CN105723259A - Polyvinyl alcohol film - Google Patents
Polyvinyl alcohol film Download PDFInfo
- Publication number
- CN105723259A CN105723259A CN201480063715.XA CN201480063715A CN105723259A CN 105723259 A CN105723259 A CN 105723259A CN 201480063715 A CN201480063715 A CN 201480063715A CN 105723259 A CN105723259 A CN 105723259A
- Authority
- CN
- China
- Prior art keywords
- film
- polyvinyl alcohol
- pva
- pva film
- alcohol film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Nonlinear Science (AREA)
- Materials Engineering (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Polarising Elements (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention is to provide a PVA film which itself has an excellent hue and from which a polarizing film can be easily produced, the polarizing film being capable of producing an LCD having excellent hues without requiring the use of an optical film having a low transmittance and being capable of producing an LCD having a bright screen. A PVA film in which the minimum value of the following slopes is -0.84 to -0.783 N/mm<2>*sec. The slopes are obtained in the following manner: a sample having a dimension of 3 cm in the width direction and cut out of the PVA film is set in an Autograph so that the chuck-to-chuck distance is 1.5 cm and that the sample is stretched in the lengthwise direction; the sample is immersed in 30 DEG C water for 1 minute and then stretched in the water in the lengthwise direction at a rate of 240 %/min; the chuck-to-chuck distance is fixed at the time when the stress reached 11.1 N/mm<2>; and the subsequent changes in stress with the lapse of time are measured to draw a graph by plotting time and stress as abscissa and ordinate, respectively, and the slopes at the points on the graph are determined.
Description
Technical field
The present invention relates to and can be easily manufactured the polarization film that the excellent polyvinyl alcohol film of polarization film of form and aspect, its manufacture method, the manufacture method employing the polarization film of this polyvinyl alcohol film and form and aspect are excellent.
Background technology
There is the polarization plate of printing opacity and shade function and for changing the basic constituent element that the liquid crystal of the polarized light state of light is liquid crystal display (LCD) in the lump.Multiple polarization plates have the protecting film such as surface mount Triafol T (TAC) film at polarization film and the structure that obtains; as the polarization film constituting polarization plate, the matrix (carry out uniaxial tension and make the stretched film of its orientation) carried out by polyvinyl alcohol film (below sometimes by " polyvinyl alcohol " referred to as " PVA ") uniaxial tension is adsorbed with iodine system pigment (I3 -、I5 -Deng) or the like dichromatic pigment and the polarization film that obtains becomes main flow.The PVA film that this polarization film is made by containing dichromatic pigment in advance carries out uniaxial tension, or while the uniaxial tension of PVA film, adsorb dichromatic pigment, or adsorb (with reference to patent documentations 1 etc.) such as dichromatic pigments after PVA film is carried out uniaxial tension again.
Use in the vast scopes such as the metering machine that LCD uses in the small machines such as computer and watch, notebook computer, liquid crystal tester, color liquid crystal projector, LCD TV, vehicle-mounted navigation system, mobile phone, indoor and outdoor.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 5-245858 publication.
Summary of the invention
The problem that invention to solve
But, in recent years, require to reduce the brightness of backlight to reduce power consumption, but when using existing polarization film, it is necessary to configure other blooming etc. and correct form and aspect, there is the problem that the picture of LCD is dimmed due to the low grade of the absorbance of this blooming.On the other hand, when using the high blooming of absorbance, there is the problem that cannot be sufficiently carried out form and aspect correction.
Thus, it is an object of the invention to, even if the form and aspect excellence providing himself does not use the blooming that absorbance is low also to be able to manufacture the excellent LCD of form and aspect and can manufacture the polarization film of the bright LCD of picture, and can be easily manufactured the PVA film of this polarization film.
Means for solving the above
The present inventor etc. are repeated further investigation to achieve these goals, found that: when the stress being used in water after stretching shows the PVA film of specific rheological parameters' change with time behavior, even if the form and aspect excellence that can be easily manufactured himself does not use the blooming that absorbance is low also to be able to manufacture the excellent LCD of form and aspect and can manufacture the polarization film of the bright LCD of picture；Under given conditions saponification degree and swellbility are in the PVA film of particular range when carrying out heat treatment, above-mentioned PVA film can be easily manufactured；And, the polarization film of particular kind of relationship is met according to the b value by b value when being configured to parallel Nicol state relative to rectilinearly polarized light and when being configured to Nicol crossed state, the form and aspect of himself are excellent, even if the blooming not using absorbance low also is able to manufacture the LCD that form and aspect are excellent, and the LCD that picture is bright can be manufactured, research is repeated further, thus completing the present invention based on this opinion.
That is, the present invention relates to:
[1] PVA film, wherein, following slope minima is-0.84 ~-0.783N/mm2Second:
Sample that the width cut out from PVA film is 3cm is placed in autoplotter with chuck spacing for 1.5cm and the mode that alongst stretches, after the water of 30 DEG C impregnates 1 minute, in this water with 240%/minute speed alongst stretch, reach 11.1N/mm at stress2Moment fixing chuck spacing, for the rheological parameters' change with time of stress thereafter, using the time as transverse axis and using stress as the longitudinal axis draw time this figure on the slope minima of each point.
