CN1512218A - Method for producing optical element - Google Patents
Method for producing optical element Download PDFInfo
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- CN1512218A CN1512218A CNA200310114973XA CN200310114973A CN1512218A CN 1512218 A CN1512218 A CN 1512218A CN A200310114973X A CNA200310114973X A CN A200310114973XA CN 200310114973 A CN200310114973 A CN 200310114973A CN 1512218 A CN1512218 A CN 1512218A
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Abstract
To provide a method for achieving sufficiently strong adhesion without causing unnecessary peeling or a defect in a liquid crystal polymer layer when manufacturing an optical element composed of a liquid crystal polymer layer/adhesive layer/translucent substrate film by means of continuous transferring and when manufacturing a product where a protecting film is laminated on the optical element.A curing type adhesive is used as an adhesive and the adhesive is irradiated with an ultraviolet ray or an electron beam on two stages.
Description
Technical field
The present invention relates to the optical element manufacture method of used for liquid crystal display element colorimetric compensation plate, used for liquid crystal display element visual angle improvement plate, optics phasic difference plate, raising briliancy plate, antireflection plate, colored Polarizer, 1/2 wavelength plate, 1/4 wavelength plate, optical activity optical element etc.
Background technology
Liquid crystal polymer, particularly demonstrating epoch-making performance improving plate, and making LCD high performance, lightweight and slimming as used for liquid crystal display element colorimetric compensation plate or used for liquid crystal display element visual angle by having fixed optical element that the liquid crystal polymer that rocks nematic structure forms.As the manufacture method of this optical element, the layer that is formed by liquid crystal polymer that has proposed to form on the orientation substrate is transferred to method on the light-transmitting substrate.By this manufacture method the effect of orientation substrate and light-transmitting substrate is separated, can produce the optical element of various goods forms, open the road that the direction of the optical element that is formed by the film-type liquid crystal polymer develops thus especially.
But particularly liquid crystal display is very strict with the performance requirement of optical element to optical element, particularly runs into various difficult problems when making banded optical element continuously.That is and since the diameter of polymer liquid crystal layer only the part of the shortcoming about 100 μ m will cause optical defect, it is residual therefore also not allow small transfer printing.In addition, the coiling step is indispensable in the manufacture process of the optical element film that is formed by banded polymer liquid crystal layer, and the distortion of the big tack coat of plastic yield causes optical distortion, therefore makes product defective.Opposite is if tack coat is really up to the mark, produces the crack when transfer printing or coiling.In addition, for keeping the optical property of liquid crystal polymer, this transfer step must be implemented in the temperature below the liquid crystal polymer Tg.In addition, these optical elements are necessary for the element of the strict failtests that satisfies thermal cycle experiment, high temperature experiment, low temperature test, hot and humid experiment etc.Because the quality requirements to the goods that use optical element is more and more stricter, therefore requires further to improve.In addition, when improving quality, also require to boost productivity.
A kind of such continuously transfer printing method had been proposed, the film polymer liquid crystal layer that forms on the banded orientation substrate is fitted on the light-transmitting substrate film with the curing type cementing agent, the layer that formation is formed by orientation substrate film/polymer liquid crystal layer/uncured adhesive layer/light-transmitting substrate film, it is used ultraviolet ray, electron ray, the energy of heat etc. shines, make adhesive cures, obtain having the banded laminated body of the layer structure that forms by orientation substrate film/polymer liquid crystal layer/adhesive layer/light-transmitting substrate film, only peel off the orientation substrate film continuously from this laminated body, polymer liquid crystal layer is transferred on the light-transmitting substrate film, obtains the optical element that adhesive layer/the light-transmitting substrate film forms (for example opening flat 7-113911 communique) with reference to the spy by polymer liquid crystal layer/curing.In addition; in order to protect the liquid crystal polymer aspect of the laminated body that polymer liquid crystal layer/adhesive layer of obtaining thus/light-transmitting substrate film forms; proposed by using curing type adhesive layer applying diaphragm; and shine with the energy of ultraviolet ray, electron ray etc.; make adhesive cures, obtain having the scheme (for example opening flat 7-120747 communique) of the optical element of the floor structure that forms by diaphragm/adhesive layer/polymer liquid crystal layer/adhesive layer/light-transmitting substrate film with reference to the spy.
In the method for this use curing type cementing agent, after the cementing agent applying, if carry the overlong time of banded laminated body until the solidification process of ultraviolet ray irradiation etc., then will produce and peel off at interlayer, or cementing agent corrodes required above polymer liquid crystal layer, or polymer liquid crystal layer generation damage, these all are to cause optical element to produce defective, the situation of infringement commodity value.On the other hand; after fitting, and then its curing is finished by cementing agent; owing to fully can not obtain enough cohesive forces near preceding curing at cementing agent and bonded layer; therefore may have to produce between light-transmitting substrate and liquid crystal liquid crystal property macromolecule layer when peeling off the orientation substrate film and peel off, perhaps the diaphragm of optical element goods produces the danger of peeling off.In these cases, the cohesive strength deficiency between each layer of the optical element of manufacturing, and can not satisfy various failtestss.
Summary of the invention
The purpose of this invention is to provide and a kind ofly when adopting the manufacturing of aforesaid continuously transfer printing method, can obtain the cohesive force of sufficient intensity during with the goods that are manufactured on this optical element superimposed layer diaphragm, and do not produce the unnecessary method of peeling off and on polymer liquid crystal layer, not producing defective by optical element that polymer liquid crystal layer/adhesive layer/the light-transmitting substrate film forms.
