CN107614578A - The manufacture method and light polarizing film of polyvinyl alcohol film, polyvinyl alcohol film - Google Patents
The manufacture method and light polarizing film of polyvinyl alcohol film, polyvinyl alcohol film Download PDFInfo
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- CN107614578A CN107614578A CN201680029754.7A CN201680029754A CN107614578A CN 107614578 A CN107614578 A CN 107614578A CN 201680029754 A CN201680029754 A CN 201680029754A CN 107614578 A CN107614578 A CN 107614578A
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- polyvinyl alcohol
- film
- alcohol film
- light polarizing
- water
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
-
- 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
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Mechanical Engineering (AREA)
- Polarising Elements (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Moulding By Coating Moulds (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
A kind of polyvinyl alcohol film is provided, it is characterized in that, for the polyvinyl alcohol film that dyeability, draftability are excellent, and for that can also obtain having high degree of polarization when carrying out the long but thin of breadth and without the polyvinyl alcohol film of the uneven light polarizing film of polarisation, tension force when being set to D (mm) by thickness, be stretched to 6 times along the flow direction (MD directions) of film in 30 DEG C of water is set to A (N/mm2), tension force when being stretched to 6 times along the flow direction (MD directions) of film in 50 DEG C of water be set to B (N/mm2) when, meet following formula (1) and (2).0.6≤the D of formula (1) × A≤1.2 formula (2), 0.2≤D × B≤0.4.
Description
Technical field
The present invention relates to polyvinyl alcohol film.More specifically, it is related to：Dyeability, drawing as the reel of light polarizing film
Stretching property is excellent, for the polyvinyl alcohol film of the excellent light polarizing film of high productivity ratio manufacture polarization property, its manufacture method,
With use light polarizing film obtained from the polyvinyl alcohol film.
Background technology
Light polarizing film is to use the pigments such as iodine to carry out the post-tensioning dyed the polyvinyl alcohol film as reel and manufacture
's.For example, after making polyvinyl alcohol film be swelled with warm water, dyed with iodine, in order that iodine molecule is arranged and stretched,
In order to keep stretching state and be crosslinked with crosslinking agents such as boric acid, clean after dry and manufacture.Sometimes it is above-mentioned it is water-swellable,
Dyeing, stretching, also replacement order or multiple processes are carried out each operation of boric acid crosslinking simultaneously.Common part is, by polyethylene
Alcohol system film continuously rolls out from roller, applies appropriate tension force using coiling machine, roll streamwise, edge horizontal direction is defeated
Side is sent to carry out.
Above-mentioned light polarizing film uses as the mechanical, electrical crucial component parts depending on waiting liquid crystal display device of personal digital assistant device.
In recent years, along with the high brightness of liquid crystal display, High precision, it is desired to have the polarisation of high light transmittance and high degree of polarization
Film, and then, along with the large screen of LCD TV etc., slimming, it is expected that the long size of breadth more further than existing product is thin
The light polarizing film of type.
In order to meet above-mentioned expectation, it is necessary to which dyeability, draftability be excellent and the polyethenol series of the long but thin of breadth
Film.In the case that the dyeability of polyvinyl alcohol film is low, sufficient degree of polarization can not be obtained, and has and easily produces polarisation
Uneven tendency.In the case that the draftability of polyvinyl alcohol film is low, fracture is produced in the manufacturing process of light polarizing film, therefore,
The light polarizing film of the long but thin of breadth can not be manufactured.Certainly, interruption is continuously manufactured due to fracture, the productivity ratio of light polarizing film is big
Width reduces.And then draftability it is low when, pigment can not be fully orientated, and therefore, have degree of polarization to reduce or easily produce inclined
The uneven tendency of light.Polyvinyl alcohol film more turns into the long but thin of breadth, and above-mentioned dyeability, the raising of draftability are more tired
It is difficult.In addition, in application type Polarizer for the purpose of so-called slimming, the process such as above-mentioned dyeing, stretching is also necessary, although
It is present in support film, but it is expected the improvement of the dyeability, draftability of the polyvinyl alcohol mesentery after coating.
In order to improve the dyeability of polyvinyl alcohol film, it is proposed that the method for the bath temperature of control swelling process (such as is joined
According to patent document 1,2).In addition, it is proposed that, using draftability for particular range polyvinyl alcohol film Polarizer (such as
With reference to patent document 3).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2006-065309 publications
Patent document 2：Japanese Unexamined Patent Publication 2014-197050 publications
Patent document 3：Japanese Unexamined Patent Publication 2002-236212 publications
The content of the invention
Problems to be solved by the invention
However, in technology disclosed in above-mentioned patent document 1 and 2, there are the following problems：It can be controlled even with bath temperature
Swellbility, if but it is inappropriate to the tension force of polyvinyl alcohol film application in bath, it can not also obtain consistent swelling shape
State, pigment will not be adsorbed equably in dyeing process afterwards.
In addition, in technology disclosed in above-mentioned patent document 3, define and polyvinyl alcohol film is stretched to 4 in water
Stress (tension force) at~6 times, but in the manufacture of actual light polarizing film, because the water temperature of each operation is different, therefore, be suitable to
The tension force of whole processes is insufficient.It should be noted that for water temperature, mostly relatively low in the processes such as swelling, dyeing
30 DEG C of temperature are nearby carried out, and are nearby carried out at 50 DEG C of higher temperatures mostly in the processes such as stretching, boric acid crosslinking.
Therefore, in the present invention, in this context, there is provided：The excellent polyvinyl alcohol film of dyeability, draftability,
And carry out to obtain there is high degree of polarization and without the uneven light polarizing film of polarisation in the case of the long but thin of breadth
Polyvinyl alcohol film.
