CN1501105A - Method for manufacturing optical elements - Google Patents
Method for manufacturing optical elements Download PDFInfo
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- CN1501105A CN1501105A CNA200310116145A CN200310116145A CN1501105A CN 1501105 A CN1501105 A CN 1501105A CN A200310116145 A CNA200310116145 A CN A200310116145A CN 200310116145 A CN200310116145 A CN 200310116145A CN 1501105 A CN1501105 A CN 1501105A
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Abstract
Provided is a separation method, without causing generation of defects, such as transfer residues of liquid crystal high polymer, cracks or the separation and wrinkles or the like of a film, in a method for manufacturing of optical elements by transferring a liquid crystal polymer layer formed on an orientation substrate film from a long laminated film to a transmissive substrate film. An optical element is manufactured which has the liquid crystal polymer layer transferred to the transmissive substrate film by separating the oriented substrate film along a separation bar provided on the side of the oriented substrate film from the long laminated layer film, comprising the orientation substrate film/the liquid crystal polymer layer/a curing adhesive layer/the transmissive substrate film.
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
The optical element that liquid crystal liquid crystal property macromolecule, the liquid crystal liquid crystal property macromolecule of particularly having been fixed by liquid crystal intrinsic orientation texture form is in the optical applications of various displays, for example demonstrate epoch-making performance, and make display high performance, lightweight and slimming as used for liquid crystal display element colorimetric compensation plate or used for liquid crystal display element visual angle improvement plate.As the manufacture method of this optical element, the floor that is formed by the liquid crystal liquid crystal property macromolecule that has proposed to form on the orientation substrate is transferred to the method (for example with reference to special claims and Fig. 1, Fig. 2 that opens flat 7-113911 communique) 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 film-type liquid crystal liquid crystal property macromolecule 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 liquid crystal liquid crystal property macromolecule 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 liquid crystal liquid crystal property macromolecule 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 high molecular optical property of liquid crystal liquid crystal property, this transfer step must be implemented in the temperature below the liquid crystal liquid crystal property macromolecule 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, the experiment of high temperature high temperature etc.Because the quality requirements to the goods that use optical element is more and more stricter, therefore requires its further improvement.In addition, when improving quality, also require to improve productive rate.
Because used liquid crystal liquid crystal property macromolecule is extremely thin film and payes attention to its orientation in these optical elements, therefore use the less macromolecule of molecular weight.For this reason by adopting cementing agent with the liquid crystal liquid crystal property macromolecule layer film and the film adhered formation stack membrane of light-transmitting substrate that on orientation substrate, form, make adhesive cures, obtain having the orientation substrate film/stack membrane of the layer structure of liquid crystal liquid crystal property macromolecule layer/cured binders layer/light-transmitting substrate film, the continuously transfer printing step of only the orientation substrate film being implemented to peel off continuously from this stack membrane, need careful especially attention in the particularly last continuous strip step, this step is the high step of difficulty.Promptly, in this continuous strip step, with the interface peel between orientation substrate film and the liquid crystal liquid crystal property macromolecule layer film is most important parts, if this peels off means and condition is not carried out optimization, and the liquid crystal liquid crystal property macromolecule layer critical defect that will produce the residual or crack of transfer printing, peel off etc. then.
As the method that addresses the aforementioned drawbacks, present inventors etc. proposed a kind of method in the past, even this stack membrane contact is by between nip rolls and the backing roll, make orientation substrate film contact passing through nip rolls respectively, make light-transmitting substrate film contact passing through backing roll, simultaneously only carry the orientation substrate film, peel off thus along nip rolls, thereby with liquid crystal liquid crystal property macromolecule layer continuously transfer printing to the light-transmitting substrate film (with reference to special claims and Fig. 1, Fig. 2 that opens flat 7-113911 communique).But more and more stricter to the quality requirements of optical thin film, even a point defect is arranged slightly, its quality is also with defective.If have dust or foreign matter on the backing roll, the pressure when then clamping will make adhesive layer or the damage of liquid crystal liquid crystal property macromolecule layer, and part liquid crystal liquid crystal property macromolecule layer remains on the orientation substrate film side when peeling off.In addition, because the surface accuracy of nip rolls or the influence of friction, when the orientation substrate film is released from being clamped to, because the influence of this film fine wrinkle will produce the irregular bad phenomenon of peeling off.
