CN101852880A - Solution film-forming method - Google Patents
Solution film-forming method Download PDFInfo
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- CN101852880A CN101852880A CN201010156445A CN201010156445A CN101852880A CN 101852880 A CN101852880 A CN 101852880A CN 201010156445 A CN201010156445 A CN 201010156445A CN 201010156445 A CN201010156445 A CN 201010156445A CN 101852880 A CN101852880 A CN 101852880A
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- film
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- supporter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
- B29C41/26—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on a rotating drum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
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- Mechanical Engineering (AREA)
- Moulding By Coating Moulds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Spray dope from the slit that is provided with at casting head towards the curtain coating drum.On the curtain coating drum, form casting films.Peel off cylinder and peel off casting films, form wetting film from the curtain coating drum.Wetting film forms film by dried.Utilize annular knurl to give cylinder, implement annular knurl processing at the Width two ends of film.The determining film thickness device is measured the thickness of film.Controller reads the thickness distribution of the film on the Width, denys the judgment processing that has the part that does not satisfy predetermined thickness condition.By judgment processing, exist under the situation of the part that does not satisfy predetermined thickness condition, controller is regulated the width of the slit corresponding with this part.
Description
Technical field
The present invention relates to solution film-forming method.
Background technology
Thin polymer film (hereinafter referred to as film) has superior photopermeability, and having can lightweight and speciality such as filming, therefore, utilizes as optical functional film is many-sided.In film, having used the cellulose esters of acylated cellulose etc. is that film has high obdurability, and its birefraction is low.Therefore, cellulose esters is a film with picture photosensitive with headed by the film, is used in the protective film of polarization plates.Polarization plates is the structure member of the liquid crystal indicator of the market expansion in recent years.And then, by the film of making being implemented the stretch processing of regulation, can also make optical compensating film with desired optical.Below, the protective film of polarization plates or optical compensating film etc. are called optical functional film.
One of manufacture method of film has solution film-forming method.Solution film-forming method is a method of being made film by the Polymer Solution that comprises polymkeric substance and solvent (hereinafter referred to as dope).Specifically, following method is arranged.Use casting head, on supporter, spray dope, on supporter, form casting films.After this casting films has self-supporting, casting films is peeled off from supporter, form wetting film.And then, with this wetting film drying, form film.In the manufacture method of film, except solution film-forming method, melt extrude method in addition.Melt extrude method and be the method for making film of extruding by molten polymer.Solution film-forming method is compared with melt extruding method, and the homogeneity that can access thickness (thickness of film) is superior, and, the film that the content of foreign matter is little.Thereby, in the manufacture method of optical functional film, as the spy opens the 2003-285367 communique, adopt solution film-forming method.
The film that utilizes the solution film-forming method manufacturing is wound in the volume core after the Width two ends are implemented annular knurl processing, form film roll.Also have, utilize the pressure of regulation, reel when compressing film, can make the pressure that produces the size of regulation on the film superimposed in film roll thus.Therefore, can prevent to be out of shape at the coiling of volume core wound film.
If the pressure distribution that the standard deviation of this thickness causes then takes place at superimposed film in the volume core in the winding film of standard deviation that thickness will take place.Usually, the situation of the tendency of the standard deviation of thickness unanimity on the length direction of film is in the majority.Therefore, the tendency of this pressure distribution is also consistent on the length direction of film.Also have, the part that the pressure that produces at superimposed film becomes more than the steady state value becomes secret note, is apparent in film roll (hereinafter referred to as the black-tape fault).If such black-tape fault takes place, then the commodity value as optical functional film sustains damage.In addition, the film generation static electrification inequality of sending from the film roll that the black-tape fault has taken place.The static electrification inequality is meant inhomogenous state of static electrification electromotive force or inhomogenous situation.Also have, the thin film cladding coating liquid sending from film roll is forming on the film under the situation of coated film, and this static electrification inequality causes the coating inequality of coating liquid or the uneven thickness of coated film, finally causes the inequality (striped inequality) of striated.From such reason, expect preventing of black-tape fault.As the countermeasure that prevents of black-tape fault, for example, open in the 2003-285367 communique the spy, disclose the method for the film of the thickness distribution that forms the regulation film.
In recent years, follow the big pictureization of liquid crystal indicator, seek width than wide in the past optical functional film., if form the wide optical functional film of width, open disclosed method in the 2003-285367 communique even then carry out the spy, this black-tape fault also still takes place frequently.In addition, this black-tape fault is followed the increase of the coiling length of optical functional film, shows identical tendency, becomes problem.
Summary of the invention
When the object of the present invention is to provide the generation that can suppress the black-tape fault, can make the solution film-forming method of film.
Solution film-forming method of the present invention comprises: film forms operation; Drying process; Annular knurl is given operation; Measure operation; Judge operation; Slit is regulated operation; The coiling operation.
Form in the operation at film, spray dope towards the supporter of advancing, on described supporter, form the film of strip from the slit that casting head, is provided with.Described dope comprises polymkeric substance and solvent.Described film only has the thickness-tapered portion that thickness successively decreases towards Width central authorities at the Width two ends.In drying process, the dry described film of peeling off from described supporter.Give in the operation at annular knurl, give annular knurl to the described thickness-tapered portion of the described film of peeling off from described supporter.In measuring operation, the thickness distribution on the prescribed direction of repeatedly measuring the described film of peeling off from described supporter on the direct of travel of described film.The direct of travel of described prescribed direction and described film intersects.In judging operation, judge whether described film satisfies first condition and second condition.Described first condition is the situation that the goods portion between a pair of described thickness-tapered portion does not comprise the part thicker than the thickness of reference position.Described second condition is that the aggregate-value of the thickness in the described goods portion is the following situation of aggregate-value of described reference position.Described reference position is arranged at the described thickness-tapered portion than the more close described Width center side of described annular knurl.Regulate the interval of regulating described slit in the operation at slit.Described adjusting is not satisfy in described judgement under the situation of described first condition and described second condition so that described film satisfies the mode of described first condition and described second condition carries out at described film.The described film of coiling in the coiling operation.
In this solution film-forming method, the difference of maximal value and minimum value is below the 3 μ m in the thickness of preferred described goods portion.
According to the present invention as can be known, make the aggregate-value of the thickness distribution of the thickness distribution of film or film satisfy the interval that the slit of casting head is regulated on rated condition ground.Therefore, reduce the standard deviation of the thickness of film.Its result can suppress the generation of black-tape fault.Thereby, according to the present invention as can be known, can suppress the generation of black-tape fault, can make film simultaneously.
Description of drawings
Above-mentioned purpose, advantage can be read the detailed explanation of preferred embodiment by with reference to accompanying drawing, and those of ordinary skills are easily understood.
Fig. 1 is the key diagram of the summary of expression solution film-forming equipment.
Fig. 2 is the stereographic map of the summary of expression casting head and curtain coating drum.
Fig. 3 be about casting head and curtain coating drum with face B direction quadrature on sectional view.
Fig. 4 is that the expression annular knurl is given cylinder, trimming device, and the vertical view of the summary of determining film thickness device.
Fig. 5 is the key diagram of the thickness distribution of the film on the expression B direction.
Embodiment
(solution film-forming method)
As shown in Figure 1, solution film-forming equipment 10 has: curtain coating chamber 12; Pin stenter 13; Clamp tenter 14; Hothouse 15; Cooling chamber 16; Coiling chamber 17.Be provided with casting head 21 in curtain coating chamber 12; Curtain coating drum 22; Relief chamber 23; Peel off cylinder 24.
(casting head)
As shown in Figure 1, casting head 21 comprises the dope 28 of polymkeric substance and solvent towards 22 ejections of curtain coating drum.Casting head 21 has die body 31 and regulates bolt 32 as shown in Figure 2.As shown in Figures 2 and 3, die body 31 comprises the first die lip plate 31a and the second die lip plate 31b.On the composition surface of the first die lip plate 31a and the composition surface of the second die lip plate 31b recess of regulation shape is set respectively.Make up the first die lip plate 31a and the second die lip plate 31b to engage these composition surfaces mode each other, form the slot 31c that forms by separately recess in die body 31 thus.In addition, the front end below die body 31, the outlet of slot 31c is that slit 31d extends ground formation on the length direction of curtain coating drum 22.In Fig. 2, to the length direction mark arrow line B of curtain coating drum 22.Therefore, the length direction with curtain coating drum 22 is called the B direction in the following description.Also have, this B direction is consistent with the Width of casting films 40.
The first die lip plate 31a has groove 35 and bolt hole 36.Groove 35 is along the length direction setting of slit 31d.A plurality of bolts hole 36 are arranged ground and are provided with on the B direction, transection slot 35 ground form.That is, flute profile becomes the heavy section that the first die lip plate 31a is divided into the thinner wall section of the leading section with bolt hole 36 and has the rearward end of bolt hole 36.Internal face at bolt hole 36 has been cut screw thread.Therefore, the adjusting bolt 32 in inserting bolt hole 36 is fixed in the first die lip plate 31a.
As Fig. 1 and shown in Figure 3, under the control of controller 37, regulate bolt 32 and rotate ormal weight to the direction of regulation.By regulating the rotation of bolt 32, the front end of regulating bolt 32 under the situation that the second die lip plate 31b compresses, can make the interval CL1 of the slit 31d corresponding with the position of the adjusting bolt 32 that rotates narrow down corresponding to the amount of spin of regulating bolt 32 front end of the first die lip plate 31a.That is,, and then tighten and regulate bolt 32, then regulate bolt 32 and send, thinner wall section is pushed towards the direction that the interval of slit 31d CL1 narrows down with respect to the described thinner wall section of the first die lip plate 31a if behind the bottom butt of the front end of adjusting bolt 32 and bolt hole 36.
Also have, regulate the temperature of bolt 32, utilize the thermal expansion of regulating bolt 32, the interval CL1 that regulates slit 31d also can.In regulating the adjustment of bolt 32, use heat regulation bolt 32 heating part (not having diagram), and the cooling cooling end (not having diagram) of regulating bolt 32 get final product.
(curtain coating drum)
It is the center rotation that curtain coating drum 22 utilizes drive unit (not shown) to come with axle 22a.By the rotation of curtain coating drum 22, side face 22b upwards advanced with the speed of regulation in week.In Fig. 1～Fig. 3, to circumferential mark arrow line A.Therefore, in the following description, will circumferentially be called the A direction.Curtain coating drum 22 is configured to side face 22b near slit 31d.Form curtain coating road from slit 31d through side face 22b from the dope 28 of the slit 31d of casting head 21 ejection, on side face 22b, become casting films 40.
Length on the B direction of curtain coating drum 22 does not limit especially.But, 1.1 times～2.0 times scope of the length of the slit 31d on the preferred B direction of the length on the B direction of curtain coating drum 22.The preferred surfaceness of side face 22b of using becomes the curtain coating drum that 0.01m polishes followingly.The surface imperfection of side face 22b need suppress to be Min..Specifically, do not have the above pin hole of 30 μ m, 10 μ m are above and be 1/m less than the pin hole of 30 μ m
2Below, be 2/m less than the pin hole of 10 μ m
2Below.Follow below the preferred 200 μ m of shift in position that the footpath of side face 22b of the rotation of curtain coating drum 22 makes progress.The speed fluctuation of preferred curtain coating drum 22 is made as below 3%, and the complications on the B direction that curtain coating drum 22 produces when rotating a time are below the 3mm.
As shown in Figure 1, connect temperature control equipment 43 at curtain coating drum 22.Be formed with the stream of heat transfer medium in the inside of curtain coating drum 22.The heat transfer medium that temperature control equipment 43 will be adjusted to desired temperatures is sent into the stream of curtain coating drum 22, make heat transfer medium and curtain coating drum 22 between circulation.By the circulation of this heat transfer medium, the temperature of the side face 22b of curtain coating drum 22 can be remained desired temperatures.In addition, omit diagram, but the condensing unit of the solvent condenses that will gasify and the retracting device of the solvent that recovery is liquefied are set in curtain coating chamber 12.Thus, the temperature that becomes the solvent liquefaction of gas in curtain coating chamber 12 can be remained the scope of regulation.
Peel off cylinder 24 and be disposed at downstream casting head 21, the A direction.Peel off cylinder 24 and peel off the casting films 40 that on side face 22b, forms, it as wetting film 44, is guided to the downstream of curtain coating chamber 12.
