CN101512401A - Composite retardation plate, method for production thereof, composite optical member, and liquid crystal display device - Google Patents
Composite retardation plate, method for production thereof, composite optical member, and liquid crystal display device Download PDFInfo
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- CN101512401A CN101512401A CNA2007800329695A CN200780032969A CN101512401A CN 101512401 A CN101512401 A CN 101512401A CN A2007800329695 A CNA2007800329695 A CN A2007800329695A CN 200780032969 A CN200780032969 A CN 200780032969A CN 101512401 A CN101512401 A CN 101512401A
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Abstract
Disclosed is a composite retardation plate which comprises a retardation plate composed of a transparent resin, a primer layer, and a coating retardation layer comprising an organic modified lay complex and a binder resin laminated in this order, wherein the primer layer is composed of a composition comprising a water-soluble organic metal compound selected from a water-soluble organic titanium compound and a water-soluble organic zirconium compound and a water-soluble resin. The composite retardation plate may further comprise a polarizing plate preferably laminated on the side of the resin retardation plate, thereby providing a composite optical member. The composite optical member may be combined with a liquid crystal cell to provide a liquid crystal display device.
Description
Technical field
The present invention relates to be fitted in composite phase difference board and the manufacture method of using on the liquid crystal lattice cell thereof, the composite optical member that uses it and liquid crystal indicator.The invention still further relates to the technology of the water tolerance that improves composite phase difference board.
Background technology
In recent years, liquid crystal indicator is being brought into play low power consumption, subnormal voltage operation, light weight, slim etc. feature, promptly popularizes with display device as information such as mobile phone, portable data assistance, display of computer, TVs.Along with the development of liquid crystal technology, the liquid crystal indicator of various patterns has been proposed, problems such as response speed, contrast, Narrow Field Of Vision angle are solved gradually.
One of this liquid crystal indicator has makes rod shaped liquid crystal molecule with the plus or minus dielectric constant anisotropy liquid crystal indicator with respect to vertical orientated (VA) pattern of substrate arranged perpendicular.This vertical alignment mode vertically is orientated with respect to substrate owing to liquid crystal molecule under non-driven state, so light passes through liquid crystal layer under the state that does not have polarized light to change.Therefore, make polarization axle vertical mutually, deceive demonstration in the time of can obtaining from top view substantially entirely, can obtain high-contrast by the straight line of configuration up and down polaroid at liquid crystal panel.But, this liquid crystal lattice cell only possesses in the liquid crystal indicator of VA pattern of polaroid, when from oblique when it is observed, because the shaft angle degree of the polaroid of configuration departs from 90 ° and the interior rod shaped liquid crystal molecule performance birefringence of lattice cell, therefore light leak, the significantly reduced situation of contrast can take place.
In order to eliminate this light leak, be necessary between liquid crystal lattice cell and straight line polaroid, to dispose optical compensation films, adopt in the past between liquid crystal lattice cell and polaroid up and down, dispose respectively the specification of 1 biaxiality polarizer, respectively every liquid crystal lattice cell up and down or 2 all in the positive uniaxiality polarizer of a side of liquid crystal lattice cell configuration and the specifications of the polarizer of biaxiality fully.
For example, open in the liquid crystal indicator of having put down in writing in the 2001-109009 communique (patent documentation 1) at vertical alignment mode the spy, between up and down polaroid and liquid crystal lattice cell, dispose a plate (that is, positive uniaxiality polarizer) and c plate (that is, the polarizer of biaxiality) fully respectively.
Positive uniaxiality polarizer is meant the phase difference value R in the face
0Phase difference value R with thickness direction
ThRatio R
0/ R
ThBe roughly 2 film, the polarizer of biaxiality is meant the phase difference value R in the face fully
0Substantially be 0 film.Here, late mutually axial refractive index is that the refractive index of leading phase shaft direction in the face of nx, film (face in late a vertical direction) mutually is that the refractive index of the thickness direction of ny, film is the thickness of nz, film when being d in making face, the phase difference value R0 that face is interior and the phase difference value R of thickness direction
ThUse following formula (I) and (II) definition respectively.
R
0＝(nx-ny)×d (I)
R
th＝〔(nx+ny)/2-nz〕×d (II)
In the positive uniaxiality film, because
, therefore
Even if positive uniaxiality film, R
0/ R
ThBecause the variation of the condition of extension also can change between about 1.8～2.2.In the film of complete biaxiality, because
, therefore
Fully the film of biaxiality also is known as the film that optic axis is positioned at normal direction because therefore the refractive index difference (little) of thickness direction only has negative uniaxiality, in addition as mentioned above, also is known as the c plate sometimes.
As one of film (c plate) of above-mentioned complete biaxiality, the film that is made of the coating that contains organic decoration clay complex is arranged.For example, the spy opens that disclosing in the 2005-338215 communique (patent documentation 2) on the polarizer that contains the transparent resin film that is orientated in face is situated between has the anisotropic coating phase separation layer of refractive index by the adhesive phase lamination, and then on the surface of this coating phase separation layer, adhesive phase is set, make composite phase difference board, also put down in writing at this resin polarizer side lamination polaroid.In addition, the spy opens and discloses in the 2006-10912 communique (patent documentation 3) that to make with the aliphatic diisocyanate be that the urethane resin of substrate is as bonding agent, the composition that will contain itself and organic decoration clay complex forms the membranaceous polarizer that forms, also having put down in writing is situated between is laminated to this polarizer on the polaroid by adhesive phase, makes composite polarizing plate.Specifically, disclose adhesive phase side transfer printing coating phase separation layer, the formation of second adhesive phase has been set on this coating phase separation layer surface at the polaroid of band bonding agent.
These spies open the 2005-338215 communique or the spy opens in the disclosed formation of 2006-10912 communique, because the coating phase separation layer is clipped between two adhesive phases, therefore be easy to be subjected to the influence that stress produced from the outside, when when composite phase difference board or composite polarizing plate apply physical external force, stress concentrates on the coating phase separation layer, rupture herein, produce light leak.
