CN104969100A - Laminate for polarizing plate, method for manufacturing laminate for polarizing plate, and polarizing plate - Google Patents
Laminate for polarizing plate, method for manufacturing laminate for polarizing plate, and polarizing plate Download PDFInfo
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- CN104969100A CN104969100A CN201480007123.6A CN201480007123A CN104969100A CN 104969100 A CN104969100 A CN 104969100A CN 201480007123 A CN201480007123 A CN 201480007123A CN 104969100 A CN104969100 A CN 104969100A
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- duplexer
- polyvinyl alcohol
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—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 including organic materials, e.g. polymeric layers
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- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polarising Elements (AREA)
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
In the present invention, in order to obtain a laminate for a polarizing plate, where the laminate is used for manufacturing a thin film polarizing plate having excellent polarizer film thickness and no irregularities in dyeing, provided is a laminate for a polarizing plate that is characterized by the following: being formed by stretching a laminate (III) of a base material film (I) and a resin layer (II) that contains a polyvinyl alcohol resin (A) having a 1,2-diol structure in a side chain; and being formed by dyeing the resin layer (II) that contains a polyvinyl alcohol resin (A) having a 1,2-diol structure in a side chain.
Description
Technical field
The present invention relates to for the effective Polarizer duplexer of manufacture Polarizer, more specifically relate to a kind of Polarizer duplexer of the Polarizer for the manufacture of film, the manufacture method of this Polarizer duplexer and use the Polarizer of this Polarizer duplexer; The film thickness uniformity of the polaroid of the Polarizer of described film is excellent, it is uneven not dye.
Background technology
All the time, use Polarizer in liquid crystal indicator, in order to form the good image of repeatability that is bright, color, Polarizer needs with high transmittance and high degree of polarization.The single or double bonding agent that such Polarizer can be used in polaroid is fitted with the Polarizer of transparent protective film, as described transparent protective film, usually uses tri acetyl cellulose system film etc.
In addition, polaroid was had the dichroic substance such as dichromatic iodine or dichroic dye in the past and manufactured by orientation in polyvinyl alcohol film, specifically, obtain by implementing swelling treatment, dyeing process, crosslinking Treatment, stretch processing, washing process, dry process etc. to polyvinyl alcohol film.
Above-mentioned polyvinyl alcohol film manufactures as follows: polyvinyl alcohol resin is dissolved in water equal solvent and after modulating stoste, the masking by solution casting method (casting), uses METAL HEATING PROCESS roller etc. to carry out drying; But when manufacturing polyvinyl alcohol film by such solution casting method, usually there is the situation being difficult to the film of manufacture less than 30 μm thickness.
On the other hand, in recent years, along with liquid crystal indicator to the movable equipment such as notebook personal computer, mobile phone expansion etc., film lightweight is required very much.
Therefore, propose following method: after the surface of base film is provided as the polyvinyl alcohol resin layer of polarization lamella, polyvinyl alcohol resin layer for each base film stretches, through dyeing and cross-linking process step and subsequent drying process, using polyvinyl alcohol resin layer as polarization lamella, the total thickness of base film and polarization lamella can be made thus to be as thin as the limit, make as polarization lamella (light polarizing film) Thickness Ratio in the past thinner (for example, referring to patent documentation 1).
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2000-338329 publication
Summary of the invention
the problem that invention will solve
But in the public technology of above-mentioned patent documentation 1, although obtain the Polarizer of the polaroid really with film, the film thickness uniformity of polaroid self is insufficient.Typically, as the polyvinyl alcohol resin that polaroid uses, the material of the material such as saponification degree more than 99 % by mole of high saponification degree can be used; But the material that the viscosity stability of the viscosity of the aqueous solution of the polyvinyl alcohol resin of so high saponification degree viscosity that is bad, that become aqueous solution is also high, thus be difficult to coat base film.Therefore, also produce by being coated with the membrane thickness unevenness etc. caused, when subsequent handling implements stretch processing and process etc. of dyeing makes polaroid, becoming insufficient from the film thickness uniformity of polaroid, the uneven viewpoint that dyes, seeking the further improvement of the Polarizer for obtaining film.
Therefore, the present invention provides a kind of Polarizer duplexer in this context, it is for the manufacture of the Polarizer of film, and wherein, the film thickness uniformity of the resin bed containing polyvinyl alcohol resin film thickness uniformity that is excellent and polaroid is excellent, it is uneven not dye.
for the scheme of dealing with problems
But, what the present inventor etc. carried out furtheing investigate in view of described situation found that, when base film forming the resin bed containing polyvinyl alcohol resin and implements stretching, dyeing, as polyvinyl alcohol resin, use has 1, the polyvinyl alcohol resin of 2-diol structure, makes the material of the film thickness uniformity excellence of the resin bed containing polyvinyl alcohol resin thus, can obtain the film thickness uniformity excellence of polaroid, do not dye uneven Polarizer.
Namely, purport of the present invention relates to a kind of Polarizer duplexer, it is that base film [I] has 1 with containing side chain, the duplexer [III] of the resin bed [II] of the polyvinyl alcohol resin (A) of 2-diol structure is stretched and has containing side chain that the resin bed [II] of the polyvinyl alcohol resin (A) of 1,2-diol structure is colored.
In addition, the manufacture method that providing package contains the Polarizer duplexer of following operation (1) ~ (3) or following operation (1) ~ (4) and then following operation (1) ~ (5) is gone back in the present invention.
Operation (1): contain upper formation of base film [I] resin bed [II] that side chain has the polyvinyl alcohol resin (A) of 1,2-diol structure, thus obtain the operation of duplexer [III].
Operation (2): the operation that duplexer [III] is stretched.
Operation (3): the operation that duplexer [III] is dyeed.
Operation (4): the operation of duplexer [III] being carried out to boron compound process.
Operation (5): after transparent protective film [IV] being fitted to resin bed [II] side containing polyvinyl alcohol resin (A), the operation of peeling base film.
And then, the Polarizer using aforesaid Polarizer duplexer is also provided in the present invention.
the effect of invention
Polarizer duplexer of the present invention uses the polyvinyl alcohol resin of ad hoc structure to form resin bed on base film; The film thickness uniformity with the resin bed that can obtain containing polyvinyl alcohol resin is excellent thus the film thickness uniformity of polaroid is excellent, the effect of the Polarizer of the uneven film that do not dye.These Polarizers are applied to the liquid crystal indicator of desk top computer, electronic clock, word processor, PC, LCD TV, PDA (Personal Digital Assistant), automobile or mechanical meter class etc., sunshade mirror, anti-glare glasses, anaglyph spectacles, display element (CRT, LCD etc.) reflection lower layer, medicine equipment, building materials, toy etc.
Embodiment
Below, the present invention is described in detail.
Polarizer duplexer of the present invention comprises the duplexer [III] of base film [I] and resin bed [II], and described resin bed [II] has the polyvinyl alcohol resin (A) of 1,2-diol structure containing side chain.