The solution used to solve the problem
Thus, the present inventor etc. furthers investigate repeatedly in view of the foregoing, as a result finds：For by polyvinyl alcohol resin
The aqueous solution discharge and be cast to casting mould and be film-made, continuously dry obtained from polyvinyl alcohol film, in different temperatures
Water in when being stretched so that tension force turns into particular range in respective water, concentrates particularly at 50 DEG C of high temperature
Tension force in water, have so as to which the polyvinyl alcohol film of manufacture can also manufacture in the case where carrying out the long but thin of breadth
High degree of polarization and without the uneven light polarizing film of polarisation.
That is, idea of the invention is that a kind of polyvinyl alcohol film, it is characterised in that thickness is set into D (mm), 30
DEG C water in tension force when being stretched to 6 times along the flow direction (MD directions) of film be set to A (N/mm2), the edge in 50 DEG C of water
The tension force when flow direction (MD directions) of film is stretched to 6 times is set to B (N/mm2) when, meet following formula (1) and (2).
0.6≤the D of formula (1) × A≤1.2
0.2≤the D of formula (2) × B≤0.4
In addition, the present invention also provides：The manufacture method of above-mentioned polyvinyl alcohol film；Use above-mentioned polyvinyl alcohol film
Obtained from light polarizing film.
The effect of invention
Dyeability, the draftability of the polyvinyl alcohol film of the present invention are excellent, in addition, carrying out the long but thin of breadth
In the case of can also obtain having high degree of polarization and without the uneven light polarizing film of polarisation, and then can be manufactured with high productivity ratio
Light polarizing film.
Embodiment
Hereinafter, the present invention is described in detail.
The polyvinyl alcohol film of the present invention is necessary for following polyvinyl alcohol film：Thickness is set to D (mm), at 30 DEG C
Water in tension force when being stretched to 6 times along the flow direction (MD directions) of film be set to A (N/mm2), in 50 DEG C of water along thin
The tension force when flow direction (MD directions) of film is stretched to 6 times is set to B (N/mm2) when, meet following formula (1) and (2),
0.6≤the D of formula (1) × A≤1.2
0.2≤the D of formula (2) × B≤0.4
Preferably meet following formula (1 ') and the polyvinyl alcohol film of (2 '),
Formula (1 ') 0.65≤D × A≤1.15
Formula (2 ') 0.25≤D × B≤0.39
Particularly preferably meet following formula (1 ") and the polyvinyl alcohol film of (2 ").
Formula (1 ") 0.7≤D × A≤1.1
Formula (2 ") 0.27≤D × B≤0.38
On above-mentioned formula (1)~(1 "), when D × A value is too low, in swelling process, dyeing process film can deform without
It is preferred that even if too high, also change is difficult without preferred for sufficiently dyeing in dyeing process.
In addition, on above-mentioned formula (2)~(2 "), when D × B value is too low, degree of polarization when forming light polarizing film reduce without
It is preferred that when too high, fracture is easily produced when manufacturing light polarizing film, without preferred.
On above-mentioned formula (1)~(1 ") and above-mentioned formula (2)~(2 "), the thickness D of polyvinyl alcohol film value is in polarisation
Preferred below the 0.04mm of aspect of the slimming of film, in terms of the further slimming of light polarizing film particularly preferred 0.03mm with
Under, further preferred 0.01~0.03mm in terms of the fracture for avoiding light polarizing film.
And then polyvinyl alcohol film of the invention preferably meets following formula (3), particularly preferably meet following formula (3 '), enter one
Step preferably meets following formula (3 ").
0.2≤B/A≤0.5 of formula (3)
Formula (3 ') 0.25≤B/A≤0.4
Formula (3 ") 0.3≤B/A≤0.35
On above-mentioned formula (3)~(3 "), when B/A value is too low, degree of polarization when having the tendency of to be formed light polarizing film reduces, mistake
Gao Shi, fracture is easily produced when having the tendency of to manufacture light polarizing film.
In addition, for the polyvinyl alcohol film of the present invention, along the flow direction (MD directions) of film in 30 DEG C of water
Tension force A preferably 15~40N/mm when being stretched to 6 times2, particularly preferred 18~35N/mm2, further preferred 20~30N/mm2。
There is film when mentioned strain A value is too low, in swelling process, dyeing process to be easily deformed, when too high, dye
There is sufficiently dyeing in color process and become difficult.
And then for the polyvinyl alcohol film of the present invention, along the flow direction (MD directions) of film in 50 DEG C of water
Value preferably 3~15N/mm of tension force B when being stretched to 6 times2, particularly preferred 4~12N/mm2, further preferred 5~10N/mm2。
When mentioned strain B value is too low, degree of polarization when having the tendency of to be formed light polarizing film reduces, and when too high, has manufacture inclined
The tendency of fracture is easily produced during light film.
Moreover, for the present invention polyvinyl alcohol film, by the storage modulus in 30 DEG C of water be set to E1 (Pa), 50 DEG C
Water in storage modulus when being set to E2 (Pa), E2/E1 value preferably 0.25~0.30, particularly preferred 0.26~0.29.
When above-mentioned E2/E1 value is too low, the degree of polarization for having the tendency of gained light polarizing film reduces, and when too high, there is manufacture polarisation
The tendency of fracture is produced during film.
And then for the polyvinyl alcohol film of the present invention, in terms of transporting, the energy storage mould in above-mentioned 30 DEG C of water
Measure E1 preferably 9~12MPa.
