CN102834748B - Polarizability stacked film, polarization plates and their manufacture method - Google Patents

Polarizability stacked film, polarization plates and their manufacture method Download PDF

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Publication number
CN102834748B
CN102834748B CN201180017093.3A CN201180017093A CN102834748B CN 102834748 B CN102834748 B CN 102834748B CN 201180017093 A CN201180017093 A CN 201180017093A CN 102834748 B CN102834748 B CN 102834748B
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polarization
film
resin
lamella
base material
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CN102834748A (en
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九内雄一朗
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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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
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B7/00—Mountings, adjusting means, or light-tight connections, for optical elements
    • G02B7/28—Systems for automatic generation of focusing signals
    • G02B7/36—Systems for automatic generation of focusing signals using image sharpness techniques, e.g. image processing techniques for generating autofocus signals
    • 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
    • G02F1/133502—Antiglare, refractive index matching layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2329/00—Polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals
    • B32B2329/04—Polyvinylalcohol
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/50—Protective arrangements

Abstract

The present invention is a kind of slim polarization plates, and described polarization plates possesses diaphragm and is formed at the polarization lamella in a face of diaphragm, and can provide good contrast ratio in liquid crystal indicator; Wherein, the thickness of polarization lamella is less than 10 μm and has the polyvinyl alcohol resin of dichromatism pigment to be formed by gas absorption quantity, the saponification degree of polyvinyl alcohol resin is less than 99.0 % by mole, and visibility correction monomer transmissivity (Ty) is more than 40% and visibility correction degree of polarization (Py) is more than 99.9%.

Description

Polarizability stacked film, polarization plates and their manufacture method
Technical field
The present invention relates to polarizability stacked film, polarization plates and their manufacture method.
Background technology
Polarization plates is widely used as the feed element etc. of the polarized light in the display device such as liquid crystal indicator.As such polarization plates; be used in the polarization plates of the bonding diaphragm formed by triacetyl cellulose on the polarizing coating formed by polyvinyl alcohol resin in the past always; but in recent years along with the development etc. of liquid crystal indicator in the mobile device such as notebook personal computer, mobile phone, require thin-wall light-weighted.
As the method manufacturing this type of slim polarization plates; propose following methods: by after base material film surface arranges polyvinyl alcohol resin; stretch; then dye; thus obtain the polarizability stacked film with polarization lamella; it is directly used as polarization plates; or after diaphragm of fitting on this polarizability stacked film; peeling base film, is used as polarization plates (such as with reference to JP2000-338329-A, JP2009-93074-A, JP2009-98653-A and JP2003-43257-A) by the stacked film obtained thus.
For obtained by above-mentioned existing method, formed for the polarization plates of polyvinyl alcohol resin layer on base material film surface, by base material film on the surface directly pva coating system resin aqueous solution and form resin bed, thus compared with using the situation of the former film of polyethylene-based resin (Off イ Le system is former anti-), exist and obtain the such advantage of very thin polyvinyl alcohol layer.
But, when the polarization plates obtained by above-mentioned existing method is used for liquid crystal indicator, sometimes may not be abundant in the contrast of liquid crystal indicator.
Therefore, the object of the present invention is to provide slim polarization plates, wherein used polarizability stacked film and their manufacture method of the contrast ratio that can to provide good in liquid crystal indicator.
Present inventor has performed deep research, found that in above-mentioned existing method, when use saponification degree more than 99.0 % by mole, general polyvinyl alcohol resin form resin bed, the polarization plates obtained polarization property in sometimes not enough, it found that the contrast ratio of the liquid crystal indicator using polarization plates may not be sufficient, thus completes the present invention.
Summary of the invention
The present invention includes following proposal.
[1] a kind of polarizability stacked film, its polarization lamella in a face that there is base material film and be formed at base material film, wherein, the thickness of polarization lamella is less than 10 μm, formed by the polyvinyl alcohol resin through dichromatism pigment gas absorption quantity, the saponification degree of polyvinyl alcohol resin is less than 99.0 % by mole, and it is more than 40% that visibility corrects monomer transmissivity (Ty), and visibility correction degree of polarization (Py) is more than 99.9%.
[2] the polarizability stacked film Gen Ju [1], wherein, polarization lamella is to be implemented uniaxial tension more than the stretching ratio of 5 times.
[3] according to [1] or the polarizability stacked film described in [2], it is used to polarization plates.
[4] according to the polarizability stacked film according to any one of [1] ~ [3], wherein, polarization lamella is formed at a face of base material film across undercoat.
[5] a kind of polarization plates; its polarization lamella in a face that there is diaphragm and be formed at diaphragm; wherein; the thickness of polarization lamella is less than 10 μm; formed by the polyvinyl alcohol resin through dichromatism pigment gas absorption quantity; the saponification degree of polyvinyl alcohol resin is less than 99.0 % by mole, and it is more than 40% that visibility corrects monomer transmissivity (Ty), and visibility correction degree of polarization (Py) is more than 99.9%.
[6] polarization plates Gen Ju [5], wherein, polarization lamella is formed at a face of diaphragm across adhesive phase or bond layer.
[7] according to [5] or the polarization plates described in [6], wherein, polarization lamella is to be implemented uniaxial tension more than the stretching ratio of 5 times.
[8] a kind of manufacture method of polarizability stacked film, it is the manufacture method of the polarizability stacked film according to any one of [1] ~ [4], comprise: form the resin bed formation process that resin bed that the polyvinyl alcohol resin being less than 99.0 % by mole by saponification degree formed obtains stacked film in face of base material film, with the stretching ratio more than 5 times, uniaxial tension carried out to stacked film and obtain the stretching process of stretched film, and the described resin bed dyeing of stretched film being formed the dyeing process of polarization lamella with dichromatism pigment.
[9] a kind of manufacture method of polarization plates, it is the manufacture method of the polarization plates according to any one of [5] ~ [8], comprise: form the resin bed formation process that resin bed that the polyvinyl alcohol resin being less than 99.0 % by mole by saponification degree formed obtains stacked film in face of base material film, with the stretching ratio more than 5 times, uniaxial tension carried out to stacked film and obtain the stretching process of stretched film, with dichromatism pigment, the dyeing of the resin bed of stretched film is formed polarization lamella, thus obtain the dyeing process of polarizability stacked film, the fitting diaphragm and obtain the bonding process of multilayer film with the face of the opposition side, face of base material film side of polarization lamella of polarizability stacked film, and the stripping process that base material film peeled off from multilayer film.
According to the present invention, may be provided in liquid crystal indicator the slim polarization plates of the display of the contrast ratio that can provide good and wherein used polarizability stacked film.In addition, according to the manufacture method of polarization plates of the present invention or polarizability stacked film, by forming the resin bed that the polyvinyl alcohol resin being less than 99.0 % by mole by saponification degree is formed on the surface of base material film, carry out uniaxial tension with the stretching ratio more than 5 times, thus play obtain the such effect of good dyeing kinetics in the dyeing process of back segment.
Accompanying drawing explanation
Fig. 1 is the summary section representing the example that the Primary layer of polarizability stacked film involved in the present invention is formed.
Fig. 2 is the summary section representing the example that the Primary layer of polarization plates involved in the present invention is formed.
Fig. 3 is the process flow diagram of an embodiment of the manufacture method representing the polarizability stacked film shown in Fig. 1.
Fig. 4 is the process flow diagram of an embodiment of the manufacture method representing the polarization plates shown in Fig. 2.
Embodiment
Preferred embodiment be described in detail to of the present invention referring to accompanying drawing.
The formation > of < polarizability stacked film
Fig. 1 is the summary section that the example that the Primary layer of polarizability stacked film involved in the present invention is formed is shown.Polarizability stacked film 10 possesses base material film 11 and is formed in the polarization lamella 12 in a face of base material film 11.The thickness of polarization lamella 12 is less than 10 μm, is formed by the polyvinyl alcohol resin through dichromatism pigment gas absorption quantity.The saponification degree of polyvinyl alcohol resin is less than 99.0 % by mole.