The inventor etc. are contained the polarizer of transparent resin and are had the anisotropic coating phase separation layer of refractive index when making composite phase difference board at lamination, replace to undercoat by the adhesive phase that will be disposed between the two, suppressed because physical external force and the caused light leak of the fracture of incident coating phase separation layer is willing to propose patented claim 2006-225058 number as the spy.This undercoat can form with the method for coating fluid by painting bottom coating on base material, and coating liquid for undercoat layer is compared to organic solvent solution and more preferably uses with the form of aqueous solution when the infringement of considering base material.Among the embodiment of above-mentioned patented claim, the coating fluid contain water soluble polyamide epoxy resin and polyvinyl alcohol (PVA) is used in the formation of undercoat, and the daiamid epoxy resin became and made polyvinyl alcohol crosslinked hardening agent this moment.Known in addition, Jie has the water tolerance of the composite phase difference board of polarizer and coating phase separation layer or Jie is had polaroid at this coating phase separation layer side lamination by bonding agent composite optical member also insufficient by this undercoat lamination, when impregnated in this composite phase difference board or composite optical member in the warm water, the phenomenon of the dissolving of undercoat end sections ground, albefaction can take place for example.
Therefore make further research, found that for having for the composite phase difference board that the anisotropic coating phase separation layer of refractive index forms by the undercoat lamination containing on the polarizer of transparent resin to be situated between, comprise water soluble resin and to contain composition with the hardening agent of its reactive high water-soluble organic titanic compound or organic zirconate by in the formation of this undercoat, using, can obtain the composite phase difference board of water tolerance excellence.
Therefore, the object of the present invention is to provide when fitting in the use of liquid crystal lattice cell, the coating phase separation layer is difficult to take place fine fracture, can suppresses to take place light leak, and the also excellent composite phase difference board of water tolerance provides its manufacture method in addition simultaneously.Another object of the present invention is to be provided at the optical layers of other optical function of demonstration of lamination on this composite phase difference board such as polaroid, can suppress light leak when fitting in the liquid crystal lattice cell, simultaneously the also excellent composite optical member of water tolerance.Another other purpose of the present invention is this composite optical member is applicable to liquid crystal indicator.
Summary of the invention
Promptly, the invention provides a kind of composite phase difference board, its coating phase separation layer that contains polarizer, the undercoat of transparent resin for lamination in order and contain organic decoration clay complex and adhesive resin forms, and this undercoat forms by containing the water-soluble organometallics that is selected from water-soluble organic titanic compound and organic zirconate and the composition of water soluble resin.
In addition, the present invention also provides the manufacture method of this composite phase difference board, this method is dissolved in the coating liquid for undercoat layer that forms in the solvent based on water for coating on the surface of the polarizer that contains transparent resin is selected from the water-soluble organometallics of water-soluble organic titanic compound and organic zirconate and water soluble resin, therefrom remove the formation undercoat that desolvates, contain the coating phase separation layer coating fluid that organic decoration clay complex and adhesive resin form in the surface coated of this undercoat in organic solvent, therefrom removing desolvates forms the coating phase separation layer.
The present invention also provides a kind of composite optical member, and it is pressed with the optical layers of other optical functions of demonstration such as polaroid on above-mentioned composite phase difference board upper strata.The present invention also provides a kind of liquid crystal indicator, and this composite optical member is configured on 1 face of liquid crystal lattice cell at least.
Description of drawings
Fig. 1 represents the cross section mode chart that composite phase difference board constitutes for summary.
Fig. 2 represents the cross section mode chart that composite optical member constitutes for summary.
Symbol description
10...... composite phase difference board,
11...... contain transparent resin polarizer,
12...... undercoat,
14...... coating phase separation layer
20...... composite optical member,
21...... show other optical function optical layers,
22...... adhesive phase
Embodiment
Below, explain embodiments of the present invention suitably with reference to accompanying drawing.
(composite phase difference board)
Among the present invention, as shown in Figure 1, lamination contains polarizer 11, undercoat 12 and the coating phase separation layer 14 of transparent resin in order, makes composite phase difference board 10.
Polarizer 11 contains transparent resin, generally is made of the resin that is orientated in face.
Here the resin that uses as long as the transparency is excellent, homogeneous on the optics, from being easy to make the viewpoint of film with orientation etc., preferably use the stretched PTFE film of transparent thermoplastic resin.Thermoplastic resin can be enumerated polycarbonate, polyacrylate, polysulfones, polyethersulfone, cellulose-based resin particularly, be the polyolefin-based resins of principal monomer, is cyclic polyolefin hydrocarbon system resin of principal monomer etc. with polycycle cyclic olefins such as norborene with alkene such as propylene or ethene.In addition, coating layer, the performance phase differential person that design contains liquid crystal liquid crystal property material etc. on transparent resin substrates such as cellulose-based resin also can be used as polarizer 11 and uses.
Phase difference value can be according to suitably selecting in the scope of purposes about 30～300nm of composite phase difference board in the face of resin polarizer 11.For example, when using composite phase difference board in small-sized liquid crystal indicators such as mobile phone or portable data assistance, resin polarizer 11 is that 1/4 wavelength plate person is favourable.
Undercoat 12 is made of the transparent resin that forms by coating.Priming paint generally is meant down coating, and undercoat 12 of the present invention plays a role as the following coating of the phase separation layer 14 that forms by coating.In addition, because the existence of undercoat 12,, can prevent that also organic solvent in this coating fluid is to the influence of polarizer 11 thereon even if directly with the coating fluid coating of coating phase separation layer 14 usefulness.Undercoat 12 is by not showing that the flexible resin that reaches bonding agent constitutes.
In general, many solution with an organic solvent in being used to form the coating fluid of undercoat, but when becoming on the resin polarizer 11 of object this organic solvent solution of coating in the present invention, how can make 11 swellings of resin polarizer or, influence its optical characteristics its corrosion.Therefore, by being that the water of non-solvent forms undercoat 12 as the coating fluid of solvent with respect to common resin.Though it should be noted that to be necessary to use,, also can add water-miscible organic solvents such as alcohols in order to regulate viscosity or adjustment form surface tension etc. with the solvent of water as main body.The example of alcohols can be enumerated methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, ethylene glycol etc.
Undercoat 12 uses water miscible resin.The example of this water soluble resin can be enumerated polyvinyl alcohol resin or water soluble acrylic resin etc.Wherein preferably use polyvinyl alcohol resin.Polyvinyl alcohol resin can also be a resin by modified polyethylene alcohol such as anion-modified polyvinyl alcohol (PVA) such as carboxyl, acetoacetyl modified polyvinylalcohol, methylol modified polyvinylalcohol, amino modified polyvinyl alcohol (PVA) except partly-hydrolysed polyvinyl alcohol (PVA) or fully saponified polyvinyl alcohol (PVA).The commercially available product of suitable polyvinyl alcohol resin can be enumerated " PVA-403 " (trade name) of the partly-hydrolysed polyvinyl alcohol (PVA) of (strain) Network ラ レ sale, " KL-506 (trade name) " of anion-modified polyvinyl alcohol (PVA) etc.The details of these Network ラ レ society system polyvinyl alcohol (PVA) is at Port バ-Le resin specialty network address＜URL:http of the said firm: //www.poval.jp/japan/poval/topics/index.html in set forth (login day: on November 2nd, 2006) as " KURARAY POVAL ".
With the polyvinyl alcohol resin be the water soluble resin of representative because it is water-soluble, poor water resistance when using separately, in order to improve water tolerance, it is crosslinked to be necessary to use several hardening agent to carry out.Crosslinked in order to carry out, can adopt the method that adds the solution of the hardening agent that the crosslinkable water soluble resin is arranged in the coating liquid for undercoat layer that is coated on.At this moment, mainly desolvate by removing, the reaction of water soluble resin and hardening agent is carried out.The reactivity of hardening agent and water soluble resin is high more, and then reacted cross-linking density is high more, so the gained undercoat shows excellent water tolerance.
Thereby, will be selected from of the hardening agent use of the water-soluble organometallics of water-soluble organic titanic compound and organic zirconate among the present invention as water soluble resin.Thus, obtain the good composite phase difference board of water tolerance.Here said water-soluble organic titanic compound and organic zirconate be meant have in the molecule at least 1 organic group Direct Bonding on titanium or zirconium or organic group be situated between and be bonded in the compound of the structure on titanium or the zirconium by oxygen atom or nitrogen-atoms etc., show water-soluble thus.Organic group is meant the functional group of containing carbon at least, for example can be alkyl, alkoxy, acyl group, amino etc.In addition, bonding is not only to refer to covalent bonding, can also be the coordination bonding that chelating shape compound etc. utilizes coordination.As mentioned above, the solvent of coating liquid for undercoat layer is preferred to be water separately, perhaps is mixed with the solvent of a small amount of organic solvent in water, and from then on viewpoint is set out, and organic titanic compound or organic zirconate also can use water-soluble substances.
The exemplary of this water-soluble organic titanic compound and organic zirconate can be enumerated following structure.
(HO)
2Ti[OCH(CH
3)COOH]
2 (1)
(C
3H
7O)
2Ti[OCH
2CH
2N(CH
2CH
2OH)
2]
2 (2)
(HO)
2Zr[OCH(CH
3)COOH]
2 (3)
(C
3H
7O)
2Zr[OCH
2CH
2N(CH
2CH
2OH)
2]
2 (4)
The suitable example of commercially available water-soluble organic titanic compound has " オ Le ガ チ Star Network ス TC-310 ", " オ Le ガ チ Star Network ス TC-315 " that loose this pharmaceuticals industry (strain) sells, " オ Le ガ チ Star Network ス TC-300 ", " オ Le ガ チ Star Network ス TC-400 " (being trade name) etc.In addition, the example of commercially available water-soluble organic zirconate has equally " オ Le ガ チ Star Network ス ZB-400 " (trade name) of being sold by this pharmaceuticals industry of pine (strain) etc.For these commercially available products, chemistry abbreviation and the chemical constitution and the concentration of producer's address is shown below.
" オ Le ガ チ Star Network ス TC-310 ": the chemistry of producer's address is called for short " lactic acid titanium "; Chemical constitution is above-mentioned formula (1); The solution of effective constituent 44 weight %, isopropyl alcohol 40 weight %, water 16 weight %.
" オ Le ガ チ Star Network ス TC-315 ": the chemistry of producer's address is called for short " lactic acid titanium "; Chemical constitution is above-mentioned formula (1); The solution of effective constituent 44 weight %, water 56 weight %.
" オ Le ガ チ Star Network ス TC-300 ": the chemistry of producer's address is called for short " lactic acid titanium "; Chemical constitution is above-mentioned formula (1); The solution of effective constituent 42 weight %, isopropyl alcohol 38 weight %, water 20 weight %.
" オ Le ガ チ Star Network ス TC-400 ": the chemistry of producer's address is called for short " triethanolamine titanium "; Chemical constitution is above-mentioned formula (2); The solution of effective constituent 80 weight %, isopropyl alcohol 20 weight %.
" オ Le ガ チ Star Network ス ZB-400 ": the chemistry of producer's address is called for short " zirconium compound "; Chemical constitution since producer maintain secrecy, therefore except being not quite clear the water miscible organic zirconate; The solution of effective constituent 30 weight %, water 70 weight %.
Being used to form undercoat 12 employed water soluble resins can select in the preferred especially scope from about 0.1～100 weight portion from respect to water soluble resin 100 weight portions, organometallics being suitably decision such as the kind of corresponding water soluble resin in the scope about 0.1～200 weight portion or the kind of organometallics with the ratio of organometallics.Organometallics both had been to be more a small amount of about 0.1～5 weight portion with respect to water soluble resin 100 weight portions, effect is also brought into play in water tolerance raising to undercoat, but cooperate about 5～100 weight portions by volume, water tolerance is improved further performance effect.
As mentioned above, among the present invention, form undercoat 12 by containing the water-soluble organometallics that is selected from water-soluble organic titanic compound and organic zirconate and the composition of water soluble resin, but said composition can also contain other hardening agent except above-mentioned water-soluble organometallics.By this other hardening agent of coupling, can control the curing rate of filming, control as the polarizer 11 of base material and the closing force of coating phase separation layer 14.
Other hardening agent of institute's coupling is not particularly limited, and can enumerate water miscible epoxy resin as preference.Water miscible epoxy resin for example can be the daiamid epoxy resin that chloropropylene oxide and the polyamide polyamine that reaction obtained reaction by dicarboxylic acids such as many alkyl polyamines such as Diethylenetriamine or three second tetramines and hexane diacids are obtained.The commercially available product of this daiamid epoxy resin has firmly changes " ス ミ レ-ズ レ ジ Application 650 (30) " or " ス ミ レ-ズ レ ジ Application 675 " (being trade name) that ケ system テ Star Network ス (strain) sells etc.
