CN101276013B - Manufacturing methods of polarized light film and polarized light piece - Google Patents
Manufacturing methods of polarized light film and polarized light piece Download PDFInfo
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- CN101276013B CN101276013B CN2008100900014A CN200810090001A CN101276013B CN 101276013 B CN101276013 B CN 101276013B CN 2008100900014 A CN2008100900014 A CN 2008100900014A CN 200810090001 A CN200810090001 A CN 200810090001A CN 101276013 B CN101276013 B CN 101276013B
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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
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
-
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
A manufacturing method for a polarized light film is following: processing the material film (1) of the polyvinyl alcohol resin through the expanding sink (3) as a procedure, processing the material in the dipping sink (4) as a procedure, the dyeing procedure for the dyeing process in the dyeing sink (5) and continuous procedure for the boric acid process in the boric acid sink (6); and processing the single shaft extending for the polarized light film (9) in one procedure at least of the dyeing sink (5) and the boric acid sink (6), the invention processes the polyvinyl alcohol resin film in the direction of the mechanism in the dipping sink (4), which reaches the extending multiplying power above 1.0 fold and below 1.05 folds. The bath in the dipping sink (4) has no pure water with dissolving components preferably. At least one side of the polarized light film (9) is adhered with a transparent protective film to manufacture the polarized light sheet.
Description
Technical field
The present invention relates to as the long size object of roller shape make, the manufacture method of the inhomogeneous few polarized light film of Width optical characteristics and in the manufacture method of the polarized light piece of at least one lamination transparent protective film of this polarized light film.
Background technology
As making the dichromatism pigment adsorb the material of orientation on the polyvinyl alcohol resin film, polarized light film is widely used.And known have with iodine be polarized light film as the iodine of dichromatism pigment and be polarized light film etc. as the dyestuff of dichromatism pigment with the dichromatism direct dyes.These polarized light films usually at its one or both sides by containing the transparent protective films such as cementing agent applying triacetyl cellulose of polyvinyl alcohol resin aqueous solution, make polarized light piece.
Manufacture method as polarized light film, for example the spy open recorded and narrated in the flat 10-153709 communique (patent documentation 1) with polyvinyl alcohol resin is thin film dipped in water, make its swelling after, use iodine staining, then stretch, fix in order to make iodine, also to carry out boric acid and handle (in other words, utilizing crosslinked water-fastization processing), carry out dry method after the washing.It is in order to make the even swelling of film before dyeing that swelling that water carries out is handled, and shortening dyeing time to reach, improving dyeing inhomogeneous etc. is that purpose is carried out.At this moment, consider, in the patent documentation 1, handle in swelling and to contain boric acid in bathing from the viewpoint such as inhomogeneous that dyes.In this patent documentation 1, in containing the aqueous solution of boric acid, stretch thin film dipped after the dyeing in addition, further be immersed in the boric acid aqueous solution then, utilize crosslinked water-fastization processing (being referred to as set or fixing in the document).
Recorded and narrated in the Te Kaiping 6-281816 communique (patent documentation 2) in order to make the abundant swelling of film, handled in swelling and add muriatic situations such as lithium chloride and zinc chloride in the bath.In addition the spy open recorded and narrated in the 2001-141926 communique (patent documentation 3) for reduce dyeing inhomogeneous, with polyvinyl alcohol resin thin film dipped in water-bath, make its swelling in, carry out 1.1～4 times stretch processing, use the dyeing processing of dichromatism pigment and the method that crosslinking Treatment is made polarized light film then.
In addition, the spy opens 2005-114990 communique (patent documentation 4) and has recorded and narrated according to the order that swelling is handled, dyeing is handled, boric acid is handled and handle continuously in bath, and when carrying out uniaxial tension manufacturing polarized light film at least one operation therein, after swelling is handled, and before dyeing is handled, wet stretching process is set, in this wet stretching process, in boric acid aqueous solution,, further improve the even situation of irregular colour thus with more than 1.1 times and be lower than 3 times stretching ratio and carry out uniaxial tension.
[patent documentation 1] spy opens flat 10-153709 communique;
[patent documentation 2] spy opens flat 6-281816 communique;
[patent documentation 3] spy opens the 2001-141926 communique;
[patent documentation 4] spy opens the 2005-114990 communique.
Summary of the invention
The present inventor for shown in the above-mentioned patent documentation 4 after swelling is handled, and the method that wet stretching process makes polarized light film be set before dyeing is handled make further research.The polarized light film that the result is clear and definite obtains with this method, though less generation irregular colour is even, it is inhomogeneous to be easy to generate form and aspect in the Width central part of roller film and end.So the present invention is to provide the method for making optical characteristics on the Width, polarized light film that particularly the form and aspect homogeneity is high and polarized light piece as research topic.
In order to solve above-mentioned problem, the present inventor has carried out research with keen determination, found that by making the polyvinyl alcohol resin film by in order by the swelling treatment process, the water retting treatment process, dyeing treatment process and boric acid treatment process are handled continuously, and when carrying out uniaxial tension manufacturing polarized light film at least one operation in dyeing treatment process and boric acid treatment process, reduce the extension ratio of film operating direction in the water retting treatment process between aforementioned swelling treatment process and dyeing treatment process as far as possible, can obtain the so new fact of the high polarized light film of optical homogeneity thus, thereby finish the present invention.
