CN1220071C - Solution film making method - Google Patents
Solution film making method Download PDFInfo
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- CN1220071C CN1220071C CNB001349007A CN00134900A CN1220071C CN 1220071 C CN1220071 C CN 1220071C CN B001349007 A CNB001349007 A CN B001349007A CN 00134900 A CN00134900 A CN 00134900A CN 1220071 C CN1220071 C CN 1220071C
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Abstract
The prevent invention provides a solution film making method which can obviously reduce the nonuniform thickness in the long direction of a resin film which is made by using the solution flow casting method of using the resin solution of a decompression chamber. The method is characterized in that the resin solution is spit out from the front end of a flow casting mould into a film shape; when the resin solution casts to a movable supporting plate body which is slightly deviated from the lower part of the front end of the flow casting mould to move, the pressure reduction and suction operation is carried out to the surface of the contact side of the resin solution extruded into a film shape and the movable supporting plate body by using the decompression chamber; in the solution film making method containing the operation, the spitting speed is 7.0 to 38.0 M / min, and the decompression degree of the decompression chamber is in the rang of-1 to-50 mmAq.
Description
The present invention relates to be applicable to the solution film-forming method of making the film that is fit to sensitive photographic material or optical applications.
The overlay of film (resin molding) in recent years as the optical compensation films of the polarization board protective film of liquid crystal display, phasic difference plate etc., plastic base, photograph with support or animation with optical materials such as element or blooming even ohp films, it is needed to increase.
Particularly nearest, liquid crystal display is easy to carry because of its quality height and because of in light weight, so be widely used in personal computer or word processor, carry, be used for showing that for liquid crystal display the Polarizer of portrait is necessary with end line, TV even digital static camera or mobile camera etc.But the quality that improves with liquid crystal display combines, and requires to improve the quality of Polarizer, meanwhile also requires to have higher quality as the transparent resin of polarization board protective film.
Optical applications films such as diaphragm for Polarizer; from the demonstration grade of resolving power or contrast ratio, must possess high transparent, low optical anisotropy, planarity, easily in the surface rational faculty, high-durability (dimensional stability, humidity resistance, water tolerance), the film and the no foreign matter in surface, the no scar in surface and difficulty in spite of wound (anti-wound property), have appropriate film rigidity (operability) and appropriate various characteristicses such as water permeability.
As resin with characteristic like this, by the film that cellulose esters, norbornene resin, allyl resin, polyacrylate resin, polycarbonate resin etc. are formed, still consider from aspects such as productivity or material prices, mainly use cellulose ester resin.Particularly the film of cellulosic triacetate is because have the high transparency, and optical anisotropy is little, the retardance is low, so be used for the optical applications advantageous particularly.
As the film-forming method of these resins, can utilize various masking techniques such as fusion system embrane method and rolling process, but in order to obtain good planarity and low optical anisotropy, solution film-forming method particularly suitable.The solution film-forming method is that raw material block is dissolved in the solvent, add plasticizer, ultraviolet light absorber, deterioration preventing agent, lubricant, peel off the solution (being called dope) of various adjuvants such as promoter to it as required, on supports such as the recycle metal band of horizontal or rotating cylinder, behind this dope of dope supply method (being called mold) curtain coating, on support, be dried to certain degree, self supportive film of giving rigidity is thus peeled off from support, then with various method for carrying make its by drying nest with except that desolvating.
When resin film is used in the purposes of optics, needs excellent above-mentioned each characteristic certainly, but also need film integral thickness homogeneity height.And, when there is heterogeneity in film integral thickness, because of its heterogeneity partly produces the optical characteristics heterogeneity, so have problems mostly as optical thin film.
Moreover, on the plastic sheeting surface of system film, be applicable to above-mentioned optical applications, just need carry out skin hardness and handle, prevent the dazzle processing, prevent emission processing, anti-pollution processing etc.Such as preventing to reflect function in order to give, when being coated with the coating fluid that anti-dazzle photosphere uses, if therefore the plastic film thickness heterogeneity then produces crawling one, overslaugh the function of film, make appearance value low simultaneously.