With water-soluble organometallics, when other hardening agent of coupling, for example during water miscible epoxy resin, the amount of other hardening agent can be from suitably decision in the scope about 1～20 weight portion with respect to water soluble resin 100 weight portions.So when other hardening agent of coupling, the coupling effect has appearred, and according to the compatibility of water-soluble organometallics, when increasing both additions, it can not negate the possibility that in coating fluid, produces precipitation, therefore, the amount of whole hardening agent that contains water-soluble organometallics is promptly enough about with respect to maximum 100 weight portions of water soluble resin 100 weight portions, preferably from about 1～50 weight portion, more preferably select in the scope from about 1～30 weight portion.
Above-mentionedly thisly contain water-soluble organometallics and water soluble resin, can also contain other composition arbitrarily, for example preferred its solid component concentration of the coating liquid for undercoat layer of other hardening agent is about 1～25 weight %.In addition, the thickness of undercoat 12 is preferably scope about 0.1～10 μ m, is preferably about 0.5～10 μ m especially.
On undercoat 12, form coating phase separation layer 14.Coating phase separation layer 14 is for removing the formed layer that desolvates in the coating fluid that contains organic decoration clay complex and adhesive resin form from organic solvent.Here, organic decoration clay complex is the complex of organism and clay mineral, specifically for example can be scattered in the organic solvent for the clay mineral that will have layer structure and the complex of compoundization of organic compound.Clay mineral with layer structure can be enumerated smectite family or swelling mica etc., by its cation exchange capacity (CEC) can with compoundization of organic compound.Wherein, therefore smectite family preferably uses because the transparency is also excellent.The material that belongs to smectite family can be enumerated hectorite, smectite, bentonitic clay etc.Wherein, transparent excellence few of the material through chemosynthesis etc. at impurity aspect preferred.Particularly, particle diameter is controlled to be very little synthetic hectorite owing to suppressed the scattering of luminous ray, therefore preferred the use.
As with the organic compound of compoundization of clay mineral, can enumerate can with the compound of the oxygen atom of clay mineral or hydroxyl reaction or can be with the ionic compound of exchangeable cation exchange etc., as long as organic decoration clay complex can swelling or is scattered in organic solvent and then is not particularly limited, can enumerate nitrogen-containing compound etc. particularly.Nitrogen-containing compound for example can enumerate primary, the second month in a season or tertiary amine, quaternary ammonium compound etc.Wherein, because cation exchange is easy, the therefore preferred quaternary ammonium compound that uses.Quaternary ammonium compound for example can be enumerated the material with chain alkyl, the material with alkyl ether chain etc.Particularly preferably have carbon number 6～30, particularly have carbon number 6～10 chain alkyl quaternary ammonium compound or have n=1～50, particularly n=5～30-(CH
2CH (CH
3) O) nH base or-(CH
2CH
2CH
2O) quaternary ammonium compound of nH base.
Owing to the various auxiliary materials that when it is made, use, can sneak into chloride compound in the organic decoration clay complex as impurity is many.The amount of this chlorine compound for a long time, make have behind the coating phase separation layer from film ooze out may.At this moment, by bonding agent this coating phase separation layer is fitted in the liquid crystal lattice cell when on glass when being situated between, bounding force in time through reducing significantly.Therefore, preferably from organic decoration clay complex, utilize washing to remove chlorine compound in advance, when with wherein chloride amount be 2, when the following state of 000ppm contains in organic solvent, can suppress the reduction of this bounding force.Removing of chlorine compound can be undertaken by the method for washing organic decoration clay complex.
Organic decoration clay complex can also be used in combination more than 2 kinds.The commercially available product of suitable organic decoration clay complex has respectively the synthetic hectorite sold with the trade name of " Le-セ Application イ ト STN " or " Le-セ Application イ ト SPN " by コ-プ ケ ミ カ Le (strain) and the complex of quaternary ammonium compound etc.
The organic decoration clay complex that can be scattered in this organic solvent is used in combination with adhesive resin from viewpoints such as the expression power of the coating easiness on undercoat 12, optical characteristics or mechanical characteristics.Preferably use organic solvents, particularly glass transition temperature such as being dissolved in toluene, dimethylbenzene, acetone, ethyl acetate to be preferably room temperature following (about's below 20 ℃) adhesive resin with the adhesive resin of organic decoration clay complex coupling.Necessary good humidity resistance and the property handled preferably have hydrophobicity in order to obtain to be applicable to liquid crystal indicator.This preferred adhesive resin can be enumerated acrylic resins such as cellulose-based resin such as polyvinyl acetal resin, acetylbutyrylcellulose, butyl acrylate, urethane resin, metha crylic resin, epoxy resin, vibrin etc. such as polyvinyl butyral or polyvinyl formal.
As the commercially available product of suitable adhesive resin, the aldehyde modified resin of the polyvinyl alcohol (PVA) that electrochemical industry (strain) sells with the trade name of " デ Application カ Block チ ラ-Le #3000-K ", acrylic resin that East Asia synthetic (strain) sells with the trade name of " ア ロ Application S1601 " are arranged, firmly change the urethane resin etc. of the isophorone diisocyanate substrate that バ イ エ Le ウ レ Application (strain) sells with the trade name of " SBU ラ Star カ-0866 ".
The ratio that can be scattered in the organic decoration clay complex of organic solvent and adhesive resin is preferably with the former: the latter's weight ratio is in the scope of 1:2～10:1, particularly is in the scope of 1:1～2:1, and its purpose is to improve the mechanical characteristic of the fracture of the layer that prevents to contain organic decoration clay complex and adhesive resin etc.
