CN108254824A - Polarization plates and image display device - Google Patents
Polarization plates and image display device Download PDFInfo
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- CN108254824A CN108254824A CN201810209407.3A CN201810209407A CN108254824A CN 108254824 A CN108254824 A CN 108254824A CN 201810209407 A CN201810209407 A CN 201810209407A CN 108254824 A CN108254824 A CN 108254824A
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- Prior art keywords
- polarizer
- polarization plates
- functional layer
- axis direction
- film
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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
-
- 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
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polarising Elements (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Liquid Crystal (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention relates to polarization plates and image display devices.The present invention provides a kind of resistance to anti-thread breakage polarization plates improved in the environment of being contacted with water.The present invention provides a kind of polarization plates, it is the polarization plates of the functional layer comprising polarizer and at least one side for being laminated in polarizer, value obtained by the elasticity modulus for the polarizer transmission axis direction that functional layer is subtracted from the elasticity modulus of the polarizer transmission axis direction of polarizer is more than -1100MPa.
Description
It is on January 16th, 2017 applying date that the application, which is, application No. is 201710028965.5, entitled " polarizations
The divisional application of the application for a patent for invention of plate and image display device ".
Technical field
The present invention relates to a kind of polarization plates that can be used for various optical applications.It is somebody's turn to do moreover, it relates to which one kind has
The image display device of polarization plates.
Background technology
The feed element of polarised light as image display device, in addition, the detecting element as polarised light, polarization plates obtain
It is used to extensive.In such polarization plates, for example, can suitably using polyvinyl alcohol resin film stretched, dyed,
Polarizer obtained by crosslinking etc..If cracked in polarizer, bad order is may result in, is claimed in addition, also resulting in
Make the not good situation optically of " light leakage ".In the past, the crackle in polarizer generated in order to prevent, proposed various schemes (ginseng
According to Patent Documents 1 to 5).
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2013-72951 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2012-145645 bulletins
Patent document 3：Japanese Unexamined Patent Publication 2011-221278 bulletins
Patent document 4：Japanese Unexamined Patent Publication 2004-29367 bulletins
Patent document 5：Japanese Unexamined Patent Publication 2004-20830 bulletins
Invention content
Problem to be solved by the invention
Crackle in polarizer generate may by it is various will be caused by.It is representative the reason is that, may because product use
The temperature change (thermal shock) drastically of middle exposed surrounding atmosphere and crack, in this case, thermal shock can be utilized
Accelerated test, such as the experiment (patent document 2) using the thermal cycle between -40 DEG C and 85 DEG C that 20 cycles are repeated
Or the experiment (patent document 4) of the thermal cycle between -35 DEG C and 85 DEG C of 500 cycles is repeated and is generated to evaluate crackle
Degree.In addition, in manufacture course of products, it will be provided with base material film and be laminated thereon and stretch the polarizer layer that forms
Polarizability stacked film to protective film transfer when (patent document 3) or to comprising polarizer polarization plates carry out cutting processing when (specially
Sharp document 4) it may be cracked due to power (physical/mechanicalness impact) applied, in this case, can after these operations
To confirm the degree of crackle generation.
In view of this, the inventors of the present invention are conceived to when crackle may be the moisture condensation because that may occur in product use and generate.
Since moisture condensation can lead to contact with water, it can be considered that be due to as described above by simple thermal shock or physics
Property/the different mechanism of crackle caused by mechanicalness impact and crack.
The object of the present invention is to provide a kind of resistance to anti-thread breakage polarization plates improved in the environment of being contacted with water.
The method for solving problem
The result of study of the inventors of the present invention distinguishes, make to be fitted on a glass comprising polarizer and be laminated in its at least one
The crackle that the sample receiving of the polarization plates of the functional layer in face simulates moisture condensation promotes experiment (including the dipping into water), result
It is that substantially can be cracked to extension on axis direction is absorbed from the end face on the side of the transmission axis direction along polarizer.In addition,
The inventors of the present invention obtain following personal opinion, that is, are laminated in the polarizer transmission of the functional layer of at least one side of polarizer
The elasticity modulus of axis direction is smaller, is more difficult to crack in the environment of contacting with water, the bullet of the transmission axis direction of polarizer
Property modulus and above-mentioned functional layer polarizer transmission axis direction elasticity modulus difference it is bigger, be more difficult in the environment of being contacted with water
To crack, and further further investigation is carried out, as a result completed the present invention.
The present invention includes following [1]~[7].
[1] a kind of polarization plates are the polarization plates of the functional layer comprising polarizer and at least one side for being laminated in polarizer,
The elasticity modulus of the polarizer transmission axis direction of functional layer is subtracted from the elasticity modulus of the polarizer transmission axis direction of polarizer
Obtained by value for more than -1100MPa.
[2] polarization plates according to described in [1], wherein, functional layer includes protective film.
[3] polarization plates according to described in [1] or [2], wherein, functional layer includes phase difference film.
[4] polarization plates recorded according to any one of [1]~[3], wherein, it is laminated with functional layer on one side in polarizer,
Adhesive phase is laminated in the another side of polarizer.
[5] polarization plates recorded according to any one of [1]~[4], wherein, the outmost surface layer in a surface side of polarization plates
It is laminated with adhesive phase or the adhesive phase with peeling layer.
[6] polarization plates according to described in [4] or [5], wherein, the springform of the polarizer transmission axis direction of adhesive phase
It measures as below 1000kPa.
[7] a kind of image display device, it includes any in liquid crystal cells or organic electroluminescent device and [1]~[6]
The polarization plates that item is recorded.
Invention effect
According to the present invention it is possible to provide the resistance to anti-thread breakage polarization plates improved in the environment of being contacted with water.In addition, root
According to the present invention, the image display device with the polarization plates can be provided.The present invention polarization plates and image display device for
Moisture condensation can show high resistance to anti-thread breakage.
Description of the drawings
Fig. 1 shows the constructed profiles of the polarization plates of an embodiment of the invention.
Fig. 2 represents the constructed profile of the polarization plates of another embodiment of the invention.
Fig. 3 represents the constructed profile of the polarization plates of another embodiment of the invention.
Fig. 4 represents the constructed profile of the image display device of an embodiment of the invention.
Specific embodiment
Hereinafter, the polarization plates and image display device to the present invention are described in detail, however the present invention is not limited to these
Embodiment.
The polarization plates of the present invention include polarizer and are laminated in the functional layer of at least one side of polarizer.For example, in this hair
In a bright embodiment, as shown in Figure 1, polarization plates 10 can include polarizer 1, the first work(for being laminated in its two sides respectively
3 and second functional layer 5 of ergosphere.The polarization plates of the present invention can be also in the surface of one surface side, polarization plates such as shown in Fig. 2
11, like that in the face with 1 opposite side of polarizer of at least one functional layer (being the second functional layer 5 in the mode of diagram), are laminated
There is adhesive phase 7, which there can be peeling layer (not shown) in outmost surface, there can not also be peeling layer.This
In the other embodiment of invention, as shown in figure 3, polarization plates 12 can include polarizer 1, the functional layer for being laminated in its one side
3 and be laminated in polarizer 1 another side adhesive phase 7.But the composition of polarization plates of the invention (lamination order etc.) is simultaneously
These embodiments are not limited to, as long as the functional layer comprising polarizer and at least one side for being laminated in polarizer, can have
It is arbitrary to form.