The manufacture method of polarized light film of the present invention just, it handles the polyvinyl alcohol resin film in order continuously by swelling treatment process, water retting treatment process, dyeing treatment process and boric acid treatment process, and when carrying out uniaxial tension manufacturing polarized light film at least one operation in dyeing treatment process and boric acid treatment process, in aforementioned water retting treatment process, handle aforementioned polyvinyl alcohol resin film, make stretching ratio reach more than 1 times and below 1.05 times with respect to operating direction.
Aforementioned water retting treatment process is preferably carried out under 10～50 ℃ temperature.In addition, this water retting treatment process is preferably carried out in the pure water that does not have solvent components basically.
The manufacture method of polarized light piece of the present invention, after making polarized light film with preceding method at the one side at least of the gained polarized light film transparent protective film of fitting.This transparent protective film can possess phase-contrast film, improve the film of brightness, the film that improves the visual angle, any one function of Transflective film.Perhaps can also on the aforementioned polarized light piece of the transparent protective film of at least simultaneously fitting, fit and be selected from phase-contrast film, the film of raising brightness, the film that improves the visual angle and at least a film of Transflective film, make optical laminates.
According to the present invention, between swelling treatment process and dyeing treatment process, the water retting treatment process is set, in this water retting treatment process, dwindle stretching ratio, can bring into play the optical characteristics of the thin-film width direction of making as the long size object of roller shape, the effect of polarized light film that particularly the form and aspect homogeneity is high the film operating direction.
Description of drawings
[Fig. 1] is the mode chart of the configuration example of the expression preferred embodiment that is used to implement the inventive method.
Symbol description
1...... the material film of polyvinyl alcohol resin;
2...... stock roll;
3...... swelling groove;
4...... water retting groove;
5...... staining trough;
6...... boric acid groove;
7...... rinsing bowl;
8...... drying oven;
9...... polarized light film.
Embodiment
Below describe the present invention in detail.The polyvinyl alcohol resin film is handled continuously by swelling treatment process, water retting treatment process, dyeing treatment process and boric acid treatment process in order, and carry out uniaxial tension at least one operation in dyeing treatment process and boric acid treatment process, make polarized light film.Because processed continuously like this relation, the material film of polyvinyl alcohol resin (former anti-Off イ Le system) provides with the form of roller shape usually.Fig. 1 represents to be used to implement the mode chart of configuration example of the preferred embodiment of polarized light film manufacture method of the present invention.
Example shown in Figure 1, from stock roll (former anti-ロ one Le) the 2 polyethenol series material films of sending 1 in order by be used to carry out swelling groove 3 that swelling handles, be used to carry out water retting groove 4 that water retting handles, the staining trough 5 handled and be used to carry out the boric acid groove 6 that boric acid is handled is used to dye.The unreacted boric acid aqueous solution that polyvinyl alcohol resin film after boric acid groove 6 comes out adheres to the groove in front by rinsing bowl 7 flush awaies usually carries out drying by drying oven 8 then, obtains polarized light film 9.Usually at the transparent protective film formation polarized light piece of at least simultaneously fitting of gained polarized light film, this point is omitted in the drawings then.
[polyvinyl alcohol resin]
The polyvinyl alcohol resin that becomes polarized light film raw material (former anti-) specifically is to be that resin carries out the resin that saponification obtains to polyvinyl acetate.The saponification degree of polyvinyl alcohol resin, preferred more than 90% mole more than 85% mole, more preferably 99～100% moles.Polyvinyl acetate is in the resin, except that the polyvinyl acetate of leifa, also has the vinyl acetate and the multipolymer etc. of other monomer of copolymerization with it.As can with other monomer of vinyl acetate copolymerization, for example can enumerate unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class, unsaturated amine etc.The degree of polymerization of polyvinyl alcohol resin is generally 1,000～10, and about 000, preferred about 1,500～5,000.
These polyvinyl alcohol resins can also carry out modification, for example can use aldehydes modified polyethylene alcohol formal, polyvinyl acetal, polyvinyl butyral etc.Usually as the raw material of polarized light film, used thickness is 20～100 μ m, is preferably the non-stretched film of the polyvinyl alcohol resin of 30～80 μ m.
The width of industrial film is 1,500～6, and is comparatively practical about 000mm.
[manufacturing of polarized light film]
Such material film 1 is implemented respectively to handle in order by swelling groove 3, water retting groove 4, staining trough 5 and boric acid treatment trough 6.After boric acid groove 6 comes out, rinsing bowl 7, wash processing, in drying oven 8, carry out drying at last.The thickness of the polyethenol series polarized light film that obtains so for example is about about 1～50 μ m.The example that a swelling groove 3, water retting groove 4, staining trough 5, boric acid groove 6 and rinsing bowl 7 are set respectively has been shown among Fig. 1, but as required a plurality of grooves can also be set in each operation.
