CN105408783B - Optical film manufacture initial film - Google Patents
Optical film manufacture initial film Download PDFInfo
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- CN105408783B CN105408783B CN201480042988.6A CN201480042988A CN105408783B CN 105408783 B CN105408783 B CN 105408783B CN 201480042988 A CN201480042988 A CN 201480042988A CN 105408783 B CN105408783 B CN 105408783B
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- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
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- 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
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- 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
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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
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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
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- 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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- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Polarising Elements (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Optical film manufacture initial film is provided and has used the manufacture method of its optical film, the optical film manufacture it is excellent with the draftability of initial film and can productivity ratio manufacture optical film well, and can easily manufacture the excellent optical film of optical characteristics and form and aspect.Optical film manufacture initial film, it includes the vinyl alcohol system polymer containing methylol, and the vinyl alcohol system polymer containing methylol includes vinyl alcohol units and following formula（1）Shown construction unit；And the manufacture method of optical film, it possesses the process for carrying out uniaxial tension with initial film using the optical film manufacture.
Description
Technical field
The present invention relates to the initial film for manufacturing the optical films such as light polarizing film（origial film）And use this first
The manufacture method of the optical film of beginning film, the initial film include：The ethenol system containing methylol with 1,3 glycol structure gathers
Compound.
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 the light polarizing film for forming polarization plates, make vinyl alcohol system polymer film（Below sometimes by " ethenol system
Polymer " is referred to as " PVA "）Carry out the matrix absorption iodine system pigment that uniaxial tension forms（I3 -、I5 -Deng）, bitintability organic dyestuff
Etc bitintability pigment obtained from light polarizing film turn into main flow.
It is color that LCD is gradually applied to the miniature instruments such as calculator and watch, 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.Accompany with this, also require light polarizing film advanced, specifically, it is desirable to degree of polarization, transmission
Degree is high, optical characteristics is excellent and form and aspect also excellent light polarizing film.
It is well known, however, that the several optical film manufacture initial film comprising modified PVA.For instance, it is known that by containing
The light polarizing film that the specific PVA of the hydrophilic functional groups such as 0.01 ~ 1 mole of % carboxylic acid group, ω-hydroxyl-alpha-alkylene is formed it is initial
It is excellent with the stretching orientation position rationality of polyvinyl alcohol film and the adsorption treatment of bitintability material（With reference to patent document 1 etc.）.
Further, it is known that contain optical characteristics and the drawing of the specific PVA of 1,2- diol bonds particular optical PVA film included in side chain
Stretching property is excellent（With reference to patent document 2）.
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.
The content of the invention
The invention problem to be solved
However, used it is existing it is known include modified PVA optical film manufacture initial film when, from obtaining optical characteristics
The optical film this point excellent with form and aspect is set out, and room for improvement also be present.In addition, on this basis, existing public affairs are used
During the optical film manufacture initial film comprising modified PVA known, especially continuously manufacture optical film when etc., still easily draw
The failures such as fracture are stretched, from the productivity ratio this point of optical film, room for improvement also be present.
Thus, it is an object of the present invention to provide optical film manufacture initial film and the system for the optical film for having used it
Make method, the optical film manufacture it is excellent with the draftability of initial film and can productivity ratio manufacture optical film, and energy well
The excellent optical film of enough easily manufacture optical characteristics and form and aspect.
The means used to solve the problem
Further investigation is repeated in the present inventor etc. to achieve these goals, as a result finds：According to comprising containing hydroxyl
Methyl PVA film and can solve the problem that above-mentioned problem, the main chain of the PVA containing methylol includes specific with 1,3- diol structures
Construction unit, further repeat to study based on the opinion, so as to complete the present invention.
That is, the present invention relates to following content：
[1] optical film manufacture initial film, it includes PVA containing methylol, and the PVA containing methylol includes vinyl alcohol list
Member and following formula（1）Shown construction unit；
[changing 1]
[2] the optical film manufacture initial film according to [1], wherein, the previously described formula in foregoing PVA containing methylol（1）
The containing ratio of shown construction unit is 0.1 ~ 2 mole of %；
[3] the optical film manufacture initial film according to [1] or [2], wherein, foregoing PVA containing methylol also includes second
Alkene unit；
[4] the optical film manufacture initial film according to [3], wherein, the ethylene unit in foregoing PVA containing methylol
Containing ratio be 1 ~ 4 mole of %；
[5] the optical film manufacture initial film according to any one of [1] ~ [4], wherein, foregoing PVA containing methylol
Saponification degree be 95 moles of more than %；
[6] the optical film manufacture initial film according to any one of [1] ~ [5], it is light polarizing film manufacture initial film；
[7] manufacture method of optical film, it possesses：The optical film manufacture any one of [1] ~ [6] is used with initially
The process that film carries out uniaxial tension.
The effect of invention
According to the present invention, there is provided optical film manufacture initial film and the manufacture method for having used its optical film, it is described
Optical film manufacture it is excellent with the draftability of initial film and can productivity ratio manufacture optical film well, and can easily manufacture
Optical characteristics and the excellent optical film of form and aspect.
