CN101387717A - Method for producing poliarization substrate - Google Patents
Method for producing poliarization substrate Download PDFInfo
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- CN101387717A CN101387717A CNA2008101769538A CN200810176953A CN101387717A CN 101387717 A CN101387717 A CN 101387717A CN A2008101769538 A CNA2008101769538 A CN A2008101769538A CN 200810176953 A CN200810176953 A CN 200810176953A CN 101387717 A CN101387717 A CN 101387717A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/10—Esters of organic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- Polymers & Plastics (AREA)
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Abstract
The invention provides a method of manufacturing a polarizing plate, over an adhesive layer, a cellulose acetate type resin film is laminated on one surface of a polarized light film made of polyvinyl alcohol type resin, and a cycloolefin type resin film is laminated on the other surface over the adhesive layer, thereby manufacturing the polarizing plate, characterized in that, before laminating the cellulose acetate type resin film and the cycloolefin type resin film, moisture ratio of the polarized light film maintains at more than 8 weight percent, and after laminating the cellulose acetate type resin film and the cycloolefin type resin film, strain keeps less than 600 N/m. The method can restrain defects of the polarizing plate, which is formed through laminating the cellulose acetate type resin film on one surface of the polarized light film made of polyvinyl alcohol type resin over the adhesive layer, and laminating cycloolefin type resin film on the other surface over the adhesive layer.
Description
Technical field
The present invention relates to stacked cellulose acetate resin film on the wherein one side of the polarization film that adhesive layer is being formed by polyvinyl alcohol resin, and make the method for polarization plates across adhesive layer stacked cyclic olefine resin molding on another side.
Background technology
Usually, polarization plates is by utilizing adhesive layer stacked guard film to constitute on the one or both sides of the polarization film that adsorbs the polyvinyl alcohol resin formation that is orientated the dichromatism pigment.Polarization plates fits on the liquid crystal cells across other pressure-sensitive adhesive for optical films as required as the component parts of liquid crystal indicator.
For polarization plates; for the characteristic that meets liquid crystal indicator requires to have various structures; usually; for diaphragm that is disposed at liquid crystal cell side or blooming phase difference characteristics there is requirement; in addition, for the clamping polarization film be disposed at the diaphragm of opposite side or blooming then according to purposes require to have dazzle (there is brightness in minute surface), character of surface such as being coated with property, anti-dazzle property (counteracting dazzle), antireflection firmly.
In TOHKEMY JP2005-208456 communique (patent documentation 1), record a kind of like this scheme, stacked cyclic olefine resin molding on the wherein one side of the polarization film that adhesive layer is being formed by polyvinyl alcohol resin, and across adhesive layer stacked cellulose acetate resin film on another side, then more easily give the cyclic olefine resin molding of phase difference characteristics and more easily give the cellulose acetate resin film of character of surface, so can extensively be suitable for various requirement owing to be disposed on each single face respectively.
In addition, a such example is disclosed in TOHKEMY 2006-106016 communique (patent documentation 2), respectively across the bonding agent that forms by the polyvinyl alcohol resin aqueous solution, stacked cyclic olefine resin (norbornene resin) film on the wherein one side of the polarization film that forms by polyvinyl alcohol resin, and stacked cellulose acetate is resin (triacetyl fiber) film on another side, to make polarization plates.
In addition; a kind of like this scheme is disclosed in TOHKEMY JP2006-313205 communique (patent documentation 3); when making polarization plates; under the tension state of the stacked film that gives polarization film and diaphragm with 60～450N/m; under the condition of 60～120 ℃ of heating-up temperatures, carry out heat treated, thereby can prevent that polarization plates is being positioned over high temperature
In high humidity environment following time, is because the shaft angle degree that pucker ﹠ bloat stress causes such as departs from the depolarization phenomenon that causes.
Yet; stacked cyclic olefine resin molding on the wherein one side of the polarization film that is forming by polyvinyl alcohol resin across adhesive layer; and in the polarization plates of adhesive layer stacked cellulose acetate resin film on another side; owing to the diaphragm clamping polarization film that forms by different resins; so cause the physical property, thermal property, engineering properties etc. of each diaphragm to produce difference, polarization plates will be easy to form defective.For example there is such problem, after polarization film is used the diaphragm clamping, produces concavity defect in the polarization plates.
In indoor polarization plates the light of fluorescent light is reflected, when its reflection image of visual inspection, for the zero defect polarization plates, the visible fluorescence lamp profile is clear and undistorted, and for the above-mentioned polarization plates that concavity defect is arranged, can see the reflection image of fluorescent light distortion.If in liquid crystal indicator, be suitable for polarization plates with such defective, at this defect part image with distortion.Therefore, rolling up in the polarization plates severing of cylinder shape to become to conform with when being suitable for liquid crystal indicator size product size, contain defect part and go out of use as defective.Therefore, it is very important reducing such generation of defects in the polarization plates manufacturing.
Summary of the invention
The present invention is for solving the problems of the technologies described above, purpose be to provide a kind of on the wherein one side of the polarization film that adhesive layer is being formed by polyvinyl alcohol resin stacked cyclic olefine resin molding, and across the manufacture method of adhesive layer polarization plates of stacked cellulose acetate resin film on another side, this method can suppress the polarization plates defective and produce.
The invention provides a kind of manufacture method of polarization plates, stacked cyclic olefine resin molding on the wherein one side of the polarization film that adhesive layer is being formed by polyvinyl alcohol resin, and across adhesive layer stacked cellulose acetate resin film and make polarization plates on another side, it is characterized in that, before stacked cellulose acetate resin film and cyclic olefine resin molding, the moisture rate of polarization film is maintained more than the 8 weight %, and, on polarization film, after stacked cellulose acetate resin film and the cyclic olefine resin molding, tension force is remained below the 600N/m.
Wherein preferably, before stacked cellulose acetate resin film and cyclic olefine resin molding, the moisture rate of polarization film is maintained more than the 8 weight % below the 12 weight %.
Preferably, in polarization plates manufacture method of the present invention, on polarization film after stacked cellulose acetate resin film and the cyclic olefine resin molding, remain tension force below the 600N/m and carry out drying.
According to the present invention; because stacked resin molding not of the same race on the two sides of the polarization film that forms by polyvinyl alcohol resin; so; the polarization plates of the diaphragm that forms with all stacked same resin in two sides is compared; can realize satisfying the required and polarization plates of giving various characteristics of its purposes, and can be in the industrial few polarization plates of defective that effectively produces.
Description of drawings
Fig. 1 schematically shows the polarization film in the polarization plates manufacture method of the present invention and the stacked oblique view of cellulose acetate resin film and cyclic olefine resin molding.
Symbol description
1-polarization film, 2-cellulose acetate resin film, 3-cyclic olefine resin molding, 4-polarization plates, 5a, 5b-nip rolls (nip roll)
Embodiment
The prerequisite of the manufacture method of polarization plates of the present invention be a kind of on the wherein one side of polarization film that adhesive layer is being formed by polyvinyl alcohol resin stacked cyclic olefine resin molding, and make the method for polarization plates across adhesive layer stacked cellulose acetate resin film on another side.
The polyvinyl alcohol resin that constitutes used polarization film in the manufacture method of the present invention is by being that the resin saponification obtains with polyvinyl acetate.As polyvinyl acetate is resin, except the homopolymer of vinyl acetate is the polyvinyl acetate, also for example can be vinyl acetate and can with other the multipolymer etc. of monomer of its copolymerization.As with other monomers of vinyl acetate copolymerization, for example can be acrylic amide of unsaturated carbon acids, unsaturated sulfonic acid class, olefines, vinyl ethers, band ammonium etc.The saponification degree of polyvinyl alcohol resin is generally 85～100 moles of %, is preferably more than 98% mole.Modification can also further take place in this polyvinyl alcohol resin, for example can also use aldehydes modified polyethylene alcohol formal (Port リ PVC ニ Le Port リ マ-Le), polyvinyl acetal etc.In addition, the average degree of polymerization that constitutes the polyvinyl alcohol resin of polarization film is generally 1000～10000, is preferably 1500～5000.
Described polyvinyl alcohol resin is made the common primary film as polarization film of membranaceous film body (polyvinyl alcohol resin film).Then be not particularly limited as method, adopt known method system film to get final product polyvinyl alcohol resin system film.The thickness of polyvinyl alcohol resin film is not particularly limited, and for example is 10～150 μ m.
Polarization film produces through following step usually, that is, with the step of this polyvinyl alcohol resin film unilateral stretching, with the dichromatism pigment polyvinyl alcohol resin film is dyeed and make it to adsorb the step of this dichromatism pigment, the polyvinyl alcohol resin film that will adsorb the dichromatism pigment is placed on step of handling in the boric acid aqueous solution and the step of washing after being handled by this boric acid aqueous solution.
Unilateral stretching can be carried out before dyeing, also can carry out simultaneously with dyeing, also can carry out after dyeing.When carrying out unilateral stretching after dyeing, this unilateral stretching can be carried out before boric acid is handled, and also can carry out in boric acid is handled.Certainly, also can in a plurality of stages in these stages, carry out unilateral stretching.For unilateral stretching, can unilateral stretching between the cylinder of different rotating speeds, also can adopt the hot-rolling unilateral stretching.In addition, can also be dry type stretching such as in atmosphere, stretch, also can be the wet type that stretches under wet face state in solvent stretches.Stretching ratio is generally 3-8 doubly.
When adopting the dichromatism pigment that the polyvinyl alcohol resin film is dyeed, for example can in the aqueous solution that contains the dichromatism pigment, flood the polyvinyl alcohol resin film.Concrete, as the dichromatism pigment, can adopt iodine, dichroic dye.In addition, the polyvinyl alcohol resin film preferably carries out the entry dip treating in advance before dyeing is handled.
As the dichromatism pigment, when adopting iodine, adopt the method that dipping polyvinyl alcohol resin film dyes in the aqueous solution that contains iodine and potassium iodide usually.The amount of iodine is generally per 100 weight parts waters and contains 0.01～1 weight portion in this aqueous solution, and normally per 100 weight parts waters of the amount of potassium iodide contain 0.5～20 weight portion.The temperature of the aqueous solution of using in the dyeing is generally 20～40 ℃, and in addition, the dip time in this aqueous solution (dyeing time) is generally 20～1800 seconds.
On the other hand, as the dichromatism pigment, when adopting dichroic dye, adopt the method that dipping polyvinyl alcohol resin film dyes in containing the aqueous solution of water-soluble dichroic dye usually.The water of normally per 100 weight portions of the amount of the dichroic dye in this aqueous solution contains 1 * 10
-410 weight portions are preferably 1 * 10
-3～1 weight portion.This aqueous solution also can contains sodium sulfate etc. inorganic salts as dyeing assistant.Dyeing is generally 20～80 ℃ with the temperature of aqueous dye solutions, and in addition, the dip time in this aqueous solution (dyeing time) is generally 10～1800 seconds.
Boric acid behind the dichromatism pigment dyeing is handled by the polyvinyl alcohol resin film immersion with dyeing and is carried out in the boronic acid containing aqueous solution.Boric acid amount in the boronic acid containing aqueous solution per 100 weight parts waters usually contains 2～15 weight portions, preferably contains 5～12 weight portions.When adopting iodine, preferably contain potassium iodide in this boronic acid containing aqueous solution as the dichromatism pigment.Potassium iodide amount in the boronic acid containing aqueous solution per 100 weight parts waters usually contains 0.1～15 weight portion, preferred 5～12 weight portions.Dip time is generally 60～1200 seconds in the boronic acid containing aqueous solution, is preferably 150～600 seconds, more preferably 200～400 seconds.The temperature of boronic acid containing aqueous solution is preferably 50～85 ℃ usually more than 50 ℃, more preferably 60～80 ℃.
Polyvinyl alcohol resin film after boric acid is handled is handled through washing usually.Washing is for example handled and can be carried out in water by the polyvinyl alcohol resin film immersion after boric acid is handled.The temperature of the water during washing is handled is generally 5～40 ℃, and dip time is generally 1～120 second.Carry out dried after the washing and obtain polarization film.
Dried adopts air drier, far infra-red heater to carry out usually.The dried temperature is generally 30～100 ℃, is preferably 50～80 ℃.The dried time is generally 60～600 seconds, is preferably 120～600 seconds.
Like this, the polyvinyl alcohol resin film is carried out unilateral stretching, dichromatism pigment dyeing and boric acid processing and obtains polarization film.The thickness of this polarization film is usually in 5～40 mu m ranges, preferably in 10～35 mu m ranges.In the polarization plates manufacture method of the present invention, stacked cellulose acetate resin film on the wherein one side of the polarization film that adhesive layer is being formed by polyvinyl alcohol resin is made polarization plates across adhesive layer stacked cyclic olefine resin molding on another side.
As the cyclic olefine resin molding that adopts in the manufacture method of the present invention, for example can be have by as norborene, encircle the film of thermoplastic resin (the being also referred to as thermoplasticity cyclic olefine resin) system of the monomeric unit that the annular alkene (cycloolefin) the norborneol alkene monomer forms more.In the present invention, the cyclic olefine resin can be the ring-opening polymerization polymer of above-mentioned cycloolefin or the hydrogenation thing that adopts the ring opening copolymer thing of the cycloolefin more than 2 kinds, also can be cycloolefin and chain alkene, have an addition polymer of the aromatics etc. of vinyl etc.In addition, the importing polar group is also very effective.
In the multipolymer of the aromatics that adopts cycloolefin and chain alkene and/or band vinyl, as chain alkene, for example can be ethene, propylene etc., in addition, the aromatics as the band vinyl for example can be styrene, α-Jia Jibenyixi, nuclear alkyl-substituted styrene etc.In such multipolymer, the monomeric unit that is formed by cycloolefin can (be preferably 15～50 moles of %) below the % for 50 moles.Especially, when the terpolymer of the aromatics that adopts cycloolefin and chain alkene and band vinyl, the amount of the monomeric unit that is formed by cycloolefin can be as above-mentioned less amount.In described terpolymer, the monomeric unit that is formed by chain alkene is generally 5～80 moles of %, and the monomeric unit that is formed by the band vinyl aromatic compounds is generally 5～80 moles of %.
The cyclic olefine resin can be suitable for suitable commercially available product, for example Topas (Ticona society system), ARTON (JSR (strain) system), ZEONOR (Japanese ZEON (strain) system), ZEONEX Japan ZEON (strain) system), APL (Mitsui Chemicals (strain) system) etc.When such cyclic olefine resin is made film, be suitable for adopting known method such as solvent injection molding, extrusion by melting.In addition, also can adopt the commercially available product of エ ス シ-Na (ponding chemical industry (strain) system), SCA40 (ponding chemical industry (strain) system), Zeonor Film ready-made cyclic olefine resin system films such as ((strain) optes systems).
The cyclic olefine resin molding can also be the film of unilateral stretching or two-way stretch.By stretching, can give the cyclic olefine resin molding with phase difference value arbitrarily.The common limit that stretches is batched film roller limit and is carried out continuously, in heating furnace, along the preceding line direction of roller, with should before vertical direction or this two direction of line direction stretch.The temperature of heating furnace usually adopts near the glass temperature of cyclic olefine resin～scope of glass temperature+100 ℃.Stretching ratio is generally 1.1～6 times, is preferably 1.1～3.5 times.
If the cyclic olefine resin molding is into volume state, the film caking that is bonded together easily each other, so, the diaphragm rolling again of fitting usually.In addition, the cyclic olefine resin molding is because generally surfactivity is poor, thus with the bonding surface of polarization film on, preferably carry out surface treatments such as plasma treatment, corona treatment, ultraviolet treatment with irradiation, flame (flame) processing, saponification processing.Especially preferred plasma treatment, the corona treatment of easily implementing.
In addition, used cellulose acetate resin film is that cellulose partly or entirely is the film of acid esterification thing in the manufacture method of the present invention, for example can be tri cellulose acetate membrane, cellulose diacetate film, cellulose acetate propionate film etc.As such cellulose acetate resin film, can be suitable for suitable commercially available product for example Off ジ Star Network TD80 (Fujiphoto (strain) system), Off ジ Star Network TD80UF (Fujiphoto (strain) system), Off ジ Star Network TD80UZ (Fujiphoto (strain) system), KC8UX2M (Konica Minolta Opt (strain) system), KC8UY (Konica MinoltaOpt (strain) system) etc.Cellulose acetate is also referred to as cellulose acetate, cellulose ethanoate.
On the surface of cellulose acetate resin film, can carry out non-glare treated, be coated with surface treatments such as processing, electrostatic prevention processing, antireflection processing firmly according to purposes.The cellulose-based resin molding of Dichlorodiphenyl Acetate can give phase difference value arbitrarily by stretching in addition.
If the cellulose acetate resin film is into volume state, the film caking that also is bonded together easily each other, so, usually the end of volume is carried out concavo-convex processing or inserted batten and rolling in the end.In addition,, be the cementability of raising, carry out saponification usually and handle with polarization film for this cellulose acetate resin film.Handle as saponification, can adopt the method that impregnated in the such alkaline aqueous solution of NaOH, potassium hydroxide.
The cyclic olefine resin molding that uses in the manufacture method of the present invention and the thin thickness of cellulose acetate resin film are a bit for well, if intensity reduces the processability variation but mistake is thin, on the other hand, if blocked up, then produce transparency and reduce problems such as polarization plates weight increasing.Therefore, the suitable thickness of these films is generally 5～200 μ m, is preferably 10～150 μ m, more preferably 20～100 μ m.
In manufacture method of the present invention, consider the cementability of cyclic olefine resin molding and cellulose acetate resin film, the tackifier that the tackifier that bonding polarization film and cyclic olefine resin molding are used, bonding polarization film and cellulose acetate resin film are used can adopt mutually different bonding agent.If easiness of operation etc. is taken into account, if cyclic olefine resin molding and cellulose acetate resin film are bonding with polarization film together, then to adopt identical tackifier be favourable on the two sides.
From the viewpoint of attenuate adhesive layer, tackifier preferably adopts the water system tackifier, is about to adhesive component and is dissolved in the water or is scattered in tackifier in the water.For example adopt polyvinyl alcohol resin, urethane resin etc. as major component usually, and, cooperate isocyanates based compound, epoxy compound etc. to make composition for improving cementability.In the occasion of the tackifier that adopts this water system, the thickness of adhesive layer below 1 μ m, even adopt ordinary optical microscope to observe the cross section, does not observe in this adhesive layer reality usually yet.
When adopting polyvinyl alcohol resin as the major component of tackifier; except partly-hydrolysed polyvinyl alcohol (PVA), fully saponified polyvinyl alcohol (PVA), can also adopt carboxy-modified polyvinyl alcohol (PVA), acetoacetyl modified polyvinylalcohol, methylol modified polyvinylalcohol, the such modified polyvinylalcohol of amino modified polyvinyl alcohol (PVA) is resin.When adopting such polyvinyl alcohol resin, the aqueous solution that adopts polyvinyl alcohol resin is as tackifier.The concentration of the polyvinyl alcohol resin in the tackifier is generally 1～10 weight portion to the water of 100 weight portions, is preferably 1～5 weight portion.
In the tackifier that forms by the polyvinyl alcohol resin aqueous solution, as mentioned above,, can cooperate epoxy compound etc. for improving cementability.The water soluble polyamide epoxy resin that in the polyamide polyamine that epoxy compound for example can adopt the reaction at the dibasic acid of polyalkylene polyamine such by diethylene triamine, trien etc. and hexane diacid etc. to obtain the chloropropylene oxide reaction is obtained.As the commercially available product of this daiamid epoxy resin, for example can be Sumirez Resin 650 (Sumica chemtex (strain) system), Sumirez Resin 675 (Sumica chemtex (strain) system), WS-525 (Japanese PMC (strain) system) etc.In the occasion that cooperates epoxy compound, its addition is generally 1～100 weight portion to the polyvinyl alcohol resin of 100 weight portions, is preferably 1～50 weight portion.
Fig. 1 schematically shows the polarization film in the polarization plates manufacture method of the present invention and the stacked skeleton view of cellulose acetate resin film and cyclic olefine resin molding.As shown in Figure 1, in polarization plates manufacture method of the present invention, after coating binder, stacked cellulose acetate resin film 2 on one of them face of the polarization film 1 that adhesive layer is being formed by polyvinyl alcohol resin, and on its another side across adhesive layer stacked ring ethylene series resin molding 3, adopt clampings such as nip rolls 5a, 5b to fit and make polarization plates 4.But polarization film 1, cellulose acetate resin film 2 and cyclic olefine resin molding 3 are transmitted at direction of transfer A shown in Figure 1 in the limit, and the limit carries out continuously that this is stacked.
Coating process as tackifier, can adopt general conventional method, for example be coated with that method, gravure are coated with method, mould is coated with method, dip coating, spray-on process etc., bonding agent coated the adhesive surface of side's film or two side's films or want method between bonding 2 films by The tape casting, meyer's method, rod.It is that the method that the limit flows down tackifier and scatters in its surface is moved on polarization film or diaphragm limit on approximate vertical direction, general horizontal direction or vergence direction between the two that The tape casting refers to coated article.
One of polarization plates manufacture method feature of the present invention is, before stacked cellulose acetate resin film 2 and cyclic olefine resin molding 3, the moisture rate of polarization film 1 maintained more than the 8 weight %.Above-mentioned stacked before, if the moisture rate deficiency of polarization film 18 weight % form easily concavity defect in the resulting polarization plates 4.Cause the reasons are as follows of such result.Be that distortion that film produces when contacting with roller exists and when showing in the defective of changing, if the moisture rate of polarization film 1 is low, then polarization film will become really up to the mark, be difficult to relax the distortion that is produced, easy residual concavity defect promptly when inferring concavity defect.On the other hand, if the moisture rate of above-mentioned stacked polarization film 1 before is too high, then polarization film 1 is dry insufficient, because the drying of protective film poststack, polarization film 1 will shrink, and the polarization plates 4 that obtains is easy to generate inequality (system ラ) shape defective.Therefore, preferred above-mentioned moisture rate is below 20 weight %.Further preferably, above-mentioned moisture rate is in the scope of 8～12 weight %.
About above-mentioned moisture rate, for example before stacked cellulose acetate resin film 2 and cyclic olefine resin molding 3 with polarization film 1 in 105 ℃ baker dry 1 hour, calculate with the weight of following formula by these front and back.
Moisture rate=[1-(dry back weight)/(weight before dry)] * 100 (%)
In addition, for before stacked cellulose acetate resin film 2 and cyclic olefine resin molding 3, the moisture rate of polarization film 1 is maintained more than the 8 weight %, and particularly, the temperature and time when making as mentioned above polyvinyl alcohol resin film after cleaning dry is suitably adjusted and is got final product.Particularly, if 1 drying oven is only arranged,, can adjust the moisture rate of polarization film 1 by suitable adjustment temperature and the hold-up time wherein.In addition, the drying oven of 2 or 2 above multistages is set, the method for adjusting the hold-up time in each kiln temperatures, each drying oven is also very effective.
In addition, one of feature of polarization plates manufacture method of the present invention is, after stacked cellulose acetate resin film 2 and the cyclic olefine resin molding 3, tension force is remained below the 600N/m on polarization film 1.When mentioned strain surpasses 600N/m, be easy to generate concavity defect in the resulting polarization plates.Infer why such reason is that tension force is big more, then the distortion that produces when film contacts with roller is big more.On the other hand, cross when low at mentioned strain, owing to be easy to generate bending (う ね り) in resulting polarization plates, preferred mentioned strain is more than 100N/m.Further preferred mentioned strain is in the scope of 300～500N/m.Example as shown in Figure 1 for example, tension force in polarization film 1 after stacked cellulose acetate resin film 2 and the cyclic olefine resin molding 3 can be adjusted by the tractive force that holds them nip rolls 5a, 5b therebetween and be located between other the nip rolls (not shown) in its downstream.
In the manufacture method of polarization plates of the present invention, preferred stacked cellulose acetate resin film 2 and on another face after the stacked cyclic olefine resin molding 3 on one of them face of 1 on the polarization film as mentioned above remains tension force below the 600N/m and carries out dried.As mentioned above; the tension force that produces in the stacked film can be adjusted by clamping nip rolls 5a, 5b as shown in Figure 1 and the tractive force of being located between other the nip rolls (not shown) in its downstream; but; the nip rolls in downstream is located near the downstream (for example the outlet of drying oven) of drying oven more, so continue to keep the tension force after the stacked guard film and carry out dried be very favourable to device.Therefore, the mentioned strain during dried is also the same with the stacked tension force afterwards of diaphragm, preferably at 100～600N/m, more preferably in the scope of 300～500N/m.
Dried for example can be undertaken by blowing hot-air, but the temperature of this moment suitably is selected from 40～100 ℃ usually, is preferably selected from 60～100 ℃ scope.Be generally 20～1200 seconds drying time.After drying preferably further room temperature (20 ℃) or than room temperature high slightly temperature for example placed 12～600 hours under 20～50 ℃ the temperature.Temperature during placement is set to such an extent that the temperature that adopts when dry is lower usually.
As mentioned above, the polarization plates that is obtained by manufacture method of the present invention is formed with adhesive layer usually on its one or both sides.When only on single face, adhesive layer being set, be provided with in any side of stacked ring ethylene series resin molding side, stacked cellulose acetate resin film side and all can, but, when being applicable to this polarization plates in the liquid crystal indicator, because be mostly the stacked side direction of cyclic olefine resin molding liquid crystal cells, so form adhesive layer in the stacked side of cyclic olefine resin molding usually.The thickness of adhesive layer is generally 5～100 μ m, is preferably 5～40 μ m.If adhesive layer crosses thin then cohesive reduces the blocked up shortcomings such as leakage that then are easy to generate bonding agent.
The bonding agent that is used to form adhesive phase normally passes through acrylic resin, phenylethylene resin series, organic siliconresin etc. as base resin, in wherein adding the crosslinking chemical be selected from isocyanate compound, epoxy compound, aziridine cpd etc., further add component such as silane coupling agent and form.
Diffusion barrier after handle with the demoulding usually on the surface of formed adhesive layer protects.Diffusion barrier was being peeled off polarization plates before applyings such as liquid crystal cells.
The polarization plates of band adhesive phase has the big roll material of shape, sheet material form usually, is the polarization plates that obtains having the regulation shape and see through axle, adopts the parting tool with sharp keen blade to cut off (severing).Therefore, in the polarization plates small pieces (chip) that cut-out obtains, will produce the state that polarization film exposes to the outside at peripheral end.If the polarization plates small pieces under this state are for example carried out endurancings such as thermal shock test, then compare with the normally used polarization plates polarization plates of the stacked cellulose acetate resin film in polarization film two sides (for example), more be easy to generate peel off, shortcoming such as crackle.Therefore, for the polarization plates small pieces of the polarization plates of utilizing manufacture method of the present invention to obtain, preferably adopt high-speed metal cutting etc. that peripheral end is cut away continuously.
List experimental example below the present invention is made explanation in further detail, but the present invention is not limited only in these experimental examples.In the example, the % of expression amount refers to weight basis if not otherwise specified.
＜experimental example 1 〉
At average degree of polymerization is about 2400, saponification degree more than 99.9%, thickness is that the polyvinyl alcohol film of 75 μ m keeps flooding swelling in 30 ℃ pure water, in wherein being stretched to 1.3 times of stretching ratios in the longitudinal direction under the situation of tense situation.This polyvinyl alcohol film is being kept under the state of described stretching ratio, (dye among iodine: potassium iodide: water=0.05:2:100 (weight ratio) in 30 ℃ the aqueous solution that contain iodine and potassium iodide, afterwards, in 54 ℃ the aqueous solution that contain potassium iodide and boric acid (potassium iodide: boric acid: water=12:5:100 (weight ratio)), carry out crosslinking Treatment, after stretching with 5.6 times of total multiplying powers simultaneously, in 12 ℃ pure water, clean.Making polyvinyl alcohol film after cleaning remain these 3 drying ovens of 65 ℃, 75 ℃ and 85 ℃ successively by temperature, is dry under 169 seconds such conditions adding up to the hold-up time, obtains the sample 1～5 of the polarization film of iodine absorption orientation in polyvinyl alcohol (PVA).At the sample 1～5 that obtains, drying is 1 hour in 105 ℃ baker, if utilize following formula to calculate moisture rate from this front and back weight, then it is 5%.
Moisture rate=[1-(dry back weight)/(weight before dry)] * 100 (%)
In addition, in the water of 100 weight portions, ((Sumirez Resin 650 (Sumica chemtex (strain) system) (Gu forming aqueous solution of branchs concentration 30%), modulate with the polyvinyl alcohol resin is the water system tackifier of major component to the water soluble polyamide epoxy resin of KURARAY POVAL KL318 (KURARAY (strain) system) and 1.5 weight portions to dissolve the carboxy-modified polyvinyl alcohol (PVA) of 3 weight portions.
As shown in Figure 1, respectively across above-mentioned tackifier, at stacked norbornene resin system film (Zeonor Film (strain) optes system), thickness after carrying out corona treatment in advance on one of them face of the sample 1～5 of polarization film: 80 μ m), at stacked cellulose triacetate system film (KC8UX2M (Konica Minolta Opt (strain) system), thickness: 80 μ m), and fit after carrying out saponification in advance and handling on another face by nip rolls.At this moment, suitably adjust, and change tension force behind sample 1～5 stacked fitting with nip rolls and being arranged near its downstream (this example is located at the drying oven outlet) nip rolls.After this, the limit keeps each tension force limit in 80 ℃ of dryings 5 minutes, obtains the sample 1～5 of polarization plates.
On the other hand, the same mode with making above-mentioned sample 1～5, use 3 respectively the 1st phase temperature remain 50 ℃, the 2nd phase temperature remains 65 ℃, the 3rd phase temperature remains 85 ℃ drying oven, be produced on that to add up to the hold-up time be to carry out drying under 169 seconds the condition to make its moisture rate be 7.9% polarization film sample 6, except the 2nd phase temperature being remained 60 ℃ and under the condition identical, carrying out drying and make it the sample 7 that moisture rate is 9.1% polarization film with sample 6, and except will add up to the hold-up time be 162 seconds and with sample 7 the same terms under carry out drying and make it the sample 8 that moisture rate is 9.5% polarization film, at these samples 6～8, all the tension force after stacked is all remained 448N/m, make the sample 6～8 of polarization plates in the same way.
In sample 1～8 that make polarization plates o'clock, the overlooker examines the polarization plates that comes from drying oven with observing, and whether the reflection image of observing the fluorescent lamp that reads on the polarization plates surface has distortion, to judge whether concavity defect is arranged.As mentioned above, at concavity defect where, then can observe the fluorescent light reflection image and have distortion.And for the current direction length 100m of the polarization plates of producing on the production line, observing concavity defect as mentioned above has what, and defective what are judged.(individual/100m) mode is shown in Table 1 with the defective number of every 100m length with the result.
Table 1
| Moisture rate (%) | Tension force (N/m) | Concavity defect occur number (individual/100m) | Remarks | |
| |
5 | 821 | >100 | Relatively |
| |
5 | 672 | >100 | Relatively |
| |
5 | 597 | 50～100 | Relatively |
| |
5 | 522 | 25～50 | Relatively |
| Sample 5 | 5 | 448 | 10 | Relatively |
| Sample 6 | 7.9 | 448 | 1～10 | Relatively |
| Sample 7 | 9.1 | 448 | <1 | The present invention |
| Sample 8 | 9.5 | 448 | <1 | The present invention |
By table 1 as seen, though the moisture rate of polarization film remained 5% o'clock, tension force reduces, and can reduce the recess defective, even tension force is reduced to 448N/m, also is to observe the concavity defect (sample 5) that there are about 10 in every polarization plates 100m length.On the other hand, keeping tension force be this 448N/m, and the polarization film moisture rate is changed, and then during the occasion (9.1% or 9.5%) of the moisture rate of stipulating in the present invention more than 8%, does not then observe concavity defect (sample 7 and 8) basically.
Above disclosed example and embodiment to should be understood to all places all be exemplary but not determinate.The scope of the invention is not limited among the above-mentioned explanation, but is limited by the claim scope, all is contained among the present invention with all changes of making in claim scope equivalents or the scope.
Claims (3)
1. the manufacture method of a polarization plates, stacked cellulose acetate resin film on the wherein one side of the polarization film that adhesive layer is being formed by polyvinyl alcohol resin, and, make polarization plates thus across adhesive layer stacked cyclic olefine resin molding on another side, it is characterized in that
Before stacked cellulose acetate resin film and cyclic olefine resin molding, the moisture rate of polarization film is maintained more than the 8 weight %, and on polarization film, after stacked cellulose acetate resin film and the cyclic olefine resin molding, tension force is remained below the 600N/m.
2. the manufacture method of polarization plates as claimed in claim 1 is characterized in that, before stacked cellulose acetate resin film and cyclic olefine resin molding, the moisture rate of polarization film is maintained more than the 8 weight % and below the 12 weight %.
3. the manufacture method of polarization plates as claimed in claim 1 or 2 is characterized in that, after stacked cellulose acetate resin film and the cyclic olefine resin molding, the limit remains 600N/m with tension force and carries out drying with bottom on polarization film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007239458 | 2007-09-14 | ||
| JP2007239458A JP5083815B2 (en) | 2007-09-14 | 2007-09-14 | Manufacturing method of polarizing plate |
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|---|---|
| CN101387717A true CN101387717A (en) | 2009-03-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008101769538A Pending CN101387717A (en) | 2007-09-14 | 2008-09-09 | Method for producing poliarization substrate |
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| Country | Link |
|---|---|
| JP (1) | JP5083815B2 (en) |
| KR (1) | KR101468225B1 (en) |
| CN (1) | CN101387717A (en) |
| TW (1) | TWI432492B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102262259A (en) * | 2011-08-16 | 2011-11-30 | 深圳市盛波光电科技有限公司 | Thin integrated three-dimensional (3D) display polarizer and manufacturing method thereof |
| CN106054302A (en) * | 2015-04-10 | 2016-10-26 | 柯尼卡美能达株式会社 | Polaroid protection film, polaroid therewith, and manufacturing method for polaroid protection film |
| CN107111033A (en) * | 2014-11-04 | 2017-08-29 | 住友化学株式会社 | The manufacture method of polarization plates plates |
| CN113272114A (en) * | 2019-01-23 | 2021-08-17 | 日本瑞翁株式会社 | Laminate, polarizing plate, method for producing laminate, method for producing polarizing plate, and method for producing display device |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6462199B2 (en) * | 2012-12-04 | 2019-01-30 | 住友化学株式会社 | Manufacturing method of polarizing film and polarizing plate |
| CN103076648B (en) * | 2013-01-31 | 2015-07-15 | 佛山纬达光电材料有限公司 | Simple manufacturing method and device of polarizing elements for laboratory |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3503830B2 (en) * | 1993-10-21 | 2004-03-08 | 日本合成化学工業株式会社 | Polarizer |
| JP2006106016A (en) * | 2004-09-10 | 2006-04-20 | Sumitomo Chemical Co Ltd | Polarizing plate and manufacturing method therefor |
| JP2006313205A (en) * | 2005-05-06 | 2006-11-16 | Nitto Denko Corp | Manufacturing method of polarizing plate, the polarizing plate obtained thereby, optical film and image display apparatus using the same |
-
2007
- 2007-09-14 JP JP2007239458A patent/JP5083815B2/en active Active
-
2008
- 2008-09-09 CN CNA2008101769538A patent/CN101387717A/en active Pending
- 2008-09-09 TW TW097134491A patent/TWI432492B/en not_active IP Right Cessation
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102262259A (en) * | 2011-08-16 | 2011-11-30 | 深圳市盛波光电科技有限公司 | Thin integrated three-dimensional (3D) display polarizer and manufacturing method thereof |
| CN107111033A (en) * | 2014-11-04 | 2017-08-29 | 住友化学株式会社 | The manufacture method of polarization plates plates |
| CN107111033B (en) * | 2014-11-04 | 2019-04-30 | 住友化学株式会社 | The manufacturing method of polarization plates plates |
| CN106054302A (en) * | 2015-04-10 | 2016-10-26 | 柯尼卡美能达株式会社 | Polaroid protection film, polaroid therewith, and manufacturing method for polaroid protection film |
| CN113272114A (en) * | 2019-01-23 | 2021-08-17 | 日本瑞翁株式会社 | Laminate, polarizing plate, method for producing laminate, method for producing polarizing plate, and method for producing display device |
| CN113272114B (en) * | 2019-01-23 | 2023-11-07 | 日本瑞翁株式会社 | Laminate, polarizing plate, method for producing laminate, method for producing polarizing plate, and method for producing display device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009069624A (en) | 2009-04-02 |
| KR101468225B1 (en) | 2014-12-03 |
| JP5083815B2 (en) | 2012-11-28 |
| TWI432492B (en) | 2014-04-01 |
| KR20090028445A (en) | 2009-03-18 |
| TW200920771A (en) | 2009-05-16 |
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