CN1332800C - Method and device for making film by casting mould - Google Patents
Method and device for making film by casting mould Download PDFInfo
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- CN1332800C CN1332800C CNB021056358A CN02105635A CN1332800C CN 1332800 C CN1332800 C CN 1332800C CN B021056358 A CNB021056358 A CN B021056358A CN 02105635 A CN02105635 A CN 02105635A CN 1332800 C CN1332800 C CN 1332800C
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Abstract
A casting die is provided with a liquid supply nozzle and a space L1 between the fore end of the liquid supply nozzle and a casting dope is set to be 0.5-3.0 mm. An angle theta of the fore end of the liquid supply nozzle formed to the casting dope is made 10 deg.-90 deg. A solvent is made to flow from the solution supply nozzle at a flow rate of 0.05-0.5 ml/ min and with the flow variation percentage thereof set at plusmn 10% in the range of 0.005-10 sec. Skinning is prevented by injection of the solvent in a minute quantity. A film cast from the casting die is suitable for a polarizing plate protecting film and can be used for a liquid crystal display device and the like.
Description
Technical field
The present invention relates to prevent to take place the solution film-forming curtain coating mould of peeling at mould otch two ends; use the solution film-forming method and the device of this curtain coating mould; be particularly related to the optical material of suitable liquid crystal display, for example the film-forming method and the device of the manufacturing of polarization board protective film and Polarizer and exhibiting optical function film.
Background technology
Generally say, use films (film) such as solution film-forming manufactured cellulose ethanoate, Merlon, celluloid.In this solution film-forming, used curtain coating mould 201 shown in Figure 12.Most of situation is that polymer solution (below be called coating) is flowed out when forming curtain coating coating 210 from 201 continuities of curtain coating mould, produces peeling 217 at the both ends of mould otch 216 because of drying.This peeling becomes to grow up to the icicle shape at mould otch 216 both ends, has upset the curtain coating coating 210 that flows out from mould otch 216, hinders and form stabilising membrane on supporter (for example continuing fluxion strap) 202.
In order to remove peeling, curtain coating speed must be reduced, reach the speed that curtain coating coating is not cut off by ectocine.This just causes making film production efficiency and significantly reduces.Remove peeling in order not cause curtain coating speed to reduce, just knew in the past to mould otch both ends to be blown into the solvent saturated gas, make coating be accompanied by the method that soluble solvent flows down.
As shown in figure 13, in the method, near the curtain coating coating end of flowing out, use the curtain coating mould 211 that has disposed solvent feed flow pipe arrangement 223 under the former solvent streams from mould otch 216.Solvent in the liquor box 221 by solution feed pump 222, flows down from the vertical direction with respect to mould otch 216.
For example, the spy opens in the flat 2-208650 communique, discloses a kind of method that prevents to produce peeling, and the stream of solvent promptly is set in the curtain coating both mold ends inside that the continuity of cellulosic triacetate solution is flowed out, and supplies with methylene base chlorinated solvent from this stream.Collaborate with the end of the cellulosic triacetate solution that continuity is flowed out this stream lower end, and solvent flows out with cellulosic triacetate solution.
A kind of method of anti-generation peeling is disclosed in No. 2687260 communique of special permission.In this method, flow out solution such as cellulosic triacetate, supply with methylene base chloride equal solvent so that carrying on the coating two ends that continuity is flowed out from the continuity of mould otch.
Yet, in these methods, owing to be easy to be subjected to the influence of wind speed around the mould otch and temperature conditions etc., so be difficult to control gas concentration and solvent streams upper/lower positions.When gas concentration is very low, easily produce peeling, even keep the saturated concentration of gas, because the change of mould environment temperature also produces dewfall.Yet the sample path length uniformity that gas flow flows to continuity on the support produces baneful influence, finally has influence on film, causes film quality inferior.Even solvent flux seldom, also be easy to generate peeling.For preventing to produce peeling, and when supplying with the solvent of requirement, solvent is moistening to the width expansion from the end of mould otch, would rather make solvent excessive sometimes.When solvent is excessive, on supporter, produces and peel off vestiges.This vestiges of peeling off constitute the reason of paying foreign material, cause the change of film thickness.This when paying foreign material when producing, have to supporter is cleaned, cause production efficiency significantly to reduce.And then during change, curtain coating coating is easy to be subjected to ectocine to the flow of solvent in the system film.Therefore, coating that continuity is flowed on supporter or vibration or flexible, the thickness that forms film becomes inhomogeneous, becomes the reason of product defect.
Summary of the invention
The purpose of this invention is to provide a kind of curtain coating mould that can prevent to produce peeling.
Another object of the present invention provides a kind of solution film-forming method and the device that can make the uniform thickness film.
Another purpose of the present invention provides high solution film-forming method of a kind of production efficiency and device.
A further object of the present invention provides a kind of solution film-forming method that suppresses the solvent flux change.
Other purposes of the present invention provide a kind of film-forming method and device of manufacturing of polarization board protective film, Polarizer, exhibiting optical function film of suitable excellent optical characteristics.
Curtain coating mould of the present invention is included as and makes curtain coating die ontology that solution continuity flows and to the feed flow nozzle of this solution donor solvent.This curtain coating die ontology has notch portion, and solution spues from this notch portion.Supply with nozzle for liquid, with the outside of arranged spaced solution end on this notch portion of 0.5～3.0mm.Give the point of nozzle for liquid, with respect to the angle setting of the continuity flow direction of solution with 10～90 °.
In solution film-forming method of the present invention and device, make solution when curtain coating mould continuity flows on the supporter, flow out solvent and supply with solution from the tip of giving nozzle for liquid.At this moment solvent flux is 0.05～0.5ml/ minute.The rate of change of this flow was in ± 50% in 0.002 second to 100 seconds, can regulate according to the flow of above-mentioned continuity fluent solution.And then above-mentioned solvent is soluble with respect to the solute of continuity fluent solution, and viscosity is that 0.2～3cp, surface tension are 15～50dyn/cm.For the solvent that above-mentioned solvent is flowed out is given nozzle for liquid,, preferably be in from the nozzle that forms 10 degree and omit in vertical state to the level that forms 90 degree for the solution that above-mentioned continuity is flowed.
Among the present invention, the solute of above-mentioned solution is cellulose ethanoate preferably.Also inclusion is in the present invention for the film-forming method that uses cellulose acyl ester solution.The solvent of above-mentioned cellulose acyl ester solution is made of methyl acetate, ketone and alcohols, and its solvent ratio, methyl acetate are preferably 20～90 weight %, and ketone is preferably 0～60 weight %, alcohols is preferably 5～30 weight %.
Above-mentioned cellulose acyl ester solution preferably contains at least a plasticizer of 0.1～20 weight % for cellulose acyl ester.Above-mentioned cellulose acyl ester solution preferably contains at least a ultra-violet absorber of 0.001～5 weight % for cellulose acyl ester.And then above-mentioned cellulose acyl ester solution preferably contains at least a powder particles of 0.001～5 weight % for cellulose acyl ester.And then above-mentioned cellulose acyl ester solution preferably contains at least a releasing agent of 0.002～2 weight % for cellulose acyl ester.Above-mentioned cellulose acyl ester solution, at least a fluorine that preferably contains 0.001～2 weight % for cellulose acyl ester is a surfactant.
Also can use among the present invention and can make the common curtain coating mould that the solution continuity is flowed more than 2 kinds.
In solution film-forming method of the present invention, supply with proper amount of solvent to solution, can be because of the expansion of notch portion influence such as moistening and wind produce and upset the liquid stream.Like this, can prevent to peel off vestiges because of dry not enough generation of solution on the supporter, thus do not need regularly to clean supporter, thus improved production efficiency.And can be suppressed at vibration of continuity fluent solution and flexible generation on the supporter, can also suppress to make the thickness deviation of film.
And then, utilize the mixed solvent of methyl acetate, ketone, alcohols, more effectively dissolving cellulos acyl ester.Can add various additives in this cellulose acyl ester solution, by the film that this solution obtains, have good optical property and rerum natura, durability is also very good simultaneously.The purposes of this film optimum polarization board protective film, Polarizer, exhibiting optical function film, liquid crystal indicator.
Description of drawings
Above-mentioned purpose and advantage by the reference accompanying drawing, are read the detailed description of most preferred embodiment, and those skilled in the art can be readily appreciated that.
Fig. 1 is to use the curtain coating belt solution film-forming device side of curtain coating mould briefly to scheme;
Fig. 2 is the plane of solution film-forming device shown in Figure 1,
Fig. 3 is the side view of curtain coating mould shown in Figure 1,
Fig. 4 is the front enlarged drawing of Fig. 2 curtain coating mould, flows out coating by the continuity of curtain coating die tip,
Fig. 5 is the part enlarged drawing of curtain coating mould, and the tip portion of nozzle is vertical with respect to the continuity flow direction of curtain coating mould.
Fig. 6 is the enlarged drawing in curtain coating mould and pressure-reducing chamber,
Fig. 7 is the solution film-forming device side view with pressure-reducing chamber,
Fig. 8 is that briefly scheme the side of curtain coating drum-type solution film-forming device,
Fig. 9 is the plane of the device of solution film-forming shown in Fig. 8,
Figure 10 is the curtain coating mould side view that supply part has been installed,
Figure 11 is second kind of embodiment of curtain coating mould of the present invention,
Figure 12 is a former curtain coating mould side view,
Figure 13 has been to use the solution film-forming device front elevation of curtain coating mould shown in Figure 12.
The specific embodiment
[polymer]
Among the present invention,, cellulose esters, Merlon etc. are for example arranged as the polymer that can be used for polymer solution (coating).As cellulose esters, cellulosic low-grade fatty acid ester is representational (for example, cellulose ethanoate, cellulose ethanoate butyl ester and cellulose ethanoate propyl ester etc.).Lower fatty acid is meant the aliphatic acid of 6 following carbon numbers.For cellulose ethanoate, comprise cellulosic triacetate (TAC) and cellulose diacetate (DAC).Preferably by cellulose acyl ester solution modulation coating, cellulose acyl ester is cellulosic triacetate preferably in the present invention.
[solvent]
As the solvent of coating, generally use the chloride and the lower aliphatic alcohols of lower aliphatic hydrocarbon.Chloride example as the lower aliphatic hydrocarbon has methylene chloride, chloroform etc.For the example of lower aliphatic alcohols, the alcohol of 1-6 carbon atoms such as methyl alcohol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanols, t-butanols, 2-methyl-2-butanols, 2-methoxyethanol and 2-fourth oxyethanol is arranged, but be not limited to these.As the example of other solvents, there is essence not contain the ketones such as ethyl ketone of halogenated hydrocarbon, the ketone of 4～12 carbon atoms such as methyl ethyl ketone, metacetone, DIBK, cyclohexanone and methyl cyclohexanone for example, but be not limited to these.Also can use the ester of 3-12 carbon atom.For example, Ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate and 2-ethoxy-ethylhexoate etc., but be not limited to these.Also can use the ether of 3-12 carbon atom, for example, diisopropyl ether, dimethoxymethane, dimethoxy ethane, 1,4-diox, 1,3-dioxolane, oxolane, anisole and phenetole etc., but be not limited to these.Also can use the ring-type hydro carbons of 5～8 carbon atoms, for example, pentamethylene, cyclohexane, cycloheptane and cyclooctane etc., but be not limited to these.
As solvent, methylene chloride preferably.Also can mix other solvents in the methylene chloride uses.But the muriatic composite rate of methylene is more fortunately more than the 70 weight %.Better mixing rate, methylene chloride are 75～93 weight %, and other solvents are 7～25 weight %.Solvent is removed in film-forming process, and the residual quantity of solvent generally is lower than 5 weight %.Yet residual quantity better is lower than 1 weight %, better is lower than 0.5 weight %.
When considering, preferably use the muriatic solvent of no methylene to the influencing of human body, environment.This situation is preferably used the mixed solvent of methyl acetate, above-mentioned ketone and alcohols.When in modulation coating usefulness polymer, selecting cellulose acyl ester, consider that from the dissolubility solvent the most handy methyl acetate is done main solvent.Better for the dissolubility that makes polymer, in methyl acetate, can mix the solvent of ketone and alcohols.At this moment, the composition of each solvent ratio, methyl acetate are preferably that 20～90 weight %, ketone are preferably 0～60 weight %, alcohols is preferably 5～30 weight %.
[additive]
Also can in coating, add additives such as plasticizer, ultra-violet absorber, anti-deterioration agent, below various additives be elaborated.
(plasticizer)
As spendable plasticizer among the present invention, there is not particular determination, preferably use following plasticizer, in the phosphate system triphenyl is arranged, the trimethylphenyl phosphate, the tolyl diphenyl phosphoester, the octyl group diphenyl phosphoester, diphenyl biphenyl phosphate, the trioctylphosphine phosphate, Tributyl phosphate ester etc., in the phthalate ester system diethyl phthalate ester is arranged, the dimethoxy ethyl phthalate ester, the dimethyl phthalate ester, dioctyl phthalate (dop) etc., in the ethyl glycolate system glyceryl triacetate is arranged, tributyrin, fourth phthaloyl butyl alcohol acid esters, second phthaloyl ethyl hexanol acid esters, first phthaloyl ethyl hexanol acid esters, fourth phthalandione butyl alcohol acid esters etc., these can use separately also and can and use.Also can add the spy open flat 11-80381 communique, with the 11-124445 communique, with the plasticizer of putting down in writing in the 11-248940 communique.The mixing of these plasticizers in coating can contain 0.1～20 weight % for cellulose acyl ester.
(ultra-violet absorber)
In coating, also can add ultra-violet absorber.The ultra-violet absorber that preferably contains one or two or more kinds.The liquid crystal ultra-violet absorber considers that from anti-liquid crystal deterioration preferably the following ultraviolet absorption ability of wavelength 370nm is good, and, consider that from the liquid crystal expressivity the above visible absorption of the most handy wavelength 400nm is few.Oxybenzone based compound, BTA based compound, salicylate based compound, benzophenone based compound, cyanoacrylate based compound, nickel complex salt based compound etc. are for example arranged.Best ultra-violet absorber is BTA based compound and benzophenone based compound.Wherein, the BTA based compound, because unwanted seldom painted to cellulose esters, so best.And then also can adding the spy, to open the BTA of putting down in writing in the flat 8-29619 communique be ultra-violet absorber or with the ultra-violet absorber of putting down in writing in the 8-239509 communique.In addition, also can add known ultra-violet absorber.These ultra-violet absorbers for cellulose acyl ester, preferably mix 0.001～5 weight % in coating.For example, also can adding the spy, to open the BTA of putting down in writing in the flat 8-29619 communique be ultra-violet absorber, or with the ultra-violet absorber of putting down in writing in the 8-239509 communique.
Prevent agent as best ultraviolet ray, have 2,6-two-tert-butyl-p-cresols, times [3-(3 for pentaerythrite-four, 5-two-tert-butyl-4-hydroxyphenyl) propionic ester], trietbhlene glycol-two [3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionic ester], 1, [3-(3 for 6-hexylene glycol-two, 5-two-tert-butyl-4-hydroxyphenyl) propionic ester], 2,4-pair-(n-octylsulfo)-6-(4-hydroxyl-3,5-two-tert-butylbenzene amido)-1,3, the 5-triazine, 2,2-sulfo--divinyl is two, and [3-(3,5-two-tert-butyl-4-hydroxyphenyl) propionic ester], octadecyl-3-(3,5-two-tert-butyl-4-hydroxyphenyl) propionic ester, N, N '-own methylene bis (3,5-two tert-butyl-4-hydroxyl-hydrogenation Na ミ De), 1,3,5-trimethyl-2,4, three times (3 of 6-, 5-two-tert-butyl-4-acrinyl) benzene, three times of (3,5-2-tert-butyl-4-acrinyl)-fulminuric acid esters etc.Preferably 2,6-two-tert-butyl-P-cresols, pentaerythrite-four times [3-(3,5-two-tert-butyl-4-hydroxyphenyl) propionic ester, trietbhlene glycol-two [3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionic ester.For example also can and use N, nonactive dose and three times phosphorus such as (2,4-two-tert-butylbenzene base) phosphide of metal of hydrazine based compounds such as N '-two [3-(3,5-two-tert-butyl-4-hydroxyphenyl) propiono] hydrazine are processing stabilizers.The addition of these compounds preferably contains 0.001-5 weight % for cellulose acyl ester.
(powder particles)
For easy the to be sliding property of improving film and the anti-cementability under the high humility, can use the roughening agent of powder particles in the coating.The average height of roughening agent surface protuberances is preferably 0.005～10 μ m, more preferably 0.01～5 μ m.Though this thrust from the teeth outwards can be a lot, when required, there is the problem that forms smog.As the roughening agent that uses, can use inorganic compound or organic compound.As inorganic compound, the fine powder that inorganic matters such as barium sulfate, colloid manganese, titanium dioxide, barium strontium sulfate, silica, aluminium oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talcum, kaolin, calcium sulfate are arranged, for example utilize silica such as synthetic silica that damp process and silicic acid gelization obtain in addition and utilize the titanium piece and dioxy titanium (rutile-type and Detitanium-ore-type) that sulfuric acid generates etc.Also can pulverize the back from the bigger for example inorganic matter more than the 20 μ m of size ratio obtains by classification (vibration screening, air classification etc.).As organic compound, it is that resin, polyolefin-based resins, polyester based resin, polyamide-based resin, poly-imines are that resin or polyvinyl fluoride are the crushing and classification thing of organic high molecular compounds such as resin, starch that polytetrafluoroethylene (PTFE), cellulose ethanoate, polystyrene, poly methyl methacrylate, poly-propyl methyl acid esters, polymethacrylates, polyethylene carbonic ester, acrylic acid phenylethylene resin series, silicone-based resin, polycarbonate resin, benzo triamido triazine resin, melamino-for maldehyde are arranged.Perhaps, use is hanged the synthetic macromolecular compound of turbid polymerization, is utilized spray drying process or dispersion method to be processed into the macromolecular compound or the inorganic compound of ball-type.When powder particles adds in a large number, can produce drawbacks such as infringement film flexibility, so preferably contain 0.001～5 weight % for cellulose acyl ester.
(releasing agent)
In order to be easy to stripping operation, also can in coating, add releasing agent.For releasing agent, the high melting point paraffin class is arranged, higher fatty acids and salt thereof or ester class, silicone oil, polyvinyl alcohol, low molecular weight polyethylene, vegetable protein derivative etc., but be not limited to these, the addition of releasing agent, owing to have influence on the gloss and the flatness of film surface, so, preferably contain 0.002～2 weight % for cellulose acyl ester.
(fluorine is a surfactant)
Adding fluorine in the also available coating is surfactant.Fluorine is that surfactant is with the surfactant of fluorocarbon chain as hydrophobic group, owing to can significantly reduce surface tension, so as smears and antistatic agent in the organic solvent.As fluorine is surfactant, and C is arranged
8F
17CH
2CH
2O-(CH
2CH
2O)
10-OSO
3Na, C
8F
17SO
2N (C
3H
7) (CH
2CH
2O)
16-H, C
8F
17SO
2N (C
3H
7) CH
2COOK, C
7F
15COONH
4, C
8F
17SO
2N (C
3H
7) (CH
2CH
2O)
4-(CH
2)
4-SO
3Na, C
8F
17SO
2N (C
3H
7) (CH
2)
3-N
+(CH
3)
3I
-, C
8F
17SO
2N (C
3H
7) CH
2CH
2CH
2N
+(CH
3)
2-CH
2COO
-, C
8F
17CH
2CH
2O (CH
2CH
2O)
16-H, C
8F
17CH
2CH
2O (CH
2)
3-N
+(CH
3)
3I
-, H (CF
2)
8-CH
2CH
2OCOCH
2CH (SO
3) COOCH
2CH
2CH
2CH
2-(CF
2)
8-H, H (CF
2)
6CH
2CH
2O (CH
2CH
2O)
16-H, H (CF
2)
8CH
2CH
2O (CH
2)
3-N
+(CH
3)
3I
-, H (CF
2)
8CH
2CH
2OCOCH
2CH (SO
3) COOCH
2CH
2CH
2CH
2C
8F
17, C
9F
17-C
6H
4-SO
2N (C
3H
7) (CH
2CH
2O)
16-H, C
9F
17-C
6H
4-CSO
2N (C
3H
7) (CH
2)
3-N
+(CH
3)
3I
-Deng, certainly not only for ground these.Fluorine is the addition of surfactant, for cellulose acyl ester, preferably contains 0.001～2 weight %.
In any stage before the solution modulation or after the modulation, also can in coating, add various additives as required.Heat stabilizers such as salt, antistatic agent, fire retardant, lubrication prescription, finish of alkaline-earth metals such as calcium, magnesium etc. are arranged.
[modulation of coating]
(swelling operation)
For the modulation of coating, describe with regard to using the situation of cellulosic triacetate in the polymer.At the beginning, with above-mentioned cellulosic triacetate particle and solvent, the swelling operation of utilizing solvent that the cellulosic triacetate particle is expanded and moistens.Best-10～55 ℃ of the temperature of swelling operation is at room temperature implemented usually.The ratio of cellulosic triacetate and solvent depends on the concentration of final gained solution.Say that generally the amount of cellulosic triacetate in the mixture is preferably 5～30 weight %, 8～20 weight % more preferably, especially good is 10～15 weight %.The mixture of solvent and cellulosic triacetate preferably is stirred to till the abundant swelling of cellulosic triacetate.Usually mixing mixing time is 1～180 minute.Sometimes only just can proceed to dissolving from swelling with mixing stirring, at this moment, heating process described later etc. make cellulosic triacetate be dissolved in operation in the solvent, have also carried out with regard to not necessarily needing.In the swelling operation, the composition except solvent and cellulosic triacetate for example also can add plasticizer, anti-deterioration agent, dyestuff and ultra-violet absorber.
(heating process)
Then carrying out heating process is heated to above-mentioned coating more than 130 ℃.Heating-up temperature is more than 130 ℃, and is better more than 160 ℃, better more than 180.Yet when surpassing 250 ℃, the cellulosic triacetate in the coating can produce decomposition, and the infringement film quality is very undesirable.In this case, the firing rate more than 1 ℃/minute is better, and better more than 2 ℃/minute, especially good more than 4 ℃/minute, ideal is more than 8 ℃/minute.The faster the better for firing rate, and 10000 ℃/second is theoretical upper limit, and 1000 ℃/second is the technology upper limit, and same, 100 ℃/second is practical upper limit.So-called firing rate is the poor of temperature when beginning to heat and final heating-up temperature, and the time that reaches final heating-up temperature when using from the heating beginning is removed the value that obtains.Heating means can adopt any methods such as autoclave mode, multi tube heat exchanger, screw extruder, static mixer.
Heat time heating time, best more than 20 seconds, below 4 hours.When being lower than 20 seconds heat time heating time, residual in the coating of heating for dissolving have an insoluble matter, can not produce high-quality film.Even utilized filtering to remove this insoluble matter,, also be disadvantageous because filter life is of short duration.Phase beginning of heat time heating time begins when achieving the goal temperature to measure, and final period, measures when the purpose temperature begins to cool down.The cooling of device can be adopted the nature cooling, also can adopt and force cooling.
(pressurization operation)
In above-mentioned heating process,, preferably coating is heated to the temperature more than the solvent boiling point under atmospheric pressure adjusting under the pressure that solution do not seethe with excitement.By pressurization, can prevent the coating foaming, can obtain uniform coating.At this moment applied pressure depends on the relation of heating-up temperature and solvent boiling point.
(refrigerating work procedure)
Before heating process, above-mentioned coating is cooled to-100～-10 ℃ and carries out refrigerating work procedure, be effectively to obtaining the optical characteristics good film.Do not allow in the diffluent system at normal temperatures and system that insoluble matter is a lot of in, cool off or heat or both when being used in combination, can modulate good coating.By cooling, solvent can be fast and is impregnated into effectively in the cellulosic triacetate, has promoted dissolving.The effective temperature condition is-100～-10 ℃.In refrigerating work procedure, for fear of when cooling dewfall cause that moisture sneaks into, preferably use closed container.When the decompression cooling, cool time can be shortened.In order to implement decompression, preferably use the resistance to pressure container.In the present invention, to implement after above-mentioned heating process also be effective to this refrigerating work procedure.In dissolving when insufficient, also can repeat to implement operation from being cooled to heat.Whether fully dissolve, can utilize the perusal solution appearance to judge.
[solution film-forming method]
The above-mentioned coating that obtains is injected in the mixing drum, stir with paddle and form homogeneous solution.At this moment can in coating, mix additives such as hydrophobicity plasticizer and ultra-violet absorber.Coating is removed foreign material with being pumped into filter.Among the present invention, for example with the method for using the continuity fluxion strap and the method that continues the rotating cylinder that flows, by this coating system film.
[the mobile mould of continuity]
The method of using the continuity fluxion strap as supporter is described at the beginning.As depicted in figs. 1 and 2, the solution film-forming device has the surface and carries out 1 pair of rotation rotating cylinder 3 of mirror process (only illustrating 1 among the figure).Reeling on this a pair of rotation rotating cylinder 3 does not have the continuity of end fluxion strap 2, and when rotation rotating cylinder 3, this continuity fluxion strap 2 moves by throughput direction A1.1 direction and side face at this rotation rotating cylinder 3 are provided with curtain coating mould 1 with leaving slightly.Be provided with pressure-reducing chamber 6 in the back of this curtain coating mould 1.This pressure-reducing chamber 6 is connected with suction machine 9 with surge chamber 8 by suction tube 7.Symbol 10a is the film that utilizes this solution film-forming device to form, and strips down from casting belt 2, presses transfer direction B and carries.
Among Fig. 3, curtain coating mould 1 is made of curtain coating die ontology 1a and a pair of feed flow nozzle 23.Connect coating feed flow pipe arrangement 20 on curtain coating die ontology 1a, by hold-up tank (not shown) coating is sent among the curtain coating die ontology 1a, feed flow nozzle 23 is fixed on the curtain coating die ontology 1a.This feed flow nozzle 23 is connected with solvent tank 21, and wherein the solvent of splendid attire is carried by liquid-feeding pump 22.In this curtain coating die ontology 1a, be provided with manifold 11 and slit 13.
As shown in Figure 4, above-mentioned manifold 11 forms coating suspension bracket shape, and its middle body is provided with the coating supply port 12 that is connected with coating feeding pipe arrangement 20.Both sides at curtain coating die ontology 1a are provided with liner 14, and manifold 11 is sealed by side plate 15 by this liner 14.Form slit 13 at the downside of manifold 11, will continue the coating 10 that flows by this slit 13 and be squeezed into the film shape, continue from the mould otch 16 of curtain coating mould 1 end and flow on the casting belt 2.
Among Fig. 5, a pair of feed flow nozzle 23 is set along the outer peripheral face of liner 14.This feed flow nozzle 23 is by having the material of corrosion resistance to form to the chlorine series solvent, as metals such as stainless steels, or resin materials such as pottery, fluororesin etc., internal diameter is preferably 0.1～0.8mm, the best 0.2～2.0mm of external diameter.The front end 23a of feed flow nozzle 23 is positioned at the end of slit 13.Distance L 1 on front end 23a and the mould otch 16 between the end of curtain coating coating 10 is 0.5～3.0mm, is preferably 1.0～2.0mm.With respect to the continuity flow direction F of curtain coating coating 10, the angle θ that the front end of feed flow nozzle 23-(nozzle segment) 23a forms is 90 degree, and angle θ suits to determine in the scope of 10～90 degree.In the scope of above-mentioned L1, θ, can feed flow nozzle 23 be installed on the curtain coating die ontology 1a any known method to set up the also configurable inboard or the outside at curtain coating die ontology 1a.
Solvent 24 is soluble for the solute of continuity fluent solution, can be only to good solvents of solute such as methylene chloride and methyl acetates, also can be the mixed solvent of good solvent and methyl alcohol, ethanol, butanols, acetone grade solvent.The ratio of inferior solvent is 0～90 weight %, best 0～60 weight %.
This solvent 24 is discharged from the front end 23a of feed flow nozzle 23, flows near the mould otch 16 in slit 13 ends.The suitable flow of solvent 24 is 0.05～0.5ml/ minute, is preferably 0.1～0.2ml/ minute.
If this flow change of control can promote to prevent the vibration of curtain coating coating on the casting belt 2 and stretch.For this flow, measure average discharge Vave, maximum stream flow Vmax, minimum discharge Vmin in the certain hour, and calculate the rate of change of flow thus.This mobility table be shown (Vmax-Vave)/Vave} * 100 or (Vmin-Vave)/Vave} * 100, be controlled at ± 50% with interior (in 0.002 second～100 seconds), preferably be controlled at ± 10% with interior (in 0.005 second～10 seconds).
In order to control the rate of change,, can use reciprocating pumps such as rotary pump, diaphragm pump, ram type pump such as gear pump, the most handy ram type pump as liquid-feeding pump 22.With the flow of flowmeter mensuration solvent 24, also can utilize the liquor charging amount of feedback controling mode control pump.
The solvent 24 that flows out by feed flow nozzle 23, on mould otch 16 expansion moistening, arrive the flow end of coating 10 of continuity.Yet when solvent 24 is difficult to expand when moistening, the solvent 24 that is spued by nozzle 23 supplying to before continuity flows on the coating 10, forms droplet-like on mould otch 16, be dropped on the continuity fluxion strap 2, constitutes the reason that influences products appearance.Solvent 24 hyper expanded on mould otch 16 is moistening, and the flow part of coating 10 of continuity invades between the end of the front end 23a of feed flow nozzle 23 and curtain coating coating 10, carries out drying, is easy to separate out solutes such as polymer.Therefore, dislike strong influence for mobile the causing of stable continuity.
For fear of this situation, the viscosity of solvent is 0.2～3.0cp, more preferably the surface tension of 0.3～1.0cp, solvent is 15～50dyn/cm, is preferably 20～30dyn/cm.In order to form stable meniscus between feed flow spray nozzle front end and coating end, the rate of outflow of feed flow nozzle is 10～110cm/ second, best 20～60cm/ second.
As the control method of above-mentioned each factor, can adjust viscosity by the mixing ratio of adjusting each solvent in the used mixed solvent or the temperature of adjusting solvent, also can be by adjusting the mixing ratio adjustment form surface tension of each solvent in the used mixed solvent.The contact angle of solvent and feed flow spray nozzle front end and mould cut end is adjusted by the roughness and the Facing material (formation such as plating, fluororesin coating) that change feed flow spray nozzle front end and mould otch front end.
As shown in Figure 6, in the pressure-reducing chamber 6, be provided with suction opening 6a in position with mobile coating 10 opposites of continuity.Suction machine 9 during by suction opening 6a suction air, reduces to continue the air pressure in the gap between coating 10 and the suction opening 6a that flows by suction tube 7 and surge chamber 8.The mobile coating 10 of continuity continues mobile with homogeneous thickness and surface on casting belt 2 like this.The coating 10 that continuity is flowed carries out drying on casting belt 2, so the mobile coating 10 of continuity be solidified into membranaceous after, as depicted in figs. 1 and 2, peel off by peeling off roller 5, be sent to stent elongator (not shown) as film 10a.As shown in Figure 7, the present invention also goes for not having the device in pressure-reducing chamber.
Utilize handle thin films 10a limit, stent elongator limit to extend and drying.The film 10a that is come out by the stent elongator is sent to dry section, after the drying, is cooled to normal temperature by the cooling zone while carrying by several rollers, and is reeled by up-coiler.Before the coiling, preferably pay annular knurl, and cut edge.The drying means that coating 10 is flowed in continuity also can adopt known any method.
In Fig. 8 and Fig. 9, the mobile coating 10 of continuity continues mobile on curtain coating rotating cylinder 4.The coating 10 that continuity is flowed behind the dry solidification, is peeled off by peeling off roller 5 on the curtain coating rotating cylinder 4 according to direction of rotation A2 rotation, presses throughput direction as film 10a and carries.
[common continuity is flowed]
Solution film-forming method of the present invention also is applicable to modulates 2 kinds to coat the solution film-forming method that carries out overlapping coating simultaneously.For example, when forming film, in the coating that internal layer is used, contain the plain triacetate of some fibre more, on the positive and negative of internal layer, form in the coating of outer usefulness and contain fewer cellulosic triacetate by 3 layers.Utilize common continuity flow method, make this coating of 3 layers continue the film that flows and form simultaneously, have good flatness, the transparency or shaping processability.
For example, shown in Figure 10, feed zone 19 has been installed in curtain coating mould 1, by feed zone 19 several coatings is collaborated.The coating 10 that is flowed out by 1 continuity of curtain coating mould has several layers (among Figure 10 being 3 layers) like this, so form by several layers of film that constitutes.
And then, as shown in figure 11, also can use the common curtain coating mould 110 of a plurality of manifold types.Curtain coating mould 110 has 3 manifolds 111,112,113 altogether, can form the film of 3-tier architecture.In curtain coating mould 110 altogether, about with Fig. 3 curtain coating mould same section and structure, pay identical symbol, omission is described.Common continuity flow method in the solution film-forming method of the present invention is not limited in the form of Figure 10 and Figure 11.
In above curtain coating mould, though used coating suspension bracket mould, be not limited in this, also can use the mould of other shapes such as T mould.
Mould compressed gap in the solution film-forming method is set at 0.2～3mm usually, is preferably 0.5～2.5mm, but is not limited in this.
Interval between curtain coating mould and the supporter (casting belt or curtain coating mould) is set at 1～10mm usually, is preferably 1.5～6mm, but is not limited in this.
The decompression degree P in pressure-reducing chamber is set at-500 usually～-10Pa, be preferably-400～-20Pa, but be not limited in this.
Continuity flowing velocity V is generally 3～150m/ minute, is preferably 10～100m/ minute, but is not limited in this.
Film thickness t is preferably 20～500 μ m, 30～300 μ m more preferably, and especially good is 35～200 μ m, this is not had particular determination.
[goods]
The film that obtains can be used as polarization board protective film.This polarization board protective film is fitted on the light polarizing film two sides that is formed by polyvinyl alcohol etc., forms Polarizer.Also can be used as the exhibiting optical function film, on film, form the optics lining and repay film as optical compensating gage paste is paid; On film, form the lamination antireflection film of antiglare layer etc.But by these goods also component part liquid crystal indicator.
Embodiment
The raw material that uses in the film making process, as follows.
Cellulosic triacetate 100 weight portions
Xenyl diphenyl phosphoester 5 weight portions
Methylene chloride 315 weight portions
Methyl alcohol 60 weight portions
N-butanols 10 weight portions
Dried products thickness 40,80 μ m
The decompression degree 0～500Pa in pressure-reducing chamber
Secondary flow coating was formed when common continuity was flowed
Cellulosic triacetate 100 weight portions
Xenyl diphenyl phosphoester 5 weight portions
Methylene chloride 400 weight portions
Methyl alcohol 75 weight portions
N-butanols 13 weight portions
Dried products thickness adds up to 80 μ m
Main flow thickness 76 μ m
Secondary flow thickness respectively is 2 μ m
Distance h=the 3.5mm of curtain coating mould and supporter
Mould otch slit d=1.0mm
Continuity flowing velocity 50m/ minute
With each condition of embodiment, estimate mould otch edge's peeling time of origin and degree, and peel off residual stain on the supporter.
[embodiment 1]
Carrying out the individual layer continuity with following condition flows.Condition to mould notching edge donor solvent is as follows.
1) flow is 0.2ml/ minute
2) speed that the spues 42.5cm/ second of feed flow nozzle inside diameter φ 0.1mm, external diameter φ 0.3mm, feed flow nozzle.
3) the viscosity 0.5cp of solvent
4) the surface tension 26dyn/cm of solvent
5) contact angle of solvent and feed flow spray nozzle front end and mould otch front end is 30 degree
6) end of the mobile coating of continuity and the distance L 1 of feed flow spray nozzle front end portion are 1.0mm
7) supply with from the along continuous straight runs position, end of the mobile coating of mould otch continuity
8) the solvent composition chloromethane supports 60 weight %
Methyl alcohol 40 weight %
9) nozzle material SUS316
Peeling not taking place through 24 hours, does not almost peel off residual stain on the supporter.
[embodiment 2]
Continue mobile jointly by following condition.Solvent is fed to the condition of mould otch upper edge, as following.
1) flow is 0.2ml/ minute
2) feed flow nozzle inside diameter φ 0.1mm, external diameter φ 0.3mm, feed flow nozzle spue speed 42.5cm/ second
3) the viscosity 0.5cp of solvent
4) the surface tension 26dyn/cm of solvent
5) contact angle of solvent and feed flow spray nozzle front end and mould otch front end is 30 degree
6) end of the mobile coating of continuity and the distance L 1 of feed flow spray nozzle front end are 1.0mm
7) supply with from the flow position of end along continuous straight runs of coating of mould otch continuity
8) solvent composition chlorination methylene 60 weight %
Methyl alcohol 40 weight %
9) nozzle material SUS316
Peeling not taking place through 24 hours, almost produces on the supporter and peel off residual stain.
[embodiment 3]
Carry out individual layer continuity by following formulation for coating material and flow, solvent is fed to condition on the mould notching edge, as follows.
Cellulosic triacetate 100 weight portions
Xenyl diphenyl phosphoester 5 weight portions
Methyl acetate 315 weight portions
Methyl alcohol 60 weight portions
N-butanols 10 weight portions
, with screw extruder cellulose iii second vinegar ester solution is sent again cellulosic triacetate swelling 30 minutes with solvent,, kept 3 minutes down at-70 ℃ by the cooling zone.Use is cooled to-80 ℃ cryogen (system Novac FC-77 of 3M society or HFE-7100) enforcement cooling by refrigerator.The solution that cooling obtains is sent in the stainless steel container made, stirred 2 hours down at 50 ℃.With absolute filtering accuracy is filter paper (Japan's filter paper (strain) system, #63) filtration of 0.01mm.
1) flow is 0.2ml/ minute
2) feed flow nozzle inside diameter φ 0.1mm, external diameter φ 0.3mm, feed flow nozzle spue speed 42.5cm/ second
3) the viscosity 0.36cp of solvent
4) the surface tension 25dyn/cm of solvent
5) contact angle of solvent and feed flow spray nozzle front end and mould otch front end is 30 degree
6) end of the mobile coating of continuity and the distance L 1 of feed flow spray nozzle front end are 1.0mm
7) supply with from the flow position of end along continuous straight runs of coating of mould otch continuity
8) solvent composition methyl acetate 100 weight %
9) nozzle material SUS316
Peeling not taking place through 24 hours, produces on supporter and peel off residual stain.
[comparative example 1]
Carrying out the individual layer continuity by following condition flows.Solvent is added drop-wise to condition on the mould notching edge, as follows.
1) flow is 1.0ml/ minute
2) speed that the spues 2.1cm/ second of feed flow nozzle inside diameter φ 0.1mm, external diameter φ 1.6mm, feed flow nozzle
3) the viscosity 0.5cp of solvent
4) the surface tension 26dyn/cm of solvent
5) contact angle of solvent and feed flow spray nozzle front end and mould otch front end is 30 degree
6) end of the mobile coating of continuity and the distance L 1 of feed flow spray nozzle front end are 3.0mm
7) with respect to the width of mould otch, supply with from the position vertically, end of the mobile coating of mould otch continuity
8) solvent composition chlorination methylene 60 weight %
Methyl alcohol 40 weight %
9) nozzle material SUS316
Also do not produce peeling through 24 hours, but it is a lot of to peel off residual stain on the skin support body.
[comparative example 2]
For the condition of comparative example 1, flow is taken as 0.6ml/ minute.The result is, produces peeling after 10 hours, can not proceed continuity and flow.
[embodiment 4]
In the formulation for coating material of embodiment 3, as secondary flow, continue mobile jointly the coating of following prescription.
Fiber triacetate (the viscosity 305mpas of 6 quality % in degree of exchange 2.83, viscosity average polymerization degree 320, moisture content 0.4 quality %, the methylene chloride solution) 25 weight portions
Methyl acetate 75 weight portions
Acetone 5 weight portions
Methyl alcohol 5 weight portions
Ethanol 5 weight portions
Plasticizer A (dipentaerythritol six acetic acid esters) 1 weight portion
Plasticizer B (triphenyl) 1 weight portion
Particulate (silica, particle diameter 20nm) 0.1 weight portion
UV agent a:(2,4-pair-(the n-suffering is at sulfo-)-6-(4-hydroxyl-3,5-two-tert-butylbenzene amido)-1,3,5-triazines 0.1 weight portion
UV agent b:2 (2 '-hydroxyl-3 ', 5 '-two-tert-butylbenzene base)-5-chlorobenzotriazole
0.1 weight portion
UV agent c:2 (2 '-hydroxyl-3 ', 5 '-two-tert-, penta phenyl)-5-chlorobenzotriazole
0.1 weight portion
C
12H
25OCH
2CH
2O-P (=O)-(OK)
20.05 weight portion
Composition methyl acetate 90 weight portions of delivery solvent
As a result, peeling not taking place yet through 24 hours, does not almost peel off residual stain on supporter.
[embodiment 5]
Press the condition of embodiment 1, use curtain coating mould shown in Figure 3, with cycle of 1Hz the flow rate of change of solvent is controlled at ± 50% in.Can suppress to make the mobile coating end disorder of continuity in the film in view of the above, and it is mobile to proceed continuity.
[embodiment 6]
Press the condition of embodiment 1 and use curtain coating mould shown in Figure 3, with cycle of 1Hz the flow rate of change of solvent is controlled at ± 10% in.In view of the above, the mobile coating end of continuity does not have disorder in the system film, and the thickness of the mobile coating of whole continuity does not produce change on supporter.Dried film does not produce bad outward appearance because of thickness deviation yet.
[comparative example 3]
Use curtain coating mould shown in Figure 3 by the condition of embodiment 1, with cycle of 1Hz the flow rate of change of solvent is controlled at ± 55% in.In this case, the end of the mobile coating of continuity produces very big disorder in the system film, can not proceed continuity and flow.
And then, use the embodiment 3 that forms by said method and the film of embodiment 4, by following sequentially built by being coated with the antireflection film that forms.
(the antiglare layer modulation of coating fluid A)
(DPHA, Japanese chemical drug (strain) system and two (the 4-methacryl thio-phenyl) sulfide of 125g (MPSMA, Sumitomo refine (strain) make) are dissolved in the mixed solvent of methyl ethyl ketone/cyclohexanone=50/50 weight % of 439g with the mixture of 125g dipentaerythritol amyl group acrylate and dipentaerythritol ethylhexyl acrylate.In the solution that obtains, add following solution, that is the solution that dissolving 5.0g Photoepolymerizationinitiater initiater (イ Le ガ キ ユ ア 907, チ バ ガ イ ギ-society's system) and 3.0g light sensitizer (カ ヤ キ ユ ア-DETX, Japanese chemical drug (strain) system) form in the 49g methyl ethyl ketone.With this solution coat, carry out UV cured and the flexion rate of filming that obtain is 1.60.And then in this solution, add 10g average grain diameter 2 μ m crosslinked polystyrene particle (trade name: SX-200H, combine chemistry (strain) system of grinding), use the high speed dispersion device, stirred 1 hour with 5000rpm, after disperseing, polypropylene filter made device with aperture 30 μ m filters, and is modulated into the coating fluid A of antiglare layer.
(the antiglare layer modulation of coating fluid B)
In the mixed solvent of 104.1g cyclohexanone, 61.3g methyl ethyl ketone, stir with gas distributor on the limit, and the limit is added 217.0g and contained the dura mater coating fluid (デ ソ ラ イ ト KZ-7886A, JSR (strain) system) that zirconia disperses thing.With this solution coat, carry out UV cured and the flexion rate of filming that obtain is 1.61.Further in this solution, add the crosslinked polystyrene particle (trade name: SX-200H, comprehensive chemistry (strain) system of grinding) of 5g average grain diameter 2 μ m, use the high speed dispersion device, stirred 1 hour with 5000rpm, after disperseing, polypropylene filter made device with aperture 30 μ m filters, and is modulated into the coating fluid B of antiglare layer.
(the antiglare layer modulation of coating fluid C)
The mixture of 91g dipentaerythritol amyl group acrylate and dipentaerythritol ethylhexyl acrylate (DPHA, Japanese chemical drug (strain) system), 199g are contained dura mater coating fluid (デ ソ ラ イ ト KZ-7115, JSR (strain) system) and the 19g that zirconia disperses thing contain the dura mater coating fluid (デ ソ ラ イ ト KZ-7161, JSR (strain) make) that zirconia disperses thing, be dissolved in the mixed solvent of methyl ethyl ketone/cyclohexanone=54/46 weight % of 52g.In the solution that obtains, add 10g Photoepolymerizationinitiater initiater (イ Le ガ キ ユ 907, チ バ ガ イ ギ-society's system).With this solution coat, carry out UV cured and the flexion rate of filming that obtain is 1.61.In this solution, add the following dispersion liquid of 29g again, promptly, in the mixed solvent of methyl ethyl ketone/cyclohexanone=54/46 weight % of 80g, stir the dispersion liquid of the crosslinked polystyrene particle that disperseed 20g average grain diameter 2 μ m in 1 hour (trade name: SX-200H, combine chemistry (strain) system of grinding) with 5000rpm with the high speed dispersion device, after the stirring, polypropylene filter made device with aperture 30 μ m filters, and is modulated into the coating fluid C of antiglare layer.
(the hard membrane layer modulation of coating fluid D)
Be added in the solution that has dissolved the UV cured property of 250g dura mater composition (デ ソ ラ イ ト KZ-7689,72 weight %, JSR (strain) system) in 62g methyl ethyl ketone and the 88g cyclohexanone, after this solution coat, carry out UV curedly, the flexion rate of filming that obtains is 1.53.Again the polypropylene filter made device of this solution with aperture 30 μ m filtered, be modulated into the coating fluid D of hard membrane layer.
(low bending analysed the modulation of rate layer with coating fluid)
In the heat cross-linking fluoropolymer (TN-0.49, JSR (strain) system) of 20093g flexion rate 1.42, add the 8gMEK-ST (SiO of average grain diameter 10～20nm, solid component concentration 30 weight %
2The MEK of colloidal sol disperses thing, daily output chemistry (strain) system) and the 100g methyl ethyl ketone, after the stirring, use the polypropylene filter made device of aperture 1 μ m to filter, be modulated into low flexion rate layer coating fluid.
With the bar type spreader above-mentioned hard membrane layer is coated on the thick triacetylcellulose film of 80 μ m that embodiment 3 makes, after 120 ℃ of following dryings, with the air cooling metal halide lamp (ア イ グ ラ Off イ Star Network ス (strain) system) of 160w/cm, with 400mw/cm with coating fluid
2Illumination, 300mJ/cm
2The exposure irradiation ultraviolet radiation makes the coating layer sclerosis, forms the thick hard membrane layer of 2.5 μ m.Be coated with above-mentioned antiglare layer coating fluid A with the bar type spreader thereon, with above-mentioned hard membrane layer the same terms under carry out drying, UV cured, form the antiglare layer that thickness is about 1.5 μ m.After upward low-refraction is used 80 ℃ of following dryings of coating fluid with the coating of bar type spreader, under 120 ℃, carry out 10 minutes heat cross-linkings more thereon, form the thick low flexion rate layer of 0.096 μ m.
Then use the film of embodiment 3, replace antiglare layer coating fluid B with antiglare layer with coating fluid A, other conditions are identical, make antireflection film.And then, replacing antiglare layer coating fluid C with antiglare layer with coating fluid A, other conditions are identical, also make antireflection film.
And then, by the film of embodiment 4, use antiglare layer coating fluid A, B, each among the C, identical with above-mentioned manufacturing conditions, make antireflection film.
[evaluation of antireflection film]
To in order to above-mentioned preparation method, (antiglare layer A, B C) and 6 kinds of antireflection films forming of the film (antiglare layer A, B, C) of embodiment 4, carry out following project appraisal by the film of embodiment 3.The result who is obtained by following evaluation method is shown in Table 1.
(1) specular reflectivity and tone
ア ダ プ -ARV-474 is installed on the spectrophotometer V-550 (Japanese beam split (strain) system), in the zone of 380～780nm wavelength, measure the specular reflectivity of the angle of emergence-5 degree of 5 ° of incidence angles, calculate the average reflectance of 450～650mm, estimate antireflection.By the reflectance spectrum of measuring, calculate L* value, a* value, b* value with respect to the CIE 1976L*a*b* colour space of the photochromic accent of expression normal reflection of the 5 degree incident lights of CIE standard light source D65, estimate catoptrical tone.
(2) integrated reflectivity
ア ダ プ -ILV-474 is installed on the spectrophotometer V-550 (Japanese beam split (strain) system), in the wavelength region may of 380～780nm, measures the integrated reflectivity of 5 ° of incidence angles, calculate the average reflectance of 450～650mm.
(3) smog
Use fume-meter MODEL 1001DP (Japanese electric look industry (strain) system) to measure the smog of gained antireflection film.
(4) pencil hardness evaluation
As the traumatic resistance index, carry out the pencil hardness evaluation of putting down in writing among the JIS K5400.Antireflection film after under 25 ℃, 60%RH moistening 2 hours, is used pencil with the 3H test of stipulating among the JIS S6006, with the 1kg loading
All do not have damage in n=5 the evaluation: zero
Damage is 1 or 2 in n=5 the evaluation: △
Damage is more than 3 in n=5 the evaluation: *
(5) contact angle determination
As the index of surperficial stain resistance, optical material damping under 25 ℃, 60%RH was measured the contact angle to water, as the index of paying property of fingerprint after 2 hours.
(6) coefficient of kinetic friction is measured
As the index of surface smoothness, with coefficient of kinetic friction evaluation.The coefficient of kinetic friction is after 2 hours, to utilize the HEIDON-14 dynamic friction to measure machine at 25 ℃, 60% time damping of relative humidity test portion, with 5mm φ stainless steel ball, loading 100g, speed 60cm/min, the value of mensuration.
(7) anti-dazzle property evaluation
That uses no louver exposes fluorescent lamp (8000cd/m
2) shine upon the anti-dazzle property film of making, by the fog-level of following its reflection image of benchmark evaluation.
Do not observe the profile of fluorescent lamp: ◎ fully
Observe the profile of fluorescent lamp a little: zero
Though the fuzzy fluorescent lamp of seeing can contour identification: △
Fluorescent lamp is fuzzy hardly: *
The planar evaluation of (8) filming
With the reverberation of fluorescent lamp with through light, translation-angle checks that sensory evaluation causes the concavo-convex program of film coated surface because of film gauge variation.
Almost do not have concavo-convex: ◎
Concavo-convex very weak, seldom: zero
Concavo-convex very weak, a lot: △
Concavo-convex very strong: *
By the antireflection film that the film of embodiment 3 and embodiment 4 forms, any one anti-dazzle property, antireflection are all very good, and tone is very weak, and be also very good as the evaluation result of reflection reflection protection film rerum naturas such as pencil hardness, paying property of fingerprint, the coefficient of kinetic friction.
Below, use the film of embodiment 4 to make anti-dazzle property, antireflection Polarizer.Use this Polarizer to make when having disposed the liquid crystal indicator of anti-reflection layer on the top layer, owing to there is not outer light to mirror, so obtain good contrast, because anti-dazzle property, so have the inapparent good sense of vision of reflection image, the fingerprint of paying is also very good.
In the foregoing description 3 and embodiment 4, change the mixed solvent ratio of components that modulation coating is used.Among the embodiment 3, methyl acetate is that 82 weight %, ketone are that 0 weight %, alcohols (ethanol, n-butanols) are 18 weight %.Among the embodiment 4, methyl acetate is that 75 weight %, ketone (cyclopentanone, acetone) are that 15 weight %, alcohols (methyl alcohol, ethanol) are 10 weight %.In such invention,, also can modulate coating by the solvent of the mixing ratio that has changed methyl acetate, ketone, alcohols.
Claims (20)
1. curtain coating mould, be from the slit of die cuts interruption-forming, solution is continued on the supporter that flow in moving, on supporter, form strippable film, it is characterized in that: in this curtain coating mould, with the interval of 0.5～3.0mm, configuration solvent is fed to the feed flow nozzle of described mould incision from the end in described slit; Described feed flow nozzle arrangement is in the scope with respect to 10～90 ° of the solution that spues from described slit.
2. solution film-forming device is characterized in that: comprise in the described solution film-forming device:
The supporter that moves freely along the 1st direction,
Have with the 1st direction roughly become the mould otch that the 2nd direction of orthogonal extends and form in this mould incision and make the solution continuity flow to the slit on the described supporter the curtain coating die ontology and
Be installed on the curtain coating die ontology from the end in described slit at interval with 0.5～3.0mm and solvent be fed to the feed flow nozzle of described mould incision;
Described feed flow nozzle arrangement is in the scope with respect to 10～90 ° of the solution that spues from described slit.
3. solution film-forming method is characterized in that: comprise in the described solution film-forming method:
With certain speed make supporter by the 1st direction move,
By the mould incision shape of curtain coating mould and along the slit that the 2nd direction that roughly becomes orthogonal with the 1st direction is extended, make the solution continuity flow on the described supporter,
By from the end in described slit with the feed flow nozzle of 0.5～3.0mm arranged spaced, with solvent be fed to described mould incision,
After described solution solidifies, from described supporter, film is stripped down;
The leading section of described feed flow nozzle, the continuity flow direction of described relatively solution forms 10～90 ° angle.
4. according to the solution film-forming method of claim 3 record, it is characterized in that: supply with described solvent with 0.05-0.5ml/ minute flow.
5. according to the solution film-forming method of claim 3 or 4 records, it is characterized in that: the liquid inventory that the quantity delivered of described solvent flows according to described continuity increases and decreases.
6. according to the solution film-forming method of claim 5 record, it is characterized in that: described solvent is supplied with the rate of change of the amount of described solution, from 0.002 second to 100 seconds, in ± 50%.
7. according to the solution film-forming method of claim 5 record, it is characterized in that: during described flow of solution, from 0.005 second to 10 seconds the described flow rate of change in ± 10%.
8. according to the solution film-forming method of claim 3 or 4 records, it is characterized in that: described solvent is soluble to the solute that continues in the mobile solution, and viscosity is 0.2～3cp, and surface tension is 15～50dyn/cm.
9. according to the solution film-forming method of claim 3 or 4 records, it is characterized in that: described solution is formed by several coatings, utilizes common continuity flow method, this solution continuity is flowed, so that coating forms double-layer.
10. according to the solution film-forming method of claim 3 or 4 records, it is characterized in that: described solution is the cellulose acyl ester solution of cellulosic triacetate.
11. solution film-forming method according to claim 10 record, it is characterized in that: the solvent of described cellulose acyl ester solution is made of methyl acetate, ketone and alcohols, the ratio of this solution, methyl acetate are that 20～90 weight %, ketone are that 0～60 weight %, alcohols are 5～30 weight %.
12. the solution film-forming method according to claim 11 record is characterized in that: described cellulose acyl ester solution, contain at least a plasticizer of 0.1～20 weight % with respect to cellulose acyl ester.
13. the solution film-forming method according to claim 11 record is characterized in that: described cellulose acyl ester solution, contain at least a ultra-violet absorber of 0.001～5 weight % with respect to cellulose acyl ester.
14. the solution film-forming method according to claim 11 record is characterized in that: described cellulose acyl ester solution, contain at least a powder particles of 0.001～5 weight % with respect to cellulose acyl ester.
15. the solution film-forming method according to claim 11 record is characterized in that: described cellulose acyl ester solution, contain at least a releasing agent of 0.002～2 weight % with respect to cellulose acyl ester.
16. according to the solution film-forming method of claim 11 record, it is characterized in that: described cellulose acyl ester solution, at least a fluorine that contains 0.001～2 weight % with respect to cellulose acyl ester is a surfactant.
17. according to the solution film-forming method of claim 11 record, it is characterized in that: described film is used for polarization board protective film.
18. according to the solution film-forming method of claim 11 record, it is characterized in that: described film is used for Polarizer.
19. the solution film-forming method according to claim 11 record is characterized in that: described film is used for optical function and gives birth to film.
20. according to the solution film-forming method of claim 11 record, it is characterized in that: described film is used for liquid crystal indicator.
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| JP2001072195 | 2001-03-14 | ||
| JP2001072195 | 2001-03-14 | ||
| JP2001204432A JP4289586B2 (en) | 2000-07-24 | 2001-07-05 | Solution casting die and solution casting method |
| JP2001204432 | 2001-07-05 |
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| CN1381346A CN1381346A (en) | 2002-11-27 |
| CN1332800C true CN1332800C (en) | 2007-08-22 |
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| CNB021056358A Expired - Fee Related CN1332800C (en) | 2001-03-14 | 2002-03-14 | Method and device for making film by casting mould |
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| DE602004023278D1 (en) * | 2003-03-03 | 2009-11-05 | Toray Industries | SLIDING NOZZLE AND METHOD AND DEVICE FOR PRODUCING BASE MATERIAL WITH COATING FILM |
| JP2007069488A (en) | 2005-09-07 | 2007-03-22 | Fujifilm Corp | Cellulosic resin film and its manufacturing method |
| US20090032993A1 (en) * | 2006-03-10 | 2009-02-05 | Fujifilm Corporation | Solution casting method and deposit removing device |
| KR101655735B1 (en) * | 2009-03-31 | 2016-09-08 | 후지필름 가부시키가이샤 | Solution film-forming method |
| KR101264834B1 (en) * | 2010-09-30 | 2013-05-15 | 가부시키가이샤 지로 코포레토 프란 | Protection sheet and polarizing plate |
| WO2012056625A1 (en) * | 2010-10-26 | 2012-05-03 | コニカミノルタオプト株式会社 | Method for producing resin film, casting die, device for producing resin film, resin film, polarizing plate, and liquid crystal display device |
| JP6741440B2 (en) * | 2016-02-29 | 2020-08-19 | 住友化学株式会社 | Laminated optical film manufacturing method and laminated optical film manufacturing apparatus |
| WO2018074019A1 (en) * | 2016-10-20 | 2018-04-26 | コニカミノルタ株式会社 | Optical film manufacturing method |
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| US5448678A (en) * | 1991-04-26 | 1995-09-05 | Booton; Harold | Electrically heated nozzle for die casting |
| JPH10193062A (en) * | 1997-01-08 | 1998-07-28 | Kawasaki Steel Corp | Production of continuously cast slab excellent in surface characteristic |
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| AU723887B3 (en) * | 2000-07-07 | 2000-09-07 | Liken Lin | Melting furnace of a die-casting machine |
| CN1334184A (en) * | 2000-07-24 | 2002-02-06 | 富士胶片株式会社 | Casting head for solution preparing of film |
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|---|---|---|---|---|
| US5448678A (en) * | 1991-04-26 | 1995-09-05 | Booton; Harold | Electrically heated nozzle for die casting |
| US5203397A (en) * | 1992-04-02 | 1993-04-20 | Hotset Corporation | Heating assembly for a die-casting machine |
| JPH10193062A (en) * | 1997-01-08 | 1998-07-28 | Kawasaki Steel Corp | Production of continuously cast slab excellent in surface characteristic |
| JP2000176621A (en) * | 1998-12-09 | 2000-06-27 | Kawaguchiko Seimitsu Co Ltd | Vacuum forming device for die casting |
| AU723887B3 (en) * | 2000-07-07 | 2000-09-07 | Liken Lin | Melting furnace of a die-casting machine |
| CN1334184A (en) * | 2000-07-24 | 2002-02-06 | 富士胶片株式会社 | Casting head for solution preparing of film |
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|---|---|
| CN1381346A (en) | 2002-11-27 |
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