[swelling processing]
Material film 1 is at first implemented swelling and is handled in swelling groove 3.This swelling handle for reach the impurity of removing film surface, remove plastifier in the film, give easy dyeing in the operation of back, purpose such as film plasticising carries out.The swelling treatment conditions in the scope that can reach these purposes, and are determined in the scope that does not produce rough sledding such as material film extremely dissolves, devitrification.For example be immersed in by the material film that will not stretch that temperature is 10～50 ℃, carry out swelling during preferred 20～50 ℃ processing is bathed and handle.The swelling processing time carries out preferably carrying out about 20～240 seconds about 5～300 seconds.
Film is in the Width swelling in the swelling treatment process, film is easy to generate problems such as wrinkle, so preferably use known expanding devices such as spreading roll, propellers, convex surface roller (Network ラ ウ Application ロ one Le), cloth guider, roller expander (ベ Application De バ one), stenter cloth gripper to eliminate the wrinkle of film on one side, Yi Bian handle thin films.In order to reach the purpose of stablizing handle thin films in bath, the current during spray control swelling is bathed in the water perhaps use EPC device (marginal position control (Edge Position Control) device simultaneously; Detect the film end, prevent the wiggly device of film) etc. all be feasible.Film also enlarges along the working direction swelling of film in this operation, so in order to eliminate film lax on throughput direction, for example preferably take the conveying roller speed that is positioned at swelling groove 3 front and back such as is controlled at means.Specifically be make swelling groove 3 outlet side conveying roller peripheral speeds with respect to the ratio of entrance side conveying roller peripheral speed (below be sometimes referred to as the roller speed ratio) according to the treatment temperature difference preferably about 1.2～2 times.In addition if desired, can also in this operation, implement uniaxial tension.
The processing of using in the swelling groove 3 is bathed, except that pure water, can also be that (spy opens the chloride described in the boric acid described in the flat 10-153709 communique, the aforementioned patent document 2 (spy opens flat 6-281816 communique), also has the aqueous solution of other mineral acid, other inorganic salts, water-miscible organic solvent, alcohols etc. at 0.01～10 weight % scope interpolation aforementioned patent document 1.But preferred use does not have the pure water of solvent components basically in this swelling groove 3.
[water retting processing]
Polyvinyl alcohol resin film after swelling is handled behind dry, is implemented water retting and is handled in water retting groove 4.It is in order to adjust the suction state of thin-film width direction that this water retting is handled, and the homogeneity that improve the mechanical properties of film, further improves final gained polarized light film optical characteristics is carried out.And in this operation to handle film with respect to operating direction (MD, the i.e. working direction of film) more than 1 times and at the stretching ratio below 1.05 times.Stretching ratio is 1 times and is meant that film had not both had elongation with respect to operating direction, did not have contraction yet.Be applied to and do not produce the tension force of relax level on the film working direction and carry out a series of operation, so the stretching ratio in this operation can not be lower than 1 times usually, if but this extension ratio surpasses 1.05 times, then there is the tendency of optical characteristics homogeneity variation in the gained polarized light film.
The temperature that used processing is bathed in the water retting groove 4 is preferably 10～50 ℃.Be lower than 10 ℃ if handle the temperature of bathing, then temperature control needs large-scale cooling device, and is uneconomical; If opposite, then there is the danger of Film Fractionation above 50 ℃.Used bath during this water retting is handled in addition, the preferred pure water that does not have solvent components basically.The tendency that when medicaments such as containing boric acid is bathed in this processing, exists uniformity of film to be damaged.
[dyeing is handled]
After water retting is handled, in staining trough 5, carry out film dyeing.The common dyeing that utilizes the dichromatism pigment is handled to purposes such as thin film adsorbs dichromatism pigment are carried out.Treatment conditions need only in the scope that can reach this purpose, and determine in the scope that does not produce rough sledding such as the extreme dissolving of material film, devitrification.
When using iodine as the dichromatism pigment, for example at 10～50 ℃, preferably under 20～40 ℃ temperature, and in the aqueous solution that contains iodine 0.003～0.2 weight portion and potassium iodide 0.1～10 weight portion with respect to water 100 weight portions, flooded for 10～600 seconds, preferably flood 30～200 seconds, the processing of dyeing thus.Can also use other iodide, for example alternative potassium iodide such as zinc iodide.In addition, can also use other iodide and potassium iodide in the lump.Can also there be iodide compound in addition simultaneously, for example boric acid, zinc chloride, cobalt chloride etc.When adding boric acid, containing aspect the iodine, it is distinguishing handling with the boric acid of back.With respect to water 100 weight portions,, promptly can be considered dye bath so long as contain the above bath of iodine 0.003 weight portion.
On the other hand, when using water-soluble dichroic dye as the dichromatism pigment, for example pass through at 20～80 ℃, under preferred 30～60 ℃ temperature, and in the aqueous solution that contains dichroic dye 0.001～0.1 weight portion with respect to water 100 weight portions, flooded for 10～600 seconds, preferably flood the processing of dyeing for 20～300 seconds.The aqueous solution of used dichroic dye can also contain stain auxiliary agent etc., for example can contain inorganic salts just like sodium sulphate, surfactant etc.Dichroic dye both can only use a kind, according to needed form and aspect, can also use the dichroic dye more than 2 kinds simultaneously.
