CN104169342A - Polyvinyl alcohol-type polymer film and method for producing same - Google Patents

Polyvinyl alcohol-type polymer film and method for producing same Download PDF

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Publication number
CN104169342A
CN104169342A CN201380017352.1A CN201380017352A CN104169342A CN 104169342 A CN104169342 A CN 104169342A CN 201380017352 A CN201380017352 A CN 201380017352A CN 104169342 A CN104169342 A CN 104169342A
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film
dryer roll
based polymer
polymer film
roll
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CN104169342B (en
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森保二郎
中居寿夫
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Kuraray Co Ltd
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Kuraray Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • 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
    • 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
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00634—Production of filters
    • B29D11/00644—Production of filters polarizing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
    • B29K2029/04—PVOH, i.e. polyvinyl alcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0034—Polarising
    • 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
    • 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
    • C08J2429/00—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
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Abstract

To provide: a PVA-type polymer film which enables the production of a polarizing film having a high absorption of light with a long wavelength region and having a high polarization degree; and a method for producing the PVA-type polymer film. A PVA-type polymer film having a crystal long period of 14.5 to 16.0 nm in water; and a PVA-type polymer film production method comprising forming a PVA-type polymer film using a film formation apparatus equipped with multiple drying rolls of which rotation axes are parallel to each other and a heat-treatment roll, wherein the PVA-type polymer film is dried in such a manner that the value of T1-2 represented by formula (I) becomes 60 to 75. T1-2 = {T1(40-V1)+T2(V1-V2)}/(40-V2) (I) (In the formula, T1 represents the temperature ( DEG C) of the surface of a first drying roll; V1 represents the volatile fraction (mass%; V1 falls within the range from 10 to 30) of the film upon the delamination of the film from the first drying roll; T2 represents the average value ( DEG C) of the temperatures of the surfaces of all of the second drying roll to the final drying roll; and V2 represents the volatile fraction (mass%) of the film upon the delamination of the film from the final drying roll).

Description

Vinol series polymer film and manufacture method thereof
Technical field
The present invention relates to a kind of vinol series polymer film (following, sometimes by " polyvinyl alcohol " referred to as " PVA ") and manufacture method thereof, and by the polarizing coating of this PVA based polymer film manufacture.More specifically, the present invention relates to a kind of absorbancy that can manufacture long wavelength region high, and PVA based polymer film and the manufacture method thereof of the polarizing coating that degree of polarization is high, and the absorbancy in the long wavelength region of being manufactured by this PVA based polymer film is high, and the high polarizing coating of degree of polarization.
Background technology
The polarizing coating with optical transmission and function of shielding is all the basic constituent element of liquid-crystal display (LCD) with the liquid crystal of the switching function with light.The miniature instrument such as counter and wrist-watch of the Application Areas that can see this LCD during also from initial stage of development expand to notebook computer in recent years, word processor, liquid crystal projection apparatus, onboard navigation system, LCD TV, mobile phone and in doors the vast scope such as the measuring instrument that uses.Along with the expansion of this LCD Application Areas, require polarization property on current material high, and for improving the polarization plates of neutral gray of form and aspect excellence of colored display quality.
Polarization plates is generally following formation: by PVA based polymer film being carried out to uniaxial extension dyeing or dyeing uniaxial extension; then be fixed processing (according to circumstances with boron compound; sometimes dye simultaneously, stretch and fix 2 above operations in processing) thus polarizing coating obtained, then the protective membranes such as cellulose triacetate (TAC) film, cellulose acetate butyrate (CAB) (CAB) film are fitted on the polarizing coating obtaining.
In order to improve the form and aspect of polarizing coating, be mainly that the viewpoints such as the structure of PVA based polymer, PVA based polymer film from manufacture raw material as polarizing coating and creating conditions while manufacturing polarizing coating are studied up to now.For example, known have by by the polymerization degree being 1500～5000, the content of ethylene unit is 1～4 % by mole, 1,2-diol bond resultant is that YI value that 1.4 % by mole of following modified PVAs are filmed is that to carry out the b value that uniaxial extension makes be the polarizing coating (referring to patent documentation 1) below 3 for PVA mesentery below 20.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2003-342322 communique
Patent documentation 2: TOHKEMY 2006-188655 communique
Non-patent literature
Non-patent literature 1:Polymer, 46,7436-7442(2005)
Non-patent literature 2:Macromolecules, 39(8), 2921-2929(2006)
Non-patent literature 3: " Polymer Physics ", publish in Springer-Verlag Tokyo, p.143-154
Non-patent literature 4:Journal of Polymer Science:Polymer Physics Edition, Vol.18,1343-1359(1980).
Summary of the invention
The problem that invention will solve
But the polarizing coating in the past of recording in patent documentation 1 can produce red stain when as liquid crystal indicator.This red stain makes visually to feel that polarizing coating is rubescent, that is, can think its reason to be polarizing coating the absorbancy of (for example visible region more than 680nm) is low in long wavelength region.In patent documentation 1, openly do not keep high-polarization, and eliminate the means of the absorbancy in red stain, raising long wavelength region.
Therefore, the object of the invention is to provide a kind of absorbancy that can manufacture long wavelength region high, and the PVA based polymer film of the high polarizing coating of degree of polarization.In addition, the object of the invention is to provide a kind of manufacture method of the PVA based polymer film that can successfully manufacture continuously this PVA based polymer film.Further, the object of the invention is to provide the absorbancy in a kind of long wavelength region high, and the high polarizing coating of degree of polarization.
For the method for dealing with problems
The absorbancy in the long wavelength region of polarizing coating can be thought to change and change along with the crystal structure of polarizing coating.Polarizing coating is generally by more than 1 or 2 in operation of each operations such as dyeing, uniaxial extension, fixing processing, by PVA based polymer film immersion in the water that is dissolved with all ingredients and manufacture, if and by PVA based polymer film immersion in water, a part for the crystallization unit of PVA based polymer film is dissolved, and it is large that the size of amorphous portion becomes.That is to say, the crystal structure of the PVA based polymer film in water from be immersed in water in before crystal structure different.The inventor etc. are in order to improve the absorbancy in long wavelength region of polarizing coating, and pay close attention to the crystal structure of the PVA based polymer film in water.Then find, by making as the crystallization long period in water of yardstick that represents this crystal structure in specific scope, the absorbancy that can easily obtain long wavelength region is high, and the high polarizing coating of degree of polarization.
In addition, the inventor etc. are in the time that by methods such as wide-angle x-ray diffraction, DSC, the drying process during to the dry masking stoste that contains PVA based polymer and by PVA based polymer film masking is studied, find in the time that the volatile component ratio of the film being formed by masking stoste is about 40 quality %, PVA based polymer starts crystallization, think thus, be the film forming conditions of 40 quality % when following by adjusting the volatile component ratio of film in masking, can adjust the crystallization long period of the PVA based polymer film obtaining in water.Then find, possess turning axle multiple dryer rolls parallel to each other and the film forming apparatus of Heat treating roll in use, the masking stoste that contains PVA based polymer is dried to being positioned in this film forming apparatus on the first dryer roll of upstream side with membranaceous spuing, and follow in the downstream side of this first dryer roll while manufacturing PVA based polymer film with further being dried of the dryer roll after the second dryer roll, be to make between the specific drying zone below 40 quality % the mean value of temperature of dryer roll in specific scope by the volatile component ratio of the film in masking, can successfully be manufactured on continuously crystallization long period in the water above-mentioned PVA based polymer film in specified range.
The inventor etc. are based on above-mentioned opinion, and further research repeatedly, has completed the present invention.That is to say, the present invention is
(1) a PVA based polymer film, is characterized in that, the crystallization long period in water is 14.5～16.0nm.
In addition, the present invention is
(2) a kind of manufacture method of PVA based polymer film, wherein, possess turning axle multiple dryer rolls parallel to each other and the film forming apparatus of Heat treating roll in use, the masking stoste that contains PVA based polymer is dried to the first dryer roll of this film forming apparatus with membranaceous spuing, then further dry and during by PVA based polymer masking, with the T shown in following formula (I) with dryer roll 1 → 2the mode that meets following formula (II) is dried.　