It should be noted that; by the kind of base film [I], the selection of material; base film [I] self also can as transparent protective film described later [IV]; in this situation; Polarizer duplexer supplies as Polarizer self, and Polarizer duplexer of the present invention also comprises such situation.
As the base film used in the present invention [I], the film such as formed by the thermoplastic resin that the transparency, physical strength, thermal stability, stretchability etc. are excellent can be used, can suitable resin be selected according to their glass transition temperature or fusing point and use.
As the concrete example of above-mentioned thermoplastic resin, can list such as: polyolefin-based resins, polyester based resin, cyclic polyolefin hydrocarbon system resin (norbornene resin), (methyl) acrylic acid (ester) are resin, cellulose esters system resin, polycarbonate-based resin, polyvinyl alcohol resin, vinyl acetate system resin, polyarylate system resin, polystyrene resin, polyethersulfone system resin, polysulfones system resin, polyamide series resin, polyimide system resin and their potpourri, multipolymer etc.
Base film [I] can be the film only formed by a kind of above-mentioned thermoplastic resin, also can be the film mixed by two or more thermoplastic resin.In addition, base film [I] can be single thin film, also can be multilayer film.
As above-mentioned polyolefin-based resins, can list such as: tygon, polypropylene etc.; They can easily stably high magnification stretch, thus preferably use.In addition, the ethylene-polypropylene multipolymer etc. obtained by propylene and ethylene copolymer can also be used.Also can carry out copolymerization with the monomer of other kinds, as can with the monomer of other kinds of copolymerization of propylene, can list such as: ethene, alpha-olefin.As alpha-olefin, preferably use the alpha-olefin of carbon number more than 4, be more preferably the alpha-olefin of carbon number 4 ~ 10.If enumerate the concrete example of the alpha-olefin of carbon number 4 ~ 10, then have such as: the straight-chain monoene hydro carbons such as 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-decene; The branched monoene hydro carbons such as 3-methyl-1-butene, 3-Methyl-1-pentene, 4-methyl-1-pentene; Vinyl cyclohexane etc.Propylene with can the multipolymer of other monomers of copolymerization with it can be random copolymers, also can be segmented copolymer.The containing ratio of the Component units from these other monomers in multipolymer according to " macromolecule analysis handbook " (nineteen ninety-five, the distribution of Kinokuniya bookstore) the 616th page of method recorded, can carry out infrared ray (IR) spectroscopic assay and obtains.
In above-mentioned, as the propylene resin forming propylene resin film, preferably use the homopolymer of propylene, Propylene-ethylene random copolymer, propylene-1-butene random copolymer and propylene-ethylene-1-butene random copolymer.
In addition, the stereoregularity forming the propylene resin of propylene resin film is preferably essentially isotaxy or syndiotaxy.The propylene resin film formed by the propylene resin in fact with isotaxy or syndyotactic stereoregularity, the relatively good and mechanical strength under hot environment of its treatability.
Above-mentioned polyester based resin is the polymkeric substance with ester bond, is mainly the condensed polymer of polybasic carboxylic acid and polyvalent alcohol.The polybasic carboxylic acid used mainly uses the dicarboxylic acid of binary, such as, have: m-phthalic acid, terephthalic acid (TPA), dimethyl terephthalate (DMT), naphthalene diformic acid dimethyl ester etc.In addition, the polyvalent alcohol used also mainly uses the glycol of binary, can list: propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol etc.As concrete resin, can list: polyethylene terephthalate, polybutylene terephthalate, PEN, PBN, polytrimethylene's ester, poly-naphthalenedicarboxylic acid trimethylene ester, polycyclohexylene's dimethyl ester, poly-naphthalenedicarboxylic acid cyclohexane dicarboxylates etc.Also their hybrid resin, multipolymer can preferably be used.In above-mentioned, preferred amorphous polyethylene terephthalate system resin, such as comprise m-phthalic acid as dicarboxylic acid multipolymer, comprise the multipolymer of cyclohexanedimethanol as glycol.
As above-mentioned cyclic polyolefin hydrocarbon system resin, preferably use norbornene resin.Cyclic polyolefin hydrocarbon system resin is the general name of the resin be polymerized as polymerized unit by cyclic olefin, can list such as: the resin recorded in Japanese Unexamined Patent Publication 1-240517 publication, Japanese Unexamined Patent Publication 3-14882 publication, Japanese Unexamined Patent Publication 3-122137 publication etc.As concrete example, can list: the multipolymer of open loop (being total to) polymkeric substance of cyclic olefin, the addition polymer of cyclic olefin, cyclic olefin and the alpha-olefin such as ethene, propylene (representative be random copolymers) and to their with the graft polymer of unsaturated carboxylic acid or derivatives thereof modification and their hydride etc.As the concrete example of cyclic olefin, can list: norborneol alkene monomer.
As cyclic polyolefin hydrocarbon system resin, commercially available have various product.As concrete example, can list: Topas (registered trademark) (Ticona Inc.), ARTON (registered trademark) (JSR Corporation system), ZEONOR (registered trademark) (Zeon Corporation system), ZEONEX (registered trademark) (ZeonCorporation system), Apelle (registered trademark) (Mitsui Chemicals society system).
Be resin as above-mentioned (methyl) acrylic acid (ester), (methyl) acrylic acid (ester) that can adopt any appropriate is resin.Can list such as: polymethylmethacrylate etc. gather (methyl) acrylate, methyl methacrylate-(methyl) acrylic copolymer, methyl methacrylate-(methyl) acrylate copolymer, methyl methacrylate-acrylate-(methyl) acrylic copolymer, (methyl) acrylate-styrene multipolymer (MS resin etc.), there is the polymkeric substance of alicyclic alkyl (such as, methyl methacrylate-cyclohexyl methacrylate multipolymer, methyl methacrylate-(methyl) acrylic acid norborene ester copolymer etc.).Preferably can list poly-(methyl) acrylic acid C1-6 Arrcostabs such as poly-(methyl) methyl acrylate.Be resin as (methyl) acrylic acid (ester), more preferably use the methyl methacrylate system resin using methyl methacrylate as principal ingredient (50 ~ 100 % by weight, be preferably 70 ~ 100 % by weight).
It should be noted that, in the present invention, (methyl) acrylic acid refers to acrylic or methacrylic acid.
Above-mentioned cellulose esters system resin is the ester of cellulose and fatty acid.As the concrete example of such cellulose esters system resin, can list: cellulosic triacetate, cellulose diacetate, cellulose tripropionate, cellulose dipropionate etc.In addition, can list: their multipolymer, the material etc. that the substituting group of other kinds of a part for hydroxyl etc. is modified.Wherein, particularly preferably cellulosic triacetate.For cellulosic triacetate, commercially available have a lot of product, is also favourable from the viewpoint of easiness of starting with, cost.As the example of the commercially available product of cellulosic triacetate, can list: FUJITAC (registered trademark) TD80 (Fujifilm Corporation system), FUJITAC (registered trademark) TD80UF (Fujifilm Corporation system), FUJITAC (registered trademark) TD80UZ (FujifilmCorporation system), FUJITAC (registered trademark) TD40UZ (Fujifilm Corporation system), KC8UX2M (Konica Minolta, Inc. make), KC4UY (Konica Minolta, Inc. system) etc.