Embodiment
The optical film manufacture of the present invention includes PVA containing methylol with initial film, and the PVA containing methylol includes vinyl alcohol list
Member and following formula（1）Shown construction unit.
[changing 2]
。
The optical film manufacture of the present invention is with the PVA containing methylol included in initial film by including above-mentioned formula（1）Shown
Construction unit with 1,3- diol structures, thus draftability improves.In addition, on this basis, according to the optical film of the present invention
Manufacture initial film, it can easily manufacture the excellent optical film of optical characteristics and form and aspect.The present invention by any restriction, does not make
The reason for for above-mentioned advantage can be obtained, it is believed that：Crystallinity factor（1）Shown construction unit and reduce and based on 1,
Influenceed caused by the high hydrogen bond force of 3- diol structures.
Formula in PVA containing methylol（1）The containing ratio of shown construction unit is not particularly limited, and contains methylol by forming
The molal quantity of PVA entire infrastructure unit is denoted as 100 moles of %, preferably in the range of 0.1 ~ 2 mole of %, more preferably 0.2 ~
In the range of 1.9 moles of %, further preferably in the range of 0.3 ~ 1.8 mole of %.By make the containing ratio for 0.1 mole of % with
On, the draftability of film further improves, in addition, the more excellent optical film of form and aspect can be obtained.On the other hand, by containing this
Rate is 2 moles of below %, can more efficiently prevent from manufacture optical film when film dissolving, in addition, optical characteristics can be obtained more
Excellent optical film.It should be noted that in this specification, construction unit refers to the repeat unit for forming polymer.
The degree of polymerization of the PVA containing methylol preferably in the range of 1,500 ~ 6,000, more preferably 1,800 ~ 5,000 model
In enclosing, further preferably in the range of 2,000 ~ 4,000.By making the degree of polymerization be 1, more than 500, can further improve
The durability of the optical film such as light polarizing film obtained from film is carried out into uniaxial tension.On the other hand, by making the degree of polymerization be 6,000
Hereinafter, process when can suppress rising, the film of manufacturing cost passes through the bad etc. of property.It should be noted that this specification
In the PVA containing methylol the degree of polymerization average degree of polymerization that refers to the record based on JIS K6726-1994 and determine.
From the viewpoint of film is carried out into the water resistance of the optical film such as light polarizing film obtained from uniaxial tension, containing methylol
PVA saponification degree is preferably 95 moles of more than %, more preferably 96 moles of more than %, more preferably 98 moles of more than %.Need
Illustrate, the saponification degree of the PVA containing methylol in this specification refers to：The vinyl alcohol units having in PVA containing methylol
Molal quantity can be converted into vinyl alcohol units with respect to saponification（-CH2-CH（OH）-）Construction unit（It is for typical case
Vinyl ester units）With the ratio of the total mole number of the vinyl alcohol units（Mole %）.The saponification degree is it is also contemplated that formula（1）It is shown
Construction unit, the amount of its derivative are simultaneously measured based on JIS K6726-1994 record.
The manufacture method of the PVA containing methylol is not particularly limited.Such as following method can be included：By vinyl acetate system monomer
With that can be copolymerized with it and an accepted way of doing sth can be changed（1）The unsaturated monomer of shown construction unit is copolymerized, by gained vinyl acetate
The vinyl ester units of based copolymer are converted into vinyl alcohol units, and on the other hand, will be derived from can change an accepted way of doing sth（1）Shown structure list
A construction unit conversion accepted way of doing sth for the unsaturated monomer of member（1）The method of shown construction unit.An accepted way of doing sth can be changed（1）Shown structure
The particular instantiation of the unsaturated monomer of unit is in following formula（2）.
[changing 3]
Formula（2）In, R represents the alkyl of carbon number 1 ~ 10.As R structure, it is not particularly limited, a part can have
There are branch, cyclic structure.In addition, a part can be substituted by other functional groups.R is preferably the alkyl of carbon number 1 ~ 5, as
The example of the alkyl, the straight chains such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, amyl group can be included
Alkyl or the alkyl with side chain.In addition, the substituent that can have as R, can include alkoxy, halogen atom, hydroxyl etc..
It should be noted that multiple R are same to each other or different to each other.
As formula（2）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..Wherein, from the sight of ease of manufacturing
From the point of view of point, preferably using 1,3- diacetoxy -2- methylene propane.
In general, other allyl type unsaturated monomers with being used in PVA modification（For example, allyl glycidyl is sweet
Oily ether etc.）Compare, formula（2）Shown unsaturated monomer easily carries out copolyreaction with vinyl acetate system monomer.Therefore, can be easily
The restriction of modified amount or the degree of polymerization when obtaining polymerization less, modified amount and the high PVA containing methylol of the degree of polymerization.In addition, it can subtract
The amount of few unreacted unsaturated monomer remained at the end of polymerization, therefore, the PVA containing methylol in the present invention is in industry
It is in terms of environment during manufacture and in terms of cost and excellent.
