CN105431751B - Vinyl alcohol system polymer film - Google Patents

Abstract

[problem], which provides, easily to manufacture the PVA film of the excellent optical film of optical characteristics, form and aspect and durability, and has used the manufacture method of the optical film of the PVA film.[solution] PVA film, by transverse relaxation time T₂Obtain and crystallize into component（a₁）, constraint amorphous component amount（a₂）With amorphous component amount（a₃）When, crystallize into component（a₁）With constraint amorphous component amount（a₂）Be aggregated in and crystallize into component（a₁）, constraint amorphous component amount（a₂）With amorphous component amount（a₃）It is total in shared ratio be 10 ~ 32%, transverse relaxation time T₂It is by handling 1 hour laggard horizontal pulse NMR measure at 60 DEG C（Observing nuclear：¹H）Obtained from；And the manufacture method of the optical film using the PVA film, the manufacture method possess the process for carrying out uniaxial tension.

Description

Vinyl alcohol system polymer film

Technical field

The present invention relates to as the initial film for manufacturing optical film（Former anti-Off ィ Le system）And useful ethenol system polymerization Thing film and the manufacture method for having used the optical films such as the light polarizing film of the vinyl alcohol system polymer film.

Background technology

Polarization plates and the liquid crystal of the polarized light state for changing light with printing opacity and shade function are liquid crystal displays Device（LCD）Basic constituent element.A variety of polarization plates have is fitted with Triafol T on the surface of light polarizing film（TAC）Film etc. The structure of diaphragm, as light polarizing film, make vinyl alcohol system polymer film（" vinyl alcohol system polymer " is referred to as sometimes below “PVA”）Carry out the matrix absorption iodine system pigment that uniaxial tension forms（I₃ ^-、I₅ ^-Deng）, bitintability organic dyestuff etc bitintability Light polarizing film obtained from pigment turns into main flow.

It is color that LCD is gradually applied to the miniature instruments such as calculator and appearance, mobile phone, notebook computer, liquid crystal display, liquid crystal The vast scopes such as the metrical instrument that color projecting apparatus, LCD TV, vehicle-mounted navigation system, indoor and outdoor use, in recent years, especially It is the advanced of requirement display quality.With this accompany, also require light polarizing film high performance, specifically, it is desirable to degree of polarization, thoroughly Degree of penetrating is high, optical characteristics is excellent and form and aspect, durability also excellent light polarizing film.

It is well known, however, that the several PVA altered comprising various structures optical film manufacture initial film.It is such as known , formed by the specific PVA of the hydrophilic functional groups such as the carboxylic acid group containing 0.01 ~ 1 mole of %, ω-hydroxyl-alpha-alkylene The initial stretching orientation position rationality for using polyvinyl alcohol film of light polarizing film and the adsorption treatment of bitintability material are excellent（With reference to specially Sharp document 1）.Further, it is known that the optics for containing the PVA of 1,2- diol bonds particular optical PVA film included in side chain is special Property and draftability are excellent（With reference to patent document 2）.And then it is known that by using by saponification degree be 92 ~ 98.5 moles of % The film that PVA is formed, can shorten the dyeing time when manufacturing light polarizing film（With reference to patent document 3）.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 8-201626 publications

Patent document 2：Japanese Unexamined Patent Publication 2009-24076 publications

Patent document 3：Japanese Unexamined Patent Publication 2012-68609 publications.

The content of the invention

The invention problem to be solved

However, when having used existing known PVA film, from obtaining the excellent optics of optical characteristics, form and aspect and durability Film this point is set out, and the leeway of improvement also be present.

Thus, it is an object of the present invention to provide can easily manufacture the excellent light of optical characteristics, form and aspect and durability The PVA film of film is learned, and has used the manufacture method of the optical film of the PVA film.

The means used to solve the problem

Further investigation is repeated in the present inventor etc. to achieve these goals, as a result finds：If by PVA film The toatl proportion for crystallizing into component and about beam amorphous component amount is set to specific scope, then can solve above-mentioned problem, based on the opinion And further repeat to study, so as to complete the present invention.

That is, the present invention relates to following content：

[1] PVA film, wherein, by spin spin relaxation time T₂Obtain and crystallize into component（a₁）, constraint amorphous component amount （a₂）With amorphous component amount（a₃）When, crystallize into component（a₁）With constraint amorphous component amount（a₂）Be aggregated in and crystallize into component （a₁）, constraint amorphous component amount（a₂）With amorphous component amount（a₃）It is total in shared ratio be 10 ~ 32%, the spin-from Revolve relaxation time T₂It is by handling 1 hour laggard horizontal pulse NMR measure at 60 DEG C（Observing nuclear：¹H）Obtained from；

[2] according to the PVA film of above-mentioned [1], wherein, constrain amorphous component amount（a₂）Crystallizing into component（a₁）, constraint it is non- Brilliant component amount（a₂）With amorphous component amount（a₃）It is total in shared ratio be more than 5%；

[3] according to the PVA film of above-mentioned [1] or [2], wherein, the PVA included in PVA film contains selected from following formula（1）Institute The construction unit shown（1）, following formula（2）Shown construction unit（2）And following formula（3）Shown construction unit（3）In extremely Few a kind of construction unit, by construction unit（1）~（3）Containing ratio be denoted as n respectively₁~n₃Mole %, the containing ratio by vinyl ester units It is denoted as n₄During mole %, meet 0.6≤n₁+n₂+2×n₃+n₄≤1.4；

[changing 1]

[in formula, R¹Represent hydrogen atom, methyl or ethyl.]

[changing 2]

[in formula, R²Represent hydrogen atom, methyl or ethyl, X²It is more than 2 to represent the carbon number with more than 1 hydroxyl Hydroxy alkyl.]

[changing 3]

[in formula, X³And X⁴Separately represent the hydroxy alkyl that the carbon number with more than 1 hydroxyl is more than 1.]

[4] according to the PVA film of above-mentioned [3], wherein, the PVA included in PVA film contains selected from construction unit（1）And structure Unit（2）In at least one kind of construction unit；

[5] according to the PVA film of any one of above-mentioned [1] ~ [4], wherein, the PVA included in PVA film is free of following formula（3） Shown construction unit（3）；

[changing 4]

[in formula, X³And X⁴Separately represent the hydroxy alkyl that the carbon number with more than 1 hydroxyl is more than 1.]

[6] according to the PVA film of any one of above-mentioned [1] ~ [5], wherein, the PVA included in PVA film the degree of polymerization is 3, Less than 000；

[7] according to the PVA film of any one of above-mentioned [1] ~ [6], wherein, the PVA included in PVA film molecular weight distribution For 2.0 ~ 4.0；

[8] according to the PVA film of any one of above-mentioned [1] ~ [7], wherein, swellbility is 160 ~ 240%；

[9] according to the PVA film of any one of above-mentioned [1] ~ [8], it is optical film 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 optical film, it uses the PVA film of above-mentioned [9] or [10], and it is single that the manufacture method possesses progress The process of axle stretching.

The effect of invention

According to the present invention, there is provided can easily manufacture the PVA of the excellent optical film of optical characteristics, form and aspect and durability Film, and used the manufacture method of the optical film of the PVA film.

Embodiment

The PVA film of the present invention is by spin spin relaxation time T₂Obtain and crystallize into component（a₁）, constraint amorphous component amount （a₂）With amorphous component amount（a₃）When, crystallize into component（a₁）With constraint amorphous component amount（a₂）Be aggregated in and crystallize into component （a₁）, constraint amorphous component amount（a₂）With amorphous component amount（a₃）It is total in shared ratio be in the range of 10 ~ 32%, institute State spin spin relaxation time T₂It is by being determined with 60 DEG C of processing, 1 hour laggard horizontal pulse NMR（Observing nuclear：¹H）And obtain 's.

Different from high resolution NMR usually used in structure determination in organic compound etc., pulse NMR is can Measure is related to the transport properties of molecules in system¹Each relaxation time of H cores and it can be utilized high quantitative to obtain in system Each motion composition presence ratio analysis method.In the present invention, component is crystallized into PVA film is obtained（a₁）, constraint Amorphous component amount（a₂）With amorphous component amount（a₃）When, use¹H spin spin relaxation time T₂.Specifically, with¹H from Rotation-spin relaxation time T₂Measure in obtained free induction decay（FID）Signal is approx applied to following formula（4）Side Formula, obtain be on the occasion of a₁、a₂、a₃、a₄、c₁、c₂And c₃.The fitting（Fitting, fitting）It is preferred that use linear least-squares Method is carried out.Among each value of gained, a₁Component is crystallized into equivalent to above-mentioned（a₁）, a₂Equivalent to above-mentioned constraint amorphous component amount （a₂）, a₃Equivalent to above-mentioned amorphous component amount（a₃）.As the specific each condition entered when horizontal pulse NMR is determined, can adopt respectively Each condition described later in embodiment.