Organic decoration clay complex and adhesive resin are coated on the undercoat 12 with the form of coating fluid with the coating phase separation layer that contains in organic solvent.At this moment, in general adhesive resin is dissolved in the organic solvent, and organic decoration clay complex is scattered in the organic solvent.The solid component concentration of this coating fluid is not so long as gelation or gonorrhoeaization take place in the no problem scope in the coating fluid after the modulation in practicality, then be not particularly limited, usually in total solid component concentration of organic decoration clay complex and adhesive resin reaches scope about 3～15 weight %, use.Best solid component concentration is because with organic decoration clay complex and adhesive resin kind or both ratio of componentss and different separately, so forms and to set according to each.In addition, can add the coating when being used to improve the system film viscosity modifier, be used for further improving various adjuvants such as hydrophobicity and/or persistent hardening agent.
The refractive index anisotropy of the coating phase separation layer thickness direction thickness direction phase difference value R that utilizes above-mentioned formula (II) definition
ThExpression, this value can be by making a slow phase difference value R as sloping shaft inclination 40 degree mensuration mutually in the face
40With phase difference value R in the face
0Calculate.That is, utilize the thickness direction phase difference value R of formula (II)
ThCan use phase difference value R in the face
0, to make slow phase axle be the sloping shaft phase difference value R that 40 degree measure that tilt
40, the thickness d of film and the mean refractive index n of film
0, utilize numerical evaluation to try to achieve nx, ny and nz by following formula (III)～(V), the above-mentioned formula of their substitutions (II) is calculated.
R
0＝(nx-ny)×d (III)
(nx+ny+nz)/3＝n0 (V)
Here,
Φ＝sin-1〔sin(40°)/n0〕
The thickness direction phase difference value R of coating phase separation layer
ThPreferably corresponding its purposes, the particularly characteristic of liquid crystal lattice cell are suitably selected in the scope from about 40～500nm.This thickness direction phase difference value R
ThBe preferably more than the 50nm, below the 400nm.
(manufacture method of composite phase difference board)
The manufacture method of composite phase difference board 10 then is described.At first, coating is selected from the water-soluble organometallics of water-soluble organic titanic compound and organic zirconate and water soluble resin and is dissolved in the coating liquid for undercoat layer that forms in the solvent based on water on the surface of the polarizer 11 that contains transparent resin.This coating fluid can also contain other composition, the hardening agent beyond the above-mentioned water-soluble organometallics for example as mentioned above.The coating method of painting bottom coating during with coating fluid is not particularly limited, and can use known various rubbing methods such as direct woodburytype, reverse gravure method, mouthful mould rubbing method, scraper type rubbing method, excellent Tu Fa.
Painting bottom coating with coating fluid after, from this coating liquid layer, remove the solvent that contains water, form undercoat 12.The removing by being heated to suitable temperature of solvent that is used to form undercoat 12 makes its dry carrying out.At this moment, though depend on temperature, utilize several minutes heating to carry out drying usually.
Further implementing thermal curing on dried ground coat promotes to solidify also effective for the raising of water tolerance.When adopting this thermal curing, its temperature is crossed the effect that can't obtain maintenance when low, and therefore the opposite change in size that might cause film when too high or aging etc. is preferably selected from about 30～80 ℃ scope.The time of thermal curing was preferably about 1～7 day.This thermal curing can begin to carry out to any stage of removing the final composite phase difference board of back acquisition that desolvates with coating fluid at painting bottom coating.
For example, can the painting bottom coating coating fluid, remove then desolvate after, carry out thermal curing, on this undercoat, form the coating phase separation layer afterwards; Also can the painting bottom coating coating fluid, remove then desolvate after, then form the coating phase separation layer thereon, implement thermal curing afterwards.
On the surface of the undercoat 12 that as above obtains, be coated on and contain the coating phase separation layer coating fluid that organic decoration clay complex and adhesive resin form in the organic solvent.This coating fluid can contain other various adjuvants as mentioned above as required.
It is the scope of 0.15～0.35 weight % that this coating phase separation layer preferably makes the water percentage that utilizes the karl Fischer moisture meter to measure with coating fluid.When this water percentage surpasses 0.35 weight %, have being separated in the water-insoluble organic solvent taken place, coating fluid is separated into 2 layers tendency.On the other hand, when this water percentage is lower than 0.15 weight %, when making the coating polarizer, the tendency that increases the mist value is arranged.The assay method of moisture has seasoning, karl Fischer method, specific inductive capacity method etc., and adopting here can be simply and the karl Fischer method of the mensuration of microunit.
The coating phase separation layer is not particularly limited with the method that the water percentage of coating fluid is adjusted into above-mentioned scope, and the method for adding water in coating fluid is simple, thereby preferred.When only utilizing the organic solvent that uses among usual way mixing the present invention, organic decoration clay complex and adhesive resin, can show the water percentage that 0.15 weight % is above hardly.Here, preferably by add a spot of water in the coating fluid that is mixed with organic solvent, organic decoration clay complex and adhesive resin, making water percentage is above-mentioned scope.Adding the method for water adds all effective in any period of the modulating process of coating fluid, be not particularly limited, through after carrying out the sampling determination water percentage behind the certain hour, the method for water of adding ormal weight is in reappearance and can precision control aspect the water percentage preferred well in the modulating process of coating fluid.The amount that it should be noted that the water that is added is not inconsistent with the measurement result of utilizing the karl Fischer moisture meter sometimes.Its reason is thought owing to caused the part of water and the interaction of organic decoration clay complex (for example absorption) etc.In addition, when making the moisture rate that utilizes the karl Fischer moisture meter to measure remain on 0.15～0.35 weight %, the mist value of gained coating polarizer is suppressed in very low.
Form coating phase separation layer 14 employed coating methods and also be not particularly limited, known various rubbing methods such as can use that direct woodburytype, reverse gravure method, mouthful mould rubbing method, scraper type rubbing method, rod are coated with.The coating composition phase separation layer with coating fluid after, from this coating liquid layer, remove and desolvate, form coating phase separation layer 14.The removing also by being heated to suitable temperature of solvent that is used to form coating phase separation layer 14 is dried and carries out.
(composite optical member)
So the composite phase difference board that obtains can be on one face lamination polaroid etc. show the optical layers of other optical function, make composite optical member.Layer example that constitutes of composite optical member is shown among Fig. 2 with the cross section mode chart.In this example, lamination shows the optical layers 21 of other optical function on the polarizer that contains transparent resin 11 sides of composite phase difference board 10 shown in Figure 1, becomes composite optical member 20.Both laminations for example can use bonding agent, in Fig. 6 it are represented as adhesive phase 22.The optical layers 21 that shows other optical function preferably contains polaroid at least, for example can enumerate formation institute that briliancy improves liquid crystal indicator such as film etc. the material of use always in addition.
The polaroid that uses as other optical layers 21 so long as have on the direction of transmission in face vibration plane rectilinearly polarized light, be absorbed in the rectilinearly polarized light that has vibration plane on the direction perpendicular in the face and get final product.
Specifically, polyvinyl alcohol film can use the film that is fitted with diaphragm on the single face at least (single face or two sides) of the polariton that the absorption of dichromatism pigment is orientated.
It is polaroid that the dichromatism pigment has the iodine that has used iodine, used the dyestuff of dichromatism organic dyestuff is polaroid, can use any one.In addition, diaphragm uses cellulose-based resins such as triacetyl cellulose, is cyclic polyolefin hydrocarbon system resin of principal monomer etc. with the cyclic olefin of polycycles such as norborene.When other optical layers 21 contains polaroid, as shown in Figure 2, preferably contain other optical layers 21 of this polaroid at the resin polarizer 11 side laminations of composite phase difference board 10.
When bonding agent was used in the applying of other optical layers 21, this bonding agent can be made of the material that with acrylic acid series polymeric compounds, silicon-type polymkeric substance, polyester, polyurethane, polyethers etc. is substrate polymer.Wherein, preferred select to use as the optical transparence excellence of acrylic adhesive, keep suitable wetting state or cohesiveness, also excellent with the cementability of base material, have weatherability or thermotolerance etc., heat or the condition of humidification under the material of the problem of peeling off such as can not float or peel off.In the acrylic adhesive, be combined with have methyl, acrylic acid Arrcostab that carbon number such as ethyl, butyl is 20 following alkyl makes the glass transition temperature be preferably below 25 ℃ with the acrylic monomer that (methyl) acrylic acid or (methyl) Hydroxyethyl Acrylate etc. contain functional group, more preferably the weight-average molecular weight below 0 ℃ is the acrylic acid series copolymer more than 100,000, and is useful as substrate polymer.
(liquid crystal indicator)
Composite optical member 20 shown in Figure 2 can be configured on 1 face of liquid crystal lattice cell at least, makes liquid crystal indicator.Can also on the two sides of liquid crystal lattice cell, dispose this composite optical member.When configuration composite optical member on the single face of liquid crystal lattice cell, on another face of liquid crystal lattice cell, be situated between as required and dispose other polaroid by polarizer.The liquid crystal lattice cell is as described in one of the background technology, preferred vertical orientation (VA) pattern, but for the liquid crystal lattice cell of alternate manners such as other curved orientation (ECB) pattern, composite phase difference board constructed in accordance or composite optical member also can be brought into play function effectively in addition.
Below, according to embodiment the present invention being described in further detail, the present invention is limited by these embodiment.In the example, the portion of expression content or use amount and % then are weight standard unless otherwise specified.
[embodiment 1～3 and comparative example 1]
(a) modulation of coating liquid for undercoat layer
(a1) coating liquid for undercoat layer of embodiment 1～3
As the hardening agent that contains organic titanic compound, " the オ Le ガ チ Star Network ス TC " series (" オ Le ガ チ Star Network ス TC " is trade name) of using this pharmaceuticals industry of pine (strain) to sell, as polyvinyl alcohol resin, use " PVA-403 " (trade name, 78.5～81.5 moles of % of saponification degree) of the partly-hydrolysed polyvinyl alcohol (PVA) of (strain) Network ラ レ sale, cooperate the coating liquid for undercoat layer of modulation embodiment 1～3 according to following composition.
The composition of the coating liquid for undercoat layer of embodiment 1～3:
100 parts in water
0.2 part of organic titanic compound " オ Le ガ チ Star Network ス TC " series
15 parts of polyvinyl alcohol (PVA) " PVA-403 "
This coating fluid such as modulated: Yi Bian heat water to 80 ℃,, be cooled to room temperature after the stirring, and then adding organic titanic compound " オ Le ガ チ Star Network ス TC " series is mixed stirring, thereby modulation Yi Bian mix with polyvinyl alcohol (PVA) " PVA-403 ".The concrete organic titanic compound that uses among each embodiment is as described below, all is identical, the solvent differences only of compound itself.It should be noted that as followsly, organic titanic compound obtains with the form of solution, and employed amount is represented with the weight of solution itself during coating liquid for undercoat layer above the modulation.
Embodiment 1: " オ Le ガ チ Star Network ス TC-300 " (trade name):
Chemical constitution (HO)
2Ti[OCH (CH
3) COOH]
2The solution of effective constituent 42%, isopropyl alcohol 38%, water 20%.
Embodiment 2: " オ Le ガ チ Star Network ス TC-310 " (trade name):
Chemical constitution (HO)
2Ti[OCH (CH
3) COOH]
2The solution of effective constituent 44%, isopropyl alcohol 40%, water 16%.
Embodiment 3: " オ Le ガ チ Star Network ス TC-315 " (trade name):
Chemical constitution (HO)
2Ti[OCH (CH
3) COOH]
2The solution of effective constituent 44%, water 56%.
(a2) coating liquid for undercoat layer of comparative example 1
Use " ス ミ レ-ズ レ ジ Application 650 (30) " (aqueous solution of trade name, solid component concentration 30%) of the daiamid epoxy resin of firmly changing ケ system テ Star Network ス (strain) sale as water miscible hardening agent, use " PVA-403 " (trade name, 78.5～81.5 moles of % of saponification degree) of the partly-hydrolysed polyvinyl alcohol (PVA) of (strain) Network ラ レ sale as polyvinyl alcohol resin, cooperate the coating liquid for undercoat layer of modulation comparative example 1 according to following composition.It should be noted that " ス ミ レ-ズ レ ジ Application 650 (30) " represents with the weight of 30% concentration of aqueous solution itself.
