CN106199808A - The manufacture method of Polarizer - Google Patents

The manufacture method of Polarizer Download PDF

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Publication number
CN106199808A
CN106199808A CN201610361648.0A CN201610361648A CN106199808A CN 106199808 A CN106199808 A CN 106199808A CN 201610361648 A CN201610361648 A CN 201610361648A CN 106199808 A CN106199808 A CN 106199808A
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CN
China
Prior art keywords
thermoplastic resin
film
resin membrane
membrane
polarizer
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Granted
Application number
CN201610361648.0A
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Chinese (zh)
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CN106199808B (en
Inventor
古谷勉
猪口雄平
武藤清
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Priority claimed from JP2015209010A external-priority patent/JP5951870B1/en
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Publication of CN106199808A publication Critical patent/CN106199808A/en
Application granted granted Critical
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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0036—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0056—Moistening
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/02—Temperature

Abstract

The present invention provides the manufacture method of a kind of Polarizer, and it includes in the following order: the 1st thermoplastic resin membrane carries out the operation of heat treated；1st thermoplastic resin membrane is added the operation of wet process；The 1st thermoplastic resin membrane is folded with the side surface upper strata at polarizing film, the operation of stacking the 2nd thermoplastic resin membrane on the opposite side surface of polarizing film, for described 2nd thermoplastic resin membrane is compared to described 1st thermoplastic resin membrane, the equilibrium moisture content under temperature 23 DEG C, relative humidity 55% is low.

Description

The manufacture method of Polarizer
Technical field
The present invention relates to the manufacture method of Polarizer, described Polarizer comprises polarizing film and the thermoplastic resin being laminated thereon Membrane of lipoprotein.
Background technology
In recent years, mobile phone terminal as smart mobile phone, design or portability in terms of, advance rapidly large screen, Lightweight.In order to realize driving for a long time with limited thickness, the Polarizer used is required high brightness, slim gently Quantify.
As Polarizer, the most generally use the protective film utilizing bonding agent will be formed by tri acetyl cellulose (TAC) Paste the Polarizer on the polarizing film formed by polyvinyl alcohol resin.But in recent years, from filming, durable From the viewpoint of property, cost, productivity ratio etc., gradually use the protective film of resin formation beyond by TAC (such as, Japanese Patent Laid-Open 2004-245925 publication).
Summary of the invention
Polarizer is more sensitive to its environment placed, and according to environmental condition, easily produces the deformation bending to arch.This explanation In book, also this deformation is referred to as " curling ".Polarizer has more to be become thin film and the most easily produces the tendency of curling.Curling point For " just crimping " and " inverse curling " two kinds.The side that in Polarizer, the image-displaying member such as existence and liquid crystal cell is pasted 2nd interarea of the 1st interarea and in contrast side, " just crimping " refers to the curling that the 1st interarea side is protruding, " inverse curling " Refer to the curling that the 2nd interarea side is protruding.If Polarizer produces inverse curling, paste it into image display via bond layer first Time on part, become prone to cause following unfavorable condition: produce and paste error, on the boundary of bond layer and image-displaying member Face is mixed into bubble.In order to suppress these unfavorable conditions, productivity ratio to implement the stickup of Polarizer and image-displaying member well, Polarizer is most preferably flat board, and when the curling of generation is for just crimping, the aspect in above-mentioned unfavorable condition and productivity ratio does not has Problem especially.
It should be noted that Japanese Unexamined Patent Publication 2006-030480 publication is recorded, in order to suppress the bar produced in Polarizer Stricture of vagina shape is concavo-convex, before by polarizing film and protective film stacking, the moisture content of protective film first adjusts the scope in regulation In.
It is an object of the invention to provide and can be made without inverse curling or the inverse method crimping the Polarizer suppressed.
The present invention provides the manufacture method of following Polarizer.
A kind of manufacture method of Polarizer, it includes in the following order:
1st thermoplastic resin membrane is carried out the operation of heat treated,
Described 1st thermoplastic resin membrane is added the operation of wet process, and
Described 1st thermoplastic resin membrane is folded, at the opposite side table of described polarizing film on a side surface upper strata of polarizing film The operation of stacking the 2nd thermoplastic resin membrane on face, described 2nd thermoplastic resin membrane is compared to described 1st thermoplastic resin For membrane of lipoprotein, the equilibrium moisture content under temperature 23 DEG C, relative humidity 55% is low.
[2] according to manufacture method described in [1], wherein, described 2nd thermoplastic resin membrane do not implemented described in add Wet process.
[3] according to the manufacture method described in [1] or [2], wherein, described 1st thermoplastic resin membrane contains fiber Prime system resin film.
[4] according to the manufacture method according to any one of [1]～[3], wherein, described 2nd thermoplastic resin membrane Containing cyclic polyolefin based resin film.
[5] according to the manufacture method according to any one of [1]～[4], wherein, temperature during described heat treated is More than described temperature when adding wet process.
When [6] according to manufacture method described in [5], wherein, adding wet process described in temperature ratio during described heat treated Temperature is high more than 30 DEG C.
[7] according to the manufacture method according to any one of [1]～[6], in the operation carrying out described heat treated, Described 1st thermoplastic resin membrane is more than temperature 50 C, be heat treatment in the environment of relative humidity less than 50%.
[8] according to the manufacture method according to any one of [1]～[7], in the operation adding wet process described in carrying out, Described 1st thermoplastic resin membrane humidified process in the environment of temperature more than 40 DEG C, relative humidity more than 60%.
[9] according to the manufacture method according to any one of [1]～[8], wherein, described 1st thermoplastic resin membrane With in described 2nd thermoplastic resin membrane at least one be layered on described polarizing film via bond layer.
[10] according to the manufacture method according to any one of [1]～[9], wherein said 1st thermoplastic resin membrane's Thickness is below 40 μm, and the thickness of described 2nd thermoplastic resin membrane is below 40 μm.
[11] according to the manufacture method according to any one of [1]～[10], wherein, the thickness of described polarizing film is Below 15 μm.
[12] according to the manufacture method according to any one of [1]～[11], wherein, described in carrying out, wet process is added In operation, described 1st thermoplastic resin membrane is added wet process so that its moisture content is than described 1st thermoplastic resin The equilibrium moisture content under temperature 23 DEG C, relative humidity 55% of thin film is high.
In accordance with the invention it is possible to be made without inverse curling or the Polarizer suppressed against curling.
Accompanying drawing explanation
Fig. 1 is the flow chart of an example of the manufacture method showing Polarizer of the present invention.
Fig. 2 is the summary sectional view of an example of the Rotating fields of the display available Polarizer of manufacturing method according to the invention.
Fig. 3 is to show the manufacture method of Polarizer of the present invention and for its pattern side of an example manufacturing device Figure.
Fig. 4 is the summary sectional view of an example of the Rotating fields of display one side protection Polarizer.
Fig. 5 is the summary sectional view of an example of the Rotating fields showing that the one side with temporary protection film protects Polarizer.
Fig. 6 is the summary sectional view of an example of the Rotating fields showing that the one side with bond layer protects Polarizer.
Description of reference numerals
1 two-sided protection Polarizer, 2 one sides protection Polarizers, 3 with temporary protection film one side protect Polarizer, 4 band There are the one side protection Polarizer of bond layer, 5 polarizing films, 10 the 1st thermoplastic resin membranes, 20 the 2nd thermoplastic resins Membrane of lipoprotein, 15 the 1st bond layers, 25 the 2nd bond layers, 30 bond layers, 40 doubling rollers, 50 the 1st is bonding Agent, 55 the 2nd bonding agents, 60 deflector rolls, 70 heating furnaces, 80 humidification stoves, 90 the 1st injection devices, 91 the 2nd inject Device.
Detailed description of the invention
With reference to Fig. 1, the manufacture method of Polarizer of the present invention, include following operation in the following order:
(1) the 1st thermoplastic resin membrane is carried out heating treatment step S100 of heat treated,
(2) the 1st thermoplastic resin membrane is added humidification treatment process S200 of wet process, and
(3) the 1st thermoplastic resin membrane is folded on the side surface upper strata at polarizing film, on the opposite side surface of polarizing film The lamination process S300 of upper stacking the 2nd thermoplastic resin membrane.2nd thermoplastic resin membrane uses equilibrium moisture content ratio the 1st The low person of thermoplastic resin membrane.Equilibrium moisture content mentioned here is to utilize dry weight method to measure in temperature 23 DEG C, the wettest The equilibrium moisture content of 24 hours rear films of keeping in the environment of degree 55%.
And then the 1st thermoplastic resin film layer that heat treated has carried out again adding wet process is laminated to the side table of polarizing film On face, opposite side surface stacking the 2nd thermoplastic resin membrane.Manufacture method according to this present invention, it is possible to reduce or anti- The inverse curling of the Polarizer obtained by only.Inverse curling refers to, as it has been described above, paste with the image-displaying member such as liquid crystal cell The opposition side of side that is the 2nd interarea projection, Polarizer bend to the deformation of arch, and generally this deformation is at individual body of Polarizer Middle generation.Long size is manufactured at the material film (the 1st and the 2nd thermoplastic resin membrane, polarizing film) using long size Polarizer time, refer to cut out from the Polarizer of long size for inverse curling typical case and individual body of Polarizer of obtaining produce Inverse curling.
It is illustrated in Fig. 2 by the one of the Rotating fields of the Polarizer obtained by manufacture method of the present invention.Polarisation shown in Fig. 2 Plate is two-sided protection Polarizer 1, and described two-sided protection Polarizer 1 comprises polarizing film 5, glues via the 1st bond layer 15 It is attached to the 1st thermoplastic resin membrane 10 of one side surface, is pasted onto the of opposite side surface via the 2nd bond layer 25 2 thermoplastic resin membranes 20.In two-sided protection Polarizer 1, the 1st and the 2nd thermoplastic resin membrane 10,20 is load The optical thin film of negative protection polarizing film 5, i.e. protective film, it is possible to use adhesive bond is on the surface of polarizing film 5. Other Rotating fields of the Polarizer obtained by manufacture method of the present invention are by aftermentioned.
Hereinafter, with reference to Fig. 3 while each operation is illustrated.Fig. 3 is the manufacture showing Polarizer of the present invention Method and the pattern side view of the example manufacturing device for it.Arrow in Fig. 3 represents the direction of transfer of thin film.Logical Often, the material film of long size as shown in Figure 3, is rolled out transmission by Polarizer continuously, while implementing each operation Process such that it is able to be continuously manufactured by long size product.But, the manufacture method of the present invention is not limited to use this long size The continuous production of material film, it is also possible to the method being the use of single film.
(1) heating treatment step S100
This operation is the operation that the 1st thermoplastic resin membrane 10 carries out heat treated.A feature of the present invention is Implement heat treated before implementing the 1st thermoplastic resin membrane 10 to add wet process, it is possible to effectively suppress or prevent partially The inverse curling (for typical case, making the curling that the interarea of the 1st thermoplastic resin membrane 10 side is protruding) of tabula rasa, it addition, with The situation only implementing to add wet process is compared, it is possible to more effectively suppress or prevent the inverse curling of Polarizer.
1st thermoplastic resin membrane 10 is by the thermoplastic resin with light transmission, the most optically transparent thermoplastic resin The thin film constituted.For constituting the thermoplastic resin of the 1st thermoplastic resin membrane 10, include, for example out, chain polyene Hydrocarbon system resin (polypropylene-based resin etc.), cyclic polyolefin hydrocarbon system resin (norbornene resin etc.) such polyolefin Resin；The such cellulose-based resin of tri acetyl cellulose, diacetyl cellulose；Polyethylene terephthalate, The such polyester based resin of polybutylene terephthalate (PBT)；Polycarbonate-based resin；Methyl methacrylate system resin is so (methyl) acrylic ester resin；Polystyrene resin；Polyvinyl chloride resin；Acrylonitrile-butadiene-styrene (ABS) It it is resin；Acrylonitrile-styrene system resin；Polyvinyl acetate system resin；Vingon system resin；Polyamide series resin； Polyacetals system resin；Noryl system resin；Polysulfones system resin；Polyether sulfone system resin；Polyarylate system resin；Polyamide Imide series resin；Polyimides system resin etc..
It should be noted that in this specification, " (methyl) acrylic ester resin " refers to select free acrylic ester tree Fat and methacrylate ester resin be grouped at least one.Other with " (methyl) " term too.
As chain polyolefin-based resins, polyvinyl resin, the homopolymer of the such chain olefin of acrylic resin can be listed, The most also can list the copolymer being made up of chain olefin of more than two kinds.More specifically example includes polypropylene-based tree Fat (homopolymer of propylene i.e. acrylic resin or the copolymer based on propylene), polyethylene-based resin (ethylene equal Polymers i.e. polyvinyl resin or the copolymer based on ethylene).
Cyclic polyolefin hydrocarbon system resin is the general name of the resin being polymerized for polymerized unit with cyclic olefin.If listing ring-type The concrete example of polyolefin-based resins, for the open loop (co) polymer of cyclic olefin, the addition polymer of cyclic olefin, ring-type Alkene and ethylene, the copolymer (representative for random copolymer) of the such chain olefin of propylene, and they are used insatiable hunger With carboxylic acid or derivatives thereof modification obtained by graft polymers, and their hydride etc..Wherein, as cyclic olefin, It is preferably used and make use of norborene system tree obtained by the norborneol alkene monomer such as norborene, multi-ring norborneol alkene monomer Fat.
Cellulose-based resin refers to obtain from the raw celluloses such as velveteen, wood pulp (broad leaf tree wood pulp, coniferous tree wood pulp) In the hydroxyl of cellulose hydrogen atom part or all by acetyl group, propiono and/or bytyry replace obtained by, cellulose Organic acid esters or cellulose mixed organic acid ester.Such as, the acetate of cellulose, propionic ester, butyrate and they The cellulose-based resin that mixed ester etc. are formed.Wherein, preferably tri acetyl cellulose, diacetyl cellulose, acetate propionate Cellulose, acetylbutyrylcellulose.
Polyester based resin is to have the resin beyond the above-mentioned cellulose-based resin of ester bond, usually polybasic carboxylic acid or derivatives thereof The resin formed with the condensation polymer of polyhydric alcohol.As polybasic carboxylic acid or derivatives thereof, it is possible to use the dicarboxylic acids of binary or its Derivant, such as, can list p-phthalic acid, M-phthalic acid, dimethyl terephthalic acid ester, naphthalenedicarboxylic acid diformazan Ester etc..As polyhydric alcohol, it is possible to use the glycol of binary, include, for example out ethylene glycol, propylene glycol, butanediol, new penta Glycol, cyclohexanedimethanol etc..The preferably example of polyester based resin includes polyethylene terephthalate.
Polycarbonate-based resin is the engineering plastics that monomeric unit is formed via polymer obtained by carbonate group bonding, is to have High-impact, thermostability, anti-flammability, the resin of the transparency.Polycarbonate-based resin is it may be that in order to reduce photoelasticity Coefficient, the resin being referred to as modified polycarbonate that polymer backbone has been modified or can also be that wavelength dependency is changed Good combined polymerization Merlon etc..
(methyl) acrylic ester resin is the polymer containing the construction unit deriving from (methyl) acrylic ester monomer. It it is the polymer containing methacrylate for this polymer typical case.Preferably comprise the structure list deriving from methacrylate The ratio of unit is, relative to general construction unit, polymer more than 50 weight %.(methyl) acrylic ester resin both may be used To be the homopolymer of methacrylate, it is also possible to be the copolymer containing the construction unit deriving from other polymerizable monomers. In this case, the ratio of the construction unit in other polymerizable monomer source is 50 weight % preferably with respect to general construction unit Below.
As may make up the methacrylate of (methyl) acrylic ester resin, preferably alkyl methacrylate.As Alkyl methacrylate, can list methyl methacrylate, ethyl methacrylate, n propyl methacrylate, first Base isopropyl acrylate, n-BMA, isobutyl methacrylate, Tert-butyl Methacrylate, metering system Acid 2-Octyl Nitrite, cyclohexyl methacrylate, the carbon number of the such alkyl of HEMA are 1～8 Alkyl methacrylate.The carbon number of alkyl contained in alkyl methacrylate is preferably 1～4.At (methyl) In acrylic ester resin, methacrylate can only be used alone a kind can also merge use two or more.
As may make up other the polymerizable monomer above-mentioned of (methyl) acrylic ester resin, can list acrylate, And other intramolecular has the compound of polymerism carbon-to-carbon double bond.Other polymerizable monomer can only be used alone a kind Can also merge and use two or more.As acrylate, preferably alkyl acrylate.As alkyl acrylate, can arrange Enumerate acrylic acid methyl ester., ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, acrylic acid different Butyl ester, tert-butyl acrylate, 2-EHA, cyclohexyl acrylate, the such alkyl of acrylic acid 2-hydroxy methacrylate The alkyl acrylate etc. that carbon number is 1～8.The carbon number of alkyl contained in alkyl acrylate be preferably 1～ 4.In (methyl) acrylic ester resin, acrylate can only be used alone a kind can also merge use 2 kinds with On.
Intramolecular as other has the compound of polymerism carbon-to-carbon double bond, can list the second such as ethylene, propylene, styrene Alkene based compound, or the such vinyl cyanide compound of acrylonitrile.Other intramolecular has the chemical combination of polymerism carbon-to-carbon double bond Thing can only be used alone a kind can also merge use two or more.
1st thermoplastic resin membrane 10 can be stacking be pasted onto a side surface of polarizing film 5, for protecting polarisation The protective film of thin film 5, or, it is also possible to it is the temporary protection film on the surface of protection polarizing film 5 temporarily.As facing Time protective film the 1st thermoplastic resin membrane 10, after constructing Polarizer, removing can be peeled off at a desired time.Separately Outward, the 1st thermoplastic resin membrane 10 can also is that phase-contrast film, luminance brightness-improving film are such and has optics merit simultaneously The protective film of energy.Such as, the thermoplastic resin membrane's stretching by being formed by above-mentioned material (is stretched uniaxially or biaxially Deng) or form liquid crystal layer etc. on the thin film, thus the phase-contrast film imparting arbitrary phase difference value can be prepared.The 1 thermoplastic resin membrane 10 can also have the hard conating of its surface stacking, antiglare layer, anti-reflection layer, antistatic backing, The such surface-treated layer of stain-proofing layer (face coat).
The thickness of the 1st thermoplastic resin membrane 10 is usually 1～100 μm, from the viewpoint of intensity and treatability etc., excellent Elect 5～60 μm, more preferably 5～50 μm as.As long as the thickness in the range of Gai, then can mechanically protect polarizing film 5, and the contraction of polarizing film 5 when Polarizer can be suppressed to be exposed under hygrothermal environment.1st thermoplastic resin membrane's 10 Thickness is the least, and Polarizer the most easily produces curling, according to the present invention, even if the thickness example of the 1st thermoplastic resin membrane 10 As being as thin as below 40 μm and then being as thin as below 30 μm, it is also possible to effectively suppress or prevent the inverse of obtained Polarizer Curling.
1st thermoplastic resin membrane 10 is that equilibrium moisture content is than the 2nd thermoplastic resin used in aftermentioned lamination process S300 The thin film that thin film 20 is high.In this specification, equilibrium moisture content is to measure at temperature 23 DEG C, relative humidity 55% by dry weight method In the environment of keeping 24 hours rear films moisture content, specifically, try to achieve according to following formula:
Equilibrium moisture content (weight %)=(film weight after film weight-dried after Bao Guan)/keeping after thin Film weight } × 100.
It is dried the process referring to that thin film is dried at 105 DEG C 2 hours.At least higher to equilibrium moisture content the 1st thermoplasticity Resin film 10 implements heat treated and and then in fact applying wet process, uses described 1st thermoplastic resin membrane 10 manufacture Polarizer.The method according to this invention, it is possible to suppress or prevent the inverse curling of obtained Polarizer.
The balance that 1st thermoplastic resin membrane the 10 and the 2nd thermoplastic resin membrane 20 preferably measures with described method is aqueous The difference of rate is more than 0.5 weight %, and the equilibrium moisture content of the i.e. the 1st thermoplastic resin membrane 10 is preferably than the 2nd thermoplastic resin More than big 0.5 weight % of thin film 20.Thus, in humidification treatment process S200 described later, it is possible to more effectively improve the 1st The moisture content of thermoplastic resin membrane 10, to the suppression of inverse curling or prevent more favourable.The difference of above-mentioned equilibrium moisture content is more excellent Elect more than 1 weight % as, more preferably more than 1.5 weight %.
The 1st preferred equilibrium moisture content of thermoplastic resin membrane 10 is more than 1.5 weight %, more than more preferably 2 weight %. Thus, in aftermentioned humidification treatment process S200, it is possible to more effectively improve the moisture content of the 1st thermoplastic resin membrane 10, To the suppression of inverse curling or prevent more favourable.The equilibrium moisture content of the 1st thermoplastic resin membrane 10 is usually below 5 weight %.
As the combination of the thermoplastic resin membrane that difference is more than 0.5 weight % of equilibrium moisture content, include, for example out fiber Prime system resin film (TAC film etc.) and the combination of cyclic polyolefin based resin film, cellulose-based resin film (TAC Thin film etc.) with the combination of (methyl) acrylate based resin film, cellulose-based resin film (TAC film etc.) with poly- The combination of ester based resin film, the combination of cellulose-based resin film (TAC film etc.) and chain film of polyolefin resin, (methyl) acrylate based resin film and the combination of cyclic polyolefin hydrocarbon system resin, (methyl) acrylate based resin film Combination etc. with polyester based resin thin film.1st thermoplastic resin membrane 10 contains with the balance of the 2nd thermoplastic resin membrane 20 The difference of water rate is usually below 5 weight %.
The equilibrium moisture content of thermoplastic resin membrane in addition to according to its material (constituting the kind of thermoplastic resin of thin film), Can also enter according to the thickness of thin film, the presence or absence of the surface-treated layer (face coat) that can be attached to film surface or material etc. Row sum-equal matrix.
Additionally, the 1st thermoplastic resin membrane 10 is preferably the thin film that moisture permeability is higher than the 2nd thermoplastic resin membrane 20.This In description, moisture permeability be by JIS Z0208 regulation moisture-inhibiting agar diffusion method measure, at temperature 40 DEG C, relative humidity 90% Under moisture permeability.At least higher to moisture permeability the 1st thermoplastic resin membrane 10 implements heat treated and to its continuous reality Apply wet process, utilize described 1st thermoplastic resin membrane 10 to manufacture Polarizer.The method according to this invention, to institute The suppression of the inverse curling of the Polarizer obtained or more favourable for preventing.
1st thermoplastic resin membrane the 10 and the 2nd thermoplastic resin membrane 20 is preferred, by the moisture-inhibiting of regulation in JIS Z0208 The difference of the moisture permeability under temperature 40 DEG C, relative humidity 90% that agar diffusion method measures is 30g/ (m2More than 24hr), the most preferably The moisture permeability of the 1st thermoplastic resin membrane 10 is than the 2nd big 30g/ (m of thermoplastic resin membrane 202More than 24hr).Thus, In aftermentioned humidification treatment process S200, it is possible to more effectively improve the moisture content of the 1st thermoplastic resin membrane 10, to inverse The suppression or more favourable for preventing of curling.The difference of above-mentioned moisture permeability is more preferably 50g/ (m2More than 24hr), the most excellent Elect 100g/ (m as2More than 24hr).
The 1st preferred moisture permeability of thermoplastic resin membrane 10 is 300g/ (m2More than 24hr), more preferably 400g/ (m2· More than 24hr).Thus, humidification treatment process S200 described later can more effectively improve the 1st thermoplastic resin membrane The moisture content of 10, to the suppression of inverse curling or for preventing more favourable.Additionally, moisture permeability is 300g/ (m2More than 24hr), When using water system bonding agent the 1st thermoplastic resin membrane 10 and polarizing film 5 to be pasted, it is possible to more effectively make water system The layer that bonding agent is formed is dried, it is possible to increase productivity ratio, is favourable from this point of view.1st thermoplastic resin membrane 10 Moisture permeability be usually 5000g/ (m224hr) below.
Difference as moisture permeability is 30g/ (m2The combination of the thermoplastic resin membrane more than 24hr), include, for example out fiber Prime system resin film (TAC film etc.) and the combination of cyclic polyolefin based resin film, cellulose-based resin film (TAC Thin film etc.) with the combination of (methyl) acrylate based resin film, cellulose-based resin film (TAC film etc.) with poly- The combination of ester based resin film, the combination of cellulose-based resin film (TAC film etc.) and chain film of polyolefin resin, (methyl) acrylate based resin film and the combination of cyclic polyolefin hydrocarbon system resin, (methyl) acrylate based resin film Combination etc. with polyester based resin thin film.The moisture permeability of the 1st thermoplastic resin membrane the 10 and the 2nd thermoplastic resin membrane 20 Difference be usually 5000g/ (m224hr) below.
The moisture permeability of thermoplastic resin membrane is in addition to according to its material (constituting the kind of the thermoplastic resin of thin film), also Can carry out according to the thickness of thin film, the presence or absence of the surface-treated layer (face coat) that can be attached to film surface or material etc. Adjust.
As long as the 1st thermoplastic resin membrane 10 can be heated by the heat treated of the 1st thermoplastic resin membrane 10 in this operation To desired temperature, then its method is not particularly limited.As it is shown on figure 3, heat treated can be by such as heating The process that it imports the 1st thermoplastic resin membrane 10 in stove 70, heat.Heating furnace 70 preferably can control in stove The heating furnace of temperature.Heating furnace 70 is the air stove that such as can be improved in-furnace temperature by the supply of hot blast etc..
Additionally, the heat treated of the 1st thermoplastic resin membrane 10 can also is that 1 that this thin film sticks to have convex surface Process on individual or more than 2 calandrias, can also be the process utilizing heater that this thin film is heated.As above-mentioned Calandria, can list inside and possess thermal source (such as, thermal medium or the infrared heater such as warm water), can improve surface temperature Roll hot rolls such as () deflector rolls that such as, surface is made up of metal of degree.As above-mentioned heater, infrared ray can be listed Heater, halogen heater, baffle heater etc..Fig. 3 shows that importing the 1st thermoplastic resin is thin in heating furnace 70 Deflector roll 60 in film 10, edge stove transmits this film side and carries out the example of heat treated.
Wherein, adjust to the heating furnace 70 of desired temperature importing the 1st thermoplastic resin membrane 10 to in-furnace temperature, In edge stove, the deflector roll 60 of 1 or more than 2 transmits the method that this film side carries out heating；This thin film, limit is transmitted with limit The method carrying out heating on the calandria of sticked to have convex surface 1 or more than 2, from can be in aftermentioned stacking To be preferred from the point of view of the surface smoothing aspect of the 1st thermoplastic resin membrane 10 before operation S300.That is, the 1st heat Although the material film of plastic resin film 10 grade has small concave-convex surface or keeping after fabrication during fabrication In operation, surface produces small concavo-convex, by making in this operation in aforementioned manners by the 1st thermoplastic resin membrane's 10 Surface smoothing such that it is able to improve the exterior quality of Polarizer, can improve and the adhesiveness of polarizing film 5 simultaneously.
Temperature T during heat treated1-1(such as, the in-furnace temperature of heating furnace 70, the surface temperature etc. of hot roll), and By temperature T of the 1st thermoplastic resin membrane 10 that heat treated reaches1-2It is preferably in aftermentioned humidification treatment process S200 Temperature T when adding wet process2-1More than (such as, the in-furnace temperature of humidification stove 80), more preferably than temperature when adding wet process Degree T2-1High.Additionally, temperature T1-1And T1-2Preferably by adding the 1st thermoplastic resin membrane's 10 that wet process reached Temperature T2-2Above, more preferably higher than temperature T2-2.Thereby, it is possible to more effectively suppress or prevent obtained Polarizer Inverse curling.That is, by meeting the relation of said temperature such that it is able to prevent from humidifying the 1st heat when treatment process S200 imports The surface of plastic resin film 10 produces condensation such that it is able to overall really to thin film under the conditions of desired temperature humidity Ground is implemented to add wet process.Thus, the suppression/preventing effectiveness of inverse curling is improved.T1-1、T1-2Preferably than T2-1、T2-2High 10 DEG C Above, the highest more than 20 DEG C, the highest more than 30 DEG C.T1-1With T2-1Or and T2-2Difference, and T1-2 With T2-1Or T2-2Difference be usually less than 70 DEG C.
It should be noted that temperature T during heat treated1-1With the 1st thermoplastic resin membrane reached by heat treated Temperature T of 101-2The most identical or mutually the most synthermal.Additionally, temperature T when adding wet process2-1With by humidification Process temperature T of the 1st thermoplastic resin membrane 10 reached2-2The most identical or mutually the most synthermal.
If in humidification treatment process S200, produce condensation on the surface of the 1st thermoplastic resin membrane 10, then due to water The latent heat of vaporization, the temperature at this condensation part thin film cannot rise to expected value, its result, it is impossible in desired temperature humidity Under the conditions of carry out adding wet process, therefore suppression/preventing effectiveness of inverse curling reduces or can not suppress inverse curling.It addition, At unreal applying heat treatment step S100, the 1st thermoplastic resin membrane 10 of such as room temperature (23 DEG C) is imported at humidification Science and engineering sequence S200, and in the case of carrying out adding wet process under the conditions of the temperature humidity not producing condensation, adding wet process can become Insufficient, it is impossible to the inverse curling of suppression Polarizer.
If it addition, the surface of the 1st thermoplastic resin membrane 10 produces condensation, then knot can be remained at this side surface of Polarizer Dew vestige (produces condensation, its dry vestige remained after drying), makes the exterior quality of Polarizer reduce.Use continues heating Carry out adding the method that the 1st thermoplastic resin membrane of wet process manufactures the present invention of Polarizer after process, additionally it is possible to reduce The generation of this condensation vestige.
Temperature T during heat treated1-1, and the temperature of the 1st thermoplastic resin membrane 10 reached by heat treated T1-2Usually 50～150 DEG C, preferably 60～130 DEG C, more preferably 70～120 DEG C.If temperature T1-1、T1-2Not enough 50 DEG C, then it is difficult to meet above-mentioned temperature relation (T1-1、T1-2≧T2-1、T2-2), even if or self disclosure satisfy that this pass System, but cannot carry out adding wet process under the conditions of suitable temperature humidity as a result, have inverse in humidification treatment process S200 The tendency that the suppression of curling/preventing effectiveness reduces.If it addition, temperature T1-1、T1-2Less than 50 DEG C, then the 1st thermoplastic resin The smoothing on the surface of thin film 10 easily becomes insufficient.On the other hand, if temperature T1-1、T1-2More than 150 DEG C, then having can 1st thermoplastic resin membrane 10 can produce heat deterioration, simultaneously cannot be to the 1st thermoplastic resin in humidification treatment process S200 Membrane of lipoprotein 10 humidifies effectively.From humidification treatment process S200 to the 1st thermoplastic resin membrane 10 effectively From the viewpoint of carrying out adding wet process, temperature T1-1、T1-2More preferably less than 110 DEG C, particularly preferably 100 DEG C with Under.
Heat treated in this operation can relative humidity less than 50%, preferably below 45% in the environment of implement.Change speech It, in this specification, " heat treated " refers to the heat treated carried out in the environment of relative humidity less than 50%, at this point On, with under relative humidity higher (such as, relative humidity more than 60%) environment, preferred limit heating edge humidification add " adding wet process " in wet process operation S200 is distinguishing.The relative humidity of heat treated environment is more preferably 30% Hereinafter, more preferably less than 20%, particularly preferably less than 10% (such as less than 5%).
For example, about the 2～300 seconds time of the heat treated in this operation, preferably about 5～120 seconds.If at heating The time of reason is the shortest, then be difficult to make temperature T of the 1st thermoplastic resin membrane 101-2Reach above-mentioned temperature.Too long of heating The process time likely can make the 1st thermoplastic resin membrane 10 produce heat deterioration, further, since need longer thin film to pass Send path, it is possible to the excessive maximization of polarisation panel manufacturing apparatus can be caused.The time of heat treated refers to that thin film is at heating furnace Time that holdup time in 70 and calandria adhere to or use time etc. of heater heating thin film.
(2) humidification treatment process S200
This operation is that the 1st thermoplastic resin membrane 10 after heat treated implements to add the operation of wet process.Adding wet process is Instigate the process that the moisture content of the 1st thermoplastic resin rises.As it has been described above, by carrying out at humidification after heat treated Reason such that it is able to effectively suppress or prevent the inverse curling of Polarizer, it addition, compared with only enforcement adds the situation of wet process, Can more effectively suppress or prevent the inverse curling of Polarizer.
1st thermoplastic resin membrane 10 adds wet process it may be that as shown in Figure 3, by humidification stove 80 Import the 1st thermoplastic resin membrane 10 thus to process that it humidifies etc., be placed on and have adjusted the ring of relative humidity Process under border.Humidification stove 80 is preferably capable controlling the humidification stove of the relative humidity in stove, more preferably can also control The humidification stove of in-furnace temperature.As a example by humidification stove 80, the supply etc. such as by hot blast improves in-furnace temperature, and can pass through Moisture in stove adjusts the oven of the relative humidity controlled in stove.
In order to make the temperature of the 1st the most heat-treated thermoplastic resin membrane 10 also be able to when importing humidification treatment process Maintain or be unlikely to be greatly reduced, heat treated and to add the interval of wet process the shortest.Fig. 3 show by from The 1st thermoplastic resin membrane 10 that heating furnace 70 is derived imports humidification stove 80 at once, and the deflector roll 60 that edge in stove transmits This film side carries out adding the example of wet process.In order to adjust the temperature adding in wet process employing humidification stove 80, it is also possible to Use above-mentioned heater or use above-mentioned calandria (such as hot roll) to replace hot blast.
It is adjusted to the relative humidity at least over 50% in have adjusted the environment of above-mentioned relative humidity, such as humidification stove 80, excellent Select more than 60%, more preferably adjust the relative humidity to more than 70%.Thereby, it is possible to effectively carry out the 1st thermoplastic resin Thin film 10 add wet process.The relative humidity of the environment that have adjusted above-mentioned relative humidity is usually less than 99%, more preferably Less than 95%.If relative humidity is too high, then temperature based on the 1st thermoplastic resin membrane 10, produces condensation sometimes.
Add temperature T during wet process2-1(have adjusted the temperature of the environment of above-mentioned relative humidity), and by adding wet process and Temperature T of the 1st thermoplastic resin membrane 10 reached2-2Usually more than 35 DEG C, preferably more than 40 DEG C, more preferably More than 45 DEG C.Temperature T2-1、T2-2More than 35 DEG C such that it is able to efficiency carries out adding wet process well.On the other hand, If temperature T2-1、T2-2Too high, then become to be difficult to meet above-mentioned temperature relation (T1-1、T1-2≧T2-1、T2-2), therefore temperature Degree T2-1、T2-2It is preferably less than 90 DEG C and meeting in the range of said temperature relation, more preferably less than 80 DEG C and expiring In the range of foot said temperature relation.
The time adding wet process in this operation is such as about 5～500 seconds, preferably about 20～300 seconds.If at humidification The time of reason is too short, then the humidification (moisture content rising) of the 1st thermoplastic resin membrane 10 becomes insufficient.It addition, mistake The long wet process time longer thin film of needs that adds transmits path, it is thus possible to can cause the most large-scale of polarisation panel manufacturing apparatus Change.The time adding wet process refers to the thin film holdup time etc. in humidification stove 80.
The preferred moisture content of the 1st thermoplastic resin membrane 10 after humidification treatment process S200 depends on the balance of this thin film Moisture content (material of this thin film for more typical).By adding wet process, the moisture content of the 1st thermoplastic resin membrane 10 Preferably adjust to the usual environment taken care of after fabrication higher than Polarizer (temperature about 23 DEG C, relative humidity about 55%) Equilibrium moisture content.Such as in the case of the 1st thermoplastic resin membrane 10 is triacetyl cellulose film, at humidification Moisture content after reason is preferably 1～5 weight %, more preferably 2～4.5 weight % (such as 2～4 weight %).Moisture content Can be measured by dry weight method in the same manner as equilibrium moisture content, specifically, try to achieve according to following formula:
Moisture content (weight %)={ before (film weight after film weight-dried before dried)/dried Film weight × 100.It is dried the process referring to that thin film is dried at 105 DEG C 2 hours.
In humidification treatment process S200, by the 1st thermoplastic resin membrane 10 is added wet process so that it is moisture content Higher than the equilibrium moisture content under temperature 23 DEG C, relative humidity 55% such that it is able to effectively suppress or prevent the inverse of Polarizer Curling.The moisture content of the 1st thermoplastic resin membrane 10 after humidification treatment process S200 and temperature 23 DEG C, relative humidity The equilibrium moisture content of the 1st thermoplastic resin membrane 10 under 55% identical or lower than it time, the suppression of inverse curling becomes insufficient.
Humidify the moisture content of the 1st thermoplastic resin membrane 10 after treatment process S200 and at temperature 23 DEG C, relative humidity The difference of the equilibrium moisture content of the 1st thermoplastic resin membrane 10 under 55% is preferably more than 0.1 weight %.Additionally from suppressing From the viewpoint of big just curling, this difference is preferably below 3 weight % (below such as 2 weight %).
Even if expecting, in the 1st thermoplastic resin membrane 10 lamination process S300 after humidification treatment process S200, also Keep or the general moisture content kept after adding wet process.
(3) lamination process S300
With reference to Fig. 3, this operation is to fold the 1st thermoplastic resin membrane 10, at polarisation on a side surface upper strata of polarizing film 5 The operation of stacking the 2nd thermoplastic resin membrane 20 on the opposite side surface of thin film 5.
(3-1) polarizing film
Polarizing film 5 can be to make dichroism pigment gas absorption quantity obtain on the polyvinyl alcohol resin thin film of uniaxial tension The polarizing film arrived.As the polyvinyl alcohol resin constituting polyvinyl alcohol resin thin film, it is possible to use by polyvinyl acetate The resin saponification of ester system and the resin that obtains.As polyvinyl acetate system resin, except the most poly-vinegar of the homopolymer of vinylacetate Outside vinyl acetate, also can exemplify vinylacetate and can be with the copolymer of other monomers of its combined polymerization.As can With other monomers of vinyl acetate copolymerized conjunction, include, for example out unsaturated carboxylic acid class, olefines, ethylene ethers, insatiable hunger With sulphonic acids, (methyl) acrylic amide etc. with ammonium.
The saponification degree of polyvinyl alcohol resin can be in the scope of 80.0～100.0 moles of %, preferably at 90.0～100.0 moles The scope of %, more preferably in the scope of 98.0～100.0 moles of %.If saponification degree is less than 80.0 moles of %, then obtained by inclined The resistance to water of tabula rasa and humidity resistance can reduce.
Saponification degree refers to, using acetoxy group contained in the polyvinyl acetate system resin of the raw material as polyvinyl alcohol resin (acetoxyl group :-OCOCH3) it is changing into, by saponifying process, the numerical value that the ratio unit ratio (mole %) of hydroxyl represents, Define with following formula:
Saponification degree (mole %)=100 × (hydroxyl value)/(hydroxyl value+acetic acid radix).Saponification degree can be according to JIS K 6726 (1994) obtain.Saponification degree is the highest, represents that the ratio of hydroxyl is the highest, therefore, hinders the ratio of acetoxy group of crystallization more Low.
The average degree of polymerization of polyvinyl alcohol resin is preferably 100～10000, and more preferably 1500～8000 are the most excellent Elect 2000～5000 as.The average degree of polymerization of polyvinyl alcohol resin can also be tried to achieve according to JIS K 6726 (1994). When average degree of polymerization is less than 100, it is difficult to obtain gratifying polarizing properties, during more than 10000, dissolving in a solvent Property be deteriorated, the formation of polyvinyl alcohol resin thin film become difficulty.
In polarizing film 5, the dichroism pigment containing (gas absorption quantity) can be iodine or dichroic organic dye.Dichromatic The concrete example of organic dyestuff can list and include, red BR, red LR, red R, pink LB, ruby red (Rubine) BL, Purplish red (Bordeaux) GS, skyblue LG, lemon yellow, blue BR, blue 2R, dark blue RY, green LG, purple LB, Purple B, black H, black B, black GSP, yellow 3G, yellow R, orange LR, orange 3R, scarlet (scarlet) GL, orangutan Red KGL, Congo red (Congo red), brilliant violet BK, super indigo plant (Supra blue) G, super blue GL, super Level orange (Supra orange) GL, direct skyblue, direct everbright fast orange S, resistance to tanned.Dichroism pigment can be only It is used alone a kind, it is also possible to merge and use two or more.Dichroism pigment is preferably iodine.
Polarizing film 5 can be manufactured by following operation: by the operation of polyvinyl alcohol resin thin film uniaxial tension；By inciting somebody to action Polyvinyl alcohol resin thin film dichroism pigment dyeing, so that the operation of dichroism pigment absorption；To being adsorbed with two The polyvinyl alcohol resin thin film of chromotropism pigment carries out the operation of crosslinking Treatment；And, carry out washing after crosslinking Treatment Operation.
Above-mentioned polyvinyl alcohol resin masking is obtained by polyvinyl alcohol resin thin film.Film-forming method limits the most especially System, can use the such known method of extrusion by melting, solvent extraction method.The thickness example of polyvinyl alcohol resin thin film About for 10～150 μm, below preferably 50 μm, below more preferably 35 μm.
The uniaxial tension of polyvinyl alcohol resin thin film can be before dichroism pigment dyeing and the while of dyeing or after dyeing Carry out.When uniaxial tension is carried out after dyeing, this uniaxial tension both can be before crosslinking Treatment or can also be in crosslinking Treatment Carry out.Furthermore it is also possible to carry out uniaxial tension in these multiple stages.
During uniaxial tension, single shaft can be stretched as between the roll that peripheral speed is different, it is possible to use hot roll is stretched as single shaft. It addition, uniaxial tension can be the dry type stretching carrying out in an atmosphere stretching, it is also possible to be to carry out polyethenol series in the solution The wet tensile of the stretching of resin film.Stretching ratio is usually about 3～8 times.
As by the polyvinyl alcohol resin thin film method of dichroism pigment dyeing, such as, can use polyethenol series Resin film is immersed in the method in the aqueous solution (staining solution) containing dichroism pigment.Polyvinyl alcohol resin thin film The impregnation process (swelling process) being preferably implemented in advance in water before dyeing processes.
In the case of using iodine as dichroism pigment, it is typically employed in the aqueous solution containing iodine and potassium iodide dipping poly- The method that vinyl alcohol resin thin film carries out dyeing.In this dyeing aqueous solution, the content of iodine is usually 0.01～1 weight portion every 100 The water of weight portion.It addition, the content of potassium iodide is usually the water of 0.5～20 every 100 weight portions of weight portion.Dyeing aqueous solution Temperature be usually about 20～40 DEG C.
On the other hand, when using dichroic organic dye as dichroism pigment, it is typically employed in containing water miscible two colors Property organic dyestuff dyeing aqueous solution in impregnate the polyvinyl alcohol resin thin film method that carries out dyeing.Two colors in dyeing aqueous solution The content of property organic dyestuff is usually 1 × 10-4～10 water of every 100 weight portions of weight portion, preferably 1 × 10-3～1 weight portion. This dyeing aqueous solution can also be containing inorganic salts such as sodium sulfate as dyeing adjuvant.Dyeing aqueous solution temperature be usually 20～ About 80 DEG C.
Utilize the crosslinking Treatment after the dyeing that dichroism pigment carries out can be by by thin for the polyvinyl alcohol resin after dyeing Film immersion is carried out in the aqueous solution containing cross-linking agent.The preference of cross-linking agent is boric acid, it is also possible to use the such boron of Borax Other cross-linking agent such as compound, Biformyl, glutaraldehyde.Cross-linking agent can only use a kind, it is also possible to merge use 2 kinds with On.
In aqueous solution containing cross-linking agent, the amount of cross-linking agent is usually the water of 2～15 every 100 weight portions of weight portion, preferably 5～ 12 weight portions.When using iodine as dichroism pigment, this aqueous solution containing cross-linking agent preferably comprises potassium iodide.Containing cross-linking agent Aqueous solution in the amount of potassium iodide be usually the water of 0.1～15 every 100 weight portions of weight portion, preferably 5～12 weight portions. The temperature of the aqueous solution containing cross-linking agent is usually more than 50 DEG C, preferably 50～85 DEG C.
Polyvinyl alcohol resin thin film process to be washed with water after crosslinking Treatment.Washing processes such as by by crosslinking Treatment The polyvinyl alcohol resin crossed is thin film dipped to be carried out in water.When washing processes, the temperature of water is usually about 1～40 DEG C.
After washing, implement dried, obtain polarizing film 5.Dried can be utilize air drier be dried, By contact with hot roll be dried, utilize far infra-red heater be dried etc..The temperature of dried be usually 30～ About 100 DEG C, preferably 50～90 DEG C.
The thickness of polarizing film 5 is usually about 2～40 μm.From the viewpoint of the filming of Polarizer, polarizing film 5 Thickness be preferably below 20 μm, below more preferably 15 μm, more preferably below 10 μm.Polarizing film 5 Thickness the least, Polarizer the most easily produces curling, according to the present invention, even if the thickness of polarizing film 5 is as thin as such as 15 μm Hereinafter, be as thin as below 10 μm further, it is also possible to effectively suppress or prevent obtained by the inverse curling of Polarizer.
By dried, the moisture content of polarizing film 5 can be reduced to practical level.This moisture content is usually 5～20 weight %, preferably 8～15 weight %.If moisture content is less than 5 weight %, then the pliability of polarizing film 5 is lost, and polarisation is thin Film 5 damages or disrumpent feelings the most sometimes.If it addition, moisture content is more than 20 weight %, polarizing film 5 the most sometimes Poor heat stability.Moisture content mentioned here utilizes dry weight method to measure, and its assay method is described above.
(3-2) the 2nd thermoplastic resin membrane
2nd thermoplastic resin membrane 20 is in the same manner as the 1st thermoplastic resin membrane 10, by the thermoplastic resin with light transmission Fat, preferred optically transparent thermoplastic resin are constituted.For the thermoplastic resin of the 2nd thermoplastic resin membrane 20 can be constituted The concrete example of fat, can quote the example described for the 1st thermoplastic resin membrane 10.But, constitute the 2nd thermoplastic resin The thermoplastic resin of membrane of lipoprotein 20 can be according to the equilibrium moisture content under temperature 23 DEG C, relative humidity 55% of this thin film than The mode that the equilibrium moisture content of 1 thermoplastic resin membrane 10 is low selects.
2nd thermoplastic resin membrane 20 and the 1st thermoplastic resin membrane 10 are likewise it is possible to be protective film, protect temporarily Protect thin film or phase-contrast film, the such protective film with optical function of luminance brightness-improving film.2nd thermoplasticity Resin film 20 can also have at the hard conating of its surface stacking, antiglare layer, anti-reflection layer, antistatic backing, stain-proofing layer Such surface-treated layer (face coat).The thickness of the 2nd thermoplastic resin membrane 20 is usually 1～100 μm, from by force From the viewpoint of degree, treatability etc., preferably 5～60 μm, more preferably 5～50 μm.2nd thermoplastic resin is thin The thickness of film 20 is the least, and Polarizer the most easily becomes to produce curling, but according to the present invention, even if the 2nd thermoplastic resin is thin The thickness of film 20 is as thin as below such as 40 μm and then is as thin as below 30 μm, it is also possible to obtained by effectively suppressing or preventing The inverse curling of Polarizer.
As it has been described above, the equilibrium moisture content of thermoplastic resin membrane (and moisture permeability) (can constitute thin film according to its material The kind of thermoplastic resin), the thickness of thin film, the having of surface-treated layer (face coat) of film surface can be attached to Nothing or material etc. are adjusted.Therefore, the 1st thermoplastic resin membrane the 10 and the 2nd thermoplastic resin membrane 20 is that balance contains The thin film that water rate is mutually different, is made up of identical thermoplastic resin sometimes.
The equilibrium moisture content of the 2nd thermoplastic resin membrane 20 is usually 0.05～1.5 weight %, preferably 0.05～1 weight %. It addition, the moisture permeability of the 2nd thermoplastic resin membrane 20 is usually 1～350g/ (m224hr), preferably 5～200g/ (m2 ·24hr).In order to constitute the thermoplastic resin of the 2nd thermoplastic resin membrane 20 that can reach described equilibrium moisture content and moisture permeability The example of fat is cyclic polyolefin hydrocarbon system resin, (methyl) acrylic ester resin, polyester based resin, chain polyolefin tree Fat etc..
Before lamination process S300, the 2nd thermoplastic resin membrane 20 can also be implemented and the 1st thermoplastic resin membrane 10 same adding wet process or heat treated and add the combination of wet process, but from suppression or the inverse curling preventing Polarizer From the point of view of viewpoint, do not implement add wet process or heat treated and add wet process to the 2nd thermoplastic resin membrane 20 Combination.But, by the 2nd thermoplastic resin membrane 20 being implemented at the heating as the 1st thermoplastic resin membrane 10 Reason such that it is able to surface smoothing by the 2nd thermoplastic resin membrane 20.
(3-3) lamination process
Reference Fig. 3, the 1st and the 2nd thermoplastic resin membrane 10,20 stacking to the polarizing film 5 in this operation, such as Can use the long size product of each material film, limit is transmitted they limits continuously and is carried out continuously.Each material film can be according to Their long side direction is the mode transmission of direction of transfer.The transmission path of thin film can be appropriately arranged with for supporting the thin of traveling The deflector roll (free roll) 60 of film, roll etc. can also be set as required drive roll.Generally, the transmission of polarizing film 5 Direction (thin film long side direction) and the direction of transfer (thin film long side direction) of the 1st and the 2nd thermoplastic resin membrane 10,20 Parallel.
When both 1st and the 2nd thermoplastic resin membranes 10,20 are protective film or have the protective film of optical function, 1st, the 2nd thermoplastic resin membrane 10,20 is generally pasted onto via the 1st, the 2nd bond layer 15,25 stacking respectively On polarizing film 5.Specifically, as shown in Figure 3, by the 1st thermoplastic resin membrane 10, polarizing film 5 and 2nd thermoplastic resin membrane 20 is according to the mode overlap parallel with their long side direction (direction of transfer) and by a pair Between doubling roller 40,40, by extruding the thin film of stacking up and down such that it is able to the stacking carrying out thin film is pasted, now, exist Before between doubling roller 40,40, use the 1st injection device the 90, the 2nd injection device 91, at polarizing film 5 and the Between 1 thermoplastic resin membrane 10, and it is injected separately into the 1st between polarizing film the 5 and the 2nd thermoplastic resin membrane 20 Bonding agent the 50, the 2nd bonding agent 55 thus at intermediate formation bond layer.
After stacking, by making bond layer be dried and/or solidifying, thus obtain the two-sided protection Polarizer 1 shown in Fig. 2.The 1 bond layer 15 is formed by the 1st bonding agent 50, and the 2nd bond layer 25 is formed by the 2nd bonding agent 55.
It should be noted that make the layer formed by bonding agent be present in the method in the middle of thin film be not limited to use injection device 90, The injection of 91, such as, can suitably select doctor blade method (De Network タ Block レ De method), bar according to the viscosity etc. of bonding agent Rubbing method (wire-bar coating), die coating method, scraper for coating method (カ Application マ U タ method), gravure coating process, leaching The such coating method of rubbing method, the tape casting, it is also possible at the sticking veneer coating adhesive of at least side thin film overlapped.
Before the 1st, the 2nd thermoplastic resin membrane 10,20 is pasted in stacking on polarizing film 5, it is also possible to thin to polarisation The sticking veneer of film the 5 and/or the 1st, the 2nd thermoplastic resin membrane 10,20 carries out Cement Composite Treated by Plasma, sided corona treatment, purple Outside line treatment with irradiation, flame (fire is scorching) process, the saponification such surface activation process of process.By this surface activation process, The cementability of polarizing film the 5 and the 1st, the 2nd thermoplastic resin membrane 10,20 can be improved.
As the 1st bonding agent the 50, the 2nd bonding agent 55, it is possible to use water system bonding agent, active energy ray-curable are viscous Connect agent or Thermocurable bonding agent, preferably water system bonding agent, active energy ray-curable bonding agent.1st bonding agent 50 With the 2nd bonding agent 55 can be bonding agent of the same race can also be bonding agent the most of the same race.When using bonding agent the most of the same race, It is easily generated the curling of Polarizer, but according to the present invention, even if also being able in this case effectively suppress or prevent Polarizer Inverse curling.
Water system bonding agent is the bonding agent being dissolved in the water by bonding agent composition or being dispersed in water.The water system being preferably used Bonding agent such as uses polyvinyl alcohol resin or polyurethane resin as the adhesive composite of main component.
When using polyvinyl alcohol resin as the main component of bonding agent, this polyvinyl alcohol resin can be partly-hydrolysed poly- Vinyl alcohol, the such polyvinyl alcohol resin of fully saponified polyvinyl alcohol, in addition to this it is possible to be carboxy-modified polyvinyl alcohol, Acetoacetyl modified polyvinyl alcohol, methylol-modified polyvinyl alcohol, the poly-second of amino modified polyvinyl alcohol such modification Enol system resin.Polyvinyl alcohol resin obtains except the i.e. polyvinyl acetate saponification of the homopolymer of vinylacetate being processed Alcotex outside, it is also possible to be by vinylacetate and can be with the copolymer saponification of other monomers of its combined polymerization The polyvinyl alcohol based copolymer processed and obtain.
Polyvinyl alcohol resin is usually as the water system bonding agent of bonding agent composition the aqueous solution of polyvinyl alcohol resin.Viscous Connect the concentration water relative to 100 weight portions of polyvinyl alcohol resin in agent, usually 1～10 weight portion, preferably 1～ 5 weight portions.
In order to make cementability improve, the bonding agent being made up of the aqueous solution of polyvinyl alcohol resin preferably comprises polyaldehyde, melamine Based compound, zirconia compound, zinc compound, Biformyl, glyoxal derivative, water-soluble epoxy resin are such solid The property changed composition or cross-linking agent.As water-soluble epoxy resin, such as, can be preferably used to diethylenetriamines, triethylene Daiamid obtained by the polyalkylenepolyaminess such as tetramine and the reaction of the dicarboxylic acids such as adipic acid makes chloropropylene oxide react and obtains Polyamide polyamine epoxy resin.As the commercially available product of polyamide polyamine epoxy resin, " Sumirez 650 " (ス can be listed ミ レ ズ レ ジ Application 650) (field chemical industry (strain) system), " Sumirez 675 " (field chemical industry (strain) System), " WS-525 " (Japan PMC (strain) system) etc..These curable compositions, cross-linking agent addition (as Its total amount when curable composition and cross-linking agent add simultaneously) relative to polyvinyl alcohol resin 100 weight portion be usually 1～ 100 weight portions, preferably 1～50 weight portions.Above-mentioned curable composition, cross-linking agent addition relative to polyethenol series When resin 100 weight portion is less than 1 weight portion, there is the tendency that the effect of cementability raising diminishes, it addition, this addition phase During for polyvinyl alcohol resin 100 weight portion more than 100 weight portion, there is the tendency that bond layer becomes fragile.
It addition, as using polyurethane resin as the preference during main component of bonding agent, Polyester can be listed from poly- The mixture of thing type polyurethane resin and the compound with glycidoxypropyl.Polyester ionomer type polyurethane resin refers to There is the polyurethane resin of polyester backbone, be wherein imported with a small amount of ionic composition (hydrophilic component).Described ionomer type Polyurethane resin is not owing to using emulsifying agent, and directly in water, emulsifying becomes emulsion, therefore preferred as the bonding agent of water system.
Active energy ray-curable bonding agent is by ultraviolet, visible ray, electron ray, X-ray such activity energy The amount irradiation of ray and the bonding agent that solidifies.When using active energy ray-curable bonding agent, it is bonding that Polarizer is had Oxidant layer is the solidification nitride layer of this bonding agent.
Active energy ray-curable bonding agent is it may be that contain the epoxy compound conduct solidified by cationic polymerization The bonding agent of curable composition, preferably comprises ultra-violet solidified bonding as curable composition of described epoxy compound Agent.Epoxy compound mentioned here means that intramolecular averagely has more than 1, the epoxy radicals of preferably more than 2 Compound.Epoxy compound can only use a kind, it is also possible to merges and uses two or more.
The concrete example of the epoxy compound preferably used, including: carry out on the aromatic rings of aromatic polyol by making Hydrogenation and the ester ring type polyhydric alcohol that obtains react with chloropropylene oxide and the hydrogenated epoxy based compound that obtains (has ester ring type ring The glycidyl ether of polyhydric alcohol)；The such aliphatic of polyglycidyl ether of aliphatic polyol or its alkylidene addition product Epoxy compound；Intramolecular has the epoxy compound i.e. ester ring type ring of more than 1 epoxy radicals closed with ester ring type ring key Oxygen based compound.
Active energy ray-curable bonding agent, as curable composition, can be containing as free-radical polymerised (methyl) Acrylate based compound is to replace above-mentioned epoxy compound, or can contain as free-radical polymerised (methyl) Acrylate based compound also contains above-mentioned epoxy compound simultaneously.As (methyl) acrylate based compound, can arrange Enumerating, intramolecular has (methyl) acrylate monomer of at least 1 (methyl) acryloxy；Make two or more contain The compound reaction of functional group and obtain, intramolecular has (methyl) propylene of at least 2 (methyl) acryloxies The compound containing (methyl) acryloxy such as acid esters oligomer.
Active energy ray-curable bonding agent contains the epoxy compound solidified by cationic polymerization as curable During composition, preferably comprise light cationic polymerization initiators.As light cationic polymerization initiators, include, for example out aromatic series Diazol；The salt such as aromatic iodonium salts or aromatic series sulfonium salt；Iron-arene complex etc..Additionally, active energy beam is solid When the property changed bonding agent contains (methyl) acrylate based compound such free-radical polymerised curable composition, preferably comprise Optical free radical polymerization initiator.As optical free radical polymerization initiator, include, for example out 1-Phenylethanone. series initiators, hexichol first Ketone series initiators, benzoin ether series initiators, thiaxanthone series initiators, xanthone, Fluorenone, camphorquinone, benzaldehyde, Anthraquinone etc..
One of them table that could be for temporarily protecting polarizing film 5 of 1st and the 2nd thermoplastic resin membrane 10,20 The temporary protection film in face.Now, in lamination process S300, do not make to deposit between polarizing film 5 and temporary protection film At bonding agent, replace and make it there is volatile liquid, or what does not the most exist ground stacking temporary protection film.Temporarily Protective film be can from polarizing film 5 peel off thin film, can Polarizer manufacture after, can the desired time (such as, Polarizer is pasted onto on liquid crystal cell) peel off removing." peelable " refers to, can not damage or injure polarizing film 5 With temporary protection film polarizing film 5 is separated with temporary protection film.
As an example, Fig. 4 shows the 2nd thermoplastic resin membrane 20 as temporary protection film, carries out lamination process After S300, temporary protection film is peeled off the Rotating fields of the one side protection Polarizer 2 removed and obtain.
Use temporary protection film time, preferably in lamination process S300, make between polarizing film 5 and temporary protection film There is volatile liquid.Thus, compared with what the most non-existent situation, it is possible to suppress inclined during manufacturing Polarizer Optical thin film 5 ruptures or produces the unfavorable condition of fold on the thin-film laminate containing polarizing film 5.
Peeling force between polarizing film 5 and temporary protection film for example, 0.01～0.5N/25mm, preferably 0.01～ 0.2N/25mm, more preferably 0.01～0.15N/25mm.When peeling force is less than 0.01N/25mm, polarizing film 5 with face Time protective film adhesion little, produce being partially stripped of temporary protection film the most sometimes, or will protect with interim Under the state that the one side protecting thin film protects Polarizer to be rolled into a roll, in keeping, polarizing film 5 can tear along draw direction.It addition, If peeling force is more than 0.5N/25mm, it becomes difficult to peel off temporary protection film from polarizing film 5, therefore face in stripping Time protective film time, polarizing film 5 easily tears along draw direction.
Above-mentioned peeling force can be by trying to achieve as follows: protects Polarizer to be cut into 25mm the one side with temporary protection film Width, obtains and measures sample, uses the accurate universal testing machine " AUTOGRAPH that Shimadzu Scisakusho Ltd manufactures AGS-50NX " (オ ト グ ラ Off AGS-50NX), catch the temporary protection film of mensuration sample and one side protection inclined Tabula rasa, measures power when peeling off along 180 ° of directions.The mensuration of peeling force peeling rate 300mm/min, temperature 23 ± 2 DEG C, Carry out in the environment of relative humidity 50 ± 5%.
The volatile liquid existed is removed by volatilization after lamination process S300.Thus, available thin with interim protection The one side protection Polarizer of film.Fig. 5 shows that the one side with temporary protection film protects an example of the Rotating fields of Polarizer 3. In the example of Fig. 5, the 2nd thermoplastic resin membrane 20 is temporary protection film.Volatile liquid can be waved by heating Send out and remove.By this heat treated, temporary protection film is direct, be laminated in the table of polarizing film 5 with the adhesion of appropriateness Face.Heating-up temperature for example, 30～90 DEG C.
The liquid that volatile liquid can be by above-mentioned heat treated and volatilizees, is preferably and does not bring bad to polarizing film 5 The liquid of impact.As long as not bringing harmful effect, it is also possible to add antistatic agent.If listing the example of volatile liquid, Include, for example the mixture etc. of water outlet or water and hydrophilic liquid.Hydrophilic liquid does not remains after being preferably heat treated Liquid, include, for example out methanol, ethanol, n-butyl alcohol, oxolane, acetone, acetonitrile, DMF, Dimethyl sulfoxide, formic acid, acetic acid etc..
(4) other operation
Water system bonding agent is used in the stacking of polarizing film the 5 and the 1st and/or the 2nd thermoplastic resin membrane 10,20 is pasted Time, after lamination process S300, preferably implement the drying process for removing water contained in water system bonding agent.It is dried temperature Spend for example, 30～90 DEG C.Via volatile liquid on polarizing film 5 during stacking temporary protection film, this drying process is also The above-mentioned heat treated for volatile liquid volatilization being removed can be had concurrently.After drying process, it is also possible to be arranged on such as The maintenance operation of maintenance is carried out at a temperature of 20～50 DEG C, preferably 30～45 DEG C.
Active-energy is used to penetrate in the stacking of polarizing film 5 with the 1st and/or the 2nd thermoplastic resin membrane 10,20 is pasted During line curable bonding agent, after lamination process S300, it is dried operation as required, then carries out by irradiating Active energy beam and make the curing process that active energy ray-curable bonding agent solidifies.The light source of active energy beam does not has It is particularly limited to, preferably has at below wavelength 400nm and send out ultraviolet photodistributed, specifically, it is possible to use low pressure mercury lamp, Medium pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, chemical lamp, black light lamp, microwave-excited mercury lamp, metal halide lamp etc..
The exposure rate of the active energy beam bond layer to being formed by active energy ray-curable bonding agent, can be according to viscous The composition connecing agent suitably determines, preferably according to the exposure rate that polymerization initiator is activated effective wavelength field reach 0.1～ 6000mW/cm2Mode set.It is 0.1mW/cm at exposure rate2Time above, the response time is long, for 6000mW/cm2Time following, the bond layer that less generation is caused by the heating when heat of radiation of light source and bonding agent solidification Xanthochromia or the deterioration of polarizing film 5.
For the irradiation time of active energy beam, suitably can determine according to the composition of bonding agent, preferably according to as above-mentioned photograph Penetrating the long-pending of intensity and irradiation time, i.e. represented integrating light quantity reaches 10～10000mJ/cm2Mode set.Integrating Light quantity is 10mJ/cm2Time above, produce with making to derive from the spike substantial amount of polymerization initiator, can more reliably carry out Curing reaction, for 10000mJ/cm2Time following, irradiation time will not become long, can maintain good productivity ratio.
One of them of 1st and the 2nd thermoplastic resin membrane 10,20 uses temporary protection film to implement lamination process S300 Time, as it has been described above, the available such as one side with temporary protection film shown in Fig. 5 protects Polarizer 3, by from it On by temporary protection film peel off remove such that it is able to obtain such as shown in Fig. 4 one side protection Polarizer 2.Need explanation , as it has been described above, in figures 4 and 5, although using the 2nd thermoplastic resin membrane 20 as temporary protection film, But the 1st thermoplastic resin membrane 10 can also become temporary protection film.This one side protection Polarizer 2 can also be arranged on The stacking polarizing film face of temporary protection film on the operation of stacking bond layer 30, obtain the such as band shown in Fig. 6 There is the one side protection Polarizer 4 of bond layer.This bond layer 30 may be used for protecting Polarizer to be pasted onto liquid crystal cell one side On part.
For the two-sided protection Polarizer 1 shown in Fig. 2, it is also possible at the 1st thermoplastic resin membrane the 10 or the 2nd thermoplastic resin The outside stacking bond layer 30 of membrane of lipoprotein 20.This bond layer 30 can be used for two-sided protection Polarizer 1 is pasted onto liquid crystal On element.In two-sided protection Polarizer 1, bond layer 30 preferably layer is stacked in the outside of the 2nd thermoplastic resin membrane 20.
Bond layer 30 can be by with (methyl) acrylic ester, rubber series, polyurethane series, ester system, silicone-based, poly- The such resin of vinyl Ether system is that the adhesive composite of main component (base polymer) is constituted.Wherein, preferably with transparent Property, the adhesive composite of polymer based on excellent (methyl) the acrylic ester resin such as weatherability, thermostability. Adhesive composite can also be active energy ray curable, thermohardening type.
As (methyl) the acrylic ester resin used in adhesive composite, such as, (methyl) acrylic acid is preferably used Butyl ester, (methyl) ethyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA are such Polymer with (methyl) acrylate one kind or two or more as monomer or copolymer.(methyl) acrylic ester tree Fat preferably makes polar monomer copolymerization.As polar monomer, include, for example out (methyl) acrylic acid, (methyl) propylene Acid 2-hydroxypropyl acrylate, (methyl) 2-(Acryloyloxy)ethanol, (methyl) acrylamide, (methyl) acrylic acid-N, N-dimethylamino Base ethyl ester, (methyl) glycidyl acrylate be such has carboxyl, hydroxyl, amide groups, amino, epoxy radicals etc. Monomer.
Adhesive composite can also is that the compositions containing only above-mentioned base polymer, contains cross-linking agent the most further. As cross-linking agent, can exemplify: for metal ion more than divalent, and between carboxyl, form carboxylic metallic salt person；For polyamine Amido link person is formed between compound, and carboxyl；For forming ester bond person between polyepoxides or polyhydric alcohol, and carboxyl； For forming amido link person between polyisocyanate compounds, and carboxyl.Wherein, preferred polyisocyanate compounds.
Active energy ray curable adhesive composite refers to, has and accepts ultraviolet, the such active-energy of electron ray The irradiation of ray and the character that solidifies, have: though before irradiating active energy beam, also have cohesiveness, can adhere to thin The adherends such as film, solidified, can adjust the adhesive composite of the character of adhesion by the irradiation of active energy beam. Active energy ray curable adhesive composite is preferably ultraviolet hardening.Active energy ray curable bonding agent combines Thing, in addition to base polymer, cross-linking agent, contains active energy beam polymerizable compound further.And then as required, Photoepolymerizationinitiater initiater, photosensitizer etc. can also be contained.
Adhesive composite can be containing for giving light scattering microgranule, beading (resin bead, bead etc.), glass Resin beyond fiber, base polymer, viscosifier, filler (metal powder or other inorganic powders etc.), antioxidant, The additives such as UV absorbent, dyestuff, pigment, coloring agent, defoamer, preservative, Photoepolymerizationinitiater initiater.
Bond layer 30 can be by being applied to the bonding agent of Polarizer by the organic solvent diluting liquid of above-mentioned adhesive composite Layer forms that face (that is, polarizing film 5, the 1st or the 2nd thermoplastic resin membrane 10,20) is upper, make it be dried and be formed. Or, it is also possible to the organic solvent diluting liquid of above-mentioned adhesive composite is coated on isolated film and (implements what the demoulding processed Thermoplastic resin membrane) on so that it is being dried after forming bond layer, the bond layer being transferred to Polarizer forms face. Either which kind of method, the most preferably outside at bond layer 30 stick isolated film, until all protecting bonding when using Oxidant layer 30.When using active energy ray curable adhesive composite, can be by irradiating activity to the bond layer formed Energy-ray thus formed and there is the solidfied material of desired curing degree.The thickness of bond layer 30 is usually 1～40 μm, But from the viewpoint of the filming of Polarizer, preferably 3～25 μm.
Two-sided protection Polarizer 1, the 1st and/or the 2nd thermoplastic resin membrane of one side protection Polarizer 2 can also be arranged on 10, the operation of the outside stacking protective film of 20.Protective film is made up of base film and the bond layer being laminated thereon. Protective film is the thin film on the surface for protecting Polarizer, generally, and the such as protected thin film of adhesive band on liquid crystal cell etc. Polarizer after, together with its bond layer having removing lifted-off together.Base film can be made up of thermoplastic resin, Such as, polyethylene-based resin, the such polyolefin-based resins of polypropylene-based resin；Cyclic polyolefin hydrocarbon system resin；Poly-to benzene two Formic acid glycol ester or the such polyester based resin of PEN；Polycarbonate-based resin；(methyl) propylene Acid esters system resin etc..
Furthermore it is also possible to be arranged on two-sided protection Polarizer 1, the 1st and/or the 2nd thermoplastic resin of one side protection Polarizer 2 The operation of other optical thin films beyond the outside stacking polarizing film of membrane of lipoprotein 10,20.The example of other optical thin film, For phase-contrast film or luminance brightness-improving film etc..Other optical thin films can carry out stacking via adhesive layer or bond layer and glue Patch.
According to manufacture method of the present invention, it is possible to suppressed or prevent Polarizer (the two-sided guarantor of inverse curling well Protect Polarizer or one side protection Polarizer) individual body.As it has been described above, inverse curling refers to, it is possible to the image such as liquid crystal cell The curling of opposition side that is the 2nd interarea projection of the side that display element is pasted, protects partially at two-sided protection Polarizer 1 or one side In tabula rasa 2, for typical case, it it is the curling of the 1st thermoplastic resin membrane 10 side projection.By the polarisation obtained by the present invention In individual body of plate, it is possible to suppress or prevent the inverse curling of this 1st thermoplastic resin membrane 10 side projection, allusion quotation well For type, be the writing board shape without curling, or there is the shape just crimped a little, even if or have inverse curling, Its amount is also the shape of slight amount.The most not there is the writing board shape of curling, or there is the shape just crimped a little.
[embodiment]
Below, it is shown that embodiment specifically describes the present invention further, but the present invention is not limited by these examples.Need Bright, in following example, the equilibrium moisture content of thin film, moisture content, moisture permeability and thickness and the curling of Polarizer Measure and measure according to following method.
(1) equilibrium moisture content W of thin filmH
Cut the test film of MD length 150mm × TD length 100mm.Measure at temperature 23 DEG C, relative humidity 55% In the environment of preserve the film weight after 24 hours.Afterwards, at 105 DEG C, carry out 2 hours dried, measure and be dried place Film weight after reason.By the film weight before and after being dried, try to achieve equilibrium moisture content W based on following formulaH:
Equilibrium moisture content (weight %)=(film weight after film weight-dried before dried)/it is dried place Film weight before reason } × 100.
(2) the moisture content W of thin film
Cut the test film of MD length 150mm × TD length 100mm, measure its weight at once.Then, at 105 DEG C Under carry out 2 hours dried, measure the film weight after dried.By the film weight before and after being dried, based on following Formula tries to achieve moisture content W:
Moisture content (weight %)={ before (film weight after film weight-dried before dried)/dried Film weight × 100.
(3) moisture permeability of thin film
According to the moisture-inhibiting agar diffusion method of regulation in JIS Z0208, measure the moisture permeability (g/ (m under temperature 40 DEG C, relative humidity 90%2 ·24hr)〕。
(4) thickness of thin film
Use the digital micrometer (digital micrometer) " MH-15M " of Co., Ltd.'s nikon system ((strain) ニ U Application) Measure.
(5) amount of curl of Polarizer
Absorb direction of principal axis (MD) according to it mode that each limit is at 45 ° is cut from obtained two-sided protection Polarizer The test film of 300mm × 200mm, places 24 hours in the environment of temperature 25 DEG C, relative humidity 55%.Make this test Sheet concave upright, the state i.e. lifted according to 4 ends is placed on datum level (horizontal stand).Measure in this condition The height of 4 angles of test film distance datum level respectively, the height at these 4 angles is average, try to achieve amount of curl (mm). When amount of curl is positive value, it is meant that the 1st thermoplastic resin membrane side becomes recessed (just crimping), during for negative value, it is meant that 2nd thermoplastic resin membrane side becomes recessed (inverse curling).It should be noted that the two-sided protection Polarizer of embodiment 2 and 3, By the 1st thermoplastic resin membrane side, the 2nd thermoplastic resin membrane side which be placed on and above the most do not produce curling.
＜ embodiment 1 ＞
(A) making of polarizing film
Transmit polyvinyl alcohol film (average degree of polymerization: about 2400, the saponification degree: 99.9 moles of % of long size on one side continuously Above, thickness: 30 μm), with dry type uniaxial tension to about 4 times, and then directly when keeping tense situation, The pure water of 40 DEG C impregnates 1 minute, then in 28 DEG C in the aqueous solution that weight ratio is 0.1/5/100 of iodine/potassium iodide/water Lower dipping 60 seconds.Afterwards, impregnate at 68 DEG C in the aqueous solution that weight ratio is 10.5/7.5/100 of potassium iodide/boric acid/water 300 seconds.Then, wash in the pure water of 5 DEG C 5 seconds, be then dried 180 seconds at 70 DEG C, obtain uniaxial tension On polyvinyl alcohol film, gas absorption quantity has the polarizing film of the long size of iodine.The thickness of polarizing film is 11 μm.
(B) making of two-sided protection Polarizer
Use the device identical with the polarisation board manufacturing apparatus shown in Fig. 3, with following sequentially built two-sided protection Polarizer. Transmit the 1st thermoplastic resin membrane (Konica Minolta Opto Products Co., the Ltd (U of long size on one side continuously ニ カ ミ ノ Le タ オ プ ト (strain)) TAC film " KC2UAW " made, thickness: 25 μm, equilibrium moisture content WH: 3.0 Weight %, moisture permeability: 1207g/ (m224hr)), importing is set as relative humidity in in-furnace temperature 95 DEG C, stove The heating furnace of 3%, then, imports and is set as in in-furnace temperature 50 DEG C, stove carrying out thin film in the humidification stove of relative humidity 70% Add wet process.In drying oven, humidification stove, the holdup time of thin film is respectively 8 seconds, 12 seconds.Humidification stove is arranged on heating furnace Afterwards, the temperature of the thin film just having imported humidification stokehold is almost identical with the in-furnace temperature of heating furnace.Heating furnace and humidification stove are the most logical Cross the supply of hot blast to improve in-furnace temperature.The moisture content W adding the 1st thermoplastic resin membrane after wet process is 3.1 weight %.
Transmit the polarizing film obtained in above-mentioned (A) continuously, meanwhile, transmit continuously and above-mentioned add the 1st heat after wet process (the cyclic polyolefin hydrocarbon system resin that JSR (strain) makes is thin for 2nd thermoplastic resin membrane of plastic resin film and long size Film, trade name " FEKB015D3 ", thickness: 15 μm, equilibrium moisture content WH: 0.8 weight %, moisture permeability: 115g/ (m224hr), do not heat, add wet process and use like this buying thing), to polarizing film and the 1st thermoplastic Property resin film between and polarizing film and the 2nd thermoplastic resin membrane between inject water system bonding agent, by paste Close between roller, make by 1 thermoplastic resin membrane/water system bond layer/polarizing film/water system bond layer/the 2nd thermoplasticity The laminate film (the 1st operation) that resin film is formed.This lamination process the 1st thermoplastic resin membrane add wet process after Carry out within 10 seconds.
Aqueous solution obtained by above-mentioned water system bonding agent use is following: by pva powder (Japan's synthetic chemical industry (strain) The trade name " GOHSEFIMER " (go セ Off ァ イ マ) of system, average degree of polymerization 1100) it is dissolved in the heat of 95 DEG C Water and obtain the polyvinyl alcohol water solution of concentration 3 weight %, being 1 weight for pva powder 10 weight portion The ratio mixed cross-linker wherein (sodiam glyoxlate that Japan's synthetic chemical industry (strain) makes) of part.
Then, the laminate film obtained by transmission, carry out 80 DEG C, the heat treated of 300 seconds by air drier, thus Water system bond layer is dried, obtains two-sided protection Polarizer.
＜ embodiment 2～3, comparative example 1～3 ＞
The holdup time of heating furnace and the furnace inner environment of humidification stove and thin film is as shown in table 1, in addition, with embodiment 1 similarly manufactures two-sided protection Polarizer.Comparative example 2 and 3 does not carry out the heat treated of the 1st thermoplastic resin membrane.
The amount of curl of the two-sided protection Polarizer obtained in embodiment 1～3 and comparative example 1～3 is shown in table 1.In table 1 together Time describe heating furnace and the humidification furnace inner environment of stove and the holdup time of thin film.This appearance 1 also show humidification The moisture content W of the 1st thermoplastic resin membrane after process, equilibrium moisture content W of the 1st thermoplastic resin membraneH, and Add the moisture content W after wet process and equilibrium moisture content WHDifference.It should be noted that in comparative example 1, although make the 1st Thermoplastic resin membrane is by humidification stove, but does not carry out adding wet process.In the comparative example 1 of table 1, " after adding wet process Moisture content " the numerical value described in a hurdle mean the moisture content of the 1st thermoplastic resin membrane by humidification furnace rear.
In any one of embodiment 1～3, comparative example 1 and comparative example 3, the surface of the 1st thermoplastic resin membrane does not confirm To condensation vestige.In comparative example 2, confirm condensation vestige on the surface of the 1st thermoplastic resin membrane.
[table 1]
＜ embodiment 4 and 5 ＞
As the 1st thermoplastic resin membrane, use hard-coated film (at Konica Minolta Opto Products Co., Ltd The upper thin film forming hard conating of the TAC film " KC2UAW " of system, thickness: 32.4 μm, equilibrium moisture content WH: 1.9 Weight %, moisture permeability: 455g/ (m224hr)), cyclic polyolefin hydrocarbon system resin is used as the 2nd thermoplastic resin membrane Thin film (trade name " ZF14-023 " that Japan zeon (strain) makes, thickness: 22.9 μm, equilibrium moisture content WH: 0.1 Weight %, moisture permeability: 17g/ (m224hr)), heating furnace and furnace inner environment and the holdup time of thin film humidifying stove As shown in table 2, in addition, two-sided protection Polarizer is manufactured similarly to Example 1.Embodiment 4 and 5 will be obtained The amount of curl of two-sided protection Polarizer be shown in table 2.Table 2 describes simultaneously heating furnace and humidification stove furnace inner environment, with And the holdup time of thin film.Additionally table 2 also show the 1st thermoplastic resin membrane after adding wet process moisture content W, Equilibrium moisture content W of the 1st thermoplastic resin membraneH, and add the moisture content W after wet process and equilibrium moisture content WHIt Difference.
[table 2]

Claims (12)

1. a manufacture method for Polarizer, it includes in the following order:
1st thermoplastic resin membrane is carried out the operation of heat treated,
Described 1st thermoplastic resin membrane is added the operation of wet process, and
Described 1st thermoplastic resin membrane is folded, at the opposite side table of described polarizing film on a side surface upper strata of polarizing film The operation of stacking the 2nd thermoplastic resin membrane on face, described 2nd thermoplastic resin membrane is compared to described 1st thermoplastic resin For membrane of lipoprotein, the equilibrium moisture content under temperature 23 DEG C, relative humidity 55% is low.
Manufacture method the most according to claim 1, wherein, described 2nd thermoplastic resin membrane did not implement described Add wet process.
Manufacture method the most according to claim 1, wherein, described 1st thermoplastic resin membrane contains cellulose-based tree Membrane of lipoprotein.
Manufacture method the most according to claim 1, wherein, described 2nd thermoplastic resin membrane contains cyclic polyolefin Based resin film.
Manufacture method the most according to claim 1, wherein, temperature during described heat treated be described in when adding wet process Temperature more than.
Manufacture method the most according to claim 5, wherein, when adding wet process described in temperature ratio during described heat treated Temperature high more than 30 DEG C.
Manufacture method the most according to claim 1, in the operation carrying out described heat treated, described 1st thermoplasticity Resin film is more than temperature 50 C, be heat treatment in the environment of relative humidity less than 50%.
Manufacture method the most according to claim 1, in the operation adding wet process described in carrying out, described 1st thermoplasticity Resin film humidified process in the environment of temperature more than 40 DEG C, relative humidity more than 60%.
Manufacture method the most according to claim 1, described 1st thermoplastic resin membrane and described 2nd thermoplastic resin At least one in membrane of lipoprotein, it is layered on described polarizing film via bond layer.
Manufacture method the most according to claim 1, wherein, the thickness of described 1st thermoplastic resin membrane is 40 μm Hereinafter, the thickness of described 2nd thermoplastic resin membrane is below 40 μm.
11. manufacture methods according to claim 1, wherein, the thickness of described polarizing film is below 15 μm.
12. according to the manufacture method according to any one of claim 1～11, wherein, adds the work of wet process described in carry out In sequence, described 1st thermoplastic resin membrane is added wet process so that its moisture content is thinner than described 1st thermoplastic resin The equilibrium moisture content under temperature 23 DEG C, relative humidity 55% of film is high.
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CN103764782A (en) * 2011-08-29 2014-04-30 日东电工株式会社 Adhesive composition for optical applications, adhesive layer for optical applications, optical member, polarizing plate, and image display device
JP2014191155A (en) * 2013-03-27 2014-10-06 Sumitomo Chemical Co Ltd Method of producing polarizing plate

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CN106896442A (en) * 2016-12-22 2017-06-27 住华科技股份有限公司 Optical film and method for manufacturing the same
CN106896442B (en) * 2016-12-22 2019-12-03 住华科技股份有限公司 Optical film and method for manufacturing the same
CN110861325A (en) * 2018-08-27 2020-03-06 日东电工株式会社 Method for producing stretched resin film, method for producing polarizing plate, and apparatus for producing stretched resin film
CN112388997A (en) * 2020-04-17 2021-02-23 住华科技股份有限公司 System for manufacturing polarizing film, method for manufacturing polarizing film, and polarizing film manufactured thereby
CN112388997B (en) * 2020-04-17 2022-12-23 住华科技股份有限公司 System for manufacturing polarizing film, method for manufacturing polarizing film, and polarizing film manufactured thereby

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