Also the same in the dyeing treatment process with the swelling treatment process, in dye bath and/or at the place, gateway of bathing, spreading roll, propellers, convex surface roller, cloth guider, roller expander etc. can be set suitably.In this dyeing treatment process, can implement uniaxial tension at operating direction simultaneously.
[boric acid processing]
Dyeing is handled the back and implement the boric acid processing in boric acid groove 6.This boric acid is handled and is carried out in the aqueous solution that contains about 1～10 weight portion of boric acid with respect to water 100 weight portions the polyvinyl alcohol resin that dyes with the dichromatism pigment is thin film dipped.When using iodine as the dichromatism pigment, this boric acid is handled and is bathed, and except that boric acid, preferably with respect to water 100 weight portions, also contains about 0.1～30 weight portion of iodide.
As iodide, can enumerate potassium iodide and zinc iodide etc.Can also there be iodide compound in addition simultaneously, for example zinc chloride, cobalt chloride, zirconium chloride, sodium thiosulfate, potassium sulfite, sodium sulphite, glazier's salt, sodium sulphate etc.
This boric acid is handled in order to obtain water-fastization and form and aspect adjustment (preventing near blue) is carried out by crosslinked.When with by crosslinked obtain water-fast when turning to purpose, as required can also with boric acid use glyoxal, crosslinking chemical such as glutaraldehyde.The boric acid processing that is used for water-fastization can also be called water-fastization processing, crosslinking Treatment, immobilization processing etc.Can also handle the processing that is interpreted as being used to adjust form and aspect to boric acid, be referred to as complementary color processing, toning processing etc.
This boric acid is handled, and carries out according to the temperature that the concentration and the processing of purpose appropriate change boric acid and iodide are bathed.The boric acid processing that form and aspect are adjusted is handled and be used for to the boric acid that is used for water-fastization, not special difference, but preferably implement under the following conditions.
When material film is implemented swelling, water retting, dyeing and boric acid in turn and is handled, when when turning to purpose by crosslinked acquisition is water-fast, boric acid is handled with the aqueous solution that contains about 3～10 weight portions of boric acid and about 1～20 weight portion of iodide with respect to water 100 weight portions and is handled bath as boric acid, usually at 50～70 ℃, carry out under preferred 53～65 ℃ temperature.Processing time was generally about 10～600 seconds, preferred 20～300 seconds, more preferably 20～100 seconds.
After being used for the boric acid processing of water-fastization, can also further be used for the boric acid processing that form and aspect are adjusted.For example when dichroic dye is iodine,, handle bath as boric acid, under the temperature about 10～45 ℃, carry out usually with the aqueous solution that contains about 1～5 weight portion of boric acid and about 3～30 weight portions of iodide with respect to water 100 weight portions in order to reach this purpose.Dip time was generally about 1～300 second, preferred 2～100 seconds.The boric acid processing that is used for the form and aspect adjustment is compared with the boric acid processing that is used for water-fastization, carries out at low temperatures usually.
This boric acid is handled and can be carried out in a plurality of grooves, and polygamy is put 1～5 groove usually.When a plurality of groove of configuration, film is implemented boric acid to this film and is handled in order by each groove.When a plurality of groove of configuration, the aqueous solution of each used boric acid treatment trough is formed and temperature, both can be identical in above-mentioned scope, and also can be different.Can in a plurality of grooves, carry out the above-mentioned boric acid that is used for water-fastization respectively and handle, be used for the boric acid processing that form and aspect are adjusted.The same in the boric acid treatment process with the dyeing treatment process, can also implement uniaxial extension at the operating direction of film.
Final accumulative total stretching ratio from the swelling treatment process to the boric acid treatment process is about 4.5～8 times, preferred 5～7 times.
[aftertreatment after boric acid is handled]
Boric acid is washed processing after handling in rinsing bowl 7.Washing is handled, and method that the thin film dipped method at water of the polyvinyl alcohol resin after for example can handling by the boric acid that will be used for water-fastization and/or form and aspect adjustment is sprayed water in the mode of spray or the method for using dipping and spraying in the lump etc. are carried out.Coolant-temperature gage during washing is handled is generally about 2～40 ℃, and the processing time was generally about 2～120 seconds.Import to after the washing and carry out film drying in the drying oven 8.This drying is carried out about about 30～600 seconds in the drying oven 8 that approximately remains to 40～100 ℃ of temperature.
[uniaxial tension]
Among the present invention, carry out uniaxial tension at least one operation in aforesaid dyeing treatment process and boric acid treatment process.This uniaxial tension both can carry out in an operation, also can carry out in two operations, preferably promptly carried out uniaxial tension in dyeing treatment process and two operations of boric acid treatment process two operations.For example stretch can be by making groove entrance side conveying roller and the outlet side conveying roller of groove method etc. with difference carry out.Final accumulative total stretching ratio preferably is about 4.5～8 times as previously mentioned, more preferably about 5～7 times.Here how long said accumulative total stretching ratio is meant in the film of standard length after all stretch processings finish of material film length direction has, even when stretching in swelling treatment process and water retting treatment process, also is the value that comprises these stretchings.For example, suppose the part of 1m in the material film, become 5m in the film after all stretch processings finish, accumulative total stretching ratio at this moment is 5 times.
[manufacturing of polarized light piece]
Like this polarized light film of Zhi Zaoing can its at least one side with the cementing agent transparent protective film of fitting, as polarized light piece.As transparent protective film, for example can enumerate the film that contains just like the acetyl fibre prime system resin of triacetyl cellulose, diacetyl cellulose; Contain film just like the polyester based resin of polyethylene terephthalate, PEN, polybutylene terephthalate; The film that contains polycarbonate-based resin; Contain with the cyclic olefin as norborene is the film etc. of the annular ethylene series resin of principal monomer.As commercially available thermoplasticity cyclic olefine resin, for example have " ト one パ ス " that テ イ コ Na (Ticona) company of Germany sells (Topas), " the ア ペ Le " of " ア one ト Application " that JSR (strain) sells, " ゼ オ ノ ア " and " ゼ オ ネ Star Network ス " that Japanese ゼ オ Application (strain) is sold, Mitsui Chemicals (strain) sale (more than be trade name).When with the film of such cyclic olefine resin system film during as protective film, the system film is fit to adopt well-known methods such as solvent cast method, melt extrusion method.The commercially available cyclic olefine resin film of making film is also arranged, for example You Plot water chemistry industry (strain) " エ ス シ one Na " and " SCA40 " sold etc.
The thickness of transparent protective film is preferably thinner, if but too thin, then intensity reduction, poor in processability; If too thick on the other hand, then the transparency reduces, and has behind the lamination problems such as the needed curing time is elongated.So the suitable thickness of protective film for example is about 5～200 μ m, is preferably 10～150 μ m, more preferably 10～100 μ m.
In order to improve the cohesiveness of cementing agent and polarized light film and/or protective film, can also implement surface treatments such as corona treatment, fiery scorching processing, Cement Composite Treated by Plasma, irradiation ultraviolet radiation, the processing of coating precoated shet, saponification processing to polarized light film and/or protective film.
For transparent protective film; can also implement surface treatments such as anti-dazzle processing, antireflection processing, hard conating processing, electrostatic prevention processing, anti-pollution processing; these surface treatments both can be carried out individual processing respectively, also can implement to make up two or more processing.In addition, the sealer of protective film and/or protective film can also contain ultraviolet light absorber and plastifier such as phenyl phosphate based compound, phthalate compound such as benzophenone based compound, benzotriazole based compound.Transparent protective film can be fitted in the one side of polarized light film, also can be fitted in the two sides.
It is that cementing agent, organic solvent are that cementing agent, heat fusing are that cementing agents such as cementing agent, no-solvent type cementing agent carry out lamination that polarized light film and transparent protective film use hydrosolvent.As hydrosolvent is cementing agent, for example can enumerate the polyvinyl alcohol resin aqueous solution, water system two-component-type ammonia ester is an emulsion binder etc.; As organic solvent is cementing agent, and for example can enumerate two-component-type ammonia ester is cementing agent etc.; As the no-solvent type cementing agent, for example can enumerate one-pack type ammonia ester is that cementing agent, epoxy are cementing agent etc.
When using with the adhesive surface of polarized light film through the acetyl fibre prime system film of hydrophilicity-imparting treatment such as saponification processing, preferably use as cementing agent with the polyvinyl alcohol resin aqueous solution as protective film.Except carrying out saponification, the polyvinyl acetate to leifa handles the alcotex that obtains as the polyvinyl alcohol resin that cementing agent uses, also have to vinyl acetate and with it the multipolymer of other monomer of copolymerization carry out saponification and handle the ethenol system copolymer that obtains, also have hydroxyl to carry out partially modified modified polyvinylalcohol based polymer etc. to them.In these cementing agents, can also cooperate polyaldehyde, soluble epoxide compound, melamine based compound etc. as crosslinking chemical.
Applying method for polarized light film and transparent protective film is not particularly limited, and for example can be set forth in evenly coating cementing agent of polarized light film or protective film surface, and overlapping another film on coated face is fitted with roller etc., and dry method etc.
Usually cementing agent is coated with under 15～40 ℃ temperature after the modulation, and the scope of binding temperature is generally about 15～30 ℃.Carry out dried after the applying, remove water equal solvent contained in the cementing agent, but baking temperature at this moment is generally 30～100 ℃, be preferably 40～80 ℃ of scopes.Then can be at 15～85 ℃, preferred 20～50 ℃, more preferably carry out the slaking about 1～90 day under 35～45 ℃ the temperature environment usually, make adhesive cures.When protective film is acetyl fibre prime system resin; can not show sufficient cohesive strength even do not implement such slaking yet; but when using the protective film contain other resin, and be cementing agent when fitting on the polarized light film, preferably implement aforesaid slaking with hydrosolvent.If should the curing time long, then production efficiency be poor, thus the curing time be preferably about 1～14 day, more preferably about 1～7 day.
Obtain like this by the polarized light piece of adhesive layer at the one or both sides applying protective film of polarized light film.
Can make among the present invention transparent protective film have function as phase-contrast film, as the function that improves the brightness film, as the function of reflective film, as the function of Transflective film, as the function of diffusion film, as the optical functions such as function of optical compensating film.At this moment; for example can pass through optically functional films such as the surperficial lamination phase-contrast film at transparent protective film, the film that improves brightness, reflective film, Transflective film, diffusion film, optical compensating film; make it have such function; in addition, can also make transparent protective film self have such function.In addition, as have the diffusion film that improves brightness film function etc., can make transparent protective film self have multiple function.
For example for above-mentioned transparent protective film; the stretch processing of recording and narrating in No. 2841377 communique of date of execution this patent, No. 3094113 communique of Jap.P. etc.; the perhaps processing described in No. 3168850 communique of date of execution this patent etc. also can make it have function as phase-contrast film by these methods.Phase difference characteristics in the phase-contrast film, for example the front phase difference value is 5～100nm, the phase difference value of thickness direction is 40～300nm scope etc., can suitably select.In addition for above-mentioned transparent protective film; can also open the method described in 2002-169025 communique and the Te Kai 2003-29030 communique by the spy makes it form micropore; or the different cholesteric liquid crystal layers more than 2 layers of lamination selection reflection kernel wavelength, can give thus as the function that improves the brightness film.
If on above-mentioned transparent protective film, form metallic film, then can give function as reflective film or Transflective film with evaporation and sputter etc.By on above-mentioned transparent protective film, being coated with the resin solution that contains particulate, can give function as diffusion film.Pass through on above-mentioned transparent protective film, to be coated with liquid crystal compounds such as dish type molecule liquid-crystal compounds in addition, and be orientated, can give function as the optical compensating film film.Can also use suitable cementing agent directly various optically functional films to be fitted on the polarized light film.As the commercially available prod of optically functional film, can enumerate film, as the film at the improvement visual angle of " WV Off イ Le system " (trade name) of selling, as the phase-contrast film of " ス ミ カ ラ イ ト " (trade name) of selling etc. by Sumitomo Chemical (strain) by the Off イ of Fuji Le system (strain) as the raising brightness of " DBEF " (trade name) of selling by 3M Company (is Sumitomo ス リ one エ system (strain) in Japan).
Embodiment
Below show embodiment and comparative example, further specify situation of the present invention.But the present invention is not subjected to the qualification of these examples.Following embodiment and comparative example carry out various processing Yi Bian with continuous conveying device one side of combination nip rolls and deflector roll the long size film of polyvinyl alcohol (PVA) is transported in the device that disposes swelling groove 3, water retting groove 4, staining trough 5, boric acid groove 6, rinsing bowl 7 and drying oven 8 in order shown in the sketch map among Fig. 1.Using the degree of polymerization as material film 1 is 2,400, and saponification degree is 99.9 moles more than the %, and thickness is that 75 μ m, width are 3, the polyvinyl alcohol film of 000mm [" the Network ラ レ PVC ニ ロ Application VF-PS#7500 " of (strain) Network ラ レ system].Stretching is to have difference by the driving nip rolls that makes the treatment trough front and back to carry out.
The optical characteristics homogeneity of gained polarized light film is with parallel form and aspect b
*Value is estimated.Parallel form and aspect are meant and make two pieces of polarized light films overlapping, and make absorption axes is identical separately the state form and aspect during the irradiation natural light down, this b
*Value is for continuous wavelength zone or the parallel spectral transmission Tp (λ) that obtains in af at wavelength lambda of wavelength interval in accordance with regulations, calculates according to JIS Z 8729 then.
Parallel transmissivity is meant and makes two pieces of polarized light films overlapping, and make absorption axes is identical separately the state transmissivity during the irradiation natural light down, therefore being meant at the parallel spectral transmission Tp of certain af at wavelength lambda (λ) makes two pieces of polarized light films overlapping, and the transmissivity when making illumination wavelength lambda natural light under the state that absorption axes is identical separately, it is of equal value with the value that obtains with method shown in following.Just to the rectilinearly polarized light of 1 piece of polarized light film illumination wavelength lambda on the direction parallel with its absorption axes, measure spectral transmission k1 (λ) at this moment, then the rectilinearly polarized light of illumination wavelength lambda on the direction vertical with absorption axes is measured spectral transmission k2 (λ) at this moment.Two pieces of polarized light films are overlapping making, and the transmissivity (parallel spectral transmission) when making illumination wavelength lambda natural light under the state that absorption axes is identical separately with the transmissivity behind twice transmission film of transmissivity k1 (λ) { k1 (λ) }
2With with the transmissivity behind twice transmission film of transmissivity k2 (λ) { k2 (λ) }
2Mean value equate, so obtain the parallel spectral transmission Tp (λ) of af at wavelength lambda according to following calculating formula (I) with these numerical value.
Tp(λ)＝[{k1(λ)}
2+{k2(λ)}
2]/2 (I)
For continuous wavelength zone or in accordance with regulations the wavelength interval carry out these mensuration and calculating, with the parallel spectral transmission Tp (λ) of each af at wavelength lambda, according to the parallel form and aspect b of JIS Z 8729 calculating
*, said here spectral transmission k1 (λ) and k2 (λ) and parallel spectral transmission Tp (λ) represent with %, all is 1 to be the value that maximal value is represented, when representing with %, it can be enlarged 100 times.
[embodiment 1]
Material film 1 is not produced in the swelling groove 3 that is adding 30 ℃ of pure water under the lax tensioning state at the maintenance film flood about 80 seconds, make the abundant swelling of film.Carry out in swelling groove 3 in the swelling, inlet is 1.2 with the roller speed ratio of outlet.Behind nip rolls control solid carbon dioxide branch, in being added with the water retting groove 4 of 30 ℃ of pure water, flood about 160 seconds.The stretching ratio of operating direction is 1.04 times in this groove.Then on one side calculate dipping in the staining trough 5 of aqueous solution that iodine/potassium iodide/water is 0.02/1.5/100 with weight ratio being added with, with the stretching ratio that be about 1.5 times carry out uniaxial tension on one side.Calculate with weight ratio in the boric acid groove 6 that potassium iodide/boric acid/water is 12/5/100 aqueous solution 56.5 ℃ of 130 seconds of dipping down being added with on one side then,, make the accumulative total stretching ratio of raw material reach 5.3 times Yi Bian carry out uniaxial tension.Last in rinsing bowl 7 pure water with 9 ℃ wash about 16 seconds, then in drying oven 8 in about 60 ℃ of following dry 160 seconds, obtaining iodine is polarized light film.
For the gained polarized light film, obtain the parallel form and aspect b of Width central part
*The parallel form and aspect b of value and Width end
*Value, the difference of the two is 2.1 as a result.
, fit respectively and contain the protective film of triacetyl cellulose by containing the cementing agent of polyvinyl alcohol resin aqueous solution on the two sides of this polarized light film, obtain polarized light piece thus.In addition respectively by cementing agent that contains the polyvinyl alcohol resin aqueous solution or the protective film that contains triacetyl cellulose by the no-solvent type cementing agent in the one side applying of above-mentioned polarized light film; fit in the another side and to contain the protective film of norbornene resin, also can obtain polarized light piece.
[comparative example 1]
Material film 1 is not produced in the swelling groove 3 that is being added with 30 ℃ of pure water under the lax tensioning state at the maintenance film flood about 50 seconds, make the abundant swelling of film.Behind nip rolls control solid carbon dioxide branch, in being added with the water retting groove 4 of 30 ℃ of pure water, flood about 160 seconds, and in this groove, stretch at the stretching ratio of operating direction with 1.20 times.Carry out 1 identical operations then, in staining trough 5, carry out uniaxial tension, in boric acid groove 6, carry out uniaxial tension, and wash and drying, obtain polarized light film with embodiment.
For the gained polarized light film, obtain the parallel form and aspect b of Width central part
*The parallel form and aspect b of value and Width end
*Value, the difference of the two is 4.9 as a result.
Industrial applicability
According to method of the present invention, can obtain film polarized light film that the optical characteristics homogeneity is high on Width or the polarized light piece made as the long size object of roller shape.Cut into the polarized light small pieces of various sizes with this polarized light piece, between each sheet, roughly show identical optical characteristics, can be effective to in the various display device headed by the liquid crystal indicator.
Claims (5)
1. the manufacture method of polarized light film, it is that the polyvinyl alcohol resin film is handled continuously by swelling treatment process, water retting treatment process, dyeing treatment process and boric acid treatment process in order, and carry out the method that uniaxial tension is made polarized light film at least one operation in dyeing treatment process and boric acid treatment process, wherein
In aforementioned water retting treatment process, handle aforementioned polyvinyl alcohol resin film, make stretching ratio in the water retting treatment process reach more than 1 times and below 1.05 times with respect to operating direction.
2. method according to claim 1, wherein, aforementioned water retting treatment process is carried out under 10～50 ℃ temperature.
3. method according to claim 1 and 2, wherein, aforementioned water retting treatment process is carried out in the pure water that does not have solvent components basically.
4. the manufacture method of polarized light piece, it is after making polarized light film with claim 1 or 2 method described in any, at the one side at least of the gained polarized light film transparent protective film of fitting.
5. the manufacture method of polarized light piece, it is after described method is made polarized light film with claim 3, at the one side at least of the gained polarized light film transparent protective film of fitting.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2007-087290 | 2007-03-29 | ||
| JP2007087290A JP5034600B2 (en) | 2007-03-29 | 2007-03-29 | Manufacturing method of polarizing film |
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| CN101276013A CN101276013A (en) | 2008-10-01 |
| CN101276013B true CN101276013B (en) | 2011-12-14 |
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| JP (1) | JP5034600B2 (en) |
| KR (1) | KR101483793B1 (en) |
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| KR101609312B1 (en) | 2009-04-15 | 2016-04-05 | 동우 화인켐 주식회사 | Method for preparing polarizer, polarizer and polarizing plate comprising the same |
| CN102029710B (en) * | 2009-10-06 | 2015-04-01 | 富士胶片株式会社 | Method for manufacturing optical film, optical film, liquid crystal display device and image display device |
| WO2011155725A2 (en) | 2010-06-09 | 2011-12-15 | 주식회사 엘지화학 | Device for manufacturing polaroid film, and method for manufacturing same |
| KR20130062194A (en) * | 2011-12-02 | 2013-06-12 | 제일모직주식회사 | Polarizer having high durability and method for preparing the same |
| JP5991883B2 (en) * | 2011-12-06 | 2016-09-14 | 日東電工株式会社 | Method for producing polarizer and method for producing polarizing plate |
| JP6054054B2 (en) * | 2012-05-11 | 2016-12-27 | 日東電工株式会社 | Manufacturing method of polarizer, polarizer, polarizing plate, optical film, and image display device |
| KR101628428B1 (en) * | 2012-12-17 | 2016-06-08 | 제일모직주식회사 | Polarizing plate, method for preparing the same and optical display apparatus comprising the same |
| CN103076648B (en) * | 2013-01-31 | 2015-07-15 | 佛山纬达光电材料有限公司 | Simple manufacturing method and device of polarizing elements for laboratory |
| JP5928378B2 (en) * | 2013-03-18 | 2016-06-01 | コニカミノルタ株式会社 | Film set, film set manufacturing method, film bonding material, information processing apparatus for searching for film, and film bonding method |
| JP6604714B2 (en) * | 2014-09-03 | 2019-11-13 | 日東電工株式会社 | Manufacturing method of polarizer |
| JP6333168B2 (en) * | 2014-12-25 | 2018-05-30 | 住友化学株式会社 | Manufacturing method of polarizing plate |
| CN104656178B (en) * | 2015-01-15 | 2017-02-01 | 张宝庆 | Imaging polaroid for LCD imaging, and dyeing manufacturing method thereof |
| KR101663698B1 (en) * | 2015-03-16 | 2016-10-07 | 동우 화인켐 주식회사 | Preparing method for polarizer |
| JP2015228036A (en) * | 2015-07-24 | 2015-12-17 | 住友化学株式会社 | Foreign matter removal device |
| CN105082491B (en) * | 2015-08-11 | 2018-09-11 | 张家港市兰航机械有限公司 | Draw the cutter device in winder |
| CN114437384B (en) * | 2020-10-30 | 2023-08-15 | 中国石油化工股份有限公司 | Polyvinyl alcohol optical film, preparation method thereof and polarizer |
| CN112327539B (en) * | 2020-11-25 | 2022-10-14 | 合肥德瑞格光电科技有限公司 | Preparation method of polaroid for TFT-LCD |
| CN112895531B (en) * | 2020-12-31 | 2023-04-11 | 南京汉旗新材料股份有限公司 | Preparation method of yellow-green night vision optical lens film |
| CN117130090B (en) * | 2023-10-26 | 2023-12-22 | 深圳市力华盛科技有限公司 | Preparation method of high Wen Pianguang-resistant film and polarizing film |
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| CN1598624A (en) * | 2003-09-10 | 2005-03-23 | 住友化学工业株式会社 | Polarization membrane and manufacturing method thereof,polarizer and optical laminate |
| CN1641381A (en) * | 2003-10-07 | 2005-07-20 | 住友化学工业株式会社 | Polarization film mfg. method, polarization sheet mfg. method and optical laminate mfg. method |
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| JP2001116922A (en) * | 1999-10-14 | 2001-04-27 | Nitto Denko Corp | Method of producing polarizing plate and polarizing film |
| JP4229932B2 (en) * | 2004-07-28 | 2009-02-25 | 日東電工株式会社 | Manufacturing method of polarizing film |
| JP4458483B2 (en) * | 2005-03-22 | 2010-04-28 | 日東電工株式会社 | Manufacturing method of polarizing film, polarizing film, polarizing plate, and image display device |
| JP4562133B2 (en) * | 2005-04-14 | 2010-10-13 | 日本化薬株式会社 | Polarizing element film, polarizing plate, and manufacturing method thereof |
| JP4339350B2 (en) * | 2006-11-20 | 2009-10-07 | 日東電工株式会社 | Manufacturing method of polarizer |
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| CN1598624A (en) * | 2003-09-10 | 2005-03-23 | 住友化学工业株式会社 | Polarization membrane and manufacturing method thereof,polarizer and optical laminate |
| CN1641381A (en) * | 2003-10-07 | 2005-07-20 | 住友化学工业株式会社 | Polarization film mfg. method, polarization sheet mfg. method and optical laminate mfg. method |
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| TWI482697B (en) | 2015-05-01 |
| KR101483793B1 (en) | 2015-01-16 |
| CN101276013A (en) | 2008-10-01 |
| KR20080088425A (en) | 2008-10-02 |
| JP5034600B2 (en) | 2012-09-26 |
| JP2008249766A (en) | 2008-10-16 |
| TW200906599A (en) | 2009-02-16 |
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