CN108139528A - Light polarizing film manufacture polyvinyl alcohol film and its light polarizing film, polarizer and light polarizing film is used to manufacture the manufacturing method with polyvinyl alcohol film - Google Patents
Light polarizing film manufacture polyvinyl alcohol film and its light polarizing film, polarizer and light polarizing film is used to manufacture the manufacturing method with polyvinyl alcohol film Download PDFInfo
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- CN108139528A CN108139528A CN201680058384.XA CN201680058384A CN108139528A CN 108139528 A CN108139528 A CN 108139528A CN 201680058384 A CN201680058384 A CN 201680058384A CN 108139528 A CN108139528 A CN 108139528A
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- film
- polyvinyl alcohol
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- light polarizing
- polarizing film
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/08—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique transverse to the direction of feed
-
- 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
-
- 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
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
Abstract
A kind of light polarizing film manufacture polyvinyl alcohol film, it is characterized in that, it is 5~60 μm of thickness, the polyvinyl alcohol film of more than width 2m, more than length 2km, when the polyvinyl alcohol film is impregnated 15 minutes in 30 DEG C of water, the swellbility X (%) of width direction (TD directions) and the swellbility Y (%) of length direction (MD directions) meet following conditions (1) and (2), (1) 110≤Y≤140, (2) 1.01≤Y/X≤1.2.
Description
Technical field
(only it is recorded as that " polyethenol series are thin sometimes below with polyvinyl alcohol film the present invention relates to light polarizing film manufacture
Film "), particularly can obtain having the polyethenol series of the light polarizing film that excellent dyeability, degree of polarization are high and irregular colour is few
Film and the light polarizing film of the polyvinyl alcohol film, polarizer and light polarizing film manufacture polyvinyl alcohol film are used
Manufacturing method.
Background technology
So far, the polyvinyl alcohol film film excellent as the transparency is used for one of many purposes, useful purposes,
Light polarizing film can be enumerated.Above-mentioned light polarizing film is used as the basic constituent element of liquid crystal display, in recent years, to requiring high-quality and height
The use of the instrument of reliability expands.
Wherein, with LCD TV, multifunction portable terminal etc. picture high brightness, High precision, large area
Change, slimming, it is desirable that the excellent light polarizing film of polarizing properties.Specifically, it further improves degree of polarization, solve irregular colour.
In general, light polarizing film manufacture polyvinyl alcohol film utilizes continuous casting by the aqueous solution of polyvinyl alcohol resin
Manufacture.Specifically, the aqueous solution curtain coating of polyvinyl alcohol resin is film-made in casting molds such as cast drum, endless belts, it will
After the film being film-made is removed by casting mold, while conveyance using nip rolls etc. in flow direction (MD directions), heat is used
Roller, floated drying machine (floating dryer) are dried, and thus manufacture above-mentioned polyvinyl alcohol film.Above-mentioned conveyance work
In sequence, the film being film-made in flow direction (MD directions) due to being stretched, and polyethenol series macromolecule is easily in MD side
To orientation.
On the other hand, usual light polarizing film makes the polyvinyl alcohol film swelling as its blank by using water (including warm water)
Afterwards, it is dyed and is stretched to manufacture with dichroic dyes such as iodine.In above-mentioned swelling process, need that polyvinyl alcohol film is made to exist
Thickness direction is rapidly swollen.And then in dyeing process, need uniformly to be swollen so that dyestuff is successfully invaded inside film.
In addition, stretching process is the dichroism in stretching in flow direction (MD directions) by the film after dyeing, make film
The height-oriented process of dyestuff, in order to improve the polarizing properties of light polarizing film, becoming the polyvinyl alcohol film of blank needs in MD
Direction has good draftability.
It should be noted that in light polarizing film manufacture, also implement stretching process and the sequence of dyeing process is contrary to the above
Example.That is, to make to be stretched after as the polyvinyl alcohol film swelling of blank by the use of water (including warm water), with dichroism such as iodine
The example of dyeing, in above-mentioned example, in order to improve the polarizing properties of light polarizing film, it is also desirable to which polyvinyl alcohol film is in thickness
Direction is with good swellability and in MD directions with good draftability.
And then in recent years in order to realize the slimming of light polarizing film, polyvinyl alcohol film is also being thinned.It is above-mentioned slim thin
Stretching when film there are problems that due to manufacture light polarizing film and the productivities such as be broken.
As the gimmick of improvement swellability, such as propose and polyalcohol is added in polyvinyl alcohol resin as water-swellable
The gimmick of auxiliary agent (referring for example to patent document 1).As the gimmick of improvement draftability, such as propose when will be film-made film
It pours into a mould the specific gimmick (referring for example to patent document 2) of the ratio between bulging speed and final film coiling speed, made with cast drum
The drying process of the be film-made film of the gimmick (referring for example to patent document 3) that is dried membrane suspension after film, control
In stretched condition gimmick (referring for example to patent document 4).
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2001-302867 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2001-315141 bulletins
Patent document 3：Japanese Unexamined Patent Publication 2001-315142 bulletins
Patent document 4：Japanese Unexamined Patent Publication 2002-79531 bulletins
Invention content
Problems to be solved by the invention
But even the gimmick of above patent document, for improvement light polarizing film manufacture when swellability and draftability and
Speech is also insufficient.
Using above patent document 1 public technology when, that is, allow to improve polyvinyl alcohol film entirety swellability,
The high molecular state of orientation of polyethenol series is not accounted for, it is difficult in flow direction when effectively improveing light polarizing film manufacture yet
Draftability on (MD directions).On the contrary, due to water-swellable dose of addition, and there are high molecular state of orientation it is chaotic, be difficult to
The tendency of Uniform Tension is carried out on flow direction (MD directions).
(shape is stretched to the level of stretch in MD directions during specific manufacture polyvinyl alcohol film in above patent document 2
Condition), but be not fill for draftability when if the stretching on TD directions for improvement light polarizing film manufacture is not accounted for
Point.Generally for the polyvinyl alcohol film being orientated in MD directions, it is difficult to be stretched when light polarizing film manufactures in MD directions.
That is, when the polyethenol series macromolecule being orientated in MD directions is further stretched in MD directions, it is tired to force and elongate strand
Difficult.On the contrary, it is to be relatively easy to that the polyethenol series macromolecule being orientated in TD directions is stretched in MD directions.But
If if the macromolecular orientation on TD directions is uneven when light polarizing film manufactures cannot equably MD directions stretch.Patent document
There is also the example (example not stretched) when polyvinyl alcohol film manufactures, less stretched in MD directions in 2, still
Merely with the above-mentioned shrinkage stress for depending on Poisson's ratio and when the shrinkage stress caused by dehydration, existing cannot will be in TD side
The problem of upward macromolecular orientation fully homogenizes.If that is, not in TD directions to stretch to a certain degree or at least yet
There is no fixed width direction, then cannot get uniform state of orientation of the macromolecule on TD directions, for improvement light polarizing film manufacture
When draftability in the MD direction for be insufficient.In addition, the not record about the orientation to thickness direction, no
Swellability when can control the light polarizing film to manufacture.
Using above patent document 3 public technology when, cannot although can be by the film evenly drying after film
High molecular orientation is controlled, is insufficient for the swellability, draftability when improvement light polarizing film manufacture.
Using above patent document 4 public technology when, although the uniform film thickness of polyvinyl alcohol film can be made,
High molecular orientation cannot be controlled, is insufficient for the swellability, draftability when improvement light polarizing film manufacture.
Therefore, in the present invention, in this background, swellability and draftability when providing light polarizing film manufacture be excellent, can be with
Obtain having high polarizing properties and the light polarizing film manufacture polyvinyl alcohol film of the few light polarizing film of irregular colour, particularly
The light polarizing film manufacture polyvinyl alcohol film that will not be produced fracture in the manufacture of slim light polarizing film, and then provide by above-mentioned
The light polarizing film and polarizer and light polarizing film that light polarizing film manufacture is formed with polyvinyl alcohol film manufacture thin with polyethenol series
The manufacturing method of film.