On the other hand, in order to improve the productivity of plastic sheeting, in above-mentioned solution film-forming method, when on support, using plastic film curtain coating dope, utilize the method for using the decompression chamber that curtain coating is partly reduced pressure and attracts from curtain coating plastic film rear.Moreover, solution film-forming method comprises following operation, resin solution is squeezed into membranaceous from curtain coating plastic film front end, curtain coating is when mobile activity is supported on the plate body by the position of departing from its curtain coating mold front end below a little, utilization is connected to the decompression chamber that decompression attracts the fan blower of usefulness by attraction pipeline, and being reduced pressure in the surface with movable support contact side that is squeezed into membranaceous resin solution attracts operation.
On the other hand, among the public Open skill Reported of the applicant's technology that discloses of on February 1st, 1994 publishing in Japan special permission Room 94-2498 number, disclose the outshot that enlarges mold front end used when adopting the solution casting method curtain coating, made the method for the good cellulosic triacetate film of planarity thus.Put down in writing from the curtain coating mold spue movable support dope flow preferably per unit basal area 2-28 liter/minute/cm
2Scope.
The present inventor finds, particularly during curtain coating, the uneven film thickness one of system film takes place easily in utilizing the solution film-forming method of above-mentioned decompression chamber, studies the reason that its uneven thickness one produces emphatically.But, found that of its research, even in the scope of above-mentioned dope flow, in the solution film-forming method of using the decompression chamber, uneven thickness one takes place in film particularly long direction easily.
The present inventor is found that of research further continuously, with dope from the decompression degree set of the speed that spues of curtain coating mold and decompression chamber in certain specific scope, can prevent the uneven thickness one of curtain coating direction thus really.
The present invention is the solution film-forming method that is used to make the film that thickness and precision improves, be characterised in that, make the resin solution that contains cellulosic low-grade fatty acid ester from curtain coating mold front end spue become membranaceous, curtain coating is to mobile activity is supported on the plate body by the position of departing from its curtain coating mold front end below a little, when making thickness and be the film of scope of 20-500 μ m, comprising reduces pressure to the surface with movable support contact side that is squeezed into membranaceous resin solution by the decompression chamber attracts the step of operation, wherein the speed of spuing is the 7.0-38.0m/ branch, and the decompression degree of this decompression chamber-1 to-50mmAq (wherein, scope 1mmAq=9.80665).
Below, enumerate the preferred embodiment of solution manufacture method of the present invention.
(1) solution film-forming method of speed that spue in 7.0-25.0m/ branch scope.
(2) the decompression degree in the decompression chamber is at-3 solution film-forming methods to-30mmAq scope.
(3) distance from movable support surface to the mold fore-end (mold height) is at the solution film-forming method of the scope of 0.5-50mm.
(4) resin solution is the solution film-forming method of cellulosic triacetate solution.
Below, will be elaborated for the solution film-forming method that is used for making film of the present invention with reference to the accompanying drawings, in the accompanying drawings:
Fig. 1 is the example skeleton diagram of curtain coating portion that expression can be used in the device of manufacture method of the present invention.
As the material resin that manufacture method of the present invention is used, can enumerate such as cellulosic low-grade fatty acid ester (such as cellulosic triacetate), polyalkenes (such as norbornene polymer), polyamide-based (such as aromatic amides), polysulfones, polyethers (containing polyether sulfone or polyethers ketone), polystyrene type, polycarbonate-based, polypropylene-base acids, polypropylene-base amide-type, polymethacrylic acid (such as polymethyl methacrylate), polymethylacrylic acid amide-type, polyvinyl alcohols, polyureas, polyesters, poly-urethanes, poly-imines class, polyvinyl acetate class, polyvinyl formaldehydes (such as polyvinyl dimethoxym ethane, polyvinyl butyral), and protein (such as gelatin). Wherein the raw material as sensitive photographic material or optical applications film is preferably cellulosic lower fatty acid, and particularly preferred is cellulosic triacetate.
At first, these material resins are dissolved in the suitable organic solvent solution (dope) of modulation resin. As the example of organic solvent, can enumerate halogenated hydrocarbon (carrene etc.), alcohols (methyl alcohol, ethanol, butanols etc.), ketone (acetone, methyl ethyl ketone etc.), ester class (methyl formate, methyl acetate etc.), ethers (dioxanes, Anaesthetie Ether etc.), hydrocarbon (benzene, hexane etc.). In the solution of resin, also can add the phosphates such as triphenyl, biphenyl diphenyl phosphoester and be the phthalic acid esters such as plasticizer, diethyl phthalate and be plasticizer, and known various plasticizers such as the poly-urethane groups rubber of polyester. Also can add as required in addition ultra-violet absorber, prevent degradation, lubricant, peel off the known various additives such as promoter.
The modulation of resin solution, can utilize and mix in the solvent material resin etc. and the method for dissolving with known method, perhaps also can adopt the hot-cold lysis method, utilization makes the mixture that should swollenly rise behind swollen the rising such as material resin be cooled to below-10 ℃ in solvent, then is warmed to the method for dissolving more than 0 ℃.
Then, use this resin solution of resin solution casting device curtain coating (dope) that is shown in Fig. 1. In the manufacturing installation shown in Fig. 1, make resin solution (dope) from curtain coating mold 1 spue and curtain coating to the surface of the movable support 2 that moves with the certain speed direction of arrow in the drawings. Simultaneously, utilize pressure-reducing chamber 3 decompressions at the rear be disposed at curtain coating mold 1 (near the surface that the movable support of the resin solution film that spues from the curtain coating mold links to each other) to attract to spue the resin solution film, make dope 4 adherence curtain coatings on movable support 2.
The scope that the decompression degree of at this moment, wishing the speed that spues of dope and pressure-reducing chamber divides at 7.0-38.0m/ respectively and-1 to-50mmAq (in the water) scope. Here, the speed of spuing of so-called dope is the speed that on average spues at the cross direction of curtain coating mold ledge front end. Make the decompression degree in the speed of spuing and pressure-reducing chamber be combined in the curtain coating that spues of carrying out dope in these scopes, can keep thus appearance value or the functional of film because preventing uneven film thickness one. Particularly preferred is that the speed of spuing is divided at 7.0-25.0m/, and decompression degree-3 is to the scope of-30mmAq.
And the mold of the distance of expression from movable support 2 to curtain coating mold 1 ledge front end is more preferably the scope at 1-10mm highly usually in the scope of 0.5-50mm.
Moreover, can be used in the device of the curtain coating of resin combination solution among the present invention, not only be defined in the device shown in Fig. 1, the such device of device in the outfit pressure-reducing chamber that any common solution film-forming method is used can be implemented the present invention. For example curtain coating mold 1 can be the mold that individual layer is used among the present invention, the perhaps common curtain coating mold used of multilayer. And movable support 2 can be the revolving cylinders such as the continous metal strip with surperficial mirror process, or chilling roll.
Then, on movable support, after the casting films of dry certain degree being given rigidity is peeled off from movable support, with suitable method for carrying by drying section further except that desolvating.Like this, can access the significantly film of the system film of minimizing of uneven thickness one.
The thickness of film among the present invention is different because the raw material of film or purposes etc. are different, but generally in the scope of 20-500 μ m, better in the scope of 40-200 μ m.
Embodiment
Embodiment 1-3
Mix each and become to be divided into following composition, modulating resin solution (dope).
Cellulosic triacetate 100 weight portions
Triphenyl 10 weight portions
Xenyl diphenyl phosphoester 5 weight portions
Methylene chloride 400 weight portions
Methyl alcohol 70 weight portions
Under the speed 8m/ that spues divides, the decompression degree that changes the decompression chamber is-3 ,-15 ,-30mmAq, the solution casting device of representing with Fig. 1 (mold height (h): 5mm) with after the dope curtain coating of modulation is to the movable support, peel off each resin casting films and dry from support, make resin film (thickness: 80 μ m).
