CN103261928A - Methods for producing polarizing laminate film and polarizing plate - Google Patents

Methods for producing polarizing laminate film and polarizing plate Download PDF

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Publication number
CN103261928A
CN103261928A CN2011800590342A CN201180059034A CN103261928A CN 103261928 A CN103261928 A CN 103261928A CN 2011800590342 A CN2011800590342 A CN 2011800590342A CN 201180059034 A CN201180059034 A CN 201180059034A CN 103261928 A CN103261928 A CN 103261928A
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film
polyvinyl alcohol
base material
layer
alcohol resin
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CN2011800590342A
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CN103261928B (en
Inventor
河村真一
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00634—Production of filters
    • B29D11/00644—Production of filters polarizing
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/0073—Optical laminates
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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

Abstract

The present invention relates to a method for producing a polarizing laminate film that includes a base film, a primer layer, and a polarizer layer in this order, wherein a primer solution employed to improve the adhesion between the base film and a polyvinyl-alcohol-based resin layer contains at least one type of cross-linking agent selected from a group consisting of dialdehyde-based cross-linking agents, isocyanate-based cross-linking agents, and metal-based cross-linking agents. With the present invention, it is possible to provide, during the method for producing the polarizing laminate film, the primer layer with water resistance that will prevent the polyvinyl-alcohol-based resin layer from peeling from the base material even at the time of immersion into a dyeing solution or a cross-linking solution.

Description

The manufacture method of polarizability stacked film and polaroid
Technical field
The present invention relates to the manufacture method of polarizability stacked film and polaroid.
Background technology
Polaroid is as the feed element of the polarized light in the display device such as liquid crystal indicator etc. and be widely used.As above-mentioned polaroid; all the time; what use is to comprise the polaroid that the last bonding diaphragm that comprises triacetyl cellulose (TAC) of the polarizing coating that polyvinyl alcohol (PVA) (PVA) is resin (polariscope layer) forms; but in recent years; be accompanied by liquid crystal indicator towards the exploitation of mobile devices such as notebook personal computer, mobile phone etc., require to make it thin-wall light-weighted.
All the time; after the film that comprises polyvinyl alcohol resin is stretched separately or when stretching; enforcement dyeing is handled, crosslinking Treatment is made polarizing coating; produce polaroid by making it be laminated in diaphragm etc.; but, can only slimming to the thickness of the independent limit of polarizing coating.Therefore, following method has been proposed, namely, be provided as the polyvinyl alcohol resin layer of polariscope layer on the surface of base material film, afterwards, together with base material film the polyvinyl alcohol resin layer carried out dry type stretching, implementing dyeing handles and crosslinking Treatment, thereby the polyvinyl alcohol resin layer is made the polariscope layer, the gross thickness of base material film and polariscope layer is as thin as in the limit, can make the thickness thinner than in the past (for example with reference to JP2000-338329-A) of polariscope layer (polarizing coating).
But, the adaptation of base material film and polyvinyl alcohol resin layer does not claim to think that there are the following problems, namely by force, when the staining solution during stretching in stretching process, in the dyeing process and the dipping in the crosslinked fluid, the problem that the polyvinyl alcohol resin layer can be peeled off from base material film.
As the method for the closing force that is used for raising base material film and polyvinyl alcohol resin layer, can consider to form the method for polyvinyl alcohol resin layer at this undercoat at base material film coating primary coat solution and after forming undercoat.At this, from suppressing the aspect to the infringement of base material film, preferred primary coat solution is aqueous solution, therefore, wishes to use the aqueous solution of water soluble polymer as primary coat solution.In this case, usually the water tolerance of the undercoat that is formed by the aqueous solution of water soluble polymer is low, and therefore, worry polyvinyl alcohol resin layer in the dipping operation in dyeing liquor, crosslinked fluid is peeled off from base material film.
The objective of the invention is to, in the manufacture method of polarizability stacked film, even the undercoat that uses for the adaptation that improves base material film and polyvinyl alcohol resin layer is given to staining solution, the polyvinyl alcohol resin layer can not peeled off such water tolerance from base material yet when flooding in the crosslinker solution, wherein, the manufacture method of described polarizability stacked film refers to, be provided as the polyvinyl alcohol resin layer of polariscope layer on the surface of base material film, together with base material film the polyvinyl alcohol resin layer is stretched afterwards, implement the manufacture method of dyeing processing and crosslinking Treatment.
Summary of the invention
The present invention includes following content.
[1] a kind of manufacture method of polarizability stacked film,
Wherein, described polarizability stacked film possesses base material film, undercoat and polariscope layer successively,
Described method comprises successively:
Undercoat forms operation, at a face coating primary coat solution of base material film and form undercoat,
The polyvinyl alcohol resin layer forms operation, forms the polyvinyl alcohol resin layer at above-mentioned undercoat, is possessed the stacked film of above-mentioned base material film, above-mentioned undercoat and above-mentioned polyvinyl alcohol resin layer successively,
Stretching process stretches to above-mentioned stacked film, and
Dyeing process uses the dichromatism pigment that the above-mentioned polyvinyl alcohol resin layer of above-mentioned stacked film is dyeed and makes the polariscope layer;
Above-mentioned primary coat solution comprises that to be selected from dialdehyde be that crosslinking chemical, isocyanate-based crosslinking chemical and metal are at least a crosslinking chemical in the crosslinking chemical.
[2] according to [1] described method, wherein, above-mentioned primary coat solution also comprises water soluble polymer.
[3] according to [1] or [2] described method, wherein, above-mentioned water soluble polymer is polyvinyl alcohol resin.
[4] according to [1] or [2] described method, wherein, the solvent of above-mentioned primary coat solution is the solvent that comprises water.
[5] according to each described method in [1]～[4], wherein, above-mentioned crosslinking chemical is water-soluble or water dispersible.
[6] according to each described method in [1]～[5], wherein, above-mentioned dialdehyde is that crosslinking chemical is glyoxal.
[7] according to each described method in [1]～[5], wherein, above-mentioned isocyanate-based crosslinking chemical is for having the polyisocyanate of more than one isocyanate group at least in a part.
[8] according to each described method in [1]～[5], wherein, above-mentioned metal is that crosslinking chemical is organometallics.
[9] according to [8] described method, wherein, above-mentioned organometallics is chelate.
[10] according to each described method in [1]～[9], wherein, the thickness before the above-mentioned stretching process of above-mentioned undercoat is 0.05～1.0 μ m.
[11] according to each described method in [1]～[10], wherein, the thickness before the above-mentioned stretching process of above-mentioned polyvinyl alcohol resin layer is 3～30 μ m.
[12] according to each described method in [1]～[11], wherein, the thickness of above-mentioned polariscope layer is below the 10 μ m.
[13] a kind of manufacture method of polaroid, wherein,
Described polaroid possesses the polariscope layer and is formed at the diaphragm of the one side of this polariscope layer,
Described method comprises successively:
The diaphragm bonding process, at the polarizability stacked film that obtains by above-mentioned [1] described method and face applying diaphragm above-mentioned base material film side opposition side, and
The base material film stripping process is peeled off above-mentioned base material film from the polarizability stacked film.
In the present invention, in the manufacture method of polarizability stacked film, by giving water tolerance to the undercoat that uses for the adaptation that improves base material film and polyvinyl alcohol resin layer, thereby can prevent to staining solution, the situation that polyvinyl alcohol resin layer when flooding in the crosslinker solution is peeled off from base material, wherein, the manufacture method of described polarizability stacked film refers to, be provided as the polyvinyl alcohol resin layer of polariscope layer on the surface of base material film, together with base material film the polyvinyl alcohol resin layer is stretched afterwards, implement the manufacture method of dyeing processing and crosslinking Treatment.
Description of drawings
Fig. 1 is the process flow diagram of a kind of embodiment of the manufacture method of expression polarizability stacked film of the present invention.
Fig. 2 is the process flow diagram of a kind of embodiment of the manufacture method of expression polaroid of the present invention.
Embodiment
In this manual, will be called " stacked film " across the duplexer that the stacked polyvinyl alcohol (PVA) of undercoat (PVA) resin forms at a face of base material film.In addition, the polyvinyl alcohol resin layer (layer that comprises polyvinyl alcohol resin) that will have as the function of polariscope is called " polariscope layer ", and the duplexer that will be equipped with the polariscope layer at a mask of base material film is called " polarizability stacked film ".In addition, the duplexer that will be equipped with diaphragm at a mask of polariscope layer is called " polaroid ".Below, each inscape is elaborated.
[base material film]
As employed resin in the base material film, for example can use thermoplastic resin excellent such as the transparency, physical strength, thermal stability, stretchability, can select suitable resin according to Tg (glass transition temperature) or the Tm (fusing point) of these resins.Concrete example as thermoplastic resin can list: polyolefin-based resins, polyester based resin, cyclic polyolefin hydrocarbon system resin (norbornene resin), (methyl) acrylic resin, cellulose esters are that resin, polycarbonate-based resin, polyvinyl alcohol resin, vinyl acetate are that resin, polyarylate are that resin, polystyrene resin, polyethersulfone are that resin, polysulfones are that resin, polyamide-based resin, polyimide are resin and their potpourri, multipolymer etc.Wherein, especially preferably use polyolefin-based resins.
As polyolefin-based resins, can list tygon, polypropylene etc., they are easy to stable and high magnification ground stretches, thereby preferred.In addition, can also use by making ethene-polypropylene copolymer that ethene and copolymerization of propylene obtain etc.Copolymerization also can use the monomer of other kinds to carry out, as can with the monomer of other kinds of copolymerization of propylene, for example can list ethene, alpha-olefin.As alpha-olefin, can preferably use carbon number is alpha-olefin more than 4, and more preferably carbon number is 4～10 alpha-olefin.If enumerate carbon number and be the concrete example of 4～10 alpha-olefin, straight chain shape monoene hydro carbons such as 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-decene are then for example arranged, a chain mono-olefin class such as 3-methyl-1-butene, 3-Methyl-1-pentene, 4-methyl-1-pentene, vinyl cyclohexane etc.Propylene and can both can be random copolymers with the multipolymer of other monomers of its copolymerization also can be segmented copolymer.The containing ratio of the formation unit that is derived from these other monomers in the multipolymer can be tried to achieve by carrying out infrared ray (IR) spectroscopic assay according to the method for the 616th page of record of " macromolecule analysis handbook " (nineteen ninety-five, Kinokuniya bookstore distribution).
In foregoing, as the propylene resin that constitutes the propylene resin film, can preferably use homopolymer, propylene-ethylene random copolymers, propylene-1-butene random copolymer and the propylene-ethylene-1-butene random copolymer of propylene.
In addition, the tacticity of the propylene resin of formation propylene resin film is preferably isotaxy or syndiotaxy basically.With regard to the propylene resin film that is formed by the propylene resin with isotaxy or syndyotactic tacticity in fact, its property handled is comparatively good, and the physical strength excellence under the hot environment.
Polyester based resin is the polymkeric substance with ester bond, is mainly the condensed polymer of polybasic carboxylic acid and polyvalent alcohol.Employed polybasic carboxylic acid mainly uses the dicarboxylic acid of divalence, for example can list: m-phthalic acid, terephthalic acid (TPA), dimethyl terephthalate (DMT), naphthalene dicarboxylic acids dimethyl ester etc.In addition, employed polyvalent alcohol also mainly uses the glycol of divalence, can list: propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol etc.As concrete resin, can list: polyethylene terephthalate, polybutylene terephthalate, PEN, PBN, PTT, poly-naphthalenedicarboxylic acid propylene glycol ester, poly terephthalic acid cyclohexane dimethyl ester, poly-naphthalenedicarboxylic acid cyclohexane dimethyl ester etc.The hybrid resin of these resins, multipolymer also can preferably use.
As cyclic polyolefin hydrocarbon system resin, can preferably use norbornene resin.Cyclic polyolefin hydrocarbon system resin is the general name of the resin that is polymerized as polymerized unit with cyclic olefin, for example can list the resin of record among JPH01-240517-A, JPH03-14882-A, the JPH03-122137-A etc.As a specific example, can list: the alpha-olefins such as addition polymer, cyclic olefin and ethene, propylene of the open loop of cyclic olefin (being total to) polymkeric substance, cyclic olefin with and multipolymer (representational is random copolymers) and these resins are carried out graft polymer that modification obtains and their hydride etc. with the unsaturated carboxylic acid or derivatives thereof.Concrete example as cyclic olefin can list the norborneol alkene monomer.
As cyclic polyolefin hydrocarbon system resin, commercially available various products.As a specific example, can list: Topas (registered trademark) (manufacturing of Ticona company), ARTON (registered trademark) (JSR (strain) manufacturing), ZEONOR (registered trademark) (Japanese ZEON (strain) manufacturing), ZEONEX (registered trademark) (Japanese ZEON (strain) manufacturing), APEL (registered trademark) (Mitsui Chemicals (strain) manufacturing) etc.
As (methyl) acrylic resin, can adopt arbitrarily suitable (methyl) acrylic resin.For example can list: polymethylmethacrylate etc. gather (methyl) acrylate, methyl methacrylate-(methyl) acrylic copolymer, methyl methacrylate-(methyl) acrylate copolymer, methyl methacrylate-acrylate-(methyl) acrylic copolymer, (methyl) methyl acrylate-styrol copolymer (MS resin etc.), have the polymkeric substance of alicyclic alkyl (for example, methyl methacrylate-cyclohexyl methacrylate multipolymer, methyl methacrylate-(methyl) acrylic acid norborneol ester copolymer etc.) 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 resin as the methyl methacrylate of principal ingredient (50～100 weight %, preferred 70～100 weight %).
Cellulose esters is that resin is the ester of cellulose and fatty acid.Be the concrete example of resin as such cellulose esters, can list: primary cellulose acetate, cellulose diacetate, cellulose tripropionate, cellulose dipropionate etc.
In addition, can also list their multipolymer, the substituting group etc. that uses other kinds is modified part of hydroxyl and material etc.Wherein, be preferably primary cellulose acetate especially.For primary cellulose acetate, commercially available have multiple product, and also be favourable aspect acquisition easiness, the cost.Example as the commercially available product of primary cellulose acetate can list: FUJITAC (registered trademark) TD80 (Fujiphoto (strain) manufacturing), FUJITAC (registered trademark) TD80UF (Fujiphoto (strain) manufacturing), FUJITAC (registered trademark) TD80UZ (Fujiphoto (strain) manufacturing), FUJITAC (registered trademark) TD40UZ (Fujiphoto (strain) manufacturing), KC8UX2M (KONICAMINOLTA OPTO (strain) manufacturing), KC4UY (KONICAMINOLTA OPTO (strain) manufacturing) etc.
Polycarbonate-based resin is to comprise the engineering plastics that make the polymkeric substance that the monomeric unit bonding forms by carbonate group, is the resin with higher resistance to impact, thermotolerance, anti-flammability.In addition, owing to have the higher transparency, therefore also be adapted at using in the optical applications.The resin that is called as modified polycarbonate that polymer backbone has been carried out modifying and so in order to reduce photoelastic coefficient, the copolymerization polycarbonate etc. of having improved wavelength dependency have also been sold on the market, and can have been performed well in the optical applications.Such polycarbonate resin extensively selling on the market, for example can list: Panlite (registered trademark) (Supreme Being people changes into (strain)), Iupilon (registered trademark) (Mitsubishi's engineering plastics (strain)), SD POLYCA (registered trademark) (Sumitomo Tao Shi (strain)), CALIBER (registered trademark) (DOW Chemical (strain)) etc.
Base material film can be the film that is only formed by a kind of above-mentioned resin, also can be the film that two or more mixed with resin is formed.This base material film can be monofilm, also can be multilayer film.
In base material film, except above-mentioned thermoplastic resin, can also add any proper additive.As such adjuvant, for example can list: ultraviolet light absorber, antioxidant, lubricant, plastifier, release agent, anti-coloring agent, fire retardant, nucleator, antistatic agent, pigment, colorant etc.The content of the illustrated thermoplastic resin of foregoing in the base material film is preferably 50～100 weight %, 50～99 weight % more preferably, and more preferably 60～98 weight % are preferably 70～97 weight % especially.Under the situation of the content of the thermoplastic resin in base material film less than 50 weight %, the original high transparent that has of thermoplastic resin etc. can't find full expression sometimes.
The thickness of the base material film before stretching can suitably determine, from the aspect of operability such as intensity, the property handled, is preferably 1～500 μ m usually, 1～300 μ m more preferably, and more preferably 5～200 μ m most preferably are 5～150 μ m.
In order further to improve the adaptation with the polyvinyl alcohol resin layer, can be at least corona treatment, Cement Composite Treated by Plasma, flame treatment etc. be carried out in the surface of the side that is formed with undercoat of base material film.
[undercoat]
In order to improve the adaptation of base material film and polyvinyl alcohol resin layer, can form undercoat on the surface of the side that is formed with the polariscope layer of base material film.
(thermoplastic resin)
As the main material that constitutes undercoat, so long as to the material of base material film and the two performance of polyvinyl alcohol resin layer stronger closing force to a certain degree, just there is no particular limitation.For example can use thermoplastic resin excellent such as the transparency, thermal stability, stretchability.As thermoplastic resin, for example can list acrylic resin, polyvinyl alcohol resin, but be not limited to these resins.Wherein, preferably use the good polyvinyl alcohol resin of adaptation.
As the polyvinyl alcohol resin that is used as undercoat, for example can list polyvinyl alcohol resin and derivant thereof.Derivant as polyvinyl alcohol resin, except polyvinyl formal, polyvinyl acetal etc., the Arrcostab, acrylamide etc. that can also list unsaturated carboxylic acids such as alkene, acrylic acid, methacrylic acid, crotonic acid such as using ethene, propylene, unsaturated carboxylic acid polyvinyl alcohol resin is carried out modification and material.In above-mentioned polyvinyl alcohol resin material, preferably use polyvinyl alcohol resin.
(crosslinking chemical)
In the present invention, in order to improve the water tolerance of undercoat, to be selected from dialdehyde be that crosslinking chemical, isocyanate-based crosslinking chemical and metal are at least a crosslinking chemical in the crosslinking chemical and add in primary coat solution.
As the isocyanate-based crosslinking chemical, for example can list: isocyanates such as toluene diisocyanate, HTDI, trimethylolpropane-toluene diisocyanate adduct, triphenylmethane triisocyanate, di-2-ethylhexylphosphine oxide (4-phenylmethane triisocyanate), isophorone diisocyanate, the ketoxime block thing that reaches them or phenolic aldehyde block thing.
Be crosslinking chemical as dialdehyde, for example can list: glyoxal, MDA, butanedial, glutaraldehyde, malealdehyde, phthalic aldehyde etc.
Be crosslinking chemical as metal, for example can list: slaine, metal oxide, metal hydroxides, organometallics etc., the kind of metal is not particularly limited, as long as suitably select.
As slaine, metal oxide, metal hydroxides, for example can list sodium, potassium, magnesium, calcium, aluminium, iron, nickel, zirconium, titanium, silicon, boron, zinc, copper, vanadium, chromium, tin etc. and have the salt of metal of the atomicity more than the divalence and oxide thereof, oxyhydroxide.
Organometallics refers to: have at least in molecule that an organic group is bonded directly to the structure of metallic atom or the compound of the structure of bonding organic group via oxygen atom or nitrogen-atoms etc.; organic group refers to: comprising the functional group of carbon at least, for example can be alkyl, alkoxy, acyl group etc.In addition, bonding is not only to refer to covalent bond, can be based on the coordination of chelating shape compound etc. and the coordination bond that produces yet.The metal that constitutes above-mentioned organometallics is preferably titanium, zirconium, aluminium, silicon, more preferably titanium, zirconium.That is, as the preferred exemplary of above-mentioned organometallics, can list titanium organic compound, zirconium organic compound, aluminum organic compound and silicon organic compound.These metal organic compounds can only use a kind of, also can mix two or more the use.
Concrete example as the titanium organic compound; for example can list: tetra-n-butyl titanate; tetraisopropyl titanate; the butyl titanate dimer; four (2-ethylhexyl) titanate esters; titanium ortho esters classes such as metatitanic acid tetramethyl ester; acetopyruvic acid titanium (チ タ ソ ア セ チ Le ア セ ト Na one ト); tetrem acyl pyruvic acid titanium (チ タ ソ テ ト ラ ア セ チ Le ア セ ト Na one ト); poly-acetopyruvic acid titanium (Port リ チ タ ソ ア セ チ Le ア セ ト Na one ト); octylene glycol titanate (octylene glycol titanate); the lactic acid titanium; triethanolamine titanium (チ タ ソ ト リ エ タ ノ one Le ア ミ ネ one ト); ethylacetoacetate titanium titanium chelate classes such as (チ タ ソ エ チ Le ア セ ト ア セ テ one ト), poly-hydroxy stearic acid titanium acidylate titanium classes such as (Port リ ヒ De ロ キ Star チ タ ソ ス テ ア レ one ト) etc.
As the zirconium organic compound, for example can list: n Propanoic acid zirconium, n-butyric acie zirconium, four zirconium acetylacetonate, single acetyl pyruvic acid zirconium, diacetyl pyruvic acid zirconium, zirconium acetylacetonate ethyl diacetoacetate (ジ Le コ ニ ウ system ア セ チ Le ア セ ト Na one ト PVC ス エ チ Le ア セ ト ア セ テ one ト) etc.
As aluminum organic compound, for example can list acetopyruvic acid aluminium, aluminium organic acid chelate etc.
As silicon organic compound, for example can list the compound with illustrated part that goes out in above-mentioned titanium organic compound and the zirconium organic compound.
With regard to crosslinking chemical, as long as suitably select the compound that is more suitable for according to employed thermoplastic resin and from these compounds.
For thermoplastic resin 100 weight portions, the ratio of the employed thermoplastic resin of undercoat and crosslinking chemical that is used to form is as long as according to suitably determining the scopes from about crosslinking chemical 0.1～100 weight portion such as kind of the kind of thermoplastic resin, crosslinking chemical, be preferably especially the scope from about 0.1～50 weight portion and selected.
(solvent)
The primary coat solution that is used to form undercoat preferably uses being dissolved under the state of solvent.As solvent, also to consider the dissolubility of base material film, the reactive low solvent of preferred use and base material film.Wherein, the primary coat solution that can preferably use the polyvinyl alcohol resin that adaptation is good to be dissolved in the water and to form.
With regard to primary coat solution, its solid component concentration is reached about 1～25 weight %.
The thickness of undercoat (before the stretching process) is preferably 0.05～1 μ m, more preferably 0.1～0.4 μ m.If thinner than 0.05 μ m, as then to exist the closing force of base material film and polyvinyl alcohol layer to reduce usually tendency, if thicker than 1 μ m, polaroid thickening then.
[polariscope layer]
Particularly, polariscope layer polyvinyl alcohol resin layer that dichromatism pigment absorption is oriented in behind the uniaxial tension obtains.
As the polyvinyl alcohol resin that constitutes the polyvinyl alcohol resin layer, can use polyvinyl acetate (PVA) is resin after the resin saponification.Be resin as polyvinyl acetate (PVA), except the polyvinyl acetate (PVA) as the homopolymer of vinyl acetate, but the multipolymer etc. of the monomer of vinyl acetate and other copolymerization can also example be shown.As can with the monomer of vinyl acetate copolymerized other, for example can list unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class, have the acrylic amide of ammonium etc.
The polyvinyl alcohol resin that constitutes polariscope layer (polyvinyl alcohol resin layer) is preferably fully saponified thing.The scope of saponification degree is preferably 80.0 moles of %～100.0 mole %, more preferably the scope of 90.0 moles of %～99.5 mole %, the more preferably scope of 94.0 moles of %～99.0 mole %.
If saponification degree is less than 80.0 moles of %, the tendency that then exists the water tolerance made behind the polaroid and humidity resistance to reduce usually.In addition, under the situation of using saponification degree above the polyvinyl alcohol resin of 99.5 moles of %, there is the slack-off tendency of dyeing kinetics usually, can't obtains sufficient polarization property sometimes, need the time of more growing than usual sometimes in the mill.
At this, saponification degree is to be that resin contained acetoxy group become numerical value that the ratio of hydroxyl represented than (unit rate) (mole %) to make polyvinyl acetate (PVA) as the raw material of polyvinyl alcohol resin by saponifying process with unit, is the numerical value by following formula definition.Can use the method for regulation among the JIS K 6726 (1994) to try to achieve.
Saponification degree (mole %)=(quantity of hydroxyl) ÷ (quantity of the quantity+acetoxy group of hydroxyl) * 100
Saponification degree is more high, and the ratio of expression hydroxyl is more high, that is, the ratio of the acetoxy group of expression obstruction crystallization is more low.
In addition, the polyvinyl alcohol resin that uses among the present invention can be the modified polyvinylalcohol that part is modified.The Arrcostab, acrylamide etc. that for example can list unsaturated carboxylic acids such as alkene, acrylic acid, methacrylic acid, crotonic acid such as using ethene, propylene, unsaturated carboxylic acid polyvinyl alcohol resin is carried out after the modification and material etc.The ratio of modification is preferably less than 30 moles of %, more preferably less than 10 moles of %.If surpass the modification of 30 moles of %, then becoming is difficult to adsorb the dichromatism pigment, has the tendency of the undesirable condition that the polarization property reduction takes place usually.
Also there is no particular limitation for the average degree of polymerization of polyvinyl alcohol resin, but be preferably 100～10000, and more preferably 1500～8000, more preferably 2000～5000.Said average degree of polymerization also is the numerical value of trying to achieve by the method for regulation among the JIS K 6726 (1994) herein.
98.0～99.0 moles of %), PVA117 (saponification degree: 98.0～99.0 moles of %), PVA624 (saponification degree: 95.0～96.0 moles of %) and PVA617 (saponification degree: 94.5～95.5 moles of %) as the polyvinyl alcohol resin with such characteristic, can list: the PVA124 that makes of (strain) Kuraray (saponification degree: for example; 97.0～98.8 moles of %), AH-22 (saponification degree: 97.5～98.5 moles of %), NH-18 (saponification degree: 98.0～99.0 moles of %) and N-300 (saponification degree: 98.0～99.0 moles of %) AH-26 that makes of Japanese synthetic chemical industry (strain) (saponification degree: for example; Japanese VAM﹠amp for example; 93.5～95.5 moles of %), JM-26 (saponification degree: 95.5～97.5 moles of %), JP-45 (saponification degree: 86.5～89.5 moles of %), JF-17 (saponification degree: 98.0～99.0 moles of %), JF-17L (saponification degree: 98.0～99.0 moles of %) and JF-20 (saponification degree: 98.0～99.0 moles of %) etc., can perform well among the present invention the JC-33 of POVAL (strain) (saponification degree: 99.0 moles more than the %), JM-33 (saponification degree:.
By to above-mentioned polyvinyl alcohol resin film processed, thereby can form the polyvinyl alcohol resin layer.Method to polyvinyl alcohol resin film processed is not particularly limited, can be by known method film processed, from the aspect of the polariscope layer that is easy to obtain required thickness, preferably be the solution film processed of resin by pva coating on base material film.
Above-mentioned polyvinyl alcohol resin layer is stretched with base material film, and is orientated, and then the dichromatism pigment is adsorbed orientation, thereby makes the polariscope layer.Stretching ratio is preferably greater than 5 times, more preferably greater than 5 times and be below 17 times.
The thickness of polariscope layer (thickness of the polyvinyl alcohol resin layer after the stretching) is below the 10 μ m, is preferably below the 7 μ m.Be below the 10 μ m by the thickness that makes the polariscope layer, thereby can constitute slim polarizability stacked film.
As the dichromatism pigment that uses in the polariscope layer, for example can enumerate iodine, organic dyestuff etc.
As organic dyestuff, for example 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, blue GL, the Si Pula orange of the blue G of brilliant violet BK, Si Pula (Supra), Si Pula GL, direct sky blue, chlorazol fast orange d S, fast black etc.These dichroic substance both can have been used a kind of, also can be also with two or more.
[diaphragm]
Diaphragm can not have optical function and only is diaphragm, can be that phase retardation film and brightness improve the such diaphragm that has optical function concurrently of film yet.
Material as diaphragm; there is no particular limitation for it; for example can list the cellulose acetate resin film of the resin that comprises cyclic polyolefin resin film, triacetyl cellulose, diacetyl cellulose and so on; the polyester based resin film that comprises the resin of polyethylene terephthalate, PEN, polybutylene terephthalate and so on; the polycarbonate resin film; the acrylic resin film, widely used film all the time in this areas such as polypropylene-based resin film.
As cyclic polyolefin hydrocarbon system resin, can suitably use suitable commercially available product, for example, Topas (registered trademark) (manufacturing of Ticona company), ARTON (registered trademark) (JSR (strain) manufacturing), ZEONOR (registered trademark) (Japanese ZEON (strain) manufacturing), ZEONEX (registered trademark) (Japanese ZEON (strain) manufacturing), APEL (registered trademark) (Mitsui Chemicals (strain) manufacturing).When such cyclic polyolefin hydrocarbon system resin film processed is formed film, can suitably use known method such as solvent cast method, extrusion by melting.In addition, can use Escena (registered trademark) (ponding chemical industry (strain) manufacturing), SCA40 (ponding chemical industry (strain) manufacturing), ZEONOR (registered trademark) film ((strain) OPTES manufacturing) etc. to carry out the commercially available product of film of the cyclic polyolefin hydrocarbon system resin manufacture of film processed in advance.
The cyclic polyolefin resin film can be uniaxial tension or biaxial stretch-formed after film.By stretching, thereby can give phase difference value arbitrarily to the cyclic polyolefin resin film.Usually can stretch continuously while rolling the film roller, can utilize heating furnace to stretch towards the direct of travel of roller, direction or this both direction vertical with this direct of travel.The temperature of heating furnace is generally near the scope till the glass transition temperature+100 ℃ glass transition temperature of cyclic polyolefin hydrocarbon system resin.The multiplying power that stretches is generally 1.1～6 times in each direction, is preferably 1.1～3.5 times.
Therefore preferably the common surfactivity of cyclic polyolefin resin film is poor, to carrying out surface treatments such as Cement Composite Treated by Plasma, corona treatment, ultraviolet treatment with irradiation, Flame (flame) processing, saponification processing with the bonding surface of polarizing coating.Wherein, the Cement Composite Treated by Plasma that preferably can implement with comparalive ease, corona treatment.
As the cellulose acetate resin film, can suitably use suitable commercially available product, for example FUJITAC (registered trademark) TD80 (Fujiphoto (strain) manufacturing), FUJITAC (registered trademark) TD80UF (Fujiphoto (strain) manufacturing), FUJITAC (registered trademark) TD80UZ (Fujiphoto (strain) manufacturing), FUJITAC (registered trademark) TD40UZ (Fujiphoto (strain) manufacturing), KC8UX2M (KONICA MINOLTA OPTO (strain) manufacturing), KC4UY (KONICAMINOLTA OPTO (strain) manufacturing) etc.
In order to improve the field angle characteristic, can form liquid crystal layer etc. on the surface of cellulose acetate resin film.In addition, in order to give phase differential, the cellulose acetate resin film is stretched.In order to improve the cementability with polarizing coating, the cellulose-based resin molding of Dichlorodiphenyl Acetate is implemented saponification and is handled usually.Handle as saponification, can adopt the method for in the aqueous solution of the alkali of NaOH, potassium hydroxide and so on, flooding.
Also can form optical layers such as hard conating, antiglare layer, anti-reflection layer on the surface of above-mentioned such diaphragm.The method that forms these optical layers on the diaphragm surface is not particularly limited, and can use known method.
According to the requirement of slimming, preferably make the thickness of diaphragm thin as much as possible, be preferably below the 90 μ m, more preferably below the 50 μ m.On the contrary, if cross thin then the intensity reduction, therefore the processability variation is preferably more than the 5 μ m.
[other optical layers]
Above-mentioned polaroid can be used as the optical layers that is laminated with other when reality is used polaroid uses.
In addition, said protection film also can have the function of these optical layers.
As other the example of optical layers, can list reflective polarizing film, the surface that certain polarized light of transmission and reflection demonstrate with the polarized light of its opposite nature and have the film with anti-dazzle function of concaveconvex shape, the film of belt surface anti-reflective function, the reflectance coating that the surface has reflection function, the Transflective film that has reflection function and transmission function concurrently, field angle compensate film.
