CN107531919A - Polyvinyl alcohol film and use its light polarizing film - Google Patents
Polyvinyl alcohol film and use its light polarizing film Download PDFInfo
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- CN107531919A CN107531919A CN201680022390.XA CN201680022390A CN107531919A CN 107531919 A CN107531919 A CN 107531919A CN 201680022390 A CN201680022390 A CN 201680022390A CN 107531919 A CN107531919 A CN 107531919A
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N3/00—Investigating strength properties of solid materials by application of mechanical stress
- G01N3/40—Investigating hardness or rebound hardness
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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
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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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Abstract
The present invention is a kind of polyvinyl alcohol film, and it is according to ISO14577：The hardness of 2002 film surface when carrying out nano indentation test under conditions of following (1)~(3) is 65~90MPa.The polyvinyl alcohol film without display bad point, the light polarizing film of color spot can be obtained therefore, it is possible to obtain.Condition (1) determination of the environment：25 DEG C of 50%RH.Condition (2) pressure head：Berkovich types (triangular pyramid type, 65 ° of vertical angles, ε=0.75, Buddha's warrior attendant are made of stones).Condition (3) maximum depth of cup：500nm.
Description
Technical field
The present invention relates to polyvinyl alcohol film.More specifically, it is related to and shows that bad point, color spot be few, wide cut suitable for manufacture
The polyvinyl alcohol film of the slim light polarizing film of strip and use light polarizing film obtained from the polyvinyl alcohol film.
Background technology
In recent years, the development of liquid crystal display device is notable, is widely used in smart mobile phone, tablet personal computer, PC, liquid crystal
TV, projecting apparatus, vehicle-mounted panel etc..Light polarizing film is used in above-mentioned liquid crystal display device, as light polarizing film, main use make iodine or
Dichroic dye is adsorbed in polyvinyl alcohol film and is orientated the film formed.In recent years, along with the High precision of picture, highlighted
Degreeization, maximization, slimming, with existing condition ratio, it is necessary to show the light polarizing film that bad point, color spot are less and wide filament is slim.
For the manufacture method of light polarizing film, for example, with water (including warm water) make polyvinyl alcohol film be swelled after, contaminated with iodine
Color, in order that iodine molecule arrangement and stretched, in order to keep the state of stretching and with cross-linking agents such as boric acid, and dry from
And manufacture.Above-mentioned manufacture is carried out when being conveyed film in the horizontal direction using coiling machine, roll.In order to reduce light polarizing film
Display bad point, the shortcomings that polyvinyl alcohol film itself should be reduced certainly, avoid scratching caused by light polarizing film manufacture etc. and lack
Point is also important.Above-mentioned scuffing can not only turn into the display bad point of light polarizing film, can also be in polarisation when being occurred with wider area
Color spot is produced in film.It should be noted that the light polarizing film in the present invention is also referred to as polarizing film, polarizer.
As the countermeasure that caused scuffing is manufactured to polyvinyl alcohol film, it is proposed that, the dynamic of stainless steel roller is rubbed
Wipe the polyvinyl alcohol film that coefficient is less than 0.03 (with reference to patent document 1).In addition, as caused by being manufactured to light polarizing film
The countermeasure of color spot, such as propose the manufacture method of following light polarizing film：Pass through the quiet of the roller that will be contacted with polyvinyl alcohol film
Coefficient of friction is set to specific scope, so as to reduce fold, stretching inequality (with reference to patent document 2).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2006-188661 publications
Patent document 2：Japanese Unexamined Patent Publication 2004-17321 publications
The content of the invention
Problems to be solved by the invention
However, in the public technology of patent document 1, even if the scuffing of polyvinyl alcohol film in itself can be reduced, also without
Method avoids scratching caused by light polarizing film manufacture, is still insufficient.Particularly when light polarizing film manufactures, such as pectin/polyvinyl alcohol
It is that film contacts with roller, then substantial amounts of fine scratch is produced, accordingly, it is difficult to manufacture the light polarizing film of large area.
In the public technology of patent document 2, even if the color spot of light polarizing film can be reduced, fine scratch can not be also avoided,
It is still insufficient.Above-mentioned scratch is obvious particularly in the manufacture of the light polarizing film of wide width thin type strip, seeks further
Improvement.
It should be noted that for above-mentioned scratch, big multiple-length is several mm on the flow direction of light polarizing film (MD directions)
Left and right, bandpass is more than several microns, depth is that more than sub-micron scratch can turn into problem.
In addition, when producing scratch, swarf is produced.Above-mentioned swarf can not only make the shortcomings that light polarizing film to increase but also can pollute partially
The manufacturing line of light film, turn into the reason for fabrication yield is greatly reduced.
Therefore, in the present invention, in this context, there is provided：Can obtain without display bad point, the light polarizing film of color spot it is poly-
Ethenol system film, using above-mentioned polyvinyl alcohol film high-quality light polarizing film.
The solution used to solve the problem
Thus, the present inventor etc. furthers investigate repeatedly in view of the foregoing, as a result finds：Use the pressure in tiny area
There is the polyvinyl alcohol film of the hardness of specific film surface in trace experiment, be not likely to produce during so as to manufacture light polarizing film and draw
Wound, it can obtain without display bad point, the light polarizing film of the high-quality of color spot.