The present invention the 1st aspect relates to a kind of manufacture method of optical element, by on banded orientation substrate, forming polymer liquid crystal layer, and by the curing type cementing agent this polymer liquid crystal layer and light-transmitting substrate are fitted and to obtain banded laminated body by orientation substrate/polymer liquid crystal layer/uncured adhesive layer/light-transmitting substrate forms, the degree of not damaging this polymer liquid crystal layer in order to corrode with this cementing agent is solidified this cementing agent, adopt the ultraviolet ray or the electron ray of MIN necessary quantity of X-rays X that this band shape laminated body is shone (phase one irradiation), place 30～120 seconds time, again with making the finish ultraviolet ray or the electron ray of required quantity of X-rays X of this adhesive cures shine (subordinate phase irradiation), obtain laminated body by orientation substrate/polymer liquid crystal layer/cured binders layer/light-transmitting substrate/the orientation substrate film forms, peel off the orientation substrate film from this laminated body, obtain the optical element that on light-transmitting substrate film transfer printing has polymer liquid crystal layer.
The 2nd aspect of the present invention relates to a kind of method, it is characterized by aspect the of the present invention the 1st, and the phase one ultraviolet irradiation amount of irradiation is 5～40mJ/cm
2
The 3rd aspect of the present invention relates to a kind of method, it is characterized by aspect the of the present invention the 1st or the 2nd, and the ultraviolet irradiation amount of subordinate phase irradiation is 250～800mJ/cm
2
The 4th aspect of the present invention relates to a kind of manufacture method of optical element; by the curing type cementing agent polymer liquid crystal layer and the diaphragm of the banded laminated body of light-transmitting substrate/adhesive layer/polymer liquid crystal layer formation are fitted; obtain by light-transmitting substrate/cured binders layer/polymer liquid crystal layer/uncured film formed banded laminated body of adhesive layer/protection; the degree of not damaging this polymer liquid crystal layer in order to corrode with this cementing agent is solidified this cementing agent; adopt the ultraviolet ray or the electron ray of MIN necessary quantity of X-rays X that this band shape laminated body is shone (phase one irradiation); place 30～120 seconds time; again with making the finish ultraviolet ray or the electron ray of required quantity of X-rays X of this adhesive cures shine (subordinate phase irradiation), obtain by the film formed optical element of light-transmitting substrate/cured binders layer/polymer liquid crystal layer/cured binders layer/protect.
The 5th aspect of the present invention relates to a kind of method, it is characterized by aspect the of the present invention the 4th, and the phase one ultraviolet irradiation amount of irradiation is 5～40mJ/cm
2
The 6th aspect of the present invention relates to a kind of method, it is characterized by aspect the of the present invention the 4th or the 5th, and the ultraviolet irradiation amount of subordinate phase irradiation is 250～800mJ/cm
2
The working of an invention form
The present invention further describes when following.In the present invention, answer the transfer printing material, when fusion, show the TLCP of liquid crystal liquid crystal property for showing the macromolecule of liquid crystal liquid crystal property.As optical element, be preferably the even single domain nematic liquid crystal phase of demonstration or rock the element of nematic liquid crystal phase.In this selected TLCP is a kind of such liquid crystal polymer, and it is to the row orientation under mesomorphic state or rocks to the row orientation, and the temperature range below liquid crystal transfer printing temperature is vitreousness.
As the liquid crystal liquid crystal property macromolecule, can exemplify out the condensation class liquid crystal liquid crystal property macromolecule that forms by compound condensation with carboxyl, alcohol radical, phenylol, amino, sulfenyl etc., with liquid crystal compounds with two keys such as acryloyl group, methacryl, vinyl, allyl etc. be the liquid crystal liquid crystal property ethene polymers that obtains of raw material, the high molecular potpourri of the above-mentioned liquid crystal liquid crystal property of liquid crystal liquid crystal property epoxy resin that synthesizes by synthetic liquid crystal liquid crystal property polysiloxane such as the liquid-crystal compounds with alkoxysilane group, by the liquid crystal compounds with epoxy radicals etc. etc.In above various liquid crystal liquid crystal property macromolecules, from the viewpoint of optical characteristics of gained film etc., most preferably condensation class liquid crystal polymer.
Condensation class liquid crystal liquid crystal property macromolecule can adopt proper method that two functional monomer's condensations are obtained usually.As this two functional monomer, be preferably two functional monomers with aromatic series or cyclohexane ring, can exemplify out two amines of phenylenediamine etc. particularly, quinhydrones, the 2-methylnaphthohydroquinone, resorcinol, catechol, the 4-methyl pyrocatechol, the 4-tert-butyl catechol, 2, the glycols of 3-dihydroxy naphthlene etc., 1,4-phenylene two mercaptan, 1, the dithiols of 2-phenylene two mercaptan etc., salicylic acid, the 3-Para Hydroxy Benzoic Acid, the 4-Para Hydroxy Benzoic Acid, 3-hydroxyl-2-naphthoic acid, 6-hydroxyl-2-naphthoic acid, the hydroxycarboxylic acid of 7-hydroxyl-2-naphthoic acid etc., the amino benzoic acid of 2-, the amino benzoic acid of 3-, the amino acids of the amino benzoic acid of 4-etc., phthalic acid, isophthalic acid, terephthalic acids, 1, the 4-naphthalene dicarboxylic acids, 2, the 6-naphthalene dicarboxylic acids, 2, the 7-naphthalene dicarboxylic acids, 4,4 '-diphenyl dicarboxylic acid, 4,4 '-stilbene dicarboxylic acid, 1, the omega-dicarboxylic acids of 4-cyclohexane dicarboxylic acid etc.Wherein most preferably contain as the hydroxyl composition, with the catechol unit serve as must structural unit condensation class liquid crystal liquid crystal property macromolecule.