It is more than 40% that the visibility of polarizability stacked film 10 corrects monomer transmissivity (Ty), and visibility correction degree of polarization (Py) is more than 99.9%.Polarizability stacked film 10 can be used as polarization plates.Because polarizability stacked film 10 has optical characteristics as above, so the display with good contrast ratio can be obtained when polarizability stacked film being used for the polarization plates of liquid crystal indicator.
It should be noted that, visibility corrects monomer transmissivity (Ty) by obtaining with under type, namely, in the scope that wavelength is 380nm ~ 780nm, obtain MD transmissivity and the TD transmissivity of polarizability stacked film or polarization plates, calculate the monomer transmissivity under each wavelength according to formula (1) as follows, and then carry out visibility correction by 2 degree of visuals field (illuminant-C) of JISZ8701.
In addition, visibility corrects degree of polarization (Py) by obtaining with under type, that is, obtain MD transmissivity and TD transmissivity as described above, calculate the degree of polarization (%) under each wavelength according to formula (2) as follows, carry out visibility correction similar to the above.
Transmissivity when " MD transmissivity " is for making the axis of homology of polarization plates sample parallel with the direction of the polarized light sent from glan-Thompson prism, is expressed as " MD " in (2) in formula (1), formula.In addition, transmissivity when " TD transmissivity " is for making the axis of homology of polarization plates sample be orthogonal with the direction of the polarized light sent from glan-Thompson prism, is expressed as " TD " in (2) in formula (1), formula.The spectrophotometric determination of all available band integrating sphere of MD transmissivity, TD transmissivity.
Monomer transmissivity (%)=(MD+TD)/2 ... formula (1)
Below each inscape is described in detail.
[base material film]
As the material of the base material film 11 used in the present invention, the thermoplastic resin that the such as transparency, physical strength, thermal stability, stretchability etc. are excellent can be used.As the instantiation of such thermoplastic resin, can the cellulose esters system resins such as primary cellulose acetate, polyester based resin, polyethersulfone system resin, polysulfones system resin, polycarbonate-based resin, polyamide series resin, polyimide system resin, polyolefin-based resins, (methyl) acrylic resin, cyclic polyolefin hydrocarbon system resin (norbornene resin), polyacrylate system resin, polystyrene resin, polyvinyl alcohol resin be listed, and their potpourri etc.
As the material of base material film, preferably containing be selected from cellulose esters system resin, polyolefin-based resins, cyclic polyolefin hydrocarbon system resin and (methyl) acrylic resin at least any one.
Cellulose esters system resin is the ester of cellulose and fatty acid.As the instantiation of such cellulose esters system resin, primary cellulose acetate, cellulose diacetate, cellulose tripropionate, cellulose dipropionate etc. can be listed.
Wherein, particularly preferably primary cellulose acetate.For primary cellulose acetate, commercially available have multiple product, and obtain easiness or cost in be also favourable.As the example of the commercially available product of primary cellulose acetate, FUJITAC (registered trademark) TD80 (Fuji Photo Film (Ltd.) is made), FUJITAC (registered trademark) TD80UF (Fuji Photo Film (Ltd.) is made), FUJITAC (registered trademark) TD80UZ (Fuji Photo Film (Ltd.) is made), FUJITAC (registered trademark) TD40UZ (Fuji Photo Film (Ltd.) is made), KC8UX2M (KONICAMINOLTAOPTO (strain) manufacture), KC4UY (KONICAMINOLTAOPTO (strain) manufacture) etc. can be listed.
As polyolefin-based resins, tygon, polypropylene etc. can be listed.When using the base material film formed by polypropylene, easily carry out stablizing and powerful stretching, therefore preferably.As cyclic polyolefin hydrocarbon system resin, preferably use norbornene resin.
Cyclic polyolefin hydrocarbon system resin is the general name of the resin be polymerized using cyclic olefin as polymerized unit, include, for example out the resin recorded in JPH01-240517-A, JPH03-14882-A, JPH03-122137-A etc.As instantiation, open loop (being total to) polymkeric substance of cyclic olefin can be listed, the addition polymer of cyclic olefin, cyclic olefin and the alpha-olefin such as ethene, propylene and its multipolymer (representational is random copolymers), and the graft polymer with unsaturated carboxylic acid or derivatives thereof, modification being carried out to these resins and obtain, and their hydride etc.As the instantiation of cyclic olefin, norborneol alkene monomer can be listed.
As cyclic polyolefin hydrocarbon system resin, commercially available have various product.As instantiation, Topas (registered trademark) (manufacture of Ticona company), ARTON (registered trademark) (JSR (strain) manufacture), ZEONOR (registered trademark) (Japanese ZEON (strain) manufacture), ZEONEX (registered trademark) (Japanese ZEON (strain) manufacture), APEL (registered trademark) (Mitsui Chemicals (strain) manufacture) etc. can be listed.
As (methyl) acrylic resin, (methyl) acrylic resin suitable arbitrarily can be adopted.Include, for example out poly-(methyl) acrylate such as polymethylmethacrylate, methyl methacrylate-(methyl) acrylic copolymer, methyl methacrylate-(methyl) acrylate copolymer, methyl methacrylate-acrylate-(methyl) acrylic copolymer, (methyl) acrylate-styrene multipolymer (MS resin etc.), there is the polymkeric substance of alicyclic alkyl (such as, methyl methacrylate-cyclohexyl methacrylate multipolymer, methyl methacrylate-(methyl) acrylic acid norborneol ester copolymer etc.).
Preferably can list poly-(methyl) acrylic acid C1-6 Arrcostabs such as poly-(methyl) methyl acrylate.As (methyl) acrylic resin, more preferably using with methyl methacrylate is the methyl methacrylate system resin of principal ingredient (50 ~ 100 % by weight, preferably 70 ~ 100 % by weight).
In base material film 11, except above-mentioned thermoplastic resin, also can add adjuvant suitable arbitrarily.As such adjuvant, include, for example out ultraviolet light absorber, antioxidant, lubricant, plastifier, release agent, anti-coloring agent, fire retardant, nucleator, antistatic agent, pigment and colorant etc.Be preferably 50 ~ 100 % by weight by the content of above-mentioned illustrative thermoplastic resin in base material film, be more preferably 50 ~ 99 % by weight, more preferably 60 ~ 98 % by weight, be particularly preferably 70 ~ 97 % by weight.This be due to the thermoplastic resin in base material film containing quantity not sufficient 50 % by weight when, the high transparent etc. that thermoplastic resin originally has likely cannot embody fully.
The thickness of base material film 11 can suitably determine, generally from the aspect of the operability such as intensity or treatability, is preferably 1 ~ 500 μm, is more preferably 1 ~ 300 μm, more preferably 5 ~ 200 μm.The thickness of base material film 11 most preferably is 5 ~ 150 μm.
For base material film 11, in order to improve the adaptation with polarization lamella 12, corona treatment, Cement Composite Treated by Plasma, flame treatment etc. can be carried out to the surface of the side being at least formed with polarization lamella 12.In addition, in order to improve adaptation, the thin layers such as undercoat can be formed on the surface being formed with the side of polarization lamella 12 of base material film 11.
[polarization lamella]
Polarization lamella 12 specifically makes dichromatism pigment gas absorption quantity obtain in the polyvinyl alcohol resin layer after uniaxial tension.As polyvinyl alcohol resin, can use and the resin after saponification is carried out to polyvinyl acetate (PVA) system resin.As polyvinyl acetate (PVA) system resin, except the polyvinyl acetate (PVA) of the homopolymer as vinyl acetate, also can be illustrated as the multipolymer etc. of the monomer of vinyl acetate and other energy copolymerization.As can with other vinyl acetate copolymerized monomer, include, for example out unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class, there is the acrylic amide etc. of ammonium.
