CN101408638A - Process for producing a liquid crystal film and laminate film for optical device - Google Patents
Process for producing a liquid crystal film and laminate film for optical device Download PDFInfo
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- CN101408638A CN101408638A CNA2008101785916A CN200810178591A CN101408638A CN 101408638 A CN101408638 A CN 101408638A CN A2008101785916 A CNA2008101785916 A CN A2008101785916A CN 200810178591 A CN200810178591 A CN 200810178591A CN 101408638 A CN101408638 A CN 101408638A
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
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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
- G02F2203/00—Function characteristic
- G02F2203/60—Temperature independent
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Abstract
The present invention provides a liquid crystalline film manufacturing method which obtains an ultra-thin optical film and can solve the prior problem of thermo-shock test resistance or interlayer peeling during reworking. The liquid crystalline film can be obtained at least through a first process, a second process and a third process, wherein, in the first process, bonding a liquid crystal substance layer with immobilized liquid crystal orientation formed on an orientation substrate and a re-stripping substrate through an adhesive (1), peeling the orientation substrate so as to transfer the liquid crystal substance layer on the re-stripping substrate, and then bonding to a temporary substrate through an adhesive (2), so as to obtain a laminated body composed of the re-stripping substrate/ the adhesive layer (1)/ the liquid crystal substance layer / the adhesive layer (2) / the temporary substrate; in the second process, peeling the re-stripping substrate from the laminated body; and in the third process, subsequently peeling between the liquid crystal substance layer and the adhesive layer (2) to obtain a liquid-crystal film composed of the adhesive layer (1) and the liquid crystal substance layer.
Description
Technical field
The present invention relates to liquid crystal film useful in various optical elements manufacture method and with this liquid crystal film and Polarizer or polarizer laminated laminate film for optical device.
Background technology
In recent years, for the optical thin film that uses in the liquid crystal indicator, except the performance of good optics, more require high-durability.Especially for the portable machine liquid crystal indicator that use, vehicle mounted of portable phone etc., it is qualified in the environmental test of the strictness of having imagined various service conditions to require.
The film (film) that constitutes by the oriented layer of liquid-crystal compounds, especially the film that constitutes by nematic structure, twisted-nematic structure or the liquid crystal material that is immobilized to the row mixed structure, the element of using as wavelength plate, colorimetric compensation or the viewing angle compensation of used for liquid crystal display element, have good performance as optical activity optical element etc. in addition, help high performance, the lightweight of various display elements.As the manufacture method of these films, proposed to make by the layer that constitutes at the liquid crystal material that forms on the orientation substrate to be transferred to method (for example with reference to patent documentation 1～3) on the light-transmitting substrate that has support substrate concurrently.
Have again, countermeasure as the harsh excessively endurancing that requires with element for anti-liquid crystal display, in addition for further slimming, lightweight, the manufacture method (for example with reference to patent documentation 4～6) of the optical element that is made of the liquid crystal material that does not use the support substrate film has been proposed also.According to such manufacture method, in a single day after will being transferred on the releasable substrate by the layer that the liquid crystal material that has formed in orientation on the orientation substrate constitutes by bonding agent, by peeling off this releasable substrate, making the optical element that is made of the liquid crystal material layer that does not have the support substrate film just becomes possibility.
Usually, these films and Polarizer or fit with phase-contrast film again and use.The optical thin film of making by the oriented layer of liquid-crystal compounds, for example in the long cyclic test of hot environment test and hot and humid environment test, can not follow the contraction of Polarizer, have easily in the unusual such problem of outward appearances such as liquid crystal aligning layer generation crackle (crack), distortion.As its solution, propose to use the method (with reference to patent documentation 7) of 2 layers of protective seam that constitutes by the curing acrylic resin bed of having stipulated glass transition temperature range.
But; under the situation of the above-mentioned form of having used 2 layers of protective seam that constitutes by the curing acrylic resin bed; in the thermal shock test that makes hot test and low-temperature test alternate repetition; exist the curing acrylic resin bed to cause the generation of line, or the closing force deficiency between liquid crystal material layer/curing acrylic resin of being immobilized of orientation cause problem such as peel off easily at this interface.
Patent documentation 1 spy opens flat 4-57017 communique
Patent documentation 2 spies open flat 4-177216 communique
Patent documentation 3 spies open flat 6-242434 communique
Patent documentation 4 spies open flat 8-278491 communique
Patent documentation 5 spies open the 2004-117422 communique
Patent documentation 6 spies open the 2004-138697 communique
Patent documentation 7 spies open the 2006-284735 communique
Summary of the invention
The purpose of this invention is to provide, even in the harsh environmental test as the thermal shock test, the outward appearance that crackle etc. does not take place in liquid crystal aligning layer yet is unusual, the extra-thin liquid crystal film that the interlayer closing force is also no problem.
The inventor etc. carry out the result that deeply and carefully studies for above-mentioned problem, have reached and have finished the present invention.
Promptly, the of the present invention the 1st relates to the manufacture method of liquid crystal film, it is characterized in that, at least through the 1st operation, each operation of the 2nd operation and the 3rd operation obtains liquid crystal film, the 1st operation be with in the liquid crystal aligning immobilization that forms on the orientation substrate substrate the liquid crystal material layer by behind bonding agent 1 and the releasable substrate bonding, peel off orientation substrate, make the transfer printing of liquid crystal material layer on the releasable substrate, bonding by bonding agent 2 and temporary base then, obtain the lamilated body (I) that constitutes by releasable substrate/adhesive phase 1/ liquid crystal material layer/adhesive phase 2/ temporary base thus, the 2nd operation is with the releasable strippable substrate from above-mentioned lamilated body (I), then the 3rd operation is by peeling off 2 of liquid crystal material layer/adhesive phases, obtaining the liquid crystal film that is made of adhesive phase 1/ liquid crystal material layer.
The of the present invention the 2nd relates to the manufacture method of liquid crystal film, it is characterized in that, at least through the 1st operation, each operation of the 2nd operation and the 3rd operation obtains liquid crystal film, the 1st operation be the liquid crystal aligning that forms on the orientation substrate take place immobilized liquid crystal material layer by bonding agent 1 and temporary base bonding after, peel off orientation substrate, make the transfer printing of liquid crystal material layer on temporary base, then by bonding agent 2 and releasable substrate bonding, obtain the lamilated body (II) that constitutes by temporary base/adhesive phase 1/ liquid crystal material layer/adhesive phase 2/ releasable substrate thus, the 2nd operation is with the releasable strippable substrate from above-mentioned lamilated body (II), then the 3rd operation is by peeling off at adhesive phase 1/ liquid crystal material interlayer, obtaining the liquid crystal film that is made of liquid crystal material layer/adhesive phase 2.
The of the present invention the 3rd relates to the manufacture method of the liquid crystal film of record in the 1st or the 2nd, it is characterized in that the liquid crystal material layer that liquid crystal aligning is immobilized is included in the above temperature generation liquid crystal aligning of liquid crystal tr pt, the high molecule liquid crystal material that the temperature below the liquid crystal tr pt becomes vitreousness.
The of the present invention the 4th relates in the 1st or the 2nd the manufacture method of the liquid crystal film of record, it is characterized in that, the liquid crystal material layer that liquid crystal aligning is immobilized be make liquid crystal aligning takes place the low molecular weight liquid crystal material carry out the liquid crystal material layer of photo-crosslinking or heat cross-linking.
The of the present invention the 5th relates to the manufacture method of the liquid crystal film of record in the 1st or the 2nd, it is characterized in that temporary base or releasable substrate have the isotropy of optics.
The of the present invention the 6th relates in the 1st or the 2nd the manufacture method of the liquid crystal film of record, it is characterized in that and surface modifier that bonding agent that temporary base is bonding contains silicon-type or fluorine system forms.
Have, the of the present invention the 7th relates to laminate film for optical device again, this laminate film with the of the present invention the 1st～the 6th any in the liquid crystal film made of the method put down in writing by bonding agent or bonding agent and Polarizer or polarizer is laminated constitutes.
Moreover in above-mentioned record, [/] is the interface of each layer of expression, below also regards similarly expression as.