For manufacture the PVA containing methylol vinyl acetate system monomer be not particularly limited, can include such as vinyl formate,
Vinylacetate, propionate, vinyl butyrate, vinyl isobutyrate ester, pivalic acid vinyl acetate, tertiary ethylene carbonate, caproic acid
Vinyl acetate, sad vinyl acetate, caprate, vinyl laurate, vinyl palmitate, stearic acid vinyl ester, oleic acid ethene
Ester, vinyl benzoate etc..From the viewpoint of economy, preferably vinylacetate.
By formula（2）Polymerization methodses when shown unsaturated monomer is copolymerized with vinyl acetate system monomer can be that interval is poly-
Any-mode in conjunction, semi-batch polymerization, continuous polymerization, semi-continuous polymerization etc., as polymerization, it can be polymerize with applied ontology
Method known to method, solution polymerization process, suspension polymerization, emulsion polymerization etc..It is typically employed in solvent-free or alcohol equal solvent
Promote the mass polymerization or solution polymerization process of polymerization.When obtaining the vinyl acetate based copolymer of high polymerization degree, further preferably emulsion
Polymerization.The solvent of solution polymerization process 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 molten according to the targeted degree of polymerization of the PVA containing methylol
The chain tra nsfer of agent and selection, such as when solvent is methanol, with the quality of the whole monomers included in solvent and polymerization system
Than=（Solvent）/（Whole monomers）Meter, select preferably in the range of 0.01 ~ 10, more preferably selected in the range of 0.05 ~ 3
Select.
Formula（2）Shown unsaturated monomer is with the polymerization initiator used in the copolymerization of vinyl acetate system monomer according to the side of polymerization
Method selects from known polymerization initiator, such as azo series initiators, peroxide series initiators, redox series initiators
.Azo series initiators are, for example, 2,2 '-azobis isobutyronitrile, 2,2 '-azo pair（2,4- methyl pentane nitriles）, 2,2 '-it is even
Nitrogen is double（4- methoxyl group -2,4- methyl pentane nitriles）.Peroxide series initiators be, for example, diisopropyl peroxydicarbonate,
The peroxocarbonate based compounds such as two -2- ethylhexyls peroxy dicarbonates, diethoxy ethyl peroxydicarbonate；Tertiary fourth
The peroxyester based compounds such as base new decanoate ester peroxide, α-cumyl new decanoate ester peroxide；Acetyl group peroxidating cyclohexyl sulphur
Acyl；2,4,4- tri-methyl-amyl -2- benzoyl peroxide epoxide acetates；Acetyl peroxide.Can also be by potassium peroxydisulfate, persulfuric acid
Ammonium, hydrogen peroxide etc. combine with above-mentioned initiator and polymerization initiator are made.Redox series initiators are, for example, by above-mentioned mistake
Oxide series initiators are combined and obtained with reducing agents such as sodium hydrogensulfite, sodium acid carbonate, tartaric acid, L-AA, rongalite
The polymerization initiator arrived.The dosage of polymerization initiator is different because of the species of polymerization initiator, therefore can not lump together, according to poly-
Sum velocity is selected.For example, polymerization initiator uses 2, when 2 '-azobis isobutyronitrile or acetyl peroxide, relative to
Vinyl acetate system monomer is preferably 0.01 ~ 0.2 mole of %, more preferably 0.02 ~ 0.15 mole of %.Polymerization temperature is not particularly limited,
Room temperature ~ 150 DEG C or so are appropriate, below preferably more than 40 DEG C and the boiling point of used solvent.
Formula（2）The copolymerization of shown unsaturated monomer and vinyl acetate system monomer can be carried out in the presence of chain-transferring agent.
Chain-transferring agent is, for example, the aldehydes such as acetaldehyde, propionic aldehyde；The ketones such as acetone, MEK；The thio-alcohols such as 2- hydroxyl ethyl mercaptans；Phosphinic acids sodium
Monohydrate grade phosphonates etc..Wherein, it is adapted to use aldehydes and ketone.The dosage of chain-transferring agent can be according to the chain to be used
The chain tra nsfer coefficient of transfer agent and the targeted degree of polymerization of the PVA containing methylol determine, are commonly angled relative to the matter of vinyl acetate system monomer 100
It is preferably 0.1 ~ 10 mass parts to measure part.
By the way that formula will be utilized（2）Shown unsaturated monomer is total to vinyl acetate system obtained from the copolymerization of vinyl acetate system monomer
Polymers carries out saponification, can obtain above-mentioned PVA containing methylol.By the way that the vinyl acetate based copolymer is carried out into saponification, vinyl acetate system
Vinyl ester units in copolymer are converted into vinyl alcohol units.In addition, the formula of being derived from（2）The construction unit of shown unsaturated monomer
Ester bond be also saponified, so as to be converted into formula（1）The shown construction unit with 1,3 glycol structure.Therefore, this contains hydroxyl
Methyl PVA the reaction such as is not hydrolyzed further after saponification 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 is, for example, the hydroxide of the alkali metal such as potassium hydroxide, sodium hydroxide；The base catalysts such as 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 containing methylol
PVA.Method for saponification is not limited to preceding method, can apply known method.
PVA containing methylol can also include formula（1）Beyond shown construction unit, vinyl alcohol units and vinyl ester units
Other structures unit.As the other structures unit, can include for example originating from can be copolymerized with vinyl acetate system monomer
The construction unit of ethylenically unsaturated monomer.Furthermore it is also possible to comprising from can be copolymerized with above-mentioned vinyl acetate system monomer and
An accepted way of doing sth can be changed（1）The construction unit of the unsaturated monomer of shown construction unit（Formula is not converted into by saponification（1）It is shown
The construction unit of construction unit）.
In PVA containing methylol, the molal quantity for the entire infrastructure unit for forming the PVA containing methylol is denoted as 100 moles of %, formula
（1）Ratio shared by the total amount of shown construction unit, vinyl alcohol units and vinyl ester units is preferably 80 moles of more than %, more
Preferably 90 moles of more than %, more preferably 95 moles of more than %, can be 99 moles of more than %.
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- ethyleneoxies 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；Allyl acetate, 2,3- diacetoxy -1- allyloxys propane, allyl
The allyl compounds such as base chlorine；The unsaturated dicarboxylics such as maleic acid, itaconic acid, fumaric acid and its salt or ester；Vinyl trimethoxy
The vinyl silyl groups such as base silane compound, isopropenyl acetate.Among these, due to while draftability improves, energy
Enough to be stretched with higher temperature, the failure of the generation such as tension failure when manufacturing optical film is minimized, the life of optical film
Yield further improves, therefore preferably ethene.When PVA containing methylol includes ethylene unit, from draftability as described above, can
From the viewpoint of draft temperature etc., the molal quantity for the entire infrastructure unit for forming the PVA containing methylol is denoted as 100 moles of %, ethene
The containing ratio of unit is preferably 1 ~ 4 mole of %, particularly preferably 2 ~ 3 moles of %.
Formula in PVA containing methylol（1）Shown construction unit, vinyl alcohol units and other rows for being formed arbitrarily unit
Row order is not particularly limited, and can be any one of random, block, interaction etc..
In the optical film manufacture initial film of the present invention, in addition to above-mentioned PVA containing methylol, plasticising can also be included
Agent.As preferable plasticizer, polyalcohol can be included, as concrete example, ethylene glycol, glycerine, propane diols, diethyl can be included
Glycol, two glycerine, triethylene glycol, tetraethylene glycol, trimethylolpropane etc..The optical film manufacture initial film of the present invention can wrap
Containing one kind or two or more in these plasticizer.It is preferably sweet from the viewpoint of the effect for improving draftability among these
Oil.
On the content of the plasticizer in the optical film manufacture initial film of the present invention, relative to the first containing hydroxyl wherein included
The mass parts of base PVA 100, preferably in the range of 1 ~ 20 mass parts, more preferably in the range of 3 ~ 17 mass parts, further it is excellent
It is selected in the range of 5 ~ 15 mass parts.By making the content for more than 1 mass parts, the draftability of film further improves.The opposing party
Face, reduced by making the content for film excessively softness, treatability below 20 mass parts, can be suppressed.
Filler, copper compound etc. can also be suitably coordinated to add as needed in the optical film manufacture initial film of the present invention
Work stabilizer, weatherability stabilizer, colouring agent, ultra-violet absorber, light stabilizer, antioxidant, antistatic additive, fire retardant,
Other thermoplastic resins, lubricant, spices, defoamer, deodorant, extender, remover, releasing agent, reinforcing agent, crosslinking agent,
The additives such as mould inhibitor, preservative, crystallization rate delayed-action activator.
The optical film manufacture of the present invention is based on the PVA containing methylol in initial film and the ratio shared by the total amount of plasticizer
Optical film manufacture is preferably more than 80 mass % with the quality of initial film, more preferably more than 90 mass %, more preferably 95
More than quality %.
The swellbility of the optical film manufacture initial film of the present invention preferably in the range of 160 ~ 240%, more preferably 170 ~
In the range of 230%, particularly preferably in the range of 180 ~ 220%.By making swellbility be more than 160%, can suppress to crystallize
Extremely promote, can stably be stretched to higher multiplying power.On the other hand, by making swellbility be less than 240%, during stretching
Dissolving is able to suppress, can also stretched under conditions of at higher temperature.It should be noted that in this specification, optical film system
Make and referred to the swellbility of initial film：Quality when optical film manufacture initial film is impregnated 30 minutes in 30 DEG C of distilled water
Divided by the percentage being worth obtained from the quality after being dried 16 hours with 105 DEG C after dipping, specifically, embodiment can be passed through
In method described later be measured.
