CN105723259B - Polyvinyl alcohol film - Google Patents
Polyvinyl alcohol film Download PDFInfo
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- CN105723259B CN105723259B CN201480063715.XA CN201480063715A CN105723259B CN 105723259 B CN105723259 B CN 105723259B CN 201480063715 A CN201480063715 A CN 201480063715A CN 105723259 B CN105723259 B CN 105723259B
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- film
- polyvinyl alcohol
- pva
- polarization
- manufacturing
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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
-
- 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
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
-
- G—PHYSICS
- G02—OPTICS
- 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
- G02F1/133528—Polarisers
-
- 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
Abstract
[project] provides the PVA film that polarization film can be easily manufactured, and the form and aspect of the polarization film itself are excellent, can manufacture the excellent LCD of form and aspect without using transmissivity low optical film, and can manufacture the bright LCD of picture.The minimum value of [solution] following slope is -0.84 ~ -0.783N/mm2The PVA film of second: the sample that the width direction cut out from PVA film is 3cm is placed in autoplotter in such a way that distance between chuck is 1.5cm and alongst stretches, after being impregnated 1 minute in 30 DEG C of water, it is alongst stretched in the water with the speed of 240%/minute, reaches 11.1N/mm in stress2At the time of fixed chuck spacing from, for the ongoing change of stress thereafter, the slope minimum value of each point on the figure using the time as horizontal axis and when being drawn using stress as the longitudinal axis.
Description
Technical field
The present invention relates to the polyvinyl alcohol film of the excellent polarization film of form and aspect can be easily manufactured, its manufacturing method, use
The excellent polarization film of the manufacturing method and form and aspect of the polarization film of the polyvinyl alcohol film.
Background technique
The liquid crystal of polarization plate and the polarized light state for changing light with light transmission and shade function is liquid crystal together
The basic constituent element of display (LCD).Multiple polarization plates have the surface mount Triafol T in polarization film
(TAC) structure obtained from the protective films such as film (has as the polarization film for constituting polarization plate by polyvinyl alcohol film below
When " polyvinyl alcohol " is referred to as " PVA ") be uniaxially stretched made of matrix (be uniaxially stretched and the stretching that is orientated it
Film) on be adsorbed with iodine system pigment (I3 -、I5 -Deng) or the like dichroism pigment obtained from polarization film become mainstream.It is this
Polarization film manufactures as follows: being uniaxially stretched to the PVA film in advance containing dichroism pigment, or draws in the single shaft of PVA film
Dichroism pigment is adsorbed while stretching, or adsorbs dichroism pigment etc. after being uniaxially stretched to PVA film again (referring to patent text
Offer 1 etc.).
LCD is in the small machines such as calculator and watch, laptop, liquid crystal tester, color liquid crystal projector, liquid crystal
It is used in the vast range such as the metering machine that TV, vehicle-mounted navigation system, mobile phone, indoor and outdoor use.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 5-245858 bulletin.
Summary of the invention
Problems to be solved by the invention
However, in recent years, when requiring the brightness for reducing backlight in order to reduce power consumption, but using existing polarization film,
Other optical films etc. are needed to configure to correct form and aspect, there are the picture of LCD is dimmed due to the low grade of the transmissivity of the optical film
Problem.When on the other hand, using the high optical film of transmissivity, there are problems that may not proceed sufficiently form and aspect correction.
Thus, even if that the object of the present invention is to provide the form and aspect of its own is excellent, without using the low optical film of transmissivity
Also the excellent LCD of form and aspect can be manufactured and the polarization film of the bright LCD of picture can be manufactured, and this can be easily manufactured partially
The PVA film of vibration light film.
The means used to solve the problem
Further investigation is repeated in the inventors of the present invention to achieve the goals above, as a result, it has been found that: using drawing in water
When stress after stretching shows the PVA film of specific ongoing change behavior, even if the form and aspect that its own can be easily manufactured are excellent, not
The excellent LCD of form and aspect can be also manufactured using the low optical film of transmissivity and can manufacture the polarization film of the bright LCD of picture；
When the PVA film for being in particular range to saponification degree and swellbility under given conditions is heat-treated, it can be easily manufactured
State PVA film；And according to by when being configured to parallel Nicol state relative to rectilinearly polarized light b value and be configured to just
B value when Nicol prism state is handed over to meet the polarization film of particular kind of relationship, the form and aspect of its own are excellent, even if without using transmission
The low optical film of rate can also manufacture the excellent LCD of form and aspect, and can manufacture the bright LCD of picture, further based on the opinion
It repeats to study, so as to complete the present invention.
That is, the present invention relates to:
[1] PVA film, wherein slope minimum value below is -0.84 ~ -0.783N/mm2Second:
The sample that the width direction cut out from PVA film is 3cm is 1.5cm with distance between chuck and is alongst drawn
The mode stretched is placed in autoplotter, after being impregnated 1 minute in 30 DEG C of water, in the water with the speed of 240%/minute along
Length direction stretches, and reaches 11.1N/mm in stress2At the time of fixed chuck spacing from for stress thereafter through time-varying
Change, the slope minimum value of each point on the figure using the time as horizontal axis and when being drawn using stress as the longitudinal axis.
[2] according to the PVA film of above-mentioned [1], wherein the saponification degree for the PVA for including in PVA film is 98 ~ 99.5 moles of %；
[3] according to the PVA film of above-mentioned [1] or [2], wherein swellbility is 180 ~ 220%；
[4] according to the PVA film of any one of above-mentioned [1] ~ [3], for the raw material film for manufacturing polarization film；
[5] manufacturing method of PVA film comprising the process for being heat-treated PVA film with 135 ~ 148 DEG C, the PVA
Film includes the PVA that saponification degree is 98 ~ 99.5 moles of % and swellbility is 250% or more；
[6] according to the manufacturing method of above-mentioned [5], heat treatment in progress 0.5 minute or more；
It [7] is the method for manufacturing the PVA film that swellbility is 180 ~ 220% according to the manufacturing method of above-mentioned [5] or [6]；
[8] manufacturing method of polarization film comprising the process that the PVA film of above-mentioned [4] is stretched；
[9] polarization film, wherein remember b value when being configured to parallel Nicol state relative to rectilinearly polarized light
When making X, and b value when being configured to Nicol crossed state relative to rectilinearly polarized light being denoted as Y, meet formula below
(I):
Y≥1.9X-8.3 (I)。
[10] according to the polarization film of above-mentioned [9], meet formula below (II):
5≥Y≥-5 (II)。
The effect of invention
According to the present invention, it is possible to provide the form and aspect of its own are excellent, can make without using transmissivity low optical film
It makes the excellent LCD of form and aspect and the polarization film and its manufacturing method of the bright LCD of picture can be manufactured；And it can easily make
Make the PVA film and its manufacturing method of the polarization film.
Specific embodiment
Hereinafter, the present invention is described in detail for needle.
(PVA film)
The slope minimum value below of PVA film of the invention is -0.84 ~ -0.783N/mm2Second.
The sample that the width direction cut out from PVA film is 3cm is 1.5cm with distance between chuck and is alongst drawn
The mode stretched is placed in autoplotter, after being impregnated 1 minute in 30 DEG C of water, in the water with the speed of 240%/minute along
Length direction stretches, and reaches 11.1N/mm in stress2At the time of fixed chuck spacing from for stress thereafter through time-varying
Change, using the time (unit: second) as horizontal axis and with stress (unit: N/mm2) each on figure when being drawn as the longitudinal axis
Slope (tangent slope) minimum value of point.
It should be noted that stress be by it is each when the tension (unit: N) inscribed divided by the sectional area of initial sample
(3cm × PVA film thickness) (unit: mm2) obtained from.
When the minimum value of above-mentioned slope is outside above range, the form and aspect of gained polarization film are reduced.The present invention is not carried out
Any restriction, the reason related to the form and aspect of gained polarization film as the minimum value of the slope, it may be considered that following reason.I.e.
It is contemplated that this is because: above-mentioned slope minimum value and using the PVA film it is practical manufacture polarization film when stretching process in
PVA molecule microscopic behavior it is related, and the microscopic behavior will affect the state of the dichroism pigments such as iodine system pigment.
From the viewpoint of the form and aspect of gained polarization film, the minimum value of the slope is preferably -0.825N/mm2Second with
Upper, more preferably -0.815N/mm2Second or more, further preferably -0.8N/mm2Second or more, additionally, it is preferred that for-
0.786N/mm2Second or less, more preferably -0.79N/mm2Second or less, further preferably -0.793N/mm2Second or less.
As the PVA for including in PVA film of the invention, can be used to by vinylacetate, vinyl formate, propionic acid second
Enester, vinyl butyrate, pivalic acid vinyl acetate, tertiary ethylene carbonate, vinyl laurate, stearic acid vinyl ester, benzoic acid second
Obtained from polyvinyl ester obtained from one kind or two or more ethylene polyisocyanate polyaddition in enester, isopropenyl acetate etc. is saponified
PVA.Among above-mentioned vinyl acetate, from the viewpoint of the ease of manufacturing of PVA, obtain easiness, cost etc., preferably acetic acid second
Enester.
One kind or two or more vinyl acetate is preferably used only as polyvinyl ester obtained from monomer, only in above-mentioned polyvinyl ester
Will within the scope of the effect of the invention, then can be one kind or two or more vinyl acetate with can be other with its copolymerization
The copolymer of monomer.
As the other monomers that can be copolymerized with above-mentioned vinyl acetate, such as ethylene, propylene, 1- butylene, isobutyl can be enumerated
The alpha-olefin of the carbon atom numbers such as alkene 2 ~ 30；(methyl) acrylic acid or its salt；(methyl) methyl acrylate, (methyl) acrylic acid second
Ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) i-butyl
Ester, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) dodecylacrylate, (methyl) third
Olefin(e) acid stearyl etc. (methyl) acrylate；(methyl) acrylamide, N- methyl (methyl) acrylamide, N- ethyl (first
Base) acrylamide, N, N- dimethyl (methyl) acrylamide, diacetone (methyl) acrylamide, the third sulphur of (methyl) acrylamide
(the first such as acid or its salt, (methyl) acrylamide propyl dimethylamine or its salt, N- methylol (methyl) acrylamide or derivatives thereof
Base) acrylamide derivative；The N- vinyl acyl such as N- vinyl formamide, N- vinyl acetamide, n-vinyl pyrrolidone
Amine；It is methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, different
The vinyl ethers such as butyl vinyl ether, tert-Butyl vinyl ether, dodecyl vinyl, stearyl vinyl ethers；(methyl)
The vinyl cyanides such as acrylonitrile；The vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride；Allyl acetate, alkene
The allyl compounds such as propyl chloride；Maleic acid or its salt, ester or acid anhydrides；Itaconic acid or its salt, ester or acid anhydrides；Vinyl trimethoxy
The vinyl silyl groups compound such as base silane；Unsaturated sulfonic acid etc..Above-mentioned polyvinyl ester can have from aforementioned other lists
One kind or two or more structural unit in body.
The aforementioned structural unit from other monomers ratio shared in above-mentioned polyvinyl ester is based on constituting polyvinyl ester
Entire infrastructure unit molal quantity be preferably 15 moles of % hereinafter, can for 10 moles of % or less so that can be 5 moles of % with
Under.
