CN102200603A - Polarizing plate - Google Patents

Polarizing plate Download PDF

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Publication number
CN102200603A
CN102200603A CN2011100769871A CN201110076987A CN102200603A CN 102200603 A CN102200603 A CN 102200603A CN 2011100769871 A CN2011100769871 A CN 2011100769871A CN 201110076987 A CN201110076987 A CN 201110076987A CN 102200603 A CN102200603 A CN 102200603A
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CN
China
Prior art keywords
resin film
film
polypropylene
based resin
polarization plates
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CN2011100769871A
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Chinese (zh)
Inventor
高畑弘明
猪口雄平
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Publication of CN102200603A publication Critical patent/CN102200603A/en
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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)

Abstract

The invention provides a polarizing plate, wherein the two sides of a polarizing film made of polyvinyl alcohol-based resin are respectively attached with a transparent resin film via a bonding agent. The water vapor transmission rate of the transparent resin films attached to the two sides of the polarizing film at 40 DEG C is below 50 g/m2 for each day. At least one of the two transparent resin films is a polypropylene resin film containing an ultraviolet absorption agent. The molecular weigh of the ultraviolet absorption agent is above 450 and the content thereof is greater than 0.1 % by weight and lower than 1.5 % by weight.

Description

Polarization plates
Technical field
The present invention relates to a kind of polarization plates of folding the polypropylene-based resin film at least one surface layer of the polarizing coating that forms by polyvinyl alcohol resin.
Background technology
Polarization plates is one of important component parts that constitutes liquid crystal indicators such as LCD TV, LCD, personal computer.Polarization plates is generally following formation; promptly; be adsorbed with the dichromatism pigment and making the one or both sides of the polarizing coating that is formed by polyvinyl alcohol resin of its orientation, via bond layer, the stacked guard film is the formation of the acetate fiber prime system diaphragm of Triafol T representative for example.Sometimes in the one side of polarizing coating, via the stacked phase retardation film that forms by norbornene resin etc. of bond layer.
But, during hydrophilic protective films such as use three cellulose acetate membrane, under high temperature wets condition more, influence the amount of moisture of the polarizing coating that forms by polyvinyl alcohol resin, how many performances as polarization plates changes sometimes.Therefore, begin one's study and replace the diaphragm that forms by hydrophilic resin and use the diaphragm that forms by hydrophobic resins such as polypropylene-based resins, have the polarization plates that constitutes (TOHKEMY 2009-258588 communique etc.) of the influence that can do one's utmost to suppress environment.
On the other hand, polarization plates is also born the effect that the liquid crystal cells of protection in the liquid crystal indicator is not subjected to influence of light, usually, adds ultraviolet light absorber in the diaphragm that is laminated in polarizing coating etc., gives the ultraviolet function below the blocking-up 400nm.But; when in the diaphragm that forms by polypropylene-based resin shown in the above-mentioned TOHKEMY 2009-258588 communique, adding ultraviolet light absorber; the ultraviolet light absorber seepage also accumulates in diaphragm and the interface of bond layer, may cause the bonding strength of diaphragm and polarizing coating to reduce.
Summary of the invention
The objective of the invention is to, a kind of polarization plates is provided, it is stacked by adding the polarization plates that ultraviolet light absorber has been given the polypropylene-based resin film of ultraviolet resistance via bond layer at least one face of polarizing coating, wherein, the bonding strength between this polypropylene-based resin film and the polarizing coating is enough high.
The present invention is in order to solve above-mentioned problem, a kind of polarization plates is provided, respectively via bonding agent applying transparent resin film, wherein, the moisture-vapor transmission when fitting in 40 ℃ of transparent resin film on the two sides is 50g/m on the two sides of the polarizing coating that is formed by polyvinyl alcohol resin for it 2Below it, fit in the transparent resin film on the two sides at least one for to comprise the polypropylene-based resin film that molecular weight is the ultraviolet light absorber more than 450 more than the 0.1 weight % and less than the content of 1.5 weight %.
According to the present invention, can provide the polarization plates that bonding strength is very high, ultraviolet resistance is excellent and environment for use is few to the influence of polarizing coating between a kind of polypropylene-based resin film and the polarizing coating.Use the excellent in te pins of durability of the liquid crystal indicator of polarization plates of the present invention, the excellent in stability of display performance.
Embodiment
＜polarization plates 〉
Polarization plates of the present invention possesses polarizing coating that is formed by polyvinyl alcohol resin and the transparent resin film with regulation moisture-vapor transmission of fitting via bond layer on the two sides of this polarizing coating.Fitting in the transparent resin film on the two sides at least one uses to comprise the polypropylene-based resin film that molecular weight is the ultraviolet light absorber more than 450 more than the 0.1 weight % and less than the content of 1.5 weight %.
(polarizing coating)
The polarizing coating that uses in the polarization plates of the present invention particularly is the polarizing coating that is adsorbed with the dichromatism pigment and makes its orientation in the polyvinyl alcohol resin film of uniaxial tension.Polyvinyl alcohol resin can be by being that the resin saponification obtains with polyvinyl acetate (PVA).As polyvinyl acetate (PVA) is resin, except that the homopolymer of vinyl acetate is polyvinyl acetate (PVA), can enumerate: vinyl acetate with can with the multipolymer of other monomer of its copolymerization, for example ethylene-vinyl acetate copolymer etc.As can with other vinyl acetate copolymerized monomer, for example can enumerate: olefines such as unsaturated carboxylic acid class, above-mentioned ethene, vinyl ethers, unsaturated sulfonic acid class, have the acrylic amide of ammonium etc.
The saponification degree of polyvinyl alcohol resin is generally 85～100 moles of %, is preferably 98 moles more than the %.Polyvinyl alcohol resin can carry out modification, for example, also can use with aldehydes modified polyethylene alcohol formal, polyvinyl acetal, polyvinyl butyral etc.The degree of polymerization of polyvinyl alcohol resin is usually in 1000～10000 scope, preferably in 1500～5000 scope.
Film by polyvinyl alcohol resin system film forms can use with the coiled strip form membrane of polarizing coating.The method of polyvinyl alcohol resin being made film is not particularly limited, and can pass through known suitable method system film in the past.The thickness of the coiled strip film that is formed by polyvinyl alcohol resin is not particularly limited, and for example is about 10～150 μ m.
Usually via following operation manufacturing, described operation is polarizing coating: with polyvinyl alcohol resin film dichromatism pigment dyeing, make its operation of adsorbing this dichromatism pigment (dyeing treatment process); The operation (boric acid treatment process) that the polyvinyl alcohol resin film that is adsorbed with the dichromatism pigment is handled with boric acid aqueous solution and handle based on this boric acid aqueous solution after the operation (washing treatment process) of washing.
In addition, when making polarizing coating, usually the polyvinyl alcohol resin film is carried out uniaxial tension, this uniaxial tension can carry out before the dyeing treatment process, also can carry out in the dyeing treatment process, can also carry out after the dyeing treatment process.When carrying out uniaxial tension after the dyeing treatment process, this uniaxial tension can carry out before the boric acid treatment process, also can carry out in the boric acid treatment process.Certainly, also can in these a plurality of operations, all carry out uniaxial tension.Uniaxial tension can stretch on single shaft ground between the different roller of rotating speed, also can use hot-rolling to carry out uniaxial tension.In addition, can be the dry type stretching that in atmosphere, stretches, also can stretch for the wet type that stretches with the state that makes its swelling with solvent.Stretching ratio is generally about 3～8 times.
The dyeing that utilizes the dichromatism pigment that the polyvinyl alcohol resin film is carried out in the dyeing treatment process is for example by carrying out the polyvinyl alcohol resin film immersion in the aqueous solution that contains the dichromatism pigment.As the dichromatism pigment, for example use iodine, dichroic dye etc.Dichroic dye comprises dichromatism direct dyess such as dichromatism direct dyes that C.I.DIRECT RED 39 grades for example form by bis-azo compound, trisazo compound, four azo-compounds.Need to prove that the polyvinyl alcohol resin film preferably implemented to be immersed in the processing in the water in advance before dyeing is handled.