In addition, in terms of transporting, storage modulus E2 preferably 2~4MPa in 50 DEG C of water.
Hereinafter, for the present invention polyvinyl alcohol film manufacture method, i.e. by the aqueous solution of polyvinyl alcohol resin
Discharge and be cast to casting mould and be film-made, continuously drying illustrates so as to manufacture the method for polyvinyl alcohol film.
, will usually using unmodified polyvinyl alcohol resin as the polyvinyl alcohol resin used in the present invention
Saponifying polyvinyl acetate obtained from vinyl acetate polyisocyanate polyaddition and the resin manufactured.As needed, can also use acetic acid
Vinyl acetate and on a small quantity (usual below the %'s of 10 moles of below %, preferably 5 moles) can be with the composition of vinyl acetate copolymerization
Copolymer carries out resin obtained from saponification.As with the composition of vinyl acetate copolymerization such as unsaturation can be enumerated
Olefines (such as ethene, propylene, n-butene, the isobutene of carboxylic acid (such as including salt, ester, acid amides, nitrile etc.), carbon number 2~30
Deng), ethene ethers, unsaturated sulfonic acid salt etc..Alternatively, it is also possible to using obtained from the hydroxyl after saponification is chemically modified
Modified polyvinylalcohol system resin.
In addition, as polyvinyl alcohol resin, the polyethenol series that there is 1,2- diol structures in side chain can also be used
Resin.The above-mentioned polyvinyl alcohol resin for having 1,2- diol structures in side chain can for example manufacture by the following method：(i) will
The method that the copolymer of vinyl acetate and 3,4- diacetoxy -1- butylene carries out saponification；(ii) by vinyl acetate and carbon
The method that the copolymer of sour vinylethylene carries out saponification and decarburization acid；(iii) by vinyl acetate and 2,2- dialkyl group -4- second
The copolymer of alkenyl -1,3- dioxolanes carries out saponification and de- ketalization method；(iv) by vinyl acetate and glycerine monoene
The method that the copolymer of propyl ether carries out saponification；Deng.
It is the weight average molecular weight of polyvinyl alcohol resin preferably 100,000~300,000, particularly preferred 110,000~280,000, further excellent
Select 120,000~260,000.When above-mentioned weight average molecular weight is too small, has to be difficult to obtain when polyvinyl alcohol resin is formed into optical thin film and fill
The tendency for the optical property divided, when excessive, stretching when having the tendency of the light polarizing film manufacture of polyvinyl alcohol film becomes difficult.Need
It is noted that the weight average molecular weight of above-mentioned polyvinyl alcohol resin is the weight average molecular weight to determine by GPC-MALS methods.
Generally preferable 98 moles of more than the % of mean saponification degree of the polyvinyl alcohol resin used in the present invention, particularly preferably
99 moles of more than %, further preferred 99.5 moles of more than %, particularly preferred 99.8 moles of more than %.Above-mentioned mean saponification degree mistake
Hour, have the tendency of that when polyvinyl alcohol film is formed into light polarizing film sufficient optical property can not be obtained.
Herein, the mean saponification degree in the present invention determines according to JIS K 6726.
As the polyvinyl alcohol resin used in the present invention, can also by modified material, modified amount, weight average molecular weight,
The different combinations of substances of more than two kinds such as mean saponification degree uses.
The polyvinyl alcohol film of the present invention can prepare polyvinyl alcohol resin water using above-mentioned polyvinyl alcohol resin
Solution (film stoste), the aqueous solution is discharged and is cast to casting mould, be filmed, dried using casting method, so as to
It is continuously manufactured by, such as is manufactured by following process.
Process (A), the process for modulating the polyvinyl alcohol resin aqueous solution.
Process (B), the polyvinyl alcohol resin aqueous solution is cast to the process poured mold and be film-made.
Process (C), make film film contacted with multiple METAL HEATING PROCESS rollers so as to heated and dry process.
Process (D), the process being heat-treated using hot blast to gained film.
Herein, mold is poured as above-mentioned, such as casting drum (drum type roller), annulus etc. can be enumerated, from breadth, long size
Change, set out in terms of the excellent in uniformity of thickness, preferably carried out with casting drum.
Hereinafter, illustrated in case of pouring mold as casting drum.
First, foregoing sequence (A) is illustrated.
In process (A), it is preferred that first, clean foregoing polyvinyl alcohol resin using water, use centrifugal separator
Etc. being dehydrated, below the weight % of moisture content 50 polyvinyl alcohol resin wet cake is formed.When moisture content is excessive, has and be difficult to shape
Into the tendency of desired concentration of aqueous solution.
Above-mentioned polyvinyl alcohol resin wet cake is dissolved in warm water, hot water, prepares the polyvinyl alcohol resin aqueous solution.
The preparation method of the polyvinyl alcohol resin aqueous solution is not particularly limited, it is, for example, possible to use by the more of heating
Prepared by screw extruder, furthermore it is possible to be put into the dissolving tank for possessing upper and lower recycle stream generation type stirring vane foregoing
Polyvinyl alcohol resin wet cake, vapor is blown into tank, so as to dissolve and prepare the aqueous solution of expectation concentration.
In the present invention, from improving degree of polarization aspect, preferably the latter, the more preferably pressurization by more than 120 DEG C is molten
Solution is modulated.
In the polyvinyl alcohol resin aqueous solution, in addition to polyvinyl alcohol resin, from Film making properties aspect, preferably
It is, as needed containing at least one of plasticizer, nonionic, anionic property and cationic surfactant.
As the plasticizer used in the present invention, such as glycerine, two glycerine, triglycerin, ethylene glycol, three second two can be enumerated
Alcohol, polyethylene glycol, trimethylolpropane etc..Wherein, from cheap aspect, preferably glycerine.
Using compounding amount during glycerine relative to polyvinyl alcohol resin preferably 5~12 weight %, particularly preferred 6~11.5
Weight %, further preferred 7~11%.
When above-mentioned compounding amount is very few, there is polyvinyl alcohol film tension force in water and increase, when excessive, there is polyethylene
A hypodynamic tendency in the water of alcohol system film.
As the surfactant used in the present invention, from going out in terms of the compatibility of the polyvinyl alcohol resin aqueous solution
Hair, preferred anionic surfactant.
The resin concentration of the so obtained polyvinyl alcohol resin aqueous solution preferably 15~60 weight %, it is particularly preferred 17~
55 weight %, further preferred 20~50 weight %.When above-mentioned resin concentration is too low, drying load becomes big, therefore, there is production energy
The tendency that power reduces, when too high, having the tendency of viscosity becomes too high and is not easy uniformly to be dissolved.
The polyvinyl alcohol resin aqueous solution as film stoste can so be obtained.Then, foregoing sequence (B) is carried out
Explanation.
Deaeration processing is carried out to the above-mentioned polyvinyl alcohol resin aqueous solution.As defoaming method, can enumerate standing and defoaming,
The methods of deaeration being carried out using the multi-screw extruder for possessing exhaust outlet.As the multi-screw extruder for possessing exhaust outlet, generally
Use the double screw extruder for possessing exhaust outlet.
After deaeration processing, the polyvinyl alcohol resin aqueous solution is directed into T-shaped slit die with a certain amount of successively, discharges cocurrent
It is extended down on the casting drum of rotation, is filmed by casting method.
It is preferably 80~100 DEG C of the resin temperature of T-shaped slit die outlet, particularly preferred 85~99 DEG C.Above-mentioned resin temperature
When too low, have the tendency of to become to flow bad, when too high, there is foaming.
The viscosity of the above-mentioned polyvinyl alcohol resin aqueous solution in discharge preferably 50~200Pas, it is particularly preferred 70~
150Pa·s。
When the viscosity of the above-mentioned aqueous solution is too low, have the tendency of to become to flow bad, when too high, there is curtain coating to become difficult and incline
To.
Preferably 0.2~5m/ points of the velocity of discharge of the polyvinyl alcohol resin aqueous solution of casting drum is expelled to from T-shaped slit die
Clock, particularly preferred 0.4~4m/ minutes, further preferred 0.6~3m/ minutes.
When the above-mentioned velocity of discharge is excessively slow, there is productivity ratio reduction, when too fast, have the tendency of curtain coating and become difficult.
During curtain coating, from breadth, long sizing, thickness uniformity etc., preferably carried out with casting drum.As
Casting drum, is generally used in the metal deposition implemented on the surface using iron as the stainless steel (SUS) of principal component for preventing cut.
As metal deposition, such as chromium plating, nickel plating, zinc-plated etc. can be enumerated, they can be used alone or more than 2 layers of stackingization and make
With.Wherein, from the durability aspect on drum surface, the preferred chromium plating of most surface.
Hereinafter, in case of using casting drum, film-forming method is illustrated.
Cast bulging preferred more than the 4m of width, particularly preferred more than 5m.When bulging width of casting is too small, width is difficult to obtain
The tendency of wide film.
Diameter preferably 2~5m, particularly preferred 2.4~4.5m, the further preferred 2.8~4m of above-mentioned casting drum.
When above-mentioned diameter is too small, has the tendency of to dry long deficiency and be not likely to produce speed, when excessive, there is transportability reduction
Tendency.
Rotating speed preferably 3~50m/ minutes of above-mentioned casting drum, particularly preferred 4~40m/ minutes, further preferred 5~35m/
Minute.When rotating speed is excessively slow, there is productivity ratio reduction, when too fast, have the tendency of to dry deficiency.
It is preferably 40~99 DEG C of the surface temperature of above-mentioned casting drum, particularly preferred 60~95 DEG C.When surface temperature is too low, there is change
The tendency of underdry is obtained, when too high, there is foaming.
So it is filmed.
Then, foregoing sequence (C) is illustrated.Process (C) is that the film for making film contacts with multiple METAL HEATING PROCESS rollers
So as to the process for being heated and being dried.
With the drying of the polyvinyl alcohol film of casting drum film by making surface and the back side and the multiple METAL HEATING PROCESSs of film
Roller is alternately contacted and carried out.The surface temperature of METAL HEATING PROCESS roller is not particularly limited, it is usually preferred to 60~150 DEG C, further
It is preferred that 70~140 DEG C.When above-mentioned surface temperature is too low, has the tendency of to become underdry, when too high, become over drying, have
Cause the tendency of the bad orders such as bending.
In the present invention, the tension force aspect from the water of control polyvinyl alcohol film, the temperature of multiple METAL HEATING PROCESS rollers
Degree is preferably following condition (a)~(d) order.
Condition (a) >=80 DEG C
Condition (b)<80℃
Condition (c) >=100 DEG C
Condition (d)<100℃
It should be noted that generally the radical of METAL HEATING PROCESS roller is 10~30, suitably setting makes it meet above-mentioned temperature
Degree condition.
After being dried using METAL HEATING PROCESS roller, by gained film in process (D), it is heat-treated using hot blast.Connect
, foregoing sequence (D) is illustrated.
It is preferably 110~140 DEG C of the temperature of heat treatment, particularly preferred 115~135 DEG C, further preferred 120~130 DEG C.On
State heat treatment temperature it is too low when, have in the water of polyvinyl alcohol film a hypodynamic tendency, when too high, have polyethenol series thin
The tendency that tension force increases in the water of film.