Summary of the invention
The present invention is directed to aforesaid present situation, its objective is provides by form the liquid crystal liquid crystal property macromolecule on banded orientation substrate film, obtain banded stack membrane by bond this liquid crystal liquid crystal property macromolecule layer and light-transmitting substrate film of cementing agent by orientation substrate film/liquid crystal liquid crystal property macromolecule layer/cured binders layer/light-transmitting substrate film forms, peel off the orientation substrate film from this stack membrane, produce and have the liquid crystal liquid crystal property macromolecule layer that is transferred on the light-transmitting substrate film, in the method, so that the liquid crystal liquid crystal property macromolecule not produce transfer printing residual, the crack, defective such as peel off and do not produce the method that the mode of film wrinkle etc. is implemented to peel off.
The present invention the 1st aspect relates to the manufacture method that on light-transmitting substrate film transfer printing has the optical element of liquid crystal liquid crystal property macromolecule layer, it is characterized in that by on banded orientation substrate film, forming the liquid crystal liquid crystal property macromolecule layer, obtain peeling off the orientation substrate film from this stack membrane along the rod of peeling off that is arranged on the orientation substrate film side by bond this liquid crystal liquid crystal property macromolecule layer and light-transmitting substrate film of cementing agent by the banded stack membrane that orientation substrate film/liquid crystal liquid crystal property macromolecule layer/cured binders layer/light-transmitting substrate film forms.
The 2nd aspect of the present invention relates to a kind of manufacture method of optical element, it is characterized in that aspect the present invention the 1st, and orientation substrate film after peeling off and the film formed angle of banded lamination be below 90 °.
The present invention the 3rd aspect relates to a kind of manufacture method of optical element, it is characterized in that aspect the present invention the 1st or the 2nd, and the diameter of peeling off rod is 5mm～30mm.
Brief description of drawings
Fig. 1 is the simple schematic side view according to the optical element manufacturing installation stripping portion of the inventive method.
The working of an invention mode
Below the present invention is further described.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 liquid crystal liquid crystal property macromolecule, and it is to the row orientation under mesomorphic state or rocks to the row orientation, and the temperature range below the liquid-crystalization 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, be the liquid crystal liquid crystal property ethene polymers that obtains of raw material, the 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. and the high molecular potpourri of above-mentioned liquid crystal liquid crystal property etc. with liquid crystal compounds with two keys such as acryloyl group, methacryl, vinyl, allyl etc. with carboxyl, alcohol radical, phenylol, amino, sulfenyl 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 common functional monomer's condensations are obtained.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, hydroxycaproic 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 suitably adopt the known any method in this field.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 suitably 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.
The molecular weight of these polymkeric substance preferably is equivalent in all kinds of solvents, for example in phenol/tetrachloroethane (weight ratio: 60/40) in the mixed solvent, be 0.05 to 3.0 30 ℃ of logarithm viscosity of measuring down, more preferably in 0.07 to 2.0 scope.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 the formation liquid crystal, 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, in 30 ℃ of logarithm viscosity of measuring down are 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 the liquid crystal liquid crystal property macromolecule, if adopt above-mentioned polyester polymer, then its cohesiveness with the propylene resin that uses as adhesive layer is good, and is therefore preferred.The liquid crystal liquid crystal property macromolecule is set orientation by orientation substrate.Orientation substrate also can be the macromolecule membrane that forms on suitable base materials.
But can be used for orientation substrate film former state of the present invention and use banded extension film continuously, perhaps, the liquid crystal polymer orientation that has contacted with this friction treatment face is obtained corresponding to this friction treatment direction by implementing friction treatment abreast or at a certain angle obliquely with MD (indulging) direction of 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.In addition, above-mentioned 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 heat reactive resin, 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.Much less, also can be roll form, also can be the continuous film for suitably folding.The length of band-like film also is 10000m according to situation.
The operation that forms banded liquid crystal liquid crystal property macromolecule layer on banded orientation substrate film can any means be implemented.That is, in suitable solvent, adopt the coating apparatus of roll coater etc. to be coated with the liquid crystal liquid crystal property macromolecule dissolution, make its dry liquid crystal liquid crystal property macromolecule layer that forms, 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 adopting 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 interior selection of scope of 100～1000mm usually at 10～2000mm.After the coating, remove by drying and to desolvate.
With respect to the MD direction abreast or be with respect to the MD direction carry out on the direction of predetermined angle incline forming the liquid crystal liquid crystal property macromolecule layer on the banded orientation substrate film that friction treatment forms after, under predetermined temperature, heat the schedule time, make the liquid crystal liquid crystal property macromolecular orientation, temperature below Tg (glass temperature) cooling then makes liquid crystal structure fix thus.At this, as the liquid crystal structure of having fixed,, for example can enumerate to the row orientation owing to the difference of the high molecular kind of used liquid crystal liquid crystal property, ratio of components etc. cannot treat different things as the same, to row heterozygosis orientation, rock to row orientation, cholesterol orientation etc.But these liquid crystal structures are exemplary, and the present invention is not subjected to the restriction of these liquid crystal structures.Fixing back liquid crystal liquid crystal property macromolecule thickness 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 liquid crystal property macromolecule membrane with the corresponding angular orientation of this friction treatment 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, can support the liquid crystal liquid crystal property macromolecule layer, it is not particularly limited, owing to need be banded, therefore can exemplify out plastic sheeting, for example poly terephthalic acid vinyl acetate, polymethylmethacrylate, 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.
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 liquid crystal liquid crystal property macromolecule 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 the optical element of goods, is preferred from these viewpoints.In addition, for this propylene quasi-oligomer, can cooperate polar ethylene monomer as the N-vinylpyrrolidone.
Below to adopting these light or electron ray curing type cementing agent, the liquid crystal liquid crystal property macromolecule 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 irradiates light or electron ray after fitting being coated with cementing agent, (2) at least one side of liquid crystal liquid crystal property macromolecule 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 liquid crystal liquid crystal property macromolecule 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 liquid crystal liquid crystal property macromolecule 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 means of lamination 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.The curing of the coating and the back adhesive layer of fitting can be implemented at the Width uniform irradiation light or the electron ray of band shape applying film according to used cementing agent under appropriate condition.
After adhesive layer solidifies, only the orientation substrate film is peeled off continuously, made the liquid crystal liquid crystal property macromolecule layer continuously transfer printing that forms on the orientation substrate film on the light-transmitting substrate film side by the adhesive layer that solidifies, and be wound into reel.In last continuous strip step, its must condition for example on the orientation substrate film side, there not to be the transfer printing of liquid crystal liquid crystal property macromolecule residual fully, on the liquid crystal liquid crystal property macromolecule layer of transfer printing, can 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 complexity.
Below with reference to the accompanying drawings stripping means of the present invention is described.What Fig. 1 represented is an embodiment of stripping means of the present invention.The present invention is passed through between nip rolls 3 (contacting with the orientation substrate film) and backing roll 2 (contacting with the light-transmitting substrate film) by the banded stack membrane 1 that the orientation substrate film/liquid crystal liquid crystal property macromolecule layer/cured binders layer/transparent thin-film forms, and this laminate film is transported to peels off excellent 5 places then.The material of nip rolls 3 and backing roll 2 is not particularly limited, and can be the two combination of metal, rubber or this.Preferred nip rolls is a metal for resilient material, backing roll as rubber.When clamping stack membrane 1, clamping pressure must not depart to the roller Width.Clamping pressure is preferably 0.01～100kgf/mm.Carry stack membrane along backing roll among Fig. 1, but also can not carry along backing roll.In addition, the diameter of nip rolls and backing roll is different among the figure, but the diameter of the two also can be identical.