The saponification degree of polyvinyl alcohol resin is preferably less than 99.0 % by mole.In the present invention, even if the reason that use saponification degree is the polyvinyl alcohol resin of less than 99.0 % by mole is also can maintain certain dyeing kinetics when implementing the uniaxial tension more than 5 times, there is advantage thus that effectively can produce the high slim polarizability stacked film of polarization property.On the other hand, when the polyvinyl alcohol resin using saponification degree more than 99.0 % by mole, dyeing kinetics is significantly slack-off, there is the situation that can not get the polarizability stacked film with enough polarization properties, there is the unfavorable condition producing and need the common several times time in the mill in addition.
In addition, the saponification degree of polyvinyl alcohol resin is preferably more than 90 % by mole, is more preferably more than 94 % by mole.If saponification degree is less than 90 % by mole, then there is the situation of water tolerance equal strength deficiency.
Saponification degree mentioned here represents with unit ratio (unitrate) (% by mole) to make the acetoxy group contained in the polyvinyl acetate (PVA) system resin as the raw material of polyvinyl alcohol resin become the ratio of hydroxyl by saponifying process, is the numerical value defined by following formula.In available JISK6726 (1994), the method for regulation is tried to achieve.
Saponification degree (% by mole)=(number of hydroxyl) ÷ (number of the number+acetoxy group of hydroxyl) × 100
Saponification degree is higher, represents that the ratio of hydroxyl is higher, namely represents that the ratio of the acetoxy group of obstruction crystallization is lower.In addition, with regard to the polyvinyl alcohol resin used in the present invention, if saponification degree is less than 99.0 % by mole, then without particular determination, it can be the modified polyvinylalcohol that part is modified.Include, for example out with the alkene such as ethene, propylene, the unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, the Arrcostab of unsaturated carboxylic acid, the material etc. that acrylamide etc. have carried out a few % degree ground modification to polyvinyl alcohol resin and obtained.The average degree of polymerization of polyvinyl alcohol resin also without particular determination, but is preferably 100 ~ 10000, is more preferably 1500 ~ 10000.
As the polyvinyl alcohol resin with such characteristic, the PVA124 (saponification degree: 98.0 ~ 99.0 % by mole) that such as (strain) Kuraray manufactures can be listed, PVA117 (saponification degree: 98.0 ~ 99.0 % by mole), PVA624 (saponification degree: 95.0 ~ 96.0 % by mole) and PVA617 (saponification degree: 94.5 ~ 95.5 % by mole), the AH-26 (saponification degree: 97.0 ~ 98.8 % by mole) that such as Japanese synthetic chemical industry (strain) manufactures, AH-22 (saponification degree: 97.5 ~ 98.5 % by mole), NH-18 (saponification degree: 98.0 ~ 99.0 % by mole) and N-300 (saponification degree: 98.0 ~ 99.0 % by mole), such as JAPANVAM & POVALCO., LTD. the JF-17 (saponification degree: 98.0 ~ 99.0 % by mole) manufactured, JF-17L (saponification degree: 98.0 ~ 99.0 % by mole) and JF-20 (saponification degree: 98.0 ~ 99.0 % by mole) etc., be applicable in the present invention.
Polarization lamella 12 involved in the present invention is formed to the film that such polyvinyl alcohol resin is filmed.The method be filmed polyvinyl alcohol resin is without particular determination, be filmed by known method, but set out in the aspect of the polarization lamella 12 of the desired thickness that is easy to get calmly, preferably on base material film 11, the solution of pva coating system resin is filmed.With preferably greater than 5 times, further preferably greater than 5 times and be that the stretching ratio of less than 17 times carries out uniaxial tension to polarization lamella 12.
For polarization lamella 12, make dichromatism pigment gas absorption quantity in polyvinyl alcohol resin as above.The thickness of polarization lamella 12 is less than 10 μm, is preferably less than 7 μm.By making the thickness of polarization lamella 12 be less than 10 μm, thus slim polarizability stacked film can be formed.
The formation > of < polarization plates
Fig. 2 is the summary section that the example that the Primary layer of polarization plates involved in the present invention is formed is shown.Polarization plates 13 possesses diaphragm 14 and is formed in the polarization lamella 12 in a face of diaphragm 14.The thickness of polarization lamella 12 is less than 10 μm, is formed by the polyvinyl alcohol resin through dichromatism pigment gas absorption quantity.The saponification degree of polyvinyl alcohol resin is less than 99.0 % by mole.
It is more than 40% that the visibility of polarization plates 13 corrects monomer transmissivity (Ty), and visibility correction degree of polarization (Py) is more than 99.9%.Polarization plates 13 can be used as the polarization plates of liquid crystal indicator.Because polarization plates 13 has optical characteristics as above, the display of good contrast ratio therefore can be obtained when polarization plates 13 is used as the polarization plates of liquid crystal indicator.
In polarization plates 13, such as, by the adhesive phase do not expressed in Fig. 3 or bond layer, diaphragm 14 and polarization lamella 12 are fitted.Below each inscape is described in detail.
[diaphragm]
As diaphragm 14, can not having optical function and be only diaphragm, also can be that phase retardation film or brightness improve the film diaphragm having optical function concurrently like this etc.As the material of diaphragm 14; without particular determination; include, for example out cyclic polyolefin resin film; the cellulose acetate resin film formed by the resin of triacetyl cellulose, diacetyl cellulose and so on; the polyester based resin film formed by the resin of polyethylene terephthalate, PEN, polybutylene terephthalate and so on; polycarbonate resin film, acrylic resin film, polypropylene-based resin film etc. is widely used in the film in this area all the time.
As cyclic polyolefin hydrocarbon system resin, can preferably use suitable commercially available product, such as Topas (registered trademark) (manufacture of Ticona company), ARTON (registered trademark) (JSR (strain) manufacture), ZEONOR (registered trademark) (Japanese ZEON (strain) manufacture), ZEONEX (registered trademark) (Japanese ZEON (strain) manufacture), APEL (registered trademark) (Mitsui Chemicals (strain) manufacture).Being filmed such cyclic polyolefin hydrocarbon system resin during film forming, suitably can adopt the known method such as solvent casting method, extrusion by melting.In addition, ESCENA (registered trademark) (ponding chemical industry (strain) manufacture), SCA40 (ponding chemical industry (strain) manufacture), ZEONOR (registered trademark) film ((strain) OPTES manufactures) etc. can be used to have carried out the commercially available product of the film of the cyclic polyolefin hydrocarbon system resin manufacture of masking in advance.
Cyclic polyolefin resin film can be through uniaxial tension or biaxial stretch-formed film.By stretching, arbitrary phase difference value can be given to cyclic polyolefin resin film.Usually can roll film roller while stretch continuously, utilize heating furnace, stretch towards the direct of travel of roller, the direction vertical with this direct of travel or this both direction.The temperature of heating furnace is generally the scope to glass transition temperature+100 DEG C near the glass transition temperature of cyclic polyolefin hydrocarbon system resin.The multiplying power stretched is generally 1.1 ~ 6 times in each direction, is preferably 1.1 ~ 3.5 times.
The general surfactivity of cyclic polyolefin resin film is poor, therefore preferably carries out the surface treatments such as Cement Composite Treated by Plasma, corona treatment, Ultraviolet radiation process, flame (flame) process, saponification process to the surface bonding with polarizing coating.Wherein, the Cement Composite Treated by Plasma preferably can implemented with comparalive ease, corona treatment.
As cellulose acetate resin film, can preferably use suitable commercially available product, such as FUJITAC (registered trademark) TD80 (Fuji Photo Film (Ltd.) is made), FUJITAC (registered trademark) TD80UF (Fuji Photo Film (Ltd.) is made), FUJITAC (registered trademark) TD80UZ (Fuji Photo Film (Ltd.) is made), FUJITAC (registered trademark) TD40UZ (Fuji Photo Film (Ltd.) is made), KC8UX2M (KONICAMINOLTAOPTO (strain) manufacture), KC4UY (KONICAMINOLTAOPTO (strain) manufacture).
In order to improve field angle characteristic, liquid crystal layer etc. can be formed on the surface of cellulose acetate resin film.In addition, in order to give phase differential, cellulose acetate resin film can be made to stretch.In order to improve the cementability with polarizing coating, the cellulose-based resin molding of usual Dichlorodiphenyl Acetate implements saponification process.As saponification process, the method for carrying out flooding in the aqueous solution of the alkali of NaOH or potassium hydroxide and so on can be adopted.
Also the optical layers such as hard conating, antiglare layer, anti-reflection layer can be formed on the surface of diaphragm 14 as above.Form the method for these optical layers on the surface without particular determination at diaphragm, known method can be adopted.
With regard to the thickness of diaphragm 14, according to the requirement of slimming, preferably thin as far as possible thickness, is preferably less than 88 μm, is more preferably less than 48 μm.On the contrary, if excessively thin, then intensity reduces, and processability is deteriorated, and is therefore preferably more than 5 μm.
[polarization lamella]
Polarization lamella 12 can be set to the formation identical with the polarization lamella 12 of above-mentioned polarizability stacked film 10.
[adhesive phase]
The composition that normally also with the addition of the crosslinking chemicals such as isocyanate compound, epoxy compound, aziridine cpd wherein by polymkeric substance based on acrylic resin, phenylethylene resin series, silicone-based resin etc. for the protection of film 14 and the bonding agent of the laminating of polarization lamella 12 is formed.
In addition, also can contain particulate, make the adhesive phase of display light scattering.
The thickness of adhesive phase is preferably 1 ~ 40 μm, but preferably do not damage processability, permanance characteristic scope in be coated with thinly, be more preferably 3 ~ 25 μm.If 3 ~ 25 μm, then there is good processability, and be also preferred thickness in the change in size suppressing polarizing coating.If adhesive phase is less than 1 μm, then cohesive reduces, if more than 40 μm, then easily the unfavorable conditions such as bonding agent spilling occurs.
By bonding agent, diaphragm 14 is being fitted in the method for polarization lamella 12, after diaphragm 14 arranges adhesive phase, polarization lamella 12 can fitted in, also can after the surface of polarization lamella 12 arrange adhesive phase, diaphragm 14 of fitting thereon.
Form the method for adhesive phase without particular determination; the solution containing each composition being representative with above-mentioned base polymer can be coated with on diaphragm 14 or polarization lamella 12; dry; form adhesive phase; then diaphragm 14 and polarization lamella 12 is made to fit; also, after can forming adhesive phase on the spacers, transfer printing is also layered on diaphragm 14 or polarization lamella 12.In addition, when diaphragm 14 or polarization lamella 12 form adhesive phase, closely sealed process can be carried out, such as corona treatment etc. to a side of diaphragm 14 or polarization lamella 12 or adhesive phase or two sides as required.
[bond layer]
The water system bonding agent employing polyvinyl alcohol resin aqueous solution, water system two liquid type polyurethane system latex bonding agent etc. is include, for example out for the protection of film 14 and the bonding agent of the laminating of polarization lamella 12.Use when carrying out the cellulose acetate mesentery after hydrophilicity-imparting treatment as diaphragm 14 by saponification process etc., be applicable to the water system bonding agent using polyvinyl alcohol resin aqueous solution as the laminating with polarization lamella 12.In the polyvinyl alcohol resin being used as bonding agent, except the alcotex obtained except the carrying out saponification process to polyvinyl acetate (PVA) of the homopolymer as vinyl acetate, also comprise Dichlorodiphenyl Acetate vinyl acetate and saponification process can be carried out with the multipolymer of other monomer of its copolymerization and the ethenol system copolymer that obtains and partially modified modified polyvinylalcohol based polymer etc. is carried out to their hydroxyl.Polyaldehyde, soluble epoxide compound, melamine based compound, zirconia compound, zinc compound etc. can also be added as adjuvant in water system bonding agent.When using such water system bonding agent, the bond layer obtained by it is generally less than 1 μm, namely uses common observation by light microscope cross section, does not in fact also observe this bond layer.
Use method that water system bonding agent is fitted to polarization lamella 12 and diaphragm 14 without particular determination; include, for example out following methods etc.: at the uniformly coating adhesive of polarization lamella 12 and/or diaphragm 14; utilize roller etc. to press at coated face another film overlapping, carry out drying.Usually, bonding agent is coated with after its preparation at the temperature of 15 ~ 40 DEG C, and binding temperature is generally the scope of 15 ~ 30 DEG C.
When using water system bonding agent, in order to remove the water contained in water system bonding agent, and after fitting to polarization lamella 12 and diaphragm 14, make it dry.The temperature of drying oven is preferably 30 DEG C ~ 90 DEG C.If less than 30 DEG C, then there is polarization lamella 12 and become with the bonding plane of diaphragm 14 tendency easily peeled off.If more than 90 DEG C, then optical property likely Yin Re and deteriorated.Drying time can be set to 10 ~ 1000 seconds, particularly from the view point of throughput rate, is preferably 60 ~ 750 seconds, more preferably 150 ~ 600 seconds.
In room temperature or the temperature slightly higher than it, such as, at the temperature of about 20 ~ 45 DEG C, 12 ~ 600 hours can be cultivated further after drying.Temperature during cultivation is generally set as that the temperature than adopting during drying is lower.
In addition, as bonding agent when fitting to polarization lamella 12 and diaphragm 14, also Photocurable adhesive agent can be used.As Photocurable adhesive agent, include, for example the potpourri etc. of bright dipping curable epoxy resin and light cationic polymerization initiators.
As the method for fitting to polarization lamella 12 and diaphragm 14 with Photocurable adhesive agent; known method can be adopted; include, for example out by the tape casting, steel wire bar rubbing method, gravure coating process, comma coater method, scraper plate method, die coating methods, dip coating, spray-on process etc.; coating adhesive on the bonding plane of polarization lamella 12 and/or diaphragm 14, and by both superimposed methods.The tape casting be while to make as the polarization lamella 12 of applied thing or diaphragm 14 to substantially vertical direction, general horizontal direction or vergence direction between the two move, and flows down to its surface the method that bonding agent makes its diffusion profile.
After the surperficial coating adhesive of polarization lamella 12 or diaphragm 14, by bonding agent coated face niproll etc., polarization lamella 12 and diaphragm 14 clamped and make it fit to carry out bonding.In addition, also preferably can adopt to make polarization lamella 12 and the superimposed state of diaphragm 14 to drip bonding agent between polarization lamella 12 and diaphragm 14, then with roller etc., this duplexer pressurizeed and make the method for its uniform spreading.Now, as the material of roller, metal or rubber etc. can be used.In addition, also preferably adopt and drip bonding agent between polarization lamella 12 and diaphragm 14, then between roller and roller, pass through this duplexer, and by the method making it sprawl of pressurizeing.Now, these rollers can be identical materials, also can be different materials.Used above-mentioned niproll etc. to carry out laminating after bond layer drying or solidification before thickness be preferably less than 5 μm and more than 0.01 μm.
In order to improve cementability, can suitably implement the surface treatments such as Cement Composite Treated by Plasma, corona treatment, Ultraviolet radiation process, flame (flame) process, saponification process to the gluing of surfaces of polarization lamella 12 and/or diaphragm 14.As saponification process, the method for flooding in the aqueous solution of the alkali of NaOH or potassium hydroxide and so on can be listed.
When using light-cured resin as bonding agent, after engaging polarization lamella 12 and diaphragm 14, by irradiating active energy beam, Photocurable adhesive agent is solidified.Although the light source of active energy beam is without particular determination, but preferably have under the wavelength of below 400nm and send out active energy beam photodistributed, specifically, low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, chemical lamp, black lamp, microwave-excited mercury lamp, metal halide lamp etc. can preferably be used.
