CN1629660A - Iodine polarizing film manufacturing method, polaroid manufacturing method and optical laminate manufacturing method - Google Patents
Iodine polarizing film manufacturing method, polaroid manufacturing method and optical laminate manufacturing method Download PDFInfo
- Publication number
- CN1629660A CN1629660A CNA200410100386XA CN200410100386A CN1629660A CN 1629660 A CN1629660 A CN 1629660A CN A200410100386X A CNA200410100386X A CN A200410100386XA CN 200410100386 A CN200410100386 A CN 200410100386A CN 1629660 A CN1629660 A CN 1629660A
- Authority
- CN
- China
- Prior art keywords
- film
- dye bath
- polarizing film
- manufacture method
- iodine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- G02B5/3041—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 comprising multiple thin layers, e.g. multilayer stacks
-
- 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
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polarising Elements (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The invention is aimed to provide a manufacturing method of polarizing film which hardly causes dyeing irregularity and permits the reduction of frequency of wrinkle generation and the reduction of tension during processes after dyeing, and to provide a polarizing plate and an optical laminate using the polarizing film. In the manufacturing method of polarizing film, uniaxial stretching is performed before and/or during a process of treating a polyvinyl alcohol base film in order of swelling, iodine dyeing and borating. Prior to the borating process, the iodine dyeing is performed in dyeing baths of two steps or more and, further, uniaxial stretching is performed in dyeing baths of two steps or more. Therein, the uniaxial stretching is performed in such a manner that (1) the stretching ratio in the initial dyeing bath is set to be higher than the sum stretching ratio in dyeing baths on and after the second step or (2) the stretching ratio in the last dyeing bath is set to be higher than the sum stretching ratio in the dyeing baths prior to the last dyeing bath.
Description
Technical field
The present invention relates to that the few and fold generation frequency of uneven dyeing reduces or the manufacture method of the iodine polarizing film that productivity improves, closed the manufacture method of polaroid of diaphragm and phase retardation film, brightness at least one surface layer of the light polarizing film that obtains and improve in film, visual angle improvement film and the transflective film any one separately or most manufacture methods of pasting the optical laminates that forms.
Background technology
As light polarizing film, the film that always makes polyvinyl alcohol (PVA) mesentery absorption bitintability pigment and make it to be orientated.That is, known is light polarizing film etc. as the iodine polarizing film of bitintability pigment with the bitintability dyestuff as the dyestuff of bitintability pigment with iodine.The bonding agent that these light polarizing film constitute in its aqueous solution of at least simultaneously, preferably passing through polyvinyl alcohol resin on the two sides is usually pasted diaphragms such as triacetyl cellulose, makes polaroid.
Manufacture method as light polarizing film, put down in writing following method in the patent documentation 1: after the polyethenol series film immersion is in the aqueous solution of iodine and potassium iodide, carries out boric acid and handle while it is stretched, after the washing, be immersed in again in the aqueous solution of iodine and potassium iodide, and dry.
Put down in writing the method for following manufacturing light polarizing film in the patent documentation 2: the film immersion that will stretch is in the aqueous solution that contains the bitintability pigment, after being immersed in other aqueous solution that contain the bitintability pigment again, in boric acid aqueous solution, stretch, drying is manufactured on the light polarizing film that thickness direction is provided with 2 absorption oriented layers thus.
Put down in writing the method for following manufacturing light polarizing film in the patent documentation 3: the polyethenol series film immersion that will stretch in the aqueous solution (dyeing liquor A) of specific bitintability dyestuff after, be immersed in the aqueous solution (dyeing liquor B) of iodine and potassium iodide, then carry out boric acid and handle, light polarizing film is made in washing.
In these patent documentations, all carried out 2 dyeing and handled., patent documentation 1 carries out 2 dyeing after boric acid is handled handles, and fold not only easily takes place under this situation, and the initial optical characteristic is poor.In addition, patent documentation 2,3 relates to the method for using the bitintability organic dyestuff.
[patent documentation 1] spy opens flat 9-133809 communique
[patent documentation 2] spy opens clear 60-66205 communique
[patent documentation 3] spy opens clear 62-70802 communique
Summary of the invention
Major subjects of the present invention is that the manufacture method of manufacture method, polaroid and the optical laminates of the few iodine polarizing film of uneven dyeing is provided.
Another problem of the present invention is, provides uneven dyeing few, and the fold occurrence frequency reduces or can reduce the manufacture method of the iodine polarizing film that tension force in the operation after dyeing is handled and productivity improve; The manufacture method of polaroid and optical laminates.
The inventor is for solving the concentrated repeatedly research of above-mentioned problem, found that by in the dye bath more than 2 sections, carrying out iodine staining before the boric acid treatment process successively, uneven dyeing tails off, and in dye bath, carry out the occasion of uniaxial tension, can reduce the fold occurrence frequency, perhaps can reduce the tension force in the operation after dyeing is handled, improve productive new fact, thereby finished the present invention.
Promptly, the 1st manufacture method of iodine polarizing film of the present invention, it is characterized in that, handle by swelling processing, iodine staining and the operation of the sequential processes polyvinyl alcohol (PVA) mesentery that boric acid is handled before and/or when carrying out uniaxial tension in the operation, in the dye bath more than 2 sections, carrying out iodine staining before the boric acid treatment process.
The 2nd manufacture method of iodine polarizing film of the present invention is characterized in that, is carrying out iodine staining before the boric acid treatment process in the dye bath more than 2 sections, meanwhile, carries out uniaxial tension at least one dye bath.
The 3rd manufacture method of iodine polarizing film of the present invention, it is characterized in that, in the dye bath more than 2 sections, carrying out iodine staining before the boric acid treatment process, meanwhile, in the dye bath more than 2 sections, carry out uniaxial tension, and carry out the uniaxial tension that stretching ratio in the initial dye bath is higher than the 2nd section total stretching ratio in the later dye bath.
The 4th manufacture method of iodine polarizing film of the present invention, it is characterized in that, in the dye bath more than 2 sections, carrying out iodine staining before the boric acid treatment process, meanwhile, in the dye bath more than 2 sections, carry out uniaxial tension, and carry out the uniaxial tension that stretching ratio in the last dye bath is higher than the total stretching ratio in before this dye bath.
Above-mentioned most dye baths more than 2 sections preferably constitute by distinguishing the mode of adjusting stretching ratio separately.In addition, preferably all dye baths contain iodide, adjust to make the content of these iodide uprise by the order of handling.
Polaroid manufacture method of the present invention is characterised in that, the one side at least of the light polarizing film that obtains at said method is pasted diaphragm.This diaphragm can possess phase retardation film, brightness and improve in film, visual angle improvement film and the transflective film any one function.Perhaps, the manufacture method of optical laminates is characterised in that, pastes to paste on the polaroid that diaphragm obtains in one side at least to be selected from polarizer, brightness and to improve film, visual angle improvement film and semi-transparent reflection plate at least a kind.
The invention effect
According to the present invention,, obtain the few iodine polarizing film of uneven dyeing by in the dye bath more than 2 sections, carrying out iodine staining before the boric acid treatment process.And, have by in dye bath, carrying out uniaxial tension, the fold occurrence frequency is reduced, perhaps can reduce tension force in the operation after dyeing is handled and the effect of boosting productivity.
Particularly, particularly owing in the dye bath more than 2 sections, carry out uniaxial tension, wherein make the stretching ratio in the initial dye bath be higher than the 2nd section total stretching ratio in the later dye bath, the wide contraction situation (being referred to as the dry shrink width of cloth usually) of film when particularly dry diminishes, and therefore the frequency that fold takes place in drying oven tails off.
In addition, particularly owing in the dye bath more than 2 sections, carry out uniaxial tension, wherein make stretching ratio in the last dye bath be higher than total stretching ratio in before this dye bath, even reduce in the later operation of boric acid treatment process to preventing that film from shrinking the tension force that applies, film also is difficult for lax, and throughput rate improves.In addition, when tension force is low, apply very big burden can not for the bearing etc. of the deflector roll that is used for transport membrane, the therefore raisings such as permanance of device, the protection management becomes easy.
Be used for liquid crystal indicator by polaroid, the optical laminates that the present invention is obtained, can obtain slim, high-quality liquid crystal display.
Embodiment
Below describe the present invention in detail.
Form the polyvinyl alcohol resin of polyvinyl alcohol (PVA) mesentery of the present invention, can exemplify polyvinyl acetate usually is the resin that the resin saponification obtains.As saponification degree, be about 85 moles more than the %, preferred about 90 moles more than the %, 99 moles of %～100 mole % more preferably from about.As polyvinyl acetate is resin, except polyvinyl acetate as the homopolymer of vinyl acetate, and the multipolymer that can also enumerate vinyl acetate and can form, for example vinyl-vinyl acetate copolymer etc. with other monomers of its copolymerization.But, can list unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class etc. as other monomers of copolymerization.As the degree of polymerization of polyvinyl alcohol resin, be 1000～10000, preferred about 1500～5000.
These polyvinyl alcohol resins also can modification, for example also can use with aldehydes modified polyethylene alcohol formal, polyvinyl acetal, polyvinyl butyral etc.Usually, as the parent material of making light polarizing film, the about 20 μ m of used thickness～100 μ m, the unstretching film of the polyvinyl alcohol resin film of preferred about 30 μ m～80 μ m.The film of industrial practicality is wide to be about 1500mm～4000mm.
This unstretching film is handled by the order that swelling processing, iodine staining are handled, boric acid is handled, washing is handled, and the thickness of final drying and the polyethenol series light polarizing film that obtains is for for example about 5～50 μ m.
The manufacture method of light polarizing film of the present invention is divided into 2 kinds substantially.1 kind of method is: the polyvinyl alcohol (PVA) mesentery behind the uniaxial tension, is carried out solution-treated by the order that swelling processing, iodine staining processing, boric acid processing and washing are handled in air or inert gas, carry out dry method at last.The 2nd kind of method is that the polyvinyl alcohol (PVA) mesentery that will not stretch carries out solution-treated by the order that swelling processing, iodine staining processing, boric acid processing and washing are handled in aqueous solution, in boric acid treatment process and/or the operation before it, carry out uniaxial tension, carry out dry method at last with wet type.
In arbitrary method, uniaxial tension can carry out in an operation, also can carry out in the operation more than 2, but preferably carry out in a plurality of operations.Drawing process can adopt known method, for example has to apply between the roller that linear differential stretches the hot-rolling pulling method that stretches, put down in writing in No. 2731813 communique of patent, stenter pulling method etc. between 2 material folding rollers of transport membrane.In addition, basically the order of operation as mentioned above, but not restriction such as quantity of handle bathing and treatment conditions.
In addition, inserting the operation of not putting down in writing with other purposes in above-mentioned operation also is freely certainly.As the example of this operation, after can being set forth in boric acid and handling, with the dip treating (iodide processings) of not borated iodide aqueous solution, perhaps usefulness boronic acid containing and contain dip treating (zinc processing) operation etc. of the aqueous solution of zinc chloride etc. not.
The swelling treatment process in order to the foreign matter of removing the film surface, remove plastifier in the film, give the easy dyeing in the subsequent processing, the plasticized of film etc.Treatment conditions and do not take place to determine in the scope of unfavorable conditions such as extreme dissolving, devitrification of base material film in the scope that can realize these purposes.Make the occasion of the film swelling that in gas, stretches in advance, for example at about 20 ℃～70 ℃, impregnated membranes in preferred about 30 ℃～60 ℃ aqueous solution and carrying out.The dip time of film is 30～300 seconds, further preferred about 60 seconds～240 seconds.Make from the occasion of initial thick (former anti-) film swelling that does not just stretch, for example at about 10 ℃～50 ℃, impregnated membranes in preferred about 20 ℃～40 ℃ aqueous solution and carrying out.The dip time of film is 30～300 seconds, further preferred about 60 seconds～240 seconds.
In the swelling treatment process, film is in horizontal swelling and easily produce the problem that occurs fold etc. on the film, therefore preferred with Stretching rollers (expander roll), propellers (spiral roll), roll (crown roll), intersection deflector roll (cross guider), curved rod (bend bar), stenter folder known expanding devices such as (tenter crip), the fold limit transport membrane of film is eliminated on the limit.Stable for film in the bath is carried, the current during perforated water spray control swelling is bathed in the water, or use EPC device (Edge Position Control device: detect the end of film, prevent the device that crawls of film) etc. also useful simultaneously.In this operation,,, preferably take the means such as speed of the conveying roller before and after the control and treatment groove for example therefore for the sag of the film of eliminating throughput direction because film enlarges at the direction of travel of film also swelling.In addition, the boron profit of using is handled and is bathed except pure water, also can use the aqueous solution of having added boric acid (spy opens in the flat 10-153709 communique and puts down in writing), chloride (spy opens in the flat 06-281816 communique and puts down in writing), mineral acid, inorganic salts, water-miscible organic solvent, alcohols etc. with the scope of 0.01 weight %～10 weight %.
Adopt the dyeing process of iodine to use so that film adsorbs iodine, and orientation.Treatment conditions and do not take place to determine in the scope of unfavorable conditions such as extreme dissolving, devitrification of base material film in the scope that can realize these purposes.The dye bath that the present invention is provided with more than 2 sections especially carries out iodine staining successively.Dye bath is preferably 2 sections～4 sections.
Dye bath also can contain boric acid.Add the occasion of boric acid, contain iodine aspect handle mutually with following boric acid and to distinguish.With respect to water 100 weight portions, contain more than about 0.003 weight portion of iodine, if temperature be about 40 ℃ with the next dye bath of regarding as.
The concentration of each dye bath is counted iodine/potassium iodide/water=about 0.003～0.2/ about 0.1～10/100, preferred about 0.003～0.1/ about 0.1～3.0/100 by weight.About the content of iodine, can each dye bath all identical, perhaps also can in above-mentioned scope, reduce or increase content by the dyeing processing sequence.
The potassium iodide concentration of each dye bath preferably is adjusted to the order of handling by dyeing and uprises.With amount, perhaps by the occasion of the order step-down of handling, when long-play, the balance of strength of fluid is destroyed, can not stably keep the quality of light polarizing film in each dye bath for the concentration of potassium iodide.Therefore that is, along with processing, the potassium iodide concentration of the dye bath of rear section side uprises, and for the potassium iodide concentration of the dye bath that reduces rear section side, must give up the liquid supplementing water.This wastes economically, and environmental loads also increases.To this,,, can prevent that also the balance of strength of fluid is destroyed even the potassium iodide concentration of the dye bath by the long-play rear section side uprises if uprise from beginning that at first potassium iodide concentration is adjusted to the order of handling by dyeing.
In addition, also can use other iodide, for example zinc iodide etc. replaces potassium iodide.In addition, also can use other iodide simultaneously with potassium iodide.All preferably being adjusted to iodide concentration in these cases uprises by the order of handling that dyes.In addition, also can make iodide compound in addition, for example coexistences such as boric acid, zinc chloride, cobalt chloride.Add the occasion of boric acid, contain iodine aspect handle mutually with following boric acid and to distinguish.If with respect to water 100 weight portions, contain the above iodine of 0.003 weight portion of having an appointment, then regard staining trough as.Boric acid is preferred especially only to be added in final dye bath.Like this, the surface state of light polarizing film becomes well, and uneven dyeing tails off.The boric acid concentration that adds in final dye bath is that about 0.05～2.0 weight portion of per 100 weight parts waters is comparatively suitable.
Dyeing in each dye bath is handled, and for example at about 10 ℃～40 ℃, under preferred about 20 ℃～35 ℃ temperature, carries out dip treating about 30 seconds～600 seconds, preferred about 60 seconds～300 seconds.
Among the present invention, when in dye bath, carrying out uniaxial tension, preferably in each dye bath, adjust stretching ratio respectively separately.For this reason, for example entrance side and the outlet side at each dye bath is provided with the material folding roller respectively, and makes the rotating ratio of two material folding rollers variable better.In addition, as long as can individually adjust stretching ratio, just can and/or bathe the gateway in dye bath Stretching rollers, propellers, roll, intersection deflector roll, curved rod etc. are set.In addition, before back, dyeing processing are handled in swelling, also can carry out the wet type stretch processing, in addition, also can between each dye bath, carry out uniaxial tension as required, washing perhaps also can be set between each dye bath bathe the polyvinyl alcohol (PVA) mesentery.
Stretching ratio in the dye bath more than 2 sections during uniaxial tension is not particularly limited, but adopts in following 2 kinds of modes any according to purpose.
(1) make the stretching ratio in the initial dye bath be higher than the 2nd section total stretching ratio in the later dye bath.Thus, the dry shrink amplitude variation when the washing back is dry is little, so the occurrence frequency of the fold in the drying oven tails off.Particularly, the stretching ratio in the preferred initial dye bath is in about 1.1～3.0 times scope, and is about 1.05～2.0 times of the 2nd section total stretching ratio in the later dye bath.
(2) make stretching ratio in the final dye bath be higher than total stretching ratio in before this dye bath.Thus, film is difficult for laxly in the later operation of boric acid treatment process, and throughput rate improves.Particularly, the stretching ratio in the preferred final dye bath is in about 1.05～2.0 times scope, and is about 1.1～3.0 times of total stretching ratio in before this dye bath.
Boric acid is handled by containing with respect to water 100 weight portions in the aqueous solution of 1～10 weight portion boric acid of having an appointment, and the polyvinyl alcohol (PVA) mesentery behind the dipping iodine staining carries out.Preferably in boric acid aqueous solution, contain about 1～30 weight portion of iodide.As iodide, can enumerate potassium iodide, zinc iodide etc.In addition, also can make iodide compound in addition, for example coexistences such as zinc chloride, cobalt chloride, zirconium chloride, sodium thiosulfate, potassium sulfite, sodium sulphate.
This boric acid is handled in order to carry out water-fastization and to adjust tone (preventing to be with blueness etc.) etc. by crosslinked.In the occasion that is used for carrying out water-fastization by crosslinked, also can be as required, except that boric acid or with boric acid use glyoxal, crosslinking chemical such as glutaraldehyde.
In addition, also use titles such as crosslinking Treatment, immobilization processing sometimes, address is used for the boric acid of water-fastization and handles.In addition, also can carry out the boric acid processing in order to adjust tone.Also sometimes with complementary color handle, title such as dyeing processings again, call this boric acid processing.In addition, in the following description, the boric acid that will be used for water-fastization is handled and the boric acid that is used to adjust tone is handled and all abbreviated boric acid as and handle.
Boric acid is handled, according to its purpose suitably change boric acid and iodide concentration, handle the temperature of bathing and carry out.The not special difference of boric acid processing of tone is handled, is used to adjust to the boric acid that is used for water-fastization, implements under the following conditions.
In the occasion that thick (former anti-) film is carried out swelling, dyeing, boric acid processing, boric acid handle with by crosslinked carry out water-fast when turning to purpose, use is handled bath with respect to the boric acid that water 100 weight portions contain 3～10 weight portion boric acid of having an appointment, about 1～20 weight portion iodide, usually at about 50 ℃～70 ℃, carry out under preferred about 55 ℃～65 ℃ temperature.Dip time was generally about 30～600 seconds, and preferred about 60～420 seconds, more preferably 90～300 seconds.
In addition, to the occasion that film dyes, boric acid is handled of prestretched, boric acid is handled the temperature of bathing and is generally about 50 ℃～85 ℃, preferred about 55 ℃～80 ℃.
After being used for the boric acid processing of water-fastization, also can be used to adjust the boric acid processing of tone.For this purpose, use the boric acid processing bath that contains 1～5 weight portion boric acid of having an appointment, about 3～30 weight portion iodide with respect to water 100 weight portions, under about 10 ℃～45 ℃ temperature, carry out usually.Dip time is generally about about 3～300 seconds, preferred about 10～240 seconds.The boric acid that is used to adjust tone is handled to handle with the boric acid that is used for water-fastization and is compared, and carries out under low boric acid concentration, high iodide concentration, low temperature usually.
These boric acid are handled and also can be carried out with a plurality of operations, carry out with 2～5 operations mostly usually.At this moment, the aqueous solution of each boric acid treatment trough of use composition, temperature can be the same or different in above-mentioned scope.Also can carry out the boric acid processing that the above-mentioned boric acid that is used for water-fastization is handled, is used to adjust tone with a plurality of operations respectively.
In the boric acid treatment process, also can carry out the stretching of film equally with dyeing process.Final accumulation stretching ratio is about 4.5～7.0 times, preferred about 5.0～6.5 times.
Boric acid is washed processing after handling.Washing is handled by the polyvinyl alcohol (PVA) mesentery after for example dipping boric acid is handled in water, with water as shower spray or use dipping and spraying to carry out simultaneously.Normally about 2～40 ℃, dip time is better about 2～120 seconds to coolant-temperature gage when washing is handled.Drying after the washing was carried out under about 40～100 ℃ temperature in drying oven about 60～600 seconds.
In the present invention, in each operation after stretch processing, carry out Tension Control and make the tension force of film reach one respectively in fact to be decided to be.In the dyeing treatment process, finish the occasion of stretching, carry out Tension Control in boric acid treatment process afterwards and the washing treatment process.
Paste diaphragm in the one side at least of the light polarizing film of making like this with bonding agent and obtain polaroid.
As diaphragm, can enumerate the film of polyester based resins such as film, polyethylene terephthalate or PEN, the polybutylene terephthalate formation of acetyl fibre prime system resins formations such as triacetyl cellulose or diacetyl cellulose, the film that polycarbonate-based resin constitutes, the film that the cyclic olefine resin constitutes.As commercially available thermoplasticity cyclic olefine resin, " Topas " (registered trademark) of the Ticona company sale of Germany, " ア-ト Application " (registered trademark), " the ゼ オ ノ ア " and " ゼ オ ネ Star Network ス " (being registered trademark) that Japanese ZEON (strain) sells that ジ エ イ エ ス ア-Le (strain) is sold, " ア ペ Le " (registered trademark) that Mitsui Chemicals (strain) is sold etc. are for example arranged.With such cyclic olefine resin system film, as diaphragm, can suitably adopt known method such as solvent casting method, extrusion by melting during the system film with the film that obtains.The cyclic olefine resin molding of system behind the film also has commercially available, for example has " エ ス シ-Na " and " SCA40 " that ponding chemical industry (strain) sells etc.
The thickness of diaphragm is preferably thin, but crosses when thin, and intensity reduces, the processability deterioration, and on the other hand, when blocked up, the transparency reduces, and occurs in behind the lamination problems such as necessary curing time is elongated.Therefore, the suitable thickness of diaphragm is preferably about 10～150 μ m, more preferably about 20～100 μ m for for example about 5～200 μ m.
In order to improve the cohesive of bonding agent and light polarizing film and/or diaphragm, also can implement surface treatments such as corona treatment, flame treatment, Cement Composite Treated by Plasma, ultraviolet ray irradiation, priming paint coating processing, saponification processing to light polarizing film and/or diaphragm.
Also can implement surface treatments such as anti-dazzle is handled, antireflection is handled, hard coating processing, anti-charged processing, antifouling processing alone or in combination to diaphragm.In addition, diaphragm and/or diaphragm sealer also can have plastifier such as ultraviolet light absorbers such as benzophenone based compound, benzotriazole based compound, phenyl phosphate based compound, phthalate compound.
This diaphragm can stick on the one side of light polarizing film, also can stick on the two sides.
Light polarizing film and diaphragm use hydrosolvent be bonding agent, organic solvent be bonding agent, hot melt be bonding agent, solvent-free be adhesive laminated such as bonding agent.As hydrosolvent is bonding agent, can enumerate the polyvinyl alcohol resin aqueous solution, water system two-liquid type urethane is an emulsion bonding agent etc.; As organic solvent is bonding agent, and can enumerate the two-liquid type urethane is bonding agent etc.; As solvent-free be bonding agent, for example listing a liquid type urethane is bonding agent etc.The acetylcellulose mesentery that will carry out hydrophilicity-imparting treatment to the adhesive surface with light polarizing film by saponification processing etc. preferably uses the polyvinyl alcohol resin aqueous solution as bonding agent as the occasion that diaphragm uses.Polyvinyl alcohol resin as the bonding agent use, handle the alcotex that obtains except the polyvinyl acetate as the homopolymer of vinyl acetate being carried out saponification, also have vinyl acetate and the multipolymer that can form with other monomers of its copolymerization are carried out that the ethenol system copolymer that obtains is handled in saponification and modified polyvinylalcohol based polymer that their hydroxylic moiety modification is obtained etc.In these bonding agents, also can use polyaldehyde, soluble epoxide compound, melamine based compound etc. as adjuvant.
The method of pasting light polarizing film and diaphragm is not particularly limited, and the surface that can be set forth in light polarizing film or diaphragm is coating adhesive equably, at the overlapping more a kind of film of coated face, and with applyings such as rollers, and dry method etc.
Usually bonding agent modulation back is coated with under about 15～40 ℃ temperature, and sticking temperature is the scope about 15～30 ℃ normally.Carry out dried after the stickup, remove contained water equal solvent in the bonding agent, the baking temperature of this moment is generally about 30～85 ℃, is preferably about 40～80 ℃ scope.Thereafter, also can be at about 15～85 ℃, preferred about 20～50 ℃, more preferably from about under 35～45 ℃ the temperature environment, maintenance made the bonding agent sclerosis about 1～90 day usually.Between this curing period when long, the throughput rate variation, so be about 1～30 day between curing period, be preferably about 1～7 day.
Like this, can obtain having pasted at the one or both sides of light polarizing film the polaroid of diaphragm by adhesive phase.
In the present invention, also can make diaphragm have function as phase retardation film, as brightness improve the function of film, as the function of reflectance coating, as the function of transflective film, as the function of diffusion barrier, as the optical functions such as function of optical compensation films.In the case; for example by making it to have such function at optical functional films such as the laminated phase retardation film in diaphragm surface, brightness raising film, reflectance coating, transflective film, diffusion barrier, optical compensation films; in addition, also can pay such function to diaphragm self.In addition, also can as diffusion barrier with function that brightness improves film etc., make diaphragm self have a plurality of functions.