The orientation substrate film side that makes the stack membrane of having carried with peel off rod and contact, to carry along peeling off the mode that rod only peels off the orientation substrate film, the optical element goods divided thin film that makes orientation substrate film and remaining liquid crystal liquid crystal property macromolecule layer/cured binders layer/light-transmitting substrate film formation thus from.Optical element goods film is carried by conveying roller, take up roll.
That peels off rod is shaped as the pole shape, and diameter is 5～30mm, be preferably 10mm～20mm.During diameter deficiency 5mm, it is crooked to peel off rod, can produce wrinkle on the film, so not preferred.In addition, when diameter surpassed 30mm, peel angle diminished, and exists the danger at orientation substrate film side residual fraction liquid crystal liquid crystal property macromolecule layer, and is therefore not preferred.The material of peeling off rod is not particularly limited, but preferred flatness is excellent and can not produce the plastics or the metal of dust.Peeling off near the rod, broken away from the orientation substrate of peeling off rod with to peeling off the formed angle of stack membrane that rod advances preferably below 90 degree.If surpass 90 degree, then peel off state labile, on the orientation substrate film side, exist the high molecular danger of residual fraction liquid crystal liquid crystal property, therefore not preferred.
The speed that the lamination sheet is peeled off continuously is not particularly limited, and can freely change in the practical zone 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 crooked state but the predetermined tension size is in film.The preferable range of tension force is 0.05～0.50kgf/mm
2Tension force almost keeps equal before and after preferably peeling off.Produce big 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.In addition, it also is effective will peeling off excellent ground connection own.
As mentioned above, when obtaining transfer film 6 by only peeling off orientation substrate film 4 from 4 stacked tunics 1 of orientation substrate film/liquid crystal liquid crystal property macromolecule layer/cured binders layer/light-transmitting substrate film formation, if peel off stack membrane 1 along peeling off rod 5, can prevent the residual or crack of the high molecular fine transfer printing of liquid crystal liquid crystal property, peel off etc., on two substrate film, do not produce fine damage yet, can stablize, implement continuously to peel off etc., so commercial value is very big.
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 optical parametric
Adopt the polarization analysis method to measure the optical parametric that rocks angle and delay (Δ nd) of liquid crystal film.(Δ n: birefringence constant, d: the thickness of liquid crystal film liquid crystal layer; The nm of unit)
(2) mensuration of logarithm viscosity
Adopt Wu Bailuode type viscosity meter, in phenol/tetrachloroethane (60/40 weight ratio) mixed solvent, measuring under 30 ℃.
What (3) the liquid crystal liquid crystal property macromolecule 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 liquid crystal liquid crystal property macromolecule of the 18.1g formula (1) of gained and the liquid crystal liquid crystal property macromolecule mixture of 1.9g formula (2) are dissolved in the 80g N-Methyl pyrrolidone preparation liquid crystal liquid crystal property Polymer 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, in polymerization 2 hours under nitrogen atmosphere under 280 ℃, 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
(Production Example of banded stack membrane)
On the friction treatment face of the banded polyetheretherketone that 500mm is wide, 10 μ m are thick of implementing friction treatment on the direction of or inclination parallel, polyimide, each film of polyhenylene thioether, adopt the wide liquid crystal phase polymer substance solution 1～3 of roll coater coating 400mm with respect to the MD direction.After the drying,, make the liquid crystal phase macromolecular orientation, be cooled to room temperature then, liquid crystal structure is fixed 220 ℃ of following heat treated 15 minutes.Use coating layer pressure device continuously coating 400mm be wide on the liquid crystal liquid crystal property macromolecule face of each orientation substrate film, 10 μ m are thick with ultraviolet irradiation apparatus with the ultraviolet hardening cementing agent (commercially available product A, viscosity be 320cp) of propylene quasi-oligomer as major component, on one side note not involving in bubble then, on one side it is fitted on the various films of 500mm is wide, 100 μ m are thick cellulosic triacetate or polyethersulfone.Irradiation ultraviolet radiation then, produce the orientation substrate shown in the table 1 by band shape thin/film L-1 that the liquid crystal phase macromolecule layer/curing type adhesive layer/light-transmitting substrate film forms is to L-6.
Table 1
| Production Example | Project | |||||
| The liquid crystal liquid crystal property macromolecule layer | The orientation substrate film | The ultraviolet hardening cementing agent | The light-transmitting substrate film | |||
| Liquid crystal liquid crystal property polymer substance solution | Thickness (μ m) | Kind | Rubbing angle | |||
| L-1 | ?2 | ?5 | Polyetheretherketone | Parallel | Commercially available product A *1 | Primary cellulose acetate |
| L-2 | ?1 | ?10 | The same | 45° | The same | The same |
| L-3 | ?1 | ?1 | Polyimide | Parallel | The same | Polyethersulfone |
| L-4 | ?3 | ?5 | The same | 45° | The same | |
| L-5 | ?2 | ?2 | The polyhenylene thioether | Parallel | The same | Primary cellulose acetate |
| L-6 | ?3 | ?10 | The same | 30° | The same | The same |
*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 %
Embodiment 1～6
Use shown in Figure 1 by nip rolls, backing roll, peel off the stripping off device that rod is formed, the banded stack membrane 1 that orientation substrate film from Production Example L-1 to L-6/liquid crystal phase macromolecule layer/cured binders layer/light-transmitting substrate film forms is only peeled off orientation substrate film 4 continuously, produces the transfer film 6 as optical element thus.Make banded stack membrane 1 by between the nip rolls 2,3, peel off orientation substrate film 4 along peeling off rod 5 then.At the nip rolls 3 of the free roller formation of the side employing 70mm of orientation substrate film 4 φ rubber system, at the backing roll 2 use 300mm φ SUS system driven rollers of light-transmitting substrate side.Clamping pressure is 0.5kgf/mm.The pole that the SUS of use 15mm φ diameter makes is as peeling off rod.Film carries pulling force from being retracted to all constant 0.1kgf/mm of being of coiling
2Orientation substrate film 4 after inspection is peeled off with peel off before the formed angle of banded stack membrane (θ) change, peel off the liquid crystal phase macromolecule whether the back orientation substrate exists not transfer printing, transfer printing the liquid crystal phase macromolecule defective that whether has the crack, peel off etc., and on two substrates whether damage is arranged.The results are shown in table 2.
Table 2
| Embodiment | Project | |||||
| The laminate film Production Example | Orientation substrate film and the angle of peeling off preceding stack membrane | Peeling rate (m/min) | The liquid crystal liquid crystal property macromolecule of transfer printing not on the orientation substrate film *1(％) | The high molecular fracture of the liquid crystal liquid crystal property of transfer printing, peel off situation *2 | Peel off the damage of back orientation substrate film *1 | |
| ????1 | ????L-1 | ????30° | ????10 | ????0 | Do not have | Do not have |
| ????2 | ????L-2 | The same | ????30 | ????0 | Do not have | Do not have |
| ????3 | ????L-3 | ????60° | ????10 | ????0 | Do not have | Do not have |
| ????4 | ????L-4 | The same | ????10 | ????0 | Do not have | Do not have |
| ????5 | ????L-5 | ????80° | ????15 | ????0 | Do not have | Do not have |
| ????6 | ????L-6 | ????100° | ????30 | ????2 | In some fracture of periphery at transfer printing position not, peel off | Do not have |
*1: adopt visual type to estimate.
*2:,, adopt visual type to estimate from bottom Polarizer irradiation white light at the top and the bottom of optical element configuration Polarizer.
Comparative example 1 and 2
Use the banded stack membrane of Production Example L-1 (comparative example 1) and L-5 (comparative example 2) and from the device of embodiment 1, removed the device of peeling off rod, the band-like film 1 that orientation substrate stack membrane/liquid crystal liquid crystal property macromolecule layer/cured binders layer/light-transmitting substrate film is formed passes through between the nip rolls 2,3, only peel off orientation substrate film 4 continuously along nip rolls 3, make transfer film as optical element.As nip rolls,, make driven rollers at the backing roll 2 employing 300mm φ SUS of light-transmitting substrate film side at the nip rolls 3 that orientation substrate film 4 sides adopt the free roller of 70mm φ rubber system to form.Clamping pressure is 0.5kgf/mm, and the conveying pulling force of film is from being retracted to all constant 0.1kgf/mm of being of coiling
2Peeling rate is the same with embodiment 1.Change the circumferential contact length of nip rolls 3 with respect to the orientation substrate film, be 1/4 week (comparative example 1) and 1/2 week (comparative example 2), the liquid crystal liquid crystal property macromolecule whether the back orientation substrate exists not transfer printing is peeled off in inspection, transfer printing the liquid crystal liquid crystal property macromolecule defective that whether has the crack, peel off etc., and on two substrates whether damage is arranged.The results are shown in table 3.
Table 3
| Comparative example | Project | |||||
| The laminate film Production Example | The contact length of orientation substrate and the whole girth of nip rolls | Peeling rate (m/min) | The liquid crystal liquid crystal property macromolecule of transfer printing not on the orientation substrate film *1(％) | The high molecular fracture of the liquid crystal liquid crystal property of transfer printing, peel off | Peel off the damage of back orientation substrate film *1 | |
| ????1 | ????L-1 | 1/4 week | ????10 | ????4 | Some crack and peeling off on transfer section periphery not | Do not have |
| ????2 | ????L-5 | 1/2 week | ????10 | ????2 | The same | Do not have |
*1: adopt visual type to estimate.
*2:,, adopt visual type to estimate from bottom Polarizer irradiation white light at the top and the bottom of optical element configuration Polarizer.
The invention effect
Can set up a kind of such technology according to the present invention, be transferred on the light-transmitting substrate film when making optical element at the liquid crystal liquid crystal property macromolecule layer that banded orientation substrate film is formed, only peel off continuously the orientation substrate film from the banded stack membrane that orientation substrate film/liquid crystal liquid crystal property macromolecule layer/cured binders layer/light-transmitting substrate film forms. Can improve thus the effective rate of utilization of optical element, and raising generative nature by leaps and bounds and economy.
Claims (3)
1. optical element manufacture method with the liquid crystal liquid crystal property macromolecule layer that is transferred on the light-transmitting substrate film, it is characterized in that by on banded orientation substrate film, forming the liquid crystal liquid crystal property macromolecule layer, obtain peeling off the orientation substrate film from this stack membrane along the rod of peeling off that is arranged on the orientation substrate film side by bond this liquid crystal liquid crystal property macromolecule layer and light-transmitting substrate film of cementing agent by the banded stack membrane that orientation substrate film/liquid crystal liquid crystal property macromolecule layer/cured binders layer/light-transmitting substrate film forms.
2. as the optical element manufacture method of claim 1 record, orientation substrate film after it is characterized in that peeling off and the film formed angle of banded lamination are below 90 °.