[2] PVA film according to above-mentioned [1], wherein, the saponification degree of the PVA comprised in PVA film is 98 ~ 99.5 moles of %；
[3] PVA film according to above-mentioned [1] or [2], wherein, swellbility is 180 ~ 220%；
[4] PVA film any one of above-mentioned [1] ~ [3], it is the raw material film for manufacturing polarization film；
[5] manufacture method of PVA film, it includes with 135 ~ 148 DEG C, PVA film is carried out heat treated operation, and described PVA film comprises PVA that saponification degree is 98 ~ 99.5 moles of % and swellbility is more than 250%；
[6] manufacture method according to above-mentioned [5], it carries out the heat treatment of more than 0.5 minute；
[7] manufacture method according to above-mentioned [5] or [6], it is the method manufacturing the PVA film that swellbility is 180 ~ 220%；
[8] manufacture method of polarization film, it includes the operation that the PVA film of above-mentioned [4] is stretched；
[9] polarization film, wherein, b value when being configured to parallel Nicol state relative to rectilinearly polarized light is denoted as X, and when b value when being configured to Nicol crossed state relative to rectilinearly polarized light is denoted as Y, meets below formula (I):
Y≥1.9X-8.3(I)。
[10] polarization film according to above-mentioned [9], it meets below formula (II):
5≥Y≥-5(II)。
The effect of invention
According to the present invention, it is possible to provide even if the form and aspect excellence of himself does not use the blooming that absorbance is low also to be able to manufacture the excellent LCD of form and aspect and can manufacture polarization film and the manufacture method thereof of the bright LCD of picture；And, PVA film and the manufacture method thereof of this polarization film can be easily manufactured.
Detailed description of the invention
Hereinafter, the present invention is described in detail for pin.
(PVA film)
The following slope minima of the PVA film of the present invention is-0.84 ~-0.783N/mm2Second.
Sample that the width cut out from PVA film is 3cm is placed in autoplotter with chuck spacing for 1.5cm and the mode that alongst stretches, after the water of 30 DEG C impregnates 1 minute, in this water with 240%/minute speed alongst stretch, reach 11.1N/mm at stress2Moment fixing chuck spacing, for the rheological parameters' change with time of stress thereafter, using the time (unit: second) as transverse axis and with stress (unit: N/mm2) slope (tangent slope) minima of each point on this figure when drawing as the longitudinal axis.
It should be noted that stress is sectional area (thickness of 3cm × PVA film) (unit: the mm divided by initial sample of the tension force (unit: N) by inscribing time each2) and obtain.
The minima of above-mentioned slope is when above-mentioned scope is outer, and the form and aspect of gained polarization film reduce.The present invention is not carried out any restriction, as the reason that the minima of this slope is relevant to the form and aspect of gained polarization film, it may be considered that following reason.Namely can this is considered because: the minima of above-mentioned slope is relevant with the molecular behavior of the PVA molecule in stretching process when using this PVA film actual manufacture polarization film, and this molecular behavior can affect the state of the dichromatic pigments such as iodine system pigment.
From the view point of the form and aspect of gained polarization film, the minima of this slope is preferably-0.825N/mm2More than second, it is more preferably-0.815N/mm2Second above, more preferably-0.8N/mm2More than second, additionally, it is preferred that be-0.786N/mm2Below second, it is more preferably-0.79N/mm2Second following, more preferably-0.793N/mm2Below second.
As the PVA comprised in the PVA film of the present invention, it is possible to use the PVA that the polyvinyl ester obtained the one kind or two or more vinyl acetate in vinylacetate, vinyl formate, propionate, vinyl butyrate, pivalic acid vinyl acetate, tertiary ethylene carbonate, vinyl laurate, stearic acid vinyl ester, vinyl benzoate, isopropenyl acetate etc. being polymerized carries out saponification and obtains.Among above-mentioned vinyl acetate, from the view point of the ease of manufacturing of PVA, acquisition easiness, cost etc., it is preferred to vinylacetate.
Above-mentioned polyvinyl ester preferably only uses the polyvinyl ester that one kind or two or more vinyl acetate obtains as monomer, as long as in the scope not damaging effect of the present invention, then can be one kind or two or more vinyl acetate with can and the copolymer of other monomer of its copolymerization.
As with other monomer of above-mentioned vinyl acetate copolymerization, can listing the alpha-olefin of the carbon numbers 2 ~ 30 such as such as ethylene, propylene, 1-butylene, isobutene.；(methyl) acrylic acid or its salt；(methyl) acrylate such as (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) dodecylacrylate, (methyl) octadecyl acrylate；(methyl) acrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, diacetone (methyl) acrylamide, (methyl) acrylamide propane sulfonic acid or its salt, (methyl) acrylamide propyl dimethylamine or (methyl) acrylamide derivative such as its salt, N-methylol (methyl) acrylamide or derivatives thereof；The N-vinylamides such as N-vinyl formamide, N-vinyl acetamide, NVP；The vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, IVE, 2-(Ethenyloxy)-2-methylpropane, dodecyl vinyl, stearyl vinyl ethers；The vinyl cyanides such as (methyl) acrylonitrile；The vinyl halides such as vinyl chloride, vinylidene chloride, fluorothene, vinylidene fluoride；The allyl compound such as allyl acetate, allyl chloride；Maleic acid or its salt, ester or anhydride；Itaconic acid or its salt, ester or anhydride；The vinyl silyl groups compounds such as vinyltrimethoxy silane；Unsaturated sulfonic acid etc..Above-mentioned polyvinyl ester can have the one kind or two or more construction unit being derived from other monomer aforementioned.
The ratio shared in above-mentioned polyvinyl ester of the aforementioned construction unit being derived from other monomer is preferably 15 moles of below % based on the molal quantity of the entire infrastructure unit constituting polyvinyl ester, it is possible to is 10 moles of below % and then can be 5 moles of below %.
Especially, when other monomer aforementioned is possible to the water miscible monomer promoting gained PVA as (methyl) acrylic acid, unsaturated sulfonic acid etc., in order to prevent PVA from dissolving in the manufacture process of polarization film, the ratio of the construction unit being derived from these monomers in polyvinyl ester is preferably 5 moles of below % based on the molal quantity of the entire infrastructure unit constituting polyvinyl ester, is more preferably 3 moles of below %.
As long as in the scope not damaging effect of the present invention, PVA can utilize and one kind or two or more can the monomer of graft copolymerization be modified.As this can the monomer of graft copolymerization, such as unsaturated carboxylic acid or derivatives thereof can be listed；Unsaturated sulfonic acid or derivatives thereof；Carbon number is the alpha-olefin etc. of 2 ~ 30.Being derived from PVA the ratio of construction unit (construction unit in graft modification part) of monomer of graft copolymerization can be preferably 5 moles of below % based on the molal quantity of entire infrastructure unit constituting PVA.
A part of hydroxyl in PVA can cross-link, it is also possible to does not cross-link.It addition, a part of hydroxyl in above-mentioned PVA can react with the aldehyde compound such as acetaldehyde, butyraldehyde etc. and form acetal structure, it is also possible to do not react with these compounds and be formed without acetal structure.
The average degree of polymerization of PVA is preferably 1000 ~ 9, and in the scope of 500, this average degree of polymerization is more preferably more than 1,500, more preferably more than 2000, it addition, be more preferably less than 9,200, more preferably less than 6,000.By making average degree of polymerization be more than 1000, the polarized light performance of polarization film improves.On the other hand, by making average degree of polymerization be less than 9,500, the productivity ratio of PVA improves.It should be noted that the average degree of polymerization of PVA can measure according to the record of JISK6726-1994.
In the saponification degree of the PVA scope preferably in 98 ~ 99.5 moles of %, this saponification degree is more preferably 98.3 moles of more than %, more preferably 98.6 moles of more than %, is particularly preferably 98.7 moles of more than %, it addition, be more preferably 99.3 moles of below %, more preferably 99.1 moles of below %, particularly preferably less than 99 moles of %.When the saponification degree of PVA is in above-mentioned scope, reason is still not clear, but can it is clear that: even if the form and aspect excellence that can more easily manufacture himself does not use the blooming that absorbance is low also to be able to manufacture the excellent LCD of form and aspect and can manufacture the polarization film of the bright LCD of picture.It should be noted that, the saponification degree of the PVA in this specification refers to: the construction unit (for vinyl ester units for typical case) that can be converted to vinyl alcohol units by saponification having relative to PVA and the total mole number of vinyl alcohol units, the ratio (mole %) shared by the molal quantity of this vinyl alcohol units.Saponification degree can measure according to the record of JISK6726-1994.
PVA film preferably comprises plasticizer from the viewpoint of the draftability improved when being stretched.As this plasticizer, can listing the polyhydric alcohol etc. such as such as ethylene glycol, glycerol, propylene glycol, diethylene glycol, diglycerol, triethylene glycol, TEG, trimethylolpropane, it is one kind or two or more that PVA film can comprise in these plasticizers.Among these, from the view point of improve the effect of draftability, it is preferred to glycerol.
The content of the plasticizer in PVA film is relative in the PVA100 mass parts wherein the comprised scope preferably in 1 ~ 20 mass parts.By making this content be more than 1 mass parts, it is possible to improve the draftability of PVA film further.On the other hand, it is below 20 mass parts by making this content, it is possible to prevent PVA film from becoming excessively soft and causing that treatability reduces.The content of the plasticizer in PVA film is more preferably more than more than 2 mass parts, more preferably 4 mass parts relative to PVA100 mass parts, is particularly preferably more than 5 mass parts, it addition, be more preferably below below 15 mass parts, more preferably 12 mass parts.
It should be noted that also different because of the manufacturing condition of polarization film etc., there is dissolution etc. in the plasticizer comprised in PVA film, therefore, its total amount not necessarily residues in polarization film when manufacturing polarization film.
PVA film can comprise the compositions such as antioxidant, anti-freezing agent, pH adjusting agent, masking agent, stainblocker, oil preparation, surfactant as required further.
From the view point of the easness etc. of preparation expectation polarization film, in the containing ratio of the PVA in the PVA film scope preferably in 50 ~ 99 mass %, this containing ratio is more preferably more than 75 mass %, more preferably more than 80 mass %, is particularly preferably more than 85 mass %, it addition, be more preferably below 98 mass %, more preferably below 96 mass %, be particularly preferably below 95 mass %.
The thickness of the PVA film of the present invention is not particularly limited, it is possible to suitably set according to the target thickness etc. of polarization film.As concrete thickness, for instance in can being set in the scope of 2 ~ 100 μm and then can be set in the scope of 5 ~ 65 μm, the scope of 8 ~ 50 μm can also being set to.
The shape of PVA film is not particularly limited, it is preferred to the PVA film of strip, this is because can use continuously when manufacturing polarization film.The length (length of length direction) of the PVA film of strip is not particularly limited, and suitably can set according to the purposes etc. of the polarization film to manufacture, for instance can be set to 1 ~ 20, in the scope of 000m.
The width of PVA film is not particularly limited, suitably can set according to purposes of the polarization film to manufacture etc., such as can be set to more than 0.1m, but in recent years, from LCD TV, liquid crystal monitor large screen just in development viewpoint, when the width of PVA film is set to more than 0.5m, is more preferably set to more than 1.0m, it is suitable for these purposes.On the other hand, when the width of PVA film is wide, there is the tendency being difficult to Uniform Tension when utilizing practical device to manufacture polarization film, therefore, the width of PVA film is preferably below 7m.
Viewpoint etc. from the productivity ratio of polarization film, performance, the swellbility of the PVA film of the present invention is preferably in the scope of 180 ~ 220%, this swellbility is more preferably more than 185%, more preferably more than 190%, be particularly preferably more than 195%, it addition, be more preferably less than 215%, more preferably less than 210%, be particularly preferably less than 205%.The swellbility of PVA film can measure according to method described later in embodiment.The swellbility of PVA film such as can be adjusted to less value by enhancing heat treatment condition.
(manufacture method of PVA film)
Method for manufacturing the PVA film of the present invention is not particularly limited, and the manufacture method according to the PVA film of the present invention set forth below can be easily manufactured the PVA film of the present invention, so preferably.That is, the manufacture method of the PVA film of the present invention includes: uses and comprises PVA that saponification degree is 98 ~ 99.5 moles of % and swellbility is the PVA film of more than 250%, with the temperature in the scope of 135 ~ 148 DEG C, it is carried out heat treated operation.
As the PVA to use, it is possible to make the PVA identical PVA already described with the explanation of the PVA film of the present invention, therefore omit the record of repetition herein.It addition, for the plasticizer that can comprise as any composition in the PVA film to use, other shape such as composition and thickness etc., it is possible to make the content that the content already described with the explanation of the PVA film of the present invention is identical, therefore omit the record of repetition herein.
Manufacture method for heat treated PVA film is not particularly limited, it is possible to use existing known method manufactures.Specifically, for instance masking stock solution that PVA is dissolved in liquid medium can be used, comprise PVA and liquid medium and masking stock solution that PVA melts carrys out masking.
As the liquid medium used in the preparation of masking stock solution, such as water, dimethyl sulfoxide, dimethylformamide, dimethyl acetylamide, N-Methyl pyrrolidone, ethylene glycol, glycerol, propylene glycol, diethylene glycol, triethylene glycol, TEG, trimethylolpropane, ethylenediamine, diethylenetriamine etc. can be listed, it is possible to use one kind or two or more among these.Wherein, from the view point of the burden that environment is caused, recyclability, water can compatibly be used.
The volatile matter rate of masking stock solution (when masking because of volatilization, evaporation and the content ratio of the volatile ingredients such as removed liquid medium) is also different because of film-forming method, film forming condition etc., it is often preferred that 50 ~ 95 mass %, more preferably 55 ~ 90 mass %, be particularly preferably 60 ~ 85 mass %.Existence following tendency when the volatile matter rate of masking stock solution is too low: the viscosity of masking stock solution becomes too high, is difficult to filtration, deaeration during preparation masking stock solution, it is difficult to manufacture foreign body, the PVA film that shortcoming is few.On the other hand, when the volatile matter rate of masking stock solution is too high, the concentration that there is masking stock solution becomes too low, is difficult to the tendency of the industrial masking of PVA film.
As to film-forming method when being filmed for heat treated PVA film, for instance film by wet method, gel masking method, casting film method, extrusion masking method etc. can be adopted.Furthermore it is also possible to adopt the method etc. of the combination based on them.Among above film-forming method, it is preferred to use casting film method or extrusion masking method, this is because be obtained in that thickness and even width and the good PVA film of physical property.
As concrete film-forming method, can list: use T-shaped slit die, hopper plate, I-mould, lip to be coated with mould etc., masking stock solution is ejected in equably on the side face of the roller (or band) rotating and heating, make a volatile ingredient surface evaporation from the film being ejected in this roller (or band) and dry thus making PVA film, or, so dried, it is further dried on the side face of one or more rotations and the roller of heating, or make it pass in hot-air drying device and be further dried, thus the method that PVA film is filmed.After PVA film after masking can utilize devices for taking-up temporarily to batch, carry out as required rolling out etc. and implement aftermentioned heat treatment, it is also possible to operate as above after continuously the PVA film of masking being implemented aftermentioned heat treatment continuously, then batch.
Surface temperature as the roller used in masking, for instance 50 ~ 100 DEG C can be set to.It addition, as baking temperature when masking stock solution is sprayed on tape, for instance 50 ~ 100 DEG C can be set to.
Swellbility for heat treated PVA film is preferably more than 300%, is more preferably more than 400%, additionally, it is preferred that be less than 1000%, this is because the PVA film of the present invention can more easily be manufactured.As the volatile matter rate for heat treated PVA film, for instance below 10 mass % can be set to and then below 8 mass % can be set to.
Temperature in heat treatment is preferably more than 137 DEG C, be more preferably more than 139 DEG C it is preferred that more than 140 DEG C, additionally, it is preferred that be less than 145 DEG C, this is because the PVA film of the present invention can more easily be manufactured.
Heat treatment time is not particularly limited, it is preferred to more than 0.5 minute, be more preferably more than 0.8 minute, additionally, it is preferred that be less than 30 minutes, be more preferably less than 15 minutes, this is because the PVA film of the present invention can more easily be manufactured.
(manufacture method of polarization film)
The purposes of the PVA film of the present invention is not particularly limited, PVA film according to the present invention, even if the form and aspect excellence that can be easily manufactured himself does not use the blooming that absorbance is low also to be able to manufacture the excellent LCD of form and aspect and can manufacture the polarization film of the bright LCD of picture, it is thus preferred to as the raw material film of polarization film manufacture.
The PVA film using the present invention manufactures the method for polarization film and is not particularly limited, can be manufactured by the method for operation including the PVA film of the present invention is stretched, specifically, such as can manufacture by the following method: first by PVA film for swelling operation, then for dyeing process, as required further for cross-linking process step, thereafter for stretching process, as required further for fixing treatment process and/or matting, and for drying process.
Swelling operation can be undertaken by PVA film be impregnated in water.As water temperature when impregnated in water, it is preferable that in the scope of 20 ~ 40 DEG C, this temperature is more preferably more than 22 DEG C, more preferably more than 25 DEG C, it addition, be more preferably less than 38 DEG C, more preferably less than 35 DEG C.By this temperature being set in the scope of 20 ~ 40 DEG C, it is possible to make PVA film swelling efficiently.It addition, as the time that impregnated in water, it is preferable that in the scope of 0.1 ~ 5 minute, more preferably in the scope of 0.5 ~ 3 minute.By being set in the scope of 0.1 ~ 5 minute, it is possible to make PVA film swelling efficiently.It should be noted that water when impregnated in water is not limited to pure water, it is possible to be the aqueous solution being dissolved with various composition, it is also possible to be the mixture of water and aqueous medium.
Dyeing in dyeing process processes and can be undertaken by being immersed in the aqueous solution comprising dichromatic pigment by PVA film.As this dichromatic pigment, iodine system pigment (I can be listed3 -、I5 -Deng), dichroic organic dye etc..Iodine system pigment such as can pass through to make iodine (I2) contact with potassium iodide and obtain.It addition, as dichroic organic dye, directly black 17,19,154 can be listed；Direct brown 44,106,195,210,223；Directly red 2,23,28,31,37,39,79,81,240,242,247；Sun blue 1,15,22,78,90,98,151,168,202,236,249,270；Directly purple 9,12,51,98；Direct green 1,85；Directly Huang 8,12,44,86,87；Direct orange 26,39,106,107 etc..Among these dichromatic pigments, from the view point of treatability, availability, polarized light performance etc., it is preferred to iodine system pigment.It should be noted that dichromatic pigment can be independent a kind, it is also possible to for two or more, for instance can also such as I3 -And I5 -It is equilibrium mixture like that.
The concentration of the dichromatic pigment in the aqueous solution comprising dichromatic pigment suitably can set according to the kind etc. of the dichromatic pigment to use, such as can be set in the scope of 0.001 ~ 1 mass %, when using IKI aqueous solution as the aqueous solution comprising dichromatic pigment, owing to iodine system pigment can be made to be adsorbed in PVA film efficiently, therefore as the iodine (I to use2) concentration, preferably in the scope in the scope of 0.01 ~ 2 mass %, more preferably in 0.02 ~ 0.5 mass %, concentration as the potassium iodide (KI) to use, in the quality of the above-mentioned potassium iodide used ratio relative to the quality of iodine used, it is preferable that in the scope of 10 ~ 200 mass times, more preferably in 15 ~ 150 mass scope again.The aqueous solution comprising dichromatic pigment can comprise the boron compounds such as the borate such as boric acid, Borax.Comprise the temperature of aqueous solution of dichromatic pigment preferably in the scope of 5 ~ 50 DEG C, more preferably in the scopes of 15 ~ 40 DEG C, this is because dichromatic pigment can be made to be adsorbed in PVA film efficiently.It should be noted that when using the PVA film containing dichromatic pigment in advance, it is possible to omit dyeing process.
By PVA film is carried out cross-linking process step, it is possible to more efficiently prevent from PVA dissolution in water when carrying out wet type stretching with higher temperature.From this viewpoint, cross-linking process step carries out preferably in after dyeing process and before stretching process.Cross-linking process step can be undertaken by dipping PVA film in the aqueous solution comprising cross-linking agent as crosslinking bath.As this cross-linking agent, it is possible to use the one kind or two or more boron compound in the borate such as boric acid, Borax etc..The concentration of the cross-linking agent in crosslinking bath is interior preferably in the scope of 1 ~ 15 mass %, be more preferably more than 2 mass %, it addition, be more preferably below 7 mass %, more preferably below 6 mass %.By making the concentration of cross-linking agent be in the scope of 1 ~ 15 mass %, it is possible to maintain sufficient draftability.Crosslinking bath can contain the auxiliary agents such as potassium iodide.The temperature of crosslinking bath is preferably set in the scope of 20 ~ 50 DEG C, is particularly preferably set in the scope of 25 ~ 40 DEG C.By making this temperature in the scope of 20 ~ 50 DEG C, it is possible to cross-link efficiently.
Drawing process when stretching PVA film is not particularly limited, it is possible to use any one in wet type pulling method and dry stretch process carries out.When wet type pulling method, it is possible to the aqueous solution of the one kind or two or more boron compound in comprising the borate such as boric acid, Borax etc. carries out, it is also possible in above-mentioned dye bath, aftermentioned fixing process in bath carry out.It addition, when dry stretch process, it is possible at room temperature it is made directly stretching, it is also possible to heat and stretch, it is also possible to stretch after absorbing water.Among these, from the view point of the thickness evenness of the width of gained polarization film, it is preferred to wet type pulling method, stretch more preferably in boric acid aqueous solution.In the boric acid concentration in the boric acid aqueous solution scope preferably in 0.5 ~ 6.0 mass %, this concentration is more preferably more than 1.0 mass %, more preferably more than 1.5 mass %, it addition, be more preferably below 5.0 mass %, more preferably below 4.0 mass %.By making boric acid concentration be in the scope of 0.5 ~ 6.0 mass %, it is possible to obtain the polarization film that the thickness evenness of width is excellent.The above-mentioned aqueous solution comprising boron compound can contain potassium iodide, in its concentration scope preferably in 0.01 ~ 10 mass %.By making potassium iodide concentration be in the scope of 0.01 ~ 10 mass %, it is possible to obtain the polarization film that polarized light performance is better.
Temperature during stretching PVA film is preferably in the scope of 5 ~ 90 DEG C, and this temperature is more preferably more than 10 DEG C, it addition, be more preferably less than 80 DEG C, more preferably less than 70 DEG C.By making this temperature in the scope of 5 ~ 90 DEG C, it is possible to obtain the polarization film that the thickness evenness of width is excellent.
Stretching ratio when stretching PVA film is preferably more than 4 times, is more preferably more than 5 times, more preferably more than 6 times.By making the stretching ratio of PVA film in above-mentioned scope, it is possible to obtain the polarization film that polarized light performance is more excellent.The upper limit of the stretching ratio of PVA film is not particularly limited, it is preferred to less than 8 times.The stretching of PVA film can carry out once, it is also possible to carries out several times, and any one, when carrying out several times, total stretching ratio that each stretching ratio stretched is multiplied and obtains is in above-mentioned scope.It should be noted that stretching ratio in this specification is based on the length of the PVA film before stretching, it is 1 times that unstretched state is equivalent to stretching ratio.