When preparation condensation class liquid crystal liquid crystal property macromolecule, in the degree of not damaging liquid crystal liquid crystal property, can in raw materials used monomer, add for example oxalic acid, fumaric acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, the aliphatic dicarboxylic acid class of decanedioic acid etc., ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, heptandiol, ethohexadiol, nonanediol, the aliphatic diol class of decanediol etc., diaminoethanes, diaminopropanes, diaminobutane, the diamido pentane, diamino hexane, the diamido heptane, the diamido octane, the diamido nonane, the aliphatic diamine class of diamino decane etc., glycolic acid, hydracrylic acid, hydroxybutyric acid, hydroxypentanoic acid, hydroxyl is acid, the hydroxyl enanthic acid, Hydroxyoctanoic acid, the hydroxyl n-nonanoic acid, the aliphatic hydroxyl carboxylic acids of hydroxydecanoic acid etc. etc.
In addition, for the end to the liquid crystal liquid crystal property high polymer main chain as required carries out modification, can in starting monomer, add simple function monomer or trifunctional monomer.Can enumerate the monomer that has a carboxyl, amino, alcohol radical, phenylol, mercapto etc. in the molecule as the simple function monomer, for example be aromatic carboxylic acid class, aliphatic carboxylic acid class, aromatic amine, aliphatics amine, phenol, aliphatics phenol.In addition, can enumerate for example trimellitic acid, dihydroxy benzoic acid, hydroxybenzoic acid, benzenetricarboxylic acid, pyromellitic acid etc. as the trifunctional monomer.
Make these monomer condenses obtain condensation class liquid crystal liquid crystal property macromolecule, be in particular the method that obtains liquid crystalline polyester and be not particularly limited, can adopt the known any method in this field suitably.For example can adopt arbitrarily by make carboxylic acid become sour halogenide or in the presence of the dicyclohexyl carbon diimide etc. with the carboxylic acid activation after, make method that itself and alcohol, amine etc. react, by after phenol is carried out acid esterification, make itself and carboxylic acid reaction the synthetic method of taking off acetic acidreaction, make carboxylic acid become carboxylate as methyl esters after, in the presence of needed suitable catalyzer, make it with the synthetic method of the dealcoholization of alcohol reaction etc.
In liquid crystal liquid crystal property macromolecule of the present invention, aforesaid condensation class liquid crystal liquid crystal property macromolecule can use separately, also can use 2 kinds or 3 kinds or the above high molecular potpourri of condensation class liquid crystal liquid crystal property.In addition in the scope of not damaging effect of the present invention, can mix the various liquid crystal liquid crystal property macromolecules that use optically active liquid crystal macromolecule, liquid crystal liquid crystal property ethene polymers, liquid crystal liquid crystal property polysiloxane, liquid crystal liquid crystal property epoxy resin etc. or non-liquid crystal polymer etc. aptly.
The molecular weight of these polymkeric substance preferably is equivalent in all kinds of solvents, in phenol/tetrachloroethane (60/40 weight ratio) mixed solvent, is 0.05 to 3.0 30 ℃ of logarithm viscosity of measuring down, more preferably in 0.07 to 2.0 scope for example.Logarithm viscosity is less than 0.05 o'clock, and the high molecular weakened of the liquid crystal liquid crystal property of gained is therefore not preferred.And greater than 3.0 o'clock, viscosity was too high in the time of will producing liquid crystal formation, and orientation reduces, the problem of orientation required time increase etc.
In addition, the molecular weight of above-mentioned optical activity macromolecular compound preferably is equivalent in phenol/tetrachloroethane for example, 30 ℃ of logarithm viscosity of measuring down in 0.05 to 5.0 scope.Logarithm viscosity was greater than 5.0 o'clock, and viscosity is too high, and the result reduces orientation, and less than 0.05 o'clock, is difficult to adjust and forms, and is therefore all not preferred.
As liquid crystal polymer, if adopt above-mentioned polyester polymer, then its cohesiveness with the propylene resin that uses as adhesive layer is good, and is therefore preferred.Liquid crystal polymer is set orientation by orientation substrate.Orientation substrate also can be the macromolecule membrane that forms on suitable base materials.
Can be used for orientation substrate film of the present invention and can directly use banded extension film continuously, perhaps implement friction treatment abreast or at a certain angle obliquely, the liquid crystal polymer orientation that has contacted with this friction treatment face is obtained corresponding to this friction treatment direction by MD (indulging) direction to banded continuous film.Can exemplify out the heat reactive resin of polyimide, epoxy resin, phenolics etc. as this orientation substrate film; The polyamide of nylon etc.; Polyetherimide; Polyetherketone; Polyetheretherketone; Polyketone; Polyethersulfone; The polyhenylene thioether; Polyhenylene oxidation thing; The polyester of poly terephthalic acid vinyl acetate, poly terephthalic acid butene esters etc.; Polyacetal; Polycarbonate; Polyacrylate; Polymethacrylate; The cellulosic resin of primary cellulose acetate etc.; The thermoplastic resin of polyvinyl alcohol (PVA) etc. etc.
