CN105431751A - Vinyl-alcohol-based polymer film - Google Patents

Vinyl-alcohol-based polymer film Download PDF

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Publication number
CN105431751A
CN105431751A CN201480042973.XA CN201480042973A CN105431751A CN 105431751 A CN105431751 A CN 105431751A CN 201480042973 A CN201480042973 A CN 201480042973A CN 105431751 A CN105431751 A CN 105431751A
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vinyl alcohol
structural unit
alcohol system
system polymer
pva
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CN105431751B (en
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高藤胜启
矶崎孝德
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Kuraray Co Ltd
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Kuraray Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—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
    • C08F216/02—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 by an alcohol radical
    • C08F216/04—Acyclic compounds
    • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F218/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polarising Elements (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

[Problem] To provide a PVA film whereby an optical film having excellent optical characteristics, hue, and durability can easily be manufactured, and to provide a method for manufacturing an optical film using the PVA film. [Solution] A PVA film in which the ratio of the sum of the crystal component amount (a1) and the restricted amorphous component amount (a2) with respect to the sum of the crystal component amount (a1), the restricted amorphous component amount (a2), and the amorphous component amount (a3) is 10-32% when the crystal component amount (a1), the restricted amorphous component amount (a2), and the amorphous component amount (a3) are calculated from the spin-spin relaxation time (T)2 obtained by pulse NMR measurement (observed nucleus: 1H) after one hour of treatment at 60 DEG C; and a method for manufacturing an optical film using the PVA film, the method having a uniaxial drawing step.

Description

Vinyl alcohol system polymer film
Technical field
The present invention relates to the manufacture method of the blooming such as useful vinyl alcohol system polymer film and the light polarizing film employing this vinyl alcohol system polymer film as the initial film (former anti-Off ィ Le system) for the manufacture of blooming.
Background technology
The polarization plates with printing opacity and shade function with for changing the basic constituent element that the liquid crystal of polarisation of light light state is all liquid crystal display (LCD).Multiple polarization plates has the structure being fitted with the diaphragms such as Triafol T (TAC) film on the surface of light polarizing film; as light polarizing film, make matrix absorption iodine system pigment (I vinyl alcohol system polymer film (sometimes " vinyl alcohol system polymer " being called " PVA " below) being carried out uniaxial tension 3 -, I 5 -deng), the bitintability pigment of bitintability organic dyestuff and so on and the light polarizing film obtained becomes main flow.
The scope that the gauging instrument etc. that LCD is applied to the miniature instrument such as counter and appearance gradually, mobile phone, notebook computer, liquid crystal display, color liquid crystal projector, LCD TV, vehicle-mounted navigational system, indoor and outdoor use is vast, in recent years, the advanced of display quality is especially required.Accompany therewith, also high performance is required to light polarizing film, specifically, require that degree of polarization, transmission are high, optical characteristics is excellent and the also excellent light polarizing film of form and aspect, permanance.
But, the known several blooming manufacture initial film comprising the PVA of various structure through changing.Such as it is known that the adsorption treatment excellence of the stretch orientation treatability of the initial polyvinyl alcohol film of the light polarizing film formed by the specific PVA of the hydrophilic functional group such as carboxylic acid group, ω-hydroxyl-alpha-alkylene containing 0.01 ~ 1 % by mole and bitintability material (with reference to patent documentation 1).Further it is known that, be included in optical characteristics and stretchability excellence (with reference to patent documentation 2) that side chain contains the particular optical PVA film of the PVA of 1,2-diol bond.And then it is known that film by using the PVA that is 92 ~ 98.5 % by mole by saponification degree to be formed, the dyeing time (reference patent documentation 3) when manufacturing light polarizing film can be shortened.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 8-201626 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2009-24076 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2012-68609 publication.
Summary of the invention
The problem that invention will solve
But, when employing existing known PVA film, from obtaining all excellent blooming this point of optical characteristics, form and aspect and permanance, also there is the leeway of improvement.
Thus, the object of the invention is to, the PVA film that easily can manufacture all excellent blooming of optical characteristics, form and aspect and permanance is provided, and employ the manufacture method of blooming of this PVA film.
For the means of dealing with problems
The present inventor etc. are repeated further investigation to achieve these goals, found that: if the toatl proportion crystallizing into component peace treaty bundle amorphous component amount in PVA film is set to specific scope, then can solve above-mentioned problem, repeat research based on this opinion further, thus complete the present invention.
That is, the present invention relates to following content:
[1] PVA film, wherein, by spin spin relaxation time T 2obtain and crystallize into component (a 1), constraint amorphous component amount (a 2) and amorphous component amount (a 3) time, crystallize into component (a 1) and constraint amorphous component amount (a 2) be aggregated in and crystallize into component (a 1), constraint amorphous component amount (a 2) and amorphous component amount (a 3) total in shared ratio be 10 ~ 32%, described spin spin relaxation time T 2be measure by processing 1 hour laggard horizontal pulse NMR at 60 DEG C (observing nuclear: 1h) obtain;
[2] according to the PVA film of above-mentioned [1], wherein, amorphous component amount (a is retrained 2) crystallizing into component (a 1), constraint amorphous component amount (a 2) and amorphous component amount (a 3) total in shared ratio be more than 5%;
[3] according to the PVA film of above-mentioned [1] or [2], wherein, the PVA comprised in PVA film contains at least a kind of structural unit be selected from the structural unit (1) shown in following formula (1), the structural unit (2) shown in following formula (2) and the structural unit (3) shown in following formula (3), and the containing ratio of structural unit (1) ~ (3) is denoted as n respectively 1~ n 3% by mole, the containing ratio of vinyl ester units is denoted as n 4% by mole time, meet 0.6≤n 1+ n 2+ 2 × n 3+ n 4≤ 1.4;
[changing 1]
[in formula, R 1represent hydrogen atom, methyl or ethyl.]
[changing 2]
[in formula, R 2represent hydrogen atom, methyl or ethyl, X 2represent that the carbon number with more than 1 hydroxyl is the hydroxy alkyl of more than 2.]
[changing 3]
[in formula, X 3and X 4separately represent that the carbon number with more than 1 hydroxyl is the hydroxy alkyl of more than 1.]
[4] according to the PVA film of above-mentioned [3], wherein, the PVA comprised in PVA film contains at least a kind of structural unit be selected from structural unit (1) and structural unit (2);
[5] the PVA film any one of above-mentioned [1] ~ [4], wherein, the PVA comprised in PVA film is not containing the structural unit (3) shown in following formula (3);
[changing 4]
[in formula, X 3and X 4separately represent that the carbon number with more than 1 hydroxyl is the hydroxy alkyl of more than 1.]
[6] the PVA film any one of above-mentioned [1] ~ [5], wherein, the degree of polymerization of the PVA comprised in PVA film is 3, less than 000;
[7] the PVA film any one of above-mentioned [1] ~ [6], wherein, the molecular weight distribution of the PVA comprised in PVA film is 2.0 ~ 4.0;
[8] the PVA film any one of above-mentioned [1] ~ [7], wherein, swellbility is 160 ~ 240%;
[9] the PVA film any one of above-mentioned [1] ~ [8], it is blooming manufacture initial film;
[10] according to the PVA film of above-mentioned [9], it is light polarizing film manufacture initial film;
[11] manufacture method of blooming, the PVA film of its use above-mentioned [9] or [10], this manufacture method possesses the operation of carrying out uniaxial tension.
The effect of invention
According to the present invention, provide the PVA film that easily can manufacture all excellent blooming of optical characteristics, form and aspect and permanance, and employ the manufacture method of blooming of this PVA film.
Embodiment
PVA film of the present invention is by spin spin relaxation time T 2obtain and crystallize into component (a 1), constraint amorphous component amount (a 2) and amorphous component amount (a 3) time, crystallize into component (a 1) and constraint amorphous component amount (a 2) be aggregated in and crystallize into component (a 1), constraint amorphous component amount (a 2) and amorphous component amount (a 3) total in shared ratio be in the scope of 10 ~ 32%, described spin spin relaxation time T 2be by measuring with 60 DEG C of process, 1 hour laggard horizontal pulse NMR (observing nuclear: 1h) obtain.
Be different from the structure of organic compound determine wait in normally used high resolution capacity NMR, PULSED NMR be can measure relevant to the transport properties of molecules in system 1each relaxation time of H core and the analytical approach that there is ratio of its high quantitative each motion composition obtained in system can be utilized.In the present invention, crystallize into component (a in PVA film obtaining 1), constraint amorphous component amount (a 2) and amorphous component amount (a 3) time, use 1the spin spin relaxation time T of H 2.Specifically, with 1the spin spin relaxation time T of H 2mensuration in free induction decay (FID) signal approximation that obtains be applied to the mode of following formula (4), obtain be on the occasion of a 1, a 2, a 3, a 4, c 1, c 2and c 3.This matching (matching, fitting) preferably uses linear least square to carry out.Among each value of gained, a 1be equivalent to above-mentionedly crystallize into component (a 1), a 2be equivalent to above-mentioned constraint amorphous component amount (a 2), a 3be equivalent to above-mentioned amorphous component amount (a 3).As concrete each condition of carrying out when PULSED NMR measures, each condition described later in an embodiment can be adopted respectively.