3. as the optical element manufacture method of claim 1 or 2 records, it is characterized in that peeling off excellent diameter is 5mm～30mm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP334209/2002 | 2002-11-18 | ||
| JP2002334209A JP2004170545A (en) | 2002-11-18 | 2002-11-18 | Manufacturing method of optical element |
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| Publication Number | Publication Date |
|---|---|
| CN1501105A true CN1501105A (en) | 2004-06-02 |
| CN1311258C CN1311258C (en) | 2007-04-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200310116145XA Expired - Fee Related CN1311258C (en) | 2002-11-18 | 2003-11-17 | Method for manufacturing optical elements |
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| Country | Link |
|---|---|
| JP (1) | JP2004170545A (en) |
| CN (1) | CN1311258C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103502850A (en) * | 2011-04-26 | 2014-01-08 | 日东电工株式会社 | Method for producing optical laminate |
| CN102186670B (en) * | 2008-08-29 | 2014-02-12 | 三菱丽阳株式会社 | Method for manufacture of resin laminated body |
| CN103823268A (en) * | 2012-11-16 | 2014-05-28 | 日东电工株式会社 | Method of manufacturing polarizing plate |
| CN105517928A (en) * | 2014-08-14 | 2016-04-20 | Lg化学株式会社 | Releasing bar for releasing polarizing film from panel, and releasing apparatus and releasing method using same |
| CN105593718A (en) * | 2013-09-30 | 2016-05-18 | Lg化学株式会社 | Method for manufacturing one-sided thin polarizing plate |
| CN108369307A (en) * | 2015-12-18 | 2018-08-03 | 住友化学株式会社 | Single side protects the manufacturing method of polarization plates |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5975258B2 (en) * | 2012-03-13 | 2016-08-23 | 住友化学株式会社 | Method for producing liquid crystal polyester film |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2549713B2 (en) * | 1988-08-19 | 1996-10-30 | 富士通株式会社 | Method for manufacturing multilayer printed circuit board having blind through holes |
| JPH0649367B2 (en) * | 1990-03-28 | 1994-06-29 | 奥山 陽一 | How to peel off defective pack paper and aluminum foil |
| JP3278951B2 (en) * | 1992-10-23 | 2002-04-30 | ソニー株式会社 | Method of forming ohmic electrode |
| JPH0813911A (en) * | 1994-06-29 | 1996-01-16 | Koito Mfg Co Ltd | Lifting/lowering device for automobile window glass |
| JPH1124251A (en) * | 1997-06-30 | 1999-01-29 | Dainippon Printing Co Ltd | Dry film, manufacture thereof, method and device for transferring to the dry film |
| US6812982B2 (en) * | 2000-05-12 | 2004-11-02 | Fuji Photo Film Co., Ltd. | Optical compensatory sheet producing method and apparatus, thermal treating method and apparatus, and dust removing method and apparatus |
-
2002
- 2002-11-18 JP JP2002334209A patent/JP2004170545A/en active Pending
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2003
- 2003-11-17 CN CNB200310116145XA patent/CN1311258C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102186670B (en) * | 2008-08-29 | 2014-02-12 | 三菱丽阳株式会社 | Method for manufacture of resin laminated body |
| CN103502850A (en) * | 2011-04-26 | 2014-01-08 | 日东电工株式会社 | Method for producing optical laminate |
| CN103823268A (en) * | 2012-11-16 | 2014-05-28 | 日东电工株式会社 | Method of manufacturing polarizing plate |
| CN103823268B (en) * | 2012-11-16 | 2017-07-07 | 日东电工株式会社 | The manufacture method of Polarizer |
| CN105593718A (en) * | 2013-09-30 | 2016-05-18 | Lg化学株式会社 | Method for manufacturing one-sided thin polarizing plate |
| CN105517928A (en) * | 2014-08-14 | 2016-04-20 | Lg化学株式会社 | Releasing bar for releasing polarizing film from panel, and releasing apparatus and releasing method using same |
| CN108369307A (en) * | 2015-12-18 | 2018-08-03 | 住友化学株式会社 | Single side protects the manufacturing method of polarization plates |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1311258C (en) | 2007-04-18 |
| JP2004170545A (en) | 2004-06-17 |
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