-20 | 2003-05-27 | Teijin Dupont Films Japan Ltd | Laminated film and surface protective film |
| JP2004010647A (en) * | 2002-06-04 | 2004-01-15 | Hitachi Chem Co Ltd | Pressure sensitive adhesive sheet with separator, and optical component assembly as well as assembling method thereof |
| JP2004058289A (en) * | 2002-07-25 | 2004-02-26 | Nitto Denko Corp | Adhesive optical film, pressure-sensitive adhesive composition for optical film and image display device |
| JP2004145139A (en) * | 2002-10-25 | 2004-05-20 | Nitto Denko Corp | Optical compensation plate, polarizing plate with optical compensation layer using the same, method for manufacturing the same optical compensation plate, and liquid crystal display device using them |
| JP2004163924A (en) * | 2002-10-24 | 2004-06-10 | Toray Ind Inc | Polarizing plate and its manufacturing method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05196812A (en) * | 1992-01-20 | 1993-08-06 | Nippon Synthetic Chem Ind Co Ltd:The | Polarizing plate having tacky adhesive layer |
| JP2001188103A (en) * | 1999-01-14 | 2001-07-10 | Sumitomo Chem Co Ltd | Antireflection film |
| JP2004078171A (en) * | 2002-06-18 | 2004-03-11 | Nitto Denko Corp | Polarizing plate with optical compensating layer and image display device using same |
-
2005
- 2005-06-23 WO PCT/JP2005/011494 patent/WO2006003827A1/en active Application Filing
- 2005-06-23 KR KR1020057020769A patent/KR100724323B1/en not_active IP Right Cessation
- 2005-06-23 CN CNB2005800006168A patent/CN100390582C/en not_active Expired - Fee Related
- 2005-06-27 TW TW094121349A patent/TWI261125B/en not_active IP Right Cessation
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2010
- 2010-08-19 JP JP2010184378A patent/JP2011017009A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1264840A (en) * | 1999-01-14 | 2000-08-30 | 住友化学工业株式会社 | Anti-reflection membrane |
| JP2002275296A (en) * | 2001-01-11 | 2002-09-25 | Teijin Ltd | Laminated polyester film for surface-protected film and surface-protected film |
| JP2003154616A (en) * | 2001-11-20 | 2003-05-27 | Teijin Dupont Films Japan Ltd | Laminated film and surface protective film |
| JP2004010647A (en) * | 2002-06-04 | 2004-01-15 | Hitachi Chem Co Ltd | Pressure sensitive adhesive sheet with separator, and optical component assembly as well as assembling method thereof |
| JP2004058289A (en) * | 2002-07-25 | 2004-02-26 | Nitto Denko Corp | Adhesive optical film, pressure-sensitive adhesive composition for optical film and image display device |
| JP2004163924A (en) * | 2002-10-24 | 2004-06-10 | Toray Ind Inc | Polarizing plate and its manufacturing method |
| JP2004145139A (en) * | 2002-10-25 | 2004-05-20 | Nitto Denko Corp | Optical compensation plate, polarizing plate with optical compensation layer using the same, method for manufacturing the same optical compensation plate, and liquid crystal display device using them |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100724323B1 (en) | 2007-06-04 |
| TW200613778A (en) | 2006-05-01 |
| JP2011017009A (en) | 2011-01-27 |
| CN1820217A (en) | 2006-08-16 |
| TWI261125B (en) | 2006-09-01 |
| KR20060033713A (en) | 2006-04-19 |
| WO2006003827A1 (en) | 2006-01-12 |
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