Suitably can determine according to the composition of Photocurable adhesive agent the photo-irradiation intensity of Photocurable adhesive agent, although without particular determination, 0.1 ~ 6000mW/cm is preferably to the exposure intensity of the effective wavelength region may of the activation of polymerization initiator 2.Be 0.1mW/cm in exposure intensity 2when above, the reaction time can not be long, is being 6000mW/cm 2when following, seldom can there is the xanthochromia of epoxy resin caused by heating when being solidified by the light and heat curability bonding agent gone out from radiation of light source or the deterioration of polarizing coating.Be the light application time that can be suitable for the Photocurable adhesive agent that will solidify to the light irradiation time of Photocurable adhesive agent, without particular determination, but preferred according to making with the integrating light quantity of the product representation of above-mentioned exposure intensity and irradiation time as 10 ~ 10000mJ/cm 2mode set.Be 10mJ/cm to the integrating light quantity of Photocurable adhesive agent 2when above, it can be made to produce the spike from polymerization initiator of sufficient quantity, curing reaction is carried out more reliably, be 10000mJ/cm 2when following, irradiation time can not be long, can maintain good throughput rate.It should be noted that, the thickness of the postradiation bond layer of active energy beam is generally about 0.001 ~ 5 μm, is preferably more than 0.01 μm and less than 2 μm, more preferably more than 0.01 μm and less than 1 μm.
When the irradiation by active energy beam makes Photocurable adhesive agent that solidification occur, preferably do not reduce the degree of polarization of polarization lamella 12, transmissivity and tone and diaphragm 14 the polarization plates such as the transparency various functions condition under be cured.
[other optical layers]
As above the polarization plates of the present invention operating manufacture can be used as being laminated with the polarization plates of other optical layers when reality uses.In addition, said protection film 14 can have the function of these optical layers.As the example of other optical layers, certain polarized light of transmission can be listed and reflective display goes out the film of the anti-dazzle function of band with the reflective polarizing film of the polarized light of its opposite nature, surface with concaveconvex shape, the film of belt surface anti-reflective function, surface have the reflectance coating of reflection function, the Transflective film having reflection function and transmission function concurrently, field angle compensate film.
As being equivalent to certain polarized light of transmission and reflective display goes out the commercially available product with the reflective polarizing film of the polarized light of its opposite nature, (3M company manufactures to include, for example out DBEF, can obtain from Sumitomo 3M (strain)), APF (3M company manufacture, can obtain from Sumitomo 3M (strain)).As field angle compensate film, liquid crystal compounds can be listed and be coated on substrate surface and there occurs the optical compensation films of orientation, the phase retardation film formed by polycarbonate-based resin, the phase retardation film that formed by cyclic polyolefin hydrocarbon system resin.Being coated on substrate surface and the commercially available product that there occurs the optical compensation films of orientation as being equivalent to liquid crystal compounds, WV film (Fuji Photo Film (Ltd.) is made), NH film (Nippon Oil(Nippon Mitsubishi Oil) (strain) manufacture), NR film (Nippon Oil(Nippon Mitsubishi Oil) (strain) manufacture) etc. can be listed.In addition, as the commercially available product being equivalent to the phase retardation film formed by cyclic polyolefin hydrocarbon system resin, ARTON (registered trademark) film (JSR (strain) manufacture), ESCENA (registered trademark) (ponding chemical industry (strain) manufacture), ZEONOR (registered trademark) film ((strain) OPTES manufactures) etc. can be listed.
The manufacture method > of < polarizability stacked film
Fig. 3 is the process flow diagram of an embodiment of the manufacture method of the polarizability stacked film 10 illustrated as shown in Figure 1.Accordingly, the manufacture method of polarizability stacked film 10 is implement the method for following operation successively, that is, the resin bed that the polyvinyl alcohol resin that a surface of base material film 11 to be formed by saponification degree be less than 99.0 % by mole is formed makes the resin bed formation process (S10) of stacked film; With the stretching ratio more than 5 times, uniaxial tension process implemented to above-mentioned stacked film and make the stretching process (S20) of stretched film; With dichromatism pigment, polarization lamella 12 is made in the dyeing of the resin bed of above-mentioned stretched film, thus obtain the dyeing process (S30) of polarizability stacked film 10.Resin bed formation process (S10), stretching process (S20) are identical with each operation corresponding in the manufacture method of aftermentioned polarization plates with dyeing process (S30).
The stacked film obtained by this manufacture method is become on the base material film 11 after stretched and possesses the polarizability stacked film 10 that thickness is the polarization lamella 12 of less than 10 μm.This polarizability stacked film also directly can be used as polarization plates, also as described later polarization lamella 12 can be used as the intermediate product be transferred on diaphragm.
The manufacture method > of < polarization plates
Fig. 4 is the process flow diagram of an embodiment of the manufacture method of the polarization plates 13 illustrated as shown in Figure 2.
Accordingly, the manufacture method of polarization plates 13 is after implementing following operation successively, that is, the resin bed that the polyvinyl alcohol resin that a surface of base material film to be formed by saponification degree be less than 99.0 % by mole is formed makes the resin bed formation process (S10) of stacked film; With the stretching ratio more than 5 times, uniaxial tension process implemented to above-mentioned stacked film and make the stretching process (S20) of stretched film; Carry out dyeing with dichromatism pigment and make polarization lamella 12, thus obtain the dyeing process (S30) of polarizability stacked film, also possesses following operation successively, that is, above-mentioned polarizability stacked film polarization lamella 12 with the face of the opposition side, face of base material film 11 side on to fit diaphragm 14 and obtain the bonding process (S40) of multilayer film; The stripping process (S50) that base material film 11 is peeled off from above-mentioned multilayer film.
The polarization plates 13 obtained by this manufacture method is become possess the polarization plates 13 that thickness is the polarization lamella 12 of less than 10 μm on diaphragm 14.This polarization plates 13 such as can re-use by after pressure sensitive bonding agent and other blooming or liquid crystal cell laminating etc.
Below each operation of the S10 ~ S50 in Fig. 3 and Fig. 4 is described in detail.It should be noted that, each operation of the S10 ~ S30 of Fig. 3 and Fig. 4 is identical operation.
[resin bed formation process (S10)]
Here, a surface of base material film forms the resin bed formed by polyvinyl alcohol resin.
Be applicable to the material of base material film as described in the explanation of the formation at above-mentioned polarizability stacked film.It should be noted that, in the present embodiment, base material film preferably uses fusing point to be the base material film of more than 110 DEG C in order to stretch in the temperature range of the stretching of applicable polyvinyl alcohol resin.Preferred use fusing point is the base material film of more than 130 DEG C.If this is because the fusing point of base material film is less than 110 DEG C, then in stretching process described later (S20), base material film easily melts, and fully cannot improve draft temperature, and the stretching more than 5 times becomes the cause of difficulty.The fusing point of base material film is the value recorded with the programming rate of 10 DEG C/min according to ISO3146.
Be applicable to the material of the polyvinyl alcohol resin in order to form resin bed as described in the explanation of the formation at polarizability stacked film.The thickness of the resin bed formed preferably more than 3 μm and less than 30 μm, more preferably 5 ~ 20 μm.If less than 3 μm, then became thin after the stretch, dyeability significantly worsens, if more than 30 μm, then the thickness of the polarization lamella finally obtained is not often beyond 10 μm, therefore preferred.
Resin bed is formed preferably by with under type, that is, make the powder dissolution of polyvinyl alcohol resin in good solvent, coated on a surface of base material film by the polyvinyl alcohol resin solution obtained thus, solvent is evaporated, and dry.By forming resin bed like this, thus can be formed thinly.As method polyvinyl alcohol resin solution coated on base material film, suitably can select to adopt the rolling methods such as steel wire bar rubbing method, oppositely coating, intaglio plate coating from known method, die coating methods, comma rubbing method, lip type rubbing method, spin-coating method, silk screen rubbing method, jetting type rubbing method, infusion process, spray-on process etc.Baking temperature is such as 50 ~ 200 DEG C, is preferably 60 ~ 150 DEG C.Drying time is such as 2 ~ 20 minutes.
It should be noted that, the mode of the former film (former anti-Off イ Le system) that the resin bed in present embodiment is also formed by polyvinyl alcohol resin by fitting on a surface of base material film is formed.
In addition, in order to improve the adaptation of base material film and polyvinyl alcohol resin, undercoat can be set between base material film and resin bed.Formed from the viewpoint preferred undercoat of adaptation by the composition containing crosslinking chemical etc. in polyvinyl alcohol resin.
[stretching process (S20)]
Here, relative to the former length of stacked film, with the stretching ratio more than 5 times, uniaxial tension is carried out to the stacked film formed by base material film and resin bed, thus obtains stretched film.Preferably with more than 5 times and be that the stretching ratio of less than 17 times carries out uniaxial tension.Preferred with more than 5 times and be that the stretching ratio of less than 8 times carries out uniaxial tension further.If stretching ratio is less than 5 times, then the resin bed formed by polyvinyl alcohol resin can not orientation fully, so the degree of polarization that result is polarization lamella can not fully improve.On the other hand, if stretching ratio is more than 17 times, then the fracture of stacked film when stretching easily occurs, and meanwhile, the thickness of stretched film becomes and is thinner than desired thickness, and the processability in subsequent handling and maneuverability likely reduce.Stretch processing in stretching process (S20) is not limited to stretch with one section, also can carry out with multistage.When carrying out with multistage, coordinate and carry out stretch processing to all sections of stretch processing with the stretching ratio more than 5 times.
In the stretching process (S20) of present embodiment, the vertical the stretch processing preferably length direction of stacked film carried out, but when and when less requiring polarization property, also can be the stiff end uniaxial tension utilizing the horizontal uniaxial tension etc. of tenter frame process to be representative.As vertical stretching mode, the drawing process etc. of drawing process between roller, compression stretching method, use stenter can be listed.Stretch processing is not limited to vertical stretch processing, also can be oblique stretch processing etc.In addition, free end uniaxial tension is preferably.
In addition, stretch processing can adopt in moistening type drawing process and dry-stretch process any one, but the aspect of temperature when selecting stretching stacked film from wide in range scope, is preferably the stretch processing using dry-stretch process.
In the present embodiment, preferably in the temperature range of-30 DEG C to+5 DEG C of the fusing point of base material film, stretch processing is carried out.-25 DEG C of the preferred fusing point at base material film are carried out stretch processing to the temperature range of fusing point further.If make draft temperature lower than-30 DEG C of the fusing point of base material film, then the high magnification more than 5 times stretches and becomes difficulty.If draft temperature exceedes+5 DEG C of the fusing point of base material film, then stretch and to become difficulty because of the fusing of base material film, thus not preferred.It should be noted that, draft temperature in above-mentioned scope, more preferably more than 120 DEG C.This be due to draft temperature be more than 120 DEG C when, even the high stretching ratio more than 5 times, stretch processing also no longer difficulty cause.The temperature adjustment of stretch processing utilizes the temperature of heating furnace to adjust usually.
[dyeing process (S30)]
Here, with dichromatism pigment, the resin bed of stretched film is dyeed.As dichromatism pigment, include, for example out iodine or organic dyestuff etc.As organic dyestuff, such as, can use red BR, red LR, red R, pink LB, rubine BL, purplish red (Bordeaux) GS, sky blue LG, lemon yellow, blue BR, blue 2R, purplish blue (Navy) RY, green LG, purple LB, purple B, black H, black B, black GSP, yellow 3G, yellow R, orange LR, orange 3R, scarlet GL, scarlet KGL, Congo red, brilliant violet BK, Si Pula (Supra) blue G, Si Pula blue GL, Si Pula orange GL, direct sky blue, chlorazol fast orange d S, fast black etc.These dichroic substance can be a kind of, also can and with two or more.
Dyeing process is such as undertaken by the whole stretched film of dipping in the solution (staining solution) containing above-mentioned dichromatism pigment.As staining solution, the solution having dissolved above-mentioned dichromatism pigment in a solvent can be used.As the solvent of staining solution, generally can use water, but also can add the organic solvent had with the intermiscibility of water further.As the concentration of dichromatism pigment, be preferably 0.01 ~ 10 % by weight, be more preferably 0.02 ~ 7 % by weight, be particularly preferably 0.025 ~ 5 % by weight.
When using iodine as dichromatism pigment, due to further staining efficiency can be improved, so preferably add iodide further.As these iodide, include, for example out potassium iodide, lithium iodide, sodium iodide, zinc iodide, silver iodide, lead iodide, cupric iodide, barium iodide, calcium iodide, stannic iodide, titanium iodide etc.In staining solution, the adding proportion of these iodide is preferably 0.01 ~ 10 % by weight.In iodide, preferably add potassium iodide.When adding potassium iodide, the ratio of iodine and potassium iodide is preferably the scope of 1: 5 ~ 1: 100 with mass ratio range, be more preferably the scope of 1: 6 ~ 1: 80, is particularly preferably the scope of 1: 7 ~ 1: 70.
Although the dip time of stretched film in staining solution is without particular determination, is usually preferably the scope of 15 seconds ~ 15 minutes, is more preferably 1 minute ~ 3 minutes.In addition, the temperature of staining solution is preferably the scope of 10 ~ 60 DEG C, is more preferably the scope of 20 ~ 40 DEG C.
In dyeing process, crosslinking Treatment can be carried out after dyeing.Crosslinking Treatment is undertaken by such as flooding stretched film in the solution (crosslinker solution) containing crosslinking chemical.As crosslinking chemical, known material can be used.Include, for example out the boron compound such as boric acid, borax or glyoxal, glutaraldehyde etc.They can be a kind of, also can be used together two or more.
As crosslinker solution, the solution being dissolved with crosslinking chemical in a solvent can be used.As solvent, such as water can be used, but also can further containing having the organic solvent with the intermiscibility of water.The concentration of the crosslinking chemical in crosslinker solution is not limited thereto, and is preferably the scope of 1 ~ 20 % by weight, is more preferably 6 ~ 15 % by weight.
Iodide can be added in crosslinker solution.By the interpolation of iodide, the polarization characteristic in the face of resin bed can be made evenly change.As iodide, include, for example out potassium iodide, lithium iodide, sodium iodide, zinc iodide, silver iodide, lead iodide, cupric iodide, barium iodide, calcium iodide, stannic iodide, titanium iodide.The content of iodide is 0.05 ~ 15 % by weight, is more preferably 0.5 ~ 8 % by weight.
The dip time of stretched film in crosslinker solution is preferably 15 seconds ~ 20 minutes usually, is more preferably 30 seconds ~ 15 minutes.In addition, the temperature of crosslinker solution is preferably the scope of 10 ~ 80 DEG C.
Preferably finally carry out washing procedure and drying process.As washing procedure, water washing can be implemented.Water washing usually by flooding stretched film to carry out in the pure water such as ion exchange water, distilled water.Water washing temperature is the scope of usual 3 ~ 50 DEG C, preferably 4 DEG C ~ 20 DEG C.Dip time was generally for 2 ~ 300 seconds, was preferably for 3 seconds ~ 240 seconds.
Washing procedure may be combined with the carrying out washing treatment and water washing that utilize iodide solution, also can use the solution being suitably combined with the liquid alcohol such as methyl alcohol, ethanol, isopropyl alcohol, butanols, propyl alcohol.
