CN104072791A - Solution film forming method - Google Patents
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- CN104072791A CN104072791A CN201410067399.5A CN201410067399A CN104072791A CN 104072791 A CN104072791 A CN 104072791A CN 201410067399 A CN201410067399 A CN 201410067399A CN 104072791 A CN104072791 A CN 104072791A
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Abstract
The invention provides a solution film forming method capable of preventing generation of strips stretching toward the long side direction. The invention provides a film having a three-layer structure formed by a first solution (41) and a second solution (42). The second solution (42) comprises particles(14), which can be wrapped by the hydrophobic group namely trimethylsilyl for the surface treatment. The surface wrapping rate of the particles (14) is at least 0.012. By adopting the following stream extension die (65), the first solution (41) and the second solution (42) can be peeled from the conveyor belt (62), and can be dried by the stretching machine (35) and the roller drying device (36) to produce the film (10).
Description
Technical field
The present invention relates to a kind of solution film-forming method.
Background technology
Polymeric film is widely used as the film of the various optical applications such as protective film for polarizing plate and phase-contrast film, more and more requires in recent years filming.Representative polymer film as this optical applications has cellulose acylate film.The cellulose acylate film that is used as optical applications is mainly manufactured by solution film-forming.As everyone knows, manufacture in the solution film-forming method of microscler cellulose acylate film, the cellulose acylate solution that has dissolved cellulose acylate in solvent is flowed out to the curtain coating supporting mass travelling continuously from casting films.Thus, as film, from curtain coating supporting mass, peel off and be formed at the casting films curtain coating supporting mass and be dried, obtain thus cellulose acylate film.
In cellulose acylate solution, conventionally comprising so-called delustering agent is particulate.Delustering agent is for improving Marresistance and the slipperiness of film, and glutinous material together each other while preventing that film is rolled into roller shape.Therefore, when manufacturing the film of single layer structure, make to form in the cellulose acylate solution of its film and when the film of manufacture multilayered structure, make to become in the cellulose acylate solution of outside layer of pellicular front and comprise delustering agent.As the particulate as delustering agent, be generally silicon-dioxide (silicon-dioxide) particulate.
When cellulose acylate solution that use comprises silicon dioxide microparticle, sometimes there is silicon-dioxide cohesion, and enter into condensation product scattered light or the catoptrical phenomenon of film.Therefore; for suppressing the cohesion of this silicon-dioxide; for example in Japanese Patent Publication 2006-070240 communique, propose: comprise the silicon-dioxide that hydrophobization processing is carried out on cellulose acylate, additive, solvent and surface, and the hydrophobic rate of silicon-dioxide is counted the cellulose acylate solution below 20% with methyl alcohol wettability (MW) value.
In addition, although comprise silicon-dioxide, also mist degree suppressed lowlyer and improve the contrast gradient while being assembled in liquid crystal indicator, in Japanese Patent Publication 2007-017626 communique, recording following optical thin film for this reason.This optical thin film possesses the layer consisting of organic compound and contains silicon-dioxide and molecular weight is the layer that the content of the organic compound below 1000 is dioxide-containing silica below 30 quality %, and the MW of silicon-dioxide meets 0≤MW≤80.And; although comprise silicon-dioxide, reduce mist degree and black brightness; in Japanese Patent Publication 2006-265382 communique, record following content for this reason; as the silicon-dioxide being contained in cellulose acylate solution, use the silicon-dioxide that the scope of MW is 80≤MW≤100, and use the cellulose acylate solution that does not have coarse grain more than 5 μ m in silicon-dioxide.
Along with the filming of film, in order to make delustering agent manifest sufficient function, the amount that need to increase silicon-dioxide compared with the past.But, if increase the amount of silicon-dioxide, can on the pellicular front of obtained film, confirm the flaw of the striated stretching to the long side direction of film.Even if in the situation that the amount that the silicon-dioxide of recording in using Japanese Patent Publication 2006-070240 communique, Japanese Patent Publication 2007-017626 communique and Japanese Patent Publication 2006-265382 communique or cellulose acylate solution increase silicon-dioxide also causes the generation of the flaw of this striated.
Summary of the invention
Therefore, the object of the present invention is to provide a kind of by prevent from pellicular front producing the solution film-forming method of the flaw stretching to the long side direction of film with silicon-dioxide.
Solution film-forming method of the present invention possesses curtain coating step (steps A) and peels off drying step (step B).In steps A, the polymers soln by making to have dissolved in solvent polymkeric substance flows out from casting films to the curtain coating supporting mass travelling continuously continuously, to form casting films on curtain coating supporting mass.Polymers soln comprises silicon dioxide microparticle.Microparticle surfaces is at least coated by hydrophobic group with 0.012 surface coating rate.In step B, from curtain coating supporting mass, peel off casting films to be dried.
When polymkeric substance is cellulose acylate, above-mentioned solution film-forming method is particularly effective.
Preferably at least a portion of hydrophobic group is TMS.
Preferred solution film-forming method also possesses dissolving step (step C), dispersion steps (step D), adds step (step e) and filtration step (step F).In step C, in a part of solvent, dissolve a part of polymkeric substance and using as raw material dope (dope).In step D, in residual polymer and residual solvent, disperse particles is to obtain particle dispersion liquid.In step e, to raw material dope, add particle dispersion liquid.In step F, the liquid obtaining in step e is filtered, thus as polymers soln.
Preferably by under the existence of water with the temperature in more than 100 ℃ 400 ℃ of following scopes to thering is silicon-dioxide and the Si (CH of hydroxyl
3)
3-NH-Si (CH
3)
3heat and obtain particulate.
According to the present invention, even if use silicon-dioxide also can prevent from producing the flaw stretching to the long side direction of film on pellicular front.
Accompanying drawing explanation
Fig. 1 is the sectional view of film.
Fig. 2 is that explanation is by the explanatory view on the particles coated surface of TMS.
Fig. 3 is that explanation is by the explanatory view on the particles coated surface of dimethyl-silicon silane alcohol base.
Fig. 4 is the sketch chart of solution film-forming equipment.
Embodiment
With reference to 1 pair of film obtaining by embodiments of the present invention of figure, describe.Film 10 shown in Fig. 1 possesses main film body 12 and is disposed at the top layer 13 of two faces of main film body 12.Although do not observe the border on main film body 12 and top layer 13, their border be shown for ease of explanatory view in Fig. 1.
Main film body 12 consists of cellulose acylate and additive.A pair of top layer 13 consists of mutually the same composition.Particularly, one of them top layer 13 consists of cellulose acylate, particulate 14 and additive with another top layer 13, and particulate 14 is mutually the same with the ratio of additive.Additive is the phase differential control agent etc. of the phase differential of softening agent, UV light absorber, inhibition film 10.The function of the so-called delustering agent of particulate 14 performance, the Marresistance that improves film 10 and slipperiness or prevent film 10 glutinous each other together with.Particulate 14, to arrange from the outstanding mode of pellicular front 10a, is given certain roughness to pellicular front 10a thus, and forms small concavo-convex.Even overlapped each other and also can not sticked together by this concavo-convex film 10, and film 10 slipperiness each other also guaranteed, and shows certain Marresistance.Particulate 14 is coated by hydrophobic group for surperficial, and takes silicon-dioxide (silicon-dioxide, the SiO of the mode of offspring
2).About the detailed description of particulate 14, utilize other accompanying drawings to carry out aftermentioned.
The cellulose acylate on main film body 12 and each top layer 13 is TAC (cellulosetri-acetate).But main film body 12 is not limited to these with each cellulose acylate on top layer 13.The cellulose acylate that for example, the cellulose acylate of main film body 12 can be made as to DAC (Cellulose diacetate), top layer 13 is made as TAC.And, in present embodiment, all adopt cellulose acylate to be used as each component of polymer on main film body 12 and top layer 13, but so long as can make by solution film-forming method the polymkeric substance of film.As other polymkeric substance, such as having cyclic polyolefin, vinylformic acid, polyethylene terephthalate (PET) etc.
In present embodiment, two top layers 13 are made as to mutually the same structure, but are not limited to this mode.For example, can form two top layers 13 by identical component, and the ratio of composition can be differing from each other while forming with a plurality of compositions.And, can be also a mode that comprises particulate of only having in two top layers 13.
The thickness T 10 of film 10 is 60 μ m, and the thickness T 12 of main film body 12 is 54 μ m, and the thickness T 13 on top layer 13 is 3 μ m.And each thickness is not limited to these, if thickness T 10 more than 10 μ m in the following scope of 80 μ m, thickness T 12 more than 9 μ μ m in the following scope of 70 μ m, thickness T 13 is more than 1 μ m in the following scope of 10 μ m.Especially, the present invention more than 2 μ m in the following scope of 5 μ m time, especially has when suppressing the rising of mist degree and preventing from becoming roller shape film 10 glutinous effect together each other in thickness T 13.Can and flow to the flow of curtain coating mould and obtain thickness T 10, T12 and T13 by calculating according to the concentration of each solid substance of the 1st dope 41 described later and the 2nd dope 42.
By the 1st polymers soln (following, to be called the 1st dope) of aftermentioned solution film-forming equipment utilization formation main film body 12 and the 2nd polymers soln (following, to be called the 2nd dope) on formation top layer 13, manufacture this film 10.The particulate 14 that becomes the raw material of the 2nd dope is scattered in dispersion medium conventionally, and particulate 14 is used when preparing the 2nd dope with the state of this dispersion liquid.As shown in the explanatory view of Fig. 2 left side, when the silica sphere of formation particulate 14 is not coated by hydrophobic group, conventionally comprise hydroxyl (hydroxyl group ,-OH).Particulate condenses because of this hydroxyl affinity to each other in curtain coating mould 65 (with reference to figure 4).Therefore, by making hydroxyl hydrophobization by hydrophobic group modified hydroxyl.
Hydrophobic group is TMS (following, to be called TMS).By by TMS modified hydroxyl, as shown in the explanatory view of Fig. 2 right side, the surface of particulate 14 becomes the state that there is no hydroxyl and be coated by TMS.Surface coating rate is at least 0.012, more than 0.012.Surface coating rate is preferably in more than 0.012 0.12 following scope, more preferably in more than 0.012 0.016 following scope.
By the carbon content rate in particulate 14, divided by specific surface area, obtain surface coating rate.That is, the carbon content rate of particulate 14 is made as to RC, when specific surface area is made as S, by RC/S, obtains surface coating rate.For example, by the ultimate analysis based on combustion method (, full-automatic Atomic Absorption SpectrophotometerICP, Pa Erjinaimo Japanese firm (PerkinElmer Japan Co., Ltd.) system), obtain carbon content rate RC.Specific surface area S measures according to BET method.
As shown in Figure 2, the hydrophobization of the silicon-dioxide based on TMS carries out in the following manner, in gas phase, under the existence of water, with the temperature in 100 ℃ of above 400 ℃ of following scopes to thering is silicon-dioxide and the Si (CH of hydroxyl
3)
3-NH-Si (CH
3)
3heat.In addition, this reaction is carried out with intermittent type.During this surface based on TMS is coated, with 1 hydroxyl of 3 methyl modifications, almost 100% hydroxyl is disappeared, and become, there is no the particulate of silanol group 14.
Except using the surperficial particulate 14 being coated by TMS, can also use surface by dimethyl-silicon silane alcohol base (Si (CH
3) OH, hereinafter referred to as DMS) coated particulate 14.The blending ratio that regulates the surperficial particulate being coated by TMS 14 and the surperficial particulate 14 being coated by DMS, surface coating rate is adjusted to more than 0.012 prescribed value thus.
As shown in Figure 3, the hydrophobization of the silicon-dioxide based on DMS carries out in the following manner, in gas phase, under the existence of water, with the temperature in 100 ℃ of above 400 ℃ of following scopes to thering is silicon-dioxide and the Si (CH of hydroxyl
3)
2cl
2heat.In addition, this reaction is carried out with continous way.So passing through Si (CH
3)
2cl
2during modified hydroxyl, owing to going back residual hydroxyl after modification, therefore as long as environment meets reaction conditions, reaction is just lasting, and does not reappear, and after hydrophobic rate (modification ratio) reaches the moment of 52% left and right, hydrophobic rate can not change.The moment that therefore, can reach 50% left and right in hydrophobic rate finishes reaction.
The solution film-forming of manufacturing film 10 for example carries out in the solution film-forming equipment 30 of Fig. 4.Solution film-forming equipment 30 possesses dope preparation facilities 31, casting device 32, tenter machine 35, roller drying installation 36 and take-up mechanism 37 successively from upstream side.
Dope preparation facilities 31 is for making the 1st dope 41 and the 2nd dope 42.As mentioned above, the 1st dope 41 forms main film body 12, the 2 dopes 42 and forms top layer 13.Dope preparation facilities 31 can be arranged at the outside of solution film-forming equipment 30, rather than in solution film-forming equipment 30.Now, the 1st dope 41 of made and the 2nd dope 42 are stored in for the time being and preserve in container etc.Dope preparation facilities 31 possesses dissolving portion 43, mixing portion 46, through part 47 and filter house 48,49.
If dissolving portion 43 is supplied to cellulose acylate 52 and solvent 53, these mixtures is heated and stirred.Can replace heating or on heating basis, carry out cooling.Be produced on thus the raw material dope 54 (dissolving step) that has dissolved cellulose acylate 52 in solvent 53.If filter house 48 is supplied to the mixture of a part of raw material dope 54 and additive 59, this is filtered and using as the 1st dope 41.
If mixing portion 46 is supplied to cellulose acylate 52, solvent 53 and particulate 14, stir the combination treatment of these mixtures.Through part 47 is disposed at the downstream of mixing portion 46, if be supplied to the mixture of cellulose acylate 52, solvent 53 and particulate 14 from through part 47, to this mixture, provides ultrasonic wave, and carries out the dispersion treatment of disperse particles 14 in liquid.In addition, also can replace providing hyperacoustic through part 47 with ball mill.If filter house 49 is supplied to the mixture consisting of the particle dispersion liquid 58 obtaining by through part 47 and another part raw material dope 54, this is filtered and using as the 2nd dope 42.
Casting device 32 is for forming film 10 by the 1st dope 41 and the 2nd dope 42.Casting device 32 possesses travelling belt 62, the 1st roller 63 and the 2nd roller 64.Travelling belt 62 is for to form the ring-type curtain coating supporting mass of ring-type, and made by stainless steel (SUS).Travelling belt 62 is hung the side face that is around in the 1st roller 63 and the 2nd roller 64.At least one in the 1st roller 63 and the 2nd roller 64 has driving part (without diagram), by driving part to rotating in a circumferential direction.By this rotation, the travelling belt 62 joining with side face circulates and travels continuously to long side direction.
The top of travelling belt 62 possesses the curtain coating mould 65 that the 1st dope 41 and the 2nd dope 42 are flowed out.The 1st dope 41 and the 2nd dope 42 are flowed out to the travelling belt 62 travelling continuously from curtain coating mould 65, thus, the 1st dope 41 and the 2nd dope 42 with the state that overlaps each other to travelling belt 62 curtain coatings, to form continuously casting films 66 (curtain coating step).In addition, the 1st dope 41 in the mode that is clipped in the 2nd dope 42 from the spout 65a of curtain coating mould 65 out.
The 1st roller 63 and the 2nd roller 64 possess the thermostat (not shown) of controlling all surface temperatures separately.Each week surface temperature of the 1st roller 63 and the 2nd roller 64 is controlled, and the temperature of casting films 66 is regulated via travelling belt 62 thus.
About the 1st dope 41 to travelling belt 62 and the 2nd dope 42, so-called liquid pearl from curtain coating mould 65, in the upstream of the travel direction of travelling belt 62, possesses underpressure chamber (without diagram).The atmosphere in the 1st dope 41 that flow out by attraction in this underpressure chamber and the upstream side region of the 2nd dope 42 reduces pressure to this region.
Casting films 66 is cured to the degree that can be sent to till tenter machine 35, with the state that comprises solvent 53, from travelling belt 62, peels off casting films afterwards.When for dry curtain coating mode with 10 quality % more than solvent in the following scope of 100 quality % contain per-cent and peel off; When the cooling curtain coating mode with 100 quality % more than solvent in the following scope of 300 quality % contain per-cent and peel off.Dry curtain coating mode refers to main by being dried the mode of solidifying casting films 66; Cooling curtain coating mode refers to mainly by cooling comes gelation to solidify the mode of casting films 66.In addition, the solvent in this specification sheets contain per-cent be by the quality of the film in moisture state 10 be made as X, quality after this film 10 is dried is while being made as Y, according to the value of [(X-Y)/Y] * 100 so-called dry basis of obtaining.
While peeling off, with peeling off with roller (following, to be called stripper roll) 70 tread support membranes 10, the position of peeling off that casting films 66 is peeled off from travelling belt 62 keeps As constant.If travelling belt 62 turns back to the curtain coating position of the 1st dope 41 and 42 curtain coatings of the 2nd dope through circulation from peeling off position, the 1st new dope 41 and the 2nd dope 42 are incited somebody to action curtain coating again.
Also can be provided with inlet pipe (without diagram), so that face and put with the curtain coating that is formed with the casting films 66 of travelling belt 62.This inlet pipe is emitted gas, dry with the casting films 66 that promotes to flow through.
Utilizing the casting films 66 that stripper roll 70 is peeled off is that film 10 is directed to tenter machine 35.Tenter machine 35, when utilizing holding member 71 to keep each sidepiece of film 10, promotes the dry of film 10.As the holding member 71 of tenter machine 35, use in clip and pin at least any one.Clip clips film 10, and pin runs through film 10 to thickness direction, keeps respectively thus film 10.
Tenter machine 35, utilizing holding member 71 to keep film 10 with when transmitting to long side direction, is given the tension force of width, and is expanded the width of film 10.In this tenter machine 35, possesses near the conduit 72 to supply with that makes dry gas flow to film 10.Film 10, when being transmitted, is dried by the dry gas from conduit 72, and can with the timing of stipulating, change width by holding member 71.
Roller drying installation 36 is for the dry film 10 being transmitted.Roller drying installation 36 possesses along the delivery direction of film 10 and is arranged with a plurality of a plurality of rollers 73, air regulator (without diagram) and chamber (without diagram).In a plurality of rollers 73, exist to the driving roll rotating in a circumferential direction, the rotating thin film 10 by this driving roll is transferred into downstream.Air regulator attracts the atmosphere of chamber interior, and the humidity and temperature of attracted gas etc. is regulated, and again this gas is sent into chamber interior afterwards.Thus, temperature and humidity of chamber interior etc. is retained as constant.Take-up mechanism 37 coils into roller shape by the film being supplied to from roller drying installation 36 10.In addition, cooling room (without diagram) can be set between roller drying installation 36 and take-up mechanism 37.This cooling room was cooled to room temperature by the inner film 10 of flowing through before batching.
The example that solution film-forming equipment 30 is embodiments of the present invention can be also other solution film-forming equipment.For example, as curtain coating supporting mass, can replace travelling belt 62 with the cylinder to rotating in a circumferential direction (without diagram).During for cooling curtain coating mode, mostly cylinder is used as to curtain coating supporting mass.And, the tenter machine (without diagram) having with tenter machine 35 same structures can be set between tenter machine 35 and roller drying installation 36.
Effect to said structure describes.If cellulose acylate 52 and solvent 53 are sent to dissolving portion 43, by heat and stirring etc., become raw material dope 54.Before a part of raw material dope 54 is directed to filter house 48, can add additive 59, under the state that is mixed with additive 59, by filter house 48, filter and become the 1st dope 41 (the 1st filtration step).
And, by TMS, the silicon-dioxide of offspring is carried out to hydrophobization processing, the surface of particulate 14 is wrapped by with at least 0.012 surface coating rate thus.If this particulate 14, cellulose acylate 52 and solvent 53 are directed to mixing portion 46, by mixing portion 46 mixed (mixing step), and from this mixing portion 46, be sent to through part 47.Particulate 14 in mixture is certain dispersity by through part 47, and obtains particle dispersion liquid 58 (dispersion steps).Particle dispersion liquid 58 is added in the raw material dope 54 of another part (interpolation step), and is directed to filter house 49, and portion 49 filters and becomes the 2nd dope 42 (the 2nd filtration step) after filtration.
The 1st dope 41 and the 2nd dope are guided to curtain coating mould 65 continuously, and flow out continuously from spout 65a.If the surface coating rate of particulate 14 is less than 0.012, particulate is easily attached to spout 65a, and because the surface of the particulate 14 of present embodiment is wrapped by with at least 0.012 surface coating rate, therefore, in the spout 65a of curtain coating mould 65, the phenomenon of adhering to state of aggregation is inhibited.Therefore, the flowing of the 2nd dope 42 out of the mobile state to clamp the 1st dope 41 from spout 65a, there will not be because of be attached to spout 65a particulate solidify the striped causing.Therefore, on the face of casting films 66, do not produce the striped stretching to long side direction yet.Casting films 66 is through utilizing the drying step of peeling off of stripper roll 70, tenter machine 35 and roller drying installation 36.Peeling off drying step has the strip step of stripper roll utilized 70 and utilizes tenter machine 35 and the drying step of roller drying installation 36.Be formed at casting films 66 on the travelling belt 62 in travelling after thering is self-supporting, with the state that comprises solvent 53, from travelling belt 62, be stripped from, become thus film 10 (strip step).Film 10 is sent to tenter machine 35, and under the state that is held parts 71 Max. Clearance _M.s by the atmosphere of the dry gas that is supplied to from conduit 72.Promote thus the dry of film 10.The film 10 that comes from tenter machine 35 is directed to roller drying installation 36, is dried (drying step) during the chamber by this roller drying installation 36 (without diagram) inside.The film 10 of drying is directed to take-up mechanism 37, and is coiled into roller shape.On the face of casting films 66, do not produce the striped stretching to long side direction, the striped yet not stretching to long side direction on the film 10 that therefore utilizes this casting films 66 to obtain.
Particulate 14 is with respect to producing between the striped stretching to long side direction and have relation in the mass ratio of the cellulose acylate 52 in the 2nd dope 42 and film 10.This relation is shown in to table 1.The data of table 1 are that when the silicon-dioxide that surface is coated by DMS is used as particulate 14 and when the surperficial silicon-dioxide being coated by TMS is used as particulate 14, change particulate 14 obtains with respect to the mass ratio of the cellulose acylate 52 in the 2nd dope 42 respectively.The method that the evaluation of striped is recorded according to aftermentioned embodiment and benchmark carry out.
[table 1]
In the 2nd dope 42, when particulate 14 is DMS, particulate 14 is below 0.050% with respect to the mass ratio of cellulose acylate 52, thus striped be evaluated as qualified grade.When particulate 14 is TMS, even if particulate 14 is 1.000% with respect to the mass ratio of cellulose acylate 52, striped evaluation is still qualified grade.So, when particulate 14 is TMS, particulate 14 is below 1.000% with respect to the mass ratio of cellulose acylate 52, and the evaluation of striped maintains qualified grade.
In present embodiment, manufacture the film 10 of the multilayered structure of so-called 3 layers, but the present invention is also still effective for the film of single layer structure.And, the film 10 of the 3-tier architecture that in present embodiment, manufacture consists of main film body 12 and a pair of top layer 13, but the film obtaining by the present invention is not limited to this.For example, also can make 4 layers of above film by common curtain coating or coating etc.In addition, when manufacturing the film of single layer structure, too, when particulate 14 is DMS, particulate 14 is below 0.050% with respect to the mass ratio of cellulose acylate 52, striped be evaluated as qualified grade.When particulate 14 is TMS, particulate 14 is below 1.000% with respect to the mass ratio of cellulose acylate 52, striped be evaluated as qualified grade.
Below, enumerate embodiments of the invention and the comparative example relative with the present invention.
[embodiment]
[embodiment 1]～[embodiment 3]
Make three kinds of particulates 14 that surface coating rate differs from one another.The surface coating rate of each particulate 14 is shown in table 2 " surface coating rate " hurdle.As particulate 14, there are following two kinds, the particulate that the silicon-dioxide being only coated by TMS by surface forms; And mixed the particulate of the silicon-dioxide that silicon-dioxide that surface is coated by DMS and surface be coated by TMS.The mixture ratio of the silicon-dioxide that the silicon-dioxide wherein, surface being coated by DMS and surface are coated by TMS is shown in " DMS:TMS " hurdle of table 2.
Utilize respectively each particulate 14 to make three kind of the 2nd dope 42.In each the 2nd dope 42, particulate 14 is 0.100% with respect to the mass ratio of cellulose acylate 52.The 1st dope 41 does not comprise particulate 14.Use the 1st dope 41 and the 2nd dope 42 and manufacture three kinds of films 10 by solution film-forming equipment 30.
Evaluate the evaluation of 1. stripeds
From each film 10 of obtain, cut out respectively 10 A4 versions (210mm * 297mm) sample.Particularly, along the width of film 10, cut out 5, apart from cutting out the position of these 5 samples along the long side direction 5m position of film 10, same broad ways cuts out 5.Mode with the long limit of from the long side direction alignment sample to film 10 cuts out each sample.About each sample, the flaw and the degree thereof that have undirected long side direction to stretch are evaluated.Evaluate and draw as follows, the width that goes out to be attached on pellicular front by visual number is that 100 μ m are above, length is the number of striped more than 5cm, and obtains the mean value of its number.About mean value with following benchmark evaluation striped.In addition, A, B are qualified grade, and C, D are defective grade.
A：0
B: be greater than 0 and be less than or equal to 0.5
C: be greater than 0.5 and be less than or equal to 1
D: be greater than 1
Evaluate the evaluation of 2. coarsnesses
And, from 31 pairs of particle dispersion liquids 58 of dope preparation facilities, sample, and in solvent, this diluted sample is become to 1～5%, utilize afterwards particle size distribution measuring instrument (name of an article LA920, hole field (HORIBA) company system) to measure size distribution.According to obtained size distribution, check the peak area of the above particle of 10 μ m in the particle that whether contains more than 10 μ m and grain size distribution curve figure, and obtain this peak area with respect to the ratio (unit: %) be used as coarsness of total peak area.With this coarsness of following benchmark evaluation.In addition, A, B are qualified grade, and C, D are defective grade.
A：0％
B: be greater than 0% and be less than or equal to 20%
C: be greater than 20% and be less than or equal to 40%
D: be greater than 40%
[table 2]
[comparative example 1], [comparative example 2]
Make two kinds of particulates that surface coating rate differs from one another.The surface coating rate of each particulate is shown in table 2 " surface coating rate " hurdle.As shown in table 2, as particulate, there are following two kinds, the particulate that the silicon-dioxide being only coated by DMS by surface forms; And mixed the particulate of the silicon-dioxide that silicon-dioxide that surface is coated by DMS and surface be coated by TMS.
Utilize respectively each particulate to make two kind of the 2nd dope.In each the 2nd dope, particulate is 0.100% with respect to the mass ratio of cellulose acylate 52.With the 2nd dope, under the condition identical with embodiment, manufacture two kinds of films with the 1st dope 41 identical with embodiment.
With the method identical with embodiment and benchmark, carry out the evaluation of striped and coarsness.The results are shown in table 2.
Claims (5)
1. a solution die-manufacturing method, possesses following steps:
(A) polymers soln that makes to have dissolved polymkeric substance in solvent flows out to the curtain coating supporting mass travelling continuously continuously from curtain coating mould, thus to the operation that forms casting films on described curtain coating supporting mass, described polymers soln comprises silicon dioxide microparticle, and the surface of described particulate is at least coated by hydrophobic group with 0.012 surface coating rate; And
(B) from described curtain coating supporting mass, peel off described casting films to carry out dry operation.
2. solution film-forming method according to claim 1, wherein,
Described polymkeric substance is cellulose acylate.
3. solution film-forming method according to claim 1 and 2, wherein,
At least a portion of described hydrophobic group is TMS.
4. solution film-forming method according to claim 1 and 2, the method also possesses following steps:
(C) in the described solvent of a part, dissolve the operation that a part of described polymkeric substance is usingd as raw material dope;
(D) in the described polymkeric substance of residue and the described solvent of residue, disperse described particulate to obtain the operation of particle dispersion liquid;
(E) to described raw material dope, add the operation of described particle dispersion liquid; And
(F) liquid obtaining in described step e is filtered, thus as the operation of described polymers soln.
5. solution film-forming method according to claim 3, wherein,
Described particulate by under the existence of water with the temperature in more than 100 ℃ 400 ℃ of following scopes to thering is silicon-dioxide and the Si (CH of hydroxyl
3)
3-NH-Si (CH
3)
3heat and obtain.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-069811 | 2013-03-28 | ||
| JP2013069811A JP5809185B2 (en) | 2013-03-28 | 2013-03-28 | Solution casting method |
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| Publication Number | Publication Date |
|---|---|
| CN104072791A true CN104072791A (en) | 2014-10-01 |
| CN104072791B CN104072791B (en) | 2019-04-05 |
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| CN201410067399.5A Active CN104072791B (en) | 2013-03-28 | 2014-02-26 | Solution film-forming method |
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| JP (1) | JP5809185B2 (en) |
| KR (1) | KR102192967B1 (en) |
| CN (1) | CN104072791B (en) |
| TW (1) | TWI597156B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910399A (en) * | 2014-03-11 | 2015-09-16 | 富士胶片株式会社 | Film, dope composition and manufacturing method thereof, and solution film-forming method |
| KR20160048654A (en) * | 2014-10-24 | 2016-05-04 | 후지필름 가부시키가이샤 | Solution film forming method and apparatus therefor |
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| DE102007024365A1 (en) * | 2007-05-22 | 2008-11-27 | Evonik Degussa Gmbh | Pyrogenated silanized and ground silicic acid |
| US8647653B2 (en) * | 2009-12-26 | 2014-02-11 | Evonik Degussa Gmbh | Water containing powder composition |
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| JP2006070240A (en) * | 2004-08-06 | 2006-03-16 | Fuji Photo Film Co Ltd | Cellulose acylate dope and method for solution film formation |
| JP2006089644A (en) * | 2004-09-24 | 2006-04-06 | Fuji Photo Film Co Ltd | Method for producing polymer solution |
| CN102124048A (en) * | 2008-08-19 | 2011-07-13 | 富士胶片株式会社 | Method of producing anti-glare film |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910399A (en) * | 2014-03-11 | 2015-09-16 | 富士胶片株式会社 | Film, dope composition and manufacturing method thereof, and solution film-forming method |
| CN104910399B (en) * | 2014-03-11 | 2019-03-19 | 富士胶片株式会社 | Film, dope composition and its manufacturing method and solution film-forming method |
| KR20160048654A (en) * | 2014-10-24 | 2016-05-04 | 후지필름 가부시키가이샤 | Solution film forming method and apparatus therefor |
| CN105538568A (en) * | 2014-10-24 | 2016-05-04 | 富士胶片株式会社 | Solution film forming method and apparatus therefor |
| CN105538568B (en) * | 2014-10-24 | 2019-11-05 | 富士胶片株式会社 | Solution film-forming method and device |
| KR102330062B1 (en) | 2014-10-24 | 2021-11-25 | 후지필름 가부시키가이샤 | Solution film forming method and apparatus therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201437004A (en) | 2014-10-01 |
| CN104072791B (en) | 2019-04-05 |
| JP5809185B2 (en) | 2015-11-10 |
| TWI597156B (en) | 2017-09-01 |
| KR20140118733A (en) | 2014-10-08 |
| JP2014189020A (en) | 2014-10-06 |
| KR102192967B1 (en) | 2020-12-18 |
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