Embodiment 4-9
In embodiment 1, remove the speed of spuing and be 10m/ branch and decompression degree as shown in table 1 being respectively-1 ,-3 ,-10 ,-15 ,-30 that changes the decompression chamber ,-50mmAq outside, identical with embodiment 1, make resin molding.
Comparative example 1,2
In embodiment 1, remove the speed of spuing and be 10m/ branch and the decompression degree that changes the decompression chamber to be respectively-0.5mmAq and-100mmAq outside, identical with embodiment 1, make the resin molding that is used for comparison.
Comparative example 10-12
In embodiment 1, remove the speed of spuing and be 15m/ branch and decompression degree as shown in table 1 being respectively-3 ,-15 that changes the decompression chamber ,-30mmAq outside, identical with embodiment 1, make resin molding.
The evaluation of film
For each film that obtains, use the small concavo-convex of light interferometer measurement surface, estimate the situation occurred of uneven thickness one with following A A-CC.
AA: do not produce uneven thickness one fully
BB: produce a little less than the uneven thickness one, do not have problems in the practicality
CC: produce uneven thickness the last one, be not suitable for practicality
The result who obtains gathered be shown in table 1.
Table 1
| The speed that spues (m/ branch) | Decompression degree (mmAq) | Uneven thickness one | |
| Embodiment 1 | 8 8 8 | -3 -15 -30 | AA AA AA |
| Embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 | 10 10 10 10 10 10 | -1 -3 -10 -15 -30 -50 | BB AA AA AA AA BB |
| Comparative example 1 comparative example 2 | 10 10 | -0.5 -100 | CC CC |
| Embodiment 10 embodiment 11 embodiment 12 | 15 15 15 | -3 -15 -30 | AA AA AA |
Embodiment 13-15
In embodiment 1, remove the speed of spuing and be 20m/ branch and decompression degree as shown in table 2 being respectively-5 ,-20 that changes the decompression chamber ,-40mmAq outside, identical with embodiment 1, make resin molding.
Embodiment 16-18
In embodiment 1, remove the speed of spuing and be 25m/ branch and decompression degree as shown in table 2 being respectively-5 ,-20 that changes the decompression chamber ,-40mmAq outside, identical with embodiment 1, make resin molding.
Embodiment 19-21
In embodiment 1, remove the speed of spuing and be 30m/ branch and decompression degree as shown in table 2 being respectively-1 ,-25 that changes the decompression chamber ,-50mmAq outside, identical with embodiment 1, make resin molding.
Embodiment 22-24
In embodiment 1, remove the speed of spuing and be 35m/ branch and decompression degree as shown in table 2 being respectively-1 ,-25 that changes the decompression chamber ,-50mmAq outside, embodiment 1 is identical, makes resin molding.
Comparative example 3
In embodiment 1, remove the speed of spuing and be 40m/ branch and the decompression degree that changes the decompression chamber for outside-the 50mmAq, identical with embodiment 1, make the resin molding that is used for comparison.
For each film that obtains, use the small concavo-convex of light interferometer measurement surface, estimate the situation occurred of uneven thickness one with following A A-CC.
AA: do not produce uneven thickness one fully
BB: produce a little less than the uneven thickness one, do not have problems in the practicality
CC: produce uneven thickness the last one, be not suitable for practicality
The result who obtains gathered be shown in table 2.
Table 2
| The speed that spues (m/ branch) | Decompression degree (mmAq) | Uneven thickness one | |
| Embodiment 13 embodiment 14 embodiment 15 | 20 20 20 | -5 -20 -40 | AA AA AA |
| Embodiment 16 embodiment 17 embodiment 18 | 25 25 25 | -5 -25 -40 | AA AA AA |
| Embodiment 19 embodiment 20 embodiment 21 | 30 30 30 | -1 -25 -50 | BB BB BB |
| Embodiment 22 embodiment 23 embodiment 24 | 35 35 35 | -1 -25 -50 | BB BB BB |
| Comparative example 3 | 40 | -50 | CC |
From the result shown in table 1 and the table 2 as can be known, curtain coating dope under according to the decompression degree of the speed that spues of the inventive method and decompression chamber and in the film (embodiment 1-24) made any, compare with the film of making under film of making under the decompression degree outside the scope of the invention (comparative example 1,2) and the different speed that spue outside the scope of the invention (comparative example 3), uneven thickness one obviously reduces.
According to the present invention, when adopt using the solution casting manufactured film of resin solution of decompression chamber (adopting the manufacturing of solution film-forming method), the decompression degree combination of the speed that spues of dope and decompression chamber set be respectively that 7.0-38.0m/ divides and-1 to-50mmAq scope, the uneven thickness one significantly reduced resin film that is specially adapted to optical applications takes place in the time of can making curtain coating thus, can improve the appearance value and the function of resin film.
Claims (9)
1. be used to make the solution film-forming method of the film that thickness and precision improves, it is characterized in that, make the resin solution that contains cellulosic low-grade fatty acid ester from curtain coating mold front end spue become membranaceous, curtain coating is to mobile activity is supported on the plate body by the position of departing from its curtain coating mold front end below a little, when making thickness and be the film of scope of 20-500 μ m, comprising reduces pressure to the surface with movable support contact side that is squeezed into membranaceous resin solution by the decompression chamber attracts the step of operation, the scope that the speed that wherein spues is divided at 7.0-38.0m/, and the decompression degree of this decompression chamber is in-1 to-50mmAq scope.
2. the described solution film-forming method of claim 1, wherein, the scope that the speed that spues is divided at 7.0-25.0m/.
3. claim 1 or 2 described solution film-forming methods, wherein, the decompression degree of decompression chamber is in-3 to-30mmAq scope.
4. the solution film-forming method described in the claim 1 or 2, wherein, the distance from movable support surface to curtain coating mold front end is in the scope of 0.5-50mm.
5. the solution film-forming method described in the claim 3, wherein, the distance from movable support surface to curtain coating mold front end is in the scope of 0.5-50mm.
6. the solution film-forming method described in the claim 1 or 2, wherein, resin solution is a cellulosic triacetate solution.
7. the solution film-forming method described in the claim 3, wherein, resin solution is a cellulosic triacetate solution.
8. the solution film-forming method described in the claim 4, wherein, resin solution is a cellulosic triacetate solution.
9. the solution film-forming method described in the claim 5, wherein, resin solution is a cellulosic triacetate solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001349007A CN1220071C (en) | 2000-10-27 | 2000-10-27 | Solution film making method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001349007A CN1220071C (en) | 2000-10-27 | 2000-10-27 | Solution film making method |
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| CN1351265A CN1351265A (en) | 2002-05-29 |
| CN1220071C true CN1220071C (en) | 2005-09-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB001349007A Expired - Lifetime CN1220071C (en) | 2000-10-27 | 2000-10-27 | Solution film making method |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007024028A1 (en) * | 2005-08-26 | 2007-03-01 | Fujifilm Corporation | Polymer film, cyclic polyolefin film, method for manufacturing the same, optical compensation film, polarizer and liquid crystal display device |
| US20120009427A1 (en) * | 2010-07-08 | 2012-01-12 | Christopher Hable | Solvent cast flame retardant polycarbonate coatings, films and laminates |
| JP5698720B2 (en) * | 2012-09-21 | 2015-04-08 | 富士フイルム株式会社 | Solution casting equipment and method |
| KR20140042652A (en) * | 2012-09-28 | 2014-04-07 | 후지필름 가부시키가이샤 | Solution film-forming method |
-
2000
- 2000-10-27 CN CNB001349007A patent/CN1220071C/en not_active Expired - Lifetime
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