Can implement friction treatment to above-mentioned macromolecule membrane self, maybe can form the organic film that forms by above-mentioned other macromolecule in its surface with these macromolecule membranes as base material.In addition, the base material as form organic film on this base material except above-mentioned macromolecule membrane, can also be the metal forming of copper, stainless steel, steel etc.Above-mentioned in addition orientation substrate itself also can be formed by the metal forming of copper, stainless steel, steel etc.Particularly preferred in the present invention orientation substrate film is the film of the base material implementing the film of friction treatment formation to having banded independence macromolecule membrane itself, particularly do not use to answer lamination etc.As the band-like film that is suitable for this purpose,, for example be the thermoplastic resin of poly terephthalic acid vinyl acetate, polyhenylene thioether, polyetheretherketone, polyvinyl alcohol (PVA) etc. for the film that thermoplastic resin in the above-mentioned film forms.As the heat reactive resin film, preferably use polyimide.
At this, band-like film refers to the continuous film with certain-length, at the industrial continuous film as gained that provides with the form that is rolled into roller that refers to.Can certainly be roll form, but the continuous film for suitably folding.The length of band-like film also is 10000m according to situation.
The operation that forms banded polymer liquid crystal layer on banded orientation substrate film can any means be implemented.That is, liquid crystal polymer is dissolved in the suitable solvent, adopts the coating apparatus of roll coater etc. to be coated with, make its dry method that forms polymer liquid crystal layer, perhaps adopt the method that melt extrudes high molecule liquid crystal etc. by T pattern etc.In addition, the quality viewpoint from thickness etc. is suitable for by solution coat and drying means.Coating process is not particularly limited, and for example can adopt rolling method, curtain to be coated with mould Tu Fa of method or sealing rubbing method etc. etc.Coating width is preferably selected in the scope of 100～1000mm usually at 10～2000mm.After the coating, remove by drying and to desolvate.
With the MD direction abreast or with the MD direction be carry out on the direction of predetermined angle incline forming polymer liquid crystal layer on the banded orientation substrate film that friction treatment forms after, under predetermined temperature, heat the schedule time, make the liquid crystal polymer orientation, be cooled to the following temperature of Tg (glass temperature) then, liquid crystal structure is fixed.The thickness of fixing back polymer liquid crystal layer, if liquid crystal layer be nematic liquid crystal mutually or rock liquid crystal phase, it is not particularly limited.Thickness is different according to optical wavelength, and for example in the field that is mainly visible light of display applications etc., thickness is more than the 0.1 μ m, is preferably more than the 2 μ m, more preferably more than the 3 μ m.During less than 0.1 μ m, be difficult to adjust accurately thickness, therefore not preferred.When too thick in addition, die down as the setting ability of optical element, therefore not preferred, from this viewpoint, suitable below 1000 μ m, preferably in the scope below 500 μ m.In the present invention, because therefore the orientation substrate film of bottom obtains the banded liquid crystal polymer film with this friction treatment respective angles orientation for implementing the banded orientation substrate film of friction treatment at a predetermined angle.
As the light-transmitting substrate film, as long as it has the transparency and optical isotropy, can support polymer liquid crystal layer, it is not particularly limited, owing to need be banded, therefore can exemplify out plastic sheeting, for example poly terephthalic acid vinyl acetate, polymethacrylate, polystyrene, polycarbonate, polyethersulfone, polyhenylene thioether, polyacrylate, EOT, amorphous poly ethene, primary cellulose acetate etc.In addition, substrate uses the thickness of film at 0.5～200 μ m, preferably in the scope of 1～100 μ m.
As diaphragm, as long as it is in the scope of the optical characteristics of not damaging liquid crystal layer, there is no particular limitation as to it, in order to design the water tolerance that improves polymer liquid crystal layer, thermotolerance, resistance to impact etc., adopts for example plastic films, hard conating etc.Also can adopt for plastic films attached to the reactive cementing agent of ultraviolet ray on the polymer liquid crystal layer, as described later or electron ray curing type, solidify to form reactive adhesive layer by it and play a role as protective seam.In addition, for reducing the thickness of banded multilayer film, also can peel off plastic films, only the hard conating that is formed by the reactive cementing agent that has solidified is as protective seam.In this case, also can adopt the plastic films that does not damage the polymer liquid crystal layer optical characteristics, but need it to have fissility with adhesive layer.
As above-mentioned plastic films, can adopt polymethylmethacrylate, polystyrene, polycarbonate, polyethersulfone, polyhenylene thioether, amorphous poly alkene, primary cellulose acetate, poly terephthalic acid vinyl acetate, poly-naphthalene vinyl acetate etc.Can apply single shaft or twin shaft extension operation to these protections with film aptly as required.In addition, on this diaphragm, also can apply the surface treatment of hydrophilicity-imparting treatment, hydrophobization processing or easy fissility processing etc., can be used alone diaphragm, also can use the multilayer film that pellicular cascade forms more than 2 kinds.The thickness of diaphragm is 10～100 μ m, is preferably 16～50 μ m.Beyond this scope, the transportation performance of film worsens, and is difficult to make banded laminated body, or the fissility deterioration, and is therefore not preferred.