Preferably after washing procedure, implement drying process.As drying process, method (such as, natural drying, air-supply drying, heat drying) suitable arbitrarily can be adopted.Such as, the baking temperature when heat drying is generally 20 ~ 95 DEG C, is generally about 1 ~ 15 minute drying time.By above dyeing process (S30), thus resin bed is made to have function as polaroid.
In this manual, be called polarization lamella using having as the resin bed of the function of polaroid, duplexer base material film possessing polarization lamella is called polarizability stacked film.
In the present embodiment, be the polyvinyl alcohol resin of less than 99.0 % by mole owing to using saponification degree in resin bed, uniaxial tension is carried out with the stretching ratio more than 5 times in addition, so good dyeing kinetics can be maintained in dyeing process (S30) in stretching process (S20).It should be noted that, the dyeing kinetics of resin bed in dyeing process (S30) employing the high polyvinyl alcohol resin of saponification degree reduces, and easily causes dyeing insufficient.
[bonding process (S40)]
Here, the fitting diaphragm and obtain multilayer film with the face of the opposition side, face of base material film side of polarization lamella of polarizability stacked film.As the method for laminating diaphragm, the method for polarization lamella 12 and diaphragm 14 being fitted by bonding agent, the method for polarization lamella 12 and diaphragm 14 being fitted by bonding agent can be listed.Be suitable as the material of diaphragm as described in the explanation of the formation in above-mentioned polarization plates.In addition, the bonding agent being applicable to using, the material of bonding agent and use them to fit to polarization lamella 12 and diaphragm 14 method for optimizing as described in the explanation of the formation in above-mentioned polarization plates.
[stripping process (S50)]
In the manufacture method of the polarization plates of present embodiment, as shown in Figure 4, after the bonding process (S40) of polarization lamella 12 diaphragm being fitted in polarizability stacked film, stripping process (S50) is carried out.In stripping process (S50), base material film is peeled off from multilayer film.The stripping means of base material film, without particular determination, is peeled off by the method same with the stripping process of the stripping film carried out in the polarization plates of common band bonding agent.After the bonding process (S40) of diaphragm, directly can peel off immediately, also can stripping process be separately set after temporarily coiling into roll and peels off.
Embodiment
Below illustrate that embodiment and comparative example specifically describe the present invention further, but the present invention does not limit by these examples.
Embodiment 1
According to manufacture method as shown in Figure 4, make polarization plates as shown in Figure 2.
(base material film)
As base material film, use thickness is polypropylene (PP) film (fusing point: 163 DEG C) do not stretched of 110 μm.
(undercoat formation process)
Pva powder (Japanese synthetic chemical industry (strain) manufactures, average degree of polymerization 1100, saponification degree 99.5 % by mole, trade name: Z-200) is dissolved in the hot water of 95 DEG C, makes the aqueous solution that concentration is 3 % by weight.In the aqueous solution obtained, relative to 6 weight portions pva powder and mix the crosslinking chemical (Sumitomo Chemical (strain) manufacture, trade name: SUMIREZ (registered trademark) RESIN650) of 5 weight portions.
Use micro-gravure coater on the base material film implementing corona treatment, be coated with the mixed aqueous solution obtained, make it 80 DEG C of dryings 10 minutes, form the undercoat that thickness is 0.2 μm.
(resin bed formation process)
Pva powder (Kuraray (strain) manufactures, average degree of polymerization 2400, saponification degree 98.0 ~ 99.0 % by mole, trade name: PVA124) is dissolved in the hot water of 95 DEG C, makes the polyvinyl alcohol water solution that concentration is 8 % by weight.On above-mentioned undercoat, be coated with the aqueous solution obtained with lip type coating machine, make it 80 DEG C of dryings 20 minutes, make the stacked film of three layers formed by base material film, undercoat, resin bed.
(stretching process)
Use tenter frame apparatus to implement the free end uniaxial tension of 5.8 times at 160 DEG C to above-mentioned stacked film, thus obtain stretched film.The thickness of the resin bed after stretching is 6.1 μm.
(dyeing process)
Then, by stretched film dipping 60 seconds in the temperature bath of 60 DEG C, flood in the staining solution of the mixed aqueous solution as iodine and potassium iodide of 30 DEG C and dye for about 150 seconds, then use the iodine liquid that the pure water rinsing of 10 DEG C is unnecessary.Then make it in the crosslinker solution of the mixed aqueous solution as boric acid and potassium iodide of 76 DEG C, flood 600 seconds.Then use pure water 4 second of 10 DEG C, finally make its dry 300 seconds at 50 DEG C.By above operation, form polarization lamella by resin bed, obtain polarizability stacked film.The compounding ratio of each solution is as follows.
< staining solution >
Water: 100 weight portions
Iodine: 0.6 weight portion
Potassium iodide: 10 weight portions
< crosslinker solution >
Water: 100 weight portions
Boric acid: 9.5 weight portions
Potassium iodide: 5 weight portions
(laminating of diaphragm)
Pva powder (manufacture of (strain) Kuraray, average degree of polymerization 1800, trade name: KL-318) is dissolved in the hot water of 95 DEG C, makes the aqueous solution that concentration is 3 % by weight.In the aqueous solution obtained, relative to 2 weight portions pva powder and mix 1 weight portion crosslinking chemical (Sumitomo Chemical (strain) manufacture, trade name: SUMIREZ (registered trademark) RESIN650), make adhesive solution.Above-mentioned polarizability stacked film polarization lamella with the face of the opposition side, face of base material film side on be coated with above-mentioned polyethenol series bonding agent; then to fit diaphragm (TAC:KC4UY that KONICAMINOLTAOPTO (strain) manufactures), thus obtain by diaphragm, bond layer, polarization lamella, undercoat, these five layers of polarization plates formed of base material film.Base material film is peeled off from the polarization plates obtained.Obtain base material film to be easy to be stripped, and by diaphragm, bond layer, polarization lamella, these four layers of polarization plates formed of undercoat.The thickness of polarization lamella is 6.1 μm.
Embodiment 2
As the polyvinyl alcohol (PVA) used in resin bed, (Japanese synthetic chemical industry (strain) manufactures to use pva powder, average degree of polymerization 2200, saponification degree 97.5 ~ 98.5 % by mole, trade name: AH-22), except in this respect, obtain stretched film by the method identical with embodiment 1.The thickness of the resin bed in stretched film is 5.5 μm.In addition, implement dyeing process, bonding process, stripping process etc. by method similarly to Example 1, thus obtain by the polarization plates of diaphragm, bond layer, polarization lamella, these four layers of embodiments formed 2 of undercoat.The thickness of polarization lamella is 5.6 μm.
Embodiment 3
As the polyvinyl alcohol (PVA) used in resin bed, use pva powder (JAPANVAM & POVALCO., LTD. manufacture, average degree of polymerization 2600, saponification degree 95.5 ~ 97.5 % by mole, trade name: JM-26), except in this respect, obtain stretched film by the method identical with embodiment 1.The thickness of the resin bed in stretched film is 5.3 μm.And then implement dyeing process, bonding process, stripping process etc. by method similarly to Example 1, thus obtain by the polarization plates of diaphragm, bond layer, polarization lamella, these four layers of embodiments formed 3 of undercoat.The thickness of polarization lamella is 5.3 μm.
Comparative example 1
As the polyvinyl alcohol (PVA) used in resin bed, (Kuraray (strain) manufactures, average degree of polymerization 1700 to use pva powder, saponification degree more than 99.3 % by mole, trade name: PVA117H), except in this respect, obtain stretched film by the method identical with embodiment 1.The thickness of the resin bed in stretched film is 6.3 μm.And then implement dyeing process, bonding process, stripping process etc. by method similarly to Example 1, obtain by the polarization plates of diaphragm, bond layer, polarization lamella, these four layers of comparative examples formed 1 of undercoat.The thickness of polarization lamella is 6.3 μm.
Comparative example 2
As the polyvinyl alcohol (PVA) used in resin bed, use polyvinyl alcohol (PVA) (Kuraray (strain) manufacture, average degree of polymerization 2400, saponification degree more than 99.9 % by mole, trade name: KURARAYPOVALVF-PS#7500) powder of fine chopping, and the stretching ratio in stretching process is set to 4.0 times, except above-mentioned aspect, obtain stretched film by the method identical with embodiment 1.The thickness of the resin bed in stretched film is 6.7 μm.And then implement dyeing process, bonding process, stripping process etc. by method similarly to Example 1, thus obtain by the polarization plates of diaphragm, bond layer, polarization lamella, these four layers of comparative examples formed 2 of undercoat.The thickness of polarization lamella is 6.7 μm.
Comparative example 3
As the polyvinyl alcohol (PVA) used in resin bed, use polyvinyl alcohol (PVA) (Kuraray (strain) manufacture, average degree of polymerization 2400, saponification degree more than 99.9 % by mole, trade name: KURARAYPOVALVF-PS#7500) powder of fine chopping, except in this respect, obtain stretched film by the method identical with embodiment 1.The thickness of the resin bed in stretched film is 6.3 μm.And then implement dyeing process, bonding process, stripping process etc. by method similarly to Example 1, thus obtain by the polarization plates of diaphragm, bond layer, polarization lamella, these four layers of comparative examples formed 3 of undercoat.The thickness of polarization lamella is 6.3 μm.
(mensuration of polarization property)
What obtain after peeling base film is measured by the MD transmissivity of diaphragm, bond layer, polarization lamella, these four layers of polarization plates formed of undercoat and the spectrophotometer (Japanese light splitting (strain) manufactures, V7100) of TD transmissivity band integrating sphere.Monomer transmissivity, the degree of polarization under each wavelength is calculated according to above-mentioned formula (1), formula (2), and then carry out visibility correction by 2 degree of visuals field (illuminant-C) of JISZ8701, obtain visibility and correct monomer transmissivity (Ty) and visibility correction degree of polarization (Py).It should be noted that, for the mensuration of polarization plates, diaphragm side is set to detecting device side, is fixed on equipment according to the mode making light inject from undercoat side.
For the polarization plates of embodiment 1 and comparative example 1 ~ 3, the visibility calculated is corrected monomer transmissivity (Ty) and visibility correction degree of polarization (Py) is shown in Table 1.
(the installation evaluation on commercially available mobile phone)
" auEXILIMKeitaiW53CA " (manufacturer: CASIO computing machine (the strain)) dismounting will sold by KDDI (strain), peels off and is fitted in the upper and lower polarization plates of liquid crystal cells, take out liquid crystal cells.
The polarization plates obtained in embodiment 1 ~ 3 and comparative example 1 ~ 3 is pasted onto down on liquid crystal cell by pressure sensitive bonding agent.Now, the absorption axle being pasted onto the polarization plates of (observation side) on the upside of liquid crystal cells is configured according to the mode being rotated counterclockwise into 170 degree under the viewpoint of observing from observation side from the minor face of liquid crystal cells.In addition, the absorption axle being pasted onto the polarization plates of (backlight side) on the downside of liquid crystal cells is configured according to the mode being rotated counterclockwise into 80 degree under the viewpoint of observing from observation side from the minor face of liquid crystal cells.It should be noted that, this arrangement angles is identical with the arrangement angles originally fitting in the absorption axle of the original polarization plate of liquid crystal cells.
Use the liquid crystal cells being pasted with the polarization plates obtained in embodiment 1 ~ 3 and comparative example 1 ~ 3 up and down, again assemble mobile phone, and show image.By estimating the sharpness of process decision chart picture in general environment within doors and darkroom, thus implement the evaluation of display state.
The evaluation result of the polarization plates of embodiment 1 ~ 3 and comparative example 1 ~ 3 is shown in Table 1.
[table 1]
With regard to embodiment 1 ~ 3, by using saponification degree to be the polyvinyl alcohol resin of less than 99.0 % by mole, and stretching ratio is set to more than 5 times, even if thus be set to the dyeing time not hindering usual production degree, also can obtain required Ty, Py.Like this, by the polarization plates obtained is used for liquid crystal indicator, thus form clear and good image display.
On the other hand, with regard to comparative example 1,3, owing to using the polyvinyl alcohol resin of saponification degree more than 99.0 % by mole, and be set to stretching ratio more than 5 times, so cannot fully dye under the dyeing time not hindering usual production degree, the value of Py is also low.Like this, if the polarization plates obtained is used for liquid crystal indicator, then form contrast ratio (CR) low, the image display of sharpness deficiency.
In addition, with regard to comparative example 2, owing to using the polyvinyl alcohol resin of saponification degree more than 99.0 % by mole, and stretching ratio is set to less than 5 times, although so can fully dye under the dyeing time not hindering usual production degree, the value of Py is low.Like this, if the polarization plates obtained is used for liquid crystal indicator, then form contrast ratio (CR) low, the image display of sharpness deficiency.
Symbol description
10, polarizability stacked film
11, base material film
12, polarization lamella
13, polarization plates
14, diaphragm

Claims (7)

1. a polarizability stacked film, its polarization lamella in a face that there is base material film and be formed at base material film, wherein,
The thickness of polarization lamella is less than 10 μm, is formed by the polyvinyl alcohol resin through dichromatism pigment gas absorption quantity,
The saponification degree of polyvinyl alcohol resin is less than 99.0 % by mole,
Visibility correction monomer transmissivity Ty is more than 40% and visibility correction degree of polarization Py is more than 99.9%,
Polarization lamella is to be implemented the longitudinal uniaxial tension of free end more than the stretching ratio of 5 times.
2. polarizability stacked film according to claim 1, it is used to polarization plates.
3. polarizability stacked film according to claim 1 and 2, wherein, polarization lamella is formed at a face of base material film across undercoat.
4. a polarization plates, its polarization lamella in a face that there is diaphragm and be formed at diaphragm, wherein,
The thickness of polarization lamella is less than 10 μm, is formed by the polyvinyl alcohol resin through dichromatism pigment gas absorption quantity,
The saponification degree of described polyvinyl alcohol resin is less than 99.0 % by mole,
Visibility correction monomer transmissivity Ty is more than 40% and visibility correction degree of polarization Py is more than 99.9%,
Polarization lamella is to be implemented the longitudinal uniaxial tension of free end more than the stretching ratio of 5 times.
5. polarization plates according to claim 4, wherein, polarization lamella is formed at a face of diaphragm across adhesive phase or bond layer.
6. a manufacture method for polarizability stacked film, it is the manufacture method of the polarizability stacked film according to any one of claims 1 to 3, comprising:
The resin bed formation process that resin bed that the polyvinyl alcohol resin being less than 99.0 % by mole by saponification degree formed obtains stacked film is formed in face of base material film,
With the stretching ratio more than 5 times, the longitudinal uniaxial tension of free end carried out to stacked film and obtain the stretching process of stretched film, and
With dichromatism pigment, the dyeing of the resin bed of stretched film is formed the dyeing process of polarization lamella.
7. a manufacture method for polarization plates, it is the manufacture method of the polarization plates described in claim 4 or 5, comprising:
The resin bed formation process that resin bed that the polyvinyl alcohol resin being less than 99.0 % by mole by saponification degree formed obtains stacked film is formed in face of base material film,
With the stretching ratio more than 5 times, the longitudinal uniaxial tension of free end carried out to stacked film and obtain the stretching process of stretched film,
With dichromatism pigment, the dyeing of the resin bed of stretched film formed polarization lamella and obtain the dyeing process of polarizability stacked film,
The fitting diaphragm and obtain the bonding process of multilayer film with the face of the opposition side, face of base material film side of polarization lamella of polarizability stacked film, and
The stripping process that base material film is peeled off from multilayer film.
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