[mathematical expression 1]

。

When entering horizontal pulse NMR measure, will be handled 1 hour with 60 DEG C in advance as the PVA film of measure object.By obtaining Component is crystallized into after being handled 1 hour with 60 DEG C（a₁）With constraining amorphous component amount（a₂）Ratio, can obtain with the present invention imitate Fruit（Durability etc.）More closely related mentioned component ratio.The processing will can be immersed in as the PVA film of measure object Being carried out in the state of in water, the PVA film after especially this can be handled is directly fed to pulse NMR measure, it is therefore preferable that NMR pipe it is medium PVA film is immersed in heavy water in the state of carry out.As the more specifically processing method and condition of the processing, The method described later in embodiment can be used.

The PVA film of the present invention is by spin spin relaxation time T₂Obtain and crystallize into component（a₁）, constraint amorphous component amount （a₂）With amorphous component amount（a₃）When, crystallize into component（a₁）With constraint amorphous component amount（a₂）Be aggregated in and crystallize into component （a₁）, constraint amorphous component amount（a₂）With amorphous component amount（a₃）It is total in shared ratio need in 10 ~ 32% scope It is interior, the spin spin relaxation time T₂It is by being determined with 60 DEG C of processing, 1 hour laggard horizontal pulse NMR（Observing nuclear：¹H）And Obtain.

When the ratio is less than 10%, the durability of the optical film obtained using the PVA film can deteriorate.On the other hand, the ratio During more than 32%, the form and aspect of the optical film obtained using the PVA film can reduce.The present invention is not by any restriction, as its reason, It is considered that：Influence is different etc. because of above-mentioned each composition to caused by the state of bitintability pigment used, can speculate the above-mentioned ratio of adjustment Example is extremely important for the effect of the present invention.From the viewpoint of form and aspect, durability from gained optical film etc., crystallised component Amount（a₁）With constraint amorphous component amount（a₂）Be aggregated in and crystallize into component（a₁）, constraint amorphous component amount（a₂）And amorphous component Amount（a₃）Add up to shared ratio to be preferably more than 10.5%, more preferably more than 11%, additionally, it is preferred that for less than 31.5%, more Preferably less than 31%.

Durability due to can further improve gained optical film etc., therefore PVA film preferably has constraint amorphous component, Especially, the constraint amorphous component amount in PVA film（a₂）Crystallizing into component（a₁）, constraint amorphous component amount（a₂）With amorphous into Component（a₃）It is total in shared ratio be preferably more than 5%, more preferably more than 6%.

The PVA included in PVA film species is not particularly limited, and component is crystallized into due to that can be readily available（a₁）Peace treaty Beam amorphous component amount（a₂）Ratio meet the PVA film of above range, it is therefore preferred to, the PVA included in PVA film includes choosing From following formula（1）Shown construction unit（1）, following formula（2）Shown construction unit（2）And following formula（3）Shown structure Unit（3）In at least one kind of construction unit, by construction unit（1）~（3）Containing ratio be set to n₁~n₃Mole %, by ethene The containing ratio of ester units is set to n₄During mole %, meet 0.6≤n₁+n₂+2×n₃+n₄≤1.4。

[changing 5]

[in formula, R¹Represent hydrogen atom, methyl or ethyl.].

[changing 6]

[in formula, R²Represent hydrogen atom, methyl or ethyl, X²It is more than 2 to represent the carbon number with more than 1 hydroxyl Hydroxy alkyl.].

[changing 7]

[in formula, X³And X⁴Separately represent the hydroxyl alkane that the carbon number with more than 1 hydroxyl is more than 1 Base.].

Formula（1）In shown construction unit, R¹Represent hydrogen atom, methyl or ethyl.Due to can more easily be crystallized Component amount（a₁）With constraint amorphous component amount（a₂）Ratio meet PVA film of above range etc., therefore R¹Preferably methyl or second Base, more preferably methyl.

Formula（2）In shown construction unit, R²Represent hydrogen atom, methyl or ethyl.Due to can more easily be crystallized Component amount（a₁）With constraint amorphous component amount（a₂）Ratio meet PVA film of above range etc., therefore R²Preferably hydrogen atom or Methyl.

Formula（2）In shown construction unit, X²Represent the hydroxyl alkane that the carbon number with more than 1 hydroxyl is more than 2 Base.Component is crystallized into due to can more easily obtain（a₁）With constraint amorphous component amount（a₂）Ratio meet the PVA of above range Film etc., therefore the carbon number of the hydroxy alkyl is preferably less than 8, more preferably less than 6, more preferably less than 4, separately Outside, hydroxyl quantity possessed by the hydroxy alkyl is preferably 1 or 2.As the concrete example of the hydroxy alkyl, example can be included Such as 2- hydroxyethyls, 3- hydroxypropyls, 1- hydroxyl -1- Methylethyls, 2- hydroxyl -1- Methylethyls, 4- hydroxybutyls, 2- hydroxyls Base -2- methyl-propyls, 3- hydroxy-2-methyls propyl group, 5- Hydroxy pentyls, 8- hydroxy octyls, 1,2- dihydroxy ethyls, 2,3- dihydroxies Base propyl group etc..Among these, preferably 2- hydroxyethyls, 3- hydroxypropyls, 4- hydroxybutyls, 5- Hydroxy pentyls, 1,2- dihydroxies Base ethyl, more preferably 1,2- dihydroxy ethyls.

Formula（3）In shown construction unit, X³And X⁴It is 1 separately to represent the carbon number with more than 1 hydroxyl Hydroxy alkyl above.Component is crystallized into due to can more easily obtain（a₁）With constraint amorphous component amount（a₂）Ratio meet PVA film of above range etc., therefore, the carbon number of the hydroxy alkyl are preferably less than 8, are more preferably less than 6, are further excellent Elect less than 4 as, in addition, hydroxyl quantity is also different because of the carbon number of the hydroxy alkyl possessed by the hydroxy alkyl, preferably 1 It is individual or 2.As the concrete example of the hydroxy alkyl, such as methylol, 2- hydroxyethyls, 3- hydroxypropyls, 1- hydroxyls can be included Base -1- Methylethyls, 2- hydroxyl -1- Methylethyls, 4- hydroxybutyls, 2- hydroxy-2-methyls propyl group, 3- hydroxy-2-methyls third Base, 8- hydroxy octyls, 1,2- dihydroxy ethyls, 2,3- dihydroxypropyls etc..Among these, preferably methylol, 2- hydroxyl second Base, 3- hydroxypropyls, 4- hydroxybutyls, more preferably 1,2- dihydroxy ethyls, methylol.X³And X⁴It is same to each other or different to each other Can, it is preferably identical.

As foregoing illustrative PVA, can include for example：Include construction unit（1）And be free of construction unit（2）With（3） PVA；Include construction unit（2）And be free of construction unit（1）With（3）PVA；Include construction unit（3）And be free of structure list Member（1）With（2）PVA；Include construction unit（1）With（2）And be free of construction unit（3）PVA；Include construction unit（1）With （3）And be free of construction unit（2）PVA；Include construction unit（2）With（3）And be free of construction unit（1）PVA；Construction unit （1）~（3）PVA included etc., it is contemplated that during ease of manufacture etc., be preferably：Include construction unit（1）And be free of structure list Member（2）With（3）PVA；Include construction unit（2）And be free of construction unit（1）With（3）PVA；Or include construction unit （3）And be free of construction unit（1）With（2）PVA.

In addition, from the viewpoint of raw material availability etc., the PVA included in PVA film is preferably free of construction unit（3）.From This viewpoint is set out, and as foregoing illustrative PVA, is preferably：Include construction unit（1）And be free of construction unit（2）With（3）'s PVA；Include construction unit（2）And be free of construction unit（1）With（3）PVA；Or include construction unit（1）With（2）And not Containing construction unit（3）PVA.

In addition, foregoing illustrative PVA is included or not comprising vinyl ester units, it is contemplated that excellent during ease of manufacture etc. Choosing includes vinyl ester units.As the vinyl ester units, for typical case, can include it is aftermentioned it is such, from for manufacturing PVA Vinyl acetate system monomer construction unit.

