CN1627107A - Manufacturing method of polarized film, and polarized sheets and optical laminates - Google Patents
Manufacturing method of polarized film, and polarized sheets and optical laminates Download PDFInfo
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- CN1627107A CN1627107A CNA2004101003874A CN200410100387A CN1627107A CN 1627107 A CN1627107 A CN 1627107A CN A2004101003874 A CNA2004101003874 A CN A2004101003874A CN 200410100387 A CN200410100387 A CN 200410100387A CN 1627107 A CN1627107 A CN 1627107A
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- film
- boric acid
- dye bath
- light polarizing
- polarizing film
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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
- 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
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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
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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
- 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
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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
- 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
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polarising Elements (AREA)
Abstract
The object of invention is to provide a manufacturing method of a polarizing film which has an excellent surface state and hardly causes the irregularity of dyeing, and to provide a manufacturing method of polarizing plate and a manufacturing method of 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, dyeing and borating. Prior to the borating process, dyeing baths of two steps or more are disposed and the dyeing is performed successively and boric acid is included in the final dyeing bath.
Description
Technical field
The present invention relates to the manufacture method of light polarizing film in apparent good order and condition, that uneven dyeing is few, the manufacture method of polaroid of using this light polarizing film and the manufacture method of optical laminates.
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, knownly be the iodine polarizing film of bitintability pigment with iodine and be that the dyestuff of bitintability pigment is a light polarizing film etc. with the bitintability dyestuff.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.
As the manufacture method of light polarizing film, put down in writing following method in the patent documentation 1, promptly, 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, promptly, with the film immersion that stretched 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 layer thus.
Put down in writing the method for following manufacturing light polarizing film in the patent documentation 3, that is, and after the polyethenol series film immersion that stretched is in the aqueous solution (dyeing liquor A) of specific bitintability dyestuff, 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.
Record is immersed in polyvinyl alcohol film in the aqueous solution that contains iodine, potassium iodide, boric acid and dyes in the patent documentation 4, then carry out uniaxial tension after, carry out boric acid and handle, make light polarizing film.
, carry out the method for the patent documentation 1-3 of 2 dyeing processing, exist surface state bad, can not get direct reflection, the problem that outward appearance is bad.On the other hand, there are the many problems of uneven dyeing in the method for the patent documentation 4 that dyes in borated dye bath.
[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
The embodiment of [patent documentation 4] special fair 3-23881 communique
Summary of the invention
Major subjects of the present invention is, the manufacture method of the light polarizing film that provide in apparent good order and condition, uneven dyeing is few, the manufacture method of using the polaroid that this polarisation touches and the manufacture method of optical laminates.
The inventor is for solving the diligently investigation repeatedly of above-mentioned problem, found that, in the dye bath more than 2 sections, carrying out iodine staining before the boric acid treatment process successively, last dye bath contains the occasion of boric acid, can obtain this new fact of light polarizing film in apparent good order and condition, that uneven dyeing is few, to such an extent as to finished the present invention.
Promptly, the manufacture method of light polarizing film of the present invention, it is characterized in that, be handle by swelling, dyeing is handled 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 treatment process, at the dye bath that is provided with before the boric acid treatment process more than 2 sections, dye successively, meanwhile make last dye bath contain boric acid.
The concentration of above-mentioned last dye bath mesoboric acid is following to be determined.Promptly, the boric acid content of dye bath last in per 100 weight parts waters is designated as a weight portion, and when (unstretching film) was designated as b to the total stretching ratio that comes out from above-mentioned last dye bath, can there be the relation that satisfies following formula in above-mentioned a and b from thick film (former anti-) with above-mentioned polyvinyl alcohol (PVA) mesentery:
b＜-0.51×a+3.77。
Boric acid content in the last dye bath per 100 weight parts waters usually is preferably about 0.05-2.0 weight portion.In addition, the temperature of the dye bath more than 2 sections can be about 10-40 ℃.
The manufacture method of polaroid of the present invention is characterized in that, the one side at least of the light polarizing film that obtains at said method is pasted diaphragm.Diaphragm preferably possesses any one function of phase retardation film, brightness raising film, visual angle improvement film and transflective film.
The manufacture method of optical laminates of the present invention is characterized in that, pastes at least a kind that is selected from phase retardation film, brightness raising film, visual angle improvement film and transflective film on the polaroid that adopts said method to obtain.
The invention effect
According to the present invention, owing in the dye bath more than 2 sections, dye successively, therefore can reduce the uneven dyeing of light polarizing film, and by making last dye bath contain boric acid, the surface state that can suppress film in the boric acid treatment process degenerates, and has the effect that optical characteristics improves.
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 %, be preferably about 90 moles more than the %, more preferably about 99 moles of %-100 mole %.As polyvinyl acetate is resin, except polyvinyl acetate as the homopolymer of vinyl acetate, but also can enumerate vinyl acetate and with the multipolymer of other monomers of its copolymerization, for example vinyl-vinyl acetate copolymer etc.But as other monomers of copolymerization, for example unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class etc.As the degree of polymerization of polyvinyl alcohol resin, be 1000-10000, preferably 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, used thickness is about 20 μ m-100 μ m, be preferably the unstretching film of the polyvinyl alcohol resin film of 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 is handled, dyeing is 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 example for about 5-50 μ m.
Light polarizing film of the present invention is the polyethenol series monadic stretching membrane that makes dichromatism pigment absorption orientation, as its manufacture method, 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 is handled, dyeing is handled, boric acid is handled and washing is 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 is handled, dyeing is handled, boric acid is handled and washing is handled in aqueous solution, in boric acid treatment process and/or the operation before it, carry out uniaxial tension with wet type, carry out dry method at last.
In the where method in office, uniaxial tension both can carry out in an operation, can carry out in the operation more than 2 again, but preferably carry out in a plurality of operations.Drawing process can adopt known method, for example, applies 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 nip rolls of transport membrane.In addition, basically the order of operation as mentioned above, but the quantity of handle bathing, treatment conditions etc. are without limits.
In addition, inserting the operation of not putting down in writing in the above-mentioned operation with other purposes also is freely certainly.As the example of this operation, can list: after boric acid is handled, dip treating (zinc processing) operation of dip treating of not borated iodide aqueous solution (iodide processing) or the not borated aqueous solution that contains zinc chloride etc. etc.
The swelling operation for the foreign matter of removing the film surface, remove plastifier in the film, pay the easy dyeing in the next operation, the purposes such as plasticized of film are carried out.Treatment conditions are determined in the scope that can reach these purposes and in the scope that unfavorable conditions such as the extreme dissolving of base material film, devitrification do not take place.In the occasion that makes the film swelling that in gas, stretched in advance, impregnated membranes and carrying out in about 20 ℃-70 ℃, preferred about 30 ℃-60 ℃ aqueous solution for example.The dip time of film is 30 seconds-300 seconds, further preferably about 60 seconds-240 seconds.Make from the occasion of initial thick (former anti-) film swelling that does not just stretch, for example impregnated membranes and carrying out in about 10 ℃-50 ℃, preferred about 20 ℃-40 ℃ aqueous solution.The dip time of film is 30 seconds-300 seconds, further preferably about 60 seconds-240 seconds.
In the swelling treatment process, film is in horizontal swelling, easily produce film and problems such as fold occur, 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), eliminate the fold of film on one side, on one side transport membrane.For making the film in the bath carry stable purpose, the current during perforated water spray control swelling is bathed in the water, or to use EPC device (Edge Position Control device: the end of detecting membrane prevents the device that film crawls) etc. simultaneously also be useful.In this operation, because film enlarges at the direction of travel of film also swelling, therefore for the sag of the film of eliminating throughput direction, preference is as taking the means such as speed of the conveying roller before and after the control and treatment groove.In addition, the boron profit of using is handled and is bathed except pure water, also can use the aqueous solution of adding 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. in the scope of 0.01 weight %-10 weight %.
The dyeing treatment process is carried out for the purpose that makes film absorption bitintability pigment and make it to be orientated.Treatment conditions are determined in scope that can reach these purposes and scope that the unfavorable conditions such as extreme dissolving, devitrification of base material film do not take place.The present invention is provided with the dye bath more than 2 sections especially, dyes successively.Dye bath is preferably 2 sections-4 sections.At this moment, make last dye bath contain boric acid.Each dye bath except last dye bath does not preferably contain boric acid.Preferably in each dye bath while carrying out the uniaxial tension processing of dyeing, but also can keep the processing of dyeing under the tense situation.
Add the occasion of boric acid, handle difference with following boric acid aspect the bitintability pigment containing.If with respect to water 100 weight portions, contain the above bitintability pigment of 0.003 weight portion of having an appointment, temperature is about below 40 ℃, then can regard staining trough as.
As the occasion of bitintability pigment use iodine, the concentration of each dye bath except last dye bath is counted iodine/potassium iodide/water=about 0.1-10/100 of about 0.003-0.2/ by weight, is preferably the about 0.1-3.0/100 of about 0.01-0.1/.The concentration of last dye bath for iodine/potassium iodide/boric acid/water=about 0.05-2.0/100 of the about 0.1-10/ of about 0.003-0.2/, is preferably the about 0.1-1.5/100 of the about 0.1-3.0/ of about 0.01-0.1/ by weight.The content of iodine is can each dye bath all identical, perhaps also can reduce or increase content by the dyeing processing sequence in above-mentioned scope.
