CN1571931A - Method for producing liquid crystal film and elliptically polarizing plate - Google Patents
Method for producing liquid crystal film and elliptically polarizing plate Download PDFInfo
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- CN1571931A CN1571931A CNA028205952A CN02820595A CN1571931A CN 1571931 A CN1571931 A CN 1571931A CN A028205952 A CNA028205952 A CN A028205952A CN 02820595 A CN02820595 A CN 02820595A CN 1571931 A CN1571931 A CN 1571931A
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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
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
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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
- G02B5/3016—Polarising elements involving passive liquid crystal elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0079—Liquid crystals
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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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
Abstract
A liquid crystal substance layer with fixed liquid crystal alignment on an alignment substrate is made to stick to a releasable substrate composed of a uniaxial stretched polyester film via an adhesive. Subsequently the liquid crystal substance layer is transferred to the releasable substrate by releasing the alignment substrate and subsequently the liquid crystal film is manufactured by releasing the releasable substrate therefrom so as to provide a method for manufacturing a liquid crystal film made to be a thin film without a supporting substrate film which satisfies mechanical strength required in manufacturing and excellent release property and facilitates optical inspection of defect.
Description
Technical field
The present invention relates to the method that a kind of preparation can advantageously be applied to the liquid crystal film and the elliptical polarized light device of various optical device.
Background technology
The film that forms by one deck orientation liquid-crystal compounds, especially have the liquid crystal material formed film of fixing orientation to row or twisted nematic structure, demonstrate good performance as the color of liquid crystal display device and visual angle compensating element, or as the optically-active optical element, and help to strengthen the performance of various display devices and reduce its weight.Japan's publication has proposed to prepare the method for this film for 4-57017 number and 4-177216 number, and one deck liquid crystal material that wherein will be formed on the alignment substrates is transferred to a translucent substrate as supporting substrates.In order to satisfy durability test at the desired strictness of liquid crystal display device, and further reduce its thickness and weight, Japanese publication proposes a kind of preparation is constituted and do not had the optical element of supporting substrates film by liquid crystal material layer method for 8-278491 number.
In the method, be formed on the alignment substrates and one deck liquid crystal material of orientation by adhesive transfer to peelable substrate, peel off described layer from described peelable substrate subsequently, make an optical element that constitutes by liquid crystal material layer but do not have the supporting substrates film thus.Because require physical strength and good rippability, so except there are coating siloxane or fluorine resin or other surface-treated optical isotropy film of process in the surface, employed peel-able film is restricted to usually and has anisotropic film in this method, for example biaxial stretch-formed polyester and biaxial stretch-formed polypropylene.
These optically isotropic film types seldom, and resistant property is very poor, for example rippability, heat impedance, intensity and film thickness, and these all characteristics all are that the preparation liquid crystal material layer is necessary.In addition, most of film is also very expensive.On the other hand, different with described optics same sex film, biaxial stretch-formed optically anisotropic peelable substrate has very big range of choice and has enough serviceable life.But when detecting the liquid crystal material layer on the peelable substrate in preparation process, because birefringent influence, the problem such as optical defect such as foreign matter and luminous point and irregular colour developing that is comprised in the liquid crystal material layer can appear being difficult to detect.In these cases, utilize traditional peel-able film just can not realize to the detection of optical defect and good rippability.
Summary of the invention
Consider the problems referred to above, the purpose of this invention is to provide a kind of method that need not the liquid crystal film of supporting substrates film of preparation, wherein detection optical defective and obtaining good stripping performance when peelable substrate film is peeled off liquid crystal material layer easily.Broad research and investigation through at this purpose have obtained the present invention based on following discovery: promptly use the uniaxial tension mylar can satisfy desired good stripping performance and physical strength when preparing, and be convenient to the detection of optical defect.
According to a first aspect of the invention, a kind of method for preparing liquid crystal film is provided, wherein this method comprises: by bonding agent one liquid crystal material layer is combined with a peelable substrate that is formed by the uniaxial tension mylar, described liquid crystal material layer has an alignment structure of fixing and is formed on the alignment substrates; By peeling off described alignment substrates, described liquid crystal material layer is transferred to described peelable substrate; And peel off described peelable substrate from described liquid crystal material layer.
According to a second aspect of the invention, a kind of method for preparing the elliptical polarized light device is provided, wherein this method comprises: by bonding agent one liquid crystal material layer is combined with a peelable substrate that is formed by the uniaxial tension mylar, described liquid crystal material layer has an alignment structure of fixing and is formed on the alignment substrates; By peeling off described alignment substrates, described liquid crystal material layer is transferred to described peelable substrate; And after peeling off described peelable substrate, a polarizer is attached on the described liquid crystal material layer.
Aspect of the present invention first and second, described uniaxial tension polyester is preferably by polyethylene terephthalate or by forming with the polyester of polyethylene terephthalate as principal ingredient.
Below the present invention will be described in more detail.
Liquid crystal material layer employed in the present invention, that have fixing alignment structure is to obtain by fixing an orientation liquid crystal material with any suitable fixing means.The example of described fixing means comprises: the polymerized liquid crystal material that is in the orientation state is quenched so that make it to be in glassy state, and fixed; Low-molecular-weight liquid crystal material or polymerized liquid crystal material with reactive functional groups are by reacting (promptly solidifying and crosslinked described functional group) by orientation and fixing.