The present invention optical film manufacture be not particularly limited with the thickness of initial film, in general, it is preferred to for 1 ~ 100 μm,
More preferably 5 ~ 75 μm, particularly preferably 10 ~ 60 μm or so.If the thickness is excessively thin, it is used to manufacture the optics such as light polarizing film
During the uniaxial tension processing of film, the tendency that tension failure easily occurs be present.If in addition, when the thickness is blocked up, it is used to manufacture
During the uniaxial tension processing of optical film, it is uneven that stretching easily occurs.
The optical film manufacture of the present invention is not particularly limited with the width of initial film, can be according to the use for the optical film to be manufactured
Way etc. determines.In recent years, from the viewpoint of the large screen of LCD TV, liquid crystal display develops, in advance by light
When more than 3m is made with the width of initial film in film manufacture, it is suitable for these purposes.On the other hand, optical film manufacture initial film
Width it is excessive when, using utility unit manufacture optical film in the case of, uniformly carry out uniaxial tension itself easily become tired
Difficulty, therefore, optical film manufacture are preferably below 7m with the width of initial film.
The optical film manufacture of the present invention is not particularly limited with the manufacture method of initial film, preferably using after film
The thickness and width of film becomes manufacture method evenly, such as can be manufactured using following film stoste：Light will be formed
Film manufacture is learned to be dissolved in liquid medium with the above-mentioned PVA containing methylol of initial film, and as needed further by above-mentioned increasing
One kind or two or more be dissolved in obtained from liquid medium among modeling agent, additive and surfactant described later etc. is film-made
Stoste；Further include plasticizer, additive, surfactant and liquid medium comprising PVA containing methylol and as needed
It is one kind or two or more Deng among, and the film stoste that PVA containing methylol is melted.The film stoste contains plasticizer, added
When adding at least one kind of in agent and surfactant, preferably these compositions equably mix.
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.Optics is manufactured by the film stoste comprising surfactant
During film manufacture initial film, surfactant can be contained in the film.The species of above-mentioned surfactant is not particularly limited, from
Set out from metallic roll, the viewpoint for the fissility for taking stripping etc., preferably anionic surfactant or non-ionic surface
Activating agent.
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 it is adapted to, the alkyl ether type such as polyoxyethylene oleyl ether；Polyoxyethylene
The alkyl phenyl ether type such as octyl phenyl ether；The alkyl esters such as polyoxyethylene laural ester；The alkyl such as polyoxyethylene laural base amino ethers
Amine type；The alkylamide type such as polyoxyethylene laural acid amides；The polypropylene glycol ether type such as polyoxyethylene poly-oxygen propylene aether；Laurate diethyl
The alkylol amide types such as alkylolamides, 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 relative to the PVA containing methylol 100 included in film stoste
Mass parts preferably exist in the range of 0.01 ~ 0.5 mass parts, more preferably in the range of 0.02 ~ 0.3 mass parts, particularly preferably
In the range of 0.05 ~ 0.1 mass parts.By making the content for more than 0.01 mass parts, Film making properties and fissility further improve.
On the other hand, optical film manufacture is oozed out into initially for surfactant below 0.5 mass parts, can be suppressed by making the content
The surface of film and occur caking, treatability reduce.
As using film-forming method during above-mentioned film stoste manufacture optical film manufacture initial film, it can include and for example press
Prolong film method, extrusion film method, film by wet method, gel film method etc..These film-forming methods can be only with a kind, can also
Combination uses two or more.Among these film-forming methods, due to the optical film that thickness and width is uniform and physical property is good can be obtained
Manufacture initial film, so it is preferred that calendering film method, extrusion film method.Manufactured film can be dried as needed, heat
Processing.
As the example of the specific manufacture method of the optical film manufacture initial film of the present invention, such as industrially preferably use
Following method：Machine mould etc. is applied using T-shaped slit die, hopper plate, I- moulds, lip, above-mentioned film stoste is equably sprayed or is cast
Rotation and the 1st heated roller positioned at most upstream side（Or band）Periphery on, make volatile ingredient from spray or curtain coating exist
1st roller（Or band）Periphery on a face of film be evaporated and dry, then be configured at 1 of side downstream or
It is further dried on multiple rotations and the periphery of heated roller, or passes through in hot-air drying device and further do
After dry, the method batched using devices for taking-up.Using the drying that heating roller is carried out with utilizing hot-air drying device progress
Drying appropriately combined can be implemented.
The optical film manufacture of the present invention uses by the use of initial film as manufacturing the initial film of optical film.As this light
Film is learned, can be included such as light polarizing film, phase retardation film.This optical film for example can be by using the optical film system of the present invention
Make and implement the processing such as uniaxial tension with initial film to manufacture.
Method when manufacturing with initial film light polarizing film using the optical film manufacture of the present invention is not particularly limited, and can use
Any means used all the time.As this method, such as can include：To the optical film manufacture initial film of the present invention
Implement dyeing and uniaxial tension or implement the side of uniaxial tension with initial film to the optical film manufacture of the invention containing dyestuff
Method.As the more body method for manufacturing light polarizing film, can include：Optical film manufacture for the present invention is implemented with initial film
Swelling, dyeing, uniaxial tension, and further implement the side of crosslinking Treatment, fixing process, drying, heat treatment etc. as needed
Method.Now, the order that swelling, dyeing, crosslinking Treatment, uniaxial tension, fixing process etc. are respectively handled is not particularly limited, can also
The processing of 1 or more than 2 is carried out simultaneously.In addition, 1 or more than 2 in each processing can also be carried out 2 times or more than 2 times.
