CN104969100B - The manufacture method and Polarizer of Polarizer layered product and Polarizer layered product - Google Patents
The manufacture method and Polarizer of Polarizer layered product and Polarizer layered product Download PDFInfo
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- CN104969100B CN104969100B CN201480007123.6A CN201480007123A CN104969100B CN 104969100 B CN104969100 B CN 104969100B CN 201480007123 A CN201480007123 A CN 201480007123A CN 104969100 B CN104969100 B CN 104969100B
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- polarizer
- layered product
- polyvinyl alcohol
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- alcohol resin
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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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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polarising Elements (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
There is provided a kind of Polarizer layered product, it is characterised in that it is used to manufacture, and the film thickness uniformity of polarizer is excellent, does not dye uneven, film Polarizer；In order to obtain the Polarizer layered product, base film [I] containing side chain with having 1, the resin bed [II] that the layered product [III] of the resin bed [II] of the polyvinyl alcohol resin (A) of 2 diol structures is stretched and has the polyvinyl alcohol resin (A) of 1,2 diol structures containing side chain is colored.
Description
Technical field
The present invention relates to for manufacturing the effective Polarizer layered product of Polarizer, more specifically it is related to a kind of for making
The Polarizer for making the Polarizer of film is used with layered product, the Polarizer with the manufacture method of layered product and using the Polarizer
The Polarizer that layered product forms；The film thickness uniformity of the polarizer of the Polarizer of the film is excellent, uneven without dyeing.
Background technology
All the time, Polarizer is used in liquid crystal display device, in order to form the good figure of bright, color repeatability
Picture, Polarizer are needed with high light transmittance and high degree of polarization.Such Polarizer can use the one side in polarizer
Or it is two-sided the Polarizer that transparent protective film forms is fitted with bonding agent, as the transparent protective film, usually using three
Acetylcellulose system film etc..
In addition, polarizer was to have dichromatic iodine or dichroic dye by being orientated in polyvinyl alcohol film in the past
Etc. dichroic substance come what is manufactured, specifically, by implementing swelling treatment to polyvinyl alcohol film, dyeing is handled, crosslinking
Processing, stretch processing, washing process, drying process etc. and obtain.
Above-mentioned polyvinyl alcohol film manufactures as follows：By polyvinyl alcohol resin be dissolved in water equal solvent and modulate stoste it
Afterwards, it is film-made by solution casting method (casting), is dried using METAL HEATING PROCESS roller etc.；But pass through such solution curtain coating
When legal system makes polyvinyl alcohol film, generally there is a situation where to be difficult to the film for manufacturing less than 30 μm thickness.
On the other hand, in recent years, set along with liquid crystal display device to notebook personal computer, mobile phone etc. are removable
Standby expansion etc., requires film lightweight very much.
Therefore, it is proposed to following method：The polyvinyl alcohol resin of polarizer layer is provided as on the surface of base film
Layer after, stretched for the polyvinyl alcohol resin layer of each base film, by dyeing and cross-linking process step and subsequent
Drying process, using polyvinyl alcohol resin layer as polarizer layer, thus enable that the total of base film and polarizer layer is thick
Degree is as thin as the limit, makes thinner (for example, referring to patent document 1) than ever as the thickness of polarizer layer (light polarizing film).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2000-338329 publications
The content of the invention
Problems to be solved by the invention
However, in the public technology of above-mentioned patent document 1, although having obtained the polarisation of the polarizer with film really
Plate, but the film thickness uniformity of polarizer itself is insufficient.Typically, as polyvinyl alcohol resin used in polarizer,
Material such as 99 moles of more than % of saponification degree of high saponification degree material can be used；But the polyvinyl alcohol of such high saponification degree
Be the viscosity of the aqueous solution of resin viscosity stability is bad, viscosity also high material as the aqueous solution, so as to be difficult to be coated with
In base film.Therefore, membrane thickness unevenness as caused by coating etc. is also produced, is implemented in subsequent handling at stretch processing and dyeing
In the case that reason etc. makes polarizer, become insufficient from the viewpoint of film thickness uniformity from polarizer, dyeing are uneven, seek
Ask the further improvement of the Polarizer for obtaining film.
Therefore, the present invention provides a kind of Polarizer layered product in this context, and it is used for the polarisation for manufacturing film
Plate, wherein, the film thickness uniformity of the resin bed containing polyvinyl alcohol resin is excellent and the film thickness uniformity of polarizer is excellent
It is different, uneven without dyeing.
The solution used to solve the problem
However, the present inventor etc. are in view of the result discovery that the situation is furtherd investigate, forms on base film and contain
When thering is the resin bed of polyvinyl alcohol resin and implementing to stretch, dye, as polyvinyl alcohol resin, using with 1,2- glycol
The polyvinyl alcohol resin of structure, the excellent thing of the film thickness uniformity of the resin bed containing polyvinyl alcohol resin is thus made
Matter, the film thickness uniformity that can obtain polarizer is excellent, without dyeing uneven Polarizer.
That is, purport of the invention is related to a kind of Polarizer layered product, and it is that base film [I] has 1 with containing side chain,
The layered product [III] of the resin bed [II] of the polyvinyl alcohol resin (A) of 2- diol structures is stretched and had containing side chain
What the resin bed [II] of the polyvinyl alcohol resin (A) of 1,2- diol structures was colored.
Following processes (1)~(3) or following processes (1)~(4) and then following works are included in addition, also being provided in the present invention
The manufacture method of the Polarizer layered product of sequence (1)~(5).
Process (1)：The polyvinyl alcohol resin containing side chain with 1,2- diol structures is formed on base film [I]
(A) resin bed [II], so as to obtain layered product [III] process.
Process (2)：The process stretched to layered product [III].
Process (3)：The process dyed to layered product [III].
Process (4)：The process that boron compound processing is carried out to layered product [III].
Process (5)：By transparent protective film [IV] fit to resin bed [II] side containing polyvinyl alcohol resin (A) it
Afterwards, the process of peeling base film.
And then also provide the Polarizer formed using foregoing Polarizer with layered product in the present invention.
The effect of invention
The Polarizer of the present invention is to be formed using the polyvinyl alcohol resin of specific structure on base film with layered product
What resin bed formed；It is excellent so as to polarizer with the film thickness uniformity that can obtain the resin bed containing polyvinyl alcohol resin
Film thickness uniformity is excellent, effect without the Polarizer for dyeing uneven film.These Polarizers are applied to electronic table
Computer, electronic clock, word processor, PC, LCD TV, PDA, automobile or mechanical metering
Liquid crystal display device, sunshade mirror, anti-glare glasses, anaglyph spectacles, the display element (CRT, LCD etc.) of device class etc. are reduced with reflection
Layer, medicine equipment, construction material, toy etc..