Can be used for cementing agent of the present invention and be not particularly limited, consider when continuously transfer printing and can solidify in the necessary utmost point short time, and in liquid crystal liquid crystal property macromolecule Tg temperature with curable, preferred light curing type or electron ray curing type.Being that the cementing agent of major component can not produce the polymer liquid crystal layer transfer error fully with the propylene quasi-oligomer particularly, can not producing fault when implementing operation such as coiling, become the reliability height of optical element goods, is preferred from these viewpoints.For this propylene quasi-oligomer, can cooperate polar ethylene monomer in addition as the N-vinylpyrrolidone.
Below to adopting these ultraviolet rays or electron ray curing type cementing agent, the polymer liquid crystal layer continuously transfer printing that forms on the orientation substrate film is described to the step on the light-transmitting substrate.Comprise that promptly (1) will be coated with that two belt base plates behind the cementing agent are film adhered, (3) stack membrane irradiating ultraviolet light or electron ray after fitting being coated with cementing agent, (2) at least one side of polymer liquid crystal layer that forms on the banded orientation substrate film or banded light-transmitting substrate film, make and only peel off the step that banded optical element film that orientation substrate film, (5) form the polymer liquid crystal layer/cured binders layer/light-transmitting substrate film that is transferred to banded light-transmitting substrate film side is implemented to reel etc. after adhesive cures, (4) adhesive cures.These steps are to implement continuously with the speed in 0.5～100m/min scope.
Method as coating cementing agent at least one side that is formed on polymer liquid crystal layer on the banded orientation substrate or banded light-transmitting substrate film, the conduct that can adopt general implementation is coated with method, spraying process etc. to the mould that rolling method, the curtain of continuous film coating means is coated with method, sealing rubbing method etc., and is not particularly limited.The adhesive thickness that is coated with is 0.5～200 μ m, is preferably 1～100 μ m, if more than 200 μ m, then the curing rate of cementing agent reduces, and solidifies insufficient, therefore not preferred.Implement being coated with the lamination means that can adopt general implementation when two substrate film behind the cementing agent are fitted, thoroughly get rid of the mode of the bubble of sneaking into during still with applying and implement.
After the applying, uniform irradiation ultraviolet ray or electron ray on the Width of the banded attaching film of carrying solidify adhesive layer continuously.The present invention implements in these 2 stages of sub irradiation.For with this cementing agent not the degree of this polymer liquid crystal layer of erosion damages solidify this cementing agent, adopt MIN necessary quantity of X-rays X that this band shape laminated body is carried out the phase one irradiation, place 30～120 seconds time, implement the subordinate phase irradiation again, adhesive cures is finished.
Phase one, irradiation was for making cementing agent be not enough to completely crued step, its state of cure must make between polymer liquid crystal layer in the conveying and the light-transmitting substrate film and not produce the degree of peeling off, and with cementing agent not excessively the exposure of etchant polycrystalline macromolecule layer degree implement.Exposure can be selected suitably according to the kind of useful to irradiation of rays and the kind of cementing agent.Preferred exposure was 5～40mJ/cm when concrete was ultraviolet
210～35mJ/cm more preferably
2
After phase one, irradiation was finished, place 30～120 seconds time, the time of preferably placing 60～90 seconds is carried out the subordinate phase irradiation again.By placing time of 30～120 seconds, make the wetting fully polymer liquid crystal layer of uncured cementing agent composition during this period, improve cohesive strength after solidifying by only corroding polymer liquid crystal layer thus.
The subordinate phase irradiation is finished bonding and is implemented in order to make the cementing agent full solidification.Exposure can be selected suitably according to the kind of useful to irradiation of rays and the kind of cementing agent.Preferred exposure was 250～800mJ/cm when concrete was ultraviolet
2450～750mJ/cm more preferably
2
Adhesive layer is only peeled off the orientation substrate film after solidifying continuously, makes the polymer liquid crystal layer continuously transfer printing that forms on the orientation substrate film on the light-transmitting substrate film side by the cured binders layer, and is wound into reel.In last continuous strip step, its must condition for example on the orientation substrate film side, there not to be the liquid crystal polymer transfer printing residual fully, on the polymer liquid crystal layer of transfer printing, do not produce the crack fully or peel off, and light-transmitting substrate film, orientation substrate film itself do not produce damage or wrinkle etc., this step particular importance, and be the high step of difficulty.
Instantiation as stripping means, be preferably along peeling off rod and only peel off the stripping means of orientation substrate film from the banded multilayer film of carrying, perhaps adopt as special open put down in writing in the flat 7-113911 communique, make banded multilayer film by between nip rolls and the backing roll, only carry the stripping means of orientation substrate film etc. along nip rolls.Particularly can prevent to produce the residual and crack of fine liquid crystal polymer transfer printing, peel off etc., on two substrate film, also not produce microlesion, can stably implement continuously to peel off etc., so its commercial value be very big along peeling off method that rod implements to peel off.
The speed that the lamination sheet is peeled off continuously is not particularly limited, and can freely change at the usage range of device.Usually at 0.1～200m/min, preferably implement in the scope at 0.5～100m/min.The tension force that film is applied is not particularly limited, and does not produce wrinkle or unflagging state but the predetermined tension size is in film.The tension force size is preferably at 0.05～0.50kgf/mm
2Scope in.Tension force almost keeps equal before and after preferably peeling off.Produce bigger stripping charge in the stripping portion of orientation substrate film, fissility is descended or cause the adverse effect of on the liquid crystal liquid crystal property macromolecule membrane, adhering to dust etc., dangerous aspect working environment, therefore adopt ionized air etc. effectively to remove.
