CN1853895A - Method for producing polyvinyl alcohol thin film - Google Patents
Method for producing polyvinyl alcohol thin film Download PDFInfo
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- CN1853895A CN1853895A CNA2006100794571A CN200610079457A CN1853895A CN 1853895 A CN1853895 A CN 1853895A CN A2006100794571 A CNA2006100794571 A CN A2006100794571A CN 200610079457 A CN200610079457 A CN 200610079457A CN 1853895 A CN1853895 A CN 1853895A
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- Prior art keywords
- film
- polyvinyl alcohol
- pva
- constant voltage
- roller
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 80
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 80
- 238000004519 manufacturing process Methods 0.000 title description 6
- 239000010409 thin film Substances 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 42
- 238000007766 curtain coating Methods 0.000 claims description 37
- 238000002360 preparation method Methods 0.000 claims description 16
- 230000010148 water-pollination Effects 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000005266 casting Methods 0.000 abstract description 7
- 239000010408 film Substances 0.000 description 126
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 230000010287 polarization Effects 0.000 description 21
- 239000004014 plasticizer Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 16
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 239000012190 activator Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 10
- -1 phthalate compound Chemical class 0.000 description 10
- 238000007127 saponification reaction Methods 0.000 description 10
- 230000004075 alteration Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004043 dyeing Methods 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- 230000004927 fusion Effects 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical compound N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- MCUCPXGEGOVZCU-UHFFFAOYSA-N [Na].C(CCCCC(=O)OCC(C)C)(=O)OCC(C)C Chemical compound [Na].C(CCCCC(=O)OCC(C)C)(=O)OCC(C)C MCUCPXGEGOVZCU-UHFFFAOYSA-N 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Chemical group 0.000 description 1
- 150000001342 alkaline earth metals Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- DROMNWUQASBTFM-UHFFFAOYSA-N dinonyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCC DROMNWUQASBTFM-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007601 warm air drying Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
- B29K2029/04—PVOH, i.e. polyvinyl alcohol
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Moulding By Coating Moulds (AREA)
- Polarising Elements (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a preparing method of polyvinyl alcohol film, which is characterized by the following: the doctor-blade casting stability and stripping stability is sourced from constant pressure suction device on the carrying-falling region of doctor-blade drum or purifying rod on the stripping region or constant pressure suction device and purifying rod to remove pressure and steam along breadth direction at constant speed.
Description
The cross reference of related application
The application requires the priority of the Korean application No.10-2005-035854 of submission on April 29th, 2005, introduces its disclosure content herein as a reference.
Invention field
The present invention relates to a kind of method that is used to make polyvinyl alcohol film, more specifically, be used to make difference in thickness by making film and delay (retardation) deviation optimization have obvious improvement characteristic (such as, transmissivity, polarization efficiency and aberration) the method for polyvinyl alcohol film, the curtain coating of film stability and peel off stability and be derived from wherein by go up installation constant voltage suction means in the Luo Zai district (landing zone) of curtain coating drum, or by the purification roller is installed on the stripping area of film, or by the constant voltage suction means being installed and being purified roller the two realizes inhaling effective removal of pressing (pinning) and moisture with constant speed broad ways.
Background of invention
Usually, polarization film prepares by being clipped between the protective layer of cellulose triacetate (TAC) film with polyvinyl alcohol (hereinafter being called PVA) film dyeing, uniaxial tension and with it.It is widely used in liquid crystal indicator.
In order to reach uniform polarization, use have homogeneous thickness, uniformly the dichroic dyestuff dyeability, do not have the PVA film of the cohesive etc. of any spot (spot), it is necessary particularly forming uniform PVA film.In this PVA resin, be different from typical thermoplastic resin, its melt temperature and decomposition temperature are very close to each other.Therefore, can not use conventional melt processing method and form film.So, in the manufacture process of PVA film, add excessive plasticizer (such as, water, polyol and phthalate compound) reduce processing temperature.