Above-mentioned polycarbonate-based resin is the engineering plastics formed via the polymkeric substance of carbonate group bonding by monomeric unit, is the resin with high resistance to impact, thermotolerance, anti-flammability.In addition, owing to having the high transparency, so be also preferred for optical applications.Also commercially available have: in order to reduce photoelastic coefficient and being called as the resin of modified polycarbonate, improving the copolymerization polycarbonate etc. of wavelength dependency of modifying polymer backbone in optical applications, also can preferably use.Such polycarbonate resin is extensively sold, and can list such as: Panlite (registered trademark) (TEIJIN LIMITED. system), Iupilon (registered trademark) (Mitsubishi Engineering-Plastics Corporation system), SDPOLYCA (registered trademark) (Sumika Styron Polycarbonate Limited. system), CALIBRE (registered trademark) (The Dow Chemical Company system) etc.
In base film [I], except above-mentioned thermoplastic resin, also can add the adjuvant of any appropriate.As such adjuvant, can list such as: ultraviolet light absorber, antioxidant, lubricant, plastifier, release agent, anti-coloring agent, fire retardant, nucleator, antistatic agent, pigment and colorant etc.The content of the above-mentioned illustrative thermoplastic resin in base film [I] is preferably 50 ~ 100 % by weight, is more preferably 50 ~ 99 % by weight, and then is preferably 60 ~ 98 % by weight, is particularly preferably 70 ~ 97 % by weight.If the content of the thermoplastic resin in base film [I] is very few, then there is the tendency that thermoplastic resin high transparent etc. inherently can not play fully.
The thickness of the base film [I] before stretching can be suitable for determining, but usually from the view point of the operability such as intensity, treatability, is preferably 1 ~ 500 μm, is more preferably 1 ~ 300 μm, and then is preferably 5 ~ 200 μm, most preferably is 5 ~ 150 μm.
In order to improve and the adaptation of the resin bed [II] containing polyvinyl alcohol resin (A) described later, at least corona treatment, Cement Composite Treated by Plasma, the scorching process of fire etc. can be implemented for the formation of the surface of resin bed [II] side to base film [I].In addition, in order to improve adaptation, also the thin layer such as prime coat, bond layer can be formed on the surface for the formation of resin bed [II] side of base film [I].
In the present invention, at the stacked resin bed [II] containing side chain with the polyvinyl alcohol resin (A) of 1,2-diol structure of base film [I].
Described resin bed [II] has the polyvinyl alcohol resin (A) of 1,2-diol structure containing side chain.
As described polyvinyl alcohol resin (A), for side chain has the polyvinyl alcohol resin of 1,2-diol structure, the polyvinyl alcohol resin usually containing 1,2-diol structure unit shown in following general formula (1) can be listed.
(herein, R
1, R
2, R
3it is separately hydrogen or alkyl.)
Such polyvinyl alcohol resin (A) can by such as carrying out saponification to manufacture to the multipolymer of (i) vinyl acetate system's monomer and 3,4-diacetoxy-1-butylene.
As described vinyl acetate system monomer, can list: vinyl formate, vinyl acetate, propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate ester, pivalic acid vinyl acetate, caprate, vinyl laurate, stearic acid vinyl ester, vinyl benzoate, tertiary ethylene carbonate (vinylversatate) etc., wherein, preferably vinyl acetate is used.They can be used alone or combinationally use two or more.
In addition, in the present invention, preferably use above-mentioned multipolymer, but also according to circumstances, not damaging within the scope of object of the present invention, except above-mentioned copolymer composition, a small amount of such as less than the 5 % by mole copolymerization of other monomer can be made, can list such as: ethene, propylene, isobutylene, α-octene, α-dodecene, the olefines such as α-octadecylene, acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, the unsaturated acids such as itaconic acid or its salt or mono alkyl ester or dialkyl etc., vinyl cyanide, the nitriles such as methacrylonitrile, diacetone acrylamide, acrylamide, the amide-types such as Methacrylamide, ethylene-sulfonic acid, allyl sulphonic acid, the alkene sulfonic acids such as methallylsulfonic acid or its salt, allylin, alkyl vinyl ethers, dimethallyl ethyl ketene, NVP, vinyl chloride, vinylidene chloride, polyoxyethylene (methyl) allyl ether, polyoxy alkylidene (methyl) allyl ethers such as polyoxypropylene (methyl) allyl ether, polyoxyethylene (methyl) acrylate, polyoxy alkylidene (methyl) acrylate such as polyoxypropylene (methyl) acrylate, polyoxyethylene (methyl) acrylamide, polyoxy alkylidene (methyl) acrylamides such as polyoxypropylene (methyl) acrylamide, polyoxyethylene (1-(methyl) acrylamide-1,1-dimethyl propyl) ester, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allyl amine, polyoxypropylene allyl amine, polyoxyethylene vinyl amine, polyoxypropylene vinyl amine, ethylene carbonate, allyl acetic acid ester etc.
And then, can also list: N acrylamide methyl trimethoxy ammonium chloride, N acrylamide ethyl-trimethyl salmiac, N acrylamide hydroxypropyltrimonium chloride, 2-acryloyloxyethyl trimethyl ammonium chloride, 2-methacryloxyethyl trimethyl ammonium chloride, 2-hydroxy-3-methyl acryloxypropyl trimethyl ammonium chloride, allyl trimethyl ammonium chloride, methacrylic trimethyl ammonium chloride, 3-butylene trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, the monomer containing cation group such as diethyl diallyl ammonium chloride, monomer etc. containing acetoacetyl.
When above-mentioned vinyl acetate system monomer and 3,4-diacetoxy-1-butylene (and then having other monomer) are carried out copolymerization, can adopt with the polymerizing condition of known vinyl acetate system monomer and be polymerized the same method of gimmick.
As polymerization gimmick, can adopt such as: the known methods such as bulk polymerization, solution polymerization, suspension polymerization, dispersin polymerization or emulsion polymerization, usually carry out solution polymerization.
In addition, the Adding Way for monomer component during copolymerization has no particular limits, and can adopt arbitrary methods such as once adding, gradation adds, add continuously; But set out from the viewpoint made in the physical property such as 3,4-diacetoxy-1-butylene distributes equably in the strand of polyvinyl ester based polymer, the fusing point reduction of polyvinyl alcohol (PVA), preferably drip polymerization, particularly preferably based on the polymerization of HANNA method.