Swelling can be by the way that optical film manufacture be immersed in water to carry out with initial film.As water when being impregnated in water
Temperature, preferably 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.
In addition, as the time for being impregnated in water, such as preferably in the range of 0.1 ~ 5 minute, more preferably in the scope of 0.5 ~ 3 minute
It is interior.It should be noted that water when being impregnated in water is not limited to pure water, it can be the aqueous solution dissolved with various composition, also may be used
To be the mixture of water and aqueous medium.
Dyeing can be by making the contact optical film manufacture of bitintability pigment be carried out with initial film.As bitintability pigment, lead to
Often use iodine system pigment.As the period of dyeing, before being uniaxial tension, uniaxial tension when, after uniaxial tension in it is any
Stage.Dyeing is generally by making optical film manufacture be immersed in by the use of initial film the solution containing iodine-potassium iodide as dye bath（Especially
It is the aqueous solution）In carry out, also be adapted for using this colouring method in the present invention.Iodine concentration in dye bath is preferably 0.01
In the range of ~ 0.5 mass %, the concentration of KI is preferably in the range of 0.01 ~ 10 mass %.In addition, the temperature of dye bath is excellent
Elect 20 ~ 50 DEG C, particularly preferably 25 ~ 40 DEG C as.
, can be more effective when carrying out wet tensile with high temperature by implementing crosslinking Treatment with initial film to optical film manufacture
Ground prevents the dissolutions of PVA containing methylol into water.From this viewpoint, crosslinking Treatment preferably contact bitintability pigment processing it
Carry out afterwards and before uniaxial tension.Crosslinking Treatment can be by being impregnated in the water comprising crosslinking agent by optical film manufacture with initial film
Solution is carried out.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.
Crosslinker concentration in the aqueous solution comprising crosslinking agent is preferably in the range of 1 ~ 15 mass %, more preferably in 2 ~ 7 mass % model
In enclosing, further preferably in the range of 3 ~ 6 mass %.In the range of 1 ~ 15 mass % is in by making the concentration of crosslinking agent, energy
Enough maintain sufficient draftability.The aqueous solution comprising crosslinking agent can contain the auxiliary agents such as KI.The aqueous solution comprising crosslinking agent
Temperature preferably in the range of 20 ~ 50 DEG C, particularly preferably in the range of 25 ~ 40 DEG C.By making the temperature at 20 ~ 50 DEG C
In the range of, can efficiently it be crosslinked.
Uniaxial tension can be carried out using any one of wet tensile method or dry stretch process.In the feelings of wet tensile method
It under condition, can carry out, can also be carried out in above-mentioned dye bath, in the bath of aftermentioned fixing process in the aqueous solution comprising boric acid.
It in addition, in the case of dry stretch process, can directly be stretched, can also be drawn while heating at room temperature
Stretch, the optical film manufacture after water suction can also be used to be carried out in atmosphere with initial film.Among these, preferably wet tensile
Method, uniaxial tension is carried out more preferably in the aqueous solution comprising boric acid.Boric acid concentration in boric acid aqueous solution is preferably 0.5 ~ 6.0
In the range of quality %, more preferably in the range of 1.0 ~ 5.0 mass %, particularly preferably in the range of 1.5 ~ 4.0 mass %.Separately
Outside, boric acid aqueous solution can contain KI, and its 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 6.8
More than times, it is more preferably more than 6.9 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 optical film manufacture of strip is carried out into uniaxial tension with initial film is not particularly limited, can
With using uniaxial tension, the horizontal uniaxial tension carried out to strip direction, the polarisation excellent due to polarised light performance can be obtained
Film, therefore be preferably the uniaxial tension carried out to strip direction.The uniaxial tension carried out to strip direction can be by using tool
The stretching device of standby multiple rollers parallel to each other, and the peripheral speed between each roller is changed to carry out.On the other hand, horizontal single shaft is drawn
Stretching can be carried out using tentering type stretching-machine.
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, acetylbutyrylcellulose（CAB）
Film, acrylic acid mesentery, polyester mesentery etc..In addition, as the bonding agent for being bonded, PVA systems bonding agent, amino first can be included
Acid esters system bonding agent etc., wherein, it is suitably for PVA systems bonding agent.
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（Various in PVA containing methylol, comparative example in embodiment change
Property PVA）Primary structure use 270MHz1H-NMR is analyzed.1Solvent when H-NMR is determined has used deuterated DMSO.
The swellbility of optical film manufacture initial film
The optical film manufacture obtained in following examples or comparative example is cut to initial film and reaches 1.5g, at 30 DEG C
Impregnated 30 minutes in distilled water.Dipping takes out the film after 30 minutes, with the water on filter paper leaching surface, obtains quality " N ".Then,
After the film is dried 16 hours with 105 DEG C of drying machine, quality " M " is obtained.Following formula is utilized by gained quality " N " and " M "（3）
Calculate the swellbility of optical film manufacture initial film.
Swellbility（%） = 100 × N/M （3）.
The draftability of optical film manufacture initial film
The width central portion of the optical film manufacture initial film obtained from following examples or comparative example, with width
5cm × length 5cm scope can carry out the mode of uniaxial tension, cutting width 5cm × length 8cm sample.By the sample
It is impregnated in 30 DEG C of pure water, and to 1.5 times of length direction uniaxial tension.Then, it is being 0.03 mass % using iodine and KI is
3.0 mass % ratio contains the aqueous solution of iodine and KI（Dye bath）（30 DEG C of temperature）Middle dipping 60 seconds, and to length
1.6 times of direction uniaxial tension（2.4 times of entirety meter stretching）And adsorb iodine.Then, it is being 3 mass % using boric acid and KI is 3
Quality % ratio contains the aqueous solution of boric acid and KI（Crosslinking bath）（30 DEG C of temperature）Middle dipping, and to length direction list
Axle stretches 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 using boric acid
The aqueous solution of boric acid and KI（Stretch bath）Middle dipping, and to length direction uniaxial tension untill cut-out, during by cutting off
Length be denoted as ultimate elongation multiplying power with the multiplying power of the length of initial film relative to the optical film manufacture before stretching.Wherein, for
The temperature of stretch bath, 1 DEG C of change carrys out determination limit stretching ratio every time from appropriate temperature, 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（4）Ts1 and Ts2 are averaged, are denoted as partially
The transmissivity Ts of light film（%）.
Ts = （Ts1+Ts2）/2 （4）.
（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（5）Obtain degree of polarization V（%）.
V=（T∥-T⊥）/（T∥+T⊥）}1/2×100 （5）.
（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（6）By gained degree of polarization V44（%）Bitintability ratio when transmissivity is 44% is obtained, as polarised light
The index of performance.
Bitintability ratio=log when transmissivity is 44%（44/100-44/100×V44/100）/log（44/100+44/
100×V44/100）（6）.
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 Lab, will determine transmissivity T ∥（%）
When b values be used as parallel b values, will measure transmissivity T ⊥（%）When b values be used as vertical b values.Each embodiment and comparative example difference
Using parallel b values as transverse axis, using vertical b values as the longitudinal axis, by the parallel b values based on the light polarizing film obtained in each embodiment or comparative example
With vertical b values, totally 5 points of plottings including 1 point obtain curve of approximation on the diagram, vertical b is obtained by the curve of approximation
Be worth for -4 when parallel b values.It should be noted that parallel b values closer to 0, then the form and aspect for being regarded as light polarizing film are better.
[embodiment 1]
（1）Make comprising the mass parts of the PVA containing methylol shown in table 1 100 as modified PVA, comprising the mass parts of glycerine 10
For plasticizer and comprising the mass parts of polyoxyethylene laurel ether sodium sulphate 0.1 as surfactant and the containing ratio of modified PVA
It is used as film stoste for the 10 mass % aqueous solution, the PVA containing methylol is by by vinylacetate and 1,3- diethyl acyl-oxygens
Obtained from the copolymer of base -2- methylene propane carries out saponification, the film stoste is done in 80 DEG C of metallic roll
It is dry, gained film is heat-treated 1 minute in air drier with defined temperature, so as to which swellbility is adjusted to 200%, so that
Manufacture the optical film manufacture initial film that thickness is 30 μm.
Optical film manufacture initial film obtained by use, draftability is evaluated by the above method.Show the result in table 1.
（2）From above-mentioned（1）In the obtained width central portion of optical film manufacture initial film, with width 5cm × length
Degree 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 contain the aqueous solution of iodine and KI（Dye bath）（30 DEG C of temperature）Middle dipping 60 seconds, and to length direction single shaft
1.6 times of stretching（2.4 times of entirety meter stretching）And adsorb iodine.Then, it is being 3 mass % by 3 mass % and KI of boric acid
Ratio contains the aqueous solution of boric acid and KI（Crosslinking bath）（30 DEG C of temperature）Middle dipping, and to length direction uniaxial tension
1.1 again（2.6 times of entirety meter stretching）.And then contain by 4 mass % and ratio that KI is 6 mass % of boric acid boric acid and
The aqueous solution of KI（Stretch bath）（The ultimate elongation multiplying power obtained in above-mentioned " optical film manufactures the draftability with initial film " reaches
To highest temperature）Middle dipping, and to length direction uniaxial tension to 0.2 times lower than ultimate elongation multiplying power of multiplying power.Thereafter,
Containing the aqueous solution of KI with 3 mass % ratio（Cleaner bath）（30 DEG C of temperature）Middle dipping 5 seconds, it is finally dry with 60 DEG C
Dry 4 minutes, 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）And form and aspect（Parallel b
Value）.Show the result in table 1.