T 1→2={T 1×（40－V 1）+T 2×（V 1－V 2）}/（40－V 2） （I）
60≤T 1→2≤75 （II）
(T herein, 1represent the first dryer roll surface temperature (DEG C), V 1the volatile component ratio (quality %) of film while representing to peel off from the first dryer roll, T 2represent from the second dryer roll to be next to Heat treating roll final dryer roll each dryer roll surface temperature mean value (DEG C), V 2the volatile component ratio (quality %) of film when expression is peeled off from being next to the final dryer roll of Heat treating roll.Wherein, V 1be 10～30(quality %).）。
Further, the present invention is
(3) polarizing coating that a kind of PVA based polymer film by aforementioned (1) is manufactured.
Invention effect
According to the present invention, can provide a kind of absorbancy that can manufacture long wavelength region high, and the PVA based polymer film of the high polarizing coating of degree of polarization.In addition, according to the present invention, can provide a kind of manufacture method of the PVA based polymer film that can successfully manufacture continuously this PVA based polymer film.Further, according to the present invention, can provide the absorbancy in a kind of long wavelength region high, and the high polarizing coating of degree of polarization.
Invention embodiment
The crystallization long period of PVA based polymer film of the present invention in water is 14.5～16.0nm.Common so-called crystallization long period, refer in film mostly the crystallization unit of random distribution and the mean length in 1 cycle of the repeat cycle of amorphous portion in situation, and the size of the crystallization unit of repeat cycle direction and amorphous portion changes (referring to patent documentation 2) according to the film forming condition of film etc.In the present invention, owing to having crystallization long period in the water unexistent formation in the past in above-mentioned scope, the absorbancy that has therefore obtained manufacturing long wavelength region is high, and the PVA based polymer film of the high polarizing coating of degree of polarization.High from obtaining the absorbancy in long wavelength region, and the viewpoint of the high polarizing coating of degree of polarization considers, more than this crystallization long period is preferably 14.7nm, more preferably more than 15.0nm, more preferably more than 15.1nm, in addition, is preferably below 15.7nm.
As the method for thickness of obtaining crystallization long period, crystallization unit, known have a small angle X ray scattering method, and it is recorded in non-patent literature 1～4 grade.The crystallization long period of PVA based polymer film of the present invention in water can be obtained by this small angle X ray scattering method, particularly, can obtain by using the small angle X ray scattering determinator of describing in the following embodiments to analyze PVA based polymer film in water.As the PVA based polymer film using in measuring, use the dipping material of 24 hours in the water (distilled water) of 22 DEG C herein.As mentioned above, by PVA based polymer film immersion, in water time, a part for the crystallization unit of PVA based polymer film is dissolved, and it is large that the size of amorphous portion becomes, and along with time process, just reach soon balanced structure.Owing to the most also reaching this balanced structure in 24 hours in the water of 22 DEG C, in therefore measuring, use the PVA based polymer film flooding 24 hours in the water of 22 DEG C.
As the PVA based polymer that forms PVA based polymer film, for example, can enumerate the polyvinylesters of vinyl ester polymerization gained is carried out to the unmodified PVA of PVA(that saponification obtains), the main chain that makes comonomer and PVA carry out graft copolymerization and modified PVA based polymer, by the modified polyvinyl ester that vinyl ester and copolymerization monomer copolymerization are obtained is carried out to the modified PVA based polymer that saponification is manufactured, with formalin, butyraldehyde, the so-called polyvinyl acetal resin that the aldehydes such as phenyl aldehyde are cross-linked a part for the hydroxyl of unmodified PVA or modified PVA based polymer etc.
In the time that the PVA based polymer of formation PVA based polymer film is modified PVA based polymer, the modification amount in PVA based polymer is preferably below 15 % by mole, more preferably below 5 % by mole.
As the aforementioned vinyl ester using in the manufacture of PVA based polymer, for example, can enumerate vinyl-acetic ester, vinyl formate, vinyl laurate, propionate, vinyl butyrate, trimethylacetic acid vinyl acetate, vinyl neodecanoate, stearic acid vinyl ester, vinyl benzoate etc.These vinyl ester can be used alone or in combination.In these vinyl ester, consider from the viewpoint of productivity, preferably vinyl-acetic ester.
In addition, as aforesaid comonomer, for example, can enumerate the olefines (alpha-olefin etc.) that the carbon numbers such as ethene, propylene, 1-butylene, iso-butylene are 2～30; Vinylformic acid or its salt; The esters of acrylic acids such as methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-EHA, dodecylacrylate, vinylformic acid stearyl (for example, acrylic acid carbon number 1～18 alkyl ester etc.); Methacrylic acid or its salt; The methyl acrylic esters such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, 2-Ethylhexyl Methacrylate, lauryl methacrylate, methacrylic acid stearyl (for example, carbon number 1～18 alkyl ester of methacrylic acid etc.); The acrylamide derivatives such as acrylamide, N methacrylamide, N-ethyl acrylamide, N,N-DMAA, diacetone-acryloamide(DAA), acrylamido propanesulfonic acid or its salt, acrylamido diemethylamine or its salt, N hydroxymethyl acrylamide or derivatives thereof; The methacrylamide derivatives such as Methacrylamide, N-methyl acrylamide, N-ethyl-methyl acrylamide, methacryloyl amido propanesulfonic acid or its salt, methacryloyl amido diemethylamine or its salt, N-methylol methacrylamide or derivatives thereof; The N-vinylamide classes such as N-vinyl formamide, N-vinyl acetamide, NVP; The vinyl ethers such as methylvinylether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, IVE, tert-Butyl vinyl ether, dodecyl vinyl, stearyl vinyl ether; The nitrile such as vinyl cyanide, methacrylonitrile; The vinyl halides base class such as vinylchlorid, vinylidene chloride, vinyl fluoride, vinylidene; The allylic cpd such as allyl acetate, chlorallylene; The derivatives such as the unsaturated dicarboxylic acid such as toxilic acid, methylene-succinic acid, its salt or its ester; The vinyl silyl compounds such as vinyltrimethoxy silane; Methylvinyl acetate; Unsaturated sulfonic acid or derivatives thereof etc.Wherein preferred alpha-olefin, particularly preferably ethene.
Consider from the viewpoint of polarization property and the weather resistance etc. of the polarizing coating of gained, the mean polymerisation degree that forms the PVA based polymer of PVA based polymer film is preferably more than 1000, more preferably more than 1500, more preferably more than 2000.On the other hand, for the upper limit of the mean polymerisation degree of PVA based polymer, consider from the viewpoint such as easiness, stretchiness of the manufacture of the PVA based polymer film of homogeneous, this mean polymerisation degree is preferably below 8000, is particularly preferably below 6000.
Herein, " mean polymerisation degree " of the PVA based polymer in this specification sheets refers to the mean polymerisation degree of measuring based on JIS K6726-1994, and it can be by the limiting viscosity of measuring in the water of 30 DEG C after the saponification again of PVA based polymer, purifying is obtained.
Consider from the viewpoint such as polarization property and weather resistance of the polarizing coating that obtains, the saponification deg that forms the PVA based polymer of PVA based polymer film is preferably more than 95.0 % by mole, more preferably more than 98.0 % by mole, more preferably more than 99.0 % by mole, most preferably be more than 99.3 % by mole.
Herein, " saponification deg " of the PVA based polymer in this specification sheets refer to respect to changing into the structural unit (being typically vinyl ester units) of vinyl alcohol units and the total mole number of vinyl alcohol units by saponification, the shared ratio of the mole number of this vinyl alcohol units (% by mole).The saponification deg of PVA based polymer can be measured in the record based on JIS K6726-1994.
PVA based polymer film, except above-mentioned PVA based polymer, can also further contain hereinafter as the explanation of manufacture method of the present invention and the softening agent of describing, tensio-active agent, various additives in addition etc. using such as amount described later.
The thickness of PVA based polymer film, is not particularly limited, and when as the initial film of polarizing coating manufacture use (former anti-) etc., is preferably 5～80 μ m.Preferred thickness is 20～80 μ m.Be below the above-mentioned upper limit by making the thickness of PVA based polymer film, in the time manufacturing polarizing coating, easily be dried rapidly, on the other hand, be more than above-mentioned lower limit by making the thickness of PVA based polymer film, in the time of the uniaxial extension for the manufacture of polarizing coating, can more effectively suppress the generation of film fracture.