As the solvent used in described copolymerization, usually can list the lower alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, the ketone such as acetone, methyl ethyl ketone etc.; Industrial preferred use methyl alcohol.
The consumption of solvent can the degree of polymerization of combining target multipolymer, consider the chain transfer constant of solvent and be suitable for selecting, such as, when solvent is methyl alcohol, can select from S (solvent)/M (monomer)=0.01 ~ 10 (weight ratio), the preferably scope of 0.05 ~ 3 (weight ratio) degree.
Polymerization catalyst can be used during copolymerization, as described polymerization catalyst, can list such as: azo series catalysts, peroxide catalyst, redox series catalysts etc., specifically, can list: the known catalysts for radical polymerization such as azo isobutyronitrile, acetyl pexoxide, benzoyl peroxide, lauroyl peroxide or the two low temperature active catalysts for radical polymerization etc. such as methyl pentane nitrile, azo bi-methoxy methyl pentane nitrile of azo.
The consumption of polymerization catalyst is different according to the kind of catalyzer, cannot treat different things as the same, can select arbitrarily according to polymerization speed.Such as, when using azo isobutyronitrile, acetyl pexoxide, be preferably 0.01 ~ 0.2 % by mole relative to vinyl acetate system monomer, be particularly preferably 0.02 ~ 0.15 % by mole.
In addition, the temperature of reaction of copolyreaction is preferably set to by 40 DEG C to boiling point degree according to the solvent used, pressure.
Then, the multipolymer obtained is by saponification, but this saponification is substantially identical with the Saponification Conditions of known polyvinyl alcohol resin.That is, usually multipolymer obtained above is dissolved or dispersed in alcohol or aqueous alcohol, uses saponification catalyst and carry out.As alcohol, can list such as: methyl alcohol, ethanol, propyl alcohol, the tert-butyl alcohol etc., but particularly preferably use methyl alcohol.The concentration of the multipolymer in alcohol is suitable according to the viscosity of system to be selected, and usually selects from the scope of 10 ~ 60 % by weight.As saponification catalyst, can list such as: the base catalyst that the alkali-metal oxyhydroxide such as NaOH, potassium hydroxide, sodium methoxide, caustic alcohol, potassium methoxide, lithium methoxide, alkoxide are such, the acid catalysts such as sulfuric acid, hydrochloric acid, nitric acid, methane-sulforic acid, zeolite, Zeo-karb.
For the consumption of described saponification catalyst, can according to suitable selections such as method for saponification, target saponification degrees, but when using base catalyst, usually relative to vinyl acetate system monomer and 3, the total amount 1 mole of 4-diacetoxy-1-butylene is 0.1 ~ 30 mM, is preferably 2 ~ 17 mMs.
In addition, for the temperature of reaction of saponification, there is no particular limitation, is preferably 10 ~ 60 DEG C, is more preferably 20 ~ 50 DEG C.
During by above-mentioned saponification, the ester moiety of vinyl acetate system monomer and the acetoxy moieties of 3,4-diacetoxy-1-butylene are converted simultaneously as hydroxyl, thus can manufacture above-mentioned polyvinyl alcohol resin (A).
This has 1 owing to can obtain side chain, the polyvinyl alcohol resin (A) of 2-diol structure, but in the present invention, the mean saponification degree of described polyvinyl alcohol resin (A) is preferably higher, be generally more than 90 % by mole, be particularly preferably more than 95 % by mole, and then be preferably more than 98 % by mole, be particularly preferably more than 99 % by mole; If described saponification degree is too small, then the tendency that water tolerance when having Polarizer to make reduces.
It should be noted that, mean saponification degree in the present invention ester moiety and 3 of vinyl acetate system monomer, the rate of change (% by mole) changed to hydroxyl in the acetoxy moieties total amount of 4-diacetoxy-1-butylene represents (in saponification, the acetoxy moieties of 3,4-diacetoxy-1-butylene is almost completely by saponification).
In addition, the viscosity of above-mentioned polyvinyl alcohol resin (A), according to the viscosity conversion of making 4 % by weight aqueous solution, is usually preferably 8 ~ 400mPas, is particularly preferably 12 ~ 300mPas, and then is preferably 16 ~ 270mPas; If the viscosity of described 4 % by weight aqueous solution is too small, there is the tendency that stretchability when manufacturing Polarizer reduces; If excessive, there is the tendency that the plane smooth of film, transmittance reduce.
And then, as the content of 1,2-diol structure of the side chain of polyvinyl alcohol resin (A), be preferably 0.01 ~ 20 % by mole, be particularly preferably 0.05 ~ 15 % by mole, and then be preferably 0.1 ~ 12 % by mole, most preferably be 0.1 ~ 6 % by mole; Be difficult at least obtain effect of the present invention if described content is crossed, if cross the tendency not only having the manufacture of polyvinyl alcohol resin to become difficulty at most on the contrary, the tendency that water tolerance when also having Polarizer to make reduces.
It should be noted that, as the manufacture method of the polyvinyl alcohol resin used in the present invention (A), for above-mentioned (i) by vinyl acetate system monomer and 3, the method of the multipolymer saponification of 4-diacetoxy-1-butylene describes in detail, but be not limited to described method, also can list such as: (ii) multipolymer to the vinyl ethylene carbonate shown in vinyl acetate system monomer and general formula (2) carries out the method for saponification and decarboxylation; (iii) saponification and de-ketalization method are carried out to the multipolymer of 2,2-dialkyl group-4-vinyl-1,3-dioxa penta rings shown in vinyl acetate system monomer and general formula (3); (iv) multipolymer of vinyl esters system monomer and allylin is carried out to the method etc. of saponification, there is no particular limitation.
(herein, R
1, R
2, R
3it is separately hydrogen or alkyl.)
(herein, R
1, R
2, R
3, R
4, R
5it is separately hydrogen or alkyl.)
In addition, in the present invention, also can combinationally use the different two or more polyvinyl alcohol resin of the content, mean saponification degree, viscosity etc. of side chain 1,2-diol structure as polyvinyl alcohol resin (A).
And then, in the present invention, the raising effect of water tolerance when making from the view point of Polarizer, as polyvinyl alcohol resin, also aforementioned polyvinyl alcohol resin (A) and the polyvinyl alcohol resin (B) beyond aforementioned polyvinyl alcohol resin (A) can be combinationally used.
When polyvinyl alcohol resin (A) and polyvinyl alcohol resin (B) being combinationally used, the average content of side chain 1, the 2-diol structure preferably calculated by following formula is the scope of 0.1 ~ 20 % by mole.
Herein, the average content (% by mole) of side chain 1,2-diol structure calculates as follows.
Namely, the content of side chain 1, the 2-diol structure of polyvinyl alcohol resin (A) is set to α % by mole, being calculated the polyvinyl alcohol resin (A) relative to polyvinyl alcohol resin (A) and polyvinyl alcohol resin (B) total amount by following formula containing during the proportional X% of being set to.
Average content (% by mole)=(the X/100) × α of side chain 1,2-diol structure
Particularly, from the view point of the effect improving stretchability, polyvinyl alcohol resin (B) can be used using polyvinyl alcohol resin (A) as body combination, such as, it is generally 95/5 ~ 50/50 containing proportional (A/B) (weight ratio), is preferably 90/10 ~ 55/45; From the view point of the effect improving water tolerance, polyvinyl alcohol resin (A) can be used using polyvinyl alcohol resin (B) as body combination, such as, it is generally 5/95 ~ 50/50 containing proportional (A/B) (weight ratio), be preferably 10/90 ~ 45/55, it is not limited, can be suitable for as required selecting compounding ratio.
As above-mentioned polyvinyl alcohol resin (B), as long as the material used in Polarizer purposes all the time, usual mean saponification degree is more than 90 % by mole, is preferably more than 95 % by mole, be particularly preferably more than 98 % by mole, and then be preferably more than 99 % by mole.If described mean saponification degree is too small, then the tendency that water tolerance when having Polarizer to make reduces.
And then the viscosity of described polyvinyl alcohol resin (B), according to the viscosity conversion of making 4 % by weight aqueous solution, is usually preferably 8 ~ 500mPas, is particularly preferably 20 ~ 400mPas, and then is preferably 40 ~ 300mPas.If the viscosity of 4 % by weight aqueous solution is too small, the tendency that stretchability when having Polarizer to make reduces, if excessive, has the tendency of the plane smooth of film, transparency reduction.
It should be noted that, described polyvinyl alcohol resin (B) is as long as polyvinyl alcohol resin beyond polyvinyl alcohol resin (A), then there is no particular limitation, but is usually preferably unmodified polyvinyl alcohol resin.In addition, also can for the olefines (ethene, propylene, n-butene, isobutylene etc.), ethene ethers, unsaturated sulfonic acid salt etc. containing a small amount of unsaturated carboxylic acid (comprising salt, ester, acid amides, nitrile etc.), carbon number 2 ~ 30 can with the polyvinyl alcohol resin of vinyl acetate copolymerized composition.
In addition, as polyvinyl alcohol resin (B), the different two or more polyvinyl alcohol resin such as viscosity of saponification degree, 4 % by weight aqueous solution can be combinationally used.
In addition, when combinationally using polyvinyl alcohol resin (A) and polyvinyl alcohol resin (B), polyvinyl alcohol resin (A) is less than 6 % by mole with the difference of the mean saponification degree of polyvinyl alcohol resin (B), from the viewpoint of the transparency preferably, be particularly preferably less than 3 % by mole, and then be preferably less than 2 % by mole.
In the present invention, 1 is had containing side chain upper formation of base film [I], during resin bed [II] of the polyvinyl alcohol resin (A) of 2-diol structure, can list such as: by the solution of the resin containing polyvinyl alcohol resin (A), be preferably aqueous solution and coat base film [I] and carry out dry method.
As the solution containing polyvinyl alcohol resin (A) as used herein, from the aspect of coating drying property, also can containing a small amount of alcohols, such as methyl alcohol, ethanol, n-propanol, isopropyl alcohol etc.
It should be noted that, in described resin solution, from the view point of the flexibility of resin bed [II], preferred compounding plastifier; From the view point of slip easiness when duplexer [III] being rolled into volume, preferred compounding surfactant; From the view point of the xanthochromia preventing film, known compounding dose of preferred compounding antioxidant etc.
When above-mentioned resin solution being coated base film [I], as rubbing method, can be suitable for selecting to adopt: the rolling methods such as coiling stick coating method, inverse painting method, gravure coating process, spin-coating method, silk screen rubbing method, jetting type rubbing method, dip coating, spraying process etc.When base film [I] has prime coat or peel ply, at this prime coat or peel ply coating aforementioned resin solution; When not having prime coat directly at base film [I] upper coating aforementioned resin solution.
For the concentration of aforementioned resin solution, from the view point of throughput rate when dissolubility and drying, be preferably 5 ~ 50 % by weight, be more preferably 7 ~ 40 % by weight, be particularly preferably 10 ~ 30 % by weight.Then there is dry load to become large and productive capacity reduces tendency when resin solution concentration is too small, then have viscosity to become too high time excessive and be difficult to uniform tendency of dissolving.
In addition, baking temperature is generally 30 ~ 200 DEG C, is preferably 40 ~ 150 DEG C, is generally about 5 ~ 30 minutes drying time.
In the present invention, the thickness of the resin bed [II] containing polyvinyl alcohol resin (A), from the view point of the operability such as intensity, treatability, thin layer, is preferably 1 ~ 50 μm, is particularly preferably 2 ~ 40 μm, and then be preferably 3 ~ 30 μm.If described thickness is crossed thin, became thin after having stretching and tendency that dyeability reduces, if blocked up, easily produce caused by foaming etc. float, peel off, thus the tendency of bad order.
In addition, base film [I] is preferably 0.02 ~ 500 with the Thickness Ratio ([I]/[II]) of resin bed [II], is particularly preferably 0.025 ~ 150.If described Thickness Ratio is too small, there is the tendency that duplexer [III] in the solution of iodine staining process etc. became soft, treatability reduces, if excessive, have the tendency that stretching easily becomes uneven.
Like this, base film [I] and the duplexer [III] containing side chain with the resin bed [II] of the polyvinyl alcohol resin (A) of 1,2-diol structure can be obtained.Then, stretch processing is implemented for duplexer [III] and utilizes the dyeing process of iodine or dichroic dye, thus Polarizer duplexer of the present invention can be obtained.
That is, Polarizer duplexer of the present invention is by comprising following operation (1) ~ (3), preferably and then comprise operation (4), also comprise the manufacture method of operation (5) and obtain.
Operation (1): contain upper formation of base film [I] resin bed [II] that side chain has the polyvinyl alcohol resin (A) of 1,2-diol structure, thus obtain the operation of duplexer [III].
Operation (2): the operation that duplexer [III] is stretched.
Operation (3): the operation that duplexer [III] is dyeed.
Operation (4): the operation of duplexer [III] being carried out to boron compound process.
Operation (5): after transparent protective film [IV] being fitted to resin bed [II] side containing polyvinyl alcohol resin (A), the operation of peeling base film.
In above-mentioned operation, operation (1) is described above, and operation (2), operation (3), operation (4), operation (5) are as described below.It should be noted that, the order of operation (2) ~ (5) can be suitable for selecting.
Polarizer duplexer of the present invention is by processing for the duplexer [III] obtained in operation (1) through common stretch processing, dyeing, preferably manufacture further across operations such as boron compound process.
