CN107001671A - Polyvinyl alcohol film - Google Patents
Polyvinyl alcohol film Download PDFInfo
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- CN107001671A CN107001671A CN201580067580.9A CN201580067580A CN107001671A CN 107001671 A CN107001671 A CN 107001671A CN 201580067580 A CN201580067580 A CN 201580067580A CN 107001671 A CN107001671 A CN 107001671A
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- film
- dryer roll
- roll
- pva
- heat treating
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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
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
- B29C41/26—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on a rotating drum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
- B29C41/46—Heating or cooling
-
- 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
-
- 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
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/08—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of polarising materials
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polarising Elements (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The present invention is PVA film, wherein, during the refractive index A and B in each face that the PVA film is determined by the incident light in the inclined direction of width from the direction perpendicular to film surface towards film（Wherein, A >=B）, A is more than 1.524 and less than 1.530；And, the manufacture method of PVA film, it uses the film forming apparatus for possessing rotary shaft dryer roll parallel to each other and Heat treating roll, on the 1st dryer roll by comprising PVA film stoste spray film-like and carry out it is partially dried after, dryer roll using the 2nd dryer roll and afterwards is further dried, thereafter it is heat-treated to manufacture PVA film using multiple Heat treating rolls, herein, by the Heat treating roll positioned at most downstream side among the Heat treating roll（Y）Peripheral speed（SY）Relative to the Heat treating roll positioned at most upstream side（X）Peripheral speed（SX）The ratio between（SY/SX）It is set to more than 0.993 and less than 0.997.
Description
Technical field
The present invention relates to the polyvinyl alcohol film that tensile elongation is high, draftability is excellent.
Background technology
Polyvinyl alcohol film（Hereinafter, " polyvinyl alcohol " is referred to as " PVA " sometimes）Mechanics physical property, the transparency, oxygen blocking
It is excellent every property, oil resistivity etc., fibre packing materials, film for agricultural use are used for all the time（Vegetables insulation purposes, vegetable cultivation are used
The film on way etc.）, gas barrier material, filter, the purposes of polarizing coating production of raw material for use film etc..
For the inner evenness of polarizing coating, it is known that by the both sides of PVA film and the respective folding of thickness direction central part
The method that the rate of penetrating is set to particular value（With reference to patent document 1 and 2）.
Prior art
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2006-219638 publications
Patent document 2：Japanese Unexamined Patent Publication 2006-305923 publications.
The content of the invention
Problems to be solved by the invention
However, polarizing coating is general by the way that PVA film high elongation is manufactured, therefore problem is, when solving to stretch PVA film
Disengagement failure.However, passing through the method described in patent document 1,2, it is impossible to fully improve draftability.Thus, mesh of the invention
Be there is provided the excellent PVA film of draftability and used the optical films such as its polarizing coating.
The solution used to solve the problem
Further investigation is repeated in the present inventor etc. to achieve these goals, as a result finds：The certain party on PVA film surface
To refractive index and the draftability of PVA film there is close relationship.It is found furthermore that：By by be film-made when Heat treating roll circumference
Speed is set to particular value, can smoothly and continuously manufacture the refractive index and be able to specific PVA film.The present inventor etc. are based on these
Opinion further repeats to study, so as to complete the present invention.
That is, the present invention relates to following technical proposals：
[1] PVA film, wherein, pass through the inclined direction of width from the direction of the film surface perpendicular to PVA film towards film
Incident light determines the refractive index in each face of the PVA film, and the refractive index in a face is denoted as into A, and by the refractive index in another face
When being denoted as B（Wherein, A >=B）, A is more than 1.524 and less than 1.530；
[2] according to the PVA film of above-mentioned [1], wherein, A is more than 1.526 and less than 1.530；
[3] according to the PVA film of above-mentioned [1] or [2], wherein, A+B is more than 3.050 and less than 3.060；
[4] manufacture method of PVA film, its using the film forming apparatus for possessing rotary shaft dryer roll parallel to each other and Heat treating roll,
The film stoste comprising PVA is being sprayed into film-like on the 1st dryer roll of most upstream side among the dryer roll and carried out
After partially dried, dryer roll using the 2nd dryer roll continued thereafter and afterwards is further dried, thereafter, using multiple
Heat treating roll is heat-treated to manufacture PVA film, herein, by the Heat treating roll positioned at most downstream side among the Heat treating roll
（Y）Peripheral speed（SY）Relative to the Heat treating roll positioned at most upstream side（X）Peripheral speed（SX）The ratio between（SY/SX）It is set to
More than 0.993 and less than 0.997；
[5] according to the manufacture method of above-mentioned [4], wherein, by the peripheral speed of the 2nd dryer roll（S2）Relative to the 1st dryer roll
Peripheral speed（S1）The ratio between（S2/S1）It is set to more than 1.000 and less than 1.040；
[6] according to the manufacture method of above-mentioned [4] or [5], wherein, the surface temperature of final dryer roll is set below 60 DEG C；
[7] optical film, it is manufactured by the PVA film of any one of above-mentioned [1] ~ [3]；
[8] according to the optical film of above-mentioned [7], it is polarizing coating；
[9] manufacture method of optical film, it has the step that uniaxial tension is carried out using the PVA film of any one of above-mentioned [1] ~ [3]
Suddenly；
[10] according to the manufacture method of above-mentioned [9], it is the manufacture method of polarizing coating.
The effect of invention
The tensile elongation of the PVA film of the present invention is high, draftability is excellent.Therefore, if the PVA film of the present invention is used for into raw material film,
The optical films such as the polarizing coating that then excellent in optical properties can be manufactured with good productivity ratio.In addition, according to the PVA film of the present invention
Manufacture method, smoothly and can be continuously manufactured by above-mentioned PVA film.
Embodiment
Hereinafter, it is specifically described for the present invention.
(PVA film)
On the PVA film of the present invention, pass through entering for the inclined direction of width from the direction perpendicular to its film surface towards film
The refractive index in each face for penetrating light to determine the PVA film, is denoted as A, and the refractive index in another face is remembered by the refractive index in a face
When making B（Wherein, A >=B）, A is more than 1.524 and less than 1.530.
If A is less than 1.524, there is the problem of PVA film easily produces fold.If in addition, A is more than 1.530, existing and drawing
The problem of stretching property is reduced.Although not causing any restriction to the present invention, the reasons why being impacted as A to draftability can be with
It is following to consider.I.e., it is possible to it is thought that because：Compared with the refractive index of the thickness direction central part of PVA film, the stretching of PVA film
Correlation between property and the refractive index on surface is higher, moreover, with by from the direction of the film surface perpendicular to PVA film towards film
Flow direction（MD）The incident light in inclined direction and the refractive index that determines is compared, the draftability of PVA film with by from perpendicular to film surface
Direction towards film width（TD）The incident light in inclined direction and the correlation between the refractive index that determines is higher,
The fracture of PVA film is produced using the destruction of film surface element as starting point, also, the influence for the high surface of refractive index more
Greatly.
From viewpoint as described above, A is preferably greater than 1.524, is more preferably more than 1.526, further preferably exceedes
1.526th, it is still more preferably more than 1.527, is most preferably more than 1.527, furthermore it is preferred that is less than 1.530, being more preferably
1.529 it is following.
It should illustrate, A and B can be used prism coupler mount as the measured value of the laser based on wavelength 532nm to ask
Go out.Herein, the incident light in the inclined direction of width from the direction of the film surface perpendicular to PVA film towards film refers to：Should
When incident light is along direction projection perpendicular to film surface, its towards and PVA film width（TD）Reach parallel（Perpendicular to
The length direction of PVA film（MD））The incident light of such direction, can be obtained by the prism of above-mentioned prism coupler mount.A
It can be specifically measured with B by method described later in embodiment.
In the PVA film of the present invention, A+B is preferably more than 3.050, is more preferably more than 3.055, more preferably
More than 3.057, furthermore it is preferred that being less than 3.060, more preferably less than 3.059, more preferably less than 3.058.By making
A+B is that more than above-mentioned lower limit, can more effectively suppress PVA film and produce fold.On the other hand, by making A+B be the above-mentioned upper limit
Hereinafter, draftability is further improved.
As the PVA for forming PVA film of the present invention, it can include：For example, polyvinyl ester obtained from ethene polyisocyanate polyaddition will be made
Carry out PVA obtained from saponification；PVA main chain is set to carry out the modified PVA of graft copolymerization with comonomer；Vinyl acetate will be made together
The modified PVA that modified poly ethylene ester obtained from polycondensation monomer copolymerization carries out saponification and manufactured；By unmodified PVA or modified PVA
A part of hydroxyl so-called polyvinyl acetal etc. obtained from being crosslinked with aldehydes such as formaldehyde, butyraldehyde, benzaldehydes.
When the PVA of formation PVA film of the present invention is modified PVA, PVA modified amount is preferably 15 moles of below %, is more preferably
5 moles of below %.
As the foregoing vinyl acetate for manufacturing PVA, such as vinyl formate, vinyl acetate, propionic acid second can be included
Alkene ester, vinyl butyrate, pivalic acid vinyl acetate, tertiary ethylene carbonate, vinyl laurate, stearic acid vinyl ester, benzoic acid second
Alkene ester etc..These vinyl acetates can be used alone, or two or more is applied in combination.Among these vinyl acetates, from productivity ratio
From the viewpoint of, preferably vinyl acetate.
In addition, as foregoing comonomers, can include the carbon number 2 such as ethene, propylene, 1- butylene, isobutene ~
30 olefines（Alpha-olefin etc.）；Acrylic acid or its salt；Methyl acrylate, ethyl acrylate, n-propyl, acrylic acid are different
Propyl ester, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-EHA, lauryl base
The esters of acrylic acids such as ester, octadecyl acrylate（For example, the Arrcostab of the carbon number 1 ~ 18 of acrylic acid）；Methacrylic acid
Or its salt；Methyl methacrylate, EMA, n propyl methacrylate, isopropyl methacrylate, methyl-prop
Olefin(e) acid N-butyl, Isobutyl methacrylate, Tert-butyl Methacrylate, 2-Ethylhexyl Methacrylate, methacrylic acid
The methyl acrylic esters such as dodecyl ester, octadecyl methacrylate（For example, the carbon number 1 ~ 18 of methacrylic acid
Arrcostab）；Acrylamide；N methacrylamide, N- ethyl acrylamides, N, N- DMAAs, two acetone third
Acrylamide, acrylamide propane sulfonic acid or its salt, acrylamide propyl dimethylamine or its salt, N hydroxymethyl acrylamide or its derivative
The acrylamide derivatives such as thing；Methacrylamide；N- methyl methacrylamides, N- ethyl methacrylamides, methyl-prop
Acrylamide propane sulfonic acid or its salt, Methacrylamide diemethylamine or its salt, N- methylol methacrylamides or its derivative
The methacrylamide derivatives such as thing；The N- ethene such as N- vinyl formamides, N- vinyl acetamides, NVP
Base amide-type；Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl base
The vinyl ethers such as ether, IVE, tert-Butyl vinyl ether, dodecyl vinyl, stearyl vinyl ethers；
The nitriles such as acrylonitrile, methacrylonitrile；The halogen vinyl such as vinyl chloride, vinylidene chloride, PVF, vinylidene fluoride；Acetic acid alkene
The allyl compounds such as propyl ester, allyl chloride；The derivatives such as the unsaturated dicarboxylics such as maleic acid, itaconic acid, its salt or its ester；Second
The vinyl silyl groups compound such as alkenyl trimethoxy silane；Methylvinyl acetate；Unsaturated sulfonic acid or derivatives thereof etc..This
Among a little, preferably alpha-olefin, particularly preferably ethene.
From the viewpoint of polarization property and durability from gained polarizing coating etc., the PVA's of formation PVA film of the present invention is averaged
The degree of polymerization is preferably more than 1,500, more preferably more than 1,700, more preferably more than 2,000.On the other hand, from homogeneous
From the viewpoint of ease of manufacturing, draftability of PVA film etc., the upper limit of PVA average degree of polymerization is preferably 8, less than 000, spy
You Xuanwei less than 6,000.
Herein, " average degree of polymerization " of the PVA in this specification refers to averagely gather according to what JIS K6726-1994 were determined
It is right, according to by PVA carry out resaponifying and it is refined after, the inherent viscosity determined in 30 DEG C of water is obtained.
From the viewpoint of the water resistance of the polarizing coating of PVA film manufacture obtained by use, above-mentioned PVA saponification degree is preferably
98.0 moles of more than %, more preferably 98.5 moles more than %, more preferably 99.0 moles of more than %.If saponification degree is less than
, then there is the tendency that the water resistance of gained polarizing coating is deteriorated in 98.0 moles of %.It should illustrate, the saponification degree of the PVA in this specification
Refer to：The construction unit of vinyl alcohol units can be changed into by saponification relative to what is had in PVA（It is vinyl acetate list for typical case
Member）With the total mole number of vinyl alcohol units, the ratio shared by the molal quantity of the vinyl alcohol units（Mole %）.Saponification degree can be according to
JIS K6726-1994 record is measured.
The PVA film of the present invention preferably comprises plasticizer.By the way that comprising plasticizer, draftability is further improved.Plasticizer can
To be coordinated when preparing and being used for and manufacture the film stoste of PVA film, thus, dissolving, meltings of the PVA in liquid medium are able to
Promote, in addition, film when the step of improved by property.
As plasticizer, polyalcohol is preferably used.As the polyalcohol, such as ethylene glycol, glycerine, two sweet can be included
Oil, propane diols, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane etc..Plasticizer can be used alone,
Two or more can be applied in combination.Among these, from the viewpoint of the excellent effect for improving draftability, preferably glycerine.
The content of plasticizer is preferably more than 0 mass parts and below 30 mass parts, more preferably relative to 100 mass parts PVA
For more than 3 mass parts and below 25 mass parts, more than particularly preferably 5 mass parts and below 20 mass parts.By making plasticizer
Content for below the above-mentioned upper limit, the treatability of gained PVA film is improved.
The PVA film of the present invention preferably comprises surfactant.Improved by the treatability comprising surfactant, PVA film.
Surfactant can be coordinated when preparing and being used for and manufacture the film stoste of PVA film, thus, from drying during manufacture PVA film
The fissility peeled off on roller is improved.
The species of surfactant is not particularly limited, and preferably uses anionic surfactant or non-ionic surface
Activating agent.
As anionic surfactant, the sulfuric esters such as the carboxylic acid type such as potassium laurate, sulfuric acid monooctyl ester can be included
Sulfonic acid types such as type, dodecyl benzene sulfonate etc..
In addition, as nonionic surfactant, the alkyl ether type such as polyoxyethylene oleyl ether, polyoxy can be included
The alkyl esters such as the alkyl phenyl such as ethene octyl phenyl ether ether type, polyoxyethylene laurate, polyoxyethylene laural base amino ethers
Deng polypropylene glycol ether type, bays such as alkylamide type, the polyoxyethylene poly-oxygen propylene aethers such as alkyl amine type, polyoxyethylene laural acid amides
The allyl phenyl ethers such as the alkylol amide types such as sour diglycollic amide, oleic acid diethyl amide, polyoxy alkylidene allyl phenyl ether
Type etc..Surfactant can be used singly or in combination of two or more.
The content of surfactant is preferably more than 0.01 mass parts and below 1 mass parts relative to 100 mass parts PVA,
More than more preferably 0.02 mass parts and below 0.5 mass parts, more than particularly preferably 0.05 mass parts and 0.3 mass parts with
Under.By making the content of surfactant for more than above-mentioned lower limit, Film making properties, fissility are improved.On the other hand, by making surface
The content of activating agent is that below the above-mentioned upper limit, the treatability of gained PVA film is improved.
The PVA film of the present invention can include other compositions in addition to above-mentioned PVA, plasticizer and surfactant, example
Such as stabilization agent（Antioxidant, ultra-violet absorber, heat stabilizer etc.）, it is compatibility agent, antiblocking agent, fire retardant, antistatic
Agent, lubricant, dispersant, flowing agent, antiseptic etc..These other compositions can be used alone, and can also be applied in combination
Two or more.
The thickness of PVA film is not particularly limited, for example, can be set to less than 100 μm and then can be set to less than 80 μm.This
Outside, the thickness can be set to more than 10 μm and then can be set to more than 20 μm, can be the thickness more than 50 μm.
The width of PVA film is not particularly limited, and liquid crystal TV set, the picture of monitor in recent years become larger, therefore
In order to be effectively used for them, width is preferably more than 2m, more preferably more than 3m, more preferably more than 4m.In addition,
When industrially manufacturing polarizing coating, if the width of film is wide, uniform uniaxial tension, therefore, PVA film are difficult to sometimes
Width is preferably below 8m.
The shape of PVA film is not particularly limited, in order to be continuously manufactured by PVA film evenly, also, even in making
With also can be continuously with its situation for manufacturing polarizing coating etc., the preferably film of strip.The length of the film of strip（Flow direction
Length）It is not particularly limited, can be suitably set according to purposes etc., for example, can be set to more than 5m and 20, below 000m model
In enclosing.
The quality swellbility of the PVA film of the present invention is preferably more than 150% and less than 250%, more preferably more than 160%
Less than 240%, it is more preferably more than 170% and less than 230%.By making quality swellbility be more than above-mentioned lower limit draftability
Further improve.On the other hand, improved by making quality swellbility for below the above-mentioned upper limit, the step of during stretching by property, this
Outside, the durability of gained polarizing coating is improved.
It should illustrate, the quality swellbility referred in this specification refers to：PVA film is impregnated 30 in 30 DEG C of distilled water
Quality during minute divided by the percentage by the PVA film after aforementioned impregnation to be worth obtained from 105 DEG C of quality after dry 16 hours
Rate.The swellbility of PVA film can reduce it by strengthening the condition of heat treatment.
(manufacture method of PVA film)
Method for manufacturing PVA film of the present invention is not particularly limited, according to following manufacture methods of the invention, can smoothly and
The PVA film of the invention described above is continuously manufactured by, so it is preferred that.
That is, in the method for the invention for manufacturing PVA film, the dryer roll parallel to each other using possessing rotary shaft（From most
Upstream side is referred to as the 1st dryer roll, the 2nd dryer roll ... successively towards downstream）With the film forming apparatus of Heat treating roll, in the dryer roll
Among on the 1st dryer roll of most upstream side by comprising PVA film stoste spray film-like and carry out it is partially dried after,
Dryer roll using the 2nd dryer roll continued thereafter and afterwards is further dried, thereafter, is carried out using multiple Heat treating rolls
It is heat-treated to manufacture PVA film, herein, by the Heat treating roll positioned at most downstream side among the Heat treating roll（Y）Peripheral speed
（SY）Relative to the Heat treating roll positioned at most upstream side（X）Peripheral speed（SX）The ratio between（SY/SX）Be set to more than 0.993 and
Less than 0.997.
In the inventive method for manufacturing PVA film, the dryer roll and Heat treating roll parallel to each other using possessing rotary shaft
Film forming apparatus, in the film stoste comprising PVA being emitted on the 1st dryer roll of most upstream side among the dryer roll
It is membranaceous and carry out it is partially dried after, dryer roll using the 2nd dryer roll continued thereafter and afterwards is further dried, its
Afterwards, it is heat-treated to manufacture PVA film using multiple Heat treating rolls.In the film forming apparatus, the quantity of dryer roll be preferably 4 with
Above, more preferably more than 5, more preferably 6 ~ 30.
Dryer roll and/or Heat treating roll are formed such as the preferably metal as nickel, chromium, copper, iron, stainless steel, especially, roller
Surface is more preferably formed by not perishable and with bright luster metal material.In addition, in order to improve at dryer roll and/or heat
Manage the durability of roller, the nickel dam of individual layer, layers of chrome, ni cr alloy-layer etc. or more than 2 layers of combination preferably by plating and obtain
Roller be used as dryer roll and/or Heat treating roll.
Above-mentioned film forming apparatus can also have hot-blast stove formula as needed in addition to dryer roll and Heat treating roll
Hot-air drying device, the annealing device of hot-blast stove formula, humidity control device etc..
On from the 1st dryer roll untill final dryer roll during heating direction when film is dried, in order to
More uniformly film can be dried, it is preferred that at the arbitrary portion of film, contact the film surface of the 1st dryer roll（It is sometimes referred to as below
For " the 1st dryer roll contact surface "）Film surface with not contacting the 1st dryer roll（Hereinafter sometimes referred to " the 1st dryer roll noncontact face "）
It is dried in the way of alternatively facing from each dryer roll of the 1st dryer roll untill final dryer roll.
When the film stoste comprising PVA being sprayed into film-like on the 1st dryer roll of film forming apparatus, for example T-shaped seam of use
Mould, hopper plate, I- moulds, lip apply membranaceous blowoff known to machine mould etc.（Membranaceous casting device）, by the film comprising PVA
Stoste sprays on the 1st dryer roll（Curtain coating）Film-like.
As the film stoste comprising PVA, solution can be made by the way that PVA is mixed with liquid medium or will include
The PVA beads fuses of liquid medium etc. and fused solution etc. is made to prepare.Dissolvings of the PVA in liquid medium, include liquid and be situated between
The melting of the PVA pellets of matter etc. can use stirring-type mixing arrangement, melt extruder etc. to carry out.It is used as the liquid now used
Body medium, can include such as water, dimethyl sulfoxide (DMSO), dimethylformamide, dimethyl acetamide, 1-METHYLPYRROLIDONE, second
Diamines, diethylenetriamine etc., these liquid mediums can be used alone, or two or more is applied in combination.It is excellent among these
Choosing uses the mixture of water, dimethyl sulfoxide (DMSO) or both, especially, more preferably using water.
It is preferred that such plasticising according to described in expecting with above-mentioned content to coordinate the explanation in PVA film in film stoste
It is one kind or two or more among agent, surfactant, other compositions etc..
The volatile matter rate of film stoste for manufacturing PVA film is preferably more than 50 mass % and below 90 mass %, more excellent
Elect as more than 60 mass % and below 75 mass %.By making the volatile matter rate of film stoste be that more than above-mentioned lower limit, will can make
The viscosity of film stoste maintains relatively low, is easily filtered, deaeration, and being film-made itself also becomes easy.On the other hand, by making system
The volatile matter rate of film stoste is that below the above-mentioned upper limit, can prevent the viscosity for being film-made stoste from becoming too low, the thickness of gained PVA film
Uniformity is improved.
The surface temperature of 1st dryer roll is not particularly limited, from the viewpoint of uniform drying, productivity ratio from film etc.,
Preferably more than 80 DEG C and less than 99 DEG C, more preferably more than 85 DEG C and less than 99 DEG C, more preferably more than 90 DEG C and 98
Below DEG C.It is less than 99 DEG C by making the surface temperature of the 1st dryer roll, film stoste can be more efficiently prevented from and dried the 1st
Foamed on roller.On the other hand, by making the surface temperature of the 1st dryer roll be more than 80 DEG C, the stripping peeled off from the 1st dryer roll
Property improve.
Being emitted into drying of the membranaceous film stoste on the 1st dryer roll can be only by the heating from the 1st dryer roll
To carry out, from the viewpoint of uniform drying, rate of drying etc., it is preferred that using the 1st dryer roll heated it is same
When, attached hot blast is blown to the 1st dryer roll noncontact face, applies heat to be dried from the two sides of film.
When blowing attached hot blast to the 1st dryer roll noncontact face of film present on the 1st dryer roll, in order that gained PVA film
Draftability further raising etc., the whole region in the dryer roll noncontact face of preferred pair the 1st blows the hot blast that attached wind speed is 1 ~ 10m/ seconds,
The hot blast that attached wind speed is 2 ~ 8m/ seconds is more preferably blown, the hot blast that attached wind speed is 3 ~ 8m/ seconds is further preferably blown.If to the 1st dryer roll
It is too small that attached hot blast wind speed is blown in noncontact face, it is likely that the condensation of vapor etc., the water are produced when being dried on the 1st dryer roll
Drop on film, cause the PVA film finally given to produce defect.On the other hand, if blowing attached to the 1st dryer roll noncontact face
Hot blast wind speed is excessive, then the PVA film finally given produces uneven thickness, associated with this, easily occurs producing the unequal event of dyeing
Barrier.
From the viewpoint of drying efficiency, uniform drying etc., attached hot blast is blown to the 1st dryer roll noncontact face of film
Temperature is preferably more than 50 DEG C and less than 99 DEG C, more preferably more than 70 DEG C and less than 98 DEG C, more preferably more than 80 DEG C
And less than 95 DEG C.In addition, the dew-point temperature for blowing the 1st dryer roll noncontact face of film attached hot blast is preferably more than 10 DEG C and 15
Below DEG C.
The mode for blowing attached hot blast for the 1st dryer roll noncontact face to film is not particularly limited, can be using can be by
The uniform hot blast of wind speed, temperature equably blows the 1st dryer roll noncontact face of film that is attached to, preferably blows and is attached in its overall mode
Any one, wherein, it is preferred to use nozzle mode, cowling panel mode or they are combined into obtained mode etc..To the of film
When attached hot blast is blown in 1 dryer roll noncontact face blow subsidiary formula to can be in face of the 1st dryer roll noncontact face direction or
Approximately along the direction of the circumferential shapes in the 1st dryer roll noncontact face of film（Approximately along the circumference of the roller surface of the 1st dryer roll
Direction）, or, it can also be direction in addition.
In addition, when the drying of film is carried out on the 1st dryer roll, the volatile ingredient that preferred pair is produced by dry from film
It is exhausted with the hot blast for blowing attached.Method for exhausting is not particularly limited, it is preferred to use the 1st dryer roll noncontact face of film is blown
Attached hot blast will not produce the method for exhausting that wind speed is uneven and temperature is uneven.
From the viewpoint of productivity ratio from uniform drying, rate of drying and PVA film etc., the peripheral speed of the 1st dryer roll
（S1）More than preferably 5m/ minutes and 50m/ minute following, more than more preferably 10m/ minute and less than 45m/ minutes, further
More than preferably 15m/ minutes and 40m/ minutes following.If the peripheral speed of the 1st dryer roll（S1）More than above-mentioned lower limit, then can
Enough reduce the value of refractive index.On the other hand, if the peripheral speed of the 1st dryer roll（S1）Below the above-mentioned upper limit, then gained PVA film
Thickness evenness improve.
The film stoste for spraying film-like on the 1st dryer roll is dried on the 1st dryer roll, in the volatile matter rate of film
（The volatile matter rate of film when being peeled off from the 1st dryer roll）Preferably more than 17 mass % and below 30 mass %, more preferably 17
More than quality % and 29 below mass %, more preferably more than 18 mass % and during below 28 mass % from quilt on the 1st dryer roll
Peel off.
Preferably, it is preferably more than 17 mass % and below 30 mass % that will be dried on the 1st dryer roll to volatile matter rate
Film peeled off from the 1st dryer roll, then, make film the 1st dryer roll noncontact face face the 2nd dryer roll, utilize the 2nd dryer roll
Film is dried.
The peripheral speed of 2nd dryer roll（S2）Relative to the peripheral speed of the 1st dryer roll（S1）The ratio between（S2/S1）Preferably
More than 1.000 and less than 1.040.By making ratio（S2/S1）Within the above range, the PVA of the present invention can more successfully be manufactured
Film.It should illustrate, if ratio（S2/S1）It is too low, then become uneven, width in the presence of the stripping position for peeling film off from the 1st dryer roll
The inequality for spending the complex refractivity index in direction becomes big tendency.From viewpoint as described above, ratio（SY/SX）Preferably 1.020 with
Above, more preferably more than 1.030, furthermore it is preferred that being less than 1.038.
The PVA film dried using the 2nd dryer roll is peeled off from the 2nd dryer roll, and according to being arranged at film forming apparatus
The quantity of dryer roll etc., using the 3rd dryer roll, the 4th dryer roll, the 5th dryer roll ... wait multiple dryer rolls to be dried successively
.
The surface temperature of each dryer roll from the 2nd dryer roll untill final dryer roll is preferably more than 40 DEG C, more excellent
Elect more than 45 DEG C, more preferably more than 50 DEG C as, furthermore it is preferred that less than 100 DEG C, more preferably less than 98 DEG C, it is further
Preferably less than 96 DEG C, can be less than 90 DEG C.
In addition, the PVA film in order to more successfully manufacture the present invention, furthermore it is possible to more efficiently prevent from the production of fold
It is raw etc., final dryer roll（Positioned at the dryer roll immediately front of Heat treating roll）Surface temperature be preferably shorter than 60 DEG C, it is more preferably low
In 57 DEG C.
Operate as above, for after the film dried on dryer roll, implementing to be heat-treated using multiple Heat treating rolls.This
In place, the inventive method for manufacturing PVA film, by the Heat treating roll positioned at most downstream side among above-mentioned multiple Heat treating rolls
（Y）Peripheral speed（SY）Relative to the Heat treating roll positioned at most upstream side（X）Peripheral speed（SX）The ratio between（SY/SX）It is set to
More than 0.993 and less than 0.997.If ratio（SY/SX）Deviate above range, be then difficult to the PVA film for obtaining the present invention.From above-mentioned
From the viewpoint of like that, ratio（SY/SX）Preferably more than 0.994, be more preferably more than 0.995, furthermore it is preferred that for 0.996 with
Under.
The surface temperature of Heat treating roll is preferably more than 100 DEG C, furthermore it is preferred that being less than 140 DEG C, more preferably 130 DEG C
Below, it is more preferably less than 120 DEG C.It should illustrate, in the inventive method for manufacturing PVA film, it may be considered that by table
Face temperature is used as dryer roll for more than 100 DEG C of roller as Heat treating roll, and using the roller that surface temperature is less than 100 DEG C.
In the inventive method for manufacturing PVA film, Heat treating roll can only exist Heat treating roll（X）And Heat treating roll
（Y）The two, can also further have Heat treating roll in addition between these Heat treating rolls.
Heat treatment time when implementing to be heat-treated using Heat treating roll is not particularly limited, in order to be made more efficiently
The PVA film of the present invention, preferably more than 3 seconds, more preferably more than 4 seconds, more preferably more than 5 seconds, furthermore it is preferred that being
Less than 120 seconds, more preferably less than 90 seconds, more preferably less than 60 seconds.
The film for operating as above and implementing heat treatment carries out conditioning, film both ends as desired by further（End
Portion）Cutting etc., web-like is finally coiled into specific length, so as to which the PVA film of the present invention is made.
The volatile matter rate of the PVA film finally given by a series of above-mentioned processing is preferably in more than 1 mass % and 5 matter
Measure below % scope, be more preferably in more than 2 mass % and below 4 mass % scope.
(purposes of PVA film)
The purposes of PVA film of the present invention is not particularly limited, and the tensile elongation of PVA film of the invention is high, draftability is excellent, because
This is preferably used as the raw material film of the optical film manufacture such as polarizing coating, phase retardation film.This optical film for example can be by using this hair
Bright PVA film simultaneously implements the processing such as uniaxial tension to manufacture.
The PVA film of the present invention is not particularly limited as raw material film to manufacture method during polarizing coating, one can be used
Any means used since straight.As this method, it can include for example：To PVA film implement dyeing and uniaxial tension or
Implement the method for uniaxial tension to the PVA film containing dyestuff.As the more body method for manufacturing polarizing coating, it can include：
For the PVA film of the present invention, implementation is swelled, dyed, uniaxial tension, and further implements fixing process, drying as needed
Deng method.Now, it is swelled, dyes, the order that uniaxial tension, fixing process etc. are respectively handled is not particularly limited, in addition, also may be used
To carry out one kind or two or more processing simultaneously, for example, can be dyed before uniaxial tension, can also be in uniaxial tension
While dyed, can also be dyed after uniaxial tension.And then, can also by 1 in each processing kind or 2 kinds with
It is upper to carry out 2 times or more than 2 times.
Being swelled can be carried out by the way that PVA film is immersed in water.As the water temperature being immersed in when in water, preferably 20 DEG C with
Upper and less than 40 DEG C scopes are interior, more preferably more than 22 DEG C and less than 38 DEG C scopes are interior, be more preferably more than 25 DEG C
And in less than 35 DEG C of scope.In addition, being used as the time being immersed in water, such as preferably more than 0.1 minute and less than 5 minutes
In the range of, in more preferably more than 0.5 minute and the scope of less than 3 minutes.It should illustrate, be immersed in water when in water and do not limit
Can be the aqueous solution for being dissolved with various composition, or the mixture of water and aqueous medium due to pure water.
As the dyestuff for dyeing, iodine system pigment or dichroic organic dye can be used（For example, DirectBlack
17、19、154；DirectBrown 44、106、195、210、223；DirectRed 2、23、28、31、37、39、79、81、
240、242、247；DirectBlue 1、15、22、78、90、98、151、168、202、236、249、270；DirectViolet
9、12、51、98；DirectGreen 1、85；DirectYellow 8、12、44、86、87；DirectOrange 26、39、
106th, 107 etc. dichroic dye）Deng.These dyestuffs can be used alone, or two or more is applied in combination.Dyeing is usual
By making PVA film be immersed in the solution containing above-mentioned dyestuff（Dye bath）In carry out, its treatment conditions, processing method are without spy
Do not limit.
When iodine system pigment is used as dyestuff, the solution containing iodine and KI is generally used for dye bath.Now, contaminate
Color bath in iodine concentration be preferably more than 0.01 mass % and below 0.5 mass % scope in, iodate potassium concn be preferably 0.01
In more than quality % and 10 below mass % scope.In addition, when using dichroic organic dye as dyestuff, in dye bath
The concentration of dichroic organic dye is preferably more than 0.1 mass % and in below 5 mass % scope.The temperature of dye bath is preferably
More than 20 DEG C and less than 50 DEG C, particularly preferably more than 25 DEG C and less than 40 DEG C.
Uniaxial tension can be carried out using any one of wet tensile method or xeothermic pulling method.In wet tensile method
In the case of, it can carry out, can also enter in above-mentioned dye bath, in the bath of aftermentioned fixing process in the aqueous solution comprising boric acid
OK.In addition, in the case of dry stretch process, the PVA film after water suction can be used to carry out in atmosphere.Among these, preferably
For wet tensile method, uniaxial tension is carried out more preferably in the aqueous solution comprising boric acid.Boric acid concentration in boric acid aqueous solution is excellent
Elect as more than 0.5 mass % and in below 6.0 mass % scope, more preferably more than 1.0 mass % and below 5.0 mass % models
Enclose in interior, more preferably more than 1.5 mass % and below 4.0 mass % scope.In addition, boric acid aqueous solution can contain iodine
Change potassium, its concentration is preferably set to more than 0.01 mass % and in below 10 mass % scope.Uniaxial tension is preferably along PVA film
Flow to carry out.
Draft temperature in uniaxial tension is not particularly limited, in the case of wet tensile method, preferably more than 30 DEG C
And in less than 90 DEG C of scope, in more preferably more than 40 DEG C and less than 70 DEG C of scope, be more preferably more than 45 DEG C and
In less than 65 DEG C of scope, in the case of xeothermic pulling method, in preferably more than 50 DEG C and less than 180 DEG C of scope.
Stretching ratio on uniaxial tension（It is total stretching ratio when dividing multistage progress uniaxial tension）, from polarizability
From the viewpoint of energy, preferably it is stretched to as far as possible untill film will cut off, specifically, preferably more than 4 times, more preferably 5
Times more than, more preferably more than 5.5 times.On the upper limit of stretching ratio, just it is not particularly limited as long as film will not be broken,
In order to uniformly be stretched, preferably less than 8.0 times.
Film after stretching（Polarizing coating）Thickness be preferably more than 5 μm and less than 35 μm, particularly preferably more than 20 μm and
Less than 30 μm.
When manufacturing polarizing coating, in order that dyestuff is firmly adsorbed in the film through uniaxial tension, processing is fixed mostly.Gu
The fixed general widely used method by film immersion in being bathed added with the fixing process of boric acid and/or boron compound of processing.Now,
Iodine compound is added in being bathed as needed to fixing process.
Carry out the film of uniaxial tension or carry out the film of uniaxial tension and fixing process preferably followed by drying.
Dry temperature is preferably more than 30 DEG C and less than 150 DEG C, particularly preferably more than 50 DEG C and less than 140 DEG C.If drying temperature
Too low, then the dimensional stability of gained polarizing coating is easily reduced, on the other hand, if drying temperature is too high, along with dyestuff
Decompose etc., polarization property is easily reduced.
Obtained from operating as above optical clear and the guarantor with mechanical strength are pasted on the two sides of polarizing coating or one side
Cuticula, so as to which polarizer is made.As diaphragm now, cellulose triacetate can be used（TAC）Film, cyclic olefin polymerization
Thing（COP）Film, cellulose acetate-butyrate（CAB）Film, acrylic acid mesentery, polyester mesentery, polypropylene mesentery, ENB system tree
Adipose membrane etc..In addition, as the bonding agent for bonding protective film, usually using PVA systems bonding agents, acrylic ester bonding agent,
Carbamate system bonding agent etc., wherein, preferably use PVA systems bonding agent.
Polarizer obtained from operating as above is covered after the adhesive of acrylic acid series etc. again, is pasted on glass substrate, so that
It can be used as the component of LCD device.By polarizing plate sticking when the glass substrate, can also further paste phase retardation film,
Angle of visibility improves film, brightness improving film etc..
Embodiment
Hereinafter, the present invention is further described by embodiment, but the present invention is not limited to these embodiments completely.
It should illustrate, the assay method of the refractive index of the flow direction on the PVA film surface used in following embodiments and comparative example and PVA film
The assay method of tensile elongation is as follows.
[refractive index of PVA film]
The PVA film obtained by following embodiments or comparative example is carried out in the environment of 23 DEG C, 50%RH to the damping of 7 days, its
Afterwards, the prism coupler mount manufactured under identical environment using Metricon companies（Model 2010/M）, it is by wavelength
532nm laser is made up of the prism of the prism coupler mount from the direction of the film surface perpendicular to PVA film towards film
The light in the inclined direction of width, a face of the PVA film is exposed to as incident light, light is reflected from it and is somebody's turn to do
The refractive index in face（Refractive index based on the surface）.Similarly operated for another face of PVA film and obtain refractive index.For
2 refractive index values of gained, are denoted as A and B respectively in the way of the relation for meeting A >=B.
[tensile elongation of PVA film]
The PVA film obtained by following embodiments or comparative example is taken care of 24 hours in the environment of 20 DEG C, 65%RH and adjusted
Wet process, thereafter, the autoplotter manufactured under identical environment using Shimadzu Seisakusho Ltd. carry out tension test.It should illustrate,
The width of PVA film sample is set to distance between 15mm, fixture and is set to 30mm, and draw speed is set to 500mm/ minutes, and draw direction is set
For the flow direction of PVA film.In the tension test, distance between the fixture of distance divided by script between fixture when PVA film is broken
（30mm）, so as to obtain tensile elongation（%）, evaluated with the average value of 10 measure.
[embodiment 1]
PVA obtained from by making the homopolymer saponification of vinyl acetate will be included（Saponification degree is that 99.9 moles of %, degree of polymerization are
2,400）100 mass parts, the mass parts of glycerine 12, the volatile matter rate of the mass parts of lauric acid diethyl amide 0.1 and water are 66 mass %
Film stoste from T-shaped slit die in the 1st dryer roll（Surface temperature is 90 DEG C, peripheral speed（S1）For 13.5m/ minutes）Upper spray
Go out film-like, the hot blast that the entirety to the 1st dryer roll noncontact face on the 1st dryer roll blew attached 90 DEG C with the wind speed of 5m/ seconds comes
Carry out partially dried.Then, peel off, enter in the way of the 1st dryer roll noncontact face faces the 2nd dryer roll from the 1st dryer roll
One step is dried.Now, the peripheral speed of the 2nd dryer roll（S2）Relative to the peripheral speed of the 1st dryer roll（S1）The ratio between（S2/
S1）For 1.035.Then, in the way of alternately facing each dryer roll by the surface and the back side of film, using the 3rd dryer roll and afterwards
Dryer roll be further dried.It should illustrate, be to positioned at final dryer roll dryer roll immediately front from the 2nd dryer roll
The surface temperature of dryer roll only is about 85 DEG C, and the surface temperature of final dryer roll is 55 DEG C.
Then, the Heat treating roll that surface temperature is 104 DEG C is utilized（X）Thereafter the surface temperature continued is 109 DEG C of heat
Treatment tube（Y）After being heat-treated, the PVA film of strip is batched and obtained（Thickness is 60 μm, width is 3m）.Herein, it is hot
Treatment tube（Y）Peripheral speed（SY）Relative to Heat treating roll（X）Peripheral speed（SX）The ratio between（SY/SX）For 0.995.
The incidence by the inclined direction of width from the direction perpendicular to film surface towards film on gained PVA film
Light and the above-mentioned refractive index determined, the refractive index in a face are that the refractive index in 1.529, another face is 1.529（A=B=1.529、
A+B=3.058）.In addition, being 438% when determining the tensile elongation of gained PVA film.
[embodiment 2]
PVA obtained from by making the homopolymer saponification of vinyl acetate will be included（Saponification degree is that 99.9 moles of %, degree of polymerization are
2,400）100 mass parts, the mass parts of glycerine 12, the volatile matter rate of the mass parts of lauric acid diethyl amide 0.1 and water are 66 mass %
Film stoste from T-shaped slit die in the 1st dryer roll（Surface temperature is 90 DEG C, peripheral speed（S1）For 13.5m/ minutes）Upper spray
Go out film-like, the hot blast that the entirety to the 1st dryer roll noncontact face on the 1st dryer roll blew attached 90 DEG C with the wind speed of 5m/ seconds comes
Carry out partially dried.
Then, peel off, further enter in the way of the 1st dryer roll noncontact face faces the 2nd dryer roll from the 1st dryer roll
Row drying.Now, the peripheral speed of the 2nd dryer roll（S2）Relative to the peripheral speed of the 1st dryer roll（S1）The ratio between（S2/S1）For
1.035.Then, in the way of alternately facing each dryer roll by the surface and the back side of film, drying using the 3rd dryer roll and afterwards
Roller is further dried.It should illustrate, it is dry untill positioned at final dryer roll dryer roll immediately front from the 2nd dryer roll
The surface temperature of dry roller is about 85 DEG C, and the surface temperature of final dryer roll is 50 DEG C.
Then, the Heat treating roll that surface temperature is 101 DEG C is utilized（X）Thereafter the surface temperature continued is 107 DEG C of heat
Treatment tube（Y）After being heat-treated, the PVA film of strip is batched and obtained（Thickness is 60 μm, width is 3m）.Herein, it is hot
Treatment tube（Y）Peripheral speed（SY）Relative to Heat treating roll（X）Peripheral speed（SX）The ratio between（SY/SX）For 0.995.
The incidence by the inclined direction of width from the direction perpendicular to film surface towards film on gained PVA film
Light and the above-mentioned refractive index determined, the refractive index in a face are that the refractive index in 1.530, another face is 1.528（A=1.530、B=
1.528、A+B=3.058）.In addition, being 437% when determining the tensile elongation of gained PVA film.
[embodiment 3]
PVA obtained from by making the homopolymer saponification of vinyl acetate will be included（Saponification degree is that 99.9 moles of %, degree of polymerization are
2,400）100 mass parts, the mass parts of glycerine 12, the volatile matter rate of the mass parts of lauric acid diethyl amide 0.1 and water are 66 mass %
Film stoste from T-shaped slit die in the 1st dryer roll（Surface temperature is 90 DEG C, peripheral speed（S1）For 13.5m/ minutes）Upper spray
Go out film-like, the hot blast that the entirety to the 1st dryer roll noncontact face on the 1st dryer roll blew attached 90 DEG C with the wind speed of 5m/ seconds comes
Carry out partially dried.
Then, peel off, further enter in the way of the 1st dryer roll noncontact face faces the 2nd dryer roll from the 1st dryer roll
Row drying.Now, the peripheral speed of the 2nd dryer roll（S2）Relative to the peripheral speed of the 1st dryer roll（S1）The ratio between（S2/S1）For
1.035.Then, in the way of alternately facing each dryer roll by the surface and the back side of film, drying using the 3rd dryer roll and afterwards
Roller is further dried.It should illustrate, it is dry untill positioned at final dryer roll dryer roll immediately front from the 2nd dryer roll
The surface temperature of dry roller is about 85 DEG C, and the surface temperature of final dryer roll is 50 DEG C.
Then, the Heat treating roll that surface temperature is 104 DEG C is utilized（X）Thereafter the surface temperature continued is 109 DEG C of heat
Treatment tube（Y）After being heat-treated, the PVA film of strip is batched and obtained（Thickness is 60 μm, width is 3m）.Herein, it is hot
Treatment tube（Y）Peripheral speed（SY）Relative to Heat treating roll（X）Peripheral speed（SX）The ratio between（SY/SX）For 0.997.
The incidence by the inclined direction of width from the direction perpendicular to film surface towards film on gained PVA film
Light and the above-mentioned refractive index determined, the refractive index in a face are that the refractive index in 1.530, another face is 1.529（A=1.530、B=
1.529、A+B=3.059）.In addition, being 435% when determining the tensile elongation of gained PVA film.
[comparative example 1]
PVA obtained from by making the homopolymer saponification of vinyl acetate will be included（Saponification degree is that 99.9 moles of %, degree of polymerization are
2,400）100 mass parts, the mass parts of glycerine 12, the volatile matter rate of the mass parts of lauric acid diethyl amide 0.1 and water are 66 mass %
Film stoste from T-shaped slit die in the 1st dryer roll（Surface temperature is 90 DEG C, peripheral speed（S1）For 13m/ minutes）It is upper to spray
Film-like, blows attached 90 DEG C of hot blast to enter on the 1st dryer roll to the overall wind speed with 5m/ seconds in the 1st dryer roll noncontact face
Row is partially dried.
Then, peel off, further enter in the way of the 1st dryer roll noncontact face faces the 2nd dryer roll from the 1st dryer roll
Row drying.Now, the peripheral speed of the 2nd dryer roll（S2）Relative to the peripheral speed of the 1st dryer roll（S1）The ratio between（S2/S1）For
1.050.Then, in the way of alternately facing each dryer roll by the surface and the back side of film, drying using the 3rd dryer roll and afterwards
Roller is further dried.It should illustrate, it is dry untill positioned at final dryer roll dryer roll immediately front from the 2nd dryer roll
The surface temperature of dry roller is about 85 DEG C, and the surface temperature of final dryer roll is 60 DEG C.
Then, the Heat treating roll that surface temperature is 102 DEG C is utilized（X）Thereafter the surface temperature continued is 107 DEG C of heat
Treatment tube（Y）After being heat-treated, the PVA film of strip is batched and obtained（Thickness is 60 μm, width is 3m）.Herein, it is hot
Treatment tube（Y）Peripheral speed（SY）Relative to Heat treating roll（X）Peripheral speed（SX）The ratio between（SY/SX）For 1.000.
The incidence by the inclined direction of width from the direction perpendicular to film surface towards film on gained PVA film
Light and the above-mentioned refractive index determined, the refractive index in a face are that the refractive index in 1.531, another face is 1.530（A=1.531、B=
1.530、A+B=3.061）.In addition, being 415% when determining the tensile elongation of gained PVA film.
[comparative example 2]
PVA obtained from by making the homopolymer saponification of vinyl acetate will be included（Saponification degree is that 99.9 moles of %, degree of polymerization are
2,400）100 mass parts, the mass parts of glycerine 12, the volatile matter rate of the mass parts of lauric acid diethyl amide 0.1 and water are 66 mass %
Film stoste from T-shaped slit die in the 1st dryer roll（Surface temperature is 90 DEG C, peripheral speed（S1）For 15.5m/ minutes）Upper spray
Go out film-like, the hot blast that the entirety to the 1st dryer roll noncontact face on the 1st dryer roll blew attached 90 DEG C with the wind speed of 5m/ seconds comes
Carry out partially dried.
Then, peel off, further enter in the way of the 1st dryer roll noncontact face faces the 2nd dryer roll from the 1st dryer roll
Row drying.Now, the peripheral speed of the 2nd dryer roll（S2）Relative to the peripheral speed of the 1st dryer roll（S1）The ratio between（S2/S1）For
1.050.Then, in the way of alternately facing each dryer roll by the surface and the back side of film, drying using the 3rd dryer roll and afterwards
Roller is further dried.It should illustrate, it is dry untill positioned at final dryer roll dryer roll immediately front from the 2nd dryer roll
The surface temperature of dry roller is about 85 DEG C, and the surface temperature of final dryer roll is 72 DEG C.
Then, the Heat treating roll that surface temperature is 108 DEG C is utilized（X）Thereafter the surface temperature continued is 114 DEG C of heat
Treatment tube（Y）After being heat-treated, the PVA film of strip is batched and obtained（Thickness is 60 μm, width is 3m）.Herein, it is hot
Treatment tube（Y）Peripheral speed（SY）Relative to Heat treating roll（X）Peripheral speed（SX）The ratio between（SY/SX）For 0.998.
The incidence by the inclined direction of width from the direction perpendicular to film surface towards film on gained PVA film
Light and the above-mentioned refractive index determined, the refractive index in a face are that the refractive index in 1.531, another face is 1.529（A=1.531、B=
1.529、A+B=3.060）.In addition, being 431% when determining the tensile elongation of gained PVA film.
Claims (10)
1. polyvinyl alcohol film, wherein, tilted by the width from the direction of the film surface perpendicular to polyvinyl alcohol film towards film
The incident light in direction determine the refractive index in each face of the polyvinyl alcohol film, the refractive index in a face is denoted as A, and will be another
When the refractive index in individual face is denoted as B, A is more than 1.524 and less than 1.530, wherein, A >=B.
2. polyvinyl alcohol film according to claim 1, wherein, A is more than 1.526 and less than 1.530.
3. polyvinyl alcohol film according to claim 1 or 2, wherein, A+B is more than 3.050 and less than 3.060.
4. the manufacture method of polyvinyl alcohol film, it is filled using the film for possessing rotary shaft dryer roll parallel to each other and Heat treating roll
Put, the film stoste comprising polyvinyl alcohol is being sprayed into film forming on the 1st dryer roll of most upstream side among the dryer roll
Shape and carry out it is partially dried after, dryer roll using the 2nd dryer roll continued thereafter and afterwards is further dried, thereafter,
It is heat-treated to manufacture polyvinyl alcohol film using multiple Heat treating rolls, herein, most downstream will be located among the Heat treating roll
The Heat treating roll of side（Y）Peripheral speed（SY）Relative to the Heat treating roll positioned at most upstream side（X）Peripheral speed（SX）The ratio between
（SY/SX）It is set to more than 0.993 and less than 0.997.
5. manufacture method according to claim 4, wherein, by the peripheral speed of the 2nd dryer roll（S2）Dried relative to the 1st
The peripheral speed of roller（S1）The ratio between（S2/S1）It is set to more than 1.000 and less than 1.040.
6. the manufacture method according to claim 4 or 5, wherein, the surface temperature of final dryer roll is set below 60 DEG C.
7. optical film, it is as the polyvinyl alcohol film manufacture any one of claim 1 ~ 3.
8. optical film according to claim 7, it is polarizing coating.
9. the manufacture method of optical film, there is the polyvinyl alcohol film any one of usage right requirement 1 ~ 3 to carry out single shaft for it
The step of stretching.
10. manufacture method according to claim 9, it is the manufacture method of polarizing coating.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014251939 | 2014-12-12 | ||
| JP2014-251939 | 2014-12-12 | ||
| PCT/JP2015/084463 WO2016093258A1 (en) | 2014-12-12 | 2015-12-09 | Polyvinyl alcohol film |
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| Publication Number | Publication Date |
|---|---|
| CN107001671A true CN107001671A (en) | 2017-08-01 |
| CN107001671B CN107001671B (en) | 2023-06-20 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201580067580.9A Active CN107001671B (en) | 2014-12-12 | 2015-12-09 | Polyvinyl alcohol film |
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| Country | Link |
|---|---|
| JP (1) | JP6572236B2 (en) |
| KR (1) | KR102387497B1 (en) |
| CN (1) | CN107001671B (en) |
| TW (2) | TWI712643B (en) |
| WO (1) | WO2016093258A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110884010A (en) * | 2019-10-30 | 2020-03-17 | 中国石油化工股份有限公司 | Preparation method of PVA film with smooth surface |
| CN114761200A (en) * | 2019-12-11 | 2022-07-15 | 株式会社可乐丽 | Method for producing optical polyvinyl alcohol film |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2022004536A1 (en) * | 2020-06-30 | 2022-01-06 | ||
| KR20230031813A (en) * | 2020-06-30 | 2023-03-07 | 주식회사 쿠라레 | Polyvinyl alcohol film and manufacturing method of optical film using the same |
| WO2023074639A1 (en) * | 2021-10-25 | 2023-05-04 | 株式会社クラレ | Polyvinyl alcohol film |
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| JP2001315146A (en) * | 2000-05-12 | 2001-11-13 | Kuraray Co Ltd | Producing method for polyvinyl alcohol-base polymer film |
| CN103442871A (en) * | 2011-03-29 | 2013-12-11 | 可乐丽股份有限公司 | Polyvinyl alcohol polymer film and process for producing same |
| CN104204046A (en) * | 2012-03-30 | 2014-12-10 | 株式会社可乐丽 | Polyvinyl alcohol-type polymer film and polarizing film |
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| JP3478536B2 (en) * | 2000-07-18 | 2003-12-15 | 株式会社クラレ | Polyvinyl alcohol film and polarizing film |
| JP4093390B2 (en) * | 2000-08-21 | 2008-06-04 | 日本合成化学工業株式会社 | Method for producing polyvinyl alcohol film for polarizing film |
| JP4433462B2 (en) * | 2004-05-12 | 2010-03-17 | 株式会社クラレ | POLYVINYL ALCOHOL POLYMER FILM AND PROCESS FOR PRODUCING THE SAME |
| JP5099997B2 (en) * | 2004-12-21 | 2012-12-19 | 日本合成化学工業株式会社 | Polyvinyl alcohol film and polarizing film |
| JP4764658B2 (en) | 2005-04-28 | 2011-09-07 | 日本合成化学工業株式会社 | Method for producing polyvinyl alcohol film |
| JP4664087B2 (en) * | 2005-02-14 | 2011-04-06 | 日本合成化学工業株式会社 | Polyvinyl alcohol film and method for producing the same |
| JP5649820B2 (en) * | 2007-08-24 | 2015-01-07 | 株式会社クラレ | Polyvinyl alcohol film and method for producing the same |
| CN102741717B (en) * | 2010-03-05 | 2014-12-31 | 日东电工株式会社 | Adhesive for polarizing plate, polarizing plate, method for producing same, optical film, and image display device |
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2015
- 2015-12-09 WO PCT/JP2015/084463 patent/WO2016093258A1/en active Application Filing
- 2015-12-09 KR KR1020177007700A patent/KR102387497B1/en active IP Right Grant
- 2015-12-09 JP JP2016563703A patent/JP6572236B2/en active Active
- 2015-12-09 CN CN201580067580.9A patent/CN107001671B/en active Active
- 2015-12-11 TW TW108114261A patent/TWI712643B/en active
- 2015-12-11 TW TW104141636A patent/TWI670314B/en active
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| JP2001315146A (en) * | 2000-05-12 | 2001-11-13 | Kuraray Co Ltd | Producing method for polyvinyl alcohol-base polymer film |
| CN103442871A (en) * | 2011-03-29 | 2013-12-11 | 可乐丽股份有限公司 | Polyvinyl alcohol polymer film and process for producing same |
| CN104204046A (en) * | 2012-03-30 | 2014-12-10 | 株式会社可乐丽 | Polyvinyl alcohol-type polymer film and polarizing film |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110884010A (en) * | 2019-10-30 | 2020-03-17 | 中国石油化工股份有限公司 | Preparation method of PVA film with smooth surface |
| CN110884010B (en) * | 2019-10-30 | 2022-04-05 | 中国石油化工股份有限公司 | Preparation method of PVA film with smooth surface |
| CN114761200A (en) * | 2019-12-11 | 2022-07-15 | 株式会社可乐丽 | Method for producing optical polyvinyl alcohol film |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102387497B1 (en) | 2022-04-15 |
| WO2016093258A1 (en) | 2016-06-16 |
| TW201627381A (en) | 2016-08-01 |
| KR20170095181A (en) | 2017-08-22 |
| TWI670314B (en) | 2019-09-01 |
| TW201930441A (en) | 2019-08-01 |
| JP6572236B2 (en) | 2019-09-04 |
| CN107001671B (en) | 2023-06-20 |
| JPWO2016093258A1 (en) | 2017-09-21 |
| TWI712643B (en) | 2020-12-11 |
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