That is, idea of the invention is that a kind of polyvinyl alcohol film, it is characterised in that according to ISO14577：2002
The hardness of film surface under conditions of following (1)~(3) during progress nano indentation test is 65~90MPa.
Condition (1) determination of the environment：25 DEG C of 50%RH
Condition (2) pressure head：Berkovich types (triangular pyramid type, 65 ° of vertical angles, ε=0.75, Buddha's warrior attendant are made of stones)
Condition (3) maximum depth of cup：500nm
In addition, the purport of the present invention also resides in a kind of light polarizing film, it is using obtained from above-mentioned polyvinyl alcohol film.
The effect of invention
The present invention polyvinyl alcohol film can reduce light polarizing film manufacture when scuffing, can obtain without display bad point,
The slim light polarizing film of the wide filament of color spot.
Embodiment
Hereinafter, the present invention is described in detail.
The maximum of the polyvinyl alcohol film of the present invention is characterised by, nanometer pressure is carried out under conditions of following (1)~(3)
The hardness of film surface when trace is tested is 65~90MPa.
Condition (1) determination of the environment：25 DEG C of 50%RH
Condition (2) pressure head：Berkovich types (triangular pyramid type, 65 ° of vertical angles, ε=0.75, Buddha's warrior attendant are made of stones)
Condition (3) maximum depth of cup：500nm
In above-mentioned nano indentation test, for the experimental condition outside specific as condition (1)~(3), as long as foundation
ISO14577：2002Metallic materials-Instrumented indentation test for hardness
And materials parameters are carried out, and the details of measuring principle is recorded in Handbook of
MicroNano/Nano Tribology (Bharat Bharat Bhushan compile CRC).
For the nano indentation test implemented in the present invention, enter small pressure head with small load pressure to tiny area, survey
Fixed displacement relative to load and and then displacement when slowly removing load, so as to calculate the hardness of film surface and
Modulus of elasticity as the film surface of the index of restoration.As bioassay standard, there is also JIS Z 2255：2003 ultra micros are small
Load hardness test method (Method for ultra-low loading hardness test), can on case hardness
To obtain similar data.
The polyvinyl alcohol film of the present invention can reduce the scratch with roller, but the production of above-mentioned scuffing also relies on
The surface roughness of the roller used in conveying, stretching.
Above-mentioned roller typically carries out mirror finish and causes surface roughness Rz to turn into less than 1 μm, but even is present in surface
The jut of height sub-micron degree can all scratch film.Therefore, it is necessary to the spy on film top layer is determined using small pressure head
Property, adjustment light polarizing film hardness optimal when manufacturing, modulus of elasticity.
As the method for the characteristic on measure film top layer, can typically enumerate in wider region, with larger load, pressure
Enter Brinell hardness (Brinell hardness), Rockwell hardness (Rockwell hardness), the Vickers hardness of larger pressure head
(Vickers hardness) etc..However, it is difficult to be evaluated exactly using these methods, the nanometer pressure implemented in the present invention
Trace experiment is effective.It should be noted that the maximum of the hardness of film surface in nano indentation test is usually
10000MPa。
The hardness of the film surface of polyvinyl alcohol film is necessary for 65~90MPa, preferably 68~85MPa, especially excellent
Elect 70~80MPa as.
When the hardness of above-mentioned film surface is less than lower limit, the scratch increase with roller, the purpose of the present invention can not be reached.Phase
Instead, the hardness of film surface exceedes higher limit and also results in the adaptation reduction of film and roller, abrades increase, can not reach this
The purpose of invention.
It is in terms of the what is worth mentioning of the present invention, in general, it is believed that film surface is more hard more is not easy to scratch, but
It must actually make it soft to the degree ensured with the adaptation of roller.When film surface is really up to the mark, film only slides on roller, nothing
Method carries out the smoothly conveying that the rotation with roller matches, and therefore, produces scratch.Above-mentioned scratch not only turns into the display of light polarizing film
Bad point, and when producing in relative broad range, have the tendency of to produce color spot in light polarizing film, Polarizer.
And then as the what is worth mentioning effect of the present invention, the self-repair function of scuffing can be enumerated.
Above-mentioned self-repair function refers to, the work(that the macromolecular chain of polyvinyl alcohol resin is moved to depressed area and planarized
Energy.Although being difficult to repair completely in the case of the depth that is recessed, for example, if then may be used for the shallow scuffing of deep sub-micron or so
To repair.When the hardness on the surface of polyvinyl alcohol film is less than above-mentioned lower limit, deep scuffing is easily produced, therefore, it is impossible to
Reach selfreparing, but with for it is more than lower limit and close to lower limit flexibility when, it is intended to show effective selfreparing work(
Energy.
As the method for the hardness on the surface for controlling above-mentioned polyvinyl alcohol film, it can enumerate and suitably adjust polyvinyl alcohol
It is method of the chemical constitution of resin, composition, the additive of polyvinyl alcohol film, manufacturing condition etc..Wherein, it is preferably suitable to adjust
The method for saving the manufacturing condition of polyvinyl alcohol film, it is therefore particularly preferred that preferably suitably regulation is dried and heat treatment condition
Method.
It is thin during progress nano indentation test under above-mentioned condition (1)~(3) for the polyvinyl alcohol film of the present invention
The modulus of elasticity on film surface be preferably 1.0~1.4GPa, particularly preferably 1.05~1.35GPa, more preferably 1.1~
1.3GPa。
When the modulus of elasticity of film surface is too low, has and deep scratch, selfreparing are easily produced in light polarizing film manufacturing process
Also it is difficult to the tendency shown, when too high, have and a large amount of shallow abrasive tendencies are easily produced in light polarizing film manufacturing process.
Herein, it is considered that, the modulus of elasticity of film surface is higher, is more difficult to scratch, but in fact, in order that because of roller table
The projection in face and caused depression planarization, preferably modulus of elasticity low to a certain degree.I.e., it is necessary to a certain degree of to possess
The film surface of pooling feature.
The polyvinyl alcohol film of the present invention manufactures by raw material of polyvinyl alcohol resin.
As the polyvinyl alcohol resin used in the present invention, usually using to unmodified polyvinyl alcohol resin, i.e.
The resin that polyvinyl acetate obtained from vinyl acetate polyisocyanate polyaddition is subjected to saponification and manufactured.As needed, can also use
By vinyl acetate and a small amount of (usual below the % of 10 moles of below %, preferably 5 moles) can be with vinyl acetate copolymerization
Resin obtained from the copolymer saponification of composition.As with the composition of vinyl acetate copolymerization such as insatiable hunger can be enumerated
With carboxylic acid (such as including salt, ester, acid amides, nitrile etc.), olefines (such as ethene, propylene, n-butene, the isobutene of carbon number 2~30
Deng), vinyl ethers, unsaturated sulfonic acid salt etc..Alternatively, it is also possible to be obtained using the hydroxyl after saponification is chemically modified
Modified polyvinylalcohol system resin.
In addition, as polyvinyl alcohol resin, the polyethenol series that there is 1,2- diol structures in side chain can also be used
Resin.It is above-mentioned side chain have the polyvinyl alcohol resins of 1,2- diol structures such as can by the following method obtain：(i)
The method that the copolymer of vinyl acetate and 3,4- diacetoxy -1- butylene is carried out to saponification；(ii) by vinyl acetate with
The method that the copolymer of vinyl ethylene carbonate carries out saponification and decarburization acid；(iii) by vinyl acetate and 2,2- dialkyl group-
The copolymer of 4- vinyl -1,3- dioxolanes carries out saponification and de- ketalization method；(iv) by vinyl acetate and glycerine
The method that the copolymer of monoallyl ether carries out saponification.
The weight average molecular weight of polyvinyl alcohol resin is preferably 100,000~300,000, is particularly preferably 110,000~280,000, enters one
Step is preferably 120,000~260,000.When above-mentioned weight average molecular weight is too small, has and be not easy when polyvinyl alcohol resin is made into optical thin film
The tendency of sufficient optical property is obtained, when excessive, has stretching when polyvinyl alcohol film to be manufactured into light polarizing film to become difficult
Tendency.It should be noted that the weight average molecular weight of above-mentioned polyvinyl alcohol resin is that the weight determined by GPC-MALS methods is equal
Molecular weight.
The mean saponification degree of the polyvinyl alcohol resin used in the present invention is preferably generally 98 moles of more than %, especially excellent
Elect 99 moles of more than %, more preferably 99.5 moles of more than %, especially preferably 99.8 moles of more than % as.It is above-mentioned average
When saponification degree is too small, sufficient optical property can not be obtained when having the tendency of polyvinyl alcohol film light polarizing film is made.
Herein, the mean saponification degree in the present invention determines according to JIS K 6726.
As the polyvinyl alcohol resin used in the present invention, modified material, modified amount can also be applied in combination, divide equally again
The different polyvinyl alcohol resins of more than two kinds such as sub- amount, mean saponification degree.
The polyvinyl alcohol film of the present invention can be continuously manufactured by as follows：Prepared using above-mentioned polyvinyl alcohol resin poly-
The vinyl alcohol resin aqueous solution, the mold cocurrent of pouring that the above-mentioned polyvinyl alcohol resin aqueous solution is expelled to rotation is prolonged, by pouring
Casting is filmed, dried, and so as to be continuously manufactured by, such as can be manufactured by following process.
Process (A), is filmed by casting method.
Process (B), the film heating of film and drying are heat-treated as needed.
Process (C), by after the both ends of dry film carry out trimming, batch in roller.
Herein, mold is poured as above-mentioned, such as casting roller (cylinder type roller), annulus etc. can be enumerated, from wide cut, length
Bar, thickness excellent in uniformity in terms of set out, preferably by casting roller carry out.
Hereinafter, illustrated in case of pouring mold as casting roller.
First, foregoing sequence (A) is illustrated.
In process (A), it is preferred that clean foregoing polyvinyl alcohol resin first by water, use centrifugal separator etc.
It is dehydrated, forms below the weight % of moisture content 50 polyvinyl alcohol resin wet cake.When moisture content is excessive, has and be difficult to be formed
The tendency of desired concentration of aqueous solution.
Above-mentioned polyvinyl alcohol resin wet cake is dissolved in warm water, hot water, prepares the polyvinyl alcohol resin aqueous solution.
The preparation method of the polyvinyl alcohol resin aqueous solution is not particularly limited, such as can use more spiral shells by heating
Prepared by bar extruder, in addition, putting into foregoing polyethylene in the dissolving tank for possessing upper and lower recycle stream generation type stirring vane
Alcohol system resin wet cake, is blown into vapor in groove, so as to dissolve and prepare the aqueous solution of expectation concentration.
From the Film making properties aspect of polyvinyl alcohol film, in the polyvinyl alcohol resin aqueous solution, except polyethylene
Outside alcohol system resin, glycerine, two glycerine, triglycerin, ethylene glycol, triethylene glycol, polyethylene glycol, trimethylolpropane are preferably comprised
Deng the plasticizer typically used, include the surfactant of at least one of nonionic, anionic property and cationic.On
State the plasticizer such as glycerine, surfactant content relative to polyvinyl alcohol resin be preferably 1~20 weight %, more preferably
5~15 weight %.
The resin concentration of the so obtained polyvinyl alcohol resin aqueous solution is preferably 15~60 weight %, is particularly preferably
17~55 weight %, more preferably 20~50 weight %.When the resin concentration of the above-mentioned aqueous solution is too low, dries burden and become
Greatly, therefore, there is production capacity reduction, when too high, viscosity becomes too high, is not easy uniform dissolution.
Then, the gained polyvinyl alcohol resin aqueous solution is subjected to deaeration processing.As defoaming method, standing can be enumerated
Deaeration, using the multi-screw extruder for possessing exhaust outlet deaeration the methods of.As the multi-screw extruder for possessing exhaust outlet, lead to
Often using the double screw extruder for possessing exhaust outlet.
After deaeration processing, the polyvinyl alcohol resin aqueous solution is gradually directed into T-shaped slit die with a certain amount of, is expelled to rotation
Casting roller on and be cast, be filmed using casting method.
The temperature of the polyvinyl alcohol resin aqueous solution of T-shaped slit die outlet is preferably 80~100 DEG C, is particularly preferably 85
~98 DEG C.
When the temperature of the above-mentioned polyvinyl alcohol resin aqueous solution is too low, have the tendency of to become to flow bad, when too high, there is hair
The tendency of bubble.
The viscosity of the above-mentioned polyvinyl alcohol resin aqueous solution is 50~200Pas preferably in discharge, is particularly preferably 70
~150Pas.
When the viscosity of the above-mentioned aqueous solution is too low, have the tendency of to become to flow bad, when too high, there is curtain coating to become difficult and incline
To.
The velocity of discharge that the polyvinyl alcohol resin aqueous solution of casting roller is expelled to from T-shaped slit die is preferably 0.2~
5m/ minutes, particularly preferably 0.4~4m/ minutes, more preferably 0.6~3m/ minutes.
When the above-mentioned velocity of discharge is excessively slow, there is productivity ratio reduction, when too fast, have the tendency of curtain coating and become difficult.
The diameter of above-mentioned casting roller be preferably 2~5m, particularly preferably 2.4~4.5m, more preferably 2.8~
4m。
When above-mentioned diameter is too small, has the tendency of to dry long deficiency and be difficult to reach speed, when excessive, there is what transporting reduced
Tendency.
The width of above-mentioned casting roller be preferably more than 4m, particularly preferably more than 4.5m, more preferably more than 5m,
Especially preferably 5~6m.
When the width of casting roller is too small, there is productivity ratio reduction.
The rotary speed of above-mentioned casting roller is preferably 3~50m/ minutes, is particularly preferably 4~40m/ minutes, further
Preferably 5~35m/ minutes.
When above-mentioned rotary speed is excessively slow, there is productivity ratio reduction, when too fast, there is the fissility from casting roller to reduce
Tendency.
The surface temperature of above-mentioned casting roller is preferably 40~99 DEG C, particularly preferably 60~95 DEG C.
When above-mentioned surface temperature is too low, the fissility having the tendency of from casting roller reduces, and when too high, there is inclining for foaming
To.
Then, foregoing sequence (B) is illustrated.Process (B) is the work that the film after film is heated and dried
Sequence.
The drying for the film being film-made using roller of casting can be added by the surface and the back side for making film with multiple metals
Hot-rolling is alternately contacted to carry out.The surface temperature of METAL HEATING PROCESS roller is usually 40~150 DEG C, is preferably 50~130 DEG C, especially
Preferably 60~110 DEG C.When above-mentioned surface temperature is too low, has the tendency of to become underdry, when too high, become over drying,
Have the tendency of to cause the bad orders such as bending.In addition, METAL HEATING PROCESS roller for example be preferably surface has been carried out hard plating processing or
Mirror surface treatment, 0.2~2m of diameter roller, it is dried usually using 2~30, preferably 10~25.
Present invention it is preferred that after being dried using METAL HEATING PROCESS roller, film is heat-treated.Heat treatment temperature
Degree is preferably 60~150 DEG C, particularly preferably 70~140 DEG C.When heat treatment temperature is too low, there is the water-fast of polyvinyl alcohol film
Property deficiency or as tendency the reason for phase difference deviation, when too high, draftability when having the tendency of light polarizing film manufacture reduces.
As above-mentioned heat treatment method, for example, can enumerate using floating type drying machine carry out method, using infrared lamp to film
Two sides irradiation near infrared ray method etc..
Drying is carried out, the film of heat treatment as needed turns into product (poly- second of the invention by foregoing sequence (C)
Enol system film).Process (C) is by the both ends trimming of film and batches the process in roller.
It should be noted that so far, pour preparing the polyvinyl alcohol resin aqueous solution, the aqueous solution being cast into rotation
Casting roller (cylinder type roller) and be filmed using casting method, drying carried out so as to manufacture the method for polyvinyl alcohol film
Illustrate, but the polyvinyl alcohol resin aqueous solution can also be cast on resin film or on metal tape and be film-made, dry.
From the slimming aspect of light polarizing film, the thickness of above-mentioned polyvinyl alcohol film is preferably 5~60 μm, from entering
Set out in terms of the slimming of one step, particularly preferably 5~45 μm, from avoid fracture, the present invention characteristic (film surface it is hard
Degree) with slimming relation in terms of set out, more preferably 10~45 μm.
In addition, the width of polyvinyl alcohol film is preferably more than 4m, from large area aspect, it is more preferably
More than 4.5m, from the aspect for avoiding fracture, particularly preferably 4.5~6m.
In addition, the length of polyvinyl alcohol film is preferably more than 4km, from large area aspect, it is more preferably
More than 4.5km, from conveying weight aspect, particularly preferably 4.5~50km.
The polyvinyl alcohol film of the present invention has appropriate hardness, and being suitable as the polyvinyl alcohol film of optics makes
With, and then used particularly preferable as the reel of light polarizing film.
Hereinafter, the manufacture method of the light polarizing film obtained to the polyvinyl alcohol film using the present invention illustrates.
The light polarizing film of the present invention manufactures as follows：Above-mentioned polyvinyl alcohol film is rolled out from roller and conveyed in the horizontal direction,
By being swelled, dyeing, boric acid crosslinking, stretching, cleaning, the process such as dry so as to manufacture.
Swelling process is implemented before dyeing process.By being swelled process, polyvinyl alcohol film can be not only cleaned
The pollutant on surface, also have by making polyvinyl alcohol film swelling prevent from dyeing unequal effect.It is swelled in process,
As treatment fluid, usually using water.As long as the treatment fluid principal component is water, a small amount of iodide, surface can also be added
The additives such as activating agent, alcohol etc..The temperature of swelling bath is usually 10~45 DEG C or so, and the dip time in swelling bath is usually
0.1~10 minute or so.In addition, stretched operation can also be carried out in processes as needed.
Dyeing process is carried out by making film be contacted with the liquid containing iodine or dichroic dye.Usually using iodo- iodine
Change the aqueous solution of potassium, it is appropriate that the concentration of iodine is 0.1~2g/L, the concentration of KI is 1~100g/L.Dyeing time is
30~500 seconds or so are practical.Handle preferably 5~50 DEG C of the temperature of bath.In the aqueous solution, in addition to aqueous solvent, it can also contain
There is a small amount of organic solvent for having compatibility with water.In addition, stretched operation can also be carried out in processes as needed.
Boric acid cross-linking process step is carried out using boron compounds such as boric acid, boraxs.Boron compound is with the aqueous solution or water-organic molten
The form of agent mixed liquor, with 10~100g/L of concentration or so use, from the stabilized aspect of polarizing properties, preferred liquid
In KI coexists.Preferably, temperature during processing be 30~70 DEG C or so, processing time be 0.1~20 minute or so,
And stretched operation can also be carried out in processes as needed.
Stretching process is preferably, and is stretched 3~10 times along single shaft direction, is preferably stretched 3.5~6 times.Now, in stretching side
To right angle orientation on can also carry out some stretchings and (prevent the drawing more than degree or the degree of the contraction of width
Stretch).Preferably 30~170 DEG C of temperature during stretching.And then as long as stretching ratio is ultimately set to aforementioned range, stretching behaviour
Work can not only be implemented with a stage, implement in the stage of any range of manufacturing process.
Matting iodide aqueous solution such as by the way that polyvinyl alcohol film is impregnated in into water, KI is carried out,
Precipitate caused by the surface of film can be removed.The use of iodate potassium concn during potassium iodide aqueous solution can be that 1~80g/L is left
It is right.Temperature during cleaning treatment is usually 5~50 DEG C, is preferably 10~45 DEG C.Processing time is usually 1~300 second, is preferably
10~240 seconds.It should be noted that water can also be cleaned and be carried out using the cleaning proper combination of potassium iodide aqueous solution.
As long as drying process is carried out 1~10 minute in an atmosphere, with 40~80 DEG C.
In addition, the degree of polarization of light polarizing film is preferably more than 99.5%, more preferably more than 99.8%.When degree of polarization is too low,
Have the tendency of that the contrast in liquid crystal display can not be ensured.
It should be noted that on degree of polarization, in general turning into same according to by 2 light polarizing films with its differently- oriented directivity
In the state of the mode in direction is overlapping, the light transmittance (H that is determined under wavelength X11), and by 2 light polarizing films with differently- oriented directivity
As mutually orthogonal directions mode it is overlapping in the state of, the light transmittance (H that is determined under wavelength X1), calculated according to following formula
Go out.
〔(H11-H1)/(H11+H1)〕1/2
And then the singleton transmittance of light polarizing film of the invention is preferably more than 42%.When above-mentioned singleton transmittance is too low, have
The tendency of the high brightness of liquid crystal display can not be reached.
Singleton transmittance is value obtained from the light transmittance using spectrophotometric determination monolithic light polarizing film.
In this way, the light polarizing film of the present invention can be obtained, light polarizing film of the invention is suitable for manufacture without display bad point, color spot
Polarizer.
Hereinafter, the manufacture method of the Polarizer of the present invention is illustrated.
The light polarizing film of the present invention pastes the resin film work of optical isotropy in its one or two sides by bonding agent
For protective film, so as to turn into Polarizer.As protective film, such as cellulosic triacetate, cellulose diethyl can be enumerated
Acid esters, makrolon, polymethyl methacrylate, cyclic olefin polymer, cyclic olefine copolymer, polystyrene, polyether sulfone, poly- Asia
The film or piece of aryl ester, poly- 4- methylpentenes, polyphenylene oxide etc..
Method of attaching can be carried out using known method, such as liquid adhesive composition is equably coated on into polarisation
Film, protective film or both, then paste both and crimp, carried out by heating, irradiating active energy beam.
In addition, for the purpose of filming, can also be coated with the one or two sides of light polarizing film carbamate system resin,
The curable resins such as acrylic resin, carbamide resin replace above-mentioned protective film, and are solidified to form Polarizer.
According to obtained light polarizing film of the invention, Polarizer without display bad point, color spot, it is preferred for：Personal digital assistant device machine,
PC, TV, projecting apparatus, nameplate, electronic desktop computer, electronic clock, word processor, Electronic Paper, game machine,
Liquid crystal display device, the sun eye of video recorder, camera, photograph album, thermometer, sound equipment, automobile, mechanical measuring instrument class etc.
Mirror, anti-glare glasses, anaglyph spectacles, wearable display, display element (CRT, LCD, organic EL, Electronic Paper etc.) use antireflection
Layer, optical communication equipment, Medical Devices, construction material, toy etc..
Embodiment
Hereinafter, enumerate embodiment to the present invention be further specifically described, as long as but the present invention be no more than its purport just
It is not limited to following embodiment.
It should be noted that in example, " % " refers to weight basis.
For each physical property, measure is carried out as follows.
＜ condition determinations ＞
(1) hardness (MPa) of film surface, the modulus of elasticity (GPa) of film surface
1cm × 1cm test film is cut out from gained polyvinyl alcohol film, is carried out 1 day with 25 DEG C of 50%RH before the test
State adjustment, then use Hysitron company system nano indentation test machines " Triboindenter " as testing machine, as
Pressure head uses the pressure head (65 ° of vertical angles, ε=0.75, Buddha's warrior attendant are made of stones) for the triangular pyramid type for being referred to as Berkovich types, at 25 DEG C
Tested in the environment of 50%RH.Experiment is carried out to film two sides, is averaged.It should be noted that before the test, use
As the vitreous silica (hardness 9250MPa, modulus of elasticity 69.6GPa) of standard specimen, obtain for pressure head pair when calculating press-in
The projected area A of sample correction coefficient.
Nano indentation test is as follows：First, by the surface of pressure head vertically contact test piece, with the press-in speed 100nm/ seconds
Slowly apply load.Then, press-in is stopped at the time of maximum depth of cup 500nm is reached, meanwhile, to extract speed
The 100nm/ seconds slowly recover load to 0.
By the maximum load P (N) and the projected area A (mm of pressure head obtained in above-mentioned experiment2), according to following formula (A), calculate
The hardness (MPa) of film surface.
Hardness=the P/A of (formula A) film surface
In addition, the tangent slope S (N/mm) when maximum load is obtained according to unloading displacement curve, by above-mentioned slope S (N/
Mm) and pressure head projected area A (mm2), according to following formula (B), calculate the modulus of elasticity (GPa) of film surface.
Modulus of elasticity=0.001 of (formula B) film surface × (S × π1/2)/(2×A1/2) (π is pi)
(2) abrade
The test film 10 that 1cm × 1cm is cut out from gained light polarizing film is opened, using KEYENCE company system laser to focusing microscope
VK-9700 (object lens：50 times), observation whether there is the scuffing of more than 10 μm of width, is evaluated with following benchmark.
(metewand)
Zero total Test piece does not scratch.
Any test films of △ have scuffing.
× total Test piece has scuffing.
(3) bad point (individual) is shown
From gained light polarizing film cut-out length 30cm × width 13cm test film, carried out in the environment of 15000lx visual
Check, the display bad point number (individual) that more than 100 μm of measure.
(4) color spot
From gained light polarizing film cut-out length 30cm × width 13cm test film, the angle with 45 ° is clamped in crossed nicols
After between 2 Polarizers (singleton transmittance 43.5%, degree of polarization 99.9%) of state, surface illuminance 14000lx light is used
Source case, optics color spot is observed in the transmission mode, is evaluated with following benchmark.
Zero without color spot.
△ slightly color spots.
× there is color spot.