The example of described reactive functional groups comprises vinyl, (methyl) acryloyl group, ethyleneoxy, epoxy radicals, oxetanyl (oxetane), carboxyl, hydroxyl, amino, isocyanate group and anhydride group, and wherein each can the suitable manner reaction.
The liquid crystal material that can be used as described liquid crystal material layer can be selected from very large-scale material, no matter and whether they are low-molecular-weight liquid crystal material or polymerized liquid crystal material according to liquid crystal film and preparation method's application target.But preferably use polymerized liquid crystal material.The molecular shape of liquid crystal material can be shaft-like or plate-like.For example, liquid crystal material can be to have discoid discoid nematic (disco-nematic) liquid-crystal compounds to row (discotic-nematic) liquid crystals.
The example of the liquid crystal phase of described liquid crystal material layer before fixing comprises: nematic phase, twisted nematic phase, cholesterol phase, mixing nematic phase (hubrid nematic), mixing twisted nematic phase, discoid nematic phase and smectic phase.
Polymerized liquid crystal material can be various backbone chain type polymerized liquid crystal materials, side chain type polymerized liquid crystal material and composition thereof.The example of described backbone chain type polymerized liquid crystal material comprises polyester-based, polyamide-based, polycarbonate-base, polyimide-based, polyurethanes, polybenzimidazoles base, polybenzoxazole base, polybenzothiozole base, poly-azomethine, polyesteramide base, polyestercarbonate base and polyester-imide base polymerized liquid crystal material and composition thereof.The example of side chain type polymerized liquid crystal material comprises that those are attached to as side chain with mesomorphic group (mesogen group) and have straight chain or ring main chain, for example polyacrylate based, polymethacrylate base, polyvinyl, polysiloxane group, polyether-based, poly-malonate (polymalonate) base and polyester-based material and composition thereof.In these materials, polyester-based backbone chain type polymerized liquid crystal material is preferred, its objective is synthetic easily and orientation.
The combinations of low molecular weight liquid crystals examples of material comprises: by above-mentioned reactive functional groups being introduced a compound (for example saturated benzoic acid, unsaturated benzoic acid, biphenyl carboxylic acids (biphenylcarboxylicacid), aromatics oxygen yl carboxylic acid (aromatic oxycarboxylic acid), Schiff bases (schiffbases), the bisdiazo methylidyne compound, azo-compound, azoxy compound, cyclohexane ester compounds or sterol compound) end obtain, show the compound of liquid crystals; And by adding the complex that crosslinkable compound obtains to the above any compound of selecting that shows liquid crystals.The example of collar plate shape (discotic) liquid-crystal compounds comprises benzo phenanthryl and three polyindenes (truxene) based compound.
Alternately, the various compounds that have functional group or have a reactive site that utilizes the light and heat cross-linking reaction can be mixed into the degree that can not suppress the liquid crystals appearance with liquid crystal material.The example of this crosslinkable functionality comprises various aforesaid reactive functional groups.
The complex that comprises above-mentioned liquid crystal material and the various compounds that add with molten state or solution form as required is coated on the alignment substrates, so that form a thin layer, and subsequent drying and heating, thereby with the liquid crystal aligning orientation.If desired, fix this orientation orientation by said fixing method, for example rayed and/or thermal treatment (polymerized/cross-linked), formation has the fixedly liquid crystal material layer of liquid crystal aligning thus.
Can dissolve among the present invention employed liquid crystal material or complex and can evaporate under optimum conditions as long as be used for preparing the solvent that is coated in the solution on the alignment substrates, then this solvent be had no particular limits.The preferred embodiment of this solvent is ketone (for example acetone, butanone and an isophorone); Ether alcohol (for example butoxyethyl group alcohol, own ethoxy-ethanol and methoxyl-2-propyl alcohol); Glycol ether (for example glycol dimethyl ether and diethylene glycol dimethyl ether); Ester (for example ethyl acetate, acetate methoxy-propyl ester and ethyl lactate); Phenols (for example phenol and chlorophenol); Acid amides (comprising N, dinethylformamide, N,N-dimethylacetamide and N-Methyl pyrrolidone); Halogenated hydrocarbons (for example methenyl choloride, tetrachloroethane and dichloro-benzenes) and composition thereof.Can be for this solution adds surfactant, defoamer or levelling agent, so that on alignment substrates, form uniform thin layer.In addition, for painted, dichroic dyestuff, normal dyestuff and pigment can also be added to can not prevent that liquid crystal material from showing the degree of liquid crystals.
As long as can keep the homogeneity of thin layer, then need not coating method is limited again.Therefore can use any traditional method, for example roller coating, mouthful pattern coating, dip coated, curtain coating and spin coating method.Can be to remove the step of desolvating after the described coating, it be dry for example to utilize well heater or hot-air blower.The film thickness of described coating when drying regime is 0.1 μ m-50 μ m, is preferably 0.2 μ m-20 μ m.Depart from the film thickness of described scope will be no longer by preferably, reason is the very poor and fully orientation aspect optical performance characteristics of thus obtained liquid crystal material layer.