[comparative example 1 ~ 3]
In embodiment 1, not changing shown in table 1 obtained from the homopolymer of vinylacetate is carried out into saponification is used respectively
Property PVA replaces modified PVA（Comparative example 1）；As modified PVA, using by vinylacetate and 3,4- diacetoxy -1- fourths
Modified PVA obtained from the copolymer of alkene carries out saponification shown in table 1（Comparative example 2）；Or as modified PVA, using by vinegar
Modified PVA obtained from the copolymer of vinyl acetate and itaconic acid carries out saponification shown in table 1（Comparative example 3）, in addition, with
Embodiment 1 equally operates and manufactures optical film manufacture initial film and light polarizing film, carries out each measure or evaluation.Show the result in table
1。
[embodiment 2 ~ 4]
In embodiment 1, as modified PVA, using by vinylacetate and 1,3- diacetoxy -2- methylene propane
Copolymer carry out PVA containing methylol obtained from saponification shown in table 1（Embodiment 2 and 3）；Or as modified PVA, make
Obtained from 3 membered copolymers of vinylacetate and 1,3- diacetoxies -2- methylene propane and ethene are carried out into saponification
PVA containing methylol shown in table 1（Embodiment 4）, in addition, operate similarly to Example 1 and manufacture optical film manufacture and use just
Beginning film and light polarizing film, carry out each measure or evaluation.Show the result in table 1.
[table 1]
It is clear that by result above：Meet the drawing of the optical film manufacture initial film of the embodiment 1 ~ 4 of code of the present invention
Stretching property is excellent, can productivity ratio manufacture optical film well.Further, since draftability is high, therefore gained optical film can be made
Area becomes big, can also obtain more optical films.In addition we know：On the basis of above-mentioned, according to meeting code of the present invention
The optical film manufacture initial film of embodiment 1 ~ 4, can easily manufacture the excellent optical film of optical characteristics and form and aspect.And then can
Know：Use in the also embodiment 4 of the PVA containing methylol comprising ethylene unit, draftability further improves, and stretchable temperature
Degree also uprises, and can manufacture optical film with better productivity ratio.
Claims (7)
1. optical film manufacture initial film, it includes the vinyl alcohol system polymer containing methylol, the vinyl alcohol containing methylol
Based polymer includes vinyl alcohol units and following formula（1）Shown construction unit,
[changing 1]
。
2. optical film manufacture initial film according to claim 1, wherein, the vinyl alcohol system polymer containing methylol
In the formula（1）The containing ratio of shown construction unit is 0.1 ~ 2 mole of %.
3. optical film manufacture initial film according to claim 1 or 2, wherein, the ethenol system containing methylol gathers
Compound also includes ethylene unit.
4. optical film manufacture initial film according to claim 3, wherein, the vinyl alcohol system polymer containing methylol
In the containing ratio of ethylene unit be 1 ~ 4 mole of %.
5. optical film manufacture initial film according to claim 1 or 2, wherein, the ethenol system containing methylol gathers
The saponification degree of compound is 95 moles of more than %.
6. optical film manufacture initial film according to claim 1 or 2, it is light polarizing film manufacture initial film.
7. the manufacture method of optical film, it possesses：Optical film manufacture initial film any one of usage right requirement 1 ~ 6
The process for carrying out uniaxial tension.
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| PCT/JP2014/070603 WO2015020044A1 (en) | 2013-08-09 | 2014-08-05 | Original film for manufacturing optical film |
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| JP6792456B2 (en) * | 2015-01-27 | 2020-11-25 | 株式会社クラレ | the film |
| WO2018164196A1 (en) * | 2017-03-08 | 2018-09-13 | 株式会社クラレ | Polarizing film, polarizing plate, and method for manufacturing same |
| EP3779534B1 (en) * | 2018-03-30 | 2023-08-30 | Sekisui Chemical Co., Ltd. | Poly(vinyl alcohol) film and production method for polarizing film |
| CN110441853B (en) * | 2019-08-14 | 2021-07-13 | 佛山纬达光电材料股份有限公司 | Xenon-lamp-resistant test polarizer and preparation method thereof |
| WO2021132435A1 (en) * | 2019-12-26 | 2021-07-01 | 株式会社クラレ | Polyvinyl alcohol film and polarizing film |
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| CN1445067A (en) * | 2002-03-20 | 2003-10-01 | 可乐丽股份有限公司 | Polyvinyl alcohol mesentery |
| CN102834439A (en) * | 2010-04-20 | 2012-12-19 | 可乐丽股份有限公司 | Polyvinyl alcohol film |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20160041921A (en) | 2016-04-18 |
| TWI636066B (en) | 2018-09-21 |
| WO2015020044A1 (en) | 2015-02-12 |
| KR102161870B1 (en) | 2020-10-05 |
| TW201509955A (en) | 2015-03-16 |
| JPWO2015020044A1 (en) | 2017-03-02 |
| CN105408783A (en) | 2016-03-16 |
| JP6383664B2 (en) | 2018-08-29 |
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