So-called " polarizer " of the present invention, is the component for having the function of for the light such as natural light to be transformed to rectilinearly polarized light,
With the axis of homology and absorption axiss.When the transmission axis direction of polarizer can be understood as making the natural light penetrate polarizer through light
Direction of vibration.On the other hand, the absorption axiss of polarizer are orthogonal with the axis of homology of polarizer.Moreover, in general, polarizer can be with
For stretched film, the absorption axis direction of polarizer can be with its draw direction (MD) unanimously, and the transmission axis direction of polarizer can be with
Width direction (TD) is consistent.
" functional layer " so-called in the present invention refers to polarizer be played or assigned certain function, for example physical, mechanical
The layer set for the purpose of property and/or optics sexual function.Functional layer is laminated in polarizer with arbitrary appropriate method, such as can be with
Utilize adhesive and polarizer gluing.
Film etc. is improved in the functional layer, such as comprising protective film, phase difference film, brightness, can be any one of them
The individual layer or arbitrary 2 layers or more of laminated body of kind.As long as protective film can play the film of the function of protection polarizer,
It without optical function or can also be able to be the film for having both optical function, such as can also be used as phase difference film or bright
Degree improves the film that film etc. plays a role.Alternatively, it is also possible in the opposite side face shape with the side of polarizer gluing of protective film
Into there is the layers such as hard conating, anti-reflection layer, antiglare layer.And the meaning of the non-limiting present invention, functional layer can be individual protective films,
Can also be protective film be bonded product etc. with phase difference film.
The polarization plates of the present invention meet following condition, that is, from the elasticity modulus of the polarizer transmission axis direction of polarizer
In subtract functional layer polarizer transmission axis direction elasticity modulus obtained by value (Δ E, hereinafter also referred to as " elasticity modulus
Difference ") it is more than -1100MPa (meeting following formula (1)).
Δ E=EP- EF>=-1100 (1)
EP：The elasticity modulus (MPa) of the polarizer transmission axis direction of polarizer
EF：The elasticity modulus (MPa) of the polarizer transmission axis direction of functional layer
The term " polarizer transmission axis direction " of the present invention, refers to parallel or substantially parallel with the transmission axis direction of polarizer
The direction of (angle is within ± 7 degree).
Because above-mentioned elastic modulus difference Δ E is more than -1100MPa, and make in the environment of being contacted with water resistance to anti-thread breakage carries
Height can provide the polarization plates of excellent in te pins of durability.Even if the polarization plates of the present invention will not be led in the environment of it can generate moisture condensation
Light leakage (light leakage when being observed in Nicol crossed with polarizing microscope), rupture etc. are caused, can be shown good inclined
It shakes characteristic.Elastic modulus difference Δ E is even more preferably about more than -1000MPa, and the upper limit is not particularly limited, for example, about 3000MPa
Hereinafter, in particular about 2500MPa hereinafter, preferably 2000MPa is hereinafter, more preferably below 1500MPa.
The elastic modulus E of the polarizer transmission axis direction of polarizerPCan according to the raw material of polarizer and preparation method etc. without
Together, such as can be about 3500~6000MPa, more preferably preferably below 5500MPa, below 5000MPa.For polarizer
Polarizer transmission axis direction elastic modulus EP, in order to increase elastic modulus difference Δ E=EP- EF, preferably it is allowed to bigger.It is another
Aspect, when inhibiting that processing is formed to polarization plates the crackle that can generate, the polarizer transmission of polarizer
The elastic modulus E of axis directionPIt is preferred that smaller.The elastic modulus E of the polarizer transmission axis direction of polarizerPDuring for above range, easily
In terms of these are had both.And the meaning of the non-limiting present invention, such as polyvinyl alcohol resin film is made to receive to stretch, is being dyed, boron
In the case of polarizer obtained from crosslinking in acid solution etc., contained by increasing stretching ratio, improving the boron in polarizer
Crosslinking agent other than the boric acid such as rate, and/or importing glyoxal, glutaraldehyde can further increase the polarizer transmission of polarizer
The elasticity modulus of axis direction.
The elasticity modulus of the polarizer transmission axis direction of polarizer is as given temperature (representative situation is 23 DEG C)
Under polarizer polarizer transmission axis direction tensile modulus of elasticity (MPa) measure.More specifically, it is cut out from polarizer
Test film, under given temperature environment, with testing machine clamp test film polarizer transmission axis direction both ends and along polarization
Piece transmission axis direction drawing, calculates according to the slope of the straight line at the initial stage of thus obtained load-deformation curve.
The elastic modulus E of the polarizer transmission axis direction of functional layerFCan be had according to the composition of functional layer, optical characteristics
Without or degree etc. and it is different, such as can be from the range of about 1000~10000MPa, according to the polarizer axis of homology of polarizer
The elastic modulus E in directionPIt is properly selected in a manner of meeting above-mentioned formula (1).Axis direction is transmitted for the polarizer of functional layer
Elastic modulus EF, in order to increase elastic modulus difference Δ E=EP- EF, preferably it is allowed to smaller.And the meaning of the non-limiting present invention,
Reduce the degree of orientation in the case of by the way that there is orientation in functional layer, and/or do not have ring structure etc. in main chain just
Property structure the material of composition form functional layer, the polarizer of functional layer can be made to transmit the elasticity modulus smaller of axis direction.
Moreover, for " the polarizer transmission axis direction " of functional layer, in the case where functional layer is laminated in polarizer, refers to and polarize
The direction of the transmission axis direction parallel or substantially parallel (angle is within ± 7 degree) of piece.
The elasticity modulus of the polarizer transmission axis direction of functional layer is as given temperature (representative situation is 23 DEG C)
Under functional layer polarizer transmission axis direction tensile modulus of elasticity (MPa) measure.More specifically, it is cut out from functional layer
Test film, under given temperature environment, with testing machine clamp test film polarizer transmission axis direction both ends and along polarization
Piece transmission axis direction drawing, can calculate according to the slope of the straight line at the initial stage of thus obtained load-deformation curve.
In the feelings for being laminated with the first functional layer 3 and the second functional layer 5 respectively on the two sides of polarizer 1 as shown in Figures 1 and 2
Under condition, polarization plates of the invention meet following condition, that is, subtract from the elasticity modulus of the polarizer transmission axis direction of polarizer
Go the polarizer of the first functional layer transmit the elasticity modulus of axis direction obtained by value be more than -1100MPa, and from polarizer
Polarizer transmission axis direction elasticity modulus in subtract the second functional layer polarizer transmission axis direction elasticity modulus and obtain
Value be more than -1100MPa.In this case, the E in above-mentioned formula (1)FAxis direction is transmitted in the polarizer of the first functional layer
The elasticity modulus of the polarizer transmission axis direction of elasticity modulus and the second functional layer is the value when identical, can be by appointing when different
The value of one big side of meaning represents.
As shown in Figures 2 and 3, (on its surface, there are peeling layers for the adhesive phase 7 that can be included in polarization plates of the invention
In the case of, it is after peeling layer is divested) it may be used to polarization plates 11,12 and be bonded with other components.
The elasticity modulus of the polarizer transmission axis direction of the adhesive phase can be 5000kPa hereinafter, preferably 1000kPa
Hereinafter, it can effectively improve when being bonded with liquid crystal display device across adhesive phase and connect with water by polarization plates folder as a result,
It is resistance to anti-thread breakage under tactile environment.Adhesive phase polarizer transmission axis direction elasticity modulus be even more preferably about 500kPa with
Under, further preferably below 150kPa.The lower limit of the elasticity modulus of the polarizer transmission axis direction of adhesive phase is not special
It limits, such as can be about more than 50kPa.And the non-limiting present invention, for example, by coordinating amino first in well known adhesive
The crosslinking agents such as the oligomer such as acid esters acrylic ester oligomer and/or addition isocyanates system crosslinking agent, it is possible thereby to will bonding
The polarizer of oxidant layer is adjusted to above range through the elasticity modulus of axis direction.The polarizer of adhesive phase penetrates the bullet of axis direction
Property modulus be above range when, can easily take into account the inhibition of change in size of polarization plates and the relaxation of stress.Moreover, for viscous
" the polarizer transmission axis direction " of mixture layer, in the case where adhesive phase is laminated in polarizer, refers to saturating with polarizer
Penetrate the direction of axis direction parallel or substantially parallel (angle is within ± 7 degree).
The elasticity modulus of the polarizer transmission axis direction of adhesive phase is that (representative situation is 23 as given temperature
DEG C) under adhesive phase polarizer transmission axis direction tensile modulus of elasticity (kPa) measure.More specifically, from adhesive
Layer in cut out test film, under given temperature environment, with testing machine clamp test film polarizer transmission axis direction both ends and
Along polarizer transmission axis direction drawing, can be calculated according to the slope of the straight line at the initial stage of thus obtained load-deformation curve
Go out.
Such as polarization plates 11 can be pressed from both sides and are bonded across adhesive phase 7 with other components 15 as shown in Figure 4, form image
Display device 20.Other components are not particularly limited, such as can be liquid crystal cells, organic electroluminescent device etc., represent
Property in the case of can form their glass plate on folder across adhesive phase be bonded polarization plates.Image display device is in liquid crystal
Liquid crystal display device is referred to as in the case of unit, is shown in the case of organic electroluminescent device referred to as organic electroluminescent
Showing device.But image display device of the invention is not limited to the embodiment, as long as including liquid crystal cells or Organic Electricity
The polarization plates of electroluminescent element and the present invention can have and arbitrarily be suitably composed.
Hereinafter, for the polarization plates and image display device of the present invention, will be carried out by their manufacturing method more detailed
Explanation.
In order to manufacture the polarization plates of the present invention, prepare polarizer, functional layer, be also prepared for bonding in addition in a situation of use where
Oxidant layer.
[polarizer]
Polarizer can be polyvinyl alcohol resin film is made to receive to stretch, dyeing, crosslinking in boric acid solution etc. and obtain
Polarizer.
As polyvinyl alcohol resin, can use resin obtained by polyvinyl acetate system resin saponification.As poly-
Vinyl acetate system resin other than it may be exemplified out the polyvinyl acetate as the homopolymer of vinyl acetate, may be used also
To exemplify vinyl acetate and the copolymer of other monomers that can be copolymerized therewith.As can be with vinyl acetate copolymerization
Other monomers, for example, unsaturated carboxylic acid, alkene, vinyl ethers, unsaturated sulfonic acid, the acrylamide with ammonium
Deng.
The saponification degree of polyvinyl alcohol resin can be the range of 80 moles of more than %, preferably 90 moles of more than %, more
The range of preferably 95 moles more than %.Polyvinyl alcohol resin can also be the modified polyvinylalcohol that a part has been modified,
For example, by alkene such as polyvinyl alcohol resin ethylene and propylene；Acrylic acid, methacrylic acid and crotonic acid etc. are no
Saturated carboxylic acid；The resin that Arrcostab and acrylamide of unsaturated carboxylic acid etc. have been modified.The average polymerization of polyvinyl alcohol resin
Degree preferably 100~10000, more preferably 1500~8000, further preferably 2000~5000.
Polarizer for example can be by carrying out uniaxial stretching to the raw material film being made of polyvinyl alcohol resin and using water
It is allowed to be swollen (swelling process), (dyeing process) is dyed with dichroism pigment, be allowed to be crosslinked (crosslinking work with boric acid aqueous solution
Sequence), (cleaning process) is cleaned with water, dry (drying process) is finally allowed to and manufactures.
The uniaxial stretching of polyvinyl alcohol resin film can be the dry type stretching stretched in the air, be drawn in bath
Any one for the wet tensile stretched can also carry out the both sides of these stretchings.In order to increase the polarizer axis of homology of polarizer
The elastic modulus E in directionP, preferably implemented with being conducive to the wet tensile of the raising of stretching ratio.For wet tensile, such as
Can be between above-mentioned dyeing process and/or cross-linking process step and/or front and rear, by polyvinyl alcohol resin film immersion in processing
Implement to stretch in the state of in bath.When implementing uniaxial stretch, polyvinyl alcohol resin film can be made to pass through peripheral speed difference
Roller between and stretched, can also be stretched using by polyvinyl alcohol resin film with the method that hot-rolling clamps.Poly- second
The final stretching ratio of enol resin film is usually 4~8 times or so.
It is swollen in process, makes polyvinyl alcohol resin membrane swelling with water.Swelling treatment can be by making polyethenol series tree
Adipose membrane is impregnated in water to implement.The temperature of water is, for example, 10~70 DEG C, and dip time is, for example, 10~600 seconds or so.
In dyeing process, polyvinyl alcohol resin film with dichroism pigment is dyed, film is made to adsorb dichroism pigment.Dyeing
Processing for example makes polyvinyl alcohol resin film immersion in the aqueous solution containing dichroism pigment.As dichroism pigment,
Specifically, iodine or dichroic dye can be used.
In the case where using iodine as dichroism pigment, generally use is by polyvinyl alcohol resin film immersion in containing iodine
And the method dyed in the aqueous solution of potassium iodide.For the content of the iodine in aqueous solution, in every 100 parts by weight water, lead to
Can be often 0.003~1 parts by weight or so.For the content of the potassium iodide in aqueous solution, in every 100 parts by weight water, usually
It is 0.1~20 parts by weight or so.The temperature of the aqueous solution is usually 10~45 DEG C or so, and dip time is usually 30~600 seconds
Left and right.
On the other hand, in the case where using dichroic dye as dichroism pigment, generally use is by polyethenol series
Resin film is impregnated in the method dyed in the aqueous solution containing water-soluble dichroic dye.For the dichroism in aqueous solution
The content of dyestuff, in every 100 parts by weight water, typically 1 × 10- 3~1 parts by weight or so.The aqueous solution can also contain sulphur
The inorganic salts such as sour sodium.The temperature of the aqueous solution is usually 20~80 DEG C or so, and dip time is usually 20~600 seconds or so.
Cross-linking process step is, for example, to make to carry out in boric acid aqueous solution through hyperchromatic polyvinyl alcohol resin film immersion.It is right
The content of boric acid in boric acid aqueous solution, in every 100 parts by weight water, usually 1~15 parts by weight or so, preferably 2~
10 parts by weight.In the case where using iodine as dichroism pigment, which preferably comprises potassium iodide.For boric acid water
The content of potassium iodide in solution, in every 100 parts by weight water, usually 1~20 parts by weight or so, preferably 5~15 weight
Part.Dip time of the film in boric acid aqueous solution is usually 10~600 seconds or so, preferably 20 seconds or more, it is additionally preferred to be 300
Below second.The temperature of boric acid aqueous solution is usually 50 DEG C or more, preferably 50~70 DEG C.In boric acid aqueous solution, it can also make
Sulfuric acid, hydrochloric acid, acetic acid, ascorbic acid etc. are added for pH adjusting agent.Boric acid aqueous solution can use different 2 such as composition and temperature
Kind or more aqueous solution, in this case, it is preferred that so that the boric acid aqueous solution below boric acid compared with initial boric acid aqueous solution is dense
Spend low mode application.
Usually to receive the cleaning process using water by the polyvinyl alcohol resin film of cross-linking process step.Cleaning treatment is for example
It is that the polyvinyl alcohol resin film immersion by crosslinking Treatment is made to be carried out in water.The temperature of water in cleaning treatment is usually
5~40 DEG C or so, dip time is usually 2~120 seconds or so.
Thereafter, by drying process, polarizer can be obtained.Drying typically uses air drier or far infrared adds
Hot device carries out.Drying temperature is usually 40~100 DEG C, and drying time is usually 30~600 seconds or so.
The thickness of polarizer for example can be about 5~30 μm.It is excellent from that can obtain about the boron containing ratio of polarizer
From the perspective of durability, preferably more than 1.5 weight %, more preferable more than 2.0 weight %, further preferred 3.0 weight %
More than, from the viewpoint of the contraction or curling (warpage) of the polarization plates caused by can inhibiting temperature change, preferably 5.5 weights
% is measured hereinafter, more preferable below 5.0 weight %.
[functional layer]
Functional layer in the case that it is representative can be protective film.Protective film can be made of thermoplastic resin it is transparent
Resin film.As thermoplastic resin, for example, chain polyolefin-based resins and ring-type by taking polypropylene-based resin as an example
The polyolefin-based resins such as polyolefin-based resins；The cellulose esters such as cellulosic triacetate and cellulose diacetate system resin；It is poly-
The polyester based resins such as ethylene glycol terephthalate, polyethylene naphthalate and polybutylene terephthalate (PBT)；Poly- carbon
Acid esters system resin；(methyl) acrylic ester resin in plexiglass；Or they it is at least two kinds of with
On mixture etc..Alternatively, it is also possible to use the copolymer at least two kinds of above monomers for forming above-mentioned resin.
Cyclic polyolefin hydrocarbon system resin is usually the general name of resin that is polymerize using cyclic olefin as polymerized unit, such as can be with
Enumerate Japanese Unexamined Patent Publication 1-240517 bulletins, Japanese Unexamined Patent Publication 3-14882 bulletins, Japanese Unexamined Patent Publication 3-122137
Resin described in bulletin etc..If enumerating the concrete example of cyclic polyolefin hydrocarbon system resin, the open loop (common) for cyclic olefin
The chain olefin of polymer, the addition polymer of cyclic olefin, ethylene and propylene etc. and the copolymer of cyclic olefin are (representative
Situation is random copolymer) and the graft polymers for being modified them with unsaturated carboxylic acid or derivatives thereof and they
Hydride etc..Wherein, the orbornene-based of the orbornene-baseds monomers such as norbornene, condensed ring orbornene-based monomer has been used
Resin is used preferably as cyclic olefin.
Cyclic polyolefin hydrocarbon system resin has various products to sell on the market.Commercially available product as cyclic polyolefin hydrocarbon system resin
Example represents with trade name, have TOPAS ADVANCED POLYMERS GmbH productions, in Japan by Polyplastics plants
Formula commercial firm sale " TOPAS " (registered trademark), by JSR Corp. sale " ARTON " (registered trademark), by Japanese ZEON
" ZEONOR " (registered trademark) and " ZEONEX " (registered trademark) of Co., Ltd.'s sale, by Mitsui Chemicals, Inc's sale
" APEL " (registered trademark) etc..
Alternatively, it is also possible to which the commercially available product of manufactured cyclic polyolefin resin film is used as protective film.As city
The example of product is sold, is represented with trade name, can enumerating " the ARTON films " sold by JSR Corp., (" ARTON " is identical
The registered trademark of company), by Sekisui Chemical Co., Ltd sale " ESCENA " (registered trademark) and " SCA40 ", by day
" ZEONOR FILM " (registered trademark) of the sale of this ZEON Co., Ltd. etc..
Cellulose esters system resin is usually the ester of cellulose and aliphatic acid.It, can as the concrete example of cellulose esters system resin
To enumerate cellulosic triacetate, cellulose diacetate, cellulose tripropionate, cellulose dipropionate etc..In addition, also may be used
To use resin obtained by they are copolymerized, by a part for hydroxyl the resin modified of others substituent groups.In them,
Particularly preferred cellulosic triacetate (triacetyl cellulose：TAC).Cellulosic triacetate has many products to sell on the market
It sells, is also advantageous from the aspect of easiness, cost is obtained.For the example of the commercially available product of cellulosic triacetate,
Represent there is " FUJITAC (registered trademark) TD80 ", " FUJITAC (registrations sold by Fuji Photo Film Co., Ltd. with trade name
Trade mark) TD80UF ", " FUJITAC (registered trademark) TD80UZ " and " FUJITAC (registered trademark) TD40UZ ", Konica
TAC film " KC8UX2M ", " KC2UA " and " KC4UY " of Minolta Co. Ltd. systems etc..
Polyester based resin is the resin having other than ester bond, above-mentioned cellulose-based resin, generally by polybasic carboxylic acid or
The resin that the condensation polymer of its derivative and polyalcohol is formed.2 yuan of dicarboxylic acids can be used as polybasic carboxylic acid or derivatives thereof
Or derivatives thereof, for example, terephthalic acid (TPA), M-phthalic acid, dimethyl terephthalate (DMT), naphthalene diformic acid dimethyl ester
Deng.2 yuan of glycol can be used as polyalcohol, for example, ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexamethylene
Alkane dimethanol etc..The example of suitable polyester based resin includes polyethylene terephthalate.
Polycarbonate-based resin is the engineering plastic by forming the polymer that monomeric unit bonding forms by carbonate group
Material, be have high-impact, heat resistance, anti-flammability, the transparency resin.Polycarbonate-based resin can also be to reduce
Photoelastic coefficient and the resin referred to as modified polycarbonate modified as polymer backbone improve wavelength dependence
Copolymerization polycarbonate of property etc..
(methyl) acrylic ester resin is the polymerization for including the Component units for coming from (methyl) acrylate monomer
Object.The polymer is the polymer containing methacrylate in the typical case.Preferably come from methacrylate
The ratio of structural unit be the polymer for including more than 50 weight % relative to entire infrastructure unit.(methyl) acrylic ester
Resin can be the homopolymer of methacrylate or comprising the Component units for coming from other polymerizable monomers
Copolymer.In this case, come from the ratio of the Component units of other polymerizable monomers preferably relative to entire infrastructure list
Member is below 50 weight %.
As the methacrylate that may be constructed (methyl) acrylic ester resin, preferably alkyl methacrylate.
As alkyl methacrylate, can enumerate methyl methacrylate, ethyl methacrylate, n propyl methacrylate,
Isopropyl methacrylate, n-BMA, Isobutyl methacrylate, Tert-butyl Methacrylate, metering system
The carbon atom number of the alkyl of sour 2- ethylhexyls, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate etc for 1~
8 alkyl methacrylate.The carbon atom number of contained alkyl is preferably 1~4 in alkyl methacrylate.At (methyl)
In acrylic ester resin, methacrylate can only be used alone a kind, can also be used together by two or more types.
As other the above-mentioned polymerizable monomers that may be constructed (methyl) acrylic ester resin, acrylic acid can be enumerated
Ester and other compounds in the molecule with polymerism carbon-to-carbon double bond.Other polymerizable monomers can only individually
Using a kind, can also be used together by two or more types.As acrylate, preferably alkyl acrylate.It, can be with as alkyl acrylate
Enumerate methyl acrylate, ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, i-butyl
The alkyl of ester, tert-butyl acrylate, 2-EHA, cyclohexyl acrylate, acrylic acid 2- hydroxy methacrylates etc
Carbon atom number is 1~8 alkyl acrylate etc..The carbon atom number of contained alkyl is preferably 1~4 in alkyl acrylate.
In (methyl) acrylic ester resin, acrylate can only be used alone a kind, can also be used together by two or more types.
As other compounds in the molecule with polymerism carbon-to-carbon double bond, ethylene, propylene, benzene second can be enumerated
The vinyl cyanide compound of the vinyl compounds such as alkene, acrylonitrile etc.It is other that there is polymerism carbon-to-carbon in the molecule
The compound of double bond can only be used alone a kind, can also be used together by two or more types.
As long as being contained in the scope of the present invention, functional layer can also have both the optics such as phase difference film and brightness raising film
The protective film of function.For example, by (being stretched uniaxially or biaxially to being stretched by the transparent resin film that above-mentioned material is formed
Deng), on the film form liquid crystal layer etc., the phase difference film for having been assigned arbitrary phase difference value can be made.Alternatively, functional layer
Can be protective film be bonded product etc. with phase difference film.
In addition, functional layer can also on the surface with polarizer opposite side of functional layer, have hard conating, antiglare layer,
The surface-treated layers such as anti-reflection layer, anti-static electricity interference layer and stain-proofing layer (coating).Surface-treated layer can utilize well known method
It is formed.
In the case of setting the first functional layer and the second functional layer on the two sides of polarizer, this 2 functional layers both can phase
Together, it can also be different.As the asynchronous example of functional layer, the type for the thermoplastic resin at least forming functional layer can be enumerated
Different combinations；At least combination different in terms of the presence or absence of optical function of functional layer or its type；At least it is being formed in table
Different combination etc. in terms of the presence or absence of the surface-treated layer in face or its type.
From the viewpoint of the filming of polarization plates, the thickness of preferred function layer is thin, and for example, 90 μm hereinafter, preferably 60
μm hereinafter, more preferably 50 μm hereinafter, further preferably less than 30 μm.On the other hand, from the viewpoint of processability, function
Layer, which preferably has, may insure the thickness of a degree of intensity, for example, 5 μm or more.
[adhesive phase]
As the adhesive for forming adhesive phase, known adhesive is selected, as long as it may in polarization plates
There is the adhesive of the adhesivity for the degree that will not cause to come off etc. in the environment of being exposed.Specifically, it can enumerate
Acrylic adhesive, silicone-based adhesive, elastomeric adhesive etc., from the transparency, weatherability, heat resistance, processability side
Face consideration, particularly preferred acrylic adhesive.
In adhesive, as needed, tackifier, plasticizer can also be mated properly into, comprising glass fibre, glass
The filler of pearl, metal powder, other inorganic powder etc., pigment, colorant, filler, antioxidant, ultra-violet absorber,
The various additives such as anti-static electricity interference agent, silane coupling agent.
Adhesive phase be typically by by the solution coating of adhesive on peeling layer (mold release film) and dry being formed.To
Coating rolling method, spin-coating method, silk screen rubbing method, jetting type such as may be used reversely coating, intaglio plate coating on peeling layer
Rubbing method, dip coating, spray-on process etc..In addition it is also possible to the coating adhesive on peeling layer, in the table of the adhesive phase formed
Other peeling layer is configured in face, utilizes the form that peeling layer is formed on the two sides of adhesive phase.
The thickness of adhesive phase is usually 3~100 μm or so, preferably 5~50 μm.
[manufactures of polarization plates]
By the way that polarizer, functional layer is laminated according to required sequence, laminate adhesive oxidant layer is gone back in a situation of use where in addition,
The polarization plates of the present invention can be manufactured.
The stacking of polarizer layer and functional layer can be implemented using arbitrary appropriate method, such as can use adhesive
Make interlayer gluing.As adhesive, water system adhesive, active energy ray-curable adhesive or Thermocurable glue can be used
Stick etc., it is preferable to use water system adhesive, active energy ray-curable adhesive from the viewpoint of productivity.For institute
The thickness of gluing oxidant layer in the polarization plates obtained, then can be 0.01~0.2 μm or so, such as example, if being water system adhesive
Fruit is active energy ray-curable adhesive, then can be 0.1~4 μm.
Water system adhesive is adhesive obtained by adhesive component is dissolved or is dispersed in water.It is preferable to use water system
Adhesive is, for example, the adhesive compound that polyvinyl alcohol resin or carbamate resins have been used as principal component.
In the case where using polyvinyl alcohol resin as the principal component of adhesive, the polyvinyl alcohol resin is in addition to can
Be partly-hydrolysed polyvinyl alcohol, fully saponified polyvinyl alcohol etc polyvinyl alcohol resin other than, can also be carboxy-modified
The process of polyvinyl alcohol, acetoacetyl modified polyvinyl alcohol, methylol-modified polyvinyl alcohol, amino modified polyvinyl alcohol etc
Modified polyvinyl alcohol resin.Polyvinyl alcohol resin is in addition to that can be the poly- acetic acid to the homopolymer as vinyl acetate
Vinyl acetate is carried out obtained by saponification process other than alcotex, can also be to vinyl acetate with can be copolymerized therewith
The copolymer of other monomers carries out polyvinyl alcohol based copolymer obtained by saponification process.
Water system adhesive using polyvinyl alcohol resin as adhesive component is usually the water-soluble of polyvinyl alcohol resin
Liquid.For the concentration of the polyvinyl alcohol resin in adhesive, relative to 100 parts by weight of water, usually 1~10 parts by weight, excellent
It is selected as 1~5 parts by weight.
In order to improve adhesivity, the adhesive being made of the aqueous solution of polyvinyl alcohol resin preferably comprises polyaldehyde, honey
Amine compound, zirconium dioxide compound, zinc compound, glyoxal, glyoxal derivative, water-soluble epoxy resin etc are consolidated
The property changed ingredient or crosslinking agent.As water-soluble epoxy resin, such as polyamide polyamine epoxy resin can be suitably used, be
Polyamide-amide is obtained by the reaction using dicarboxylic acids such as polyalkylenepolyamines and adipic acid such as two sub- second triamines, tetramines,
Epichlorohydrin is made to be reacted with gained polyamide-amide and is obtained.As the commercially available product of the polyamide polyamine epoxy resin, can enumerate
" Sumirez Resin 650 " (field ridge chemical industry (strain) system), " Sumirez Resin 675 " (field ridge chemical industry (strain)
System), " WS-525 " (Japanese PMC (strain) system) etc..The additive amount of these curability compositions or crosslinking agent (as curability into
Point and crosslinking agent be its total amount when adding together) relative to 100 parts by weight of polyvinyl alcohol resin, usually 1~100 weight
Part, preferably 1~50 parts by weight.In the additive amount of above-mentioned curability composition or crosslinking agent relative to polyvinyl alcohol resin 100
Parts by weight be less than 1 parts by weight in the case of, adhesivity improve effect have the tendency that becoming smaller, in addition, the additive amount relative to
In the case that 100 parts by weight of polyvinyl alcohol resin are more than 100 parts by weight, gluing oxidant layer has the tendency that becoming fragile.
In addition, for using suitable example during carbamate resins as the principal component of adhesive, can enumerate
Polyester ionomer type carbamate resins and the mixture of the compound with glycidoxypropyl.So-called Polyester is from poly-
Object type carbamate resins are the carbamate resins with polyester backbone, and have imported on a small quantity ionic thereto
Ingredient (hydrophilic component).It is directly emulsified into breast in water since the ionomer type carbamate resins do not use emulsifier
Liquid is consequently adapted to as water-based adhesive.
Active energy ray-curable adhesive is because of the active-energy of ultraviolet light, visible ray, electron beam, X ray etc
The irradiation of ray and cured adhesive.In the case where using active energy ray-curable adhesive, polarization plates are had
Gluing oxidant layer be the adhesive solidified material layer.
Active energy ray-curable adhesive can be contain as curability composition it is cured when the cationic polymerization
The adhesive of epoxy based compound preferably contains the ultra-violet solidified gluing of the epoxy based compound as curability composition
Agent.So-called epoxy based compound described herein refers to there is 1 or more average, preferably 2 or more epoxy groups in the molecule
Compound.Epoxy based compound can both be used only a kind, can also be used together by two or more types.
The concrete example of epoxy based compound that can suitably use includes：Hydrogenated epoxy based compound (has ester ring type
The glycidol ether of the polyalcohol of ring), be by carrying out hydrogenation to the aromatic rings of aromatic polyol, make epichlorohydrin with
The ester ring type polyol reaction of gained and obtain；The polyglycidyl ether of aliphatic polyol or its alkylene oxide adducts etc
Aliphatic epoxy based compound；Ester ring type epoxy based compound is bonded to have 1 or more in the molecule with ester ring
Epoxy group epoxy based compound.
Active energy ray-curable adhesive can be used as curability composition, replace above-mentioned epoxy based compound or
Contain therewith and belong to free-radical polymerised (methyl) acrylate based compound.As (methyl) acrylic ester
Object is closed, (methyl) acrylate monomer in the molecule at least one (methyl) acryloxy can be enumerated；Make 2 kinds with
On containing functional group compound reaction and obtain and in the molecule at least two (methyl) acryloxy (methyl) third
Olefin(e) acid ester oligomer etc. contains the compound of (methyl) acryloxy.
Active energy ray-curable adhesive contains through cationic polymerization as curability composition and cured ring
In the case of oxygen based compound, light cationic polymerization initiator is preferably comprised.As light cationic polymerization initiator, such as can be with
Enumerate aromatic diazonium salt；The salt such as aromatic iodonium salts or aromatic series sulfonium salt；Iron-arene complex etc..In addition, in activity
Energy ray-curable adhesive contains the free-radical polymerised curability composition of (methyl) acrylate based compound etc
In the case of, preferably comprise optical free radical polymerization initiator.As optical free radical polymerization initiator, for example, acetophenone system
Initiator, benzophenone series initiators, benzoin ether series initiators, thioxanthones series initiators, xanthone, fluorenes, camphorquinone, benzene
Formaldehyde, anthraquinone etc..
Before protective film is fitted in polarizing coating, plasma can be carried out to the binding face of polarizing coating and/or protective film
The surface activation process of body processing, sided corona treatment, ultraviolet treatment with irradiation, flame (flame) processing, saponification process etc.Profit
With the surface activation process, the adhesivity of polarizing coating and protective film can be improved.
In the case where using adhesive phase, the adhesiveness of its own can be utilized, is laminated in polarizer layer or functional layer.
It more specifically, can be by divesting the peeling layer and will bond in the case where the lamination surface of adhesive phase is there are peeling layer
Oxidant layer is transferred to polarizer layer or functional layer and is laminated.
[manufacture of image display device]
The polarization plates manufactured as described above are pressed from both sides and fit in other components (optical component) across adhesive phase, it is possible to
Obtain image display device.More specifically, in the case where the binding face of adhesive phase is there are peeling layer, the stripping can be divested
Polarization plates are bonded by absciss layer using the adhesiveness of adhesive phase to other components.For example, by the way that polarization plates are fitted in liquid crystal list
Member can obtain liquid crystal display device, by fitting in organic electroluminescent device, can obtain ORGANIC ELECTROLUMINESCENCE DISPLAYS dress
It puts.Existing product is used by the liquid crystal cells of fitting polarization plates or organic electroluminescent device.Liquid crystal cells are organic
In electroluminescent cell, the inscapes of polarization plates is directly fitted in the case that representative as glass plate.
However, it should be noted that the purposes of the polarization plates of the present invention is not limited to image display device, can be used for various
Optical applications.
[embodiment]
1 ＞ of ＜ embodiments
(A) making of polarizer
Continuously transport the polyvinyl alcohol film (average degree of polymerization of long size：About 2400, saponification degree：99.9 moles of more than %,
Thickness：60 μm), it is immersed in the swelling bath comprising 20 DEG C of pure water (swelling process) with the residence time of 31 seconds.Thereafter, make from
The film pulled out in swelling bath was immersed in 30 containing iodine DEG C of the potassium iodide/water as 2/100 (weight ratio) using the residence time of 122 seconds
Dye bath in (dyeing process).Then, the film pulled out from dye bath is made to be immersed in potassium iodide/boron with the residence time of 70 seconds
During acid/water is bathed for 56 DEG C of crosslinking of 12/4.1/100 (weight ratio), next, being immersed in iodate with the residence time of 13 seconds
Potassium/boric acid/water is (cross-linking process step) in 40 DEG C of the crosslinking bath of 9/2.9/100 (weight ratio).In dyeing process and cross-linking process step
In, carry out longitudinal uniaxial stretching using being stretched between the roller in bath.Total stretching ratio on the basis of raw material film is set as 5.5
Times.Then, make the film pulled out in being bathed from crosslinking (clear after being immersed in the cleaner bath comprising 5 DEG C of pure water with the residence time of 3 seconds
Wash process), 80 DEG C of drying oven was imported with the residence time of 190 seconds and is dried (drying process), obtains polarizer.This reality
The thickness for applying the polarizer obtained in example is 23.6 μm.
(B) making of polarization plates
The polarizer obtained in above-mentioned (A) is continuously transported, and continuously transports the first functional layer (first of long size
Protective film) (TAC film " KC8UX ", the thickness of Konica Minolta Opto Co. Ltd. systems：80 μm) and long size second
Functional layer (the second protective film) (TAC film " KC8UX ", the thickness of Konica Minolta Opto Co. Ltd. systems：80 μm),
While water system adhesive is injected between polarizer and the first functional layer and between polarizer and the second functional layer, in doubling roller
Between by obtaining including the stacking of the functional layer of the first functional layer/water system gluing oxidant layer/polarizer/water system gluing oxidant layer/second
Film.Next, transport the stacked film of gained, 60 DEG C of drying oven was imported with the residence time of 100 seconds and heated, by
This dries water system gluing oxidant layer, obtains polarization plates.As above-mentioned water system adhesive, the aqueous solution obtained as follows has been used,
It is that is, pva powder (trade name " Gosefimer " of Japanese synthetic chemical industry (strain) system, average degree of polymerization 1100) is molten
Solution is in 95 DEG C of hot water, into the polyvinyl alcohol water solution of the 3 weight % of concentration of gained, relative to 10 weight of pva powder
Amount part is obtained with the ratio mixed cross-linker (sodiam glyoxlate of Japanese synthetic chemical industry (strain) system) of 1 parts by weight.
(C) making of the polarization plates with adhesive phase
Using the thickness that 25 μm are formed on peeling layer (mold release film) commercially available acrylic adhesive piece it is commercially available
Product form the adhesive phase of 25 μm of thickness in the second functional layer of the polarization plates obtained in above-mentioned (B), produce with bonding
The polarization plates of oxidant layer.
(D) elasticity modulus (tensile modulus of elasticity) of the polarizer transmission axis direction of polarizer
In the polarizer obtained from above-mentioned (A), cut out the long 100mm in polarizer transmission axis direction and inhaled in polarizer
Receive the rectangular test film of width 20mm in axis direction.Then, cupping machine (Shimadzu Scisakusho Ltd's system is utilized
Autograph AG-1S testing machines) fixture up and down, the length of above-mentioned test film is clamped in a manner of being divided into 5cm between making fixture
Direction (polarizer transmission axis direction) both ends are spent, in the environment of 23 DEG C, with the tensile speed of 5mm/ minutes to test film edge
Length direction (polarizer transmission axis direction) is stretched, the straight line at the initial stage in the load-deformation curve of gained it is oblique
Rate calculates the elasticity modulus (tensile modulus of elasticity) (MPa) of the polarizer transmission axis direction of 23 DEG C of polarizer.Thus it calculates
The elastic modulus E of the polarizer transmission axis direction of the polarizer of the present embodimentPFor 4773MPa.
(E) the boron containing ratio of polarizer
Polarization agreement that contracts a film or TV play to an actor or actress 0.2g is added in pure water 170ml, after being allowed to be completely dissolved at 95 DEG C, adds in Osmitrol
(12.5 weight %) 30g and test sample solution is made.Sodium hydrate aqueous solution (1mol/l) is added dropwise, until the measure sample
Product solution reaches the point of neutralization, according to its dripping quantity by the boron containing ratio (weight %) in following formula calculating polyvinyl alcohol film.Thus it calculates
The boron containing ratio of the polarizer of the present embodiment gone out is 3.8 weight %.
The weight (g) of boron containing ratio=1.08 × sodium hydrate aqueous solution dripping quantity (ml)/polarizing coating
(F) elasticity modulus (tensile modulus of elasticity) of the polarizer transmission axis direction of functional layer
From the polarization plates for manufacturing above-mentioned (B) when the first functional layer and the second functional layer that use in, cut out in the inclined of gained
It is absorbed on the parallel direction of axis direction with long 100mm on the parallel direction of polarizer transmission axis direction in vibration plate and with polarizer
The rectangular test film of wide 20mm.Then, cupping machine (Shimadzu Scisakusho Ltd Autograph AG- are utilized
1S testing machines) fixture up and down, the length direction of above-mentioned test film is clamped in a manner of being divided into 5cm between making fixture (with polarization
The parallel direction of piece transmission axis direction) both ends, it is long to test film edge with the tensile speed of 5mm/ minutes in the environment of 23 DEG C
Degree direction (direction parallel with polarizer transmission axis direction) is stretched, according to the initial stage in the load-deformation curve of gained
Straight line slope, calculate 23 DEG C functional layer polarizer transmission axis direction elasticity modulus (tensile modulus of elasticity) (MPa).
The elastic modulus E of the polarizer transmission axis direction of first functional layer of the present embodiment thus calculatedF1And second functional layer it is inclined
The piece that shakes transmits the elastic modulus E of axis directionF2For 4169MPa.
(G) elasticity modulus (tensile modulus of elasticity) of the polarizer transmission axis direction of adhesive phase
From the polarization plates with adhesive phase for manufacturing above-mentioned (C) when the adhesive sheet that uses in, only adhesive phase is made
It is cut out for rectangular test film, on test film direction parallel with polarizer transmission axis direction in the polarization plates of gained
Long 50mm and the width 5mm on the direction parallel with polarizer absorption axis direction.Then, (the strain formula meeting of accurate universal testing machine is utilized
Shimadzu Seisakusho Ltd. of society Autograph AGS-50NX testing machines) fixture up and down, in a manner of being divided into 3cm between making fixture
Length direction (direction parallel with polarizer transmission axis direction) both ends of above-mentioned test film are clamped, in the environment of 23 DEG C,
With the tensile speed of 300mm/ minutes, to test film, (direction parallel with polarizer transmission axis direction) was drawn along its length
It stretches, the slope of the straight line at the initial stage in the load-deformation curve of gained, the polarizer for calculating 23 DEG C of adhesive phase is saturating
Penetrate the elasticity modulus (tensile modulus of elasticity) (kPa) of axis direction.The polarizer of the adhesive phase of the present embodiment thus calculated is saturating
Penetrate the elastic modulus E of axis directionPSAFor 135kPa.
(H) elastic modulus difference
As elastic modulus difference Δ E, the elasticity modulus of the polarizer transmission axis direction of the polarizer obtained from above-mentioned (D)
EPIn subtract EFAnd it calculates, the EFThe elasticity modulus of the polarizer transmission axis direction of the first functional layer obtained in above-mentioned (F)
EF1With the elastic modulus E of the polarizer transmission axis direction of the second functional layerF2It is then any one when different for the value when identical
The value of an a big side.The elastic modulus difference Δ E of the present embodiment thus calculated is 604MPa.
(I) resistance to anti-thread breakage evaluation
In the polarization plates with adhesive phase obtained from above-mentioned (C), cut out long in polarizer transmission axis direction
80mm and polarizer absorb axis direction on width 60mm rectangular test film.Test film is fitted in into glass plate, input 80
DEG C baking oven in 1 hour.After the test film for fitting in glass plate is taken out from baking oven, in 23 DEG C and the ring of relative humidity 55%
It takes care of 15 minutes under border, then, is impregnated 30 minutes in 23 DEG C of water.The test film for fitting in glass plate is taken out from water
Afterwards, remove the moisture of test film using air injection.Thereafter, the length of test film is visually observed using magnifying glass (10 times of multiplying power)
Direction (polarizer transmission axis direction) end counts the item number of crackle.Crackle is not seen in the present embodiment.
2~4 ＞ of ＜ embodiments
Other than the first functional layer and the second functional layer in addition to will manufacture polarization plates when change as shown in table 1, with implementation
Example 1 produces polarization plates and the polarization plates with adhesive phase in the same manner.Details as Follows for the abbreviation of the functional layer in table 1 herein
It is shown.
〔a〕TAC1：80 μm of TAC film " KC8UX2MW " thickness of Konica Minolta Opto Co. Ltd. systems
〔b〕TAC2：40 μm of TAC film " KC4UYW " thickness of Konica Minolta Opto Co. Ltd. systems
〔c〕TAC3：25 μm of TAC film " KC2UAW " thickness of Konica Minolta Opto Co. Ltd. systems
〔d〕COP1：Trade name " the ARTON FILM as cyclic polyolefin resin film of JSR Corp.
15 μm of FEKB015D3 " thickness
〔e〕COP2：Trade name " the ZEONOR as cyclic polyolefin resin film of Japanese ZEON Co. Ltd. systems
23 μm of FILM ZF14-023 " thickness
〔f〕COP3：Trade name " the ZEONOR as cyclic polyolefin resin film of Japanese ZEON Co. Ltd. systems
Phase difference 90nm, thickness phase difference 79nm in 21 μm of FILM ZT12-090079 " thickness, face
＜ embodiments 5,1~3 ＞ of comparative example
In addition to when manufacturing polarizer, potassium iodide/boric acid/water is immersed in as 12/1.5/100 using the residence time of 70 seconds
In 56 DEG C of the crosslinking bath of (weight ratio), next, being immersed in potassium iodide/boric acid/water as 9/1.5/ using the residence time of 13 seconds
100 (weight ratios) 40 DEG C of crosslinking bath in (cross-linking process step), and by manufacture polarization plates when the first functional layer and the second function
Other than layer changes as shown in table 1, polarization plates and the polarization plates with adhesive phase are produced same as Example 1ly.
6 ＞ of ＜ embodiments
In addition to when manufacturing polarizer, potassium iodide/boric acid/water is immersed in as 12/5.0/100 using the residence time of 70 seconds
In 56 DEG C of the crosslinking bath of (weight ratio), next, being immersed in potassium iodide/boric acid/water as 9/5.0/100 using 13 second residence time
(weight ratio) 40 DEG C of crosslinking bath in (cross-linking process step), and by manufacture polarization plates when the first functional layer and the second functional layer such as
Other than being changed shown in table 1, polarization plates and the polarization plates with adhesive phase are produced same as Example 1ly.
7 ＞ of ＜ embodiments
Polyvinyl alcohol film (average degree of polymerization in addition to using long size：About 2400, saponification degree：99.9 moles of more than %, thickness
Degree：30 μm), and the first functional layer when will manufacture polarization plates and other than the second functional layer changes as shown in table 1, with embodiment
1 produces polarization plates and the polarization plates with adhesive phase in the same manner.
8 ＞ of ＜ embodiments
Other than total stretching ratio on the basis of raw material film when manufacturing polarizer is set as 5.4 times, with implementation
Example 7 produces polarization plates and the polarization plates with adhesive phase in the same manner.
9 ＞ of ＜ embodiments
In addition to when manufacturing polarizer, potassium iodide/boric acid/water is immersed in as 12/1.5/100 using the residence time of 70 seconds
In 56 DEG C of the crosslinking bath of (weight ratio), next, being immersed in potassium iodide/boric acid/water as 9/1.5/ using the residence time of 13 seconds
100 (weight ratios) 40 DEG C of crosslinking bath in (cross-linking process step), and by manufacture polarization plates when the first functional layer and the second function
Other than layer changes as shown in table 1, polarization plates and the polarization plates with adhesive phase are produced same as Example 7ly.
4 ＞ of ＜ comparative examples
Other than the first functional layer and the second functional layer in addition to will manufacture polarization plates when change as shown in table 1, with implementation
Example 9 produces polarization plates and the polarization plates with adhesive phase in the same manner.
It will be shown in table 1 in each embodiment and the condition and result set of comparative example.
[table 1]
With reference to table 1, in the Examples 1 to 9 for being more than -1100MPa in elastic modulus difference Δ E, crackle item number for 20 with
Under, and crackle item number is 80 or more in the comparative example 1~4 that elastic modulus difference Δ E is below -1200MPa, is confirmed apparent
Ground is reduced.
<Embodiment 10~13>
Using from different commercially available acrylic adhesive piece used in embodiment 1 polarization plates the 2nd functional layer
The upper adhesive phase for forming 25 μm of thickness, makes the polarization plates with adhesive phase in the same manner as embodiment 1 or 6 in addition to this.
The elastic modulus E of the polarizer transmission axis direction of each adhesive phasePSAAs shown in table 2.
The condition of each embodiment and the results are shown in Table 2.
Industrial availability
The polarization plates of the present invention can be used for various optical applications, such as can be as the polarised light of image display device
Feed element and detecting element as polarised light are widely used.
The explanation of symbol
1 polarizer, 3,5 functional layers, 7 adhesive phases, 10,11,12 polarization plates, 15 others components (such as liquid crystal cells,
Organic electroluminescent device etc.), 20 image display devices.
Claims (7)
1. a kind of polarization plates are the polarization plates of the functional layer comprising polarizer and at least one side for being laminated in polarizer, from polarization
The polarizer of piece is transmitted obtained by the elasticity modulus for the polarizer transmission axis direction that functional layer is subtracted in the elasticity modulus of axis direction
It is worth to be more than -1100MPa.
2. polarization plates according to claim 1, wherein, functional layer includes protective film.
3. polarization plates according to claim 1 or 2, wherein, functional layer includes phase difference film.
4. polarization plates described in any one of claim 1 to 3, wherein, it is laminated with functional layer on one side in polarizer,
The another side of polarizer is laminated with adhesive phase.
5. polarization plates according to any one of claims 1 to 4, wherein, it is laminated on the surface of a surface side of polarization plates
Adhesive phase or the adhesive phase with peeling layer.
6. polarization plates according to claim 4 or 5, wherein, the elasticity modulus of the polarizer transmission axis direction of adhesive phase
For below 1000kPa.
7. a kind of image display device, it includes any in liquid crystal cells or organic electroluminescent device and claim 1~6
Polarization plates described in.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-007769 | 2016-01-19 | ||
| JP2016007769 | 2016-01-19 | ||
| CN201710028965.5A CN106980148B (en) | 2016-01-19 | 2017-01-16 | Polarization plates and image display device |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710028965.5A Division CN106980148B (en) | 2016-01-19 | 2017-01-16 | Polarization plates and image display device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108254824A true CN108254824A (en) | 2018-07-06 |
| CN108254824B CN108254824B (en) | 2023-03-28 |
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| CN201810209407.3A Active CN108254824B (en) | 2016-01-19 | 2017-01-16 | Polarizing plate and image display device |
| CN201710028965.5A Active CN106980148B (en) | 2016-01-19 | 2017-01-16 | Polarization plates and image display device |
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| JP (2) | JP6185203B2 (en) |
| KR (2) | KR101803675B1 (en) |
| CN (2) | CN108254824B (en) |
| TW (2) | TWI746648B (en) |
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|---|---|---|---|---|
| JP7240090B2 (en) * | 2017-10-03 | 2023-03-15 | 日東電工株式会社 | Polarizing plate, image display device, and method for manufacturing polarizing plate |
| JP2019207391A (en) * | 2018-05-25 | 2019-12-05 | 住友化学株式会社 | Manufacturing method for optical laminate |
| CN113272688A (en) * | 2018-12-27 | 2021-08-17 | 日东电工株式会社 | Polarizing plate and polarizing plate roll |
| CN110572910A (en) * | 2019-09-20 | 2019-12-13 | 山东旭程照明科技有限公司 | Automatic control device circuit of water leakage and electric shock preventing LED lamp |
| JP6792736B1 (en) * | 2019-11-20 | 2020-11-25 | 住友化学株式会社 | Optical laminate and display device |
| JP7005803B1 (en) | 2020-10-26 | 2022-01-24 | 住友化学株式会社 | Laminate |
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- 2017-01-16 CN CN201810209407.3A patent/CN108254824B/en active Active
- 2017-01-16 JP JP2017004833A patent/JP6185203B2/en active Active
- 2017-01-16 CN CN201710028965.5A patent/CN106980148B/en active Active
- 2017-01-17 TW TW106132821A patent/TWI746648B/en active
- 2017-01-17 TW TW106101532A patent/TWI604234B/en active
- 2017-07-26 JP JP2017144216A patent/JP2017204003A/en active Pending
- 2017-11-20 KR KR1020170154584A patent/KR102413813B1/en active IP Right Grant
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Also Published As
| Publication number | Publication date |
|---|---|
| KR101803675B1 (en) | 2017-11-30 |
| KR20170132112A (en) | 2017-12-01 |
| KR20170087030A (en) | 2017-07-27 |
| JP2017204003A (en) | 2017-11-16 |
| JP6185203B2 (en) | 2017-08-23 |
| CN106980148B (en) | 2018-04-17 |
| TWI604234B (en) | 2017-11-01 |
| KR102413813B1 (en) | 2022-06-29 |
| TWI746648B (en) | 2021-11-21 |
| JP2017129859A (en) | 2017-07-27 |
| TW201809761A (en) | 2018-03-16 |
| TW201732334A (en) | 2017-09-16 |
| CN106980148A (en) | 2017-07-25 |
| CN108254824B (en) | 2023-03-28 |
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