As above-mentioned heat-treating methods, from the aspect that temperature control is excellent, carried out preferably by floating drying machine
Method.
The both ends for the film being heat-treated are cut, batched in roller and as the polyvinyl alcohol film of web-like.
In addition, from the breadth aspect of light polarizing film, preferred more than the 4m of width of above-mentioned polyvinyl alcohol film, from
Set out in terms of further breadth, particularly preferred more than 4.5m, from the aspect for avoiding fracture, further preferred 4.5
~6m.
For the length of above-mentioned polyvinyl alcohol film, from the large area aspect of light polarizing film, preferably 4km with
On, from further large area aspect, particularly preferred more than 4.5km, from hauled weight aspect, further
It is preferred that 4.5~50km.
For above-mentioned polyvinyl alcohol film, from batching property aspect, along film in 20 DEG C of 65%RH air
Tension force preferably 40~80N/mm of the flow direction (MD directions) when being stretched to 4 times2, from keeping when stability in terms of go out
Hair, particularly preferred 43~75N/mm2, the easiness aspect of the control of tension force from water, further preferred 46~70N/mm2。
For above-mentioned polyvinyl alcohol film, the uniformity aspect of tension force from water, phase difference is preferred in face
Below 50nm, particularly preferred below 40nm, further preferred below 30nm.
The polyvinyl alcohol film of the present invention can so be obtained.
The excellent in optical properties of the polyvinyl alcohol film of the present invention, the polyethenol series that can be suitable as optics are thin
Film uses, and then is used particularly preferable as the reel of light polarizing film.
Hereinafter, the manufacture method of the light polarizing film obtained to the polyvinyl alcohol film using the present invention illustrates.
The light polarizing film of the present invention is that above-mentioned polyvinyl alcohol film is rolled out from roller and is transported in the horizontal direction, by molten
It is swollen, dyeing, boric acid crosslinking, stretching, cleaning, dry etc. process and manufacture.
Swelling process is implemented before dyeing process.By being swelled process, polyvinyl alcohol film surface can be cleaned
Dirt, and by being swelled polyvinyl alcohol film, prevent from dyeing unequal effect so as to also have.It is swelled in process,
As treatment fluid, usually using water.As long as the principal component of the treatment fluid is water, a small amount of iodate chemical combination can also be added
The additives such as thing, surfactant, alcohol etc..The temperature of swelling bath is usually 10~45 DEG C or so, the dip time in swelling bath
Usually 0.1~10 minute or so.In addition, stretched operation can also be carried out in processes as needed.
Dyeing process is carried out by making film be contacted with the liquid containing iodine or dichroic dye.Usually using iodo- iodine
Change the aqueous solution of potassium, it is appropriate that the concentration of iodine is 0.1~2g/L, the concentration of KI is 1~100g/L.Dyeing time is real
It is 30~500 seconds or so.Handle preferably 5~50 DEG C of the temperature of bath.In the aqueous solution, in addition to aqueous solvent, it can also contain
A small amount of organic solvent for having compatibility with water.In addition, stretched operation can also be carried out in processes as needed.
Boric acid cross-linking process step is carried out using boron compounds such as boric acid, boraxs.Boron compound is with the aqueous solution or water-have
The form of solvent mixed liquor, used with 10~100g/L of concentration or so, from the stabilized aspect of polarization property, preferably
KI is set to coexist in liquid.Preferably 30~70 DEG C or so of temperature, processing time preferably 0.1~20 minute left side during processing
The right side, and stretched operation can also be carried out in processes as needed.
Stretching process is preferably, and is stretched 3~10 times along single shaft direction, is preferably stretched 3.5~6 times.At this time it is also possible to edge
The right angle orientation of draw direction carries out fraction of stretching (preventing the degree of the contraction of width or the stretching more than it).Draw
Preferably 30~170 DEG C of temperature when stretching.And then as long as stretching ratio is ultimately set to aforementioned range, stretched operation can be with
Only carried out, can implemented in the stage of any range of manufacturing process with a stage.
Matting iodide aqueous solution such as by the way that polyvinyl alcohol film is impregnated in into water, KI is carried out,
Precipitate caused by surface in film can be removed.Using iodate potassium concn during potassium iodide aqueous solution can be 1~
80g/L or so.Temperature during cleaning treatment is usually 5~50 DEG C, preferably 10~45 DEG C.Processing time is usual 1~300 second, excellent
Select 10~240 seconds.It should be noted that can also by water clean and using potassium iodide aqueous solution progress cleaning proper combination and
Carry out.
As long as drying process is carried out 1~10 minute in an atmosphere, with 40~80 DEG C.
In addition, the degree of polarization of light polarizing film preferably more than 99.5%, more preferably more than 99.8%.When degree of polarization is too low, whether there is
Method ensures the tendency of the contrast in liquid crystal display.
It should be noted that degree of polarization typically calculates as follows：Make 2 light polarizing films overlapping so that its differently- oriented directivity turns into same
According to the light transmittance (H determined under wavelength X in the state of one direction11) and make 2 light polarizing films overlapping so that differently- oriented directivity
Light transmittance (the H determined in the state of mutually orthogonal directions under wavelength X1), calculated according to following formula.
〔(H11-H1)/(H11+H1)〕1/2
And then the singleton transmittance of light polarizing film of the invention preferably more than 42%.When above-mentioned singleton transmittance is too low, whether there is
Method reaches the tendency of the high brightness of liquid crystal display.
Singleton transmittance is value obtained from the light transmittance using spectrophotometric determination light polarizing film monolithic.
The light polarizing film of the present invention can be so obtained, light polarizing film of the invention is suitable for manufacturing the few polarisation of irregular colour
Plate.
Hereinafter, the manufacture method of the Polarizer of the present invention is illustrated.
The light polarizing film of the present invention is in its one or two sides by bonding agent, the resin film of fitting optical isotropy
Turn into Polarizer as diaphragm.As diaphragm, for example, can enumerate cellulosic triacetate, cellulose diacetate,
Makrolon, polymethyl methacrylate, cyclic olefin polymer, cyclic olefine copolymer, polystyrene, polyether sulfone, polyarylate,
The film or piece of poly- 4- methylpentenes, polyphenylene oxide etc..
Applying method is carried out in a known manner, for example, by the adhesive composite of liquid be equably coated on light polarizing film,
After diaphragm or both, both is bonded and is crimped, heat, irradiate active energy beam so as to carry out.
In addition, for light polarizing film, for filming, instead of said protection film, can also be coated with its one or two sides
The curable resins such as polyurethane series resin, acrylic resin, carbamide resin are simultaneously solidified to form Polarizer.
The face of the polarization property for the light polarizing film that the polyvinyl alcohol film obtained by the manufacture method by the present invention is formed
Interior uniformity is also excellent, is preferred for：Personal digital assistant device machine, PC, TV, projecting apparatus, billboard, desktop computer,
It is electronic clock, word processor, Electronic Paper, game machine, video camera, camera, photo frame, thermometer, sound equipment, automobile, mechanical
Meters etc. liquid crystal display device, sunglasses, anti-glare glasses, anaglyph spectacles, wearable display, display element
(CRT, LCD, organic EL, Electronic Paper etc.) uses anti-reflection layer, optical communication equipment, Medical Devices, construction material, toy etc..
Embodiment
Hereinafter, enumerate embodiment to the present invention be further specifically described, as long as but the present invention be no more than its purport just
It is not limited to following embodiment.
It should be noted that " part ", " % " refer to weight basis in example.
<Condition determination>
(1) tensile stress (N/mm in water2)
From gained polyvinyl alcohol film cut-out length (MD directions) 50mm × width (TD directions) 35mm × thickness D (mm)
Test film, in a manner of chuck spacing turns into 20mm, by the both ends of length direction with the clamping of wide 35mm chuck after, 30
DEG C and 50 DEG C of water in, with spring scale measure along MD directions be stretched to 6 times with speed 18mm/ minutes when stress (N).Will be above-mentioned
Value is used as tensile stress (N/mm obtained from the sectional area of stress divided by film2)。
(2) tensile stress (N/mm in air2)
Gained polyvinyl alcohol film is carried out in 20 DEG C of 65%RH air after state adjusts one day, cut-out length
(MD directions) 120mm × width (TD directions) 15mm × thickness D (mm) test film, use society of Shimadzu Seisakusho Ltd. system " precision ten thousand
Energy testing machine, AUTOGRAPH (AG-IS) ", it is in a manner of chuck spacing turns into 50mm, the both ends of length direction are wide
After 15mm chuck clamping, in 20 DEG C of 65%RH air, determine along MD directions and be stretched to 4 times with speed 1000mm/ minutes
When stress (N).Using value obtained from the sectional area of above-mentioned stress divided by film as the tensile stress (N/mm in air2)。
(3) phase difference (nm) in face
From gained polyvinyl alcohol film cut-out length (MD directions) 20cm × width (TD directions) 20cm test film, make
With two-dimentional birefringence evaluation system (Photonic Lattice, Inc. systems：" PA-110L "), phase difference (nm) in aspect of measure.
(4) degree of polarization (%), singleton transmittance (%)
From gained light polarizing film cut-out length 4cm × width 4cm sample, device (Japan is determined using automatic polarizing film
It is divided Co. Ltd. system：VAP7070), degree of polarization (%) and singleton transmittance (%) are determined.
(5) polarisation is uneven
From gained light polarizing film cut-out length 30cm × width 30cm test film, crossed nicols are held on 45 ° of angle
After between 2 Polarizers (singleton transmittance 43.5%, degree of polarization 99.9%) of state, the lux of surface illuminance 14000 is used
(lx) lamp box, optical irregular colour is observed in the transmission mode, evaluated with following benchmark.
(metewand)
Zero without irregular colour
△ slightly irregular colours
× there is irregular colour
<Embodiment 1>
(manufacture of polyvinyl alcohol film)
Weight average molecular weight 142000,99.8 moles of % of saponification degree polyethenol series tree are added in 5000L dissolving tank
Fat 1000kg, water 2500kg, the glycerine 105kg as plasticizer and the dodecyl sodium sulfate as surfactant
0.25kg, to 150 DEG C of progress dissolved under pressure, the polyvinyl alcohol resin for obtaining resin concentration 25% is water-soluble for warming while stirring
Liquid.
Then, the polyvinyl alcohol resin aqueous solution is supplied to the double screw extruder for possessing exhaust outlet, after deaeration, made
Aqueous temperature is 95 DEG C, discharges and is cast to the casting drum rotated with 20m/ minutes from T-shaped slit die outlet and be film-made.Will
Gained film is peeled off from casting drum, while making the surface of film and alternately contact edge enters with adding up to the METAL HEATING PROCESS roller of 20 at the back side
Row drying.Above-mentioned METAL HEATING PROCESS roller is configured with 90 DEG C, 70 DEG C, 110 DEG C, 85 DEG C of temperature sequence.Then, blowed from film two sides
140 DEG C of hot blast and after being heat-treated, finally cut and batch, obtain the polyvinyl alcohol film (film thickness of web-like
0.03mm, width 5m, length 5km).The characteristic of gained polyvinyl alcohol film is as shown in table 1.
(manufacture of light polarizing film)
Gained polyvinyl alcohol film is rolled out from roller, edge horizontal direction conveying, while being impregnated in the tank of 30 DEG C of water temperature
And after being swelled it, 1.7 times are stretched to along MD directions.Then, while in 30 DEG C formed by iodine 0.5g/L, KI 30g/L
Impregnate and dye in the aqueous solution, edge MD directions are stretched to 1.6 times, then, while being impregnated in boric acid 40g/L, KI 30g/L
(50 DEG C) progress boric acid crosslinkings of the aqueous solution of composition, edge MD directions uniaxial tension is to 2.1 times.Finally, potassium iodide aqueous solution is used
Cleaned, afterwards, with 50 DEG C of progress drying in 2 minutes, obtain the light polarizing film of total 5.7 times of stretching ratio.Do not have in above-mentioned manufacture
Cause fracture, the characteristic of gained light polarizing film is as shown in table 2.
<Embodiment 2>
In embodiment 1, blow 130 DEG C of hot blast and be heat-treated, in addition, obtain poly- second similarly to Example 1
Enol system film and light polarizing film.For gained light polarizing film, evaluation similarly to Example 1 is carried out.Evaluation result is shown in the He of table 1
Table 2.
<Embodiment 3>
In embodiment 1, the rotating speed for drum of casting is changed to 10m/ minutes, it is 0.06mm to make film thickness, blows 120 DEG C
Hot blast is heat-treated, and in addition, obtains polyvinyl alcohol film and light polarizing film similarly to Example 1.It is inclined for gained
Light film, carry out evaluation similarly to Example 1.Evaluation result is shown in Tables 1 and 2.
<The ＞ of embodiment 4
In embodiment 1, the rotating speed for drum of casting is changed to 10m/ minutes, it is 0.06mm to make film thickness, makes heat treatment temperature
Spend for 110 DEG C, in addition, obtain polyvinyl alcohol film and light polarizing film similarly to Example 1.For gained light polarizing film,
Carry out evaluation similarly to Example 1.Evaluation result is shown in Tables 1 and 2.
<The ＞ of comparative example 1
In embodiment 1, the rotating speed for drum of casting is changed to 10m/ minutes, it is 0.06mm to make film thickness, makes heat treatment temperature
Spend for 100 DEG C, in addition, obtain polyvinyl alcohol film and light polarizing film similarly to Example 1.For gained light polarizing film,
Carry out evaluation similarly to Example 1.Evaluation result is shown in Tables 1 and 2.
<The ＞ of comparative example 2
In embodiment 1, it is 150 DEG C to make heat treatment temperature, in addition, obtains polyethenol series similarly to Example 1
Film.Start to manufacture light polarizing film using the polyvinyl alcohol film, but in factory length 1km light polarizing film, boric acid crosslinking work
Fracture is produced in the stretching of sequence, target light polarizing film can not be obtained.
<The ＞ of comparative example 3
In embodiment 1, make all 80 DEG C of METAL HEATING PROCESS roll temperature, in addition, obtain poly- second similarly to Example 1
Enol system film and light polarizing film.For gained light polarizing film, evaluation similarly to Example 1 is carried out.Evaluation result is shown in the He of table 1
Table 2.
[table 1]
[table 2]
For the polyvinyl alcohol film of embodiment 1~4, thickness is set to D (mm), in 30 DEG C of water along the stream of film
Tension force when dynamic direction (MD directions) is stretched to 6 times is set to A (N/mm2), in 50 DEG C of water along flow direction (the MD side of film
To) be stretched to 6 times when tension force be set to B (N/mm2) when, D × A and D × B value are satisfied by formula (1) and (2), on the other hand, right
In the polyvinyl alcohol film of comparative example 1, D × B value is in outside the scope of formula (2), for the polyvinyl alcohol of comparative example 2 and 3
It is film, D × A value is in outside the scope of formula (1), and D × B value is also at outside the scope of formula (2).
And understand, for the polarized light property of the light polarizing film obtained by each polyvinyl alcohol film, embodiment 1~4 is compared
It is also excellent compared with example 1 and 3, and then in comparative example 2, light polarizing film can not be obtained due to fracture.
And then the polyvinyl alcohol film for being obtained in embodiment 3 and 4, comparative example 1, according to following methods, measure storage
Energy modulus E1, E2, calculate E2/E1 value.
(6) storage modulus (MPa)
From gained polyvinyl alcohol film cut-out length (MD directions) 25mm × width (TD directions) 5mm test film, make
With ITKCO., LTD. DVA-225, the storage modulus in 30 DEG C and 50 DEG C of water is determined.Detailed experimental condition is as described below.
Frequency：10Hz
Chuck spacing：15mm
Load：Dynamic strain along MD directions is 0.3%, quiet move than (the ratio between static strain and dynamic strain) is 6
By the storage modulus E1 (MPa) after 30 DEG C of water rettings 10 minutes and the energy storage after 50 DEG C of water rettings 10 minutes
Modulus E2 (MPa), calculates E2/E1.It should be noted that used for the thickness for calculating the storage modulus in water before water retting
Thickness.
The result of measure is：Embodiment 3：E2/E1=0.28, embodiment 4：E2/E1=0.27, comparative example 1：E2/E1=
0.25, it is thus identified that, in the case that E2/E1 value is low, degree of polarization when forming light polarizing film reduces.
In above-described embodiment, the concrete mode in the present invention is shown, but above-described embodiment only simple example,
Being not construed as limiting property is explained.It will be apparent to those skilled in the art that various modifications mean in the scope of the present invention.
Industrial applicability
The face of the polarization property for the light polarizing film that the polyvinyl alcohol film obtained by the manufacture method by the present invention is formed
Interior uniformity is also excellent, is preferred for：Personal digital assistant device machine, PC, TV, projecting apparatus, billboard, desktop computer,
It is electronic clock, word processor, Electronic Paper, game machine, video camera, camera, photo frame, thermometer, sound equipment, automobile, mechanical
Meters etc. liquid crystal display device, sunglasses, anti-glare glasses, anaglyph spectacles, wearable display, display element
(CRT, LCD, organic EL, Electronic Paper etc.) uses anti-reflection layer, optical communication equipment, Medical Devices, construction material, toy etc..
Claims (13)
- A kind of 1. polyvinyl alcohol film, it is characterised in thatBy thickness be set to D (mm),Tension force when being stretched to 6 times along the flow direction (MD directions) of film in 30 DEG C of water is set to A (N/mm2)、Tension force when being stretched to 6 times along the flow direction (MD directions) of film in 50 DEG C of water is set to B (N/mm2) when,Meet following formula (1) and (2),0.6≤the D of formula (1) × A≤1.20.2≤the D of formula (2) × B≤0.4.
- 2. polyvinyl alcohol film according to claim 1, it is characterised in that meet following formula (3),0.2≤B/A≤0.5 of formula (3).
- 3. polyvinyl alcohol film according to claim 1 or 2, it is characterised in that by the storage modulus in 30 DEG C of water When the storage modulus being set in E1 (Pa), 50 DEG C of water is set to E2 (Pa), E2/E1 is 0.25~0.30.
- 4. according to polyvinyl alcohol film according to any one of claims 1 to 3, it is characterised in that polyvinyl alcohol film Thickness D be below 0.04mm.
- 5. according to polyvinyl alcohol film according to any one of claims 1 to 4, it is characterised in that polyvinyl alcohol film Width be more than 4m and length is more than 4km.
- 6. according to polyvinyl alcohol film according to any one of claims 1 to 5, it is characterised in that 20 DEG C of 65%RH's In air, tension force when being stretched to 4 times along the flow direction (MD directions) of film is 40~80N/mm2。
- 7. according to polyvinyl alcohol film according to any one of claims 1 to 6, it is characterised in that phase difference is in face Below 50nm.
- 8. a kind of manufacture method of polyvinyl alcohol film, it is characterised in that it is any one of manufacturing claims 1~7 institute The method for the polyvinyl alcohol film stated, the polyvinyl alcohol film manufacture by following processes (A)~(D),Process (A), the process for modulating the polyvinyl alcohol resin aqueous solution；Process (B), the polyvinyl alcohol resin aqueous solution is cast to the process poured mold and be film-made；Process (C), make film film contacted with multiple METAL HEATING PROCESS rollers so as to heated and dry process；Process (D), the process being heat-treated using hot blast to gained film.
- 9. the manufacture method of polyvinyl alcohol film according to claim 8, it is characterised in that right in the process (A) In polyvinyl alcohol resin, 5~12 weight % of compounding glycerine.
- 10. the manufacture method of polyvinyl alcohol film according to claim 8 or claim 9, it is characterised in that the process (C) In multiple METAL HEATING PROCESS rollers temperature be following condition (a)~(d) order,Condition (a) >=80 DEG CCondition (b)<80℃Condition (c) >=100 DEG CCondition (d)<100℃.
- 11. the manufacture method of the polyvinyl alcohol film according to any one of claim 8~10, it is characterised in that institute It is 110~140 DEG C to state the heat treatment temperature in process (D).
- 12. a kind of polyvinyl alcohol film, it is characterised in that it is with the manufacturer any one of claim 8~11 Method and manufacture.
- 13. a kind of light polarizing film, it is characterised in that it is thin as the polyethenol series any one of claim 1~7,12 What film was formed.
Applications Claiming Priority (3)
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| JP2015-126122 | 2015-06-24 | ||
| JP2015126122 | 2015-06-24 | ||
| PCT/JP2016/068598 WO2016208652A1 (en) | 2015-06-24 | 2016-06-23 | Poly(vinyl alcohol)-based film, process for producing poly(vinyl alcohol)-based film, and polarizing film |
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| JP (2) | JP6883990B2 (en) |
| KR (1) | KR102475405B1 (en) |
| CN (1) | CN107614578A (en) |
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| CN107531919A (en) * | 2015-08-18 | 2018-01-02 | 日本合成化学工业株式会社 | Polyvinyl alcohol film and use its light polarizing film |
| CN110356025A (en) * | 2018-04-09 | 2019-10-22 | 日东电工株式会社 | The manufacturing method of polarizing film |
Families Citing this family (1)
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| TW202239861A (en) * | 2020-12-23 | 2022-10-16 | 日商三菱化學股份有限公司 | Polyvinyl alcohol film for producing polarizing film, method for producing polyvinyl alcohol film for producing polarizing film, and polarizing film |
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| KR102475405B1 (en) | 2022-12-07 |
| TW201710303A (en) | 2017-03-16 |
| KR20180022648A (en) | 2018-03-06 |
| WO2016208652A1 (en) | 2016-12-29 |
| JP6883990B2 (en) | 2021-06-09 |
| JPWO2016208652A1 (en) | 2018-04-12 |
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| TWI676638B (en) | 2019-11-11 |
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