[mathematical expression 1]
。
When carrying out PULSED NMR and measuring, will the PVA film of determination object be become in advance with 60 DEG C of process 1 hour.By obtain with 60 DEG C process 1 hour after crystallize into component (a 1) and constraint amorphous component amount (a 2) ratio, mentioned component ratio more closely-related with effect of the present invention (permanance etc.) can be obtained.PVA film after this process being undertaken under the state of the PVA film immersion becoming determination object in water, especially directly can be supplied to PULSED NMR and measure by this process, therefore, is preferably undertaken under the state of PVA film immersion in heavy water NMR pipe is medium.As disposal route more specifically and the condition of this process, method described later in an embodiment can be adopted.
PVA film of the present invention is by spin spin relaxation time T 2obtain and crystallize into component (a 1), constraint amorphous component amount (a 2) and amorphous component amount (a 3) time, crystallize into component (a 1) and constraint amorphous component amount (a 2) be aggregated in and crystallize into component (a 1), constraint amorphous component amount (a 2) and amorphous component amount (a 3) total in shared ratio need to be in the scope of 10 ~ 32%, described spin spin relaxation time T 2be by measuring with 60 DEG C of process, 1 hour laggard horizontal pulse NMR (observing nuclear: 1h) obtain.
When this ratio is less than 10%, the permanance of the blooming using this PVA film to obtain can worsen.On the other hand, when this ratio is more than 32%, the form and aspect of the blooming using this PVA film to obtain can reduce.The present invention, not by any restriction, as its reason, can think: the impact caused the state of bitintability pigment used is different etc. because of above-mentioned each composition, can infer that adjustment aforementioned proportion is extremely important for effect of the present invention.From the view point of the form and aspect, permanance etc. of gained blooming, crystallize into component (a 1) and constraint amorphous component amount (a 2) be aggregated in and crystallize into component (a 1), constraint amorphous component amount (a 2) and amorphous component amount (a 3) the ratio shared by total be preferably more than 10.5%, be more preferably more than 11%, in addition, be preferably less than 31.5%, be more preferably less than 31%.
Owing to can improve the permanance etc. of gained blooming further, therefore PVA film preferably has constraint amorphous component, especially, and the constraint amorphous component amount (a in PVA film 2) crystallizing into component (a 1), constraint amorphous component amount (a 2) and amorphous component amount (a 3) total in shared ratio be preferably more than 5%, be more preferably more than 6%.
The kind of the PVA comprised in PVA film is not particularly limited, and crystallizes into component (a owing to can easily obtain 1) and constraint amorphous component amount (a 2) ratio meet the PVA film of above-mentioned scope, therefore preferably, the PVA comprised in PVA film comprises at least a kind of structural unit be selected from the structural unit (1) shown in following formula (1), the structural unit (2) shown in following formula (2) and the structural unit (3) shown in following formula (3), and the containing ratio of structural unit (1) ~ (3) is set to n respectively 1~ n 3% by mole, the containing ratio of vinyl ester units is set to n 4% by mole time, meet 0.6≤n 1+ n 2+ 2 × n 3+ n 4≤ 1.4.
[changing 5]
[in formula, R 1represent hydrogen atom, methyl or ethyl.]。
[changing 6]
[in formula, R 2represent hydrogen atom, methyl or ethyl, X 2represent that the carbon number with more than 1 hydroxyl is the hydroxy alkyl of more than 2.]。
[changing 7]
[in formula, X 3and X 4separately represent that the carbon number with more than 1 hydroxyl is the hydroxy alkyl of more than 1.]。
In structural unit shown in formula (1), R 1represent hydrogen atom, methyl or ethyl.Component (a is crystallized into owing to can more easily obtain 1) and constraint amorphous component amount (a 2) ratio meet the PVA film etc. of above-mentioned scope, therefore R 1be preferably methyl or ethyl, be more preferably methyl.
In structural unit shown in formula (2), R 2represent hydrogen atom, methyl or ethyl.Component (a is crystallized into owing to can more easily obtain 1) and constraint amorphous component amount (a 2) ratio meet the PVA film etc. of above-mentioned scope, therefore R 2be preferably hydrogen atom or methyl.
In structural unit shown in formula (2), X 2represent that the carbon number with more than 1 hydroxyl is the hydroxy alkyl of more than 2.Component (a is crystallized into owing to can more easily obtain 1) and constraint amorphous component amount (a 2) ratio meet the PVA film etc. of above-mentioned scope, therefore the carbon number of this hydroxy alkyl is preferably less than 8, is more preferably less than 6, more preferably less than 4, and in addition, the hydroxyl quantity that this hydroxy alkyl has is preferably 1 or 2.As the concrete example of this hydroxy alkyl, such as 2-hydroxyethyl, 3-hydroxypropyl, 1-hydroxyl-1-Methylethyl, 2-hydroxyl-1-Methylethyl, 4-hydroxybutyl, 2-hydroxy-2-methyl propyl group, 3-hydroxy-2-methyl propyl group, 5-Hydroxy pentyl, 8-hydroxy octyl, 1 can be listed, 2-dihydroxy ethyl, 2,3-dihydroxypropyls etc.Among these, be preferably 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-Hydroxy pentyl, 1,2-dihydroxy ethyl, be more preferably 1,2-dihydroxy ethyl.
In structural unit shown in formula (3), X 3and X 4separately represent that the carbon number with more than 1 hydroxyl is the hydroxy alkyl of more than 1.Component (a is crystallized into owing to can more easily obtain 1) and constraint amorphous component amount (a 2) ratio meet the PVA film etc. of above-mentioned scope, therefore, the carbon number of this hydroxy alkyl is preferably less than 8, is more preferably less than 6, more preferably less than 4, in addition, the hydroxyl quantity that this hydroxy alkyl has is also different because of the carbon number of this hydroxy alkyl, is preferably 1 or 2.As the concrete example of this hydroxy alkyl, such as methylol, 2-hydroxyethyl, 3-hydroxypropyl, 1-hydroxyl-1-Methylethyl, 2-hydroxyl-1-Methylethyl, 4-hydroxybutyl, 2-hydroxy-2-methyl propyl group, 3-hydroxy-2-methyl propyl group, 8-hydroxy octyl, 1 can be listed, 2-dihydroxy ethyl, 2,3-dihydroxypropyls etc.Among these, be preferably methylol, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 1,2-dihydroxy ethyl, be more preferably methylol.X 3and X 4be same to each other or different to each other, preferably identical.
As above-mentioned illustrative PVA, can list such as: comprise structural unit (1) and not containing the PVA of structural unit (2) and (3); Comprise structural unit (2) and not containing the PVA of structural unit (1) and (3); Comprise structural unit (3) and not containing the PVA of structural unit (1) and (2); Comprise structural unit (1) and (2) and not containing the PVA of structural unit (3); Comprise structural unit (1) and (3) and not containing the PVA of structural unit (2); Comprise structural unit (2) and (3) and not containing the PVA of structural unit (1); The PVA etc. that structural unit (1) ~ (3) all comprise, when considering ease of manufacture etc., is preferably: comprise structural unit (1) and not containing the PVA of structural unit (2) and (3); Comprise structural unit (2) and not containing the PVA of structural unit (1) and (3); Or, comprise structural unit (3) and not containing the PVA of structural unit (1) and (2).
In addition, from the view point of raw material availability etc., the PVA comprised in PVA film is not preferably containing structural unit (3).From this point of view, as above-mentioned illustrative PVA, be preferably: comprise structural unit (1) and not containing the PVA of structural unit (2) and (3); Comprise structural unit (2) and not containing the PVA of structural unit (1) and (3); Or, comprise structural unit (1) and (2) and not containing the PVA of structural unit (3).
In addition, above-mentioned illustrative PVA comprises or does not comprise vinyl ester units, when considering ease of manufacture etc., preferably comprises vinyl ester units.As this vinyl ester units, typical case, can list aftermentioned like that, the structural unit that is derived from the vinyl acetate system monomer for the manufacture of PVA.
In above-mentioned illustrative PVA, the containing ratio of structural unit (1) ~ (3) is denoted as n respectively 1~ n 3% by mole, the containing ratio of vinyl ester units is denoted as n 4% by mole time, meet 0.6≤n 1+ n 2+ 2 × n 3+ n 4≤ 1.4.By making n 1+ n 2+ 2 × n 3+ n 4value be more than 0.6 % by mole, use the PVA film comprising this PVA and the form and aspect of blooming obtained improve.On the other hand, by making n 1+ n 2+ 2 × n 3+ n 4value be less than 1.4 % by mole, use the PVA film comprising this PVA and the permanance of blooming obtained improves.From the view point of the form and aspect, permanance etc. of gained blooming, n 1+ n 2+ 2 × n 3+ n 4value be preferably more than 0.63 % by mole, be more preferably more than 0.65 % by mole, in addition, be more preferably less than 1.38 % by mole, more preferably less than 1.35 % by mole.It should be noted that, in this instructions, structural unit refers to the repetitive forming polymkeric substance, the containing ratio of structural unit (1) ~ (3) refer to the molal quantity of structural unit (1) ~ (3) respectively relative to the entire infrastructure unit forming PVA molal quantity shared by ratio, the containing ratio of vinyl ester units refer to the molal quantity of vinyl ester units relative to the entire infrastructure unit forming PVA molal quantity shared by ratio.
In above-mentioned illustrative PVA, as long as the containing ratio n of vinyl ester units 1+ n 2+ 2 × n 3+ n 4value be in above-mentioned scope, be just not particularly limited, consider more easily obtain crystallize into component (a 1) and constraint amorphous component amount (a 2) ratio when meeting the PVA film, ease of manufacture etc. of above-mentioned scope, be preferably less than 1.35 % by mole, be more preferably less than 1.3 % by mole, more preferably less than 1 % by mole, less than 0.5 % by mole and then can be less than 0.3 % by mole, in addition, be preferably more than 0.01 % by mole, be more preferably more than 0.05 % by mole, more preferably more than 0.1 % by mole.
The manufacture method of above-mentioned illustrative PVA is not particularly limited.Such as following method can be listed: by vinyl acetate system monomer with can with its copolymerization and the unsaturated monomer that can convert at least a kind of structural unit be selected from structural unit (1) ~ (3) to carries out copolymerization, convert the vinyl ester units of gained vinyl acetate based copolymer to vinyl alcohol units, and then convert the structural unit being derived from the unsaturated monomer that can convert at least a kind of structural unit be selected from structural unit (1) ~ (3) to the method for at least a kind of structural unit be selected from structural unit (1) ~ (3) to.As the unsaturated monomer that can convert structural unit (1) to, the such as unsaturated monomer shown in following formula (5) can be listed.As the unsaturated monomer that can convert structural unit (2) to, the such as unsaturated monomer shown in following formula (6) can be listed.As the unsaturated monomer that can convert structural unit (3) to, the such as unsaturated monomer shown in following formula (7) can be listed.
[changing 8]
[in formula, R 1represent hydrogen atom, methyl or ethyl, Y 1represent methylol (ヒ De ロ メ チ Le base) or there is the group of structure of the protected base protection of hydroxyl contained by this methylol.]。
[changing 9]
[in formula, R 2represent hydrogen atom, methyl or ethyl, Y 2represent the group of the structure that there is hydroxy alkyl that the carbon number of more than 1 hydroxyl is more than 2 or there is the protected base protection of hydroxyl contained by this hydroxy alkyl.]。
[changing 10]
[in formula, Y 3and Y 4separately represent the group of the structure that there is hydroxy alkyl that the carbon number of more than 1 hydroxyl is more than 1 or there is the protected base protection of hydroxyl contained by this hydroxy alkyl.]。
In formula (5), R 1related description and formula (1) in R 1identical, omit herein and repeat to record.
In formula (5), Y 1when representing the group of the structure of the protected base protection of hydroxyl had contained by methylol, as this protecting group, the acyl group such as acetyl group, propiono can be listed; Acetal radical; Carbonate groups etc., among these, owing to can remove this protecting group when vinyl ester units being converted to vinyl alcohol units, being therefore preferably acyl group, being more preferably acetyl group.Because above-mentioned illustrative PVA easily manufactures, therefore Y 1preferably there is the group of the structure of the protected base protection of hydroxyl contained by methylol.
In formula (6), R 2related description and formula (2) in R 2identical, omit herein and repeat to record.
In formula (6), Y 2the carbon number with more than 1 hydroxyl represented is the X in the related description of the hydroxy alkyl of more than 2 and formula (2) 2the carbon number with more than 1 hydroxyl represented is the related description of the hydroxy alkyl of more than 2 is identical, omits herein and repeats to record.In addition, Y 2when representing the group of the structure of the protected base protection of hydroxyl had contained by above-mentioned hydroxy alkyl, as this protecting group, the acyl group such as acetyl group, propiono can be listed; The acetal radicals such as isopropylidene; Carbonate groups etc., among these, owing to can remove this protecting group when vinyl ester units being converted to vinyl alcohol units, being therefore preferably acyl group, being more preferably acetyl group.Y 2when representing the group of the structure of the protected base protection of hydroxyl had contained by above-mentioned hydroxy alkyl; as its concrete example; such as 2-Acetoxvethyl, 3-acetyloxypropyl, 1-acetoxyl group-1-Methylethyl, 2-acetoxyl group-1-Methylethyl, 4-Acetoxybutyl, 2-acetoxyl group-2-methyl-propyl, 3-acetoxyl group-2-methyl-propyl, 8-acetoxyl group octyl group, 1 can be listed; 2-diacetoxy ethyl, 2,3-diacetoxy propyl group etc.Because above-mentioned illustrative PVA easily manufactures, therefore Y 2preferably there is the group of following structure, described structure be have the protected base of hydroxyl that hydroxy alkyl that the carbon number of more than 1 hydroxyl is more than 2 has protection and obtain.
As the unsaturated monomer shown in formula (6), such as 4-acetoxyl group-1-butylene, 5-acetoxyl group-1-amylene, 6-acetoxyl group-1-hexene, 7-acetoxyl group-1-heptene, 3 can be listed, 4-diacetoxy-1-butylene etc., are preferably 3,4-diacetoxy-1-butylene.
In formula (7), Y 3and/or Y 4the carbon number with more than 1 hydroxyl represented is the X in the related description of the hydroxy alkyl of more than 1 and formula (3) 3and/or X 4the carbon number with more than 1 hydroxyl represented is the related description of the hydroxy alkyl of more than 1 is identical, omits herein and repeats to record.In addition, Y 3and/or Y 4when representing the group of the structure of the protected base protection of hydroxyl had contained by above-mentioned hydroxy alkyl, as this protecting group, the acyl group such as acetyl group, propiono can be listed; The acetal radicals such as isopropylidene; Carbonate groups etc., among these, owing to can remove this protecting group when vinyl ester units being converted to vinyl alcohol units, being therefore preferably acyl group, being more preferably acetyl group.Y 3and/or Y 4when representing the group of the structure of the protected base protection of hydroxyl had contained by above-mentioned hydroxy alkyl; as its concrete example; such as acetoxy-methyl, 2-Acetoxvethyl, 3-acetyloxypropyl, 1-acetoxyl group-1-Methylethyl, 2-acetoxyl group-1-Methylethyl, 4-Acetoxybutyl, 2-acetoxyl group-2-methyl-propyl, 3-acetoxyl group-2-methyl-propyl, 8-acetoxyl group octyl group, 1 can be listed; 2-diacetoxy ethyl, 2,3-diacetoxy propyl group etc.Because above-mentioned illustrative PVA easily manufactures, therefore Y 3and/or Y 4preferably have the group of following structure, described structure is that the protected base of the hydroxyl of carbon number contained by the hydroxy alkyl of more than 1 with more than 1 hydroxyl is protected and obtains, it is further preferred that Y 3and Y 4both are the group with following structure, and described structure is that the protected base of the hydroxyl of carbon number contained by the hydroxy alkyl of more than 1 with more than 1 hydroxyl is protected and obtains.
As the unsaturated monomer shown in formula (7), such as 1,3-diacetoxy-2-methylene propane, 1 can be listed, 3-bis-propionyloxy-2-methylene propane, 1,3-bis-butyryl acyloxy-2-methylene propane etc., are preferably 1,3-diacetoxy-2-methylene propane.
Vinyl acetate system monomer for the manufacture of above-mentioned illustrative PVA is not particularly limited, such as vinyl formate, vinyl acetate, propionate, vinyl butyrate, vinyl isobutyrate ester, pivalic acid vinyl acetate, tertiary ethylene carbonate, vinyl caproate, sad vinyl acetate, caprate, vinyl laurate, vinyl palmitate, stearic acid vinyl ester, oleic acid vinyl acetate, vinyl benzoate etc. can be listed, from ease of manufacturing, the viewpoint such as acquisition easiness, cost etc. of PVA, be preferably vinyl acetate.
By vinyl acetate system monomer with can with its copolymerization and the unsaturated monomer that can convert at least a kind of structural unit be selected from structural unit (1) ~ (3) to carries out copolymerization time polymerization methods can be any-mode in batchwise polymerization, semi-batch polymerization, continuous polymerization, semi-continuous polymerization etc., as polymerization, can the known method such as applied ontology polymerization, solution polymerization process, suspension polymerization, emulsion polymerization.Be typically employed in the mass polymerization or the solution polymerization process that advance polymerization in solvent-free or alcohol equal solvent.When obtaining the vinyl acetate based copolymer of high polymerization degree, also preferred emulsion polymerization.The solvent of solution polymerization process is not particularly limited, such as, be alcohol.The alcohol used in the solvent of solution polymerization process is such as the lower alcohols such as methyl alcohol, ethanol, propyl alcohol.Solvent load in polymerization system is considered the chain tra nsfer of solvent according to the targeted degree of polymerization of PVA and is selected, such as, when solvent is methyl alcohol, in the mass ratio of the whole monomers comprised in solvent and polymerization system {=(solvent)/(whole monomer) }, preferably select in the scope of 0.01 ~ 10, more preferably select in the scope of 0.05 ~ 3.
By vinyl acetate system monomer with can convert the polymerization initiator used in the copolymerization of the unsaturated monomer of at least a kind of structural unit be selected from structural unit (1) ~ (3) to select from known polymerization initiator, such as azo series initiators, superoxide series initiators, redox series initiators according to polymerization with its copolymerization.Azo series initiators is such as 2,2 '-azobis isobutyronitrile, 2,2 '-azo two (2,4-methyl pentane nitrile), 2,2 '-azo two (4-methoxyl-2,4-methyl pentane nitrile).Superoxide series initiators is such as the peroxocarbonate based compounds such as diisopropyl peroxydicarbonate, two-2-ethylhexyl peroxy dicarbonates, diethoxy ethyl peroxydicarbonate; The peroxyester based compounds such as tert-butyl hydroperoxide neodecanoic acid ester, α-cumyl new decanoate ester peroxide; Acetyl group peroxidating cyclohexylsulfonyl; 2,4,4-tri-methyl-amyl-2-peroxidating phenoxy group acetate; Acetyl peroxide.Also potassium persulfate, ammonium persulfate, hydrogen peroxide etc. can be combined with above-mentioned initiating agent and make polymerization initiator.Redox series initiators is such as the polymerization initiator being combined by the reductive agents such as above-mentioned superoxide series initiators and sodium bisulfite, sodium bicarbonate, tartrate, L-AA, rongalite and obtain.The consumption of polymerization initiator is different because of the kind of polymerization initiator, therefore cannot lump together, and carries out selecting according to polymerization speed.Such as, polymerization initiator uses 2, when 2 '-azobis isobutyronitrile or acetyl peroxide, is preferably 0.01 ~ 0.2 % by mole relative to vinyl acetate system monomer, is more preferably 0.02 ~ 0.15 % by mole.
Vinyl acetate system monomer with can with its copolymerization and the copolymerization that can convert the unsaturated monomer of at least a kind of structural unit be selected from structural unit (1) ~ (3) to can carry out under the existence of chain-transferring agent.Chain-transferring agent is such as the aldehydes such as acetaldehyde, propionic aldehyde; The ketone such as acetone, MEK; The thio-alcohols such as 2-hydroxyl ethyl mercaptan; Phosphinic acids sodium-hydrate grade phosphonates etc.Wherein, be applicable to using aldehydes and ketone.The consumption of chain-transferring agent can decide according to the targeted degree of polymerization of the chain tra nsfer coefficient of the chain-transferring agent that will use and PVA, is usually preferably 0.1 ~ 10 mass parts relative to vinyl acetate system monomer 100 mass parts.
By will vinyl acetate system monomer be utilized and can convert the copolymerization of the unsaturated monomer of at least a kind of structural unit be selected from structural unit (1) ~ (3) to its copolymerization and obtain vinyl acetate based copolymer and carry out saponification, above-mentioned illustrative PVA can be obtained.By this vinyl acetate based copolymer is carried out saponification, the vinyl ester units in vinyl acetate based copolymer is converted into vinyl alcohol units.In addition, such as, in the unsaturated monomer shown in formula (3), as Y 1the situation being the group with the structure that hydroxyl that methylol has is protected by acyl group is such; copolymerization can be carried out with vinyl acetate system monomer and the unsaturated monomer that can convert at least a kind of structural unit be selected from structural unit (1) ~ (3) to has the hydroxyl protected by acyl group time, the ester bond being derived from this acyl moiety in the structural unit of this unsaturated monomer is also produced hydroxyl by saponification.Therefore, even if this PVA is not hydrolyzed further etc. after saponification, reaction also can manufacture.
Carry out under the state that the saponification of vinyl acetate based copolymer such as can be dissolved with this vinyl acetate based copolymer in alcohol or aqueous alcohol.The alcohol used in saponification can list the such as lower alcohol such as methyl alcohol, ethanol, is preferably methyl alcohol.The alcohol used in saponification such as can comprise other solvents such as acetone, methyl acetate, ethyl acetate, benzene with the ratio of below the 40 quality % of its quality.The catalyzer used in saponification is such as the acid catalysts such as base catalyst, mineral acid such as the alkali-metal oxyhydroxide such as potassium hydroxide, NaOH, sodium methoxide.The temperature of carrying out saponification does not limit, and is adapted in the scope of 20 ~ 60 DEG C.When separating out gelatinous product gradually along with the propelling of saponification, after product is pulverized, carry out cleaning, dry, thus can PVA be obtained.Method for saponification is not limited to preceding method, can apply known method.
Above-mentioned illustrative PVA can also comprise other structural unit beyond structural unit (1) ~ (3), vinyl alcohol units and vinyl ester units.As this other structural unit, can list and such as be derived from and can carry out the structural unit of the ethylenically unsaturated monomer of copolymerization with vinyl acetate system monomer.In addition; can also comprise to be derived from and can carry out copolymerization with above-mentioned vinyl acetate system monomer and the structural unit (in the process of deprotection, not being converted into the structural unit of at least a kind of structural unit be selected from structural unit (1) ~ (3)) that can convert the unsaturated monomer of at least a kind of structural unit be selected from structural unit (1) ~ (3) to.
In above-mentioned illustrative PVA, the molal quantity of entire infrastructure unit forming this PVA is denoted as 100 % by mole, the ratio shared by total of structural unit (1) ~ (3), vinyl alcohol units and vinyl ester units is preferably more than 90 % by mole, be more preferably more than 98 % by mole, more preferably more than 99 % by mole, more than 99.5 % by mole, more than 99.8 % by mole, more than 99.9 % by mole and then can be 100 % by mole.
As above-mentioned ethylenically unsaturated monomer, such as, be the alpha-olefines such as ethene, propylene, n-butene, isobutylene, 1-hexene; Acrylic acid and salt thereof; There is acrylate-based unsaturated monomer; Methacrylic acid and salt thereof; There is methacrylate based unsaturated monomer; Acrylamide; The acrylamide derivatives such as N methacrylamide, N-ethyl acrylamide, N,N-DMAA, diacetone acrylamide, acrylamide propane sulfonic acid and salt thereof, acrylamide propyl dimethylamine and salt (such as quaternary ammonium salt) thereof; Methacrylamide; The methacrylamide derivatives such as N-methyl methacrylamide, N-ethyl methacrylamide, Methacrylamide propane sulfonic acid and salt thereof, Methacrylamide diemethylamine and salt (such as quaternary ammonium salt) thereof; The vinyl ethers such as methyl vinyl ether, 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, 2,3-diacetoxy-1-vinyl Ethylene Oxides; The vinyl cyanide such as vinyl cyanide, methacrylonitrile class; The vinyl halides such as vinyl chloride, fluorothene class; Vinylidene chloride, vinylidene fluoride isogonic dihalo vinyl; The allyl compounds such as 2,3-diacetoxy-1-allyloxy propane, allyl chloride; The unsaturated dicarboxylics such as maleic acid, itaconic acid, fumaric acid and salt thereof or ester; The vinyl silyl groups compounds such as vinyltrimethoxy silane; Isopropenyl acetate.
Be selected from least a kind of structural unit in structural unit (1) ~ (3), vinyl alcohol units and other putting in order of any Component units in above-mentioned illustrative PVA are not particularly limited, can be random, block, mutual etc. in any one.
Component (a is crystallized into owing to more easily obtaining 1) and constraint amorphous component amount (a 2) ratio meet the PVA film of above-mentioned scope and the form and aspect raising etc. of the blooming using this PVA film and obtain, therefore the degree of polymerization of above-mentioned illustrative PVA is preferably less than 3,000, is more preferably less than less than 2,900, more preferably 2,800.On the other hand, owing to using the PVA film comprising this PVA, the permanance of blooming obtained improves, and therefore this degree of polymerization is preferably greater than 2,000, more preferably above 2,100, further preferably greater than 2, and 200.It should be noted that, the degree of polymerization of the PVA in this instructions refers to the average degree of polymerization measured according to the record of JISK6726-1994.
In addition, component (a is crystallized into owing to more easily obtaining 1) and constraint amorphous component amount (a 2) ratio meet the PVA film of above-mentioned scope, therefore the molecular weight distribution of above-mentioned illustrative PVA is preferably 2.0 ~ 4.0, this molecular weight distribution is more preferably more than 2.2, more preferably more than 2.4, in addition, is more preferably less than 3.8, more preferably less than 3.6.It should be noted that, the molecular weight distribution of the PVA in this instructions refers to the value calculated by matter average molecular weight (Mw)/number-average molecular weight (Mn).Matter average molecular weight (Mw) and number-average molecular weight (Mn) can be obtained as follows: using single dispersing polymethylmethacrylate as standard items, hexafluoroisopropanol containing 20mmol/L sodium trifluoroacetate is used for mobile phase, with 40 DEG C, flow 0.2mL/ minute carries out gel permeation chromatography (TOSOH Co., Ltd's system, device: HLC-8220GPC, post: GMHHR-H(S)) measure, thus to obtain.
In PVA film of the present invention, except above-mentioned PVA, plastifier can also be comprised.As preferred plastifier, can polyvalent alcohol be listed, as concrete example, ethylene glycol, glycerine, propylene glycol, diethylene glycol, two glycerine, triethylene glycol, TEG, trimethylolpropane etc. can be listed.It is one kind or two or more that PVA film of the present invention can comprise in these plastifier.Among these, from the view point of the effect improving stretchability, be preferably glycerine.
About the content of the plastifier in PVA film of the present invention, relative to the PVA100 mass parts wherein comprised, be preferably more than 1 mass parts, be more preferably more than more than 3 mass parts, more preferably 5 mass parts, in addition, be preferably below 20 mass parts, be more preferably below below 17 mass parts, more preferably 15 mass parts.By making this content be more than 1 mass parts, the stretchability of film improves further.On the other hand, by making this content be below 20 mass parts, too softness, treatability reduce can to suppress film.
The adjuvants such as the processing stabilizers such as filling agent, copper compound, weatherability stabilizing agent, colorant, ultraviolet light absorber, light stabilizer, antioxidant, antistatic agent, fire retardant, other thermoplastic resin, lubricant, spices, defoamer, deodorant, extender, remover, release agent, reinforcing agent, crosslinking chemical, mildewproof agent, antiseptic, crystallization rate delayed-action activator suitably can also be coordinated as required in PVA film of the present invention.
PVA in PVA film of the present invention and the ratio shared by total of plastifier are elected more than 80 quality % as based on the Functionality, quality and appealing design of PVA film, are more preferably more than 90 quality %, more preferably more than 95 quality %.
The swellbility of PVA film of the present invention preferably in the scope of 160 ~ 240%, more preferably in the scope of 170 ~ 230%, particularly preferably in the scope of 180 ~ 220%.By making swellbility be more than 160%, can more effectively prevent with 60 DEG C process 1 hour after crystallize into component (a 1) and constraint amorphous component amount (a 2) total ratio become too high, use this PVA film and the form and aspect of blooming that obtain improve.On the other hand, by making swellbility be less than 240%, can more effectively prevent with 60 DEG C process 1 hour after crystallize into component (a 1) and constraint amorphous component amount (a 2) total ratio become too low, use this PVA film and the permanance of blooming that obtains improves.It should be noted that, in this instructions, the swellbility of PVA film refers to: quality when PVA film being flooded in the distilled water of 30 DEG C 30 minutes is divided by the percent of the value obtained with the quality of 105 DEG C of dryings after 16 hours after dipping, specifically, can be measured by method described later in embodiment.Swellbility such as by changing heat treated condition to adjust, can reduce swellbility by raising heat treatment temperature, prolongation heat treatment time usually.
PVA film of the present invention easily can manufacture all excellent blooming of optical characteristics, form and aspect and permanance, therefore when Thickness Ratio is in the past thinner, can especially effectively use.The thickness of this PVA film is preferably 1 ~ 60 μm, is more preferably 5 ~ 55 μm, is particularly preferably 10 ~ 50 μm.When this thickness is less than 1 μm, during uniaxial tension process for the manufacture of bloomings such as light polarizing film, there is the tendency that tension failure easily occurs.In addition, when this thickness is blocked up, during uniaxial tension process for the manufacture of blooming, exist and easily the uneven tendency that stretches occurs.
The width of PVA film of the present invention is not particularly limited, and can decide according to its purposes etc.In recent years, develop from the view point of the large screen of LCD TV, liquid crystal display, when in advance the width of PVA film being made more than 3m, they are suitable for the purposes making end article.On the other hand, when the width of PVA film is excessive, when utilize utility unit manufacture blooming, sometimes produce carry out equably uniaxial tension self easily become difficulty etc. problem, therefore, the width of PVA film is preferably below 7m.
The manufacture method of PVA film of the present invention is not particularly limited, can preferably adopt the thickness of the film after masking and width to become evenly manufacture method, following masking stoste such as can be used to manufacture: be dissolved in liquid medium by the above-mentioned PVA forming PVA film, and as required further by the one kind or two or more masking stoste obtained in liquid medium that is dissolved among above-mentioned plastifier, adjuvant and surfactant described later etc.; What comprise PVA and comprise among plastifier, adjuvant, surfactant and liquid medium etc. as required further is one kind or two or more, and the masking stoste of PVA melting.When this masking stoste contains at least a kind in plastifier, adjuvant and surfactant, preferably these uniform composition ground mixing.
As the aforesaid liquid medium for the preparation of masking stoste, can list such as water, dimethyl sulfoxide (DMSO), dimethyl formamide, dimethyl acetamide, 1-METHYLPYRROLIDONE, ethylene glycol, glycerine, propylene glycol, diethylene glycol, triethylene glycol, TEG, trimethylolpropane, ethylenediamine, Diethylenetriamine etc., what can use among these is one kind or two or more.Wherein, from the view point of the burden caused environment, recyclability, be preferably water.
The volatile matter rate of masking stoste (during masking because of volatilization, evaporation and the volatile ingredients such as removed liquid medium in masking stoste containing proportional) also different because of film-forming method, film forming condition etc., in general, preferably in the scope of 50 ~ 95 quality %, more preferably in the scope of 55 ~ 90 quality %, preferred in the scope of 60 ~ 85 quality % further.By making the volatile matter rate of masking stoste be more than 50 quality %, the viscosity of masking stoste can not become too high, and filtration, deaeration during preparation masking stoste are successfully carried out, and easily manufactures foreign matter, film that shortcoming is few.On the other hand, by making the volatile matter rate of masking stoste be below 95 quality %, the concentration of masking stoste can not become too low, industrial easy manufacture film.
Masking stoste preferably comprises surfactant.By comprising surfactant, masking improves, suppress film generation uneven thickness, and film easily from for masking metallic roll, bring stripping.When manufacturing PVA film by the masking stoste comprising surfactant, in this film, surfactant can be contained.The kind of above-mentioned surfactant is not particularly limited, and from from metallic roll, the viewpoint etc. bringing the fissility of stripping, is preferably anionic surfactant or nonionic surfactant.
As anionic surfactant, such as, be applicable to, the carboxylic acid types such as potassium laurate; The sulfuric acid ester types such as polyoxyethylene lauryl ether sulfate, sulfuric acid monooctyl ester; The sulfonic acid types etc. such as dodecyl benzene sulfonate.
As nonionic surfactant, such as, be applicable to, the alkyl ether types such as polyoxyethylene oleyl ether; The alkyl phenyl ether type such as NONIN HS 240; The alkyl ester such as polyoxyethylene laural ester; The alkyl amine type such as polyoxyethylene laural base amino ethers; The alkylamide types such as polyoxyethylene laural acid amides; The polypropylene glycol ether type such as polyoxyethylene poly-oxygen propylene aether; The alkylol amide type such as lauric acid diethyl amide, oleic acid diethyl amide; The allyl phenyl ether type etc. such as polyoxy alkylidene allyl phenyl ether.
These surfactants can be used alone a kind, or combinationally use two or more.
When masking stoste comprises surfactant, its content is relative in the scope of the PVA100 mass parts comprised in masking stoste preferably in the scope of 0.01 ~ 0.5 mass parts, more preferably in the scope of 0.02 ~ 0.3 mass parts, particularly preferably in 0.05 ~ 0.1 mass parts.By making this content be more than 0.01 mass parts, masking and fissility improve further.On the other hand, by making this content be below 0.5 mass parts, surfactant can be suppressed to ooze out into the surface of PVA film and lump, treatability reduce.
As film-forming method during use above-mentioned masking stoste manufacture PVA film, masking method of such as rolling can be listed, extrude masking method, film by wet method, gel masking method etc.These film-forming methods can only adopt a kind, also can combine and adopt two or more.Among these film-forming methods, due to thickness and even width can be obtained and the good PVA film of physical property, so preferably calendering masking method, extrude masking method.Manufactured film can carry out drying, thermal treatment as required.
As the example of the concrete manufacture method of PVA film of the present invention, such as industrially preferably to adopt with the following method: use T-shaped slit die, hopper plate, I-mould, lip is coated with machine mould etc., above-mentioned masking stoste to be sprayed equably or curtain coating is being positioned at the rotation of side, most upstream and on the periphery of the 1st roller (or band) of heating, a face of volatile ingredient film on the periphery of the 1st roller (or band) from ejection or curtain coating is made to carry out evaporating and dry, then dry further on the periphery being configured at one or more rotations in its downstream and the roller of heating, or make it pass in hot-air drying device after further drying, take-up mechanism is utilized to carry out the method for batching.The drying utilizing warm-up mill to carry out and the drying utilizing hot-air drying device to carry out can appropriately combinedly be implemented.
The purposes of PVA film of the present invention is not particularly limited, and according to PVA film of the present invention, owing to easily can manufacture all excellent blooming of optical characteristics, form and aspect and permanance, therefore, preferably uses as the initial film for the manufacture of blooming.As this blooming, such as light polarizing film, phase retardation film etc. can be listed, be preferably light polarizing film.This blooming such as can by being used as the method for blooming manufacture initial film and the method possessing the operation of carrying out uniaxial tension manufactures by PVA film of the present invention, specifically, can be manufactured by the method possessing following operation, described operation be to PVA film of the present invention self or implement aftermentioned swelling treatment etc. and produce be derived from PVA film of the present invention PVA film (following, sometimes will " PVA film of the present invention " and " being derived from the PVA film of PVA film of the present invention " be referred to as " based on PVA film of the present invention ") carry out uniaxial tension.
Use method during PVA film of the present invention manufacture light polarizing film to be not particularly limited, any means all the time adopted can be adopted.As this method, can list such as to implementing dyeing and uniaxial tension based on PVA film of the present invention or to the method based on PVA film enforcement uniaxial tension of the present invention containing dyestuff.As the more specifically method for the manufacture of light polarizing film, can list: for based on PVA film of the present invention, implement swelling, dyeing, uniaxial tension, and implement the method for crosslinking Treatment, fixing process, drying, thermal treatment etc. as required further.Now, the order of each process such as swelling, dyeing, crosslinking Treatment, uniaxial tension, fixing process is not particularly limited, and also can carry out the process of more than 1 or 2 simultaneously.In addition, more than 1 or 2 in each process also can be carried out more than 2 times or 2 times.
Swelling can by carrying out in water based on PVA film immersion of the present invention.As water temperature when impregnated in water, preferably in the scope of 20 ~ 40 DEG C, more preferably in the scope of 22 ~ 38 DEG C, preferred in the scope of 25 ~ 35 DEG C further.In addition, as the time that impregnated in water, such as preferred in the scope of 0.1 ~ 5 minute, more preferably in the scope of 0.5 ~ 3 minute.It should be noted that, water when impregnated in water is not limited to pure water, can be the aqueous solution being dissolved with various composition, also can be the potpourri of water and aqueous medium.
Dye by making the contact of bitintability pigment carry out based on PVA film of the present invention.As bitintability pigment, usually use iodine system pigment.As the period of dyeing, can be before uniaxial tension, uniaxial tension time, after uniaxial tension in any stage.Dyeing by being that PVA film immersion carried out as containing in the solution (especially aqueous solution) of IKI of dye bath, is also applicable in the present invention adopting this colouring method usually.Iodine concentration in dye bath preferably in the scope of 0.01 ~ 0.5 quality %, the concentration of potassium iodide is preferably in the scope of 0.01 ~ 10 quality %.In addition, the temperature of dye bath is preferably 20 ~ 50 DEG C, is particularly preferably 25 ~ 40 DEG C.
By implementing crosslinking Treatment to based on PVA film of the present invention, PVA stripping more effectively can be prevented in water when carrying out wet type stretching with high temperature.From this viewpoint, crosslinking Treatment is preferably carried out before uniaxial tension after the process of contact bitintability pigment.Crosslinking Treatment can by carrying out based on PVA film immersion of the present invention in the aqueous solution comprising crosslinking chemical.As this crosslinking chemical, what can use in the boron compounds such as the borate such as boric acid, borax is one kind or two or more.Comprise crosslinker concentration in the aqueous solution of crosslinking chemical preferably in the scope of 1 ~ 15 quality %, more preferably in the scope of 2 ~ 7 quality %, preferred in the scope of 3 ~ 6 quality % further.By making the concentration of crosslinking chemical be in the scope of 1 ~ 15 quality %, sufficient stretchability can be maintained.The aqueous solution comprising crosslinking chemical can containing potassium iodide etc.The temperature comprising the aqueous solution of crosslinking chemical preferably in the scope of 20 ~ 50 DEG C, particularly preferably in the scopes of 25 ~ 40 DEG C.By making this temperature in the scope of 20 ~ 50 DEG C, can be cross-linked efficiently.
Uniaxial tension based on PVA film of the present invention can utilize in wet type pulling method or dry stretch process any one carry out.When wet type pulling method, can carry out in the borated aqueous solution of bag, also can carry out in above-mentioned dye bath, in aftermentioned fixing process bath.In addition, when dry stretch process, at room temperature directly can stretch, also can stretch while heating, the PVA film after water suction can also be used to carry out in atmosphere.Among these, owing to stretching equably in the direction of the width, be therefore preferably wet type pulling method, more preferably in the borated aqueous solution of bag, carry out uniaxial tension.In the scope of boric acid concentration in boric acid aqueous solution preferably in the scope of 0.5 ~ 6.0 quality %, more preferably in the scope of 1.0 ~ 5.0 quality %, particularly preferably in 1.5 ~ 4.0 quality %.In addition, boric acid aqueous solution can contain potassium iodide, and the concentration of potassium iodide is preferably in the scope of 0.01 ~ 10 quality %.
Draft temperature during uniaxial tension preferably in the scope of 30 ~ 90 DEG C, more preferably in the scope of 40 ~ 80 DEG C, particularly preferably in the scopes of 50 ~ 70 DEG C.
In addition, from the view point of the polarized light performance of gained light polarizing film, stretching ratio during uniaxial tension is preferably more than 6.6 times, is more preferably more than 6.8 times, is particularly preferably more than 7.0 times.The upper limit of stretching ratio is not particularly limited, and stretching ratio is preferably less than 8 times.
Uniaxial tension direction when rectangular PVA film being carried out uniaxial tension is not particularly limited, the uniaxial tension carried out to rectangular direction, horizontal uniaxial tension can be adopted, due to the light polarizing film of polarized light excellent performance can be obtained, the uniaxial tension therefore preferably carried out to rectangular direction.The uniaxial tension carried out to rectangular direction can possess the stretching device of multiple rollers parallel to each other by use, and the peripheral speed changed between each roller is carried out.On the other hand, horizontal uniaxial tension can use tentering type drawing machine to carry out.
When manufacturing light polarizing film, in order to make bitintability pigment (iodine system pigment etc.) firmly be adsorbed in film, be preferably fixed process.As the fixing process bath used in fixing process, the one kind or two or more aqueous solution comprised in the boron compound such as boric acid, borax can be used.In addition, iodine compound, metallic compound can be added in fixing process bath as required.The concentration of the boron compound in fixing process bath is usually preferably 2 ~ 15 quality %, is particularly preferably about 3 ~ 10 quality %.By making this concentration in the scope of 2 ~ 15 quality %, can more firmly adsorb bitintability pigment.The temperature of fixing process bath is preferably 15 ~ 60 DEG C, is particularly preferably 25 ~ 40 DEG C.
Dry condition is not particularly limited, and preferably in the scope of 30 ~ 150 DEG C, particularly preferably at the temperature in the scopes of 50 ~ 130 DEG C, carries out drying.By carrying out drying with the temperature within the scope of 30 ~ 150 DEG C, easily obtain the light polarizing film of excellent in dimensional stability.
As above operate and the light polarizing film that obtains or single-sided lamination optical clear two-sided at it and be used as polarization plates after there is the diaphragm of physical strength usually.As diaphragm, Triafol T (TAC) film, cyclic olefin polymer (COP) film, acetylbutyrylcellulose (CAB) film, acrylic acid mesentery, polyester mesentery etc. can be used.In addition, as the bonding agent for fitting, PVA system bonding agent, carbamate system bonding agent, acrylic ester ultraviolet hardening bonding agent etc. can be listed.
As above operate and the polarization plates that obtains after the bonding agents such as coating acrylic acid series, fit in glass substrate and can be used as the parts of LCD.Simultaneously can fit phase retardation film, angle of visibility improves film, brightness improving film etc.
Embodiment
Below, illustrate in greater detail the present invention by embodiment, but the present invention is not limited to these embodiments completely.It should be noted that, each mensuration adopted in following examples and comparative example or evaluation method as follows.
the primary structure of PVA
The primary structure of the PVA used in following examples and comparative example uses 400MHz 1h-NMR analyzes. 1solvent when H-NMR measures employs deuterated DMSO.
the swellbility of PVA film
The PVA film obtained in following examples or comparative example is cut to and reaches 1.5g, flood 30 minutes in the distilled water of 30 DEG C.Flood and take out this film after 30 minutes, with the water on filter paper leaching surface, obtain quality " N ".Then, this film after dry 16 hours, is obtained quality " M " with the dryer of 105 DEG C.Following formula (8) is utilized to calculate the swellbility of PVA film by gained quality " N " and " M ".
Swellbility (%)=100 × N/M(8).
component (a is crystallized in PVA film 1 ) and constraint amorphous component amount (a 2 )
By fine for the sample (100mg) obtained by the PVA film obtained in following examples or comparative example cut into the size of about 5mm × 5mm after, be jointly fed in NMR pipe with 1mL heavy water.This NMR pipe is flooded 1 hour in the calibration cell of 60 DEG C.Thereafter, with 20 DEG C of keepings 24 hours, as mensuration sample.Use PULSED NMR (BrukerBioSpinK.K. system " minispecmq20WVT "), for this mensuration Specimen Determination 1the spin spin relaxation time T of H 2.Condition determination is as follows.
Spike train: Solid-Echo method (90x-τ-90y)
RF pulse width (Pw1): 2.1 μ s
Recurrent interval (Pi1): 1 μ s
Pulse-recurrence time: 1s
Measure temperature: 30 DEG C.
Utilize linear least square by free induction decay (FID) signal fitting that obtains in said determination in above-mentioned formula (4), obtain be on the occasion of crystallize into component (a 1), constraint amorphous component amount (a 2) and amorphous component amount (a 3), calculate the ratio of each composition relative to the total amount of these 3 kinds of compositions.
the stretchability of PVA film
The Width central portion of the PVA film obtained from following embodiment or comparative example, can carry out the mode of uniaxial tension with the scope of width 5cm × length 5cm, the sample of cutting width 5cm × length 8cm.This sample be impregnated in the pure water of 30 DEG C, and to length direction uniaxial tension 1.5 times.Then, to contain in the aqueous solution (dye bath) (temperature 30 DEG C) of iodine and potassium iodide 60 seconds of dipping in the ratio of to take iodine as 0.03 quality % and potassium iodide be 3.0 quality %, and to length direction uniaxial tension 1.6 times (stretching 2.4 times of all meters), iodine is adsorbed.Then, dipping in the aqueous solution (crosslinked bath) (temperature 30 DEG C) of boric acid and potassium iodide is contained in the ratio of to take boric acid as 3 quality % and potassium iodide be 3 quality %, and to length direction uniaxial tension 1.1 times (stretching 2.6 times of all meters).And then, dipping in the aqueous solution (stretch bath) of boric acid and potassium iodide is contained in the ratio of to take boric acid as 4 quality % and potassium iodide be 6 quality %, and to length direction uniaxial tension to cut-out, length when cutting off is denoted as ultimate elongation multiplying power relative to the multiplying power of the length of the PVA film before stretching.Wherein, for the temperature of stretch bath, change 1 DEG C from suitable temperature at every turn and carry out determination limit stretching ratio, selection limit stretching ratio reaches the highest temperature.
the optical characteristics (bitintability ratio) of light polarizing film
(1) mensuration of transmissivity Ts
The central portion of the light polarizing film obtained from following examples or comparative example takes the length direction of 2 light polarizing film to be the sample of 2cm, use the spectrophotometer (Japan Spectroscopy Corporation's system " V7100 ") of subsidiary integrating sphere, assay method according to JISZ8722(object color), carry out illuminant-C, 2 ° of visuals field visible region visibility correct, for 1 sample, measure relative to light transmission during length direction inclination+45 ° with relative to light transmission during length direction inclination-45 °, obtain their mean value Ts1(%).Operate too for another 1 sample, light transmission when light transmission during mensuration inclination+45 ° and inclination-45 °, obtains their mean value Ts2(%).By following formula (9), Ts1 and Ts2 is averaged, is denoted as the transmissivity Ts(% of light polarizing film).
Ts=（Ts1+Ts2）/2（9）。
(2) mensuration of degree of polarization V
Light transmission T ∥ (%) when carrying out overlap for 2 samples will taked in the mensuration of above-mentioned transmissivity Ts in the mode that its length direction is parallel, light transmission T ⊥ (%) when to carry out overlap in the mode that length direction is vertical, measure with same operation of situation of above-mentioned " mensuration of (1) transmissivity Ts ", obtain degree of polarization V(% by following formula (10)).
V=｛（T∥-T⊥）/（T∥+T⊥）｝ 1/2×100（10）。
(3) calculating of bitintability ratio when transmissivity is 44%
In following each embodiment and comparative example, iodine concentration in dye bath is changed 4 times in each scope of 0.02 ~ 0.04 quality % and the concentration of potassium iodide is changed in each scope of 2.0 ~ 4.0 quality % 4 times (wherein, the concentration of iodine: the concentration=1:100 of potassium iodide), carry out identical operation, thus manufacture the 4 slice light polarizing film different from the bitintability pigment adsorbance of the light polarizing film manufactured in each embodiment or comparative example.For these 4 light polarizing film, said method is utilized to obtain transmissivity Ts(% respectively) and degree of polarization V(%), each embodiment and comparative example are respectively with transmissivity Ts(%) for transverse axis, with degree of polarization V(%) be the longitudinal axis, transmissivity Ts(% by based on the light polarizing film obtained in each embodiment or comparative example) and degree of polarization V(%), totally 5 plottings of comprising at 1 obtain curve of approximation on figure, obtain transmissivity Ts(% by this curve of approximation) degree of polarization V when being 44% 44(%).
By following formula (11) by gained degree of polarization V 44(%) bitintability ratio when transmissivity is 44% is obtained, as the index of polarized light performance.It should be noted that, bitintability is better than the optical characteristics of higher then light polarizing film, bitintability is judged to be "○" (well) than the situation being more than 66, bitintability is judged to be "×" (bad) than the situation less than 66.
Bitintability ratio=log(44/100-44/100 × V when transmissivity is 44% 44/ 100)/log(44/100+44/100 × V 44/ 100) (11).
the form and aspect (parallel b value) of light polarizing film
In above-mentioned " optical characteristics (bitintability ratio) of light polarizing film ", when obtaining the degree of polarization V of 4 different light polarizing film of bitintability pigment adsorbance, the Lab color space is measured when measuring transmissivity T ∥ (%) and transmissivity T ⊥ (%), using b value when measuring transmissivity T ∥ (%) as parallel b value, b value when will measure transmissivity T ⊥ (%) is as orthogonal b value.Each embodiment and comparative example respectively with parallel b value be transverse axis, with orthogonal b value for the longitudinal axis, be worth, comprise totally 5 plottings of 1 to obtain curve of approximation on figure by based on the parallel b value of the light polarizing film obtained in each embodiment or comparative example and orthogonal b, parallel b value when to obtain orthogonal b value be-4 by this curve of approximation.It should be noted that, the form and aspect of parallel b value more close to 0 light polarizing film are better, are judged to be "○" (well) when parallel b value is less than 2.2, are judged to be "×" (bad) when parallel b value is more than 2.2.
the permanance (absorbance residual rate) of light polarizing film
For each embodiment or comparative example, among totally 5 light polarizing film of the light polarizing film obtained in 4 light polarizing film that the bitintability pigment adsorbance manufactured from above-mentioned " optical characteristics of light polarizing film (bitintability than) " is different and each embodiment or comparative example, select 1 transmissivity be in 44 ~ 45% scope and mensuration transmissivity T ⊥ (%) time the absorbance (vertical absorbance) at wavelength 610nm place obtained be 2.95 ~ 3.05 light polarizing film.
By this light polarizing film 60 DEG C, expose 4 hours under the environment of 90%RH, the vertical absorbance at initial wavelength 610nm place is denoted as A 0h, and the vertical absorbance at the wavelength 610nm place of exposure after 4 hours is denoted as A 4h, residual rate (absorbance residual rate) D(% using the vertical absorbance obtained by following formula (12)) evaluate as the permanance of light polarizing film.It should be noted that, the permanance of the higher then light polarizing film of absorbance residual rate is better, is judged to be "○" (well) when absorbance residual rate is more than 20%, is judged to be "×" (bad) when absorbance residual rate is less than 20%.
D（%）=100×A 4h/A 0h（12）。
[embodiment 1 ~ 6 and comparative example 1 ~ 5]
(1) the PVA100 mass parts shown in table 1 will be comprised, as glycerine 10 mass parts of plastifier, and as polyoxyethylene laurel ether sodium sulphate 0.1 mass parts of surfactant and the aqueous solution that the containing ratio of PVA is 10 quality % is used as masking stoste, described PVA is by by vinyl acetate and acetic acid 2-methyl-2-propylene, 3, 4-diacetoxy-1-butylene, 7-acetoxyl group-1-butylene or 1, the multipolymer of 3-diacetoxy-2-methylene propane is (in comparative example 1, homopolymer for vinyl acetate) carry out saponification and obtain, described masking stoste is carried out drying in the metallic roll of 80 DEG C, by gained film in air drier with the heat treatment 1 minute of regulation, thus swellbility is adjusted to 200%, thus manufacture the PVA film that thickness is 30 μm.
Use gained PVA film, obtained by said method and crystallize into component (a 1) and constraint amorphous component amount (a 2) ratio, and evaluate stretchability.Show the result in table 1.
(2) the Width central portion of the PVA film obtained from above-mentioned (1), can carry out the mode of uniaxial tension with the scope of width 5cm × length 5cm, the sample of cutting width 5cm × length 8cm.This sample be impregnated in the pure water of 30 DEG C, and to length direction uniaxial tension 1.5 times.Then, to contain in the aqueous solution (dye bath) (temperature 30 DEG C) of iodine and potassium iodide 60 seconds of dipping in the ratio of to take iodine as 0.03 quality % and potassium iodide be 3.0 quality %, and to length direction uniaxial tension 1.6 times (stretching 2.4 times of all meters), iodine is adsorbed.Then, dipping in the aqueous solution (crosslinked bath) (temperature 30 DEG C) of boric acid and potassium iodide is contained, to length direction uniaxial tension 1.1 times (stretching 2.6 times of all meters) in the ratio of to take boric acid as 3 quality % and potassium iodide be 3 quality %.And then, dipping in the aqueous solution (stretch bath) (the ultimate elongation multiplying power obtained in above-mentioned " stretchability of PVA film " reaches the highest temperature) of boric acid and potassium iodide is contained in the ratio of to take boric acid as 4 quality % and potassium iodide be 6 quality %, and to the multiplying power of length direction uniaxial tension to lower than ultimate elongation multiplying power 0.2 times.Thereafter, in the aqueous solution (cleaner bath) (temperature 30 DEG C) containing potassium iodide with the ratio of 3 quality %, flooded for 5 seconds, finally with 60 DEG C of dryings 4 minutes, thus manufacture light polarizing film.
Use gained light polarizing film, evaluate the optical characteristics (bitintability than) of light polarizing film, form and aspect (parallel b value) and permanance by said method.Show the result in table 1.
[table 1]
From above result clearly: according to the PVA film of embodiment 1 ~ 6 meeting code of the present invention, the blooming that optical characteristics, form and aspect and permanance are all excellent can easily be manufactured.

Claims (11)

1. vinyl alcohol system polymer film, wherein, by spin spin relaxation time T 2obtain and crystallize into component (a 1), constraint amorphous component amount (a 2) and amorphous component amount (a 3) time, crystallize into component (a 1) and constraint amorphous component amount (a 2) be aggregated in and crystallize into component (a 1), constraint amorphous component amount (a 2) and amorphous component amount (a 3) total in shared ratio be 10 ~ 32%, described spin spin relaxation time T 2obtain by processing 1 hour laggard horizontal pulse NMR mensuration at 60 DEG C, the observing nuclear that described PULSED NMR measures is 1h.
2. vinyl alcohol system polymer film according to claim 1, wherein, constraint amorphous component amount (a 2) crystallizing into component (a 1), constraint amorphous component amount (a 2) and amorphous component amount (a 3) total in shared ratio be more than 5%.
3. vinyl alcohol system polymer film according to claim 1 and 2, wherein, the vinyl alcohol system polymer comprised in vinyl alcohol system polymer film contains at least a kind of structural unit be selected from the structural unit (1) shown in following formula (1), the structural unit (2) shown in following formula (2) and the structural unit (3) shown in following formula (3), and the containing ratio of structural unit (1) ~ (3) is denoted as n respectively 1~ n 3% by mole, the containing ratio of vinyl ester units is denoted as n 4% by mole time, meet 0.6≤n 1+ n 2+ 2 × n 3+ n 4≤ 1.4,
[changing 1]
In formula, R 1represent hydrogen atom, methyl or ethyl,
[changing 2]
In formula, R 2represent hydrogen atom, methyl or ethyl, X 2represent that the carbon number with more than 1 hydroxyl is the hydroxy alkyl of more than 2,
[changing 3]
In formula, X 3and X 4separately represent that the carbon number with more than 1 hydroxyl is the hydroxy alkyl of more than 1.
4. vinyl alcohol system polymer film according to claim 3, wherein, the vinyl alcohol system polymer comprised in vinyl alcohol system polymer film contains at least a kind of structural unit be selected from structural unit (1) and structural unit (2).
5. the vinyl alcohol system polymer film according to any one of claim 1 ~ 4, wherein, the vinyl alcohol system polymer comprised in vinyl alcohol system polymer film does not contain the structural unit (3) shown in following formula (3),
[changing 4]
In formula, X 3and X 4separately represent that the carbon number with more than 1 hydroxyl is the hydroxy alkyl of more than 1.
6. the vinyl alcohol system polymer film according to any one of claim 1 ~ 5, wherein, the degree of polymerization of the vinyl alcohol system polymer comprised in vinyl alcohol system polymer film is 3, less than 000.
7. the vinyl alcohol system polymer film according to any one of claim 1 ~ 6, wherein, the molecular weight distribution of the vinyl alcohol system polymer comprised in vinyl alcohol system polymer film is 2.0 ~ 4.0.
8. the vinyl alcohol system polymer film according to any one of claim 1 ~ 7, wherein, swellbility is 160 ~ 240%.
9. the vinyl alcohol system polymer film according to any one of claim 1 ~ 8, it is blooming manufacture initial film.
10. vinyl alcohol system polymer film according to claim 9, it is light polarizing film manufacture initial film.
The manufacture method of 11. bloomings, it uses the vinyl alcohol system polymer film described in claim 9 or 10, and this manufacture method possesses the operation of carrying out uniaxial tension.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5399334A (en) * 1977-02-08 1978-08-30 Bayer Ag Antiitumor agent
JPH07278377A (en) * 1994-04-15 1995-10-24 Mitsubishi Chem Corp Propylene polymer film
CN1445067A (en) * 2002-03-20 2003-10-01 可乐丽股份有限公司 Polyvinyl alcohol mesentery
JP2006233179A (en) * 2005-01-31 2006-09-07 Nippon Synthetic Chem Ind Co Ltd:The Polyvinyl alcohol-based film for optical use and polarizing film, polarizing plate
CN101162277A (en) * 2006-10-11 2008-04-16 富士胶片株式会社 Polymer recovery method from polarizing plates and methods of producing recycled polymer films and polarizing plates
US20080280129A1 (en) * 2007-04-27 2008-11-13 The Nippon Synthetic Chemical Industry Co., Ltd. Chaff molding and production method thereof
CN101778888A (en) * 2007-08-20 2010-07-14 株式会社可乐丽 Polyvinyl alcohol film

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3497903B2 (en) 1995-01-23 2004-02-16 株式会社クラレ Polyvinyl alcohol film for raw material of polarizing film
JP4764658B2 (en) * 2005-04-28 2011-09-07 日本合成化学工業株式会社 Method for producing polyvinyl alcohol film
TWI403543B (en) * 2005-01-31 2013-08-01 Nippon Synthetic Chem Ind A polyvinyl alcohol-based film for optical use, a polarizing film, and a polarizing plate
JP4800269B2 (en) 2007-07-19 2011-10-26 日本合成化学工業株式会社 Polyvinyl alcohol film for polarizing film, polarizing film, and polarizing plate
JP5735302B2 (en) 2010-08-25 2015-06-17 積水化学工業株式会社 Manufacturing method of polarizing film, polarizing film, and PVA resin for polarizing film
JP6121091B2 (en) * 2011-08-09 2017-04-26 日東電工株式会社 Polarizer and manufacturing method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5399334A (en) * 1977-02-08 1978-08-30 Bayer Ag Antiitumor agent
JPH07278377A (en) * 1994-04-15 1995-10-24 Mitsubishi Chem Corp Propylene polymer film
CN1445067A (en) * 2002-03-20 2003-10-01 可乐丽股份有限公司 Polyvinyl alcohol mesentery
JP2006233179A (en) * 2005-01-31 2006-09-07 Nippon Synthetic Chem Ind Co Ltd:The Polyvinyl alcohol-based film for optical use and polarizing film, polarizing plate
CN101162277A (en) * 2006-10-11 2008-04-16 富士胶片株式会社 Polymer recovery method from polarizing plates and methods of producing recycled polymer films and polarizing plates
US20080280129A1 (en) * 2007-04-27 2008-11-13 The Nippon Synthetic Chemical Industry Co., Ltd. Chaff molding and production method thereof
CN101778888A (en) * 2007-08-20 2010-07-14 株式会社可乐丽 Polyvinyl alcohol film

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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TWI801543B (en) * 2018-03-30 2023-05-11 日商積水化學工業股份有限公司 Production method of polyvinyl alcohol film and polarizing film
US11947144B2 (en) 2018-03-30 2024-04-02 Sekisui Chemical Co., Ltd. Poly(vinyl alcohol) film and production method for polarizing film
CN113226687A (en) * 2018-12-28 2021-08-06 株式会社可乐丽 Water-soluble film, method for producing same, and package
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