CN107223213A - The manufacture method of polarization plates - Google Patents
The manufacture method of polarization plates Download PDFInfo
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- CN107223213A CN107223213A CN201580011574.1A CN201580011574A CN107223213A CN 107223213 A CN107223213 A CN 107223213A CN 201580011574 A CN201580011574 A CN 201580011574A CN 107223213 A CN107223213 A CN 107223213A
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- 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
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- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polarising Elements (AREA)
Abstract
The present invention provides a kind of manufacture method of polarization plates, and it is included successively：Bonding process, on the polarizer layer of polarizability stacked film for possessing polarizer layer at least one side of base material film, folder is across gluing oxidant layer laminating diaphragm；Drying process, is heat-treated in the environment of relative humidity more than 25% and dries gluing oxidant layer；With the process for peeling off removing base material film.
Description
Technical field
The present invention relates to a kind of manufacture method of polarization plates.
Background technology
Polarization plates are in the display devices such as liquid crystal display device, especially in recent years in slim TV, various mobile devices
In be used widely.As polarization plates, generally fitted diaphragm using adhesive in the one or both sides of polarizer
The polarization plates of composition.
Polarization plates are pressed from both sides across gluing oxidant layer except that can utilize on the polarizer (light polarizing film) comprising monomer (independent) film
The method of laminating diaphragm is (below also referred to as " monomer embrane method ".) beyond manufacture, can also be using following method (following also referred to as
Make " rubbing method ".) manufacture, it includes：The process for forming resin bed on base material film using coating (coating)；Stretched,
Polarizer layer is made in the resin bed by dyeing, the process for obtaining polarizability stacked film；On the polarizer layer of polarizability stacked film
The process for pressing from both sides diaphragm of being fitted across gluing oxidant layer；The process for removing base material film is peeled off after laminating diaphragm.The method of the latter
On this point of on this point disposal of the film in process is excellent and the polarizer layer for being readily available film, is favourable.
In Japanese Unexamined Patent Publication 2009-098653 publications (patent document 1) and Japanese Unexamined Patent Publication 2009-093074 publications (specially
Sharp document 2) in, record the content that polarization plates are manufactured using the method similar with rubbing method.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2009-098653 publications
Patent document 2：Japanese Unexamined Patent Publication 2009-093074 publications
The content of the invention
Invent problem to be solved
With the popularization of slim TV, mobile device, the requirement to the slimming of polarization plates is gradually stepped up in recent years.So
And, the problem of polarization plates are easy for producing curling is thinned if there are.If producing inappropriate curling in polarization plates, utilizing
Adhesive phase fits polarization plates on the display units such as liquid crystal cells and is easy for being mixed into bubble when display device is made.If in liquid
There is such bubble in the display device of crystal device etc, light scattering will be produced because of bubble when being allowed to light,
There may be the not good situation under black dispaly state in (bubble is changed into bright spot) display of light leak.
Described in patent document 1 and 2, according to the method similar with foregoing rubbing method, the curling of polarization plates can be suppressed.
But the polarization plates that so-called curling described in these documents is inhibited, it is not shell the base material film in foregoing rubbing method
The polarization plates used without change as the diaphragm of polarizer layer from removing, are obtained for base material film is peeled off into removing
, the curlings of the polarization plates comprising polarizer layer and diaphragm do not refer to.
It is an object of the present invention to provide a kind of manufacture method, is that such as foregoing rubbing method is such in polarizability layer
On the polarizer layer of folded film after laminating diaphragm, by the method that base material film peels off removing and manufactures polarization plates, gained can be suppressed
Polarization plates curling.
Method for solving problem
The present invention provides the manufacture method of polarization plates as shown below.
[1] a kind of manufacture method of polarization plates, it is included successively：
Bonding process, to the polarizer layer for the polarizability stacked film for possessing polarizer layer at least one side of base material film
On, folder is across gluing oxidant layer laminating diaphragm；
Drying process, is heat-treated in the environment of relative humidity more than 25% and dries the gluing oxidant layer；With
Peel off the process for removing the base material film.
[2] manufacture method according to described in [1], wherein,
The adhesive for forming the gluing oxidant layer is water system adhesive.
[3] manufacture method according to described in [1] or [2], wherein,
The method manufacture that the polarizability stacked film is utilized as described below, it includes：
After being coated with the coating fluid containing polyvinyl alcohol resin at least one side of the base material film, drying is allowed to, by
This process for forming polyvinyl alcohol resin layer and obtaining stacked film；
The process for stretching the stacked film and obtaining stretched film；
The polyvinyl alcohol resin layer dichroism pigment of the stretched film is dyed and the polarizer layer is formed, thus
The process for obtaining polarizability stacked film.
[4] manufacture method recorded according to any one of [1]~[3], wherein,
The diaphragm includes cellulose esters system resin or (methyl) acrylic resin.
[5] manufacture method recorded according to any one of [1]~[4], wherein,
The thickness of the polarizer layer is less than 10 μm.
Invention effect
According to the present invention, after diaphragm of being fitted on the polarizer layer of polarizability stacked film, peel off removing base material film and make
In the method for making the polarization plates comprising polarizer layer and the diaphragm for fitting in its at least one side, the polarization plates of gained can be suppressed
Curling.
Brief description of the drawings
Fig. 1 is the preferred flow chart of one for the manufacture method for representing the polarization plates of the present invention.
Fig. 2 is the preferred flow chart of one for the manufacture method for representing polarizability stacked film.
Fig. 3 is the preferred flow chart of other one for the manufacture method for representing the polarization plates of the present invention.
Fig. 4 is to represent the constructed profile of one that the layer of the stacked film obtained in resin bed formation process is constituted.
Fig. 5 is to represent the constructed profile of one that the layer of the stretched film obtained in stretching process is constituted.
Fig. 6 is to represent the constructed profile of one that the layer of the polarizability stacked film obtained in dyeing process is constituted.
Fig. 7 is that the layer for representing the polarizability stacked film with diaphragm obtained in the first diaphragm bonding process is constituted
The constructed profile of one.
Fig. 8 is to represent the constructed profile that the layer of polarization plates of the one side with diaphragm obtained in stripping process is constituted.
Fig. 9 be represent the two-sided polarization plates with diaphragm obtained in the second diaphragm bonding process layer constitute show
Meaning profile.
Embodiment
Fig. 1 is the preferred flow chart of one for the manufacture method for representing the polarization plates of the present invention.As shown in figure 1, this hair
Bright manufacture method includes following processes：
(1) first diaphragm bonding process S10, to the polarizability layer for possessing polarizer layer at least one side of base material film
On the polarizer layer of folded film, folder is across gluing oxidant layer the first diaphragm of laminating；
(2) drying process S20, is heat-treated in the environment of relative humidity more than 25% and dries gluing oxidant layer；
(3) stripping process S30, peels off and removes base material film.
In addition as shown in Fig. 2 polarizability stacked film is as foregoing rubbing method, preferably by including the side of following processes
Method is manufactured, i.e.,：
(a) resin bed formation process S1-1, is coated with the painting containing polyvinyl alcohol resin at least one side of base material film
After cloth liquid, drying is allowed to, polyvinyl alcohol resin layer is consequently formed and obtains stacked film；
(b) stretching process S1-2, stretches stacked film and obtains stretched film；
(c) dyeing process S1-3, the polyvinyl alcohol resin layer of stretched film is dyed with dichroism pigment and is formed and polarized
Lamella, thus obtains polarizability stacked film.
