CN101604045A - Polarization plates roller and use polarization plates roller, polarization plates, the liquid crystal indicator of its band pressure sensitive adhesive layer - Google Patents
Polarization plates roller and use polarization plates roller, polarization plates, the liquid crystal indicator of its band pressure sensitive adhesive layer Download PDFInfo
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- CN101604045A CN101604045A CNA2009102033672A CN200910203367A CN101604045A CN 101604045 A CN101604045 A CN 101604045A CN A2009102033672 A CNA2009102033672 A CN A2009102033672A CN 200910203367 A CN200910203367 A CN 200910203367A CN 101604045 A CN101604045 A CN 101604045A
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- 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
- G02F1/133528—Polarisers
Abstract
The invention provides a kind of polarization plates roller and use polarization plates roller, polarization plates, the liquid crystal indicator of its band pressure sensitive adhesive layer, described polarization plates roller contains: the basal film that is formed by the transparent resin that is selected from polypropylene-based resin, PET series resin, polyethylene-based resin and the polyvinyl chloride resin; Undercoat; Be disposed on this basal film and comprise the polaroid of the polyvinyl alcohol resin that contains the dichromatism pigment across this undercoat, wherein, the absorption axes of this polaroid with the direction of the flow direction quadrature of roller on, basal film with the direction of the flow direction quadrature of roller on be orientated in the generating plane, and the Δ n that is defined by following formula is more than 0.01.
Description
Technical field
The present invention relates to be used to make the polarization plates roller of polarization plates, the polarization plates roller of band pressure sensitive adhesive layer and polarization plates, the liquid crystal indicator that uses this polarization plates roller.
Background technology
In recent years, consume information display devices such as electric power watch-dog low, that use as mobile phone, personal digital assistant device, computing machine with low voltage operating, light-duty and slim LCD, televisor, universal apace.Along with the development of liquid crystal technology, the LCD of various patterns has been proposed.For example, comprise and be called as IPS (In-plane Switching: the transverse electric field) liquid crystal mode of pattern, VA (Vertical Alignment: vertical orientated) pattern, TN (Twisted Nematic: pattern etc. twisted-nematic).
Though there is the LCD of such various modes, in nearly all pattern, the film that is called as polarization plates becomes necessary member.
In liquid crystal indicator, polarization plates is the member that can not lack when showing, almost all is configured in the two sides of liquid crystal cells in all cases and uses, so can be with 2 as 1 group of use.Under the situation of such formation, will compare the more close polarization plates that is disposed at the identification side sometimes with liquid crystal cells and be called preceding polarization plates, the more close polarization plates that is disposed at the backlight side is called retrodeviates vibration plate.
In addition, polarization plates still has the optical component of feature as described below, is becoming the light that only vibrates, so-called rectilinearly polarized light by the light after this polarization plates on a certain specific direction that is:.There are kinds such as absorption-type, reflection-type, scatter-type in such polarization plates, in LCD, although the most normal use is the low but absorptive-type polarization plates of the type that the polarized light performance is the highest of utilization ratio as light.
The polarized light performance compares with the index that is called as degree of polarization (Py), and it is the value by following formula (1) definition, and the side expression polarized light that degree of polarization is high is separated fully.At this, Tp, Tc are the measured values of utilizing spectrophotometric determination polarized light ultraviolet-visible absorption spectroscopy to obtain, respectively the transmissivity (Tc) of the relation mensuration of transmissivity (Tp), utilization and the quadrature Niccol measured of the expression rectilinearly polarized light that utilizes incident and the relation of parallel-nicol.
Degree of polarization (Py)=100 * (Tp-Tc)/(Tp+Tc) ... formula (1)
In addition, polarization plates is utilized the index that is called as monomer transmissivity (Ty) of following formula (2) definition in addition, we can say that the monomer transmissivity is high more, and then the utilization ratio of light is high more.
Monomer transmissivity (Ty)=0.5 * (Tp+Tc) ... formula (2)
That is, we can say that degree of polarization and monomer transmissivity are high more, then polarization plates good goods of performance.
Nowadays, such LCD also spreads in the TV market, and the maximization that is in its picture dimension is status of development apace.At present, has a part that overriding key point is how to make large-sized liquid crystal cells in the maximization of LCD TV size.But, recently, making the enough big liquid crystal cells that the diagonal angle surpasses 65 inches, up-to-date situation has become a side's of polarization plates undergage.
In most cases, the formation of large-scale LCD almost is configured to the absorption axes of preceding polarization plates parallel with the long side direction of TV, and the absorption axes that retrodeviates vibration plate is configured to the absorption axes quadrature with preceding polarization plates.In this case, the short side direction that retrodeviates vibration plate becomes absorption axes.
The polarization plates roller is the polarization plates that is rolled into the roller shape, usually, this polarization plates roller is cut into the sheet (cutting-out) of necessary size, is provided in the described purposes.