Embodiment
Hereinafter, it is described in detail for the present invention.
The Polarizer of the present invention includes the layered product [III] of base film [I] and resin bed [II], the tree with layered product
Lipid layer [II] has the polyvinyl alcohol resin (A) of 1,2- diol structures containing side chain.
It should be noted that the selection of the species, material by base film [I], base film [I] can also be made itself
For transparent protective film described later [IV], in this case, Polarizer supplies by the use of layered product itself as Polarizer, it is of the invention
Polarizer is with layered product also comprising such situation.
As the base film [I] used in the present invention, can use for example by the transparency, mechanical strength, heat endurance,
The film that the excellent thermoplastic resin such as draftability is formed, it is suitable to be selected according to their glass transition temperature or fusing point
Resin and use.
As the concrete example of above-mentioned thermoplastic resin, can include for example：Polyolefin-based resins, polyester based resin, ring
Shape polyolefin-based resins (norbornene resin), (methyl) acrylic acid (ester) are resin, cellulose esters system resin, makrolon
It is resin, polyvinyl alcohol resin, vinylacetate system resin, polyarylate system resin, polystyrene resin, polyether sulfone system tree
Fat, polysulfones system resin, polyamide series resin, polyimides system resins and their mixture, copolymer etc..
Base film [I] can be a film formed by a kind of above-mentioned thermoplastic resin or will be two or more
The film that thermoplastic resin mixes.In addition, base film [I] can be single thin film or plural layers.
As above-mentioned polyolefin-based resins, can include for example：Polyethylene, polypropylene etc.；They can easily stablize
Ground high magnification stretching, thus preferably use.Alternatively, it is also possible to use the ethene-poly- third as obtained from propylene and ethylene copolymer
Alkene copolymer etc..Can also be copolymerized with other kinds of monomer, as can with propylene be copolymerized other kinds of monomer,
It can include for example：Ethene, alpha-olefin.As alpha-olefin, preferably using the alpha-olefin of carbon number more than 4, more preferably carbon
The alpha-olefin of atomicity 4~10.If enumerating the concrete example of the alpha-olefin of carbon number 4~10, have for example：1- butylene, 1-
The straight-chain monoene hydro carbons such as amylene, 1- hexenes, 1- heptene, 1- octenes, 1- decene；3-methyl-1-butene, 3- Methyl-1-pentenes,
The branched monoene hydro carbons such as 4-methyl-1-pentene；Vinyl cyclohexane etc..Propylene is total to other monomers that can be copolymerized therewith
Polymers can be random copolymer, or block copolymer.Component units from the other monomers in copolymer
Containing ratio can be according to《Macromolecule analyzes handbook》(nineteen ninety-five, the distribution of Kinokuniya bookstore) method recorded of page 616, is carried out
Infrared ray (IR) spectroscopic assay and obtain.
In above-mentioned, as form propylene resin film propylene resin, preferably using the homopolymer of propylene, propylene-
Ethylene atactic copolymer, propylene -1- butene random copolymers and propylene-ethylene -1- butene random copolymers.
In addition, form propylene resin film propylene resin stereoregularity be preferably essentially isotaxy or
Syndiotaxy.By the propylene tree that substantially there is the propylene resin of isotaxy or syndyotactic stereoregularity to be formed
Membrane of lipoprotein, its treatability is relatively good and hot environment under mechanical strength.
Above-mentioned polyester based resin is the condensation polymer of the polymer with ester bond, predominantly polybasic carboxylic acid and polyalcohol.Institute
The polybasic carboxylic acid used mainly uses the dicarboxylic acids of binary, such as has：M-phthalic acid, terephthalic acid (TPA), terephthalic acid (TPA) two
Methyl esters, naphthalene diformic acid dimethyl ester etc..In addition, used polyalcohol also mainly uses the glycol of binary, can include：The third two
Alcohol, butanediol, neopentyl glycol, cyclohexanedimethanol etc..As specific resin, can include：Polyethylene terephthalate
Ester, polybutylene terephthalate (PBT), PEN, PBN, poly terephthalic acid three
Methylene base ester, poly- naphthalenedicarboxylic acid trimethylene ester, polycyclohexylene's dimethyl ester, poly- naphthalenedicarboxylic acid cyclohexane dicarboxylates
Deng.Also their hybrid resin, copolymer is preferably used.In above-mentioned, preferably amorphous PET system
Resin, for example, comprising M-phthalic acid as dicarboxylic acids copolymer, include copolymer cyclohexanedimethanol as glycol.
As above-mentioned cyclic polyolefin hydrocarbon system resin, preferably using norbornene resin.Cyclic polyolefin hydrocarbon system resin is
The general name for the resin that cyclic olefin is polymerize as polymerized unit, it can include for example：Japanese Unexamined Patent Publication 1-240517 publications,
Resin described in Japanese Unexamined Patent Publication 3-14882 publications, Japanese Unexamined Patent Publication 3-122137 publications etc.., can as concrete example
Include：The α such as the open loop (co) polymer of cyclic olefin, the addition polymer of cyclic olefin, cyclic olefin and ethene, propylene-
The copolymer (representative for random copolymer) of alkene and they are gathered with the modified grafting of unsaturated carboxylic acid or derivatives thereof
Compound and their hydride etc..As the concrete example of cyclic olefin, can include：Norborneol alkene monomer.
It is commercially available to have various products as cyclic polyolefin hydrocarbon system resin.As concrete example, can include：Topas (registrars
Mark) (Ticona company systems), ARTON (registration mark) (JSR Corporation systems), ZEONOR (registration mark) (Zeon
Corporation systems), ZEONEX (registration mark) (Zeon Corporation systems), Apelle (registration mark) (Mitsui Chemicals
Society's system).
It is resin as above-mentioned (methyl) acrylic acid (ester), any appropriate (methyl) acrylic acid (ester) system can be used
Resin.It can include for example：Poly- (methyl) acrylate such as polymethyl methacrylate, methyl methacrylate-(methyl) third
Olefin(e) acid copolymer, methyl methacrylate-(methyl) acrylate copolymer, methyl methacrylate-acrylate-(methyl)
Acrylic copolymer, (methyl) acrylate-styrene copolymer (MS resins etc.), the polymer with alicyclic alkyl
(for example, methyl methacrylate-cyclohexyl methacrylate copolymer, methyl methacrylate-(methyl) acrylic acid norborneol
Enoate copolymer etc.).It is preferred that poly- (methyl) the acrylic acid C1-6 Arrcostabs such as poly- (methyl) methyl acrylate can be included.As
(methyl) acrylic acid (ester) is resin, more preferably use using methyl methacrylate as main component (50~100 weight %,
Preferably 70~100 weight %) methyl methacrylate system resin.
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 aliphatic acid.Tool as such cellulose esters system resin
Style, it can include：Cellulosic triacetate, cellulose diacetate, cellulose tripropionate, cellulose dipropionate etc..
In addition, it can include：Their copolymer, the material for forming a part for hydroxyl with modifications such as other kinds of substituents
Deng.Wherein, particularly preferred cellulosic triacetate.It is commercially available to have many products for cellulosic triacetate, hold from starting with
It is also advantageous from the viewpoint of Yi Xing, cost.As the example of the commercially available product of cellulosic triacetate, can include：
FUJITAC (registration mark) TD80 (Fujifilm Corporation systems), FUJITAC (registration mark) TD80UF
(Fujifilm Corporation systems), FUJITAC (registration mark) TD80UZ (Fujifilm Corporation systems),
FUJITAC (registration mark) TD40UZ (Fujifilm Corporation systems), KC8UX2M (Konica Minolta, Inc.
System), KC4UY (Konica Minolta, Inc. system) etc..
Above-mentioned polycarbonate-based resin is the work that the polymer formed by monomeric unit via carbonate group bonding is formed
Engineering plastics, it is the resin with high impact resistance, heat resistance, anti-flammability.Further, since with the high transparency, so
It is preferred for optical applications.Also it is commercially available to have：Polymer backbone is repaiied in order to reduce photoelastic coefficient in optical applications
Copolymerization polycarbonate for being referred to as the resin of modified polycarbonate, improving wavelength dependency of decorations etc., can also preferably be used.
Such polycarbonate resin is sold extensively, can be included for example：Panlite (registration mark) (TEIJIN LIMITED.
System), Iupilon (registration mark) (Mitsubishi Engineering-Plastics Corporation systems), SD
POLYCA (registration mark) (Sumika Styron Polycarbonate Limited. systems), CALIBRE (registration mark)
(The Dow Chemical Company systems) etc..
In base film [I], in addition to above-mentioned thermoplastic resin, any appropriate additive can also be added.Make
For such additive, can include for example：Ultra-violet absorber, antioxidant, lubricant, plasticizer, releasing agent, anti-coloring
Agent, fire retardant, nucleator, antistatic additive, pigment and colouring agent etc..Foregoing illustrative thermoplastic resin in base film [I]
Content be preferably 50~100 weight %, more preferably 50~99 weight %, and then preferably 60~98 weight % are especially excellent
Elect 70~97 weight % as.If the content of the thermoplastic resin in base film [I] is very few, there is thermoplastic resin to have originally
High transparency having the tendency of etc. can not be played fully.
The thickness of base film [I] before stretching can be determined suitably, but the sight operational generally from intensity, treatability etc.
Point sets out, preferably 1~500 μm, more preferably 1~300 μm, and then preferably 5~200 μm, most preferably 5~150 μm.
, can be to base material in order to improve the adaptation with the resin bed [II] described later containing polyvinyl alcohol resin (A)
Implement scorching processing of sided corona treatment, corona treatment, fire etc. in the surface for being at least used to be formed resin bed [II] side of film [I].
In addition, in order to improve adaptation, priming paint can also be formed on the surface for being used to be formed resin bed [II] side of base film [I]
The thin layers such as layer, bond layer.
In the present invention, there is the polyvinyl alcohol resin (A) of 1,2- diol structures in base film [I] stacking containing side chain
Resin bed [II].
The resin bed [II] has the polyvinyl alcohol resin (A) of 1,2- diol structures containing side chain.
As the polyvinyl alcohol resin (A), for polyvinyl alcohol resin of the side chain with 1,2- diol structures, you can
Include the polyvinyl alcohol resin for usually containing the 1,2- diol structure units shown in following formulas (1).
(herein, R1、R2、R3It is separately hydrogen or alkyl.)
Such polyvinyl alcohol resin (A) can for example, by (i) vinyl acetate system's monomer and 3,4- diacetoxies-
The copolymer of 1- butylene carries out saponification to manufacture.
As described vinyl acetate system monomer, can include：Vinyl formate, vinylacetate, propionate, valeric acid
Vinyl acetate, vinyl butyrate, vinyl isobutyrate ester, pivalic acid vinyl acetate, caprate, vinyl laurate, stearic acid second
Alkene ester, vinyl benzoate, tertiary ethylene carbonate (vinyl versatate) etc., wherein, preferably using vinylacetate.It
Can be used alone or be applied in combination it is two or more.
In addition, preferably using above-mentioned copolymer in the present invention, but according to circumstances it can not also damage the purpose of the present invention
In the range of, in addition to above-mentioned copolymer composition, it is copolymerized a small amount of such as 5 moles of below the % of other monomers；Example can be included
Such as：The olefines such as ethene, propylene, isobutene, α-octene, α-laurylene, α-octadecylene, acrylic acid, methacrylic acid, crotons
The unsaturated acids such as acid, maleic acid, maleic anhydride, itaconic acid or its salt or monoalkyl ester or dialkyl ester etc., acrylonitrile, first
The amide-type such as the nitriles such as base acrylonitrile, DAAM, acrylamide, Methacrylamide, ethylene-sulfonic acid, allyl
The alkene sulfonic acids such as base sulfonic acid, methallylsulfonic acid or its salt, allylin, alkyl vinyl ethers, dimethyl alkene
Propyl ethylene ketone, NVP, vinyl chloride, vinylidene chloride, polyoxyethylene (methyl) allyl ether, polyoxy are sub-
Propyl group (methyl) allyl ether etc. polyoxy alkylidene (methyl) allyl ether, polyoxyethylene (methyl) acrylate, polyoxy are sub-
Propyl group (methyl) acrylate etc. polyoxy alkylidene (methyl) acrylate, polyoxyethylene (methyl) acrylamide, polyoxy are sub-
Propyl group (methyl) acrylamide etc. polyoxy alkylidene (methyl) acrylamide, polyoxyethylene (1- (methyl) acrylamide -1,1-
Dimethyl propyl) ester, polyoxyethylene vinyl ethers, polyoxypropylene vinyl ethers, polyoxyethylene allyl amine, polyoxy be sub-
Allyl amine, polyoxyethylene vinyl amine, polyoxypropylene vinyl amine, ethylene carbonate, allyl acetic acid ester etc..
And then it can also include：N acrylamide methyl trimethoxy ammonium chloride, N acrylamide ethyl-trimethyl chlorination
Ammonium, N acrylamide hydroxypropyltrimonium chloride, 2- acryloyloxyethyl trimethyls ammonium chloride, 2- methacryloxy second
Base trimethyl ammonium chloride, 2- hydroxy-3-methyl acryloxypropyls trimethyl ammonium chloride, pi-allyl trimethyl ammonium chloride, methyl
Pi-allyl trimethyl ammonium chloride, 3- butylene trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, diethyl diallyl chlorination
The monomer containing cation group such as ammonium, monomer containing acetoacetyl etc..
Above-mentioned vinyl acetate system monomer and 3,4- diacetoxy -1- butylene (and then there are other monomers) are copolymerized
When, it can use and the polymerizing condition of known vinyl acetate system monomer and method that to polymerize gimmick same.
As polymerization gimmick, can use for example：Polymerisation in bulk, polymerisation in solution, suspension polymerisation, dispersin polymerization or emulsion are gathered
Method known to conjunction etc., generally carries out polymerisation in solution.
In addition, the Adding Way of monomer component during for copolymerization has no particular limits, can use once add, point
It is secondary the arbitrary method such as to add, be continuously added to；But from make 3,4- diacetoxy -1- butylene polyvinyl ester based polymer point
It is evenly distributed in subchain, from the viewpoint of the fusing point of polyvinyl alcohol reduces etc. in terms of physical property, polymerization is preferably added dropwise, it is especially excellent
Select the polymerization based on HANNA methods.
As the solvent used in the copolymerization, the lower alcohols such as methanol, ethanol, propyl alcohol, butanol can be generally included, third
Ketones such as ketone, methyl ethyl ketone etc.；Industrially preferably use methanol.
The dosage of solvent can consider the chain transfer constant of solvent and suitably selected with the degree of polymerization of combining target copolymer,
For example, when solvent is methanol, can from S (solvent)/M (monomer)=0.01~10 (weight ratio), be preferably 0.05~3 (weight
Amount ratio) scope of degree selects.
Polymerization catalyst can be used during copolymerization, as the polymerization catalyst, can be included for example：Azo system is catalyzed
Agent, peroxide catalyst, redox series catalysts etc., specifically, it can include：Azo isobutyronitrile, acetyl peroxidating
Catalysts for radical polymerization known to thing, benzoyl peroxide, lauroyl peroxide etc. or azobis dimethyl valeronitrile, azo are double
Low temperature active catalysts for radical polymerization such as methoxyl group methyl pentane nitrile etc..
The dosage of polymerization catalyst is different according to the species of catalyst, it is impossible to lumps together, can be according to polymerization speed
Any selection.For example, in the case of using azo isobutyronitrile, acetyl pexoxide, it is preferably relative to vinyl acetate system monomer
0.01~0.2 mole of %, particularly preferably 0.02~0.15 mole of %.
In addition, the reaction temperature of copolyreaction is preferably set to by 40 DEG C to boiling point degree according to the solvent that uses, pressure.
Then, the copolymer obtained is saponified, but the saponification and the Saponification Conditions of known polyvinyl alcohol resin
It is essentially identical.That is, generally copolymer obtained above is dissolved or dispersed in alcohol or aqueous alcohol, entered using saponification catalyst
OK.As alcohol, can include for example：Methanol, ethanol, propyl alcohol, tert-butyl alcohol etc., but particularly preferably use methanol.Copolymerization in alcohol
The concentration of thing suitably selects according to the viscosity of system, is generally selected from 10~60 weight % scope.As saponification catalyst,
It can include for example：The hydroxide of the alkali metal such as sodium hydroxide, potassium hydroxide, sodium methoxide, caustic alcohol, potassium methoxide, lithium methoxide,
The acid catalyst such as base catalyst as alkoxide, sulfuric acid, hydrochloric acid, nitric acid, methanesulfonic acid, zeolite, cationic ion-exchange resin.
For the dosage of the saponification catalyst, can suitably be selected according to method for saponification, target saponification degree etc., but use
In the case of base catalyst, 1 mole of total amount for being commonly angled relative to vinyl acetate system monomer and 3,4- diacetoxy -1- butylene is
0.1~30 mM, preferably 2~17 mMs.
In addition, for the reaction temperature of saponification, there is no particular limitation, preferably 10~60 DEG C, more preferably 20
~50 DEG C.
During by above-mentioned saponification, the ester moiety of vinyl acetate system monomer and the acetoxyl group of 3,4- diacetoxy -1- butylene
Part is converted simultaneously as hydroxyl, so as to manufacture above-mentioned polyvinyl alcohol resin (A).
This is due to that can obtain side chain to have the polyvinyl alcohol resin (A) of 1,2- diol structures, but in the present invention,
The mean saponification degree of the polyvinyl alcohol resin (A) is preferably higher, usually 90 moles of more than %, and particularly preferably 95 rub
You are more than %, and then preferably 98 moles of more than %, particularly preferably 99 moles of more than %；If the saponification degree is too small,
Water resistance when having the tendency of Polarizer making reduces.
It should be noted that the ester moiety and 3,4- diethyl acyl-oxygen of the mean saponification degree vinyl acetate system monomer in the present invention
In the acetoxy moieties total amount of base -1- butylene to hydroxyl change rate of change (mole %) represent (in saponification, 3,4- bis-
The acetoxy moieties of acetoxyl group -1- butylene are almost saponified completely).
In addition, the viscosity of above-mentioned polyvinyl alcohol resin (A) is according to the viscosity conversion that the 4 weight % aqueous solution are made, generally
Preferably 8~400mPas, particularly preferably 12~300mPas, and then preferably 16~270mPas；If described 4
The viscosity of the weight % aqueous solution is too small, and draftability when having the tendency of to manufacture Polarizer reduces；There is the flat of film if excessive
The tendency that face flatness, light transmittance reduce.
And then as polyvinyl alcohol resin (A) side chain 1,2- diol structures content, preferably 0.01~20 rubs
You are %, particularly preferably 0.05~15 mole of %, and then preferably 0.1~12 mole of %, most preferably 0.1~6 mole of %；Such as
Content described in fruit, which is crossed, to be difficult to obtain the effect of the present invention at least, on the contrary if crossing the system at most not only having polyvinyl alcohol resin
The tendency for becoming difficult is made, the tendency that water resistance when also Polarizer makes reduces.
It should be noted that the manufacture method as the polyvinyl alcohol resin (A) used in the present invention, for above-mentioned
(i) method by the copolymer saponification of vinyl acetate system monomer and 3,4- diacetoxy -1- butylene has carried out detailed narration, but not
Methods described is defined in, can also be included for example：(ii) to the ethylene alkenyl Asia second shown in vinyl acetate system monomer and formula (2)
The method that the copolymer of ester carries out saponification and decarboxylation；(iii) the 2,2- dialkyl group to vinyl acetate system monomer and shown in formula (3)-
The copolymer of 4- vinyl -1,3- dioxolanes carries out saponification and de- ketalization method；(iv) to vinyl esters system monomer
Method for carrying out saponification with the copolymer of allylin etc., there is no particular limitation.