The composition of the coating liquid for undercoat layer of comparative example 1:
Water: 100 parts
7.5 parts of daiamid epoxy resins " ス ミ レ-ズ レ ジ Application 650 (30) "
15 parts of polyvinyl alcohol (PVA) " PVA-403 "
B) the coating phase separation layer modulation of coating fluid
Use " Le-セ Application イ ト STN " (trade name) of the コ-synthetic hectorite of プ ケ ミ カ Le (strain) sale and the complex of tricaprylmethylammonium ion as organic decoration clay complex, use " SBU ラ Star カ-0866 " (trade name) of the lacquer type organic coating of the polyurethane resin firmly change バ イ エ Le ウ レ Application (strain) and to sell, solid component concentration 30% as the isophorone diisocyanate substrate as adhesive resin, cooperate modulation coating phase separation layer coating fluid according to following composition.
The coating phase separation layer composition of coating fluid:
Urethane resin lacquer " SBU ラ Star カ-0866 " 16.0 parts
7.2 parts of organic decoration viscosity complexs " Le-セ Application イ ト STN "
76.8 parts of toluene
0.3 part in water
Organic decoration clay complex used herein is to carry out acid elution behind the synthetic hectorite before the manufacturing organic decoration in producer, with its organic decoration, and then washing, obtain with this state.Its contained chlorine dose is 1,111ppm.In addition, this coating fluid is after mixing, stir with above-mentioned composition, to utilize the filter of aperture 1 μ m to filter the back modulation, and the water percentage that utilizes the karl Fischer moisture meter to measure is 0.25%.The solid state component weight ratio of the organic decoration clay complex/adhesive resin of this coating fluid is 6/4.
(c) making of composite phase difference board
Going up the coating liquid for undercoat layer that is coated with above-mentioned 4 kinds as the polarizer of the uniaxial extension film of norbornene resin (phase difference value 120nm in Sumitomo Chemical (strain) " CSES430120Z-S-KY " (trade name) of selling, the face), drying is about 1.5 minutes under 80 ℃, forms the undercoat of the about 2 μ m of thickness.Then, coating above-mentioned coating phase separation layer coating fluid on this undercoat, afterwards 90 ℃ dry 3 minutes down, formation coating phase separation layer obtains the composite phase difference board that lamination in order has resin polarizer/undercoat/coating phase separation layer.When the gained composite phase difference board uses any coating liquid for undercoat layer, also can not peel off even if for example peel off three layers with hand, three layers bonding with full intensity.
(d) making of composite optical member
On the resin polarizer side surface of the composite phase difference board that above-mentioned (c) obtains, be polaroid (" SRW062AP6-HC2 " (trade name) that Sumitomo Chemical (strain) is sold), make the composite optical member that lamination in order has polaroid/adhesive phase/resin polarizer/undercoat/coating phase separation layer at the fit polyvinyl alcohol (PVA)/iodine of band bonding agent of its adhesive phase side.
(e) evaluation of composite optical member
(e1) evaluation of water tolerance
The composite optical member that above-mentioned (d) made impregnated in 60 ℃ the warm water after 30 minutes, takes out, and when utilizing the microscopic examination end, the part that observe the undercoat dissolving, disappears.Here, try to achieve the ultimate range of the end of the part of dissolving, estimate water tolerance apart from undercoat.Show the result in table 1.
Table 1 water tolerance evaluation result
| Example No. | Hardening agent | Undercoat dissolving distance (maximal value) apart from the end |
| Embodiment 1 | オルガチツクスTC-300 | 0.4mm |
| Embodiment 2 | オルガチツクスTC-310 | 0.4mm |
| Embodiment 3 | オルガチツクスTC-315 | 0.5mm |
| Comparative example 1 | スミレ—ズレジン650(30) | 1.0mm |
(e2) evaluation of the caused light leak of fracture of the coating phase separation layer that causes of external force
The composite optical member that above-mentioned (d) made is fitted on the glass plate by acrylic adhesive Jie of its coating phase separation layer side place, use pencil scratching tester to push with the pencil of hardness H from the polaroid side, along with the loading that increases pencil, carry out the evaluation of the caused light leak of fracture of the coating phase separation layer that external force causes.At this moment, other polaroid is disposed on the opposite face of the composite optical member face that is fitted with glass plate, makes polaroid become the state of cross Nicols lens, on negatoscope, confirm light leak with composite optical member.As a result, for the situation of using any coating liquid for undercoat layer,, can not produce light leak even if apply loading as the 2.0kg of loading limit yet.
[embodiment 4～10 and comparative example 2]
(a) modulation of coating liquid for undercoat layer
(a1) coating liquid for undercoat layer of embodiment 4～10
Use " KL-506 " (trade name of the anion-modified partly-hydrolysed polyvinyl alcohol (PVA) of (strain) Network ラ レ sale as water soluble resin, 74～80 moles of % of saponification degree), use and embodiment 2 used identical " オ Le ガ チ Star Network ス TC-310 " as the hardening agent that contains water-soluble organic titanic compound, in embodiment 9 and 10, use " ス ミ レ-ズ レ ジ Application 650 (30) " (aqueous solution of solid component concentration 30%) with the used identical daiamid epoxy resin of comparative example 1 as second hardening agent, only make water or make water and isopropyl alcohol (being abbreviated as " IPA " in the table) as solvent with 85/15 weight ratio, cooperate the coating liquid for undercoat layer of modulation embodiment 4～10 according to following composition.The organic titanic compound " オ Le ガ チ Star Network ス TC-310 " and the amount of daiamid epoxy resin " ス ミ レ-ズ レ ジ Application 650 (30) " are shown in table 2 as solution weight respectively.
The composition of the coating liquid for undercoat layer of embodiment 4～10:
100 parts of solvents (only being the coupling of water or water and isopropyl alcohol)
15 parts of anion-modified polyvinyl alcohol (PVA) " KL-506 "
Organic titanic compound " オ Le ガ チ Star Network ス TC-310 " (being recorded in table 2)
Daiamid epoxy resin " ス ミ レ-ズ レ ジ Application 650 (30) " (being recorded in table 2)
(a2) coating liquid for undercoat layer of comparative example 2
Use " KL-506 " (trade name, 74～80 moles of % of saponification degree) of the anion-modified partly-hydrolysed polyvinyl alcohol (PVA) of (strain) Network ラ レ sale as water soluble resin, " ス ミ レ-ズ レ ジ Application 650 (30) " (aqueous solution of solid component concentration 30%) as the used identical daiamid epoxy resin of water soluble solid agent use and comparative example 1, cooperate the coating liquid for undercoat layer of modulation comparative example 2 according to following composition.
The coating liquid for undercoat layer of comparative example 2 is formed:
100 parts in water
15 parts of anion-modified polyvinyl alcohol (PVA) " KL-506 "
7.5 parts of daiamid epoxy resins " ス ミ レ-ズ レ ジ Application 650 (30) "
(b) making of composite phase difference board and evaluation
The coating liquid for undercoat layer of above-mentioned except using (a) modulation, utilize the method identical to make composite phase difference board with embodiment 1～3 (c), use this composite phase difference board, utilize the method identical to make composite optical member, and then the utilization method identical with embodiment 1～3 (e1) carried out the evaluation of water tolerance with embodiment 1～3 (d).The result is shown in table 2 with the use amount and the solvent for use of hardening agent.In addition, for the composite optical member that each example is made, the coating phase separation layer that utilizes the method evaluation external force identical the to cause caused light leak that ruptures with embodiment 1～3 (e2).As a result, for using any coating liquid for undercoat layer, even if apply loading as the 2.0kg of loading limit, light leak can not take place yet.
The variable of table 2 coating liquid for undercoat layer and water tolerance evaluation result
[comparative example 3]
The coating phase separation layer coating fluid shown in the coating embodiment 1～3 (b) on the demoulding treated side of the polyethylene terephthalate film (being called " mold release film " in this example) of the thickness 38 μ m that handle through the demoulding, descended dry 3 minutes at 90 ℃ afterwards, form the coating phase separation layer.On the surface of this coating phase separation layer, to have with embodiment 1～3 (c) in phase difference value, single face are provided with adhesive phase in the identical material of used resin polarizer and the identical faces polarizer (" CSES430120Z6-F8-KY " (trade name) that Sumitomo Chemical (strain) is sold) fit at this adhesive phase side place, make four layers of formation of resin polarizer/adhesive phase/coating phase separation layer/mold release film.Then, on this resin polarizer side surface, will fit at this adhesive phase side place, make six layers of formation of polaroid/adhesive phase/resin polarizer/adhesive phase/coating phase separation layer/mold release film with the used identical band bonding agent polaroid " SRW062AP6-HC2 " of embodiment 1～3 (d).After peeling off mold release film then, be fitted on the glass plate by acrylic adhesive Jie of coating phase separation layer side place who exposes.Under this state, estimate the light leak that external force caused that utilizes the pencil scratching tester identical with embodiment 1～3 (e2).As a result, when applying the 600g loading, observe light leak.
Industrial applicability
Composite phase difference board of the present invention contains between the polarizer and coating phase separation layer of transparent resin by fitting with priming coat, when it being fitted on the liquid crystal lattice cell, can effectively suppress owing to physical external force and the light leak that the fracture of incident coating polarizer causes, simultaneously by in the primary coat coating fluid, containing simultaneously water-soluble resin and containing water-soluble and reactive high organic titanic compound or the curing agent of organic zirconate, its coating is formed priming coat, can improve the resistance to water of priming coat. Therefore, used that combination has that this composite phase difference board and polarizer etc. show that the show state of liquid crystal indicator of composite optical member of optical layers of other optical functions is excellent, also excellence of resistance to water.
Claims (11)
1. composite phase difference board, its coating phase separation layer that contains polarizer, the undercoat of transparent resin for lamination in order and contain organic decoration clay complex and adhesive resin forms, and this undercoat forms by containing the water-soluble organometallics that is selected from water-soluble organic titanic compound and organic zirconate and the composition of water soluble resin.
2. composite phase difference board as claimed in claim 1, the polarizer that wherein contains transparent resin contains the transparent resin film that is orientated in face.
3. composite phase difference board as claimed in claim 1 or 2, the water soluble resin that wherein constitutes undercoat is a polyvinyl alcohol resin.
4. composite phase difference board as claimed in claim 1, the composition that wherein forms undercoat further contains above-mentioned water-soluble organometallics hardening agent in addition.
5. the hardening agent beyond the composite phase difference board as claimed in claim 4, wherein water-soluble organometallics is a water-soluble epoxy resin.
6. the manufacture method of a composite phase difference board, it is coated with the water-soluble organometallics that will be selected from water-soluble organic titanic compound and organic zirconate and water soluble resin and is dissolved in the coating liquid for undercoat layer that the solvent based on water forms on the surface of the polarizer that contains transparent resin, therefrom remove the formation undercoat that desolvates then, be coated on the surface of this undercoat and contain the coating phase separation layer coating fluid that organic decoration clay complex and adhesive resin form in the organic solvent, removing then desolvates forms the coating phase separation layer.
7. method as claimed in claim 6, it is at the painting bottom coating coating fluid, therefrom removing desolvates form undercoat after, under 30～80 ℃ temperature, carry out thermal curing.
8. composite optical member, it is pressed with the optical layers that shows other optical function on the described composite phase difference board of claim 1 upper strata.
9. composite optical member as claimed in claim 8, wherein other optical layers contains polaroid at least.
10. composite optical member as claimed in claim 9, its coating phase separation layer side lamination at composite phase difference board has polaroid.
11. a liquid crystal indicator, it disposes each described composite optical member of claim 8～10 at least 1 face of liquid crystal lattice cell.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006239979 | 2006-09-05 | ||
| JP239979/2006 | 2006-09-05 | ||
| JP301252/2006 | 2006-11-07 |
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|---|---|
| CN101512401A true CN101512401A (en) | 2009-08-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800329695A Pending CN101512401A (en) | 2006-09-05 | 2007-08-28 | Composite retardation plate, method for production thereof, composite optical member, and liquid crystal display device |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180049A (en) * | 2009-12-01 | 2011-09-14 | 株式会社理光 | Thermoreversible recording medium, and thermoreversible recording member |
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2007
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180049A (en) * | 2009-12-01 | 2011-09-14 | 株式会社理光 | Thermoreversible recording medium, and thermoreversible recording member |
| US8530377B2 (en) | 2009-12-01 | 2013-09-10 | Ricoh Company, Ltd. | Thermoreversible recording medium, and thermoreversible recording member |
| CN102180049B (en) * | 2009-12-01 | 2014-04-09 | 株式会社理光 | Thermoreversible recording medium, and thermoreversible recording member |
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