Common polarization plates roller is that the flow direction (coiling direction of roller or its reverse direction) to roller stretches and quilt is made, thereby absorption axes becomes the flow direction of roller inevitably.Under these circumstances, make polarization plates (polarization plate) if cut into slices from the polarization plates roller, then the upper limit of its size becomes very limited little scope for the Width from the polarization plates roller downcuts the long limit of polarization plate.On the contrary, under the situation of polarization plates, the Width of polarization plates roller becomes the short brink of polarization plate before making, so the upper limit of the size of downcutting is very big.
Under such situation, come at present correspondingly by the width that enlarges the polarization plates roller, but must make device become wide cut in order to realize this purpose or make reel become wide cut.Under any circumstance, any one of the member of constituent apparatus or polarization plates can not realize all being difficult to enlarge the width of polarization plates roller under the situation of wide cut correspondence.In addition, owing to also have the limit, so diagonal-size is that polarization plates about 65 inches becomes can the corresponding upper limit at present in the operability of the polarization plates roller of manufacture view etc.
On the other hand, relative LCD more than 70 inches has also been taked for example to connect to use 2 gimmicks that retrodeviate vibration plate, but present situation is that tie point display quality partly is still poor.
As mentioned above, although can be by using wide member film or the wide polarization plates production line (line) of width of width, make the large-scale polarization plates of large-scale liquid crystal display television by using, but there is the limit of aspects such as operability in its wide cutization, is difficult to obtain the polarization plates of the liquid crystal display television by using more than 65 inches.
Wherein, retrodeviate vibration plate in order to make with the size identical with preceding polarization plates, if can access the absorption axes of polarization plates roller and roller the flow direction quadrature retrodeviate vibration plate.In this case, downcut on the direction identical owing to retrodeviate vibration plate, so can realize very large maximization with preceding polarization plates.
On the other hand, also knownly stretch, dye together with base film, make the polarization plates of thin-walled by on the base film that constitutes by thermoplastic resin, forming the coating layer of polyvinyl alcohol resin.For example, open the 2000-338329 communique (with reference to patent documentation 1 the spy, especially patent documentation 2) in put down in writing one side the thermoplastic resin membrane, form the polyvinyl alcohol resin layer with the thickness more than the 6 μ m, below the 30 μ m, stacked state is drop-down stretches at this, dyeing is given polarization luminous energy to the polyvinyl alcohol resin layer, thereby is become the polarization plates of thin-walled then.
In addition; for example open in the 2001-343521 communique (patent documentation 2) and disclose a kind of polarization plates the spy; the purpose of this patent documentation is to provide a kind of polarization plates of using the little polarized light film of thin-walled and differential contraction stress, and this polarization plates is that the one side at least of the polarized light film below the thick 10 μ m that the are principal ingredient protective film of fitting forms with the polyvinyl alcohol resin.And then open in the 2001-343522 communique (patent documentation 3) the spy and to disclose a kind of polarized light film, the purpose of this patent documentation is to provide a kind of thin-walled and the little polarized light film of differential contraction stress equally, this polarized light film is a principal ingredient with the polyvinyl alcohol resin of unilateral stretching, and the thickness d of film (μ m) and long-pending d * e of stretching ratio e (doubly) are below 30.In addition, in such patent documentation 2,3, also put down in writing and utilized stenter (tenter) method that the laminate film that has been coated with polyvinyl alcohol resin on the substrate resin film is carried out horizontal unilateral stretching.
Summary of the invention
The object of the present invention is to provide a kind of flow direction of polarization plates and the polarization plates roller of absorption axes quadrature.
In polarization plates roller of the present invention, contain the basal film that forms by the transparent resin that is selected from polypropylene-based resin, PET series resin, polyethylene-based resin and the polyvinyl chloride resin, undercoat and be disposed on this basal film and comprise the polaroid of the polyvinyl alcohol resin that contains the dichromatism pigment across this undercoat, wherein
The absorption axes of polaroid is positioned on the direction with the flow direction quadrature of roller,
Basal film with the direction of the flow direction quadrature of roller on be orientated in the generating plane, and, be more than 0.01 by the Δ n of following formula definition.
Δn＝n
x-n
y
(at this, n
xBeing illustrated in the interior refractive index of pellicular front becomes the refractive index of maximum direction, n
yBe illustrated in the pellicular front and n
xThe refractive index of direction of direction quadrature.)
In polarization plates roller of the present invention, the saponification degree of preferably polyethylene alcohol resin is 98 moles more than the %, and the degree of polymerization is more than 1000.
In polarization plates roller of the present invention, preferred undercoat is the transparent resin layer that is formed by the composition that contains modified polyvinylalcohol resin and crosslinking chemical.
In addition, polarization plates roller of the present invention preferably at the face of the polaroid side of polarization plates roller, disposes protective clear layer across adhesive phase.