Using the manufacture method of the above, the one side that the one side that can be obtained in polarizer layer is fitted with the first diaphragm is carried
The polarization plates of diaphragm.As shown in figure 3, the second diaphragm bonding process S40 can be set after stripping process S30, i.e.
The face folder of the polarizer layer side of polarization plates of the one side with diaphragm obtains two-sided band across gluing oxidant layer the second diaphragm of laminating
There are the polarization plates of diaphragm.
Moreover, the so-called polarization plates (polarization plates obtained using the manufacture method of the present invention) of the present invention, are comprising polarization
Lamella and folder are laminated on component (that is, polarization plates of the one side with diaphragm of the diaphragm of its at least one side across adhesive layer by layer
Or the two-sided polarization plates with diaphragm), without the base material film included in the polarizability stacked film as its precursor.But
It is that the polarization plates obtained using the manufacture method of the present invention can be laminated other optics of other films, layer etc thereon
Component (surrounding member) and be changed into composite polarizing plate, or used as such composite polarizing plate.Polarizer layer can be in warp
Cross uniaxial tension polyvinyl alcohol resin layer (or film) on absorption dichroism pigment and be allowed to orientation obtained by layer.
In addition, the so-called polarizability stacked film of the present invention, refers to possess base material film and is laminated in inclined in its at least one side
Shake lamella and without laminating diaphragm stacked film.For being pasted in the first diaphragm bonding process S10 on polarizer layer
The polarizability stacked film of the first diaphragm is closed, below in order to be distinguished with polarizability stacked film, also referred to as " with diaphragm
Polarizability stacked film ".
Hereinafter, each operation is described in detail.And in resin bed formation process S1-1, can also be in base material film
Two sides forms polyvinyl alcohol resin layer, but the following main situation to being formed in one side is illustrated.
<First diaphragm bonding process S10>
As it was previously stated, polarizability stacked film is preferably by including (a) resin bed formation process S1-1, (b) stretching process S1-
2 and (c) dyeing process S1-3 method manufacture.
(a) resin bed formation process S1-1
Reference picture 4, this process is to obtain stacked film at least one side formation polyvinyl alcohol resin layer 6 of base material film 30
100 process.Polyvinyl alcohol resin layer 6 is stretched process S1-2 and dyeing process S1-3 and becomes polarizer layer 5
Layer.Polyvinyl alcohol resin layer 6 can by by the coating solution containing polyvinyl alcohol resin in the one of base material film 30
Face or two sides simultaneously make coating dry and be formed.
Base material film 30 can be made up of thermoplastic resin, wherein it is preferred that by the transparency, mechanical strength, heat endurance, stretching
Property etc. excellent thermoplastic resin constitute.The concrete example of such thermoplastic resin for example including：Chain polyolefin-based resins, ring
The polyolefin-based resins of shape polyolefin-based resins (norbornene resin etc.) etc；Polyester based resin；(methyl) acrylic acid series
Resin；The cellulose esters system resin of cellulosic triacetate, cellulose diacetate etc；Polycarbonate-based resin；Polyethylene
Alcohol system resin；Polyvinyl acetate system resin；Polyarylate system resin；Polystyrene resin；Polyether sulfone system resin；Polysulfones system tree
Fat；Polyamide series resin；Polyimides system resins；And their mixture, copolymer.
Moreover, " (methyl) acrylic acid " so-called in this specification, refers in acrylic acid and methacrylic acid at least
One.It is also identical when " (methyl) acryloyl group " etc. for being denoted as.
Base material film 30 can be the individual layer knot being made up of 1 resin bed comprising one kind or two or more thermoplastic resin
Structure or the sandwich construction by the resin bed laminated multi-layer comprising one kind or two or more thermoplastic resin.Base material film 30
It is preferred that during by being stretched in stretching process S1-2 described later to stacked film 100, can be suitable for stretching polyethylene alcohol system tree
The resin that the draft temperature of lipid layer 6 is stretched is constituted.
Base material film 30 can contain additive.As additive, can for example enumerate ultra-violet absorber, antioxidant,
Lubricant, plasticizer, releasing agent, anti-coloring agent, fire retardant, nucleator, antistatic agent, pigment and colouring agent etc..Base material film
The content of thermoplastic resin in 30 is preferably 50~100 weight %, more preferably 50~99 weight %, more preferably 60
~98 weight %, particularly preferably 70~97 weight %.
It is 1~500 μm generally from the aspect of the operability such as intensity, disposal property for the thickness of base material film 30, it is excellent
Elect 1~300 μm, more preferably more preferably 5~200 μm, 5~150 μm as.
The coating fluid for being coated on base material film 30 is preferably that the powder of polyvinyl alcohol resin is dissolved in into good solvent (for example
Water) in obtained by polyvinyl alcohol resin solution.As polyvinyl alcohol resin, can for example enumerate polyvinyl alcohol resin and its
Derivative.As the derivative of polyvinyl alcohol resin, except can enumerate polyvinyl formal, polyvinyl acetal etc. with
Outside, the derivative for being modified polyvinyl alcohol resin with the olefines of ethene, propylene etc can also be enumerated；With acrylic acid, first
The derivative that the unsaturated carboxylic acid class of base acrylic acid, crotonic acid etc has been modified；It is ester modified with the alkyl of unsaturated carboxylic acid
Derivative；With (methyl) acrylic amide modified derivative etc..Modified ratio is preferably less than 30mol%, more preferably
Less than 10mol%.In the case where carrying out the modification more than 30mol%, it is difficult to adsorb dichroism pigment, it is possible to create polarizability
The not good situation that can be reduced.Among above-mentioned polyvinyl alcohol resin, polyvinyl alcohol resin is preferably used.
The average degree of polymerization of polyvinyl alcohol resin is preferably in 100~10000 scope, it is more preferably in 1000~
10000 scope, further preferably in 1500~8000 scope, is most preferably in 2000~5000 scope.It is average poly-
It is right to be obtained using method specified in JIS K 6726-1994 " polyvinyl alcohol test method ".If average degree of polymerization is small
In 100, then it is difficult to obtain preferred polarization property, if more than 10000, dissolubility in a solvent deteriorates, polyethenol series
The formation of resin bed becomes difficult.
Polyvinyl alcohol resin is preferably the saponification product of polyvinyl acetate system resin.Saponification degree is ranged preferably from
More than 80mol%, more preferably more than 90mol%, especially preferably more than 94mol%.If saponification degree is too low, polarization is made
Water resistance, humidity resistance when property stacked film, polarization plates are possible to not abundant enough.In addition, though can be fully saponified product (soap
Change degree be 100mol% material), if but saponification degree is too high, dyeing kinetics are slack-off, in order to assign enough polarization properties,
Manufacturing time is elongated, or can not according to circumstances obtain the polarizer layer with enough polarization properties sometimes.Thus, its saponification degree
Preferably below 99.5mol%, more preferably below 99.0mol%.
So-called saponification degree, is that will be used as second contained in the polyvinyl acetate system resin of the raw material of polyvinyl alcohol resin
Acidic group (acetoxyl group：-OCOCH3) it is changed into the value that the ratio of hydroxyl is represented with unit ratio (mol%) because of saponification process, under
Formula is defined：
Saponification degree (mol%)=((number of hydroxyl) ÷ (number of number+acetate of hydroxyl)) × 100
Saponification degree can be obtained according to JIS K 6726 (1994).Saponification degree is higher, then it represents that the ratio of hydroxyl is higher, because
And hinder the ratio of the acetate of crystallization lower.
As polyvinyl acetate system resin, the poly- acetic acid second except the homopolymer as vinyl acetate can be exemplified
Beyond alkene ester, can also exemplify vinyl acetate with can be with the copolymer of the other monomers of its copolymerization etc..As can be with
The other monomers of vinyl acetate copolymerization, for example, can enumerate unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulphur
Acids, (methyl) acrylic amide with ammonium etc..
Coating fluid can also contain the additives such as plasticizer, surfactant as needed.As plasticizer, it can use
Polyalcohol or its condensation product etc., such as can exemplify glycerine, diglycerol, triglycerin, ethylene glycol, propane diols, polyethylene glycol.
The use level of additive is preferably set to below 20 weight % of polyvinyl alcohol resin.
Can be from wire rod rubbing method in the method for base material film 30 by above-mentioned coating solution；Reversion coating, intaglio plate coating
Etc rolling method；Die coating method；Comma rubbing method；Die lip rubbing method；Spin-coating method；Silk screen rubbing method；Jetting type rubbing method；Dip-coating
Method；Properly selected in the methods such as spraying process.
The drying temperature of coating (the polyvinyl alcohol resin layer before drying) and drying time can be according to institutes in coating fluid
The species setting of the solvent contained.Drying temperature is, for example, 50~200 DEG C, preferably 60~150 DEG C.Contain the situation of water in solvent
Under, drying temperature is preferably more than 80 DEG C.
Polyvinyl alcohol resin layer 6 can only be formed at the one side of base material film 30, can also be formed at two sides.If being formed at
Two sides, due to that can obtain 2 polarization plates by 1 polarizability stacked film 300, therefore also has in terms of the production efficiency of polarization plates
Profit.
The thickness of polyvinyl alcohol resin layer 6 in stacked film 100 is preferably 3~30 μm, more preferably 5~20 μm.If
For with the polyvinyl alcohol resin of the thickness in the range of this layer 6, then by stretching process S1-2 described later and dyeing process S1-
3, can obtain dichroism pigment dyeability is good and polarization property is excellent and sufficiently thin (such as below 10 μm of thickness
) polarizer layer 5.If the thickness of polyvinyl alcohol resin layer 6 is less than 3 μm, is become too thin after stretching and have dyeability evil
The trend of change.
Can be before the coating of coating fluid, in order to improve the adaptation of base material film 30 and polyvinyl alcohol resin layer 6, extremely
Sided corona treatment, corona treatment, fire are implemented in few surface to being formed with the base material film 30 of the side of polyvinyl alcohol resin layer 6
Flame (flame) processing etc..
Furthermore it is possible to before the coating of coating fluid, in order to improve the closely sealed of base material film 30 and polyvinyl alcohol resin layer 6
Property, pressed from both sides on base material film 30 across the formation polyvinyl alcohol resin such as prime coat layer 6.
Prime coat can by by prime coat formation with coating solution in be allowed to behind the surface of base material film 30 dry and shape
Into.Prime coat formation coating fluid contains a certain degree of strong close with base material film 30 and both performances of polyvinyl alcohol resin layer 6
Composition with joint efforts.Prime coat formation usually contains the resin component and solvent for assigning such closing force with coating fluid.It is used as tree
Fat composition preferably uses the excellent thermoplastic resin such as the transparency, heat endurance, draftability, for example, can enumerate (methyl) propylene
Acid system resin, polyvinyl alcohol resin etc..Wherein, the polyvinyl alcohol resin for assigning good closing force is preferably used.It is more excellent
Elect polyvinyl alcohol resin as.It is molten usually using the general organic solvent or water system that can dissolve above-mentioned resin component as solvent
Agent, but it is preferred that prime coat is formed by the coating fluid using water as solvent.
, can be to prime coat formation with adding crosslinking agent in coating fluid in order to improve the intensity of prime coat.According to being used
Thermoplastic resin species, properly select suitable crosslinking agent from crosslinking agent known to organic system, inorganic system etc..To
Enumerate the example of crosslinking agent, for example, epoxy, isocyanates system, dialdehyde system, metal system (for example metal salt, metal oxide,
Metal hydroxides, organo-metallic compound), the crosslinking agent of macromolecular.Used as the resin component for forming prime coat
In the case of polyvinyl alcohol resin, Polyamide Epoxy, methylolated melamine resin, the crosslinking of dialdehyde system are preferably used
Agent, meal chelate compounds system crosslinking agent etc..
The thickness of prime coat is preferably 0.05~1 μm or so, more preferably 0.1~0.4 μm.If less than 0.05 μm, base
The effect that the closing force of material film 30 and polyvinyl alcohol resin layer 6 is improved is small, if more than 1 μm, being unfavorable for the film of polarization plates
Change.
Prime coat formation coating solution can be formed in the method for base material film 30 with polyvinyl alcohol resin layer and used
Coating fluid it is identical.Prime coat is applied to the face of the coating fluid of pva coating resin formation.Include prime coat
Formation is, for example, 50~200 DEG C with the drying temperature of the coating of coating fluid, preferably 60~150 DEG C.Contain the feelings of water in solvent
Under condition, drying temperature is preferably more than 80 DEG C.
(b) stretching process S1-2
Reference picture 5, this process is stacked film 100 of the stretching comprising base material film 30 and polyvinyl alcohol resin layer 6, wrapped
The process of stretched film 200 containing stretched base material film 30 ' and polyvinyl alcohol resin layer 6 '.Stretch processing is usually single shaft
Stretching.
The stretching ratio of stacked film 100 can be properly selected according to desired polarization characteristic, but preferably with respect to
The original of stacked film 100 is long more than 5 times and to be less than 17 times, more preferably greater than 5 times and is less than 8 times.If stretching ratio be 5 times with
Under, then polyvinyl alcohol resin layer 6 ' will not be fully orientated, therefore the degree of polarization of polarizer layer 5 will not become sufficiently high.Separately
On the one hand, if stretching ratio is more than 17 times, easily produce the fracture of film during stretching, and stretched film 200 thickness of thin to must
Need more than degree, the processability and disposal property in subsequent handling are likely to decrease.
Stretch processing is not limited to the stretching of a step, can also carry out to multistep.In this case, can will be all many
The stretch processing of step is continuously carried out before dyeing process S1-3, can also be by the later stretch processing of second step and dyeing process
Dyeing processing and/or crosslinking Treatment in S1-3 are simultaneously carried out.It is excellent in the case of carrying out stretch processing in multistep like this
Select and carry out stretch processing in the way of all steps of stretch processing are added into the stretching ratio reached more than 5 times.
Stretch processing also may be used in addition to it can be the longitudinal stretching stretched along film length direction (film conveyance direction)
To be cross directional stretch or oblique extension for being stretched along film width etc..As longitudinal stretching mode, it can enumerate and use
Stretching, compression stretching between the roller that roller is stretched, the stretching for having used chuck (clip) etc., can be with as cross directional stretch mode
Enumerate tenter frame process etc..Stretch processing can use any one of wet tensile method, dry-stretch process, but from can be with
Selected from big scope from the aspect of draft temperature, preferably use dry-stretch process.
Draft temperature be set to can stretching polyethylene alcohol resin 6 and the overall degree of base material film 30 show
It is more than the temperature of mobility, the preferably model of -30 DEG C to+30 DEG C of the phase transition temperature (fusing point or glass transition temperature) of base material film 30
Enclose, more preferably -30 DEG C to+5 DEG C of scope, more preferably -25 DEG C to+0 DEG C of scope.In base material film 30 comprising multiple
In the case of resin bed, above-mentioned phase transition temperature means the highest phase alternating temperature in the phase transition temperature shown by the plurality of resin bed
Degree.
If making draft temperature be less than -30 DEG C of phase transition temperature, it is difficult to the high magnification more than 5 times and stretches, or because of base material
The mobility of film 30 is too low and stretch processing is had the trend for becoming difficult.If draft temperature is more than+30 DEG C of phase transition temperature, because
The mobility of base material film 30 is excessive and stretching is had the trend for becoming difficult.Due to being easier to realize the high stretching times more than 5 times
Rate, therefore draft temperature is preferably more preferably more than 120 DEG C in above range.
As the heating means of the stacked film 100 in stretch processing, there is region heating (for example to be adjusted being blown into hot blast
The method heated in drawing zone for the given heating furnace of temperature etc.)；Add in the case where being stretched using roller
The method of hot-rolling in itself；Heater heating is (in infrared heater setting up and down, halogen heater, the panel of stacked film 100
Heater etc. and the method heated with radiant heat) etc..Between roller in stretching mode, from the viewpoint of the uniformity of draft temperature
Consider favored area heating.
The pre-heat treatment process for preheating stacked film 100 can be set before stretching process S1-2.It is used as preheating side
Method, can be used and the heating means identical method in stretch processing.Preheating temperature is preferably that -50 DEG C of draft temperature arrives ± 0
DEG C scope, more preferably -40 DEG C to -10 DEG C of draft temperature scope.
Furthermore it is possible to after stretching process S1-2 stretch processing, set heat fixation treatment process.Heat fixation processing be
It is hot using being carried out in the state of the end of clip grab tensile film 200 while maintenance tense situation, more than crystallized temperature
The processing of processing.The crystallization of polyvinyl alcohol resin layer 6 ' can be promoted by being handled using the heat fixation.The temperature of heat fixation processing
Degree is preferably the scope of the scope, more preferably -0 DEG C~-50 DEG C of draft temperature of -0 DEG C~-80 DEG C of draft temperature.
(c) dyeing process S1-3
Reference picture 6, this process is that the polyvinyl alcohol resin layer 6 ' of stretched film 200 is dyed with dichroism pigment and is adsorbed
The pigment is simultaneously allowed to the process that is orientated, polarizer layer 5 is made.It can be obtained in the one side of base material film 30 ' or two by this process
Surface layer is laminated with the polarizability stacked film 300 of polarizer layer 5.As dichroism pigment, iodine or dichroism can be specifically used
Organic dyestuff.
Dyeing process can be by the entirety of dipping stretched film 200 into the solution (staining solution) containing dichroism pigment
Carry out.As staining solution, it can use and dissolve solution obtained by above-mentioned dichroism pigment in a solvent.It is used as staining solution
Solvent, typically using water, but can also add organic solvent having a miscibility with water again.Dichroism color in staining solution
The concentration of element is preferably 0.01~10 weight %, more preferably 0.02~7 weight %, more preferably 0.025~5 weight
Measure %.
In the case where using iodine as dichroism pigment, due to can further improve staining efficiency, therefore preferably to
Iodide are added in staining solution containing iodine again.As iodide, for example, it can enumerate KI, lithium iodide, sodium iodide, iodine
Change zinc, silver iodide, lead iodide, cupric iodide, barium iodide, calcium iodide, stannic iodide, titanium iodide etc..Iodide in staining solution
Concentration is preferably 0.01~20 weight %.In iodide, KI is preferably added.Add KI in the case of, iodine with
The ratio of KI is preferably in 1: 5~1: 100 scope with weight ratio meter, is more preferably in 1: 6~1: 80 scope, enters one
Step is preferably in 1: 7~1: 70 scope.The temperature of staining solution is preferably in 10~60 DEG C of scope, it is more preferably in 20~
40 DEG C of scope.
And, although dyeing process S1-3 can be also carried out before stretching process S1-2, or carries out these processes simultaneously, so
And in order to which the dichroism pigment that can make to be adsorbed in polyvinyl alcohol resin layer is orientated well, preferably to stacked film 100 to
Implement to implement dyeing process S1-3 after a certain degree of stretch processing less.That is, except that will can implement to draw in stretching process S1-2
Processing is stretched to reaching that stretched film 200 is supplied to beyond dyeing process S1-3 obtained by the multiplying power of target, can also be in stretching process
To be carried out less than the multiplying power of target after stretch processing in S1-2, implement stretch processing in dyeing process S1-3 to total stretching ratio
Reach the multiplying power of target.As the embodiment of the latter, such a way etc. can be enumerated：1) with low in stretching process S1-2
Carried out in the multiplying power of target after stretch processing, so that total stretching ratio reaches target in dyeing process S1-3 dyeing processing
The mode of multiplying power carries out stretch processing；As described later, in the case of carrying out crosslinking Treatment after dyeing processing, 2) in stretching process
To be carried out less than the multiplying power of target after stretch processing in S1-2, in dyeing process S1-3 dyeing processing, stretch processing is carried out
The multiplying power degree of target is not reaching to total stretching ratio, then, so that side of the final total stretching ratio for the multiplying power of target
Formula carries out stretch processing in crosslinking Treatment.
Dyeing process S1-3 can include being connected on the crosslinking Treatment process implemented after dyeing processing.Crosslinking Treatment can lead to
Crossing will be carried out through hyperchromatic film immersion in the solution (crosslinker solution) containing crosslinking agent.As crosslinking agent, it can use
Known material, such as the boron compound, glyoxal, glutaraldehyde that can enumerate boric acid, borax etc.Crosslinking agent can be with
1 kind is only used alone, and two or more can also be used.
Crosslinker solution can be specifically by crosslinking agent be dissolved in solvent obtained by solution.As solvent, for example may be used
To use water, but it can also also contain organic solvent having a miscibility with water.The concentration of crosslinking agent in crosslinker solution is excellent
Elect the scope of 1~20 weight % scope, more preferably 6~15 weight % as.
Crosslinker solution can contain iodide.Using the addition of iodide, the polarizability in the face of polarizer layer 5 can be made
Can more it homogenize.As iodide, for example, it can enumerate KI, lithium iodide, sodium iodide, zinc iodide, silver iodide, iodate
Lead, cupric iodide, barium iodide, calcium iodide, stannic iodide, titanium iodide etc..The concentration of iodide in crosslinker solution is preferably 0.05~
15 weight %, more preferably 0.5~8 weight %.The temperature of crosslinker solution is preferably in 10~90 DEG C of scope.
By the way that crosslinking agent is coupled in staining solution crosslinking Treatment can also be simultaneously carried out with dyeing processing.Separately
Outside, stretch processing can also be carried out in crosslinking Treatment.Implement for example preceding institute of specific mode of stretch processing in crosslinking Treatment
State.It is impregnated in alternatively, it is also possible to using different crosslinker solutions of more than two kinds are constituted, carry out more than 2 times in crosslinker solution
Processing.
It is preferred that carrying out matting and drying process after dyeing process S1-3, before the first diaphragm of laminating.Matting
Generally include water matting.Water cleaning treatment can pass through dip dyeing in the pure water to ion exchange water, distilled water etc
Film after after processing or crosslinking Treatment and carry out.Water cleaning temperature is usually 3~50 DEG C, preferably 4~20 DEG C of scope.Clearly
Wash the combination that process can also be water matting and the matting by iodide solution.
As the drying process carried out after a washing process, it can be appointed using natural drying, forced air drying, heat drying etc.
The suitable method of meaning.For example in the case of heat drying, drying temperature is usually 20~95 DEG C.
The thickness for the polarizer layer 5 that polarizability stacked film 300 has can be for example less than 30 μm, can be further
Less than 20 μm, but from the viewpoint of the slimming of polarization plates, preferably less than 10 μm, more preferably less than 8 μm.Polarizer
The thickness of layer 5 is usually more than 2 μm.
In first diaphragm bonding process S10, reference picture 7, on the polarizer layer 5 of above-mentioned polarizability stacked film 300, folder
Across gluing oxidant layer 15 the first diaphragm 10 of laminating, the polarizability stacked film 400 with diaphragm is obtained.In polarizability stacked film
In the case that 300 have polarizer layer 5 on the two sides of base material film 30 ', the laminating protection respectively generally on the polarizer layer 5 on two sides
Film.In this case, these diaphragms can be diaphragm or different types of diaphragm of the same race.
The material for constituting the first diaphragm 10 is preferably (being preferably optically transparent) thermoplastic resin with translucency
Fat, as such resin, such as chain polyolefin-based resins (polypropylene-based resin), cyclic polyolefin hydrocarbon system tree can be enumerated
The polyolefin-based resins of fat (norbornene resin etc.) etc；The fibre of cellulosic triacetate, cellulose diacetate etc
The plain ester system resin of dimension；Polyester based resin；Polycarbonate-based resin；(methyl) acrylic resin；Polystyrene resin；Or it
Mixture, copolymer etc..
Due to the present invention method be in drying process S20 described later using make dry environment relative humidity be in
The method of fixed scope is come the method for realizing the suppression of curling, therefore with no matter how the species of diaphragm can suppress institute
The advantage of the curling of the polarization plates obtained.Wherein, cellulose esters system resin (such as cellulosic triacetate) or (first are being used
Base) acrylic resin (such as plexiglass) etc the high diaphragm of moisture permeability in the case of, due to
The size difference caused by the change of moisture rate is big, therefore the power corrected along just crimp direction is big, and advantage of the invention is big.
First diaphragm 10 can also be the diaphragm for having optical function concurrently of phase retardation film, brightness enhancement film etc.For example, can
With by the way that the film comprising above-mentioned thermoplastic resin is stretched and (is stretched uniaxially or biaxially) or liquid is formed on the film
Crystal layer etc., and the phase retardation film for imparting arbitrary phase difference value is made.
As chain polyolefin-based resins, except the homopolymer of the chain olefin of polyvinyl resin, acrylic resin etc
In addition, the copolymer for including chain olefin of more than two kinds can also be enumerated.
Cyclic polyolefin hydrocarbon system resin is the general name for the resin polymerizeing using cyclic olefin as polymerized unit.If enumerating ring-type to gather
The concrete example of olefin-based resin, then be the open loop (co) polymer of cyclic olefin, the addition polymer of cyclic olefin, cyclic olefin
Used with the copolymer (being random copolymer in the case of representational) of the chain olefin of ethene, propylene etc and by them
Graft polymers and their hydride that unsaturated carboxylic acid or derivatives thereof has been modified etc..Wherein, it is preferably used as ring
Shape alkene has used the norbornene resin of the norborneol alkene monomer such as ENB or condensed ring norborneol alkene monomer.
Cellulose esters system resin is the ester of cellulose and aliphatic acid.The concrete example of cellulose esters system resin includes cellulose iii
Acetic acid esters, cellulose diacetate, cellulose tripropionate, cellulose dipropionate.Alternatively, it is also possible to use their copolymerization
The polymer that a part for thing or hydroxyl has been modified by other substituents.Among them, particularly preferred cellulosic triacetate
(triacetyl cellulose：TAC).
Polyester based resin is the resin with ester bond, the condensation polymer generally comprising polyacid or derivatives thereof with polyalcohol
Resin.Dicarboxylic acids of binary or derivatives thereof, such as terephthalic acid (TPA), isophthalic can be used as polyacid or derivatives thereof
Dioctyl phthalate, dimethyl terephthalate (DMT), naphthalene diformic acid dimethyl ester etc..The glycol of binary can be used as polyalcohol, for example may be used
To enumerate ethylene glycol, propane diols, butanediol, neopentyl glycol, cyclohexanedimethanol etc..
The concrete example of polyester based resin includes polyethylene terephthalate, polybutylene terephthalate (PBT), poly- naphthalene
It is naphthalate, PBN, PTT, polytrimethylene naphthalate, poly-
Terephthalic acid (TPA) cyclohexanedimethanoester ester, poly- naphthalenedicarboxylic acid cyclohexanedimethanoester ester.
Polycarbonate-based resin includes the polymer for being bonded monomeric unit by carbonate group.Polycarbonate-based resin
Can be resin referred to as modified polycarbonate or copolymerization polycarbonate for having modified as polymer backbone etc..
(methyl) acrylic resin is the tree using the compound with (methyl) acryloyl group as main composition monomer
Fat.Poly- (methyl) acrylate of the concrete example of (methyl) acrylic resin for example including polymethyl methacrylate etc；
Methyl methacrylate-(methyl) acrylic copolymer；Methyl methacrylate-(methyl) acrylate copolymer；Methyl-prop
E pioic acid methyl ester-acrylate-(methyl) acrylic copolymer；(methyl) acrylate-styrene copolymer (MS resins etc.)；
Methyl methacrylate and copolymer (such as methyl methacrylate-methacrylic acid of the compound with alicyclic alkyl
Hexamethylene ester copolymer, methyl methacrylate-(methyl) acrylic acid norborneol ester copolymer etc.).Preferably use with poly- (methyl)
Poly- (methyl) the acrylic acid C of methyl acrylate etc1-6Arrcostab is more preferably used with methyl-prop as the polymer of principal component
E pioic acid methyl ester as principal component (50~100 weight %, preferably 70~100 weight %) methyl methacrylate system resin.
Moreover, the explanation for each thermoplastic resin illustrated above is readily applicable to constitute the thermoplasticity of base material film 30
Resin.
It can also form hard conating, antiglare layer on the surface with the opposite side of polarizer layer 5 of the first diaphragm 10, prevent
The surface-treated layer (coating) in reflecting layer, antistatic backing, stain-proofing layer etc.The method for forming surface-treated layer on diaphragm surface
It is not particularly limited, known method can be used.
From the viewpoint of the slimming of polarization plates, the thickness of preferably the first diaphragm 10 is small, if but too small, intensity
Reduce and poor in processability.Thus, the thickness of the first diaphragm 10 is preferably less than 5~90 μm, more preferably 5~60 μm, enters one
Step is preferably 5~50 μm.
As adhesive used in laminating, can use needs the adhesive of drying process (removing of solvent), for example
Water system adhesive or the photo-curable adhesive containing solvent (organic solvent etc.) can be used.Preferably water system adhesive.Make
For water system adhesive, the adhesive comprising the polyvinyl alcohol resin aqueous solution, water system two-component-type carbamate can be enumerated
It is emulsion adhesive etc..Especially (parent is being surface-treated as the first diaphragm 10 using saponification process etc. is utilized
Hydration process) cellulose esters resin film in the case of, preferably use the water system glue comprising the polyvinyl alcohol resin aqueous solution
Stick.
As polyvinyl alcohol resin, except the polyvinyl acetate to the homopolymer as vinyl acetate can be used
Carry out obtained by saponification process beyond alcotex, can also use to vinyl acetate with can be copolymerized therewith other
The copolymer of monomer carries out polyvinyl alcohol based copolymer obtained by saponification process or changing of being modified their hydroxylic moiety
Property vinol series polymer etc..Water system adhesive can contain polyaldehyde, soluble epoxide compound, melamine series chemical combination
The additives such as thing, zirconia compound, zinc compound.
Water system adhesive is coated on to the laminating of the diaphragm 10 of polarizer layer 5 and/or first of polarizability stacked film 300
Face, these films folder is fitted across gluing oxidant layer, is preferably used doubling roller etc. and is pressurizeed and be allowed to closely sealed, thus implements laminating work
Sequence.The coating method of water system adhesive (also identical for photo-curable adhesive) is not particularly limited, can use the tape casting,
Meyer rod coating method, gravure coating process, comma rubbing method, scraper for coating method, die coating method, dip coating, spray-on process etc. were in the past known
Method.
Fitted on polarizer layer 5 first diaphragm 10 when, for the binding face of the first diaphragm 10, in order to improve with partially
Shake the adhesivity of lamella 5, can carry out corona treatment, sided corona treatment, ultraviolet treatment with irradiation, flame (flame) processing,
The surface treatment such as saponification process (easy gluing processing), wherein, preferably carry out corona treatment, sided corona treatment or saponification process.
For example in the case where the first diaphragm 10 includes cyclic polyolefin hydrocarbon system resin, corona treatment, sided corona treatment are generally carried out.
In addition, in the case of comprising cellulose esters system resin, generally carrying out saponification process.As saponification process, dipping can be enumerated
Method in the aqueous alkali of sodium hydroxide, potassium hydroxide etc.
So-called photo-curable adhesive, refer to solidify by the active energy beam of irradiation ultraviolet radiation etc is gluing
Agent, for example, can enumerate the adhesive containing polymerizable compound and Photoepolymerizationinitiater initiater, containing the gluing of light reactive resin
Agent, adhesive containing resin glue and photoreactivity crosslinking agent etc..As polymerizable compound, photo-curable can be enumerated
The photopolymerization monomer of epoxy monomer, light-curable acrylic's ester system monomer, photo-curable carbamate system monomer etc,
Or the oligomer from photopolymerization monomer.As Photoepolymerizationinitiater initiater, it can enumerate containing the active energy because of ultraviolet etc
Measure the irradiation of ray and produce Neutral radical, radical anion, the material of spike as radical cation and draw
Send out agent.As the photo-curable adhesive containing polymerizable compound and Photoepolymerizationinitiater initiater, it is preferable to use solid containing light
The adhesive of the property changed epoxy monomer and light cationic polymerization initiator.
<Drying process S20>
In this process, the drying of the gluing oxidant layer 15 of the polarizability stacked film 400 with diaphragm is carried out, adhesive is removed
Solvent in layer 15 (if water system adhesive is then water, if photo-hardening adhesive is, for example, then organic solvent).Now, originally
Carried out in invention in the environment of relative humidity more than 25% for dry heat treatment.By implementing to do under such circumstances
Dry processing, can effectively suppress by the polarization plates peeled off the stripping process S30 of removing base material film 30 ' and manufactured (such as preceding institute
State, so-called polarization plates mentioned here refer to the guarantor for being laminated on its at least one side layer by layer across adhesive comprising polarizer layer and folder
The polarization plates of cuticula.) curling.In the case where implementing drying process in the environment of relative humidity is less than 25%, it is impossible to see
Crimp inhibition.
Herein, to polarization plates curling and the curling inhibition of the present invention is illustrated.So-called curling, be polarization plates it
Film (including the stacked film of class.) it is bent into the phenomenon of arciform (or being bent into tubular in the case of obvious).If just in polarization
The one side folder of lamella 5 is carried across the one side of gluing oxidant layer 15 the first diaphragm 10 of laminating for the polarization plates of diaphragm,
Then by the state referred to as just crimp crimped using the side of the first diaphragm 10 as inner side, it will be crimped using the side of polarizer layer 5 as inner side
State to be referred to as warp bent.
Situation of the curling as problem is that polarization plates folder is being fitted in into liquid crystal cells across adhesive phase in polarization plates
The situation of curling is produced during Deng display unit in the polarization plates.That is, at the time of the display units such as liquid crystal cells are fitted in, partially
Vibration plate generally turns into composite polarizing plate by other surrounding members of the various films of laminating, layer etc, it is therefore important that at this
Suppress curling in composite polarizing plate.As surrounding member, the protecting film of the antisitic defect fitted on diaphragm can be enumerated；Layer
Be laminated on diaphragm on (such as the situations of the two-sided polarization plates with diaphragm) or polarizer layer (for example one side carry diaphragm
Polarization plates situation) be used for polarization plates are fitted in the adhesive phases of display unit, other optical components；It is laminated in bonding
The barrier film of the outside of oxidant layer；(such as the situations of the two-sided polarization plates with diaphragm) or polarizer layer are laminated on diaphragm
The optical compensation films or other optics work(of the phase retardation film of upper (situations of polarization plates of such as one side with diaphragm) etc
Can property film；Surface-treated layer being laminated on diaphragm etc..
Composite polarizing plate can without curling but it is flat, or the adhesive phase side having using composite polarizing plate as
Outside (convex) and the degree that slightly crimps is just suitable.Thus, when composite polarizing plate is fitted in into display unit, it can suppress
Bubble is mixed between adhesive phase and display unit, so as to prevent from producing in a display device the not good situation in display,
Or bad not good situation is produced in the end of binding face.If on the contrary, making composite polarizing using adhesive phase side as inner side (recessed)
Coiled sheet is bent, then bubble is easily mixed into when fitting, and the possibility for producing above-mentioned not good situation is high.
Fit surrounding member when, although can intentionally suppress to a certain extent composite polarizing plate amount of curl or
Curl direction is corrected, if but being crimped not in the state of at least one side of polarizer layer fits the polarization plates of diaphragm
It is small, then still it is difficult to control to the curling of composite polarizing plate.Protected therefore, it is important that suppressing to fit at least one side of polarizer layer
The curling of the polarization plates of cuticula in itself.
That is, polarizer layer at least one side fit diaphragm polarization plates curling either just crimp or anti-
Curling, is all preferably reduced to the degree that can be corrected using the laminating of surrounding member, more preferably as flat as possible.Root
According to the present invention, it is possible to achieve the purpose.Particularly, in conventional rubbing method, if after diaphragm is fitted in into polarizer layer
Peel off and remove base material film, then the polarization plates of gained have the trend significantly crimped along anti-curl direction, but according to the present invention, especially
It is bent that it can effectively suppress the warp.
It is bent for easily producing warp in conventional rubbing method, it is believed that to be the restraining force because being caused by base material film
Work.It may be considered because polarizer layer is because of the rigidity of base material film in the polarizability stacked film using rubbing method formation
And as the state not being retracted, base material film is removed if being peeled off after laminating diaphragm, receipts can be produced in polarizer layer
Contracting.Moreover, different, across gluing oxidant layer diaphragm is fitted in the polarizer that is made up of monomer (independent) film in folder (inclined
Light film) monomer embrane method in the case of, laminating diaphragm before because of moisture evaporation, drying, tension force etc., polarizer has filled
Point ground shrinks, therefore is fitted in after diaphragm and will not also cause so big change in size in polarizer, is natively difficult to produce
The problem of raw curling.
Carry out removing base material for peeling off after dry heat treatment in the environment of relative humidity more than 25% for utilizing
The method of the invention of film 30 ' can effectively suppress the reason for warp is bent, and it is the reasons why being based on following that can estimate.That is, exist
Need a certain degree of time when gluing oxidant layer 15 is cured sufficiently or is hardened using the heat treatment of drying process, if thus
The moisture rate of the first diaphragm 10 is greatly lowered during before curing sufficiently or hardening, then the film will shrink, and is filling
The first diaphragm 10 is fitted with polarizer layer 5, fixed in the state of dividing ground contraction.In this case, in the polarization plates of gained
The power that the first diaphragm 10 is intended to shrink is not produced substantially.It is different, in the present invention, due to that can suppress to come from first
Processing is dried while the moisture transpiration of diaphragm 10, therefore the first diaphragm 10 is had in the polarization plates of gained and is intended to
The power that the power of contraction, i.e. intention are corrected along just crimp direction plays a role.It is bent that the power can suppress warp.