The following method of choice for use can be suitable in the present invention, such as, have: duplexer [III] stretches and after impregnated in the staining solution of iodine or dichroic dye dyeing, carries out the method for boron compound process by (1); (2), after carrying out stretching and dyeing, carry out the method for boron compound process simultaneously; (3) dye with iodine or dichroic dye and after stretching, carry out the method for boron compound process; (4), after dyeing, in the solution of boron compound, the method stretched is carried out; (5) stretch and carry out the poststaining of boron compound process, in the solution of boron compound, carrying out the method stretched; (6) method etc. of dyeing process and boron compound process is carried out on stretching limit in limit.Like this, the stretching of duplexer [III] (duplexer do not stretched) and dyeing and then boron compound process both can be carried out respectively, also can side by side carry out.
In the present invention, from the view point of optical characteristics, at least one operation of dyeing process (3), boron compound treatment process (4), preferably carry out the stretching process (2) of duplexer [III].
In addition, in the present invention, from the view point of optical characteristics, the stretching ratio in the stretching process (2) of preferred duplexer [III] is more than 2 times, and then is preferably 2 ~ 10 times, is particularly preferably 2 ~ 7 times.If stretching ratio is too small, then there is the tendency that can not get sufficient optical characteristics.
It should be noted that, as the front operation of the dyeing process (3) of duplexer [III], carry out stretch processing in advance, this from improve polyvinyl alcohol resin orientation, namely obtain good optical characteristics viewpoint and preferably, stretching ratio in this situation is 1.1 ~ 5 times, is particularly preferably 1.2 ~ 4 times.
Total stretching ratio of duplexer [III] is 3 ~ 10 times in single shaft direction usually, is preferably 3.5 ~ 7 times, as above-mentioned, particularly preferably be and in the liquid such as dyeing process, boron compound treatment process, carry out more than 2 times stretch.Now, also carry out a little stretching (being stretched as more than the degree or its preventing Width from shrinking) in the vertical direction of draw direction to be also fine.Temperature during stretching is preferably selected from 20 ~ 170 DEG C, if consider to carry out stretching process (2) further at least one operation of dyeing process (3) and boron compound treatment process (4), then be preferably 20 ~ 90 DEG C, be particularly preferably 25 ~ 80 DEG C.And then as long as stretching ratio is finally set in aforementioned range, stretched operation not only can be implemented a stage, also can implement in the stage of any range of manufacturing process.
The dyeing of duplexer [III] is contacted by making the liquid containing iodine or dichroic dye with duplexer [III] and carried out.Usually can use the solution containing iodine, wherein, preferably use the compounding aqueous solution having the IKI with potassium iodide; Described potassium iodide has and more easily produces for the useful I of the optical property of polaroid
3 -, I
5 -the effect of isoionic auxiliary agent.In the aqueous solution of IKI, the concentration of iodine is 0.1 ~ 2%, and the concentration of potassium iodide is 0.1 ~ 50%, and the weight ratio of potassium iodide/iodine is preferably 3 ~ 60.On the other hand, as dichroic dye, known dichroic dye can be used, preferably can use Azo.Above-mentioned containing in the solution of dichroic dye, sodium chloride, sodium sulphate, anhydrous sodium sulfate, sodium tripolyphosphate etc. can be contained as dyeing assistant.
Dyeing time is about 30 ~ 500 seconds is practical.The temperature of process bath is preferably 5 ~ 50 DEG C.In aqueous solution, except hydrosolvent, also can on a small quantity containing having the organic solvent with the intermiscibility of water.As contact means, the arbitrary means such as dipping, coating, spraying can be used.
The duplexer [III] being preferably colored process then processes with boron compound.As boron compound, boric acid, borax are practical.Boron compound can with the form of aqueous solution or water-organic solvent mixed liquor, use with the degree of concentration 0.5 ~ 10 % by weight, and making potassium iodide coexist with the degree of concentration 0.1 ~ 10 % by weight is in a liquid preferred in practical.Facture is preferably infusion process, can certainly implement rubbing method, spray-on process.Temperature during preferred process is about 20 ~ 80 DEG C, and the processing time is 15 seconds ~ about 20 minutes, in addition, also preferably carries out stretched operation in processes as required.
Like this, obtain Polarizer duplexer of the present invention, namely be that base film [I] has 1 with containing side chain, the duplexer [III] of the resin bed [II] of the polyvinyl alcohol resin (A) of 2-diol structure is stretched and the Polarizer duplexer be colored containing the resin bed [II] that side chain has the polyvinyl alcohol resin (A) of 1,2-diol structure.
It should be noted that, by being dyeed by the resin bed [II] containing polyvinyl alcohol resin (A), resin bed [II] becomes polaroid thus.
In the present invention; Polarizer duplexer obtained above (stretched and dyeing duplexer) has base film [I] at the one-sided of resin bed [II] (polaroid), described base film [I] can directly as Polarizer transparent protective film [IV] and use.On the other hand, can in resin bed [II] (polaroid) do not have base film [I] side fit transparent protective film [IV].In addition, can by resin bed [II] (polaroid) from base film [I] peel off after, the both sides of this resin bed [II] (polaroid) laminating transparent protective film [IV].In addition, resin bed [II] (polaroid) in the Polarizer duplexer obtained can be transferred to other base material.After fitting with other base film (such as transparent protective film [IV]) at resin bed [II] (polaroid), base film [I] can be peeled off, thus carry out transfer printing; In addition, by making this resin bed [II] (polaroid) and other base material fit after resin bed [II] (polaroid) being peeled off from base film [I], thus transfer printing can be carried out.
In above-mentioned; from the viewpoint of optical characteristics and the method for preferable process (5): after transparent protective film [IV] being fitted to resin bed [II] (polaroid) side containing polyvinyl alcohol resin (A), peeling base film [I].It should be noted that, base film [I] albefaction due to stretching, dyeing condition etc. sometimes, thus light transmission reduces.
As transparent protective film [IV], can use and the aforementioned material that illustrative material is same as base film [I].The thickness of transparent protective film [IV] can be suitable for determining, usually from viewpoints such as the operability such as intensity, treatability, thin layers, is about 1 ~ 500 μm.Be particularly preferably 1 ~ 300 μm, be more preferably 5 ~ 200 μm.
In addition, transparent protective film [IV] is preferably 0.04 ~ 1000 with the Thickness Ratio ([IV]/[II]) of resin bed [II] (polaroid), is particularly preferably 0.05 ~ 300.If described Thickness Ratio is too small, then transparent protective film [IV] is had to become the tendency of difficulty with the laminating of resin bed [II] (polaroid); If excessive, there is the tendency that thin layer is lost and optical property reduces.
It should be noted that; when the both sides of resin bed [II] (polaroid) are provided with transparent protective film [IV]; also can use transparent protective film [IV] (the comprising base film) that formed by identical polymeric material in its table, also can use the transparent protective film [IV] formed by different polymeric materials etc.
In addition, transparent protective film [IV] is fitted to aforementioned resin bed [II] (polaroid) containing polyvinyl alcohol resin (A) by bonding agent usually, carries out surface modification treatment before also can stating bonding agent before coating.As concrete process, can list: corona treatment, Cement Composite Treated by Plasma, prime treatment, saponification process, utilize the process etc. of coupling agent.
For not bonding with resin bed [II] (polaroid) face of aforementioned transparent protective film [IV], also can implement hard conating or antireflection process, anti-adhesion, by spread and anti-dazzle for the purpose of process.
It should be noted that, aforementioned anti-reflection layer, anti adhering layer, diffusion layer, antiglare layer etc. directly can be arranged to transparent protective film [IV], in addition, also can arrange respectively as other optical layers and transparent protective film [IV].
Aforementioned resin layer [II] (polaroid) can use bonding agent with the bonding process of transparent protective film [IV].As bonding agent, can exemplify: isocyanate-based bonding agent, polyethenol series bonding agent, gelatin system bonding agent, latex system of ethene system, water system polyester etc.Aforementioned bonding agent uses usually used as the bonding agent comprising aqueous solution, usually contains the solid constituent of 0.5 ~ 60 % by weight.Outside above-mentioned, as resin bed [II] (polaroid) bonding agent with transparent protective film [IV], can list: ultraviolet hardening bonding agent, electron ray curing type bonding agent etc.Above-mentioned electron ray curing type bonding agent shows suitable cohesive for above-mentioned various transparent protective film [IV].Particularly, good cohesive is also shown for being difficult to meet fusible acrylic acid (ester) resin.In addition, in bonding agent used in the present invention, metallic compound filler can be contained.
The Polarizer obtained in the present invention also sometimes its side surface as required, form transparent adhesive phase and for practicality by usually known method.As adhesive phase, using the multipolymer of the α-monoolefin carboxylic acids such as the acrylate such as butyl acrylate, ethyl acrylate, methyl acrylate, 2-EHA and acrylic acid, maleic acid, itaconic acid, methacrylic acid, crotonic acid (also comprising the material that with the addition of the such vinyl monomer of vinyl cyanide, vinyl acetate, styrene) as main body; Due to the polarized light property of Polarizer can not be hindered thus particularly preferably, it is not limited, as long as the bonding agent with the transparency then can use, such as polyvinylether system, rubber series etc.
The Polarizer obtained in the present invention can be effectively applied to the liquid crystal indicator of desk top computer, electronic clock, word processor, PC, TV, PDA (Personal Digital Assistant), automobile or mechanical gauge class etc., sunshade mirror, anti-glare glasses, anaglyph spectacles, display element (CRT, LCD etc.) with reducing reflection horizon, medicine equipment, building materials, toy etc.
Embodiment
Below, list embodiment and the present invention is described in more detail, but the present invention is in the scope not exceeding its main idea, be not limited to these embodiments.
It should be noted that, in example, " part ", " % " represent weight basis.
Each physical property is carried out as follows.
(1) content (% by mole) of 1,2-diol structure of side chain
With
1h-NMR (internal standard compound: tetramethylsilane, solvent: d
6-DMSO) carry out measuring and calculating.
(2) mean saponification degree (% by mole) of polyvinyl alcohol resin
Analyze with the alkali consumption required for the hydrolysis of residual vinyl acetate units.
(3) viscosity (mPas) of 4% aqueous solution of polyvinyl alcohol resin
By lower water temperature to 20 DEG C, measure with Hoeppler rolling ball viscosimeter.
(embodiment 1)
Side chain is used to have 1, polyvinyl alcohol (PVA) (the A) (side chain 1 of 2-diol structure, the content of 2-diol structure: 1.0 % by mole, mean saponification degree: 99.8 % by mole, the viscosity (20 DEG C) of 4% aqueous solution: 85mPas), the polyvinyl alcohol water solution of modulation concentration 14%.
At described 14% polyvinyl alcohol water solution of the upper coating of amorphism polyethylene terephthalate (PET) film (thickness: 100 μm) as base film [I], 10 μm are become to make dried thickness, at baking temperature 60 DEG C, carry out drying, obtain the duplexer [III] of PET film/polyvinyl alcohol layer thus.
For the duplexer obtained [III], as follows the film thickness uniformity of resin bed is evaluated.
(film thickness uniformity of polyvinyl alcohol resin layer)
From duplexer obtained above [III] peeling base film [I], about described resin bed [II], film thickness gauge (society of tail rugged making institute system " DIGITAL LINEAR GAUGES D-10HS ") is used to evaluate film thickness uniformity to the Width of resin bed [II].Described mensuration measures the thickness of 20 with 5mm spacing, and the amplitude of variation (maximal value-minimum value) of thickness, relative to the ratio of average film thickness, is evaluated as follows.
Zero is less than 10%
△ more than 10% and be less than 15%
More than × 15%
Then, for described duplexer [III], carry out stretch processing, dyeing process, boron compound process according to following condition, obtain Polarizer duplexer.
That is, after 1.8 times of uniaxial tensions being carried out to duplexer [III] at 130 DEG C, dipping 30 seconds in the aqueous solution (30 DEG C) of boric acid 3%.Afterwards, after flooding 60 seconds in the staining trough (30 DEG C) comprising iodine 0.4%, potassium iodide 1.2% (iodine: potassium iodide=1:3 (weight ratio)), flood 60 seconds at 40 DEG C in the aqueous solution of boric acid 3%, potassium iodide 3%.And then, flood 120 seconds and uniaxial tension to 3.3 times at 70 DEG C in the aqueous solution of boric acid 4%, potassium iodide 5%, thus obtain the Polarizer duplexer being formed with polaroid.
For the Polarizer duplexer obtained, as follows optical characteristics is evaluated.
(optical characteristics)
Polaroid is peeled off from Polarizer duplexer obtained above, about described polaroid, use the spectrophotometer (Japanese light splitting society system " VAP7070 ") with integrating sphere, measure singleton transmittance (%), degree of polarization (%).
(embodiment 2 ~ 3, comparative example 1)
Except the condition of table 1, arrange similarly to Example 1, obtain duplexer [III] and Polarizer duplexer.For the Polarizer duplexer obtained, carry out evaluation similarly to Example 1.
The evaluation result of embodiment and comparative example is shown in following table 1.
[table 1]
By the above results, when the existing unmodified polyvinyl alcohol resin using comparative example 1 such, although optical characteristics is good, the film thickness uniformity of the resin bed containing polyvinyl alcohol resin is poor; On the other hand, when using the polyvinyl alcohol resin of the such ad hoc structure of embodiment 1 ~ 3, the viscosity stability of polyvinyl alcohol resin is very excellent, so the film thickness uniformity containing the resin bed of polyvinyl alcohol resin is excellent and then optical characteristics is also good.Therefore, the film thickness uniformity of the polaroid obtained is very excellent, it is uneven not dye, very useful as film Polarizer.
It should be noted that, concrete mode of the present invention has been shown in above-described embodiment, but above-described embodiment is only simple illustration, does not do the explanation limited.Those skilled in the art can seek various obvious distortion within the scope of the invention.
utilizability in industry
The base film [I] of Polarizer duplexer of the present invention has 1 with containing side chain, the duplexer [III] of the resin bed [II] of the polyvinyl alcohol resin (A) of 2-diol structure is stretched and has 1 containing side chain, the resin bed [II] of the polyvinyl alcohol resin (A) of 2-diol structure is colored, so the film thickness uniformity of resin bed [II] is excellent and then the film thickness uniformity of polaroid is excellent, it is uneven not dye.And, the Polarizer obtained is as the reel film of light polarizing film, the reel film that 1/2 wavelength plate or 1/4 wavelength plate use, the reel film of the phase-contrast film that liquid crystal indicator uses is very useful, described light polarizing film is applied to desk top computer, electronic clock, word processor, PC, TV, PDA (Personal Digital Assistant), the liquid crystal indicator of automobile or mechanical gauge class etc., sunshade mirror, anti-glare glasses, anaglyph spectacles, display element (CRT, LCD etc.) with reducing reflection horizon, medicine equipment, building materials, toy etc.
Claims (12)
1. a Polarizer duplexer, it is characterized in that, it is that base film [I] has 1 with containing side chain, the duplexer [III] of the resin bed [II] of the polyvinyl alcohol resin (A) of 2-diol structure is stretched and has containing side chain that the resin bed [II] of the polyvinyl alcohol resin (A) of 1,2-diol structure is colored.
2. Polarizer duplexer according to claim 1, is characterized in that, the stretching ratio of duplexer [III] is more than 2 times.
3. Polarizer duplexer according to claim 1 and 2, is characterized in that, the content of 1,2-diol structure of the side chain of polyvinyl alcohol resin (A) is 0.01 ~ 20 % by mole.
4. the Polarizer duplexer according to any one of claims 1 to 3, is characterized in that, the mean saponification degree of polyvinyl alcohol resin (A) is more than 90 % by mole.
5. the Polarizer duplexer according to any one of Claims 1 to 4, is characterized in that, the viscosity of polyvinyl alcohol resin (A) is 8 ~ 400mPas according to the viscosity conversion of making 4 % by weight aqueous solution.
6. the Polarizer duplexer according to any one of Claims 1 to 5, is characterized in that, the thickness of the resin bed [II] containing polyvinyl alcohol resin (A) is 1 ~ 50 μm.
7. a manufacture method for Polarizer duplexer, is characterized in that, comprises following operation (1) ~ (3):
Operation (1): contain upper formation of base film [I] resin bed [II] that side chain has the polyvinyl alcohol resin (A) of 1,2-diol structure, thus obtain the operation of duplexer [III];
Operation (2): the operation that duplexer [III] is stretched;
Operation (3): the operation that duplexer [III] is dyeed.
8. the manufacture method of Polarizer duplexer according to claim 7, is characterized in that, also comprises following operation (4):
Operation (4): the operation of duplexer [III] being carried out to boron compound process.
9. the manufacture method of Polarizer duplexer according to claim 8, it is characterized in that, at least one operation of dyeing process (3) and boron compound treatment process (4), carry out the stretching process (2) of duplexer [III].
10. the manufacture method of the Polarizer duplexer according to any one of claim 7 ~ 9, is characterized in that, the stretching ratio in the stretching process (2) of duplexer [III] is more than 2 times.
The manufacture method of 11. Polarizer duplexers according to any one of claim 7 ~ 10, is characterized in that, also comprise following operation (5):
Operation (5): after transparent protective film [IV] being fitted to resin bed [II] side containing polyvinyl alcohol resin (A), the operation of peeling base film [I].
12. 1 kinds of Polarizers, is characterized in that, it is the Polarizer duplexer described in any one using claim 1 ~ 6.
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| JP2013054564 | 2013-03-18 | ||
| JP2013-054564 | 2013-03-18 | ||
| PCT/JP2014/057066 WO2014148413A1 (en) | 2013-03-18 | 2014-03-17 | Laminate for polarizing plate, method for manufacturing laminate for polarizing plate, and polarizing plate |
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| CN107219583A (en) * | 2016-03-22 | 2017-09-29 | 住友化学株式会社 | The manufacture method of polarizer, polarizing coating and polarizer |
| CN108430667A (en) * | 2015-12-24 | 2018-08-21 | 花王株式会社 | Casting coat composition |
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| JP6734745B2 (en) * | 2015-10-14 | 2020-08-05 | 日東電工株式会社 | Polarizer and manufacturing method thereof |
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| JP2000338329A (en) * | 1999-06-01 | 2000-12-08 | Sanritsutsu:Kk | Polarizing plate and its production |
| JP2009013368A (en) * | 2007-07-09 | 2009-01-22 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol-based film for use in optics, polarizing membrane, and polarizing plate |
| JP2009024076A (en) * | 2007-07-19 | 2009-02-05 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol-based film for optical use, polarizing film and polarizing plate |
| CN101528817A (en) * | 2006-07-27 | 2009-09-09 | 日本合成化学工业株式会社 | Polyvinyl alcohol-based film for optical uses and polarizing membrane and polarizing plate |
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| JP5089045B2 (en) * | 2005-02-14 | 2012-12-05 | 日本合成化学工業株式会社 | Polyvinyl alcohol film and method for producing the same |
| JP2006282951A (en) * | 2005-04-05 | 2006-10-19 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol-based film and use of the same |
| JP2008050574A (en) * | 2006-07-24 | 2008-03-06 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol-based film for optical use, polarizing film and polarizing plate |
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- 2014-03-17 JP JP2014053001A patent/JP2014206735A/en active Pending
- 2014-03-17 CN CN201480007123.6A patent/CN104969100B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000338329A (en) * | 1999-06-01 | 2000-12-08 | Sanritsutsu:Kk | Polarizing plate and its production |
| CN101528817A (en) * | 2006-07-27 | 2009-09-09 | 日本合成化学工业株式会社 | Polyvinyl alcohol-based film for optical uses and polarizing membrane and polarizing plate |
| JP2009013368A (en) * | 2007-07-09 | 2009-01-22 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol-based film for use in optics, polarizing membrane, and polarizing plate |
| JP2009024076A (en) * | 2007-07-19 | 2009-02-05 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol-based film for optical use, polarizing film and polarizing plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108430667A (en) * | 2015-12-24 | 2018-08-21 | 花王株式会社 | Casting coat composition |
| CN108430667B (en) * | 2015-12-24 | 2019-09-03 | 花王株式会社 | Casting coat composition |
| CN107219583A (en) * | 2016-03-22 | 2017-09-29 | 住友化学株式会社 | The manufacture method of polarizer, polarizing coating and polarizer |
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| CN104969100B (en) | 2018-01-23 |
| KR20150132102A (en) | 2015-11-25 |
| JP2014206735A (en) | 2014-10-30 |
| WO2014148413A1 (en) | 2014-09-25 |
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