In addition, the present invention also provides a kind of polarization plates roller that is formed with the band pressure sensitive adhesive layer of pressure sensitive adhesive layer in the one side at least of described polarization plates roller of the present invention.
In addition, the present invention also provides a kind of polarization plates, and it is the polarization plates roller of described band pressure sensitive adhesive layer of the present invention to be cut into slices form.
And then the present invention also provides a kind of liquid crystal indicator, and it possesses the polarization plates of liquid crystal cells and described band pressure sensitive adhesive layer, and the described pressure sensitive adhesive layer of polarization plates is fitted in described liquid crystal cells.
If utilize the flow direction of polarization plates and the polarization plates roller of the present invention of absorption axes quadrature, then can be with the Width of polarization plates roller as short brink, to retrodeviate vibration plate and cut into slices (chip-cut), so the upper limit of the size that retrodeviates vibration plate of downcutting becomes very big.
Description of drawings
Fig. 1 (a) is the stereographic map of the polarization plates roller 1 of a pattern ground expression preference of the present invention, and Fig. 1 (b) is the expression of pattern ground from the cut into slices exploded perspective view of the polarization plates of the present invention (polarization plate) 11 that forms of the polarization plates roller 1 shown in Fig. 1 (a).
Among the figure, 1-polarization plates roller, 11-polarization plates, 12-basal film, 13-polaroid, 14-undercoat.
Embodiment
Fig. 1 (a) is the stereographic map of the polarization plates roller 1 of a pattern ground expression preference of the present invention, and Fig. 1 (b) is the expression of pattern ground from the cut into slices exploded perspective view of the polarization plates of the present invention (polarization plate) 11 that forms of the polarization plates roller 1 shown in Fig. 1 (a).Polarization plates roller 1 of the present invention is that absorption axes is in the polarization plates roller with the direction of the flow direction quadrature of roller, possesses to contain the polaroid that the dichromatism pigment forms be configured in the basic structure that forms on the basal film that is formed by transparent resin across undercoat in polyvinyl alcohol resin.
For make polyvinyl alcohol resin with the direction of the flow direction quadrature of roller on be orientated, improve the phase difference value (Δ n) of this per unit thickness, as the basal film that in polarization plates roller of the present invention, uses, must become the basal film that the layer of the polyvinyl alcohol resin of polaroid wait to be handled for carrying out stretching together with basal film.This be because, the Δ n of polyvinyl alcohol resin that becomes polaroid in polarization plates roller of the present invention is high more, then the Δ n of dichromatism pigment becomes high more, becomes good more as the performance of the polarization plates that obtains from this polarization plates roller.As the basal film that uses in the present invention, film that preferably can high magnification ground stretching on the direction vertical with the flow direction of roller.From such viewpoint, in the present invention, can use utilization can promptly be selected from the basal film that the transparent resin in polypropylene-based resin, PET series resin, polyethylene-based resin and the polyvinyl chloride resin forms usually with the crystalline resin that high magnification stretches.Wherein, polyolefins etc. is because the price of resin is low and preferred.In addition, the easy degree that also preferably can stretch and as the optimized multipolymer of the intensity of protective film etc. etc. by its ratio of components of optimization.From these viewpoints, in above-mentioned, the preferred basal film that utilizes as the propylene resin formation of propylene-ethylene copolymers.
The method of the polyvinyl alcohol resin that becomes polaroid as stretching together with basal film, usually can enumerate with tentering type drawing machine etc. is the stiff end unilateral stretching of representative, perhaps, can on flow direction, carry out the pin stenter (pin tenter) that overfeeding (overfeed) shrinks and be the drawing process of representative.By utilizing such method to stretch, can obtain that picture uses in polarization plates roller of the present invention with the direction of the flow direction quadrature of roller on carried out the basal film that is orientated in the face.
In addition, under the situation of carrying out above-mentioned stretch processing, the Δ n that is attached to the layer of the polyvinyl alcohol resin on the basal film greatly is subjected to the control of the stretching of basal film.That is, under the good situation of the state of orientation of basal film, we can say the state of orientation of the polyvinyl alcohol resin that on basal film, disposes, so the Δ n height of the basal film in the preferred polarization plates roller of the present invention across undercoat.In polarization plates roller of the present invention, from the viewpoint of the polarized light film of the relation that can obtain good transmissivity and degree of polarization, the value of using Δ n is the basal film of (more preferably more than 0.02, and then be preferably more than 0.25) more than 0.01.
Wherein, the Δ n of basal film described herein is with the anisotropy definition of the refractive index in the face, is meant with the front delay that utilizes double refraction detection device KOBRA-WPR (prince's instrumentation machine (strain) system) mensurations of etc.ing to serve as the phase difference value of the basic per unit thickness that is defined by following formula that calculates.