The solution to the problem
However, the inventors of the present invention further investigate in view of the above problems, as a result, it has been found that, the swelling of width direction (TD directions)
The polyvinyl alcohol film that the ratio of degree X (%) and the swellbility Y (%) of flow direction (MD directions) is within a certain range exists
It is excellent in terms of swellability and draftability when light polarizing film manufactures, become tool using the light polarizing film that above-mentioned polyvinyl alcohol film obtains
There are high polarizing properties and the few light polarizing film of irregular colour.
That is, the first purport of the present invention is a kind of light polarizing film manufacture polyvinyl alcohol film, which is characterized in that it is
5~60 μm of thickness, more than width 2m, more than length 2km polyvinyl alcohol film, by the polyvinyl alcohol film at 30 DEG C
When being impregnated 15 minutes in water, the swellbility X (%) of width direction (TD directions) and the swellbility Y (%) of length direction (MD directions)
Meet following conditions (1) and (2).
(1)110≤Y≤140
(2)1.01≤Y/X≤1.2
Particularly, the second purport of the invention is a kind of light polarizing film manufacture polyvinyl alcohol film, which is characterized in that
When above-mentioned polyvinyl alcohol film is impregnated 15 minutes in 30 DEG C of water, the swellbility Z (%) of thickness direction meets following
Part (3).
And then third purport of the invention is a kind of light polarizing film manufacture polyvinyl alcohol film, which is characterized in that wide
Spend the deviation of the deviation delta X (%) of the swellbility X (%) in direction (TD directions), the swellbility Y (%) of length direction (MD directions)
The deviation delta Z (%) of the swellbility Z (%) of Δ Y (%) and thickness direction is within 5%.
Also, the 4th purport of the present invention is a kind of light polarizing film manufacture polyvinyl alcohol film, which is characterized in that its
Meet following conditions (4) and (5).
(4) phase difference Rxy (nm) in face：100~200nm
(5) axis of orientation, i.e. slow axis and the angle of the crossing θ (°) of width direction, i.e. TD directions are less than 20 °
Here, phase difference Rxy (nm) is by the folding in width direction (TD directions) in polyvinyl alcohol film in above-mentioned face
The rate of penetrating is set as nx, the refractive index of length direction (MD directions) is set as ny, thickness is set as being calculated with following formula (A) in the case of d (nm)
The value gone out.
(A) Rxy (nm)=| nx-ny | × d (nm)
Particularly, the 5th purport of the invention is a kind of light polarizing film manufacture polyvinyl alcohol film, which is characterized in that
The deviation delta Rxy (nm) of phase difference Rxy (nm) is below 10nm in above-mentioned face in width direction (TD directions).
Wherein, the 6th purport of the invention is a kind of light polarizing film manufacture polyvinyl alcohol film, which is characterized in that on
The deviation delta θ (°) for stating angle of the crossing θ (°) is less than 10 °.
And then the 7th purport of the invention is a kind of light polarizing film manufacture polyvinyl alcohol film, which is characterized in that on
The thickness for stating polyvinyl alcohol film is 5~30 μm.
In addition, the 8th purport of the present invention is a kind of light polarizing film, which is characterized in that it is used using the manufacture of above-mentioned light polarizing film
Polyvinyl alcohol film.
In addition, the 9th purport of the present invention is a kind of polarizer, which is characterized in that it has above-mentioned light polarizing film and sets
It is placed in the protective film of at least single side of above-mentioned light polarizing film.
Also, the tenth purport of the present invention is a kind of manufacturing method of light polarizing film manufacture polyvinyl alcohol film,
It is characterized in that having following process：The process for being film-made the aqueous solution of polyvinyl alcohol resin using continuous casting；From pouring
Injection molding tool stripping after, while conveyance in flow direction (MD directions), continuously dry process；With in width direction (TD side
To) stretch process, when manufactured polyvinyl alcohol film is impregnated 15 minutes in 30 DEG C of water, width direction (TD side
To) swellbility X (%) and the swellbility Y (%) in flow direction (MD directions) meet following conditions (1) and (2).
(1)110≤Y≤140
(2)1.01≤Y/X≤1.2
Particularly, the 11st purport of the invention is a kind of manufacturer of light polarizing film manufacture polyvinyl alcohol film
Method, which is characterized in that stretched for 1.05~1.5 times with stretching ratio in width direction (TD directions).
And then the 12nd purport of the invention is a kind of manufacturing method of light polarizing film manufacture polyvinyl alcohol film,
It is characterized in that, in width direction (TD directions) be stretching in 50~150 DEG C at carry out.
Also, the 13rd purport of the present invention is a kind of manufacturing method of light polarizing film manufacture polyvinyl alcohol film,
It is characterized in that, the moisture content of the film before stretching in width direction (TD directions) is 0.5~15 weight %.
Wherein, the 14th purport of the invention is a kind of manufacturing method of light polarizing film manufacture polyvinyl alcohol film,
It is characterized in that, after width direction (TD directions) is temporarily stretched beyond 1.3 times, dimensional contraction is carried out so that final width side
It it is 1.05~1.5 times to the stretching ratio in (TD directions).
And then the 15th purport of the invention is a kind of manufacturing method of light polarizing film manufacture polyvinyl alcohol film,
It is characterized in that, the size changing rate of the flow direction (MD directions) of film before and after the stretching of width direction (TD directions) is
0.8~1.0.
The effect of invention
The light polarizing film manufacture of the present invention is in terms of swellability of the polyvinyl alcohol film when light polarizing film manufactures and draftability
It is excellent, even if will not be produced fracture in the case of manufacturing slim light polarizing film, it can provide and show high polarizing properties simultaneously
And the light polarizing film that irregular colour is few.
It should be noted that the present invention is based upon improving polyvinyl alcohol film on flow direction (MD directions)
Swellability come improve light polarizing film manufacture when swellability, draftability technological thought invention.
Specific embodiment
It is described in detail below for the present invention.
The present invention light polarizing film manufacture with polyvinyl alcohol film be 5~60 μm of thickness, more than width 2m, length 2km with
Polyvinyl alcohol films upper and with following characteristics.Specifically, a kind of polyvinyl alcohol film, is to utilize continuously to pour
Note method by the aqueous solution of polyvinyl alcohol resin film, by the film being film-made from after casting mold stripping, in flow direction (MD
Direction) conveyance while, it is continuously dry and obtained from width direction (TD directions) stretching.
For the polyvinyl alcohol film of the present invention, by the polyvinyl alcohol film manufactured by the above method 30
DEG C water in when impregnating 15 minutes, the swellbility X (%) of width direction (TD directions) and the swellbility Y in flow direction (MD directions)
(%) meets the physics value of both following conditions (1) and (2).This is feature of the invention.Even if only meet the physical property of one
Value, can not reach the object of the invention.
(1)110≤Y≤140
(2)1.01≤Y/X≤1.2
Above-mentioned condition (1) and (2) can for example pass through the stretching of the width direction (TD directions) of the film for being film-made
Processing is reached, stretching ratio at this time is preferably 1.05~1.5 times, it is further preferred 1.1~1.45 times, particularly preferred 1.2
~1.4 times.The stretching ratio of width direction (TD directions) is too low or excessively high, all exists and is difficult to control width direction (TD directions)
The tendency of the swellbility Y (%) and uncontrollable phase difference in swellbility X (%) and flow direction (MD directions), there are light polarizing films
The tendency that swellability, draftability during manufacture reduce.
The specific swellbility Y (%) on flow direction (MD directions) of condition (1), in the range of known technology.On
Stating swellbility Y (%) needs for more than 110% and less than 140%, preferably more than 115% and less than 135%, further preferably
More than 120% and less than 130%.During above-mentioned swellbility Y (%) is insufficient lower limiting value, draftability when light polarizing film manufactures reduce without
It is preferred that on the contrary, the degree of polarization of light polarizing film is reduced without preferred if more than upper limit value.