For example, said protection film is implemented No. 2841377 communique of patent, No. 3094113 described stretch processing such as communique of patent, or implement No. 3168850 described processing such as communique of patent, can pay function thus as phase retardation film.In addition; on said protection film, open 2002-169025 communique or the special method formation minute aperture of putting down in writing in the 2003-29030 communique of opening with the spy; the different cholesteric more than 2 layers of centre wavelength of overlapping in addition selection reflection can be paid the function that improves film as brightness thus.By on said protection film, adopting evaporation or sputter etc. to form metallic film, can pay function as reflectance coating or transflective film.Contain atomic resin solution by on said protection film, applying, can pay function as diffusion barrier.In addition, by on said protection film, applying liquid crystal compounds such as collar plate shape (デ イ ス コ テ イ Star Network) liquid crystal compounds and making it orientation, can pay function as optical compensation films.In addition, also can use suitable adhesive, directly paste the brightness that trade name: DBEF (ス リ-エ system (strain) system) waits and improve film, trade name on light polarizing film: the commercially available optical functional films such as phase retardation film of film, trade name: ス ミ カ ラ イ ト (registered trademark) (Sumitomo Chemical (strain)) etc. are improved at the visual angle of WV film (Fujiphoto (strain) system) etc.
Below provide embodiment and be described more specifically the present invention, but the present invention is not limited by these embodiment.
Embodiment 1
The polyvinyl alcohol film of thickness 75 μ m (Network ラ レ PVC ニ ロ Application VF-PS#7500, the degree of polymerization 2400, saponification degree 99.9 moles more than the %) in 30 ℃ pure water, keeping tense situation to make under the unflagging state of film dipping about 130 seconds, is made the abundant swelling of film.
Secondly, in the weight ratio of iodine/potassium iodide/water is 30 ℃ of aqueous solution of 0.02/1.0/100, flood, carry out uniaxial tension to 2.50 times simultaneously.The weight ratio that is immersed in iodine/potassium iodide/water again is in 30 ℃ of aqueous solution of 0.025/1.5/100, carries out uniaxial tension to 1.04 times simultaneously.Thereafter, the weight ratio that is immersed in potassium iodide/boric acid/water is in 60 ℃ of aqueous solution of 10/5/100, carries out boric acid and handles, and carries out uniaxial tension simultaneously and reaches 5.9 times up to the accumulation stretching ratio that begins from thick film.After boric acid is handled, in 10 ℃ pure water, wash about 10 seconds.After the washing,, obtain the iodine polarizing film of thickness 28 μ m 60 ℃ of dryings 2 minutes.
Obtaining the dry shrink width of cloth by film after the firm washing wide (W1) and dried film wide (W2), is 13%.
Two sided coatings polyethenol series bonding agent in above-mentioned light polarizing film; two sides applying diaphragm (tri acetyl cellulose membrane that saponification is handled, " Off ジ Star Network (registered trademark) T80NUL ", Fujiphoto (strain) system, thickness 80 μ m have been implemented in the surface); 60 ℃ of dryings 5 minutes, obtain polaroid.
Under Niccol quadrature (Nicol cross) state in the darkroom this polaroid of visual inspection, can't see uneven dyeing substantially.In addition, uneven dyeing is confirmed according to the light leak degree from polaroid.
Embodiment 2
The polyvinyl alcohol film of thickness 75 μ m (Network ラ レ PVC ニ ロ Application VF-PS#7500, the degree of polymerization 2400, saponification degree 99.9 moles more than the %) in 30 ℃ pure water, keeping tense situation to make under the unflagging state of film dipping about 130 seconds, is made the abundant swelling of film.
Secondly, in the weight ratio of iodine/potassium iodide/water is 30 ℃ of aqueous solution of 0.02/1.0/100, flood, carry out uniaxial tension to 1.04 times simultaneously.The weight ratio that is immersed in iodine/potassium iodide/water again is in 30 ℃ of aqueous solution of 0.025/1.5/100, carries out uniaxial tension to 2.50 times simultaneously.Thereafter, the weight ratio that is immersed in potassium iodide/boric acid/water is in 60 ℃ of aqueous solution of 10/5/100, carries out boric acid and handles, and carries out uniaxial tension simultaneously and reaches 5.9 times up to the accumulation stretching ratio that begins from thick film.After boric acid is handled, in 10 ℃ pure water, wash about 10 seconds.After the washing,, obtain the iodine polarizing film of thickness 28 μ m 60 ℃ of dryings 2 minutes.
The tension force of the unflagging washing procedure of film when adopting the pure water washing before commercially available differential conduction pattern tensiometer is measured drying.As a result, film relaxes under the wide tension force of 850N/m.
Use this iodine polarizing film, carry out similarly to Example 1, obtain polaroid.
Under Niccol quadrature (Nicol cross) state in the darkroom this polaroid of visual inspection, can't see uneven dyeing substantially.
Comparative example 1
The polyvinyl alcohol film of thickness 75 μ m that will be identical with embodiment 1 keeping tense situation to make under the unflagging state of film dipping about 130 seconds, makes the abundant swelling of film in 30 ℃ pure water.
Secondly, in the weight ratio of iodine/potassium iodide/water is 30 ℃ of aqueous solution of 0.025/1.5/100, flood, carry out uniaxial tension to 2.60 times, make the length after the stretching reach identical with embodiment 1.Below similarly to Example 1, carry out boric acid and handle and washing and drying, obtain the iodine polarizing film of thickness 28 μ m.
Obtaining the dry shrink width of cloth by film after the firm washing wide (W1) and dried film wide (W2), is 15%.
In addition, when measuring the pure water washing before dry similarly to Example 2, the tension force of the unflagging washing procedure of film, though under the wide tension force of 1200N/m film also relax (about 2%).
Use this iodine polarizing film, carry out similarly to Example 1, obtain polaroid.
Under Niccol quadrature (Nicol cross) state in the darkroom this polaroid of visual inspection, can see some uneven dyeings.
Claims (9)
1. the manufacture method of an iodine polarizing film, be handle by swelling processing, iodine staining and the operation of the sequential processes polyvinyl alcohol (PVA) mesentery that boric acid is handled before and/or carry out the manufacture method of the light polarizing film of uniaxial tension in the operation, it is characterized in that, in the dye bath more than 2 sections, carrying out iodine staining before the boric acid treatment process.
2. the manufacture method of iodine polarizing film according to claim 1 is characterized in that, carries out uniaxial tension at least one dye bath.
3. the manufacture method of iodine polarizing film according to claim 1, it is characterized in that, in the dye bath more than 2 sections, carry out uniaxial tension, and carry out the uniaxial tension that stretching ratio in the initial dye bath is higher than the 2nd section total stretching ratio in the later dye bath.
4. the manufacture method of iodine polarizing film according to claim 1 is characterized in that, carries out uniaxial tension in the dye bath more than 2 sections, and carries out the uniaxial tension that stretching ratio in the last dye bath is higher than the total stretching ratio in before this dye bath.
5. according to the manufacture method of claim 3 or 4 described iodine polarizing films, it is characterized in that, in a plurality of dye baths more than 2 sections, adjust stretching ratio respectively separately.
6. according to the manufacture method of wantonly 1 described iodine polarizing film in the claim 1～4, wherein, whole dye baths contain iodide, adjust to make the content of these iodide uprise by the order of handling.
7. the manufacture method of a polaroid is characterized in that, pastes diaphragm in the one side at least of the light polarizing film that obtains by the described method of claim 1～4.
8. the manufacture method of polaroid according to claim 7 is characterized in that, said protection film possesses phase retardation film, brightness and improves in film, visual angle improvement film and the transflective film any one function.
9. the manufacture method of an optical laminates is characterized in that, will be by the described method of claim 7 polaroid that obtains and at least a kind of stickup that is selected from phase retardation film, brightness raising film, visual angle improvement film and transflective film.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP416892/2003 | 2003-12-15 | ||
| JP2003416892A JP4421886B2 (en) | 2003-12-15 | 2003-12-15 | Method for producing iodine polarizing film and method for producing polarizing plate |
| JP416892/03 | 2003-12-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1629660A true CN1629660A (en) | 2005-06-22 |
| CN100437162C CN100437162C (en) | 2008-11-26 |
Family
ID=34735968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200410100386XA Active CN100437162C (en) | 2003-12-15 | 2004-12-09 | Iodine polarizing film manufacturing method, polaroid manufacturing method and optical laminate manufacturing method |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4421886B2 (en) |
| KR (1) | KR101137644B1 (en) |
| CN (1) | CN100437162C (en) |
| TW (1) | TWI389946B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101852879A (en) * | 2009-03-30 | 2010-10-06 | 住友化学株式会社 | The manufacture method of light polarizing film |
| CN101025456B (en) * | 2006-02-24 | 2010-11-03 | 日东电工株式会社 | Method for manufacturing polarizer, polarizer, polarizing plate, optical film, image display device and cleaning device |
| CN103080790A (en) * | 2010-09-03 | 2013-05-01 | 日东电工株式会社 | Thin polarizing film, optical laminate with thin polarizing film, and production method for thin polarizing film |
| CN103725037A (en) * | 2014-01-20 | 2014-04-16 | 云南云天化股份有限公司 | Iodine dye and preparation method of iodine polarizing film |
| CN107003464A (en) * | 2014-12-12 | 2017-08-01 | 住友化学株式会社 | The manufacture method and polarizing coating of polarizing coating |
| CN107497733A (en) * | 2017-06-14 | 2017-12-22 | 住华科技股份有限公司 | Liquid removing device and method for manufacturing optical film material |
| CN108351453A (en) * | 2015-11-05 | 2018-07-31 | 住友化学株式会社 | Polarizing film and its manufacturing method |
| US10160173B2 (en) | 2010-09-09 | 2018-12-25 | Nitto Denko Corporation | Method of producing thin polarizing film involving in-air stretching, underwater stretching, and stretching while drying |
| CN111095053A (en) * | 2017-09-13 | 2020-05-01 | 日东电工株式会社 | Polarizing plate, polarizing plate roll, and method for producing polarizing film |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7494267B2 (en) | 2022-08-02 | 2024-06-03 | 長春石油化學股▲分▼有限公司 | Polyvinyl alcohol film, optical film and manufacturing method |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0243504A (en) * | 1988-08-03 | 1990-02-14 | Toray Ind Inc | Production of polarizing film |