Δn＝(n
x-n
y)＝R
o/d
(at this, n
xBeing illustrated in the interior refractive index of pellicular front becomes the refractive index of maximum direction, n
yBe illustrated in the pellicular front and n
xThe refractive index of direction of direction quadrature.In addition, R
oPositive postpone (nm) of expression, d represents film thickness (nm).)
Wherein, for the polarization plates roller of reality, when measuring the Δ n of basal film, peel off polaroid, only basal film is measured with above-mentioned double refraction detection device from basal film.As the method for peeling off polaroid, for example can adopt the hot water that utilizes 60～80 ℃ to make polyvinyl alcohol resin swelling as polaroid, method that strips from basal film etc. then.
In polarization plates roller of the present invention, can use the polaroid that comprises the polyvinyl alcohol resin that contains the dichromatism pigment.Shown in Fig. 1 (a), the absorption axes B of the polaroid in the polarization plates roller 1 of the present invention is in the direction with the flow direction A quadrature of polarization plates roller.As polyvinyl alcohol resin, except polyvinyl acetate, can also use by the saponification vinyl acetate and the polyvinyl alcohol resin that can obtain with multipolymer of other monomers (for example unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class etc.) of its copolymerization etc. as the self-aggregate of vinyl acetate.
In addition, saponification degree is preferably 98.0 moles more than the % to the polyvinyl alcohol resin that uses in the polaroid in the present invention because water tolerance is outstanding, more preferably 99.0 moles more than the %.In addition, same from the outstanding viewpoint of water tolerance, the degree of polymerization of the polyvinyl alcohol resin that uses in the polaroid in the present invention is preferably more than 1000, more preferably more than 1500.As having the so preferred saponification degree and the polyvinyl alcohol resin of the degree of polymerization, particularly, can use PVA117 (saponification degree: 98.0～99.0 moles of % well, the degree of polymerization: about 1700) ((strain) Kuraray (Network ラ レ) system), (saponification degree: 99.3 moles more than the % for PVA117H, the degree of polymerization: about 1700) ((strain) Kuraray system), PVA124 (saponification degree: 98.0～99.0 moles of %, the degree of polymerization: about 2400) ((strain) Kuraray system), Kuraray Vinylon VF-PS#7500 (saponification degree: more than 99.3, about 2400) degree of polymerization: commercially available product such as.
Dichromatism pigment as containing in polyvinyl alcohol resin for example can use iodine, dichroic dye etc.The dichromatism direct dyes that dichroic dye for example comprises dichromatism direct dyes that C.I.DIRECT RED 39 grades are made of disazo compound, is made of compounds such as azido, bisdiazos.
In polarization plates roller of the present invention, being situated between between basal film and polaroid has undercoat.This undercoat is the layer that is provided with in order to strengthen the adhesion between polaroid and the basal film, is not having under the situation of undercoat, when polaroid being dyeed etc., the bad situation that polaroid strips off from basal film takes place easily.
As undercoat, without limits, and, following described advantage is arranged by using the high poly-modified vinyl alcohol of dissolubility of relative water, that is: the making of solution becomes easily, can obtain low viscous good aqueous solution, and coating becomes good thus.And then, by be used in combination crosslinking chemical with it, behind the system film, can obtain excellent water tolerance.From these viewpoints, the preferred transparent resin layer that forms by the composition that contains modified polyvinylalcohol resin and crosslinking chemical.Modified polyvinylalcohol resin is meant and has applied modified polyethylene alcohol resin cation-modified, anion-modified isoiony; particularly, can enumerate as by the KL-506 of carboxy-modified polyvinyl alcohol resin (selling) from (strain) Kuraray, as by the Gao Saifuaima of acetoacetyl modified polyethylene alcohol resin (go one セ Off ア イ マ one) Z200 (selling) etc. from Japanese synthetic chemical industry (strain).
As the crosslinking chemical that in undercoat, uses, for example can enumerate daiamid epoxy resin, glutaraldehyde or glyoxal etc. two ketones, water miscible metal complexs such as methylolation melamine resin, zirconyl nitrate or titanium chelate etc., and in order to obtain the good cementability with base material, preferred polyamide epoxy resin.The daiamid epoxy resin for example can use chloropropylene oxide, the product that the polyamide polyamine that obtains with the reaction of the dicarboxylic acid of the polyalkylene polyamine of diethylene triamine or trien and so on and hexane diacid and so on reacts and obtains, particularly, can enumerate Si Milaizilazhen 650 (30) (selling) etc. from firmly changing Chemtex (strain).
For example can utilize the method that comprises following (A)～(C) operation to make aforesaid polarization plates roller of the present invention.
(A) across undercoat, on basal film, be coated on the polyvinyl alcohol resin that uses in the polaroid, thereby obtain the operation of laminate film,
(B) utilize stenter etc. that the laminate film that obtains in operation (A) is carried out the horizontal unilateral stretching of stiff end, make its orientation, thereby obtain the operation of oriented film,
(C) operation that the oriented film that obtains in operation (B) is dyeed.
In above-mentioned (A) operation, at first, the above-mentioned composition that contains modified polyvinylalcohol resin and crosslinking chemical (primary coat PVA aqueous solution) of coating on the basal film of having implemented Corona discharge Treatment in advance, form undercoat, pva coating resin aqueous solution on this undercoat (polaroid PVA aqueous solution).At this moment, can utilize method as described below to make the aqueous solution of polyvinyl alcohol resin.At first, in the water of normal temperature, immerse polyvinyl alcohol (PVA), make its swelling.Then, water temperature is heated to more than 60 ℃, polyvinyl alcohol resin is dissolved fully.The aqueous solution of the polyvinyl alcohol resin that obtains can directly be utilized the coating machine of the applicator head with band temp regulating function etc., on basal film, be coated with, also can be after making its aqueous solution that becomes the polyvinyl alcohol resin that temporarily is cooled to room temperature, at normal temperatures, utilize common coating machine, on basal film, be coated with.
Mode to the pva coating resin aqueous solution is not particularly limited, can enumerate common described application pattern, for example intaglio application pattern, chill coating (ダ イ コ one ト) mode, comma coating (カ Application マ コ one ト) mode, lip formula coating (リ Star プ コ one ト) mode etc.
In above-mentioned (B) operation, can implement horizontal stretching to the laminate film that in above-mentioned (A) operation, obtains together with basal film, and for the method that stretches, without limits.
For example, can be for being the horizontal unilateral stretching of stiff end of representative with stenter etc., also can be for utilizing pin stenter etc. that it is shunk on flow direction and carrying out the horizontal stretching of overfeeding of horizontal stretching simultaneously.
In addition, to the colouring method in above-mentioned (C) operation, also without limits, can carry out with common condition.For example, can be for the method for the staining trough that above-mentioned oriented film is immersed successively the swelling groove that constitutes by about 40 ℃～80 ℃ warm water, constitute by the aqueous solution of iodine/potassium iodide, dissolving boric acid forms in 50 ℃～90 ℃ warm water crosslinked groove etc.
Wherein, staining trough also can be that dissolving iodine dichromatism pigment in addition forms.
Polarization plates roller of the present invention preferably disposes protective clear layer at the face of the polaroid side of polarization plates roller across adhesive phase.As protective clear layer; for example can enumerate cellulose acetate based resin films such as cyclic olefine resin film, triacetyl cellulose, diacetyl cellulose; polyester based resin films such as polyethylene terephthalate, PEN, polybutylene terephthalate; the polycarbonate based resin film; the acrylic resin film, the film that polypropylene based resin film etc. are widely used in this field always.
The cyclic olefine resin that uses in can protective clear layer in the present invention can use suitable commercially available product well, for example Topas (Ticona corporate system), ARTON (JSR (strain) system), ZEONOR (Japanese Zeon (strain) system), ZEONEX (Japanese Zeon (strain) system), APEL (Mitsui Chemicals (strain) system) etc.When such cyclic olefine resin system film is become film, can suitably use known method such as solvent casting method, extrusion by melting.In addition, for example also can use Ai Sixina (エ ス シ-Na) (ponding chemical industry (strain) system), SCA40 (ponding chemical industry (strain) system), Zeonor Film ((strain) Optes system) etc. in advance by the commercially available product of the resinous film of cyclic olefine of system film.
In addition; as the cellulose acetate based resin film that uses in can protective film in the present invention; can use suitable commercially available product well, for example Fujitac TD80 (Fujiphoto (strain) system), Fujitac TD80UF (Fujiphoto (strain) system), Fujitac TD80UZ (Fujiphoto (strain) system), Fujitac TD40UZ (Fujiphoto (strain) system), KC8UX2M (KONICAMINOLTA OPTO (strain) system), KC4UY (KONICA MINOLTA OPTO (strain) system) etc.
As the bonding agent that in the applying of polaroid and protective clear layer, uses, from the viewpoint of attenuate adhesive phase, can enumerate the bonding agent of water system, that is, and with the be dissolved in the water bonding agent that forms or be scattered in the bonding agent that forms in the water of adhesive ingredients.As preferred adhesive, for example can enumerate use polyvinyl alcohol resin or urethane resin composition as principal ingredient.
Using under the situation of polyvinyl alcohol resin as the principal ingredient of bonding agent; this polyvinyl alcohol resin except partly-hydrolysed polyvinyl alcohol (PVA), fully saponified polyvinyl alcohol (PVA), the also polyvinyl alcohol resin that can be modified for carboxy-modified polyvinyl alcohol (PVA), acetoacetyl modified polyvinylalcohol, methylol modified polyvinylalcohol, amino modified polyvinyl alcohol (PVA) etc.In this case, can use the aqueous solution of polyvinyl alcohol resin as bonding agent.Relative 100 weight parts waters of the concentration of the polyvinyl alcohol resin in the bonding agent are generally 1～10 weight portion, are preferably 1～5 weight portion.
In order to improve cementability, preferably in the bonding agent that the aqueous solution by polyvinyl alcohol resin constitutes, add glyoxal, curable composition, crosslinking chemical such as water-soluble epoxy resin.As water-soluble epoxy resin, for example can use chloropropylene oxide well, the polyamide polyamine epoxy resin that the polyamide polyamine that obtains with the reaction of dicarboxylic acid such as polyalkylene polyamine such as diethylene triamine or trien and hexane diacid reacts and obtains.As the commercially available product of this type of polyamide polyamine epoxy resin, can enumerate Si Milaizilazhen (ス ミ レ one ズ レ ジ Application) 650 (firmly changing Chemtex (strain) system), Si Milaizilazhen 675 (firmly changing Chemtex (strain) system), WS-525 (Japanese PMC (strain) system) etc.The relative 100 weight account polyethylene alcohol of the addition of these curable compositions, crosslinking chemical (together under the situation of Tian Jiaing, being its total amount) are resin, are generally 1～100 weight portion, are preferably 1～50 weight portion.
In addition, the present invention also is provided at the polarization plates roller that at least simultaneously forms the band pressure sensitive adhesive layer of pressure sensitive adhesive layer of any one above-mentioned polarization plates roller of the present invention.Pressure sensitive bonding agent (bonding agent) as using in such pressure sensitive adhesive layer can use known in the past suitable adhesive ad lib, for example can enumerate acrylic adhesive, polyurethane series bonding agent, silicone-based adhesive etc.Wherein, from viewpoints such as the transparency, clinging power, reliability, (rework) property of doing over again, preferably use acrylic adhesive.Pressure sensitive adhesive layer can utilize method setting as described below, for example uses such bonding agent with the form of organic solvent solution that is:, utilizes chill coating machine or intaglio coating machine etc. that it is coated on the base film, makes its drying.In addition, can also utilize method setting as described below, that is: transfer printing is gone up the sheet bonding agent that forms at the plastic sheeting (being called separating film (separate film)) of implementing demoulding processing on base film.Thickness to pressure sensitive adhesive layer is not particularly limited, and is preferred usually in the scope of 2～40 μ m.
In addition, the present invention also provides the polarization plates (polarization plate) that the polarization plates roller of above-mentioned band pressure sensitive adhesive layer of the present invention is cut into slices and formed.Fig. 1 (b) is the exploded perspective view of pattern ground expression from the 1 tableted polarization plates of the present invention (polarization plate) 11 of the polarization plates roller shown in Fig. 1 (a).Polarization plates 11 of the present invention possesses on basal film 12 structure across undercoat 14 laminated polarizing sheets (polarized light film) 13 shown in Fig. 1 (b).The polarization plates 11 of the example shown in Fig. 1 (b) is cut into rectangular, and its short side direction becomes absorption axes, in LCD, and can be well as the vibration plate that retrodeviates that is disposed at the backlight side.
The present invention also further provides liquid crystal indicator, wherein, possesses liquid crystal cells and above-mentioned polarization plates of the present invention, and the described pressure sensitive adhesive layer of polarization plates is fitted in described liquid crystal cells.In liquid crystal indicator of the present invention, for for the part the above-mentioned feature, can adopt the suitable formation of known liquid crystal indicator in the past, the constitutive requirements (light diffusing sheet, backlight etc.) that liquid crystal indicator is possessed except liquid crystal panel usually without limits.
Below enumerate embodiment and comparative example, illustrate in greater detail the present invention, but the present invention is not limited by these.
＜embodiment 1～7, comparative example 1～3 〉
In 100 weight parts waters; mix 1.5 weight portion acetoacetyl modified polyvinylalcohol resins (Gao Saifuaima (go-セ Off ア イ マ-) Z200; sell from Japanese synthetic chemical industry (strain)); make its swelling a moment at room temperature; be warming up to 90 ℃ then; with making the polyvinyl alcohol resin dissolving in 1 hour while stirring, thereby obtain the aqueous solution of homogeneous.In this polyvinyl alcohol resin, add 1.25 weight parts of polyamide epoxy resin (Si Milaizilazhen 650 (30), firmly change Chemtex (strain) system), obtain primary coat PVA aqueous solution.
(the polaroid making of PVA aqueous solution)
The resin pellet of the polyvinyl alcohol (PVA) shown in the following table of selling from (strain) Kuraray 1, add entry, leave standstill an evening, make its swelling.The solid constituent amount is adjusted to ready-made viscosity in aqueous solution approximately becomes 1200mPasec, is warming up to 90 ℃ then, stirs polyethylene dissolving alcohol resin pellet 4 hours.Then, be cooled to room temperature, obtain aqueous solution.Wherein, because the KurarayVinylon VF-PS#7500 in the table 1 do not sell with the form of resin pellet, so the diaphragm nicking that obtains is become square about the 2cm of limit, immerse in about 40 ℃ warm water, wash glycerine off, under 70 ℃, make its vacuum drying 4 hours then, use then.