Especially, aforementioned other monomers are possible to promote gained as (methyl) acrylic acid, unsaturated sulfonic acid etc.
When the water-soluble monomer of PVA, in order to prevent PVA from dissolving in the manufacturing process of polarization film, this is originated from polyvinyl ester
Molal quantity of the ratio of the structural unit of a little monomers based on the entire infrastructure unit for constituting polyvinyl ester be preferably 5 moles of % or less,
More preferably 3 moles of % or less.
As long as within the scope of the effect of the invention, PVA can use it is one kind or two or more can graft copolymerization
Monomer is modified.As this can graft copolymerization monomer, such as unsaturated carboxylic acid or derivatives thereof can be enumerated；Unsaturated sulphur
Acid or derivatives thereof；The alpha-olefin etc. that carbon atom number is 2 ~ 30.In PVA be originated from can graft copolymerization monomer structural unit
Molal quantity of the ratio of (structural unit in graft modification part) based on the entire infrastructure unit for constituting PVA is preferably 5 moles of %
Below.
A part of hydroxyl in PVA can be crosslinked, and can not also be crosslinked.In addition, a part of hydroxyl in above-mentioned PVA
Can be reacted with aldehyde compounds such as acetaldehyde, butyraldehyde etc. and form acetal structure, can not also be reacted with these compounds without
Form acetal structure.
The average degree of polymerization of PVA is preferably in the range of 1000 ~ 9,500, the average degree of polymerization be more preferably 1,500 with
Above, further preferably 2000 or more, in addition, more preferably 9,200 or less, further preferably 6,000 or less.By making to put down
Right homopolymerization is 1000 or more, and the polarised light performance of polarization film improves.On the other hand, by making average degree of polymerization 9,500
Hereinafter, the productivity of PVA improves.It should be noted that the average degree of polymerization of PVA can come according to the record of JIS K6726-1994
Measurement.
The saponification degree of PVA preferably in the range of 98 ~ 99.5 moles of %, the saponification degree be more preferably 98.3 moles of % or more,
Further preferably 98.6 moles of % or more, particularly preferably 98.7 moles of % or more, in addition, more preferably 99.3 moles of % or less,
Further preferably 99.1 moles of % or less, particularly preferred less than 99 moles %.The saponification degree of PVA within the above range when, reason
By being still not clear, but can it is clear that: even if the form and aspect that can more easily manufacture its own it is excellent, without using the low light of transmissivity
Learn the polarization film that film can also manufacture the excellent LCD of form and aspect and can manufacture the bright LCD of picture.It should be noted that this
The saponification degree of PVA in specification refers to: relative to the knot that can be converted into vinyl alcohol units possessed by PVA by being saponified
The total mole number of structure unit (typical for be vinyl ester units) and vinyl alcohol units, shared by the molal quantity of the vinyl alcohol units
Ratio (mole %).Saponification degree can be measured according to the record of JIS K6726-1994.
PVA film preferably comprises plasticizer from the viewpoint of improving draftability when being stretched.It, can as the plasticizer
Enumerate such as ethylene glycol, glycerol, propylene glycol, diethylene glycol, diglycerol, triethylene glycol, tetraethylene glycol, trihydroxy methyl third
Polyalcohols such as alkane etc., PVA film may include one kind or two or more in these plasticizer.Among these, from raising draftability
From the perspective of effect, preferably glycerol.
The content of plasticizer in PVA film is relative to PVA100 mass parts wherein included preferably in the model of 1 ~ 20 mass parts
In enclosing.By making 1 mass parts of content or more, the draftability of PVA film can be further increased.On the other hand, by making this
Content below the mass, can prevent PVA film from becoming excessively soft and treatability is caused to reduce for 20.Plasticizer in PVA film
Content be more preferably 2 mass parts or more, further preferably more than 4 mass parts, particularly preferably relative to PVA100 mass parts
More than 5 mass parts, in addition, more preferably 15 below the mass, further preferably 12 below the mass.
It should be noted that also different because of manufacturing condition of polarization film etc., the plasticizer for including in PVA film is inclined in manufacture
Dissolution etc. occurs when vibration light film, therefore, total amount not necessarily remains in polarization film.
PVA film can further include antioxidant, anti-freezing agent, pH adjusting agent, masking agent, anti-coloring as needed
The ingredients such as agent, finish, surfactant.
From the viewpoint of easness etc. of preparation expectation polarization film, the containing ratio of the PVA in PVA film preferably 50 ~
In the range of 99 mass %, which is more preferably 75 mass % or more, is more preferably 80 mass % or more, particularly preferred
For 85 mass % or more, in addition, more preferably 98 mass % or less, further preferably 96 mass % or less, particularly preferably 95 matter
Measure % or less.
The thickness of PVA film of the invention is not particularly limited, and can suitably be set according to target thickness of polarization film etc.
It is fixed.As specific thickness, for example, in the range of can be set to 2 ~ 100 μm and then in the range of can be set to 5 ~ 65 μm, can also be with
It is set as in the range of 8 ~ 50 μm.
The shape of PVA film is not particularly limited, preferably the PVA film of strip, this is because the energy when manufacturing polarization film
Enough continuous uses.The length (length of length direction) of the PVA film of strip is not particularly limited, can be according to the polarised light to be manufactured
Purposes of film etc. is suitably set, such as can be set to 1 ~ 20, in the range of 000m.
The width of PVA film is not particularly limited, and can be suitably set, example according to purposes for the polarization film to be manufactured etc.
It such as can be set to 0.1m or more, but in recent years, the viewpoint developed from the large screen of LCD TV, liquid crystal monitor goes out
Hair is suitable for these purposes when being set as 0.5m or more by the width of PVA film, be more preferably set as 1.0m or more.On the other hand, PVA
When the width of film is wide, exists using practical device manufacturing polarization film and be difficult to inclining for Uniform Tension
To therefore, the width of PVA film is preferably 7m or less.