Be disposed with pin stenter 13 in the downstream of curtain coating chamber 12, clamp tenter 14, hothouse 15, cooling chamber 16 and coiling chamber 17.13 transition part 45 from curtain coating chamber 12 to pin stenter, utilize cylinder 46 to carry the wetting film of sending from curtain coating chamber 12 44, wetting film 44 is imported pin stenters 13.Pin stenter 13 has a plurality of needle plates.Each needle plate connects pin the two ends and the maintenance of the B direction of wetting film 44.This needle plate is advanced in orbit.The wetting film 44 of advancing to remaining on needle plate is carried dry wind.By this air-supply, dry wetting film 44 becomes film 50.
Clamp tenter 14 and have a plurality of anchor clamps.Each anchor clamps is controlled the two ends of the B direction of film 50.These anchor clamps are advanced on extension rail.The film 50 that utilizes anchor clamps to advance is carried dry wind.Film 50 is implemented to the stretch processing of thin-film width direction and based on the dried of dry wind.Also have, omit clamping tenter 14 and also can.
Be respectively arranged with trimming device 52,53 in the downstream of pin stenter 13 and the downstream of clamping tenter 14. Trimming device 52,53 cuts off the two ends of the B direction of film 50.This part that cuts off is sent to crushing machine (not shown) by air-supply, is slightly cut off, and utilizes as the raw material of dope 28 grades again.
Be provided with a plurality of cylinders 54 at hothouse 15.Film 50 is wound on these cylinders 54 and carries.The temperature of the atmosphere in the hothouse 15 or humidity etc. are regulated by not shown air conditioner.By process hothouse 15, film 50 is dried.Connect absorbing recovery device 55 at hothouse 15.Absorbing recovery device 55 is by adsorbing the solvent that reclaims from film 50 evaporations.
Outlet side at hothouse 15 is provided with cooling chamber 16, at this cooling chamber 16 film 50 is cooled to room temperature.Between cooling chamber 16 and coiling chamber 17, begin to set gradually except that torch 61, annular knurl and give cylinder 62, trimming device 63, and determining film thickness device 64 from upstream side.Removing torch 61 carries out from the processing of being sent by cooling chamber 16 and the film 50 of static electrification is removed electricity that destatics.
As Fig. 1 and shown in Figure 4, annular knurl is given near the B direction both ends that cylinder 62 is disposed at film 50 respectively.Annular knurl is given a pair of clamping cylinder 62a, the 62b that cylinder 62 comprises clamping film 50.The jut 67 of a plurality of frustum of a pyramid shapes is set at the side face of cylinder 62a.Jut 67 disposes with the spacing of regulation respectively.Also have, jut 67 is not limited to the jut of frustum of a pyramid shape, can be circular cone shape or cima shape.In addition, the jut identical with jut 67 is not arranged at the side face of cylinder 62a, and the side face that is arranged at cylinder 62b also can, the side face that is arranged at cylinder 62a and 62b respectively also can.
As shown in Figure 4, determining film thickness device 64 is measured the thickness distribution of the integral body of the film 50 on the B direction.As determining film thickness device 64, preferably use known determining film thickness devices such as infrared ray infiltration type film thickness gauge.Also have, the mensuration direction of thickness distribution be so long as the direction of intersecting with the direct of travel of film 50 just can be the B direction, also can be the direction of intersecting with the B direction.
Be provided with up-coiler 73 with pressing roller 71 and volume core 72 in coiling chamber 17.When the film 50 pressurized cylinders 71 that are sent to coiling chamber 17 compress, be wound in core 72, become the roller shape.The diameter of volume core 72 does not limit especially.
Secondly, effect of the present invention is described.As shown in Figure 1, dope 28 is sent to casting head 21.Utilization is arranged at the adjustment machine (not shown) of casting head 21, and the temperature of dope 28 is being adjusted to constant more than 30 ℃ and in the scope below 35 ℃.
Casting head 21 sprays the side face 22b of dope 28 towards curtain coating drum 22 from slit 31d (with reference to Fig. 3).Utilize the dope 28 of ejection, on side face 22b, form casting films 40.By regulating the adjusting of bolt 32, casting films 40 becomes the thickness-tapered portion that comprises the goods portion that is positioned at B direction central portion and be positioned at B direction both ends.The thickness of goods portion is constant on the B direction.The thickness of thickness-tapered portion reduces towards goods portion.The dope 28 that constitutes casting films 40 is cooled on side face 22b, becomes gel.Its result shows self-supporting in casting films 40.Then, peel off the casting films 40 that cylinder 24 will have self-supporting and peel off as wetting film 44 from curtain coating drum 22, via transition part 45 to pin stenter 13 guiding.
At this, gelation also comprises the state of the flowability that has lost dope except the state of colloidal solution with the curing of jelly shape.Also have, " having lost the flowability of dope " comprising: at solute is under the high molecular situation, solvent loses flowability under the maintained state in the strand of solute, its result, lost solution flowability state and be under the low molecular situation at solute, the interaction of the molecule by solvent and the molecule of solute, its result has lost the state of the flowability of solution.
More than the preferred 250 weight % of the residual solvent amount of the casting films 40 when peeling off and below the 300 weight %.Also have, in the present invention, will be in casting films 40 or each film residual quantity of solvent by the quantity of solvent shown in the dry basis as the residual solvent amount.In addition, in its assay method,, the weight of this sample is made as x from the film collected specimens of object, when dry weight behind the sample is made as y, by (x-y)/calculate y} * 100.
In pin stenter 13, a plurality of pins are inserted the two ends of wetting films 44 and fix.Carried out fixing after, carry this wetting film 44 during, promote dryly, form film 50.Also have, the film 50 that still comprises the state of solvent is sent into clamped tenter 14.From pin stenter 13 and clamp film 50 that tenter 14 comes out by trimming device 52,53, the two ends of film 50 are cut off.
The film 50 that two ends are cut off by hothouse 15 and cooling chamber 16, is implemented predetermined process successively in each chamber.The film of sending from cooling chamber 16 50 is implemented based on the processing that destatics that removes torch 61.
As Fig. 1 and shown in Figure 4, annular knurl is given cylinder 62 clampings and is implemented the film 50 that destatics processing, is sent to trimming device 63.By the clamping that annular knurl is given cylinder 62, a pair of thickness-tapered 50a of portion, 50b at the B direction two ends that are positioned at film 50 form knurled portions 51a, 51b.Then, trimming device 63 cut off in the film 50, the part in the outside of a pair of knurled portions 51a, 51b on the B direction.
The film 50 that determining film thickness device 64 is cut off about the part in the outside of a pair of knurled portions 51a, 51b is measured thickness distribution.The thickness distribution of film shown in Fig. 5 50.In Fig. 5, the longitudinal axis is represented thickness, and transverse axis is represented the position on the B direction.Like this, in the mensuration of thickness distribution, at a plurality of position finding thickness of prescribed direction, the relation of setting up the Determination of thickness value and locating.
The judgment processing that 37 pairs of films 50 of controller are stipulated.Below, the details based on the judgment processing of controller 37 is described.
At first, controller 37 reads the thickness distribution of film 50 from determining film thickness device 64, carries out first judgment processing.In first judgment processing, whether judgement satisfies Rule of judgment from the thickness distribution of the film 50 that determining film thickness device 64 reads.At this, Rule of judgment is " 50c of goods portion does not comprise the thick part of thickness T Hs than the reference position Ps that is provided with at the 50a of thickness-tapered portion, 50b ".
In first judgment processing, the thickness distribution that is judged as film 50 does not satisfy under the situation of Rule of judgment, and controller 37 reads new thickness distribution from determining film thickness device 64.Also have, controller 37 is calculated the aggregate-value of the thickness distribution of film 50 by a plurality of thickness distribution that read.Then, controller 37 carries out second judgment processing.In second judgment processing, judge whether the aggregate-value of the thickness distribution of film 50 satisfies Rule of judgment.At this, Rule of judgment is " aggregate-value of the thickness among the 50c of goods portion is that the aggregate-value of thickness T Hs of reference position Ps is following ".
The aggregate-value of the thickness distribution of film 50 for example carries out as described below.At first, in a plurality of thickness distribution that read, will be from an end along the B direction away from the thickness addition each other of the position of distance X degree.By being to carry out this addition in 0 the scope till the width W of film in distance X, can calculate the aggregate-value of the thickness distribution of film 50 by a plurality of thickness distribution that read.The quantity of the thickness distribution of using in the calculating of this aggregate-value is to get final product more than 2, but more preferably 3 or 4.
In second judgment processing, the aggregate-value that is judged as thickness distribution does not satisfy under the situation of Rule of judgment, feed back the result of each judgment processing, make the aggregate-value of the thickness distribution of the thickness distribution of film 50 or film 50 satisfy the interval CL1 (with reference to Fig. 3) that slit 31d is regulated on Rule of judgment ground.
On the other hand, in first judgment processing and second judgment processing, be judged as under the situation that satisfies Rule of judgment, read new thickness distribution, carry out first judgment processing about new thickness distribution from determining film thickness device 64.
Like this, in the present invention, feed back the result of first judgment processing and second judgment processing, regulate the interval CL1 of slit 31d, therefore,, also suppress the strong contact between the superimposed film 50 even film 50 is wound in core 72.Thereby, according to the present invention as can be known, when can suppress the generation of black-tape fault, can make film 50.
Utilize the length L of up-coiler 73 wound film 50 preferably on length direction (curtain coating direction), to be at least more than the 100m.In addition, more than the preferred 1000mm of the width W of film 50 and below the 3500mm.In addition, the present invention is also effective under the width of film 50 situation wideer than 2500mm.And then, be more than the 5 μ m and also be suitable for the present invention during the film below the 80 μ m at the thickness of making film 50.At this, when the thickness of film 50 is made as V at the volume with film 50, represent by V/ (LW).Also have, as the method for obtaining of volume V, the weight of film 50 also can divided by the proportion of film 50.
4.0 * 10 of the width W of the interval CL2 preferred film 50 on the B direction of a pair of knurled portions 51a, 51b and reference position Ps
-3Doubly above and 20 * 10
-3Doubly, for example, more than the preferred 1mm and below the 15mm.In addition, the length We preferred 2.5 * 10 of the B direction of a pair of knurled portions 51a, 51b
-3Doubly above and 35 * 10
-3Doubly, for example, more than the preferred 5mm and below the 30mm.Also have, on the B direction, the 50c of the goods portion side of a pair of knurled portions 51a, the 51b length till the two ends of film 50 is made as We also can.
In the thickness of the 50c of goods portion below the preferred 3 μ m of the poor Δ TH of maximal value and minimum value, more preferably below the 1 μ m.
Also have, under the different situation of the thickness of a pair of reference position Ps, preferably the thickness with a thick side is made as THs.
In the above-described embodiment, about having passed through the film 50 of trimming device 63, carried out the mensuration of thickness distribution, but the invention is not restricted to this, measure thickness distribution for the film 50 that comes out from wetting film 44 or pin stenter 13, based on this measurement result, the interval CL1 that regulates slit 31d also can.
In the above-described embodiment,, make casting films 40 show self-supportings, but the invention is not restricted to this,, make casting films 40 show that self-supportings also can by the evaporation of the solvent that comprises in the casting films 40 by cooling.
In the above-described embodiment, as supporter, used curtain coating drum 22, but the invention is not restricted to this, used to be erected at cylinder and the rotation by cylinder, the casting belt of advancing continuously also can.
Below, the raw material that uses when preparing dope 28 in the present invention is described.
(polymkeric substance)
In the present embodiment,, used acylated cellulose as polymkeric substance, as acylated cellulose, especially preferred cellulose triacetate (TAC).Also have, in acylated cellulose, also more preferably satisfy whole acylated cellulose of following formula (I)～(III) to the degree of substitution of the acyl group of cellulosic hydroxyl.Also have, in following formula (I)～(III), A and B represent the degree of substitution to the acyl group of the hydrogen atom in the cellulosic hydroxyl, and A is the degree of substitution of acetyl group, and B is that carbon number is the degree of substitution of 3～22 acyl group.Also have, the 90 weight % of preferred TAC are above for having the particle of 0.1～4mm particle diameter.But operable in the present invention polymkeric substance is not limited to acylated cellulose.
(I)2.5≤A+B≤3.0
(II)0≤A≤3.0
(III)0≤B≤2.9
The glucose unit that constitutes cellulosic β-1,4 bonding has free hydroxyl at 2,3 and 6.Acylated cellulose is to utilize the acyl group of carbon number more than 2 that part or all of these hydroxyls carried out the polymkeric substance (polymer) of esterification.The acyl substituted degree is meant: respectively about 2,3 and 6, and the esterified ratio of cellulosic hydroxyl (situation of the esterification with 100% is made as degree of substitution 1).
Total acyl substituted degree is that the value of DS2+DS3+DS6 is preferred 2.00～3.00, more preferably 2.22～2.90, especially preferred 2.40～2.88.In addition, the value of DS6/ (DS2+DS3+DS6) is preferred more than 0.28, more preferably more than 0.30, and especially preferred 0.31～0.34.At this; DS2 is that the hydrogen of 2 hydroxyl in the glucose unit is by the ratio of acyl substituted (hereinafter referred to as 2 acyl substituted degree); DS3 be the hydrogen of 3 hydroxyl in the glucose unit by the ratio of acyl substituted (hereinafter referred to as 3 acyl substituted degree), DS6 is that the hydrogen of 6 hydroxyl in the glucose unit is by the ratio of acyl substituted (hereinafter referred to as 6 acyl substituted degree).
The acyl group that in acylated cellulose of the present invention, uses only for a kind of also can, or use two or more acyl groups also can.When using two or more acyl groups, preferred one is individual to be acetyl group.If the summation of the degree that 2,3 and 6 s' hydroxyl is replaced by acetyl group is made as DSA; 2,3 and 6 s' hydroxyl is made as DSB by the summation of the degree of the acyl substituted beyond the acetyl group; then the value of DSA+DSB preferred 2.22～2.90, especially preferred 2.40～2.88.
In addition, DSB is preferred more than 0.30, and is especially preferred more than 0.7.And then, DSB preferred its be the substituting group of 6 hydroxyls more than 20%, more preferably more than 25%, and then preferred more than 30%, especially preferred more than 33%.And then the value of the DSA+DSB in 6 of acylated cellulose is more than 0.75, and then preferred more than 0.80, and also especially preferred acylated cellulose more than 0.85 by using these acylated celluloses, can be made the more superior dope of dissolubility.Especially, use under the situation of chlorine-free organic solvent, can make the superior dissolubility of demonstration, the dope that low viscosity and filterableness are superior.
Can obtain also can by any of cotton linter, paper pulp as the cellulose of the raw material of acylated cellulose.
The acyl group of carbon number more than 2 as acylated cellulose of the present invention can be fatty group, also can be aryl, do not limit especially.For example, can enumerate cellulosic alkyl-carbonyl ester, alkenyl carbonyl ester, aromatic series carbonyl ester, aromatic series alkyl-carbonyl ester etc., have respectively and then substituted group also can.As these preferred example, can enumerate propiono, bytyry, valeryl, caproyl, caprylyl, capryl, 12 carbonic acyl radicals, 13 carbonic acyl radicals, 14 carbonic acyl radicals, 16 carbonic acyl radicals, 18 carbonic acyl radicals, isobutyryl, uncle's bytyry, cyclohexane carbonyl, oleoyl, benzoyl, naphthyl carbonyl, cinnamoyl etc.Wherein, more preferably propiono, bytyry, 12 carbonic acyl radicals, 18 carbonic acyl radicals, uncle's bytyry, oleoyl, benzoyl, naphthyl carbonyl, cinnamoyl etc., especially preferred propiono, bytyry.
(solvent)
Solvent as the preparation dope, (for example can enumerate aromatic hydrocarbon, benzene, toluene etc.), halogenated hydrocarbon (for example, methylene chloride, chlorobenzene etc.), alcohol (for example, methyl alcohol, ethanol, n-propanol, normal butyl alcohol, diethylene glycol etc.), ketone (for example, acetone, MEK etc.), ester (for example, methyl acetate, ethyl acetate, propyl acetate etc.) and ether (for example, tetrahydrofuran, methyl cellosolve etc.) etc.Also have, dope is meant by with polymer dissolution or be scattered in polymer solution or the dispersion liquid that solvent obtains in the present invention.
In above-mentioned halogenated hydrocarbon, preferably use the halogenated hydrocarbon of carbon number 1～7, most preferably use methylene chloride.From the dissolubility of polymkeric substance, from the viewpoint of rerum naturas such as the physical strength of the fissility of the self-supporter of casting films, film and optical characteristics, preferably except methylene chloride, mix a kind of alcohol to several carbon numbers 1～5.The content of alcohol is 2～25 weight % with respect to solvent integral body preferably, more preferably 5～20 weight %.As alcohol, can enumerate methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol etc., but preferably use methyl alcohol, ethanol, normal butyl alcohol or these potpourri.
Recently, for the purpose of Min. ground inhibition, also inquire into the solvent composition that does not use methylene chloride to the influence of environment.In this case, preferred carbon number is that 4～12 ether, carbon number are that 3～12 ketone, carbon number are 3～12 ester, the alcohol of carbon number 1～12, also suitably mixes sometimes and uses these.For example, can enumerate the mixed solvent of methyl acetate, acetone, ethanol, normal butyl alcohol.These ethers, ketone, ester and alcohol have ring texture and also can.In addition, with the functional group of ether, ketone, ester and alcohol (promptly-O-,-CO-,-COO-reaches-OH) any have plural compound and also can be used as solvent.
About the details of acylated cellulose, be recorded in the spy and open [0140] paragraph of 2005-104148 number in [0195] paragraph, these records also go for the present invention.In addition, about solvent and plastifier, deterioration preventing agent, ultraviolet light absorber (UV agent), optical anisotropy controlling agent, postpone controlling agent, dyestuff, matting agent, remover, peel off adjuvant such as promoter, at length be recorded in the spy too and open [0196] paragraph of 2005-104148 number in [0516] paragraph, these records also are applicable among the present invention.
Claims (2)
1. solution film-forming method, it comprises:
Spray dope from the slit that is arranged at casting head towards the supporter of advancing, and on described supporter, form the operation of the film of strip, described dope comprises polymkeric substance and solvent, and described film only has the thickness-tapered portion that thickness successively decreases towards Width central authorities at the Width two ends;
The operation of the dry described film of peeling off from described supporter;
The operation of giving annular knurl to the described thickness-tapered portion of the described film of peeling off from described supporter;
The operation of the thickness distribution on the prescribed direction of repeatedly measuring the described film of peeling off from described supporter on the direct of travel of described film, the direct of travel of described prescribed direction and described film intersects;
Judge whether described film satisfies the operation of first condition and second condition, described first condition is the situation that the goods portion between a pair of described thickness-tapered portion does not comprise the thickness part thicker than the thickness of reference position, described second condition is that the aggregate-value of the thickness in the described goods portion is the following situation of aggregate-value of described reference position, and described reference position is arranged at the described thickness-tapered portion than the more close described Width center side of described annular knurl;
Regulate the operation at the interval of described slit, described adjusting is not satisfy in described judgement under the situation of described first condition and described second condition so that described film satisfies the mode of described first condition and described second condition carries out at described film; And
The reel operation of described film.
2. solution film-forming method according to claim 1, wherein,
In the thickness of described goods portion, the difference of maximal value and minimum value is below the 3 μ m.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2009-086163 | 2009-03-31 | ||
| JP2009086163 | 2009-03-31 |
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| JP (1) | JP5513192B2 (en) |
| KR (1) | KR101655735B1 (en) |
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| CN106985425A (en) * | 2015-09-30 | 2017-07-28 | 富士胶片株式会社 | Mould, equipment for making film, solution film-forming method and melted masking method |
| CN109789710A (en) * | 2016-07-27 | 2019-05-21 | 麦斯印刷解决方案有限公司 | For the equipment of printed cellulosic materials and the technique of the printing fibrous material |
| TWI670157B (en) * | 2014-03-31 | 2019-09-01 | 日商富士軟片股份有限公司 | Solution casting method and apparatus |
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|---|---|---|---|---|
| JP2013252614A (en) * | 2012-06-05 | 2013-12-19 | Fujifilm Corp | Method and equipment for casting solution |
| EP3352960A1 (en) * | 2015-09-22 | 2018-08-01 | Dow Global Technologies LLC | Closed impregnation process and apparatus therefor |
| KR102162520B1 (en) * | 2019-10-01 | 2020-10-06 | 박건호 | The Manufacturing Apparatus for Film |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN101852880B (en) | 2014-10-15 |
| JP5513192B2 (en) | 2014-06-04 |
| KR20100109385A (en) | 2010-10-08 |
| KR101655735B1 (en) | 2016-09-08 |
| JP2010253935A (en) | 2010-11-11 |
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