[table 1]
| Trade name | Saponification degree (mol%) | The degree of polymerization | Solid constituent amount (wt%) | Viscosity (mPas) |
| ??PVA117 | ??98.0～99.0 | About 1700 | ??10.3 | ??1273 |
| ??PVA117H | 99.3 more than | About 1700 | ??8.3 | ??1211 |
| ??PVA124 | ??98.0～99.0 | About 2400 | ??10.1 | ??1114 |
| ??Kuraray?Vinylon?VF-PS#7500 | 99.3 more than | About 2400 | ??7.5 | ??1250 |
(coating of undercoat)
Use is from the polypropylene-based resin platen roller of the thick 100 μ m of propylene-ethylene copolymers (Sumitomo promise not blue (ノ one Block レ Application) W151 (Sumitomo Chemical (strain) system)) system film, on the surface of this reel, continuously with accumulative total exposure 280Wmin/m
2Condition, implement Corona discharge Treatment.And then, on this mandrel surface, utilize nick version mode of printing, the primary coat of the above-mentioned making of continuously coating PVA aqueous solution obtains the basal film with undercoat.The thickness of the thickness of the basal film before the mensuration coating and the basal film of the band undercoat after the coating, the result as can be known, be 100.0～100.3 μ m, and become about 100.1～100.5 μ m after the coating that undercoat is the thickness about 0.1～0.5 μ m before coating.
(the polaroid coating of PVA aqueous solution)
On the undercoat of the basal film of the above-mentioned band undercoat that obtains, use the metal mold rubbing method, be coated with 4 kinds of polaroid PVA aqueous solution of above-mentioned making continuously, make dried thickness become 15 μ m, obtain acrylic resin platen roller (4 kinds) with the polyvinyl alcohol resin layer.
(stretching)
Under the condition of 131 ℃ of waste heats, 121 ℃ of stretchings, utilize the stenter mode, with the multiplying power of the regulation shown in the table 2, be with the polypropylene-based resin roller of polyvinyl alcohol resin layers to carry out the horizontal unilateral stretching of stiff end, the film that obtains on Width, being orientated continuously to 4 kinds of obtaining.As shown in table 2, to PVA117H and PVA124, change stretching ratio, repeatedly test, so obtain 10 kinds of films altogether at this.
(dyeing)
Utilize following gimmick respectively, to 10 kinds of films that obtain processing of dyeing.
(1) in 60 ℃ warm water, with 90 seconds hold-up times, the dipping film made its swelling.
(2) then, with 300 seconds hold-up times, dipping adsorbed iodine on polyvinyl alcohol (PVA) in the iodine/potassium iodide aqueous solution (28 ℃) of following composition.
(composition of iodine/potassium iodide aqueous solution)
Water 100 weight portions
Iodine 0.6 weight portion
Potassium iodide 5 weight portions
(3) and then, with 600 seconds hold-up times, dipping in the boric acid/potassium iodide aqueous solution (76 ℃) of following composition, it is crosslinked that polyvinyl alcohol (PVA) is taken place.
(composition of boric acid/potassium iodide aqueous solution)
Water 100 weight portions
Boric acid 15 weight portions
Potassium iodide 9 weight portions
(4) with 2 seconds hold-up times, in 6 ℃ cold water, flood, wash the residual pharmacy of film surface off.
(5) utilize 50 ℃ drying oven,, carry out drying with 300 seconds hold-up time.
[evaluation test]
To the embodiment 1～7 that obtains as described above, the polarization plates roller of comparative example 1～3, use ultraviolet-visible pectrophotometer V-7100 (Japanese beam split (strain) system), measure degree of polarization (Py) and monomer transmissivity (Ty).In addition, the Δ n of the basal film in the polarization plates roller of embodiment 1～7, comparative example 1～3 makes the polaroid swelling at the hot water with 80 ℃, strip after, utilize measuring difference of phases device KOBRA-WPR (prince's instrumentation machine (strain) system) to measure.
[table 2]
| The PVA kind | Stretching ratio (doubly) | Thickness (μ m) | ??Py(％) | ??Ty(％) | The Δ n of basal film | |
| Embodiment 1 | ??PVA117H | ??5.5 | ?23 | ??99.991 | ??38.9 | ?0.022 |
| Embodiment 2 | ??PVA117H | ??5.9 | ?22 | ??99.854 | ??41.2 | ?0.018 |
| Embodiment 3 | ??PVA117H | ??6.1 | ?22 | ??99.988 | ??38.5 | ?0.031 |
| |
??PVA117H | ??6.4 | ?22 | ??99.989 | ??38.7 | ?0.026 |
| Embodiment 5 | ??PVA117 | ??5.5 | ?22 | ??99.852 | ??39.0 | ?0.019 |
| Embodiment 6 | ??PVA124 | ??5.5 | ?23 | ??99.992 | ??39.2 | ?0.035 |
| Embodiment 7 | ??VF-PS#7500 | ??5.5 | ?22 | ??99.990 | ??38.0 | ?0.030 |
| Comparative example 1 | ??PVA117H | ??2.0 | ?75 | ??41.225 | ??50.1 | ?0.009 |
| Comparative example 2 | ??PVA117H | ??1.5 | ?90 | ??21.200 | ??80.2 | ?0.005 |
| Comparative example 3 | ??PVA124 | ??2.0 | ?78 | ??25.504 | ??82.1 | ?0.007 |
From the polarization plates roller that among embodiment 1, obtains, utilize 80 ℃ hot water to make the polaroid swelling and strip, measure the thickness of basal film, the result is 20 μ m.Therefore, the thickness that can predict polaroid is 3 μ m, and the ratio before stretching as can be known is roughly the same.
(before stretching) basal film thickness/polaroid thickness=100/15=6.67
(back stretches) basal film thickness/polaroid thickness=20/3=6.67
＜comparative example 4 〉
Carry out similarly to Example 1, Corona discharge Treatment is implemented on surface to polypropylene-based resin cylinder roller, then, does not carry out the formation of undercoat, coating polaroid PVA aqueous solution, in addition, carry out similarly to Example 1, make the polarization plates roller, but owing to there is not undercoat, so when dyeing, polaroid is peeled off from basal film, thereby can not obtain polarization plates.
This time disclosed embodiment and embodiment are illustration, are not restrictions.Above-mentioned explanation is not a scope of the present invention, utilizes the scope of claims that scope of the present invention is shown, with the claim scope be in the impartial meaning and scope, comprise whole changes.
Claims (7)
1. polarization plates roller, wherein, contain:
The basal film that forms by the transparent resin that is selected from polypropylene-based resin, PET series resin, polyethylene-based resin and the polyvinyl chloride resin;
Undercoat; And
Be disposed on this basal film and comprise the polaroid of the polyvinyl alcohol resin that contains the dichromatism pigment across this undercoat,
Wherein, the absorption axes of this polaroid is positioned on the direction with the flow direction quadrature of roller,
Basal film with the direction of the flow direction quadrature of roller on be orientated in the generating plane, and be more than 0.01 by the Δ n of following formula definition,
Δn＝n
x-n
y
At this, n
xBeing illustrated in the interior refractive index of pellicular front becomes the refractive index of maximum direction, n
yBe illustrated in the pellicular front and n
xThe refractive index of direction of direction quadrature.
2. polarization plates roller according to claim 1, wherein,
The saponification degree of polyvinyl alcohol resin is 98 moles more than the %, and the degree of polymerization is more than 1000.
3. polarization plates roller according to claim 1 and 2, wherein,
Undercoat is the transparent resin layer that is formed by the composition that contains modified polyvinylalcohol resin and crosslinking chemical.
4. according to any described polarization plates roller in the claim 1～3, wherein,
Face in the polaroid side of polarization plates roller disposes protective clear layer across adhesive phase.
5. polarization plates roller with pressure sensitive adhesive layer, wherein,
At least the one side of any described polarization plates roller is formed with pressure sensitive adhesive layer in claim 1～4.
6. polarization plates, it is that polarization plates roller section with the described band pressure sensitive adhesive layer of claim 5 forms.
7. liquid crystal indicator, wherein,
The polarization plates that possesses the described band pressure sensitive adhesive layer of liquid crystal cells and claim 6,
Wherein, the described pressure sensitive adhesive layer of polarization plates is fitted in described liquid crystal cells.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-155633 | 2008-06-13 | ||
| JP2008155633A JP2009300768A (en) | 2008-06-13 | 2008-06-13 | Polarizing plate roll, and polarizing plate roll with pressure sensitive adhesive layer, polarizing plate and liquid crystal display device using the same |
| JP2008155633 | 2008-06-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101604045A true CN101604045A (en) | 2009-12-16 |
| CN101604045B CN101604045B (en) | 2013-01-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009102033672A Expired - Fee Related CN101604045B (en) | 2008-06-13 | 2009-06-09 | Polarizing plate roller, and polarizing plate roller, polarizing plate, liquid crystal display device using same and provided with pressure sensitive adhesive layer |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2009300768A (en) |
| KR (1) | KR20090129947A (en) |
| CN (1) | CN101604045B (en) |
| TW (1) | TW201005335A (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| TW201005335A (en) | 2010-02-01 |
| JP2009300768A (en) | 2009-12-24 |
| KR20090129947A (en) | 2009-12-17 |
| CN101604045B (en) | 2013-01-09 |
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