Obtain the banded laminated body that light-transmitting substrate/adhesive layer/polymer liquid crystal layer forms thus; can produce the optical element of suitable size by this laminated body; during for the surface lamination diaphragm of protection polymer liquid crystal layer, the kind of cementing agent, the coating process situation when light-transmitting substrate film and polymer liquid crystal layer are bondd is the same.
The adhesive thickness that is coated with is 0.5～200 μ m, is preferably 1～100 μ m, if thickness more than 200 μ m, then because adhesive cures speed reduces, solidifies insufficient, therefore not preferred.To be coated with two substrate film behind the cementing agent when fitting, generally can adopt the lamination means to implement, but the mode of sneaking into thorough eliminating bubble when fitting is implemented.
After the applying, uniform irradiation ultraviolet ray or electron ray on the Width of the banded attaching film of carrying solidify adhesive layer continuously.The present invention implements in these 2 stages of sub irradiation.For with this cementing agent not the degree of this polymer liquid crystal layer of erosion damages solidify this cementing agent, adopt MIN necessary quantity of X-rays X to carry out phase one irradiation, places 30～120 seconds time, implement subordinate phase again and shine, adhesive cures is finished.
Phase one, irradiation was for making cementing agent be not enough to completely crued step; its state of cure must make between polymer liquid crystal layer in the conveying and the protective film and not produce the degree of peeling off, and with cementing agent not excessively the exposure of etchant polycrystalline macromolecule layer degree implement.Exposure can be selected suitably according to the kind of useful to irradiation of rays and the kind of cementing agent.Preferred exposure was 5～40mJ/cm when concrete was ultraviolet
210～35mJ/cm more preferably
2
After phase one, irradiation was finished, place 30～120 seconds time, the time of preferably placing 60～90 seconds is carried out the subordinate phase irradiation again.By placing time of 30～120 seconds, make the wetting fully polymer liquid crystal layer of uncured cementing agent composition during this period, improve cohesive strength after solidifying by only corroding polymer liquid crystal layer thus.
The subordinate phase irradiation is finished bonding and is implemented in order to make the cementing agent full solidification.Exposure can be selected suitably according to the kind of useful to irradiation of rays and the kind of cementing agent.Preferred exposure was 250～800mJ/cm when concrete was ultraviolet
2450～750mJ/cm more preferably
2
Embodiment
Followingly the present invention is specifically described, but the present invention is not subjected to the restriction of these embodiment according to embodiment.
Various analytical approachs used among reference example and the embodiment are as follows.
(1) mensuration of logarithm viscosity
Adopt Wu Bailuode type viscosity meter, in phenol/tetrachloroethane (60/40 weight ratio) mixed solvent, measuring under 30 ℃.
What (2) the liquid crystal liquid crystal property material was formed determines
Liquid crystalline polyester is dissolved in the heavy-hydrogenated chloroform, adopts 400MHz's
1H-NMR (JNM-GX400 that NEC is made) measures, and determines its composition.
(reference example 1)
Synthesize the liquid crystal liquid crystal property polymer substance (logarithm viscosity=0.22dl/g, Tg=61 ℃) of formula (1) and comprise (R)-3-methyl hexane-1 of formula (2), and the optically active liquid crystal polymer substance of 6-diol units (logarithm viscosity=0.17dl/g).
The synthetic of these macromolecular materials is in the o-dichlorobenzene solvent, under triethylamine coexistence, makes the react enforcement of the sour chloride corresponding with dicarboxylic acid units and diol compound.
The potpourri of the liquid crystal liquid crystal property polymer substance of the liquid crystal liquid crystal property macromolecule of the 18.1g formula (1) of gained and 1.9g formula (2) is dissolved in the 80g N-Methyl pyrrolidone preparation liquid crystal liquid crystal property polymer substance solution-1.
(formula 1)
(formula 2)
*Expression optical activity carbon
(reference example 2)
Adopt 80mmol terephthalic acid (TPA), 23mmol heptandioic acid, 55mmol quinhydrones diacetate, 50mmol isopropyl catechol diacetate esters and as the sodium acetate of catalyzer, under nitrogen atmosphere 280 ℃ of following polymerizations 2 hours, at 300 ℃ of following polymerizations 2 hours, the liquid crystal liquid crystal property polymer substance of acquisition formula (3).
Then gained liquid crystal liquid crystal property polymer substance is dissolved in the tetrachloroethane, after this adopts methyl alcohol to precipitate again, obtain the refining liquid crystal liquid crystal property polymer substance of 26g.The logarithm viscosity of this liquid crystal liquid crystal property polymer substance is 0.31dl/g, and DSC measures and the result of polarized light microscope observing is that liquid crystal phase is a nematic phase, is the glassy phase that does not have crystallization phase at the low-temp. portion lower than liquid crystal phase temperature, and Tg is 117 ℃.
This liquid crystal liquid crystal property polymer substance of 15g is dissolved in the 85g tetrachloroethane preparation liquid crystal phase polymer substance solution-2.
(formula 3)
In the formula, the numeric representation mole ratio of components of each unit
(reference example 3)
Synthesize the liquid crystal liquid crystal property polymer substance (logarithm viscosity=0.21dl/g, Tg=60 ℃) of formula (4) and comprise (R)-3-methyl hexane-1 of formula (5), and the optically active liquid crystal polymer substance of 6-diol units (logarithm viscosity=0.18dl/g).
The synthetic of these macromolecular materials is in the o-dichlorobenzene solvent, under triethylamine coexistence, makes the react enforcement of the sour chloride corresponding with dicarboxylic acid units and diol compound.
The potpourri of the liquid crystal liquid crystal property polymer substance of the liquid crystal liquid crystal property polymer substance of the 9.2g formula (4) of gained and 0.8g formula (5) is dissolved in the 90g N-Methyl pyrrolidone preparation liquid crystal liquid crystal property Polymer Solution-3.
(formula 4)
(formula 5)
*Expression optical activity carbon
＜embodiment 1-3 〉
On the friction treatment face of the banded poly (ether ether ketone) film that 500mm is wide, 10 μ m are thick of implementing friction treatment on the direction with respect to the inclination (45 °) of MD direction, adopt the wide liquid crystal polymer substance solution 1～3 of roll coater coating 400mm.After the drying,, make the liquid crystal polymer orientation, be cooled to room temperature then, liquid crystal structure is fixed 220 ℃ of following heat treated 15 minutes.After this, what adopt the intaglio plate coating machine coating 400mm is wide continuously on liquid crystal liquid crystal property macromolecule face, 10 μ m are thick is the ultraviolet hardening cementing agent (commercially available product A, viscosity are 320cp) of major component with the propylene quasi-oligomer, note not involving in bubble then on one side, on one side it is fitted on the cellulosic triacetate that 500mm is wide, 100 μ m are thick continuously.After this quantity of X-rays X shown in the employing table 1 divides 2 stage irradiation ultraviolet radiations, produces the laminate film 1-4 that orientation substrate film/polymer liquid crystal layer/cured binders layer/light-transmitting substrate film forms by band shape.Adopt the special method of opening flat 7-113911 record to peel off the orientation substrate film continuously, obtain its performance being estimated by the laminated body that the liquid crystal liquid crystal property macromolecule layer/the cured binders layer/the light-transmitting substrate film forms from the gained laminated body.The results are shown in table 1.
＜comparative example 1 〉
Implement the ultraviolet ray irradiation except being regardless of for 2 stages, adopt the mode the same to implement with embodiment 2.The results are shown in table 1.
Table 1
*1: the composition of commercially available product A
Epoxies propylene oligomer 25 weight %
Carbamates propylene oligomer 25 weight %
Acrylic acid tetrahydro furfuryl ester 30 weight %
N-vinyl-2-Pyrrolidone 20 weight %
*2: adopt visual type to estimate.
*3:,, adopt visual type to estimate from bottom Polarizer irradiation white light at the top and the bottom of optical element configuration Polarizer.
＜embodiment 5～8 〉
On liquid crystal polymer aspect by the polymer liquid crystal layer/laminated body that the cured binders layer/the light-transmitting substrate film forms of embodiment 2～4 gained; what adopt that the intaglio plate coating machine is coated with continuously that 400mm is wide, 10 μ m are thick is the ultraviolet hardening cementing agent (commercially available product A, viscosity are 320cp) of major component with the propylene quasi-oligomer; note not involving in bubble then on one side, on one side it is fitted in continuously on the poly terephthalic acid vinyl acetate enforcement demoulding diaphragm that handle, that 50 μ m are thick.After this quantity of X-rays X shown in the employing table 2 divides 2 stage irradiation ultraviolet radiations, produces the multilayer film that diaphragm/cured binders layer/polymer liquid crystal layer/the cured binders layer/the light-transmitting substrate film forms by band shape.Its performance is estimated.The results are shown in table 2.
＜comparative example 2 〉
Implement the ultraviolet ray irradiation except being regardless of for 2 stages, adopt the mode the same to implement with embodiment 6.The results are shown in table 2.
Table 2
| Numbering | The kind of liquid crystal polymer | The ultraviolet hardening cementing agent | Ultraviolet ray useful to irradiation of rays amount (mJ/cm 2) | Estimate | ||
| Phase one | Subordinate phase | The situation of peeling off of diaphragm in the course of conveying *2(％) | The state of liquid crystal polymer *3 | |||
| Embodiment 5 | ????1 | Commercially available product A *1 | ????2 | ??450 | Do not have | Produce than multiple cracks owing to corrode |
| Embodiment 6 | ????1 | The same | ????8 | ??350 | The same | No abnormal situation |
| Embodiment 7 | ????2 | The same | ????15 | ??550 | The same | The same |
| Embodiment 8 | ????3 | The same | ????30 | ??750 | The same | The same |
| Comparative example 2 | ????1 | The same | ????350 | Do not have | ????10 | The same |
*1 He
*3: identical with in the table 1
*2: employing range estimation mode is estimated the multilayer film in the course of conveying
The invention effect
Only peel off continuously the orientation substrate film and produce the method by the polymer liquid crystal layer of continuously transfer printing to the light-transmitting substrate film/cured binders layer/optical element that the light-transmitting substrate film forms at the banded multilayer film that forms from orientation substrate film/polymer liquid crystal layer/cured binders layer/light-transmitting substrate film, make the curing type adhesive cures by minute 2 stage energy exposure, do not peel off or misplace so that do not produce on the interface of liquid crystal liquid crystal property macromolecule layer and light-transmitting substrate film in the film supplying step, the erosion composition in the binding agent does not corrode polymer liquid crystal layer yet. In addition; when the polymer liquid crystal layer bonding of the laminated body that forms at this polymer liquid crystal layer/cured binders layer/light-transmitting substrate film, lamination diaphragm; make the curing type adhesive cures by minute 2 stage energy exposure; do not peel off or misplace so that do not produce on the interface of the liquid crystal liquid crystal property macromolecule layer of in this step, carrying and diaphragm, and the erosion composition in the binding agent does not corrode polymer liquid crystal layer yet. The effective rate of utilization of optical element be can improve thus, and productivity and economy increased substantially.
Claims (6)
1. the manufacture method of an optical element, by on banded orientation substrate, forming polymer liquid crystal layer, and by the curing type cementing agent this polymer liquid crystal layer and light-transmitting substrate are fitted and to obtain banded laminated body by orientation substrate/polymer liquid crystal layer/uncured adhesive layer/light-transmitting substrate forms, the degree of not damaging this polymer liquid crystal layer in order to corrode with this cementing agent is solidified this cementing agent, adopt the ultraviolet ray or the electron ray of MIN necessary quantity of X-rays X that this band shape laminated body is shone (phase one irradiation), place 30～120 seconds time, again with making the finish ultraviolet ray or the electron ray of required quantity of X-rays X of this adhesive cures shine (subordinate phase irradiation), obtain laminated body by orientation substrate/polymer liquid crystal layer/cured binders layer/light-transmitting substrate/the orientation substrate film forms, peel off the orientation substrate film from this laminated body, obtain the optical element that on light-transmitting substrate film transfer printing has polymer liquid crystal layer.
2. optical element manufacture method as claimed in claim 1, the ultraviolet irradiation amount that it is characterized by the phase one irradiation is 5～40mJ/cm
2
3. as the optical element manufacture method of claim 1 or 2, the ultraviolet irradiation amount that it is characterized by the subordinate phase irradiation is 250～800mJ/cm
2
4. the manufacture method of an optical element; by the curing type cementing agent polymer liquid crystal layer and the diaphragm of the banded laminated body of light-transmitting substrate/adhesive layer/polymer liquid crystal layer formation are fitted; obtain by light-transmitting substrate/cured binders layer/polymer liquid crystal layer/uncured film formed banded laminated body of adhesive layer/protection; the degree of not damaging this polymer liquid crystal layer in order to corrode with this cementing agent is solidified this cementing agent; adopt the ultraviolet ray or the electron ray of MIN necessary quantity of X-rays X that this band shape laminated body is shone (phase one irradiation); place 30～120 seconds time; again with making the finish ultraviolet ray or the electron ray of required quantity of X-rays X of this adhesive cures shine (subordinate phase irradiation), obtain by the film formed optical element of light-transmitting substrate/cured binders layer/polymer liquid crystal layer/cured binders layer/protect.
5. optical element manufacture method as claimed in claim 4, the ultraviolet irradiation amount that it is characterized by the phase one irradiation is 5～40mJ/cm
2
6. as the optical element manufacture method of claim 4 or 5, the ultraviolet irradiation amount that it is characterized by the subordinate phase irradiation is 250～800mJ/cm
2
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP377648/2002 | 2002-12-26 | ||
| JP2002377648A JP4243952B2 (en) | 2002-12-26 | 2002-12-26 | Optical element manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1512218A true CN1512218A (en) | 2004-07-14 |
| CN100365482C CN100365482C (en) | 2008-01-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200310114973XA Expired - Fee Related CN100365482C (en) | 2002-12-26 | 2003-11-14 | Method for producing optical element |
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| CN (1) | CN100365482C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102692666A (en) * | 2011-03-25 | 2012-09-26 | 住友化学株式会社 | Manufacture method of polarizing plate |
| CN103874943A (en) * | 2011-10-07 | 2014-06-18 | 住友化学株式会社 | Method for manufacturing polarizer |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5346969B2 (en) * | 2011-03-04 | 2013-11-20 | 富士フイルム株式会社 | Method for producing antiglare film |
| JP6727390B1 (en) * | 2019-02-01 | 2020-07-22 | 住友化学株式会社 | Laminate, laminate with adhesive layer, optical laminate with substrate layer, optical laminate, and method for producing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3398437B2 (en) * | 1993-10-22 | 2003-04-21 | 新日本石油化学株式会社 | Manufacturing method of liquid crystal polymer film with surface protection layer |
| JPH08304626A (en) * | 1995-04-28 | 1996-11-22 | Nippon Petrochem Co Ltd | Optical element |
| JP3905661B2 (en) * | 1999-02-25 | 2007-04-18 | 株式会社クラレ | Method for manufacturing surface light source element |
-
2002
- 2002-12-26 JP JP2002377648A patent/JP4243952B2/en not_active Expired - Lifetime
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2003
- 2003-11-14 CN CNB200310114973XA patent/CN100365482C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102692666A (en) * | 2011-03-25 | 2012-09-26 | 住友化学株式会社 | Manufacture method of polarizing plate |
| CN102692666B (en) * | 2011-03-25 | 2015-11-18 | 住友化学株式会社 | The manufacture method of polarization plates |
| CN103874943A (en) * | 2011-10-07 | 2014-06-18 | 住友化学株式会社 | Method for manufacturing polarizer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004205987A (en) | 2004-07-22 |
| CN100365482C (en) | 2008-01-30 |
| JP4243952B2 (en) | 2009-03-25 |
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