Therefore if desired, after forming the liquid crystal aligning structure, liquid crystal material can heat-treat.In this heat treatment process, liquid crystal material is heated to this material and is in the temperature range of liquid crystal phase, so that the regiospecific that utilizes himself is with the liquid crystal aligning orientation.Therefore heat treated top condition and finite value can not be determined very for certain owing to can change according to the liquid crystal phase characteristic temperature (transition temperature) of use liquid crystal material.Yet, this thermal treatment normally 10 ℃ to 300 ℃, preferably in 30 ℃ to 250 ℃ temperature range, carry out.If temperature is too low, the orientation of liquid crystal material can not fully be carried out; And temperature is too high, and liquid crystal material will decompose or alignment substrates will be adversely affected.Described thermal treatment was carried out 3 seconds to 60 minutes, preferably 10 seconds to 30 minutes usually.Be shorter than then not preferred thermal treatment in 3 seconds, this is because liquid crystal material might not finished orientation.And be longer than 60 minutes thermal treatment equally no longer by preferably, reason is can seriously reduce throughput rate like this.At liquid crystal material by thermal treatment with liquid crystal aligning after the complete orientation, on an alignment substrates, fix this liquid crystal material layer with the method for the liquid crystal material that is suitable for described use.
The example of alignment substrates comprises the film of following material, for example polyimide, polyamide, polyamidoimide, polyphenylene sulfide, polyphenylene oxide, polyetherketone, polyetheretherketone, polyethersulfone, polysulfones, polyethylene terephthalate, Polyethylene Naphthalate, polyarylate, triacetyl cellulose, epoxy resin and phenolics.
Some described films even be not used to provide the processing of regiospecific, can be that liquid crystal material used in the present invention shows sufficient regiospecific according to film-forming method also.But if a film does not have sufficient regiospecific or do not have regiospecific at all, this film can be stretched under the proper heat treatment operation; Carry out friction treatment, wherein utilize Artificial Fibers cloth this film that in a direction, rubs, perhaps this film of friction after forming the both alignment layers that constitutes by traditional orientation agent (for example polyimide, polyvinyl alcohol (PVA) or silane coupling agent) above this film; Perhaps the combination operation of above these processing has regiospecific so that make it.
Alternately, described alignment substrates can be the sheet metal of aluminium, iron or copper one-tenth and the various glass plates that rule of surface ground is formed with little raceway groove.
The described liquid crystal material layer that is formed on the alignment substrates utilizes bonding agent to combine with a peelable substrate that is formed by the uniaxial tension mylar.
As long as bonding agent of the present invention satisfies following condition, and the present invention does not have other special restriction again to this bonding agent: promptly described bonding agent should have the cohesiveness that enough is adhered to liquid crystal material layer and peelable substrate (being the uniaxial tension mylar); The uniaxial tension mylar is peeled off with liquid crystal material layer in technology subsequently; And the optical property that can not damage liquid crystal material layer.For example, bonding agent can be acrylic resin base, methacrylic resin base, epoxy resin-matrix, ethylene vinyl acetate copolymer base, rubber-based, urethane groups, polyvinylether based adhesive and composition thereof; With various for example thermohardening types and/or light-cured type and electronic radiation solidifying type reactive adhesive.Some described bonding agents have the effect as the protective clear layer of protection liquid crystal material layer.Tacky adhesion can be used as described bonding agent.
Reaction conditions, promptly be used to solidify the reaction conditions of described reactive adhesive and change according to composition, viscosity and the temperature of reaction of this bonding agent.Therefore, described reactive adhesive can solidify under the condition of suitable selection.For example, the light reaction that Photocurable pressure-sensitive adhesive can mix and utilize a light source to send with various known light triggers, this light source for example has metal halide lamp, high-pressure sodium lamp, low pressure mercury lamp, xenon lamp, arc discharge lamp, laser instrument and synchrotron radiation light source.In total radiation, unit area (1cm
2) radiant quantity usually in the scope of 1 to 2,000 milli burnt (mJ), preferably at 10 millis burnt (mJ) in the scope of 1,000 milli burnt (mJ).But, when the absorption region of light trigger is different from the frequency spectrum of light source fully or compound of reaction self can absorb light time in the described optical source wavelength, described radiation need not to be limited in the above-described scope.In these cases, can use a kind of following method, wherein can use suitable photosensitizer or two or more types and light trigger that have the absorbing wavelength that differs from one another.Electronic radiation solidifying type bonding agent can be generally 10kV to 200kV, preferably 50kV is cured under the accelerating potential of 100kV.
The thickness of described bonding agent changes according to its applied element, intensity and temperature, but is generally 1 to 50 μ m, is preferably 3 to 30 μ m.Thickness outside this scope will be no longer by preferably, this is because bond strength is not enough and bonding agent can ooze out from the edge of the layer that is applied with this bonding agent.
Alternately, for the control optical property, can add various particulates for these bonding agents, the degree of interpolation is advisable with the performance of not damaging this bonding agent.The example of this particulate comprise those have with the compound that constitutes this bonding agent different refractive index particulate, be used to improve antistatic property and the particulate that do not damage the electrically conductive particles of transparency and be used to improve wearing quality.Example has silica microparticle, ITO (tin indium oxide indium tin oxide) particulate, silver-colored particulate and various synthetic resin particulate more specifically.Can also be that in addition this bonding agent adds the adjuvant of various for example antioxidant and ultraviolet absorbers etc., the degree of interpolation is advisable with the effect of not damaging the present invention and being obtained.
Making peelable substrate used in this invention is the uniaxial tension mylar.Composition to this film is also without particular limitation.Yet preferred film be its 80% or the repetitive of more molar percentages be ethylene terephthalate or 2,6-naphthalenedicarboxylic acid second diester.The example of other copolymer composition comprises the dicarboxylic acid component, for example isophthalic acid, p-β-oxygen base oxethyl benzoic acid, 4,4 '-biphenyl dicarboxylic acid (4,4 '-dicarboxydiphenyl), 4,4 '-benzophenone dicarboxylic acid, two (4-carboxy phenyl) ethane, hexane diacid, decanedioic acid, 5-sulfoisophthalic acid sodium and 1,4-dicarboxyl cyclohexane; And diol component, for example ethylene oxide adduct of propylene glycol, butylene glycol, neopentyl glycol, diglycol, cyclohexanediol, bisphenol-A, polyglycol, polypropylene glycol and polytetramethylene glycol.
If desired, can be used in combination two or more described dicarboxylic acid component or diol component.In addition, hydroxycarboxylic acid (oxycarboxylic acid) (for example p-oxybenzene formic acid) can be used in combination with described dicarboxylic acid component or diol component.In addition, mylar can comprise the compound comprising smallest number amido link, urethane bond, ehter bond and carbonic acid ester bond.
The manufacture method of polyester can be any means, for example the direct polymerization that is directly reacted with glycol by aromatic dicarboxylic acid and make dimethyl ester in the aromatic dicarboxylic acid and the ester interchange reaction method of diol replaces.
The peeling force of peelable substrate can not accurately determine, this is because promptly use identical materials to make substrate, described peeling force also can according to its manufacture method, surface appearance and and bonding agent between wettable change.Yet at the adhesive interface place, the peeling force of peelable substrate (peel off for 180 °, 30cm/ minute peeling rate at room temperature detects) is generally 0.38-12N/m, is preferably 0.38-8.0N/m.The state of peeling off that peeling force can not obtain at required interface less than the peelable substrate of 0.38N/m and can not transmit liquid crystal material layer fully, this is because when therefrom peeling off alignment substrates again after liquid crystal material layer is attached on the peelable substrate, because more weak peeling force, peelable substrate can part raise up from liquid crystal material layer.And peeling force will make liquid crystal material layer break greater than the peelable substrate of 12N/m or can not be stripped from down from required interface.
In order to adjust the rippability of peelable substrate, can add lubricant.Optical defect detects and rippability as long as can have influence on sharply, the restriction that the kind and the quantity of lubricant is not had other.The object lesson of this lubricant comprises silica flour and alumina powder.The addition of this lubricant is selected such that the haze value (haze value) of peelable substrate is generally 50% or littler, is preferably 30% or littler.Haze value will have influence on the detection of optical defect unfriendly greater than 50% peelable substrate.
Replacedly, if desired, described peelable substrate can comprise various known additives, for example anti blocking agent, antioxidant, antistatic agent, thermal stabilizer and impact strength modifier.
For example, described uniaxial tension polyester makes by following method: utilize expander cross directional stretch under being equal to or higher than the temperature of glass transformation temperature to heat subsequently and fix described polyester by melting and pushing the non-orientation polyester of any sheet shape that obtains in the above-mentioned polyester.
Preparation method according to liquid crystal film of the present invention is characterised in that described method comprises: make a liquid crystal material layer attached on the peelable substrate that is formed by the uniaxial tension mylar by bonding agent, described liquid crystal material layer has an alignment structure that is fixed on the alignment substrates; By peeling off described alignment substrates, described liquid crystal material layer is transferred to described peelable substrate; And peel off described peelable substrate from described liquid crystal material layer.
Except using the peelable substrate that forms by the uniaxial tension mylar, described method there is not other special restriction.For example, liquid crystal film can be made by following method:
At first, after utilizing appropriate method to be formed on a liquid crystal material film on one alignment substrates and then removing solvent if desired, heat this film, utilize the various modes that are suitable for liquid crystal material to fix this film subsequently so that finish orientation.After this, adhesive phase is formed on the liquid crystal material layer and/or uniaxial tension mylar (can peel off substrate) with fixing alignment structure, so that utilize this bonding agent in conjunction with described liquid crystal material layer and peelable substrate.Promptly solidify back (if necessary) in the adhesive phase reaction, peel off described alignment substrates.
Like this, the liquid crystal material layer with fixing alignment structure can be transferred to described peelable substrate.In the present invention,, peel off described uniaxial tension mylar, obtain liquid crystal film thus by after utilizing bonding agent liquid crystal material layer to be attached to obtain laminated product on the formed peelable substrate by the uniaxial tension mylar.Promptly made liquid crystal film by this way.
In the middle of manufacture process, promptly can easily detect the optical defect that is formed on the liquid crystal material film on the peelable substrate that is obtained.
In addition, peel off the uniaxial tension mylar and neither can cause liquid crystal material layer to break, also can not relate to the sur-face peeling of not expecting, can obtain good stripper surface thus owing to peeling off defective.
Method to the detection optical defective is also without particular limitation.For example, can carry out the detection of optical defect like this: make the ground orientation that overlaps each other of two thin slice polarizers,, between this polarizer, be placed with the laminated product that uniaxial tension mylar and liquid crystal material layer form so that make its extinction axle orthogonal; From bottom irradiation white light; Visual observation or by the automatic polarizer surface of observation top of line camera (linecamera).Because according to the delay (being the product of the thickness of birefringence and liquid crystal material layer) of liquid crystal material layer, the extinction axle of polarizer need not orthogonal, so polarizer can orientation become make its extinction axle to intersect at any angle, so that the optical defect detection.
To obtain the liquid crystal material laminar surface of liquid crystal film in order protecting, a protective clear layer can be set thereon, perhaps surface protective film of lamination on liquid crystal material layer.This protective clear layer or surface protective film can be formed by any of above-mentioned bonding agent.
In the present invention, can prepare the elliptical polarized light device by the following method equally: utilize bonding agent that one liquid crystal material layer is combined with a peelable substrate that is formed by the uniaxial tension mylar, described liquid crystal material layer has an alignment structure of fixing and is formed on the alignment substrates; By peeling off described alignment substrates, described liquid crystal material layer is transferred to described peelable substrate; Peel off described peelable substrate, obtain a liquid crystal film thus; And on this liquid crystal film lamination one polarizer.
Which surface laminated polarizer on this liquid crystal film is also without particular limitation.Therefore, polarizer can be laminated to surface of having peeled off alignment substrates or the surface of having peeled off peelable substrate.Preparation can at random be selected according to its application and production technology attached to the surface of the polarizer on the liquid crystal film.
Elliptical polarized light device of the present invention can also comprise one or more anti-reflecting layers, anti-layer, hard membrane layer and the light diffusion layer of dazzling except polarizer and liquid crystal film.To being used for the bonding agent of combination or lamination polarizer, then there is not other special restriction as long as belong to a luminosity (optical grade).For example can use any one that from above-mentioned bonding agent, select.
As long as can realize purpose of the present invention, then employed polarizer in the elliptical polarized light device of the present invention be there is no other special restriction.Therefore can use any traditional polarizer that is used for liquid crystal display device.The film-type polarizer of preferred polarizer for designing and put on market recently.More specifically, described polarizer can be selected from the basic polarizing film of PVA (polyvinyl alcohol (PVA)), for example PVA and part acetal PVA; Polarizing film comprises the partly-hydrolysed product of ethylene vinyl acetate copolymer and absorbs iodine and dichroic dyestuff for example by the stretching hydrophilic polymer film; Polarizing film is the film of polyenoid orientation (polyene-orientation) for example, for example the dechlorination product of the dehydration product of PVA and Polyvinylchloride.Alternately can use the reflection-type polarizer.
These polarizers can use separately or be used in combination with a surface or two lip-deep protective clear layers of being arranged on polarizer, so that strengthen intensity, moisture resistance and heat impedance.The example of protective clear layer is included on the polarizer by protective clear layer direct or that utilize adhesive phase, laminated transparent plastic material film (for example polyester and tri acetyl cellulose) to form; Coated resin bed; And acrylic or epoxy radicals light-cured type resin bed.When two surfaces of polarizer all were coated with protective seam, described protective seam can be identical, also can be different.
Alternately, in above-mentioned preparation process, can be before or after peeling off the uniaxial tension mylar, by lamination or in conjunction with liquid crystal film and other optically anisotropic film, can peel off this mylar subsequently if desired, thereby obtain various optical elements with liquid crystal film.
Even under the situation of liquid crystal film as an element of described optical element, before described liquid crystal film is laminated to an optically anisotropic film, also can be easily for being formed on the liquid crystal material layer detection optical defective on the uniaxial tension mylar.
In addition, if desired, can be on described optical element some described various films of lamination and layer.Can use the described liquid crystal material layer of tacky adhesion/adhesive lamination, so that described liquid crystal material layer is faced with each other.
Have in the various optical elements of liquid crystal material film of the present invention at these, have optical element that fixing nematic phase or twisted nematic be orientated mutually as the optical delay film, and can be used as the compensating plate of STN, TN, OCB or HAN emission type or reflective type liquid crystal display device.Have polarisation emission film, reflective color filters that the liquid crystal film of fixing cholesteric or dish shape orientation can strengthen as brightness and various Security elements and the decorative film who realizes catoptrical tonal variation according to visual angle owing to select to reflect.Optical element with fixing nematic phase hybrid orientation can be used as from forward observation realizes that promptly the optical delay film that postpones or wavelength plate and the visual angle that obtains the TN type LCD of asymmetrical characteristic owing to length of delay direction (inclination of molecular axis) improve film.In addition, the optical element with 1/4 wavelength plate and polarizer function can be used as elliptical polarized light device and the antireflection light filter that is used for reflective type liquid crystal display device and electroluminescence (EL) display device.
Industrial applicibility
Because the uniaxial tension polyester is as peelable substrate, the present invention can easily realize convenient optical defect (for example foreign matter) and luminous point and the irregular colour developing that comprises in the liquid crystal material layer that detect; Good stripping performance in the time of also can obtaining to peel off easily, and this point has been found that it is to utilize traditional peelable substrate to be difficult to realize.
Embodiment
The present invention will be described with following examples, but the present invention should not be interpreted as only being limited to this.
Embodiment 1
In nitrogen atmosphere, utilize 50mmol terephthalic acids, 50mmol 2, the methylhydroquinone diacetate of 6-naphthalenedicarboxylic acid (2,6-naphthalene dicarboxylic acid), 40mmol, the catechol diacetate esters (catecholdiacetate) of 60mmol and 60 milligrams N-methylimidazole carry out 12 hours polycondensation reaction under 270 ℃ of temperature.The reaction product that is obtained is dissolved in the tetrachloroethane, utilizes methyl alcohol to be precipitated so that purify subsequently again, thereby obtains the liquid crystal polyester (polymkeric substance 1) of 14.7g.This polymkeric substance 1 finds to have the logarithmic viscosity number of 0.17dl/g when measuring in the mixed solvent of the phenol/tetrachloroethane under 30 ℃ (mass ratio is 6/4), and this polymkeric substance 1 embodies the nematic phase that liquid crystal phase has.What be confirmed equally is, utilizes differential scanning calorimeter (DSC) to measure transition temperature between the described isotropic phase-liquid crystal phase that is obtained and glass transition temperature and is respectively 250 ℃ or higher and 115 ℃.
Make the biphenyl dimethyl chloride (biphenyldicarbonyl chloride) of 90mmol, the paraphthaloyl chloride (terephthaloyl chloride) of 10mmol and the S-2-methyl isophthalic acid of 105mmol, (S-2-methyl-1 4-butanediol) at room temperature reacted 20 hours in methylene chloride the 4-butylene glycol.The reaction solution that is obtained inserted in the methyl alcohol precipitate again, thereby obtain the liquid crystal polyester (polymkeric substance 2) of 12.0g so that purify.The logarithmic viscosity number of this polymkeric substance 2 is 0.12dl/g.
The polymkeric substance 1 of 19.82g and the polymkeric substance 2 of 0.18g are dissolved in the N-N-methyl-2-2-pyrrolidone N-of 80g, prepare solution thus.It is one that produced by E.I.Du Pont Company and utilized on the Kapton " KAPTON " that the Artificial Fibers cloth repeated friction crosses that described solution is spin-coated on.Dry described coating solution is so that remove wherein solvent, and subsequently 210 ℃ of heating 20 minutes down, forms a twisted nematic orientation texture thus.Described film is cooled to room temperature so that solidify described twisted nematic orientation texture, and it is consistent and have a liquid crystal material layer (liquid crystal material layer 1) of 3.0 μ m actual (real) thickness to obtain orientation thus on described Kapton.Described thickness utilizes contact pilotage type thickness instrumentation amount to obtain.
Described liquid crystal material layer 1 (with described Kapton facing surfaces) go up coating can from commercial acquisition by Toagosei Co., Ltd. produces, thickness is the UV curing adhesive " UV-3400 " of 5 μ m.Lamination one thickness is uniaxial tension polyethylene terephthalate (PET) film of 38 μ m on described bonding agent, and this film is as peelable substrate; Use the ultraviolet radiation of about 600 millis burnt (mJ) subsequently, so that solidify described bonding agent.From the laminated product that described uniaxial tension PET film/adhesive phase/liquid crystal material layer 1/ Kapton is formed, peel off described Kapton subsequently, so that liquid crystal material layer 1 is transferred to described peelable substrate, be uniaxial tension PET film, obtain liquid crystal film laminated product 1 thus.
In order to check the optical defect in the liquid crystal film laminated product 1, two thin slice polarizers are placed with overlapping each other, so that make its extinction axle orthogonal; Making size is that 14 inches liquid crystal film laminated product 1 is arranged between the described polarizer, so that make the draw direction of described single axle drawn membrane and the extinction axle or the light-emitting axis of one of them polarizer be in same direction.In addition, the rayed of sending from a white light fluorescence light source and is carried out visual observation from the polarizer that is positioned at the top to the polarizer that is positioned at the below, so as to detect whether for example peculiar material is arranged in the liquid crystal film laminated product 1, scar or similarly defective exist.
The result is verified, can not be subjected to detect defective under the birefringent situation about influencing of uniaxial tension PET film.More than needed for 11 seconds and finish detection to liquid crystal film laminated product 1.
Comparative example 1
Be different from embodiment 1, can from commercial acquisition, thickness is 5 μ m and by ToagoseiCo., the adhesive phase of the UV curing adhesive " UV-3400 " that Ltd. produces is formed on by repeating on the liquid crystal material layer 1 (with described Kapton facing surfaces) that the step identical with embodiment 1 obtain.
On described adhesive phase lamination one can from commercial acquisition, thickness is 35 μ m and by Toray Industries, the biaxial stretch-formed PET film " S10 " that Inc. produces, this film is as peelable substrate.Shine described laminated product with the ultraviolet ray that is about 600 millis burnt (mJ), so that solidify described bonding agent.From the laminated product that described biaxial stretch-formed PET film/adhesive phase/liquid crystal material layer 1/ Kapton is formed, peel off described Kapton subsequently, so that liquid crystal material layer is transferred to described biaxial stretch-formed PET film, obtains liquid crystal film laminated product 2 thus.
In order to check the optical defect in the liquid crystal film laminated product 2, two thin slice polarizers are placed with overlapping each other, so that make its extinction axle orthogonal; Making size is that 14 inches liquid crystal film laminated product 2 is arranged between the described polarizer.In addition, the rayed of sending from a white light fluorescence light source and is carried out visual observation from the polarizer that is positioned at the top to the polarizer that is positioned at the below, so as to detect whether for example peculiar material is arranged in the liquid crystal film laminated product 2, scar or similarly defective exist.
As a result,, be difficult to detect defective, therefore do not detect owing to be subjected to the birefringent influence of biaxial stretch-formed PET film.
Even the angle of the crossing of the axle of two polarizers changes or changed by the orientation axle of liquid crystal material layer 1 and the formed angle of extinction axle of polarizer,, therefore still be difficult to detect defective owing to can not eliminate the interference that birefringence brings.
Embodiment 2
The tacky adhesive layer 1 that thickness is about 25 μ m and has an independent film is laminated on the exposed liquid crystal material laminar surface of the liquid crystal film laminated product 1 that the foregoing description 1 obtained.From the laminated product that described uniaxial tension PET film/adhesive phase/liquid crystal material layer 1/ tacky adhesive layer 1/ independent film is formed, peel off described uniaxial tension PET film.Peeling force between described single axle drawn membrane and adhesive phase is 2.0N/m.
By thickness is the tacky adhesive layer of 25 μ m, with a kind of by SumitomoChemical Co., Ltd. the thickness of Sheng Chaning is that the polarizer " SQ-1852AP " of 180 μ m is laminated on the laminated product of being made up of adhesive phase/liquid crystal material layer 1/ tacky adhesive layer 1/ independent film that is obtained, and obtains the elliptical polarized light device that is formed by the laminated product that described polarizer/tacky adhesive layer 2/ adhesive phase/liquid crystal material layer 1/ tacky adhesive layer 1/ independent film is formed thus.In preparation process, not only can detect the optical defect of liquid crystal film laminated product 1 satisfactorily, and uniaxial tension PET film has good rippability, therefore can normally peel off described uniaxial tension PET film from adhesive interface.
Comparative example 2
The tacky adhesive layer 1 that thickness is about 25 μ m and has an independent film is laminated on the exposed liquid crystal material laminar surface of the liquid crystal film laminated product 1 that above-mentioned comparative example 1 obtained.From the laminated product that described biaxial stretch-formed PET film/adhesive phase/liquid crystal material layer 1/ tacky adhesive layer 1/ independent film is formed, peel off described biaxial stretch-formed PET film.Peeling force between described biaxially oriented film " S10 " and adhesive phase is 3.9N/m.
In preparation process, because the birefringent influence of twin shaft PET film can not detect optical defect from liquid crystal film laminated product 2 well.The rippability of described biaxial stretch-formed PET film is equally also very poor, and the area of the described biaxial stretch-formed PET film of normally peeling off from adhesive interface of a part accounts for 60% of the total area.
Comparative example 3
Except being to use Mitsubishi Rayon Co., Ltd. produce, thickness is that the acrylic resin film " ACRYPLEN " of 50 μ m is not beyond the thick uniaxial tension PET film of 38 μ m, repeat the step of embodiment 2, obtain liquid crystal film laminated product 3 thus.Peeling force between described acrylic resin film " ACRYPLEN " and adhesive phase is 31N/m.
In preparation process, can satisfactoryly detect the optical defect of liquid crystal film laminated product 3.The rippability of " but ACRYPLEN " film is very poor, therefore can not obtain the normal released part of " ACRYPLEN " film from adhesive interface.
Comparative example 4
TPX film " OPULENT X44B " that Mitsui Chemicals produces except being to use, that thickness is 50 μ m is not the thick uniaxial tension PET film of 38 μ m, repeats the step of embodiment 2, obtains liquid crystal film laminated product 4 thus.Peeling force between described TPX film " OPULENT X44B " and adhesive phase is 0.2N/m.
In preparation process, can satisfactoryly detect the optical defect of liquid crystal film laminated product 4.But very poor as the tack of TPX film on bonding agent of peelable substrate, can strip down from adhesive phase easily at each working stage of preparation process.Therefore be difficult to stably prepare described liquid crystal film.
Comparative example 5
Except being to use Toray Industries, Inc. produces, thickness is that the biaxial stretch-formed PET film " T60 " of 50 μ m is not beyond the thick uniaxial tension PET film of 38 μ m, repeats the step of embodiment 2, obtains liquid crystal film laminated product 5 thus.Peeling force between described biaxial stretch-formed PET film " T60 " and adhesive phase is 4.5N/m.
In preparation process, because the birefringent influence of twin shaft PET film can not detect optical defect from liquid crystal film laminated product 5 well.The rippability of described biaxial stretch-formed PET film is equally also very poor, and the area of the described biaxial stretch-formed PET film of normally peeling off from adhesive interface of a part accounts for 30% of the total area.
Comparative example 6
Except being to use TEIJIN Limited, Inc. produce, thickness is that the biaxial stretch-formed PET film " #52 " of the surface applied siloxane of 50 μ m is not beyond the thick uniaxial tension PET film of 38 μ m, repeat the step of embodiment 2, obtain liquid crystal film laminated product 6 thus.Peeling force between described " #52 " film and adhesive phase is 0.77N/m.
In preparation process, because the birefringent influence of twin shaft PET film can not detect optical defect from liquid crystal film laminated product 6 well.The rippability of described " #52 " film is fine, is enough to normally be stripped from from adhesive interface.
Comparative example 7
Except being to use TEIJIN Limited, Inc. the thickness of Sheng Chaning is that the biaxial stretch-formed PET film " #51 " of the surface applied siloxane of 50 μ m is not beyond the thick uniaxial tension PET film of 38 μ m, repeat the step of embodiment 2, obtain liquid crystal film laminated product 7 thus.Peeling force between described " #51 " film and adhesive phase is 2.0N/m.
In preparation process, because the birefringent influence of biaxial stretch-formed PET film can not detect optical defect from liquid crystal film laminated product 7 well.The rippability of described " #51 " film is fine, is enough to normally be stripped from from adhesive interface
The result of embodiment 2 and comparative example 2-7 thereof is summarized as follows shown in the table 1:
Table 1
| Peelable substrate | Detect | Rippability | |
| Embodiment 2 | Uniaxial tension PET | ????○ | ??○ |
| Comparative example 2 | Biaxial stretch-formed PET " S10 " | ????× | ??× |
| Comparative example 3 | Acrylic resin film " ACRYPLEN " | ????○ | ??× |
| Comparative example 4 | TPX film " X44B " | ????○ | ??× |
| Comparative example 5 | Biaxial stretch-formed PET " T60 " | ????× | ??× |
| Comparative example 6 | The biaxial stretch-formed PET film " #52 " of coating siloxane | ????× | ??○ |
| Comparative example 7 | The biaxial stretch-formed PET film " #51 " of coating siloxane | ????× | ??○ |
Claims (4)
1. method for preparing liquid crystal film, wherein this method comprises: by bonding agent one liquid crystal material layer is combined with a peelable substrate that is formed by the uniaxial tension mylar, described liquid crystal material layer has an alignment structure of fixing and is formed on the alignment substrates; By peeling off described alignment substrates, described liquid crystal material layer is transferred to described peelable substrate; And peel off described peelable substrate from described liquid crystal material layer.
2. method for preparing the elliptical polarized light device, wherein this method comprises: by bonding agent one liquid crystal material layer is combined with a peelable substrate that is formed by the uniaxial tension mylar, described liquid crystal material layer has an alignment structure of fixing and is formed on the alignment substrates; By peeling off described alignment substrates, described liquid crystal material layer is transferred to described peelable substrate; And after peeling off described peelable substrate, a polarizer is attached on the described liquid crystal material layer.
3. the method for claim 1, wherein said uniaxial tension polyester is by polyethylene terephthalate or by forming with the polyester of polyethylene terephthalate as principal ingredient.
4. method as claimed in claim 2, wherein said uniaxial tension polyester is by polyethylene terephthalate or by forming with the polyester of polyethylene terephthalate as principal ingredient.
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| Application Number | Priority Date | Filing Date | Title |
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| JP313506/2001 | 2001-10-11 | ||
| JP2001313506A JP4335484B2 (en) | 2001-10-11 | 2001-10-11 | Method for producing liquid crystal film and elliptically polarizing plate |
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| CN1571931A true CN1571931A (en) | 2005-01-26 |
| CN100385271C CN100385271C (en) | 2008-04-30 |
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| JP (1) | JP4335484B2 (en) |
| KR (1) | KR100955747B1 (en) |
| CN (1) | CN100385271C (en) |
| TW (1) | TW594066B (en) |
| WO (1) | WO2003034107A1 (en) |
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| CN107065238A (en) * | 2017-01-22 | 2017-08-18 | 京东方科技集团股份有限公司 | A kind of alignment film film surface detection means and method |
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| CN100392488C (en) * | 2004-08-02 | 2008-06-04 | 日东电工株式会社 | Method for manufacturing liquid crystal alignment film, liquid crystal alignment film, optical film and image viewing display |
| JP5975258B2 (en) * | 2012-03-13 | 2016-08-23 | 住友化学株式会社 | Method for producing liquid crystal polyester film |
| CN110181829B (en) * | 2019-05-27 | 2021-04-02 | 陈祚 | Industrial production process of liquid crystal polyester film |
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| JPH0726223A (en) * | 1993-07-08 | 1995-01-27 | Dainippon Printing Co Ltd | Highly transparent and slightly sticky antistatic protective film |
| JP3366154B2 (en) * | 1995-04-07 | 2003-01-14 | 新日本石油株式会社 | Method for producing liquid crystalline polymer film |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107065238A (en) * | 2017-01-22 | 2017-08-18 | 京东方科技集团股份有限公司 | A kind of alignment film film surface detection means and method |
| CN107065238B (en) * | 2017-01-22 | 2020-07-03 | 京东方科技集团股份有限公司 | Alignment film surface detection device and method |
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| WO2003034107A1 (en) | 2003-04-24 |
| JP2003121643A (en) | 2003-04-23 |
| KR100955747B1 (en) | 2010-04-30 |
| TW594066B (en) | 2004-06-21 |
| CN100385271C (en) | 2008-04-30 |
| KR20050035144A (en) | 2005-04-15 |
| JP4335484B2 (en) | 2009-09-30 |
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