(herein, R1、R2、R3It is separately hydrogen or alkyl.)
(herein, R1、R2、R3、R4、R5It is separately hydrogen or alkyl.)
In addition, in the present invention, side chain 1 can also be applied in combination as polyvinyl alcohol resin (A), 2- diol structures contain
The different two or more polyvinyl alcohol resins such as amount, mean saponification degree, viscosity.
And then in the present invention, from the viewpoint of the raising effect of water resistance when being made from Polarizer, as polyvinyl alcohol
It is resin, can also be by the polyethenol series tree beyond foregoing polyvinyl alcohol resin (A) and foregoing polyvinyl alcohol resin (A)
Fat (B) is applied in combination.
When polyvinyl alcohol resin (A) and polyvinyl alcohol resin (B) are applied in combination, the side that is preferably calculated with following formula
The average content of chain 1,2- diol structures is 0.1~20 mole of % scope.
Herein, side chain 1, the average content (mole %) of 2- diol structures calculate as follows.
That is, by the side chain 1 of polyvinyl alcohol resin (A), the contents of 2- diol structures is set to α moles of %, will be relative to poly-
When the content ratio of vinyl alcohol resin (A) and the polyvinyl alcohol resin (A) of polyvinyl alcohol resin (B) total amount is set to X%
Calculated by following formula.
Average content (mole %)=(X/100) × α of side chain 1,2- diol structures
Particularly, from the viewpoint of the effect for improving draftability, main body group can be used as using polyvinyl alcohol resin (A)
Conjunction uses polyvinyl alcohol resin (B), for example, its content ratio (A/B) (weight ratio) is usually 95/5~50/50, is preferably
90/10~55/45；From the viewpoint of the effect for improving water resistance, body combination can be used as using polyvinyl alcohol resin (B)
Using polyvinyl alcohol resin (A), for example, its content ratio (A/B) (weight ratio) is usually 5/95~50/50, preferably 10/
90~45/55, it is not limited, can suitably select compounding ratio as needed.
As above-mentioned polyvinyl alcohol resin (B), as long as the material used in Polarizer purposes all the time
, usual mean saponification degree is 90 moles of more than %, preferably 95 moles of more than %, particularly preferably 98 moles of more than %,
And then preferably 99 moles of more than %.If the mean saponification degree is too small, there is what water resistance during Polarizer making reduced
Tendency.
And then the viscosity of the polyvinyl alcohol resin (B) is according to the viscosity conversion that the 4 weight % aqueous solution are made, generally
Preferably 8~500mPas, particularly preferably 20~400mPas, and then preferably 40~300mPas.If 4 weights
The viscosity of the amount % aqueous solution is too small, and draftability when having the tendency of Polarizer making reduces, and has the plane of film if excessive
The tendency that flatness, the transparency reduce.
It should be noted that the polyvinyl alcohol resin (B) as long as polyethylene beyond polyvinyl alcohol resin (A)
Alcohol system resin, then there is no particular limitation, but preferably generally unmodified polyvinyl alcohol resin.Alternatively, it is also possible to for containing
There are olefines (ethene, propylene, the positive fourth of a small amount of unsaturated carboxylic acid (including salt, ester, acid amides, nitrile etc.), carbon number 2~30
Alkene, isobutene etc.), ethene ethers, unsaturated sulfonic acid salt etc. can be with the polyethenol series tree of vinyl acetate copolymerized composition
Fat.
In addition, as polyvinyl alcohol resin (B), viscosity of saponification degree, the 4 weight % aqueous solution etc. can be applied in combination no
Same two or more polyvinyl alcohol resins.
In addition, when polyvinyl alcohol resin (A) and polyvinyl alcohol resin (B) is applied in combination, polyvinyl alcohol resin (A)
Difference with the mean saponification degree of polyvinyl alcohol resin (B) is 6 moles of below %, from the viewpoint of the transparency and it is preferred that, it is special
You Xuanwei not 3 moles of below %, and then preferably 2 moles of below %.
In the present invention, the polyvinyl alcohol resin that there is 1,2- diol structures containing side chain is formed on base film [I]
(A) during resin bed [II], can include for example：The solution, preferably water-soluble of the resin of polyvinyl alcohol resin (A) will be contained
The method that liquid is coated on base film [I] and is dried.
As the solution as used herein containing polyvinyl alcohol resin (A), from coating drying property aspect,
A small amount of alcohols, such as methanol, ethanol, normal propyl alcohol, isopropanol etc. can be contained.
It should be noted that in the resin solution, from the viewpoint of resin bed [II] flexibility, preferably compounding increases
Mould agent；From the viewpoint of it will slide easiness during layered product [III] rolled, surfactant is preferably compounded；It is thin from preventing
From the viewpoint of the xanthochromia of film, preferably it is compounded known to antioxidant etc. and matches somebody with somebody mixture.
When above-mentioned resin solution is coated on into base film [I], as rubbing method, it can suitably select to use：Wire rod
The rolling method such as coating, inverse coating, gravure coating process, spin-coating method, silk screen rubbing method, jetting type rubbing method, dip coating, spraying process
Deng.In the case that base film [I] has prime coat or peel ply, in the prime coat or peel ply coating aforementioned resin solution；
Aforementioned resin solution is coated with directly on base film [I] in the case of without prime coat.
For the concentration of aforementioned resin solution, from the viewpoint of productivity ratio when from dissolubility and drying, preferably 5~50
Weight %, more preferably 7~40 weight %, particularly preferably 10~30 weight %.Resin solution concentration then has drying when too small
Load becomes tendency big and that production capacity reduces, and then having the tendency of viscosity when excessive becomes too high and be difficult to uniformly dissolve.
In addition, drying temperature is usually 30~200 DEG C, preferably 40~150 DEG C, drying time is usually 5~30 minutes
Left and right.
In the present invention, the thickness of the resin bed [II] containing polyvinyl alcohol resin (A), operated from intensity, treatability etc.
From the viewpoint of property, thin layer, preferably 1~50 μm, particularly preferably 2~40 μm, and then preferably 3~30 μm.If institute
It is excessively thin to state thickness, is become too thin after having the tendency of stretching and dyeability reduction, easy produce is caused by foaming etc. if blocked up
Float, peel off, so as to bad order tendency.
In addition, the thickness ratio ([I]/[II]) of base film [I] and resin bed [II] is preferably 0.02~500, it is especially excellent
Elect 0.025~150 as.There is the layered product [III] in the solution of iodine staining processing etc. to become if the thickness ratio is too small
The tendency that soft, treatability reduces, having the tendency of stretching if excessive easily becomes uneven.
In such manner, it is possible to base film [I] is obtained with having the polyvinyl alcohol resin (A) of 1,2- diol structures containing side chain
Resin bed [II] layered product [III].Then, implement stretch processing for layered product [III] and contaminated using iodine or dichroism
The dyeing processing of material, so as to obtain the Polarizer layered product of the present invention.
That is, Polarizer layered product of the invention is by including following processes (1)~(3), preferably include process
(4) in addition to the manufacture method of process (5) and obtain.
Process (1)：The polyvinyl alcohol resin containing side chain with 1,2- diol structures is formed on base film [I]
(A) resin bed [II], so as to obtain layered product [III] process.
Process (2)：The process stretched to layered product [III].
Process (3)：The process dyed to layered product [III].
Process (4)：The process that boron compound processing is carried out to layered product [III].
Process (5)：By transparent protective film [IV] fit to resin bed [II] side containing polyvinyl alcohol resin (A) it
Afterwards, the process of peeling base film.
In above-mentioned operation, process (1) is as described above, process (2), process (3), process (4), process (5) are as described below.Need
It is noted that the order of process (2)~(5) can be selected suitably.
The Polarizer of the present invention is with layered product by passing through common drawing for the layered product [III] obtained in process (1)
Stretch processing, dyeing processing, preferably further manufactured by processes such as boron compound processing.
It can suitably select with the following method, such as have in the present invention：(1) layered product [III] is stretched and is impregnated in
After being dyed in the staining solution of iodine or dichroic dye, the method for progress boron compound processing；(2) while stretched and contaminated
After color, the method for progress boron compound processing；(3) after being dyed and stretched with iodine or dichroic dye, boron compound is carried out
The method of processing；(4) after dyeing, the method that is stretched in the solution of boron compound；(5) stretch and carry out boron compound
The poststaining of processing, the method stretched in the solution of boron compound；(6) dyeing processing is carried out in stretching and boronation is closed
Method of thing processing etc..So, the stretching and dyeing and then boron compound processing of layered product [III] (non-stretched layered product)
Both it can respectively carry out, can also simultaneously carry out.
In the present invention, from the viewpoint of optical characteristics, preferably in dyeing process (3), boron compound treatment process (4)
The stretching process (2) of layered product [III] is carried out at least one process.
In addition, in the present invention, from the viewpoint of optical characteristics, the drawing preferably in the stretching process (2) of layered product [III]
Multiplying power is stretched for more than 2 times, and then preferably 2~10 times, particularly preferably 2~7 times.If stretching ratio is too small, have not
To the tendency of sufficient optical characteristics.
It should be noted that the preceding process of the dyeing process (3) as layered product [III], carries out stretch processing in advance, this
From improve the orientation of polyvinyl alcohol resin, obtain from the viewpoint of good optical characteristics and it is preferred that, in this case
Stretching ratio is 1.1~5 times, particularly preferably 1.2~4 times.
Total stretching ratio of layered product [III] generally single shaft direction be 3~10 times, preferably 3.5~7 times, as described above,
Particularly preferably in the liquid such as dyeing process, boron compound treatment process stretch for more than 2 times.Now, in stretching side
To vertical direction also carry out fraction of stretching (be stretched as preventing degree that width shrinks or its more than) and can be with
's.Temperature during stretching preferably selects from 20~170 DEG C, if it is considered that further at dyeing process (3) and boron compound
Stretching process (2) is carried out at least one process of science and engineering sequence (4), then preferably 20~90 DEG C, particularly preferably 25~80 DEG C.
And then as long as stretching ratio is finally set in aforementioned range, stretched operation can not only be implemented a stage, can also
Implement in the stage of any range of manufacturing process.
To layered product [III] dyeing by the liquid containing iodine or dichroic dye is contacted with layered product [III] and
Carry out.The solution containing iodine can be generally used, wherein, preferably use compounded with the water-soluble of the iodine-potassium iodide with KI
Liquid；The KI, which has, to be more prone to for the useful I of the optical property of polarizer3 -、I5 -The work of the auxiliary agent of plasma
With.In the aqueous solution of iodine-potassium iodide, the concentration of iodine is 0.1~2%, and the concentration of KI is 0.1~50%, KI/iodine
Weight ratio preferably 3~60.On the other hand, as dichroic dye, known dichroic dye can be used, can preferably be made
Use Azo.In the above-mentioned solution containing dichroic dye, sodium chloride, sodium sulphate, anhydrous sodium sulfate, three can be contained
Polyphosphate sodium etc. is used as dyeing assistant.
Dyeing time was practical for 30~500 seconds or so.The temperature of processing bath is preferably 5~50 DEG C.In the aqueous solution, remove
Beyond aqueous solvent, it can also contain on a small quantity with the organic solvent with the intermiscibility of water.As contact means, leaching can be used
The arbitrary means such as stain, coating, spraying.
It is preferred that the layered product [III] for being colored processing is then handled with boron compound.As boron compound, boric acid,
Borax is practical.Boron compound can in the form of the aqueous solution or water-organic solvent mixed liquor, with the weight of concentration 0.5~10
The degree for measuring % uses, and it is preferable in practical KI is coexisted with the weight % of concentration 0.1~10 degree in a liquid.
Facture is preferably infusion process, naturally it is also possible to implements rubbing method, spray-on process.Temperature during preferred process is 20~80 DEG C of left sides
The right side, processing time is 15 seconds~20 minutes or so, in addition, it is also preferred that carrying out stretched operation in processes as needed.
So, the Polarizer layered product of the present invention is obtained, is that base film [I] has 1,2- glycol with containing side chain
The layered product [III] of the resin bed [II] of the polyvinyl alcohol resin (A) of structure is stretched and has 1,2- bis- containing side chain
The Polarizer layered product that the resin bed [II] of the polyvinyl alcohol resin (A) of alcohol structure is colored.
It should be noted that dyed by the resin bed [II] that will contain polyvinyl alcohol resin (A), thus resin bed
[II] turns into polarizer.
In the present invention, Polarizer obtained above is with layered product (stretched and dyeing layered product) at resin bed [II]
The one side of (polarizer) has base film [I], and the base film [I] can be directly as the transparent protective film of Polarizer
[IV] and use.On the other hand, can be in resin bed [II] (polarizer) be bonded without base film [I] side is transparency protected
Film [IV].Furthermore it is possible to by resin bed [II] (polarizer) from base film [I] stripping after, in the resin bed [II]
The both sides fitting transparent protective film [IV] of (polarizer).In addition, the resin bed [II] in obtained Polarizer layered product is (partially
Shake piece) other base materials can be transferred to.Can be by (such as saturating in resin bed [II] (polarizer) and other base films
Bright protective film [IV]) fitting after by base film [I] peel off, so as to be transferred；Furthermore it is possible to by thin from base material
Film [I] makes the resin bed [II] (polarizer) be bonded with other base materials after resin bed [II] (polarizer) is peeled off, so as to
Transferred.
In above-mentioned, the method for preferable process (5) from the viewpoint of optical characteristics：Transparent protective film [IV] is bonded
To after resin bed [II] (polarizer) side containing polyvinyl alcohol resin (A), peeling base film [I].Need what is illustrated
It is that base film [I] is sometimes due to stretching, dyeing condition etc. and albefaction, so as to which translucency reduces.
As transparent protective film [IV], can use same with the foregoing material illustrated as base film [I]
Material.The thickness of transparent protective film [IV] can be determined suitably, generally be seen from the operability such as intensity, treatability, thin layer etc.
Point sets out, and is 1~500 μm or so.Particularly preferably 1~300 μm, more preferably 5~200 μm.
In addition, the thickness ratio ([IV]/[II]) of transparent protective film [IV] and resin bed [II] (polarizer) is preferably
0.04~1000, particularly preferably 0.05~300.If the thickness ratio is too small, there are transparent protective film [IV] and resin
The fitting of layer [II] (polarizer) becomes difficult tendency；There is thin layer if excessive to lose and optical property reduction.
It should be noted that in the case of being provided with transparent protective film [IV] in the both sides of resin bed [II] (polarizer),
Can also also may be used in its table using the transparent protective film [IV] (including base film) formed by identical polymeric material
To use the transparent protective film [IV] formed by different polymeric material etc..
In addition, transparent protective film [IV] generally fitted to by bonding agent it is foregoing containing polyvinyl alcohol resin (A)
Resin bed [II] (polarizer), surface modification treatment is carried out before bonding agent can also be stated before coating.Handled as specific,
It can include：Sided corona treatment, corona treatment, prime treatment, saponification process, utilize processing of coupling agent etc..
For the not face Nian Jie with resin bed [II] (polarizer) of aforementioned transparent protective film [IV], can also implement hard
Coating or antireflection process, anti-adhesion, the processing for the purpose of spreading and be anti-dazzle.
It should be noted that foregoing anti-reflection layer, anti adhering layer, diffusion layer, antiglare layer etc. can be provided directly as it is transparent
Protective film [IV], in addition it is also possible to be set respectively as other optical layer and transparent protective film [IV].
Aforementioned resin layer [II] (polarizer) processing bonding with transparent protective film [IV] can use bonding agent.As
Bonding agent, it can exemplify：Isocyanates system bonding agent, polyethenol series bonding agent, gelatin system bonding agent, latex system of ethene system,
Water system polyester etc..Foregoing bonding agent uses usually as the bonding agent comprising the aqueous solution, usually contains 0.5~60 weight %'s
Solid constituent.Outside above-mentioned, as resin bed [II] (polarizer) and the bonding agent of transparent protective film [IV], it can include：
Ultraviolet hardening bonding agent, electron ray curing type bonding agent etc..Above-mentioned electron ray curing type bonding agent is for above-mentioned each
Kind transparent protective film [IV] shows suitable cohesive.Particularly, for being difficult to meet that the acrylic acid (ester) of cohesive is set
Fat also shows good cohesive.In addition, in bonding agent used in the present invention, metallic compound filler can be contained.
The Polarizer obtained in the present invention is also sometimes as needed on the surface of its side, is formed with commonly known method
Transparent adhesive phase and for practicality.As adhesive phase, with butyl acrylate, ethyl acrylate, methyl acrylate, propylene
α-the monoolefin carboxylic acid such as the acrylate such as sour 2- ethylhexyls and acrylic acid, maleic acid, itaconic acid, methacrylic acid, crotonic acid
Copolymer (also including with the addition of acrylonitrile, vinylacetate, the material of vinyl monomer as styrene) be used as main body；By
In that will not hinder, the polarized light property of Polarizer is thus particularly preferred, and it is not limited, as long as the adhesive with the transparency
It can then use, such as polyvinylether system, rubber series etc..
The Polarizer obtained in the present invention can be effectively applied to desk top computer, electronic clock, word processor,
It is the liquid crystal display device of PC, TV, PDA, automobile or mechanical gauge class etc., sunshade mirror, anti-dazzle
Mesh glasses, anaglyph spectacles, display element (CRT, LCD etc.) reduction reflecting layer, medicine equipment, construction material, toy etc..
Embodiment
Hereinafter, include embodiment to illustrate the present invention in more detail, but the present invention is without departing from its main idea
Scope, it is not limited to these embodiments.
It should be noted that " part ", " % " represent weight basis in example.
It is carried out as follows for each physical property.
(1) content (mole %) of the 1,2- diol structures of side chain
With1H-NMR (internal standard compounds：Tetramethylsilane, solvent：d6- DMSO) it is measured and calculates.
(2) mean saponification degree (mole %) of polyvinyl alcohol resin
Analyzed 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, it is measured with Hoppler viscosimeter.
(embodiment 1)
There is polyvinyl alcohol (the A) (content of side chain 1,2- diol structures of 1,2- diol structures using side chain：1.0 rub
That %, mean saponification degree：99.8 moles of %, 4% aqueous solution viscosity (20 DEG C)：85mPas), the poly- second of concentration 14% is modulated
The enol aqueous solution.
In amorphism PET (PET) film (thickness as base film [I]：100 μm) on apply
14% polyvinyl alcohol water solution described in cloth, so that dried thickness turns into 10 μm, it is dried at 60 DEG C of drying temperature, by
This obtains the layered product [III] of PET film/polyvinyl alcohol layer.
For obtained layered product [III], the film thickness uniformity of resin bed is evaluated as follows.
(film thickness uniformity of polyvinyl alcohol resin layer)
From layered product obtained above [III] peeling base film [I], on the resin bed [II], film thickness gauge is used
(society of tail rugged making institute system " DIGITAL LINEAR GAUGES D-10HS ") to the width evaluation thickness of resin bed [II]
Uniformity.The measure determines 20 points of thickness with 5mm spacing, and the amplitude of variation (maximum-minimum value) of thickness is relative to flat
The ratio of equal thickness, is carried out as follows evaluation.
Zero is less than 10%
△ 10% is less than 15%
More than × 15%
Then, for the layered product [III], stretch processing, dyeing processing, boron compound are carried out according to following conditions
Processing, obtains Polarizer layered product.
That is, after carrying out 1.8 times of uniaxial tensions to layered product [III] at 130 DEG C, in the aqueous solution (30 of boric acid 3%
DEG C) in dipping 30 seconds.Afterwards, the iodine 0.4%, (iodine of KI 1.2% are being included：KI=1：3 (weight ratios)) staining trough
Dipping is after 60 seconds in (30 DEG C), boric acid 3%, KI 3% the aqueous solution in impregnate 60 seconds at 40 DEG C.And then in boron
Sour 4%, impregnated 120 seconds at 70 DEG C in the aqueous solution of KI 5% and uniaxial tension is to 3.3 times, so as to obtain formed with inclined
Shake the Polarizer layered product of piece.
For obtained Polarizer layered product, optical characteristics is evaluated as follows.
(optical characteristics)
Polarizer is peeled off from Polarizer obtained above with layered product, on the polarizer, using with integrating sphere
Spectrophotometer (Japan's light splitting society's system " VAP7070 "), measure singleton transmittance (%), degree of polarization (%).
(embodiment 2~3, comparative example 1)
In addition to the condition of table 1, set similarly to Example 1, obtain layered product [III] and Polarizer stacking
Body.For obtained Polarizer layered product, evaluation similarly to Example 1 is carried out.
The evaluation result of embodiment and comparative example is shown in table 1 below.
[table 1]
By the above results, in the case of using existing unmodified polyvinyl alcohol resin as comparative example 1, although
Optical characteristics is good, but the film thickness uniformity of the resin bed containing polyvinyl alcohol resin is poor；On the other hand, using embodiment 1
In the case of the polyvinyl alcohol resin of specific structure as~3, the viscosity stability of polyvinyl alcohol resin is very excellent,
So the film thickness uniformity of the resin bed containing polyvinyl alcohol resin is excellent and then optical characteristics is also good.Therefore, obtain
The film thickness uniformity of polarizer is very excellent, uneven without dyeing, highly useful as film Polarizer.
It should be noted that the specific mode of the present invention is shown in above-described embodiment, but above-described embodiment is only
It is simple to illustrate, the explanation limited is not done.Those skilled in the art can seek various obvious within the scope of the invention
Deformation.
Industrial applicability
The base film [I] of the Polarizer layered product of the present invention and the polyethylene containing side chain with 1,2- diol structures
The layered product [III] of the resin bed [II] of alcohol system resin (A) is stretched and has the poly- second of 1,2- diol structures containing side chain
The resin bed [II] of enol system resin (A) is colored, so the film thickness uniformity of resin bed [II] is excellent and then the film of polarizer
Thick excellent in uniformity, no dyeing are uneven.Moreover, obtained Polarizer as the reel film of light polarizing film, 1/2 wavelength plate or
Reel film used in 1/4 wavelength plate, the reel film of phase-contrast film used in liquid crystal display device are highly useful
, the light polarizing film is applied to desk top computer, electronic clock, word processor, PC, TV, individual digital and helped
Liquid crystal display device, sunshade mirror, anti-glare glasses, anaglyph spectacles, the display element of reason machine, automobile or mechanical gauge class etc.
(CRT, LCD etc.), which is used, reduces reflecting layer, medicine equipment, construction material, toy etc..
Claims (11)
1. a kind of Polarizer layered product, it is characterised in that it is base film [I] with having 1,2- diol structures containing side chain
Polyvinyl alcohol resin (A), the layered product [III] for the resin bed [II] that thickness is 1~50 μm is stretched and contains side chain
What the resin bed [II] of the polyvinyl alcohol resin (A) with 1,2- diol structures was colored.
2. Polarizer layered product according to claim 1, it is characterised in that the stretching ratio of layered product [III] is 2 times
More than.
3. Polarizer layered product according to claim 1 or 2, it is characterised in that the side chain of polyvinyl alcohol resin (A)
The contents of 1,2- diol structures be 0.01~20 mole of %.
4. Polarizer layered product according to claim 1 or 2, it is characterised in that polyvinyl alcohol resin (A's) is averaged
Saponification degree is 90 moles of more than %.
5. Polarizer layered product according to claim 1 or 2, it is characterised in that the viscosity of polyvinyl alcohol resin (A)
It is 8~400mPas according to the viscosity conversions of the 4 weight % aqueous solution is made.
6. a kind of manufacture method of Polarizer layered product, it is characterised in that including following processes (1)~(3)：
Process (1)：The polyvinyl alcohol resin (A) that there is 1,2- diol structures containing side chain, thickness are formed on base film [I]
The resin bed [II] for 1~50 μm is spent, so as to obtain layered product [III] process；
Process (2)：The process stretched to layered product [III]；
Process (3)：The process dyed to layered product [III].
7. the manufacture method of Polarizer layered product according to claim 6, it is characterised in that also including following processes
(4)：
Process (4)：The process that boron compound processing is carried out to layered product [III].
8. the manufacture method of Polarizer layered product according to claim 7, it is characterised in that in dyeing process (3) and
The stretching process (2) of layered product [III] is carried out at least one process of boron compound treatment process (4).
9. the manufacture method of the Polarizer layered product according to any one of claim 6~8, it is characterised in that stacking
Stretching ratio in the stretching process (2) of body [III] is more than 2 times.
10. the manufacture method of the Polarizer layered product according to any one of claim 6~8, it is characterised in that also wrap
Include following processes (5)：
Process (5)：After transparent protective film [IV] is fitted into resin bed [II] side containing polyvinyl alcohol resin (A),
The process of peeling base film [I].
11. a kind of Polarizer, it is characterised in that it is the Polarizer layered product described in any one of usage right requirement 1~5
Form.
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| JP2013-054564 | 2013-03-18 | ||
| JP2013054564 | 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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| CN104969100A CN104969100A (en) | 2015-10-07 |
| CN104969100B true CN104969100B (en) | 2018-01-23 |
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| JP6770532B2 (en) * | 2015-12-24 | 2020-10-14 | 花王株式会社 | Mold release composition for casting |
| CN107219583B (en) * | 2016-03-22 | 2021-12-03 | 住友化学株式会社 | Polarizing plate, polarizing film, and method for producing polarizing plate |
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| 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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| JP4279944B2 (en) * | 1999-06-01 | 2009-06-17 | 株式会社サンリッツ | Manufacturing method of polarizing plate |
| 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 |
| 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 |
| JP4800269B2 (en) * | 2007-07-19 | 2011-10-26 | 日本合成化学工業株式会社 | Polyvinyl alcohol film for polarizing film, polarizing film, and polarizing plate |
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- 2014-03-17 JP JP2014053001A patent/JP2014206735A/en active Pending
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| KR102173669B1 (en) | 2020-11-03 |
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