The width of PVA based polymer film is not particularly limited, LCD TV, the continuous large screen of indicating meter in recent years, therefore, for can be effectively for these purposes, more than width is preferably 2m, more preferably more than 3m, more preferably more than 4m.In addition, in the time using real production manufacture polarization plates, if the width of film is excessive, be difficult to stretch uniformly, therefore the width of PVA based polymer film is preferably below 8m.The length of PVA based polymer film is not particularly limited, and for example, can be 50～30000m.
The length of delay of PVA based polymer film is not particularly limited, and length of delay is less, and the polarizing coating of gained more has in the phase differential inequality of width the tendency being improved, and is therefore preferably below 100nm.This length of delay can be measured by the method for describing in the embodiment below.
The quality swelling capacity of PVA based polymer film is preferably 180～250%, and more preferably 185～240%, more preferably 190～230%.Be more than above-mentioned lower limit by making the quality swelling capacity of PVA based polymer film, easily stretch, have the tendency of the polarizing coating of more easily manufacturing polarization property excellence, on the other hand, be below the above-mentioned upper limit by making quality swelling capacity, operation trafficability characteristic when stretching improves, and has the tendency of the polarizing coating of more easily manufacturing high-durability.
So-called quality swelling capacity herein, refer to the percentage of the value that the quality after dry 16 hours obtains at 105 DEG C after quality while flooding 30 minutes with PVA based polymer film in the distilled water of 30 DEG C is divided by dipping, particularly, can measure by the method for describing in the embodiment below.
The method for making of PVA based polymer film of the present invention is not particularly limited, and according to following manufacture method of the present invention, can successfully manufacture continuously PVA based polymer film of the present invention.
That is to say, for the manufacture of the manufacture method of the present invention of PVA based polymer film, to possess turning axle multiple dryer rolls parallel to each other (from upstream side towards downstream side in use, be called successively the first dryer roll, the second dryer roll ...) and the film forming apparatus of Heat treating roll, the masking stoste that contains PVA based polymer is dried to the first dryer roll of this film forming apparatus with membranaceous spuing, then further dry and during by vinol series polymer masking, with the T shown in following formula (I) with dryer roll 1 → 2the mode that meets following formula (II) is dried.　
T 1→2={T 1×（40－V 1）+T 2×（V 1－V 2）}/（40－V 2） （I）
60≤T 1→2≤75 （II）。
In above-mentioned formula (I) with (II), T 1represent the first dryer roll surface temperature (DEG C), V 1the volatile component ratio (quality %) of film while representing to peel off from the first dryer roll, T 2represent from the second dryer roll to be next to Heat treating roll final dryer roll each dryer roll surface temperature mean value (DEG C), V 2the volatile component ratio (quality %) of film when expression is peeled off from being next to the final dryer roll of Heat treating roll.And, V 1be 10～30(quality %).
As mentioned above, the discoveries such as the inventor are in the time that the volatile component ratio of the film being formed by masking stoste is about 40 quality %, PVA based polymer starts crystallization, think thus, be the film forming conditions of 40 quality % when following by adjusting the volatile component ratio of film in masking, can adjust the crystallization long period of the PVA based polymer film obtaining in water, for the mean value of the temperature of the dryer roll that one of represents in this film forming condition, use the surface temperature (T by the first dryer roll 1), the volatile component ratio (V of film while peeling off from the first dryer roll 1), the mean value (T of the surface temperature of each dryer roll from the second dryer roll to final dryer roll 2) and the volatile component ratio (V of film while peeling off from final dryer roll 2) form above-mentioned formula (I).
It should be noted that, above-mentioned formula (I) derives as follows.That is to say, the masking stoste that contains PVA based polymer is spued to surface temperature T with membranaceous 1(DEG C) the first dryer roll on, on this first dryer roll, be dried to the volatile component ratio of the film in masking via V 0(quality %) reaches V 1(quality %), by this film, after the first dryer roll is peeled off, with the later multiple dryer rolls of the second dryer roll, (mean value of the surface temperature of each dryer roll is T 2(DEG C)) further dry, when the volatile component ratio of film is V 2when (quality %), in the case of from the final dryer roll that is next to Heat treating roll is peeled off, from volatile component ratio V 0(quality %) is to volatile component ratio V 2the mean value T of the surface temperature of dryer roll between the drying zone of (quality %) ave(DEG C) can represent by following formula (I ').　
T Ave=T 1×（V 0－V 1）/（V 0－V 2）+ T 2×（V 1－V 2）/（V 0－V 2） （I’）
Herein, as mentioned above, be the film forming conditions of 40 quality % when following in order to adjust the volatile component ratio of film in masking, the V of above-mentioned formula (I ') 0for V 0=40(quality %) time, T aveequal the T of above-mentioned formula (I) 1 → 2.
In manufacture method of the present invention, must meet above-mentioned formula (II), i.e. T in above-mentioned formula (I) 1 → 2value must be in 60～75 scope.By making T 1 → 2within the scope of this, can successfully be manufactured on continuously crystallization long period in the water above-mentioned PVA based polymer film in specified range.Consider T from the viewpoint that can more easily manufacture this PVA based polymer film 1 → 2be preferably more than 61, more preferably more than 63, more preferably more than 64, be particularly preferably more than 64.5, most preferably be more than 65, in addition, T 1 → 2be preferably below 72, more preferably below 69.5.
In manufacture method of the present invention, use possesses turning axle multiple dryer rolls parallel to each other and the film forming apparatus of Heat treating roll, the masking stoste that contains PVA based polymer is dried to the first dryer roll of this film forming apparatus with membranaceous spuing, and is then further dried and manufacture PVA based polymer film with the dryer roll after the second dryer roll in the downstream side of this first dryer roll.In this film forming apparatus, the quantity of dryer roll is preferably more than 3, more preferably more than 4, and more preferably 5～30.
Multiple dryer rolls are for example preferably formed by metals such as nickel, chromium, copper, iron, stainless steels, and particularly, the surface of dryer roll is more preferably formed by metallic substance not perishable and that have a specular gloss.In addition, in order to improve the weather resistance of dryer roll, more preferably use plating to have the dryer roll of individual layer or the two-layer above nickel dam combining, chromium layer, nickel/chromium alloy layer etc.
For from the first dryer roll to heating direction when desciccator diaphragm being next to the process of final dryer roll of Heat treating roll, from the viewpoint consideration of desciccator diaphragm more equably, preferably (following with the face contacting with the first dryer roll in the arbitrary portion of film, be sometimes referred to as " the first dryer roll contact surface ") with the face not contacting with the first dryer roll (following, be sometimes referred to as " the first dryer roll noncontact face ") alternately relative with each dryer roll from the first dryer roll to final dryer roll to mode be dried.
If the surface temperature of multiple dryer rolls is too high, have and in a part for PVA based polymer film, produce heat treated effect, crystal structure becomes inhomogeneous tendency, in addition, if too low, there is the tendency that is difficult to efficient drying, therefore preferably in the scope of 30～95 DEG C, more preferably in the scope of 40～85 DEG C, further preferably in the scope of 60～75 DEG C.For the surface temperature more specifically of indivedual dryer rolls as described later.
The masking stoste that contains PVA based polymer is spued on the first dryer roll of film forming apparatus time with membranaceous, for example, use the known membranaceous device for discharging fixed (membranaceous casting device) such as T-shaped slit die, hopper plate, I-mould, lip coating machine mould, by the masking stoste that contains PVA based polymer with membranaceous spuing (curtain coating) to the first dryer roll.
As the masking stoste that contains PVA based polymer, can be by PVA based polymer and liquid medium be mixed to form to solution, maybe the PVA based polymer particle fusion that contains liquid medium etc. is formed to fused solution etc. and modulate.
As liquid medium now used, for example, can enumerate water, dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, quadrol, Diethylenetriamine etc., these liquid mediums can use separately a kind, or and use two or more.Wherein, preferably make water, dimethyl sulfoxide (DMSO) or both mixtures, particularly more preferably make water.
The viewpoints such as the stretchiness of operation trafficability characteristic when dissolving, melting, the raising PVA based polymer film from promotion PVA based polymer liquid medium manufactured, the PVA based polymer film of raising gained are considered, preferably in masking stoste, add softening agent.
As softening agent, preferably use polyvalent alcohol, for example, can enumerate ethylene glycol, glycerine, Glycerol dimer, propylene glycol, Diethylene Glycol, triethylene glycol, TEG, TriMethylolPropane(TMP) etc., these softening agent can use separately a kind, or and use two or more.Consider from the viewpoint of the raising effect excellence of stretchiness, wherein one kind or two or more in preferably glycerine, Glycerol dimer and ethylene glycol.
The addition of softening agent is preferably 0～30 mass parts with respect to PVA based polymer 100 mass parts.Be below 30 mass parts by making the addition of softening agent with respect to PVA based polymer 100 mass parts, the PVA based polymer film of gained can be too not soft, can suppress the situation that operability reduces.From the viewpoint of the operability of the PVA based polymer film of gained and the more successfully consideration such as viewpoint of manufacturing objective PVA based polymer film, the addition of softening agent is with respect to PVA based polymer 100 mass parts more preferably more than 3 mass parts, more preferably more than 5 mass parts, in addition, more preferably below 25 mass parts, more preferably, below 20 mass parts, be particularly preferably below 15 mass parts.
The viewpoints such as the operability of the separability the dryer roll during from raising from manufacture PVA based polymer film, the PVA based polymer film of gained are considered, preferably in masking stoste, add tensio-active agent.As the kind of tensio-active agent, be not particularly limited, preferably use anionic surfactant or nonionic surfactant.
As anionic surfactant, for example, the anionic surfactant of the sulfonic acid types such as sulfuric acid ester type, dodecylbenzene sulfonate such as carboxylic acid type, sulfuric acid monooctyl ester such as preferred potassium laurate.
In addition, as nonionic surfactant, for example, preferred nonionic surfactants such as the allyl phenyl ether such as alkylolamide type, polyoxyalkylene allyl phenyl ether type such as polypropylene glycol ether type, lauric acid diethyl amide, oleic acid diethyl amide such as alkylamine type, the polyoxyethylene laurylamide etc. such as the alkyl ester types such as the alkyl phenyl ether such as alkyl ether type, polyoxyethylene octyl phenyl ether type, polyoxyethylene lauric acid ester, polyoxyethylene lauryl amino ethers alkylamide type, polyoxyethylene poly-oxygen propylene aether such as polyoxyethylene oleyl ether.These tensio-active agents can use separately a kind or and use two or more.
The addition of tensio-active agent is preferably 0.01～1 mass parts with respect to PVA based polymer 100 mass parts, and more preferably 0.02～0.5 mass parts, is particularly preferably 0.05～0.3 mass parts.Be more than 0.01 mass parts by making the addition of tensio-active agent with respect to PVA based polymer 100 mass parts, easily show the raising effect of masking, separability etc., on the other hand, by being below 1 mass parts, can suppress tensio-active agent becomes the reason of adhesion in film surface stripping, and can suppress the situation that operability reduces.
In masking stoste, except mentioned component, can also contain various additives, such as stablizer (oxidation inhibitor, UV light absorber, thermo-stabilizer etc.), compatilizer, anti blocking agent, fire retardant, static inhibitor, lubricant, dispersion agent, liquid agent, antiseptic-germicide etc.These additives can use separately a kind, or and use two or more.
For the manufacture of the volatile component ratio of the masking stoste of PVA based polymer film, more than being generally 40 quality %, be preferably 50～90 quality %, more preferably 60～80 quality %.If the volatile component ratio of masking stoste is too low, the viscosity of masking stoste is too high, is difficult to filtration, deaeration, and masking itself also becomes difficulty sometimes.On the other hand, if the volatile component ratio of masking stoste is too high, viscosity is too low, damages sometimes the homogeneity of the thickness of PVA based polymer film.
Herein, so-called in this specification sheets " the volatile component ratio of masking stoste " is the volatile component ratio of obtaining by following formula (III).　
Volatile component ratio (quality %)={ (Wa-Wb)/Wa} × 100 (III) of masking stoste
The masking stoste of (herein, Wa represents the quality (g) of masking stoste, and Wb represents Wa(g) is dry quality (g) after 16 hours in the electric air drier of 105 DEG C.）。
While being dried with the membranaceous masking stoste spuing, consider the surface temperature (T of the first dryer roll from the viewpoint that can more successfully manufacture PVA based polymer film of the present invention on the first dryer roll 1) be preferably 60～90 DEG C.In addition, from guaranteeing the viewpoint considerations such as more stable productivity, the roll surface temperature (T of the first dryer roll 1) more preferably more than 65 DEG C, more preferably more than 70 DEG C, in addition, more preferably, below 85 DEG C, more preferably, below 80 DEG C, be particularly preferably below 75 DEG C.
Being dried with the membranaceous masking stoste spuing on the first dryer roll, can only be undertaken by the heating from the first dryer roll, and consider from viewpoints such as even drying property, rate of dryings, preferably in the first dryer roll heating, spray hot blast to the first dryer roll noncontact face, give heat and be dried from the two sides of film.
In the time spraying hot blast to the first dryer roll noncontact face that is positioned at the film on the first dryer roll, be preferably 1～10m/ hot blast of second to the whole area spray wind speed of the first dryer roll noncontact face, more preferably spraying wind speed is 2～8m/ hot blast of second, and further preferably spraying wind speed is 3～8m/ hot blast of second.If the wind speed of hot blast spraying to the first dryer roll noncontact face is too small, when dry on the first dryer roll, produce the dewfall of water vapour etc., this water droplet drops onto on film, in the PVA based polymer film finally obtaining, may produce defect.On the other hand, if the wind speed of the hot blast spraying to the first dryer roll noncontact face is excessive, on the PVA based polymer film finally obtaining, produce uneven thickness, the following unequal problem of dyeing that easily produces.
Consider from viewpoints such as drying efficiency, dry homogeneities, the temperature of the hot blast spraying to the first dryer roll noncontact face of film is preferably 50～150 DEG C, and more preferably 70～120 DEG C, more preferably 80～95 DEG C.If the temperature of hot blast of spraying to the first dryer roll noncontact face of film is too low, produce the dewfall of water vapour etc., this water droplet drops onto on film, in the PVA based polymer film finally obtaining, may produce defect.On the other hand, if this excess Temperature produces uneven drying along the wind direction of hot blast, may produce the uneven thickness of the PVA based polymer film finally obtaining.
The dew-point temperature of the hot blast spraying to the first dryer roll noncontact face of film in addition, is preferably 5～20 DEG C, more preferably 10～15 DEG C.If the dew-point temperature of the hot blast spraying to the first dryer roll noncontact face of film is too low, drying efficiency, even drying property etc. easily decline, and on the other hand, if dew-point temperature is too high, easily produces and foam.
Be not particularly limited for the mode of spraying hot blast to the first dryer roll noncontact face of film, can adopt can be to the first dryer roll noncontact face of film, preferably its entirety is sprayed any mode of the even and uniform hot blast of temperature of wind speed equably, wherein preferably adopts nozzle mode, cowling panel mode or their combination etc.Hot blast is to the injection direction of the first dryer roll noncontact face of film, both can be the direction relative with the first dryer roll noncontact face, also can be the direction along the circumferential shapes of the first dryer roll noncontact face of the film direction of the circumference on the roller surface of the first dryer roll (roughly along) roughly, or can be also direction in addition.
In addition, when the film on the first dryer roll dry, preferably the hot blast by the dry volatile component being produced by film and after spraying will be carried out to exhaust.The method of exhaust is not particularly limited, and preferably employing can not produce the wind speed inequality of the hot blast that the first dryer roll noncontact face of film is sprayed and the method for exhausting of temperature inequality.
Consider the peripheral speed (S of the first dryer roll from viewpoints such as the productivity of rate of drying and PVA based polymer film 1) be preferably 5～30m/ minute.If the peripheral speed (S of the first dryer roll 1) lower than 5m/ minute, productivity reduces, and the tendency that exists the stretchiness of rewarding PVA based polymer film to decline.On the other hand, if the circumferential speed (S of the first dryer roll 1) exceed 30m/ minute,, in the time of the both ends of cutting film, the roughness that has its cut surface becomes large tendency.
With the membranaceous masking stoste spuing to the first dryer roll, when the volatile component ratio of the film being dried on the first dryer roll (the volatile component ratio of film when the first dryer roll is peeled off; V 1(quality %)) peel off from the first dryer roll while being 10～30 quality %.If the volatile component ratio (V of film when the first dryer roll is peeled off 1) be less than 10 quality %, by the film hardening of the first dryer roll, operation trafficability characteristic declines, therefore not preferred.On the other hand, if when the first dryer roll is peeled off the volatile component ratio (V of film 1) exceed 30 quality %, the first dryer roll contact surface side is dry insufficient, and easily generation is peeled off bad.Consider the volatile component ratio (V of film when the first dryer roll is peeled off from above-mentioned viewpoint 1) be preferably 15 quality % more than, more preferably more than 18 quality %, more preferably more than 20 quality %, in addition, be preferably below 29 quality %, more preferably below 28 quality %, more preferably below 27 quality %.
Herein, so-called in this specification sheets " the volatile component ratio of film " refers to the volatile component ratio of obtaining by following formula (IV).　
V(quality %)={ (Wc-Wd)/Wc} × 100 (IV)
(herein, V represents the volatile component ratio (quality %) of film, Wc represents the quality (g) of the sample of taking from film, and Wd represents Wc(g) the quality (g) of aforementioned sample while putting in temperature 50 C, Vacuumdrier below pressure 0.1kPa dry 4 hours.）。
Peel off at the first dryer roll and be dried to above-mentioned volatile component ratio (V from the first dryer roll 1) film, this less preferred first dryer roll noncontact face of film that makes is relative with the second dryer roll, desciccator diaphragm on the second dryer roll.
Peripheral speed (the S of the second dryer roll 2) with respect to the peripheral speed (S of the first dryer roll 1) ratio (S 2/ S 1), be preferably 1.005～1.150, more preferably 1.010～1.100.If ratio (S 2/ S 1) be less than 1.005, be difficult to peel off from the first dryer roll, film can rupture sometimes.In addition, if ratio (S 2/ S 1) exceed 1.150, there is the tendency that is difficult to manufacturing objective PVA based polymer film.
Consider from the viewpoint that can more successfully manufacture PVA based polymer film of the present invention, from the second dryer roll to the mean value (T of surface temperature of each dryer roll of final dryer roll that is next to Heat treating roll 2) (value that the surface temperature of each dryer roll is averaged) be preferably 50～75 DEG C.Consider especially this mean value (T from the viewpoint of guaranteeing more stable productivity 2) more preferably more than 55 DEG C, more preferably 60 DEG C, in addition, more preferably below 70 DEG C, more preferably below 68 DEG C.
Volatile component ratio (the V of film when final dryer roll is peeled off 2), depend on above-mentioned when the first dryer roll is peeled off the volatile component ratio (V of film 1) etc., but consider this volatile component ratio (V from the viewpoint that can more successfully manufacture PVA based polymer film of the present invention 2) be preferably 1 quality % more than, more preferably more than 3 quality %, in addition, be preferably below 15 quality %, more preferably below 10 quality %, more preferably below 9 quality %.
In order more successfully to manufacture PVA based polymer film of the present invention, the peripheral speed (S of final dryer roll l) with respect to the peripheral speed (S of the first dryer roll 1) ratio (S l/ S 1), be preferably 0.975～1.150, more preferably 0.980～1.100.If than (S l/ S 1) be less than 0.975, between dryer roll, film is easily lax, in addition, if than (S l/ S 1) exceed 1.150, there is the tendency that is difficult to manufacturing objective PVA based polymer film.
Peel off from final dryer roll carrying out as mentioned above dry film, and implement thermal treatment by the Heat treating roll that is positioned at its downstream side.The number of Heat treating roll can be 1, can be also multiple.
From suitably carrying out crystallization, obtain the viewpoint consideration of the PVA based polymer film of hot water resistance excellence, the surface temperature of Heat treating roll is preferably more than 90 DEG C, more preferably more than 95 DEG C, more preferably more than 100 DEG C.In addition, from improve gained PVA based polymer film stretchiness viewpoint consider, the surface temperature of Heat treating roll is preferably below 150 DEG C, more preferably below 130 DEG C, more preferably below 120 DEG C.
Heat treatment time is not particularly limited, from the more successfully viewpoint consideration of manufacturing objective PVA based polymer film, preferably in the scope in 3～60 seconds, more preferably in the scope in 5～30 seconds.
The volatile component ratio of the film before heat-treating, conventionally with above-mentioned V 2value consistent.In thermal treatment, the volatile component ratio of film can change, and also can not change, and for example, in thermal treatment, can compare V 2value decline.In manufacture method of the present invention, the mean value (T of the surface temperature of the each dryer roll from the second dryer roll to final dryer roll 2) be preferably as mentioned above 50～75 DEG C, in order to reach this mean value (T 2), the surface temperature of the each dryer roll from the second dryer roll to final dryer roll also preferably in the scope of 50～75 DEG C, and being when more than 90 DEG C as mentioned above by the surface temperature of Heat treating roll, can be distinguished each dryer roll and Heat treating roll clearly.
Above-mentioned film forming apparatus can have hot-air drying device, humidity control device etc. as required, for example, can after above-mentioned thermal treatment, implement conditioning.In addition, can cut as required the both ends (edge part) of film.
The volatile component ratio of the PVA based polymer film finally obtaining by above-mentioned a series of processing is preferably in the scope of 1～5 quality %, more preferably in the scope of 2～4 quality %.The PVA based polymer film of gained preferably batches as roller shape with the length of regulation.
In the time manufacturing polarizing coating by PVA based polymer film of the present invention, for example, as long as to PVA based polymer film dye, uniaxial extension, fixing processing, drying treatment and thermal treatment as required.The order of dyeing and uniaxial extension is not particularly limited, and the processing of can dyeing before uniaxial extension is processed, also can process the processing of simultaneously dyeing with uniaxial extension, or the processing of also can dyeing after uniaxial extension is processed.In addition, the operation such as uniaxial extension, dyeing can be repeatedly.Particularly, when uniaxial extension is divided into 2 stages when above, easily stretch uniformly, therefore preferred.
As the dyestuff using, can use iodine or dichroism organic dye (for example, direct black (DirectBlack) 17,19,154 in the dyeing of PVA based polymer film; Direct brown (DirectBrown) 44,106,195,210,223; Directly red (DirectRed) 2,23,28,31,37,39,79,81,240,242,247; Directly blue (DirectBlue) 1,15,22,78,90,98,151,168,202,236,249,270; Directly purple (DirectViolet) 9,12,51,98; Sun green (DirectGreen) 1,85; Directly yellow (DirectYellow) 8,12,44,86,87; The dichroic dyes such as direct orange (DirectOrange) 26,39,106,107) etc.These fuel can use separately one, or are used in combination two or more.Dyeing conventionally can be by PVA based polymer film immersion is carried out in the solution that contains above-mentioned dyestuff, and its treatment condition and treatment process are not particularly limited.
The uniaxial extension that PVA based polymer film is stretched along flow direction (MD) etc., can adopt any method in wet type stretching method or xeothermic stretching method to carry out, and consider preferably wet type stretching method from the performance of polarizing coating of gained and the viewpoint of the stability of quality.As wet type stretching method, can enumerate the method that PVA based polymer film is stretched at pure water, the aqueous solution that contains the various compositions such as additive, aqueous medium or in being dispersed with the aqueous dispersions of various compositions, as the object lesson of uniaxial extension method that adopts wet type stretching method, can be set forth in the warm water that contains boric acid, carry out the method for uniaxial extension, in the solution that contains aforementioned dyestuff or fixing processing described later carry out the method etc. of uniaxial extension in bathing.In addition, also can use the PVA based polymer film after water suction in air, to carry out uniaxial extension, can also carry out uniaxial extension by additive method.
Draft temperature when uniaxial extension is not particularly limited, and preferably adopts 20～90 DEG C in the time that wet type stretches, and more preferably 25～70 DEG C, the further preferred temperature within the scope of 30～65 DEG C preferably adopts the temperature within the scope of 50～180 DEG C in the time of xeothermic stretching.
For the stretching ratio (stretching ratio as adding up in the time carrying out uniaxial extension taking multistage) of uniaxial extension processing, consider from the viewpoint of polarization property, preferably be stretched to as much as possible by before cutting off film, particularly, be preferably more than 4 times, more preferably more than 5 times, more preferably more than 5.5 times.For the upper limit of stretching ratio, as long as film does not rupture, to be just not particularly limited, and in order stretching uniformly, to be preferably below 8.0 times.
In the time manufacturing polarizing coating, in order to make the absorption on the film of dyestuff after uniaxial extension firm, be mostly fixed processing.The general extensive employing of fixing processing is the method in the processing that is added with boric acid and/or boron compound is bathed by film immersion.Now, can in bathing, processing add iodine compound as required.
Then, preferably to having carried out, uniaxial extension is processed or uniaxial extension is processed and the fixing film of processing carries out drying treatment (thermal treatment).The temperature of drying treatment (thermal treatment) is preferably 30～150 DEG C, is particularly preferably 50～140 DEG C.If the temperature of drying treatment (thermal treatment) is too low, the dimensional stability of the polarizing coating of gained easily reduces, and on the other hand, if too high, easily follow the decomposition etc. of dyestuff and the reduction of polarization property occurs.
According to PVA based polymer film of the present invention, the absorbancy that can manufacture long wavelength region is high, be difficult to produce the polarizing coating of red stain.As the index of absorbancy in long wavelength region that represents polarizing coating, can adopt and in the time of specific transmissivity, measure the absorbancy under wavelength 700nm.The polarizing coating of being manufactured by PVA based polymer film of the present invention is preferably more than 3.0 in the absorbancy (Abs) of measuring under wavelength 700nm in the time that transmissivity is 43.5%, is particularly preferably more than 3.1.This absorbancy (Abs) can be obtained by the method for describing in embodiment below.
Fit in the two sides of the polarizing coating obtaining as mentioned above or one side optical clear and have the protective membrane of physical strength, can form polarization plates.As protective membrane at this moment, use cellulose triacetate (TAC) film, cellulose acetate butyrate (CAB) film, vinylformic acid mesentery, polyester mesentery etc.In addition, as the caking agent for the protective membrane of fitting, generally using PVA is caking agent, urethane adhesive etc., and wherein preferably using PVA is caking agent.
The polarization plates obtaining as mentioned above can fit in glass substrate after the caking agents such as coating acrylic acid series, uses as the parts of LCD device.When polarization plates is fitted in to glass substrate, the phase retardation film of can simultaneously fitting, viewing-angle increasing film, brightness improve film etc.
Embodiment
Below, be described more specifically the present invention by embodiment, but the present invention is not subject to any restriction of following examples.
In following embodiment and comparative example, the surface temperature of the volatile component ratio of masking stoste, volatile component ratio, dryer roll and the Heat treating roll of film, PVA based polymer film crystallization long period, crystallization thickness and amorphous thickness, the length of delay of PVA based polymer film, the quality swelling capacity of PVA based polymer film and the optical property of polarizing coating in water measured by the following method.
(1) the volatile component ratio of masking stoste
The masking stoste of getting about 10g in the thermally resistant container of glass system, thermally resistant container is airtight, measures the quality Wa(g except the masking stoste of unlap) to after radix point 4.Then, this masking stoste is put into together with thermally resistant container in the electric air drier of 105 DEG C of temperature, under the state of opening thermally resistant container lid dry 16 hours, is then measured the quality Wb(g except the masking stoste of unlap) to after radix point 4.By quality Wa and the Wb of gained, obtain the volatile component ratio (quality %) of masking stoste by above-mentioned formula (III).
(2) the volatile component ratio of film
For between the roller of adjacency (between the first dryer roll and the second dryer roll, or between final dryer roll and Heat treating roll), the approximately 5g membrane sample cutting from width (TD) central part of the film by between roller, or from the approximately 5g membrane sample of width (TD) the central part cutting of the PVA film of gained, they are put in the thermally resistant container of glass system airtight, measure the quality Wc(g except the film of unlap) to after radix point 4.Then, this film is put in temperature 50 C, Vacuumdrier below pressure 0.1kPa together with thermally resistant container, under the state of opening thermally resistant container lid dry 4 hours, is then measured the quality Wd(g except the film of unlap) to after radix point 4.By quality Wc and the Wd of gained, obtain the volatile component ratio V(quality % of film by above-mentioned formula (IV)).
(3) surface temperature of dryer roll and Heat treating roll
On the width of dryer roll or Heat treating roll, set 5 measuring points.Particularly, using the position of width central authorities as central measuring point, get respectively 2 points in its both sides with the interval of 10cm, 5 measuring points are arranged on straight line altogether.Then, use contactless land surface pyrometer measure the roll surface temperature of each point (DEG C) to after radix point 1.Surface temperature using the mean value of the roll surface temperature of each point as each dryer roll or Heat treating roll.
(4) crystallization long period, crystallization thickness and the amorphous thickness of PVA based polymer film in water
In the present invention, with reference to above-mentioned document, being immersed in, sample under the state in water, obtains crystallization long period, crystallization thickness and amorphous thickness.Herein, the following institute of crystallization long period, crystallization thickness (thickness of crystallization unit) and amorphous thickness (thickness of amorphous portion) is described in detail, by related function K(z) derive.It should be noted that related function K(z) be to give by the scattering function being obtained by small angle X ray scattering method is carried out to Fourier transform, and define as formula V.　
K（z）∝∫[0→∞]{q2·I（q）·cos（qz）}·dq （V）。
Crystallization long period, crystallization thickness and the amorphous thickness of the central part of width (TD) of obtaining the PVA film obtaining by the method shown in the project of following " assay method of " 1 " crystal structure " and " analytical method of " 2 " crystal structure " in following embodiment or comparative example in water.It should be noted that, consider the deviation of mensuration, 5 places different from the position of flow direction (MD) in the central part of the width (TD) of PVA film, obtain crystallization long period, crystallization thickness and amorphous thickness, by for crystallization long period, crystallization thickness and amorphous thickness respectively 5 values of gained average, using the mean value of the gained crystallization long period in water, crystallization thickness in water and the amorphous thickness in water as this PVA film respectively.
" 1 " assay method of crystal structure:
Width (TD) the central part cutting multi-disc MD(flow direction of the PVA film obtaining from following embodiment or comparative example) sample film of × TD=2cm × 1cm size.This sample film is reached to about 1mm so that equidirectional is overlapping to thickness, and make not enter between it bubble, then flood 24 hours in the mass ratio of 22 DEG C is about the distilled water of 1000 times.Mode taking MD as vertical direction is tucked into this sample in the box of measuring use in water, uses nano level x-ray structure evaluating apparatus (small angle X ray scattering determinator) " Nano Viewer " (Rigaku of Co., Ltd. system) to implement transmission measurement.
It should be noted that, the structure of box be used thickness be the Kapton film of 7.5 μ m as the window material of incident light side and reflected light side, the interval between window material is made as to about 1.5mm, and can by measure sample airtight in water.If use this box, can sample be placed in water with the configuration of conventional determining in said apparatus.
[condition determination]
X ray: CuK α line
Wavelength: 0.15418nm
Output: 40kv-20mA
The 1st slit: φ 0.4mm
The 2nd slit: φ 0.2mm
The 3rd slit: φ 0.45mm
Detector: imaging plate size: 127mm × 127mm
Pixel Dimensions: 50 μ m × 50 μ m
Camera length: 960mm
The X ray time shutter: 2 hours
Envrionment temperature: 22 DEG C.
" 2 " analytical method of crystal structure:
First, from each determination data, deduct the dark noise being produced by the dark current of detector.The mensuration of dark noise data be with the identical configuration of mensuration of sample, do not carry out x-ray bombardment and obtain.
In addition, in the mensuration of small angle X ray scattering method, the scattering producing by the air of part and the water of box inside due to the devices such as slit, X ray and the scattering of PVA film are overlapping, therefore need these scatterings to revise as a setting, therefore the present invention is in the scattering strength of mensuration sample gained, calculate in addition the scattering strength producing because of above-mentioned situation, and from measure the scattering strength of sample gained, deduct and revise.
Further, by the scattering strength image that uses two-dimensional detector to measure, will carry out integration to azimuth direction with respect to the scattering strength of scattering vector q, derive scattering vector q and scattering strength I(q) the relation of one-dimensional profile, obtain dispersion curve.It should be noted that, be 2nm for q -1the scattering strength in above region, carries out matching with the method for least squares of utilizing constant c, and the constant c obtaining is deducted from scattering strength as baseline.In addition, be to obtain related function K(z owing to using constant c revised data deviation) principal element of time error, therefore use the least square fitting of Gaussian function.Use the dispersion curve so obtaining, and pass through Fourier transform and derive related function K(z).
Using the related function K(z deriving as mentioned above) the z coordinate figure of maximal point as crystallization long period.In addition, by by by related function K(z) the straight line of slope 0 of minimal point be defined as crystallization thickness with the value calculating at the intersection point of the z straight line approximate compared with zonule.Particularly, in the present invention, obtain by related function K(z) minimal point slope 0 straight line be 1.0～2.5nm for z scope is used method of least squares pair correlation function K(z) carry out the intersection point of approximate straight line, using the z coordinate figure of this intersection point as crystallization thickness.Further, calculate by crystallization long period and deduct value that crystallization thickness obtains as amorphous thickness.
(5) length of delay of PVA based polymer film
" KOBRA-WFD " (prince's instrumentation machine Co., Ltd. system of use, measure wavelength 590nm) for the PVA film obtaining in following embodiment or comparative example, on width, on whole width, measure length of delay with 50mm spacing, the length of delay using its mean value as PVA film.
(6) the quality swelling capacity of PVA based polymer film
The PVA film that cutting obtains in following examples or comparative example, make it be about 1.5g, and it is flooded 30 minutes in the distilled water 1000g of 30 DEG C, flood and take out PVA film after 30 minutes, draw after surperficial water with filter paper, measure its quality We(g) to after radix point 4.Then, in the drying machine of 105 DEG C, by dry this PVA film 16 hours, then measure its quality Wf(g) to after radix point 4.By quality We and the Wf of gained, obtain the quality swelling capacity of PVA film by above-mentioned formula (VI).　
Quality swelling capacity (%)=(We/Wf) × 100 (VI).
(7) optical property of polarizing coating
(i) degree of polarization when transmissivity is 43.5%
As described in following embodiment and comparative example, in each embodiment or comparative example, 5 kinds of polarizing coatings having manufactured having changed the iodine concentration in the iodine/potassiumiodide/boric acid aqueous solution of 2nd stage while stretching respectively, use following method to obtain monomer transmissivity (Y) and degree of polarization (P), for each embodiment or comparative example, taking monomer transmissivity (Y) as transverse axis, taking degree of polarization (P) as the longitudinal axis, by 5 point-renderings on figure, make curve of approximation, obtained the value of the degree of polarization (P) in the time that monomer transmissivity (Y) is 43.5% by this curve of approximation, set it as " degree of polarization when transmissivity is 43.5% ".
" 1 " assay method of monomer transmissivity (Y):
From the central part of the width of polarizing coating, take the draw direction of 2 4cm(uniaxial extensions) × 4cm(is vertical direction with respect to the draw direction of uniaxial extension) square sample.For these samples, use the spectrophotometer " V-7100 " of Japan Spectroscopy Corporation's system, measure its optical transmittance.It should be noted that the measuring method based on JIS Z 8722(object color in the time measuring), use illuminant-C, carry out the visual sense degree correction of the visible region in the 2 degree visuals field.For 1 sample, measure with respect to the draw direction of uniaxial extension+45 optical transmission rates while spending that tilt, and with respect to the draw direction of uniaxial extension-45 optical transmission rates while spending that tilt, obtain their mean value (Y 1) (%).For another sheet sample, the optical transmission rate when similarly measuring+45 optical transmission rates while spending and inclination-45 and spending, obtains their mean value (Y 2) (%).Then, in order to following formula (VII) to the Y obtaining 1and Y 2average, and the monomer transmissivity (Y) that sets it as this polarizing coating (%).　
Monomer transmissivity (Y) (%)=(Y 1+ Y 2)/2 (VII).
" 2 " assay method of degree of polarization (P):
By 2 samples taking in above-mentioned " assay method of " 1 " monomer transmissivity (Y) ", the parallel mode of draw direction of uniaxial extension with them is piled up, (%), the optical transmission rate (Y ⊥) when the mode vertical with the draw direction of the uniaxial extension with them is piled up (%) to measure at this moment optical transmission rate (Y ∥).For transmissivity (Y ∥) and (Y ⊥), with above-mentioned " assay method of " 1 " monomer transmissivity (Y) " similarly, obtain as the tilt mean value of+45 optical transmission rates while spending and the inclination-45 optical transmission rate while spending of the draw direction of the uniaxial extension with respect to the opposing party's sample.By transmissivity (Y ∥) and (Y ⊥), the degree of polarization (P) based on obtain this polarizing coating with following formula (VIII) (%).　
Degree of polarization (P) (%)={ (Y ∥-Y ⊥)/(Y ∥+Y ⊥) } 1/2× 100 (VIII).
(ii) the absorbancy (Abs) when transmissivity is 43.5% under mensuration wavelength 700nm
First, described in embodiment described as follows and comparative example, in each embodiment or comparative example, 5 kinds of polarizing coatings (monomer transmissivity (Y) is all in 42～44% scope) of having manufactured having changed the iodine concentration in the iodine/potassiumiodide/boric acid aqueous solution of 2nd stage while stretching respectively, the absorbancy (Abs) of obtaining under mensuration wavelength 700nm as described below.That is to say, Glan-Taylor prism is arranged on the spectrophotometer " V-7100 " of Japan Spectroscopy Corporation's system, and the sample that 1 polarizing coating is set on the position vertical with optical axis is (in above-mentioned " assay method of degree of polarization " 1 " the monomer transmissivity (Y) when (i) transmissivity is 43.5% ", in 2 samples taking for each polarizing coating any 1), the optical transmission rate of the wavelength 700nm of the light of measuring the mensuration wavelength 380～780nm that becomes rectilinearly polarized light from light source by prism in the time seeing through above-mentioned sample.At this moment, above-mentioned sample is rotated in the plane vertical with optical axis, measures transmission change, obtain the maximum of T of transmissivity 0minimum value T with transmissivity 90, and by calculating this polarizing coating with following formula (IX) at the vertical transmissivity Tc measuring under wavelength 700nm.　
Tc=T 0× T90/100 （IX）。
Then, use this vertical transmissivity Tc, by calculating this polarizing coating with following formula (X) in the absorbancy (Abs) of measuring under wavelength 700nm.　
Abs=2－logTc （X）。
Then, by the result of the absorbancy (Abs) under above-mentioned " assay method of degree of polarization " 1 " the monomer transmissivity (Y) when (i) transmissivity is 43.5% " and mensuration wavelength 700nm, using the monomer transmissivity (Y) of polarizing coating as transverse axis, to measure absorbancy (Abs) under wavelength 700nm as the longitudinal axis, by 5 point-renderings corresponding to above-mentioned 5 kinds of polarizing coatings on figure, make curve of approximation, when the monomer transmissivity (Y) of obtaining polarizing coating by this curve of approximation is 43.5% in the absorbancy (A) of measuring under wavelength 700nm, set it as " absorbancy (Abs) when transmissivity is 43.5% under mensuration wavelength 700nm ".
" embodiment 1 "
(1) manufacture of PVA based polymer film
(i) being that 99.9 % by mole, the polymerization degree are 2400 by the PVA(saponification deg by by polyvinyl acetate saponification is obtained) the volatile component ratio made of 100 mass parts, glycerine 12 mass parts, lauric acid diethyl amide 0.1 mass parts and water is that the masking stoste of 66 quality % spues to the first dryer roll (surface temperature (T of film forming apparatus that possesses turning axle multiple dryer rolls parallel to each other and Heat treating roll with membranaceous from T-shaped mould 1) be 70 DEG C, weekly (S 1) be 5.0m/ minute) upper, on the first dryer roll, whole the first dryer roll noncontact face is sprayed to the hot blast of 90 DEG C with the wind speed of 5m/ second on one side, be dried to volatile component ratio (V on one side 1) reach 20 quality %, then, peel off the mode alternately contacting with each dryer roll with the back side with the surface of the arbitrary portion of film from the first dryer roll, further dry to being next between the final dryer roll of Heat treating roll at the second dryer roll, then peel off from final dryer roll.At this moment, the mean value (T of the surface temperature of the each dryer roll from the second dryer roll to final dryer roll 2) be 61 DEG C.Volatile component ratio (the V of the film while peeling off from final dryer roll in addition, 2) be 8 quality %.Finally, after heat-treating with the Heat treating roll that surface temperature is 105 DEG C, batch as roller shape, obtain PVA film (thickness is that 75 μ m, width are that 3.3m, volatile component ratio are 3 quality %).
In this embodiment 1, by the peripheral speed (S of the second dryer roll 2) with respect to the peripheral speed (S of the first dryer roll 1) ratio (S 2/ S 1) be set as 1.025, by the peripheral speed (S of final dryer roll l) with respect to the peripheral speed (S of the first dryer roll 1) ratio (S l/ S 1) be set as 0.982.In addition the T in above-mentioned formula (I), 1 → 2be calculated as 67.Above-mentioned film forming condition is summarized in following table 1.
(ii) measure crystallization long period, crystallization thickness and the amorphous thickness of the above-mentioned PVA film obtaining in (i) in water by aforesaid method; Length of delay and quality swelling capacity, result as described in Table 2.
(2) manufacture of polarizing coating
(i) the central part of the width (TD) of the PVA film obtaining from above-mentioned (1) is taked the test film of flow direction (MD) × width (TD)=10cm × 12cm, stretching clamp is fixed on in the two ends of the flow direction of this test film, make stretched portion be of a size of flow direction (MD) × width (TD)=6cm × 12cm, in the water of 30 DEG C of temperature, flood, go up 1.5 times to raw footage of uniaxial extension (first stage stretching) with the draw speed of 12cm/ minute at flow direction (MD) during this period, then containing iodine with the concentration of 0.028 quality %, in iodine/potassiumiodide/boric acid aqueous solution that the temperature that contains potassiumiodide and contain boric acid with the concentration of 1 quality % with the concentration of 1 quality % is 30 DEG C, flood, go up 2.25 times to raw footage of uniaxial extension (subordinate phase stretching) with the draw speed of 12cm/ minute at flow direction (MD) during this period, then, in the boric acid/potassium iodide aqueous solution of 53 DEG C of the temperature that contains boric acid with the concentration of 4 quality % and contain potassiumiodide with the concentration of 4 quality %, flood, go up 5.8 times to raw footage of uniaxial extension (phase III stretching) with the draw speed of 12cm/ minute at flow direction (MD) during this period, then in the drying machine of 60 DEG C, be dried 4 minutes, manufacture polarizing coating.
Above-mentioned (i) in, iodine concentration in iodine/potassiumiodide/boric acid aqueous solution that temperature when subordinate phase is stretched is 30 DEG C is changed into 0.03 quality % from 0.028 quality %, in addition, carry out and above-mentioned (i) same operation, manufacture the polarizing coating of [draw speed of each draw stage all with the above-mentioned 12cm/ minute that is (i) similarly].
Above-mentioned (i) in, iodine concentration in iodine/potassiumiodide/boric acid aqueous solution that temperature when subordinate phase is stretched is 30 DEG C is changed into 0.032 quality % from 0.028 quality %, in addition, carry out and above-mentioned (i) same operation, make the polarizing coating of [draw speed of each draw stage all with the above-mentioned 12cm/ minute that is (i) similarly].
Above-mentioned (i) in, iodine concentration in iodine/potassiumiodide/boric acid aqueous solution that temperature when subordinate phase is stretched is 30 DEG C is changed into 0.034 quality % from 0.028 quality %, in addition, carry out and above-mentioned (i) same operation, make the polarizing coating of [draw speed of each draw stage all with the above-mentioned 12cm/ minute that is (i) similarly].
Above-mentioned (i) in, iodine concentration in iodine/potassiumiodide/boric acid aqueous solution that temperature when subordinate phase is stretched is 30 DEG C is changed into 0.036 quality % from 0.028 quality %, in addition, carry out and above-mentioned (i) same operation, make the polarizing coating of [draw speed of each draw stage all with the above-mentioned 12cm/ minute that is (i) similarly].
(vi) use (i) above-mentioned～5 kinds of polarizing coatings manufacturing in (v), measure this degree of polarization by the method for recording in when (i) transmissivity is 43.5% " optical property of (7) polarizing coating degree of polarization " project, result is 99.9%.In addition, measure this absorbancy (Abs) by the method for recording in " optical property of (7) polarizing coating when (ii) transmissivity is 43.5% in the absorbancy (Abs) of measuring under wavelength 700nm " project, result is 3.2.These the results are shown in following table 2.
" embodiment 2～7 "
In embodiment 1, as described in following table 1, change the film forming condition while manufacturing PVA film, similarly manufacture PVA film and polarizing coating with embodiment 1 (1) and (2).
Use the polarizing coating of manufacturing, the aforesaid method of recording in the projects by when (i) transmissivity is 43.5% " optical property of (7) polarizing coating degree of polarization " and " optical property of (7) polarizing coating is the absorbancy (Abs) under mensuration wavelength 700nm when (ii) transmissivity is 43.5% " is measured this degree of polarization and absorbancy (Abs).The results are shown in following table 2.
" comparative example 1～6 "
In embodiment 1, as described in following table 1, change the film forming condition while manufacturing PVA film, similarly manufacture PVA film and polarizing coating with embodiment 1 (1) and (2).
Use the polarizing coating of manufacturing, the aforesaid method of recording in the projects by when (i) transmissivity is 43.5% " optical property of (7) polarizing coating degree of polarization " and " optical property of (7) polarizing coating is the absorbancy (Abs) under mensuration wavelength 700nm when (ii) transmissivity is 43.5% " is measured this degree of polarization and absorbancy (Abs).The results are shown in following table 2.
" comparative example 7 "
In embodiment 1, as described in following table 1, change the film forming condition while manufacturing PVA film, result is underdry on the first dryer roll, cannot be from the first dryer roll stripping film, film fracture.The volatile component ratio of measuring the film of fracture, result is 31 quality %.
utilizability in industry
PVA based polymer film of the present invention, crystallization long period in water is 14.5～16.0nm, and in the time using this PVA based polymer film as raw material, the absorbancy that can manufacture long wavelength region is high, and the polarizing coating that degree of polarization is high, therefore this PVA based polymer film is exceedingly useful as the initial film for the manufacture of polarizing coating (former anti-Off ィ Le system), and manufacture method of the present invention is as being useful for the method for successfully manufacturing continuously PVA based polymer film of the present invention.

Claims (3)

1. a vinol series polymer film, is characterized in that, the crystallization long period in water is 14.5～16.0nm.
2. the manufacture method of a vinol series polymer film, wherein, possess turning axle multiple dryer rolls parallel to each other and the film forming apparatus of Heat treating roll in use, the masking stoste that contains vinol series polymer is dried to the first dryer roll of this film forming apparatus with membranaceous spuing, then further dry and during by vinol series polymer masking, with the T shown in following formula (I) with dryer roll 1 → 2the mode that meets following formula (II) is dried,
T 1→2={T 1×（40－V 1）+T 2×（V 1－V 2）}/（40－V 2） （I）
60≤T 1→2≤75 （II）
Herein, T 1represent the first dryer roll surface temperature (DEG C), V 1the volatile component ratio (quality %) of film while representing to peel off from the first dryer roll, T 2represent from the second dryer roll to be next to Heat treating roll final dryer roll each dryer roll surface temperature mean value (DEG C), V 2the volatile component ratio (quality %) of film when expression is peeled off from being next to the final dryer roll of Heat treating roll,
Wherein, V 1be 10～30(quality %).
3. a polarizing coating of being manufactured by vinol series polymer film claimed in claim 1.
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