When using iodine, usually, adopt the method for in the aqueous solution that contains iodine and potassium iodide, flooding the polyvinyl alcohol resin film and dyeing as the dichromatism pigment.The content of the iodine in this aqueous solution is 0.01～1 weight portion with respect to water 100 weight portions usually, and the content of potassium iodide is 0.5～20 weight portion with respect to water 100 weight portions usually.When using iodine as the dichromatism pigment, the temperature of the aqueous solution that is used to dye is generally 20～40 ℃, and in addition, the dip time in this aqueous solution (dyeing time) is generally 20～1800 seconds.
On the other hand, when using dichroic dye, usually, adopt the method for in containing the aqueous solution of dichroic dye, flooding the polyvinyl alcohol resin film and dyeing usually as the dichromatism pigment.The content of the dichroic dye in this aqueous solution is 1 * 10 with respect to water 100 weight portions usually -4～10 weight portions are preferably 1 * 10 -3～1 weight portion is preferably 1 * 10 especially -3～1 * 10 -2Weight portion.This aqueous solution also can contain inorganic salts such as sodium sulphate as dyeing assistant.When using dichroic dye as the dichromatism pigment, the temperature of the aqueous dye solutions that is used to dye is generally 20～80 ℃, and in addition, the dip time in this aqueous solution (dyeing time) is generally 10～1800 seconds.
The boric acid treatment process is carried out in containing the aqueous solution of boric acid by the polyvinyl alcohol resin film immersion that will utilize the dichromatism pigment dyeing.The content that contains the boric acid in the aqueous solution of boric acid is generally 2～15 weight portions with respect to water 100 weight portions, is preferably 5～12 weight portions.As the dichromatism pigment in the above-mentioned dyeing treatment process, when using iodine, the aqueous solution of using in this boric acid treatment process that contains boric acid preferably contains potassium iodide.Under this situation, the content that contains the potassium iodide in the aqueous solution of boric acid is generally 0.1～15 weight portion with respect to water 100 weight portions, is preferably 5～12 weight portions.Dip time in containing the aqueous solution of boric acid is generally 60～1200 seconds, is preferably 150～600 seconds, more preferably 200～400 seconds.The temperature that contains the aqueous solution of boric acid is generally more than 50 ℃, is preferably 50～85 ℃, more preferably 60～80 ℃.
In ensuing washing treatment process, for example washing processing in the water by the polyvinyl alcohol resin film immersion after above-mentioned boric acid is handled.The temperature of water was generally 5～40 ℃ during washing was handled, and dip time is generally 1～120 second.Washing is implemented dried after handling usually, obtains polarizing coating.Dried can preferably be used for example air drier, far infra-red heater etc.The temperature of dried is generally 30～100 ℃, is preferably 50～80 ℃.The time of dried is generally 60～600 seconds, is preferably 120～600 seconds.
Thus, dyeing, boric acid processing and washing processing to the polyvinyl alcohol resin film is implemented uniaxial tension, utilized the dichromatism pigment to carry out obtain polarizing coating.The thickness of polarizing coating is usually in the scope of 5～40 μ m.
(transparent resin film)
The transparent resin film that fits in the two sides of above-mentioned polarizing coating can be the film that is formed by resin material of the same race, the film that the resin material not of the same race of also can serving as reasons forms, and the moisture-vapor transmission when two transparent resin films all use 40 ℃ is 50g/m 2The resin molding that it is following.Moisture-vapor transmission is preferably 10g/m 2Below it.Thus, the influence of environment for use, particularly moisture can be effectively suppressed, the long-time stability of optical characteristics can be given the polarization plates that obtains to polarizing coating.
Moisture-vapor transmission in the time of 40 ℃ is measured based on JIS Z 0208.Promptly, moisture-vapor transmission in the time of 40 ℃ is following mensuration, promptly, 40 ℃ of temperature with sample film as the interface, the air of one side is remained on relative humidity 90%, with hygroscopic agent the air of opposite side remained on drying regime, the quality (g) of the water vapor by this interface in 24 hours (1 day) is scaled the every 1m of this sample film 2The value of gained is as moisture-vapor transmission.
Transparent resin film can be for being used to protect the diaphragm of polarizing coating, also can be for having given the phase retardation film of prescribed phases difference.
Among the present invention, fit in the polypropylene-based resin film that at least one use in the transparent resin film on two sides of polarizing coating contains the ultraviolet light absorber of regulation molecular weight.The moisture-vapor transmission of another transparent resin film in the time of 40 ℃ is 50g/m 2Get final product below it, be not particularly limited, can be the polypropylene-based resin film, also can be other resin molding.As other resin molding, can enumerate: comprise the polyolefin-based resins film beyond the polypropylene-based resin films such as norbornene resin film from the formation unit of cycloolefin monomers, polycarbonate resin film, polyester based resin film, polystyrene resin film, acrylic resin film, 4-methyl-1-pentene resin film.
Polarization plates of the present invention one of preferred embodiment be: on a face of polarizing coating; via bond layer; applying is to comprise the diaphragm that molecular weight is the polypropylene-based resin film of the ultraviolet light absorber more than 450 more than the 0.1 weight % and less than the content of 1.5 weight %; at another side; via bond layer, applying norbornene resin film.A transparent resin film can be given polarization plates with rigidity by using the norbornene resin film.This norbornene resin film preferably carries out single shaft or biaxial stretch-formed processing.
(1) contains the polypropylene-based resin film of ultraviolet light absorber
Fit in transparent resin film at least one face of polarizing coating for to contain the polypropylene-based resin film that molecular weight is the ultraviolet light absorber more than 450 more than the 0.1 weight % and less than the content of 1.5 weight %.By using molecular weight is ultraviolet light absorber more than 450, few from oozing out of polypropylene-based resin film, the ultraviolet light absorber of ormal weight can be remained in the film, therefore, can improve the bonding strength between polypropylene-based resin film and the polarizing coating, simultaneously, can give polarization plates with good ultraviolet resistance.This polypropylene-based resin film can be diaphragm and phase retardation film etc.
The molecular weight of ultraviolet light absorber is preferably more than 480, more preferably more than 500.In addition, the molecular weight of ultraviolet light absorber is preferably below 1200.Molecular weight surpasses at 1200 o'clock, is a problem the infringement transparency sometimes with the intermiscibility of polypropylene-based resin.When not producing the problems referred to above, also can use by molecular weight to surpass the ultraviolet light absorber that 1200 oligomer or polymkeric substance form.
As the ultraviolet light absorber of molecular weight contained in the polypropylene-based resin film more than 450, can use dihydroxy benaophenonel system, hydroxybenzotriazole system, hydroxyl triazine is ultraviolet light absorber.Wherein, hydroxybenzotriazole system, the hydroxyl triazine that forms hydrogen bond between N atom and the hydroxyl is more excellent aspect the bonding strength of ultraviolet light absorber between polypropylene-based resin film and polarizing coating.Can enumerate the concrete example of the ultraviolet light absorber of preferred use, for example, be as hydroxybenzotriazole, can enumerate: 2,2 '-ethylenebis [6-(2H-benzotriazole-2-yl)-4-(1,1,3, the 3-tetramethyl butyl) phenol], as hydroxyl triazine system, can enumerate: 2-[4,6-two (2, the 4-xylyl)-1,3,5-triazines-2-yl]-the 5-phenol octyloxy etc.
The addition of the ultraviolet light absorber of molecular weight more than 450 is more than the 0.1 weight % and less than 1.5 weight % in the polypropylene-based resin film.When addition was lower than 0.1 weight %, the ultraviolet resistance deficiency in addition, was 1.5 weight % when above, because from the oozing out of polypropylene-based resin film, bonding strength can reduce, and simultaneously, may damage the outward appearance of film.The addition of ultraviolet light absorber preferably is 0.2～1.2 weight % in the polypropylene-based resin film.
In addition, in order to regulate the ultraviolet resistance of polarization plates, can with the ultraviolet light absorber of molecular weight more than 450 together, and with molecular weight less than 450 ultraviolet light absorber.But under this situation, molecular weight preferably is below the 0.3 weight % in the polypropylene-based resin film less than the addition of 450 ultraviolet light absorber.When addition surpassed 0.3 weight %, the bonding strength of polypropylene-based resin film and polarizing coating may reduce.
As the polypropylene-based resin that constitutes the polypropylene-based resin film, can enumerate: comprise propylene and can with other monomer of its copolymerization for example various multipolymers, and the homopolymer of propylene of random copolymers, 3 membered copolymers or the segmented copolymer of ethene or alpha-olefin.The carbon number of above-mentioned alpha-olefin is more than 4, is preferably the alpha-olefin of carbon number 4～10.Can enumerate the concrete example of the alpha-olefin of carbon number 4～10, for example be: straight chain shape monoene hydro carbons such as 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-decene; A chain mono-olefin class such as 3-methyl-1-butene, 3-Methyl-1-pentene, 4-methyl-1-pentene; Vinyl cyclohexane etc.
Wherein, in the present invention, consider from the viewpoint of resin transparent, preferably use propylene and can with the random copolymers of other monomer of its copolymerization or the homopolymer of propylene.In the random copolymers, more preferably use propylene-ethylene random copolymer, propylene/1-butene random copolymer.The also preferred resin combination that polypropylene-based resin mixes more than 2 kinds that uses in the homopolymer that is selected from random copolymers and propylene.
Polypropylene-based resin is considered from the viewpoint of the shaping easiness on film, be preferably based on melt flow rate (MFR) that JIS K 7210 measures under the 21.18N at 230 ℃ of temperature, load in the scope that 1～20g/10 divides, more preferably in the scope that 2～18g/10 divides, 4～15g/10 branch more preferably.
Polypropylene-based resin can as catalyst for polymerization, for example can be enumerated following catalyzer for polymkeric substance or the multipolymer that uses known catalyst for polymerization polymerization to obtain.
[i] by the Ti-Mg series catalysts that constitutes as the solid catalyst component of neccessary composition with magnesium, titanium and halogen,
[ii] the ternary catalyzer of the sub-property of the power supply compound grade in an imperial examination system that as combination in must the solid catalyst component of Shall composition organo-aluminum compound is arranged with magnesium, titanium and halogen and use as required,
[iii] metallocene series catalysts etc.
Polypropylene-based resin can be by for example using hexane, heptane, octane, silane, cyclohexane, methylcyclohexane, benzene,toluene,xylene and so on hydrocarbon compound as the solution polymerization process of the inert solvent of representative, use liquid monomer as the mass polymerization of solvent, directly make the manufacturings such as gaseous polymerization of gaseous monomer polymerization.Polymerization in these methods can be carried out with batch-type, also can carry out with continous way.
In the polypropylene-based resin film, in the scope of not damaging effect of the present invention, can cooperate above-mentioned ultraviolet light absorber adjuvant in addition.As adjuvant, for example can enumerate: antioxidant, antistatic agent, lubricant, nucleator, antifoggant, anti blocking agent, neutralizing agent etc.Adjuvant can be also with multiple.
As antioxidant, for example can enumerate: phenol is that antioxidant, phosphorous antioxidant, sulphur are that antioxidant, hindered amine are light stabilizer etc., in addition, also can use in 1 molecule, to comprise and for example have simultaneously that phenol is that oxidation-resisting structure and phosphorus are the composite type antioxidant agent of the unit of oxidation-resisting structure.
Antistatic agent can be in polymer-type, oligomeric, the haplotype any.
As lubricant, can enumerate: senior fatty acid such as senior fatty acid amide such as erucyl amide and oleamide, stearic acid and salt thereof etc.
As anti blocking agent, can use the spherical or intimate spherical shape of microparticles of inorganic system or organic system.
In above illustrative adjuvant, when illustration can not damaged the adjuvant of the preferred use of the deterioration of polypropylene-based resin in the manufacturing process that effect of the present invention ground suppresses the polypropylene-based resin film, can enumerate: antioxidants such as " Irgafos P168 ", " Irganox 1076 " of " the Sumilizer GP " that sumitomo chemical company is sold, the sale of vapour Bagong department, " Irganox 1010 "; Reach neutralizing agents such as hydrotalcite, calcium hydroxide, magnesium hydroxide etc.In the polypropylene-based resin film, the preferred addition of antioxidant is below the above 2 weight % of 0.01 weight %, and the preferred addition of neutralizing agent is below the above 0.01 weight % of 0.001 weight %.
Above-mentioned nucleator can for inorganic be in nucleator, the organic system nucleator any.As inorganic be nucleator, can enumerate: talcum, clay, lime carbonate etc.In addition, as the organic system nucleator, can enumerate: metallic salts such as the metallic salt of aromatic carboxylic acid, the metallic salt of aromatic phosphoric acid, high density polyethylene, poly--3-methyl butene-1, poly-cyclopentene, polyvinyl eyclohexane etc.Wherein, preferred organic nuclear agent, more preferably above-mentioned metallic salt and high density polyethylene of being tied to form.The addition of the nucleator in the polypropylene-based resin film is preferably 0.01～3 weight %, more preferably 0.05～1.5 weight %.
The polypropylene-based resin film that contains ultraviolet light absorber can utilize that melt extruding is shaped makes, describedly melt extrude in the shaping, after ultraviolet light absorber and the resin that is combined with other adjuvant as required being carried out melting mixing with extruder, from the T mould, extrude, cool off with chill roll.At this, the method as with polypropylene-based resin and ultraviolet light absorber input extruder, can adopt following method:
The method that [i] drops into the form that particle or pulverous polypropylene-based resin and ultraviolet light absorber is pre-mixed into the polypropylene-based resin potpourri of regulation ratio of components,
[ii] in the hopper of extruder, while respectively with feed screw or weight charger etc. with particle or pulverous polypropylene-based resin and ultraviolet light absorber measure the method that drops into respectively,
[iii] prepares the polypropylene-based resin particle (masterbatch) that contains this ultraviolet light absorber with the concentration higher than the amount of the ultraviolet light absorber that should contain in the polypropylene-based resin film earlier in addition, after this masterbatch and polypropylene-based resin thought that the mode of target UVA agent concentration is mixed, drop into extruder method,
[iv] is in the hopper of extruder, Yi Bian Yi Bian the in addition masterbatch of preparation and the method that the polypropylene-based resin particle drops into respectively etc. of metering respectively.In these methods, when using the mode of [iii], the excellent dispersion of ultraviolet light absorber in the polypropylene-based resin film, and production efficiency is also excellent, and therefore preferred.
In melt extruding shaping, in order to make more high-qualityization of the polypropylene-based resin film that obtains, can between extruder and T mould, be provided for suppressing the gear-type pump of extrusion capacity variation or the filter unit (for example video disc type filter) that filtering accuracy is 2～10 μ m, remove impurity.Need to prove that in order to prevent the oxidative degradation of resin, the melting mixing that utilizes extruder to carry out preferably carries out under atmosphere of inert gases.As inert gas, can use nitrogen (N 2), argon gas (Ar), helium (He), neon (Ne) etc., consider preferred nitrogen (N from the operating cost aspect 2).The purity of inert gas is preferably more than the 99.8 volume %, more preferably more than the 99.9 volume %.In addition, consider that from preventing the viewpoint that oxidative degradation prevents the polypropylene-based resin of putting in the extruder (being generally particle) preferably fully keeps in advance in atmosphere of inert gases.
Polypropylene-based resin film preferably clear excellence, particularly, the haze value of measuring based on JIS K 7136 is preferably 0～5%.Haze value surpasses at 5% o'clock, is assembled with the contrast of LCD degree variation of polarization plates of the present invention sometimes.The haze value of polypropylene-based resin film more preferably 0～3%.
For the haze value that makes the polypropylene-based resin film in above-mentioned scope, also depend on the process velocity that melt extrudes when being shaped and the diameter of chill roll, but in utilizing the cooling procedure of chill roll, preferably the temperature with described chill roll is set at below 30 ℃, and the polypropylene-based resin of the fusion sheet extruded is cooled off fast.At this moment, the method for fusion sheet polypropylene-based resin driving fit on chill roll extruded exerted an influence to the haze value of the polypropylene-based resin film that obtains sometimes.When enumerating the preferred form that makes the method for fusion sheet polypropylene-based resin driving fit on chill roll, following method is for example arranged:
A) give static to fusion sheet polypropylene-based resin, to make its driving fit be on the chill roll of minute surface in surface state and the method for cooling,
B) fusion sheet polypropylene-based resin is clamped between the metallic roll or metal tape of the elastically deformable that chill roll that surface state is a minute surface and surface state be minute surface, make its driving fit on chill roll and the method for cooling,
C) making fusion sheet polypropylene-based resin is on the semilustrous chill roll and the method etc. of cooling with the driving fit of air bag method in surface state.
In the said method, c) using the adhesion method of air bag method is being favourable aspect the bonding strength of polypropylene-based resin film and polarizing coating.
Above-mentioned c) air bag method is to along sending into air and utilize static air pressure to make the method for film driving fit on chill roll in the air bag of the film contact point setting of chill roll.In the air bag method, cave in (neck in) or guarantee the stability of ear for the ear that prevents film, preferably use ear that air nozzle makes film than other position earlier driving fit on chill roll.Also can replace air nozzle, use the nozzle that does not make the Electrostatic Absorption mode of its driving fit on chill roll by static by air.
Pressure in the air bag is preferably below the 300Pa, more preferably below the 200Pa.When surpassing 300Pa, air flows out to outside the air bag, make the fusion sheet polypropylene-based resin swing of extruding, thereby the thickness and precision of film may reduce.
The chill roll that uses in the air bag method is not a mirror roller, is preferably semilustrous chill roll.Particularly, surfaceness (the maximum height R based on JIS B 0601 of chill roll Max) be preferably 0.5～2 μ m, more preferably 0.8～1.5 μ m.Surfaceness (R Max) during less than 0.5 μ m, enter between fusion sheet polypropylene-based resin and the chill roll under the situation of air, this air does not leak, and therefore, produces concavo-convexly on polypropylene-based resin film surface, may cause bad order.In addition, surfaceness (R Max) when surpassing 2 μ m,, on chill roll, the concavo-convex of chill roll surface is transferred on the polypropylene-based resin film surface by driving fit, same, may cause bad order.In addition, consider that from the surfaceness of the polypropylene-based resin film that obtains and the viewpoint of the transparency surface state of chill roll is preferably pears skin shape.
The thickness of polypropylene-based resin film is preferably about 3～200 μ m, more preferably 10 μ m～below the 150 μ m.In addition, its thickness and precision preferably is respectively central value ± below 5% at the flow direction of film and Width, more preferably central value ± below 3%.
(2) norbornene resin film
The above-mentioned norbornene resin film that uses in is preferred embodiment served as reasons and is contained from norborene, encircles the film that the thermoplastic resin of the formation unit of cycloolefin (cyclic olefin) such as norborneol alkene monomer constitutes more.The norbornene resin film be except that can and using the hydride of ring opening copolymer thing of cycloolefin more than 2 kinds for the hydride of the ring-opening polymerization polymer of above-mentioned cycloolefin, can also and/or have the addition copolymer of the aromatics etc. of vinyl for cycloolefin and chain alkene.In addition, the polymkeric substance of importing polar group also is effective.
When using cycloolefin and chain alkene and/or having the multipolymer of aromatics of vinyl, as chain alkene, can enumerate ethene, propylene etc., in addition, as aromatics, can enumerate: the styrene that styrene, α-Jia Jibenyixi, nuclear are replaced by alkyl etc. with vinyl.In such multipolymer, can (be preferably 15～50 moles of %) below the % for 50 moles from the content of the formation unit of cycloolefin.In particular for cycloolefin and chain alkene with when having the terpolymer of aromatics of vinyl, can be made as less amount as mentioned above from the formation unit of cycloolefin.In this terpolymer, be generally 5～80 moles of % from the content of the formation unit of chain alkene, be generally 5～80 moles of % from the content of the formation unit of aromatics with vinyl.
As norbornene resin, can preferably use suitable commercially available product, for example " Topas " (Topas Advanced Polymers GmbH corporate system), " ARTON " (JSR (strain) system), " ZEONOR " (Japanese Zeon (strain) system), " ZEONEX " (Japanese Zeon (strain) system), " Apel " (Mitsui Chemicals (strain) system) etc.When such norbornene resin is made film, preferably use the solvent cast method, melt extrude known method such as forming process.In addition, also for example can use " Escena " (ponding chemical industry (strain) system), " SCA40 " (ponding chemical industry (strain) system), " ZEONOR film " (Japanese Zeon (strain) system), " ARTON film " (JSR (strain) system) etc. to make the commercially available product of the norbornene resin film of film.
The optical compensation that the norbornene resin film can be given liquid crystal by stretching at least one direction can (viewing angle compensation function) thereby is formed phase retardation film.Be used for liquid crystal indicator by the polarization plates that will possess such stretching norbornene resin film, can realize that the visual angle of liquid crystal indicator enlarges.As the norbornene resin film of phase retardation film preferably in the face of film the refractive index of slow-axis direction be made as n x, will be in face perpendicular crossing direction (quick shaft direction) refractive index be made as n y, and the refractive index of thickness direction be made as n z, film thickness when being made as d, phase difference value R in the face of the film of following formula (I) expression 040～100nm (more preferably in 40～80nm) the scope, and, the thickness direction phase difference value R of following formula (II) expression ThBe that 80～300nm is (more preferably in 100～250nm) the scope.
R 0＝(n x-n y)×d (I)
R th＝[(n x+n y)/2-n z]×d (II)
Phase difference value R in the face 0During less than 40nm or when surpassing 100nm, the viewing angle compensation function of polarization plates has the tendency of reduction.In addition, thickness direction phase difference value R ThDuring less than 80nm or when surpassing 300nm, the viewing angle compensation ability of polarization plates still has the tendency of reduction.Need to prove phase difference value R in the face 0And thickness direction phase difference value R ThCan use for example " KOBRA 21ADH " (prince's instrumentation machine (strain) system) mensuration.
In order to obtain having as above-mentioned formula (I) and the norbornene resin film of the refractive index characteristic (II), except that suitably regulating stretching ratio and draw speed, all temps and temperature setting program figure thereof such as the preheat temperature when suitably selecting to stretch, draft temperature, heat-set temperature, chilling temperature.By under slow condition, stretching, obtain aforesaid refractive index characteristic.Stretching ratio for example is preferably the scope below 1.6 times more than 1.05 times, more preferably more than 1.1 times below 1.5 times.Under biaxial stretch-formed situation, the stretching ratio of maximum tension direction is that above-mentioned scope gets final product.
The thickness of having implemented the norbornene resin film that stretches is preferably in the scope of 20～80 μ m, more preferably in the scope of 40～80 μ m.This be because, the thickness of stretching norbornene resin film is during less than 20 μ m, has the processing of film to become difficult or is difficult to the tendency of the phase difference value that obtains to stipulate.On the other hand, when the thickness of norbornene resin film surpassed 80 μ m, the processability variation in addition, may cause the weight of the polarization plates that the transparency reduces, obtains to become situation such as big.
(bond layer)
As being used for above-mentioned transparent resin film is fitted in bonding agent on the polarizing coating, from the thin viewpoint of bond layer is considered, can be enumerated the water system bonding agent be the bonding agent composition be dissolved in the water gained bonding agent or be dispersed in bonding agent, and the Photocurable adhesive agent that solidifies by the irradiation active energy beam etc. of gained in the water.Wherein, consider, preferably use Photocurable adhesive agent from the viewpoint of the bonding strength between transparent resin film and the polarizing coating.The fit bonding agent of another transparent resin film of the bonding agent and being used to of a transparent resin film of being used to fit can be bonding agent of the same race, also can plant bonding agent for difference.
As Photocurable adhesive agent, for example preferred composition epoxy resin that contains photo-curable photoreactive epoxy resin cationic polymerization initiators that uses.This composition epoxy resin is extremely effective improving transparent resin film, particularly the polypropylene-based resin film of the above-mentioned ultraviolet light absorber that contains regulation and the bonding strength of polarizing coating.
As photo-curable epoxy resin, for example can preferably use the alicyclic epoxy compound, can enumerate: 3,4-epoxycyclohexyl methyl-3, the 4-epoxycyclohexane carboxylate, 1,2-epoxy-4-vinyl cyclohexane, 1,2-epoxy-1-methyl-4-(1-methyl epoxy ethyl) cyclohexane, 3,4-epoxycyclohexyl methyl acrylate, 2, the 4-(1, the 2-epoxy ethyl)-1 of two (the methylol)-1-butanols of 2-, 2-7-oxa-bicyclo[4.1.0 addition product, ethylenebis (3, the 4-epoxycyclohexane carboxylate), oxo di ethylene bis (3, the 4-epoxycyclohexane carboxylate), 1,4-cyclohexane dimethyl-two (3, the 4-epoxycyclohexane carboxylate), 3-(3,4-epoxycyclohexyl methoxycarbonyl) propyl group-3,4-epoxycyclohexane carboxylate etc.
As the photo-curable epoxy compound beyond the alicyclic epoxy compound, for example can enumerate: have the glycidyl etherificate thing of the aromatics of hydroxyl or chain compound, glycidyl-amino thing, epoxide, and their oligomer etc. with chain compound of the two keys of C-C with amino compound.Photo-curable epoxy compound beyond these alicyclic epoxy compounds and the alicyclic epoxy compound can be distinguished use separately, and also two or more kinds may be used.
In addition, Photocurable adhesive agent also can contain the oxetane compound as the active energy ray-curable compound beyond the photo-curable epoxy resin.By also using oxetane compound, the curing rate of Photocurable adhesive agent is improved.
The light cationic polymerization initiators can produce kation kind or lewis acid by irradiation luminous ray, ultraviolet ray, X ray or electron beam isoreactivity energy-ray, thereby causes the polyreaction of epoxy radicals.
As producing kation kind or lewis acidic compound by the irradiation active energy beam, be not particularly limited, for example can enumerate: the aromatic series diazo salt; The salt of aromatic series salt compounded of iodine and aromatic series sulfonium salt and so on; And iron-aromatic hydrocarbons complex compound etc.
As the aromatic series diazo salt, for example can enumerate: benzene diazonium hexafluoro antimonate, benzene diazonium hexafluorophosphate, benzene diazonium hexafluoro borate etc.
As the aromatic series salt compounded of iodine, for example can enumerate: diphenyl iodine four (pentafluorophenyl group) borate, diphenyl iodine hexafluorophosphate, diphenyl iodine hexafluoro antimonate, two (4-nonyl phenyl) iodine hexafluorophosphate etc.
As the aromatic series sulfonium salt; for example can enumerate: the triphenylsulfonium hexafluorophosphate; the triphenylsulfonium hexafluoro antimonate; triphenylsulfonium four (pentafluorophenyl group) borate; diphenyl [4-(phenyl sulphur) phenyl] sulfonium hexafluoro antimonate; 4; the two hexafluorophosphates of 4 '-two [diphenyl sulfonium base] diphenyl sulfide; 4; the two hexafluoro antimonates of 4 '-two [two (beta-hydroxy ethoxy) phenyl sulfonium base] diphenyl sulfide; the two hexafluorophosphates of 4,4 '-two [two (beta-hydroxy ethoxy) phenyl sulfonium base] diphenyl sulfide; 7-[two (toluoyl base) sulfonium base]-2-isopropyl thioxanthone hexafluoro antimonate; 7-[two (toluoyl base) sulfonium base]-2-isopropyl thioxanthone four (pentafluorophenyl group) borate; 4-phenylcarbonyl group-4 '-diphenyl sulfonium base-diphenyl sulfide hexafluorophosphate; 4-(to the tert-butyl-phenyl carbonyl)-4 '-diphenyl sulfonium base-diphenyl sulfide hexafluoro antimonate; 4-(to the tert-butyl-phenyl carbonyl)-4 '-two (toluoyl base) sulfonium base-diphenyl sulfide four (pentafluorophenyl group) borates etc.
As iron-aromatic hydrocarbons complex compound, for example can enumerate: dimethylbenzene-cyclopentadienyl group iron (II) hexafluoro antimonate, cumyl-cyclopentadienyl group iron (II) hexafluorophosphate, dimethylbenzene-cyclopentadienyl group iron (II)-three (trifluoromethyl sulfonyl) methanides etc.
These light cationic polymerization initiators can be distinguished use separately, also can mix more than 2 kinds and use.Wherein, the wavelength coverage of aromatic series sulfonium salt more than 300nm also has the UVA characteristic, the bond layer that can obtain the curable excellence, have excellent mechanical intensity and bonding strength, therefore preferred the use.
The use level of light cationic polymerization initiators is generally 0.5～20 weight portion with respect to photo-curable epoxy resin isoreactivity energy ray-curable compound 100 weight portions contained in the Photocurable adhesive agent, is preferably 1～15 weight portion.When use level was lower than 0.5 weight portion, curing became insufficient, and the physical strength of bond layer and bonding strength reduce sometimes.In addition, when use level surpassed 20 weight portions, the ionic substance in the bond layer increased, thereby the hydroscopicity of bond layer uprises, and the endurance quality of the polarization plates that obtains sometimes reduces.
Photocurable adhesive agent can contain photosensitizer as required.By using photosensitizer, the reactive raising can further be improved the physical strength and the bonding strength of bond layer.
As photosensitizer, for example can enumerate: carbonyls, organosulfur compound, persulfide, redox based compound, azo and diazo-compounds, halogen compounds and photo-reduction pigment etc.
When enumerating the example of concrete photosensitizer, have: benzoin methyl ether, benzoin isopropyl ether, α, alpha, alpha-dimethyl oxygen base-α-benzoin derivatives such as phenyl acetophenone; Benzophenone, 2,4-dichloro benzophenone, o-benzoyl yl benzoic acid methyl esters, 4,4 '-two (dimethylamino) benzophenone, 4,4 '-benzophenone derivates such as two (diethylamino) benzophenone; Anthraquinone derivatives such as 2-chloroanthraquinone, 2-methylanthraquinone; Acridone derivativeses such as N-methylacridine ketone, N-butyl acridone; α, acetophenone derivs such as α-diethoxy acetophenone; The xanthone derivant; Fluorenone derivatives; 9, anthracene compounds such as 10-dibutoxy anthracene; Thio-xanthene-one derivants such as 2-chlorine thio-xanthene-one, 2-isopropyl thioxanthone; The benzil compound; Uranyl compound etc.
Photosensitizer can only use a kind, and also two or more kinds may be used.The use level of photosensitizer is 0.1～20 weight portion with respect to active energy ray-curable compound 100 weight portions contained in the Photocurable adhesive agent preferably.
On the other hand, as the preferred example of above-mentioned water system bonding agent, for example can enumerate: comprise polyvinyl alcohol resin or ammonia ester resin adhesive composite as major component.
Major component as bonding agent; when using polyvinyl alcohol resin; this polyvinyl alcohol resin can also be a resin for modified polyvinylalcohols such as carboxy-modified polyvinyl alcohol (PVA), acetoacetyl modified polyvinylalcohol, methylol modified polyvinylalcohol, amino modified polyvinyl alcohol (PVA) except that being partly-hydrolysed polyvinyl alcohol (PVA), the fully saponified polyvinyl alcohol (PVA).Be generally aqueous solution with polyvinyl alcohol resin as the water system bonding agent of major component.The concentration of the polyvinyl alcohol resin in the bonding agent is generally 1～10 weight portion with respect to water 100 weight portions, is preferably 1～5 weight portion.
In addition, as the major component of bonding agent, when using ammonia ester resin, as the example of the adhesive composite that is fit to, can enumerate: comprising polyester is ionomer type ammonia ester resin and the adhesive composite with compound of glycidoxy.Here said polyester is that ionomer type ammonia ester resin is the ammonia ester resin with polyester backbone, and wherein a small amount of the importing has ionic composition (hydrophilic component).This ionomer type ammonia ester resin do not use emulsifying agent and directly in water emulsification form emulsion, therefore, be preferably used as the water system bonding agent.
Polyester is that ionomer type ammonia ester resin itself is exactly known, for example in Japanese kokai publication hei 7-97504 communique, put down in writing and be used for making phenol resin to be dispersed in the example of the macromolecule dispersing agent of aqueous medium, in TOHKEMY 2005-70140 communique and TOHKEMY 2005-208456 communique, disclose with comprise polyester be ionomer type ammonia ester resin and compound compositions with glycidoxy as bonding agent, the form of adapter ring ethylene series resin molding on the polarizing coating that forms by polyvinyl alcohol resin.
As using on polarizing coating, the fit method of above-mentioned transparent resin film of bonding agent, usually can be general known method, for example can enumerate: be coated with the methods that coating adhesive overlaps both on the bonding plane of polarizing coating and/or transparent resin film such as method, dip coated method, spray-on process with The tape casting, line rod rubbing method, intaglio plate rubbing method, unfilled corner wheel rubbing method, scraper rubbing method, mould.The tape casting be make applied thing be film in an approximate vertical direction, general horizontal direction or the method that makes bonding agent flow down and spread when being between the two oblique mobile on its surface.Behind the coating adhesive, make the two applying with clamping polarizing coatings such as roll and transparent resin film.In addition, can after dripping bonding agent between polarizing coating and the transparent resin film, evenly push diffusion, carry out the applying of film, under this situation,, can use metal and rubber etc. as the material of roller with pressurizations such as rollers.In addition, also can make it by between roller and the roller after dripping bonding agent between polarizing coating and the transparent resin film, diffusion be evenly pushed in pressurization, carries out the applying of film, and under this situation, the material that these rollers can be identical also can be different materials.
Need to prove, on the bonding agent coated face of transparent resin film or the surface of bond layer, in order to improve cementability, can before fitting, implement surface treatments such as Cement Composite Treated by Plasma, corona treatment, ultraviolet treatment with irradiation, flame treatment, saponification processing with polarizing coating.Handle as saponification, can enumerate the method in the aqueous solution of the alkali that is immersed in NaOH or potassium hydroxide and so on.
Also can behind the stacked transparent resin film, implement heat treated via bond layer on the two sides of polarizing coating.Heat treated is undertaken by for example blowing hot blast, and its temperature is usually in 40～100 ℃ scope, preferably in 60～100 ℃ scope.In addition, be generally 20～1200 seconds drying time.
Dry water system bonding agent and the thickness of the bond layer that obtains is generally about 0.01～5 μ m is preferably below the 2 μ m, more preferably below the 1 μ m.The thickness of bond layer is during less than 0.01 μ m, bonding may be insufficient, in addition, when the thickness of bond layer surpasses 5 μ m, may produce the bad order of polarization plates.
As bonding agent, when using Photocurable adhesive agent, behind the stacked transparent resin film, shine active energy beam via bond layer on the two sides of polarizing coating, bond layer is solidified.The light source of active energy beam is not particularly limited, the active energy beam that preferably below wavelength 400nm, has luminescence distribution, particularly, preferred lower pressure mercury vapor lamp, middle medium pressure mercury lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, chemical lamp, black lamp etc., microwave-excitation mercury vapor lamp, metal halide lamp etc.
The rayed intensity of active energy beam suitably determines according to the composition of Photocurable adhesive agent, be not particularly limited, to the exposure intensity of the effective wavelength coverage of activation of light cationic polymerization initiators preferably at 0.1～6000mW/cm 2Scope in.Rayed intensity is by being 0.1mW/cm 2More than, the reaction time can be not long, by being 6000mW/cm 2Below, the epoxy resin xanthochromia that the heating when being solidified by the heat of radiation of light source and Photocurable adhesive agent causes and the possibility of polarizing coating deterioration are little.The rayed time to Photocurable adhesive agent is controlled according to each Photocurable adhesive agent, be not particularly limited, preferably with the accumulation light quantity of the product representation of above-mentioned rayed intensity and irradiation time at 10～10000mJ/m 2Scope in mode set.The accumulation light quantity is by being 10mJ/m 2More than, can produce the spike from the light cationic polymerization initiators of q.s, can be cured reaction more reliably, in addition, by being 10000mJ/m 2Below, it is long that irradiation time can not become, and can keep good throughput rate.
Preferably under the condition that the various functions of the polarization plates such as the transparency of degree of polarization, transmissivity and the form and aspect of polarizing coating and transparent resin film do not reduce, carry out the irradiation of active energy beam.When using Photocurable adhesive agent, the thickness of the bond layer after the curing is generally about 0.01～10 μ m, is preferably more than the 0.1 μ m, is preferably simultaneously below the 5 μ m.
(other parts)
Polarization plates of the present invention can have and is layered in an adhesive phase on the transparent resin film.This adhesive phase for example can be preferred for the applying with liquid crystal cells when polarization plates is used for liquid crystal indicator.Fit at face of polarizing coating contain the polypropylene-based resin film of ultraviolet light absorber, during at another side applying norbornene resin film, when particularly the norbornene resin film was phase retardation film, usually, adhesive phase was layered on the norbornene resin film.
As the bonding agent that is used for adhesive phase, can be not particularly limited to use known in the past suitable bonding agent, for example can enumerate: acrylic adhesive, ammonia ester are bonding agent, silicone-based adhesive etc.Wherein, consider, preferably use acrylic adhesive from viewpoints such as the transparency, bounding force, reliability, reappearances.Adhesive phase is being coated with by mould on the transparent resin film or coating such as intaglio plate coating contains the solution of bonding agent and makes its dry method setting except that utilizing, and also can utilize will be formed at the adhesive phase of having implemented on the plastic foil (being called separation membrane) that the demoulding handles and be transferred to method setting on the transparent resin film.The thickness of adhesive phase is preferred usually in the scope of 2～40 μ m.
Polarization plates of the present invention can go up at transparent resin film (for example norbornene resin film or polypropylene-based resin film) possesses other optical functional film by adhesive phase.As the example that can preferably stick on the optical functional film on the transparent resin film that becomes liquid crystal cell side, can enumerate the optical compensation films in substrate surface coating fluid crystallinity compound and orientation, the phase retardation film that forms by transparent resins such as polycarbonate-based resins etc.As can preferably sticking on the example that becomes apart from the liquid crystal cells of rear side polarization plates, can enumerate reflective polarizing film that certain polarized light of transmission and reflection show the polarized light of the character opposite with it, reflectance coating that the surface has reflection function, have a Transflective film etc. of reflection function and transmission function simultaneously than the optical functional film on the transparent resin film of distally (being the backlight side).
As with substrate surface coating fluid crystallinity compound and the orientation the suitable commercially available product of optical compensation films, can enumerate: " WV film " (FUJIFILM (strain) system), " NH film " (Nippon Oil(Nippon Mitsubishi Oil) (strain) system), " LC film " (Nippon Oil(Nippon Mitsubishi Oil) (strain) system) etc.As showing the suitable commercially available product of reflective polarizing film of the polarized light of opposite character, for example can enumerate: " DBEF " (3M corporate system, can from SUMITOMO CHEMICAL 3M (strain) acquisition) etc. with it with certain polarized light of transmission and reflection.
＜liquid crystal indicator 〉
Polarization plates of the present invention can be preferred for liquid crystal indicator.In liquid crystal indicator, polarization plates of the present invention can be configured in the rear side of liquid crystal panel by adhesive phase.At this moment, polarization plates of the present invention is than the distally, promptly dispose with the opposed mode of backlight apart from liquid crystal cells with the described polypropylene-based resin film that contains ultraviolet light absorber.This liquid crystal indicator uses polarization plates of the present invention, therefore, and excellent in te pins of durability, the excellent in stability of display performance simultaneously.In liquid crystal indicator, for the part beyond the above-mentioned feature, can adopt the formation that is fit to of known liquid crystal indicator in the past, liquid crystal indicator can suitably possess the component parts (light diffusing sheet, backlight etc.) that possesses usually except liquid crystal panel.Need to prove, the backlight side when " rear side " of liquid crystal panel is meant liquid crystal panel is equipped on liquid crystal indicator, on the other hand, the identification side when " front face side " of liquid crystal panel is meant liquid crystal panel is equipped on liquid crystal indicator.
The polarization plates (hereinafter referred to as the front face side polarization plates) that is arranged on the front face side of liquid crystal panel can be used known in the past suitable polarization plates, wherein, consider from display characteristic aspects such as contrast of LCD degree and visual angles, preferred use a face of the polarizing coating that forms by polyvinyl alcohol resin fit cellulose-based resin molding, be the polarization plates of 0.1～40% polyethylene terephthalate film at another side applying haze value.This polarization plates preferably with the opposed mode of the liquid crystal cells cellulose-based resin molding side of fitting.The engineering properties of polyethylene terephthalate film, solvent resistance, scratch-resistant, cost etc. are all excellent.
The polarizing coating of front face side polarization plates can use and the identical polarizing coating of the described polarizing coating of the polarization plates of the invention described above.
The polyethylene terephthalate that constitutes the polyethylene terephthalate film of front face side polarization plates is the above resins that are made of ethylene glycol terephthalate of 80 moles of % of repetitive.As other copolymer composition, can enumerate: m-phthalic acid, 4,4 '-dicarboxylate biphenyl, 4,4 '-benzophenonedicarboxylic acid, two (4-carboxyl phenyl) ethane, hexane diacid, decanedioic acid, 5-sulfo-m-phthalic acid sodium, 1, dicarboxylic acid compositions such as 4-dicarboxyl cyclohexane; Diol components such as the ethylene oxide adduct of propylene glycol, butylene glycol, neopentyl glycol, diethylene glycol, cyclohexanediol, bisphenol-A, polyglycol, polypropylene glycol, PolyTHF.These dicarboxylic acid compositions and diol component can be used in combination more than 2 kinds as required.In addition, also can together also use P-hydroxybenzoic acid, right-hydroxycarboxylic acids such as beta-hydroxy ethoxybenzoic acid with above-mentioned dicarboxylic acid composition and diol component.Other copolymer composition so also can comprise the compound with a spot of amido link, ammonia ester bond, ehter bond, carbonic acid ester bond etc.
As the manufacture method of polyethylene terephthalate, can use direct direct polymerization, the dimethyl ester of terephthalic acid (TPA) and the ester exchange reaction method that ethylene glycol carries out ester exchange reaction etc. of reacting of terephthalic acid (TPA) and ethylene glycol manufacture method arbitrarily.In addition, in polyethylene terephthalate, as required, can contain known adjuvant.For example, can contain lubricant, anti blocking agent, thermal stabilizer, antioxidant, antistatic agent, photostabilizer, resistance to impact modifying agent etc.Wherein, consider that from the viewpoint of the transparency of film the addition of adjuvant is preferably irreducible minimum.
The polyethylene terephthalate film is preferably the film that stretched, and it can be by being configured as above-mentioned polyethylene terephthalate membranaceous and implementing stretch processing and make.Stretching can utilize along the uniaxial tension of MD (membrane flow direction) or TD (direction vertical with the membrane flow direction) stretching, not carry out along any methods such as oblique extension biaxial stretch-formed, that neither also do not stretch along the TD direction along MD of MD and the stretching of TD both direction.By implementing this stretched operation, can obtain the high polyethylene terephthalate film of physical strength.Wherein, the polyethylene terephthalate film of uniaxial tension is difficult for producing in liquid crystal indicator interferes inequality, therefore preferred.
The method for making of the polyethylene terephthalate film of uniaxial tension is arbitrarily, be not particularly limited, can enumerate with make above-mentioned polyethylene terephthalate fusion and extrusion molding be sheet no alignment films under the temperature more than the glass temperature with stenter cross directional stretch (stretching) along the TD direction after, implement the method that heat fixation is handled.Draft temperature is preferably 80～130 ℃, more preferably 90～120 ℃.Stretching ratio is preferably 2.5～6 times, more preferably 3～5.5 times.When stretching ratio hanged down, the polyethylene terephthalate film had the tendency that does not show the sufficient transparency.When biaxial stretch-formed, for example can enumerate following method: with extrusion molding is the no alignment films of sheet longitudinal stretching (stretching along the MD direction), the then method of cross directional stretch (stretching along the TD direction) under the temperature more than the glass temperature; And simultaneously longitudinally with the method for cross directional stretch etc.
Need to prove, consider that from the viewpoint of the deflection of the orientation main shaft that reduces the polyethylene terephthalate film relaxation processes is implemented in the preferred back that stretches.For example, can enumerate when making monadic stretching membrane, behind the cross directional stretch and carry out heat fixation and film is carried out the method for relaxation processes along its length before handling by above-mentioned cross directional stretch.Temperature during relaxation processes is 90～200 ℃, is preferably 120～180 ℃.Slack is according to stretching condition and difference, is that mode below 2% is set slack and temperature with the percent thermal shrinkage 150 ℃ time of the film after the relaxation processes preferably.
The temperature that heat fixation is handled is generally 180～250 ℃, is preferably 200～245 ℃.Heat fixation is handled and preferably at first to be handled under said temperature with fixed length and then carry out relaxation processes in the mode that the lax ratio of the Width of film reaches 1～10% (being preferably 2～5%).Thus, can reduce the deflection of orientation main shaft, obtain the polyethylene terephthalate film of the stretching of excellent heat resistance.
The maximal value of the orientation main shaft deflection of polyethylene terephthalate film is preferably below 10 degree, more preferably below 8 degree, more preferably below 5 degree.When using the maximal value that is orientated the main shaft deflection to surpass the polyethylene terephthalate film of 10 degree, in the time of in the liquid crystal indicator of the polarization plates of using such polyethylene terephthalate film, there is the big tendency of painted bad change.Need to prove that the maximal value of the orientation main shaft deflection of polyethylene terephthalate film for example can use phase retardation film testing fixture " RETS system " (big tomb electronics (strain) system) to measure.
The thickness of polyethylene terephthalate film is considered from the viewpoint of the thin-walled property of the processing of film and polarization plates, is preferably 20～50 μ m.
The haze value of polyethylene terephthalate film is preferably in 0.1～40% scope.Haze value can not fully suppress the interference inequality of liquid crystal indicator less than 0.1% o'clock.In addition, haze value surpasses at 40% o'clock, and light spread strong, and there are the tendency that reduces in the front face brightness of liquid crystal indicator and identification.Need to prove that defined among the haze value of polyethylene terephthalate film such as the JIS K 7136 with the ratio definition of diffusion transmitance with total light penetration, can use commercially available mist degree measuring instrument to measure.
As the method for giving mist degree, can enumerate the polyethylene terephthalate film: in polyethylene terephthalate, mix inorganic particles or organic fine particles method, inorganic particles or organic fine particles are mixed in the method etc. of the coating fluid of gained in the resinoid bond in polyethylene terephthalate film surface coated.As inorganic particles, can enumerate: silicon dioxide, cataloid, aluminium oxide, alumina sol, alumina silicate, aluminium oxide-silicon oxide composite oxides, porcelain earth, talcum, mica, lime carbonate, calcium phosphate etc.As organic fine particles, can enumerate: heat-resistant resin particles such as crosslinked polypropylene acid particles, crosslinked polystyrene particle, crosslinked polymethylmethacrylaparticles particle, silicone resin particle, polyimide particle.
Phase difference value R in the preferred face of polyethylene terephthalate film 0More than 1000nm, more preferably more than the 3000nm.Phase difference value R in the face 0During less than 1000nm, from the interference inequality in the front of the liquid crystal indicator more significantly tendency that becomes.Phase difference value R in the face of polyethylene terephthalate film 0On be limited to about 10000nm.
Can on the polyethylene terephthalate film, give easy adhesive linkage.The polyethylene terephthalate film of having given easy adhesive linkage can utilize following method to make; On the film of all stretching process that is through with, form the method for easy adhesive linkage; In the operation of stretching polyethylene terephthalate, for example between longitudinal stretching operation and cross directional stretch operation, form the method for easy adhesive linkage; Before bonding with polarizing coating or bonding back form the method etc. of easy adhesive linkage.When making biaxially-stretched film, consider, preferably adopt the method that after the polyethylene terephthalate film is carried out longitudinal stretching, forms easy adhesive linkage and proceed cross directional stretch from the viewpoint of throughput rate.Can give easy adhesive linkage on the two sides of polyethylene terephthalate film or give easy adhesive linkage via a bonding face of bond layer and polarizing coating.
The composition that constitutes easy adhesive linkage is not particularly limited, and for example can enumerate: having polyester based resin, the ammonia ester that polar group and molecular weight are lower, glass temperature is also lower on the skeleton is resin or acrylic resin etc.In addition, as required, also can contain crosslinking chemical, organic or inorganic filler, surfactant, lubricant etc.
On the face of the opposition side of the face of fitting with polarizing coating of polyethylene terephthalate film, can implement non-glare treated, rod is coated with surface treatments such as processing, electrostatic prevention processing.In addition, also can form the coating layer that forms by liquid crystal compounds and high-molecular weight compounds etc. thereof.Need to prove, replace the polyethylene terephthalate film and use poly (ethylene naphthalate) film also can obtain much at one effect.
The cellulose-based resin molding that can be used for the front face side polarization plates is by cellulosic partial esterification thing or the complete film that forms of carboxylate, for example can enumerate: cellulosic acetate, propionic ester, butyric ester, their film of formation such as mixed ester.More specifically, can enumerate: three cellulose acetate membrane, cellulose diacetate film, cellulose ethanoate propionic ester film, cellulose acetate butyrate film etc.As such cellulose ester membrane, can use suitable commercially available product, for example " Fujitac TD80 " (FUJIFILM (strain) system), " Fujitac TD80UF " (FUJIFILM (strain) system), " Fujitac TD80UZ " (FUJIFILM (strain) system), " KC8UX2M " (Konicaminolta (strain) system), " KC8U Y " (Konicaminolta (strain) system) etc.
Be used for the bonding agent that polyethylene terephthalate film, cellulose-based resin molding are fitted on the polarizing coating can be above-mentioned Photocurable adhesive agent or water system bonding agent.
Example
The present invention will be described in more detail below to enumerate embodiment, but the present invention is not limited to these embodiment.The evaluation of the mensuration of the phase difference value of film, the moisture-vapor transmission 40 ℃ time the and transmittance and the bonding strength of polarization plates can be carried out according to method shown below.
[mensuration of phase difference value]
Use measuring difference of phases device " KOBRA-WR " (prince's instrumentation machine (strain) system) under mensuration wavelength 590nm, to measure.
[mensuration of moisture-vapor transmission]
According to JIS Z 0208, under the condition of 40 ℃ of temperature, relative humidity 90%, measure, with every 1m 2Membrane area amount of moisture by this film in 24 hours is calculated.
[mensuration of transmittance]
Use the ultraviolet-visible pectrophotometer " UV-2450 " of (strain) Shimadzu Seisakusho Ltd. system, after the polypropylene-based resin film being determined at the optical transmission rate of the every 1nm of scope of wavelength 220～700nm, with the mxm. in the transmissivity of each wavelength between wavelength 300～340nm as transmittance.This value is more little, show blocking-up wavelength 300～340nm light, be that ultraviolet resistance is excellent more.
[evaluation of bonding strength]
By adjusting the dispensing area of bonding agent on the polypropylene-based resin film, make between polypropylene-based resin film and the polarizing coating, be the end to the zone of length direction 20mm be the polarization plates in the zone of uncoated bonding agent, be cut into Width 25mm * length direction 150mm (among this 150mm, the zone that begins 20mm from the end does not have bonding agent) strip, make to add up to 5 test films.To these 5 test films, carry out never having the hand disbonded test of the end Bao From of bonding agent with hand, according to following metewand, estimate the bonding strength between polypropylene-based resin film and the polarizing coating.
A: the number that can peel off the above test film of 5mm is 0, has good bonding strength.
B: the number that can peel off the above test film of 5mm is 1～3, and bonding strength is low slightly.
C: the number that can peel off the above test film of 5mm is 4～5, and bonding strength is low.
＜embodiment 1 〉
Will be by carrying out melting mixing at the 50mm φ extruder that is heated to 275 ℃ for the propylene/ethylene copolymer of polypropylene-based resin (ethylene contents=0.4 weight %, MFR=9g/10 branch) 99 weight portions and the resin combination that forms for " Adekastub LA-31 " (ADEKA corporate system, molecular weight 664, hydroxybenzotriazole are ultraviolet light absorber) 1 weight portion of ultraviolet light absorber, then extrude with molten condition with the wide T mould of 600mm, with adjustment is 25 ℃ chill roll cooling, obtains the film of thickness 80 μ m.Moisture-vapor transmission when the haze value based on JIS K 7136 mensuration of this polypropylene-based resin film (the content 1.0 weight % of ultraviolet light absorber) is 0.9%, 40 ℃ is 4g/m 2My god.
Then, after the one side enforcement corona treatment to above-mentioned polypropylene-based resin film, contain the Photocurable adhesive agent of photo-curable photoreactive epoxy resin cationic polymerization initiators with thickness 4 μ m coating at the corona treatment face.On the other hand, to the norbornene resin film of biaxial stretch-formed mistake (phase difference value R in thickness=60 μ m, the face 0=63nm, thickness direction phase difference value R Th=225nm, the moisture-vapor transmission=1g/m 40 ℃ the time 2My god) one side implement corona treatment after, on the corona treatment face with above-mentioned similarly with thickness 4 μ m coating Photocurable adhesive agent.
Then, on a face of polarizing coating,, on another side,, carry out cramping with a pair roller of 100mm φ via the stacked above-mentioned norbornene resin film of bond layer via the stacked above-mentioned polypropylene-based resin film of bond layer., from norbornene resin film side irradiation ultraviolet radiation, two bond layers solidified, obtain polarization plates thereafter.
＜embodiment 2 〉
The content of the ultraviolet light absorber in the polypropylene-based resin film is made as 0.3 weight %, and in addition, operation obtains polarization plates similarly to Example 1.
＜embodiment 3 〉
As ultraviolet light absorber, use " Cyasorb UV1164 " (Cyatech corporate system, molecular weight 509, hydroxyl triazine are ultraviolet light absorber), in addition, operation obtains polarization plates similarly to Example 1.
＜comparative example 1 〉
Except that the polypropylene-based resin film did not contain ultraviolet light absorber, operation obtained polarization plates similarly to Example 1.
＜comparative example 2 〉
Except that the content with the ultraviolet light absorber in the polypropylene-based resin film was set at 1.5 weight %, operation obtained polarization plates similarly to Example 3.
＜comparative example 3 〉
As ultraviolet light absorber, use " Sumisorb 200 " (sumitomo chemical company system, molecular weight 225, hydroxybenzotriazole are ultraviolet light absorber), the content of the ultraviolet light absorber in the polypropylene-based resin film is made as 0.5 weight %, in addition, operation obtains polarization plates similarly to Example 1.
＜comparative example 4 〉
As ultraviolet light absorber, use " Sumisorb 130 " (sumitomo chemical company system, molecular weight 326, dihydroxy benaophenonel are ultraviolet light absorber), in addition, operation obtains polarization plates similarly to Example 1.
＜comparative example 5 〉
The content of the ultraviolet light absorber in the polypropylene-based resin film is set at 0.05 weight %, and in addition, operation obtains polarization plates similarly to Example 3.
Kind, molecular weight and the content thereof of employed ultraviolet light absorber, the haze value of polypropylene-based resin film and the evaluation result of the bonding strength between transmittance and polypropylene-based resin film and the polarizing coating together are shown in table 1.
Table 1
Figure BSA00000461827100241

Claims (5)

1. polarization plates, its be on the two sides of the polarizing coating that forms by polyvinyl alcohol resin respectively via the polarization plates of bonding agent applying transparent resin film, wherein,
Moisture-vapor transmission during 40 ℃ of the described transparent resin film that fits in the two sides is 50g/m 2Below it,
In the described transparent resin film that fits in the two sides at least one is for to comprise the polypropylene-based resin film that molecular weight is the ultraviolet light absorber more than 450 more than the 0.1 weight % and less than the content of 1.5 weight %.
2. polarization plates as claimed in claim 1, wherein, the transparent resin film of a face that fits in described polarizing coating is for containing the polypropylene-based resin film that molecular weight is the ultraviolet light absorber more than 450 more than the 0.1 weight % and less than the content of 1.5 weight %,
The transparent resin film that fits in the another side of described polarizing coating is the norbornene resin film.
3. polarization plates as claimed in claim 1, wherein, described ultraviolet light absorber is the ultraviolet light absorber of hydroxybenzotriazole system or hydroxyl triazine system.
4. polarization plates as claimed in claim 1, wherein, the polypropylene-based resin that constitutes described polypropylene-based resin film is the multipolymer of propylene and ethene or the homopolymer of propylene.
5. liquid crystal indicator that possesses the described polarization plates of claim 1.
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