The swellbility Y (%) in condition (2) particular flow direction (MD directions) and the swellbility X of width direction (TD directions)
The ratio between (%) (Y/X).The present invention maximum be characterized in that, the swellbility Y (%) in flow direction (MD directions) in particular range
More than the swellbility X (%) of width direction (TD directions).
The above-mentioned ratio of previous polyvinyl alcohol film is mostly less than 1.This is because, high molecular point of polyethenol series
Subchain usually is difficult to be swollen in flow direction (MD directions) orientation, in the direction.
The ratio between the swellbility Y (%) of above-mentioned flow direction (MD directions) and the swellbility X (%) of width direction (TD directions)
(Y/X) it needs to meet (2) 1.01≤Y/X≤1.2 of condition, preferably satisfies following conditions (2 '), particularly preferably meets following conditions
(2”)。
(2’)1.03≤Y/X≤1.15
(2”)1.05≤Y/X≤1.1
During above-mentioned Y/X deficiencies lower limiting value, draftability when light polarizing film manufactures is insufficient without preferred, if being more than upper on the contrary
Limit value then light polarizing film degree of polarization reduce without preferred.
And then for the polyvinyl alcohol film of the present invention, polyvinyl alcohol film is impregnated in 30 DEG C of water
At 15 minutes, the swellbility Z (%) of thickness direction preferably satisfy following conditions (3), further preferably meet following conditions (3 '),
Particularly preferably meet following conditions (3 ").
(3)140≤Z≤170
(3’)143≤Z≤169
(3”)145≤Z≤168
Swellbility Z (%) in the present invention, for by width direction (TD directions) swellbility X (%), flow direction (MD side
To) swellbility Y (%) and impregnated thin film after weight and by the weight after the film drying impregnated according to the following formula
The numerical value of calculating.
Weight (g)/dried weight (g)/X/Y after swellbility Z (%)=1000000 × dipping
There are the tendency that swellability during light polarizing film manufacture reduces if above-mentioned swellbility Z (%) is too low, even if on the contrary
The tendency that the excessively high degree of polarization there is also light polarizing film reduces.
Swellbility Z (%) is by condition (1), (2) and (3) it is found that swellbility, flowing side than width direction (TD directions)
Swellbility to (MD directions) is big.This is because, the high molecular strand of polyethenol series formed mainly face direction orientation,
The chemical constitution that thickness direction is easily swollen.By above-mentioned chemical constitution, can in the swelling process when light polarizing film manufactures, make
Polyvinyl alcohol film is quickly and uniformly swollen.
And then the deviation delta X of the swellbility X (%) in polyvinyl alcohol film preferable width direction (TD directions) of the invention
The deviation of the deviation delta Y (%) of the swellbility Y (%) of (%), flow direction (MD directions) and the swellbility Z (%) of thickness direction
Δ Z (%) is within 5%, within further preferred 4%, within particularly preferred 3%.There are polarisations if above-mentioned deviation is excessive
Film generates the tendency of irregular colour.
It should be noted that in the present invention, as meeting the gimmick of condition (1), (2) and (3), in addition to such as this hair
It is bright that from other than the gimmick that the film that casting mold is removed is stretched in width direction (TD directions), will can also to enumerate adjusting like that poly-
The gimmick of the drying condition of vinyl alcohol resin aqueous solution, the gimmick of chemical constitution for adjusting polyvinyl alcohol resin etc..
In addition, both following conditions (4) and (5) are preferably satisfied by the polyvinyl alcohol film that the above method manufactures
Physics value.
(4) phase difference Rxy (nm) in face：100~200nm
(5) axis of orientation (slow axis) and the angle of the crossing θ (°) of width direction (TD directions) are less than 20 °
Here, phase difference Rxy (nm) is by the refractive index in width direction (TD directions) in polyvinyl alcohol film in face
It is set as nx, the refractive index in flow direction (MD directions) is set as ny, thickness is set as being calculated with following formula (A) in the case of d (nm)
The value arrived.
(A) Rxy (nm)=| nx-ny | × d (nm)
Further preferred 110~the 180nm of phase difference Rxy (nm), particularly preferred 130~170nm in face.If phase in above-mentioned face
Potential difference Rxy (nm) is too small, and there are the tendencies that draftability during light polarizing film manufacture in the MD direction reduces, and exist if excessive inclined
Light film generates the tendency of irregular colour.
In face in width direction (TD directions) the deviation delta Rxy (nm) of phase difference Rxy (nm) be preferably below 10nm, into
Preferred below the 5nm of one step, particularly preferred below 3nm.If above-mentioned deviation delta Rxy is excessive color is easily generated there are light polarizing film not
Equal tendency.
The angle of the crossing θ (°) of axis of orientation (slow axis) and width direction (TD directions) is preferably less than 20 °, further preferred
Less than 10 °, it is less than 5 ° particularly preferred.There are stretchings during light polarizing film manufacture in the MD direction if above-mentioned angle of the crossing θ (°) is excessive
Property reduce tendency.
The deviation delta θ (°) of angle of the crossing θ (°) in width direction (TD directions) is preferably less than 10 °, 5 ° further preferred
Below, particularly preferred less than 3 °.The tendency of irregular colour is easily generated there are light polarizing film if above-mentioned deviation delta θ (°) is excessive.
It should be noted that as the gimmick for controlling phase difference Rxy (nm), angle of the crossing θ (°) in above-mentioned face, in addition to such as originally
Invention is such by from other than the gimmick that the film that casting mold is removed is stretched in width direction (TD directions), can also enumerate tune
The gimmick of the drying condition of aqueous solution, the gimmick of chemical constitution for adjusting polyvinyl alcohol resin etc..
Here, the manufacturing method of the light polarizing film manufacture polyvinyl alcohol film of the present invention is carried out according to process sequence
It is described in more detail.
[thin-film material]
It is illustrated firstly for the polyvinyl alcohol resin and its aqueous solution used in the present invention.
In the present invention, as the polyvinyl alcohol resin for forming polyvinyl alcohol film, usually using unmodified poly- second
Enol system resin will polymerize the resin that the polyvinyl acetate that vinyl acetate obtains carries out saponification and manufactures.As needed
Can also use by vinyl acetate and a small amount of (usual below the % of 10 moles of below %, preferably 5 moles) can be with acetic acid second
The copolymer of the ingredient of enester copolymerization carries out resin obtained from saponification.It, can as can be with the ingredient of vinyl acetate copolymerization
Enumerate olefines (such as ethylene, third such as unsaturated carboxylic acid (such as including salt, ester, amide, nitrile), carbon number 2~30
Alkene, n-butene, isobutene etc.), vinyl ethers, unsaturated sulfonic acid salt etc..Alternatively, it is also possible to use by the hydroxyl after saponification into
Modified polyvinylalcohol system resin obtained from row chemical modification.They can be used alone or combine two or more use.
In addition, as polyvinyl alcohol resin, it can also use side chain that there is the polyethenol series tree of 1,2- diol structures
Fat.Above-mentioned side chain has the polyvinyl alcohol resins of 1,2- diol structures for example by (i) by vinyl acetate and 3,4- diethyls
The method of the copolymer saponification of acyloxy -1- butylene, (ii) are by vinyl acetate and the copolymer soap of vinyl ethylene carbonate
Change and the method for decarboxylation, (iii) are total to vinyl acetate and 2,2- dialkyl group -4- vinyl -1,3- dioxolane
Polymers saponification and de- ketalization method, (iv) are by the method for the copolymer saponification of vinyl acetate and allylin
Etc. obtaining.
The weight average molecular weight of polyvinyl alcohol resin is preferably 100,000~300,000, further preferred 110,000~280,000, especially
It is preferred that 120,000~260,000.There is hardly possible in the case that polyvinyl alcohol resin if above-mentioned weight average molecular weight is too small forms optical thin film
To obtain the tendency of sufficient optical property, stretching when existing if excessive using polyvinyl alcohol film manufacture light polarizing film becomes
Obtain difficult tendency.It should be noted that the weight average molecular weight of above-mentioned polyvinyl alcohol resin is to be measured using GPC-MALS methods
Obtained weight average molecular weight.
The mean saponification degree of the polyvinyl alcohol resin used in the present invention be preferably generally 98 moles of more than %, further
It is preferred that 99 moles of more than %, particularly preferred 99.5 moles of more than %, particularly preferred 99.8 moles of more than %.If mean saponification degree mistake
Small, then in the case of forming light polarizing film there is the tendency that cannot get sufficient optical property in polyvinyl alcohol film.
Here, the mean saponification degree in the present invention is measured according to JIS K 6726.
Modified type, modified amount, Weight-average molecular can be applied in combination in polyvinyl alcohol resin used in the present invention
The different two or more polyvinyl alcohol resins such as amount, mean saponification degree.
In polyvinyl alcohol resin aqueous solution, other than polyvinyl alcohol resin, as needed, from the viewpoint of Film making properties
Consider preferably also containing glycerine, two glycerine, triglycerin, ethylene glycol, triethylene glycol, polyethylene glycol, trimethylolpropane etc. usually to make
Plasticizer, at least one of nonionic, anionic property and cationic surfactant.They can individually make
With or combination is two or more uses.
The resin concentration of obtained polyvinyl alcohol resin aqueous solution be preferably 15~60 weight %, further preferably
17~55 weight %, particularly preferred 20~50 weight %.Drying load increases if the resin concentration of above-mentioned aqueous solution is too low, because
This is excessively high there are viscosity if excessively high and be difficult to the tendency of uniform dissolution there are the tendency that production capacity reduces.
Then, deaeration processing is carried out for obtained polyvinyl alcohol resin aqueous solution.As defoaming method, can enumerate
The methods of going out standing and defoaming, the deaeration carried out using multi-screw extruder.As multi-screw extruder, if with gas vent
Multi-screw extruder, usually using the double screw extruder with gas vent.
[film making process]
After deaeration processing, polyvinyl alcohol resin aqueous solution is imported into T-shaped slit die per a certain amount of, discharge and be cast in
On the cast drum of rotation, it is film-made using continuous casting.
Continuous casting in the present invention for example refer to by the aqueous solution of polyvinyl alcohol resin by T-shaped slit die discharge with
And the gimmick that curtain coating is film-made in the casting mold of cast drum, endless belt, the resin film of rotation etc..The film being film-made pours certainly
It after injection molding tool stripping, while being transported in flow direction (MD directions), is continuously dried with hot-rolling, such as is done with floated
Dry machine is heat-treated.
The resin temperature of the polyvinyl alcohol resin aqueous solution of T-shaped slit die outlet is preferably 80~100 DEG C, particularly preferred 85
~98 DEG C.
Exist if the resin temperature of above-mentioned polyvinyl alcohol resin aqueous solution is too low and flow undesirable tendency, if excessively high
There are the tendencies of foaming.
The viscosity of above-mentioned polyvinyl alcohol resin aqueous solution in discharge preferably 50~200Pas, it is particularly preferred 70~
150Pa·s。
Exist if the viscosity of above-mentioned aqueous solution is too low and flow undesirable tendency, if excessively high incline in the presence of be difficult to be cast
To.
The velocity of discharge that the polyvinyl alcohol resin aqueous solution of cast drum is discharged to by T-shaped slit die is preferably 0.2~5m/ points
It is clock, 0.4~4m/ minutes further preferred, 0.6~3m/ minutes particularly preferred.
There are the tendency that productivity reduces if the above-mentioned velocity of discharge is excessively slow, if too fast presence is difficult to the tendency being cast.
The diameter of above-mentioned cast drum is preferably 2~5m, further preferred 2.4~4.5m, particularly preferred 2.8~4m.
The drying section poured into a mould if above-mentioned diameter is too small on drum is shortened, therefore there is the tendency for being difficult to improve speed, if
Excessive, there are the tendencies that transporting reduces.
The width of above-mentioned cast drum is preferably more than 4m, further preferred more than 4.5m, particularly preferred more than 5m, especially excellent
Select 5~6m.
There are the tendencies that productivity reduces if the width of cast drum is too small.
The rotary speed of above-mentioned cast drum is preferably 3~50m/ minutes, it is 4~40m/ minutes further preferred, particularly preferred 5
~35m/ minutes.
There are the tendency that productivity reduces if above-mentioned rotary speed is excessively slow, if too fast incline in the presence of drying is insufficient
To.
The surface temperature of above-mentioned cast drum is preferably 40~99 DEG C, 60~95 DEG C particularly preferred.
There are the tendency of underdry if above-mentioned surface temperature is too low, if the excessively high tendency that there is foaming.
[film being film-made]
Being film-made the moisture content of film [film before the stretching of width direction (TD directions)] formed as described above is preferably
0.5~15 weight %, further preferred 1~13 weight %, particularly preferred 2~12 weight %.Above-mentioned moisture content is too low or excessively high,
All exist and be difficult to show the high molecular orientation of purpose, the i.e. swellbility of purpose, the tendency of draftability.
In order to adjust above-mentioned moisture content, the excessively high situation of the moisture content of the film before the stretching of width direction (TD directions)
Under, preferably before being stretched to width direction (TD directions), by film drying, on the contrary, the stretching in width direction (TD directions)
In the case that the moisture content of preceding film is too low, damping is preferably carried out before being stretched to width direction (TD directions).More preferably adjust
The condition of whole drying process so that moisture content within the above range.
Above-mentioned drying can use heating roller, infrared heater etc. to be carried out using known gimmick, but in the present invention, it is excellent
Multiple heating rollers is selected to carry out, the temperature of further preferred heating roller is 40~150 DEG C, 50~120 DEG C particularly preferred.In addition,
In order to adjust moisture content, damping region can also be set before being stretched to width direction (TD directions).
[conveyance stretching process]
Then, the film that be film-made as described above, moisture content is adjusted is transported in flow direction (MD directions) same
When, it is continuously or intermittently stretched in width direction (TD directions).
In the present invention, without the film being film-made especially stretches flow direction (MD directions), if with film not
The tensile stress conveyance of meeting bending degree is then sufficient.Certainly, by being stretched to width direction (TD directions), in flow direction
(MD directions) generates the contracting for depending on Poisson's ratio, and syneresis is also generated, therefore thin in flow direction (MD directions) in drying
Film generates slightly dimensional contraction in flow direction (MD directions).
Would rather not preferred direction of flow (MD directions) size elongation degree the stretching on flow direction (MD directions).
Before and after the stretching in width direction (TD directions), the size changing rate in flow direction (MD directions) is preferably 0.8~1.0, into one
Step preferably 0.9~1.0, particularly preferred 0.95~1.0.Above-mentioned size changing rate is too small or excessive, all there are the deviations of swellbility
Increased tendency exists and is difficult to the high molecular orientation for showing purpose, the i.e. tendency of the swellbility of purpose.
The film being film-made is 5~30m/ minutes to the preferred scope of the conveyance speed in flow direction (MD directions), into one
Step preferably 7~25m/ minutes, it is 8~20m/ minutes particularly preferred.There are what productivity reduced if above-mentioned conveyance speed is excessively slow to incline
To there are the increased tendencies of the irregular colour of light polarizing film if too fast.
Conveyance of the film being film-made to flow direction (MD directions) and the stretching to width direction (TD directions) simultaneously into
Capable gimmick, is not particularly limited, such as preferably clamps to be carried out at the same time with multiple clips by the width direction both ends of film
Conveyance and stretching.Under the above situation, preferred below the spacing 200mm of configuration, the further preferred spacing 100mm of the clip of each end
Below, particularly preferred below spacing 50mm.
The film deposited if the spacing of above-mentioned clip is wide after the stretch generates bending or obtained polyethenol series
The uneven increased tendency of uneven thickness, phase difference at the width direction both ends of film.In addition, clip position (the clip of clip
Front end) below the width direction both ends 100mm of film that is film-made of preferred distance.If the clip position (front end) of clip
Excessively then increase positioned at the width direction central part of film in the presence of the film end cancelled, the tendency that product width narrows.
Specific polyvinyl alcohol film can be as mentioned before by the film for being film-made in width in the present invention
Stretch processing on degree direction (TD directions) is reached, and stretching ratio at this time is preferably 1.05~1.5 times, further preferably
1.1~1.45 times, it is 1.15~1.4 times particularly preferred, 1.2~1.3 times particularly preferred.The stretching ratio of width direction (TD directions)
It is too high or too low, all there are during light polarizing film manufacture swellability, draftability reduce tendency.
The successional stretching process of above-mentioned width direction (TD directions) can be 1 stage (1 time), or Duo Gejie
Section (multiple) is so that total stretching ratio (also referred to as gradually stretches) in the range of being in above-mentioned stretching ratio.Such as can carry out
After first stage stretches, the simple conveyance in width direction (TD directions) has been fixed, has carried out the later stretching of second stage.
Particularly in the case of thin gauge film, by being inserted into simple conveyance process, the stress relaxation of film is carried out, it can
It avoids being broken.
In the case of being inserted into the fixed conveyance process of width, it can also make fixed width than wide after the stretching of first stage
It spends narrow.Film after just stretching easily is shunk due to stress relaxation, is also generated and is dehydrated adjoint contraction, therefore can be made solid
Fixed width degree constriction is to these contracted widths.But more than the constriction to contracted width if film generate bending, so not preferably.
Above-mentioned stretching process preferably carries out after the drying process of film, but can also before the drying process of film and
It individually carries out, can also be carried out in drying process at least one after drying process.
As the preferably mode of the present invention, the width direction (TD directions) in film can be used temporarily to be stretched beyond
After 1.3 times, the gimmick of size for making that the stretching ratio of final width direction (TD directions) is 1.05~1.5 times is shunk.It is above-mentioned
In the case of, after being temporarily stretched beyond 1.3 times, film is merely transported with the fixed width of stretching ratio 1.05~1.5.It is logical
Above-mentioned gimmick is crossed, in the case of carrying out the stress relaxation of film, particularly thin gauge film, can avoid being broken.
In the present invention, for the stretching of the width direction (TD directions) of film that is film-made preferably at 50~150 DEG C into
Capable, further preferred 60~140 DEG C, it is 70~130 DEG C particularly preferred.Draft temperature is too low or excessively high, and all there are light polarizing film manufactures
When draftability reduce tendency.Gradually stretch, in the case of intermittently stretching, above-mentioned draft temperature can be in each stretching rank
Duan Biangeng, can also in stretching set temperature gradient.
In the present invention, for be film-made the stretching of the width direction (TD directions) of film when stretching time be preferably 2
~60 seconds, it is 5~45 seconds further preferred, 10~30 seconds particularly preferred.It is easily produced there are film if above-mentioned stretching time is too short
The tendency of raw fracture, there are the increased tendencies of machine utilization if long on the contrary.It carries out in the case of gradually stretching, above-mentioned drawing
Stretching the time can change in each draw stage.
In the present invention, can also implement for the stretching in width direction (TD directions) for the film being film-made after,
It is heat-treated with floated drying machine etc..The temperature of above-mentioned heat treatment is preferably 60~200 DEG C, further preferred 70~150
DEG C, it is 100~140 DEG C particularly preferred.
There are the tendency that dimensional stability is easily reduced if above-mentioned heat treatment temperature is too low, on the contrary, even if excessively high
There are the tendencies that draftability during light polarizing film manufacture reduces.
In addition, heat treatment time be preferably 1~60 second, it is 5~30 seconds particularly preferred.There are rulers if heat treatment time is too short
The tendency that very little stability reduces, on the contrary, if if long there are during light polarizing film manufacture swellability, the tendency that reduces of draftability.
[light polarizing film manufacture polyvinyl alcohol film]
The light polarizing film manufacture polyvinyl alcohol film of the present invention is so obtained, finally batches coiled and forms product.On
It from the viewpoint of phase difference is 5~60 μm that the thickness of polyvinyl alcohol film, which is stated, out of face, from the viewpoint of the slimming of light polarizing film
Consider, further preferably 5~45 μm, 5~30 μm particularly preferred, from the viewpoint of fracture is avoided, particularly preferred 10~20 μ
m.The thickness of above-mentioned polyvinyl alcohol film passes through the resin concentration in polyvinyl alcohol resin aqueous solution, the row to casting mold
The adjustment such as output (velocity of discharge), stretching ratio.
The width of above-mentioned polyvinyl alcohol film be more than 2m, from the viewpoint of large area be more preferably 3m with
Above, particularly preferably 4~6m from the viewpoint of fracture is avoided.
The length of above-mentioned polyvinyl alcohol film is more than 2km, from the viewpoint of large area, further preferably
More than 3km, particularly preferably 3~50km from the viewpoint of conveying weight.
Blank film of the light polarizing film manufacture by the use of polyvinyl alcohol film as light polarizing film of the present invention be it is highly useful, with
Under the light polarizing film and the manufacturing method of polarizer that are formed by the polyvinyl alcohol film are illustrated.
[manufacturing method of light polarizing film]
For the light polarizing film of the present invention by exporting above-mentioned polyvinyl alcohol film from roller and transferring in the horizontal direction, process is molten
The processes manufacture such as swollen, dyeing, boric acid crosslinking, stretching, washing, dry.
Swelling process is implemented before dyeing process.By being swollen process, polyvinyl alcohol film surface can be washed
Dirt, in addition to this by being swollen polyvinyl alcohol film, also having prevents from dyeing unequal effect.It is swollen in process,
As treatment fluid, usually using water.The treatment fluid can add in a small amount of iodinated compounds if main component is water, surface is lived
Additives, the alcohol such as property agent etc..The temperature of swelling bath is usually 10~45 DEG C or so, and the dip time to swelling bath is usually 0.1
~10 minutes or so.
In the swelling process, the swellbility of polyvinyl alcohol film of the invention in 30 DEG C of water as it was noted above, impregnate
During the swellbility for measuring film in 15 minutes, the swellbility X (%) of width direction (TD directions) and flow direction (MD directions) it is molten
Expansibility Y (%) meets the physics value of both following conditions (1) and (2).
(1)110≤Y≤140
(2)1.01≤Y/X≤1.2
And then as it was noted above, the swellbility Z (%) of thickness direction preferably satisfies following conditions (3).
(3)140≤Z≤170
Dyeing process is by making film contact to carry out with the liquid containing iodine or dichroic dye.Usually using iodo- iodine
Change the aqueous solution of potassium, a concentration of 0.1~2g/L of iodine, a concentration of 1~100g/L of potassium iodide are suitable.Dyeing time is 30
~500 seconds or so are practical.The temperature of processing bath is preferably 5~50 DEG C.In aqueous solution, can also it contain other than aqueous solvent
There is a small amount of organic solvent with water with compatibility.
Boric acid cross-linking process step is carried out by using boron compounds such as boric acid, boraxs.Boron compound is with aqueous solution or water-organic
Stabilisation of the potassium iodide from polarizing properties coexists with 10~100g/L of concentration or so use in the form of solvent mixed liquor in a liquid
From the viewpoint of preferably.Temperature during preferred process is 30~70 DEG C or so, processing time is 0.1~20 minute or so, in addition
It can carry out stretched operation in processes as needed.
Film is preferably stretched 3~10 times, preferably 3.5~6 times by stretching process in uniaxial direction.At this time it is also possible to drawing
The right angle orientation for stretching direction carries out several stretching (preventing the degree of the contraction of width direction or a greater degree of stretching).It draws
Temperature when stretching is preferably 40~170 DEG C.And then stretching ratio is finally set in aforementioned range, stretched operation can be with
Only implement once, can also implement in manufacturing process repeatedly.
Polyvinyl alcohol film is impregnated in washing procedure iodide aqueous solution such as by water, potassium iodide to carry out,
The precipitate for resulting from film surface can be removed.A concentration of 1~80g/L of potassium iodide during using potassium iodide aqueous solution or so
It can.Temperature during carrying out washing treatment is usually 5~50 DEG C, preferably 10~45 DEG C.Processing time is usually 1~300 second, preferably 10~
240 seconds.It should be noted that water washing and appropriately combined can be carried out using the washing of potassium iodide aqueous solution.
Drying process dries 1~10 minute for example by film to carry out in an atmosphere, at 40~80 DEG C.
Light polarizing film so is obtained, the degree of polarization of above-mentioned light polarizing film is preferably more than 99.5%, particularly preferred more than 99.8%.
The tendency that contrast in a liquid crystal display reduces is deposited if degree of polarization is too low.It should be noted that usually degree of polarization is as follows
It calculates, 2 light polarizing films is being measured into light transmittance under overlap condition in a manner that its differently- oriented directivity is the same direction under wavelength X
(H11), it is measured thoroughly under wavelength X under overlap condition in a manner that differently- oriented directivity forms mutually orthogonal direction by 2 light polarizing films
Light rate (H1), by light transmittance (H11) and light transmittance (H1) above-mentioned degree of polarization is calculated according to the following formula.
Degree of polarization=[(H11-H1)/(H11+H1)]1/2
And then the single plate transmission of light polarizing film of the invention is preferably more than 44%.If above-mentioned single plate transmission is too low
In the presence of the tendency for the high brightness that cannot reach liquid crystal display.
Single plate transmission is using value obtained from the light transmittance of spectrophotometric determination light polarizing film monolithic.
It is illustrated sequentially for the manufacturing method of the polarizer of the present invention for the light polarizing film for having used the present invention.
The light polarizing film of the present invention is suitable for the manufacture polarizer that irregular colour is few, polarizing properties are excellent.
[manufacturing method of polarizer]
The polarizer of the present invention is bonded optically each by the one or two sides of the light polarizing film in the present invention via bonding agent
It is made to the resin film of the same sex as protective film.As protective film, such as cellulosic triacetate, fibre can be enumerated
Dimension plain diacetate esters, polymethyl methacrylate, cyclic olefin polymer, cyclic olefine copolymer, polystyrene, gather makrolon
The film or sheet material of ether sulfone, poly (arylene ether) ester, poly- 4- methylpentenes, polyphenylene oxide etc..
Applying method is carried out using known gimmick, such as by the way that the adhesive composite of liquid is equably coated on polarisation
After film, protective film or the two, the two is bonded and carries out pressurized adhesion, heating irradiates active energy beam to carry out.
It should be noted that can also the one or two sides of light polarizing film be coated with polyurethane series resin, acrylic resin,
The curable resins such as carbamide resin be formed by curing cured layer and form polarizer.It operates if so, then above-mentioned cured layer becomes
The replacement of above-mentioned protective film can realize filming.
It is excellent in terms of polarizing properties using the light polarizing film and polarizer of the polyvinyl alcohol film of the present invention, it is preferred for
Personal digital assistant, personal computer, TV, projector, billboard, desk-top electronic calculator, electronic watch, word processing
The liquid of mechanical, electrical sub- paper, game machine, video recorder, camera, photograph album, thermometer, sound equipment, automobile, mechanical metrical instrument class etc.
Crystal device, sunglasses, anti-dazzle spectacles, anaglyph spectacles, wearable display, display element (CRT, LCD, organic EL, electronics
Paper etc.) with anti-reflection layer, fiber optic communication instrument, Medical Instruments, construction material, toy etc..
Embodiment
Embodiment is exemplified below out to be more particularly described the present invention, but the present invention as long as no more than as long as its purport not
It is limited by following embodiment.
It should be noted that " part " refers to weight basis in example.
Then, the polyvinyl alcohol film in following embodiment and comparative example characteristic (swellbility, swellbility it is inclined
Difference, phase difference in face, the deviation of phase difference, the angle of the crossing of axis of orientation and width direction, size changing rate in face) and light polarizing film
The measure of characteristic (degree of polarization, single plate transmission, irregular colour) and evaluation carry out as described below.
<Determination condition>
[swellbility (%) of polyvinyl alcohol film]
By the central portion of the width direction of obtained polyvinyl alcohol film and left and right ends portion, width 100mm is cut out
Each 1 of the film of × length 100mm is impregnated 15 minutes in 30 DEG C of water and is swollen.By impregnating front and rear size, under
Formula calculates the swellbility X (%) of width direction (TD directions), the swellbility Y (%) in flow direction (MD directions).For thickness side
To swellbility Z (%) for, by the central portion of the width direction of polyvinyl alcohol film and left and right ends portion, cut out width
Each 1 of the film of 100mm × length 100mm is impregnated 15 minutes in 30 DEG C of water after being swollen, and film is taken out, in filter paper
Film is unfolded on (5A).And then filter paper (5A) is overlapped on film, on it load 150mm × 150mm × 4mm (4.4 ×
10-2g/mm2) SUS plates 5 seconds, remove the attached water of film surface.The film is rapidly encased in measuring cup, measures weight,
As " weight after dipping ".Aforesaid operations carry out in the environment of 23 DEG C, 50%RH.
Then, which in 105 DEG C of drying machine is placed 16 hours, removes the moisture in film, then take out thin
Film is rapidly encased in measuring cup, weight is measured, as " dried weight ".Thickness side is calculated then according to following formula
To swellbility Z (%).
The width (mm) in the TD directions before the width (mm) in the TD directions after swellbility X (%)=100 × dipping/dipping
The width (mm) in the MD directions before the width (mm) in the MD directions after swellbility Y (%)=100 × dipping/dipping
Weight (g)/dried weight (g)/X/Y after swellbility Z (%)=1000000 × dipping
[deviation (%) of swellbility]
By value (central portion and the left and right ends of the swellbility X (%) of width direction (TD directions) obtained in said determination
This 3 points of portion) among, using deviation delta X of the difference of maxima and minima as the swellbility of width direction (TD directions)
(%).Similarly be obtained the deviation delta Y (%) of the swellbility of flow direction (MD directions), the swellbility of thickness direction deviation delta
Z (%).
[phase difference Rxy (nm) in face, in face phase difference deviation delta Rxy (nm), axis of orientation (slow axis) and width direction
The deviation delta θ (°) of the angle of the crossing θ (°) and angle of the crossing θ in (TD directions)]
By the central portion of the width direction of obtained polyvinyl alcohol film and left and right ends portion (from film end to
On the inside of 10cm) test film of cut-out length 4cm × width 4cm, use retardation (retardation) measurement device (" KOBRA-
WR " princes measure machine Co. Ltd. system), phase difference Rxy (nm) and axis of orientation (slow axis) and width direction in aspect of measure
The angle of the crossing θ (°) in (TD directions).And then central portion in the width direction by being obtained in said determination and left and right ends portion
In face among phase difference Rxy (nm), using deviation delta Rxy (nm) of the difference of maxima and minima as phase difference in face.Separately
Outside, among by the central portion in the width direction that is obtained in said determination and the angle of the crossing θ (°) in left and right ends portion, using maximum
Deviation delta θ (°) of the difference of value and minimum value as angle of the crossing θ (°).
[size changing rate]
Before the stretching in width direction (TD directions), the note of distance 1m is left in flow direction (MD directions) with omnipotent ink
Number (2 points).After the stretching in width direction (TD directions), the distance between above-mentioned 2 points L (m) are measured with vernier caliper, under
Formula calculates size changing rate.
Size changing rate=L (m)/1 (m)
[degree of polarization (%), single plate transmission (%)]
By the test film of central portion cut-out length 4cm × width 4cm of the width direction of obtained light polarizing film, using certainly
Dynamic polarizing film measurement device (Japan's light splitting corporation：VAP7070), degree of polarization (%) and single plate transmission (%) are measured.
[irregular colour]
By the test film of central portion cut-out length 30cm × width 30cm of the width direction of obtained light polarizing film, with
After 45 ° of angle is sandwiched between 2 polarizers (single plate transmission 43.5%, degree of polarization 99.9%) of crossed Nicol state,
Using the lamp box of surface illuminance 14000lx, with the irregular colour through pattern observation optically, commented according to following benchmark
Valency.
(evaluation criteria)
Zero ... without irregular colour
There are faint irregular colours by △ ...
× ... there are irregular colours
<Embodiment 1>
(making of polyvinyl alcohol film)
Into the dissolving tank of 5000L add in weight average molecular weight 142000,99.8 moles of % of saponification degree polyethenol series tree
Fat 1000kg, water 2500kg, the glycerine 105kg as plasticizer and the polyoxyethylenelauryl base amine as surfactant
0.25kg, stirring while, are warming up to 150 DEG C of progress dissolved under pressure, are adjusted by concentration, obtain 25 weight %'s of resin concentration
The aqueous solution of polyvinyl alcohol resin.Then, which is supplied to double screw extruder to take off
After bubble, it is 95 DEG C to make aqueous temperature, by T-shaped slit die outlet, discharges (velocity of discharge 2.5m/ minutes) and curtain coating in rotation
Cast rouse and be film-made.By the film being film-made from drum stripping is poured into a mould, while conveyance in flow direction (MD directions), make thin
The surface and the back side of film alternately contact and are dried with amounting to 10 hot-rollings.The thin of 10 weight % of moisture content is obtained as a result,
Film (60 μm of width 2m, thickness).Then, with the left and right ends portion of clip spacing 45mm clamping films, by film in flow direction
While (MD directions) is with speed conveyance in 8m/ minutes, 1.2 are stretched in width direction (TD directions) using stretching-machine at 120 DEG C
Times.The size changing rate of flow direction (MD directions) before and after the stretching of width direction (TD directions) is 0.96.Finally at 120 DEG C
It is lower be heat-treated within 10 seconds, obtain polyvinyl alcohol film (width 2.4m, 50 μm of thickness, length 2km).Obtained polyethylene
The characteristic of alcohol system film is as shown in Table 1 and Table 2.
(making of light polarizing film and polarizer)
Obtained polyvinyl alcohol film from roller is exported, while conveyance in the horizontal direction, is impregnated in 30 DEG C of water temperature
Sink while be swollen, be stretched to 1.7 times in flow direction (MD directions).Then it is impregnated in comprising iodine 0.5g/L, iodine
In 30 DEG C of aqueous solution for changing potassium 30g/L, while dyeing, 1.6 times are stretched in flow direction (MD directions), is then soaked
Stain is while (50 DEG C) of the aqueous solution of boric acid 40g/L, the composition of potassium iodide 30g/L carries out boric acid crosslinking in flow direction (MD
Direction) single shaft is stretched to 2.1 times.Finally, it is washed, is always stretched with potassium iodide aqueous solution within dry 2 minutes at 50 DEG C
The light polarizing film that 5.8 times of multiplying power.It is not produced fracture in above-mentioned manufacture, the characteristic of obtained light polarizing film is as shown in table 2.
On the two sides of light polarizing film obtained above, using polyvinyl alcohol water solution as bonding agent, 40 μm of film thickness of fitting
Triacetylcellulose film is dried at 70 DEG C and obtains polarizer.
<Embodiment 2>
In embodiment 1, it for the film being film-made, is drawn at 120 DEG C in width direction (TD directions) using stretching-machine
After stretching 1.4 times, transported with fixed width 2.4m (being equivalent to 1.2 times of stretchings), in addition to this, gathered similarly to Example 1
Ethenol system film (width 2.4m, 50 μm of thickness, length 2km).Flow direction before and after the stretching of width direction (TD directions)
The size changing rate in (MD directions) is 0.96.The characteristic of obtained polyvinyl alcohol film is as shown in Table 1 and Table 2.
And then using the polyvinyl alcohol film, light polarizing film and polarizer are obtained similarly to Example 1.Above-mentioned manufacture
In do not produce fracture.The characteristic of obtained light polarizing film is as shown in table 2.
<Embodiment 3>
In embodiment 1, velocity of discharge during film is set as 0.8m/ minutes, by the film (width of 5 weight % of moisture content
20 μm of 2m, thickness) after width direction (TD directions) stretches 1.4 times, it is removed with fixed width 2.6m (being equivalent to 1.3 times of stretchings)
It send, in addition to this, obtains polyvinyl alcohol film (width 2.6m, 15 μm of thickness, length 2km) similarly to Example 1.Width
The size changing rate of flow direction (MD directions) before and after the stretching in direction (TD directions) is 0.98.Obtained polyethenol series
The characteristic of film is as shown in Table 1 and Table 2.
And then using the polyvinyl alcohol film, light polarizing film and polarizer are obtained similarly to Example 1.Although blank
Polyvinyl alcohol film to be slim, also do not produced fracture in the stretching process when light polarizing film manufactures.Obtained polarisation
The characteristic of film is as shown in table 3.
<Comparative example 1>
In embodiment 1, it for the film being film-made, is not stretched in width direction (TD directions) using stretching-machine,
In addition to this, polyvinyl alcohol film (width 2m, 60 μm of thickness, length 2km) is obtained similarly to Example 1.It is obtained
The characteristic of polyvinyl alcohol film is as shown in Table 1 and Table 2.
And then using the polyvinyl alcohol film, light polarizing film and polarizer are obtained similarly to Example 1.It is obtained
The characteristic of light polarizing film is as shown in table 3.
<Comparative example 2>
In embodiment 3, it for the film being film-made, is not stretched in width direction (TD directions) using stretching-machine,
In addition to this, polyvinyl alcohol film (width 2m, 20 μm of thickness, length 2km) is obtained similarly to Example 3.It is obtained
The characteristic of polyvinyl alcohol film is as shown in Table 1 and Table 2.
And then using the polyvinyl alcohol film, light polarizing film and polarizer are obtained similarly to Example 1.It is obtained
The characteristic of light polarizing film is as shown in table 3.
[table 1]
[table 2]
[table 3]
By the result of above-described embodiment and comparative example it is found that by the swellbility X (%) of width direction (TD directions) with flowing
The ratio of the swellbility Y (%) in direction (MD directions) meets the polyethenol series using aforementioned condition (1) and (2) specific range
The light polarizing film for the Examples 1 to 3 that film obtains has the degree of polarization of height and no irregular colour.On the other hand, by width
The ratio for spending the swellbility X (%) and the swellbility Y (%) in flow direction (MD directions) in direction (TD directions) is in using aforementioned
The light polarizing film of comparative example 1 and 2 that polyvinyl alcohol film except condition (1) and (2) specific range obtains, degree of polarization become
Difference also observes irregular colour.
In addition we know, by phase difference in face (Rxy) and the angle of the crossing of axis of orientation (slow axis) and width direction (TD directions)
θ (°) meets the polarisation of Examples 1 to 3 obtained using the polyvinyl alcohol film of aforementioned condition (4) and (5) specific range
Film has the degree of polarization of height and no irregular colour.On the other hand, it is (stagnant by phase difference in face (Rxy) and axis of orientation
Phase axis) it is poly- except the specific range of aforementioned condition (4) and (5) in utilizing with the angle of the crossing θ (°) of width direction (TD directions)
The light polarizing film of comparative example 1 and 2 that ethenol system film obtains, degree of polarization are deteriorated, and also observe irregular colour.
In above-described embodiment, the concrete mode in the present invention is shown, but above-described embodiment only simple illustration,
And non-limiting explanation.Obvious deformation is within the scope of the invention to those skilled in the art.
Industrial availability
It is excellent in terms of polarizing properties using the light polarizing film and polarizer of the polyvinyl alcohol film of the present invention, it is preferred for
Personal digital assistant, personal computer, TV, projector, billboard, desk-top electronic calculator, electronic watch, word processing
The liquid of mechanical, electrical sub- paper, game machine, video recorder, camera, photograph album, thermometer, sound equipment, automobile, mechanical metrical instrument class etc.
Crystal device, sunglasses, anti-dazzle spectacles, anaglyph spectacles, wearable display, display element (CRT, LCD, organic EL, electronics
Paper etc.) with anti-reflection layer, fiber optic communication instrument, Medical Instruments, construction material, toy etc..
Claims (15)
1. a kind of light polarizing film manufacture polyvinyl alcohol film, which is characterized in that it is 5~60 μm of thickness, more than width 2m, length
Spend the polyvinyl alcohol film of more than 2km, when which is impregnated 15 minutes in 30 DEG C of water, width side
Meet following conditions (1) and (2) to, the i.e. swellbility X (%) in TD directions and length direction, i.e. the swellbility Y (%) in MD directions,
(1)110≤Y≤140
(2)1.01≤Y/X≤1.2。
2. light polarizing film manufacture polyvinyl alcohol film according to claim 1, which is characterized in that by the polyvinyl alcohol
When being that film impregnates 15 minutes in 30 DEG C of water, the swellbility Z (%) of thickness direction meets following conditions (3),
(3)140≤Z≤170。
3. light polarizing film manufacture polyvinyl alcohol film according to claim 1 or 2, which is characterized in that width direction, i.e.
The deviation delta X (%) of the swellbility X (%) in TD directions, length direction, the i.e. deviation delta Y (%) of the swellbility Y (%) in MD directions,
Deviation delta Z (%) with the swellbility Z (%) of thickness direction is within 5%.
4. light polarizing film manufacture polyvinyl alcohol film described in any one of claim 1 to 3, which is characterized in that its
Meet following conditions (4) and (5),
(4) phase difference Rxy (nm) in face：100~200nm
(5) axis of orientation, i.e. slow axis and the angle of the crossing θ (°) of width direction, i.e. TD directions are less than 20 °
Here, phase difference Rxy (nm) is by width direction, the i.e. refractive index in TD directions in polyvinyl alcohol film in the face
Be set as nx, length direction, i.e. MD directions refractive index be set as ny, thickness is set as being calculated with following formula (A) in the case of d (nm)
The value arrived,
(A) Rxy (nm)=| nx-ny | × d (nm).
5. light polarizing film manufacture polyvinyl alcohol film according to claim 4, which is characterized in that width direction, i.e. TD
The deviation delta Rxy (nm) of phase difference Rxy (nm) is below 10nm in the face in direction.
6. light polarizing film manufacture polyvinyl alcohol film according to claim 4 or 5, which is characterized in that the angle of the crossing θ
The deviation delta θ (°) of (°) is less than 10 °.
7. according to light polarizing film manufacture polyvinyl alcohol film according to any one of claims 1 to 6, which is characterized in that institute
The thickness for stating polyvinyl alcohol film is 5~30 μm.
8. a kind of light polarizing film, which is characterized in that it manufactures poly- second using the light polarizing film described in any one of claim 1~7
Enol system film.
9. a kind of polarizer, which is characterized in that it has light polarizing film according to any one of claims 8 and is set to the light polarizing film
At least protective film of single side.
10. a kind of manufacturing method of light polarizing film manufacture polyvinyl alcohol film, which is characterized in that it has following process：Profit
The process for being film-made the aqueous solution of polyvinyl alcohol resin with continuous casting；From after casting mold stripping, in flow direction, i.e.
Process while MD directions transport, continuously dried；It, will be manufactured with the process stretched in width direction, i.e. TD directions
When polyvinyl alcohol film impregnates 15 minutes in 30 DEG C of water, the swellbility X (%) in width direction, i.e. TD directions and flowing side
Meet following conditions (1) and (2) to the swellbility Y (%) in, i.e. MD directions,
(1)110≤Y≤140
(2)1.01≤Y/X≤1.2。
11. the manufacturing method of light polarizing film manufacture polyvinyl alcohol film according to claim 10, which is characterized in that
Width direction, i.e. TD directions are stretched for 1.05~1.5 times with stretching ratio.
12. the manufacturing method of the light polarizing film manufacture polyvinyl alcohol film according to claim 10 or 11, feature exist
In, in width direction, i.e. TD directions be stretching in 50~150 DEG C at carry out.
13. the manufacturing method of the light polarizing film manufacture polyvinyl alcohol film according to any one of claim 10~12,
It is characterized in that, the moisture content of the film before stretching in width direction, i.e. TD directions is 0.5~15 weight %.
14. the manufacturing method of the light polarizing film manufacture polyvinyl alcohol film according to any one of claim 10~13,
It is characterized in that, in width direction, after i.e. TD directions are temporarily stretched beyond 1.3 times, dimensional contraction is carried out so that final width
The stretching ratio in direction, i.e. TD directions is 1.05~1.5 times.
15. the manufacturing method of the light polarizing film manufacture polyvinyl alcohol film according to any one of claim 10~14,
It is characterized in that, width direction, i.e., the flow direction of film before and after the stretching in TD directions, the i.e. size changing rate in MD directions are
0.8~1.0.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-210958 | 2015-10-27 | ||
| JP2015210958 | 2015-10-27 | ||
| JP2015-226890 | 2015-11-19 | ||
| JP2015-226889 | 2015-11-19 | ||
| JP2015226890 | 2015-11-19 | ||
| JP2015226889 | 2015-11-19 | ||
| PCT/JP2016/081793 WO2017073639A1 (en) | 2015-10-27 | 2016-10-27 | Polyvinyl alcohol film for producing polarizing film, polarizing film and polarizing plate using polyvinyl alcohol film for producing polarizing film, and production method for polyvinyl alcohol film for producing polarizing film |
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| Publication Number | Publication Date |
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| CN108139528A true CN108139528A (en) | 2018-06-08 |
| CN108139528B CN108139528B (en) | 2021-09-10 |
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| CN201680058384.XA Active CN108139528B (en) | 2015-10-27 | 2016-10-27 | Polyvinyl alcohol film for producing polarizing film, polarizing film using same, polarizing plate, and method for producing polyvinyl alcohol film for producing polarizing film |
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| Country | Link |
|---|---|
| KR (1) | KR102629982B1 (en) |
| CN (1) | CN108139528B (en) |
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| CN107167860A (en) * | 2017-05-27 | 2017-09-15 | 中国石油化工集团公司 | Polyvinyl alcohol film and its method of testing |
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| KR20110006461A (en) * | 2009-07-14 | 2011-01-20 | 동우 화인켐 주식회사 | Method for preparing polarizer |
| JP5624803B2 (en) * | 2010-05-31 | 2014-11-12 | 株式会社クラレ | Polyvinyl alcohol polymer film |
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- 2016-10-27 CN CN201680058384.XA patent/CN108139528B/en active Active
- 2016-10-27 KR KR1020187009707A patent/KR102629982B1/en active IP Right Grant
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| CN108139528B (en) | 2021-09-10 |
| TWI737640B (en) | 2021-09-01 |
| WO2017073639A1 (en) | 2017-05-04 |
| KR102629982B1 (en) | 2024-01-29 |
| TW201730252A (en) | 2017-09-01 |
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