CN103744141B - A kind of preparation method of Pva Polarizing Film - Google Patents
A kind of preparation method of Pva Polarizing Film Download PDFInfo
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- CN103744141B CN103744141B CN201310728333.1A CN201310728333A CN103744141B CN 103744141 B CN103744141 B CN 103744141B CN 201310728333 A CN201310728333 A CN 201310728333A CN 103744141 B CN103744141 B CN 103744141B
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Abstract
The invention provides a kind of Pva Polarizing Film, including hydrophobically modified polyvinyl alcohol film and the stain being arranged at described hydrophobically modified polyvinyl alcohol film surface；Described hydrophobically modified polyvinyl alcohol film is silane coupler modified polyvinyl alcohol film.Containing silane coupler modified polyvinyl alcohol film in Pva Polarizing Film provided by the invention, hydrophobic group in silane coupler can interact with the hydroxyl in polyvinyl alcohol film, polyvinyl alcohol film is formed the netted hydrophobic membrane of densification of one layer of crosslinking, makes polyvinyl alcohol film become hydrophobically modified polyvinyl alcohol film.This hydrophobically modified polyvinyl alcohol film in the present invention not easily dissolves in water, it is possible to increase the resistance to water of Pva Polarizing Film；And in the present invention, silane coupler will not interact with stain, degree of staining and anti-solution ability on stain do not affect, and therefore Pva Polarizing Film provided by the invention also has good optical property while having higher resistance to water.
Description
Technical field
The present invention relates to optical material preparing technical field, particularly relate to a kind of Pva Polarizing Film and preparation method thereof.
Background technology
Light polarizing film is to have dichroic transparent membrane, and it allows to be parallel to the axial light of printing opacity and passes through, and is perpendicular to the axial light of printing opacity and is then absorbed.Light polarizing film can be made into polarized lenses, and polarized lenses is the important component part of liquid crystal display (LCD), it is possible to controls the optical activity of permeate crystal display light.Light polarizing film is usually by dichromatic iodine or what dichromatic dyestuff oriented adsorption was prepared from polyvinyl alcohol film, and light polarizing film can be divided into iodine polarizing film and dyeing according to the difference of adsorbent on polyvinyl alcohol film is light polarizing film.
The preparation method of light polarizing film divides according to the drawing process of polyvinyl alcohol film, wet method drawing process and the big class of dry-stretch process two can be divided into, dry-stretch process refers to when uniform temperature, humidity, polyvinyl alcohol film is stretched to certain multiplying power by the environment of noble gas, then carry out dyeing, fixation, compound, the preparation technology such as dry；Wet method drawing process refers to and is first dyeed by polyvinyl alcohol film, then carry out in the solution stretching, fixation, compound, dry production method.Adopt the light polarizing film that wet method drawing process prepares to be superior to the light polarizing film that dry-stretch process prepares in tone evenness and durability, therefore generally adopt wet method drawing process to prepare light polarizing film.The preparation method that Chinese patent if application number is 200510053760.X discloses a kind of light polarizing film, by the degree of polymerization be 2400, thickness be that the polyvinyl alcohol film of 75 μm carries out single shaft 3 times stretching 120 DEG C add in hot tank；Then the polyvinyl alcohol film after stretching is carried out expansion process 3 minutes in the rinsing bowl of 30 DEG C；Then by the crosslinking dyeing in the dyeing crosslinking bath of 33 DEG C of the polyvinyl alcohol film after expansion process；The polyvinyl alcohol film after crosslinking dyeing is carried out in the stretch slot containing polyvinyl alcohol crosslinked dose wet type again and stretches 3 times of process, and impregnate 5 minutes, then dry at 60 DEG C and can obtain light polarizing film in 5 minutes.
Although the light polarizing film that prior art prepares has good optical property, but the resistance to water of this light polarizing film is poor, limits light polarizing film use in a humid environment.
Summary of the invention
In view of this, it is an object of the invention to provide a kind of Pva Polarizing Film, this Pva Polarizing Film has good water resistance, it is possible to be widely used in the environment of humidity.
The invention provides a kind of Pva Polarizing Film, including hydrophobically modified polyvinyl alcohol film and the stain being arranged at described hydrophobically modified polyvinyl alcohol film surface；
Described hydrophobically modified polyvinyl alcohol film is silane coupler modified polyvinyl alcohol film.
Preferably, the preparation method of described hydrophobically modified polyvinyl alcohol film is:
Polyvinyl alcohol film is impregnated in silane coupler solution, obtains hydrophobically modified polyvinyl alcohol film.
Preferably, the mass concentration of described silane coupler solution is 0.01%～30%.
Preferably, described silane coupler includes one or more in chlorosilane coupling agent, alcoxyl base class coupling agent and silazane class coupling agent.
Preferably, described stain is one or both in iodine and potassium iodide.
The preparation method that the invention provides a kind of Pva Polarizing Film, comprises the following steps:
A, carrying out hydrophobically modified polyvinyl alcohol film impregnating and first stretch in stain solution, obtaining the first intermediate coat, described hydrophobically modified polyvinyl alcohol film is silane coupler modified polyvinyl alcohol film；
B, described first intermediate coat is fixed in fixative solution process and second stretch, obtain the second intermediate coat；
C, described second intermediate coat is carried out heat treatment, obtain Pva Polarizing Film.
Preferably, in described step a, stain solution is one or both in iodine solution and liquor kalii iodide.
Preferably, in described step a, the mass concentration of stain solution is 3.3g/L～3.7g/L.
Preferably, in described step a, the time of dipping is 180s～220s.
Preferably, in described step a, the first stretching ratio stretched is 130%～170%.
The invention provides a kind of Pva Polarizing Film, including hydrophobically modified polyvinyl alcohol film and the stain being arranged at described hydrophobically modified polyvinyl alcohol film surface；Described hydrophobically modified polyvinyl alcohol film is silane coupler modified polyvinyl alcohol film.Containing hydrophobically modified polyvinyl alcohol film in Pva Polarizing Film provided by the invention, this hydrophobically modified polyvinyl alcohol film is silane coupler modified polyvinyl alcohol film, hydrophobic group in silane coupler can interact with the hydroxyl in polyvinyl alcohol film, polyvinyl alcohol film is formed the netted hydrophobic membrane of densification of one layer of crosslinking, makes polyvinyl alcohol membrane modifying.This hydrophobically modified polyvinyl alcohol film in the present invention has good resistance to water, is not easily susceptible to the erosion of hydrone and dissolves, thus improve the resistance to water of Pva Polarizing Film；And in the present invention, silane coupler will not interact with stain, degree of staining and anti-solution ability on stain do not affect, therefore Pva Polarizing Film provided by the invention relatively also has good optical property while enhanced water resistance having, it is possible to be widely used in the environment of humidity.Additionally, Pva Polarizing Film provided by the invention also has good ductility.
Test result indicate that, the swellbility of Pva Polarizing Film provided by the invention is 121%～156%, and elongation at break is 312%～489%, and hot strength is 41MPa～51MPa, and transmitance is 36%～47.8%, and degree of polarization is 81.9%～98.1%.
Detailed description of the invention
The invention provides a kind of Pva Polarizing Film, including hydrophobically modified polyvinyl alcohol film and the stain being arranged at described hydrophobically modified polyvinyl alcohol film surface；
Described hydrophobically modified polyvinyl alcohol film is silane coupler modified polyvinyl alcohol film.
Containing hydrophobically modified polyvinyl alcohol film in Pva Polarizing Film provided by the invention, this hydrophobically modified polyvinyl alcohol film is silane coupler modified polyvinyl alcohol film, hydrophobic group in silane coupler can interact with the hydroxyl in polyvinyl alcohol film, polyvinyl alcohol film is formed the netted hydrophobic membrane of densification of one layer of crosslinking, makes polyvinyl alcohol membrane modifying.This hydrophobically modified polyvinyl alcohol film in the present invention has good resistance to water, is not easily susceptible to the erosion of hydrone and dissolves, thus improve the resistance to water of Pva Polarizing Film；And in the present invention, silane coupler will not interact with stain, degree of staining and anti-solution ability on stain do not affect, therefore Pva Polarizing Film provided by the invention relatively also has good optical property while enhanced water resistance having, it is possible to be widely used in the environment of humidity.
Pva Polarizing Film provided by the invention includes hydrophobically modified polyvinyl alcohol film, and described hydrophobically modified polyvinyl alcohol film is silane coupler modified polyvinyl alcohol film.In the present invention, hydrophobic group in silane coupler can interact with the hydroxyl in polyvinyl alcohol film, polyvinyl alcohol film is formed the netted hydrophobic membrane of densification of one layer of crosslinking, make polyvinyl alcohol membrane modifying, obtain hydrophobically modified polyvinyl alcohol film, described hydrophobically modified polyvinyl alcohol film has good resistance to water, is not easily susceptible to the erosion of hydrone and dissolves, improves the resistance to water of the Pva Polarizing Film that the present invention obtains.
nullIn the present invention，Described silane coupler is preferably chlorosilane coupling agent、One or more in alcoxyl base class coupling agent and silazane class coupling agent，It is more preferably trim,ethylchlorosilane、N-octyl chloride silane、Dimethyldichlorosilane、Methyl trichlorosilane、N-octytriethoxysilane、Butyl triethoxysilane、Phenyltrimethoxysila,e、MTMS、Dimethyl trimethoxy silane、Dimethyl triethoxysilane、N-butyltrimethoxysilane、Trimethoxysilane、N-hexyl trimethoxy silane、N-octylmethoxysilane、Decyl trimethoxy silane、Aminopropyl triethoxysilane、HMDS，Divinyl tetramethyl-disilazane、Trimethyldisilazane、Heptamethyldisilazane、Phenyl three silazane、Tetramethyl-disilazane、Nine methyl three silazane、Dibutyl tetramethylsilazanes、One or more in diphenyltetramethyldisilazane；It most preferably is the one in trim,ethylchlorosilane, n-octytriethoxysilane, trimethyldisilazane.In the present invention, described silane coupler will not interact with stain, and degree of staining and anti-solution ability on stain do not affect, and therefore Pva Polarizing Film provided by the invention relatively also has good optical property while enhanced water resistance having.The source of described silane coupler is not had special restriction by the present invention, adopts the silane coupler of mentioned kind well known to those skilled in the art；Obtain as bought by market.
In the present invention, the preparation method of described hydrophobically modified polyvinyl alcohol film is preferably:
Polyvinyl alcohol film is impregnated in silane coupler solution, obtains hydrophobically modified polyvinyl alcohol film.
Polyvinyl alcohol film is impregnated by the present invention in silane coupler solution, obtains hydrophobically modified polyvinyl alcohol film.In the present invention, the mass concentration of described silane coupler solution is preferably 0.01%～30%, more preferably 0.05%～20%, it is most preferred that be 0.1%～10%.Solvent in described silane coupler solution is not had special restriction by the present invention, adopts the solvent of silane coupler described in solubilized technique scheme well known to those skilled in the art.In the present invention, the solvent in described silane coupler solution is preferably toluene, dimethyl sulfoxide, ethylene glycol, N-Methyl pyrrolidone, dimethyl acetylamide, trihydroxy methyl acetone, glycerol or water, more preferably toluene or water.The source of solvent in described silane coupler solution is not had special restriction by the present invention, adopts the solvent of mentioned kind well known to those skilled in the art, obtains as bought by market.
In the present invention, the time that described polyvinyl alcohol film impregnates in silane coupler solution is preferably 3h～12h, more preferably 4h～10h, it is most preferred that for 5h～8h；The temperature that described polyvinyl alcohol film impregnates in silane coupler solution is preferably 15 DEG C～30 DEG C, more preferably 20 DEG C～28 DEG C, it is most preferred that be 23 DEG C～26 DEG C.
In the present invention, the stretching of film material is had large effect by the thickness of described polyvinyl alcohol film, and the thickness of described polyvinyl alcohol film is preferably 20 μm～120 μm, more preferably 40 μm～100 μm, it most preferably is 60 μm～80 μm, is the most preferably 70 μm～76 μm.In the present invention, the thickness of described polyvinyl alcohol film need to keep homogeneity, the difference of described polyvinyl alcohol film thickness preferably≤4 μm, more preferably 0.5 μm～2 μm, it is most preferred that be 1 μm.The source of described polyvinyl alcohol film is not had special restriction by the present invention, and the method preparing polyvinyl alcohol film well known to those skilled in the art can be adopted to prepare.In the present invention, described polyvinyl alcohol film preferably prepares by the following method:
Polyvinyl alcohol, plasticizer and solvent are mixed, obtains mixed solution；
Described mixed solution is carried out film forming process, obtains polyvinyl alcohol film.
Polyvinyl alcohol, plasticizer and solvent are preferably mixed by the present invention, obtain mixed solution.The method of described mixing is not had special restriction by the present invention, adopts hybrid technology scheme well known to those skilled in the art by described polyvinyl alcohol, plasticizer and solvent mix homogeneously.In the present invention, the degree of polymerization of described polyvinyl alcohol is preferably 1500～6000, more preferably 2000～5000, it is most preferred that be 3000～4000；The alcoholysis degree of described polyvinyl alcohol is preferably >=99%.The source of described polyvinyl alcohol is not had special restriction by the present invention, obtains as bought by market.In the present invention, described solvent can be identical with the solvent in the silane coupler solution described in technique scheme, it is also possible to different.In the present invention, described solvent is preferably dimethyl sulfoxide, ethylene glycol, N-Methyl pyrrolidone, dimethyl acetylamide, trihydroxy methyl acetone, glycerol or water, more preferably trihydroxy methyl acetone or water.In the present invention, the mass ratio of described polyethylene alcohol and solvent is preferably (3～800): 100, more preferably (5～30): 100, it is most preferred that for (6～20): 100.
In the present invention, described plasticizer is preferably polyhydric alcohol, it is more preferably one or more in ethylene glycol, glycerol, two glycerol, propylene glycol, diethylene glycol, triethylene glycol, TEG, trimethylolpropane, it is most preferred that for one or more in glycerol, two glycerol and ethylene glycol.In the present invention, the ductility of the consumption of the described plasticizer polyvinyl alcohol film to preparing has large effect, and when described plasticizer consumption is less, the ductility of the polyvinyl alcohol film prepared is relatively low；When described plasticizer consumption is too much, the polyvinyl alcohol film prepared is excessively soft, treatability is relatively low.In the present invention, the mass ratio of described plasticizer and polyvinyl alcohol is preferably (1～70): 100, more preferably (3～50): 100, it is most preferred that for (4～30): 100, is the most preferably (5～18): 100.The source of described plasticizer is not had special restriction by the present invention, adopts the plasticizer of mentioned kind well known to those skilled in the art, obtains as bought by market.
In the present invention, described mixed solution preferably also includes surfactant.In the present invention, the fissility of the consumption of the described surfactant polyvinyl alcohol film to preparing has large effect, and when the consumption of described surfactant is very few, the polyvinyl alcohol film prepared cannot present peeling effect；When the consumption of described surfactant is too much, the polyvinyl alcohol film prepared there will be the defects such as surface dissolution, caking, affects membrane property.In the present invention, the mass ratio of described surfactant and polyvinyl alcohol is preferably (0.01～3): 100, more preferably (0.02～0.5): 100, it is most preferred that for (0.05～0.3): 100.
The kind of described surfactant is not had special restriction by the present invention, adopts surfactant well known to those skilled in the art.nullIn the present invention，Described surfactant is preferably one or more in anionic surfactant and nonionic surfactant，It is more preferably carboxylic acid type surfactant、Sulfuric acid ester type surfactant、Sulfonic acid type surfactant、Alkane ether type nonionic surfactant、Alkylbenzene ether type nonionic surfactant、Alkane ester type nonionic surfactant、Alkanamine type nonionic surfactant、Alkylamide type nonionic surfactant、Polypropylene glycol ether type nonionic surfactant、Alkanolamide type nonionic surfactant、One or more in allyl benzene ether type nonionic surfactant，It is more preferably potassium laurate、Octyl salicylate、DBS、Sodium lauryl sulphate、Polyethylene glycol oxide oil ether、Polyoxyethylene octyl phenylate、Polyoxyethylene lauryl acid esters、Polyoxyethylene lauryl base amidogen ether、Polyoxyethylene lauryl acid amide、Polyethylene glycol oxide、Polypropylene oxide ether、Oleic acid diethyl amide、One or more in polyoxyalkylene pi-allyl phenylate，It most preferably is the one in sodium lauryl sulphate and polyoxyethylene lauryl acid esters.The source of described surfactant is not had special restriction by the present invention, adopts the surfactant of mentioned kind well known to those skilled in the art, obtains as bought by market.
After obtaining mixed solution, described mixed solution is preferably carried out film forming process by the present invention, obtains polyvinyl alcohol film.The present invention does not have special restriction to by the method that described film forming processes, adopt the technical scheme of masking well known to those skilled in the art, can adopt the methods such as extrusion by melting, casting film method, film by wet method or gel masking method to as described in mixed solution carry out film forming process, obtain polyvinyl alcohol film.Concrete, described mixed solution can be carried out film forming process by the present invention by the following method:
Described mixed solution is heated, removes the bubble within described mixed solution, the mixed solution after removing bubble is adopted tape-casting, obtains polyvinyl alcohol film.
The method of described heating is not had special restriction by the present invention, adopts the technical scheme of heating well known to those skilled in the art；In the present invention, the temperature of described heating is preferably 90 DEG C～100 DEG C, more preferably 93 DEG C～97 DEG C, it is most preferred that be 95 DEG C.The time of described heating is not had special restriction, the material in described mixed solution can stop heating after all dissolving by the present invention.
After completing the heating to described mixed solution, the mixed solution after heating is preferably stood by the present invention, removes bubble therein, the mixed solution after removing bubble is adopted tape-casting, obtains polyvinyl alcohol film.The method of described standing is not had special restriction by the present invention, adopts standing technical scheme well known to those skilled in the art；In the present invention, described standing is preferably vacuum standing.The time stood is not had special restriction by the present invention, does not have during bubble and can stop standing in the mixed solution after above-mentioned heating.The equipment that described tape-casting adopts is not had special restriction by the present invention, adopts casting machine well known to those skilled in the art.In the present invention, the drying temperature of described tape-casting is preferably 40 DEG C～150 DEG C, more preferably 60 DEG C～130 DEG C, it is most preferred that be 65 DEG C～120 DEG C；The furnace drying method of described tape-casting is preferably forced air drying or Infrared Heating dries.
Described mixed solution can also be carried out film forming process by the present invention by the following method:
Described mixed solution is suppressed in a mold, obtains polyvinyl alcohol film.
Described mixed solution is preferably carried out vacuum compacting by the present invention in a mold, obtains polyvinyl alcohol film.Described mould is not had special restriction by the present invention, adopts the mould for masking well known to those skilled in the art.In the present invention, the temperature of described compacting is preferably 190 DEG C～230 DEG C, more preferably 200 DEG C～220 DEG C, it is most preferred that be 205 DEG C～215 DEG C；The pressure of described compacting is preferably 15MPa～25MPa, more preferably 18MPa～22MPa, it is most preferred that for 20MPa；The time of described compacting is preferably 480s～520s, more preferably 490s～510s, it is most preferred that for 495s～505s.
Complete after described polyvinyl alcohol film dipping in silane coupler solution, the present invention preferably by the polyvinyl alcohol film rinse after dipping to neutral, obtain hydrophobically modified polyvinyl alcohol film.The method of described polyvinyl alcohol film rinse is not had special restriction by the present invention, adopts the technical scheme of rinse well known to those skilled in the art.In the present invention, the reagent of described polyvinyl alcohol film rinse is preferably water, more preferably deionized water.
Pva Polarizing Film provided by the invention includes stain, and described stain is arranged at the surface of described hydrophobically modified polyvinyl alcohol film.In the present invention, described stain is preferably one or both in iodine and potassium iodide, more preferably iodine and in potassium iodide two kinds.The consumption of described stain is not had special restriction by the present invention, adopts the conventional amount used of stain in light polarizing film well known to those skilled in the art.
The preparation method that the invention provides a kind of Pva Polarizing Film, comprises the following steps:
A, carrying out hydrophobically modified polyvinyl alcohol film impregnating and first stretch in stain solution, obtaining the first intermediate coat, described hydrophobically modified polyvinyl alcohol film is silane coupler modified polyvinyl alcohol film.
B, described first intermediate coat is fixed in fixative solution process and second stretch, obtain the second intermediate coat；
C, described second intermediate coat is carried out heat treatment, obtain Pva Polarizing Film.
Hydrophobically modified polyvinyl alcohol film is carried out dipping and first in stain solution and stretches by the present invention, obtains the first intermediate coat.In the present invention, described hydrophobically modified polyvinyl alcohol film is consistent with the hydrophobically modified polyvinyl alcohol film described in technique scheme, does not repeat them here.In the present invention, described stain solution is preferably one or both in iodine solution and liquor kalii iodide, more preferably the mixed solution of iodine and potassium iodide.In the present invention, the mass concentration of described stain solution is preferably 3.3g/L～3.7g/L, more preferably 3.4g/L～3.6g/L, it is most preferred that for 3.5g/L.Described hydrophobically modified polyvinyl alcohol film is preferably immersed in the chroma tank equipped with stain solution and impregnates by the present invention.Described chroma tank is not had special restriction by the present invention, adopts the chroma tank used in preparation light polarizing film process well known to those skilled in the art.
In the present invention, the time that described hydrophobically modified polyvinyl alcohol film impregnates in stain solution is preferably 180s～220s, more preferably 190s～210s, it is most preferred that for 200s.In the present invention, the temperature that described hydrophobically modified polyvinyl alcohol film impregnates in stain solution is preferably 15 DEG C～30 DEG C, more preferably 20 DEG C～28 DEG C, it is most preferred that be 23 DEG C～26 DEG C.
Described first method stretched is not had special restriction by the present invention, adopts the technical scheme of stretching well known to those skilled in the art.In the present invention, the described first stretching ratio stretched is preferably 130%～170%, more preferably 140%～160%, it is most preferred that be 145%～155%.Described hydrophobically modified polyvinyl alcohol film is carried out the first stretching while preferably carrying out hydrophobically modified polyvinyl alcohol film in stain solution impregnating by the present invention, obtains the first intermediate coat.
After completing described hydrophobically modified polyvinyl alcohol film dipping in stain solution and first are stretched, the present invention preferably stretch obtain first after hydrophobically modified polyvinyl alcohol film carry out rinse, obtain the first intermediate coat.The equipment of described rinse is not had special restriction by the present invention, adopts rinse equipment well known to those skilled in the art, as the hydrophobically modified polyvinyl alcohol film after rinse groove can be adopted to stretch first carries out rinse, obtains the first intermediate coat.Described rinse groove is not had special restriction by the present invention, adopts the rinse groove used in preparation light polarizing film process well known to those skilled in the art.In the present invention, the described time to the hydrophobically modified polyvinyl alcohol film rinse after the first stretching is preferably 10s～20s, more preferably 12s～18s, it is most preferred that for 14s～16s.In the present invention, the described reagent to the hydrophobically modified polyvinyl alcohol film rinse after the first stretching is preferably water, more preferably deionized water.
After obtaining the first intermediate coat, described first intermediate coat is fixed process and second in fixative solution and stretches by the present invention, obtains the second intermediate coat；Preferably described first intermediate coat is immersed and fixative solution is fixed process and the second stretching, obtain the second intermediate coat.In the present invention, the temperature of described fixing process is preferably 15 DEG C～30 DEG C, more preferably 20 DEG C～28 DEG C, it is most preferred that be 23 DEG C～26 DEG C；The time of described fixing process is preferably 2min～6min, more preferably 3min～5min, it is most preferred that for 4min.
Described fixative solution is not had special restriction by the present invention, adopts the fixative solution used in preparation light polarizing film process well known to those skilled in the art.In the present invention, described fixative solution is preferably the mixed solution of boric acid and potassium iodide.In the present invention, the mass concentration of the mixed solution mesoboric acid of described boric acid and potassium iodide is preferably 15g/L～25g/L, more preferably 18g/L～22g/L, it is most preferred that for 20g/L；In the mixed solution of described boric acid and potassium iodide, the mass concentration of potassium iodide is preferably 10g/L～15g/L, more preferably 11g/L～13g/L, it is most preferred that for 12g/L.
In the present invention, described second preferably uniaxial tension is stretched.In the present invention, the described second stretching ratio stretched is preferably 230%～270%, more preferably 240%～260%, it is most preferred that be 245%～255%.In the present invention, the described second time stretched was preferably 2min～6min, more preferably 3min～5min, it is most preferred that for 4min.Described first intermediate coat is carried out the second stretching while preferably described first intermediate coat being fixed in fixative solution process by the present invention, obtains the second intermediate coat.
After obtaining the second intermediate coat, described second intermediate coat is carried out heat treatment by the present invention, obtains Pva Polarizing Film.In the present invention, described heat treated temperature is preferably 100 DEG C～150 DEG C, more preferably 110 DEG C～140 DEG C, it is most preferred that be 120 DEG C～130 DEG C；The described heat treated time is preferably 1min～2min.
After obtaining Pva Polarizing Film, the present invention tests the swellbility of Pva Polarizing Film, elongation at break, hot strength, transmitance and the degree of polarization that obtain.In the present invention, the method for testing of described Pva Polarizing Film swellbility is:
First intermediate coat obtained above is cut into the sample of 5cm × 5cm, take out after described sample is impregnated in the deionized water of 30 DEG C 4h, the sample after dipping is clamped with two filter clothes that absorb water, absorb sample surfaces moisture after impregnating, again the sample after water suction is weighed, the quality claimed is designated as W0；Again the sample after weighing is dried 16 hours in the drying machine of 105 DEG C, again weigh after then the sample after drying being cooled down 1h in desiccator, the quality claimed is designated as Wt；Shown in formula (I), formula calculates the swellbility A of Pva Polarizing Film:
Result of calculation shows, the swellbility of Pva Polarizing Film provided by the invention is 121%～156%.
In the present invention, the elongation at break of described Pva Polarizing Film and hot strength detect according to the standard of the GB/T12683 assay method of film tensile property " chip base with ".Testing result shows, the elongation at break of Pva Polarizing Film provided by the invention is 312%～489%, and hot strength is 41MPa～51MPa.
In the present invention, the detection method of described Pva Polarizing Film transmitance is:
In the width middle position of Pva Polarizing Film, cut the sample of 4cm × 4cm, adopt Japan's Shimadzu UV-2200 type spectrophotometer, test the transmitance of described sample according to the Japanese Industrial Standards that standard No. is JISZ870.Test result indicate that, the transmitance of Pva Polarizing Film provided by the invention is 36%～47.8%.
In the present invention, the detection method of described Pva Polarizing Film degree of polarization is:
By 2 Pva Polarizing Films in the way of parallel with polarizing axis overlapping, adopt the transmitance of the light polarizing film after Japan's Shimadzu UV-2200 type spectrophotometric determination overlap, be designated as parallel transmitance Y//；By 2 Pva Polarizing Films in the way of orthogonal with polarizing axis overlapping, adopt the transmitance of the light polarizing film after Japan's Shimadzu UV-2200 type spectrophotometric determination overlap, be designated as orthogonal transmitance Y ⊥；Shown in formula (II), formula calculates the degree of polarization V of Pva Polarizing Film:
Result of calculation shows, the degree of polarization of Pva Polarizing Film provided by the invention is 81.9%～98.1%.
The invention provides a kind of Pva Polarizing Film, including hydrophobically modified polyvinyl alcohol film and the stain being arranged at described hydrophobically modified polyvinyl alcohol film surface；Described hydrophobically modified polyvinyl alcohol film is silane coupler modified polyvinyl alcohol film.Containing hydrophobically modified polyvinyl alcohol film in Pva Polarizing Film provided by the invention, this hydrophobically modified polyvinyl alcohol film is silane coupler modified polyvinyl alcohol film, hydrophobic group in silane coupler can interact with the hydroxyl in polyvinyl alcohol film, polyvinyl alcohol film is formed the netted hydrophobic membrane of densification of one layer of crosslinking, makes polyvinyl alcohol membrane modifying.This hydrophobically modified polyvinyl alcohol film in the present invention has good resistance to water, is not easily susceptible to the erosion of hydrone and dissolves, thus improve the resistance to water of Pva Polarizing Film；And in the present invention, silane coupler will not interact with stain, degree of staining and anti-solution ability on stain do not affect, therefore Pva Polarizing Film provided by the invention relatively also has good optical property while enhanced water resistance having, it is possible to be widely used in the environment of humidity.Additionally, Pva Polarizing Film provided by the invention also has good ductility.
In order to make those skilled in the art be better understood from technical scheme, below in conjunction with specific embodiment, the present invention is described in more detail, it will be appreciated by those skilled in the art that protection scope of the present invention is not limited to these specific embodiments.
Embodiment 1
Polyvinyl alcohol, glycerol, sodium lauryl sulphate and water are mixed, obtains mixed solution；The mass ratio of described polyvinyl alcohol, glycerol, sodium lauryl sulphate and water is 15:1.5:0.15:100, and the degree of polymerization of described polyvinyl alcohol is 2600, and saponification degree is 99.7%.
Mixed solution obtained above is heated to 95 DEG C, by standing the bubble within the mixed solution after removing heating, adopts casting film method to prepare into the polyvinyl alcohol film that thickness is 75 μm the mixed solution after removing bubble；The mode dried in described casting film method is that Infrared Heating dries, and is divided into two stages to carry out Infrared Heating and dries, and the baking temperature of first stage is 90 DEG C, and drying time is 7min；The baking temperature of second stage is 150 DEG C, and drying time is 1.5min.
Trim,ethylchlorosilane and trihydroxy methyl acetone are mixed, obtains silane coupler solution；Described trim,ethylchlorosilane and trihydroxy methyl acetone quality are than for 10:100, and the pH value of described silane coupler solution is 10.By the above-mentioned polyvinyl alcohol film prepared at 15 DEG C, described silane coupler solution impregnates 3h, then the polyvinyl alcohol film after dipping is taken out, with deionized water rinse to neutral, obtain hydrophobically modified polyvinyl alcohol film.
The mixed solution of iodine and potassium iodide is added in chroma tank, in the mixed solution of described iodine and potassium iodide, the mass concentration of iodine and potassium iodide gross mass is 3.5g/L, the above-mentioned hydrophobically modified polyvinyl alcohol film prepared is impregnated at 15 DEG C, in described chroma tank 200s, with the stretching ratio of 150%, the hydrophobically modified polyvinyl alcohol film in described chroma tank is carried out the first stretching simultaneously；Hydrophobically modified polyvinyl alcohol film rinse 15s in the sink after stretching first again, removes the stain on its surface, obtains the first intermediate coat；
First intermediate coat obtained above is immersed at 15 DEG C boric acid mass concentration to be 20g/L, potassium iodide mass concentration be in the boric acid of 12g/L and potassium iodide mixed solution and be fixed process, with the stretching ratio of 250%, first intermediate coat of fixing process is carried out uniaxial tension 4min simultaneously, obtain the second intermediate coat；
By the second intermediate coat obtained above heat treatment 1min at 100 DEG C, obtain Pva Polarizing Film.
Detection method described in technique scheme, the present invention detects the swellbility of the Pva Polarizing Film that embodiment 1 obtains, elongation at break, hot strength, transmitance and degree of polarization, test result is as shown in table 1, the testing result of table 1 is the embodiment of the present invention and comparative example obtains the swellbility of Pva Polarizing Film, elongation at break, hot strength, transmitance and degree of polarization.
Embodiment 2
Polyvinyl alcohol, glycerol, sodium lauryl sulphate and water are mixed, obtains mixed solution；The mass ratio of described polyvinyl alcohol, glycerol, sodium lauryl sulphate and water is 3:0.3:0.09:100, and the degree of polymerization of described polyvinyl alcohol is 6000, and saponification degree is 99.7%.
Mixed solution obtained above is heated to 95 DEG C, stands the bubble within the mixed solution after removing heating by vacuum, adopt casting film method to prepare into the polyvinyl alcohol film that thickness is 20 μm the mixed solution after removing bubble；The mode dried in described casting film method is forced air drying, and the baking temperature of described forced air drying is 40 DEG C.
N-octytriethoxysilane and water are mixed, obtains silane coupler solution；Described n-octytriethoxysilane and water quality are than for 30:100, and the pH value of described silane coupler solution is 11.By the above-mentioned polyvinyl alcohol film prepared at 30 DEG C, described silane coupler solution impregnates 6h, then the polyvinyl alcohol film after dipping is taken out, with deionized water rinse to neutral, obtain hydrophobically modified polyvinyl alcohol film.
The mixed solution of iodine and potassium iodide is added in chroma tank, in the mixed solution of described iodine and potassium iodide, the mass concentration of iodine and potassium iodide gross mass is 3.5g/L, the above-mentioned hydrophobically modified polyvinyl alcohol film prepared is impregnated at 30 DEG C, in described chroma tank 200s, with the stretching ratio of 150%, the hydrophobically modified polyvinyl alcohol film in described chroma tank is carried out the first stretching simultaneously；Hydrophobically modified polyvinyl alcohol film rinse 15s in the sink after stretching first again, removes the stain on its surface, obtains the first intermediate coat；
First intermediate coat obtained above is immersed at 30 DEG C boric acid mass concentration to be 20g/L, potassium iodide mass concentration be in the boric acid of 12g/L and potassium iodide mixed solution and be fixed process, with the stretching ratio of 250%, first intermediate coat of fixing process is carried out uniaxial tension 4min simultaneously, obtain the second intermediate coat；
By the second intermediate coat obtained above heat treatment 2min at 120 DEG C, obtain Pva Polarizing Film.
Detection method described in technique scheme, the present invention detects the swellbility of the Pva Polarizing Film that embodiment 2 obtains, elongation at break, hot strength, transmitance and degree of polarization, and test result is as shown in table 1.
Embodiment 3
Polyvinyl alcohol, glycerol and water are mixed, obtains mixed solution；The mass ratio of described polyvinyl alcohol, glycerol and water is 80:20:10, and the degree of polymerization of described polyvinyl alcohol is 1500, and saponification degree is 99.7%.
Mixed solution obtained above is positioned in mould, 210 DEG C, 20MPa when vacuum compacting 500s, make the polyvinyl alcohol film that thickness is 120 μm.
N-octytriethoxysilane and water are mixed, obtains silane coupler solution；Described n-octytriethoxysilane and water quality are than for 20:100, and the pH value of described silane coupler solution is 12.By the above-mentioned polyvinyl alcohol film prepared at 25 DEG C, described silane coupler solution impregnates 6h, then the polyvinyl alcohol film after dipping is taken out, with deionized water rinse to neutral, obtain hydrophobically modified polyvinyl alcohol film.
The mixed solution of iodine and potassium iodide is added in chroma tank, in the mixed solution of described iodine and potassium iodide, the mass concentration of iodine and potassium iodide gross mass is 3.5g/L, the above-mentioned hydrophobically modified polyvinyl alcohol film prepared is impregnated at 25 DEG C, in described chroma tank 200s, with the stretching ratio of 150%, the hydrophobically modified polyvinyl alcohol film in described chroma tank is carried out the first stretching simultaneously；Hydrophobically modified polyvinyl alcohol film rinse 15s in the sink after stretching first again, removes the stain on its surface, obtains the first intermediate coat；
First intermediate coat obtained above is immersed at 25 DEG C boric acid mass concentration to be 20g/L, potassium iodide mass concentration be in the boric acid of 12g/L and potassium iodide mixed solution and be fixed process, with the stretching ratio of 250%, first intermediate coat of fixing process is carried out uniaxial tension 4min simultaneously, obtain the second intermediate coat；
By the second intermediate coat obtained above heat treatment 2min at 140 DEG C, obtain Pva Polarizing Film.
Detection method described in technique scheme, the present invention detects the swellbility of the Pva Polarizing Film that embodiment 3 obtains, elongation at break, hot strength, transmitance and degree of polarization, and test result is as shown in table 1.
Embodiment 4
Polyvinyl alcohol, glycerol, sodium lauryl sulphate and dimethyl sulfoxide are mixed, obtains mixed solution；The mass ratio of described polyvinyl alcohol, glycerol, sodium lauryl sulphate and dimethyl sulfoxide is 60:0.6:0.006:100, and the degree of polymerization of described polyvinyl alcohol is 2600, and saponification degree is 99.7%.
Mixed solution obtained above is heated to 95 DEG C, by standing the bubble within the mixed solution after removing heating, adopts casting film method to prepare into the polyvinyl alcohol film that thickness is 74 μm the mixed solution after removing bubble；The mode dried in described casting film method is that Infrared Heating dries, and the baking temperature that described Infrared Heating dries is 95 DEG C.
Trimethyldisilazane and toluene are mixed, obtains silane coupler solution；The mass ratio of described trimethyldisilazane and toluene is 0.01:100, and the pH value of described silane coupler solution is 13.By the above-mentioned polyvinyl alcohol film prepared at 20 DEG C, described silane coupler solution impregnates 12h, then the polyvinyl alcohol film after dipping is taken out, with deionized water rinse to neutral, obtain hydrophobically modified polyvinyl alcohol film.
The mixed solution of iodine and potassium iodide is added in chroma tank, in the mixed solution of described iodine and potassium iodide, the mass concentration of iodine and potassium iodide gross mass is 3.3g/L, the above-mentioned hydrophobically modified polyvinyl alcohol film prepared is impregnated at 20 DEG C, in described chroma tank 180s, with the stretching ratio of 130%, the hydrophobically modified polyvinyl alcohol film in described chroma tank is carried out the first stretching simultaneously；Hydrophobically modified polyvinyl alcohol film rinse 10s in the sink after stretching first again, removes the stain on its surface, obtains the first intermediate coat；
First intermediate coat obtained above is immersed at 20 DEG C boric acid mass concentration to be 15g/L, potassium iodide mass concentration be in the boric acid of 10g/L and potassium iodide mixed solution and be fixed process, with the stretching ratio of 230%, first intermediate coat of fixing process is carried out uniaxial tension 2min simultaneously, obtain the second intermediate coat；
By the second intermediate coat obtained above heat treatment 1min at 150 DEG C, obtain Pva Polarizing Film.
Detection method described in technique scheme, the present invention detects the swellbility of the Pva Polarizing Film that embodiment 4 obtains, elongation at break, hot strength, transmitance and degree of polarization, and test result is as shown in table 1.
Embodiment 5
Polyvinyl alcohol, ethylene glycol, glycerol, polyoxyethylene lauryl acid esters and water are mixed, obtains mixed solution；The mass ratio of described polyvinyl alcohol, ethylene glycol, glycerol, polyoxyethylene lauryl acid esters and water is 100:30:40:0.4:10, and the degree of polymerization of described polyvinyl alcohol is 1700, and saponification degree is 99.7%.
Mixed solution obtained above is positioned in mould, 230 DEG C, 25MPa when vacuum compacting 505s, make the polyvinyl alcohol film that thickness is 74 μm.
N-octytriethoxysilane and water are mixed, obtains silane coupler solution；Described n-octytriethoxysilane and water quality are than for 20:100, and the pH value of described silane coupler solution is 12.By the above-mentioned polyvinyl alcohol film prepared at 20 DEG C, described silane coupler solution impregnates 4h, then the polyvinyl alcohol film after dipping is taken out, with deionized water rinse to neutral, obtain hydrophobically modified polyvinyl alcohol film.
The mixed solution of iodine and potassium iodide is added in chroma tank, in the mixed solution of described iodine and potassium iodide, the mass concentration of iodine and potassium iodide gross mass is 3.7g/L, the above-mentioned hydrophobically modified polyvinyl alcohol film prepared is impregnated at 20 DEG C, in described chroma tank 220s, with the stretching ratio of 170%, the hydrophobically modified polyvinyl alcohol film in described chroma tank is carried out the first stretching simultaneously；Hydrophobically modified polyvinyl alcohol film rinse 20s in the sink after stretching first again, removes the stain on its surface, obtains the first intermediate coat；
First intermediate coat obtained above is immersed at 20 DEG C boric acid mass concentration to be 25g/L, potassium iodide mass concentration be in the boric acid of 20g/L and potassium iodide mixed solution and be fixed process, with the stretching ratio of 270%, first intermediate coat of fixing process is carried out uniaxial tension 6min simultaneously, obtain the second intermediate coat；
By the second intermediate coat obtained above heat treatment 1.5min at 100 DEG C, obtain Pva Polarizing Film.
Detection method described in technique scheme, the present invention detects the swellbility of the Pva Polarizing Film that embodiment 5 obtains, elongation at break, hot strength, transmitance and degree of polarization, and test result is as shown in table 1.
Comparative example 1
Polyvinyl alcohol, glycerol, sodium lauryl sulphate and water are mixed, obtains mixed solution；The mass ratio of described polyvinyl alcohol, glycerol, sodium lauryl sulphate and water is 15:1.5:0.15:100, and the degree of polymerization of described polyvinyl alcohol is 2600, and saponification degree is 99.7%.
Mixed solution obtained above is heated to 95 DEG C, by standing the bubble within the mixed solution after removing heating, casting film method is adopted to prepare into the polyvinyl alcohol film that thickness is 74 μm the mixed solution after removing bubble, the mode dried in described casting film method is forced air drying, and the baking temperature of described forced air drying is 40 DEG C.
The mixed solution of iodine and potassium iodide is added in chroma tank, in the mixed solution of described iodine and potassium iodide, the mass concentration of iodine and potassium iodide gross mass is 3.5g/L, by the above-mentioned polyvinyl alcohol film prepared at 20 DEG C, described chroma tank impregnates 200s, with the stretching ratio of 150%, the polyvinyl alcohol film in described chroma tank is stretched simultaneously；Polyvinyl alcohol film rinse 15s in the sink after stretching first again, removes the stain on its surface, obtains the first intermediate coat；
First intermediate coat obtained above is immersed at 20 DEG C boric acid mass concentration to be 20g/L, potassium iodide mass concentration be in the boric acid of 12g/L and potassium iodide mixed solution and be fixed process, with the stretching ratio of 250%, first intermediate coat of fixing process is carried out uniaxial tension 4min simultaneously, obtain the second intermediate coat；
By the second intermediate coat obtained above heat treatment 1min at 100 DEG C, obtain Pva Polarizing Film.
Detection method described in technique scheme, the present invention detects the swellbility of the Pva Polarizing Film that comparative example 1 obtains, elongation at break, hot strength, transmitance and degree of polarization, testing result is as shown in table 1, the testing result of table 1 is the embodiment of the present invention and comparative example obtains the swellbility of Pva Polarizing Film, elongation at break, hot strength, transmitance and degree of polarization.
The swellbility of the Pva Polarizing Film that table 1 embodiment of the present invention and comparative example obtain, extension at break
The testing result of rate, hot strength, transmitance and degree of polarization
| Embodiment | Swellbility % | Elongation at break % | Hot strength MPa | Transmitance % | Degree of polarization % |
| 1 | 136 | 425 | 41 | 45.2 | 97.5 |
| 2 | 125 | 410 | 43 | 45.3 | 97.2 |
| 3 | 121 | 312 | 51 | 36 | 81.9 |
| 4 | 156 | 451 | 44 | 47.8 | 98.1 |
| 5 | 126 | 489 | 41 | 40.6 | 83.1 |
| Comparative example 1 | 1605 | 421 | 42 | - | - |
As shown in Table 1, the swellbility of the Pva Polarizing Film that the present invention obtains is 121%～156%, and elongation at break is 312%～489%, and hot strength is 41MPa～51MPa, and transmitance is 36%～47.8%, and degree of polarization is 81.9%～98.1%.Pva Polarizing Film provided by the invention has good resistance to water, ductility and optical property.
The invention provides a kind of Pva Polarizing Film, including hydrophobically modified polyvinyl alcohol film and the stain being arranged at described hydrophobically modified polyvinyl alcohol film surface；Described hydrophobically modified polyvinyl alcohol film is silane coupler modified polyvinyl alcohol film.Containing hydrophobically modified polyvinyl alcohol film in Pva Polarizing Film provided by the invention, this hydrophobically modified polyvinyl alcohol film is silane coupler modified polyvinyl alcohol film, hydrophobic group in silane coupler can interact with the hydroxyl in polyvinyl alcohol film, polyvinyl alcohol film is formed the netted hydrophobic membrane of densification of one layer of crosslinking, makes polyvinyl alcohol membrane modifying.This hydrophobically modified polyvinyl alcohol film in the present invention has good resistance to water, is not easily susceptible to the erosion of hydrone and dissolves, thus improve the resistance to water of Pva Polarizing Film；And in the present invention, silane coupler will not interact with stain, degree of staining and anti-solution ability on stain do not affect, therefore Pva Polarizing Film provided by the invention relatively also has good optical property while enhanced water resistance having, it is possible to be widely used in the environment of humidity.Additionally, Pva Polarizing Film provided by the invention also has good ductility.
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.It should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention carries out some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.The multiple amendment of these embodiments is apparent from for those skilled in the art, and generic principles defined herein can realize without departing from the spirit or scope of the present invention in other embodiments.Therefore, the present invention is not intended to be limited to the embodiments shown herein, and is to fit to the widest scope consistent with principles disclosed herein and features of novelty.
Claims (5)
1. a preparation method for Pva Polarizing Film, comprises the following steps:
A, carrying out hydrophobically modified polyvinyl alcohol film impregnating and first stretch in stain solution, obtaining the first intermediate coat, described hydrophobically modified polyvinyl alcohol film is silane coupler modified polyvinyl alcohol film；
B, described first intermediate coat is fixed in fixative solution process and second stretch, obtain the second intermediate coat；
C, described second intermediate coat is carried out heat treatment, obtain Pva Polarizing Film.
2. method according to claim 1, it is characterised in that in described step a, stain solution is one or both in iodine solution and liquor kalii iodide.
3. method according to claim 1, it is characterised in that in described step a, the mass concentration of stain solution is 3.3g/L～3.7g/L.
4. method according to claim 1, it is characterised in that in described step a, the time of dipping is 180s～220s.
5. method according to claim 1, it is characterised in that in described step a, the first stretching ratio stretched is 130%～170%.
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| CN109487398A (en) * | 2017-09-11 | 2019-03-19 | 苏州存异新材料科技有限公司 | A kind of Antistatic Fabric and its preparation process |
| CN107619566B (en) * | 2017-10-18 | 2020-06-05 | 中国石油化工集团公司 | Preparation method of polyvinyl alcohol polarizer |
| TWI788127B (en) * | 2021-12-03 | 2022-12-21 | 財團法人工業技術研究院 | Hydrophobic polyvinyl alcohol and method for preparing hydrophobic polyvinyl alcohol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6197348A (en) * | 1984-10-17 | 1986-05-15 | Kao Corp | Water-soluble film having excellent moisture resistance and moistureproofness |
| CN102466835A (en) * | 2010-10-29 | 2012-05-23 | 住友化学株式会社 | Method for producing polarizing plate |
| CN102807682A (en) * | 2012-08-24 | 2012-12-05 | 东北林业大学 | Method for preparing modified single hydrophobic polyvinyl alcohol film |
| CN103059486A (en) * | 2012-12-03 | 2013-04-24 | 云南云天化股份有限公司 | Manufacturing method of water-resistant polyvinyl alcohol film |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6197348A (en) * | 1984-10-17 | 1986-05-15 | Kao Corp | Water-soluble film having excellent moisture resistance and moistureproofness |
| CN102466835A (en) * | 2010-10-29 | 2012-05-23 | 住友化学株式会社 | Method for producing polarizing plate |
| CN102807682A (en) * | 2012-08-24 | 2012-12-05 | 东北林业大学 | Method for preparing modified single hydrophobic polyvinyl alcohol film |
| CN103059486A (en) * | 2012-12-03 | 2013-04-24 | 云南云天化股份有限公司 | Manufacturing method of water-resistant polyvinyl alcohol film |
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