Flow of solution casting and extrusion molding are generally used for making the PVA film, and wherein the flow of solution casting is implemented behind the solution for preparing the low concentration with about 5-20wt% by the time of the PVA resin being dissolved length in suitable solvent (comprising water).It is the water of hundreds of wt% that this method also needs the dry excessive weight based on final film of drying steps, so it is uneconomic.
Because the above-mentioned shortcoming of flow of solution casting, extrusion molding is being made the welcome that is subjected to people aspect the PVA film more, and it utilizes extruder to implement, and it is consuming time shorter and can process under higher concentration than the flow of solution casting.
In extruder the polymer melt of fusion be forced to by die head with the shape that produces film and in the curtain coating drum of preheating curtain coating, be transformed into it stable solid-state from unsettled molten state by water content being brought down below an appropriate amount.Day disclosure No.2001-315143 has disclosed the curtain coating drum outside and has adopted warm air or hot-air drying, thereby can remove the moisture that produces from film effectively.Yet, when film falls to being downloaded on the curtain coating drum, this warm air or hot-air can produce vibrations to the film of fusion, and, although it can remove moisture effectively from the surface of the film that is exposed to air, but it can not remove moisture from the surface that contacts with the curtain coating drum, thereby causes the uneven distribution of moisture in film.This inhomogeneous and then cause thickness, refractive index etc. to lack homogeneity.
Polarization film prepares by utilizing the PVA film to carry out swelling, stretching, dyeing, fixation (fixation), washing and drying steps.Stretching step can adopt two kinds of diverse ways to implement: dry method and wet method.If film is inhomogeneous during the swelling step, it can become wrinkling during stretching step, and perhaps because the dyeing of carrying out during staining procedure is inhomogeneous, it can can't produce good color homogeneity.
For using PVA film preparation polarization film, owing to the scrambling of uneven curtain coating and the irregular difference in thickness of peeling off the film that causes and delay be important disadvantages and to the demand of the polarization film that is used for liquid crystal indicator along with the demand to large tracts of land and high-quality LCD increases.
Summary of the invention
The present invention relates to a kind of method that is applicable to the polyvinyl alcohol film of producing LCD that is used to make, than conventional film, thickness and the difference optimization of delay and can more significantly improve performance such as polarization efficiency, transmissivity, color fidelity of this method by making film, wherein this optimized difference is derived from installs the constant voltage suction means that comprises two passages in the Luo Zai district of curtain coating drum, design this constant voltage suction means and apply uniform suction to control suction and to run through film; Perhaps on the stripping area of film, install and purify roller; The constant voltage suction means perhaps is installed and purify roller the two, thereby in the preparation process of PVA film, fall to being downloaded on the casting roller when solidifying from die head when unsettled fused films, make broad ways inhale and press, remove the moisture that in this technology, produces effectively and produce uniform surface tension with constant speed.
Therefore, in one embodiment of the invention, provide that a kind of the two makes the method for polyvinyl alcohol film by installing and use constant voltage suction means that comprises two passages in the Luo Zai district of curtain coating drum or the purification roller on the stripping area at film or constant voltage suction means and purification roller.
The accompanying drawing summary
Above-mentioned aspect of the present invention and further feature will explain in ensuing detailed description, in conjunction with the accompanying drawings, and wherein:
Fig. 1 illustrates the schematic diagram that is used to make the method for polyvinyl alcohol film according to of the present invention.
Detailed Description Of The Invention
The present invention aims to provide a kind of method for the manufacture of polyvinyl alcohol film, in making the process of polyvinyl alcohol film the method utilization in the Luo Zai district of curtain coating drum the constant voltage suction means that comprises two passages or the purification roller on the stripping area at film or utilize simultaneously the constant voltage suction means and purify roller the two, wherein polyvinyl alcohol film is through extruder 30, filter 40, gear pump 50 and die head 60 shapings and curtain coating on curtain coating drum 70.
The present invention is specified in hereinafter.
The present invention relates to a kind of method that is applicable to the polyvinyl alcohol film of producing LCD that is used to make, than conventional film, thickness and the difference optimization of delay and can more significantly improve performance such as polarization efficiency, transmissivity, color fidelity of this method by making film, wherein this optimized difference is derived from installs the constant voltage suction means that comprises two passages in the Luo Zai district of curtain coating drum, design this constant voltage suction means and apply uniform suction to control suction and to run through film; Perhaps on the stripping area of film, install and purify roller; The constant voltage suction means perhaps is installed and purify roller the two, thereby in the preparation process of PVA film, be unloaded on the casting roller when solidifying from die head when unsettled fused films, make broad ways inhale and press, remove the moisture that in this technology, produces effectively and produce uniform surface tension with constant speed.
Saponification degree is represented with the degree of hydroxylation of the acetate group in polyvinyl alcohol (PVA) chain.Even PVA has identical molecular weight, also depend on saponification degree and be classified as water-soluble, slightly water-soluble and water-insoluble.Above-mentioned classification is based on the following fact: when size was replaced by the hydroxyl of reduced size greater than the acetate group of hydroxyl, the interval between strand narrowed down, thereby forms stronger hydrogen bond between hydroxyl.
By above-mentioned reasoning as can be seen, the formation of insoluble substance is to be caused by the strong hydrogen bonding between the PVA molecular resin chain in the PVA melt.Especially, between strand, have stronger hydrogen bond, adopt simple extrusion molding to be difficult to produce the not molten mass completely of residual insoluble substance because have the PVA resin of 99.9mol% saponification degree.
Therefore, before extrusion process, it is important that the hydrogen bond that forms between the PVA strand is remained on minimum level.In saponification process (it is the pilot process of preparation PVA resin), adding and dipping (impregnate) are by the anionic hydrophilic activator of formula 1 expression and nonionic hydrophily activator and the plasticizer of being represented by formula 2.
R wherein
1Be H or COOR
2, R
2For H or have the alkyl of 1-20 carbon atom, M is alkali metal or alkaline-earth metal, and m is the integer of 1-20, and n is the integer of 0-20, and x is the integer of 1-7 and (x+y) is the integer of 9-11.
The nonionic hydrophily activator of anionic hydrophilic activator that employed hydrophily activator is a formula 1 and formula 2 is used to improve the surface tension and the contact angle of PVA film.
More preferably use the compound of formula 2, wherein m is the integer of 3-18.
The consumption of each anionic hydrophilic activator and nonionic hydrophily activator is the 0.001-0.3 weight portion, and preferred 0.002-0.1 weight portion is respectively based on 100 weight portion PVA resins.
If the consumption of every kind of hydrophily activator is less than 0.001 weight portion, then activator to the effect of surface tension and contact angle with variation.Opposite, if consumption surpasses 0.3 weight portion, will be in storage process owing to adhering between film produces fold.Therefore, it is required keeping above-mentioned scope, thereby uniform swelling, dyeing and drying are provided, and forms the polarization film with good color fidelity thus.
In addition, use typical plasticizer reducing the temperature during the extrusion process in the present invention, and avoid forming the hydrogen bond between the strand, thereby allow the interval between the strand.Can from many alkyl compounds, water and phthalic acid ester, select at least two kinds of plasticizer.The example of many alkyl compounds comprises glycerine, ethylene glycol, propane diols, diethylene glycol (DEG) and triethylene glycol.The example of phthalate compound comprises dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, diisooctyl phthalate, dinonyl phthalate, diisononyl phthalate and diisooctyl phthalate.
Plasticizer comprises many alkyl compounds of 1-35 weight portion, preferred 5-25 weight portion; The water of 30-350 weight portion, preferred 80-250 weight portion; With the phthalate compound of 1-100ppm, preferred 3-50ppm.
If the many alkyl compounds that are contained in the plasticizer are less than 1 weight portion, it will can not produce any obvious effects.Simultaneously, if its content in plasticizer can't be removed it in the manufacture process of polarization film fully greater than 35 weight portions, it will be residual to a certain extent, thereby can make the optical characteristics deterioration of resulting polarization film, and make the flexible excessive of polarization film and can not handle.In addition, if the water yield that is contained in the plasticizer is less than 30 weight portions, it will cause the thermal decomposition of polyvinyl alcohol.On the contrary, if its content greater than 350 weight portions, it will become and be difficult to handle (for example, the conveying in extruder 30) and because moisture to be removed makes processing invalid too much.In addition, if the phthalate compound that is contained in the plasticizer is less than 1ppm, it will cause the effect of difference.On the contrary, if its content surpasses 100ppm, it will reduce the transmissivity of film.Therefore, preferably keep above-mentioned scope.
Especially, use many alkyl compounds (such as, glycerine) and phthalic acid ester during as the component of plasticizer, with only make water and compare as the situation of plasticizer, produced lower volatility, therefore more effectively avoided hydrogen bond formation, improved stability, long-time stability of preserving and reduced viscosity between the contained compound, therefore improved flowability.
These effects make material in extrusion process from screw rod feeding machine 20 charging equably, this film that causes making has homogeneous thickness.
Extrude according to method well known in the art by the polyvinyl alcohol resin compound that dipping hydrophily activator and plasticizer during the saponification process prepare.When resin complexes at 50 ℃-150 ℃, preferred 80 ℃-120 ℃ when extruding, have undissolved material hardly, thereby uniform melt be provided.If temperature is lower than 50 ℃, the PVA resin is not fusion, thereby can not extrude.On the contrary, if be higher than 150 ℃, it causes the portion of hot of PVA resin to decompose, and causes the color deterioration thus.Therefore, preferably keep said temperature.
Then, melt is by filter 40, gear pump 50 and die head 60 and be configured as the shape of film, its curtain coating in rotary-type curtain coating drum 70 of now.For the PVA film is carried out uniform curtain coating, install in the Luo Zai district of curtain coating drum install on the constant voltage suction means 80 that comprises two passages or the stripping area at film purify roller or the constant voltage suction means is installed and the purification roller the two.
At this, the constant voltage suction means comprises two passages and this constant voltage suction means of design applies uniform suction to be used to controlling suction and to run through film.
Therefore, when this controlled constant suction ran through film and applies, it made to inhale with constant speed along width of film and presses and avoids moisture to flow into effectively or be condensed between the surface and curtain coating drum 70 of film, thus produce height fall to carrying stability.
The suction of the first passage of constant voltage suction means is 0.01-0.5Kgf/cm
2, preferred 0.05-0.2Kgf/cm
2And the suction of second channel is 0.1-5.0Kgf/cm
2, preferred 0.3-2.0Kgf/cm
2
When the suction of first passage is lower than 0.01Kgf/cm
2The time, its poor effect.On the contrary, be higher than 0.5Kgf/cm when it
2The time, because the disturbance during film falls to carrying, it causes film to curl.When the suction of second channel is lower than 0.1Kgf/cm
2The time, its poor effect.On the contrary, be higher than 5.0Kgf/cm when it
2The time, the vibration during film falls to carrying of the film of fusion.
Purify the highly hydrophilic PVA foamed material preparation that roller 90 utilizes porosity with open pore structure and 30-150%, 50-120% and 1-500 μ m, preferred 10-120 μ m aperture, can not cause any negative effect the PVA film because water is suitable as the solvent that is used for surface modification most.If porosity is lower than 1 μ m, it can't have open hole; And if it is higher than 500 μ m, it can't be held in roller owing to low elastic modelling quantity.
Solvent (for example, water and alcohol) with the hydrophily of height and 100 ℃ or lower boiling point can join and purify in the roller.The example of alcohol comprises methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol and analog thereof.
Water and alcohol can separately or be used in combination as solvent.
The PVA film is dried in curtain coating drum 70 for the first time, and the moisture that contains in the PVA film is reduced in the 5-70 weight portion of 100 weight portion PVA resins and separated.When too much water was removed at short notice, its difference owing to moisture moisture regain (regain) between the curtain coating surface of film and the air surface caused the warpage of film, and when moisture not fully during removal, film is out of shape when peeling off.
The inboard and the outside of the PVA film that separates have unequal water capacity, and as mentioned above, this can cause the distortion of film during drying steps.Therefore, unequal water capacity can be stabilized by after the curtain coating drum several dryer rolls with minor diameter being set.
Comprise the unsteady drier of a plurality of air nozzles and remain on 30 ℃ of-180 ℃ of films that have required water capacity with final generation by the PVA film process stable by dryer roll.
At film drying to the required water capacity, cut with cutting machine marginal portion with inconsistent thickness, and film reels with spool, at this, for the distortion that makes the PVA film and the viscosity between the PVA film minimize, film is reeled under tension-free state.
Polarization film carries out swelling, stretching, dyeing, fixation, washing and drying steps by the PVA film to the present invention's preparation and prepares, and each step will be specified in hereinafter.
It is necessary having consistent swellability in the extremely short time.If time lengthening, it can cause the PVA film surface to produce fold during stretching step, causes poor color fidelity.Swelling character is improved with the reduction of film surface tension force.Wet method and dry method all can be used for stretching step.Single shaft stretches in swelling can and dyeing pot.Staining procedure does not have the dyeing of the unanimity of irregular tone by carrying out in the film that iodine or dichroic dye is attached to stretching so that final film to be provided.
The fixation process is carried out with stabilizing dye-PVA complex structure in the presence of boron or boron compound and is carried out washing step and remove dyestuff and the boron compound that remains on the film surface with water, then carries out drying steps with dry moisture.At this, the contact angle of PVA film should be sufficiently low so that water is not assembled and is integrated into water droplet in the process of drying, this can cause the irregular of tone.
Polyvinyl alcohol film prepared in accordance with the present invention demonstrates excellent characteristic than conventional film, such as, having improved curtain coating stability and peel off stable polarization efficiency, transmissivity, color fidelity, it is applicable to the manufacturing of polarization film thus.
The present invention will describe in more detail with reference to following examples, but it should not be considered as limiting the scope of the invention.
Embodiment 1
In the preparation of polyvinyl alcohol film with 99.98mol% saponification degree and 2400 degree of polymerization, dipping is as the dioctyl phthalate of the water of the glycerine of 11 weight portions of plasticizer, 150 weight portions, 30ppm, as the diisobutyl adipate sodium sulfonate (diisobutyl sodium sulfur adipate) of 0.050 weight portion of hydrophily activator and the polyoxyethylene lauryl ether of 0.050 weight portion, based on the PVA resin of 100 weight portions in the saponification process.
The composite of dipping is fed in the multi-screw extruder that is preheated to 100 ℃.
The composite of fusion is curtain coating in 85 ℃ the curtain coating drum by die head with film forming shape and in temperature in extruder, then carries out the drying steps first time.
First that is installed in two passages on the curtain coating drum is set at 0.1Kgf/cm
2Apply uniform suction to control suction and to run through film, second is set at 1.3Kgf/cm
2To remove the moisture that in the curtain coating step, produces.
The drying second time of PVA film is carried out in top and bottom all are equipped with the unsteady drier of a plurality of air nozzles.Edge with out-of-flatness part is cut, and film is reeled with spool.
Embodiment 2
The preparation of PVA film is with embodiment 1, except PVA has the saponification degree of 99.95mol% and 1700 the degree of polymerization; Use is as the dioctyl phthalate of the water of the glycerine of 9 weight portions of plasticizer, 100 weight portions, 30ppm, as the diisobutyl adipate sodium sulfonate of 0.050 weight portion of hydrophily activator and the polyoxyethylene lauryl ether of 0.050 weight portion, based on the PVA resin of 100 weight portions; With the temperature of extruder be 90 ℃.
Embodiment 3
The preparation of PVA film is with embodiment 1, except the constant voltage suction means is removed and has only one to purify roller and be installed on the right side of top, stripping area of film to provide consistent surface tension on the whole width of curtain coating drum.
Embodiment 4
The preparation of PVA film is with embodiment 2, except the constant voltage suction means is removed and has only one to purify roller and be installed on the right side of top, stripping area of film to provide consistent surface tension on the whole width of curtain coating drum.Purifying roller adopts the poroid PVA foamed material of opening in the aperture with 90% porosity and 90 μ m to make and use water as solvent.
Embodiment 5
The preparation of PVA film is with embodiment 1, is installed on the right side of top, stripping area of film so that consistent surface tension to be provided except purifying roller on the whole width of curtain coating drum.Purifying roller adopts the poroid PVA foamed material of opening in the aperture with 90% porosity and 90 μ m to make and use water as solvent.
Embodiment 6
The preparation of PVA film is with embodiment 2, is installed on the right side of top, stripping area of film so that consistent surface tension to be provided except purifying roller on the whole width of curtain coating drum.
Purifying roller adopts the poroid PVA foamed material of opening in the aperture with 90% porosity and 90 μ m to make and use water as solvent.
Comparative Examples 1
The preparation of PVA film is with embodiment 1, except the constant voltage suction means is not installed.
It demonstrates the aberration of the strip with 5-10mm width and 50-100mm length that causes owing to uneven dyeing.
Comparative Examples 2
The preparation of PVA film is with embodiment 2, except the constant voltage suction means is not installed.
It demonstrates the aberration of the strip with 3-6mm width and 30-60mm length that causes owing to uneven dyeing.
Any additives that is used in the type of PVA resin of embodiment 1-6 and Comparative Examples 1-2 and amount, plasticizer, hydrophily activator and uses in the saponification process is summarized in the table 1.
Table 1
| Type | The degree of polymerization | Saponification degree (mol%) | Plasticizer (in weight portion) | The device that is used for curtain coating stability | |||
| Many alkyl compounds | Water | Phthalate compound (ppm) | The constant voltage suction means | Purify roller | |||
| Embodiment 1 | 2400 | 99.98 | 11 | 150 | 30 | Install | Do not install |
| Embodiment 2 | 1700 | 99.95 | 9 | 100 | 30 | Install | Do not install |
| Embodiment 3 | 2400 | 99.98 | 11 | 150 | 30 | Do not install | Install |
| Embodiment 4 | 1700 | 99.95 | 9 | 100 | 30 | Do not install | Install |
| Embodiment 5 | 2400 | 99.98 | 11 | 150 | 30 | Install | Install |
| Embodiment 6 | 1700 | 99.95 | 9 | 100 | 30 | Install | Install |
| Comparative example 1 | 2400 | 99.98 | 11 | 150 | 30 | Do not install | Do not install |
| Comparative example 2 | 1700 | 99.98 | 9 | 100 | 30 | Do not install | Do not install |
EXPERIMENTAL EXAMPLE
The mensuration of physical characteristic
(1) difference in thickness:
The 5cm interval of the thickness of width-based thin film overall width.
Extrude the thickness-KG6001A type Thickness measuring instrument mensuration of employing Anritz Co. under 20 ℃ of direction, the 20cm interval, number is consistent with the measurement of width with measuring.
(2) postpone (R):
R=tx Δ n (wherein, t=film thickness (nm), Δ n=birefringence)
Postponing (R) adopts the automatic birefringence measurement instrument of KOBRA WR to measure.
Delay distortion (Δ R): a bit locate the maximum of length of delay and the difference between the minimum of a value in certain of film overall width.
(3) transmissivity (%) and polarization efficiency (%): (UV-2450 Shimadzu) measures to adopt the UV-Vis spectrophotometer with one 100% polarizer.
(4) aberration: have 1m
2The aberration of the polarizing plate of size adopts polariscope (model 243, PTG Instrument) to measure.
The width of the PVA film for preparing among embodiment 1-6 and the Comparative Examples 1-2 and to extrude thickness, delay distortion, transmissivity, polarization efficiency and the aberration of direction all determined and be summarized in table 2.
Table 2
| Type | Extrude the film thickness difference (μ m) of direction | The film thickness difference of width (μ m) | Delay distortion Δ Re (nm) | Polarization efficiency (%) | Transmissivity (%) | Aberration |
| Embodiment 1 | 75±0.4 | 75±2.7 | 44 | 99.7 | 43.6 | Not |
| Embodiment 2 | 75±0.5 | 75±2.5 | 42 | 99.2 | 42.9 | Not |
| Embodiment 3 | 75±3.0 | 75±0.6 | 25 | 99.1 | 44.1 | Not |
| Embodiment 4 | 75±3.6 | 75±0.5 | 22 | 98.8 | 43.7 | Not |
| Embodiment 5 | 75±0.3 | 75±0.3 | 13 | 99.9 | 44.3 | Not |
| Embodiment 6 | 75±0.2 | 75±0.3 | 12 | 99.7 | 43.8 | Not |
| Comparative example 1 | 75±5.2 | 75±4.7 | 103 | 95.3 | 42.1 | Be |
| Comparative example 2 | 75±6.7 | 75±5.6 | 110 | 93.7 | 41.7 | Be |
As shown in table 2, it should be noted that and utilize the film of the prepared PVA film of device according to the present invention among the embodiment 1-6 than Comparative Examples 1-2, demonstrate the excellent specific property aspect difference in thickness, delay distortion, transmissivity, polarization efficiency and aberration.
Especially, when utilizing the difference in thickness of polarization film of conventional polyvinyl alcohol preparation and delay distortion to hinder the manufacturing of large scale article, the difference in thickness of PVA film of the present invention and delay distortion significantly reduce, so it can provide the effect of excellence.
Industrial applicibility
As mentioned above, the invention provides a kind of be used to make difference in thickness by making film and delay distortion optimization have obvious improvement characteristic (such as, transmissivity, polarization efficiency and aberration) the method for polyvinyl alcohol film, wherein the curtain coating of film stability and peel off stability be derived from by the constant voltage suction means is installed in the Luo Zai district of curtain coating drum or by stripping area at film on install and purify roller or the two realizes inhaling with constant speed broad ways effective removal of pressure and steam by the constant voltage suction means being installed and being purified roller.
Although above description provides different embodiments of the present invention, should be appreciated that foregoing description should not regard limitation of the present invention as because increase, variation, modifying and replace will be without departing from the spirit or scope of the invention.It will be apparent for a person skilled in the art that the present invention can other form, structure, setting and ratio implement, and can use other element, material and component.Therefore embodiment disclosed here can be considered illustrative in all respects and nonrestrictive, and scope of the present invention is pointed out by additional claim but do not limited by aforementioned.
Claims (4)
1. method that is used to prepare polyvinyl alcohol film, its utilize install in the Luo Zai district of rotary-type curtain coating drum install on the constant voltage suction means that comprises two passages or the stripping area at film purify roller or the constant voltage suction means is installed and the purification roller the two.
2. the method that is used to prepare polyvinyl alcohol film of claim 1, wherein said constant voltage suction means applies uniform suction towards all positions of film overall width, and the suction of first passage of this constant voltage suction means is 0.01-0.5Kgf/cm
2With the suction of second passage be 0.1-5.0Kgf/cm
2
3. the method that is used to prepare polyvinyl alcohol film of claim 1, wherein said purification roller has open pore structure, and it adopts the highly hydrophilic PVA foamed material preparation in the aperture of porosity with 30-150% and 1-500 μ m.
4. the method that is used to prepare polyvinyl alcohol film of claim 3, wherein said purification roller are equipped with hydrophily and boiling point with height and are lower than 100 ℃ solvent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020050035854A KR100675201B1 (en) | 2005-04-29 | 2005-04-29 | Method for manufacturing Polyvinyl alcohol film |
| KR1020050035854 | 2005-04-29 |
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| Publication Number | Publication Date |
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| CN1853895A true CN1853895A (en) | 2006-11-01 |
| CN100544928C CN100544928C (en) | 2009-09-30 |
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| CNB2006100794571A Expired - Fee Related CN100544928C (en) | 2005-04-29 | 2006-04-29 | Make the method for polyvinyl alcohol film |
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| KR (1) | KR100675201B1 (en) |
| CN (1) | CN100544928C (en) |
| TW (1) | TWI383013B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105599197A (en) * | 2016-03-10 | 2016-05-25 | 安徽皖维高新材料股份有限公司 | Method for heating curtain coating roller of polyvinyl alcohol water solution |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100886322B1 (en) * | 2006-06-26 | 2009-03-04 | 주식회사 엘지화학 | Preparation method of polyvinyl alcohol polarizer film having good surface uniformity |
| KR101113040B1 (en) * | 2006-11-03 | 2012-02-13 | 주식회사 엘지화학 | Method for producing polyvinyl alcohol having high degree of saponification and high degree of purity, and polyvinyl alcohol produced using the same |
| CN114834027A (en) * | 2022-03-22 | 2022-08-02 | 重庆光谱新材料科技有限公司 | Die for extrusion molding of polyvinyl alcohol film, optical polyvinyl alcohol film, polarizing film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4114229A1 (en) * | 1990-10-13 | 1992-04-16 | Bayer Ag | METHOD FOR PRODUCING POLARIZATION FILMS |
| KR0184702B1 (en) * | 1991-08-27 | 1999-05-15 | 야마모또 도시오 | Skin material back-coated with thin film latax form and integrated formed productilizing the skin material |
| DE60108550T2 (en) * | 2000-05-02 | 2006-01-12 | KURARAY CO., LTD, Kurashiki | Polymer film of polyvinyl alcohol, process for their preparation and polarizing film |
| TWI230275B (en) | 2000-05-12 | 2005-04-01 | Kuraray Co | Polyvinyl alcohol film and polarization film |
| JP4289586B2 (en) * | 2000-07-24 | 2009-07-01 | 富士フイルム株式会社 | Solution casting die and solution casting method |
| JP4041964B2 (en) * | 2002-09-25 | 2008-02-06 | 富士フイルム株式会社 | Prism-like sheet manufacturing method and apparatus |
| TW200428040A (en) * | 2003-03-31 | 2004-12-16 | Sumitomo Chemical Co | Polarizer and method for producing the polarizer |
| TWI359832B (en) * | 2003-09-24 | 2012-03-11 | Fujifilm Corp | Method and equipment for producing polymer film |
-
2005
- 2005-04-29 KR KR1020050035854A patent/KR100675201B1/en active IP Right Grant
-
2006
- 2006-01-11 TW TW095101012A patent/TWI383013B/en not_active IP Right Cessation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105599197A (en) * | 2016-03-10 | 2016-05-25 | 安徽皖维高新材料股份有限公司 | Method for heating curtain coating roller of polyvinyl alcohol water solution |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100675201B1 (en) | 2007-01-30 |
| KR20060113040A (en) | 2006-11-02 |
| TWI383013B (en) | 2013-01-21 |
| CN100544928C (en) | 2009-09-30 |
| TW200637883A (en) | 2006-11-01 |
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