Demonstrate commercially available product with the reflective polarizing film of the polarized light of its opposite nature as being equivalent to certain polarized light of transmission and reflection, for example can list: (3M company makes DBEF, can obtain from Sumitomo 3M (strain)), APF (3M company makes, and can obtain from Sumitomo 3M (strain)).As the field angle compensate film, can list at substrate surface coating fluid crystallinity compound and the optical compensation films of orientation has taken place, the phase retardation film that formed by polycarbonate-based resin, by the phase retardation film of cyclic polyolefin hydrocarbon system resin-shaped one-tenth.Commercially available product as the optical compensation films that is equivalent at substrate surface coating fluid crystallinity compound and has taken place to be orientated can list: WV film (Fujiphoto (strain) manufacturing), NH film (Nippon Oil(Nippon Mitsubishi Oil) (strain) manufacturing), NR film (Nippon Oil(Nippon Mitsubishi Oil) (strain) manufacturing) etc.In addition, commercially available product as the phase retardation film that is equivalent to be become by cyclic polyolefin hydrocarbon system resin-shaped can list: ARTON (registered trademark) film (JSR (strain) manufacturing), Escena (registered trademark) (ponding chemical industry (strain) manufacturing), ZEONOR (registered trademark) film ((strain) OPTES manufacturing) etc.
The manufacture method of＜polarizability stacked film 〉
Fig. 1 is the process flow diagram of a kind of embodiment of the manufacture method of expression polarizability stacked film.As shown in Figure 1, the manufacture method of polarizability stacked film is implemented following operation successively:
Undercoat forms operation (S10), at a face coating primary coat solution of base material film and form undercoat,
The polyvinyl alcohol resin layer forms operation (S20), forms the polyvinyl alcohol resin layer at above-mentioned undercoat, is possessed the stacked film of above-mentioned base material film, above-mentioned undercoat and above-mentioned polyvinyl alcohol resin layer successively,
Stretching process (S30) stretches to above-mentioned stacked film, and
Dyeing process (S40) uses the dichromatism pigment that the above-mentioned polyvinyl alcohol resin layer of above-mentioned stacked film is dyeed and makes the polariscope layer.
The polarizability stacked film that utilizes this manufacture method to obtain becomes at the base material film after the stretching and possesses the polarizability stacked film that thickness is the polariscope layer below the 10 μ m.Both it directly can be used as polaroid, also can as being used for the intermediate product of polariscope course diaphragm transfer printing be used as described later.
The manufacture method of＜polaroid 〉
Fig. 2 is the process flow diagram of a kind of embodiment of the manufacture method of expression polaroid.As shown in Figure 2, the manufacture method of polaroid possesses successively:
The operation identical with the manufacture method of above-mentioned polarizability stacked film (S10～S40);
Diaphragm bonding process (S50) is at the polarizability stacked film and applying diaphragm in surface above-mentioned base material film side opposition side;
Base material film stripping process (S60) is peeled off above-mentioned base material film from the polarizability stacked film.
The polaroid that utilizes this manufacture method to obtain becomes at diaphragm and possesses the polaroid that thickness is the polariscope layer below the 10 μ m.This polaroid for example can be by pressure sensitive bonding agent and other blooming, liquid crystal cell applying etc. and is used.
＜each manufacturing process 〉
Below, each operation of the S10～S60 among Fig. 1 and Fig. 2 is elaborated.Need to prove that each operation of S10～S40 of Fig. 1 and Fig. 2 is identical operation.
[undercoat forms operation (S10)]
At this, form undercoat at a face of base material film.
Be fit to the material of base material film shown in the material described in the explanation of the formation of above-mentioned polarizability stacked film.Need to prove that in the present embodiment, base material film preferably uses the material that can stretch in the temperature range of the stretching that is suitable for polyvinyl alcohol resin.
The thickness (before the stretching process) of the undercoat that forms at base material film is preferably 0.05～1 μ m.0.1～0.4 μ m more preferably.If thinner than 0.05 μ m, as then to exist the closing force of base material film and polyvinyl alcohol layer to reduce usually tendency, if thicker than 1 μ m, polaroid thickening then.
The preferred following mode of undercoat forms, that is, the powder of polyvinyl alcohol resin and crosslinking chemical be dissolved in the solvent and obtain primary coat solution, with the primary coat solution coat of gained on a surface of base material film, make the solvent evaporation and carry out drying, form undercoat thus.The composition of primary coat solution as mentioned above.
In order to make the driving fit well of base material film and undercoat, can carry out the processing that corona treatment, Cement Composite Treated by Plasma, flame treatment etc. are used for improving adaptation to base material film.
As the method at base material film coating primary coat solution, can be from line rod rubbing method, rolling methods such as reverse rubbing method, intaglio plate rubbing method, mould is coated with in the known method such as method, comma rubbing method, lip formula rubbing method, spin-coating method, silk screen rubbing method, spray formula rubbing method, infusion process, gunite and suitably Selects and Applies.
It for example is 50～200 ℃ that baking temperature is preferably, more preferably 60～150 ℃.Be preferably 1～30 minute drying time, more preferably for example 2～20 minutes.Particularly, be under the situation of water at the solvent of primary coat solution, baking temperature is preferably 50～200 ℃, is preferably 1～60 minute drying time.
[the PVA resin forms operation (S20)]
At this, form the resin bed that comprises polyvinyl alcohol resin on the surface of undercoat.Thus, can obtain the stacked film that on base material film, forms across the stacked polyvinyl alcohol resin layer of undercoat.
The thickness of formed polyvinyl alcohol resin layer (stretch before) is preferably and is thicker than 3 μ m and is below the 30 μ m, more preferably 5～20 μ m.Usually, if be below the 3 μ m, became thin after then stretching, had the tendency of dyeability variation, and if surpass 30 μ m, then caused the thickness of the polariscope layer that finally obtains to surpass 10 μ m sometimes.
The polyvinyl alcohol resin layer preferably forms in the following way, namely, on the surface of polyvinyl alcohol resin solution coat at base material film that the powder dissolution that makes polyvinyl alcohol resin is obtained in good solvent, make solvent evaporation and dry, form the polyvinyl alcohol resin layer thus.By forming the polyvinyl alcohol resin layer by this way, thereby can make the polyvinyl alcohol resin attenuation.Be the method for resin solution as pva coating on base material film, can be from line rod rubbing method, rolling methods such as oppositely coating, intaglio plate coating, mould is coated with in the known method such as method, comma rubbing method, lip formula rubbing method, spin-coating method, silk screen rubbing method, spray formula rubbing method, infusion process, gunite and suitably Selects and Applies.Baking temperature is 50～200 ℃ for example, is preferably 60～150 ℃.For example be 2～20 minutes drying time.
[stretching process (S30)]
At this, the stacked film that is formed by base material film and polyvinyl alcohol resin layer is stretched.Preferably with greater than 5 times and be that stretching ratio below 17 times carries out uniaxial tension.Further preferably with greater than 5 times and be that stretching ratio below 8 times carries out uniaxial tension.If stretching ratio is below 5 times, then the polyvinyl alcohol resin layer is not orientated fully usually, and therefore, the result can't fully improve the degree of polarization of polariscope layer sometimes.
On the other hand, surpass under 17 times the situation at stretching ratio, the fracture of the stacked film when taking place to stretch easily usually, meanwhile, the thickness of the stacked film after the stretching becomes and is thinner than desired thickness, worries to reduce processability and maneuverability in the subsequent handling.Stretch processing in the stretching process (S30) is not limited to the stretching carried out with a stage, also can carry out with the multistage.Under the situation of carrying out with the multistage, in all stages of stretch processing, carry out stretch processing in the mode greater than 5 times stretching ratio.
Horizontal stretch processing that in the stretching process of present embodiment (S30), can implement vertical stretch processing that the length direction to stacked film carries out, Width is stretched etc.
As vertical stretching mode, can list drawing process between roller, compression stretching method etc., as horizontal stretching mode, can list stenter method etc.
In addition, stretch processing can be adopted any one in moistening type drawing process and the dry type stretching method, and when using the dry type stretching method, the temperature in the time of can selecting the stretching stacked film from wideer scope is preferred from this point.
[dyeing process (S40)]
At this, use the dichromatism pigment that the polyvinyl alcohol resin layer of stretched film is dyeed.
As the dichromatism pigment, for example can list iodine, organic dyestuff etc.As organic dyestuff, for example can use red BR, red LR, red R, pink LB, rubine BL, purplish red GS, sky blue LG, lemon yellow, blue BR, blue 2R, purplish blue 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, blue GL, the Si Pula orange of blue G, Si Pula of brilliant violet BK, Si Pula GL, direct sky blue, chlorazol fast orange d S, fast black etc.These dichroic substance can be used a kind of, also can be also with two or more.
Dyeing process is for example undertaken by the whole stretched film of dipping in the solution that contains above-mentioned dichromatism pigment (staining solution).As staining solution, can use the solution that in solvent, has dissolved above-mentioned dichromatism pigment and got.As the solvent of staining solution, can make water usually, also can further add the organic solvent that intermiscibility is arranged with glassware for drinking water.As the concentration of dichromatism pigment, be preferably 0.01～10 weight %, more preferably 0.02～7 weight % is preferably 0.025～5 weight % especially.
Using under the situation of iodine as the dichromatism pigment, from can further improving the aspect of dyeing efficient, the preferred iodide that further add.As these iodide, for example can list 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 0.01～20 weight %.In iodide, preferably add potassium iodide.Adding under the situation of potassium iodide, the ratio of iodine and potassium iodide preferably is in 1: 5～1: 100 scope in weight ratio, more preferably is in 1: 6～1: 80 scope, is preferably 1: 7～1: 70 scope especially.
The dip time of stretched film in staining solution is not particularly limited, and is preferably 15 seconds usually～15 minutes scope, more preferably 1 minute～3 minutes.In addition, the temperature of staining solution is preferably 10～60 ℃ scope, more preferably 20～40 ℃ scope.
In dyeing process, can after dyeing, carry out crosslinking Treatment.Crosslinking Treatment for example can be undertaken by stretched film is flooded in containing the solution of crosslinking chemical (crosslinker solution).
As crosslinking chemical, can use existing known material.For example can list boron compounds such as boric acid, borax, glyoxal, glutaraldehyde etc.These materials can use a kind of, also can be also with two or more.
As crosslinker solution, can use the solution that in solvent, has dissolved crosslinking chemical and got.As solvent, for example can make water, also can further contain the organic solvent that intermiscibility is arranged with glassware for drinking water.The concentration of the crosslinking chemical in the crosslinker solution is not limited thereto, and is preferably the scope of 1～20 weight %, more preferably 6～15 weight %.
Can add iodide in the crosslinker solution.By the interpolation of iodide, thereby can make the polarization characteristic in the face of polyvinyl alcohol resin layer more even.As iodide, for example can list: 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 weight %, more preferably 0.5～8 weight %.
The dip time of stretched film in crosslinker solution be preferably 15 seconds usually～and 20 minutes, more preferably 30 seconds～15 minutes.In addition, the temperature of crosslinker solution is preferably 10～80 ℃ scope.
By above dyeing process (S40), thereby make the polyvinyl alcohol resin layer have function as the polariscope layer.In this manual, the polyvinyl alcohol resin layer that will have as the function of polariscope is called the polariscope layer, will be called the polarizability stacked film at the duplexer that base material film possesses the polariscope layer.
Preferably in the end carry out washing procedure and drying process.As washing procedure, can implement water washing and handle.Water washing is handled and can be undertaken by stretched film is immersed in the pure water such as ion exchange water, distilled water usually.The water washing temperature is generally 3～50 ℃, is preferably 4 ℃～20 ℃ scope.Dip time was generally for 2～300 seconds, was preferably for 3 seconds～240 seconds.
Washing procedure can will utilize carrying out washing treatment and the water washing treatment combination of iodide solution, also can use liquid alcohols such as suitably having cooperated methyl alcohol, ethanol, isopropyl alcohol, butanols, propyl alcohol and solution.
Preferably after washing procedure, implement drying process.As drying process, can adopt suitable arbitrarily method (for example air dry, dry, the heat drying of air-supply).For example, the baking temperature under the situation of heat drying is generally 20～95 ℃, is generally drying time about 1～15 minute.Need to prove, also the operation that dewaters of having used niproll, air knife etc. can be set after washing procedure.
[diaphragm bonding process (S50)]
At this, at the polariscope layer and face applying diaphragm base material film side opposition side of the polarizability stacked film that obtains via above-mentioned operation.As the method that polariscope layer and diaphragm are fitted, can list the method for polariscope layer and diaphragm being fitted by adhesive phase, bond layer.Be suitable as the material of diaphragm shown in the material described in the explanation of the formation of above-mentioned polaroid.
(adhesive phase)
The bonding agent that constitutes adhesive phase comprises usually: with acrylic resin, phenylethylene resin series, silicon-type resin etc. as base polymer, to wherein having added crosslinking chemical such as isocyanate compound, epoxy compound, aziridine cpd composition.And, also can in bonding agent, cooperate particulate, thereby form the adhesive phase of display light scattering.
The thickness of adhesive phase is preferably 1～40 μ m, preferably is coated with thinly in the scope of the characteristic of not damaging processability, permanance, more preferably 3～25 μ m.If be 3～25 μ m, then have good processability, and also be preferred thickness aspect the change in size that suppresses polarizing coating.If adhesive phase is less than 1 μ m usually, then cohesive reduces, if surpass 40 μ m, then takes place that bonding agent overflows easily etc.
The method that forms adhesive phase at diaphragm, polariscope is not particularly limited; can be the solution of each composition of representative protecting the coating of face or polariscope aspect to contain with above-mentioned base polymer; carry out drying; form adhesive phase; fit with the film of distance piece, other kinds afterwards; also can be after distance piece form adhesive phase, attach and be layered on protection face or the polariscope aspect.In addition, when diaphragm or polariscope aspect formation adhesive phase, can implement the driving fit processing to the side in diaphragm or polariscope aspect or the adhesive phase or both sides as required, for example implement corona treatment etc.
(bond layer)
As the bonding agent that constitutes bond layer, for example can list and use polyvinyl alcohol resin aqueous solution, water system two liquid type polyurethane is the water system bonding agent of emulsion bonding agent etc.Wherein, can preferably use the polyvinyl alcohol resin aqueous solution.With regard to the polyvinyl alcohol resin that uses as bonding agent, the alcotex that obtains except the polyvinyl acetate (PVA) as the homopolymer of vinyl acetate being carried out saponification handle, also have the Dichlorodiphenyl Acetate vinyl acetate and can carry out saponification to handle with the multipolymer of other monomers of its copolymerization and the ethenol system copolymer that obtains and carry out partially modified and the modified polyvinylalcohol based polymer that obtains etc. to their hydroxyl.In the water system bonding agent, can add polyaldehyde, soluble epoxide compound, melamine based compound, zirconia compound, zinc compound etc. as adjuvant.Under the situation of using such water system bonding agent, bond layer therefrom is thinner than 1 μ m usually far away, even use common optical microscope pair cross-section to observe, in fact also can't observe this bond layer.
Used the applying method of the film of water system bonding agent to be not particularly limited, can list following method etc.: the surface at film is coated with or pours into a mould bonding agent equably, at overlapping another film of coated face, and utilizes roller etc. to fit, and makes its drying.Usually, bonding agent is coated with under 15～40 ℃ temperature in its preparation back, and binding temperature is generally 15～30 ℃ scope.
Under the situation of using the water system bonding agent, in order to remove water contained in the water system bonding agent, and after the film of having fitted, make its drying.The temperature of drying oven is preferably 30 ℃～90 ℃.If less than 30 ℃, the tendency that then exists bonding plane to become and be easy to peel off.If be more than 90 ℃, then the optical property of polariscope etc. can be because of the heat deterioration sometimes.Can be made as drying time 10～1000 seconds.
Can also be in room temperature or than for example maintenance about 12～600 hours under the temperature about 20～45 ℃ of its slightly high temperature after the drying.Temperature during maintenance is set at the temperature that adopts when being lower than drying usually.
In addition, as the bonding agent of non-water system, also can use Photocurable adhesive agent.As Photocurable adhesive agent, for example can list the potpourri of photo-curable photoreactive epoxy resin cationic polymerization initiators etc.
As utilizing Photocurable adhesive agent to carry out the method that film is fitted, can use existing known method, for example can list and utilize The tape casting, line rod rubbing method, intaglio plate rubbing method, comma coating machine method, scraper plate method, mould to be coated with coating adhesive on the bonding plane of film such as method, dip coating, spray-on process, with two methods that film is overlapping.The tape casting refers on one side two films as applied thing be moved along approximate vertical direction, general horizontal direction or vergence direction between the two, to its surface flow down bonding agent and make the method for its diffusion profile on one side.
Behind the surperficial coating adhesive of film, by using clampings such as the niproll film of fitting, carry out bonding thus.In addition, also can preferably use this duplexer with pressurizations such as rollers and make the method for its uniform spreading.In this case, as the material of roller, can use metal, rubber etc.And, also preferably adopt and between roller and roller, pass through this duplexer, and the method that it is sprawled by pressurization.At this moment, these rollers can be identical materials, also can be different materials.Use bond layer after above-mentioned niproll etc. has carried out fitting, dry or solidify before thickness to be preferably 5 μ m following and more than the 0.01 μ m.
In order to improve cementability, can suitably implement surface treatments such as Cement Composite Treated by Plasma, corona treatment, ultraviolet treatment with irradiation, FLAME (flame) processing, saponification processing to the gluing of surfaces of film.
Handle as saponification, can list the method for in the aqueous solution of the alkali of NaOH, potassium hydroxide and so on, flooding.
Using under the situation of light-cured resin as bonding agent, after with film-stack, by the irradiation active energy beam Photocurable adhesive agent is solidified.The light source of active energy beam is not particularly limited, be preferably the active energy beam that below wavelength 400nm, has luminous distribution, particularly, can preferably use low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, chemical lamp, black lamp, microwave-excitation mercury lamp, metal halide lamp etc.
Intensity is penetrated in the illumination of Photocurable adhesive agent can suitably be determined according to the composition of Photocurable adhesive agent, is not particularly limited, and the exposure intensity of the effective wavelength region may of activation of polymerization initiator is preferably 0.1～6000mW/cm 2Be 0.1mW/cm in exposure intensity 2Under the above situation, the reaction time can be not long, at 6000mW/cm 2Under the following situation, the xanthochromia of the caused epoxy resin of heating the when curing because of the light and heat curing property bonding agent that goes out from radiation of light source seldom can take place, the deterioration of polarizing coating.The illumination of Photocurable adhesive agent is penetrated the time so long as the suitable light application time of Photocurable adhesive agent to solidifying, then be not particularly limited, preferably reach 10～10000mJ/cm according to the accumulative total light quantity with the product representation of above-mentioned exposure intensity and irradiation time 2Mode set.Be 10mJ/cm in the accumulative total light quantity to Photocurable adhesive agent 2Under the above situation, can produce the spike that is derived from polymerization initiator of sufficient quantity, can be cured reaction more reliably, at 10000mJ/cm 2Under the following situation, irradiation time can be not long, can keep good throughput rate.Need to prove that the thickness of the postradiation bond layer of active energy beam is generally about 0.001～5 μ m, be preferably more than the 0.01 μ m and below the 2 μ m, more preferably more than the 0.01 μ m and below the 1 μ m.
Make under the situation that the Photocurable adhesive agent of the film that comprises polariscope layer, diaphragm take place to solidify in the irradiation by active energy beam, preferably under all multi-functional condition of the polaroids such as the transparency of the degree of polarization that does not reduce the polariscope layer, transmissivity and tone and diaphragm, be cured.
[base material film stripping process (S60)]
At diaphragm bonding process (S50) afterwards, carry out peeling off from the polarizability stacked film base material film stripping process (S60) of base material film.The stripping means of base material film is not particularly limited, and can adopt the same method of stripping film stripping process of carrying out with the common polaroid that has bonding agent.At diaphragm bonding process (S50) afterwards, can under this state, peel off immediately, also can after temporarily coiling into the roller shape, in addition stripping process be set and peel off.
Embodiment
Embodiment 1
According to manufacture method shown in Figure 1, proceed to till the stretching process (S30) in the making of polarizability stacked film.
(undercoat formation operation)
(1) base material film
As base material film, used thickness is the HOPP film that does not stretch of 100 μ m.
(2) preparation of primary coat solution
As the crosslinking chemical that in primary coat solution, adds, used " Orgatix TC-310 (trade name) " (this pharmaceuticals industry of pine (strain) manufacturing as organometallics (titanium complex).Effective constituent (chemical constitution: (HO) 2Ti[OCH (CH 3) COOH] 2) 44%, the solution of isopropyl alcohol 40% and water 16%).
At first, water, isopropyl alcohol being reached " Orgatix TC-310 " mixes so that water: the weight ratio of isopropyl alcohol: TC-310 reaches 85: 15: 7.5, prepares solution A.At this, the weight ratio of TC-310 represents to contain the weight of the whole solution of organometallics.
In addition, in 80 ℃ water, make with respect to water 100 weight portions pva powder (Kuraray (strain) is made, saponification degree: about 80 moles of %, trade name: KL506) 15 parts of dissolvings, prepare polyvinyl alcohol water solution (solution B) thus.
Solution A and solution B are mixed so that solution A: the weight ratio of solution B reaches 1.3: 4, thereby prepares primary coat solution.
(3) formation of undercoat
The primary coat solution coat of gained is being implemented on the base material film after the corona treatment, and drying is 10 minutes under 80 ℃, and forming thickness is the undercoat of 0.2 μ m.
(the PVA resin forms operation)
Pva powder (Kuraray (strain) is made, average degree of polymerization 2400, average 98～99 moles of % of saponification degree) is dissolved in 95 ℃ the hot water, prepares the polyvinyl alcohol water solution that concentration is 8 weight %.The polyvinyl alcohol water solution of gained is coated on the above-mentioned undercoat, and drying is 20 minutes under 80 ℃, produces and stacks gradually the stacked film that base material film, undercoat and polyvinyl alcohol resin layer form.The thickness of the polyvinyl alcohol resin layer of this moment (before stretching) is 15 μ m.
(stretching process)
Use the tentering drawing machine with the stacked film of gained uniaxial tension to 5.5 times longitudinally.The thickness of the polyvinyl alcohol resin layer after the stretching is 7.6 μ m.
(dyeing process)
Stacked film dipping after will stretching in 60 ℃ temperature are bathed is after 60 seconds, mixed aqueous solution at 30 ℃ iodine and potassium iodide is that staining solution is (for water 100 weight portions, iodine is 0.3 weight portion, potassium iodide is 5 weight portions) the middle dipping 300 seconds, afterwards, use 10 ℃ the unnecessary iodine liquid of pure water rinsing.Then, the mixed aqueous solution at 76 ℃ boric acid and potassium iodide is to flood 300 seconds in the crosslinker solution (for water 100 weight portions, boric acid is 8 weight portions, and potassium iodide is 5 weight portions).Afterwards, use 10 ℃ pure water to wash for 4 seconds, under 50 ℃, carry out the drying in 300 seconds, obtain the polarizability stacked film.
(diaphragm bonding process)
Use comprises the bonding agent of triacetyl cellulose (TAC) and polyvinyl alcohol (PVA) (PVA) and goes up the applying diaphragm (TAC:KC4UY that KONICA MINOLTA OPTO (strain) makes in the polariscope side of above-mentioned polarizability stacked film (polariscope with the face base material film opposition side); thickness is 40 μ m); drying is 5 minutes under 80 ℃, thereby obtains having the polarizability stacked film of base material film and diaphragm.
As above-mentioned polyethenol series bonding agent, use the following adhesive solution of making: make pva powder ((strain) Kuraray manufacturing, average degree of polymerization is 1800, trade name: KL-318) be dissolved in 95 ℃ the hot water, prepare the aqueous solution that concentration is 3 weight %, (firmly changing Chemtex (strain) makes mix 1 parts by weight of cross-linking agent solution in the aqueous solution of gained for pva powder 2 weight portions, trade name: Sumirez (registered trademark) Resin650), thus make adhesive solution.
(base material film stripping process)
Peel off base material film with hand.Base material film easily is stripped from, and obtains comprising diaphragm, bond layer, polariscope layer, this polaroid of four layers of undercoat.The thickness of the polariscope layer in the thickness of the polariscope layer in the polaroid of gained and the above-mentioned polarizability stacked film is identical, is 7.4 μ m.
In above operation, in the time of in impregnated in staining solution, crosslinker solution, the polyvinyl alcohol resin layer can not take place from the peeling off of base material film, in addition, there is not special problem when peeling off base material film yet, can make polaroid.
Embodiment 2
In the preparation of the solution A of embodiment 1, as crosslinking chemical, use is as " Orgatix ZB-400 " (this pharmaceuticals industry of pine (strain) manufacturing of organometallics (water miscible organic zirconate), the solution of effective constituent 30 weight % and water 70 weight %) so that water: the weight ratio of isopropyl alcohol: ZB-400 becomes 85: 15: 1, in addition, carry out 1 identical operations with embodiment, prepare primary coat solution.
In addition, carry out 1 identical operations with embodiment, prepare and stack gradually the stacked film that base material film, undercoat and polyvinyl alcohol resin layer form.The thickness of the polyvinyl alcohol resin layer of this moment (before stretching) is 15 μ m.Use the stacked film of gained, carry out the making of polaroid similarly to Example 1.The thickness of polariscope layer is 7.2 μ m.
In the present embodiment, when impregnated in staining solution, crosslinker solution, the polyvinyl alcohol resin layer can not take place from the peeling off of base material film, in addition, not have special problem when peeling off base material film yet, can make polaroid.
Embodiment 3
As crosslinking chemical, having used water-dispersible polyisocyanates is crosslinking chemical (big Japanese ink chemical industry (strain) is made trade name: Bamock DWN-5000, the diethylene glycol dimethyl ether solution of solid component concentration about 80%).
Heat water to 80 ℃ on one side, on one side (Kuraray (strain) is made, saponification degree: about 80% with pva powder, trade name PVA-403) mixes, after the stirring, be cooled to room temperature, add above-mentioned water-dispersible polyisocyanates crosslinking chemical then and stir, prepare primary coat solution.Need to prove that the use level with crosslinking chemical for pva powder 15 weight portions is made as 5 weight portions.At this, the weight of polyisocyanate crosslinking agent represents to comprise the weight of the whole solution of solvent.
Except the preparation of above-mentioned primary coat solution, carry out 1 identical operations with embodiment, produce and stack gradually the stacked film that base material film, undercoat and polyvinyl alcohol resin layer form.The thickness of the polyvinyl alcohol resin layer of this moment (before stretching) is 15 μ m.
Use the stacked film of gained, carry out the making of polaroid similarly to Example 1.The thickness of polariscope layer is 7.5 μ m.
In the present embodiment, when impregnated in staining solution, crosslinker solution, the polyvinyl alcohol resin layer can not take place from the peeling off of base material film, in addition, not have special problem when peeling off base material film yet, can make polaroid.
Embodiment 4
(average degree of polymerization is about 1700 to make fully saponified PVA, saponification degree is more than 99.6%) be dissolved in the aqueous solution for preparing 3 weight % in 95 ℃ the water, after being cooled to room temperature, adding is the glyoxal of crosslinking chemical as dialdehyde and stirs so that fully saponified PVA: water: glyoxal weight ratio reach 5: 100: 0.6, prepare primary coat solution.
In addition, carry out 1 identical operations with embodiment, produce and stack gradually the stacked film that base material film, undercoat and polyvinyl alcohol resin layer form.The thickness of the polyvinyl alcohol resin layer of this moment (before stretching) is 16 μ m.Use the stacked film of gained, carry out the making of polaroid similarly to Example 1.The thickness of polariscope layer is 7.8 μ m.
In the present embodiment, when impregnated in staining solution, crosslinker solution, the polyvinyl alcohol resin layer can not take place from the peeling off of base material film, in addition, not have special problem when peeling off base material film yet, can make polaroid.
Comparative example 1
As crosslinking chemical, having used by the daiamid epoxy resin of firmly changing Chemtex (strain) sale is " Sumirez Resin 650 (30) " (trade name, the aqueous solution of solid component concentration 30%), in addition, carry out 1 identical operations with embodiment, produce and stack gradually the stacked film that base material film, undercoat and polyvinyl alcohol resin layer form.
＜heatproof water-based test 〉
In the making of the polarizability stacked film in embodiment 1～4 and comparative example 1, for each stacked film of the state of (before the dyeing process) behind the stretching process, at the face applying pressure-sensitive adhesive (acrylic adhesive) of polyvinyl alcohol resin layer side.With this stacked film be cut into the tensile axis direction be 60mm, with the rectangular direction of tensile axis be the size of 35mm, at binder side applying glass plate, make heatproof water-based test sample.In 60 ℃ warm water, the sample dipping after 60 minutes, is measured the overburden amount from the base material film of polyvinyl alcohol resin layer.Show the result in table 1.
As shown in table 1, for the stacked film of embodiment 1～4, almost do not find peeling off of the base material film that causes because of warm water immersion.Hence one can see that, even carry out the dipping in dyeing liquor, crosslinked fluid, produces the polarizability stacked film with problem such as also can not peeling off especially.Relative therewith, about the stacked film of comparative example 1, clearly find peeling off of the base material film that causes because of warm water immersion.
By this result as can be known, invention according to the application, in the manufacture method of polarizability stacked film, can give water tolerance to the undercoat that uses for the adaptation that improves base material film and polyvinyl alcohol resin layer, wherein, the manufacture method of described polarizability stacked film refers to, is provided as the polyvinyl alcohol resin layer of polariscope layer on the surface of base material film, together with base material film the polyvinyl alcohol resin layer is stretched afterwards, implement the manufacture method of dyeing processing and crosslinking Treatment.Thus, in the operation that can prevent from staining solution, crosslinker solution, flooding, the polyvinyl alcohol resin layer peels off from base material film.
＜adhesion experiment 〉
In the making of the stacked film of above-described embodiment 1～4 and comparative example 1, for the base material film of the state that has only formed undercoat, carry out experiment as follows, confirmed the degree of adhesion.Show the result in table 1.
(1) preparation is coated with the film of the undercoat of the above size of 300mm * 220mm.
(2) so that the overlapping primary coat coated film of mode that the primary coat coated face contacts with base material film (PP) face.
(3) film after overlapping is clamped between the glass of 300mm * 220mm, the weight of mounting 2kg is put in 40 ℃ the baking oven.
Take out after (4) 9 days, film is peeled off, in percent the adhesion part proportion among 100mm * 100mm is estimated.
In embodiment 1～4, for the base material film of the state that has only formed undercoat, even under the situation of temporarily having carried out coiling process, also can not stick together as can be known.
[table 1]
In addition, in table 1, the thickness of the polyvinyl alcohol resin layer in the polarizability stacked film is represented also that the thickness (back stretches) that has obtained in an embodiment of the present invention as can be known as the polyvinyl alcohol layer of polariscope layer is the following stacked films of 10 μ m.

Claims (13)

1. the manufacture method of a polarizability stacked film, wherein,
Described polarizability stacked film possesses base material film, undercoat and polariscope layer successively,
Described method comprises successively:
Undercoat forms operation, at a face coating primary coat solution of base material film and form undercoat,
The polyvinyl alcohol resin layer forms operation, forms the polyvinyl alcohol resin layer at described undercoat, is possessed the stacked film of described base material film, described undercoat and described polyvinyl alcohol resin layer successively,
Stretching process stretches to described stacked film, and
Dyeing process uses the dichromatism pigment that the described polyvinyl alcohol resin layer of described stacked film is dyeed and makes the polariscope layer;
Described primary coat solution comprises that to be selected from dialdehyde be that crosslinking chemical, isocyanate-based crosslinking chemical and metal are at least a crosslinking chemical in the crosslinking chemical.
2. method according to claim 1, wherein, described primary coat solution also comprises water soluble polymer.
3. method according to claim 1 and 2, wherein, described water soluble polymer is polyvinyl alcohol resin.
4. according to each described method in the claim 1～3, wherein, the solvent of described primary coat solution is the solvent that comprises water.
5. according to each described method in the claim 1～4, wherein, described crosslinking chemical is water-soluble or water dispersible.
6. according to each described method in the claim 1～5, wherein, described dialdehyde is that crosslinking chemical is glyoxal.
7. according to each described method in the claim 1～5, wherein, described isocyanate-based crosslinking chemical is the polyisocyanate that has more than one isocyanate group in a part at least.
8. according to each described method in the claim 1～5, wherein, described metal is that crosslinking chemical is organometallics.
9. method according to claim 8, wherein, described organometallics is chelate.
10. according to each described method in the claim 1～9, wherein, the thickness before the described stretching process of described undercoat is 0.05～1.0 μ m.
11. according to each described method in the claim 1～10, wherein, the thickness before the described stretching process of described polyvinyl alcohol resin layer is 3～30 μ m.
12. according to each described method in the claim 1～11, wherein, the thickness of described polariscope layer is below the 10 μ m.
13. the manufacture method of a polaroid, wherein,
Described polaroid possesses the polariscope layer and is formed at the diaphragm of a face of this polariscope layer,
Described method comprises successively:
The diaphragm bonding process, at the polarizability stacked film that obtains by the described method of claim 1 and face applying diaphragm described base material film side opposition side, and
The base material film stripping process is peeled off described base material film from the polarizability stacked film.
CN201180059034.2A 2010-12-09 2011-12-06 The manufacture method of polarizability stacked film and polaroid Expired - Fee Related CN103261928B (en)

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