According to the present invention, obtain extra-thin optical thin film, and can to solve be the thermal shock test patience of problem in the past or the problem that remakes the splitting of time spent, therefore the value of industry is high.
Embodiment
Below, explain the present invention.
The liquid crystal material layer that the orientation of the liquid crystal that uses among the present invention is immobilized is immobilized layer by using the immobilized means of liquid crystal material will be in state of orientation.As the immobilized means of the orientation that makes liquid crystal, occasion at the high molecule liquid crystal material, can enumerate from state of orientation and carry out chilling formation vitrifacation state and fixing method, after making low molecular weight liquid crystal material with reactive functional group or high molecule liquid crystal material orientation, make above-mentioned functional group's reaction (solidify, crosslinked etc.) and immobilized method etc.
As above-mentioned reactive functional group, can enumerate vinyl, (methyl) acryloyl group, ethyleneoxy, epoxy radicals, oxetanyl, carboxyl, hydroxyl, amino, isocyanate group, acid anhydrides etc., react with the method that is applicable to base separately.
The liquid crystal material that can in the liquid crystal material layer, use, according to purposes or the manufacture method of liquid crystal film as purpose, regardless of low molecular weight liquid crystal material, high molecule liquid crystal material, can be from scope be selected widely, the still preferential high molecule liquid crystal material of selecting.Have again, the molecular shape of liquid crystal material, no matter be bar-shaped or discoid can.The disc liquid-crystal compounds that for example shows the plate-like nematic liquid crystal also can use.
As the liquid crystal phase of the liquid crystal material layer before the immobilization, can enumerate nematic phase, twisted-nematic phase, cholesterol phase, mix nematic phase, mix the twisted-nematic phase, plate-like nematic phase, smectic equate.In addition, as state of orientation, also example is illustrated in the even orientation of orientation substrate face horizontal alignment or vertical orientated vertical plane orientation etc.
As above-mentioned high molecule liquid crystal material, can use various backbone chain type high molecule liquid crystal material, side chain type high molecule liquid crystal material or its potpourri.
As backbone chain type high molecule liquid crystal material, can enumerate macromolecule liquid crystal materials such as polyester system, polyamide-based, polycarbonate-based, polyimide system, polyurethane series, polybenzimidazoles system, polybenzoxazole system, polybenzothiozole system, polyazo methine system, polyesteramide system, polyestercarbonate system, polyester-imide system, perhaps its potpourri etc.
In addition, as side chain type high molecule liquid crystal material, can enumerate on the material of skeleton as high molecule liquid crystal material or its potpourri of side chain in conjunction with the liquid crystal original hase with straight chain shape such as polyacrylate system, polymethacrylate system, polyethylene-based, polysiloxane series, polyethers system, poly-malonate system, polyester system or ring texture.
Especially in these high molecule liquid crystal materials,, preferentially select the polyester system of backbone chain type high molecule liquid crystal material from considerations such as easy degree synthetic or orientation.
As the low molecular weight liquid crystal material, can enumerate end in saturated benzoic acids, unsaturated benzoic acids, diphenic acid class, aromatic hydroxy group acids, azomethine type class, bisdiazo methine compounds, azo-compound class, azoxy compound class, cyclohexane ester compounds class, sterol compound class etc. and import the demonstration liquid crystal compounds of above-mentioned reactive functional group or among the above-claimed cpd class, show the composition that adds cross-linked compound in the compound of liquid crystal liquid crystal property etc.
In addition, as disc liquid-crystal compounds, can enumerate Sanya benzene series, Sanya indenes system etc.
Have again, can be in liquid crystal material with the functional group that do not hinder the range fit that manifests liquid crystal liquid crystal property to have can to react or all cpds at position by heat or photo-crosslinking etc.Functional group as can cross-linking reaction can enumerate above-mentioned various reactive functional group etc.
The liquid crystal material layer that the orientation of liquid crystal is immobilized, utilization is coated with the method for compositions of all cpds that contains above-mentioned liquid crystal material or add as required on orientation substrate with molten condition, or the formation such as method of solution of coating said composition on orientation substrate, be coated on filming on the orientation substrate through super-dry, thermal treatment (orientation of liquid crystal), that uses rayed and/or heat treated etc. as required will be orientated immobilized means, form by making the orientation immobilization.
About the solvent that in the preparation of above-mentioned solution, uses, if can dissolve liquid crystal material or the composition that uses among the present invention, the solvent that can heat up in a steamer with suitable condition, just not restriction especially, ordinary priority is used acetone, methyl ethyl ketone, ketones such as isophorone, butyl cellosolve, own ethoxy-ethanol, methoxyl-ether alcohol classes such as 2-propyl alcohol, glycol dimethyl ether, gylcol ethers such as diethylene glycol dimethyl ether, ethyl acetate, acetate methoxyl propyl ester, ester classes such as ethyl lactate, phenol, phenols such as chlorophenol, N, dinethylformamide, N, the N-dimethyl acetamide, amide-types such as N-Methyl pyrrolidone, chloroform, tetrachloroethane, halogenated hydrocarbons such as dichloro-benzenes etc. or their mixed stocker.In addition, film uniformly, in solution, also can add surfactant, defoamer, levelling agent etc. in order on orientation substrate, to form.Have again,, in the scope that does not hinder liquid crystal liquid crystal property to manifest, also can add dichroic dye or common dyestuff or pigment etc. to be colored as purpose.
About coating process, if guarantee the inhomogeneity method of filming, just do not limited especially, can adopt known method.For example can enumerate rolling method, mouthful pattern rubbing method, dip coated method, curtain formula rubbing method, method of spin coating etc.After coating, can comprise removal of solvents (drying) operation of methods such as utilizing well heater or blowing hot-air.Thickness under the drying regime of the film that is coated with, normally 0.1 μ m～50 μ m are more preferably 0.2 μ m～20 μ m, preferably 0.3 μ m～10 μ m.Beyond this scope, the optical property deficiency of resulting liquid crystal material, or the orientation of liquid crystal material becomes insufficient etc., is not preferred.
Then, if necessary, after the orientation by formation liquid crystal such as thermal treatments, the immobilization that is orientated.Thermal treatment is to manifest temperature range by being heated to liquid crystal phase, and the auto-orientation that the liquid crystal material utilization had originally can make liquid crystal aligning.As heat treated condition, because of liquid crystal phase behavior temperature (transition temperature) difference of employed liquid crystal material, optimum condition or boundary value are also different, therefore can not be without exception, but normally 10～300 ℃, and 30～250 ℃ scope preferably.At low temperature too, the danger that has the orientation of liquid crystal to carry out deficiently, and at high temperature, liquid crystal material or decomposition, or have pair orientation substrate to give the danger of baneful influence.In addition, about heat treatment time, normally 3 seconds～60 minutes, preferably 10 seconds～30 minutes scope.Than the heat treatment time of 3 seconds weak point, the danger that has the orientation of liquid crystal to finish deficiently, and surpass 60 minutes heat treatment time, throughput rate becomes extreme and worsens, so any situation is all unsatisfactory.After liquid crystal material is finished the orientation of liquid crystal with thermal treatment etc., use the means that are suitable for used liquid crystal material to make liquid crystal material layer immobilization on the orientation substrate with state intactly.
As above-mentioned orientation substrate, the film of polyimide, polyamide, polyamidoimide, polyphenylene sulfide, polyphenylene oxide, polyetherketone, polyetheretherketone, polyethersulfone, polysulfones, polyethylene terephthalate, the inferior second diester of naphthalenedicarboxylic acid, polyarylate, triacetyl cellulose, epoxy resin, phenolics etc. can routine be shown.
These films are according to manufacture method, even no longer carry out in order to manifest the processing of orientation energy, orientation can fully for the liquid crystal material that uses among the present invention demonstration also, can be insufficient in orientation, perhaps occasion such as display orientation energy not, these films extend under the heating of appropriateness, with the so-called friction treatment at a direction friction film face such as rayon cloth, on film, be provided with by polyimide, polyvinyl alcohol (PVA), the alignment films that known alignment agent such as silane coupling agent constitutes, carry out friction treatment, also can use oblique side's vapor deposition treatment of monox etc., perhaps suit to make up these processing and wait the film that orientation can be manifested.