Preferably carried out for dry heat treatment under environment of the relative humidity below 50%, more preferably in relative humidity
Carried out under less than 40% environment.If relative humidity is higher than 50%, particularly had in the case where using water system adhesive
The situation of the underdry (not reaching) of gluing oxidant layer 15.Although relative humidity can also be made to be more than 40%, be further
More than 50% and implement drying process, but in this case, in order to prevent underdry, preferably in preferred scope described later
Drying temperature is inside set higher.
Drying temperature is preferably 30~80 DEG C.If drying temperature is less than 30 DEG C, the drying of gluing oxidant layer 15 is insufficient, the
One diaphragm 10 is easily peeled off from polarizer layer 5.If in addition, drying temperature is higher than 80 DEG C under relative humidity more than 25%,
Then it is present in amount of moisture in air excessive, therefore by the polarizability stacked film 400 with diaphragm for drying process
Condensation or local near the gateway of drying device (drying oven) occurs for the moment film being positioned in the dry environment
Low temperature part condenses, it is possible to which the drying to gluing oxidant layer 15 has undesirable effect.
The drying of gluing oxidant layer 15 can adjust warm and humid by the way that the polarizability stacked film 400 with diaphragm is imported
Carried out in the drying oven of degree.Can also be using the humidistat set up in addition to adjusting relative humidity in drying oven.
After drying process, can also be arranged on room temperature or than slightly higher temperature, such as 20~45 DEG C or so of temperature
The maintenance process conserved.Curing temperature is generally set at less than drying temperature.
In the case where using photo-curable adhesive as adhesive, after drying process is implemented, carry out by irradiation
Active energy beam and make photo-curable adhesive solidify curing process.The light source of active energy beam is not particularly limited,
But it is preferred that there is the active energy beam of luminous distribution in below wavelength 400nm, specifically, preferably use low pressure mercury lamp,
Medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, chemical lamp, black light lamp, microwave-excited mercury lamp, metal halide lamp etc..
<Stripping process S30>
Reference picture 8, this process is after drying process S20, peels off the process for removing base material film 30 '.In this process
The polarization plates 1 of diaphragm are carried to one side.Polarizability stacked film 300 have on the two sides of base material film 30 ' polarizer layer 5,
, can be by 1 polarizability stacked film using stripping process S30 in the case that the two polarizer layers 5 are fitted with diaphragm
300 obtain the polarization plates 1 that 2 one sides carry diaphragm.
The method for peeling off removing base material film 30 ' is not particularly limited, it is possible to use with the common polarization with adhesive
The stripping process identical method of the dividing plate (stripping film) carried out in plate is peeled off.Base material film 30 ' can be after drying process S20
Directly peel off immediately, can also first be wound into a roll tubular after drying process S20, rolled out in process behind while
Peel off.
<Second diaphragm bonding process S40>
Reference picture 3 and Fig. 9, if implementing to press from both sides across glue in the face of the side of polarizer layer 5 of polarization plates 1 of the one side with diaphragm
This process of the second diaphragm 20 of laminating of adhesive layer 25, then can obtain the two-sided polarization plates 2 with diaphragm.Protected for second
Cuticula 20 and its gluing oxidant layer 25 of fitting, can be quoted on the description described in the first diaphragm 10 and gluing oxidant layer.First
The diaphragm 20 of diaphragm 10 and second can be diaphragm or different types of diaphragm of the same race each other.Adhesive
Layer 15 and gluing oxidant layer 25 can be formed by adhesive of the same race each other, can also be formed by different types of adhesive.
If the drying with gluing oxidant layer 15 is identical, also in relative humidity more than 25% in the drying process of gluing oxidant layer 25
In the environment of implement for dry heat treatment, then can further improve the curling of the two-sided polarization plates 2 with diaphragm.
As it was previously stated, polarization plates 1, two-sided polarization plates 2 with diaphragm of the one side of gained with diaphragm can be pasted
Conjunction is illustrated above such surrounding member and composite polarizing plate is made, or is used as such composite polarizing plate.
Belonging to the adhesive phase of one of surrounding member can be laminated in arbitrarily in the two-sided polarization plates 2 with diaphragm
The outside of one diaphragm, in polarization plates 1 of the one side with diaphragm, can for example be laminated in polarizer layer and diaphragm
The face of opposite side.The adhesive for forming adhesive phase is generally comprised with (methyl) acrylic resin, phenylethylene resin series, silicon
Based on ketone system resin etc. polymer and isocyanate compound, epoxide, aziridine cpd are added thereto
Etc crosslinking agent adhesive composition.It can also be also made containing particulate and show light scattering adhesive phase.It is viscous
The thickness of mixture layer is usually 1~40 μm, preferably 3~25 μm.
In addition, as the optical functional film of other one for belonging to surrounding member, can enumerate and transmit certain polarization
Light, reflective display go out the reflection type polarizing film of the polarised light of property in contrast；Have carrying for concaveconvex shape anti-on surface
The film of dizzy function；Film with anti-surface reflection function；There is the reflectance coating of reflection function on surface；Have reflection function concurrently and saturating
Penetrate the Transflective film of function；Compensation film for angular field of view etc..
Embodiment
Hereinafter, will provide embodiment and comparative example and more specific description carried out to the present invention, however the present invention not by
These examples are limited.
<Embodiment 1>
(1) prime coat formation process
By pva powder (" Z-200 ", average degree of polymerization 1100, the saponification degree of Japanese synthetic chemical industry (strain) system
In the hot water for 99.5mol%) being dissolved in 95 DEG C, the weight % of concentration 3 polyvinyl alcohol water solution is prepared.To the aqueous solution of gained
In using relative to the parts by weight of pva powder 6 as 5 parts by weight ratio mixed cross-linker (field ridge chemical industry (strain) system
" Sumirez Resin 650 "), obtain prime coat formation coating fluid.
Then, thick 110 μm non-stretched polypropylene (PP) film (fusing point is prepared as base material film：163 DEG C), to its one side
Implement after sided corona treatment, above-mentioned prime coat formation coating fluid is coated with using micro gravure coating machine in its sided corona treatment face,
80 DEG C of dryings 10 minutes, are consequently formed thick 0.2 μm prime coat.
(2) making (resin bed formation process) of stacked film
By pva powder ((strain) Kuraray " PVA124 ", average degree of polymerization 2400, saponification degree 98.0~
In the hot water for 99.0mol%) being dissolved in 95 DEG C, the weight % of concentration 8 polyvinyl alcohol water solution is prepared, as polyethylene
Alcohol resin formation coating fluid.
The primer coat surface of the base material film with prime coat made in above-mentioned (1) is coated with above-mentioned using die lip coating machine
After polyvinyl alcohol resin layer formation coating fluid, dried 20 minutes at 80 DEG C, polyethenol series are thus formed on prime coat
Resin bed, obtains including the stacked film of base material film/prime coat/polyvinyl alcohol resin layer.
(3) making (stretching process) of stretched film
To the stacked film made in above-mentioned (2), the free end single shaft for implementing 5.8 times at 160 DEG C using tenter frame apparatus is drawn
Stretch, obtain stretched film.The thickness of polyvinyl alcohol resin layer after stretching is 3.0 μm.
(4) making (dyeing process) of polarizability stacked film
The stretched film made in above-mentioned (3) is immersed in 26 DEG C of the dyeing aqueous solution (every 100 weight containing iodine and KI
Measure and contain the parts by weight of iodine 0.35, the parts by weight of KI 10 in part water.) in and carry out after dyeing processing, containing boric acid and iodate
78 DEG C of the crosslinking aqueous solution of potassium (contains the parts by weight of boric acid 9.5, the parts by weight of KI 5 in every 100 parts by weight water.) middle dipping
300 seconds and carried out crosslinking Treatment.Thereafter, cleaned with 8 DEG C of pure water 10 seconds, finally dry 200 seconds, thus obtain at 40~50 DEG C
To the polarizability stacked film for including base material film/prime coat/polarizer layer.
(5) making (diaphragm bonding process, drying process and stripping process) of polarization plates
Pva powder ((strain) Kuraray " KL-318 ", average degree of polymerization 1800) is dissolved in 95 DEG C of heat
In water, the weight % of concentration 3 polyvinyl alcohol water solution is prepared.Into the aqueous solution of gained with relative to pva powder 2
Parts by weight are the ratio mixed cross-linker (field ridge chemical industry (strain) system " Sumirez Resin 650 ") of 1 parts by weight, are made
The adhesive aqueous solution.
Then, the outside (binding face) of the polarizer layer of the polarizability stacked film made in above-mentioned (4) is coated with above-mentioned glue
After the stick aqueous solution, laminating diaphragm (includes transparent protective film (the Konica Minolta Opto of triacetyl cellulose (TAC)
" KC4UY " of (strain) system), it is thick 40 μm), by between a pair of doubling roller by and crimped.Then, import and be adjusted to 60
In DEG C 35%RH drying oven, be heat-treated within 10 minutes, thus dry gluing oxidant layer, obtain comprising base material film/prime coat/
The polarizability stacked film with diaphragm of polarizer layer/gluing oxidant layer/diaphragm.
Finally, peeled off from the polarizability stacked film with diaphragm and remove base material film.Base material film is thereafter easily released, and is obtained
One side carries the polarization plates of diaphragm.
<Embodiment 2, comparative example 1~2>
In addition to making the drying condition of gluing oxidant layer as shown in table 1, one side is produced same as Example 1ly with guarantor
The polarization plates of cuticula.
(measure of the amount of curl of polarization plates and its evaluation)
From polarization plates of the one side with diaphragm of gained, absorption direction of principal axis (MD) 80mm × transmission direction of principal axis is cut out
(TD) 80mm test film, is placed 24 hours in the environment of 25 DEG C of 55%RH.It is interior that the test film, which has using polarizer layer side,
Side and the warp that crimps is bent, if making concave surface to be upper in reference plane (platform of level), 2 facing end edges are lifted, experiment
Piece is changed into tubular, and (2 end edges lifted are the degree that will not be contacted.).The barrel shape formed in this condition to test film
The diameter of two ends is measured, and obtains amount of curl as being averaged for they, curling is have rated according to following metewands
The degree of suppression.It the results are shown in Table 1.The smaller then warp Qu Yueqiang of amount of curl, the more big then warp of amount of curl is bent weaker.
A：Amount of curl is more than 17mm, and the curling of polarization plates is adequately suppressed.
B：Amount of curl is less than 17mm, and the curling of polarization plates is obvious.
The reasons why above-mentioned metewand is based on following.When above-mentioned amount of curl is more than 17mm, if in one side with protection
Laminating prevents the protecting film of damage from (carrying the polyethylene terephthalate of adhesive phase outside the diaphragm of the polarization plates of film
Ester film), then it can obtain almost flat composite polarizing plate.Used even if being fitted again outside the polarizer layer of the composite polarizing plate
In the adhesive phase for fitting in liquid crystal cells, composite polarizing plate also keeps almost flat state.
It is different, when above-mentioned amount of curl is less than 17mm, the laminating protecting film outside the diaphragm, gained it is compound
Polarization plates can also be crimped along anti-curl direction.Even if being fitted again outside the polarizer layer of the composite polarizing plate for fitting in liquid
The adhesive phase of brilliant unit, also maintains the bent state of warp.In addition, being placed in the environment of 23 DEG C of 55%RH after a couple of days again
Observed, as a result, producing warp song further becomes big not good situation.
[table 1]
The explanation of symbol
Polarization plates of 1 one side with diaphragm, the 2 two-sided polarization plates with diaphragm, 5 polarizer layers, 6 polyethenol series
Resin bed, 6 ' stretched polyvinyl alcohol resin layers, 10 first diaphragms, 15,25 gluing oxidant layer, 20 the 2nd diaphragms, 30
Base material film, 30 ' stretched base material films, 100 stacked films, 200 stretched films, 300 polarizability stacked films, 400 carry diaphragm
Polarizability stacked film.
Claims (5)
1. a kind of manufacture method of polarization plates, it is included successively：
Bonding process, on the polarizer layer of polarizability stacked film for possessing polarizer layer at least one side of base material film, folder
Across gluing oxidant layer laminating diaphragm；
Drying process, is heat-treated in the environment of relative humidity more than 25% and dries the gluing oxidant layer；With
Peel off the process for removing the base material film.
2. manufacture method according to claim 1, wherein,
The adhesive for forming the gluing oxidant layer is water system adhesive.
3. manufacture method according to claim 1 or 2, wherein,
The polarizability stacked film is manufactured using following method, and it includes：
After being coated with the coating fluid containing polyvinyl alcohol resin at least one side of the base material film, drying is allowed to, thus shape
Into polyvinyl alcohol resin layer and the process that obtains stacked film；
The process for stretching the stacked film and obtaining stretched film；With
The polyvinyl alcohol resin layer dichroism pigment of the stretched film is dyed and the polarizer layer is formed, is derived from
The process of polarizability stacked film.
4. according to manufacture method according to any one of claims 1 to 3, wherein,
The diaphragm includes cellulose esters system resin or (methyl) acrylic resin.
5. according to manufacture method according to any one of claims 1 to 4, wherein,
The thickness of the polarizer layer is less than 10 μm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-044132 | 2014-03-06 | ||
| JP2014044132A JP6321999B2 (en) | 2014-03-06 | 2014-03-06 | Manufacturing method of polarizing plate |
| PCT/JP2015/054389 WO2015133270A1 (en) | 2014-03-06 | 2015-02-18 | Polarizing plate manufacturing method |
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| Publication Number | Publication Date |
|---|---|
| CN107223213A true CN107223213A (en) | 2017-09-29 |
| CN107223213B CN107223213B (en) | 2020-09-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580011574.1A Active CN107223213B (en) | 2014-03-06 | 2015-02-18 | Method for manufacturing polarizing plate |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6321999B2 (en) |
| KR (1) | KR102328404B1 (en) |
| CN (1) | CN107223213B (en) |
| TW (1) | TW201536558A (en) |
| WO (1) | WO2015133270A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6257680B2 (en) * | 2016-03-31 | 2018-01-10 | 住友化学株式会社 | Manufacturing method of polarizing film, laminated film |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2015133270A1 (en) | 2015-09-11 |
| KR20160130244A (en) | 2016-11-10 |
| TW201536558A (en) | 2015-10-01 |
| JP6321999B2 (en) | 2018-05-09 |
| CN107223213B (en) | 2020-09-22 |
| JP2015169778A (en) | 2015-09-28 |
| KR102328404B1 (en) | 2021-11-18 |
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