From the productivity of polarization film, the viewpoint of performance grade, the swellbility of PVA film of the invention preferably 180 ~
In the range of 220%, which is more preferably 185% or more, further preferably 190% or more, particularly preferably 195% with
On, in addition, more preferably 215% or less, further preferably 210% or less, particularly preferably 205% or less.The swelling of PVA film
Degree can be measured according to method aftermentioned in embodiment.The swellbility of PVA film can for example be adjusted by enhancing heat treatment condition
Whole to smaller value.
(manufacturing method of PVA film)
The method of PVA film for manufacturing the present invention is not particularly limited, according to the PVA film of the invention of following record
PVA film of the invention can be easily manufactured in manufacturing method, so it is preferred that.That is, the manufacturing method of PVA film of the invention includes: to make
With comprising the PVA that saponification degree is 98 ~ 99.5 moles of % and the PVA film that swellbility is 250% or more, by it with 135 ~ 148 DEG C of model
The process that temperature in enclosing is heat-treated.
As PVA to be used, PVA identical with PVA already described in the explanation of PVA film of the invention can be made, because
This omits duplicate record herein.In addition, in PVA film to be used the plasticizer that can be used as any ingredient and include,
Content identical with content already described in the explanation of PVA film of the invention can be made in shapes such as other ingredients and thickness etc., because
This omits duplicate record herein.
The manufacturing method of PVA film for heat treatment is not particularly limited, and can use conventionally known method to manufacture.
Specifically, film stoste made of PVA is dissolved in liquid medium can be used for example, comprising PVA and liquid medium and PVA
Stoste is film-made made of melting to be film-made.
Liquid medium used in preparation as film stoste, can enumerate such as water, dimethyl sulfoxide, dimethyl methyl
Amide, dimethyl acetamide, N-Methyl pyrrolidone, ethylene glycol, glycerol, propylene glycol, diethylene glycol, triethylene glycol, tetrem two
Alcohol, trimethylolpropane, ethylenediamine, diethylenetriamine etc. can be used one kind or two or more among these.Wherein, from right
From the perspective of burden, recyclability caused by environment, water can be compatibly used.
It is film-made the volatile matter rate (volatile components such as liquid medium being removed in film by volatilization, evaporation of stoste
Content ratio) it is also different because of film-forming method, film forming condition etc., it is often preferred that 50 ~ 95 mass %, further preferably 55 ~ 90
Quality %, particularly preferably 60 ~ 85 mass %.There is following tendency in the volatile matter rate of film stoste: being film-made the viscous of stoste when too low
Degree becomes excessively high, and when preparation film stoste is difficult to filter, deaeration, it is difficult to manufacture the few PVA film of foreign matter, disadvantage.On the other hand, it makes
When the volatile matter rate of film stoste is excessively high, the concentration that there is film stoste becomes too low, is difficult to carry out inclining for the industry film of PVA film
To.
As the film-forming method when PVA film for heat treatment is filmed, such as film by wet method can be used, coagulated
Glue is film-made method, casting film method, extrusion film method etc..Furthermore it is also possible to using the method etc. based on their combination.The above system
Among film method, it is preferred to use casting film method or squeeze out film method, this is because can obtain thickness and width uniformly and object
The good PVA film of property.
It as specific film-forming method, can enumerate: apply mold etc. using T-type slit die, hopper plate, I- mold, lip,
It will be film-made on the circumferential surface for the roller (or band) that stoste is equably ejected in rotation and heating, and make volatile component from being ejected in the roller
The surface evaporation and drying of film on (or band) to which PVA film be made, alternatively, it is such it is dry after, in one or more rotations
Turn and be further dried on the circumferential surface of the roller of heating, or it is made to pass through and be further dried in hot-air drying device, thus
The method that PVA film is filmed.PVA film after film can use after devices for taking-up temporarily batches, and be rolled up as needed
It waits out and implements aftermentioned heat treatment, can also as above operate after continuously continuously implementing aftermentioned heat treatment to the PVA film of film,
It is batched again.
As the surface temperature of roller used in film, such as it can be set to 50 ~ 100 DEG C.In addition, as stoste will be film-made
Drying temperature when spraying on tape, such as can be set to 50 ~ 100 DEG C.
The swellbility of PVA film for heat treatment is preferably 300% or more, more preferably 400% or more, additionally, it is preferred that being
1000% hereinafter, this is because can more easily manufacture PVA film of the invention.Volatile matter as the PVA film for heat treatment
Rate, such as can be set to 10 mass % or less and then can be set to 8 mass % or less.
Temperature in heat treatment is preferably 137 DEG C or more, is more preferably 139 DEG C or more, further preferably more than 140 DEG C,
Additionally, it is preferred that for 145 DEG C hereinafter, this is because can more easily manufacture PVA film of the invention.
Heat treatment time is not particularly limited, and preferably 0.5 minute or more, more preferably 0.8 minute or more, in addition, excellent
It is selected as 30 minutes or less, is more preferably 15 minutes hereinafter, this is because can more easily manufacture PVA film of the invention.
(manufacturing method of polarization film)
The purposes of PVA film of the invention is not particularly limited, its own can be easily manufactured in PVA film according to the present invention
Form and aspect it is excellent, the excellent LCD of form and aspect can be manufactured without using transmissivity low optical film and can to manufacture picture bright
The polarization film of bright LCD, therefore it is preferably used as the raw material film of polarization film manufacture.