The potassium iodide concentration of each dye bath preferably is adjusted to the order of handling by dyeing and uprises.The concentration of potassium iodide same amount or by the occasion of the order step-down of handling, during long-play, the balance of strength of fluid is destroyed, can not stably keep the quality of light polarizing film in each dye bath.
In addition, also can replace potassium iodide, use other iodide, for example zinc iodide etc.In addition, also can and use other iodide and 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 coexistence such as zinc chloride, cobalt chloride.
Boric acid concentration in the last dye bath as mentioned above, and stretching ratio between preferably satisfy following formula, in the occasion that does not satisfy this relation, worry that the surface state of light polarizing film worsens.
b＜-0.51×a+3.77
At this, a represents the boric acid content (weight portion) of per 100 weight parts waters, b represent the polyvinyl alcohol (PVA) mesentery from thick film to the total stretching ratio that comes out from above-mentioned last dye bath.
Dyeing in each dye bath is handled, and for example carries out dip treating about 30 seconds-600 seconds, preferred about 60 seconds-300 seconds under about 10 ℃-40 ℃, preferred about 20 ℃-35 ℃ temperature.At this, the temperature of each dye bath is during less than about 10 ℃, and boric acid is difficult to dissolving, on the contrary, when surpassing about 40 ℃, worries that the dissolving of polyvinyl alcohol (PVA) becomes many.
When in each dye bath, carrying out uniaxial tension, preferably in each dye bath, adjust stretching ratio respectively separately.For this reason, for example can nip rolls be set respectively, and change the rotational speed ratio of two nip rolls at the entrance side and the outlet side of each dye bath.In addition, can be in dye bath and/or bathe the gateway and Stretching rollers, propellers, roll, intersection deflector roll, curved rod etc. are set carry out uniaxial tension.
In addition, also can swelling handle back, dyeing handle before wet type stretch processing polyvinyl alcohol (PVA) mesentery, in addition, also carry out uniaxial tension among at least 1 between each dye bath as required, perhaps also can at least 1 between each dye bath the washing bath be set.
Carry out the occasion of uniaxial tension in each dye bath more than 2 sections, stretching ratio does not have special restriction, but preferably adopts following 2 kinds of schemes any.
(1) make stretching ratio in the initial dye bath be higher than total stretching ratio in the 2nd section later dye bath.Thus, the dry shrink amplitude variation during dry after the washing is little, and therefore the fold occurrence frequency in drying oven tails off.Specifically, the stretching ratio in the preferred initial dye bath is in about 1.1-3.0 scope doubly, and the stretching ratio in the initial dye bath is about 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 dye bath before it.Thus, film is difficult for relaxing in the later operation of boric acid treatment process, obtains the high light polarizing film of degree of polarization.Specifically, the stretching ratio in the preferred final dye bath and is about about 1.1-3.0 a times of total stretching ratio in dye bath before it in about 1.05-2.0 scope doubly.
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, perhaps 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, carry out the occasion that boric acid is handled in order to adjust tone, sometimes with complementary color handle, title such as dyeing processings again, call this boric acid processing.In addition, in the present invention, 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.
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, " Zeonor " and " Zeonex " (being registered trademark) that " Topas " (registered trademark) that the Ticona company of Germany sells, Arton (registered trademark), Japanese ZEON (strain) that ジ ェ イ エ ス ア-Le (strain) is sold sell, " Apel " (registered trademark) of Mitsui Chemicals (strain) sale 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, to said protection film implement No. 2841377 communique of patent, No. 3094113 communique of patent etc. fast stretch processing, 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 (Sumikalight) (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
With 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, dipping is about 130 seconds under the unflagging state of maintenance film forming, makes the abundant swelling of film (swelling is to about 1.2 times).
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 1.75 times simultaneously.The weight ratio that is immersed in iodine/potassium iodide/boric acid/water again is in 30 ℃ of aqueous solution of 0.02/1.5/0.2/100, carries out uniaxial tension to 1.4 times simultaneously, and making the total stretching ratio that begins from thick film is 3 times.Thereafter, the weight ratio that is immersed in potassium iodide/boric acid/water is in 60 ℃ of aqueous solution of 10/5/100, to carry out water-fastization processing, carries out uniaxial tension simultaneously and reaches 5.9 times up to the accumulation stretching ratio that begins from thick film.After the water-fastization processing, wash about 10 seconds with 10 ℃ pure water.After the washing,, obtain the iodine polarizing film of thickness 28 μ m 60 ℃ of dryings 2 minutes.The surface state of this light polarizing film of visualization, the film surface demonstrates good direct reflection.
Two sided coatings polyethenol series bonding agent in above-mentioned light polarizing film; paste diaphragm (tri acetyl cellulose membrane that saponification is handled, " Off ジ ッ Network (registered trademark) T80NUL " Fujiphoto (strain) system, thickness 80 μ m have been implemented in the surface) on the two sides; 60 ℃ of dryings 5 minutes, obtain polaroid.Under Niccol quadrature (Nicol cross) state in the darkroom this polaroid of visualization, uneven dyeing is slight.In addition, uneven dyeing is according to confirming from the light leak degree of polaroid.
Comparative example 1
Except do not put into boric acid in the 2nd section dye bath, other carry out similarly to Example 1, obtain polarizing coating.The not display mirror reflection of the surface state of this light polarizing film of visualization, the reflected light of fluorescent light looks and turns white slightly, bad order.
Comparative example 2
Except add 0.2 weight portion boric acid in the 1st section dye bath, other carry out similarly to Example 1, obtain polarizing coating.Under Niccol quadrature (Nicol cross) state in the darkroom this polaroid of visualization, observe uneven dyeing than embodiment more than 1.
Claims (7)
1. the manufacture method of a light polarizing film, its handle by swelling, dyeing is handled and the operation of the sequential processes polyvinyl alcohol (PVA) mesentery that boric acid is handled before and/or carry out uniaxial tension in the operation, it is characterized in that, the dye bath that was provided with in the past more than 2 sections in the boric acid treatment process dyes successively, meanwhile makes last dye bath contain boric acid.
2. the manufacture method of light polarizing film according to claim 1, it is characterized in that, boric acid content in the above-mentioned last dye bath in per 100 weight parts waters is designated as a weight portion, and with above-mentioned polyvinyl alcohol (PVA) mesentery be designated as b from thick film to the total stretching ratio that comes out from above-mentioned last dye bath the time, there are the relation that satisfies following formula in above-mentioned a and b:
b＜-0.51×a+3.77。
3. the manufacture method of light polarizing film according to claim 1 and 2 is characterized in that, the boric acid content in per 100 weight parts waters in the above-mentioned last dye bath is the 0.05-2.0 weight portion.
4. according to the manufacture method of wantonly 1 described light polarizing film of claim 1-3, it is characterized in that the temperature of above-mentioned dye bath more than 2 sections is 10-40 ℃.
5. 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 with the described method of claim 1-4.
6. the manufacture method of polaroid according to claim 5 is characterized in that, said protection film possesses any one function of phase retardation film, brightness raising film, visual angle improvement film and transflective film.
7. the manufacture method of an optical laminates is characterized in that, pastes at least a kind that is selected from phase retardation film, brightness raising film, visual angle improvement film and transflective film on the polaroid that adopts the described method of claim 5 to obtain.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP413276/03 | 2003-12-11 | ||
| JP413276/2003 | 2003-12-11 | ||
| JP2003413276A JP4394431B2 (en) | 2003-12-11 | 2003-12-11 | Manufacturing method of polarizing film and manufacturing method of polarizing plate |
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| Publication Number | Publication Date |
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| CN1627107A true CN1627107A (en) | 2005-06-15 |
| CN100409044C CN100409044C (en) | 2008-08-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2004101003874A Active CN100409044C (en) | 2003-12-11 | 2004-12-09 | Manufacturing method of polarized film, and polarized sheets and optical laminates |
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| Country | Link |
|---|---|
| JP (1) | JP4394431B2 (en) |
| KR (1) | KR101137551B1 (en) |
| CN (1) | CN100409044C (en) |
| TW (1) | TWI359286B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101852879A (en) * | 2009-03-30 | 2010-10-06 | 住友化学株式会社 | The manufacture method of light polarizing film |
| CN106772755A (en) * | 2017-02-27 | 2017-05-31 | 合肥京东方光电科技有限公司 | A kind of polaroid and liquid crystal display |
| CN106842403A (en) * | 2015-11-27 | 2017-06-13 | 住友化学株式会社 | The manufacture method of polarizer |
| CN106950634A (en) * | 2015-11-27 | 2017-07-14 | 住友化学株式会社 | The manufacture method of polarizer and the detection method of polyvinyl alcohol |
| 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 |
| CN111279231A (en) * | 2017-10-27 | 2020-06-12 | 住友化学株式会社 | Polarizing film and method for producing same |
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| JP4838283B2 (en) * | 2007-05-29 | 2011-12-14 | 日東電工株式会社 | Manufacturing method of polarizer, polarizer, polarizing plate, optical film, and image display device |
| KR100947936B1 (en) * | 2007-12-24 | 2010-03-15 | 주식회사 에이스 디지텍 | Method for manufacturing polarizer |
| KR100947937B1 (en) * | 2007-12-26 | 2010-03-15 | 주식회사 에이스 디지텍 | Method for manufacturing polarizer |
| KR100947939B1 (en) * | 2007-12-26 | 2010-03-15 | 주식회사 에이스 디지텍 | Method for manufacturing polarizer |
| KR100947938B1 (en) * | 2007-12-26 | 2010-03-15 | 주식회사 에이스 디지텍 | Method for manufacturing polarizer |
| CN102501462B (en) * | 2011-10-28 | 2014-11-26 | 陈美琴 | Polarization concealed image and preparing method thereof |
| CN103059486B (en) * | 2012-12-03 | 2016-03-02 | 云南云天化股份有限公司 | The manufacture method of water-resistant polyvinyl alcohol film |
| WO2015037929A1 (en) * | 2013-09-12 | 2015-03-19 | 주식회사 엘지화학 | Apparatus for manufacturing polarizing film |
| JP6105794B1 (en) * | 2015-11-27 | 2017-03-29 | 住友化学株式会社 | Manufacturing method of polarizer |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0273309A (en) * | 1988-09-09 | 1990-03-13 | Nippon Synthetic Chem Ind Co Ltd:The | Method for dying polarizing film |
| JP3145747B2 (en) * | 1991-10-09 | 2001-03-12 | 株式会社クラレ | Polarizing film |
| JPH08304624A (en) * | 1995-05-12 | 1996-11-22 | Sumitomo Chem Co Ltd | Polarizing plate and its production |
| JP3680709B2 (en) * | 1999-07-13 | 2005-08-10 | 住友化学株式会社 | Manufacturing method of polarizing film |
| JP3448011B2 (en) * | 2000-04-25 | 2003-09-16 | 株式会社クラレ | Manufacturing method of polarizing film |
| JP4043263B2 (en) * | 2002-03-18 | 2008-02-06 | 日東電工株式会社 | Manufacturing method of polarizer, polarizer, polarizing plate, and image display device |
-
2003
- 2003-12-11 JP JP2003413276A patent/JP4394431B2/en not_active Expired - Lifetime
-
2004
- 2004-11-11 TW TW093134500A patent/TWI359286B/en active
- 2004-12-07 KR KR1020040102092A patent/KR101137551B1/en active IP Right Grant
- 2004-12-09 CN CNB2004101003874A patent/CN100409044C/en active Active
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101852879A (en) * | 2009-03-30 | 2010-10-06 | 住友化学株式会社 | The manufacture method of light polarizing film |
| CN101852879B (en) * | 2009-03-30 | 2014-02-26 | 住友化学株式会社 | Process for producing a 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 |
| CN106842403A (en) * | 2015-11-27 | 2017-06-13 | 住友化学株式会社 | The manufacture method of polarizer |
| CN106950634A (en) * | 2015-11-27 | 2017-07-14 | 住友化学株式会社 | The manufacture method of polarizer and the detection method of polyvinyl alcohol |
| CN106950634B (en) * | 2015-11-27 | 2018-01-26 | 住友化学株式会社 | The manufacture method of polarizer and the detection method of polyvinyl alcohol |
| CN106772755A (en) * | 2017-02-27 | 2017-05-31 | 合肥京东方光电科技有限公司 | A kind of polaroid and liquid crystal display |
| WO2018153076A1 (en) * | 2017-02-27 | 2018-08-30 | 京东方科技集团股份有限公司 | Polarizer and liquid crystal display device |
| US11016333B2 (en) | 2017-02-27 | 2021-05-25 | Boe Technology Group Co., Ltd. | Polarizer and liquid crystal display device having porous protective layer |
| CN111279231A (en) * | 2017-10-27 | 2020-06-12 | 住友化学株式会社 | Polarizing film and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20050058196A (en) | 2005-06-16 |
| KR101137551B1 (en) | 2012-04-19 |
| TW200519427A (en) | 2005-06-16 |
| JP2005173217A (en) | 2005-06-30 |
| CN100409044C (en) | 2008-08-06 |
| TWI359286B (en) | 2012-03-01 |
| JP4394431B2 (en) | 2010-01-06 |
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