From the view point of the performance of gained polarization film, the stretching of PVA film is preferably uniaxial tension.Uniaxial tension direction when stretching PVA film is not particularly limited, it is possible to adopt the uniaxial tension on length direction, horizontal uniaxial tension, owing to being obtained in that the polarization film of excellence by polarized light performance, it is thus preferred to for the uniaxial tension on length direction.Uniaxial tension on length direction can pass through to use possess the stretching device of the multiple rollers being parallel to each other, and change the peripheral speed between each roller and carry out.On the other hand, horizontal uniaxial tension can use tenter stretcher to carry out.
Fixing treatment process is primarily to and makes iodine system pigment firmly be adsorbed in PVA film and carry out.Fixing treatment process can by by before stretching, stretch in or PVA film after stretching impregnated in and fixing process bath and carry out.Bath is processed, it is possible to use comprise the aqueous solution of one kind or two or more boron compound in the borate such as boric acid, Borax etc. as fixing.It addition, bath can be added iodine compound, metallic compound to fixing process as required.In the generally preferable scope in the scope of 0.1 ~ 15 mass %, particularly preferably in 1 ~ 10 mass % of concentration of the boron compound being used as in the fixing aqueous solution comprising boron compound processing bath.By making this concentration in the scope of 0.1 ~ 15 mass %, it is possible to more securely absorption iodine system pigment.The fixing temperature bathed that processes is preferably in the scope of 10 ~ 60 DEG C, particularly preferably in the scopes of 15 ~ 40 DEG C.By making this temperature in the scope of 10 ~ 60 DEG C, it is possible to more securely absorption iodine system pigment.
Matting be mostly in order to remove the unnecessary chemical drugs category on film surface or foreign body or the optical property of polarization film that adjustment finally gives and carry out.Matting can by making PVA film impregnated in cleaner bath or carry out to PVA film distribution cleanout fluid.As cleaner bath, cleanout fluid, it is possible to use water, they can also contain potassium iodide.
Drying condition in drying process is not particularly limited, it is preferable that within the scope of 30 ~ 150 DEG C, be dried particularly preferably at the temperature within the scope of 50 ~ 130 DEG C.By being dried at the temperature within the scope of 30 ~ 150 DEG C, it is easy to obtain the polarization film of excellent in dimensional stability.
(polarization film)
Manufacture method according to above-mentioned polarization film, b value when being configured to parallel Nicol state relative to rectilinearly polarized light is denoted as X, and when b value when being configured to Nicol crossed state relative to rectilinearly polarized light is denoted as Y, it is obtained in that the polarization film meeting below formula (I), the form and aspect of this polarization film self are excellent, even if the blooming not using absorbance low also is able to manufacture the LCD that form and aspect are excellent, and can manufacture the LCD that picture is bright.
Y≥1.9X-8.3(I)。
Above-mentioned X and Y preferably meets below formula (I '), more preferably meets below formula (I ").
Y≥1.9X-8(I’)
Y≥1.9X-7.5(I”)。
It should be noted that above-mentioned X and Y can use spectrophotometer (" V7100 " that such as Japan Spectroscopy Corporation manufactures etc.) to obtain, specifically, can be obtained by aftermentioned method in an embodiment.
Above-mentioned Y is also different because of use form of polarization film etc., but preferably meets below formula (II), more preferably meets below formula (II ') it is preferred that meet below formula (II ").
5≥Y≥-5(II)
3.5≥Y≥-3.5(II’)
3≥Y≥-3(II”)。
(use form)
Polarization film is generally two-sided at it or one side bonding protective film and make polarization plate and use.As protecting film, optical clear can be listed and there is the protecting film of mechanical strength, specifically, it is possible to use such as Triafol T (TAC) film, acetylbutyrylcellulose (CAB) film, acrylic films, polyester mesentery etc..It addition, as the bonding agent for fitting, PVA system bonding agent, urethane system bonding agent etc. can be listed, is suitably for PVA system bonding agent.
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 below embodiment described below and comparative example adopt, PVA film is stretched in water after the rheological parameters' change with time behavior (slope minima) of stress, the swellbility of PVA film and polarization film when being configured to parallel Nicol state and Nicol crossed state each assay method of b value (X and Y).
[the rheological parameters' change with time behavior (slope minima) of the stress after PVA film is stretched in water]
The width central part of the PVA film after the heat treatment obtained from below embodiment or comparative example cuts out the Rectangular samples of width 3cm × length direction 5.5cm, it is placed in autoplotter (" AG-I " that Shimadzu Seisakusho Ltd. manufactures) with chuck spacing for 1.5cm and the mode that alongst stretches, in the water of 30 DEG C (pure water), dipping is after 1 minute, in this water with 240%/minute speed alongst stretch, reach 11.1N/mm at stress2Moment fixing chuck spacing, measure the rheological parameters' change with time of stress thereafter.By the data obtained using the time (unit: second) as transverse axis and with stress (unit: N/mm2) draw as the longitudinal axis, obtain the minima among the slope (tangent slope) of each point on this figure.
[swellbility of PVA film]
From becoming the PVA film measuring object, to cut out width be 10cm, length direction be the Rectangular samples of 20cm, and it be 2 ~ 3mm, length is the short strip shape of 20cm that this sample is cut into width further.Thereafter, by these whole direct impregnation of short strip shape sample in the 1000g distilled water of 30 DEG C.Remove short strip shape sample after impregnating 30 minutes, use centrifugal separator (KOKUSANXEM-KL-5886) with 3000rpm centrifuge dehydration 5 minutes, measure the quality " N " after dehydration (total total of short strip shape sample).Then, after this short strip shape sample is dried 16 hours in the drying machine of 105 DEG C, quality measurement " M " (total total of short strip shape sample), calculate swellbility by following formula (III).It should be noted that carry out 3 identical mensuration, adopt its meansigma methods.
Swellbility (%)=100 × N/M (III).
[b value (X and Y) of polarization film when being configured to parallel Nicol state and Nicol crossed state]
The Rectangular samples that length direction is 4cm of polarization film taked by the central part of the width of the polarization film obtained from following example or comparative example, use the spectrophotometer (" V7100 " that Japan Spectroscopy Corporation manufactures) with integrating sphere, this sample is provided parallel to Nicol prism state relative to this spectrophotometric polarization plate and obtains b value, this value is denoted as X.Then, above-mentioned sample is set to Nicol crossed state relative to this spectrophotometric polarization plate and obtains b value, this value is denoted as Y.It should be noted that in the mensuration of b value, according to JISZ8722 (assay method of object color), carry out the visibility correction of the visible region in illuminant-C, 2 ° of visuals field.
[embodiment 1]
By including PVA, (saponified, the degree of polymerization of the homopolymer of vinylacetate are 2,400, saponification degree is 98.9 moles of %) 100 mass parts, glycerol 10 mass parts as plasticizer, polyoxyethylene laurel ether sodium sulfate 0.1 mass parts as surfactant and water and masking stock solution curtain coating that volatile matter rate is 85 mass % be in the metal drum of 80 DEG C, it is dried to till volatile matter rate (moisture content) reaches 5 mass %, thus making the strip PVA film (PVA film before heat treatment) of thickness 30 μm, length 1.5m, width 30cm.The swellbility of this PVA film is 480%.
By this PVA film temperature heat treatment 10 minutes with 142 DEG C.The minima of the above-mentioned slope of gained PVA film (PVA film after heat treatment) is-0.796N/mm2Second, swellbility is 200%, and thickness is 30 μm.
By carrying out swelling operation, dyeing process, cross-linking process step, stretching process, fixing treatment process and drying process for above-mentioned PVA film (PVA film after heat treatment), thus manufacturing polarization film.
Namely, above-mentioned PVA film is impregnated in the water that temperature is 30 DEG C in the process of 1 minute, alongst (MD) uniaxial tension (the 1st stage stretched) is to 2 times of raw footage, in the process being mixed in the dye bath that temperature be 30 DEG C of water with iodine for 0.02 mass % and concentration that potassium iodide is 0.6 mass % as consumption to impregnate 2 minutes, alongst (MD) uniaxial tension (the 2nd stage stretched) is to 3 times of raw footage, then in contain the crosslinking bath that the temperature of boric acid is 32 DEG C with the concentration of 2.5 mass % in the dipping process of 2 minutes, alongst (MD) uniaxial tension (the 3rd stage stretched) is to 3.6 times of raw footage, and then in contain the boric acid/potassium iodide aqueous solution of boric acid and the temperature 57 DEG C that contains potassium iodide with the concentration of 5 mass % with the concentration of 2.8 mass % in the process of dipping, alongst (MD) uniaxial tension (the 4th stage stretched) is to 6.2 times of raw footage, thereafter, dipping 5 seconds in contain the potassium iodide aqueous solution of boric acid and the temperature 22 DEG C that contains potassium iodide with the concentration of 5 mass % with the concentration of 1.5 mass %, thus film is carried out, then pass through and dry 240 seconds with the drying machine of 60 DEG C, manufacture the polarization film that thickness is 12 μm.Use gained polarization film, obtain X and Y by said method.
The above results are shown in table 1.
[embodiment 2]
Except the temperature in heat treatment is changed to except 138 DEG C from 142 DEG C, operate similarly to Example 1, manufacture PVA film and polarization film, carry out the evaluation identical with embodiment 1.
The above results are shown in table 1.
[comparative example 1]
Outside the PVA that saponification degree is 99.9 moles of %, operate similarly to Example 1, manufacture PVA film and polarization film, carry out the evaluation identical with embodiment 1.
The above results are shown in table 1.
[comparative example 2]
Except the temperature in heat treatment is changed to except 125 DEG C from 142 DEG C, same with comparative example 1 operate, manufacture PVA film and polarization film, carry out the evaluation identical with embodiment 1.
The above results are shown in table 1.
[comparative example 3]
Except the temperature in heat treatment is changed to except 133 DEG C from 142 DEG C, operate similarly to Example 1, manufacture PVA film and polarization film, carry out the evaluation identical with embodiment 1.
The above results are shown in table 1.
[table 1]
Claims (10)
1. polyvinyl alcohol film, wherein, following slope minima is-0.84 ~-0.783N/mm2Second:
Sample that the width cut out from polyvinyl alcohol film is 3cm is placed in autoplotter with chuck spacing for 1.5cm and the mode that alongst stretches, after the water of 30 DEG C impregnates 1 minute, in this water with 240%/minute speed alongst stretch, reach 11.1N/mm at stress2Moment fixing chuck spacing, for the rheological parameters' change with time of stress thereafter, using the time as transverse axis and using stress as the longitudinal axis draw time this figure on the slope minima of each point.
2. polyvinyl alcohol film according to claim 1, wherein, the saponification degree of the polyvinyl alcohol comprised in polyvinyl alcohol film is 98 ~ 99.5 moles of %.
3. polyvinyl alcohol film according to claim 1 and 2, wherein, swellbility is 180 ~ 220%.
4. the polyvinyl alcohol film according to any one of claim 1 ~ 3, it is the raw material film for manufacturing polarization film.
5. the manufacture method of polyvinyl alcohol film, it includes with 135 ~ 148 DEG C, polyvinyl alcohol film is carried out heat treated operation, and described polyvinyl alcohol film comprises polyvinyl alcohol that saponification degree is 98 ~ 99.5 moles of % and swellbility is more than 250%.
6. manufacture method according to claim 5, it carries out the heat treatment of more than 0.5 minute.
7. the manufacture method according to claim 5 or 6, it is the method manufacturing the polyvinyl alcohol film that swellbility is 180 ~ 220%.
8. the manufacture method of polarization film, it includes the operation that the polyvinyl alcohol film described in claim 4 is stretched.
9. polarization film, wherein, is denoted as b value when being configured to parallel Nicol state relative to rectilinearly polarized light X, and when b value when being configured to Nicol crossed state relative to rectilinearly polarized light is denoted as Y, meets below formula (I):
Y≥1.9X-8.3(I)。
10. polarization film according to claim 9, it meets below formula (II):
5≥Y≥-5(II)。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-240638 | 2013-11-21 | ||
| JP2013240638 | 2013-11-21 | ||
| PCT/JP2014/080018 WO2015076169A1 (en) | 2013-11-21 | 2014-11-13 | Polyvinyl alcohol film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105723259A true CN105723259A (en) | 2016-06-29 |
| CN105723259B CN105723259B (en) | 2019-05-10 |
Family
ID=53179436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480063715.XA Active CN105723259B (en) | 2013-11-21 | 2014-11-13 | Polyvinyl alcohol film |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6402096B2 (en) |
| KR (1) | KR102364529B1 (en) |
| CN (1) | CN105723259B (en) |
| TW (1) | TWI644960B (en) |
| WO (1) | WO2015076169A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111819479A (en) * | 2018-03-12 | 2020-10-23 | 株式会社可乐丽 | Film roll and method for producing same |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| TW202006026A (en) * | 2018-06-21 | 2020-02-01 | 日商可樂麗股份有限公司 | Polyvinyl alcohol film and method for producing same |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2012082395A (en) * | 2010-09-15 | 2012-04-26 | Kuraray Co Ltd | Polyvinyl alcohol film |
| CN102909862A (en) * | 2011-08-05 | 2013-02-06 | 日东电工株式会社 | Manufacturing method for polarizing film |
| CN102909863A (en) * | 2011-08-05 | 2013-02-06 | 日东电工株式会社 | Method of manufacturing polarizing film |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4741741B1 (en) * | 1968-04-22 | 1972-10-21 | ||
| JP3283564B2 (en) | 1992-03-04 | 2002-05-20 | 株式会社クラレ | Method for producing polyvinyl alcohol-based film |
| JP4281261B2 (en) * | 2000-09-21 | 2009-06-17 | 住友化学株式会社 | Iodine polarizing plate and method for producing the same |
| JP4926367B2 (en) * | 2003-01-23 | 2012-05-09 | 株式会社クラレ | Polarized film |
| 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 |
| KR101624072B1 (en) * | 2012-09-26 | 2016-05-24 | 주식회사 쿠라레 | Polyvinyl alcohol film and polarizing film |
-
2014
- 2014-11-13 CN CN201480063715.XA patent/CN105723259B/en active Active
- 2014-11-13 WO PCT/JP2014/080018 patent/WO2015076169A1/en active Application Filing
- 2014-11-13 JP JP2015513925A patent/JP6402096B2/en active Active
- 2014-11-13 KR KR1020167010088A patent/KR102364529B1/en active IP Right Grant
- 2014-11-19 TW TW103139994A patent/TWI644960B/en active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2012082395A (en) * | 2010-09-15 | 2012-04-26 | Kuraray Co Ltd | Polyvinyl alcohol film |
| CN102909862A (en) * | 2011-08-05 | 2013-02-06 | 日东电工株式会社 | Manufacturing method for polarizing film |
| CN102909863A (en) * | 2011-08-05 | 2013-02-06 | 日东电工株式会社 | Method of manufacturing polarizing film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111819479A (en) * | 2018-03-12 | 2020-10-23 | 株式会社可乐丽 | Film roll and method for producing same |
| CN111819479B (en) * | 2018-03-12 | 2022-06-21 | 株式会社可乐丽 | Film roll and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2015076169A1 (en) | 2017-03-16 |
| TWI644960B (en) | 2018-12-21 |
| CN105723259B (en) | 2019-05-10 |
| JP6402096B2 (en) | 2018-10-10 |
| WO2015076169A1 (en) | 2015-05-28 |
| TW201529681A (en) | 2015-08-01 |
| KR102364529B1 (en) | 2022-02-17 |
| KR20160089349A (en) | 2016-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105723259A (en) | Polyvinyl alcohol film | |
| CN103442871B (en) | Polymer film of polyvinyl alcohol and manufacture method thereof | |
| CN104204046B (en) | Polyvinyl alcohol film and light polarizing film | |
| CN104662071B (en) | Polymer film of polyvinyl alcohol and its manufacturing method | |
| CN104169342B (en) | Polyvinyl alcohol film and its manufacture method | |
| CN104602912A (en) | Layered object, polarizing film, and process for producing polarizing film | |
| JP5624803B2 (en) | Polyvinyl alcohol polymer film | |
| CN104169341B (en) | Ethylene-modified polyvinyl alcohol polymer film | |
| TW201617652A (en) | Polarizing film | |
| KR102387498B1 (en) | Polyvinyl alcohol film and method for manufacturing same | |
| TWI628471B (en) | Polarizing film and manufacturing method thereof | |
| CN105745563A (en) | Polarizing-film manufacturing method | |
| WO2019208618A1 (en) | Polyvinyl alcohol film and method for producing polarizing film using same | |
| JP6735541B2 (en) | Polarizing film | |
| JP2016126021A (en) | Manufacturing method of polarizing film | |
| KR20210021471A (en) | Polyvinyl alcohol film and its manufacturing method | |
| JP6534305B2 (en) | Evaluation method of optical spots of polyvinyl alcohol film | |
| TW201927887A (en) | Poly(vinyl alcohol)-based film for producing polarizing film, polarizing film obtained using same, and aqueous solution of poly(vinyl alcohol)-based resin | |
| CN106062596A (en) | Polarizing film | |
| TW202026351A (en) | Polyvinyl alcohol film and method for producing polarizing film using same | |
| JP2016176971A (en) | Polyvinyl alcohol film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |