CN104395791B

CN104395791B - Thin Polarizer and its manufacture method

Info

Publication number: CN104395791B
Application number: CN201480000911.2A
Authority: CN
Inventors: 南星铉; 罗钧日; 郑棕炫; 柳惠珉
Original assignee: LG Chemical Co Ltd
Current assignee: Shanjin Optoelectronics Nanjing Co Ltd
Priority date: 2013-06-18
Filing date: 2014-06-13
Publication date: 2018-03-13
Anticipated expiration: 2034-06-13
Also published as: CN104395791A; WO2014204134A1

Abstract

The invention provides a kind of method for preparing thin Polarizer, it includes：The non-stretched film based on polyvinyl alcohol (PVA) is attached on non-stretched basilar memebrane to form film laminates by using gravitation therebetween or using adhesive；Stretch the film laminates；First diaphragm is attached on the film based on PVA of the film laminates of the stretching；And being separated based on PVA film from the basilar memebrane for the first diaphragm will be pasted with thereon.

Description

Thin Polarizer and its manufacture method

Technical field

This disclosure relates to a kind of thin Polarizer and its manufacture method, and be 10 μ including thickness more particularly, to one kind The thin Polarizer of below m polaroid and the manufacture method for making different types of Polarizer be manufactured during single.

Background technology

The polaroid used in Polarizer is inclined in particular directions for natural light or random polarised light to be changed into The optics of the light to shake, and it is had been widely used for such as liquid crystal display (LCDs) and Organic Light Emitting Diode (OLED) Display device in.As the polaroid commonly used in this display device, generally used containing iodine compound or Dichroic dyestuff and the light polarizing film based on polyvinyl alcohol (PVA) with the strand being orientated in a predetermined direction.

Light polarizing film based on PVA can dye film based on PVA and then with predetermined party by using iodine or dichroic dyestuff To the stretching film and manufacture film crosslinking.In this case, stretching step can be by such as boric acid aqueous solution or iodine water Wet method stretching, aerial dry method tension in the solution of solution etc. are carried out.According to the foregoing manufacturing process of correlation technique In, in order to be stretched it without being broken, before the film is stretched, the film based on PVA is needed more than 60 μm Thickness.In the case where the thickness of film of the stretching step foregoing description based on PVA is equal to or less than 60 μm, the film based on PVA Interior swellbility can increase, and the modulus of the per unit area of this film can increase in drawing process, thus may hold The fracture of film easily occurs.

Meanwhile according to the trend of nearest display device slimming, it is also desirable to which Polarizer has the thickness reduced.But In the case of using the film based on PVA of the thickness more than 60 μm according to correlation technique, exist in terms of the thickness of polaroid is reduced Limitation.Therefore, the research to manufacturing the polaroid with the thickness reduced has been carried out.

Korean Patent Publication No. 2010-0071998 discloses a kind of method that thin polaroid is manufactured using layered product, institute Layered product is stated to form the material of basalis by using hydrophilic polymer layer coated substrate layer or coextrusion and form hydrophily The material of polymeric layer manufactures.But in the case where using the coating or coetrusion, PVA layers after the stretch It may be not easy to separate each other with basalis.The peel strength of high intensity is needed due to they being separated each other, therefore, is being separated During may occur such as the defects of the PVA layers damage or deformation, so as to cause the optical property of the film based on PVA The deterioration of (for example, degree of polarization etc.).In addition, in the case where using the coating or coetrusion, due to by melting PVA trees Then fat is coextruded the PVA layers and basalis to manufacture the film based on PVA, or is used as coating solution by preparing Then the coating solution is coated on the basalis to manufacture the film based on PVA by PVA resins, so, according to extrusion Condition, coated conditions or film formation condition, the physical property of manufactured PVA film can easily vary.Therefore, it is resulting The physical property of PVA film may deteriorate, also it is possible to which its uniformity can not be obtained.

It is therefore desirable to manufacture a kind of Polarizer for including the film polarizers with excellent optical property.

The content of the invention

Technical problem

In order to solve the above problems, an aspect of this disclosure provides a kind of (especially, single saturating with excellent optical property Light rate is 40% to 45% and degree of polarization is more than 99%) and show in terms of curling the thin Polarizer of excellent performance And its manufacture method.

Technical scheme

According to an aspect of this disclosure, there is provided a kind of method for manufacturing thin Polarizer, it includes：By using the two Between gravitation or using adhesive by the non-stretched film based on polyvinyl alcohol (PVA) attach on non-stretched basilar memebrane come Form film laminates；Stretch the film laminates；First diaphragm is attached to the film laminates of the stretching based on PVA's On film；And being separated based on PVA film from the basilar memebrane for the first diaphragm will be pasted with thereon.

Methods described may further include, before the film laminates are stretched, with iodine and dichroic dyestuff extremely Lack one kind to dye the film laminates.

Methods described may further include, and after the film laminates are stretched, dry the film laminates of the stretching.

Methods described may further include, by be pasted with thereon the first diaphragm based on PVA film from the base After being separated on counterdie, the second diaphragm is attached on the surface without diaphragm of the film based on PVA.

Methods described may further include, be pasted with thereon the first diaphragm based on PVA film from the substrate After being separated on film, viscous layer is formed on the surface without diaphragm of the film based on PVA.

According to another aspect of the disclosure, there is provided a kind of thin Polarizer, it includes：Thickness be less than 10 μm based on The polaroid of polyvinyl alcohol (PVA)；With the first diaphragm being attached on a surface of the polaroid based on PVA, its Described in Polarizer have 40% to 45% single light transmittance and more than 99.0% degree of polarization.

Beneficial effect

In the method for the thin Polarizer of manufacture of the illustrative embodiments according to the disclosure, it is possible to produce have excellent Optical property thin Polarizer.Situation on two surfaces that the film for being based on polyvinyl alcohol (PVA) is attached into basilar memebrane Under, manufacturing the productivity ratio of Polarizer can improve and different types of Polarizer can be manufactured during single.

In addition, the thin Polarizer manufactured using the method for the thin Polarizer of manufacture of the illustrative embodiments according to the disclosure It can less be curled, therefore, when such thin Polarizer is applied in display device, light leak can be minimized.

Brief description of the drawings

Fig. 1 is the figure for the method that display measures bonding strength using texture analyser；

Fig. 2 is the photo of the state for the film laminates that display manufactures according to comparative example 1；

Fig. 3 be display according to an embodiment of the invention and comparative example 3 and 4 manufacture thin Polarizer crimp property photograph Piece；

Fig. 4 is display after the stretch according to the photo of the crimp of the side of the film laminates of comparative example 6；And

Fig. 5 is to show after the stretch the photo of the state of 2 film laminates according to an embodiment of the invention.

Embodiment

Best mode

Hereinafter, it will be described in detail with reference to the accompanying drawings embodiment of the present disclosure.

But the disclosure can come in a number of different ways example and should not be construed as be limited to it is listed here Embodiment.In fact, these embodiments are provided so that the disclosure is thoroughly and complete, and these embodiment party Formula also can be to the complete reception and registration the scope of the present disclosure of those skilled in the art.

As to manufacturing with excellent optical property simultaneously notable thin (that is, the thickness with less than 10 μm) but not sending out The result repeatedly studied of the polaroid of raw fracture, the inventors found that：Draw by using therebetween weak Power is attached to the film based on polyvinyl alcohol (PVA) on basilar memebrane using adhesive, then stretches the film of the attaching with regard to energy Above-mentioned purpose is enough realized, and have submitted korean patent application related to this 10-2012-0130576th and 10-2012- No. 0130577.

By extra research, the inventors discovered that：The manufacture film polarizers illustrated in the application having been filed on Method in basilar memebrane and based on attaching to the first diaphragm before being separated between PVA film on the film based on PVA In the case of, the film based on PVA can be separated more neatly from the basilar memebrane, therefore, it is possible to produce crimped Aspect shows the thin Polarizer of excellent properties, and can significantly improve and manufacture its productivity ratio, and is tied based on the research Fruit has invented polaroid set forth herein.

More particularly, can be included according to the method for the thin Polarizer of manufacture of the illustrative embodiments of the disclosure：Pass through The non-stretched film based on PVA is attached on non-stretched basilar memebrane come shape using gravitation therebetween or using adhesive Film forming layered product；Stretch the film laminates；First diaphragm is attached to the film based on PVA of the film laminates of the stretching On；And being separated based on PVA film from the basilar memebrane for the first diaphragm will be pasted with thereon.

Gravitation therebetween can be utilized or attached to the non-stretched film based on PVA using adhesive non-stretched On basilar memebrane, the film laminates are consequently formed.Here, described in can the non-stretched film based on PVA be attached to not On the surface or two surfaces of the basilar memebrane of stretching.In view of productivity ratio and processing stability, it may be preferable that by institute The film based on PVA is stated to attach on two surfaces of the non-stretched basilar memebrane.

Herein, there is provided the non-stretched basilar memebrane is to prevent the disconnected of the film based on PVA described in drawing process Split, and, it is preferable that can be the polymer film with more than 5 times of maximum tension multiplying power at a temperature of 20 DEG C to 85 DEG C. In this case, stretching ratio maximum tension multiplying power refers to be broken at once before.Meanwhile the stretching step Can be that dry method tension or wet method stretch.In the case where wet method stretches, maximum tension multiplying power can refer to is in boric acid concentration Multiplying power when being stretched in 1.0wt% to 5wt% boric acid aqueous solution.

Above-mentioned basilar memebrane is not restricted, but by way of example, it can be density polyethylene film with high, polyurethane Film, polypropylene screen, polyolefin film, the film based on ester, low density polyethylene films, high density polyethylene (HDPE) and low density polyethylene (LDPE) are total to Extruded film, there is the copolymer resin adipose membrane of ethylene vinyl acetate being included in high density polyethylene (HDPE), be acrylic film, poly- to benzene Dioctyl phthalate second diester film, the film based on PVA, cellulose membrane etc..

It is excellent meanwhile the thickness of the basilar memebrane used in the illustrative embodiments of the disclosure can be 20 μm to 100 μm Elect 30 μm to 80 μm, more preferably 40 μm to 60 μm as.In the case where the thickness of basilar memebrane is less than 20 μm, it is laminated in stretched film During body, the basilar memebrane is likely difficult to be fully supported the film based on PVA, causes fracture etc. occurs.In the thickness of basilar memebrane In the case that degree is more than 100 μm, the draw efficiency of the film laminates can be reduced and can be upset being based in the drying process Steady contraction on the width of PVA film, thus the optical property of resulting polaroid may deteriorate.

In addition, the glass transition temperature of the basilar memebrane can be less than the glass transition temperature of the film based on PVA Degree.For example, the glass transition temperature of the basilar memebrane can be 20 DEG C to 60 DEG C, preferably 30 DEG C to 60 DEG C.Generally, it is contemplated that The glass transition temperature of film based on PVA is 70 DEG C to 80 DEG C, and the glass transition temperature of the basilar memebrane is in above range Interior, the basilar memebrane can become softer under the conditions of draft temperature, so that the film based on PVA can suitably be drawn Stretch.But in the case where the glass transition temperature of the basilar memebrane is too low, it may occur under relatively high stretching ratio Fracture.Therefore, the glass transition temperature of the basilar memebrane can be more than 20 DEG C.Meanwhile means of differential scanning calorimetry can be used Method (DSC) measures glass transition temperature.About 10mg sample film is sealed in DSC disks and in predetermined temperature for example, working as When being heated under the conditions of degree rise, the amount and the amount of heat that can be absorbed heat according to caused by temperature observations due to the phase transformation of sample film, Thus the glass transition temperature of the sample film is determined.

In addition, the modulus of the basilar memebrane can be 200Mpa to 1500Mpa at 25 DEG C of room temperature, preferably 350Mpa is extremely 1300Mpa.Can be difficult to be stretched under relatively high multiplying power in the case where the modulus of the basilar memebrane is more than 1500Mpa. In the case where the modulus of the basilar memebrane is less than 200Mpa, may be broken during stretching step.Here, the mould The measure of amount can be carried out by the following method：The both ends of the sample film prepared according to standard (JIS-K6251-1) are fixed, and And to the film applying power on the direction perpendicular with the thickness direction of the film, and per unit face is measured according to strain rate Long-pending stress.As measurement apparatus, it is, for example, possible to use Zwick/Roell Z010UTM for extension test etc..

In addition, the power at 25 DEG C of room temperature at the breakaway poing of the basilar memebrane can be 5N to 40N, preferably 10N to 30N. Here, fracture strength can refer in applying power on the vertical direction of the thickness direction relative to the film when the basilar memebrane breaks Tensile strength when splitting, and can be for example, by the Zwick/Roell Z010UTM measurements for extension test.In the base The fracture strength of counterdie outside the above range in the case of, it may be difficult to the film, Huo Zhe are stretched with relatively high multiplying power Film fracture may occur during stretching step.

Next, the thickness of the non-stretched film based on PVA attached on the basilar memebrane can be 10 μm to 60 μm, It is preferred that 10 μm to 40 μm.The film based on PVA thickness more than 60 μm in the case of, even if after the stretch, may be also difficult So that the thickness of the PVA film is less than 10 μm.In the case where the thickness of the film based on PVA is less than 10 μm, stretching Fracture may easily be produced by crossing the film based on PVA described in step journey.

Meanwhile the film based on PVA can have about 1,000 to 10,000, preferably approximately 1,500 to 5,000 The degree of polymerization, but it is not restricted to this.The film based on PVA the degree of polymerization within the above range in the case of, molecule can from Moved by ground and can successfully be combined with iodine, dichroic dyestuff etc..

Meanwhile according to the film based on PVA of the illustrative embodiments of the disclosure can be the commercially available film based on PVA, For example, PS30, PE30 or PE60 for being manufactured by Kuraray (Kuraray), or by the Nippon Synthetic Chemical Industry Co., Ltd M2000, M3000 or M6000 of (Nippon Synthetic Chemical Industry Co., Ltd.) manufacture etc..

Meanwhile in the illustrative embodiments of the disclosure, using on the surface of basilar memebrane and non-stretched based on PVA's Caused weak gravitation between the surface of film and without separating medium (in the case of without single medium) or using adhesive, can So that the basilar memebrane and the film based on PVA to be attached each other.

, can be to basilar memebrane in the case where being attached basilar memebrane and the non-stretched film based on PVA each other using gravitation Or it is surface-treated on one or two surface of the film based on PVA so that they have the bonding strength of appropriate level. This, the surface treatment can be carried out by known various surface treatment methods in the technical field belonging to the disclosure, for example, Sided corona treatment, corona treatment or the surface modification treatment using strong alkaline aqueous solution (such as NaOH or KOH).

Meanwhile in the case where attaching basilar memebrane and film based on PVA each other using adhesive, stretching the film layer Before laminate, the thickness of described adhesive layer can be 20nm to 4,000nm, and preferably 20nm to 1,000nm, more preferably 20nm are extremely 500nm.After the film laminates are stretched, the thickness of described adhesive layer can be 10nm to 1,000nm, and preferably 10nm is extremely 500nm, more preferably 10nm are to 200nm.When the thickness of the described adhesive layer before or after the film laminates are stretched is upper When in the range of stating, stretching and after drying steps the separation of the film based on PVA can be easier and without damage.

Meanwhile the material of described adhesive is not particularly limited, and can be without limitation using belonging to the disclosure Known various types of adhesives in technical field.For example, described adhesive layer can be by the adhesive based on water or ultraviolet Line solidification adhesive is formed.

In the case where described adhesive layer is formed by the adhesive based on water, the adhesive based on water can include The resin based on PVA containing acetoacetyl and the metallic compound crosslinking agent based on amine.More particularly, described adhesive can To be the metallization based on amine based on PVA resin and 1 to 50 parts by weight containing acetoacetyl for including 100 parts by weight Compound crosslinking agent.

According to the result of study of the present inventor, by basilar memebrane and it is based on based on the adhesive of water using conventional In the case that PVA film attaches, because its low water resistance makes described glue during stretching and cleaning by permeable Mixture dissolve, basilar memebrane and based between PVA film attach can by it is non-it is homogeneous in a manner of implement, cause in stretching step mistake Increasing for incidence is broken in journey.In this case, after basilar memebrane and film based on PVA are attached each other, due to The difference of swellbility between basilar memebrane and film based on PVA may cause occur substantial amounts of gauffer in the form of surface crack, Thus surface state may be very poor and be likely to occur crimp in the side of described film after the stretch.It is because existing Adhesive may be exposed in water and be dissolved in the water, so as to by it is non-it is homogeneous in a manner of implement in basilar memebrane and based on PVA Film between attaching.But including the base containing acetoacetyl using the illustrative embodiments according to the disclosure In the case of the adhesive based on water of resin in PVA and the metallic compound crosslinking agent based on amine, in solidification adhesive When can crosslink reaction between the metallic compound crosslinking agent based on amine and the acetoacetyl of the resin based on PVA, by This, significantly improves the water resistance of adhesive phase after hardening.So can solve by the existing adhesive based on PVA Insufficient water resistance caused by foregoing problems.

Meanwhile the degree of polymerization and saponification degree of the resin based on PVA are not particularly limited, as long as the tree based on PVA Fat includes acetoacetyl.Resin based on PVA can have 200 to 4,000 degree of polymerization, and can have 70mol% to 99.9mol% saponification degree.In view of the freedom of the molecular motion of the flexible mixing for included material, gather It is right can be 1,500 to 2,500 and saponification degree can be 90mol% to 99.9mol%.Here, the resin based on PVA can To include 0.1mol% to 30mol% acetoacetyl.Within the above range, the tree based on PVA can satisfactorily be carried out Reaction between fat and metallic compound crosslinking agent based on amine, and described adhesive can have desired water resistance.

The metallic compound crosslinking agent based on amine can be comprising having predetermined reaction to the resin based on PVA Property functional group water-soluble cross-linker, and can be to include the metal complex of the part based on amine.The metal Complex can include selected from zirconium (Zr), titanium (Ti), hafnium (Hf), tungsten (W), iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), Transition metal in osmium (Os), rhodium (Rh), iridium (Ir), palladium (Pd) and platinum (Pt).Being coupled to the part of central metal can include At least one amido, such as primary amine, secondary amine, tertiary amine or ammonium hydroxide.

In addition, the resin based on PVA comprising acetoacetyl can have 1wt% to 10wt% solid content. In the case where the solid content of the resin based on PVA is less than 1wt%, described adhesive does not ensure that enough water resistancees, because This, during the stretching step reduce be broken incidence in terms of can be that validity is relatively low.In consolidating for the resin based on PVA In the case that content is more than 10wt%, the machinability of described adhesive may deteriorate, and be based on PVA separated when The surface of film may be damaged.

Meanwhile the pH value of described adhesive can be 4.5 to 9.In the pH situations within the above range of described adhesive Under, described adhesive can be more advantageous in terms of storage stability and durability under high wet atmosphere.

Meanwhile the pH of described adhesive can be adjusted by adding acid into the aqueous solution.Here, the pH adjusting agent can To be strong acid or weak acid.For example, the pH adjusting agent can be nitric acid, hydrochloric acid, sulfuric acid, acetic acid etc..

Before the film laminates are stretched, by aforementioned adhesion dosage form into adhesive phase thickness can be 80nm extremely 200nm, preferably 80nm are to 150nm, and after the film laminates are stretched, and its thickness can be 10nm to 100nm, preferably 10nmn to 80nm.Described adhesive thickness within the above range in the case of, can suitably may be maintained at polyurethane film and Bonding strength between film based on PVA, fracture incidence can be reduced during stretching step, while can be separated When minimize the damage on the polaroid surface.

In the case of described adhesive, when solidifying adhesive, in the metallic compound based on amine and the tree based on PVA Reaction is crosslinked between the acetoacetyl of fat, the water resistance of described adhesive can be significantly improved after hardening. Using such adhesive by polymer film and film layer based on PVA it is folded in the case of, institute can be made when carrying out wet method stretching The phenomenon that adhesive is dissolved in the water is stated to minimize.Therefore, described adhesive may be advantageously used with wet method stretching step.

Meanwhile described adhesive layer can be formed by ultraviolet curing adhesive.For example, described adhesive layer can be by wrapping First epoxide of the glass transition temperature containing the homopolymer with more than 120 DEG C, with less than 60 DEG C of homopolymers The second epoxide of glass transition temperature and the ultraviolet curing adhesive of cationic photopolymerization initiator formed. Especially, the ultraviolet curing adhesive can include the vitrifying with more than 120 DEG C of homopolymer turn of 100 parts by weight The glass transition temperature with less than 60 DEG C of homopolymer of first epoxide of temperature, 30 to 100 parts by weight The cationic photopolymerization initiator of second epoxide and 0.5 to 20 parts by weight.

The epoxide being described herein can refer to has more than one epoxide group in a molecule, preferably exists There is the compound of two or more epoxide group in one molecule, and can be understood as comprising monomer, polymer and resin Form.Can be the form of resin according to the epoxide of the illustrative embodiments of the disclosure.

Meanwhile first epoxide is not particularly limited, as long as its glass with more than 120 DEG C of homopolymer Glass transition temperature.For example, can be by with more than 120 DEG C of homopolymer in the illustrative embodiments of the disclosure The alicyclic epoxide compound and/or aromatic epoxy compound of glass transition temperature are used as the first epoxide.It is described The example of the epoxide of glass transition temperature with more than 120 DEG C of homopolymer includes 3,4- epoxycyclohexyl first Base -3,4'- epoxycyclohexane carboxylates, vinyl cyclohexene dioxide, dicyclopentadiene, double (epoxide rings penta Base) ether, the epoxide based on bisphenol-A, epoxide based on Bisphenol F etc..Meanwhile first epoxide can With with the homopolymer glass transition temperature for 120 DEG C to 200 DEG C.

Next, second epoxide is not particularly limited, as long as it has less than 60 DEG C of homopolymer Glass transition temperature.For example, alicyclic epoxide compound, aliphatic epoxy compound etc. may be used as in the disclosure Illustrative embodiments in the second epoxide.

Here, the alicyclic epoxide compound can be a kind of difunctional epoxy compound, i.e. have two epoxy radicals The compound of group, wherein, described two epoxide groups are cycloaliphatic epoxy groups.But the alicyclic epoxide compound It is not limited to this.

The aliphatic epoxy compound can be that one kind has aliphatic epoxide groups rather than cycloaliphatic epoxy groups Epoxide.For example, as aliphatic epoxy compound, the poly epihydric alcohol base ether of aliphatic polyol can be used； The polyglycidyl ether of the alkylene oxide addition products of aliphatic polyol；Aliphatic polyol and aliphatic polycarboxylic acid's is poly- The poly epihydric alcohol base ether of ester polyol；The poly epihydric alcohol base ether of aliphatic polycarboxylic acid；Aliphatic polyol and aliphatic The poly epihydric alcohol base ether of the polyester polycarboxylic acid of polybasic carboxylic acid；It is sweet by glycidyl acrylate or Glycidyl methacrylate Dimer, oligomer or the polymer that the vinyl polymerization of grease obtains；By different from glycidyl acrylate or methyl The oligomer or polymer that the vinyl polymerization of the monomer based on vinyl of glycidyl acrylate obtains.Preferably, may be used To use the poly epihydric alcohol of the polyglycidyl ether of aliphatic polyol or the alkylene oxide addition products of aliphatic polyol Ether.But the aliphatic epoxy compound is not limited to this.

The aliphatic polyol can be with 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 To 8 carbon atoms or the aliphatic polyol of 2 to 4 carbon atoms.For example, the aliphatic polyol can include：Aliphatic Glycol, such as ethylene glycol, 1,2-PD, 1,3-PD, 2- methyl isophthalic acids, ammediol, 2- butyl -2- ethyls -1,3- third Glycol, 1,4- butanediols, neopentyl glycol, 3- methyl -2,4-PD, 2,4-PD, 1,5- pentanediols, 3- methyl isophthalic acids, 5- Pentanediol, 2- methyl -2,4- pentanediols, 2,4- diethyl -1,5- pentanediols, 1,6-HD, 1,7- heptandiols, 3,5- heptan Glycol, 1,8- ethohexadiols, 2- methyl isophthalic acids, 8- ethohexadiols, 1,9- nonanediols, 1,10- decanediols etc.；Cycloaliphatic diols, such as Cyclohexanedimethanol, cyclohexanediol, hydrogenated bisphenol A, A Hydrogenated Bisphenol A F, trimethylolethane, trimethylolpropane, hexitol, penta Sugar alcohol, glycerine, polyglycereol (polyglycerine), pentaerythrite, dipentaerythritol, tetra methylol propane etc..

In addition, the epoxyalkane can be with 1 to 20 carbon atom, 1 to 16 carbon atom, 1 to 12 carbon atom, The epoxyalkane of 1 to 8 carbon atom or 1 to 4 carbon atom.For example, the epoxyalkane can include oxirane, epoxy third Alkane, epoxy butane etc..

Moreover, the aliphatic polycarboxylic acid can include, for example, ethanedioic acid, malonic acid, succinic acid, glutaric acid, two Acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, dodecylic acid, 2- methylsuccinic acids, 2- methyl adipic acid, 3- methyl oneself two Acid, 3 methylvaleric acid, 2- methyloctanoic acids, 3,8- dimethyl capric acid, 3,7- dimethyl capric acid, 1,20- eicosane methylene dicarboxyls Sour (eicosamethylenedicarboxylicacid), 1,2- cyclopentane dicarboxylic acids, 1,3- cyclopentane dicarboxylic acids, 1,2- rings Hexane dicarboxylic acid, 1,3- cyclohexane dicarboxylic acids, 1,4- cyclohexane dicarboxylic acids, 1,4- dicarboxyls methylenecyclohexane, 1,2,3- third Alkane tricarboxylic acids, 1,2,3,4- BTCAs, 1,2,3,4- cyclobutane tetrabasic carboxylic acids etc., but it is not limited to this.

Preferably, the second epoxide in the illustrative embodiments of the disclosure can include one or more shrink Glyceryl ether group.For example, the second epoxide in the illustrative embodiments of the disclosure can be selected from Isosorbide-5-Nitrae-hexamethylene Alkane dimethanol diglycidyl ether, 1,4- butanediol diglycidyl ethers, 1,6 hexanediol diglycidylether, neopentyl two Glycidol ether, resorcinolformaldehyde resin, diethylene glycol diglycidyl glycerin ether, ethylene glycol diglycidylether, three hydroxyls Methylpropane triglycidyl ether, normal-butyl diglycidyl ether, 2- hexyl glycidyl ethers, phenyl glycidyl ether At least one of with o-tolyl glycidol ether.

Meanwhile glass transition temperature of second epoxide with 0 DEG C to 60 DEG C of homopolymer.

Meanwhile according to the illustrative embodiments of the disclosure, it is preferable that can use comprising at least one epoxidised fat The combination of first epoxide of ring group and the second epoxide comprising at least one glycidyl ether is used as described Epoxide, without other limitation.

Meanwhile form the film layer on two surfaces by the way that the film based on PVA is attached into the basilar memebrane After laminate, the film laminates can be stretched.Here, stretching step can be carried out so that the thickness of the film based on PVA For less than 10 μm.For example, can by it is described based on PVA film stretching to thickness be 1 μm to 10 μm, thickness be 3 μm to 10 μm or Thickness is 1 μm to 5 μm.

In addition, by making the shrinkage factor of the film based on PVA in the width direction reach 30% to 80%, it is preferably 60% to 80% carries out the stretching step.In the shrinkage in width rate situation within the above range of the film based on PVA Under, excellent optical property can be obtained.

Meanwhile had no particular limits according to the illustrative embodiments of the disclosure, the stretching condition.For example, can be with Using multiplying power as 5 to 15 times at a temperature of 20 DEG C to 85 DEG C, preferably entered at a temperature of 40 DEG C to 80 DEG C using multiplying power as 5 to 12 times The row stretching step.

Here, the stretching step can be carried out by wet method stretching or dry method tension.The wet method stretching step compares institute Dry method tension step is stated to be more suitable for, reason is because it allow basilar memebrane and based between PVA film than dry tensile step Stronger surface bonding intensity, so it can stably be carried out in the case where not needing single medium.Meanwhile Ke Yi The wet method stretching step is carried out in boric acid aqueous solution, wherein boric acid concentration can be 1.0wt% to 5wt%.

When carrying out the wet method stretching step in boric acid aqueous solution as described above, because boric acid is crosslinked, the PVA film Fracture incidence can reduce, so as to improve processing stability, and the generation of the fold on PVA film is (in wet method Easily produced in process) it is controllable.In addition, can advantageously it enter at a temperature of less than the temperature of dry method tension step Row wet method stretching step.

Meanwhile manufacture the process of polarization element and can generally include cleaning, swelling, dyeing, cleaning, stretching, complementary color and dry Dry step etc..In the illustrative embodiments of the disclosure, the cleaning and stretching step can be in boric acid aqueous solutions Carry out.More specifically, can be 0.1wt% to 2.5wt% in cleaning mesoboric acid concentration, preferably 0.5wt% is extremely 2.0wt%, also, can be 1.0wt% to 5.0wt% in stretching step mesoboric acid concentration, preferably 1.5wt% is extremely 4.5wt%.

Meanwhile stretching step can be with being dyed with iodine and/or dichroic dyestuff to the film based on PVE the step of and At least one step in the step of being crosslinked the film based on PVE that this is dyed with iodine and/or dichroic dyestuff is carried out together.

For example, stretching step can be carried out in the aqueous solution containing iodine and/or dichroic dyestuff and boric acid, so as to To be dyed, be crosslinked and stretching step simultaneously.Or can by by film laminates be impregnated into containing iodine and/or two to After carrying out staining procedure in the aqueous solution of color dyestuff, by by the film laminates of dyeing be impregnated into boric acid aqueous solution and Stretched, while be crosslinked and stretching step in boric acid aqueous solution.

Meanwhile after stretch the film laminates, in film of the stretching based on PVA and the basilar memebrane of the stretching Between bonding strength can be below 2N/2cm, preferably 0.1 to 2N/2cm, more preferably 0.1 to 1N/2cm.In the drawing Bonding strength between the basilar memebrane and the film based on PVA of the stretching stretched within the above range in the case of, in its separation During, it can make to damage the damage on its surface minimizing.In the manufacture method according to the illustrative embodiments of the disclosure, Between the film based on PVA and the basilar memebrane formed adhesive phase in the case of, described adhesive layer can with based on PVA film and basilar memebrane is stretched together, so as to which the thickness of described adhesive layer can reduce to its original thickness before stretching The 10% to 50% of degree.Therefore, the bonding strength between the film based on PVA and the basilar memebrane can be with as little as 2N/2cm Hereinafter, so as to easily that they are separated from each other.Meanwhile it is 2cm that the bonding strength, which can refer to attaching length, Sample film in the case of the bonding force that measures, and show measuring method in Fig. 1.In the exemplary embodiment party of the disclosure In formula, the bonding strength between film refers to：After the PVA film A of film laminates is fixed with print clamper H, by with film layer Apply force to peel off the stripping measured during the PVA film A of film laminates from basilar memebrane B on the vertical direction of the in-plane of laminate Intensity.Here, measurement apparatus is the texture analyser (model name produced by Stable Micro Systems：TA-XT Plus)。

Meanwhile after stretching step, if it is desired, the film laminates of the stretching can be dried.Here, can be 20 DEG C at 100 DEG C, preferably at 40 DEG C to 90 DEG C, step is dried, and drying time can be 1 to 10 minute.It is described dry Dry step can be used for remove PVA film surface on or surface in moisture, so as to prevent in the manufacturing process of Polarizer by The deterioration of the performance of PVA polaroids caused by moisture.In addition, drying steps can be used for during drying steps gently Cause the contraction of the PVA film of the stretching in the width direction, and for increase formed by polyvinyl alcohol and iodine it is compound The orientation of thing, so as to improve the degree of polarization of polaroid.

After stretch film layers laminate as described above, first diaphragm can be attached to the film layer of the drawn On the film based on PVA of laminate.In the case where the film based on PVA is attached on two surfaces of the basilar memebrane, First diaphragm can be pasted on each film based on PVA.

It is used as polarizing plate protective film or phase shift films, brightness raising here, can use in disclosure art Various types of films of film, without limiting.For example, first diaphragm can be selected from the polymer based on polyester, base Polymer in styrene, the polymer based on cellulose, the polymer based on polyether sulfone, the polymer based on makrolon, Polymer based on acrylic acid, the polymer based on polyolefin, the polymer based on polyamide, the polymerization based on polyimides Thing, the polymer based on sulfone, the polymer based on polyether sulfone, the polymer based on polyether-ether-ketone, the polymerization based on polyphenylene sulfide Thing, the polymer based on vinyl alcohol, vinylidene chloride polymer, the polymer based on vinyl butyral, based on arylide At least one of polymer, the polymer based on polyformaldehyde, the polymer based on epoxy and its mixture.Meanwhile inciting somebody to action In the case that the film based on PVA attaches to two surfaces of basilar memebrane, what is attached on the film based on PVA first protects Cuticula can be with mutually the same or different from each other.Different diaphragms as the first diaphragm are being attached to the two of film laminates In the case of on individual surface, the Polarizer with different diaphragms can be advantageously manufactured during single.

Meanwhile the attaching of first diaphragm can be carried out using adhesive.Here, workable herein bond Agent can be known in the art for the adhesive of Polarizer, adhesive etc. described in the disclosure.Here, will by consideration The material of the second diaphragm to be used etc., adhesive or adhesive can be properly selected.For example, by based on cellulose In the case that film is used as the first diaphragm, the adhesive (such as adhesive based on PVA) based on water can be used.By propylene In the case that sorrel, cyclic olefin polymer (COP) film etc. are used as the first diaphragm, Photocurable adhesive or thermosetting can be used Adhesive, for example, the adhesive based on acrylic acid, adhesive based on epoxy etc..

Then, the film based on PVA for being attached the first diaphragm can separate from basilar memebrane.In separating step In, can to by attach the first diaphragm the film or basilar memebrane based on PVA on applied weak peel strength in order to make two Tunic separates each other.Here, peel strength can be below 2N/2cm.For example, peel strength can be 0.1 to 2N/2cm, it is excellent 0.1 is elected as to 1N/2cm.In the illustrative embodiments of the disclosure, due in basilar memebrane and based on viscous between PVA film Close intensity it is weak and the first diaphragm and based on the bonding strength between PVA film than basilar memebrane and the film based on PVA it Between bonding strength it is of a relatively high, so, when applying weak peel strength to it, can be cleanly separated out from basilar memebrane Film based on PVA.Because the degree of the peel strength required for film and basilar memebrane of the separation based on PVA is significantly weak, with Compared, easily can separated two membranes each other without individually step using the situation of coating or coetrusion stacked film Rapid or device.In addition, the damage to PVA film can be reduced during separating step, so as to so that its show it is significantly excellent Different optical property.

After above separating step is completed, a kind of Polarizer can be obtained, wherein the first diaphragm has been attached to Thickness is on a surface of less than 10 μm of the film based on PVA.Two surfaces of basilar memebrane are attached in the film based on PVA In the case of upper, two kinds of Polarizers can be obtained by single process.

In the case of the Polarizer of the first diaphragm on a surface for attaching to the film based on PVA, in base Viscous layer can further be formed by being attached in the diaphragm of nothing first of PVA film on another surface thereon, and/or based on The second diaphragm can be further formed on another surface of the diaphragm of nothing first of PVA film.

Here, the viscous layer formed can by by with selected from the copolymer based on acrylic acid, based on epoxy Resin, the resin based on polyurethane, the resin based on silicon, the resin based on polyethers, the resin based on polyamide, based on PVA's The adhesive composition of at least one of resin is coated on another surface of the diaphragm of nothing first of the film based on PVA, And use up or thermal exposure described adhesive composition is so that it solidifies.

Meanwhile the attaching of second diaphragm can be carried out using adhesive.Here, workable herein bond Agent can be the known adhesive for being used for Polarizer, adhesive etc. in disclosure art.Here, by considering to make The material of first diaphragm etc., adhesive or adhesive can be properly selected.For example, used by the film based on cellulose In the case of making the second diaphragm, the adhesive (such as adhesive based on PVA) based on water can be used.By acrylic acid In the case that film, cycloolefin film etc. are used as the second diaphragm, Photocurable adhesive or resinoid can be used, for example, Adhesive based on acrylic acid, adhesive based on epoxy etc..

Here, being used as various types of films of polarizing plate protective film or phase shift films in the field belonging to the disclosure can use Make the second diaphragm, without limiting.For example, second diaphragm can be selected from the polymer based on polyester, based on benzene The polymer of ethene, the polymer based on cellulose, the polymer based on polyether sulfone, the polymer based on makrolon, it is based on The polymer of acrylic acid, the polymer based on polyolefin, the polymer based on polyamide, the polymer based on polyimides, base Polymer in sulfone, the polymer based on polyether sulfone, the polymer based on polyether-ether-ketone, the polymer based on polyphenylene sulfide, base In the polymer of vinyl alcohol, vinylidene chloride polymer, the polymer based on vinyl butyral, gathering based on arylide At least one of compound, the polymer based on polyformaldehyde, the polymer based on epoxy and its mixture.

Meanwhile on two surfaces that the film based on PVA is attached to basilar memebrane in the case of, can be obtained in single process Two kinds of Polarizers are obtained, so as to have preferable productivity ratio.Film layer pressure is attached in the different diaphragms as the first diaphragm In the case of two surfaces of body, the production of two kinds of different products can be advantageously carried out during single.

In addition, in Polarizer with the first diaphragm on a surface for attaching to the film based on PVA and with formation In the case of viscous layer on another surface of the film based on PVA, it is possible to produce on a surface of the film based on PVA The upper one side Polarizer with diaphragm.In the case where the second diaphragm is further attached thereon, it is possible to produce two-sided Polarizer.Therefore, it can be manufactured various types of Polarizers according to the manufacture method of the illustrative embodiments of the disclosure Out.

Meanwhile the exemplary embodiment party according to the disclosure can be carried out using known method in the field belonging to the disclosure The method of the thin Polarizer of manufacture of formula, for example, piece is to piece method (sheet-to-sheet process), piece to roller method (sheet- To-roll process), roll-to-roll method (roll-to-roll process) etc..Here, piece uses to piece method has pre- scale Very little single film is as raw material film (namely based on PVA film, basilar memebrane and diaphragm), and piece is wound to roller method use on roller Long roll shape film as one of raw material film and using the single film with preliminary dimension as another raw material film.In addition, institute State roll-to-roll method and use roll shape film as raw material film.In view of the continuity and productivity ratio of process, roller can be especially used To roller method.

For example, can be included according to the method for the thin Polarizer of manufacture of the illustrative embodiments of the disclosure makes basilar memebrane By using gravitation or there is 2N/ while unwinding respectively from substrate deflector roll and in the deflector roll based on PVA with the film based on PVA Basilar memebrane and film based on PVA are attached and form film laminates by the adhesive of below 2cm bonding strength；Stretch the film layer Laminate；On the film based on PVA for the film laminates that the first diaphragm unwind from the first protection deflector roll is attached into stretching；With And the film based on PVA for being pasted with the first diaphragm is separated from basilar memebrane.

After basilar memebrane and film based on PVA are attached each other, they can be by again on roller, then can be with Film laminates are unwind and are incorporated into stretching step from the roller of the film laminates wound again afterwards, or be directed into stretching Without winding steps again in step.

In addition, separating step can by basilar memebrane and based between PVA film insert stripping off device (for example, peel off Roller), separation is in basilar memebrane and based on interface between PVA film and by the basilar memebrane of separation and the film based on PVA of separation It is wound on different rollers and carries out.

In the case where making Polarizer using roll-to-roll legal system, long roll shape Polarizer can be obtained.

The Polarizer manufactured using the above method can include thickness for 10 μm or smaller (for example, 1 μm to 10 μm, 3 μm is arrived 10 μm or 1 μm to 5 μm) the Polarizer based on PVA；With the first protection on a surface for attaching to the polaroid based on PVA Film.If desired, the Polarizer may further include viscous layer and/or attach to the polaroid based on PVA with The second diaphragm being pasted with another surface of a surface of the first diaphragm conversely.

In addition, even if there is such thickness being substantially reduced, the Polarizer can have 40% to 45% single printing opacity Rate, and with more than 99%, preferably more than 99.5%, more preferably more than 99.7% degree of polarization, show significantly excellent Optical property.

In addition, can be with degree of polarization in the direction of the width according to the Polarizer of the illustrative embodiments of the disclosure Significantly excellent uniformity.Specifically, the degree of polarization of 10 equidistant point measurements in the direction of the width on Polarizer Standard deviation can be 0.002% or less.

In addition, excellent flatness can be shown according to the Polarizer of the illustrative embodiments of the disclosure, without producing Raw curling.More specifically, Polarizer can be by being placed flat on, measuring Polarizer by the flatness of the Polarizer Four edges and the distance between its bottom surface and determined with the method average measurement value of arithmetic, and be in flatness In the case of below 5mm, it may determine that being significantly excellent flatness.

Meanwhile in addition to the first diaphragm, the second diaphragm and/or viscous layer, according to the exemplary implementation of the disclosure The Polarizer of mode can further include functional optical layer, as brightness improve film, prime coat, hard conating, anti-dazzle photosphere, Anti-reflection layer etc..The method of optical layer as formation has no particular limits, and can be public in disclosure art The method known.

It is relative thin compared with existing Polarizer due to the Polarizer of the illustrative embodiments according to the disclosure And there is more excellent optical property, so, the Polarizer may be advantageously used with display device (such as liquid crystal display (LCD) Panel, organic electroluminescence device etc.) in.

The mode of the present invention

Embodiments of the invention 1

The manufacture experiment of film polarizers is that PVA film is attached to 60 μm of thermoplasticity by using gravitation therebetween Form film laminates on two surfaces of polyurethane-base counterdie, and carried out film laminates stretching by wet method stretching. Here, the PVA film (the M3000 levels manufactured by the Nippon Synthetic Chemical Industry Co., Ltd) that the PVA film is 30 μm.At 25 DEG C PVA film is subjected to swelling process after 15 seconds in pure water solution, to it in the solution that iodine concentration is 0.3wt% at 25 DEG C Carry out dyeing 60 seconds.Then, by PVA film at 25 DEG C boric acid concentration be 1wt% solution in carry out cleaning process 15 After second, they are stretched in the solution that boric acid concentration is 2.5wt% at 52 DEG C with 7 times of multiplying power.Stretching step it Afterwards, the PVA film is subjected to complementary color process in the solution that KI concentration is 5wt%, 5 points is then dried in 80 DEG C of baking oven Clock.The thickness of the PVA film of the drying is 6 μm to 8 μm.After the drying step, with the water solubility based on PVA being placed in therebetween 40 μm triacetyl cellulose (TAC) film is arranged on the respective PVA polarisations on two surfaces for attaching to basilar memebrane by adhesive On one surface of piece, and bonded them together with laminating machine.The film laminates of gained are done in 80 DEG C of baking oven Dry 5 minutes.Hereafter, the respective PVA polaroids in one surface with TAC film are divided from two surfaces of basilar memebrane Leave, thus obtain PVA polaroids, each PVA polaroid has the TAC film attached in one surface.Then, use It is placed in another surface that 40 μm of TAC film is arranged on to respective PVA polaroids based on PVA water-soluble binder therebetween On, and be combined together their uses with laminating machine.Resulting film laminates are dried 5 points in 80 DEG C of baking oven Clock.Therefore, thin Polarizer is manufactured that, each Polarizer has TAC/PVA/TAC structures.

Comparative example 1

By at 100 DEG C by PVA film (by the Nippon Synthetic Chemical Industry Co., Ltd manufacture M levels, average degree of polymerization： 2400, mean saponification degree：99mol%) it is dissolved in after preparing the PVA aqueous solution in pure water, using lip type coating machine at 200 μm The PVA aqueous solution is coated on PET base film (the NOVA-Clear SG007 levels manufactured by MGC companies), and in 80 DEG C of baking Dried 10 minutes in case, so as to form film laminates.Here, the thickness of the PVA film is 10 μm.Exist by the film laminates Swelling process is carried out after 15 seconds in pure water solution at 25 DEG C, is in iodine concentration at 25 DEG C by the film laminates Dyed 60 seconds in 0.3wt% iodine solution.Hereafter, by the film laminates at 25 DEG C boric acid concentration be 1wt% it is molten Cleaning process is carried out in liquid after 15 seconds, and is drawn at 52 DEG C in the solution that boric acid concentration is 2.5wt% with 5.5 times of multiplying power Stretch.After stretching step, by the film laminates KI concentration be 5wt% solution in carry out complementary color process, then Dried 5 minutes in 80 DEG C of baking oven.But the PVA coatings are stripped in stretching step, so as to which thin PVA film can not be manufactured. Fig. 2 is the photo for the state for showing the film laminates manufactured according to comparative example 1.

Comparative example 2

By at 100 DEG C by PVA film (by the Nippon Synthetic Chemical Industry Co., Ltd manufacture M levels, average degree of polymerization： 2400, mean saponification degree：99mol%) it is dissolved in after preparing the PVA aqueous solution in pure water, using lip type coating machine at 200 μm The PVA aqueous solution is coated on PET base film (the NOVA-Clear SG007 levels manufactured by MGC companies), and in 80 DEG C of baking Dried 10 minutes in case, so as to form film laminates.Here, the thickness of the PVA film is 10 μm.Exist by the film laminates Swelling process is carried out after 15 seconds in the aqueous solution that boric acid concentration is 1.0wt% at 25 DEG C, by the film laminates at 25 DEG C Under dyed 60 seconds in the iodine solution that iodine concentration is 0.3wt% and boric acid concentration is 3.0wt%.Hereafter, by the film laminates At 25 DEG C cleaning process is carried out in the solution that boric acid concentration is 1.0wt% 15 seconds, and by the film laminates at 60 DEG C Stretched in the solution that boric acid concentration is 2.5wt% with 5.5 times of multiplying power.After stretching step, the film laminates are existed Complementary color process is carried out in the solution that KI concentration is 5wt%, is then dried 8 minutes in 100 DEG C of baking oven.Through dry PVA film Thickness be 4 μm to 4.5 μm.After the drying step, be placed in therebetween based on PVA water-soluble binder by 40 μm TAC film is arranged on a surface of the respective PVA polaroids on two surfaces for attaching to basilar memebrane, and uses laminating machine Bond them together.Resulting film laminates are dried 5 minutes in 80 DEG C of baking oven.Hereafter, will be in one table The respective PVA polaroids with TAC film separate from two surfaces of basilar memebrane on face, are derived from PVA polaroids, often Individual PVA polaroids all have the TAC film for attaching to one surface.Then, with the water soluble adhesive based on PVA being placed in therebetween 40 μm of TAC film is arranged on another surface of respective PVA polaroids by agent, and they are used into combination with laminating machine Together.Resulting film laminates are dried 5 minutes in 80 DEG C of baking oven.Therefore, thin Polarizer is manufactured that, each Polarizer all has TAC/PVA/TAC structures.Use the thin Polarizer manufactured by JASCO V-7100 spectrophotometer measurements Optical property.

Comparative example 3

In the case of without using basilar memebrane, used in embodiments of the invention 30 μm of PVA films (are synthesized by Japan Chemical industry Co., Ltd. manufacture M3000 levels) with embodiments of the invention identical stretching condition with 6 times of multiplying power list Solely stretching, it is consequently formed 13 μm of polarization element.Using be placed in therebetween based on PVA water-soluble binder by 40 μm of TAC Film is arranged on two surfaces of the polarization element, and is bonded them together using laminating machine.By the film layer pressure of gained Body is dried 5 minutes in 80 DEG C of baking oven.Therefore, it is manufactured that the Polarizer with TAC/PVA/TAC structures.

Comparative example 4

In the case of without using basilar memebrane, used in embodiments of the invention 60 μm of PVA films (are synthesized by Japan Chemical industry Co., Ltd. manufacture M6000 levels) with embodiments of the invention identical stretching condition with 6 times of multiplying power list Solely stretching, it is consequently formed 22 μm of conventional polarization element.Using be placed in therebetween based on PVA water-soluble binder by 40 μm TAC film be arranged on two surfaces of the polarization element, and bonded them together using laminating machine.By gained film layer Laminate is dried 5 minutes in 80 DEG C of baking oven.Therefore, it is manufactured that the Polarizer with TAC/PVA/TAC structures.

Experimental example 1- optical characteristics

Using JASCO V-7100 spectrophotometer measurements according to an embodiment of the invention 1 and comparative example 2 manufacture it is thin partially Single light transmittance (Ts) of tabula rasa, cross transmittance (Tc), degree of polarization (DOP), monochromatic (a, b) and colour contamination (cross color) (a, b)。

【Table 1】

According to table 1, although embodiments of the invention have higher single light transmittance (Ts) compared with comparative example 2, its Show the degree of polarization (DOP) higher than comparative example 2.Thus, it will be seen that embodiments of the invention, compared with comparative example 2, tool There is more preferably optical property.

Meanwhile as in comparative example 1, with using cladding process under embodiments of the invention identical fabrication process condition In the case of manufacturing thin polaroid, as illustrated by comparative example 2, coated PVA film is stripped, and causes that film can not be manufactured inclined Mating plate.In the case where wherein adding boric acid in swelling and staining procedure and improving the comparative example 2 of draft temperature, painting is used The method of covering can manufacture PVA film, but its on light transmittance on deteriorate.It is thus impossible to produce such as in the exemplary reality of the disclosure Apply mentioned in mode with more than 99.0% degree of polarization simultaneously the polaroid with 40% to 45% light transmittance.

Experimental example 2- crimp properties

Detect by an unaided eye according to an embodiment of the invention and comparative example 3 and 4 manufacture Polarizer crimp property.In Fig. 3 In show corresponding to Polarizer photo.With reference to figure 3, it can be seen that compared with the Polarizer manufactured according to comparative example 3 and 4, The Polarizer manufactured according to an embodiment of the invention has lower crimpness.

The uniformity of experimental example 3-assessment degree of polarization

The polaroid manufactured on according to an embodiment of the invention 1 and comparative example 2, in the direction of the width in each polaroid On 10 equidistant point measurement degree of polarizations, then calculate the standard deviations of measured degree of polarization.Use JASCO V- 7100 spectrophotometer measurement degree of polarizations.Measurement result is shown in table 2.

【Table 2】

Embodiments of the invention 2

The PVA of acetoacetyl containing 5wt% (is manufactured, average polymerization by the Nippon Synthetic Chemical Industry Co., Ltd Degree：2,000, mean saponification degree：94mol%) it is dissolved in pure water, so as to prepare the 4wt% PVA aqueous solution.Simultaneously by titanium amine Complex crosslinking agent (trade name：TYZOR TE, are manufactured by E.I.Du Pont Company) relative to the PVA of 100 parts by weight with 6.7 parts by weight Ratio is added in the PVA aqueous solution, and they are stirred and mixed, thus prepares adhesive A.

On described adhesive A to be coated to two surfaces of 40 μm of thermoplastic polyurethane basilar memebrane and by 20 μm After PVA film (the M2000 levels manufactured by the Nippon Synthetic Chemical Industry Co., Ltd) is laminated thereon, them are made to pass through laminating machine So as to form film laminates.The film laminates are subjected to swelling process after 15 seconds in pure water at 25 DEG C, at 25 DEG C Dyed 60 seconds in the solution that iodine concentration is 0.3wt%.Then, by the film laminates at 25 DEG C in boric acid concentration To carry out cleaning process 15 seconds in 1wt% solution, and by its at 52 DEG C boric acid concentration be 2.5wt% solution in 7 Multiplying power stretching again.After stretching step, the film laminates are subjected to complementary color mistake in the solution that KI concentration is 5wt% Journey, then dried 5 minutes in 80 DEG C of baking oven.The thickness of the PVA film of the drying is 7.5 μm.After the drying process, use Be placed in 40 μm of TAC film is arranged on two surfaces for attaching to basilar memebrane based on PVA water-soluble binder therebetween On one surface of respective PVA polaroids, and bonded them together with laminating machine.By the film laminates of gained 80 DEG C baking oven in dry 5 minutes.Hereafter, the peel strength with 0.7N/2cm will have the respective of TAC film in one surface PVA polaroids separated from two surfaces of basilar memebrane, thus obtain PVA polaroids, each PVA polaroid has There is the TAC film for attaching to one surface.Then, between being placed in one based on PVA water-soluble binder by 40 μm of TAC Film is arranged on another surface of respective PVA polaroids, is then combined together their uses with laminating machine.By gained To film laminates in 80 DEG C of baking oven dry 5 minutes.Therefore, thin Polarizer is manufactured that, each Polarizer has TAC/PVA/TAC structures.

Comparative example 5

In the commercially available adhesive (trade name based on PVA by solid content for 4wt%：JC25, by Japanese VAM＆POVAL Co., Ltd. manufactures) on two surfaces of the thermoplastic polyurethane basilar memebrane that is coated to 40 μm and by 20 μm of PVA film (by day The M2000 levels of this synthetic chemical industry Co., Ltd. manufacture) be laminated thereon after, make them through laminating machine so as to forming film Layered product.The film laminates are subjected to swelling process 15 seconds at 25 DEG C in pure water solution, and by its at 25 DEG C Iodine concentration is to be dyed 60 seconds in 0.3wt% solution.Then, it is being in boric acid concentration at 25 DEG C by the film laminates Cleaning process is carried out in 1wt% solution 15 seconds, and by its at 52 DEG C boric acid concentration be 2.5wt% solution in 7 times Multiplying power stretching.But the film laminates are broken during stretching step.

Comparative example 6

In the commercially available adhesive (trade name based on PVA by solid content for 4wt%：JC25, by Japanese VAM＆POVAL Co., Ltd. manufactures) on two surfaces of the thermoplastic polyurethane basilar memebrane that is coated to 40 μm and by 20 μm of PVA film (by day The M2000 levels of this synthetic chemical industry Co., Ltd. manufacture) be laminated thereon after, make them through laminating machine so as to forming film Layered product.The film laminates are subjected to swelling process 15 seconds at 25 DEG C in pure water solution, and by its at 25 DEG C Iodine concentration is to be dyed 60 seconds in 0.3wt% solution.Then, it is being in boric acid concentration at 25 DEG C by the film laminates Cleaning process is carried out in 1wt% solution 15 seconds, and by its at 52 DEG C boric acid concentration be 2.5wt% solution in 6 times Multiplying power stretching.Then, the film laminates are subjected to complementary color process in the solution that KI concentration is 5wt%, then at 80 DEG C Baking oven in dry 5 minutes.

In this case, the film laminates are not broken during stretching with cleaning process, still, by drawing The side curling for the film laminates stretched.Fig. 4 is display after the stretch according to the photo of the state of the film laminates of comparative example 6.Together When, Fig. 5 is to show after the stretch the photo of the state of 2 film laminates according to an embodiment of the invention.Such as Fig. 4 and Fig. 5 institutes Show, crimped after the stretch according to the side of the film laminates of comparative example 6, and such phenomenon does not have in the reality according to the present invention Apply and occur in the film laminates of example 2.

[description of reference numerals]

H：Clamper

A：Film based on polyvinyl alcohol

B：Basilar memebrane

MD：Machine-direction oriented direction

Claims

1. a kind of method for manufacturing thin Polarizer, methods described include：

The non-stretched film based on polyvinyl alcohol (PVA) is attached to not by using gravitation therebetween or using adhesive Film laminates are formed on the basilar memebrane of stretching；

Stretch the film laminates；

First diaphragm is attached on the film based on PVA of the film laminates of the stretching；And

Being separated based on PVA film from the basilar memebrane for the first diaphragm will be pasted with thereon,

Wherein, the drawing of the film laminates is carried out by wet method stretching with 7 to 15 times of multiplying power at a temperature of 20 DEG C to 85 DEG C Stretch,

Wherein, the thickness of the non-stretched film based on PVA is 10 μm to 60 μm,

Wherein, described adhesive includes the resin based on PVA containing acetoacetyl and the metallic compound crosslinking based on amine Agent,

Wherein, carry out the film laminates stretch so that the film based on PVA thickness be less than 10 μm,

Wherein, using below 2N/2cm peel strength by be pasted with thereon the first diaphragm based on PVA film from the base Separated on counterdie,

Wherein, the basilar memebrane is thermoplastic polyurethane film, and

Wherein, the glass transition temperature of the basilar memebrane is 20 DEG C to 60 DEG C.

2. according to the method for claim 1, wherein, it in boric acid concentration is 1% to 5% that the stretchings of the film laminates, which is, Carried out in boric acid aqueous solution.

3. according to the method for claim 1, it further comprises, before the film laminates are stretched, with iodine and two to At least one of color dyestuff dyes to the film laminates.

4. according to the method for claim 1, it further comprises, after the film laminates are stretched, dries the film Layered product.

5. according to the method for claim 1, it further comprises, by be pasted with thereon the first diaphragm based on PVA Film separated from the basilar memebrane after, the second diaphragm is attached on the surface without diaphragm of the film based on PVA.

6. according to the method for claim 1, it further comprises, by be pasted with thereon the first diaphragm based on PVA Film separated from the basilar memebrane after, form viscous layer on the surface without diaphragm of the film based on PVA.

7. according to the method for claim 1, wherein, the basilar memebrane has more than 5 times at a temperature of 20 DEG C to 85 DEG C Maximum tension multiplying power.

8. according to the method for claim 1, wherein, first diaphragm is included selected from the polymer based on polyester, base Polymer in cellulose, the polymer based on acrylic acid, the polymer based on polyolefin, the polymer based on polyamide, base Polymer in polyimides, the polymer based on sulfone, the polymer based on polyether-ether-ketone, the polymer based on vinyl alcohol, partially Vinylidene chloride polymerization thing, the polymer based on vinyl butyral, the polymer based on arylide, the polymerization based on polyformaldehyde At least one of thing, the polymer based on epoxy and its mixture.

9. according to the method for claim 1, wherein, first diaphragm includes being selected from the polymerization based on makrolon At least one of thing, the polymer of styrene-based, the polymer based on polyether sulfone and polymer based on polyphenylene sulfide.

10. according to the method for claim 5, wherein, second diaphragm is included selected from the polymer based on polyester, base Polymer in cellulose, the polymer based on acrylic resin, the polymer based on polyolefin, the polymerization based on polyamide Thing, the polymer based on polyimides, the polymer based on sulfone, the polymer based on polyether-ether-ketone, the polymerization based on vinyl alcohol Thing, vinylidene chloride polymer, the polymer based on vinyl butyral, the polymer based on arylide, based on polyformaldehyde At least one of polymer, the polymer based on epoxy and its mixture.

11. according to the method for claim 5, wherein, second diaphragm includes being selected from the polymerization based on makrolon At least one of thing, the polymer of styrene-based, the polymer based on polyether sulfone and polymer based on polyphenylene sulfide.