The ＞ of ＜ embodiments 1
(manufacture of polyvinyl alcohol film)
Add weight average molecular weight 142000,99.8 moles of % of saponification degree polyvinyl alcohol resin 1000kg, water 2500kg,
As the glycerine 100kg of plasticizer, warming while stirring carries out concentration and adjusted to resin concentration 25%, obtain uniformly to 140 DEG C
The lysed polyvinyl alcohol resin aqueous solution in ground.Then, the polyvinyl alcohol resin aqueous solution is supplied to possessing exhaust outlet
Double screw extruder carry out deaeration, then make aqueous temperature be 90 DEG C, be expelled to pouring for rotation from T-shaped slit die outlet
Casting roller is simultaneously cast, so as to be film-made.From casting drum peel film, while making surface and the back side and the multiple METAL HEATING PROCESS rollers of film
(86 DEG C of maximum temperature) alternately contacts, and causes the moisture content of film to turn into less than 10% while being dried.And then use floating
Formula drying machine, 133 DEG C of hot blast is blowed from film two sides, be dried until the moisture content of film enters both ends as 2%
Row trimming is simultaneously batched in roller, obtains width 4.8m, 45 μm of thickness, length 5km polyvinyl alcohol film.By gained polyvinyl alcohol
It is that the characteristic of film is shown in table 1.
(manufacture of light polarizing film)
Gained polyvinyl alcohol film is conveyed in the horizontal direction using conveying roller, first, while being impregnated in 25 DEG C of water temperature
Tank makes its swelling side be stretched to 1.7 times to flow direction.Then, while be impregnated in comprising iodine 0.5g/L, KI 30g/L 28
DEG C the aqueous solution in dyed, while 1.6 times are stretched to flow direction, then, while being impregnated in boric acid 40g/L, KI
(55 DEG C) progress boric acid crosslinkings of the aqueous solution of 30g/L composition, while to flow direction uniaxial tension to 2.1 times.Finally, iodate is used
Aqueous solutions of potassium is cleaned, and afterwards with 60 DEG C of progress drying in 2 minutes, obtains the light polarizing film of total 5.7 times of stretching ratio.Gained is inclined
The characteristic of light film is shown in table 1.
＜ embodiments 2,3, comparative example 1,2 ＞
Manufactured under the conditions shown in Table 1, in addition, similarly to Example 1, obtain polyvinyl alcohol film
And light polarizing film.The characteristic of gained polyvinyl alcohol film and light polarizing film is as shown in table 1.
[table 1]
Understand, for the polyvinyl alcohol film of embodiment 1~3, the hardness of the film surface in nano indentation test exists
In the particular range of the present invention, therefore, it can obtain scratching few light polarizing film, and for the polyvinyl alcohol using comparative example 1,2
It is the light polarizing film of film, outside the particular range of the present invention, its result scratches more the hardness on polyvinyl alcohol film surface.
And understand, it is real for each evaluation of the display bad point, color spot of the light polarizing film that are obtained by each polyvinyl alcohol film
It is better than comparative example 1,2 to apply example 1~3.
In above-described embodiment, the concrete mode in the present invention is shown, but above-described embodiment is only simple example, is not made
Limited explanation.It will be apparent to those skilled in the art that various modifications meaning within the scope of the invention.
Industrial applicability
It is also excellent without display bad point, color spot, the inner evenness of polarizing properties by obtained light polarizing film of the invention, Polarizer
It is different, it is preferred for：When personal digital assistant device machine, PC, TV, projecting apparatus, nameplate, electronic desktop computer, electronics
Clock, word processor, Electronic Paper, game machine, video recorder, camera, photograph album, thermometer, sound equipment, automobile, mechanical measurement
Liquid crystal display device, sunglasses, anti-glare glasses, anaglyph spectacles, wearable display, the display element of instrument class etc.
(CRT, LCD, organic EL, Electronic Paper etc.) uses anti-reflection layer, optical communication equipment, Medical Devices, construction material, toy etc..
Claims (4)
1. a kind of polyvinyl alcohol film, it is characterised in that according to ISO14577：2002 enter under conditions of following (1)~(3)
The hardness of film surface during row nano indentation test is 65~90MPa,
Condition (1) determination of the environment：25 DEG C of 50%RH
Condition (2) pressure head：Berkovich types (triangular pyramid type, 65 ° of vertical angles, ε=0.75, Buddha's warrior attendant are made of stones)
Condition (3) maximum depth of cup：500nm.
2. polyvinyl alcohol film according to claim 1, it is characterised in that carried out under conditions of (1)~(3)
The modulus of elasticity of film surface during nano indentation test is 1.0~1.4GPa.
3. polyvinyl alcohol film according to claim 1 or 2, it is characterised in that thickness is 5~45 μm.
A kind of 4. light polarizing film, it is characterised in that its be usage right requirement 3 described in polyvinyl alcohol film obtained from.
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| CN202111114369.1A CN113900163A (en) | 2015-08-18 | 2016-06-23 | Polyvinyl alcohol film and polarizing film using same |
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| JP2015-160809 | 2015-08-18 | ||
| JP2015160809 | 2015-08-18 | ||
| PCT/JP2016/068600 WO2017029881A1 (en) | 2015-08-18 | 2016-06-23 | Polyvinyl alcohol film, and polarizing film in which same is used |
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| CN201680022390.XA Active CN107531919B (en) | 2015-08-18 | 2016-06-23 | Polyvinyl alcohol film and polarizing film using same |
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| KR (1) | KR102475406B1 (en) |
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| CN112533848A (en) * | 2018-09-11 | 2021-03-19 | 三菱化学株式会社 | Polyvinyl alcohol film roll and method for producing same |
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| KR101971871B1 (en) * | 2017-02-28 | 2019-04-24 | 동우 화인켐 주식회사 | Surface treatment film for polarizing plate, polarising plate and image display device including the same |
| JPWO2023074639A1 (en) * | 2021-10-25 | 2023-05-04 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006070627A1 (en) * | 2004-12-28 | 2006-07-06 | The Nippon Synthetic Chemical Industry Co., Ltd. | Polyvinyl alcohol film, polarizing film using same, and polarizing plate |
| CN107405806A (en) * | 2015-05-29 | 2017-11-28 | 日本合成化学工业株式会社 | The manufacture method and light polarizing film of polyvinyl alcohol film, polyvinyl alcohol film |
| CN107614578A (en) * | 2015-06-24 | 2018-01-19 | 日本合成化学工业株式会社 | The manufacture method and light polarizing film of polyvinyl alcohol film, polyvinyl alcohol film |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3283564B2 (en) * | 1992-03-04 | 2002-05-20 | 株式会社クラレ | Method for producing polyvinyl alcohol-based film |
| JP3909990B2 (en) * | 1998-11-13 | 2007-04-25 | 三井化学株式会社 | Organic polymer / inorganic fine particle dispersed aqueous solution excellent in dispersion stability and use thereof |
| JP4085554B2 (en) * | 2000-05-10 | 2008-05-14 | コニカミノルタホールディングス株式会社 | Method for producing cellulose ester film |
| JP2003170456A (en) * | 2001-12-10 | 2003-06-17 | Kuraray Co Ltd | Manufacturing method for vinyl alcohol polymer film, and polarizing film |
| JP3796198B2 (en) | 2002-06-12 | 2006-07-12 | 株式会社クラレ | Manufacturing method of polarizing film |
| JP2004020636A (en) * | 2002-06-12 | 2004-01-22 | Kuraray Co Ltd | Method of manufacturing polarizing film |
| JP3911465B2 (en) * | 2002-09-19 | 2007-05-09 | 日本合成化学工業株式会社 | Production method of polyvinyl alcohol film |
| JP4531574B2 (en) * | 2004-01-26 | 2010-08-25 | 日本合成化学工業株式会社 | Method for producing polyvinyl alcohol film and method for producing polarizing film using the film |
| WO2006049168A1 (en) * | 2004-11-02 | 2006-05-11 | The Nippon Synthetic Chemical Industry Co., Ltd. | Polyvinyl alcohol film and method for producing same |
| JP5348823B2 (en) | 2004-11-02 | 2013-11-20 | 日本合成化学工業株式会社 | Polyvinyl alcohol film for polarizing film, polarizing film, and polarizing plate |
| JP4761945B2 (en) * | 2005-01-31 | 2011-08-31 | 日本合成化学工業株式会社 | Polyvinyl alcohol film for polarizing film, polarizing film, polarizing plate |
| JP4740184B2 (en) * | 2006-05-16 | 2011-08-03 | 日東電工株式会社 | Polarizing plate and image display device using the same |
| WO2010093030A1 (en) * | 2009-02-10 | 2010-08-19 | 住友化学株式会社 | Polarizer, and liquid-crystal panel and liquid-crystal display device each including same |
| TWI437008B (en) * | 2010-07-02 | 2014-05-11 | Nippon Synthetic Chem Ind | Polyvinyl alcohol-based film, method for manufacturing polyvinyl alcohol-based film, polarized film, and polarizing plate |
| CN104311853B (en) * | 2011-03-29 | 2018-05-25 | 可乐丽股份有限公司 | Polymer film of polyvinyl alcohol and its manufacturing method |
| JP2015022245A (en) * | 2013-07-23 | 2015-02-02 | 日本合成化学工業株式会社 | Method for manufacturing retardation plate |
| TW201710331A (en) * | 2015-07-07 | 2017-03-16 | 日本合成化學工業股份有限公司 | Poly(vinyl alcohol)-based polarizing film and polarizing plate |
-
2016
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- 2016-06-23 JP JP2016542789A patent/JP6642434B2/en active Active
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006070627A1 (en) * | 2004-12-28 | 2006-07-06 | The Nippon Synthetic Chemical Industry Co., Ltd. | Polyvinyl alcohol film, polarizing film using same, and polarizing plate |
| CN107405806A (en) * | 2015-05-29 | 2017-11-28 | 日本合成化学工业株式会社 | The manufacture method and light polarizing film of polyvinyl alcohol film, polyvinyl alcohol film |
| CN107614578A (en) * | 2015-06-24 | 2018-01-19 | 日本合成化学工业株式会社 | The manufacture method and light polarizing film of polyvinyl alcohol film, polyvinyl alcohol film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112533848A (en) * | 2018-09-11 | 2021-03-19 | 三菱化学株式会社 | Polyvinyl alcohol film roll and method for producing same |
| CN112533848B (en) * | 2018-09-11 | 2023-02-17 | 三菱化学株式会社 | Polyvinyl alcohol film roll and method for producing same |
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| KR102475406B1 (en) | 2022-12-07 |
| JPWO2017029881A1 (en) | 2018-06-07 |
| JP6642434B2 (en) | 2020-02-05 |
| KR20180041090A (en) | 2018-04-23 |
| CN107531919B (en) | 2021-10-15 |
| TW201707980A (en) | 2017-03-01 |
| TWI692404B (en) | 2020-05-01 |
| WO2017029881A1 (en) | 2017-02-23 |
| CN113900163A (en) | 2022-01-07 |
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