In addition as orientation substrate, also can use the sheet metal of aluminium that the fine ditch of a plurality of rules is set on the surface, iron, copper etc. or various glass plates etc.
At this, do not limit especially as the orientation process direction of orientation substrate, can handle and select aptly according to carry out above-mentioned each in direction arbitrarily.Especially, during the liquid crystal film that forms on using elongated orientation substrate, the angle stipulated of vertical (MD) of this elongated continuous film selection is more carried out orientation process at tilted direction according to need relatively, is desirable like this.Carrying out orientation process by angle direction in regulation, when disposing laminated liquid crystal film can bring into play the such axle of best optical characteristics, the applying (so-called roll-in is to the applying of roller) of the state that reaches unanimity from the MD that makes elongate thin film becomes possibility, perhaps the aspects such as acquisition efficient raising of goods see that the utmost point has advantage.
Below, about being narrated in the method that the liquid crystal material layer that forms on the orientation substrate is transferred on releasable substrate or the temporary base.
As the releasable substrate that uses among the present invention, temporary base, can use tygon, polypropylene, ethylene series resins such as 4-methylpentene-1 resin, polyamide, polyimide, polyamidoimide, polyetherimide, polyetherketone, polyetheretherketone, polyethersulfone, polyketone sulfide, polysulfones, polystyrene, polyphenylene sulfide, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyacetal, the unilateral stretching polyester, polycarbonate, polyvinyl alcohol (PVA), polymethylmethacrylate, polyacrylate, amorphous polyolefin, norbornene resin, the film of triacetyl cellulose or epoxy resin etc.
Especially, the preferential use is being to be isotropic film on the good transparency and the optics on the inspectability of the defective of optics: the plastic sheeting of 4-methylpentene-1 resin, polymethylmethacrylate, polystyrene, polycarbonate, polyethersulfone, polyarylate, amorphous polyolefin, norbornene resin, triacetyl cellulose or epoxy resin etc.
Moreover releasable substrate and temporary base also can be identical material, can be according to its manufacture method or various processing, also have the selected of the bonding agent that uses in the present invention etc., and cooperate suitable purpose to use.
In addition, as the thickness of these substrates, hope is 10～100 μ m, and special hope is 25～50 μ m.Thickness is blocked up, just peels off the position instability, and the danger that fissility worsens is thin excessively on the other hand, and the physical strength of film just can not guarantee, so the danger of the fault of tearing etc. is arranged in the mill.
As the releasable substrate, during the film stated in the use,, can perhaps can be pre-formed organic film or inorganic thin film in advance at its surperficial pre-coating silicone or fluorine in order to keep the releasable of appropriateness.In addition,, implement the chemical treatment of saponification processing etc. on the surface of plastic sheeting, perhaps also can implement the processing of the physics as Corona discharge Treatment or ultraviolet ray-ozone treatment in advance with same purpose.
In addition, in order to adjust the fissility of releasable substrate, on above-mentioned film, also can contain lubricant or surface modifier.As above-mentioned lubricant, if to the inspectability of the defective of optics or the scope that fissility does not bring baneful influence, kind, addition be restriction especially just.As the concrete example of lubricant, can enumerate small silica, tiny aluminium oxide etc.As the index of addition, the mist value of releasable substrate needs only to be become below 50% usually, it is like that just passable preferably to become below 30%.If addition just be can't see additive effect very few, and on the other hand, when too much adding, the inspectability of optics worsens, and is not preferred therefore.
In addition, as required, also can contain other known various adjuvants, for example anti blocking agent, antioxidant, antistatic agent, thermal stabilizer, impact modifier etc.
In addition in the present invention, owing to use at the releasable substrate that is pre-formed the separating layer that may peel off from this substrate on the releasable real estate, it also is possible forming separating layer between liquid crystal material and other layer.Owing to form separating layer, obtain being used to suppressing during fabrication or the stress barrier effect of the appearance change of the liquid crystal material layer of the film during environmental test (for example fluctuation etc.).Moreover, as separating layer,, preferentially select the hyaline layer of optical isotropy at this though do not limit especially, for example can enumerate polymkeric substance and their potpourris of acrylic acid series, metha crylic, nitrocellulose prime system, epoxy based compound etc.Thickness as separating layer, be below the above 40 μ m of 0.3 μ m, be more preferably below the above 10 μ m of 0.5 μ m, it is the hyaline layer of glass temperature (Tg) more than 20 ℃, better optical isotropy more than 50 ℃, if significantly do not damage the optical characteristics of liquid crystal material layer, just not restriction especially on material.Thickness and glass temperature are beyond this scope, or its effect deficiency, or from the goods viewpoint such as blocked up that becomes, are not preferred.
In addition, above-mentioned separating layer also can be carried out control of physical properties by partial cross-linked, the interpolation of plastifier that is produced by the interpolation of crosslinked composition, the interpolation of lubricant etc.
Again relevant for the formation method of separating layer; though also not restriction especially; but for example can enumerate on releasable substrate film such as tygon, polypropylene, polyethylene terephthalate by being coated with, being extruded as the material of separating layer in advance with above-mentioned thickness; should layer bonding via bond layer or adhesive phase or protective clear layer then, the transfer printing of again the releasable substrate film being peeled off etc. after this.
On the other hand,, during the film stated in the use, be necessary, therefore require and the cohesive of the appropriateness of adhesive phase to carry out stripping process with the bonding form of adhesive phase as temporary base.To obtain bounding force is purpose, also can form organic film or inorganic thin film on its surface in advance, or implement Corona discharge Treatment or ultraviolet ray-ozone treatment.
Move on on picture above-mentioned the releasable substrate or temporary base in order to make at the liquid crystal material layer that forms on the orientation substrate, after giving light-cured type acrylic resin bonding agent on the liquid crystal material layer, applying releasable substrate or temporary base, irradiates light carries out photocuring and after bonding on it from the lateral, if peel off orientation substrate, just transfer printing easily.The acrylic oligomers or the monomer of coating curable make it solidify the curing acrylic resin bed that just forms as bonding agent.
Employed curable acrylate, for example can use as the light-cured type acrylic adhesive knownly, for example example illustrates various acrylic oligomers such as polyester acrylate, epoxy acrylate, urethanes acrylate, polyether acrylate, silicone acrylate or monomer, their potpourri or the potpourri of they and various reaction diluents.
In addition, in these bonding agents, also can add various particulates etc. or surface modifier with the scope of not damaging its characteristic.
As above-mentioned particulate, can example the refractive index particulate different with the compound that constitutes bonding agent be shown, not damage the transparency and be used for the conductive particle that antistatic performance improves, the particulate that is used for the mar proof raising etc., more specifically can enumerate small silica, tiny aluminium oxide, ITO (tin indium oxide) particulate, fine silver particle, various synthetic resin particulates etc.
In addition, as above-mentioned surface modifier, so long as good with the intermiscibility of bonding agent, to the curable of bonding agent or the optical property after solidifying do not bring influence, just restriction especially, water soluble surfactant active, oil soluble surfactant, high molecular surfactant, the fluorine that can use ionic or nonionic are that surfactant, silicone-based surfactant, organic metal are surfactant, reactive surfactant etc.
The present invention, the bonding agent of the bonding agent of releasable substrate-side and temporary base side also can use different types of bonding agent as required.Especially, the bonding agent that uses in the releasable substrate-side is wished and the releasable substrate low bounding force of extent of exfoliation easily, and and the bonding agent of liquid crystal material layer with sufficient adhesive, the bonding agent that uses in the temporary base side the opposing party wishes and the liquid crystal material layer low bounding force of extent of exfoliation easily, and has to a certain degree sufficient adhesive with temporary base.
About the peeling force between releasable substrate/adhesive phase, even releasable substrate by the same material manufacturing, also because of manufacture method, surface state or with different variations the such as wetting state of the bonding agent that uses, therefore can not determine without exception, but the peeling force at the interface of hope and bonding agent (is peeled off for 180 °, peeling rate 30cm/min measures under the room temperature) normally 0.3～12N/m, 0.5～8.0N/m preferably.When peeling force is lower than this value, after making the liquid crystal material layer and releasable substrate bonding on the orientation substrate, when peeling off orientation substrate, peeling force is low excessively, sees unsteady on the releasable substrate, can not get the good state of peeling off at desirable interface, the transfer printing of liquid crystal material course releasable substrate becomes insufficient, in addition when peeling force is too high, when peeling off the releasable substrate, take place the liquid crystal material layer destruction or and desirable interface can not peel off etc., be not preferred therefore.
As adhesive phase that uses in the releasable substrate-side and the bounding force between the liquid crystal material layer, the peeling force (peel off for 180 °, peeling rate 30cm/min measures under the room temperature) of wishing this interface is normally more than the 3.9N/m, preferably more than the 5.8N/m.When peeling force is lower than this value, after the liquid crystal cell in the goods when the operation that adds man-hour or after Polarizer and adhesive phase etc. are laminated is fitted peel off (remaking usefulness) again the time, the danger of peeling off at this interface is arranged, so is not preferred.
On the other hand, about the bounding force between temporary base/adhesive phase, even temporary base by the same material manufacturing, also because of manufacture method, surface state or with different variations the such as wetting state of the bonding agent that uses, therefore can not determine without exception, but the bounding force (peel off for 180 °, peeling rate 30cm/min measures under the room temperature) of wishing this interface normally 2.0N/m above, preferably more than the 3.7N/m.When bounding force is lower than this value, when when the liquid crystal material layer is peeled off temporary base and adhesive phase, between temporary base/adhesive phase, take place to float or peel off, having at desirable interface (between adhesive phase/liquid crystal material layer) to can not get the danger of the good state of peeling off, is not preferred therefore.
Have again,, wish at the peeling force (peel off for 180 °, peeling rate 30cm/min measures under the room temperature) at this interface normally 0.3～3.1N/m, 0.9～1.9N/m preferably as adhesive phase that uses in the temporary base side and the bounding force between the liquid crystal material layer.When peeling force is lower than this value,, be not preferred therefore peeling off the medium danger that between adhesive phase/liquid crystal material layer, exists generation to float or peel off in processing way of releasable substrate.In addition, when peeling force is too high, when peeling off temporary base, the destruction of liquid crystal material layer is taken place or takes place to peel off at the interface with the layer of hope etc., is not preferred therefore.
Especially, in the bonding agent that the temporary base side is used, if add surface modifier, just can peel off smoothly as required with the interface of liquid crystal material layer.As surface modifier, as long as and the intermiscibility of bonding agent is good, not to the bonding agent curable or the optical property after solidifying bring just not restriction especially of influence, water soluble surfactant active, oil soluble surfactant, high molecular surfactant, the fluorine that can use ionic or nonionic is that surfactant, silicone-based surfactant, organic metal are surfactant, reactive surfactant etc.Wherein, especially fluorine is surfactant or silicone-based surfactant, and it is big that peeling force reduces effect, is preferential the selection.
Addition during as the above-mentioned surfactant of interpolation, with the amount of binder before adding during as 100 parts by weight, be 0.01 parts by weight～15 parts by weight, hope is 0.05 parts by weight～12 parts by weight, more wishes it is 0.1 parts by weight～10 parts by weight.Under the very few situation of addition, worry that almost can't see additive effect is arranged, in addition under too much situation, the foaming fierceness of bonding agent, having bubbles sneaks into danger in the solidfied material, is not preferred therefore.
The curing of these curable acrylic adhesives then, is described.
Curing is restriction especially, but can example for example illustrate be heating and curing, activation light curing such as redox system normal temperature cure, anaerobic curing, ultraviolet ray, electron beam etc.The preferential curing of selecting is the solidification method that is caused by activation rays such as ultraviolet ray, electron beams.This solidification method does not have the generation of heat or few, and therefore the influence to the immobilized liquid crystal material layer of orientation is few, is preferential the selection.Can add various known light triggers, irradiation is reacted from the light of light sources such as metal halide lamp, high-pressure mercury-vapor lamp, Cooper-Hewitt lamp, xenon lamp, arc light etc., laser, synchrotron radiation light source.As the exposure of per unit area (1 square centimeter), as cumulative exposure normally 1～2000mJ, the preferably scope of 10～1000mJ.But, the occasion that the absorption region of light trigger and the spectrum of light source are significantly different or self have at reactive compound light source wavelength absorption can occasion etc., be not limited to above-mentioned scope.In these occasions, also can adopt and mix the method for using suitable photosensitizer or the light trigger that absorbing wavelength is different more than 2 kinds etc.The accelerating potential of electronic beam solidified occasion is 10kV～200kV normally, preferably 50kV～100kV.
In addition, the trigger for optical solidification when being cured as utilization activation ray, for example example illustrates benzoin ether, benzoin ethyl ether, benzyl methyl ketal, hydroxy phenyl ketone, 1, the benzophenone of 1-dichloroacetophenone, thioxanthene ketone or amine and usefulness etc.Its use amount adopts the scope of 0.1～10 weight % of resin.
In the method for the invention, make liquid crystal material layer and releasable substrate or the temporary base applying that on orientation substrate, forms, obtain following lamilated body by bonding agent.
Lamilated body (I): releasable substrate/adhesive phase 1/ liquid crystal material layer/adhesive phase 2/ temporary base
Lamilated body (II): temporary base/adhesive phase 1/ liquid crystal material layer/adhesive phase 2/ releasable substrate
By peeling off releasable substrate and adhesive phase/temporary base respectively, can access the slim liquid crystal film as following from this lamilated body.
Adhesive phase 1/ liquid crystal material layer
Liquid crystal material layer/adhesive phase 2
Here, the adhesive phase of Shi Yonging in the present invention, wishing to use glass temperature (Tg) after solidifying is more than 20 ℃ below 250 ℃, is more preferably the adhesive phase below 200 ℃ more than 30 ℃.If the Tg of adhesive phase is lower than 20 ℃, in the environmental test of high temperature, high humidity etc. or the thermal shock test between circulation environmental test, high temperature and low temperature between high temperature and high humidity etc., adhesive phase and liquid crystal material layer become outward appearance unusual (crackle, distortion etc.) take place easily.On the other hand, if glass temperature is more too high than 250 ℃, when adding man-hour or environmental test, problems such as being easy to generate crackle becomes on adhesive phase.
In addition, the thickness of adhesive phase all is respectively 0.1～50 μ m, and hope is 0.5～20 μ m, more wishes it is 1～10 μ m.If thickness is thinner excessively than this thickness, the protection effect of the liquid crystal material layer in environmental test is just not enough, in addition, if blocked up, needs in the curing of acrylic resin layer for a long time, and products thickness is thickening also, is not preferred therefore.
The liquid crystal film of the present invention that obtains as described above, as the colorimetric compensation plate of used for liquid crystal display element or view angle compensation when waiting use, usually as Polarizer or as required as polarizer, also laminatedly be used to be attached to formation of pressure-sensitive adhesive layer on liquid crystal aligning film or macromolecule oriented film, the liquid crystal cell etc.Here, Polarizer, liquid crystal aligning film, macromolecule oriented film etc. laminated can make the bonding agent of the known transparency or bonding agent carry out laminated between the centre.As the lamilated body that obtains like this, for example can example illustrate
(1) Polarizer/bonding (bonding) adhesive layer/liquid crystal film/bonding (bonding) adhesive layer/dividing plate
(2) Polarizer/bonding (bonding) adhesive layer/phasic difference plate (macromolecule oriented film)/bonding (bonding) adhesive layer/liquid crystal film/bonding (bonding) adhesive layer/dividing plate
(3) Polarizer/bonding (bonding) adhesive layer/liquid crystal film/bonding (bonding) adhesive layer/liquid crystal film/bonding (bonding) adhesive layer/dividing plate (here, liquid crystal film can be identical according to purposes, also can be different)
(4) Polarizer/bonding (bonding) adhesive layer/liquid crystal film/bonding (bonding) adhesive layer/phasic difference plate (macromolecule oriented film)/bonding (bonding) adhesive layer/dividing plate or the like.
Here, also can several pieces of liquid crystal films, liquid crystal aligning film, macromolecule oriented film etc. are laminated.
As above-mentioned Polarizer, do not limit especially, can use normally used Polarizer in liquid crystal indicator aptly, but wish the preferably Polarizer of the film-type of exploitation listing in recent years.Can to use PVA as the PVA of polyvinyl alcohol (PVA) (PVA) or part hydroformylation particularly be polarizing film, absorption iodine and/or bitintability pigment and the polarizing film that stretched, the polarizing film that is made of the polyenoid oriented film as the desalination acid treatment thing of the processed thing of PVA or Polyvinylchloride etc. etc. on the hydrophilic macromolecule macromolecule membrane that is made of the partly-hydrolysed thing of vinyl-vinyl acetate copolymer etc.In addition, also can use the polarizing film of reflection-type.
Polarizer also can use polarizing film separately, is purpose with intensity raising, moisture-proof raising, thermotolerance raising etc., also can be on the one side or the two sides of polarizing film transparent protective seam etc. to be set.As transparent protective seam, can enumerate directly or by the protective seam of transparent plastic films such as laminated polyester of adhesive phase or triacetyl cellulose, the light-cured type resin beds such as coating layer, acrylic acid series or epoxy system of resin etc.Be covered on the two sides of the polarizing film occasion of these transparent protective seams can be provided with identical transparent protective seam on the two sides, and different transparent protective seams also can be set.
As above-mentioned macromolecule oriented film, can the unidirectional or two-way stretch phase-contrast film that be made of cellulose-based, polycarbonate-based, polyarylate system, polysulfones system, polyethenol series (PVA), polyacrylic, polyethersulfone system, cyclic polyolefin hydrocarbon system etc. be shown example.Especially, consider, preferentially select the monodirectional tension film of cyclic polyolefin hydrocarbon systems such as polycarbonate-based, norborene system from the easiness made or the homogeneity or the optical characteristics aspect of film.
Here, as the direction that stretches, restriction especially is by carrying out and can select aptly in direction arbitrarily.Especially, when handling elongated macromolecule oriented film, wish MD to this elongated continuous film with the angle of regulation, carry out tilted direction (tiltedly stretching) stretch processing as required, perhaps Width (TD) stretch (horizontal stretching) handle.Carry out stretch processing by direction at predetermined angular, oriented film and liquid crystal film or Polarizer are cooperated when laminated can bring into play the such axle of best optical characteristics, so that the applying of the state that the MD of elongate thin film reaches unanimity (so-called roll-in is to the applying of roller) becomes possibility,, be extremely advantageous perhaps from the aspects such as acquisition efficient raising of goods.
The method of the laminate film for optical device of making liquid crystal film of the present invention and Polarizer applying then, is described.
At first, with the order of previous narration, obtain picture following illustrative lamilated body (I) or (II).
Lamilated body (I): releasable substrate/adhesive phase 1/ liquid crystal material layer/adhesive phase 2/ temporary base
Lamilated body (II): temporary base/adhesive phase 1/ liquid crystal material layer/adhesive phase 2/ releasable substrate
After this order, according to use or carry out laminated the other side, do not limit especially, but can example illustrate from lamilated body (I) or (II) peel off releasable substrate or temporary base, after by the bonded adhesives stick Polarizer, macromolecule oriented film, liquid crystal aligning film, dividing plate etc. being fitted, the method that residual temporary base and adhesive phase are peeled off together.Here, wish releasable substrate and temporary base any optically is isotropic at least, and carry out defective or inhomogeneous inspection under the polarized light.
For example about the releasable substrate optically anisotropy, temporary base optically be isotropic situation, later operation is described.
At first, by peeling off the releasable substrate earlier, intactly to adhere to the state of temporary base, the inspection under polarized light becomes possibility.Then, after fitting by bonded adhesives stick and Polarizer, macromolecule oriented film, other liquid crystal aligning film, dividing plate etc. thereon, by peel off temporary base with adhesive phase, just can laminated liquid crystal film of the present invention.According to purposes or needs, re-use the bonded adhesives stick can be laminated successively other member (Polarizer, macromolecule oriented film, other liquid crystal aligning film, dividing plate etc.).
As laminated order, the acquisition efficient of consideration production efficiency or member waits to be selected.For example bring into play optical property to greatest extent for employed liquid crystal film and Polarizer or polarizer, the applying (so-called roll-in is fitted to roller) of the state that reaches unanimity at the MD that can not make elongate thin film, at least either party thinly sliced the roll-in of fitting behind the shape to thin slice fit or thin slice under the situation that thin slice is fitted, from above-mentioned lamilated body (I) or (II) peel off the releasable substrate, utilize bonded adhesives stick and dividing plate at first with roll-in after roller is fitted, with other member (Polarizer, the macromolecule oriented film, other liquid crystal aligning films etc.) laminated successively method is effective.
The laminate film for optical device that liquid crystal film of the present invention and Polarizer or polarizer are fitted and formed, according to the optical parametric of liquid crystal material layer, can be as compensation member, elliptical polarization plate, the rotatory polarization plate performance function of various liquid crystal indicators.
Promptly constitute the liquid crystal material layer of laminate film for optical device, for example make to row orientation, the immobilized liquid crystal material layer of twisted nematic orientation and bring into play function as polarizer, therefore with the of the present invention laminate film for optical device of this liquid crystal material layer, can see through or the compensating plate of reflection-type liquid-crystal display device uses as STN type, TN type, OCB type, HAN type etc. as member of formation.
In addition, make to the immobilized liquid crystal material layer of row hybrid orientation, the delay of utilization when the front is seen, can be as polarizer or wavelength plate utilization, and produce the asymmetry that the direction (inclination of the molecular axis of film thickness direction) by length of delay causes, also can improve utilization in the member etc. at the angle of visibility of TN type liquid crystal indicator.
In addition, have the liquid crystal material layer of 1/4 wavelength plate function,,, can be used as the liquid crystal indicator of rotatory polarization plate or reflection-type or the reflection of EL display device and prevent uses such as filtrator by making up with Polarizer as the present invention.Especially, broadband district 1/4 wavelength plate for the broadband district performance function that obtains spreading all over the visible light field, the general known state that intersects with its slow axis with the phasic difference of the birefringent light under the monochromatic light of 550nm be the phasic difference of the birefringent light under the monochromatic light of 1/4 wavelength plate of about 1/4 wavelength and 550nm be 1/2 wavelength plate of about 1/2 wavelength laminated be effective, in fact, in liquid crystal indicator of reflection-type etc., be widely used.
That is, as in the present invention, if use the technology of the laminate film for optical device obtain approaching, can obtain in the past only by macromolecule oriented film slim broadband district 1/4 wavelength plate of difficulty relatively.Here, the length of delay of 1/4 wavelength plate is 70nm～180nm normally, is more preferably 90nm～160nm, the special preferably scope of 120nm～150nm.In addition, the length of delay of 1/2 wavelength plate is 180nm～320nm normally, is more preferably 200nm～300nm, the special preferably scope of 220nm～280nm.The delay scope of 1/4 wavelength plate and 1/2 wavelength plate is beyond above-mentioned the time, and the danger of the unnecessary band look of in liquid crystal indicator generation is arranged.Moreover so-called length of delay is represented amassing of birefringence n and thickness d.
Have again, in laminate film for optical device of the present invention, constitute the liquid crystal material layer of this lamilated body if make courage steroid orientation or smectic is orientated immobilized liquid crystal material layer, just can brightness improve polarisation reflective film, the reflection-type of usefulness chromatic filter, produce by resulting from utilization in the various Security elements of the catoptrical change color that the visual angle of selecting reflected energy causes or the decorating film etc.
Below, utilize embodiment to be described more specifically the present invention, but the present invention is not subjected to the restriction of these embodiment.Moreover the delay in the present embodiment (birefringence n and thickness d long-pending) only otherwise explanation especially is the value among the wavelength 550nm.
Preparation example
Use 50mmol terephthalic acid (TPA), 50mmol 2,6-naphthalene dicarboxylic acids, 40mmol methylhydroquinone diacetate, 60mmol catechol diacetate esters and 60mg N-methylimidazole under nitrogen atmosphere, carry out polycondensation in 12 hours in 270 ℃.After the resultant of reaction that then obtains is dissolved in tetrachloroethane, precipitate again to make with extra care, obtain the 14.6g liquid crystalline polyester with methyl alcohol.The logarithm viscosity of this liquid crystalline polyester (polymkeric substance 1) (phenol/tetrachloroethane (6/4 mass ratio) mixed solvent: 30 ℃) is 0.16dl/g, keep nematic phase as liquid crystal phase, isotropic phase-liquid crystal phase transition temperature is more than 250 ℃, and the glass temperature of being measured by differential scanning calorimetry (DSC) is 112 ℃.
Make the polymkeric substance 1 of 20g be dissolved in the N-N-methyl-2-2-pyrrolidone N-of 80g, be prepared into solution.Use rotary coating, going up this solution of coating by the Kapton (trade name " カ プ ト Application ", デ ユ Port Application corporate system) after the rayon cloth friction treatment, solvent is carried out drying removal after, carry out thermal treatment in 20 minutes at 210 ℃, form to the row orientation texture.After the thermal treatment, be cooled to below the room temperature, make, on Kapton, obtain the liquid crystal material layer (liquid crystal material layer 1) of the even orientation of real thickness 0.7 μ m to the immobilization of row orientation texture.Real thickness uses the contact pin type film thickness gauge to measure.
Embodiment 1
On the liquid crystal material layer 1 that preparation example obtains (face opposite) with polyimide film, the ultraviolet hardening acrylic adhesive 1 (Toagosei Co., Ltd's system) of 47 ℃ of glass temperatures (Tg) is coated with into the thickness of 5 μ m as acrylic resin layer 1, polyethylene terephthalate (PET) film of laminated thereon thickness 50 μ m (Co., Ltd.'s east レ system) solidifies this acrylic resin layer 1 by the ultraviolet ray irradiation of shining about 600mJ.After this, peel off from the lamilated body that the PET film/curing acrylic resin 1/ liquid crystal material layer 1/ Kapton becomes one and peel off Kapton, the transfer printing of liquid crystal material layer on the PET film, obtained the lamilated body by the PET film/curing acrylic resin 1/ liquid crystal material layer 1 constitutes.
Again Tg=135 ℃ ultraviolet hardening acrylic adhesive 2 (Toagosei Co., Ltd's system) is coated with into the thickness of 5 μ m on the liquid crystal material layer 1 of this lamilated body as acrylic resin layer 2, triacetyl cellulose (TAC) film of laminated thereon thickness 40 μ m (film Co., Ltd. of Fuji system), by the ultraviolet ray of shining about 600mJ this acrylic resin layer 2 is solidified, obtain lamilated body (A) by the PET film/curing acrylic resin 1/ liquid crystal material layer 1/ curing acrylic resin 2/TAC film constitutes.Here, the Δ nd that peels off the lamilated body behind PET film and the TAC film is 128nm.
Then, after peeling off the PET film of this lamilated body (A), at the film of the adhesive phase of formation thickness 25 μ m on the dividing plate of thickness 38 μ m in advance of fitting on the face of curing acrylic resin 1, obtain lamilated body (B) by dividing plate/adhesive phase/curing acrylic resin 1/ liquid crystal material layer 1/ curing acrylic resin 2/TAC film constitutes.
Then, from this lamilated body (B) after liquid crystal material layer 1/ curing acrylic resin bed 2 interface peel TAC film side, bonding agent by thickness 20 μ m will fit into ゼ オ ノ ア film (ゼ オ Application Co., Ltd. system of thickness 40 μ m of the angle of hope in advance, Δ nd is 275nm) and Polarizer (Sumitomo Chemical Co's system) applying, obtain by Polarizer/adhesive phase/ゼ オ ノ ア/adhesive phase/liquid crystal material layer 1/ curing acrylic resin laminate film for optical device that 1/ adhesive phase/dividing plate constitutes.
The laminate film for optical device that obtains is cut into the square size of 5cm, dividing plate is peeled off on the soda-lime glass that is fitted in thickness 2mm, carry out carrying out following test after autoclave handles (50 ℃, 490kPa, 20 minutes).
Thermal shock test
When making the thermal shock test of 85 ℃ (30 minutes) and-40 ℃ of (30 minutes) alternate repetitions, do not see fully that the outward appearance of crackle generation etc. is unusual after 500 circulations yet.
Remake usefulness (rework) test
After the corner part that is fitted in substrate on glass gives the beginning with blade, substrate peeled remake with when test, at the interface of adhesive phase and glass hot tearing taking place peels off, do not see other the peeling off unusually of interlayer fully.
Embodiment 2
Except replacing ultraviolet hardening acrylic resin layer 2, it is surface modifier (メ ガ Off ア Star Network F472SF that 5 weight portion fluorine have been added in use, big Japanese イ Application キ Co., Ltd. system) Tg=110 ℃ ultraviolet hardening acrylic adhesive 3 (Toagosei Co., Ltd's system) in addition, make with embodiment 1 identically, obtain laminate film for optical device.
Similarly carry out thermal shock test and remake using test with embodiment 1, but do not see special unusual.
Embodiment 3
Except replacing ultraviolet hardening acrylic resin layer 2,4 weight portion silicone-based surface modifiers (ペ イ Application Star De 32 has been added in use, east レ ダ ウ コ-ニ Application グ Co., Ltd. system) Tg=105 ℃ ultraviolet hardening acrylic adhesive 4 (Toagosei Co., Ltd's system) in addition, make with embodiment 1 identically, obtain laminate film for optical device.
Similarly carry out thermal shock test and remake using test with embodiment 1, but do not see special unusual.
Embodiment 4
On the liquid crystal material layer 1 that preparation example obtains (with the face of Kapton opposition side) the ultraviolet hardening acrylic adhesive 5 (Toagosei Co., Ltd's system) of 126 ℃ of glass temperatures is coated with into the thickness of 5 μ m as acrylic resin layer 5, the laminated thereon TAC film (film Co., Ltd. of Fuji system) that in advance surface is carried out the thick 40 μ m of Corona discharge Treatment, by the ultraviolet ray irradiation of about 600mJ, this acrylic resin layer 5 is solidified.After this, by peeling off Kapton from the lamilated body that the TAC film/curing acrylic resin 5/ liquid crystal material layer 1/ Kapton becomes one, make the transfer printing of liquid crystal material layer on the TAC film, obtain lamilated body by the TAC film/curing acrylic resin 5/ liquid crystal material layer 1 constitutes.
On the liquid crystal material layer 1 of this lamilated body, Tg=54 ℃ ultraviolet curing acrylic adhesive 6 (Toagosei Co., Ltd's system) is coated with into the thickness of 5 μ m again as acrylic resin layer 6, the PET film of laminated thereon thickness 38 μ m (East Asia Co., Ltd. system), ultraviolet ray irradiation by about 600mJ, this acrylic resin layer 6 is solidified, obtain lamilated body (C) by the TAC film/curing acrylic resin 5/ liquid crystal material layer 1/ curing acrylic resin 6/PET film constitutes.
Then, after peeling off the PET film of this lamilated body (C), on the face of curing acrylic resin 6, applying has formed the film of the adhesive phase of thickness 25 μ m in advance on the dividing plate of thick 38 μ m, obtain the lamilated body (D) by dividing plate/adhesive phase/curing acrylic resin 6/ liquid crystal material layer 1/ curing acrylic resin 5/TAC film constitutes.
Then, from lamilated body (D) after the interface peel TAC film side of liquid crystal material layer 1/ curing acrylic resin 5, bonding agent by thickness 20 μ m will fit into the ゼ オ ノ ア film (ゼ オ Application Co., Ltd. system) and the Polarizer (Sumitomo Chemical Co's system) of thickness 40 μ m of the angle of hope in advance and fit, and obtain by Polarizer/adhesive phase/ゼ オ ノ ア/adhesive phase/liquid crystal material layer 1/ curing acrylic resin laminate film for optical device that 6/ adhesive phase/dividing plate constitutes.
The laminate film for optical device that obtains is cut into the square size of 5cm, dividing plate is peeled off on the soda-lime glass that is fitted in thickness 2mm, carry out autoclave and handle after (50 ℃, 490kPa, 20 minutes) and embodiment 1 similarly carries out thermal shock test and remakes with test.Its result does not see special unusual.
Embodiment 5
Except replacing ultraviolet hardening acrylic resin layer 5, it is surface modifier (サ-Off ロ Application S-386 that 6 weight portion fluorine have been added in use, セ イ ミ ケ ミ カ Le Co., Ltd. system) Tg=108 ℃ ultraviolet hardening acrylic adhesive 7 (Toagosei Co., Ltd's system) in addition, make with embodiment 4 identically, obtain laminate film for optical device.
Similarly carry out thermal shock test and remake using test with embodiment 1, but do not see special unusual.
Embodiment 6
Except replacing ultraviolet hardening acrylic resin layer 5,3 weight portion silicone-based surface modifiers (ペ イ Application Star De 29 has been added in use, east レ ダ ウ コ-ニ Application グ Co., Ltd. system) Tg=112 ℃ ultraviolet hardening acrylic adhesive 8 (Toagosei Co., Ltd's system) in addition, make with embodiment 4 identically, obtain laminate film for optical device.
Similarly carry out thermal shock test and remake using test with embodiment 1, but do not see special unusual.
Comparative Examples 1
On the liquid crystal material layer 1 that preparation example obtains (with the face of Kapton opposition side) the ultraviolet hardening acrylic adhesive 9 (Toagosei Co., Ltd's system) of 40 ℃ of glass temperatures (Tg) is coated with into the thickness of 5 μ m as acrylic resin layer 9, the polyethylene terephthalate of laminated thereon thick 50 μ m (PET) film (Co., Ltd.'s east レ system), by the ultraviolet ray irradiation of about 600mJ, this acrylic resin layer 9 is solidified.After this, peel off Kapton from the lamilated body that the PET film/curing acrylic resin 9/ liquid crystal material layer 1/ Kapton becomes one, make the transfer printing of liquid crystal material layer on the PET film, obtain lamilated body by the PET film/curing acrylic resin 9/ liquid crystal material layer 1 constitutes.
On the liquid crystal material layer 1 of this lamilated body, Tg=132 ℃ ultraviolet hardening acrylic adhesive 10 (Toagosei Co., Ltd's system) is coated with into the thickness of 5 μ m again as acrylic resin layer 10, laminated thereon triacetyl cellulose (TAC) film of having implemented the thick 40 μ m of saponification processing, ultraviolet ray irradiation by about 600mJ, this acrylic resin layer 10 is solidified, obtain lamilated body (E) by the PET film/curing acrylic resin 9/ liquid crystal material layer 1/ curing acrylic resin 10/ saponification TAC film constitutes.
Then, after peeling off the PET film of this lamilated body (E), at the film of the adhesive phase of formation thickness 25 μ m on the dividing plate of thick 38 μ m in advance of fitting on the face of curing acrylic resin 9, obtain lamilated body (F) by dividing plate/adhesive phase/curing acrylic resin 9/ liquid crystal material layer 1/ curing acrylic resin 10/ saponification TAC film constitutes.
Then, after peeling off saponification TAC film from lamilated body (F), bonding agent by thickness 20 μ m will fit into the ゼ オ ノ ア film (ゼ オ Application Co., Ltd. system) and the Polarizer (Sumitomo Chemical Co's system) of thickness 40 μ m of the angle of hope in advance and fit, and obtain by Polarizer/adhesive phase/ゼ オ ノ ア/adhesive phase/curing acrylic resin 10/ liquid crystal material layer 1/ curing acrylic resin laminate film for optical device that 9/ adhesive phase/dividing plate constitutes.
Square and the embodiment 1 that the laminate film for optical device that obtains is cut into 5cm similarly carries out thermal shock test and remakes using test.
The result of thermal shock test has produced crackle 150 circulation backs on liquid crystal material layer and curing acrylic resin.In addition, in remaking with test, at the interface of liquid crystal material layer and curing acrylic resin part takes place and peel off.
Comparative Examples 2
On the liquid crystal material layer 1 that preparation example obtains (with the face of Kapton opposition side) the ultraviolet hardening acrylic adhesive 10 (Toagosei Co., Ltd's system) of 132 ℃ of glass temperatures (Tg) is coated with into the thickness of 5 μ m as acrylic resin layer 10, laminated surface carries out triacetyl cellulose (TAC) film of the thickness 40 μ m of saponification processing in advance thereon, by the ultraviolet ray irradiation of about 600mJ, this acrylic resin layer 10 is solidified.After this, peel off Kapton from the lamilated body that saponification TAC film/curing acrylic resin 10/ liquid crystal material layer 1/ Kapton becomes one, make the transfer printing of liquid crystal material layer on saponification TAC film, obtain lamilated body by the TAC film/curing acrylic resin 10/ liquid crystal material layer 1 constitutes.
On the liquid crystal material layer 1 of this lamilated body, Tg=40 ℃ ultraviolet hardening acrylic adhesive 9 (Toagosei Co., Ltd's system) is coated with into the thickness of 5 μ m again as acrylic resin layer 9, the polyethylene terephthalate of laminated thereon thick 50 μ m (PET) film (Co., Ltd.'s east レ system), ultraviolet ray irradiation by about 600mJ, this acrylic resin layer 9 is solidified, obtain lamilated body (G) by saponification TAC film/curing acrylic resin 10/ liquid crystal material layer 1/ curing acrylic resin 9/PET film constitutes.
Then, after peeling off the PET film of this lamilated body (G), at the film of the adhesive phase of formation thickness 25 μ m on the dividing plate of thick 38 μ m in advance of fitting on the face of curing acrylic resin 9, obtain lamilated body (H) by dividing plate/adhesive phase/curing acrylic resin 9/ liquid crystal material layer 1/ curing acrylic resin 10/ saponification TAC film constitutes.
Then, after peeling off saponification TAC film from lamilated body (H), bonding agent by thickness 20 μ m will fit into the ゼ オ ノ ア film (ゼ オ Application Co., Ltd. system) and the Polarizer (Sumitomo Chemical Co's system) of thickness 40 μ m of the angle of hope in advance and fit, and obtain by Polarizer/adhesive phase/ゼ オ ノ ア/adhesive phase/curing acrylic resin 10/ liquid crystal material layer 1/ curing acrylic resin laminate film for optical device that 9/ adhesive phase/dividing plate constitutes.
Square and the embodiment 1 that the laminate film for optical device that obtains is cut into 5cm similarly carries out thermal shock test and remakes using test.
The result of thermal shock test has produced crackle 150 circulation backs on liquid crystal material layer and curing acrylic resin.In addition, in remaking with test, at the interface of liquid crystal material layer and curing acrylic resin part takes place and peel off.
Comparative Examples 3
Except replacing ultraviolet hardening acrylic resin layer 9,10, use beyond the bonding agent of Tg=52 ℃, Tg=63 ℃ respectively and Comparative Examples 1 is made identically, obtain laminate film for optical device.
The result of thermal shock test has produced crackle 250 circulation backs on liquid crystal material layer and curing acrylic resin.In addition, in remaking with test, at the interface of liquid crystal material layer and curing acrylic resin part takes place and peel off.
Comparative Examples 4
Except replacing ultraviolet hardening acrylic resin layer 9,10, use beyond the bonding agent of Tg=96 ℃, Tg=84 ℃ respectively and Comparative Examples 2 is made identically, obtain laminate film for optical device.
The result of thermal shock test has produced crackle 50 circulation backs on liquid crystal material layer and curing acrylic resin.In addition, in remaking with test, at the interface of liquid crystal material layer and curing acrylic resin part takes place and peel off.
The thermal shock test of the laminate film for optical device that embodiment 1～6 and Comparative Examples 1～4 obtain and the evaluation result that remakes with test are summarized in the table 1.
Table 1
| Thermal shock test result | Remake and use test findings | |
| Embodiment 1 | Not unusual after 500 circulations yet | Between adhesive/glass, peel off neatly |
| Embodiment 2 | Not unusual after 500 circulations yet | Between adhesive/glass, peel off neatly |
| Embodiment 3 | Not unusual after 500 circulations yet | Between adhesive/glass, peel off neatly |
| Embodiment 4 | Not unusual after 500 circulations yet | Between adhesive/glass, peel off neatly |
| Embodiment 5 | Not unusual after 500 circulations yet | Between adhesive/glass, peel off neatly |
| Embodiment 6 | Not unusual after 500 circulations yet | Between adhesive/glass, peel off neatly |
| Comparative Examples 1 | Crack 150 circulations | Part takes place between liquid crystal material layer/acrylic resin layer to be peeled off |
| Comparative Examples 2 | Crack 150 circulations | Part takes place between liquid crystal material layer/acrylic resin layer to be peeled off |
| Comparative Examples 3 | Crack 250 circulations | Part takes place between liquid crystal material layer/acrylic resin layer to be peeled off |
| Comparative Examples 4 | Crack 50 circulations | Part takes place between liquid crystal material layer/acrylic resin layer to be peeled off |
Claims (7)
1. the manufacture method of liquid crystal film is characterized in that, at least through each operation of the 1st operation, the 2nd operation and the 3rd operation and obtain,
The 1st operation: make behind liquid crystal material layer that forms on the orientation substrate, liquid crystal aligning is immobilized and releasable substrate bonding by bonding agent (1), peel off orientation substrate and make the transfer printing of liquid crystal material layer on the releasable substrate, bonding by bonding agent (2) and temporary base then, obtain lamilated body (I) thus by releasable substrate/adhesive phase (1)/liquid crystal material layer/adhesive phase (2)/temporary base formation
The 2nd operation: (I) peels off the releasable substrate from above-mentioned lamilated body,
The 3rd operation: then, make between liquid crystal material layer/adhesive phase (2) and peel off, obtain the liquid crystal film that constitutes by adhesive phase (1)/liquid crystal material layer.
2. the manufacture method of liquid crystal film is characterized in that, at least through each operation of the 1st operation, the 2nd operation and the 3rd operation and obtain,
The 1st operation: make after the liquid crystal material layer that forms on the orientation substrate, liquid crystal aligning is immobilized and temporary base are bonding by bonding agent (1), peel off orientation substrate and make the transfer printing of liquid crystal material layer on temporary base, then by bonding agent (2) and releasable substrate bonding, obtain lamilated body (II) thus by temporary base/adhesive phase (1)/liquid crystal material layer/adhesive phase (2)/releasable substrate formation
The 2nd operation: (II) peels off the releasable substrate from above-mentioned lamilated body,
The 3rd operation: then, make between adhesive phase (1)/liquid crystal material layer and peel off, obtain the liquid crystal film that constitutes by liquid crystal material layer/adhesive phase (2).
3. the manufacture method of liquid crystal film according to claim 1 and 2, it is characterized in that, the liquid crystal material layer that liquid crystal aligning is immobilized is made of the high molecule liquid crystal material that becomes vitreousness in the temperature generation liquid crystal aligning more than the liquid crystal tr pt and the temperature below the liquid crystal tr pt.
4. the manufacture method of liquid crystal film according to claim 1 and 2 is characterized in that, the liquid crystal material layer that liquid crystal aligning is immobilized is to make low molecular weight liquid crystal material behind the liquid crystal aligning carry out photo-crosslinking or heat cross-linking and the liquid crystal material layer that forms.
5. the manufacture method of liquid crystal film according to claim 1 and 2 is characterized in that, temporary base or releasable substrate have the isotropy of optics.
6. the manufacture method of liquid crystal film according to claim 1 and 2 is characterized in that, the surface modifier that contains silicone-based or fluorine system with the bonding bonding agent of temporary base is formed.
7. laminate film for optical device, it is the liquid crystal film made from the method for putting down in writing in each of claim 1～6, by bonding agent or bonding agent and Polarizer or polarizer is laminated forms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007019439A JP2008183812A (en) | 2007-01-30 | 2007-01-30 | Manufacturing process of liquid crystal film and lamination film for optical device |
| JP2007019439 | 2007-01-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101408638A true CN101408638A (en) | 2009-04-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008101785916A Pending CN101408638A (en) | 2007-01-30 | 2008-01-30 | Process for producing a liquid crystal film and laminate film for optical device |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2008183812A (en) |
| KR (1) | KR20080071503A (en) |
| CN (1) | CN101408638A (en) |
| TW (1) | TW200843959A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103959152A (en) * | 2011-11-29 | 2014-07-30 | 日产化学工业株式会社 | Method for manufacturing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element |
| CN105229503A (en) * | 2013-05-21 | 2016-01-06 | 富士胶片株式会社 | Polaroid and manufacture method thereof and optical film material |
| CN105229504A (en) * | 2013-05-21 | 2016-01-06 | 富士胶片株式会社 | Polaroid and manufacture method thereof and transfer materials |
| CN103959152B (en) * | 2011-11-29 | 2016-11-30 | 日产化学工业株式会社 | The manufacture method of liquid crystal orientation film, liquid crystal orientation film and liquid crystal display cells |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103748488B (en) * | 2011-08-19 | 2016-04-06 | Lg化学株式会社 | Polarizer |
| JP2014182217A (en) * | 2013-03-18 | 2014-09-29 | Fujifilm Corp | Optical film material |
| JP2014182311A (en) * | 2013-03-19 | 2014-09-29 | Fujifilm Corp | Polarizing plate and method for manufacturing the same |
| WO2015016297A1 (en) * | 2013-08-01 | 2015-02-05 | 富士フイルム株式会社 | Production method for polarizing plate |
| JP2015079230A (en) | 2013-09-10 | 2015-04-23 | 住友化学株式会社 | Manufacturing method for laminate |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4298846B2 (en) * | 1999-06-07 | 2009-07-22 | 新日本石油株式会社 | Method for producing polarized diffractive cholesteric liquid crystal film |
| JP2004117522A (en) * | 2002-09-24 | 2004-04-15 | Nippon Oil Corp | Method for manufacturing liquid crystal film and elliptic polarizing plate |
| JP2004133152A (en) * | 2002-10-10 | 2004-04-30 | Nippon Oil Corp | Transferable liquid crystal laminate |
| JP2004138697A (en) * | 2002-10-16 | 2004-05-13 | Nippon Oil Corp | Method for manufacturing liquid crystal film and elliptically polarizing plate |
| JP4079748B2 (en) * | 2002-10-22 | 2008-04-23 | 大阪シーリング印刷株式会社 | Liquid crystal laminate and liquid crystal laminate continuum |
| JP2004226756A (en) * | 2003-01-23 | 2004-08-12 | Nippon Oil Corp | Method for manufacturing optical layered body, and elliptically polarizing plate, circularly polarizing plate and liquid crystal display comprising the layered body |
-
2007
- 2007-01-30 JP JP2007019439A patent/JP2008183812A/en active Pending
-
2008
- 2008-01-28 TW TW097103153A patent/TW200843959A/en unknown
- 2008-01-29 KR KR1020080008889A patent/KR20080071503A/en not_active Application Discontinuation
- 2008-01-30 CN CNA2008101785916A patent/CN101408638A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103959152A (en) * | 2011-11-29 | 2014-07-30 | 日产化学工业株式会社 | Method for manufacturing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element |
| CN103959152B (en) * | 2011-11-29 | 2016-11-30 | 日产化学工业株式会社 | The manufacture method of liquid crystal orientation film, liquid crystal orientation film and liquid crystal display cells |
| CN105229503A (en) * | 2013-05-21 | 2016-01-06 | 富士胶片株式会社 | Polaroid and manufacture method thereof and optical film material |
| CN105229504A (en) * | 2013-05-21 | 2016-01-06 | 富士胶片株式会社 | Polaroid and manufacture method thereof and transfer materials |
| US9671539B2 (en) | 2013-05-21 | 2017-06-06 | Fujifilm Corporation | Polarizing plate comprising an optical film including an alignment layer, an anisotropic layer, and an isotropic acrylic polymer layer and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200843959A (en) | 2008-11-16 |
| JP2008183812A (en) | 2008-08-14 |
| KR20080071503A (en) | 2008-08-04 |
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