CN105074516A - Phase shift film manufacturing method - Google Patents
Phase shift film manufacturing method Download PDFInfo
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- CN105074516A CN105074516A CN201480019223.0A CN201480019223A CN105074516A CN 105074516 A CN105074516 A CN 105074516A CN 201480019223 A CN201480019223 A CN 201480019223A CN 105074516 A CN105074516 A CN 105074516A
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- film
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
Abstract
Provided is a manufacturing method of a phase shift film which has improved adhesion between the support body and the optically anisotropic layer, and fewer liquid crystal orientation defects. This phase shift film manufacturing method involves: a step for preparing a band-form support body which contains a plasticizer and/or an optical properties modifier; a coating step for forming a film on the support body by coating a raw material liquid obtained by dissolving a rod-form polymerizable liquid crystal compound, an orientation control agent and an orientation auxiliary agent in a solvent which dissolves or swells the support body; a drying step for drying the film coated on the support body to form a coating film comprising the inside of the support substrate that has been impregnated by said solvent; a heat treatment step for heating the coating film such that the internal temperature of the coating film becomes a temperature at which the orientation control agent and the orientation auxiliary agent are displaced to the surface of the coating film; a cooling step for cooling such that the internal temperature of the coating film becomes a temperature at which position of the orientation control agent and the orientation auxiliary agent is fixed; and a curing step for irradiating the coating film with active radiation to cure the coating film.
Description
Technical field
The present invention relates to the manufacture method of the phase retardation film with the optical anisotropic layer making liquid-crystal compounds orientation.
Background technology
In recent years, the very fast expansion of purposes of liquid crystal indicator, is used in mobile phone, notebook display, TV, liquid crystal projection apparatus etc.
In general, liquid crystal indicator passes through with TN (TwistedNematic, twisted-nematic) pattern, VA (VerticalAlignment, vertical orientated) pattern, IPS (In-PlaneSwitching, in face switch) pattern, OCB (OpticallyCompensatoryBend, optical compensation curved) pattern, ECB (ElectricallyControlledBirefringence, electrically conerolled birefringence) display mode such as pattern makes liquid crystal work, carries out electric control and to the light by liquid crystal by light and shade differential disply on picture.Thus, liquid crystal indicator display word or image.
As such liquid crystal indicator, in general known TFT (ThinFilmTransistor, thin film transistor (TFT))-LCD.In recent years, along with the purposes of liquid crystal indicator further expands, the expectation brightness caused by angle of visibility or colourity being changed to little display device is increased.In order to expecting, the research of the liquid crystal indicator of IPS pattern is constantly in progress.IPS pattern is used as the display of panel computer etc. more, and the brightness of picture improves greatly.Therefore, as display quality reduce reason, in the past and non-problems black display time the small light leak on angular direction is become obvious.
For such problem, following method is described: be coated with bar-shaped polymerizable liquid crystal compound dissolving coating fluid in organic solvent on the supporter with middle layer in patent documentation 1, coating fluid is dry, dried coating fluid is heated, irradiating active radioactive ray to the coating fluid through heating makes it solidify, thus forms optical anisotropic layer.
In addition, following method is described: on supporter, form restraining barrier and middle layer in patent documentation 2, by the coating fluid of coating containing liquid crystal compounds on it, the temperature of this coating fluid is increased to after more than phase transition temperature, through remaining on the drying-heating-curing process of below phase transition temperature, form optical anisotropic layer.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2010-211110 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2002-277637 publication
Summary of the invention
The technical matters of invention for solving
In the method for patent documentation 1, because orientation anchor force (anchoringstrength) is weak and the heat time not enough, therefore cannot avoid the generation of orientation defect.
In addition, in the method for patent documentation 2, due to needs formation 2 layers of intermediate coat, therefore operation becomes loaded down with trivial details, does not use the solvent dissolving supporter, therefore there is the problem of the closely sealed poor performance of supporter and intermediate coat in coating fluid when intermediate coat is formed.
As mentioned above, in order to make liquid crystal aligning on supporter, how middle layer being set on supporter, forming liquid crystal phase on the intermediate layer.This is because, middle layer has the function making the function of liquid crystal aligning and prevent supporter constituent from spreading to liquid crystal film.
But, owing to needing the technique forming middle layer, therefore there is the problem in the performance quality such as manufacturing cost rising, dust.Thus, the present application person have extensively studied the method for carrying out orientation when not forming middle layer.
When directly forming liquid crystal vertical-tropism film on supporter when not using middle layer, need the surface treatment surface of supporter being carried out to the Te such as friction treatment or Cement Composite Treated by Plasma Do.This surface has manufacturing cost rising, dust etc. to be mixed into the possibility of caused quality decline.
In addition, when forming optical anisotropic layer (also referred to as liquid crystal layer) by coating, when IPS pattern phase retardation film, the problem that the adaptation (closing force) between supporter and liquid crystal layer is not enough, liquid crystal layer peels off becomes obvious.The deficiency of adaptation thinks the factor owing to not making supporter be combined with liquid crystal layer.
As the solvent of coating fluid that liquid crystal layer is formed, use supporter dissolved or swelling solvent to improve the adaptation between supporter-liquid crystal layer.But the bad generation of orientation, trade-off problem between adaptation and orientation become obvious.
Therefore, what inventors conducted in-depth research found that, the bad reason of liquid crystal aligning is composition stripping in supporter and is mixed in liquid crystal layer, hinders liquid crystal aligning and orientation defect occurs.
The present invention considers that such problem completes, and its object is to improve the adaptation between supporter and optical anisotropic layer, provides the manufacture method of the bad few phase retardation film of liquid crystal aligning.
For solving the method for problem
In a mode of the present invention, the manufacture method of phase retardation film possesses following operation: the operation preparing the banded supporter containing plastifier and/or optical characteristics adjusting agent; The supporter be continuously traveling is coated on the material liquid being dissolved with rod-like polymerizable liquid crystal compound, tropism control agent and orientation assistant in the solvent of dissolving or swelling supporter, forms the painting process of film; By drying coated film on supporter, the position of tropism control agent and orientation assistant is fixed and formed the drying process making solvent penetrate into the film of inner more than 0.3 μm of supporter; The heat treatment step making tropism control agent and orientation assistant heat more than 25 seconds to film to the mode of the temperature of film coated surface movement is reached according to the internal temperature of film; After heat treatment step, the mode reaching the temperature of being fixed the position of tropism control agent and orientation assistant according to the internal temperature of film carries out the refrigerating work procedure cooled; With after refrigerating work procedure, film residual solvent ratio being less than to 3 quality % irradiates active radioactive ray, by curing of coating, forms the curing process of optical anisotropic layer.
Solvent contained in preferred feedstock liquid has ± 2 [(J/cm relative to the raw-material solubility parameter SP value of supporter
3)
1/2] solubility parameter SP value in scope.
Preferred feedstock liquid except dissolving supporter, except swelling solvent, also containing other multi-solvents.
Preferably comprise in drying process with 0.1 [g/m
2sec] following rate of drying is by the operation of film drying.
Preferred supporter is cellulose mesentery.
Invention effect
According to the present invention, the adaptation that can manufacture between supporter and optical anisotropic layer improves, the bad few phase retardation film of liquid crystal aligning.
Accompanying drawing explanation
Fig. 1 is the schematic configuration diagram of the manufacturing equipment of phase retardation film.
Fig. 2 A is the key diagram of effect representing liquid-crystal compounds, tropism control agent, orientation assistant.
Fig. 2 B is the key diagram of effect representing liquid-crystal compounds, tropism control agent, orientation assistant.
Fig. 2 C is the key diagram of effect representing liquid-crystal compounds, tropism control agent, orientation assistant.
Fig. 2 D is the key diagram of effect representing liquid-crystal compounds, tropism control agent, orientation assistant.
Fig. 3 is the chart of the result representing embodiment.
Fig. 4 is the chart of the result representing embodiment.
Embodiment
Below with reference to the accompanying drawings the preferred embodiment of the present invention is described.The present invention is described by following preferred implementation, but multiple gimmick can be utilized without departing from the present invention to change, and can utilize other embodiments beyond present embodiment.Therefore, the whole changes in the scope of the invention comprise within the scope of the claims.
Here, be the identical element with identical function by the part that same-sign represents in figure.In addition, when using " ~ " to represent numerical range in this instructions, the numerical value of the upper limit shown in " ~ ", lower limit is also contained in numerical range.
(manufacture method of phase retardation film)
The manufacture method of the phase retardation film of the manner comprises following operation: the operation preparing the banded supporter containing plastifier and/or optical characteristics adjusting agent; The supporter be continuously traveling is coated with rod-like polymerizable liquid crystal compound, tropism control agent and orientation assistant are dissolved in the material liquid in supporter dissolving or swelling solvent, form the painting process of film; Dry by the film that will be coated on supporter, the position of tropism control agent and orientation assistant is fixed, and forms the drying process making solvent penetrate into the film of inner more than 0.3 μm of supporter; Reach the mode making tropism control agent and orientation assistant temperature of movement in film coated surface according to the internal temperature of film, film is heated to the heat treatment step of more than 25 seconds; After heat treatment step, reach the refrigerating work procedure temperature that the position of tropism control agent and orientation assistant is fixed being carried out cooling to make the internal temperature of film; After refrigerating work procedure, film residual solvent ratio being less than to 3 quality % irradiates active radioactive ray, by curing of coating, forms the curing process of optical anisotropic layer.
When supporter directly forms optical anisotropic layer with coating method, use and supporter is dissolved or swelling solvent, make the material liquid containing polymerizable liquid crystal compound, tropism control agent and orientation assistant.By using, supporter is dissolved or swelling solvent, the region that solvent penetrates into supporter inside in drying process, formation supporter mixes with film.By carrying out active wire irradiation, solidification in this case, the adaptation between supporter and optical anisotropic layer can be improved.Wherein, infiltration thickness is made to be 0.3 μm when infiltrating with Shangdi, closely sealed more firmly.
On the other hand, utilize containing supporter is dissolved or the material liquid of swelling solvent forms optical anisotropic layer time, as composition in supporter plastifier and/or optical characteristics adjusting agent is mixed exists in optical anisotropic layer.Now, due to plastifier and/or optical characteristics adjusting agent, orientation is subject to hindering, is particularly hindered in the orientation of interface portion office of the supporter/optical anisotropic film that there is a large amount of plastifier and/or optical characteristics adjusting agent film (liquid crystal film) after drying process, and orientation defect occurs.
Here, heat treatment step is set after drying process to improve temperature, the reduction viscosity of film.Thus, the liquid-crystal compounds in film moves, make film be in No yield point state and make tropism control agent and orientation assistant to film/Air Interface diffusion.Maintain this state after more than 25 seconds, utilize refrigerating work procedure to reduce temperature, the raising viscosity of film at active wire pre-irradiation.Find thus, the movement of the liquid-crystal compounds in film is become slowly, orientation and the diffusion of tropism control agent and orientation assistant stop again making liquid-crystal compounds.Making curing of coating by carrying out active wire irradiation in this case, the optical anisotropic layer (liquid crystal phase) not having orientation defect can be formed.
Here, tropism control agent play make liquid-crystal compounds vertically orientation effect, go far towards the orientation of supporter interface side.In addition, although the tropism control agent orientation orientation anchor force that also contributes to Air Interface side is weak.What support is the adjuvant being referred to as orientation assistant.Orientation assistant plays and tropism control agent conveyance is made the effect of its local distribution to Air Interface side.The tropism control agent moving to Air Interface side contributes to the vertical orientated of the liquid-crystal compounds at Air Interface place.Preferably surfactant is used as orientation assistant.
In drying process, before tropism control agent and orientation assistant diffuse to Air Interface side, by dried coating film, immobilization.In heat treatment step afterwards, by reducing the viscosity of film, tropism control agent and orientation assistant spread again.Its result, there is a large amount of tropism control agent and orientation assistant in Air Interface, utilize the tropism control agent diffusing to Air Interface side, the orientation anchor force of Air Interface side is strengthened.
Film after drying process, due to the effect of tropism control agent, is hindered although liquid-crystal compounds carries out the vertical orientated interface portion office orientation at a part of supporter/film.In heat treatment step afterwards, comprise the interface portion of supporter/film that there occurs orientation and hinder, the orientation of the liquid-crystal compounds made in film is temporarily No yield point state.After supposition, by cooling at active wire pre-irradiation, make liquid-crystal compounds orientation again, but now because the orientation anchor force of Air Interface side is strengthened, therefore the orientation of the interface portion of supporter/film is supported, orientation integral ground is good.
With regard to heat treatment step, heat treatment temperature needs to be that liquid crystal is in No yield point state and the temperature again spread through immobilized tropism control agent and orientation assistant.In addition, by making heat treatment time be more than 25 seconds, the time needed for orientation obstacle of the interface portion disintegrating supporter/film can be guaranteed, tropism control agent and orientation assistant can be guaranteed fully to the time of Air Interface diffusion.Its result, the orientation of liquid-crystal compounds is optimized.
With regard to refrigerating work procedure, chilling temperature needs to be that liquid crystal carries out orientation and the temperature of tropism control agent and orientation assistant being fixed again again.
< supporter >
Supporter is preferably optically transparent and has birefringent resin molding.In engineering transparent refer to have more than 60% transmitance, more preferably more than 80% transmitance.In addition, the birefringence delay Rth of the delay Re in face and film thickness direction represents,
Re＝(n
x-n
y)×d
(n
x: in support dignity, become refractive index, the n on the direction of largest refractive index
y: the refractive index in the direction vertical with in x-axis face, d: film thickness)
Rth＝((n
x-n
y)/2-n
z)×d
(n
z: the refractive index of thickness direction)
Re, Rth are all preferably 0 ~ 150nm, are particularly preferably 70 ~ 120nm.
Supporter can enumerate cellulose mesentery (cellulose diacetate, Triafol T, acetylbutyrylcellulose etc.), polyester mesentery, polycarbonate membrane, polyester mesentery (polyethylene terephthalate), polyethylene film, polypropylene screen, polychloride system film, polyvinyl alcohol film, polymethyl methacrylate film, acrylic film, norborene mesentery particularly.As such material optimum fiber cellulose ester film.
In addition, the plastifier containing the physical property for making it have expectation in supporter and/or the optical characteristics adjusting agent for the optical property that makes it have expectation.
Be not particularly limited as plastifier, phthalic ester system, phosphate system, geocerellite system etc. can be enumerated as its preferred example.
Be not particularly limited as optical characteristics adjusting agent, the compound that the optical anisotropies such as the compound containing aromatic cycle compound, liquid-crystal compounds, Anisotropic shapes of the nitrogen-containing compound shown in Japanese Unexamined Patent Publication 2012-234094 are large can be enumerated as its preferred example.
< material liquid >
(polymerizable liquid crystal compound)
Rod-like liquid crystal compound contained by optical anisotropic layer is such as rod-like nematic liquid crystal compound.As rod-like nematic liquid crystal compound, such as, preferably use azomethine class, azoxy class, cyanobiphenyl class, cyano-phenyl ester class, benzoates, cyclohexanecarboxylic acid's ester class, cyanophenylcyclohexanes class, cyano group substituted-phenyl miazines, alkoxy substituted phenyl miazines, Ben Ji dioxane, diphenyl acetylene class and alkenylcyclohexyl alkane benzonitrile class.Be not only low molecular weight liquid crystal compound, also can use high molecule liquid crystal compound.
Polymerizable liquid crystal compound is by being directed into liquid-crystal compounds to obtain by polymerizable group.The example of polymerizable group comprises unsaturated polymerizable group, epoxy radicals and aziridinyl, preferred unsaturated polymerizable group, particularly preferably the unsaturated polymerizable group of ethylenic.Polymerizable group can utilize various methods to be directed in the molecule of liquid-crystal compounds.The number of the polymerizable group that polymerizable liquid crystal compound has is preferably 1 ~ 6, is more preferably 1 ~ 3.The example of polymerizable liquid crystal compound comprises Makromol.Chem., 190 volumes, 2255 pages (1989), AdvancedMaterials, 5 volumes, 107 pages (1993), United States Patent (USP) No. 4683327 instructions, United States Patent (USP) No. 5622648 instructions, United States Patent (USP) No. 5770107 instructions, International Publication WO95/22586 publication, International Publication No. 95/24455 publication, International Publication No. 97/00600 publication, International Publication No. 98/23580 publication, International Publication No. 98/52905 publication, Japanese Unexamined Patent Publication 1-272551 publication, Japanese Unexamined Patent Publication 6-16616 publication, Japanese Unexamined Patent Publication 7-110469 publication, the compound recorded in Japanese Unexamined Patent Publication 11-80081 publication and Japanese Unexamined Patent Publication 2001-328973 publication etc.Also can and use polymerizable liquid crystal compound of more than two kinds.
In addition, the amount of contained in material liquid polymerizable liquid crystal compound is preferably 10 ~ 50 quality %, is more preferably 20 ~ 40 quality %, is particularly preferably 25 ~ 35 quality %.
(tropism control agent)
The orientation of the effect making liquid-crystal compounds vertical orientated, the liquid-crystal compounds contributing to intermediate coat interface side is played in tropism control agent.That is, the molecule substantial orthogonality ground orientation of liquid-crystal compounds is made by tropism control agent.As long as tropism control agent can make the molecule substantial orthogonality ground orientation of liquid-crystal compounds, be then not particularly limited.Preferred example comprises the compound shown in following general formula.Can containing be selected from wherein two or more.
As tropism control agent, consider club shaped structure for making liquid-crystal compounds vertical orientated (namely main chain is long to a certain degree) and there are the starting material being easy to the hydrophilic radical be combined with intermediate coat, orientation assistant.Such as ,-the N-C of following chemical formula (chemical formula 1) is thought
2h
6part is relevant with the function of tropism control agent.
[chemical formula 1]
In general formula, R represent carbon number be 1 ~ 30 alkoxy, more preferably carbon number be 1 ~ 20 alkoxy, further preferably carbon number be the alkoxy of 1 ~ 15.But, the CH of more than 1 in alkoxy
2and the CH of non-conterminous more than 2 mutually
2can also by-O-,-S-,-OCO-,-COO-,-NRa-,-NRaCO-,-CONRa-,-NRaSO
2-or-SO
2nRa-replaces.Ra represents that hydrogen atom or carbon number are the alkyl of 1 ~ 5.
Vertical orientatedly refer to that long axis of liquid crystal molecule is vertical with face.But, do not require strictly vertical, in this instructions, refer to the orientation that long axis of liquid crystal molecule is less than 30 degree with pitch angle (=inclination angle) formed by the face perpendicular to face.
The consumption of tropism control agent be preferably the solid constituent of material liquid 0.001 ~ 1 quality %, be more preferably 0.005 ~ 0.5 quality %, be particularly preferably 0.01 ~ 0.1 quality %.
(orientation assistant)
Orientation assistant play by tropism control agent conveyance to Air Interface side, the effect making its local distribution, contribute to the vertical orientated of the liquid-crystal compounds at Air Interface place.Although above-mentioned tropism control agent also contributes to the orientation of Air Interface side but orientation anchor force is not strong.The orientation of orientation assistant support air interface side.As orientation assistant, preferably use surfactant.But orientation assistant is not limited thereto.
As preferred example, comprise following general formula (I), the compound shown in (II).Orientation assistant itself owing to needing driving force for walking in Air Interface, therefore preferred orientation assistant have with the poor compatibility of liquid-crystal compounds contain the group of F and the hydrophilic radical for being combined with tropism control agent.Such as, in chemical formula 2, chemical formula 3 (general formula (I), (II)), be equivalent to the group in left side as the group containing F, be equivalent to the part of-COOR-on right side as hydrophilic radical.Think that these groups are relevant with the function of orientation assistant.
[chemical formula 2]
[chemical formula 3]
In general formula, R represent carbon number be 1 ~ 30 alkoxy, more preferably carbon number be 1 ~ 20 alkoxy, further preferably carbon number be the alkoxy of 1 ~ 15.
In addition, in described general formula, between the part with *, represent bonding.
In addition, in described general formula, a and b represents ratio contained in compound.
The consumption of orientation assistant be preferably relative to liquid-crystal compounds (being solid constituent when material liquid) 0.001 ~ 1 quality %, be more preferably 0.005 ~ 0.5 quality %, be particularly preferably 0.01 ~ 0.1 quality %.
(solvent)
Solvent has liquid-crystal compounds dissolving and is dissolved or swelling characteristic by supporter.Such as dissolve or swelling solvent as by cellulose esters, have MEK, acetone, methyl acetate, ethyl acetate, methylene chloride, ethylene dichloride, tetrachloroethane, trichloroethanes, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate etc.In addition, also supporter can be dissolved or swelling solvent multiple combination.
Here, swellingly refer to while the shape of the solid state maintaining the polymer substance such as resin, space that the solvent molecule of low relative molecular amount enters into polymer substance carries out permeating thus the state of volumetric expansion, is specifically that polymeric membrane dipping 10 minutes in a solvent, the thickness of 0.1mm increases by more than 1% by thickness.Thickness measures by film thickness instrument (Anritsu KB601).In addition, dissolve the state referring to and to be dissociated by the macromolecular chain that solvent molecule surrounds, disperse in a solvent, specifically refer to that the weight of film reduced more than 0.1% before and after dipping by the polymeric membrane of 50mm × 50mm × 0.1mm dipping 10 minutes in a solvent.Weight measures by electronic balance (MettlerToredo XS104).
In addition, also it can not made to dissolve or swelling solvent containing some.These solvents are preferred for controlling the dissolving of such as supporter-swelling.Such as there are alcohols (ethanol, methyl alcohol, normal butyl alcohol, isopropyl alcohol, n-propanol etc.), hydro carbons (dimethylbenzene, toluene etc.) etc.
As mentioned above, material liquid is except dissolving supporter or except swelling solvent, can also containing other multi-solvents.
Solvent contained by material liquid preferably has ± 2 (J/cm relative to the raw-material solubility parameter SP value of supporter
3)
1/2solubility parameter SP value in scope.Specifically, 9.3), acetone (SP value: 10.0), methyl acetate (SP value: 9.6), ethyl acetate (SP value: combination 9.0) relative to cellulose esters, (SP value: 10.9) can enumerate MEK (SP value:.
By using the solvent of above-mentioned scope, the adaptation of optical anisotropic layer and supporter can be improved.
As long as dissolve or swelling solvent (solvent that=SP value is close relative to supporter) containing by supporter in material liquid, then other multi-solvents can also be contained.The dissolubility of supporter can be controlled by other solvents, therefore, it is possible to improve adaptation, thus more preferred.
< polymerization initiator >
Preferably containing polymerization initiator in material liquid.In the mode of carrying out being made polyreaction by Ultraviolet radiation, the polymerization initiator used can the Photoepolymerizationinitiater initiater of initiated polymerization preferably through Ultraviolet radiation.The example of Photoepolymerizationinitiater initiater can enumerate alpha-carbonyl compound (No. 2367661st, United States Patent (USP), each instructions of No. 2367670th, United States Patent (USP) is recorded), acyloin ether (United States Patent (USP) No. 2448828 instructions is recorded), α-hydrocarbon substituted aromatic acyloin com (United States Patent (USP) No. 2722512 instructions is recorded), multinuclear naphtoquinone compounds (No. 3046127th, United States Patent (USP), the each instructions of No. 2951758th, United States Patent (USP) is recorded), the combination (United States Patent (USP) No. 3549367 instructions is recorded) of triarylimidazoles dipolymer and p-aminophenyl ketone, acridine and compound phenazine (Japanese Laid-Open Patent Publication 60-105667 publication, ) recorded by United States Patent (USP) No. 4239850 instructions Ji oxadiazole compound (United States Patent (USP) No. 4212970 instructions is recorded) etc.The consumption of described Photoepolymerizationinitiater initiater be preferably the solid constituent of the 2nd material liquid 0.1 ~ 20 quality %, be more preferably 1 ~ 8 quality %.
(preparation of material liquid)
Material liquid is to be dissolved with the form preparation of coating fluid of liquid-crystal compounds, tropism control agent and orientation assistant in a solvent.Preferably in material liquid, Photoepolymerizationinitiater initiater is added in the manufacture method of present embodiment.In the painting process of present embodiment, preferably by the surface of coating solution at intermediate coat.As coating process, coiling rod rubbing method, extrusion coating methods, directly gravure coating process, the reverse various method such as gravure coating process, mould Tu Fa can be utilized to carry out.
(manufacturing process)
Fig. 1 represents one of the manufacturing equipment of the phase retardation film of present embodiment example.The manufacture method of the phase retardation film of this manufacturing equipment is used to have the painting process of coating feedstock liquid on banded supporter; Make the drying process of dried coating film; After drying to the heat treatment step that film is heat-treated; After heat treatment film is irradiated to the curing process of the formation optical anisotropic layer that active radioactive ray make it solidify.Manufacturing equipment and each operation are described.
The manufacturing equipment 10 of phase retardation film possess send supporter W carrying device 12, the dispense tip 14 of coating feedstock liquid, the decompression chamber 18 keeping the backing roll 16 of supporter W, the upstream side of dispense tip 14, drying device 20, annealing device 22, cooling device 24, active wire irradiation unit 26, temperature adjustment roller 28 and take-up mechanism 30.
A () prepares the operation of banded supporter
Banded supporter W has the web-like be entangled in core.Use send the supporter W of roll device 12, make it be continuously traveling.Carrying device 12 possesses the roller (not shown) of the supporter W that can arrange the roll be entangled in core.By making this roller rotate, banded supporter W is transported continuously on apparatus for coating etc.
The painting process of (b) coating feedstock liquid, formation film
In painting process, use apparatus for coating coating feedstock liquid on the banded supporter W of conveyance continuously.As apparatus for coating, common apparatus for coating can be used with not limiting.Such as following apparatus for coating, its have keep the backing roll 16 of the banded supporter W transported continuously, be entangled in coating feedstock liquid on the banded supporter W on backing roll 16 dispense tip 14, in order to make to be formed at the decompression chamber 18 of the upstream side from the stable dispense tip 14 of the liquid pearl (accumulation of coating fluid) between on the material liquid of dispense tip 14 and banded supporter.The flow of the 1st material liquid supplied by dispense tip 14 is adjusted according to the mode reaching required film thickness by pump.In addition, the degree of decompression of decompression chamber 18 is adjusted by drawdown pump.Space with backing roll 16 is adjusted narrower stably to form liquid pearl.
C () is by the film be coated on supporter drying, the drying process making film
In drying process, use the drying device 20 that film is heated, drying is carried out to the film be coated in painting process on banded supporter W.As drying device 20, common drying device can be used with not limiting.Such as, can use and utilize the convective drying mode of hot blast, utilize the photothermal radiant drying modes etc. such as infrared ray.When using hot blast, the temperature of adjustment hot blast and air quantity are to control the drying of film.In addition, brush method as hot blast, gap nozzle (there is the nozzle of slit-shaped openings shape on the Width of banded supporter) or punching nozzle (flat plate nozzles of porous type) etc. can be used.In drying process, by dried coating film before film arrives dryin-up point.Here, dryin-up point refers to that the film surface temperature of film reaches the position in the drying process of the temperature identical with the dry wind temperature near film, the evaporation be dried to the solvent from film reaches equilibrium state, disappear with the thermonegative reaction of evaporation position (=namely, the solvent in film reduces, evaporation becomes the position occurred hardly).Painting film viscosity is now more than 5000mPas.The viscosity of film can measure as follows: wiped off rapidly, put into medicine bottle by the film arrived on the supporter of dryin-up point, utilize vibration viscometer (AandD system, SV-10) to measure.
The solvent contained by material liquid is made to infiltrate inner more than 0.3 μm of supporter W in drying process.Thus, the region that supporter W mixes with film is formed.
In addition, by controlling rate of drying in drying process, the dissolubility of solvent to supporter W can be controlled.Be 0.1 [g/m by making rate of drying
2sec] below, because closely sealed performance improves further, therefore more preferred.By slowing down rate of drying, solvent increases the infiltration capacity of supporter, can improve adaptation.
In addition, by carrying out drying to film, the position of tropism control agent and orientation assistant is fixed.
D heat treatment step that () heats film
In heat treatment step, in order to heat-treat the film with the banded supporter W of film in drying process drying, there is annealing device 22.Heat more than 25 seconds to reach the temperature making tropism control agent and orientation assistant diffuse to film coated surface.The temperature of this film is preferably made to be the scope of 90 ~ 120 DEG C.
Annealing device 22 can use common heating arrangement with not limiting.Such as, use utilizes the convective drying mode of hot blast, utilizes the photothermal radiant drying modes etc. such as infrared ray.When using hot blast, the temperature of adjustment hot blast and air quantity are to control the drying of film.In addition, brush method as hot blast, gap nozzle (there is the nozzle of slit-shaped openings shape on the Width of banded supporter) or punching nozzle (flat plate nozzles of porous type) etc. can be used.In addition, heat treatment step can also be do not have compartment of terrain to arrange continuously with drying process.
E () is irradiated active radioactive ray to film, is formed the curing process of optical anisotropic layer
In heat treatment step, in refrigerating work procedure, utilize cooling device 24 to be adjusted to be suitable for the temperature of the active radiation exposure of curing process through the heat treated banded supporter W with film.As cooling device 24, in general use the convection current type of cooling etc. utilizing cooling air to carry out.When using cooling air, the temperature of adjustment cooling air and air quantity are to control the temperature of film.In addition, brush method as cooling air, gap nozzle (there is the nozzle of slit-shaped openings shape on the Width of banded supporter) or punching nozzle (flat plate nozzles of porous type) etc. can be used.In addition, particularly when not arranging the film temperature that refrigerating work procedure also becomes suitable, also can not cooling device be set.The temperature of carrying out cooling is liquid-crystal compounds orientation and by temperature fixing for the position of described tropism control agent and described orientation assistant again.
In curing process, active wire irradiation unit 26 is used to irradiate active wire, by curing of coating to film cooled in refrigerating work procedure.As active wire irradiation unit 26, such as, use ultraviolet lamp etc.When using ultraviolet lamp, adjustment ultraviolet irradiation intensity and exposure, the degree of cure of adjustment film.Exposure intensity is preferably 10 ~ 1000mW/cm
2, be more preferably 100 ~ 400mW/cm
2.In addition, cumulative exposure is preferably 10 ~ 1000mJ/cm
2, be more preferably 20 ~ 200mJ/cm
2.In addition, also can reduce the oxygen concentration of film periphery atmosphere when irradiating active wire as required to adjust the degree of cure of film, be preferably 50 ~ 1000ppm.Utilizing active wire irradiation unit 26 to carry out active wire pre-irradiation, making the residual solvent ratio of film be less than 3 quality %.When making the residual solvent ratio in film be more than 3 quality %, there is the bad or film strength of orientation and reduce in the cross-linking reaction that the residual solvent hindered in film carries out orientation and utilizes active wire to irradiate afterwards.
In addition, the film temperature of active wire pre-irradiation can utilize arbitrary method to adjust, such as, banded supporter can be entangled in the enterprising Row sum-equal matrix of temperature adjustment roller 28.Be preferably 5 ~ 80 DEG C, be more preferably 20 ~ 50 DEG C.
After curing process, in coiling process, take-up mechanism 30 is utilized to be batched by the banded supporter W being formed with middle layer.Take-up mechanism 30 possess core can be set roller (not shown), by make roller rotate and banded supporter W is batched continuously.
Then, the effect of liquid-crystal compounds, tropism control agent, orientation assistant is described with reference to Fig. 2 A ~ Fig. 2 D.
Fig. 2 A to represent in painting process material liquid containing liquid-crystal compounds, tropism control agent, orientation assistant of on supporter coating and defines the state of film.The equal No yield point ground configuration of all raw material of liquid-crystal compounds, tropism control agent, orientation assistant.
Fig. 2 B represents the state of having carried out film drying in drying process.In the interface of middle layer and film, a part of liquid-crystal compounds is by tropism control agent orientation in vertical direction.On the interface of film and air, utilize and make liquid-crystal compounds vertically orientation because of orientation assistant to the tropism control agent of Air Interface side diffusion.When the drying of film is carried out, the diffusion of tropism control agent and orientation assistant stops.Its result, makes a part of liquid-crystal compounds not orientation in vertical direction.In addition, solvent is made to penetrate into inner more than 0.3 μm of supporter.
Fig. 2 C represents that film is by the state heated in heat treatment step.The viscosity of film reduces, tropism control agent and orientation assistant spread to Air Interface side.In addition, the orientation of liquid-crystal compounds is destroyed, liquid-crystal compounds becomes random configuration.
Fig. 2 D represents the state of irradiating active wire through refrigerating work procedure.By cooling at active wire pre-irradiation, liquid-crystal compounds is orientation again.In addition, now because tropism control agent and orientation assistant move to Air Interface side, therefore the orientation anchor force of the liquid-crystal compounds of Air Interface side is strengthened.Its results presumption, the orientation of the interface portion of supporter/optical anisotropic layer is supported, the orientation integral of the liquid-crystal compounds of optical anisotropic layer is optimized.
Embodiment 1
Below enumerate embodiments of the invention and in more detail the present invention is described.But the present invention is not limited to these embodiments.
The preparation > of < supporter
Prepare commercially available Fuji Photo Film Co., Ltd.'s three cellulose acetate membrane (TAC) i.e. FujiTacTD40UZ.Use time-of-flight type ion microprobe TOF-SIMS (ION-TOF TOFSIMS5) to analyze the composition of this film, result detects molion (the supporter composition: C produced by supporter and additive
5h
5o
2 +, plasticiser component; C
14h
15o
6(phthalic ester source), optics visualization reagent composition: C
24h
25n
6(nitrogen compound source)).
The preparation > of < material liquid
By the polymerizable liquid crystal compound be made up of following compound 20 quality % shown in compound 80 quality % following chemical formula (chemical formula 4) Suo Shi and following chemical formula (chemical formula 5) (liquid crystal phase-isotropic phase transition temperature utilizes means of differential scanning calorimetry to measure DCS (TAInstrument Q20) and calculates), following Photoepolymerizationinitiater initiater IRGACURE907 (BASF AG's system shown in chemical formula (chemical formula 6), IRGACURE is registered trademark) 3 quality %, the following tropism control agent 1 quality % shown in chemical formula (chemical formula 7) and the orientation assistant shown in following chemical formula (chemical formula 8): 0.4 quality % is dissolved in and is mixed with in the solvent of MEK and cyclohexanone with the ratio of 80:20, thus prepare the material liquid of the solid component concentration 33 quality % that optical anisotropic film is formed.As other organic solvents, may be used singly or in combin MEK (MEK), cyclohexanone, MIBK (methyl isobutyl ketone).
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
[chemical formula 8]
The formation > of < optical anisotropic layer
Prepared material liquid is supplied to the slit die of the manufacturing equipment shown in Fig. 1, is coated on film.After coating, by the solvent seasoning of film, formation film in drying process.Specifically, use 55 DEG C of warm airs to carry out being dried to reaching dryin-up point, form film.Wherein, dryin-up point confirms as follows: measure the film temperature of drying process and do not have the film surface temperature (the dry wind temperature near=film) of the banded supporter of film after being coated with, finding out the position reaching identical temperature.Here, the film surface temperature of film temperature and banded supporter arranges non-contact thermometer (IT2-80, Keyence Inc.) to measure.Afterwards, through the temperature of film being cooled to polymerizable liquid crystal compound orientation and the refrigerating work procedure of the temperature of tropism control agent and being fixed of orientation assistant again, making the temperature before Ultraviolet radiation reach the temperature recorded in table, is utilize high-pressure sodium lamp to carry out 300mJ/cm in 300ppm atmosphere at oxygen concentration
2the Ultraviolet radiation of accumulated light.
Change manufacturing condition, create the phase retardation film of embodiment 1-10, comparative example 1-11.Here, rate of drying is controlled by the temperature or solvent gas concentration regulating drying process.In addition, the rate of drying of coated film is calculated by the solid component concentration after drying process, solid component concentration after drying process be to drying process after film sample, calculate except the quality before and after desolventizing by utilizing Minton dryer (YAMATOSCIENTIFIC DP22).Quality utilizes electronic balance (MettlerToredo XS104) to measure.
In addition, the residual solvent ratio after heat treatment step is same with rate of drying, samples to the film after heat treatment step, calculates except the quality before and after desolventizing by utilizing Minton dryer (YAMATOSCIENTIFIC DP22).Quality utilizes electronic balance (MettlerToredo XS104) to measure.
In addition, with regard to the infiltration thickness of solvent in supporter, utilize focused ion beam (FIB) to be cut out in the cross section of the sample through active illuminated line operation, use scanning electron microscope (SEM) to observe, thus measure.(the FEI Helios400S that FIB with SEM operative installations becomes to be integrated evaluates.)
The evaluation > of < orientation defect
Be clipped in Nicol crossed by gained film, visualization is with or without the gonorrhoea portion seen because of orientation defect.
A: do not have gonorrhoea portion
B: a little gonorrhoea portion can be seen but practical no problem
C: clearly existing problems in visible gonorrhoea portion, practicality
The evaluation > of < adaptation
The cross-section method based on JISK5600-5-6 (JIS: Japanese Industrial Standards, JISK5600-5-6 correspond to ISO2409, ISO: standardization international organization) is utilized to evaluate.
A: departed from for 0% (not departing from)
B: disengaging is within 5%
C: disengaging is within 10%
D: depart from more than 10%
< evaluation result >
Fig. 3 and Fig. 4 indicates manufacturing condition and evaluation result.
Embodiment 1 ~ 10 about adaptation be more than C evaluation, be evaluated as more than B about orientation defect.Embodiment 3 is 1.5 μm owing to infiltrating thickness, is evaluated as A therefore about adaptation.And embodiment 8 is 0.5 μm owing to infiltrating thickness, be evaluated as C therefore about adaptation.
In heat treatment step meet 100 DEG C, 60 seconds conditions embodiment 1 ~ 3,6,8 ~ 10 about orientation defect be evaluated as A.Consider that tropism control agent and orientation assistant diffuse to the surface of film.And in heat treatment step, be 26 seconds owing to being time in slightly higher than liquid crystal phase-isotropic phase transition temperature 87 DEG C, embodiment 5 in embodiment 4, therefore about orientation defect, respective is evaluated as B.Consider that the diffusion ratio embodiment 1 ~ 3,6,8 ~ 10 of tropism control agent and orientation assistant is few.In refrigerating work procedure, embodiment 7 is 83 DEG C lower than liquid crystal phase-isotropic phase transition temperature.Be evaluated as B.
In comparative example 1, owing to employing MIBK as solvent, therefore infiltrating thickness is 0.1 μm.Thus, about adaptation, be evaluated as D.
In comparative example 2, employ PET as supporter, employ MEK as solvent.Owing to being 0.1 μm, therefore about adaptation, be evaluated as D.
In comparative example 3,4, relative to liquid crystal phase-isotropic phase transition temperature be ± 1 DEG C, the diffusion of tropism control agent and orientation assistant is insufficient, about orientation defect, is evaluated as C.
In comparative example 5, because heat treatment time is 24 seconds, therefore about orientation defect, be evaluated as C.In comparative example 6, because residual solvent ratio is 4 quality %, therefore about orientation defect, be evaluated as C.
In comparative example 7, owing to being 0.2 μm, therefore about adaptation, be evaluated as D.
In comparative example 8, due to higher than liquid crystal phase-isotropic phase transition temperature in refrigerating work procedure, therefore about orientation defect, be evaluated as C.In comparative example 9 ~ 11, due to not containing tropism control agent, any one or both in orientation assistant, therefore about orientation defect, be evaluated as C.
Symbol description
The manufacturing equipment of 10 phase retardation films
12 carrying devices
14 dispense tips
16 backing rolls
18 decompression chamber
20 drying devices
22 annealing devices
24 cooling devices
26 active wire irradiation units
28 temperature adjustment rollers
30 take-up mechanisms
Claims (5)
1. a manufacture method for phase retardation film, it comprises following operation:
Prepare the operation containing the banded supporter of at least a kind in plastifier and optical characteristics adjusting agent;
The described supporter be continuously traveling is coated on the material liquid being dissolved with rod-like polymerizable liquid crystal compound, tropism control agent and orientation assistant in the solvent of dissolving or swelling described supporter, forms the painting process of film;
By drying coated film on described supporter, the position of described tropism control agent and described orientation assistant is fixed and formed the drying process making described solvent penetrate into the film of inner more than 0.3 μm of described supporter;
Reaching according to the internal temperature of described film makes described tropism control agent and described orientation assistant to the mode of the temperature of described film coated surface movement, described film is heated to the heat treatment step of more than 25 seconds;
After described heat treatment step, the mode reaching the temperature of being fixed the position of described tropism control agent and described orientation assistant according to the internal temperature of described film carries out the refrigerating work procedure cooled; With
After described refrigerating work procedure, described film residual solvent ratio being less than to 3 quality % irradiates active radioactive ray, by described curing of coating, forms the curing process of optical anisotropic layer.
2. the manufacture method of phase retardation film according to claim 1, wherein, it is ± 2 (J/cm that described solvent contained in described material liquid has relative to the raw-material solubility parameter SP value of described supporter
3)
1/2solubility parameter SP value in scope.
3. the manufacture method of phase retardation film according to claim 1 and 2, wherein, described material liquid except dissolve or swelling described supporter described solvent except, also containing other multi-solvents.
4. the manufacture method of the phase retardation film according to any one of claims 1 to 3, wherein, in described drying process, comprises with 0.1g/m
2the rate of drying of below sec is by the operation of described film drying.
5. the manufacture method of the phase retardation film according to any one of Claims 1 to 4, wherein, described supporter is cellulose mesentery.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013073104 | 2013-03-29 | ||
| JP2013-073104 | 2013-03-29 | ||
| PCT/JP2014/057819 WO2014156981A1 (en) | 2013-03-29 | 2014-03-20 | Phase shift film manufacturing method |
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| CN105074516A true CN105074516A (en) | 2015-11-18 |
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| CN201480019223.0A Pending CN105074516A (en) | 2013-03-29 | 2014-03-20 | Phase shift film manufacturing method |
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| Country | Link |
|---|---|
| JP (1) | JP6146935B2 (en) |
| KR (1) | KR101745235B1 (en) |
| CN (1) | CN105074516A (en) |
| WO (1) | WO2014156981A1 (en) |
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| CN109564317A (en) * | 2016-08-12 | 2019-04-02 | 富士胶片株式会社 | Optical thin film, polarizing film and image display device |
| CN115151847A (en) * | 2020-02-20 | 2022-10-04 | 富士胶片株式会社 | Optical laminate, polarizing plate, and image display device |
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|---|---|---|---|---|
| JP6668605B2 (en) * | 2015-04-15 | 2020-03-18 | 大日本印刷株式会社 | Optical film |
| JP6665420B2 (en) * | 2015-04-15 | 2020-03-13 | 大日本印刷株式会社 | Optical film |
| KR20220032587A (en) * | 2019-08-16 | 2022-03-15 | 후지필름 가부시키가이샤 | Manufacturing method of optical film |
| JPWO2022176884A1 (en) * | 2021-02-16 | 2022-08-25 |
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Also Published As
| Publication number | Publication date |
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| JPWO2014156981A1 (en) | 2017-02-16 |
| JP6146935B2 (en) | 2017-06-14 |
| KR20150119471A (en) | 2015-10-23 |
| KR101745235B1 (en) | 2017-06-08 |
| WO2014156981A1 (en) | 2014-10-02 |
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