In foregoing illustrative PVA, by construction unit（1）~（3）Containing ratio be denoted as n respectively₁~n₃Mole %, by vinyl acetate list The containing ratio of member is denoted as n₄During mole %, meet 0.6≤n₁+n₂+2×n₃+n₄≤1.4.By making n₁+n₂+2×n₃+n₄Value be 0.6 mole of more than %, improved using the form and aspect of optical film obtained from the PVA film comprising the PVA.On the other hand, by making n₁+n₂ +2×n₃+n₄Value be 1.4 moles of below %, use optical film obtained from the PVA film comprising the PVA durability improve.From From the viewpoint of the form and aspect of gained optical film, durability etc., n₁+n₂+2×n₃+n₄Value be preferably 0.63 mole of more than %, it is more excellent 0.65 mole of more than % is elected as, in addition, more preferably 1.38 moles of below %, more preferably 1.35 moles of below %.Need Bright, in this specification, construction unit refers to the repeat unit for forming polymer, construction unit（1）~（3）Containing ratio point Construction unit is not referred to（1）~（3）Molal quantity relative to form PVA entire infrastructure unit molal quantity shared by ratio, second The containing ratio of alkene ester units refers to the molal quantity of vinyl ester units relative to shared by the molal quantity for the entire infrastructure unit for forming PVA Ratio.

In foregoing illustrative PVA, as long as the containing ratio n of vinyl ester units₁+n₂+2×n₃+n₄Value be in above-mentioned model Enclose, be just not particularly limited, it is contemplated that easily obtain and crystallize into component（a₁）With constraint amorphous component amount（a₂）Ratio meet When the PVA film of above range, ease of manufacture etc., preferably 1.35 moles of below %, more preferably 1.3 moles of below %, enter one Step is preferably 1 mole of below %, 0.5 mole of below % and then can be 0.3 mole of below %, additionally, it is preferred that be 0.01 mole of % with Upper, more preferably 0.05 mole of more than %, more preferably 0.1 mole of more than %.

Foregoing illustrative PVA manufacture method is not particularly limited.For example following method can be included：Vinyl acetate system is single Body with it with that can be copolymerized and can be converted into being selected from construction unit（1）~（3）In at least one kind of construction unit unsaturation it is single Body is copolymerized, and the vinyl ester units of gained vinyl acetate based copolymer is converted into vinyl alcohol units, and then will be derived from and can turn Change into and be selected from construction unit（1）~（3）In at least one kind of construction unit unsaturated monomer construction unit be converted into selected from knot Structure unit（1）~（3）In at least one kind of construction unit method.As construction unit can be converted into（1）Unsaturated monomer, Such as following formula can be included（5）Shown unsaturated monomer.As construction unit can be converted into（2）Unsaturated monomer, Such as following formula can be included（6）Shown unsaturated monomer.As construction unit can be converted into（3）Unsaturated monomer, Such as following formula can be included（7）Shown unsaturated monomer.

[changing 8]

[in formula, R¹Represent hydrogen atom, methyl or ethyl, Y¹Represent methylol（ヒ De ロ メ チ Le bases）Or have and be somebody's turn to do The group for the structure that hydroxyl contained by methylol is protected by protection group.].

[changing 9]

[in formula, R²Represent hydrogen atom, methyl or ethyl, Y²It is more than 2 to represent the carbon number with more than 1 hydroxyl The group of hydroxy alkyl or the structure protected with the hydroxyl contained by the hydroxy alkyl by protection group.].

[changing 10]

[in formula, Y³And Y⁴Separately represent hydroxy alkyl that the carbon number with more than 1 hydroxyl is more than 1, Or the group for the structure protected with the hydroxyl contained by the hydroxy alkyl by protection group.].

Formula（5）In, R¹Related description and formula（1）In R¹It is identical, omit herein and repeat to record.

Formula（5）In, Y¹During the group for the structure that expression is protected with the hydroxyl contained by methylol by protection group, as the guarantor Base is protected, the acyl groups such as acetyl group, propiono can be included；Acetal radical；Carbonate group etc., among these, due to can be by ethene Ester units are converted into removing the protection group during vinyl alcohol units, therefore preferably acyl group, more preferably acetyl group.Due to above-mentioned example PVA easy to manufacture shown etc., therefore Y¹The group for the structure preferably protected with the hydroxyl contained by methylol by protection group.

Formula（6）In, R²Related description and formula（2）In R²It is identical, omit herein and repeat to record.

Formula（6）In, Y²What is represented has the related description for the hydroxy alkyl that the carbon number of more than 1 hydroxyl is more than 2 With formula（2）In X²The carbon number with more than 1 hydroxyl represented is that the related description of more than 2 hydroxy alkyl is identical , omit herein and repeat to record.In addition, Y²The structure that expression is protected with the hydroxyl contained by above-mentioned hydroxy alkyl by protection group During group, as the protection group, the acyl groups such as acetyl group, propiono can be included；The acetal radicals such as isopropylidene；Carbonate group etc., Among these, due to that can remove the protection group when vinyl ester units are converted into vinyl alcohol units, therefore preferably acyl group, More preferably acetyl group.Y²During the group for the structure that expression is protected with the hydroxyl contained by above-mentioned hydroxy alkyl by protection group, make For its concrete example, such as 2- Acetoxvethyls, 3- acetyloxypropyls, 1- acetoxyl group -1- Methylethyls, 2- can be included Acetoxyl group -1- Methylethyls, 4- Acetoxybutyls, 2- acetoxyl group -2- methyl-propyls, 3- acetoxyl group -2- methyl-props Base, 8- acetoxyl groups octyl group, 1,2- diacetoxies ethyl, 2,3- diacetoxy propyl group etc..Because foregoing illustrative PVA holds Easily manufacture etc., therefore Y²Preferably there is the group of following structure, the structure is that the carbon number with more than 1 hydroxyl is Hydroxyl is obtained from the protection of protection group possessed by more than 2 hydroxy alkyl.

As formula（6）Shown unsaturated monomer, such as 4- acetoxyl groups -1- butylene, 5- acetoxyl groups -1- can be included Amylene, 6- acetoxyl group -1- hexenes, 7- acetoxyl group -1- heptene, 3,4- diacetoxy -1- butylene etc., preferably 3,4- bis- Acetoxyl group -1- butylene.

Formula（7）In, Y³And/or Y⁴What is represented has the phase for the hydroxy alkyl that the carbon number of more than 1 hydroxyl is more than 1 Speak on somebody's behalf bright and formula（3）In X³And/or X⁴What is represented has the phase for the hydroxy alkyl that the carbon number of more than 1 hydroxyl is more than 1 It is identical to speak on somebody's behalf bright, omits herein and repeats to record.In addition, Y³And/or Y⁴Represent with the hydroxyl quilt contained by above-mentioned hydroxy alkyl During the group of the structure of protection group protection, as the protection group, the acyl groups such as acetyl group, propiono can be included；Isopropylidene etc. Acetal radical；Carbonate group etc., among these, due to the protection can be removed when vinyl ester units are converted into vinyl alcohol units Base, therefore preferably acyl group, more preferably acetyl group.Y³And/or Y⁴Represent to be protected with the hydroxyl contained by above-mentioned hydroxy alkyl During the group of the structure of base protection, as its concrete example, such as acetoxy-methyl, 2- Acetoxvethyls, 3- can be included Acetyloxypropyl, 1- acetoxyl group -1- Methylethyls, 2- acetoxyl group -1- Methylethyls, 4- Acetoxybutyls, 2- second Acyloxy -2- methyl-propyls, 3- acetoxyl group -2- methyl-propyls, 8- acetoxyl groups octyl group, 1,2- diacetoxies ethyl, 2, 3- diacetoxy propyl group etc..Due to foregoing illustrative PVA easy to manufacture etc., therefore Y³And/or Y⁴Preferably there is following structure Group, the structure is hydroxyl contained by the hydroxy alkyl that the carbon number with more than 1 hydroxyl is more than 1 by protection group Obtained from protection, it is further preferred that Y³And Y⁴Both are the group with following structure, and the structure is that have more than 1 The carbon number of hydroxyl is obtained from the hydroxyl contained by more than 1 hydroxy alkyl is protected by protection group.

As formula（7）Shown unsaturated monomer, such as 1,3- diacetoxy -2- methylene propane, 1 can be included, Propionyloxy -2- methylene the propane of 3- bis-, the butyryl acyloxy -2- methylene propane of 1,3- bis- etc., preferably 1,3- diacetoxies - 2- methylene propane.

Vinyl acetate system monomer for manufacturing foregoing illustrative PVA is not particularly limited, and can include such as vinyl formate Ester, vinylacetate, propionate, vinyl butyrate, vinyl isobutyrate ester, pivalic acid vinyl acetate, tertiary ethylene carbonate, oneself Vinyl acetate, sad vinyl acetate, caprate, vinyl laurate, vinyl palmitate, stearic acid vinyl ester, oleic acid second The viewpoint, preferably acetic acid second such as alkene ester, vinyl benzoate etc., ease of manufacturing, acquisition easiness, cost from PVA Alkene ester.

By vinyl acetate system monomer with that can be copolymerized with it and can be converted into being selected from construction unit（1）~（3）In at least 1 The polymerization methodses when unsaturated monomer of kind of construction unit is copolymerized can be batchwise polymerization, semi-batch polymerization, continuous polymerization, Any-mode in semi-continuous polymerization etc., can be with applied ontology polymerization, solution polymerization process, suspension polymerisation as polymerization Method known to method, emulsion polymerization etc..Be typically employed in mass polymerization that polymerization is promoted in solvent-free or alcohol equal solvent or Solution polymerization process.When obtaining the vinyl acetate based copolymer of high polymerization degree, further preferably emulsion polymerization.The solvent of solution polymerization process It is not particularly limited, for example, alcohol.The alcohol used in the solvent of solution polymerization process is, for example, the lower alcohols such as methanol, ethanol, propyl alcohol. Solvent load in polymerization system considers that chain tra nsfer and the selection of solvent, such as solvent are according to PVA targeted degree of polymerization During methanol, with the mass ratioes of whole monomers for being included in solvent and polymerization system=（Solvent）/（Whole monomers）Meter, preferably from Select in the range of 0.01 ~ 10, more preferably selected in the range of 0.05 ~ 3.

By vinyl acetate system monomer with that can be copolymerized with it and can be converted into being selected from construction unit（1）~（3）In at least 1 The polymerization initiator used in the copolymerization of the unsaturated monomer of kind of construction unit according to polymerization from known polymerization initiator, Such as selected in azo series initiators, peroxide series initiators, redox series initiators.Azo series initiators are for example It is double for 2,2 '-azobis isobutyronitrile, 2,2 '-azo（2,4- methyl pentane nitriles）, 2,2 '-azo it is double（4- methoxyl group -2,4- diformazans Base valeronitrile）.Peroxide series initiators are, for example, diisopropyl peroxydicarbonate, the carbon of two -2- ethylhexyls peroxidating two The peroxocarbonate based compounds such as acid esters, diethoxy ethyl peroxydicarbonate；Tert-butyl hydroperoxide neodecanoic acid ester, α-cumyl The peroxyester based compound such as new decanoate ester peroxide；Acetyl group peroxidating cyclohexylsulfonyl；2,4,4- tri-methyl-amyl -2- mistakes Aoxidize phenoxy group acetate；Acetyl peroxide.Can also be by potassium peroxydisulfate, ammonium persulfate, hydrogen peroxide etc. and above-mentioned initiator Combine and polymerization initiator is made.Redox series initiators are, for example, by above-mentioned peroxide series initiators and bisulfite Polymerization initiator obtained from the combination of the reducing agents such as sodium, sodium acid carbonate, tartaric acid, L-AA, rongalite.Polymerization initiator Dosage it is different because of the species of polymerization initiator, therefore can not lump together, be selected according to polymerization speed.For example, Polymerization initiator uses 2, when 2 '-azobis isobutyronitrile or acetyl peroxide, relative to vinyl acetate system monomer be preferably 0.01 ~ 0.2 mole of %, more preferably 0.02 ~ 0.15 mole of %.

Vinyl acetate system monomer with it with that can be copolymerized and can be converted into being selected from construction unit（1）~（3）In it is at least one kind of The copolymerization of the unsaturated monomer of construction unit can be carried out in the presence of chain-transferring agent.Chain-transferring agent is, for example, acetaldehyde, propionic aldehyde Deng aldehydes；The ketones such as acetone, MEK；The thio-alcohols such as 2- hydroxyl ethyl mercaptans；Phosphinic acids sodium-hydrate grade phosphonates etc.. Wherein, it is adapted to use aldehydes and ketone.The dosage of chain-transferring agent can be according to the chain tra nsfer coefficient and PVA of the chain-transferring agent to be used Targeted degree of polymerization determine that to be commonly angled relative to the mass parts of vinyl acetate system monomer 100 be preferably 0.1 ~ 10 mass parts.

By the way that vinyl acetate system monomer will be utilized with that can be copolymerized with it and can be converted into being selected from construction unit（1）~（3）In At least one kind of construction unit unsaturated monomer copolymerization and obtain vinyl acetate based copolymer carry out saponification, can obtain above-mentioned The PVA of illustration.By the way that the vinyl acetate based copolymer is carried out into saponification, the vinyl ester units in vinyl acetate based copolymer are converted into Vinyl alcohol units.In addition, such as formula（3）In shown unsaturated monomer, such as Y¹It is by acyl with hydroxyl possessed by methylol The situation of the group of the structure of base protection is such, can be copolymerized with vinyl acetate system monomer and can be converted into being selected from structure list Member（1）~（3）In at least one kind of construction unit unsaturated monomer have by acyl group protect hydroxyl when, from unsaturation singly The ester bond of the acyl moiety in the construction unit of body is also saponified and produces hydroxyl.Therefore, the PVA does not enter after saponification One step the reaction such as is hydrolyzed and can also manufactured.

The saponification of vinyl acetate based copolymer can for example be dissolved with the shape of the vinyl acetate based copolymer in alcohol or aqueous alcohol Carried out under state.The alcohol used in saponification can include the lower alcohol such as methanol, ethanol, preferably methanol.Used in saponification Alcohol other solvents such as can include acetone, methyl acetate, ethyl acetate, benzene with below the 40 mass % of its quality ratio. The catalyst used in saponification be, for example, the base catalysts such as the hydroxide of the alkali metal such as potassium hydroxide, sodium hydroxide, sodium methoxide, The acid catalysts such as inorganic acid.The temperature for carrying out saponification does not limit, and is adapted in the range of 20 ~ 60 DEG C.With the propulsion of saponification And when gradually separating out gelatinous product, after product is crushed, cleaned, dried, so as to obtain PVA.Saponification side Method is not limited to preceding method, can apply known method.

Foregoing illustrative PVA can also include construction unit（1）~（3）, its beyond vinyl alcohol units and vinyl ester units Its construction unit.As the other structures unit, can include for example originating from the alkene that can be copolymerized with vinyl acetate system monomer Belong to the construction unit of unsaturated monomer.Furthermore it is also possible to comprising from can be copolymerized with above-mentioned vinyl acetate system monomer and energy Enough it is converted into being selected from construction unit（1）~（3）In at least one kind of construction unit unsaturated monomer construction unit（It is being deprotected During, it is not translated to be selected from construction unit（1）~（3）In at least one kind of construction unit construction unit）.

In foregoing illustrative PVA, the molal quantity for the entire infrastructure unit for forming the PVA is denoted as 100 moles of %, structure list Member（1）~（3）, vinyl alcohol units and vinyl ester units add up to the shared ratio to be preferably 90 moles of more than %, more preferably 98 Mole more than %, more preferably 99 moles of more than %, 99.5 moles of more than %, 99.8 moles of more than %, 99.9 moles of more than %, And then can be 100 moles of %.

As above-mentioned ethylenically unsaturated monomer, for example, alpha-olefin such as ethene, propylene, n-butene, isobutene, 1- hexenes Class；Acrylic acid and its salt；With acrylate-based unsaturated monomer；Methacrylic acid and its salt；With methacrylate The unsaturated monomer of base；Acrylamide；N methacrylamide, N- ethyl acrylamides, N, N- DMAAs, dipropyl Ketone acrylamide, acrylamide propane sulfonic acid and its salt, acrylamide propyl dimethylamine and its salt（Such as quaternary ammonium salt）Deng acryloyl Amine derivative；Methacrylamide；N- methyl methacrylamides, N- ethyl methacrylamides, the sulphur of Methacrylamide third Acid and its salt, Methacrylamide diemethylamine and its salt（Such as quaternary ammonium salt）Etc. methacrylamide derivatives；Methyl second Alkene ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, isobutyl vinyl ether-glycidyl Ether, tert-Butyl vinyl ether, dodecyl vinyl, stearyl vinyl ethers, 2,3- diacetoxy -1- vinyl oxygen third The vinyl ethers such as alkane；The vinyl cyanide class such as acrylonitrile, methacrylonitrile；The vinyl halides class such as vinyl chloride, PVF；Inclined dichloro The dihalo vinyl partially such as ethene, vinylidene fluoride；The allyls such as 2,3- diacetoxy -1- allyloxys propane, allyl chloride Based compound；The unsaturated dicarboxylics such as maleic acid, itaconic acid, fumaric acid and its salt or ester；The second such as vinyltrimethoxy silane Alkenyl silyl compound；Isopropenyl acetate.

Construction unit is selected from foregoing illustrative PVA（1）~（3）In at least one kind of construction unit, vinyl alcohol units and Others are formed arbitrarily putting in order for unit and are not particularly limited, and can be any one of random, block, interaction etc..

Component is crystallized into due to being easier acquisition（a₁）With constraint amorphous component amount（a₂）Ratio meet above range PVA film and improved etc. using the form and aspect of optical film obtained from the PVA film, therefore the foregoing illustrative PVA degree of polymerization is preferably Less than 3,000, less than 2,900, more preferably less than 2,800 are more preferably.On the other hand, because use includes the PVA PVA film obtained from the durability of optical film improve, therefore the degree of polymerization be preferably greater than 2,000, more preferably above 2,100, Further preferably more than 2,200.It should be noted that the degree of polymerization of the PVA in this specification refers to according to JIS K6726- The average degree of polymerization of 1994 record measure.

Further, since easily acquisition crystallizes into component（a₁）With constraint amorphous component amount（a₂）Ratio meet above-mentioned model The PVA film enclosed, therefore foregoing illustrative PVA molecular weight distribution is preferably 2.0 ~ 4.0, the molecular weight distribution is more preferably 2.2 Above, more preferably more than 2.4, in addition, more preferably less than 3.8, more preferably less than 3.6.Need what is illustrated It is that the molecular weight distribution of the PVA in this specification refers to pass through matter average molecular weight（Mw）/ number-average molecular weight（Mn）The value calculated. Matter average molecular weight（Mw）And number-average molecular weight（Mn）It can obtain as follows：Using single dispersing polymethyl methacrylate as standard Product, the hexafluoroisopropanol containing 20mmol/L sodium trifluoroacetates is used for mobile phase, coagulated with 40 DEG C, flow 0.2mL/ minutes Glue penetration chromatogram（TOSOH Co., Ltd's system, device：HLC-8220GPC, post：GMHHR-H（S））Measure, so as to obtain.

In the PVA film of the present invention, in addition to above-mentioned PVA, plasticizer can also be included., can as preferable plasticizer Include polyalcohol, as concrete example, can include ethylene glycol, glycerine, propane diols, diethylene glycol, two glycerine, triethylene glycol, Tetraethylene glycol, trimethylolpropane etc..The PVA film of the present invention can include one kind or two or more in these plasticizer.These Among, from the viewpoint of the effect for improving draftability, preferably glycerine.

On the content of the plasticizer in the PVA film of the present invention, relative to the mass parts of PVA 100 wherein included, preferably For more than 1 mass parts, more preferably more than 3 mass parts, more preferably more than 5 mass parts, additionally, it is preferred that being 20 mass parts Below, it is more preferably below 17 mass parts, is more preferably below 15 mass parts.By making the content to be more than 1 mass parts, The draftability of film further improves.On the other hand, by make the content for below 20 mass parts, can suppress film it is excessively soft, Treatability reduces.

Processing stabilizers such as filler, copper compound, weather-proof can also suitably be coordinated in the PVA film of the present invention as needed Property stabilizer, colouring agent, ultra-violet absorber, light stabilizer, antioxidant, antistatic additive, fire retardant, other thermoplastic resins Fat, lubricant, spices, defoamer, deodorant, extender, remover, releasing agent, reinforcing agent, crosslinking agent, mould inhibitor, anti-corrosion The additives such as agent, crystallization rate delayed-action activator.

Total shared quality of the ratio based on PVA film of PVA and plasticizer in the PVA film of the present invention are preferably 80 matter Measure more than %, more preferably more than 90 mass %, more preferably more than 95 mass %.

The present invention PVA film swellbility preferably in the range of 160 ~ 240%, more preferably in the range of 170 ~ 230%, Particularly preferably in the range of 180 ~ 220%.By making swellbility be more than 160%, can more efficiently prevent from 60 DEG C of processing 1 Component is crystallized into after hour（a₁）With constraint amorphous component amount（a₂）Total ratio become too high, obtained using the PVA film Optical film form and aspect improve.On the other hand, by making swellbility be less than 240%, can more efficiently prevent from 60 DEG C of processing Component is crystallized into after 1 hour（a₁）With constraint amorphous component amount（a₂）Total ratio become too low, obtained using the PVA film The durability of the optical film arrived improves.It should be noted that in this specification, the swellbility of PVA film refers to：By PVA film 30 DEG C distilled water in dried 16 hours with 105 DEG C after quality when impregnating 30 minutes divided by dipping after quality obtained from be worth Percentage, specifically, it can be measured by method described later in embodiment.Swellbility for example can be by changing at heat The condition of reason adjusts, generally can be by improving heat treatment temperature, extending heat treatment time to reduce swellbility.

The PVA film of the present invention can easily manufacture the excellent optical film of optical characteristics, form and aspect and durability, therefore in thickness In the case that degree is thinner than ever, can particularly effectively it use.The thickness of the PVA film is preferably 1 ~ 60 μm, more preferably 5 ~ 55 μ M, 10 ~ 50 μm are particularly preferably.When the thickness is less than 1 μm, when the uniaxial tension for manufacturing the optical films such as light polarizing film is handled, deposit The tendency of tension failure is easily occurring.In addition, when the thickness is blocked up, when the uniaxial tension for manufacturing optical film is handled, deposit The uneven tendency of stretching occurs easy.

The width of the PVA film of the present invention is not particularly limited, and can be determined according to its purposes etc..In recent years, from liquid crystal From the viewpoint of TV, the large screen of liquid crystal display develop, when the width of PVA film being made into more than 3m in advance, it Be suitable for being made the purposes of end article.On the other hand, when the width of PVA film is excessive, utility unit manufacture optics is being utilized In the case of film, produce sometimes and equably carry out the problems such as uniaxial tension itself easily becomes difficulty, therefore, the width of PVA film Preferably below 7m.

The manufacture method of the PVA film of the present invention is not particularly limited, preferably using the thickness and width of the film after film Degree becomes manufacture method evenly, such as can be manufactured using following film stoste：The above-mentioned PVA of PVA film will be formed Be dissolved in liquid medium, and as needed further by above-mentioned plasticizer, additive and surfactant described later etc. it In one kind or two or more be dissolved in obtained from liquid medium be film-made stoste；As needed include comprising PVA and further It is one kind or two or more among plasticizer, additive, surfactant and liquid medium etc., and the film that PVA has been melted is former Liquid.When the film stoste contains at least one kind of in plasticizer, additive and surfactant, preferably these compositions equably mix Close.

As the aforesaid liquid medium for preparing film stoste, such as water, dimethyl sulfoxide (DMSO), dimethyl methyl can be included Acid amides, dimethyl acetamide, 1-METHYLPYRROLIDONE, ethylene glycol, glycerine, propane diols, diethylene glycol, triethylene glycol, tetrem two Alcohol, trimethylolpropane, ethylenediamine, Diethylenetriamine etc., can be using one kind or two or more among these.Wherein, to ring Born caused by border, from the viewpoint of recyclability, preferably water.

It is film-made the volatile matter rate of stoste（Because the volatile ingredients such as the liquid medium that volatilizees, evaporating and being removed exist during film The content ratio being film-made in stoste）It is also different because of film-forming method, film forming condition etc., in general, it is preferred to 50 ~ 95 mass %'s In the range of, more preferably in the range of 55 ~ 90 mass %, further preferably in the range of 60 ~ 85 mass %.By making film former The volatile matter rate of liquid is more than 50 mass %, and being film-made the viscosity of stoste will not become too high, filtering, taking off when preparing film stoste Bubble is successfully carried out, the few film of easy to manufacture foreign matter, shortcoming.On the other hand, by making the volatile matter rate of film stoste be Below 95 mass %, being film-made the concentration of stoste will not become too low, industrial easy to manufacture film.

Film stoste preferably comprises surfactant.By the way that comprising surfactant, Film making properties improve, suppress film generation thickness Degree is uneven, and film easily from the metallic roll for film, take stripping.PVA is manufactured by the film stoste comprising surfactant During film, surfactant can be contained in the film.The species of above-mentioned surfactant is not particularly limited, from from metallic roll, band Viewpoint of the fissility of upper stripping etc. is set out, preferably anionic surfactant or nonionic surfactant.

As anionic surfactant, such as it is adapted to, the carboxylic acid type such as potassium laurate；Polyoxyethylene lauryl ether The sulfuric acid ester types such as sulfate, sulfuric acid monooctyl ester；Sulfonic acid types such as dodecyl benzene sulfonate etc..

As nonionic surfactant, such as be adapted to, the alkyl ether type such as polyoxyethylene oleyl ether；Polyoxyethylene is pungent The alkyl phenyl ether type such as base phenyl ether；The alkyl esters such as polyoxyethylene laural ester；The alkylamines such as polyoxyethylene laural base amino ethers Type；The alkylamide type such as polyoxyethylene laural acid amides；The polypropylene glycol ether type such as polyoxyethylene poly-oxygen propylene aether；Laurate diethanol The alkylol amide types such as acid amides, oleic acid diethyl amide；Allyl phenyl ether type such as polyoxy alkylidene allyl phenyl ether etc..

These surfactants can be used alone, or two or more is applied in combination.

When film stoste includes surfactant, its content is excellent relative to the mass parts of PVA 100 included in film stoste In the range of being selected in 0.01 ~ 0.5 mass parts, more preferably in the range of 0.02 ~ 0.3 mass parts, particularly preferably 0.05 ~ 0.1 In the range of mass parts.By making the content for more than 0.01 mass parts, Film making properties and fissility further improve.The opposing party Face, ooze out into the surface of PVA film for surfactant below 0.5 mass parts, can be suppressed by making the content and occur caking, Treatability reduces.

As using film-forming method during above-mentioned film stoste manufacture PVA film, film method of for example rolling, extrusion can be included Film method, film by wet method, gel film method etc..These film-forming methods can only with a kind, can also combine use 2 kinds with On.Among these film-forming methods, due to the PVA film that thickness and width is uniform and physical property is good can be obtained, so it is preferred that calendering Film method, extrusion film method.Manufactured film can be dried, be heat-treated as needed.

As the example of the specific manufacture method of the PVA film of the present invention, such as industrially preferably with the following method：Use T-shaped slit die, hopper plate, I- moulds, lip apply machine mould etc., and above-mentioned film stoste is equably sprayed or is cast positioned at most upstream side Rotation and the 1st heated roller（Or band）Periphery on, make volatile ingredient from spray or be cast in the 1st roller（Or band）'s One face of the film on periphery is evaporated and dried, and is then being configured at one or more rotations of side downstream and is heating Roller periphery on be further dried, or pass through in hot-air drying device and after being further dried, using batching dress Put the method batched.Using heating roller carry out drying with using hot-air drying device progress drying can it is appropriately combined come Implement.

The purposes of the PVA film of the present invention is not particularly limited, according to the PVA film of the present invention, due to can easily manufacture light Characteristic, form and aspect and the excellent optical film of durability are learned, it is therefore preferable that being used as being used to manufacturing the initial film of optical film. As this optical film, can include such as light polarizing film, phase retardation film, preferably light polarizing film.This optical film for example can be with By the way that the PVA film of the present invention is used as into optical film manufacture with the method for initial film and possesses the method for the process for carrying out uniaxial tension To manufacture, specifically, can be manufactured by possessing the method for following process, the process be to the present invention PVA film from Body or implement aftermentioned swelling treatment etc. and the caused PVA film from PVA film of the present invention（Hereinafter, sometimes will the " present invention PVA film " be referred to as with the PVA film of PVA film of the present invention " be derived from " " PVA film based on the present invention "）Carry out uniaxial tension.

Method when manufacturing light polarizing film using the PVA film of the present invention is not particularly limited, and can use and use all the time Any means.As this method, can include for example the PVA film based on the present invention is implemented dyeing and uniaxial tension or The method that person implements uniaxial tension to the PVA film based on the present invention containing dyestuff.As for manufacturing the more specific of light polarizing film Method, it can include：For the PVA film based on the present invention, implement swelling, dyeing, uniaxial tension, and as needed further Implement the method for crosslinking Treatment, fixing process, drying, heat treatment etc..Now, swelling, dyeing, crosslinking Treatment, uniaxial tension, solid The order that fixed processing etc. is respectively handled is not particularly limited, and can also carry out the processing of 1 or more than 2 simultaneously.In addition, each processing In 1 or more than 2 can also carry out 2 times or more than 2 times.

Swelling can be by the way that the PVA film based on the present invention be immersed in water to carry out.As water temperature when being impregnated in water, It is preferred that in the range of 20 ~ 40 DEG C, more preferably in the range of 22 ~ 38 DEG C, further preferably in the range of 25 ~ 35 DEG C.Separately Outside, as the time for being impregnated in water, such as preferably in the range of 0.1 ~ 5 minute, more preferably in the range of 0.5 ~ 3 minute. It should be noted that water when being impregnated in water is not limited to pure water, can be the aqueous solution dissolved with various composition or The mixture of water and aqueous medium.

Dyeing can be by making the contact of bitintability pigment be carried out based on the PVA film of the present invention.As bitintability pigment, generally Use iodine system pigment.As the period of dyeing, before being uniaxial tension, uniaxial tension when, after uniaxial tension in arbitrary order Section.Dyeing is generally by being that PVA film is immersed in and is used as the solution containing iodine-potassium iodide of dye bath（The especially aqueous solution） Carry out, also be adapted for using this colouring method in the present invention.Iodine concentration in dye bath is preferably in 0.01 ~ 0.5 mass % scope Interior, KI concentration is preferably in the range of 0.01 ~ 10 mass %.In addition, the temperature of dye bath is preferably 20 ~ 50 DEG C, especially Preferably 25 ~ 40 DEG C.

, can be more effective when carrying out wet tensile with high temperature by implementing crosslinking Treatment to the PVA film based on the present invention Ground prevents PVA dissolutions into water.From this viewpoint, crosslinking Treatment preferably contact bitintability pigment processing after and single shaft Carried out before stretching.Crosslinking Treatment can be by being impregnated in the aqueous solution comprising crosslinking agent to enter by the PVA film based on the present invention OK.As the crosslinking agent, can use one kind or two or more in the boron compounds such as the borates such as boric acid, borax.Include crosslinking Crosslinker concentration in the aqueous solution of agent preferably in the range of 1 ~ 15 mass %, more preferably in the range of 2 ~ 7 mass %, enter one Step is preferably in the range of 3 ~ 6 mass %.In the range of 1 ~ 15 mass % is in by making the concentration of crosslinking agent, it is able to maintain that fully Draftability.The aqueous solution comprising crosslinking agent can contain KI etc..The temperature of the aqueous solution comprising crosslinking agent preferably 20 ~ In the range of 50 DEG C, particularly preferably in the range of 25 ~ 40 DEG C., can be efficient by making the temperature in the range of 20 ~ 50 DEG C Ground is crosslinked.

The uniaxial tension of PVA film based on the present invention can utilize any one of wet tensile method or dry stretch process to enter OK.In the case of wet tensile method, can be carried out in the aqueous solution comprising boric acid, can also in above-mentioned dye bath, after State and carried out in fixing process bath.In addition, in the case of dry stretch process, can directly be stretched at room temperature, can also Stretched while heating, the PVA film after water suction can also be used to carry out in atmosphere.Among these, due to can be Be evenly stretched on width, thus preferably wet tensile method, single shaft is more preferably carried out in the aqueous solution comprising boric acid Stretching.Boric acid concentration in boric acid aqueous solution is preferably in the range of 0.5 ~ 6.0 mass %, more preferably 1.0 ~ 5.0 mass %'s In the range of, particularly preferably in the range of 1.5 ~ 4.0 mass %.In addition, boric acid aqueous solution can contain KI, KI Concentration is preferably in the range of 0.01 ~ 10 mass %.

Draft temperature during uniaxial tension is preferably in the range of 30 ~ 90 DEG C, more preferably in the range of 40 ~ 80 DEG C, spy Not preferably in the range of 50 ~ 70 DEG C.

In addition, from the viewpoint of the polarised light performance of gained light polarizing film, stretching ratio during uniaxial tension is preferably 6.6 More than times, it is more preferably more than 6.8 times, particularly preferably more than 7.0 times.The upper limit of stretching ratio is not particularly limited, stretching Multiplying power is preferably less than 8 times.

Uniaxial tension direction when the PVA film of strip is carried out into uniaxial tension is not particularly limited, and can use to strip Uniaxial tension, the horizontal uniaxial tension of direction progress, the light polarizing film excellent due to polarised light performance can be obtained, therefore be preferably The uniaxial tension carried out to strip direction.The uniaxial tension carried out to strip direction can be parallel to each other more by using possessing The stretching device of individual roller, and the peripheral speed between each roller is changed to carry out.On the other hand, horizontal uniaxial tension can use tentering Type stretching-machine is carried out.

When manufacturing light polarizing film, in order that bitintability pigment（Iodine system pigment etc.）Film is firmly adsorbed in, is preferably fixed Processing.As the fixing process bath used in fixing process, can use comprising a kind or 2 in the boron compounds such as boric acid, borax The aqueous solution of the kind above.In addition, add iodine compound, metallic compound in being bathed as needed to fixing process.Bearing The concentration of boron compound in reason bath is preferably generally 2 ~ 15 mass %, particularly preferably 3 ~ 10 mass % or so.By making this dense Degree can more securely adsorb bitintability pigment in the range of 2 ~ 15 mass %.The temperature of fixing process bath is preferably 15 ~ 60 DEG C, particularly preferably 25 ~ 40 DEG C.

Dry condition is not particularly limited, preferably in the range of 30 ~ 150 DEG C, particularly preferably in 50 ~ 130 DEG C of model Enclose and be dried at interior temperature.By being dried with the temperature in the range of 30 ~ 150 DEG C, it is excellent to be readily available dimensional stability Different light polarizing film.

Light polarizing film obtained from operating as above generally in its two-sided or single-sided lamination optical clear and has mechanical strength It is used as polarization plates after diaphragm.As diaphragm, Triafol T can be used（TAC）Film, cyclic olefin polymer（COP）Film, Acetylbutyrylcellulose（CAB）Film, acrylic acid mesentery, polyester mesentery etc..In addition, as the bonding agent for being bonded, can arrange Enumerate PVA systems bonding agent, carbamate system bonding agent, acrylic ester ultraviolet hardening bonding agent etc..

Polarization plates obtained from operating as above fit in glass substrate and can be used as after the adhesives such as coating acrylic acid series LCD part.Phase retardation film can be bonded simultaneously, angle of visibility improves film, brightness improving film etc..

Embodiment

Hereinafter, the present invention is described in more detail by embodiment, but the present invention is not limited to these embodiments completely.Need Illustrate, each measure or evaluation method used in following examples and comparative example is as follows.

PVA primary structure

The PVA used in following examples and comparative example primary structure uses 400MHz¹H-NMR is analyzed.¹H- Solvent when NMR is determined has used deuterated DMSO.

The swellbility of PVA film

The PVA film obtained in following examples or comparative example is cut to and reaches 1.5g, is impregnated in 30 DEG C of distilled water 30 minutes.Dipping takes out the film after 30 minutes, with the water on filter paper leaching surface, obtains quality " N ".Then, by the film with 105 DEG C Drying machine dry 16 hours after, obtain quality " M ".Following formula is utilized by gained quality " N " and " M "（8）Calculate the molten of PVA film Expansibility.

Swellbility（%） = 100 × N/M （8）.

Component is crystallized into PVA film（a₁）With constraint amorphous component amount（a₂）

The sample that will be obtained by the PVA film obtained in following examples or comparative example（100mg）It is fine cut into 5mm × After 5mm or so size, put into jointly into NMR pipes with 1mL heavy water.It is small that the NMR pipes are impregnated in 60 DEG C of thermostat to 1 When.Thereafter, with 20 DEG C of keepings 24 hours, as measure sample.Use pulse NMR（Bruker BioSpin K.K. systems “minispec mq20 WVT”）, for the measure Specimen Determination¹H spin spin relaxation time T₂.The following institute of condition determination Show.

The train of impulses：Solid-Echo methods（90x-τ-90y）

RF pulse widths（Pw1）：2.1μs

Pulse spacing（Pi1）：1μs

Pulse-recurrence time：1s

Measurement temperature：30℃.

The free induction decay that will be obtained using linear least square in said determination（FID）Signal fitting is in above-mentioned formula （4）, obtain be on the occasion of crystallize into component（a₁）, constraint amorphous component amount（a₂）With amorphous component amount（a₃）, calculate each composition Relative to the ratio of the total amount of this 3 kinds of compositions.

The draftability of PVA film

The width central portion of the PVA film obtained from following embodiment or comparative example, with width 5cm × length 5cm scope can carry out the mode of uniaxial tension, cutting width 5cm × length 8cm sample.The sample is impregnated in 30 DEG C Pure water, and to 1.5 times of length direction uniaxial tension.Then, it is being 3.0 mass % by 0.03 mass % and KI of iodine Ratio contains the aqueous solution of iodine and KI（Dye bath）（30 DEG C of temperature）Middle dipping 60 seconds, and drawn to length direction single shaft Stretch 1.6 times（2.4 times of entirety meter stretching）And adsorb iodine.Then, using boric acid as 3 mass % and ratio that KI is 3 mass % The aqueous solution of the example containing boric acid and KI（Crosslinking bath）（30 DEG C of temperature）Middle dipping, and to length direction uniaxial tension 1.1 Times（2.6 times of entirety meter stretching）.And then it is being that 4 mass % and ratio that KI is 6 mass % contain boric acid and iodate using boric acid The aqueous solution of potassium（Stretch bath）Middle dipping, and to length direction uniaxial tension untill cut-out, length when cutting off is relative The multiplying power of the length of PVA film before stretching is denoted as ultimate elongation multiplying power.Wherein, for the temperature of stretch bath, from appropriate temperature 1 DEG C of change carrys out determination limit stretching ratio to degree every time, and selection limit stretching ratio reaches highest temperature.

The optical characteristics of light polarizing film（Bitintability ratio）

（1）Transmissivity Ts measure

The central portion of the light polarizing film obtained from following examples or comparative example takes the length direction of 2 light polarizing films to be 2cm sample, use the spectrophotometer of subsidiary integrating sphere（Japan Spectroscopy Corporation's system " V7100 "）, according to JIS Z 8722（The assay method of object color）, carry out illuminant-C, 2 ° of visuals field visible region visibility correction, for 1 sample, Light transmission of measure when tilting+45 ° relative to length direction and light transmission when tilting -45 ° relative to length direction, are asked Go out their average value Ts1（%）.Similarly operated for another 1 sample, measure tilt+45 ° when light transmission and inclination- Light transmission at 45 °, obtain their average value Ts2（%）.Pass through following formula（9）Ts1 and Ts2 are averaged, are denoted as partially The transmissivity Ts of light film（%）.

Ts = （Ts1+Ts2）/2 （9）.

（2）Degree of polarization V measure

It is overlapping for 2 samples taken in above-mentioned transmissivity Ts measure are carried out in a manner of its length direction is parallel When light transmission T ∥（%）, light transmission T ⊥ when carrying out overlapping in a manner of length direction is vertical（%）, with it is above-mentioned "（1） The situation of transmissivity Ts measure " is equally operated to determine, and passes through following formula（10）Obtain degree of polarization V（%）.

V=（T∥-T⊥）/（T∥+T⊥）}^1/2×100 （10）.

（3）Transmissivity be 44% when bitintability than calculate

In following each embodiment and comparative example, by the iodine concentration in dye bath 0.02 ~ 0.04 mass % each scope It is interior to change 4 times and change the concentration of KI 4 times in 2.0 ~ 4.0 mass % each scope（Wherein, the concentration of iodine:KI Concentration=1:100）, identical operation is carried out, so as to manufacture the bitintability of the light polarizing film with being manufactured in each embodiment or comparative example 4 different light polarizing films of pigment adsorbance.For these 4 light polarizing films, it is utilized respectively the above method and obtains transmissivity Ts（%）With Degree of polarization V（%）, each embodiment and comparative example are respectively with transmissivity Ts（%）For transverse axis, with degree of polarization V（%）For the longitudinal axis, will be based on The transmissivity Ts of the light polarizing film obtained in each embodiment or comparative example（%）With degree of polarization V（%）, totally 5 points including 1 point Plotting obtains curve of approximation on the diagram, and transmissivity Ts is obtained by the curve of approximation（%）For 44% when degree of polarization V₄₄（%）.

Pass through following formula（11）By gained degree of polarization V₄₄（%）Bitintability ratio when transmissivity is 44% is obtained, as polarised light The index of performance.It should be noted that bitintability is better than the optical characteristics of more high then light polarizing film, by bitintability ratio be 66 with On situation be determined as "○"（Well）, bitintability is determined as "×" than the situation less than 66（It is bad）.

Bitintability ratio=log when transmissivity is 44%（44/100-44/100×V₄₄/100）/log（44/100+44/ 100×V₄₄/100）（11）.

The form and aspect of light polarizing film（Parallel b values）

In the above-mentioned " optical characteristics of light polarizing film（Bitintability ratio）" in, obtain bitintability pigment adsorbance different 4 partially During the degree of polarization V of light film, in measure transmissivity T ∥（%）With transmissivity T ⊥（%）When determine the Lab colour spaces, will determine transmissivity T ∥（%）When b values be used as parallel b values, will measure transmissivity T ⊥（%）When b values as orthogonal b values.Each embodiment and comparative example , will be flat based on the light polarizing film obtained in each embodiment or comparative example respectively using parallel b values as transverse axis, using orthogonal b values as the longitudinal axis Row b values and orthogonal b are worth, totally 5 points of plottings including 1 point obtain curve of approximation on the diagram, are obtained by the curve of approximation Parallel b values when orthogonal b values are -4.It should be noted that parallel b values are better closer to the form and aspect of 0 light polarizing film, parallel b It is determined as "○" when being worth less than 2.2（Well）, parallel b values be more than 2.2 when be determined as "×"（It is bad）.

The durability of light polarizing film（Absorbance residual rate）

For each embodiment or comparative example, from the above-mentioned " optical characteristics of light polarizing film（Bitintability ratio）" in manufacture it is double-colored Totally 5 light polarizing films of the light polarizing film obtained in property 4 different light polarizing films of pigment adsorbance and each embodiment or comparative example it In, select 1 transmissivity to be in 44 ~ 45% scope and measure transmissivity T ⊥（%）When the wavelength 610nm that obtains at absorbance （Vertical absorbance）For 2.95 ~ 3.05 light polarizing film.

The light polarizing film is exposed 4 hours in the environment of 60 DEG C, 90%RH, by the vertical absorbance at initial wavelength 610nm It is denoted as A_0h, and the vertical absorbance at the wavelength 610nm after exposing 4 hours is denoted as A_4h, following formula will be passed through（12）Obtain The residual rate of vertical absorbance（Absorbance residual rate）D（%）Durability as light polarizing film is evaluated.It should be noted that The durability of the more high then light polarizing film of absorbance residual rate is better, and absorbance residual rate is determined as "○" when being more than 20%（It is good It is good）, it is determined as "×" when absorbance residual rate is less than 20%（It is bad）.

D（%）=100 × A_4h/A_0h（12）.

[embodiment 1 ~ 6 and comparative example 1 ~ 5]

（1）Using comprising the mass parts of PVA 100 shown in table 1, the mass parts of glycerine 10 as plasticizer and as surface It is former that the aqueous solution that the mass parts of polyoxyethylene laurel ether sodium sulphate 0.1 of activating agent and PVA containing ratio are 10 mass % is used as film Liquid, the PVA are by by vinylacetate and acetic acid 2- methyl -2- propylenes, 3,4- diacetoxy -1- butylene, 7- second The copolymer of acyloxy -1- butylene or 1,3- diacetoxy -2- methylene propane（It is the equal of vinylacetate in comparative example 1 Polymers）Obtained from carrying out saponification, the film stoste is dried in 80 DEG C of metallic roll, by gained film in hot air drying It is heat-treated 1 minute with defined temperature in dry machine, so as to which swellbility is adjusted to 200%, so as to manufacture the PVA that thickness is 30 μm Film.

PVA film obtained by use, is obtained by the above method and crystallizes into component（a₁）With constraint amorphous component amount（a₂）Ratio Example, and evaluate draftability.Show the result in table 1.

（2）From above-mentioned（1）In the obtained width central portion of PVA film, with width 5cm × length 5cm scope energy Enough carry out the mode of uniaxial tension, cutting width 5cm × length 8cm sample.The sample is impregnated in 30 DEG C of pure water, and To 1.5 times of length direction uniaxial tension.Then, it is being that 0.03 mass % and ratio that KI is 3.0 mass % contain iodine using iodine With the aqueous solution of KI（Dye bath）（30 DEG C of temperature）Middle dipping 60 seconds, and to 1.6 times of length direction uniaxial tension（Entirely Body meter stretches 2.4 times）And adsorb iodine.Then, it is being that 3 mass % and ratio that KI is 3 mass % contain boric acid using boric acid With the aqueous solution of KI（Crosslinking bath）（30 DEG C of temperature）Middle dipping, to 1.1 times of length direction uniaxial tension（Entirety meter stretching 2.6 again）.And then in the aqueous solution for containing boric acid and KI using boric acid as 4 mass % and ratio that KI is 6 mass %（Draw Stretch bath）（The ultimate elongation multiplying power obtained in above-mentioned " draftability of PVA film " reaches highest temperature）Middle dipping, and to length The multiplying power of direction uniaxial tension to 0.2 times lower than ultimate elongation multiplying power.Thereafter, the water of KI is being contained with 3 mass % ratio Solution（Cleaner bath）（30 DEG C of temperature）Middle dipping 5 seconds, is finally dried 4 minutes with 60 DEG C, so as to manufacture light polarizing film.

Light polarizing film obtained by use, the optical characteristics of light polarizing film is evaluated by the above method（Bitintability ratio）, form and aspect（Parallel b Value）And durability.Show the result in table 1.

[table 1]

It is clear that by result above：According to the PVA film for the embodiment 1 ~ 6 for meeting code of the present invention, can easily manufacture The excellent optical film of optical characteristics, form and aspect and durability.

Claims (14)

1. vinyl alcohol system polymer film, wherein, by spin spin relaxation time T₂Obtain and crystallize into component a₁, constraint amorphous component Measure a₂With amorphous component amount a₃When, crystallize into component a₁With constraint amorphous component amount a₂Be aggregated in and crystallize into component a₁, constraint it is non- Brilliant component amount a₂With amorphous component amount a₃It is total in shared ratio be 10 ~ 32%, the spin spin relaxation time T₂It is logical Cross obtained from 1 hour laggard horizontal pulse NMR measure is handled at 60 DEG C, the observing nuclear of the pulse NMR measure is¹H。

2. vinyl alcohol system polymer film according to claim 1, wherein, constraint amorphous component amount a₂Crystallizing into component a₁、 Constrain amorphous component amount a₂With amorphous component amount a₃It is total in shared ratio be more than 5%.

3. vinyl alcohol system polymer film according to claim 1, wherein, the vinyl alcohol included in vinyl alcohol system polymer film Based polymer contains selected from following formula（1）Shown construction unit 1, following formula（2）Shown construction unit 2 and following formula（3） At least one kind of construction unit in shown construction unit 3, the containing ratio of construction unit 1 ~ 3 is denoted as n respectively₁~n₃Mole %, will The containing ratio of vinyl ester units is denoted as n₄During mole %, meet 0.6≤n₁+n₂+2×n₃+n₄≤ 1.4,

[formula 1]

In formula, R¹Hydrogen atom, methyl or ethyl are represented,

[formula 2]

In formula, R²Represent hydrogen atom, methyl or ethyl, X²Represent the hydroxyl that the carbon number with more than 1 hydroxyl is more than 2 Alkyl,

[formula 3]

In formula, X³And X⁴Separately represent the hydroxy alkyl that the carbon number with more than 1 hydroxyl is more than 1.

4. vinyl alcohol system polymer film according to claim 2, wherein, the vinyl alcohol included in vinyl alcohol system polymer film Based polymer contains selected from following formula（1）Shown construction unit 1, following formula（2）Shown construction unit 2 and following formula（3） At least one kind of construction unit in shown construction unit 3, the containing ratio of construction unit 1 ~ 3 is denoted as n respectively₁~n₃Mole %, will The containing ratio of vinyl ester units is denoted as n₄During mole %, meet 0.6≤n₁+n₂+2×n₃+n₄≤ 1.4,

[formula 1]

In formula, R¹Hydrogen atom, methyl or ethyl are represented,

[formula 2]

In formula, R²Represent hydrogen atom, methyl or ethyl, X²Represent the hydroxyl that the carbon number with more than 1 hydroxyl is more than 2 Alkyl,

[formula 3]

In formula, X³And X⁴Separately represent the hydroxy alkyl that the carbon number with more than 1 hydroxyl is more than 1.

5. vinyl alcohol system polymer film according to claim 3, wherein, the vinyl alcohol included in vinyl alcohol system polymer film Based polymer contains at least one kind of construction unit in construction unit 1 and construction unit 2.

6. vinyl alcohol system polymer film according to claim 4, wherein, the vinyl alcohol included in vinyl alcohol system polymer film Based polymer contains at least one kind of construction unit in construction unit 1 and construction unit 2.

7. the vinyl alcohol system polymer film according to any one of claim 1 ~ 6, wherein, wrapped in vinyl alcohol system polymer film The vinyl alcohol system polymer contained is free of following formula（3）Shown construction unit 3,

[formula 4]

In formula, X³And X⁴Separately represent the hydroxy alkyl that the carbon number with more than 1 hydroxyl is more than 1.

8. the vinyl alcohol system polymer film according to any one of claim 1 ~ 6, wherein, wrapped in vinyl alcohol system polymer film The degree of polymerization of the vinyl alcohol system polymer contained is less than 3,000.

9. the vinyl alcohol system polymer film according to any one of claim 1 ~ 6, wherein, wrapped in vinyl alcohol system polymer film The molecular weight distribution of the vinyl alcohol system polymer contained is 2.0 ~ 4.0.

10. the vinyl alcohol system polymer film according to any one of claim 1 ~ 6, wherein, swellbility is 160 ~ 240%.

11. the vinyl alcohol system polymer film according to any one of claim 1 ~ 6, it is optical film manufacture initial film.

12. vinyl alcohol system polymer film according to claim 11, it is light polarizing film manufacture initial film.

13. the manufacture method of optical film, the vinyl alcohol system polymer film described in its usage right requirement 11, the manufacture method possess The process for carrying out uniaxial tension.

14. the manufacture method of optical film, the vinyl alcohol system polymer film described in its usage right requirement 12, the manufacture method possess The process for carrying out uniaxial tension.