CN107003467B - The manufacturing method of polarizing coating - Google Patents
The manufacturing method of polarizing coating Download PDFInfo
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- CN107003467B CN107003467B CN201680004123.XA CN201680004123A CN107003467B CN 107003467 B CN107003467 B CN 107003467B CN 201680004123 A CN201680004123 A CN 201680004123A CN 107003467 B CN107003467 B CN 107003467B
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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
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Abstract
The present invention provides a kind of manufacturing method of polarizing coating, is the manufacturing method for the polarizing coating that polarizing coating (23) is made by polyvinyl alcohol resin film (10), which includes:Dipping process makes the polyvinyl alcohol resin film immersion in the treatment fluid being housed in treatment trough (13,15,17,19);Transportation process makes to be impregnated in the polyvinyl alcohol resin film in the treatment fluid and is carried along roller;And roller cleaning process, the surface of the roller (32,35,38,41,51,52,53,54) is cleaned with roller cleaning solution.
Description
Technical field
The present invention relates to a kind of manufacturing methods for the polarizing coating that can be used as the member of formation of polarization plates.
Background technology
As polarizing coating, in the past always using the polyvinyl alcohol resin film absorption iodine or dichroism made by being uniaxially stretched
The dichroism pigment of dyestuff etc and the polarizing coating of orientation.Polarizing coating is usually protected in its one or both sides using adhesive fitting
Cuticula and polarization plates are made, for being with the liquid crystal display device of LCD TV, PC monitor and portable phone etc.
In the image display device of representative.
In general, polarizing coating is implemented successively by the polyvinyl alcohol resin film of the long size to continuously being carried
It is impregnated in handling the processing in bath while implementing during these a series of processing for swelling bath, dye bath, crosslinking bath etc
Stretch processing and manufacture (such as patent document 1).
Existing technical literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 2015-11151 bulletins
Invention content
Problem to be solved by the invention
Polarizing coating can be by continuously rolling out film from the former material reel of polyvinyl alcohol resin film (winding product)
Meanwhile the roller of polyvinyl alcohol resin layer is carried in configuration in the transport path between various processing baths as described above, and by with
The mode for pulling out and being impregnated in next processing bath after polyvinyl alcohol resin layer is impregnated in a processing bath is carried, and
Continuous manufacture.
But if observation is using the polarizing coating continuously produced, there will be generate to adhere to dirt etc. on its surface
The case where defect.The reason of defect, is studied, as a result, it has been found that one of reason is, the carrying between being configured at processing bath
The surface of roller in path is attached to the treatment fluid in the processing bath that polyvinyl alcohol resin film is brought into, because of the salt in treatment fluid
Deng precipitation etc., the surface of roller is contaminated.Because the roller being contaminated by surface is carried, and the oriented polyvinyl alcohol resin film of meeting
The case where surface transfer dirt.In particular, the treatment fluid in dye bath or crosslinking bath is that salt is made to dissolve and prepare, therefore by poly- second
The pollution on the surface of roller caused by treatment fluid in the processing bath that enol resin film is brought into be easy in order to from dye bath or
The surface of roller for pulling out polyvinyl alcohol resin film in crosslinking bath and configuring generates.In addition, polyvinyl alcohol resin film is hydrophilic
Property, the state being swollen by treatment fluid is immediately become after being pulled out in being bathed from processing, therefore easy to produce turn of the dirt of roller surface
Deformation caused by the dirt of print or roller surface.In addition it is easy roller surface due to the dissolved element from polyvinyl alcohol resin film
Pollution.
Thus, the object of the present invention is to provide a kind of method, this method inhibits removing between being configured at various processing baths
The pollution for transporting the surface of the roller of the carrying polyvinyl alcohol resin film in path, so as to manufacture the surface defects such as dirt attachment
The polarizing coating that is inhibited of generation.
The method for solving problem
The present invention provides the manufacturing method of polarizing coating as shown below.
[1] a kind of manufacturing method of polarizing coating is by the manufacture of the polarizing coating of polyvinyl alcohol resin film production polarizing coating
Method has:
Dipping process makes the polyvinyl alcohol resin film immersion in the treatment fluid being housed in treatment trough;
Transportation process makes to be impregnated in the polyvinyl alcohol resin film in the treatment fluid and is carried along roller;And
Roller cleaning process cleans the surface of the roller with roller cleaning solution.
[2] according to the manufacturing method of the polarizing coating described in [1], wherein in the roller cleaning process, as the roller
Cleaning solution uses the treatment fluid.
[3] according to the manufacturing method of the polarizing coating described in [2], wherein the roller cleaning solution is in the roller cleaning process
After be recycled in the treatment trough.
[4] manufacturing method for the polarizing coating recorded according to any one of [1]~[3], wherein the dipping process is to make institute
State the dyeing treatment process or make the poly- second that polyvinyl alcohol resin film immersion dyes in dyeing liquor and with dichroism pigment
Enol resin film is impregnated in crosslinked fluid and carries out crosslinked crosslinking Treatment process.
[5] manufacturing method for the polarizing coating recorded according to any one of [1]~[4], wherein the roller cleaning process includes
The process of the roller cleaning solution is exported to the surface of the roller or the surface of the roller is made to be impregnated in the work in the roller cleaning solution
Sequence.
Invention effect
According to the method for the present invention, in the continuous manufacture of polarizing coating, the transport road being configured between processing bath can be inhibited
The surface of roller in diameter is contaminated, so as to manufacture the polarizing coating that the surface defects such as dirt attachment are inhibited.
Description of the drawings
Fig. 1 is in the manufacturing method and the manufacturing method of the polarizing coating for schematically showing the first embodiment of the present invention
The sectional view of an example of polarization film manufacturing device used.
Fig. 2 is the stereogram of an example for the relationship for indicating niproll and spray thrower shown in FIG. 1.
Fig. 3 is in the manufacturing method and the manufacturing method of the polarizing coating for schematically showing second embodiment of the present invention
The sectional view of an example of polarization film manufacturing device used.
Fig. 4 is the chart of the measurement result of the boric acid content for the first crosslinking bath for indicating embodiment 2 and comparative example 2.
Fig. 5 is the chart of the measurement result of the boric acid content for the second crosslinking bath for indicating embodiment 2 and comparative example 2.
Specific implementation mode
The manufacturing method > of < polarizing coatings
In the present invention polarizing coating be through absorption dichroism pigment on the polyvinyl alcohol resin film that being uniaxially stretched (iodine or
Dichroic dye) and be orientated film.The polyvinyl alcohol resin for constituting polyvinyl alcohol resin film is typically to pass through poly- acetic acid
The resin saponification of vinyl acetate system and obtain.Its saponification degree is typically about 85 moles of % or more, preferably from about 90 moles of % or more, more excellent
It is selected as about 99 moles of % or more.Polyvinyl acetate system resin for example can be the poly- acetic acid of the homopolymer as vinyl acetate
Vinyl acetate can also be the copolymer etc. of vinyl acetate and other monomers that can be copolymerized therewith in addition.As can be copolymerized
Other monomers, for example, unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class etc..Polyvinyl alcohol
It is that the degree of polymerization of resin is typically about 1000~10000, preferably from about 1500~5000 or so.
These polyvinyl alcohol resins can also be modified, such as can also use the polyvinyl alcohol contracting being modified by aldehydes
Formaldehyde, polyvinyl acetal, polyvinyl butyral etc..
The use of thickness is 65 μm or less (such as 60 μm or less), excellent as the starting material of polarizing coating manufacture in the present invention
It is selected as 50 μm or less, more preferably 35 μm or less, further preferably 30 μm of non-stretched polyvinyl alcohol resin films below
(former material film).Thus it can be obtained by the polarizing coating of the increasing film of the market demand.Former material film can also be in advance in gas
The polyvinyl alcohol resin film of stretch processing has been carried out in phase.
The width of former material film is not particularly limited, such as can be 400~6000mm or so, however film width is bigger,
The trend for more easy ting produce film fracture is had when stretch processing.
Former material film is accurate by the reel (former material reel) of the non-stretched polyvinyl alcohol resin film as long size in the present invention
It is standby.
Polarizing coating can be by while rolling out the former material film of above-mentioned long size, along polarization from former material reel
The film transport path of film manufacturing device continuously carries and implements given treatment process and the polarizing coating as long size is continuous
Manufacture.Given treatment process has:Former material film is set to be impregnated in the treatment fluid (following also referred to as " processing being housed in treatment trough
Bath ") in dipping process and make from processing bathe in the transportation process carried along roller of the former material film that pulls out.To different processing
Such dipping process and transportation process is repeated in bath, and produces polarizing coating.
In the present invention, with for by polyvinyl alcohol resin film production polarizing coating dipping process and transportation process together with,
It is also equipped with the roller cleaning process that the roller for carrying the former material film pulled out from processing bath is cleaned with roller cleaning solution.The roller cleaning process is excellent
It is simultaneously carried out when being selected in the continuous manufacture of polarizing coating.The present invention can prevent from carrying former material film because having roller cleaning process
Roller surface pollution, can prevent due to the pollution the reason of the defects of surface of polarizing coating generates dirt attachment.
As roller cleaning solution, other than pure water, can also use and the processing that is contained in the adjacent treatment trough in front
The identical treatment fluid of liquid is, it is preferable to use treatment fluid.Treatment fluid is used by being used as roller cleaning solution, even if in the polyethylene being handled upside down
In the case that alcohol resin film is in direct contact with roller cleaning solution, and in the polyvinyl alcohol resin film being handled upside down and it is attached to roller
In the case of the roller cleaning solution contact on surface, it is also possible to prevent to carry out defect to polyvinyl alcohol resin film strips.It is cleaned as roller
In the case that liquid uses treatment fluid, it is preferably provided with after roller cleaning process and treatment fluid is recovered in the adjacent treatment trough in front
Mechanism.In the case where not using treatment fluid as roller cleaning solution, when roller cleaning solution is contacted with polyvinyl alcohol resin film, gather
Treatment fluid concentration on vinyl alcohol resin film will change, it is possible to produce it is uneven the defects of.As a result, as roller cleaning solution
By roller preferably in the way of making that roller cleaning solution is not direct and being contacted with polyvinyl alcohol resin film in the case of without using treatment fluid
Cleaning solution is supplied to roller surface.Additionally, it is preferred that by roller cleaning solution scraper plate for being attached to roller surface etc. according to not with polyvinyl alcohol
The mode of resin film contact recycles.
As above-mentioned dipping process, specifically, can enumerate makes former material film be impregnated in the swelling being housed in swelling slot
Swelling treatment process in liquid (following also referred to as " swelling bath ") makes thereafter the film after being pulled out in being bathed from swelling using transportation process
The dyeing treatment process that is impregnated in the dyeing liquor (also referred to as following " dye bath ") being housed in staining trough makes thereafter using removing
Film immersion of the fortune process after being pulled out in dye bath is in the crosslinked fluid (following also referred to as " crosslinking bath ") being housed in crosslinking slot
Crosslinking Treatment process, make the film immersion after being pulled out in being bathed from crosslinking using transportation process in being housed in Membrane cleaning slot thereafter
Membrane cleaning process etc. in Membrane cleaning liquid (following to be also referred to as " Membrane cleaning bath ").In these a series of dipping process and porter
During sequence (that is, in dipping process more than any one front and back and/or dipping process more than any one), with wet type or
Dry type implementation is uniaxially stretched processing.As needed, other treatment process can also be added.Above-mentioned each dipping process can be
Make processing of the film immersion in 1 slot, the processing that can also be impregnated in successively in 2 or more slots.
Hereinafter, referring to Fig.1~Fig. 3 while, to the present invention polarizing coating manufacturing method be further described.
[first embodiment]
Fig. 1 is in the manufacturing method and the manufacturing method of the polarizing coating for schematically showing the first embodiment of the present invention
The sectional view of an example of polarization film manufacturing device used.Polarization film manufacturing device shown in FIG. 1 is constituted as follows, that is, makes packet
Former material (non-stretched) film 10 containing polyvinyl alcohol resin is alonged film while continuously being rolled out from former material reel 11 and is carried
Path is carried, and is thus allowed to pass sequentially through swelling bath 13, dye bath 15, crosslinking in film transport path and is bathed 17, Yi Jiqing
Bathing 19, finally by drying oven 21.The polarizing coating 23 of gained for example can directly be transported to following polarization plates production process
(in the process that the one or both sides of polarizing coating 23 are bonded protective film).Arrow in Fig. 1 indicates the carry direction of membrane.
Moreover, Fig. 1 shows the examples for going out swelling bath 13, dye bath 15, crosslinking bath 17 and cleaner bath 19 being respectively set 1 slot
Son, however as needed, the processing more than any one can also be bathed to 2 slots of setting or more.In above description " treatment trough "
Be include be swollen slot, staining trough, crosslinking slot and rinse bath general name, " treatment fluid " be include swelling solution, dyeing liquor, crosslinked fluid and
The general name of cleaning solution, " processing bath " are the general names for including swelling bath, dye bath, crosslinking bath and cleaner bath.
The film transport path for polarizing film manufacturing device can be by by above-mentioned processing is bathed, in addition there are can support to be handled upside down
Film or can also change film carry direction deflector roll 30~41,60,61, can squeeze, the film being handled upside down be clamped and to film
The niproll 50~55 for assigning the driving force brought by its rotation or can also changing film carry direction is configured in position appropriate
It sets to build.Deflector roll, niproll can be configured in the front and back or processing bath of each processing bath, be bathed to processing it is possible thereby to carry out film
In importing, dipping and from processing bathe in pull-out (referring to Fig.1).For example, by throughout managing setting 1 or more in bath
Deflector roll carries film along these deflector rolls, so that it may so that film immersion is in each processing bath.
Polarization film manufacturing device shown in FIG. 1 throughout manages the front and back of bath and is configured with niproll (niproll 50~54), by
This, it will be able to is in arbitrary more than one processing bath, between being configured at application difference the niproll before and after it and reality
It applies and stretches between the roller being longitudinally uniaxially stretched.
It is shown in FIG. 1 polarization film manufacturing device according to be configured at it is each processing bath 13,15,17,19 after deflector roll 32,35,
38,41 and the facing mode of niproll 51~54 be equipped with spray thrower 71~78.In the continuous manufacture of polarizing coating, spray is utilized
Device 71~78 cleans deflector roll 32,35,38,41 to deflector roll 32,35,38,41 and the surface outlet roller cleaning solution of niproll 51~54
And the surface (roller cleaning process) of niproll 51~54.Hereinafter, being illustrated to each process.
(swelling treatment process)
Swelling treatment process is for removing the foreign matter on former material film 10 surface, remove plasticizer in former material film 10, assign
The purpose of plasticizing of dyeability and former material film 10 and carry out.Treatment conditions be in the range that these purposes may be implemented,
And it is determined in the range of the not good situations such as extreme dissolving, the devitrification that not will produce former material film 10.
Referring to Fig.1, swelling treatment process can continuously be rolled out former material film 10 from former material reel 11 by one side, and one
Edge the carrying of film transport path, and former material film 10 is impregnated given time in swelling bath 13, then pulls out and implements.Fig. 1's
In example, from former material film 10 is rolled out to during being impregnated in swelling bath 13, former material film 10 is by along by deflector roll 60,61 and clamping
The film transport path that roller 50 is built is carried.In swelling treatment, carried along the film transport path built by deflector roll 30~32.
Swelling solution as swelling bath 13 can also use other than it can use pure water in about 0.01~10 weight
It measures in the range of % and is added to boric acid (Japanese Unexamined Patent Publication 10-153709 bulletins), chloride (Japanese Unexamined Patent Publication 06-
No. 281816 bulletins), the aqueous solution of inorganic acid, inorganic salts, water-miscible organic solvent, alcohols etc..
The temperature of swelling bath 13 is, for example, 10~50 DEG C or so, preferably 10~40 DEG C or so, more preferably 15~30 DEG C
Left and right.The dip time of former material film 10 is preferably 10~300 seconds or so, more preferably 20~200 seconds or so.In addition, in former material
In the case that film 10 is the polyvinyl alcohol resin film stretched in gas in advance, the temperature of swelling bath 13 is, for example, 20
~70 DEG C or so, preferably 30~60 DEG C or so.The dip time of former material film 10 is preferably 30~300 seconds or so, more preferably
60~240 seconds or so.
In swelling treatment, it is easy to lead to the problem of the formation gauffer in film because former material film 10 is swollen in the direction of the width.
As 1 method for carrying film while removing the gauffer, it can enumerate to use as deflector roll 30,31 and/or 32 and relax
That opens up roller, felt windening roll, crowned roll (Network ラ ウ ン ロ ー Le) etc has the roller of broadening function or using guide, roller, drawing
Other broadening devices of cloth pincers etc.It is to implement stretch processing for inhibiting another method of the generation of gauffer.For example, can
To implement to be uniaxially stretched processing in swelling bath 13 using the difference of niproll 50 and niproll 51.
In swelling treatment, since film is also swollen expansion in the carry direction of film, in the drawing for not carrying out active to film
In the case of stretching, in order to eliminate carry direction film relaxation, such as preferably take control configuration swelling bath 13 before and after
The methods of the speed of niproll 50,51.In addition, carrying stabilized purpose for making swelling bathe the film in 13, sprayed in water
Device control swelling bathes the flow in 13 or EPC devices (Edge Position Control devices is used in combination:The end of detection film,
Prevent the device of film wriggled) etc. be also useful way.
In example shown in FIG. 1, from swelling bath 13 film that pulls out pass sequentially through deflector roll 32, niproll 51 and be imported into dye
Color bath 15.
(dyeing treatment process)
Dyeing treatment process is for making the absorption dichroism pigment of the polyvinyl alcohol resin film after swelling treatment and be allowed to
The purpose of orientation and carry out.Treatment conditions are in the range that these purposes may be implemented and not generate the extreme of film
It is determined in the range of the not good situations such as dissolving, devitrification.Referring to Fig.1, dyeing treatment process can be by along by deflector roll 33~35
And the film transport path that niproll 51 is built carries and (is contained in the film after swelling treatment in staining trough in dye bath 15
Treatment fluid) in dipping given time then pull out and implement.In order to improve the dyeability of dichroism pigment, it is supplied at dyeing
The film of science and engineering sequence, which is preferably at least, implements a degree of film for being uniaxially stretched processing, or preferably before substituted dyeing processing
It is uniaxially stretched processing, or being uniaxially stretched other than processing before dyeing processing, carries out being uniaxially stretched processing when dyeing processing.
In the case where using iodine as dichroism pigment, as the dyeing liquor of dye bath 15, concentration can be used for example
Using weight ratio meter as the aqueous solution of iodine/potassium iodide/water=about 0.003~0.3/ about 0.1~10/100.Iodate can also be replaced
Potassium, and using other iodide such as zinc iodide, potassium iodide and other iodide can also be used in combination.Alternatively, it is also possible to make
Compound other than iodide coexists such as boric acid, zinc chloride, cobalt chloride.In the case where adding boric acid, containing iodine this
A little on be different from aftermentioned crosslinking Treatment, as long as aqueous solution relative to 100 parts by weight of water contain about 0.003 parts by weight of iodine with
On, so that it may to be considered as dye bath 15.The temperature of dye bath 15 when impregnated membranes is usually 10~45 DEG C or so, preferably 10~40
DEG C, more preferably 20~35 DEG C, the dip time of film is usually 30~600 seconds or so, preferably 60~300 seconds.
In the case where using water-soluble dichroic dye as dichroism pigment, as the dyeing liquor of dye bath 15, example
Can such as it use concentration using weight ratio meter as the aqueous solution of dichroic dye/water=about 0.001~0.1/100.In the dye bath
In 15, dyeing assistant etc. can also be made to coexist, such as the inorganic salts or surfactant etc. such as sodium sulphate can also be contained.Dichroism
Dyestuff can only be used alone a kind, the dichroic dye that can also be used in combination of two or more.The temperature of dye bath 15 when impregnated membranes
For example, 20~80 DEG C or so, preferably 30~70 DEG C, the dip time of film are usually 30~600 seconds or so, preferably 60~
300 seconds or so.
As described above, in dyeing treatment process, being uniaxially stretched for film can be carried out in dye bath 15.Film is uniaxially stretched
Can using to be configured between the front and back niproll 51 and niproll 52 of dye bath 15 apply the methods of difference come
It carries out.
In dyeing processing, polyethenol series tree in order to identical as swelling treatment is carried while except the gauffer of striping
Adipose membrane, can also be used as deflector roll 33,34 and/or 35 using spreader roll, felt windening roll, crowned roll etc with broadening function
Roller broadens devices using the other of guide, roller, stenter clip etc.For inhibit gauffer generation another
Method is identical as swelling treatment, it is possible to implement stretch processing.
In example shown in FIG. 1, the film that is pulled out from dye bath 15 pass sequentially through deflector roll 35, niproll 52 and be imported into friendship
Connection bath 17.
(crosslinking Treatment process)
Crosslinking Treatment process be for by the purpose of crosslinked resistance to aquation, hue adjustment (preventing film bit bluish etc.) and
The processing of progress.Referring to Fig.1, crosslinking Treatment can be by along the film transport path built by deflector roll 36~38 and niproll 52
It carries, dipping given time and then draw dyeing treated film in crosslinking bath 17 (crosslinked fluids being housed in crosslinking slot)
Go out and implements.
Can be the boron relative to 100 parts by weight of water for example containing about 1~10 parts by weight as the crosslinked fluid of crosslinking bath 17
The aqueous solution of acid.In the case that the dichroism pigment that crosslinked fluid uses in dyeing processing is iodine, preferably also contain other than boric acid
There are iodide, amount that can for example be set as 1~30 parts by weight relative to 100 parts by weight of water.As iodide, iodate can be enumerated
Potassium, zinc iodide etc..Alternatively, it is also possible to make compound other than iodide, such as zinc chloride, cobalt chloride, zirconium chloride, thiosulfuric acid
Sodium, potassium sulfite, sodium sulphate etc. coexist.
In crosslinking Treatment, according to its purpose, concentration and the crosslinking bath 17 of boric acid and iodide can be changed as appropriate
Temperature.For example, the purpose in crosslinking Treatment is to implement to be swollen successively by crosslinked resistance to aquation, to polyvinyl alcohol resin film
In the case of processing, dyeing processing and crosslinking Treatment, being crosslinked the crosslinking agent of bath, to contain liquid can be concentration using weight ratio meter as boron
The aqueous solution of acid/iodide/water=3~10/1~20/100.As needed, can also substituted boracic acid and use glyoxal or penta
Boric acid and other crosslinking agents can also be used in combination for the others crosslinking agent such as dialdehyde.The temperature of crosslinking bath when impregnated membranes is usual
It is 50~70 DEG C or so, preferably 53~65 DEG C, the dip time of film is usually 10~600 seconds or so, preferably 20~300
Second, more preferably 20~200 seconds.In addition, the polyvinyl alcohol resin film stretched in advance before to swelling treatment is successively
In the case of implementing dyeing processing and crosslinking Treatment, the temperature of crosslinking bath 17 is usually 50~85 DEG C or so, preferably 55~80
℃。
In crosslinking Treatment for the purpose of by hue adjustment, such as in the case where having used iodine as dichroism pigment,
Liquid can be contained by the crosslinking agent of boric acid/iodide/water=1~5/3~30/100 of weight ratio meter using concentration.When impregnated membranes
Crosslinking bath temperature be usually 10~45 DEG C or so, the dip time of film is usually 1~300 second or so, preferably 2~100
Second.
Crosslinking Treatment can carry out repeatedly, usually carry out 2~5 times.In this case, it is used it is each crosslinking bath composition and
As long as temperature then may be the same or different in above-mentioned range.For by crosslinked resistance to aquation crosslinking Treatment and
Crosslinking Treatment for hue adjustment can be carried out respectively with multiple processes.
The difference of niproll 52 and niproll 53 can also be utilized to implement to be uniaxially stretched processing in crosslinking bath 17.
In crosslinking Treatment, polyethenol series tree in order to identical as swelling treatment is carried while except the gauffer of striping
Adipose membrane, can also be used as deflector roll 36,37 and/or 38 using spreader roll, felt windening roll, crowned roll etc with broadening function
Roller broadens devices using the other of guide, roller, stenter clip etc.For inhibit gauffer generation another
Method is identical as swelling treatment, it is possible to implement stretch processing.
In example shown in FIG. 1, from crosslinking bath 17 film that pulls out pass sequentially through deflector roll 38, niproll 53 and be imported into film
Cleaner bath 19.
(Membrane cleaning treatment process)
The manufacturing method of the present invention may include the Membrane cleaning treatment process after crosslinking Treatment process.Membrane cleaning processing is
It is carried out in the purpose for removing the medicaments such as extra boric acid, the iodine being attached on polyvinyl alcohol resin film.Membrane cleaning handles example
It such as can be by the way that the polyvinyl alcohol resin film immersion of crosslinking Treatment will have been carried out in Membrane cleaning bath 19 or to film spraying film
Cleaning solution or by these methods and for carrying out.
In Fig. 1, there is shown example when starting the cleaning processing polyvinyl alcohol resin film immersion in Membrane cleaning bath 19
Son.The temperature of Membrane cleaning bath 19 in Membrane cleaning processing is usually 2~40 DEG C or so, and the dip time of film is usually 2~120 seconds
Left and right.
Moreover, Membrane cleaning processing in, for while free of wrinkles carry polyvinyl alcohol resin film purpose,
Roller or the use with broadening function of spreader roll, felt windening roll, crowned roll etc can be used as deflector roll 39,40 and/or 41
Other broadening devices of guide, roller, stenter clip etc.In addition, in Membrane cleaning processing, in order to inhibit the production of gauffer
Life can also implement stretch processing.
(stretch processing process)
As described above, former material film 10 during above-mentioned a series for the treatment of process (that is, the treatment process more than any one
Front and back and/or treatment process more than any one in), carried out being uniaxially stretched processing with wet type or dry type.It is uniaxially stretched
Processing specific method for example can be to constitute film transport path 2 niprolls (such as be configured at processing bath it is front and back
2 niprolls) between apply difference and stretched between the roller that is longitudinally uniaxially stretched, such as Japanese Patent No. 2731813
Hot-rolling shown in described in number bulletin stretches, stenter stretches etc., is preferably stretched between roller.Being uniaxially stretched treatment process can be
From former material film 10, implementation is multiple to obtaining polarizing coating 23.As described above, generation of the stretch processing for the gauffer of inhibition film
Also advantageous.
The final accumulative stretching ratio of polarizing coating 23 on the basis of former material film 10 is usually 4.5~7 times or so, preferably
It is 5~6.5 times.
Stretch processing process can carry out in arbitrary treatment process, be stretched in 2 or more treatment process
In the case of processing, stretch processing can also carry out in arbitrary treatment process.According to the present invention, swelling treatment process with
It is carried out in the case of being uniaxially stretched processing in any stage of (including swelling treatment process) afterwards, can efficiently inhibit to stretch
Film fracture when processing.
(being dried process)
After cleaning treatment process, preferably into the processing for exercising the drying of polyvinyl alcohol resin film.The drying of film is without spy
It does not limit, example that can be as shown in Figure 1 is carried out using drying oven 21 like that.Drying temperature is, for example, 30~100 DEG C or so, is done
The dry time is, for example, 30~600 seconds or so.The thickness of the polarizing coating 23 obtained as described above is, for example, about 5~30 μm or so.
(for other treatment process of polyvinyl alcohol resin film)
The processing other than above-mentioned processing can also be added.The example for the processing that can be added is included in crosslinking Treatment process
The impregnation (complementary color processing) into the iodide aqueous solution without containing boric acid that carries out afterwards contains chlorine to without containing boric acid
Change the impregnation (zinc processing) in the aqueous solution of zinc etc..
(roller cleaning process)
Roller cleaning process is cleaned with roller in the above-mentioned continuous manufacture by polyvinyl alcohol resin film production polarizing coating
Liquid cleaning is configured at the cleaning process of each roller in the transport road between two processing baths.The cleaning method of roller is not particularly limited,
However can be as shown in Figure 1 example it is such, suitably using using with each roller (deflector roll 32,35,38,41 and niproll 51,
52,53,54) surface outlet roller cleaning solution from the spray thrower 71~78 that surface configures face to face to each roller, make the table of each roller
The method that face is cleaned.
Cleaning using each roller of roller cleaning solution is preferably implemented in the continuous manufacture of polarizing coating, preferably in continuous manufacture
Implement always.Using such roller cleaning process, even if the polyvinyl alcohol resin film 10 being handled upside down will handle the processing in bathing
Liquid band enters, which is attached to the surface of each roller, is washed out immediately due to being utilized roller cleaning solution, is also possible to prevent roller table
Face is contaminated because of the precipitation of salt etc..Spray thrower 71~78 is relative to the allocation position of roller, the derived quantity of roller cleaning solution and export
Angle can suitably adjust, can relative to roller by roller cleaning solution to the upstream side of the upside of roller, downside or carry direction,
Any one of downstream side pours leaching, or pours leaching in any combination, is preferably regulated as not making roller cleaning solution directly to pour to pour and be handled upside down
Polyvinyl alcohol resin film.In addition, the derived quantity of roller cleaning solution is at least set as inhibiting the pollution of roller surface and required
Amount.
In Fig. 1, exemplify for be configured at whole rollers after each treatment trough (deflector roll 32,35,38,41 and niproll 51,
52,53,54) be equipped with the composition of the spray thrower 71~78 for cleaning them, however can also be only be configured at be easy it is contaminated
Roller surface composition, constituted in the way of being configured face to face with the surface of at least one roller.It is contaminated as being easy
Roller, deflector roll 35 after immediately dye bath 15 and niproll 52 and the immediately deflector roll 38 after crosslinking bath 17 can be enumerated
And niproll 53.Due to being passed through compared with others processing bath in the dyeing liquor in dye bath 15 and the crosslinked fluid in crosslinking bath 17
Normal salinity higher, therefore in the case where roller surface shortly after is attached with these treatment fluids, can be in and be easy to be precipitated
In the situation of salt.
Fig. 2 is the relationship of the top side roller and spray thrower 72,74,76,78 for the niproll 51,52,53,54 for indicating Fig. 1
The stereogram of an example.Spray thrower 72,74,76,78 has from one end of the width direction of roller 51,52,53,54 towards other end etc.
Compartment of terrain is arranged with the composition of multiple nozzles, and when the outlet roller cleaning solution from spray thrower 72,74,76,78, roller cleaning solution will
It is contacted with the width direction whole region of roller surface.So due to roller in the state that polyvinyl alcohol resin film is handled upside down into
Row rotation, therefore when continuing the outlet roller cleaning solution from spray thrower 72,74,76,78, so that it may so that roller cleaning solution and roller 51,
52,53,54 all surfaces contact, the pollution of roller surface are prevented.
Roller cleaning used in the spray thrower 71,72 of the deflector roll 32 and niproll 51 that are configured at after swelling bath 13 as cleaning
Liquid is suitably for swelling solution.In addition, be preferably provided with will be to roller cleaning solution derived from deflector roll 32 and niproll 51 for polarization film manufacturing device
The mechanism being recovered in swelling slot.
Roller cleaning used in the spray thrower 73,74 of the deflector roll 35 and niproll 52 that are configured at as cleaning after dye bath 15
Liquid is suitably for dyeing liquor.In addition, be preferably provided with will be to roller cleaning solution derived from deflector roll 35 and niproll 52 for polarization film manufacturing device
The mechanism being recovered in staining trough.
Roller cleaning used in the spray thrower 75,76 of the deflector roll 38 and niproll 53 that are configured at after crosslinking bath 17 as cleaning
Liquid is suitably for crosslinked fluid.In addition, be preferably provided with will be to roller cleaning solution derived from deflector roll 38 and niproll 53 for polarization film manufacturing device
The mechanism being recovered in crosslinking slot.
Roller is clear used in the spray thrower 77,78 of the deflector roll 41 and niproll 54 that are configured at after Membrane cleaning bath 19 as cleaning
Washing lotion is suitably for Membrane cleaning liquid.In addition, be preferably provided with will be clear to roller derived from deflector roll 41 and niproll 54 for polarization film manufacturing device
Washing lotion is recovered to the mechanism in Membrane cleaning slot.
As described above, being handled used in treatment trough before being suitably for the roller immediately to be cleaned as roller cleaning solution
Liquid.Furthermore it is preferred that having the roller cleaning solution that will be cleaned for roller is recovered to the processing for using the roller cleaning solution as treatment fluid
Mechanism in slot.Moreover, from preventing from from the viewpoint of foreign matter is mixed into, to the roller cleaning solution cleaned for roller to implement
It is recovered in treatment trough after filter processing.
Polarizing coating is produced using polarization film manufacturing device shown in FIG. 1, as a result, dirt is not observed on its surface
The defects of object adheres to.
In Fig. 1, spray thrower is given as the component for the surface outlet roller cleaning solution to roller, as long as however it can be with
Component derived from surface by from roller cleaning solution to roller, then be not limited to spray thrower.Spray thrower makes the linear ejection of cleaning solution
Component, other than spray thrower, can also enumerate makes cleaning solution so that roller is cleaned in droplet-like or the misty component sprayed, using gravity
Under drop or the component flowed down, the component etc. that roller cleaning solution is coated on to roller surface.Alternatively, it is also possible to being following mode, that is,
Roller of cleaning object itself has the structure from internal exudation roller cleaning solution, thus from inside to roller surface outlet roller cleaning solution and
Carry out roller cleaning process.As the component that roller cleaning solution is coated on to roller surface, the structure of exudation roller cleaning solution may be exemplified out
Brush, the mode cleaned to the roller surface of cleaning object with roller cleaning solution using the brush can be enumerated.Moreover, roller is clear
It can not also includes to the process of the surface outlet roller cleaning solution of the roller of cleaning object to wash process, but include making cleaning object
The surface of roller is impregnated in the process in roller cleaning solution.Specifically, following method etc. can be enumerated, that is, in cleaning object
The liquid pool of roller cleaning solution is set in the rotating path of roller, and all surfaces of each rotating central roll are cleaned by the liquid pool.
In this method, after treatment fluid used in treatment trough immediately front is preferably also used as roller cleaning solution and cleans roller
Roller cleaning solution is recovered to the composition in treatment trough immediately front.
[second embodiment]
Fig. 3 is in the manufacturing method and the manufacturing method of the polarizing coating for schematically showing second embodiment of the present invention
The sectional view of an example of polarization film manufacturing device used.Polarization film manufacturing device shown in Fig. 3 is constituted as follows, that is, from
Along film transport path while continuously rolling out former material (non-stretched) film 10 comprising polyvinyl alcohol resin in former material reel 11
It carries, is thus allowed to pass sequentially through swelling bath 13, the crosslinking bath of dye bath 15, first 17a, the second friendship in film transport path
Connection bath 17b and cleaner bath 19, finally by drying oven 21.The polarizing coating 23 of gained for example can directly be transported to following
Polarization plates production process (in the process that the one or both sides of polarizing coating 23 are bonded protective film).Arrow in Fig. 3 indicates membrane
Carry direction.
Polarization film manufacturing device shown in Fig. 3 can by by above-mentioned processing bath, in addition there are can support to be handled upside down
Film or can also change film carry direction deflector roll 130~148,60,61, can squeeze, the film being handled upside down be clamped and to film
Assign by its driving force for bringing of rotation or can also change film carry direction niproll 50,51,52,53a, 53b, 54,
55 are configured at position appropriate to build.Deflector roll, niproll can be configured in the front and back or processing bath of each processing bath, thus may be used
With carry out the importing during film is bathed to processing, dipping and from processing bathe in pull-out (with reference to Fig. 3).
It is shown in Fig. 3 polarization film manufacturing device throughout manage bath it is front and back configured with niproll (niproll 50,51,52,
53a、53b、54、55).Thus, it will be able in arbitrary more than one processing is bathed, be applied between being configured at the niproll before and after it
Add difference and implements to stretch between the roller being longitudinally uniaxially stretched.
In polarization film manufacturing device shown in Fig. 3, according to be configured at each processing bath 13,15,17a, 17b, the folder after 19
Hold roller 51,52,53a, 53b, 54 facing modes be equipped with spray thrower 171a, 171b, 172a, 172b, 173a, 173b, 174a,
174b、175a、175b.Polarizing coating it is continuous manufacture in, using spray thrower 171a, 171b, 172a, 172b, 173a, 173b,
174a, 174b, 175a, 175b to niproll 51,52,53a, 53b, 54 surface outlet roller cleaning solution, make niproll 51,52,
53a, 53b, 54 surface cleaned (roller cleaning process).In addition, polarization film manufacturing device shown in Fig. 3 is constituted as follows,
That is, be equipped with recycling plate 81,82,83,84,85 corresponding with each treatment trough, as a result, each niproll 51,52,53a, 53b, 54 table
Roller cleaning solution used in the cleaning in face is just recycled in the treatment trough before immediately each niproll 51,52,53a, 53b, 54.
Hereinafter, being illustrated to each process.
Swelling treatment process, crosslinking Treatment process, Membrane cleaning treatment process, stretch processing process, is done dyeing treatment process
Dry treatment process, to illustrating in the details of other treatment process of polyvinyl alcohol resin film and above-mentioned first embodiment in
Hold identical.In this second embodiment, the first crosslinking crosslinking baths of bath 17a and second 17b has been used in crosslinking Treatment process.It can be with
First crosslinking is bathed into 17a for illustrating in the crosslinking Treatment process of first embodiment at the water-fast crosslinking for turning to purpose
In reason, the second crosslinking is bathed into 17b for illustrating in the crosslinking Treatment process of first embodiment for the purpose of color adjustment
In crosslinking Treatment.First crosslinking bath 17a crosslinked fluid can be using weight ratio meter as boric acid/iodide/water=3~10/1~
The content of boric acid can be set as 2~10 weight % by 20/100 aqueous solution.In the first crosslinking bath 17a, due to polyvinyl alcohol
Resin film is easy to absorb boric acid, therefore in the case of continuously manufacture polarizing coating, in order to keep the boron in the first crosslinking bath 17a
Acid concentration, can every given time, or often carry specified rate polyvinyl alcohol resin film when, to first crosslinking bath 17a
Middle addition boric acid.
(roller cleaning process)
Roller cleaning process is cleaned in the above-mentioned continuous manufacture by polyvinyl alcohol resin film production polarizing coating, with roller
Liquid cleaning be configured at two processing bath between transport road in each niproll 51,52,53a, 53b, 54 cleaning process.Using with
Each niproll 51,52,53a, 53b, 54 surface configure face to face spray thrower 171a, 171b, 172a, 172b, 173a,
173b, 174a, 174b, 175a, 175b make the surface of each niproll obtain clearly to the surface outlet roller cleaning solution of each niproll
It washes.
Cleaning using each roller of roller cleaning solution is preferably implemented in the continuous manufacture of polarizing coating, preferably in continuous manufacture
Implement always.Using such roller cleaning process, even if the polyvinyl alcohol resin film 10 being handled upside down will handle the processing in bathing
Liquid band enters, which is attached to the surface of each roller, due to being washed out immediately by roller cleaning solution, roller surface can be prevented because of salt
Deng precipitation and be contaminated.Spray thrower 171a, 171b, 172a, 172b, 173a, 173b, 174a, 174b, 175a, 175b are opposite
It can suitably adjust, can clean roller relative to roller in the allocation position of roller, the derived quantity of roller cleaning solution and export angle
Liquid pours leaching to any one of the upstream side of the upside of roller, downside or carry direction, downstream side, or can be in any combination
Leaching is poured, however is preferably regulated as roller cleaning solution is not made directly to pour pouring on the polyvinyl alcohol resin film being handled upside down.In addition, roller is clear
The derived quantity of washing lotion is at least set as inhibiting the pollution of roller surface and required amount.
In Fig. 3, exemplify relative to be configured at whole niprolls 51 after each treatment trough, 52,53a, 53b, 54 be equipped with and use
In the composition for cleaning their spray thrower 171a, 171b, 172a, 172b, 173a, 173b, 174a, 174b, 175a, 175b, so
And can also be the composition on the surface for being only configured at easy contaminated roller, match face to face according to the surface at least one roller
The mode set is constituted.As easy contaminated roller, after the crosslinking bath of the niproll after dye bath 15 52, first 17a can be enumerated
Niproll 53a, second crosslinking bath 17b after niproll 53b.In dyeing liquor and crosslinking bath 17a, 17b in dye bath 15
Crosslinked fluid in others processing bath compared to frequent salinity height, therefore be attached to roller surface thereafter in these treatment fluids
In the case of, the situation for being easy that salt is precipitated can be in.In addition, the spray thrower for cleaning roller is not limited to be only oriented towards niproll
Configuration, can also be configured at deflector roll identical with first embodimently.
It is configured at swelling as cleaning and bathes roller cleaning solution used in spray thrower 171a, 171b of the niproll 51 after 13,
It is suitably for swelling solution.It is recycled to via recycling plate 81 from spray thrower 171a, 171b to roller cleaning solution derived from niproll 51 molten
In swollen bath 13.Thus, even if the swelling solution in swelling bath 13 is gone out by the polyvinyl alcohol resin film strips being handled upside down and the swelling
In the case that liquid is attached on niproll 51, the cleaning process of niproll 51 can also be utilized to be recovered in swelling bath 13, in addition
Swelling solution is used by being used as roller cleaning solution, the composition of the swelling solution in swelling bath 13 can be kept certain.Spray thrower 171a,
Swelling solution used in 171b can also be from 13 supply of swelling bath.By constituting as described, swelling solution is just recycled, because
The composition of swelling solution in swelling bath 13 and liquid measure can be kept certain by this.
Roller cleaning solution used in spray thrower 172a, 172b of the niproll 52 after dye bath 15 is configured at as cleaning,
It is suitably for dyeing liquor.From spray thrower 172a, 172b to roller cleaning solution derived from niproll 52 dye is recycled to via recycling plate 82
In color bath 15.Thus, even if the dyeing liquor in dye bath 15 is gone out by the polyvinyl alcohol resin film strips being handled upside down and the dyeing
In the case that liquid is attached on niproll 52, the cleaning process of niproll 52 can also be utilized to be recovered in dye bath 15, in addition
Dyeing liquor is used by being used as roller cleaning solution, the composition of the dyeing liquor in dye bath 15 can be kept certain.Spray thrower 172a,
Dyeing liquor used in 172b can also be supplied from dye bath 15.By constituting as described, dyeing liquor is just recycled, because
The composition of dyeing liquor in dye bath 15 and liquid measure can be kept certain by this.
It is clear that roller used in spray thrower 173a, 173b of the niproll 53a after the first crosslinking bath 17a is configured at as cleaning
Washing lotion is suitably for the crosslinked fluid with the crosslinked fluid same composition in the first crosslinking bath 17a.From spray thrower 173a, 173b to clamping
Roller cleaning solution derived from roller 53a is recycled to via recycling plate 83 in the first crosslinking bath 17a.Thus, even if in the first crosslinking bath
Crosslinked fluid in 17a is gone out by the polyvinyl alcohol resin film strips being handled upside down and the crosslinked fluid is attached to the situation on niproll 53a
Under, it can also be recovered to using the cleaning process of niproll 53a in the first crosslinking bath 17a, be made in addition by being used as roller cleaning solution
With crosslinked fluid, the composition for being easy to bathe the first crosslinking the crosslinked fluid in 17a keeps certain.Used in spray thrower 173a, 173b
Crosslinked fluid can also be from the first crosslinking bath 17a supplies.By constituting as described, crosslinked fluid is just recycled, therefore is easy
First crosslinking is bathed to the composition of the crosslinked fluid in 17a and liquid measure keeps certain.
It is clear that roller used in spray thrower 174a, 174b of the niproll 53b after the second crosslinking bath 17b is configured at as cleaning
Washing lotion is suitably for the crosslinked fluid with the crosslinked fluid same composition in the second crosslinking bath 17b.From spray thrower 174a, 174b to clamping
Roller cleaning solution derived from roller 53b is recycled to via recycling plate 84 in the second crosslinking bath 17b.Thus, even if in the second crosslinking bath
Crosslinked fluid in 17b is gone out by the polyvinyl alcohol resin film strips being handled upside down and the crosslinked fluid is attached to the situation on niproll 53b
Under, it can also be recovered to using the cleaning process of niproll 53b in the second crosslinking bath 17b, be made in addition by being used as roller cleaning solution
With crosslinked fluid, the composition that the second crosslinking can be bathed to the crosslinked fluid in 17b keeps certain.Used in spray thrower 174a, 174b
Crosslinked fluid can also be from the second crosslinking bath 17b supplies.By constituting as described, crosslinked fluid is just recycled, therefore can be with
Second crosslinking is bathed to the composition of the crosslinked fluid in 17b and liquid measure keeps certain.
It is configured at Membrane cleaning as cleaning and bathes roller cleaning used in spray thrower 175a, 175b of the niproll 54 after 19
Liquid is suitably for Membrane cleaning liquid.It is recovered via recycling plate 85 from spray thrower 175a, 175b to roller cleaning solution derived from niproll 54
Into Membrane cleaning bath 19.Thus, even if the Membrane cleaning liquid in Membrane cleaning bath 19 is by the polyvinyl alcohol resin film strips that are handled upside down
Go out and in the case that the Membrane cleaning liquid is attached on niproll 54, the cleaning process of niproll 54 can also be utilized to be recovered to film clear
In bathing 19, Membrane cleaning liquid is used by being used as roller cleaning solution in addition, Membrane cleaning can be bathed to the composition of the Membrane cleaning liquid in 19
Keep certain.Membrane cleaning liquid used in spray thrower 175a, 175b can also bathe 19 supplies from Membrane cleaning.By as described
It constitutes, Membrane cleaning liquid is just recycled, therefore can the composition of the Membrane cleaning liquid in Membrane cleaning bath 19 and liquid measure be kept certain.
As described above, even if the treatment fluid in treatment trough is gone out by the polyvinyl alcohol resin film strips being handled upside down and the processing
In the case that liquid is attached on roller, the cleaning process of roller can also be utilized to be recovered in treatment trough, therefore can will be in treatment trough
Composition keep certain, even if in the case of continuously manufacture polarizing coating, the polarizing coating with uniform properties can also be manufactured.
Moreover, from preventing that from the viewpoint of foreign matter is mixed into, filtering can also implemented to the roller cleaning solution cleaned for roller
It is recovered in treatment trough after processing.
Polarizing coating is produced using polarization film manufacturing device shown in Fig. 3, as a result, not observing dirt on its surface
The defects of object adheres to.It, can be in addition, even if continuously manufacturing variation not big if polarizing coating is throughout managed in terms of the composition of bath
The polarizing coating of continuous manufacture uniform properties.
< polarization plates >
Protective film is bonded by adhesive, so that it may by at least one side in the polarizing coating manufactured as described above to obtain
Polarization plates.As protective film, for example, the acetyl fibre prime system comprising triacetyl cellulose, diacetyl cellulose etc
The film of resin;Including polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate (PBT) it
The film of the polyester based resin of class;Polycarbonate-based resin film, cyclic olefine resin film;Acrylic resin film;Including polypropylene
It is the film of the chain olefin system resin of resin.
In order to improve the adhesivity of polarizing coating and protective film, electricity can be implemented to the binding face of polarizing coating and/or protective film
The surface treatments such as dizzy processing, flame treatment, corona treatment, ultraviolet light irradiation, primary coat processing, saponification process.As polarization
Adhesive used in being bonded of film and protective film, the active energy beam that can enumerate ultra-violet solidified adhesive etc are solid
The property changed adhesive, the aqueous solution of polyvinyl alcohol resin is combined with the aqueous solution of crosslinking agent, carbamate system breast wherein
The water system adhesive of liquid glue stick etc.Ultraviolet curing adhesive can be that acrylic compounds polymerize with optical free radical
The mixture of initiator, the mixture etc. of epoxide and light cationic polymerization initiator.Alternatively, it is also possible to which cation is poly-
The epoxide of conjunction property is used in combination with free-radical polymerised acrylic compounds, draws light cationic polymerization as initiator
Hair agent is used in combination with optical free radical polymerization initiator.
Embodiment
Hereinafter, provide embodiment and more specific description is carried out to the present invention, however the present invention is not limited by these examples
It is fixed.
1 > of < embodiments
In addition to having used 2 crosslinking baths 17 (first crosslinking bath to be referred to as the first crosslinking bath 17a below, second is handed over
Connection bath is referred to as the second crosslinking bath 17b.) other than, go out polarization using device manufacturing identical with polarization film manufacturing device shown in FIG. 1
Film.Flat roll is all employed as deflector roll 30~41 entirely.
By polyvinyl alcohol (PVA) former material film (trade name " Kuraray of (strain) Kuraray of thick 30 μm of long size
99.9 moles of Poval Film VF-PE#3000 ", average degree of polymerization 2400, saponification degree % or more) it is rolled out from reel on one side
It continuously carries on one side, is allowed to be immersed in (swelling treatment in the swelling bath 13 being made of 20 DEG C of pure water with 31 seconds residence times
Process).Thereafter, the film pulled out from swelling bath 13 is made to be immersed in potassium iodide/water with 122 seconds residence times as 2/100 (weight
Than) 30 containing iodine DEG C dye bath 15 in (dyeing treatment process).Then, make the film pulled out from dye bath 15 to be detained
70 seconds time was immersed in 56 DEG C that boric acid/potassium iodide/water is 4.1/12/100 (weight ratio) of the first crosslinking bath 17a, connect down
Come, 40 DEG C that boric acid/potassium iodide/water is 2.9/9/100 (weight ratio) of the second crosslinking bath 17b was immersed in 13 seconds residence times
In (crosslinking Treatment process).In dyeing treatment process and crosslinking Treatment process, longitudinal direction has been carried out using being stretched between the roller in bath
It is uniaxially stretched.Total stretching ratio on the basis of former material film is set as 5.36 times.Then, make to pull out from the second crosslinking bath 17b
Film was immersed in the cleaner bath 19 being made of 5 DEG C of pure water (cleaning treatment process) with 3 seconds residence times.Thereafter, at 60 DEG C
It is 190 seconds dry in drying oven 21, obtain thick 13.1 μm of polarizing coating.
During continuously manufacture polarizing coating, cleaned for poly- from pull-out in bath 13 is swollen with pure water using spray thrower 71
The deflector roll 32 of vinyl alcohol film is cleaned with the dyeing liquor with 15 same composition of dye bath for from dye bath 15 using spray thrower 73
The deflector roll 35 for pulling out polyvinyl alcohol film cleans use using spray thrower 75,76 with the crosslinked fluid with the second crosslinking bath 17b same compositions
In the deflector roll 38 and niproll 53 that pull out polyvinyl alcohol film from the second crosslinking bath 17b, cleaned with pure water using spray thrower 77,78
Deflector roll 41 and niproll 54 for pulling out polyvinyl alcohol film from cleaner bath 19.
The deflector roll and niproll pulled out from each processing bath by one side cleaning, manufactures polarizing coating on one side, even if continuous system
It makes polarizing coating 7 hours, does not also generate the precipitation of salt etc. on the surface of each roller.In addition, also generating roller table not in polarizing coating
Defect caused by the pollution in face.
2 > of < embodiments
Go out polarizing coating using the identical device manufacturing of polarization film manufacturing device as shown in figure 3.As deflector roll 130~148
All employ flat roll entirely.Although moreover, not representing the spray of cleaning deflector roll 132,136,140,144,148 in figure 3
Device, however the cleaning of these deflector rolls is also to carry out identically as the cleaning for being configured at niproll immediately rear in the present embodiment.
By polyvinyl alcohol (PVA) former material film (quotient of (strain) Kuraray of 30 μm thick, width direction 450mm long size
99.9 moles of name of an article " Kuraray Poval Film VF-PE#3000 ", average degree of polymerization 2400, saponification degree % or more) on one side
It rolls out from reel, was continuously carried with 16m/ hours on one side, be immersed in 31 seconds residence times and to be made of 20 DEG C of pure water
In swelling bath 13 (swelling treatment process).Thereafter, the film pulled out from swelling bath 13 is made to be immersed in iodate within 122 seconds with the residence time
Potassium/water is (dyeing treatment process) in the dye bath 15 of 30 containing iodine DEG C of 2/100 (weight ratio).Then, make from dye bath
It is 4.1/12/100 (weight ratio) and the first crosslinking that the film pulled out in 15 was immersed in boric acid/potassium iodide/water with 70 seconds residence times
In the first crosslinking bath 17a that the liquid measure of liquid is 56 DEG C of 280L, next, with 13 seconds residence times be immersed in boric acid/potassium iodide/
Water is (crosslinking Treatment in the second crosslinking bath 17b that the liquid measure of 2.9/9/100 (weight ratio) and the second crosslinked fluid is 40 DEG C of 75L
Process).In dyeing treatment process and crosslinking Treatment process, longitudinal direction is carried out using stretching between the roller in bath and has been uniaxially stretched.With
Total stretching ratio on the basis of former material film is set as 5.36 times.Then, make the film pulled out from the second crosslinking bath 17b with the residence time
It is immersed within 3 seconds in the cleaner bath 19 being made of 5 DEG C of pure water (cleaning treatment process).Thereafter, it is done in 60 DEG C of drying oven 21
Dry 190 seconds, obtain thick 13.1 μm of polarizing coating.Moreover, into the first crosslinking bath 17a, every warp from the carrying for starting polarizing coating
The boric acid for crossing 1 hour addition 10g is supplied due to being absorbed and the boric acid amount of reduction by film.
During continuously manufacture polarizing coating, the folder after cleaning swelling bath 13 with pure water using spray thrower 171a, 171b
Roller 51 is held, the niproll after cleaning dye bath 15 with the dyeing liquor with 15 same composition of dye bath using spray thrower 172a, 172b
52, after cleaning the first crosslinking bath 17a with the crosslinked fluid with the first crosslinking bath 17a same compositions using spray thrower 173a, 173b
Niproll 53a cleans the second crosslinking with the crosslinked fluid with the second crosslinking bath 17b same compositions using spray thrower 174a, 174b and bathes
Niproll 53b after 17b, the niproll 54 after cleaning cleaner bath 19 with pure water using spray thrower 175a, 175b.In addition, for
Be configured at each niproll 51,52,53a, 53b, 54 deflector roll 132,136,140,144,148 immediately front, also utilize and clamping
The identical method of roller is cleaned.
The niproll 51 after each processing bath, 52,53a, 53b, 54 are configured at by one side cleaning, manufacture polarizing coating on one side,
Even if continuously in the precipitation of the surface of each roller generation salt etc. if manufacture polarizing coating 7 hours.In addition, not having in polarizing coating yet
There is defect caused by the pollution for generating roller surface.
1 > of < comparative examples
Other than not cleaning the deflector roll and niproll that are pulled out from each processing bath, produce same as Example 1ly
The polarizing coating of comparative example 1.
It is small in continuously manufacture polarizing coating 1 in the case of the deflector roll and niproll that no cleaning is pulled out from each processing bath
Shi Hou confirms there is pollution on each roller.Especially for pulling out 38 He of deflector roll of polyvinyl alcohol film from the second crosslinking bath 17b
Many pollutions are observed on niproll 53.In addition, confirming have in manufactured polarizing coating after 1 hour in continuously manufacture polarizing coating
The defects of having transferred deformation, the attachment foreign matter of the pollution on each roller.
2 > of < comparative examples
Other than there is no cleaning to be configured at the niproll 51 after each processing is bathed, 52,53a, 53b, 54, with 2 phase of embodiment
The polarizing coating of comparative example 2 is produced together.In comparative example 2, after continuously manufacture polarizing coating 1 hour, niproll 51,52,
53a, 53b, confirm there is pollution on 54.Many pollutions are observed in niproll 53b especially after the second crosslinking bath 17b.Separately
Outside, confirm to have in manufactured polarizing coating after continuously manufacture polarizing coating 1 hour and transferred deforming, being attached for the pollution on each roller
The defects of foreign matter.
The composition measuring > of the boric acid concentration of < crosslinking baths
In the manufacturing process of embodiment 2 and comparative example 2, the first crosslinking bath before the manufacture for starting polarizing coating is determined
17a and second crosslinking bath 17b boric acid content and start polarizing coating manufacture after often pass through 1 hour first crosslinking bath 17a and
The boric acid content of second crosslinking bath 17b.Moreover, often pass through 1 hour the first crosslinking bath 17a after the manufacture for starting polarizing coating
Boric acid content is measured immediately after adding 10g boric acid.It is to the first crosslinking crosslinking baths of bath 17a or second for boric acid content
Pure water 170ml and Osmitrol (12.5 weight %) 30g is added in 17b about 5g and test sample solution is made, is added dropwise
Sodium hydrate aqueous solution (1mol/l) is determined using following formula based on the drop until the test sample solution reaches the point of neutralization
The boron content of the first crosslinking crosslinking baths of bath 17a or second 17b of dosage:
Boron content (parts by weight)=(6.18 × sodium hydrate aqueous solution dripping quantity (ml)/(crosslinking bath foam weight (g)-
6.18 × sodium hydrate aqueous solution dripping quantity (ml)))
Table 1 represents the measurement result of the boric acid content of the first crosslinking bath 17a.Table 2 represents the boron of the second crosslinking bath 17b
The measurement result of acid content.
[table 1]
[table 2]
Fig. 4, Fig. 5 are respectively the figure for graphically illustrating out result shown in table 1, table 2.According to table 1, table 2, in embodiment 2
In the case of, the difference of the maxima and minima of the boric acid content in the first crosslinking crosslinking baths of bath 17a and second 17b is respectively
0.06 parts by weight and 0.05 parts by weight, on the other hand, in the case of comparative example 2, the first crosslinking crosslinking baths of bath 17a and second
The difference of the maxima and minima of boric acid content in 17b is respectively 0.08 parts by weight and 0.13 parts by weight, compared with Example 2
It is larger.According to embodiment 2, the variation of the composition since the first crosslinking crosslinking baths of bath 17a and second 17b can be further suppressed,
Therefore the polarizing coating of uniform properties can be manufactured.
The explanation of symbol
10 include the former material film of polyvinyl alcohol resin, 11 former material reels, and 13 swellings are bathed, 15 dye baths, 17 crosslinking baths, and 19
Cleaner bath, 21 drying ovens, 23 polarizing coatings, 30,31,32,33,34,35,36,37,38,39,40,41,60,61 deflector rolls, 50,51,
52,53,54,55 niproll, 71,72,73,74,75,76,77,78,171a, 171b, 172a, 172b, 173a, 173b, 174a,
174b, 175a, 175b spray thrower.
Claims (4)
1. a kind of manufacturing method of polarizing coating, be by the manufacturing method of the polarizing coating of polyvinyl alcohol resin film production polarizing coating,
The manufacturing method has:
Dipping process makes the polyvinyl alcohol resin film immersion in the treatment fluid being housed in treatment trough;
Transportation process makes to be impregnated in the polyvinyl alcohol resin film in the treatment fluid and is carried along roller;And
Roller cleaning process cleans the surface of the roller with roller cleaning solution,
Immediately the treatment fluid in the treatment trough in the dipping process before the roller cleaning process is by as institute
Roller cleaning solution is stated to export to the surface of the roller and carry out the roller cleaning process,
The roller cleaning solution is recycled to the dipping work before the immediately roller cleaning process after the roller cleaning process
In the treatment trough in sequence.
2. the manufacturing method of polarizing coating according to claim 1, wherein
The dipping process is the dye for making the polyvinyl alcohol resin film immersion be dyed in dyeing liquor and with dichroism pigment
Color treatment process makes the polyvinyl alcohol resin film immersion carry out crosslinked crosslinking Treatment process in crosslinked fluid.
3. a kind of manufacturing device of polarizing coating, be by the manufacturing device of the polarizing coating of polyvinyl alcohol resin film production polarizing coating,
The manufacturing device has:
Impregnating mechanism makes the polyvinyl alcohol resin film immersion in the treatment fluid being housed in treatment trough;
Carrying mechanism makes to be impregnated in the polyvinyl alcohol resin film in the treatment fluid and is carried along roller;And
Roller cleaning machine structure cleans the surface of the roller with roller cleaning solution,
Immediately the treatment fluid in the treatment trough in the impregnating mechanism before the roller cleaning machine structure is by as institute
It states roller cleaning solution and exports to the surface of the roller and the surface of cleaning the roller,
The roller cleaning solution is before being recycled to the immediately roller cleaning machine structure after being used for the cleaning on surface of the roller
In the treatment trough in the impregnating mechanism.
4. the manufacturing device of polarizing coating according to claim 3, wherein
The impregnating mechanism is the dye for making the polyvinyl alcohol resin film immersion be dyed in dyeing liquor and with dichroism pigment
Color processing mechanism makes the polyvinyl alcohol resin film immersion carry out crosslinked crosslinking Treatment mechanism in crosslinked fluid.
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JP7177590B2 (en) * | 2017-12-07 | 2022-11-24 | 日東電工株式会社 | Polarizing film manufacturing method and polarizing film manufacturing apparatus |
JP7292130B2 (en) * | 2019-06-28 | 2023-06-16 | 日東電工株式会社 | Polarizer manufacturing method and polarizer manufacturing apparatus |
JP7012891B2 (en) * | 2020-02-07 | 2022-01-28 | 住友化学株式会社 | Method for manufacturing polarizing film |
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TW201702649A (en) | 2017-01-16 |
WO2016190316A1 (en) | 2016-12-01 |
TWI604233B (en) | 2017-11-01 |
KR101802722B1 (en) | 2017-11-28 |
CN107003467A (en) | 2017-08-01 |
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