| JP3264816B2 (en) * | 1995-11-09 | 2002-03-11 | 日本合成化学工業株式会社 | Polarizer |
| JP3448011B2 (en) * | 2000-04-25 | 2003-09-16 | 株式会社クラレ | Manufacturing method of polarizing film |
| TWI230275B (en) * | 2000-05-12 | 2005-04-01 | Kuraray Co | Polyvinyl alcohol film and polarization film |
| JP2001343522A (en) * | 2000-05-31 | 2001-12-14 | Sumitomo Chem Co Ltd | Polarizer film and its manufacturing method |
| JP3976220B2 (en) * | 2000-08-21 | 2007-09-12 | 日本合成化学工業株式会社 | Polyvinyl alcohol film for polarizing film |
| JP2004294808A (en) * | 2003-03-27 | 2004-10-21 | Sumitomo Chem Co Ltd | Iodine-based polarizing film, method for manufacturing the same and polarizing plate |
-
2003
- 2003-12-15 JP JP2003416892A patent/JP4421886B2/en not_active Expired - Fee Related
-
2004
- 2004-11-19 TW TW093135684A patent/TWI389946B/en active
- 2004-12-07 KR KR1020040102087A patent/KR101137644B1/en active IP Right Grant
- 2004-12-09 CN CNB200410100386XA patent/CN100437162C/en active Active
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101025456B (en) * | 2006-02-24 | 2010-11-03 | 日东电工株式会社 | Method for manufacturing polarizer, polarizer, polarizing plate, optical film, image display device and cleaning device |
| CN101852879B (en) * | 2009-03-30 | 2014-02-26 | 住友化学株式会社 | Process for producing a polarizing film |
| CN101852879A (en) * | 2009-03-30 | 2010-10-06 | 住友化学株式会社 | The manufacture method of light polarizing film |
| CN103080790B (en) * | 2010-09-03 | 2016-03-02 | 日东电工株式会社 | The production method of slim light polarizing film and slim light polarizing film |
| US9227222B2 (en) | 2010-09-03 | 2016-01-05 | Nitto Denko Corporation | Thin polarizing film, optical laminate with thin polarizing film, and production method for thin polarizing film |
| CN103080790A (en) * | 2010-09-03 | 2013-05-01 | 日东电工株式会社 | Thin polarizing film, optical laminate with thin polarizing film, and production method for thin polarizing film |
| US9453953B2 (en) | 2010-09-03 | 2016-09-27 | Nitto Denko Corporation | Thin polarizing film, optical laminate with thin polarizing film, and production method for thin polarizing film |
| US10160173B2 (en) | 2010-09-09 | 2018-12-25 | Nitto Denko Corporation | Method of producing thin polarizing film involving in-air stretching, underwater stretching, and stretching while drying |
| CN103725037A (en) * | 2014-01-20 | 2014-04-16 | 云南云天化股份有限公司 | Iodine dye and preparation method of iodine polarizing film |
| CN103725037B (en) * | 2014-01-20 | 2016-05-25 | 云南云天化股份有限公司 | The preparation method of iodine based dye, iodine polarizing film |
| CN107003464A (en) * | 2014-12-12 | 2017-08-01 | 住友化学株式会社 | The manufacture method and polarizing coating of polarizing coating |
| CN107003464B (en) * | 2014-12-12 | 2020-05-19 | 住友化学株式会社 | Polarizing film manufacturing method and polarizing film |
| CN108351453A (en) * | 2015-11-05 | 2018-07-31 | 住友化学株式会社 | Polarizing film and its manufacturing method |
| CN107497733A (en) * | 2017-06-14 | 2017-12-22 | 住华科技股份有限公司 | Liquid removing device and method for manufacturing optical film material |
| CN111095053A (en) * | 2017-09-13 | 2020-05-01 | 日东电工株式会社 | Polarizing plate, polarizing plate roll, and method for producing polarizing film |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200526715A (en) | 2005-08-16 |
| CN100437162C (en) | 2008-11-26 |
| KR20050059993A (en) | 2005-06-21 |
| JP2005173495A (en) | 2005-06-30 |
| TWI389946B (en) | 2013-03-21 |
| KR101137644B1 (en) | 2012-04-19 |
| JP4421886B2 (en) | 2010-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI685685B (en) | Method for manufacturing polarizing film and polarizing film | |
| CN100472250C (en) | Manufacturing method of polaroid film, polaroid plate and optical laminate | |
| JP5831249B2 (en) | Polarizing film, method for producing the same, and polarizing plate | |
| TWI684032B (en) | Method for manufacturing polarizing film and polarizing film | |
| CN100501464C (en) | Manufacturing method of polarized light film, polarized light slice and optical laminate style | |
| KR101483793B1 (en) | A process for producing a polarizing film and a process for producing a polarizer | |
| KR101638196B1 (en) | Process for producing a polarizing film | |
| CN1800881B (en) | Manufacturing method of polarized light film, polarized light slice and optical laminate style | |
| CN100409044C (en) | Manufacturing method of polarized film, and polarized sheets and optical laminates | |
| CN1598624A (en) | Polarization membrane and manufacturing method thereof,polarizer and optical laminate | |
| CN1595211A (en) | Polarization film and its manufacturing method, polarization sheet and optical laminating body | |
| CN100399071C (en) | Polarization film mfg. method, polarization sheet mfg. method and optical laminate mfg. method | |
| CN1657983A (en) | Manufacturing method of polaroid, polarizer and optical laminate thereof | |
| CN1629660A (en) | Iodine polarizing film manufacturing method, polaroid manufacturing method and optical laminate manufacturing method | |
| CN108780171A (en) | Polarizing film | |
| CN1627106A (en) | Manufacturing method of polarized film, and polarized sheets and optical laminates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |