CN104730611B - The manufacture method of optical laminate - Google Patents
The manufacture method of optical laminate Download PDFInfo
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- CN104730611B CN104730611B CN201410822343.6A CN201410822343A CN104730611B CN 104730611 B CN104730611 B CN 104730611B CN 201410822343 A CN201410822343 A CN 201410822343A CN 104730611 B CN104730611 B CN 104730611B
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polarising Elements (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention relates to the manufacture method of optical laminate.The manufacture method of the light polarizing film of excellent appearance is provided.The manufacture method of the optical laminate of embodiments of the present invention includes following operation：Layered product with resin base material and the unilateral polyvinyl alcohol resin layer for being formed at the resin base material is stretched and dyeed, so as to make the operation of light polarizing film on the resin base material；Above-mentioned layered product is set to impregnated in the operation that the cleaning fluid comprising iodide is cleaned；And, remove cleaning fluid so that the adhesion amount of the cleaning fluid on the resin base material side surface of above-mentioned layered product is 0.005g/m2Hereinafter, then by the dry operation of above-mentioned layered product.
Description
Technical field
The present invention relates to the manufacture method of the optical laminate with light polarizing film.
Background technology
For the liquid crystal display device as representational image display device, because of its image forming mode in liquid crystal list
The both sides of unit are configured with light polarizing film.As the manufacture method of light polarizing film, for example, propose following methods：Will with resin base material and
The layered product of polyvinyl alcohol (PVA) resin is stretched, and then implements dyeing treatment, and light polarizing film is obtained on resin base material
Method (such as Japanese Unexamined Patent Publication 2000-338329 publications).Using such method, the polarisation of thinner thickness can be obtained
Film, attracts attention therefore, it is possible to be conducive to the slimming of image display device in recent years.
However, producing the apparent problem such as concavo-convex bad point sometimes using the light polarizing film that above-mentioned resin base material makes.
The content of the invention
Problems to be solved by the invention
The present invention makes to solve the above problems, its main purpose is, providing concavo-convex bad point etc. in appearance
The manufacture method of light polarizing film that is improved of problem.
The scheme for solving problem
On above-mentioned concavo-convex bad point, the present inventor etc. is studied, as a result for example following supposition of its mechanism.That is, on
Light polarizing film is stated to manufacture as follows：Layered product with resin base material and PVA resins is stretched and dyeed, it is then representative
Ground is cleaned with the cleaning fluid comprising iodide, is finally dried, so as to manufacture.Herein, remained on layered product surface
Have in the state of the cleaning fluid comprising iodide when being dried, compared with PVA resins (light polarizing film) side surface, hydrophobic
Property degree resin base material side surface high on iodide separated out with larger particle diameter.Then, by the layered product of such state with defeated
When sending roller conveying or wound into rolls and being reclaimed, due to the thinner thickness of light polarizing film, so speculating the shape of the precipitate
Shape is easily transferred to light polarizing film so as to produce concavo-convex bad point.
The present inventor etc. are studied based on above-mentioned supposition, are as a result found：By utilizing the cleaning comprising iodide
After liquid is cleaned, the adhesion amount of the cleaning fluid on the resin base material side surface of above-mentioned layered product is adjusted to the scope of regulation,
Then it is dried, such that it is able to improve the apparent problem such as concavo-convex bad point, this completes the present invention.
The manufacture method of the optical laminate that light polarizing film is laminated with resin base material of the invention includes following operation：Will
Layered product with resin base material and the unilateral polyvinyl alcohol resin layer for being formed at the resin base material is stretched and dyeed,
So as to make the operation of light polarizing film on the resin base material；Above-mentioned layered product is impregnated in the cleaning fluid comprising iodide is carried out clearly
The operation washed；And, remove cleaning fluid so that the adhesion amount of the cleaning fluid on the resin base material side surface of above-mentioned layered product is
0.005g/m2Hereinafter, then by the dry operation of above-mentioned layered product.
In 1 implementation method, the water contact angle of the resin base material side surface of above-mentioned layered product is 60 °~80 °.
In 1 implementation method, the thickness of above-mentioned light polarizing film is 0.5 μm~15 μm.
In 1 implementation method, iodide concentration in above-mentioned cleaning fluid is 0.5 weight %~10 weight %.
In 1 implementation method, above-mentioned stretching includes being stretched in water.
In 1 implementation method, the removal of the cleaning fluid on the resin base material side surface of above-mentioned layered product by wiping or
Gas is blowed to carry out.
Another technical scheme of the invention, there is provided optical laminate.Optical laminate of the invention is by upper
Obtained from stating manufacture method.
The effect of invention
According to the present invention, by cleaning fluid of the layered product comprising iodide that light polarizing film will be laminated with resin base material
After being cleaned, by the adhesion amount of the cleaning fluid on the resin base material side surface of the layered product adjust to regulation scope, then
It is dried, such that it is able to suppress the precipitation of iodide, as a result, the apparent problem such as concavo-convex bad point can be improved.
Brief description of the drawings
Fig. 1 is the partial section of the layered product of the preferred embodiment of the present invention.
Fig. 2 is of the drying process of the cleaning fluid for illustrating the resin base material side surface by wiping removal layered product
Schematic diagram.
Fig. 3 is of the drying process of the cleaning fluid for illustrating the resin base material side surface by wiping removal layered product
Schematic diagram.
Fig. 4 is the one of the drying process of the cleaning fluid for illustrating the resin base material side surface by blowing gas-removal layers stack
The schematic diagram of example.
Description of reference numerals
10 layered products
11 resin base materials
12 polyvinyl alcohol resins layer (light polarizing film)
20 give damping roller
30 remove liquid roller
40 scraper plates
50 blowning installations
60 dry component
Specific embodiment
Hereinafter, the preferred embodiment of the present invention is illustrated, but the present invention is not limited to these implementation methods.
The manufacture method of optical laminate of the invention includes following operation：With resin base material and the resin will be formed at
The layered product of the unilateral polyvinyl alcohol resin layer of base material is stretched and dyeed, so as to make polarisation on the resin base material
The operation of film；Above-mentioned layered product is set to impregnated in the operation that the cleaning fluid comprising iodide is cleaned；And, cleaning fluid is removed,
So that the adhesion amount of the cleaning fluid on the resin base material side surface of above-mentioned layered product is 0.005g/m2Hereinafter, then by above-mentioned layer
The dry operation of stack.Hereinafter, each operation is illustrated.
A. the production process of light polarizing film
A-1. layered product
Fig. 1 is the partial section of the layered product of the preferred embodiment of the present invention.Layered product 10 has resin base material 11
With polyvinyl alcohol resin layer 12.Layered product 10 is by forming polyvinyl alcohol resin layer on the resin base material 11 of strip
12 and make.As the forming method of polyvinyl alcohol resin layer 12, can be using any appropriate method.Preferably,
Coating fluid of the coating comprising polyvinyl alcohol resin (hereinafter referred to as " PVA systems resin "), is dried on resin base material 11, from
And form PVA resins 12.
As the formation material of above-mentioned resin base material, can be using any appropriate thermoplastic resin.As thermoplastic resin
Fat, for example, can enumerate：The cyclic olefines such as the ester such as PET series resin system resin, norbornene resin
The olefin-based resins such as resin, polypropylene, polyamide series resin, polycarbonate-based resin, their copolymer resin etc..Wherein,
Preferably norbornene resin, amorphous PET series resin.
In 1 implementation method, amorphous (crystallization) PET series tree is preferably used
Fat.Wherein, non-crystalline (being difficult to what is crystallized) PET series resin is particularly preferably used.As amorphous
The concrete example of the PET series resin of property, can enumerate：Further comprising M-phthalic acid as dicarboxyl
Acid copolymer, further comprising cyclohexanedimethanol as glycol copolymer.
Using during stretching mode, above-mentioned resin base material absorbs water in water in aftermentioned stretching, water plays the effect of plasticizer, can
To carry out plasticized.As a result, tensile stress can be greatly reduced, can be stretched with high magnification, with aerial drawing
Compared when stretching, draftability can be more excellent.As a result, the light polarizing film with excellent optical characteristics can be made.In 1 implementation
In mode, the water absorption rate of resin base material is preferably more than 0.2%, more preferably more than 0.3%.On the other hand, resin base
The water absorption rate of material is preferably less than 3.0%, more preferably less than 1.0%.By using such resin base material, can in case
When only manufacturing dimensional stability substantially reduce and a problem that the deteriorated appearance of gained light polarizing film.Furthermore it is possible in preventing water
Base material fracture or PVA resins are peeled off from resin base material during stretching.It should be noted that the water absorption rate of resin base material is for example
Adjusted by importing modified group in material is formed.Water absorption rate is the value obtained according to JIS K 7209.
The glass transition temperature (Tg) of resin base material is preferably less than 170 DEG C.By using such resin base material, can
To suppress the crystallization of PVA resins, and can fully ensure the draftability of layered product.And then, if considering using water
The plasticized of resin base material and enter well in water-filling stretch, then more preferably less than 120 DEG C.In 1 implementation method, tree
The glass transition temperature of aliphatic radical material is preferably more than 60 DEG C.By using such resin base material, will be comprising above-mentioned PVA systems tree
When the coating fluid of fat is coated and dries, resin base material deformation (such as the generation of concavo-convex, lax, fold etc.) etc. is prevented from
Unfavorable condition, can well make layered product.Furthermore it is possible to be carried out well at suitable temperature (such as 60 DEG C or so)
The stretching of PVA resins.In other embodiments, when the coating fluid comprising PVA systems resin being coated and dried, only
Want resin base material indeformable, then can also be less than 60 DEG C of glass transition temperature.It should be noted that the glass of resin base material
Glass transition temperature for example can by using formed material in import modified group, crystallised material and heated from
And adjust.Glass transition temperature (Tg) is the value obtained according to JIS K 7121.
Thickness before the stretching of resin base material is preferably 20 μm~300 μm, more preferably 50 μm~200 μm.Less than 20 μm
When, the formation for having PVA resins becomes difficult worry.During more than 300 μm, such as in being stretched in water, there is resin base material to inhale
Receiving water needs the long period, and stretching needs the worry of excessive load.
As the PVA systems resin for forming above-mentioned PVA resins, can be using any appropriate resin.Can for example lift
Go out polyvinyl alcohol, ethylene-vinyl alcohol copolymer.Polyvinyl alcohol is by by obtained from saponifying polyvinyl acetate.Ethene-second
Enol copolymer is by by obtained from vinyl-vinyl acetate copolymer saponification.The saponification degree of PVA systems resin is usually 85
Mole %~100 mole %, preferably 95.0 moles %~99.95 mole %, more preferably 99.0 moles %~99.93
Mole %.Saponification degree can be obtained according to JIS K 6726-1994.By using the PVA systems resin of such saponification degree, can
To obtain the light polarizing film of excellent in te pins of durability.When saponification degree is too high, there is the worry that gelation occurs.
The average degree of polymerization of PVA systems resin can suitably be selected according to purpose.Average degree of polymerization is usually 1000~
10000, preferably 1200~5000, more preferably 1500~4500.It should be noted that average degree of polymerization can foundation
JIS K 6726-1994 and obtain.
Above-mentioned coating fluid is typically above-mentioned PVA systems resin is dissolved in the solution of solvent.As solvent, for example
Can enumerate：Water, dimethyl sulfoxide (DMSO), dimethylformamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, various glycols, three
The amines such as the polyalcohols such as hydroxymethyl-propane, ethylenediamine, diethylenetriamine.They can be used alone, or combine two or more
Use.Wherein, preferably water.The PVA systems resin concentration of solution is preferably 3 weight portion~20 weights relative to 100 parts by weight solvent
Amount part.If such resin concentration, then the uniform coated film closely sealed with resin base material can be formed.
Additive can be compounded in coating fluid.As additive, for example, can enumerate plasticizer, surfactant etc..
As plasticizer, for example, can enumerate the polyalcohols such as ethylene glycol, glycerine.As surfactant, for example, can enumerate nonionic
Surfactant.These additives can be to further improve uniformity, dyeability, the stretching of gained PVA resins
Property and use.In addition, as additive, such as easy bonding composition can be enumerated.By using easy bonding composition, can improve
The adaptation of resin base material and PVA resins.As a result, it is bad from base material stripping etc. for example to suppress PVA resins
Situation, can carry out being stretched in aftermentioned dyeing, water well.
As above-mentioned easy bonding composition, for example, can use the modified PVAs such as acetoacetyl modified PVA.As acetyl second
Acyl modified PVA, it may be preferred to use the polymer at least with the repeat unit shown in following logical formula (I)s.
In above-mentioned formula (I), ratios (modified degree) of the n relative to l+m+n is preferably 1%~10%.
The saponification degree of acetoacetyl modified PVA is preferably 97 moles of more than %.In addition, the 4 of acetoacetyl modified PVA
The pH of the weight % aqueous solution is preferably 3.5~5.5.
Modified PVA is preferably added with more than the 3 weight % of the overall weight of PVA systems resin contained in above-mentioned coating fluid
Plus, more preferably more than 5 weight %.On the other hand, the addition of the modified PVA is preferably below 30 weight %.
As the coating method of coating fluid, can be using any appropriate method.Can for example enumerate：Rolling method, spin coating
Method, bar rubbing method, dip coating, die coating method, curtain coating, spraying process, scraper for coating method (comma rubbing method etc.) etc..
Coating/the drying temperature of above-mentioned coating fluid is preferably more than 50 DEG C.
Thickness before the stretching of PVA resins is preferably 3 μm~40 μm, is preferably 5 μm~20 μm.
Before PVA resins are formed, surface treatment (such as sided corona treatment etc.) can be implemented to resin base material, it is also possible to
Adhesive layer is formed on resin base material.Wherein, it is preferably formed as adhesive layer (coating process).As the material for forming adhesive layer
Material, for example, can use acrylic resin, polyvinyl alcohol resin etc., particularly preferred polyvinyl alcohol resin.As poly- second
Enol system resin, for example, can enumerate polyvinyl alcohol resin and its modifier.As the modifier of polyvinyl alcohol resin, Ke Yiju
Go out above-mentioned acetoacetyl modified PVA.It should be noted that the thickness of adhesive layer is preferably set to 0.05~1 μm or so.Pass through
Such treatment is carried out, the adaptation of resin base material and PVA resins can be improved.As a result, can for example suppress PVA systems
Resin bed from base material peel off a problem that, can carry out stretching in aftermentioned dyeing, water well.
The water contact angle of the resin base material side surface of layered product is usually 60 °~80 °, for example, 65 °~75 °.Water is contacted
Angle is determined using sessile drop method.
A-2. the stretching of layered product
As the drawing process of layered product, can be using any appropriate method.Specifically, can be drawn for fixing end
Stretch, or free end stretching (for example by layered product between the different roller of peripheral speed by carrying out the side of uniaxial tension
Method).Preferably free end stretching.
The draw direction of layered product can suitably set.In 1 implementation method, along the length of the layered product of strip
Direction is stretched.In the case of above-mentioned, typically using by layered product between the different roller of peripheral speed by being drawn
The method stretched.In other embodiments, stretched along the width of the layered product of strip.In the case of above-mentioned, generation
Method of the table ground using being stretched using tentering stretching-machine.
Stretching mode is not particularly limited, can be aerial stretching mode, or stretching mode in water.Preferably
Stretching mode in water.Using stretching mode in water, can be in the glass transition less than above-mentioned resin base material, PVA resins
Stretched at a temperature of temperature (being typically 80 DEG C or so), for PVA resins, its crystallization can be suppressed, and
And stretched with high magnification.As a result, the light polarizing film with excellent optical characteristics can be made.
The stretching of layered product can be carried out with a stage, it is also possible to be carried out with the multistage.When being carried out with the multistage, for example may be used
Stretched with combining above-mentioned free end stretching and fixing end, it is also possible to combine stretching mode and aerial stretching mode in above-mentioned water.Separately
Outward, when being carried out with the multistage, the stretching ratio (maximum tension multiplying power) of aftermentioned layered product is the product of the stretching ratio in each stage.
The draft temperature of layered product can be set as any appropriate according to formation material, stretching mode of resin base material etc.
Value.During using aerial stretching mode, draft temperature is preferably more than the glass transition temperature of resin base material (Tg), further
Preferably more than+10 DEG C, particularly preferably more than Tg+15 DEG C of the glass transition temperature (Tg) of resin base material.On the other hand, layer
The draft temperature of stack is preferably less than 170 DEG C.By being stretched at such temperatures, PVA systems resin can be suppressed
Crystallization is quickly propelled, and can suppress (for example to hinder the PVA systems tree carried out using stretching by unfavorable condition caused by the crystallization
The orientation of lipid layer).
Using during stretching mode, the liquid temperature of stretch bath is preferably 40 DEG C~85 DEG C, more preferably 50 DEG C~85 DEG C in water.Such as
Fruit is such temperature, then can suppress the dissolving of PVA resins, and stretched with high magnification.Specifically, as described above
Like that, the glass transition temperature (Tg) of resin base material has relation, preferably more than 60 DEG C with the formation of PVA resins.On
In the case of stating, when draft temperature is less than 40 DEG C, even if considering the plasticized using the resin base material of water, also have to enter well
The worry of row stretching.On the other hand, the temperature of stretch bath is higher, and the dissolubility of PVA resins is higher, and having cannot obtain excellent
Optical characteristics worry.Dip time of the layered product in stretch bath is preferably 15 seconds~5 minutes.
Impregnated in boric acid aqueous solution to be stretched (in boric acid water using layered product is made in water during stretching mode, preferably
Stretching).By using boric acid aqueous solution as stretch bath, what is applied when can assign resistance to Tensile to PVA resins opens
The rigidity of power and it is not dissolved in the water resistance of water.Specifically, boric acid can generate in aqueous tetrahydroxy boric acid it is cloudy from
Son, is crosslinked with PVA systems resins by hydrogen bond.As a result, rigidity and water resistance can be assigned to PVA resins, well
Stretched, the light polarizing film with excellent optical characteristics can be made.
Above-mentioned boric acid aqueous solution is preferably obtained by being dissolved in boric acid and/or borate as the water of solvent.Boric acid
Concentration is preferably 1 weight portion~10 weight portion relative to 100 weight portion water.It is set to more than 1 weight portion by by boric acid concentration, can
Effectively to suppress the dissolving of PVA resins, the light polarizing film of characteristic higher can be made.It should be noted that can also make
With water obtained from the boron compounds such as borax, glyoxal, glutaraldehyde etc. also are dissolved in into solvent in addition to boric acid or borate
Solution.
By aftermentioned dyeing, when being adsorbed with dichroic substance (being typically iodine) on PVA resins in advance, preferably
The compounding iodide in above-mentioned stretch bath (boric acid aqueous solution).By being compounded iodide, can suppress to be adsorbed in PVA resins
Iodine dissolution.As iodide, for example, can enumerate：KI, lithium iodide, sodium iodide, zinc iodide, silver iodide, lead iodide,
Cupric iodide, barium iodide, calcium iodide, stannic iodide, titanium iodide etc..Wherein, preferably KI.The concentration of iodide is relative to 100
Weight portion water is preferably 0.05 weight portion~15 weight portion, more preferably 0.5 weight portion~8 weight portion.
The stretching ratio (maximum tension multiplying power) of layered product is preferably more than 5.0 times relative to the raw footage of layered product.This
The stretching ratio high of sample can for example be realized by using stretching mode in water (being stretched in boric acid water).It should be noted that
In this specification, " maximum tension multiplying power " refers to the stretching ratio before layered product will be broken, in addition, referring to confirm that layered product breaks
Stretching ratio, lower than its value 0.2 value split.
In a preferred embodiment, above-mentioned layered product is stretched in the air under high temperature (such as more than 95 DEG C), so
After carry out stretching and aftermentioned dyeing in above-mentioned boric acid water.Such aerial stretching can be orientated as pre- for what is stretched in boric acid water
Standby stretching or assisting tension, therefore hereinafter referred to as " aerial assisting tension ".
By combining aerial assisting tension, layered product can be stretched with more high magnification sometimes.As a result, can make having
The light polarizing film of more excellent optical characteristics (such as degree of polarization).For example, using poly terephthalic acid second as above-mentioned resin base material
During diol ester system resin, compared with stretching carries out stretching in only passing through boric acid water, drawing in aerial assisting tension and boric acid water is combined
When stretching, stretched while resin base material orientation can be suppressed.With the raising of its orientation, tensile stress becomes big to the resin base material,
The stretching of stabilization becomes difficult or is broken.Therefore, stretched with being orientated by suppressing resin base material, can be with more high power
Rate stretches layered product.
In addition, by combining aerial assisting tension, the orientation of PVA systems resin can be improved, thus, drawn in boric acid water
The orientation of PVA systems resin can also be improved after stretching.Specifically, thus it is speculated that as follows：Carried by advancing with aerial assisting tension
The orientation of PVA systems high resin, PVA systems resin becomes easily to be crosslinked with boric acid when being stretched in boric acid water, turns into boric acid and connects
Stretched in the state of contact, so as to the orientation of PVA systems resin after being stretched in boric acid water is also high.As a result, can make
Make the light polarizing film with excellent optical characteristics (such as degree of polarization).
Stretching ratio in aerial assisting tension is preferably less than 3.5 times.The draft temperature of aerial assisting tension is preferably
It is more than the glass transition temperature of PVA systems resin.Draft temperature is preferably 95 DEG C~150 DEG C.It should be noted that combination is aerial
In assisting tension and above-mentioned boric acid water stretch when maximum tension multiplying power relative to the raw footage of layered product be preferably 5.0 times with
Above, more preferably more than 5.5 times, more preferably more than 6.0 times.
A-3. dye
The dyeing of above-mentioned layered product is next typically by making dichroic substance (preferably iodine) be adsorbed in PVA resins
Carry out.As the adsorption method, for example, can enumerate：PVA resins (layered product) are made to impregnated in the dyeing liquor comprising iodine
Method；The method that the dyeing liquor is coated on PVA resins；The dyeing liquor is sprayed to method of PVA resins etc..It is excellent
Elect the method for making layered product impregnated in dyeing liquor as.This is because, iodine can be adsorbed well.
Above-mentioned dyeing liquor is preferably iodine aqueous solution.The compounding amount of iodine relative to 100 weight portion water be preferably 0.1 weight portion~
0.5 weight portion.In order to improve solubility of the iodine in water, iodide are preferably compounded in iodine aqueous solution.The concrete example of iodide
As described above.The compounding amount of iodide is preferably 0.02 weight portion~20 weight portion, is more preferably relative to 100 weight portion water
0.1 weight portion~10 weight portion.For dyeing liquor dyeing when liquid temperature, in order to suppress the dissolving of PVA systems resin, preferably 20
DEG C~50 DEG C.When PVA resins is impregnated in dyeing liquor, for dip time, in order to ensure the transmission of PVA resins
Rate, preferably 5 seconds~5 minutes.Furthermore it is possible to set dyeing condition (concentration, liquid temperature, dip time) so that finally give
The degree of polarization or singleton transmittance of light polarizing film are the scope of regulation.In 1 implementation method, dip time is set, make gained partially
The degree of polarization of light film is more than 99.98%.In other embodiments, dip time is set, makes the monomer of gained light polarizing film saturating
It is 40%~44% to cross rate.
Dyeing treatment can be carried out under any appropriate opportunity.When stretch in above-mentioned water, stretched preferably in water
Before carry out.
A-4. other treatment
Above-mentioned layered product can also be appropriately carried out for its PVA resin to be made into polarisation in addition to stretching, dyeing
The treatment of film.As the treatment for being made light polarizing film, for example, can enumerate insoluble treatment, crosslinking Treatment etc..Need explanation
, these number of processing, order etc. are not particularly limited.
Above-mentioned insoluble treatment is carried out typically by PVA resins impregnated in boric acid aqueous solution.Pass through
Implement insoluble treatment, water resistance can be assigned to PVA resins.The concentration of the boric acid aqueous solution is relative to 100 weight portions
Water is preferably 1 weight portion~4 weight portion.The liquid temperature of insoluble bath (boric acid aqueous solution) is preferably 20 DEG C~50 DEG C.Insoluble place
Reason stretching, above-mentioned dyeing before processing preferably in above-mentioned water are carried out.
Above-mentioned crosslinking Treatment is carried out typically by PVA resins impregnated in boric acid aqueous solution.By reality
Crosslinking Treatment is applied, water resistance can be assigned to PVA resins.The concentration of the boric acid aqueous solution is excellent relative to 100 weight portion water
Elect 1 weight portion~5 weight portion as.In addition, when carrying out crosslinking Treatment after above-mentioned dyeing treatment, being preferably further compounded iodate
Thing.By being compounded iodide, the dissolution of the iodine that can suppress to be adsorbed in PVA resins.The compounding amount of iodide is relative to 100
Weight portion water is preferably 1 weight portion~5 weight portion.The concrete example of iodide is as described above.The liquid of crosslinking bath (boric acid aqueous solution)
Temperature is preferably 20 DEG C~60 DEG C.Crosslinking Treatment is preferably carried out before stretching in above-mentioned water.In a preferred embodiment, enter successively
Stretched in row dyeing treatment, crosslinking Treatment and water.
A-5. light polarizing film
Above-mentioned light polarizing film is essentially gas absorption quantity the PVA resin films of dichroic substance.The thickness of light polarizing film is represented
Property ground be less than 25 μm, preferably less than 15 μm, more preferably less than 10 μm, more preferably less than 7 μm, particularly preferably
Less than 5 μm.On the other hand, the thickness of light polarizing film is preferably more than 0.5 μm, more preferably more than 1.5 μm.Light polarizing film is preferably in ripple
Absorption dichroism is shown under any wavelength in 380nm~780nm long.The singleton transmittance of light polarizing film be preferably 40.0% with
Above, more preferably more than 41.0%, more preferably more than 42.0%, particularly preferably more than 43.0%.Light polarizing film it is inclined
Luminosity is preferably more than 99.8%, more preferably more than 99.9%, more preferably more than 99.95%.
B. matting
In matting, make what is obtained in the production process of above-mentioned light polarizing film light polarizing film is laminated with resin base material
Layered product impregnated in the cleaning fluid comprising iodide and be cleaned.The concrete example of iodide is as described above, it is preferred to be KI.
In 1 implementation method, cleaning fluid is potassium iodide aqueous solution.Iodide concentration in cleaning fluid is preferably 0.5 weight %~10 weight
Amount %, it is preferably 0.5 weight %~5 weight %, more preferably 1 weight %~4 weight %.The temperature of cleaning fluid is usually 10 DEG C
~50 DEG C, preferably 20 DEG C~35 DEG C.Dip time is usually 1 second~1 minute, is preferably 10 seconds~1 minute.Cleaning is insufficient
When, separate out boric acid from gained light polarizing film sometimes.
C. drying process
In drying process, cleaning fluid is removed so that the resin base material side table of the layered product cleaned in above-mentioned matting
The adhesion amount of the cleaning fluid on face is 0.005g/m2Below, it is preferably 0.003g/m2Below, it is more preferably 0.002g/m2Hereinafter,
Then the layered product is dried.Will be on resin base material side surface with more than 0.005g/m2Amount be attached with the stacking of cleaning fluid
When body is for dried process, the concavo-convex bad point (such as a diameter of more than 150 μm of concavo-convex bad points) of visual size is produced sometimes.
It should be noted that after matting terminates, in general the time untill for dried process be 60 seconds
Within, in addition, the conveying of layered product due to carrying out at room temperature, therefore without the concern for by caused cleaning fluids such as natural dryings
Change in concentration, but above-mentioned cleaning fluid removal preferably layered product by after cleaner bath immediately (such as within 30 seconds, preferably 15
Within second) carry out.
The removal of above-mentioned cleaning fluid can be carried out using any appropriate method.The removal of cleaning fluid can for example pass through
Wiping the cleaning fluid of the resin base material side surface of above-mentioned layered product or to the surface blowing gas is carried out.
Wiping for cleaning fluid can be carried out using suction roll, except any appropriate Wiping member such as liquid roller, scraper plate.Wipe
Component can be used alone, it is also possible to by a kind of Wiping member using multiple, can also combine two or more Wiping members
Use.Fig. 2 and Fig. 3 are respectively explanation by wiping the drying process of the cleaning fluid of the resin base material side surface of removal layered product
The schematic diagram of one.
During using suction roll (reference picture 2), for example, with the above-mentioned layered product 10 after being impregnated in cleaner bath 100
The mode for conveying and rotating, makes suction roll 20 be contacted with the side surface of resin base material 11 of layered product 10.For suction roll, generation
Table ground, surface is formed by porous materials such as sponge, non-woven fabrics, fabrics.As sponge, polyurethane sponge, rubber can be enumerated
Sponge, polyolefin sponge.Roller diameter is, for example, 80mm~110mm.It should be noted that in figure 110 is conveying roller.
During using except liquid roller (reference picture 2 and Fig. 3), for example, in the way of to clamp above-mentioned layered product 10, making a pair except liquid roller
30 relative configurations.Except the one side of liquid roller 30 rotates with the conveying of above-mentioned layered product 10, while layered product 10 is extruded from positive and negative,
Thus carry out except liquid.It is typically rubber system except liquid roller.In addition, except liquid roller can have crown shape.By with crown shape,
Can equably be carried out except liquid throughout the width of layered product ground.
During using scraper plate 40 (reference picture 3), typically, configure scraper plate 40 so that its front end with it is alongst defeated
The side surface sliding contact of resin base material 11 of the above-mentioned layered product 10 for sending.It is defeated with layered product 10 by so being configured
Send and utilize scraper plate 40 to wipe water from its side surface of resin base material 10.As the formation material of scraper plate, rubber, tree can be enumerated
Fat, metal etc..For scraper plate and the part of above-mentioned layered product sliding contact, from from the viewpoint of avoiding generation scuffing, can fall
Angle is processed as curve shape.
Blowing gas to the resin base material side surface of layered product can be carried out using commercially available blowning installation.Fig. 4 is to say
The bright schematic diagram by blowing of the drying process of the cleaning fluid of the resin base material side surface of gas-removal layers stack.Blow
Device 50 is matched somebody with somebody in the way of air is preferably 25 °~65 ° relative to the spray angle of the side surface of resin base material 11 of layered product 10
Put.The condition of air blowing can suitably set according to species of resin base material etc..The pressure of air is, for example, 20~25KPa.It is empty
The wind speed of gas is, for example, 20~60m/min.It should be noted that example like that, can be applied in combination Wiping member (diagram as shown
For suction roll 20 and except liquid roller 30 in example) and blowning installation 50.
The drying of the layered product after removal cleaning fluid can be by spontaneously dry, blow drying, heat drying, heated-air drying
Carried out Deng any appropriate drying means.Preferably with the heat drying of the heaters such as baking oven 60.Drying temperature is for example
It is 30 DEG C~100 DEG C, preferably 40 DEG C~100 DEG C.Drying time can suitably set according to drying temperature, for example, 10 seconds
~10 minutes.
D. optical laminate
The optical laminate of the invention obtained by above-mentioned drying process possesses resin base material and is formed at its one side
Light polarizing film.Optical laminate of the invention typically coils into web-like using devices for taking-up, for keeping or in layered product
Operation of light polarizing film side stacking optical functional film (such as diaphragm) etc..Optical laminate of the invention as noted previously, as
It is dried in the state of the attachment of the cleaning fluid on resin base material side surface is reduced, so on resin base material side surface
The precipitation of iodide can be suppressed.Even if as a result, when gained optical laminate is coiled into web-like, it is also possible to suppress by analysing
Go out the deformation (as the result of the deformation, causing concavo-convex bad point) of light polarizing film caused by thing.
The optical functional film layered product for being laminated with optical functional film (has [resin base material/light polarizing film/optical function
Film] structure) Polarizer can be directly used as.Or, it is also possible to resin base material is peeled off from the optical functional film layered product,
Other optical functional films (such as diaphragm) are laminated in the release surface, there is [optical functional film/light polarizing film/light
Learn function film] structure Polarizer.
Embodiment
Hereinafter, the present invention is specifically described by embodiment, but the present invention is not limited to these embodiments.Need explanation
It is that the assay method of each characteristic is as described below.
1. thickness
It is measured using digital micrometer (manufacture of ANRITSU Co., Ltd., ProductName " KC-351C ").
2. glass transition temperature (Tg)
It is measured according to JIS K 7121.
3. water contact angle
Automatic contact angle meter DM500 is manufactured using consonance interface science Co., Ltd. to be measured, use FAMAS (contacts
Angle determines Add-ons) it is analyzed.
4. the evaluation of concavo-convex bad point
32 inches of TV (models that SHARP is manufactured：LC32-SC1) and Panasonic manufacture 32 inches of TV (types
Number：THL32C3 backlight side) and the light polarizing film stripping depending on recognizing side, instead of the light polarizing film, using adhesive is by embodiment or compares
The optical laminate obtained in example is pasted on backlight side and depending on recognizing side.Lighted in darkroom liquid crystal display device be black show
Show state, counting regards the bright spot number that the major diameter recognized in region is as more than 150 μm.
5. the measure of the amount of moisture of the resin base material side surface of layered product
Make suction roll that certain hour is contacted with the resin base material side surface of layered product, absorb moisture, then gravimetry, root
The amount of moisture of per unit area is determined according to the variable quantity of weight.
[embodiment 1]
As resin base material, strip and water absorption rate 0.60%, Tg80 DEG C, the noncrystalline of elastic modelling quantity 2.5GPa are used
Polyethylene terephthalate (A-PET) film (Mitsubishi chemical Co., Ltd's manufacture, trade name " NOVA CLEAR ", thickness：
100μm)。
One side to resin base material implements sided corona treatment (treatment conditions：55W·min/m2), at 60 DEG C, will be comprising poly-
Vinyl alcohol (degree of polymerization 4200,99.2 moles of % of saponification degree) 90 weight portions and the acetoacetyl modified PVA (degree of polymerization 1200, second
The modified degree 4.6%, 99.0 moles of more than % of saponification degree of acyl acetyl group, the Nippon Synthetic Chemical Industry Co., Ltd's manufacture, trade name
" Gohsefimer Z200 ") 10 weight portions the aqueous solution coat the sided corona treatment face and dry, formed 10 μm of thickness PVA
Resin, makes layered product.The water contact angle of the resin base material side surface of gained layered product is 60 °.
By gained layered product in 120 DEG C of baking oven, between the different roller of peripheral speed, along longitudinal direction (length direction) certainly
By end uniaxial tension (aerial assisting tension) to 1.8 times.
Then, the insoluble bath for making layered product impregnated in 30 DEG C of liquid temperature (is compounded 4 part by weight of boric acid for 100 weight portion water
Obtained from boric acid aqueous solution) 30 seconds (insoluble treatment).
Then, the dye bath that it impregnated in 30 DEG C of liquid temperature is made (for iodine, compounding that 100 weight portion water are compounded 0.2 weight portion
Iodine aqueous solution obtained from the KI of 1.0 weight portions) 60 seconds (dyeing treatment).
Then, its crosslinking bath that impregnated in 30 DEG C of liquid temperature is made (to be compounded the KI of 3 weight portions for 100 weight portion water, match somebody with somebody
Boric acid aqueous solution obtained from the boric acid of mixed 3 weight portions) 30 seconds (crosslinking Treatment).
Then, layered product is made while the boric acid aqueous solution that impregnated in 70 DEG C of liquid temperature (is compounded 4 weight for 100 weight portion water
The boric acid of part, the aqueous solution obtained from the KI of 5 weight portions of compounding), while along longitudinal direction between the different roller of peripheral speed
(length direction) carries out uniaxial tension (being stretched in water).Herein, (maximum is drawn untill before layered product will be broken to carry out stretching
Multiplying power is stretched for 6.0 times).
Then, layered product is made to impregnated in the cleaner bath of 30 DEG C of liquid temperature (for the iodate that 100 weight portion water are compounded 4 weight portions
The aqueous solution obtained from potassium) (cleaning treatment).
Then, as shown in Figure 2, the cleaning fluid of the resin base material side surface of removal layered product.Specifically, one is used
To rubber system except liquid roller, carry out the layered product that self-cleaning bath conveying comes except liquid, then, with the resin base material side with layered product
The mode of surface contact configures 3 suction rolls and (is formed by polyurethane sponge materialRoller), with layered product
Convey and rotate roller, so as to wipe cleaning fluid.
Afterwards, layered product is conveyed in 60 DEG C of baking oven to being maintained, is heated 5 minutes, make the light polarizing film with 5 μm of thickness
Optical laminate.Then, gained optical laminate devices for taking-up is coiled into web-like.It should be noted that just removing
On the resin base material side surface of the layered product after cleaning fluid (just by the 3rd to after damping roller) amount of moisture (cleaning fluid it is attached
The amount of wearing) it is 0.0016g/m2。
[embodiment 2]
The cleaning fluid of the resin base material side surface of layered product is removed using blowning installation instead of suction roll, in addition, with
Embodiment 1 is similarly operated, and makes optical laminate, and web-like is coiled into devices for taking-up.The removal of cleaning fluid is specifically such as
Hereinafter carry out like that.That is, using a pair of rubber systems except liquid roller, carry out the layered product that self-cleaning bath conveying comes except liquid, then,
The distance for being about 45 ° and jet and the surface relative to the resin base material side surface of layered product with the spray angle of air is about
For the mode of 2cm configures blowning installation (Hitachi Industrial Equipment Systems Co., Ltd. manufacture, product
Product number " VB-060-E2 "), spray air.The pressure of air is 23kPa.In addition, the wind speed of air is 30m/min.Need
It is bright, just remove the amount of moisture (cleaning of the resin base material side surface of the layered product of (after just spraying air) after cleaning fluid
The adhesion amount of liquid) it is 0.0045g/m2。
[comparative example 1]
Carry out, except liquid, the removal of further cleaning fluid not being carried out afterwards using except liquid roller, and layered product is delivered to baking
In case, in addition, operate similarly to Example 1, make optical laminate, web-like is coiled into devices for taking-up.Will be defeated
The amount of moisture (adhesion amount of cleaning fluid) for delivering to the resin base material side surface of the layered product before baking oven is 0.0064g/m2。
The evaluation of the concavo-convex bad point in each embodiment and comparative example is shown in table 1.It should be noted that panel is depending on recognizing region
In quality evaluated according to following benchmark.
[metewand]
Well：When lighting liquid crystal display device in darkroom and being black display state, there is no major diameter in region depending on recognizing
It is more than 150 μm bright spots.
It is bad：When lighting liquid crystal display device in darkroom and being black dispaly state, regard and recognize in region that to have major diameter be 150
Bright spot more than μm.
[table 1]
As shown in table 1, regulation is reduced to by the adhesion amount of the cleaning fluid on the resin base material side surface by layered product
Scope in the state of dry layered product, such that it is able to reduce concavo-convex bad point.
Industrial applicability
Optical laminate of the invention can be suitable as LCD TV, liquid crystal display, mobile phone, digital camera, number
The liquid crystal panel of video camera, portable game, automated navigation system, duplicator, printer, facsimile machine, clock and watch, electric stove etc., have
The antireflection film of machine EL devices.
Claims (7)
1. a kind of manufacture method of the optical laminate that light polarizing film is laminated with resin base material,
The manufacture method includes following operation：
Layered product with resin base material and the unilateral polyvinyl alcohol resin layer for being formed at the resin base material is stretched
And dyeing, so as to make the operation of light polarizing film on the resin base material；
The layered product is set to impregnated in the operation that the cleaning fluid comprising iodide is cleaned；And
Removal cleaning fluid so that the adhesion amount of the cleaning fluid on the resin base material side surface of the layered product is 0.005g/m2With
Under, then by the dry operation of the layered product.
2. manufacture method according to claim 1, wherein, the water contact angle of the resin base material side surface of the layered product is
60 °~80 °.
3. manufacture method according to claim 1, wherein, the thickness of the light polarizing film is 0.5 μm~15 μm.
4. manufacture method according to claim 1, wherein, iodide concentration in the cleaning fluid for 0.5 weight %~
10 weight %.
5. manufacture method according to claim 1, wherein, the stretching includes stretching in water.
6. manufacture method according to claim 1, wherein, cleaning fluid on the resin base material side surface of the layered product
Removal is carried out by wiping or blowing gas.
7. a kind of optical laminate, it is by obtained from the manufacture method described in claim 1.
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| JP2013265171A JP5961158B2 (en) | 2013-12-24 | 2013-12-24 | Method for producing optical laminate |
| JP2013-265171 | 2013-12-24 |
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| JP (1) | JP5961158B2 (en) |
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| JP7055662B2 (en) * | 2017-03-03 | 2022-04-18 | 住友化学株式会社 | Film manufacturing equipment and film manufacturing method |
| JP6434186B1 (en) * | 2018-05-08 | 2018-12-05 | 住友化学株式会社 | Laminated body and method for producing the same |
| CN110125563A (en) * | 2019-04-30 | 2019-08-16 | 大族激光科技产业集团股份有限公司 | A method of except polarizing film iodine molecule layer |
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|---|---|---|---|---|
| CN1826542A (en) * | 2003-04-21 | 2006-08-30 | 日东电工株式会社 | Polarizer, method for producing the same, polarizing plate, optical film and image display |
| CN102385088A (en) * | 2010-09-03 | 2012-03-21 | 日东电工株式会社 | Method and apparatus for sequentially laminating optical film including polarizing film, to rectangular-shaped panel |
| CN103080793A (en) * | 2010-09-03 | 2013-05-01 | 日东电工株式会社 | Adhesive optical film, manufacturing method for same and image display device |
| CN103080791A (en) * | 2010-09-03 | 2013-05-01 | 日东电工株式会社 | Method of producing thin polarizing film |
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| JP4293543B2 (en) * | 2003-04-21 | 2009-07-08 | 日東電工株式会社 | Polarizer, production method thereof, polarizing plate, optical film, and image display device |
| TWI272409B (en) * | 2005-02-04 | 2007-02-01 | Optimax Tech Corp | Polarizing film and its manufacturing method |
| JP2008134270A (en) * | 2006-10-27 | 2008-06-12 | Nitto Denko Corp | Liquid crystal panel and liquid crystal display apparatus |
| JP4774004B2 (en) * | 2007-03-30 | 2011-09-14 | 富士フイルム株式会社 | Cleaning method and apparatus for web-like object to be cleaned |
| JP5361941B2 (en) * | 2010-09-03 | 2013-12-04 | 日東電工株式会社 | Method for producing laminate strip roll having polarizing film |
| JP5782297B2 (en) * | 2010-09-09 | 2015-09-24 | 日東電工株式会社 | Manufacturing method of thin polarizing film |
| JP5685222B2 (en) * | 2012-06-06 | 2015-03-18 | 日東電工株式会社 | Polarizing film containing modified PVA and optical laminate having the polarizing film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1826542A (en) * | 2003-04-21 | 2006-08-30 | 日东电工株式会社 | Polarizer, method for producing the same, polarizing plate, optical film and image display |
| CN102385088A (en) * | 2010-09-03 | 2012-03-21 | 日东电工株式会社 | Method and apparatus for sequentially laminating optical film including polarizing film, to rectangular-shaped panel |
| CN103080793A (en) * | 2010-09-03 | 2013-05-01 | 日东电工株式会社 | Adhesive optical film, manufacturing method for same and image display device |
| CN103080791A (en) * | 2010-09-03 | 2013-05-01 | 日东电工株式会社 | Method of producing thin polarizing film |
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| CN104730611A (en) | 2015-06-24 |
| TW201527809A (en) | 2015-07-16 |
| TWI570462B (en) | 2017-02-11 |
| JP2015121658A (en) | 2015-07-02 |
| KR101703504B1 (en) | 2017-02-07 |
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