It is not particularly limited using the method for PVA film manufacture polarization film of the invention, it can be by including to of the invention
The method for the process that PVA film is stretched manufactures, specifically, can for example manufacture by the following method: first by PVA film
For being swollen process, then for dyeing process, as needed further for cross-linking process step, thereafter for stretching process, root
According to needs further for fixing process process and/or cleaning process, and for drying process.
Swelling process can be carried out by the way that PVA film is impregnated in water.As water temperature when being impregnated in water, preferably 20 ~ 40
In the range of DEG C, which is more preferably 22 DEG C or more, further preferably 25 DEG C or more, in addition, more preferably 38 DEG C or less,
Further preferably 35 DEG C or less.In the range of the temperature is set as 20 ~ 40 DEG C, PVA film can be made efficiently to be swollen.Separately
Outside, as the time for being impregnated in water, preferably in the range of 0.1 ~ 5 minute, more preferably in the range of 0.5 ~ 3 minute.Pass through
It is set as in the range of 0.1 ~ 5 minute, PVA film can be made efficiently to be swollen.It should be noted that water when being impregnated in water does not limit
For pure water, the aqueous solution dissolved with various composition can be, be also possible to the mixture of water and aqueous medium.
In dyeing process dyeing processing can by by PVA film be immersed in the aqueous solution comprising dichroism pigment come into
Row.As the dichroism pigment, iodine system pigment (I can be enumerated3 -、I5 -Deng), dichroic organic dye etc..Iodine system pigment is for example
It can be by making iodine (I2) contact and obtain with potassium iodide.In addition, as dichroic organic dye, can enumerate directly black 17,19,
154；Direct brown 44,106,195,210,223；Direct red 2,23,28,31,37,39,79,81,240,242,247；It is directly blue
1,15,22,78,90,98,151,168,202,236,249,270；Directly purple 9,12,51,98；Direct green 1,85；Directly yellow 8,
12,44,86,87；Direct orange 26,39,106,107 etc..Among these dichroism pigments, from treatability, availability, polarization photosensitiveness
Can it is equal from the perspective of, preferably iodine system pigment.It should be noted that dichroism pigment can be independent a kind, or 2
Kind or more, such as can also be such as I3 -And I5 -It like that is equilibrium mixture.
The concentration of dichroism pigment in aqueous solution comprising dichroism pigment can be according to dichroism pigment to be used
Type etc. is suitably set, such as in the range of can be set to 0.001 ~ 1 mass %, as the aqueous solution comprising dichroism pigment
And when using iodine-potassium iodide aqueous solution, since iodine system pigment can be made efficiently to be adsorbed in PVA film, as to be used
Iodine (I2) concentration, preferably in the range of 0.01 ~ 2 mass %, more preferably in the range of 0.02 ~ 0.5 mass %, as making
The concentration of potassium iodide (KI) preferably exists by the quality of above-mentioned potassium iodide used based on the ratio of the quality of iodine used
In the range of 10 ~ 200 mass times, more preferably in the range of 15 ~ 150 mass times.It can in aqueous solution comprising dichroism pigment
To include the boron compounds such as the borates such as boric acid, borax.The temperature of aqueous solution comprising dichroism pigment is preferably at 5 ~ 50 DEG C
In range, more preferably in the range of 15 ~ 40 DEG C, this is because dichroism pigment can be made efficiently to be adsorbed in PVA film.It needs
Illustrate, when using PVA film containing dichroism pigment in advance, dyeing process can be omitted.
By carrying out cross-linking process step to PVA film, can be more efficiently prevented from when carrying out wet tensile with higher temperature
PVA is dissolved out in water.From this viewpoint, cross-linking process step carries out preferably after dyeing process and before stretching process.Cross-linking process step
It can be carried out by impregnating PVA film in as the aqueous solution comprising crosslinking agent for being crosslinked bath.As the crosslinking agent, can make
With the one kind or two or more boron compound in borates such as boric acid, borax etc..The concentration of crosslinking agent in crosslinking bath is preferably 1
In the range of ~ 15 mass %, 2 mass % or more are more preferably, in addition, more preferably 7 mass % or less, further preferably 6 matter
Measure % or less.In the range of concentration by making crosslinking agent is in 1 ~ 15 mass %, it is able to maintain that sufficient draftability.Crosslinking bath can
To contain the auxiliary agents such as potassium iodide.Crosslinking bath temperature be preferably set to 20 ~ 50 DEG C in the range of, be particularly preferably set as 25 ~ 40 DEG C
In range.By making the temperature in the range of 20 ~ 50 DEG C, crosslinking can be carried out efficiently.
Drawing process when stretching PVA film is not particularly limited, and can use in wet tensile method and dry stretch process
Any one is carried out.It, can be comprising one kind or two or more in borates such as boric acid, borax etc. in the case where wet tensile method
It carries out, can also be carried out in above-mentioned dye bath, in the bath of aftermentioned fixing process in the aqueous solution of boron compound.In addition, in dry type
It in the case where pulling method, can directly be stretched, can also be stretched while heating at room temperature, it can also be after absorbing water
It is stretched.Among these, from the viewpoint of the thickness uniformity of the width direction of gained polarization film, preferably wet type is drawn
Method is stretched, is more preferably stretched in boric acid aqueous solution.Boric acid concentration in boric acid aqueous solution is preferably 0.5 ~ 6.0 mass %'s
In range, which is more preferably 1.0 mass % or more, further preferably 1.5 mass % or more, in addition, more preferably 5.0 matter
Measure % or less, further preferably 4.0 mass % or less.It, can in the range of making boric acid concentration be in 0.5 ~ 6.0 mass %
Obtain the excellent polarization film of the thickness uniformity of width direction.The above-mentioned aqueous solution comprising boron compound can contain iodate
Potassium, concentration is preferably in the range of 0.01 ~ 10 mass %.In the range of making iodate potassium concn be in 0.01 ~ 10 mass %,
The more good polarization film of polarised light performance can be obtained.
Temperature when stretching PVA film is preferably in the range of 5 ~ 90 DEG C, which is more preferably 10 DEG C or more, in addition, more
Preferably 80 DEG C or less, further preferably 70 DEG C or less.By making the temperature in the range of 5 ~ 90 DEG C, width can be obtained
The excellent polarization film of the thickness uniformity in direction.
Stretching ratio when stretching PVA film is preferably 4 times or more, more preferably 5 times or more, be more preferably 6 times with
On.By making the stretching ratio of PVA film in above-mentioned range, the superior polarization film of polarised light performance can be obtained.PVA
The upper limit of the stretching ratio of film is not particularly limited, and preferably 8 times or less.The stretching of PVA film can carry out once, can also dividing
Repeatedly carry out, any one, when being performed in multiple times, the stretching ratio respectively stretched total stretching ratio obtained from being multiplied is in upper
It states in range.It should be noted that length of the stretching ratio based on the PVA film before stretching in this specification, non-stretched
It is 1 times that state, which is equivalent to stretching ratio,.
From the viewpoint of the performance of gained polarization film, the stretching of PVA film is preferably uniaxially stretched.When stretching PVA film
The direction that is uniaxially stretched be not particularly limited, can be using being uniaxially stretched on length direction, be laterally uniaxially stretched, due to passing through
Polarised light performance and excellent polarization film can be obtained, therefore preferably being uniaxially stretched on length direction.On length direction
Be uniaxially stretched can by using the stretching device for having the multiple rollers being parallel to each other, and change the peripheral speed between each roller come
It carries out.On the other hand, it is laterally uniaxially stretched and tenter stretcher can be used to carry out.
Fixing process process is primarily to make iodine system pigment firmly be adsorbed in PVA film and carry out.Bearing's science and engineering
Sequence can by before stretching, stretch in or PVA film after stretching be impregnated in fixing process bath and carry out.As fixing process
Bath, can be used the aqueous solution comprising the one kind or two or more boron compound in borates such as boric acid, borax etc..In addition, according to
Iodine compound, metallic compound are added in needing to bathe to fixing process.Be used as fixing process bath includes boron compound
Aqueous solution in boron compound concentration generally preferably in the range of 0.1 ~ 15 mass %, particularly preferably 1 ~ 10 mass %'s
In range.By making the concentration in the range of 0.1 ~ 15 mass %, iodine system pigment can be more securely adsorbed.Fixing process bath
Temperature preferably in the range of 10 ~ 60 DEG C, particularly preferably in the range of 15 ~ 40 DEG C.By making the temperature at 10 ~ 60 DEG C
In range, iodine system pigment can be more securely adsorbed.
Cleaning process is that the unnecessary chemical drugs category or foreign matter or adjustment in order to remove film surface finally obtain mostly
Polarization film optical property and carry out.Cleaning process can be by making PVA film be impregnated in cleaner bath or spread to PVA film
Cleaning solution carries out.As cleaner bath, cleaning solution, water can be used, they can also contain potassium iodide.
Drying condition in drying process is not particularly limited, preferably within the scope of 30 ~ 150 DEG C, particularly preferably 50 ~
It is dried at a temperature in the range of 130 DEG C.By being dried at a temperature in the range of 30 ~ 150 DEG C, it is easy to get size
The polarization film of excellent in stability.
(polarization film)
According to the manufacturing method of above-mentioned polarization film, parallel Nicol state will be configured to relative to rectilinearly polarized light
When b value be denoted as X, can and when b value when being configured to Nicol crossed state relative to rectilinearly polarized light is denoted as Y
The polarization film for meeting following formula (I) is obtained, the form and aspect of the polarization film itself are excellent, even if the optics low without using transmissivity
Film can also manufacture the excellent LCD of form and aspect, and can manufacture the bright LCD of picture.
Y≥1.9X-8.3 (I)。
Above-mentioned X and Y preferably satisfies formula below (I '), more preferably meets formula (I ") below.
Y≥1.9X-8 (I’)
Y≥1.9X-7.5 (I”)。
It should be noted that above-mentioned X and Y can be used spectrophotometer (such as Japan Spectroscopy Corporation manufacture
" V7100 " etc.) it finds out, specifically, can be found out in embodiment by aftermentioned method.
Above-mentioned Y is also different because of use form of polarization film etc., but preferably satisfy formula below (II), more preferably meet with
Under formula (II '), further preferably meet formula (II ") below.
5≥Y≥-5 (II)
3.5≥Y≥-3.5 (II’)
3≥Y≥-3 (II”)。
(using form)
Polarization film usually its two-sided or single side bonding protective film be made polarization plate come using.As protective film,
Optical clear and the protective film with mechanical strength can be enumerated, specifically, such as Triafol T (TAC) can be used
Film, acetylbutyrylcellulose (CAB) film, acrylic films, polyester mesentery etc..In addition, as the bonding agent for fitting, it can
PVA system bonding agent, urethane system bonding agent etc. are enumerated, PVA system bonding agent is suitably for.
Embodiment
Illustrate the present invention by the following examples, but the present invention is not limited to these embodiments completely.
It should be noted that used in following examples described below and comparative example, PVA film is stretched in water after
The ongoing change behavior (slope minimum value) of stress, the swellbility of PVA film and it is configured to parallel Nicol state and just
Each measuring method of the b value (X and Y) of polarization film when friendship Nicol prism state.
[the ongoing change behavior (slope minimum value) of the stress after stretching PVA film in water]
The width direction central portion of PVA film after being heat-treated obtained in the following examples or comparative example cuts out width side
To 3cm × length direction 5.5cm Rectangular samples, it is 1.5cm with distance between chuck and is alongst stretched
Mode is placed in autoplotter (" AG-I " of Shimadzu Seisakusho Ltd.'s manufacture), and dipping is after 1 minute in 30 DEG C of water (pure water), at this
It is alongst stretched in water with the speed of 240%/minute, reaches 11.1N/mm in stress2At the time of fixed chuck spacing
From measuring the ongoing change of stress thereafter.By the data obtained using the time (unit: second) as horizontal axis and with stress (unit: N/
mm2) draw as the longitudinal axis, find out the minimum value among the slope (tangent slope) of each point on the figure.
[swellbility of PVA film]
The Rectangular samples that width direction is 10cm, length direction is 20cm are cut out from the PVA film for becoming measure object, it will
The sample is further cut into the short strip shape that width is 2 ~ 3mm, length is 20cm.Thereafter, these short strip shape samples are all direct
It is immersed in 30 DEG C of 1000g distilled water.Dipping removes short strip shape sample after 30 minutes, use centrifugal separator (KOKUSAN
XEM-KL-5886) with 3000rpm centrifugal dehydration 5 minutes, dewatered quality " N " (short strip shape sample total total) is measured.It connects
, by the short strip shape sample in 105 DEG C of drying machine after drying 16 hours, quality measurement " M " (sum total of short strip shape sample
Meter), swellbility is calculated by lower formula (III).It should be noted that 3 identical measurements are carried out, using its average value.
Swellbility (%)=100 × N/M (III).
[the b value (X and Y) of polarization film when being configured to parallel Nicol state and Nicol crossed state]
The central portion of the width direction of the polarization film obtained in the following embodiment or comparative example takes polarization film
Length direction is the Rectangular samples of 4cm, and using the spectrophotometer with integrating sphere, (Japan Spectroscopy Corporation is manufactured
" V7100 "), which is provided parallel to Nicol prism state relative to the polarization plate of the spectrophotometer and finds out b
Value, is denoted as X for the value.Then, cross Nicols rib is set relative to the polarization plate of the spectrophotometer by above-mentioned sample
Specular state simultaneously finds out b value, which is denoted as Y.It should be noted that in the measurement of b value, according to JIS Z 8722 (object color
Measuring method), carry out illuminant-C, 2 ° of visuals field visible region visibility correction.
[embodiment 1]
To include PVA (the saponified of the homopolymer of vinylacetate, the degree of polymerization 2,400, saponification degree are 98.9 moles of %)
100 mass parts, 10 mass parts of glycerol as plasticizer, 0.1 matter of polyoxyethylene laurel ether sodium sulphate as surfactant
It measures part and water and volatile matter rate to be cast in 80 DEG C of metal drum for the film stoste of 85 mass %, drying is (aqueous to volatile matter rate
Rate) reach 5 mass % until, so that the strip PVA film (PVA before heat treatment of 30 μm of thickness, length 1.5m, width 30cm be made
Film).The swellbility of the PVA film is 480%.
The PVA film is heat-treated 10 minutes with 142 DEG C of temperature.Gained PVA film (PVA film after heat treatment) it is above-mentioned tiltedly
The minimum value of rate is -0.796N/mm2Second, swellbility 200%, with a thickness of 30 μm.
By carrying out swelling process, dyeing process, cross-linking process step, stretching for above-mentioned PVA film (PVA film after heat treatment)
Process, fixing process process and drying process, to manufacture polarization film.
That is, alongst (MD) is single during above-mentioned PVA film is impregnated 1 minute in the water that temperature is 30 DEG C
It is being 0.02 mass % with iodine as dosage and potassium iodide is 0.6 matter after axis stretches (stretching of the 1st stage) to 2 times of raw footage
During the concentration of amount % is mixed in temperature made of water to impregnate 2 minutes in 30 DEG C of dye bath, alongst (MD)
(stretching of the 2nd stage) is uniaxially stretched to 3 times of raw footage, is then 32 DEG C in the temperature for containing boric acid with the concentration of 2.5 mass %
Crosslinking bath in impregnate 2 minutes during, alongst (MD) is uniaxially stretched (stretching of the 3rd stage) to raw footage
3.6 times, and then in 57 DEG C of temperature of boron for containing boric acid with the concentration of 2.8 mass % and containing potassium iodide with the concentration of 5 mass %
During impregnating in acid/potassium iodide aqueous solution, alongst (MD) is uniaxially stretched (stretching of the 4th stage) to raw footage
6.2 times, thereafter, in 22 DEG C of temperature of iodine for containing boric acid with the concentration of 1.5 mass % and containing potassium iodide with the concentration of 5 mass %
Change and impregnated 5 seconds in aqueous solutions of potassium, to clean to film, then passes through 240 seconds dry, the manufacture with 60 DEG C of drying machine
With a thickness of 12 μm of polarization film.Polarization film obtained by use, finds out X and Y by the above method.
It the above results are shown in table 1.
[embodiment 2]
In addition to by heat treatment in temperature from 142 DEG C be changed to 138 DEG C other than, operate similarly to Example 1, manufacture PVA
Film and polarization film carry out evaluation same as Example 1.
It the above results are shown in table 1.
[comparative example 1]
It other than using the PVA that saponification degree is 99.9 moles of %, operates similarly to Example 1, manufactures PVA film and polarization
Light film carries out evaluation same as Example 1.
It the above results are shown in table 1.
[comparative example 2]
In addition to by heat treatment in temperature from 142 DEG C be changed to 125 DEG C other than, with comparative example 1 equally operate, manufacture PVA
Film and polarization film carry out evaluation same as Example 1.
It the above results are shown in table 1.
[comparative example 3]
In addition to by heat treatment in temperature from 142 DEG C be changed to 133 DEG C other than, operate similarly to Example 1, manufacture PVA
Film and polarization film carry out evaluation same as Example 1.
It the above results are shown in table 1.
[table 1]
Claims (10)
1. polyvinyl alcohol film, wherein slope minimum value below is -0.84 ~ -0.783N/mm2Second:
It with distance between chuck is 1.5cm and alongst by the sample that the width direction cut out from polyvinyl alcohol film is 3cm
The mode of stretching is placed in autoplotter, after impregnating 1 minute in 30 DEG C of water, with the speed edge of 240%/minute in the water
Length direction stretch, reach 11.1N/mm in stress2At the time of fixed chuck spacing from for stress thereafter through time-varying
Change, the slope minimum value of each point on the figure using the time as horizontal axis and when being drawn using stress as the longitudinal axis.
2. polyvinyl alcohol film according to claim 1, wherein the saponification degree for the polyvinyl alcohol for including in polyvinyl alcohol film is
98 ~ 99.5 moles of %.
3. polyvinyl alcohol film according to claim 1 or 2, wherein swellbility is 180 ~ 220%.
4. polyvinyl alcohol film according to claim 1 or 2, for the raw material film for manufacturing polarization film.
5. the manufacturing method of polyvinyl alcohol film is the method for polyvinyl alcohol film described in manufacturing claims 1, the method packet
The process for being heat-treated polyvinyl alcohol film with 135 ~ 148 DEG C is included, the polyvinyl alcohol film includes that saponification degree rubs for 98 ~ 99.5
The polyvinyl alcohol and swellbility of your % is 250% or more.
6. manufacturing method according to claim 5, heat treatment in progress 0.5 minute or more.
7. manufacturing method according to claim 5 or 6 is the side for manufacturing the polyvinyl alcohol film that swellbility is 180 ~ 220%
Method.
8. the manufacturing method of polarization film comprising the process stretched to polyvinyl alcohol film as claimed in claim 4.
9. polarization film is the polarization film manufactured by the manufacturing method of polarization film according to any one of claims 8, described inclined
B value when being configured to parallel Nicol state relative to rectilinearly polarized light is denoted as X by vibration light film, and will be inclined relative to straight line
When b value when vibration light is configured to Nicol crossed state is denoted as Y, meet formula below (I):
Y≥1.9X-8.3 (I)。
10. polarization film according to claim 9 meets formula below (II):
5≥Y≥-5 (II)。
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| JP2013240638 | 2013-11-21 | ||
| JP2013-240638 | 2013-11-21 | ||
| PCT/JP2014/080018 WO2015076169A1 (en) | 2013-11-21 | 2014-11-13 | Polyvinyl alcohol film |
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| JP (1) | JP6402096B2 (en) |
| KR (1) | KR102364529B1 (en) |
| CN (1) | CN105723259B (en) |
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| JP6214594B2 (en) | 2014-04-25 | 2017-10-18 | 日東電工株式会社 | Polarizer, polarizing plate and image display device |
| JP6215864B2 (en) | 2014-04-25 | 2017-10-18 | 日東電工株式会社 | Polarizer, polarizing plate and image display device |
| JP6215261B2 (en) | 2014-06-27 | 2017-10-18 | 日東電工株式会社 | Long polarizer, long polarizing plate and image display device |
| JP7163000B2 (en) | 2015-06-25 | 2022-10-31 | 日東電工株式会社 | Polarizer with non-polarizing portion |
| TWI794442B (en) * | 2018-03-12 | 2023-03-01 | 日商可樂麗股份有限公司 | Film roll and method for producing same |
| KR20210021471A (en) * | 2018-06-21 | 2021-02-26 | 주식회사 쿠라레 | Polyvinyl alcohol film and its manufacturing method |
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| JP5073589B2 (en) * | 2007-12-13 | 2012-11-14 | 日東電工株式会社 | Manufacturing method of polarizer, polarizer, polarizing plate, optical film, and image display device |
| CN104640912B (en) * | 2012-09-26 | 2019-07-26 | 株式会社可乐丽 | Polyvinyl alcohol film and polarizing coating |
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2014
- 2014-11-13 KR KR1020167010088A patent/KR102364529B1/en active IP Right Grant
- 2014-11-13 WO PCT/JP2014/080018 patent/WO2015076169A1/en active Application Filing
- 2014-11-13 CN CN201480063715.XA patent/CN105723259B/en active Active
- 2014-11-13 JP JP2015513925A patent/JP6402096B2/en active Active
- 2014-11-19 TW TW103139994A patent/TWI644960B/en active
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| JPH06177510A (en) * | 1992-12-02 | 1994-06-24 | Nippon Synthetic Chem Ind Co Ltd:The | Manufacture of printed wiring board |
| CN1826542A (en) * | 2003-04-21 | 2006-08-30 | 日东电工株式会社 | Polarizer, method for producing the same, polarizing plate, optical film and image display |
| CN101516646A (en) * | 2006-07-24 | 2009-08-26 | 株式会社普利司通 | Multilayer body, method for producing the same, inner liner for pneumatic tire and pneumatic tire |
| WO2010071094A1 (en) * | 2008-12-18 | 2010-06-24 | 株式会社クラレ | Polyvinyl alcohol film |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR102364529B1 (en) | 2022-02-17 |
| WO2015076169A1 (en) | 2015-05-28 |
| JP6402096B2 (en) | 2018-10-10 |
| CN105723259A (en) | 2016-06-29 |
| JPWO2015076169A1 (en) | 2017-03-16 |
| KR20160089349A (en) | 2016-07-27 |
| TW201529681A (en) | 2015-08-01 |
| TWI644960B (en) | 2018-12-21 |
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