CN103588884A - Polymer purifying method and facility, solution film forming method and facility, and flocculent and granular deposited polymer - Google Patents

Polymer purifying method and facility, solution film forming method and facility, and flocculent and granular deposited polymer Download PDF

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Publication number
CN103588884A
CN103588884A CN201310288194.5A CN201310288194A CN103588884A CN 103588884 A CN103588884 A CN 103588884A CN 201310288194 A CN201310288194 A CN 201310288194A CN 103588884 A CN103588884 A CN 103588884A
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polymkeric substance
separating out
polymer
solvent
wet type
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CN201310288194.5A
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CN103588884B (en
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横山和正
鹫谷公人
下田泰久
笠原诚治
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Fujifilm Corp
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Fujifilm Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
    • 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
    • B29C41/28—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 an endless belt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Biochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Moulding By Coating Moulds (AREA)

Abstract

The invention relates to a polymer purifying method and facility, a solution film forming method and facility, and a flocculent and granular deposited polymer. In a dissolving box, a raw material of acylation cellulose (CA) is dissolved in methylene dichloride to form a thin stoste with 7% polymer concentration. The thin stoste is filtered by a filter. Hot water heated to be hotter above a boiling point of methylene dichloride is put in a separator. The thin stoste is sprayed on the hot water inside the separator via a first nozzle. Methylene dichloride of the thin stoste contacted with the hot water evaporates, and then acylation cellulose is separated. The acylation cellulose (CA) is separated from the water, and hot water contained in the cellulose is extruded out. Then, the separated acylation cellulose is dried by a vibration dryer. The acylation cellulose is obtained through the thin stoste dissolved in a solution, so the separated acylation cellulose with excellent dissolvability through utilization of a solution can be obtained.

Description

Polymer purification method and apparatus, solution film-forming method and equipment and the cotton-shaped and granular polymkeric substance of separating out
Technical field
The present invention relates to a kind of polymer purification method and apparatus, solution film-forming method and equipment and cotton-shaped (flocculating) and the granular polymkeric substance of separating out.
Background technology
The thermoplastic film with photopermeability is because of lightweight and be easily shaped, and as blooming for many aspects.Wherein, the acylated cellulose mesentery of use acylated cellulose (cellulose acylate) etc.; take photosensitive film as representative, and for the component parts of the liquid crystal indicator that market is expanding in recent years, be blooming (such as phase retardation film or polarization board protective film etc.).
Described film is made by solution film-forming method.Solution film-forming method is that the polymers soln (curtain coating stoste (flow casting dope)) that comprises polymkeric substance and solvent is flowed on supporter, and forms casting films.Secondly, casting films reach can conveyance after, casting films is peeled off and is formed moistening film from supporter.Then, this moistening film is delivered in kiln.In kiln, one side is wound on conveyance on roller by moistening film, and one side makes solvent form film from moistening film evaporation.
When using described film as the situation of blooming, along with liquid-crystal display (liquid crystal display in recent years, popularizing of the mobile model terminating sets such as high-precision refinement LCD), smart phone (smartphone) (multifunctional mobile telephone), dull and stereotyped (tablet) type computer, requires foreign matter fault few.
For example, in patent documentation 1, as reducing the method for foreign matter, disclose following method, that is, after filtering acylated cellobiose cellulose solution, carried out degasification, dry.In addition; in patent documentation 2, disclose the manufacture method that has following acylated cellulose; have: after acylated cellobiose cellulose solution is mixed with alcohols (alcohols); and then mix with poor solvent (poor solvent) and acidylate the step of Cellulose precipitates; the solubility parameter of the organic solvent using while making to prepare acylated cellobiose cellulose solution, solubility parameter (solubility parameter; SP) in the scope that value is 18.5～25.0, and the content of minimizing foreign matter.
In addition,, along with the high-precision refinement of liquid-crystal display and popularizing of mobile model terminating set, need various types of bloomings that characteristic is different.When changing the situation of characteristic, change kind or its allotment ratio of additive liquid, or change stock polymer.When the situation of stock polymer; when the source of raw material is for example the situation of acylated cellulose; can judge because of the cellulosic difference of the raw material as obtaining from paper pulp or cotton etc. or the difference in its place of production, and cause optical characteristics or other characteristics that slight variation occurs.
In patent documentation 3, make the benchmark stoste that comprises polymkeric substance and solvent, in the right on of casting mold (flow casting die), benchmark stoste is added to the distinctive additive liquid of each kind.And, when switching film kind, according to kind, change additive liquid.Thus, when making the situation of film of different varieties, do not make the cost of producing apparatus increase, and can suppress the generation of manufacturing time or goods loss.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 2008-56819 communique
[patent documentation 2] Japanese Patent Laid-Open 2012-25896 communique
[patent documentation 3] Japanese Patent Laid-Open 2010-100042 communique
In the method that patent documentation 1 and patent documentation 2 are recorded, reduce impurity the content of foreign matter is tailed off.Yet these methods, when carrying out polymers soln dry, and reckon without energy-saving and high productivity.
In the method that patent documentation 3 is recorded, by making benchmark stoste, and according to kind, benchmark stoste has been added to additive liquid, made the film of new variety.Yet, according to the difference of kind, also there is the situation that needs change polymkeric substance self.During this situation, ground as in the past, manufactures the new benchmark stoste corresponding with new variety.And, must replace as follows, after old benchmark stoste, flow through new benchmark stoste, with new benchmark stoste, be full of whole stoste stream.
With regard to described displacement, due to benchmark stoste manufacturing step through having, dissolve case or retention tank mixing portion, to after stoste heating in addition cooling the and then dissolving portion of filtering, there is the concentrated portion of well heater or flash lamp house (flash tank) and store the various devices such as reservoir of concentrated stoste, therefore this stoste stream capacity is for example 100,000 liters (liter, L).Therefore,, when the situation of change benchmark stoste self, must flow through the new stoste of 300,000 liters of left and right of 3 times of left and right of stoste stream capacity.Stoste in this displacement is that new and old stoste mixes, and cannot use and go out of use as goods.
Summary of the invention
The present invention is for solving described problem, its object be to provide a kind of foreign matter content few, can take into account energy-conservation and large-duty polymer purification method and apparatus and separate out polymkeric substance.
In addition, the object of the invention is to, provide a kind of applicable to a small amount of many kinds manufacture, and few solution film-forming method and the equipment of the running loss of material loss or producing apparatus.
The present invention completes based on following knowledge opinion; in the performance history of manufacturing in a small amount of many kinds; make to filter complete stoste (described stoste (dope) means: by material dissolves in solvent and the solution with mobility obtaining) acylated cellulose of separating out dry and that make is very easy to be dissolved in solvent; and; because being was once filtered, so foreign.
Polymer purification method of the present invention comprises: dissolving step, makes polymer dissolution in solvent and obtain polymers soln; Filtration step, filters polymers soln; And polymkeric substance separates out step, it is liquid more than non-intermiscibility and the boiling point that is heated to solvent that the polymers soln through filtration step is dispersed in polymkeric substance and solvent, makes solvent evaporation and separates out polymkeric substance.
In addition, more than the polymer solution concentration in dissolving step is preferably 2 quality % and below 19 quality %.More than filtering precision in filtration step is preferably 2 μ m and below 30 μ m.Preferred solvents is single solvent.In addition, be preferably, polymkeric substance is acylated cellulose, and solvent is methylene dichloride (methylene chloride), and liquid is water.At polymkeric substance, separate out in step, be preferably, more than the temperature of acylated cellobiose cellulose solution is 20 ℃ and below 120 ℃, more than the temperature of water is 40 ℃ and below 100 ℃.
Polymer purification method is preferably and comprises: thick drying step, wet type granulation step and final drying step.Thick drying step is to carry out after polymkeric substance is separated out step, and the polymkeric substance of separating out is slightly dried.Wet type granulation step is, by wet type, the polymkeric substance of separating out through thick drying step is carried out to granulation.Final drying step is that the polymkeric substance of separating out through wet type granulation step is finally dried.Be preferably, in thick drying step, the amount of moisture that makes to separate out polymkeric substance is more than 20% and below 150%, and in final drying step, and the amount of moisture that makes to separate out polymkeric substance is more than 0.1% and below 3%.The polymkeric substance of separating out of the present invention is manufactured by described polymer purification method.And, being preferably, the polymkeric substance of separating out of the present invention is with cotton-shaped or granular providing.
In addition, solution film-forming method of the present invention comprises: the 1st step, make the polymers soln that the 1st kind is used; The 2nd step, makes the polymers soln that the 2nd kind is used; Add step; Curtain coating step; And drying step; And from any one the polymers soln from the 1st step and the 2nd step, switch to any another the polymers soln in the 1st step and the 2nd step, and continuity ground carries out kind switching.The 1st step is used has the 1st polymers soln manufacturing installation that dissolves case and pump (pump), make by described polymer purification method acquisition separate out polymer dissolution in solvent, and make the polymers soln that the 1st kind is used.The 2nd step is used has the 2nd polymers soln manufacturing installation that dissolves case and pump, make by described polymer purification method acquisition separate out polymer dissolution in solvent, and make the polymers soln that the 2nd kind is used.Adding step is the polymers soln to an acquisition from the 1st step and the 2nd step, and on line, (in line) adds the additive liquid that is mixed with additive.Curtain coating step is to make the polymers soln that is added with additive liquid as curtain coating stoste, from casting mold, flows to curtain coating supporter and forms casting films.Drying step is that casting films is peeled off and is dried from curtain coating supporter.In addition, be preferably, add step and be and use a plurality of additive liquid retention tanks to make the additive liquid that additive liquid that the 1st kind uses and the 2nd kind are used, the additive liquid that the additive liquid that these the 1st kinds are used and the 2nd kind are used switches and carries, and carries out adding on line.
Polymer purification equipment of the present invention is characterised in that and comprises: dissolve case, make polymer dissolution in solvent and obtain polymers soln; Strainer, to filtering in the polymers soln that dissolves case dissolving; Polymkeric substance is separated out device, and taking in polymers soln is liquid more than non-intermiscibility and the boiling point that is heated to solvent, the polymers soln to liquid dissemination from dissolving case; And retrieving arrangement, from liquids recovery, at polymkeric substance, separate out the polymkeric substance that device is separated out.
In addition, to be preferably and to make polymer solution concentration be that 2 quality % are above and below 19 quality % to liquor box.In addition more than, the filtering precision of strainer is preferably 2 μ m and below 30 μ m.In addition, preferred solvents is single solvent.Be preferably, polymkeric substance is acylated cellulose, and solvent is methylene dichloride, and liquid is water.Be preferably, the temperature of separating out the acylated cellobiose cellulose solution that device scatters by polymkeric substance be 20 ℃ above and below 120 ℃, and the temperature of water be 40 ℃ above and below 100 ℃.
Polymer purification equipment is preferably and comprises: thick drying machine, wet type tablets press and final drying machine.Thick drying machine is slightly dried separating out polymkeric substance.Wet type tablets press carries out granulation by wet type to the polymkeric substance of separating out through slightly dry.Final drying machine is finally dried the polymkeric substance of separating out of granulation.Be preferably, the amount of moisture that thick drying machine makes to separate out polymkeric substance is more than 20% and below 150%, and finally to make to separate out the amount of moisture of polymkeric substance be more than 0.1% and below 3% to drying machine.
Solution film-forming equipment of the present invention comprises: polymer purification equipment, a plurality of dissolver, adding set, casting device and film dryer part.Dissolver comprises: dissolve case, make to separate out polymer dissolution in solvent; And pump, transport from the polymers soln that dissolves case.Adding set comprises: a plurality of additive liquid retention tanks, have additive liquid; Liquor charging portion, from these a plurality of additive liquid retention tanks feeding additive liquid optionally; And addition portion on line, the additive from this liquor charging portion is mixed in to the polymers soln from dissolver.Casting device makes the polymers soln that is added with additive liquid as curtain coating stoste, and is cast to mobile curtain coating supporter, to form casting films on curtain coating supporter.Film dryer part is dried the casting films of peeling off from casting device.In addition, be preferably, adding set is used a plurality of additive liquid retention tanks, makes the additive liquid that additive liquid that the 1st kind uses and the 2nd kind are used, the additive liquid that the additive liquid that these the 1st kinds are used and the 2nd kind are used switches and carries, and carries out adding on line.
[effect of invention]
According to the present invention, the utilising efficiency of heat energy is excellent, can carry out solvent evaporation rapidly, and can carry out continuous polymer purification.In addition the polymeric impurities obtaining, tails off.Thus, can carry out the solution film-forming that foreign matter fault is few.
Polymkeric substance is separated out in use, make to separate out polymer dissolution and in solvent, make curtain coating stoste, this separate out polymkeric substance be make solvent from stock polymer is dissolved in solvent and filter and polymers soln evaporation and obtain, thus, without the heating cold filtration step through in the past or photoflash lamp enrichment step etc., in dissolving case, be only solubilized, for example can obtain polymer concentration is the stoste of 20 quality % left and right.Therefore, can make the necessary curtain coating stoste of these each steps stream capacity be reduced to 1/30 left and right in the past.Therefore,, during the situation switched in kind that must change stock polymer, be reduced to 1/30 left and right in the past with the former liquid measure of the required new variety of the displacement of old stoste.And new and old stoste time swap also can correspondingly shorten the degree that has curtain coating stoste stream capacity to reduce, thereby the operation rate that obtains goods can be improved, the film of new variety can be manufactured efficiently.
Accompanying drawing explanation
Fig. 1 means the side-view of the summary of polymer purification equipment.
Fig. 2 means the side-view of the summary of separating out device and vibrating dryer.
Fig. 3 means the side-view of the summary of solution film-forming equipment.
Fig. 4 means the side-view of the summary of mixing device.
Fig. 5 means the stereographic map of static mixer.
Fig. 6 means the sectional view of dynamic mixer.
Fig. 7 means the side-view of the summary of separating out device, vibratory screening apparatus, hot air dryer of other embodiments.
Fig. 8 means the functional diagram of the summary of granulating equipment.
[explanation of symbol]
5: polymer purification equipment
6,80: dissolve case
6a, 39c, 80a: stirrer
6b, 39b, 57a: chuck
7: stoste supply line
7a, 28a, 38a, 51a, 55a, 57b, 87a, 87b, 92a, 92b, 92c: switching valve
7b: pressure regulator valve
8: separate out device
8a: relief outlet
9,46: discharge portion
10,113: vibrating dryer
11,28b, 38b, 51b, 55b, 81,91: pump
12,28c, 38c, 84: strainer
13: solvent supply line
14: solvent storage case
17: raw material acylated cellulose (acylated cellulose)
18: methylene dichloride
21: thin stoste
22: hot water
25: the 1 nozzles
26: the 2 nozzles
26a: nozzle head
26b: nozzle body
27,89c: agitating vane
27a: turning axle
27b: blade body
28: hot water supply pipeline
28d, 38d: vacuum breaker
28e: thermoswitch
29: electric motor
30: separate out acylated cellulose (acylated cellulose)
30a: the 1st separates out acylated cellulose
30b: the 2nd separates out acylated cellulose
31: the cotton-shaped acylated cellulose throw out of separating out
32: the granular acylated cellobiose crude granule of separating out
32a: drying granular is separated out acylated cellobiose crude granule
33,34: extrusion roll
35a: the 1st guide plate
35b: the 2nd guide plate
35c: the 3rd guide plate
37: overflow recoverer
38: water recycling pipeline
39: hot-water storage case
39a: well heater
40～42,47,48: door
49: can elastic container
51: water-supply line
51c: pure water filtration unit
55: solvent recuperation pipeline
56: condenser
57: separator tank
60: pure water retention tank
61: vibratory screening apparatus
61a: sieve main body
61b: Recovery of the hot water groove
62,63: extrusion roll
64: guide plate
65: turning valve
66: hot air dryer
67: pulverizer
68: solution film-forming equipment
69: mixing device
70A, 70B: dissolve unit
71: adding device
73: casting device
73a: curtain coating chamber
74: pin tenter
75: kiln
75a: roller
76: take-up mechanism
78: casting mold
79: solvent
82: static mixer
82a: stream
82b: the 1st element
82c: the 2nd element
83: dynamic mixer
83a: pipe arrangement
83b: stator
83c: rotor
83d: drive shaft
83e: sealing element
83f: labyrinth ring
83g: spiral ridge
85: curtain coating stoste
86: add nozzle
88: additive liquid liquor charging portion
89a, 89b: additive liquid retention tank
90: 3-way valve
93a, 93b: additive liquid
95: curtain coating rotating cylinder
96: angle stripper
97: casting films
98: moistening film
99: cross-over connection portion
99a: carrying roller
100: film
101: side shears
102: cooling room
110: thick drying machine
111: quantitative feeder
112: wet type tablets press
Embodiment
(polymer purification equipment)
As shown in Figure 1, polymer purification equipment 5 comprises: dissolve case 6, stoste supply line 7, separate out device 8, discharge portion 9 (retrieving arrangement) and vibrating dryer 10.Stoste supply line 7 comprises: switching valve 7a, pump 11, strainer 12 and pressure regulator valve 7b.
Raw material acylated cellulose (hereinafter referred to as raw material CA) 17 as stock polymer is fed in dissolving case 6.In addition, solvent storage case 14 is connected in via solvent supply line 13 and dissolves case 6.In this solvent storage case 14, store the methylene dichloride (methylene chloride) 18 as solvent.And, from solvent storage case 14, by solvent supply line 13, to dissolving case 6, drop into methylene dichloride 18.Dissolve case 6 and there is stirrer 6a.By this stirrer 6a, promote raw material CA 17 to the dissolving of methylene dichloride 18, thereby obtain raw material CA 17, be dissolved in thin polymers soln (thin stoste) 21 (dissolving steps) that form in methylene dichloride 18.The concentration (polymer solution concentration) of raw material CA 17 in thin stoste 21 is for example 7 quality %.This polymer concentration is more than 2 quality % and below 19 quality %, more than being preferably 5 quality % and below 14 quality %.If polymer concentration does not reach 2 quality %, solvent is removed that cost uprises and is not good enough.In addition, if polymer concentration surpasses 19 quality %, viscosity is high, filters that the pressure-losses causing uprises and not good enough.
Dissolve in case 6, by the heating, the heat insulation effect that utilize chuck (jacket) 6b, and the temperature of thin stoste 21 is remained on to for example 120 ℃.In addition, except thin stoste 21 being heated in dissolving case 6, also can heating unit be set separately in the downstream side of dissolving case 6, and thin stoste 21 is heated to specified temperature.More than the temperature of this thin stoste 21 is preferably 20 ℃ and below 120 ℃.If the temperature of thin stoste 21 does not reach 20 ℃, must carry out coolingly, in addition, evaporate required can quantitative change large, thereby not good enough.In addition,, if the temperature of thin stoste 21 surpasses 120 ℃, normally pipe arrangement starting material easily produce corrosion, thereby not good enough.With regard to the design temperature of thin stoste 21, before pressure regulator valve 7b, maintain for example 120 ℃, as described later, from the state of the 1st nozzle (nozzle) 25 ejections, become near 40 ℃.The thin stoste 21 obtaining is transported to the strainer 12 of stoste supply line 7.
In strainer 12, the thin stoste 21 of coming from conveying is removed for example foreign matter (filtration step) of 5 μ m left and right.The kind of strainer 12 is also not particularly limited, and is preferably used additives filter type, metal filtration mode, the filter paper filtering mode etc. of making.The filtering precision of each filter type, more than 2 μ m and in the scope of 30 μ m, is preferably according to application target and determines filtering precision.For example, filtering precision 5 μ m refer to below: the removable 5 μ m that more than 99.9% are of a size of.
Through the thin stoste 21 of strainer 12, by pressure regulator valve 7b, pressure is remained fixingly, and be delivered to and separate out device 8.
Utilization is separated out the polymkeric substance of device 8 and is separated out step for example for shown below.As shown in Figure 2, separating out device 8 is that inner gas and liquid can not leak to outside airtight type, for example, use horizontal type cylinder case.In the internal storage of separating out device 8, be maintained at the hot water 22 of the temperature more than boiling point of methylene dichloride 18, so that the methylene dichloride 18 in thin stoste 21 is evaporated.
In the bottom of separating out device 8, dispose the discharge nozzle 24 of rare gas element (air or nitrogen etc.).The temperature that is delivered to the rare gas element of discharge nozzle 24 remain on 20 ℃ above and below 100 ℃.The rare gas element of discharging from this discharge nozzle 24, diffusion has as the methylene dichloride 18 that is difficult to be dissolved in the composition of water.Concentration dichloromethane in the rare gas element bubble at initial stage is 0, and with respect to this, during the high situation of concentration dichloromethane in water, take this concentration difference as motivating force, and minute limitans by water and bubble makes methylene dichloride 18 move to bubble from water.And bubble temperature is higher, the saturation vapour pressure in bubble is higher, thereby movably quantity of dichloromethane increases.As a result of, promote the evaporation of the methylene dichloride 18 in thin stoste 21, thereby efficiency improves.In addition, if the temperature of rare gas element surpasses 100 ℃, there is the worry of water boiling, its result, the water ratio in steam increases, and is made as thus below 100 ℃.
The temperature that is supplied to the hot water 22 of separating out device 8 be preferably 40 ℃ above and below 100 ℃.If do not reach 40 ℃, methylene dichloride 18 does not evaporate, thereby cannot separate out.In addition, if surpass 100 ℃, for water is remained to liquid state and the running of must exerting pressure, therefore all not good enough.
On the internal surface top of separating out device 8, dispose the 1st nozzle 25 and the 2nd nozzle 26.In addition, there is agitating vane 27 separating out device 8 internal configuration.Agitating vane 27 is fixed on turning axle 27a by a plurality of blade body 27b and above forms.The mode that this agitating vane 27 becomes level with turning axle 27a, separates out in device 8 and be arranged on.Expose to outside from separating out device 8 one end of turning axle 27a, on one end of turning axle 27a, links and have electric motor (motor) 29.And the rotation by electric motor 29 makes agitating vane 27 rotations, and the hot water 22 of separating out in device 8 is stirred, and becomes fixing mode keep hot water 22 with water surface temperature.
The turning axle 27a of agitating vane 27 can be 1 and also can be many.When the situation that is many, at the turning axle 27a of adjacency each other, both can change sense of rotation, also can be equidirectional.And, being preferably, hot water 22 flows to relief outlet 8a near the water surface.In addition, the configuration direction of agitating vane 27 or the form of agitating vane 27 are not limited to illustrated example, generally speaking, as long as can stir the hot water 22 of separating out in device 8.
As shown in Figure 1, stoste supply line 7 is connected in the 1st nozzle 25.Thus, from the 1st nozzle 25, spray thin stoste 21 (with reference to Fig. 2) and scatter to the water surface.From pressure regulator valve 7b, to the pipeline 7 of separating out till the 1st nozzle 25 of device 8, form shortlyer, thin stoste 21 stably utilizes photoflash lamp to evaporate in separating out device 8.In addition, the 1st nozzle 25 only disposes 1, but configuration radical is not limited to 1, also can suitably increase.
Hot water supply pipeline 28 is connected in the 2nd nozzle 26.As shown in Figure 2, the 2nd nozzle 26 comprises: nozzle head 26a, is configured in the long side direction of separating out device 8; And a plurality of nozzle body 26b, with prescribed distance, be configured in this nozzle head 26a.Hot water supply pipeline 28 is delivered to the 2nd nozzle 26 by the hot water from hot water retention tank 39 22.Thus, from the 2nd nozzle 26, spray hot water 22 and scatter to the water surface.
Utilize the distribution of the thin stoste 21 that the 1st nozzle 25 carries out and utilize the distribution of the hot water 22 that the 2nd nozzle 26 carries out, be preferably along the width of cylinder case and carry out equably.Thus, can carry out efficiently separating out of acylated cellulose.
As shown in Figure 1, hot water supply pipeline 28, except having the switching valve 28a arranging as required and suitably, also has: pump 28b, strainer 28c, vacuum breaker 28d and thermoswitch 28e.Pump 28b regulates the flow of hot water 22 by adjusting rotation number.Strainer 28c filters foreign matter from hot water 22.Thermoswitch 28e carries out outlet temperature adjustment to carried out thermoregulator hot water 22 in hot-water storage case 39.Thus, from the 2nd nozzle 26, with the flow of stipulating, to the water surface, spray the hot water 22 (with reference to Fig. 2) that is heated to proper temperature.
The thin stoste 21 of spraying from the 1st nozzle 25 as shown in Figure 2, is contacted with the hot water 22 of separating out in device 8.More than hot water 22 is heated the boiling point that remains on methylene dichloride 18.Therefore, the methylene dichloride 18 in the thin stoste 21 contacting with hot water 22, the flash evapn by utilizing heating that hot water 22 carries out, raw material CA 17 for example separates out with wire, and become, separates out acylated cellulose (following, to be called simply and to separate out CA) 30.In present embodiment, also, from the top of the water surface, from the 2nd nozzle 26, scatter the hot water 22 of more than boiling point that is heated to methylene dichloride 18 (for example 80 ℃), thereby promote the evaporation of the methylene dichloride 18 in thin stoste 21.
The relief outlet 8a that separates out CA 30 is separating out an end opening of device 8.So that separate out the mode that CA 30 advances towards relief outlet 8a, by the rotation of agitating vane 27, and near the hot water 22 water surface is flowed to relief outlet 8a.In addition, a plurality of nozzle body 26b of the 2nd nozzle 26 with emission direction towards separating out the mode of discharge direction of CA 30 and tilted configuration.Therefore, the extruding that also can be undertaken by the hot water 22 by spraying from the 2nd nozzle 26, sends to relief outlet 8a and make to separate out CA 30.In addition, also can replace the sending of the caused CA of separating out 30 of the impetus of the injection undertaken by the 1st nozzle 25 and the 2nd nozzle 26, or in addition, also by making hot water 22 overflows (overflow), will separate out CA 30 and send to relief outlet 8a.In addition, make hot water 22 overflows make to separate out the method that CA 30 discharges, in the 2nd embodiment shown in Fig. 7, be described in detail.
The discharge portion 9 of separating out CA 30 is to be connected in relief outlet 8a.In addition, to clip the mode of relief outlet 8a, separating out device 8 side configuration the 1st extrusion rolls (squeeze roller) 33, and at discharge portion 9 configuration the 2nd extrusion rolls 34.
The 1st extrusion roll 33 and the 2nd extrusion roll 34 consist of 1 breaker roll (nip roller).These extrusion rolls 33, extrusion roll 34 can individually rotate, and when common discharge, both rotate with identical speed.In addition, when separating out the cutting of CA 30, stopping the 1st extrusion roll 33, clamp and separate out under the state of CA 30, make the 2nd extrusion roll 34 rotations.Thus, between these extrusion rolls 33, extrusion roll 34, the continuous CA 30 that separates out disconnects.In addition, the disconnection that also can replace utilizing indivedual rotations of this extrusion roll 33, extrusion roll 34 to carry out, and by the shut-off device being formed by cutting unit etc., the continuous CA 30 that separates out is cut off.
Front and back in cramping (nip) position of extrusion roll 33, extrusion roll 34, dispose the guide plate 35a～guide plate 35c that is arc-shaped bend.CA 30 is separated out in these guide plate 35a～guide plates 35c guiding.The 1st guide plate 35a is fixed, by the cramping position that CA 30 is directed to the 1st extrusion roll 33 of separating out from the water surface.The 2nd guide plate 35b, the 3rd guide plate 35c are movable.The 2nd guide plate 35b will separate out till the cramping position of CA 30 from the 1st extrusion roll 33 be directed to the cramping position of the 2nd extrusion roll 34.The 3rd guide plate 35c is directed in discharge portion 9 from the cramping position of the 2nd extrusion roll 34 separating out CA 30.The 2nd guide plate 35b and the 3rd guide plate 35c, can move in linkage with the switch motion of the 1st 40 and the 2nd 41, at door 40, door 41 while closing, from guiding position be displaced to each 40, door 41 retreating positions that can not disturb.
By the injection of the hot water 22 from the 2nd nozzle 26, at the hot water 22 of separating out device 8 interior overflows, from overflow recoverer 37, by water recycling pipeline 38, be back to hot-water storage case 39 (with reference to Fig. 1).As shown in Figure 1, water recycling pipeline 38 comprises: switching valve 38a, pump 38b, strainer 38c and vacuum breaker 38d.After with strainer 38c, contained foreign matter filters in to hot water 22, this hot water 22 is back to hot-water storage case 39.
As shown in Figure 2, at the relief outlet 8a that separates out device 8, dispose the 1st 40, at the relief outlet 8a of overflow recoverer 37, dispose the 2nd 41, and dispose the 3rd 42 in the outlet of discharge portion 9.When closing for the 1st 40, make to separate out device 8 interior airtight.When closing for the 2nd 41, make overflow recoverer 37 interior airtight.When closing for the 3rd 42, make discharge portion 9 interior airtight.These door 40～door 42 individually starts.Be generally open state for the 1st 40 and the 2nd 41.And, when in the interior delay of discharge portion 9, have fixed amount separate out CA 30 time, the 1st the 40～3rd 42 corresponding to separating out the disconnection action of CA 30 and linking.Thus, can in the situation that maintain the air-tight state of separating out in device 8, will separate out CA 30 and send to ensuing vibrating dryer 10.
First, when in the interior delay of discharge portion 9, have fixed amount separate out CA 30 time, by extrusion roll 33, extrusion roll 34 are individually rotated to control, and disconnect, separate out CA 30.1st 40 close thereafter.In addition, after separating out CA 30 disconnections, on the opportunity (timing) of exposing from overflow recoverer 37 in the rear end of separating out CA 30 disconnecting, close for the 2nd 41.After the 2nd 41 is closed, open for the 1st 40.In addition, after the 2nd 41 is closed, open for the 3rd 42.Thus, delay separates out CA 30 landings to the vibrating dryer 10 of next step.When separating out CA 30 from discharge portion 9 discharge, close for the 3rd 42., 2nd 41 open, below according to identical processing sequence, discharge and separate out CA 30 thereafter.
In vibrating dryer 10, the CA 30 that separates out that one side is sent from discharge portion 9 from 44 pairs of vibrating mechanisms applies vibration, and one side blows out dry wind from pipeline (duct) 45, from separating out the dry moisture of CA 30.In addition, also can not carry out blowing out of dry wind, but only apply vibration, make moisture from separating out CA 30 separation.During this situation, drying installation is set separately in downstream side, by taking care of the set time etc. such as warm air drying or in dry storehouse, from separating out CA 30, removes moisture and be dried.
Vibrating dryer 10 has discharge portion 46 in the outlet of separating out CA 30.Discharge portion 46 comprises: the 1st 47 and the 2nd 48, one side remains air-tight state by vibrating dryer 10, and one side is discharged and separated out CA 30 from vibrating dryer 10.Close for common the 2nd 48, when reaching output, the 2nd 48 opening after the 1st 47 is closed.Thus, gather separate out CA 30 cast to be arranged on below for example can elastic container (flexible container) 49 in.Separating out after CA 30 casts, close for the 2nd 48, the 1st 47 opening, separates out CA 30 and is collected at discharge portion 46 thereafter.In addition, to can casting of elastic container 49 be separating out CA30Wei unit and carrying out of disconnecting, but also can, by disconnecting device is set separately, and will separate out at an arbitrary position CA 30, disconnect and cast.
The CA 30 that separates out obtaining is in this way: for each kind of raw material CA 17 or the place of production etc., carry out assortment, and preserved as separating out CA 30.This separates out CA 30 when manufacturing the different new variety film of optical characteristics, can suitably select its kind and uses.
In addition, also can be with to separate out device 8 identical, at the outlet side of vibrating dryer 10, be provided with extrusion roll 33, extrusion roll 34, by extrusion roll 33, extrusion roll 34 and from separating out CA extrusion moisture.
As shown in Figure 1, hot-water storage case 39 comprises: well heater 39a, chuck 39b and stirrer 39c.Well heater 39a is heated to be fixed temperature by the hot water in hot-water storage case 39 22.Heat agent and circulate in chuck 39b, and the water in hot-water storage case 39 is remained to fixed temperature.In addition,, if the hot water 22 in hot-water storage case 39 becomes below fixed amount, from pure water retention tank 60, by water-supply line 51, to hot water retention tank 39, supplement the hot water 22 of fixed amount.Water-supply line 51 comprises: switching valve 51a, pump 51b and pure water filtration unit 51c.Pure water filters the impurity in hot water 22 with filtration unit 51c.
The methylene dichloride 18 using in present embodiment is considered from carrying capacity of environment and to the worry of people's toxicity, according to pollutant emission and transfer registration (PRTR, Pollutant Release and Transfer Register) method, for utilizing and the discarded material coming under observation.Therefore, must avoid from industrial building to outdoor discharge.Thus, except making factory building for example for double-layer structural improves stopping property, also must do one's utmost to reduce the methylene dichloride gas of revealing from each machine.Therefore,, in present embodiment, methylene dichloride 18 is only circulated in the airtight recycle system.And, separate out device 8, discharge portion 9, vibrating dryer 10 and hot-water storage case 39 difference airtight.And, this airtight each machine 8～10,39 is connected to solvent recuperation pipelines 55, in the mode of again utilizing, prevent that methylene dichloride gas from revealing to outside in the recycle system.
At the methylene dichloride 18 of separating out device 8, discharge portion 9, vibrating dryer 10 and the 39 inner evaporations of hot-water storage case, via solvent recuperation pipeline 55, be delivered to condenser (condenser) 56.Solvent recuperation pipeline 55 comprises: switching valve 55a and pump 55b.The methylene dichloride 18 of carrying from solvent recuperation pipeline 55 as explained below as, again recycle after separated with water.
In addition, though the diagram of omission, the configuration space of factory building or each machine is separated into airtight space.And, for the unit of separating respectively, reclaim methylene dichloride gas, and adsorb recovery by adsorption tower etc.Therefore,, even if during the situation of revealing from each machine 8～10,39 at methylene dichloride gas, this methylene dichloride gas finally also can be hunted down, and can not be released into the outside of factory building.
In condenser 56, make to carry and gas that the steam that comes and methylene dichloride 18 mix for example carries out heat exchange with cold water and condenses and liquefy from each machine 8～10,39.The liquid of cohesion is transported to separator tank 57.Separator tank 57 utilizes proportion and is methylene dichloride 18 and hot water 22 by liquid separation.And methylene dichloride 18 is positioned at lower floor, hot water 22 is positioned at upper strata.Therefore, separator tank 57 comprises: chuck 57a and switching valve 57b.For example water circulates in chuck 57a as temperature control medium, and methylene dichloride 18 and hot water 22 are remained on to proper temperature.
Respectively, hot water 22 separated in separator tank 57 is transferred and is stored in pure water retention tank 60, and methylene dichloride 18 is transferred and is stored in solvent storage case 14.
Being supplied to the hot water 22 of separating out device 8 is to be stored in hot-water storage case 39.Hot-water storage case 39 has chuck 39b, and the circulation by temperature control medium remains on fixed temperature.From the water of hot-water storage case 39, by hot water supply pipeline 28, be transported to the 2nd nozzle 26 of separating out in device 8, and scatter to the water surface by the 2nd nozzle 26.And, by thermoswitch 28e, regulate the temperature of hot water 22.In addition, by the rotation number of control pump 28b, regulate the flow of hot water 22, make the water surface of separating out in device 8 remain on fixed position.
By extrusion roll 34, from separating out the hot water 22 of CA 30 separation, by overflow recoverer 37 and water recycling pipeline 38, be back to hot-water storage case 39.In addition, for supplementing the hot water 22 reducing because of evaporation, and via water-supply line 51, supplement the water of fixed amount from pure water retention tank 60.
Secondly, to using, there are solution film-forming equipment 68 and the solution film-forming method of separating out CA 30 that with described polymer purification equipment 5, obtain to describe.When manufacturing the film of a small amount of many kinds, in the mixing equipment with large-scale dissolving step in the past, when switching to new variety, must flow from dissolving case to the new variety curtain coating stoste of 3 times of the stream capacity till casting mold, spread all over whole stream old stoste is replaced into new stoste.And the stoste in displacement is that new and old stoste mixes, and cannot use as goods.In the present invention, for shortening, utilize new stoste to replace the required time of old stoste, and the stoste stream capacity that the stoste stream capacity that makes mixing device 69 is mixing device in the past 1/30.
The reason that can reduce the stoste stream capacity of mixing device 69 is as described below.Separating out CA 30 is: to raw material CA 17 being dissolved in the solvent of methylene dichloride 18 and thin stoste 21 be dried and must, be easily dissolved in solvent.In addition, when making to separate out CA 30 purifying, the thin stoste 21 that becomes the state of removing foreign matter from filtering with thin concentration will be separated out CA 30 and separate out, therefore make to separate out CA 30 dissolves and stoste in foreign matter considerably less.By these reasons, do not need the various devices such as the portion of necessary stream mixing capacious in the past, dissolving portion, concentrated portion and reservoir.Therefore, the loss of curtain coating stoste 85 or replace required time loss etc., correspondingly reduce the degree that has stream capacity to reduce, thus the manufacture that can carry out efficiently new variety is switched.Below, with reference to Fig. 3, solution film-forming equipment 68 is described.
[solution film-forming equipment]
As shown in Figure 3, solution film-forming equipment 68 comprises: mixing device 69, casting device 73, pin tenter (pin tenter) 74, kiln 75 (film dryer part) and take-up mechanism 76.
As shown in Figure 4, mixing device 69 at least comprises: the 1st of two system dissolves unit 70A (the 1st polymers soln manufacturing installation, dissolver), the 2nd and dissolves unit 70B (the 2nd polymers soln manufacturing installation, dissolver), and the adding device of line upper type (adding set) 71.
The 1st dissolves unit 70A comprises: dissolve case 80, pump 81 and switching valve 87a, switching valve 87b.Dissolving case 80 is the formation identical with dissolving case 6.From the 1st of the 1st raw material CA 17a acquisition, separate out CA 30a and dissolve the 1st solvent 79 of separating out CA 30a and be fed into this dissolving case 80.After input, by stirrer 80a, stir, the 1st separate out CA 30a and be dissolved in (the 1st step) in solvent 79 thus.The 2nd dissolves unit 70B also forms in the same manner with the 1st dissolving unit 70A, and same parts is enclosed to same-sign.From the 2nd of the 2nd raw material CA 17b acquisition different from described the 1st raw material CA 17a, separate out CA 30b and be fed into the 2nd dissolving unit 70B (the 2nd step) together with solvent 79.By being used alternatingly these the 1st dissolving unit 70A and the 2nd, dissolve unit 70B, and can distinguish individually, make: use the 1st to separate out the curtain coating stoste 85 of current kind (polymers soln that the 1st kind is used) of CA 30a and use the 2nd to separate out the curtain coating stoste 85 of next kind (polymers soln that the 2nd kind is used) of CA 30b.
The 1st switching valve 87a becomes open mode when carrying stoste, and the 2nd switching valve 87b becomes closing condition.In addition, when using another to dissolve unit 70B, each switching valve 87a, switching valve 87b become on off state contrary when carrying stoste, and become the 1st switching valve 87a, close, the 2nd switching valve 87b opens, and does not carry curtain coating stoste 85 but curtain coating stoste 85 is circulated.After circulation, the curtain coating stoste 85 in this dissolving case 80 is delivered in not shown retention tank, to seek recycling.In addition,, after manufacturing the film of new variety, while using the situation of original curtain coating stoste 85, directly make curtain coating stoste 85 circulate.
Though the diagram of omission, Cleaning Line or stoste exhausting line are connected in and respectively dissolve unit 70A, dissolving unit 70B.Stoste exhausting line is carried remaining curtain coating stoste 85 be recovered in other retention tank etc.Cleaning Line becomes under idle state carrying remaining curtain coating stoste 85, for example, drop into solvent, to dissolving in case 80, cleans for next new stoste.
By what use foreign and be easily dissolved in solvent, separate out CA 30, and can be by the dissolving operation in dissolving case 80, there is for example curtain coating stoste 85 of the concentration about 20 quality % dissolving the interior manufacture of case 80.Therefore the running cost (running cost) that, need not use complex appts through the necessary heating of preparation stoste in the past, pressurization, concentrated etc. is high various steps also.And, only remove at the foreign matter of sneaking into while processing (handling) etc. separating out CA 30a, without the high-precision filtration under the former liquid status of high density, strainer described later is also on a small scale and small-sized (compact).
In addition, need not adopt complicated apparatus to form, only by dissolving case 80, form mixing device 69, therefore, can make comparing with situation in the past to the stream capacity till casting mold 78 of curtain coating stoste 85, be reduced to 1/30 left and right.Therefore, when switching kind, the amount in the curtain coating stoste 85 that makes new variety with 3 times of left and right of its stream capacity flows, and while switching to the situation of stoste of new variety, can make the flow of displacement compare and be reduced to 1/30 left and right with situation in the past.In addition,, because the stock solution flow of displacement is few, therefore, also can shorten the required time of switching of new variety, thereby can switch to efficiently the stoste of new variety.
The curtain coating stoste 85 of dissolving in dissolving case 80 is delivered to adding device 71 by pump 81.Adding device 71 comprises: add nozzle 86 (addition portion on line), static mixer (static mixer) 82, dynamic mixer (dynamic mixer) 83, strainer 84 and additive liquid liquor charging portion 88.
Utilize the interpolation step of adding device 71 for example for as described below.Additive liquid liquor charging portion 88 is connected in and adds nozzle 86.Additive liquid liquor charging portion 88 comprises: additive liquid retention tank 89a, the 89b of two system, 3-way valve 90, pump 91 and switching valve 92a～switching valve 92c.Additive liquid, for example additive liquid 93a of any one in 3-way valve 90 selection additive liquid retention tank 89a, additive liquid retention tank 89b.Pump 91 is delivered to the additive liquid 93a of selection to add nozzle 86.Switching valve 92a～switching valve 92c is switch when switching additive liquid 93a, additive liquid 93b, thereby arbitrary additive liquid 93a, additive liquid 93b are optionally transported to interpolation nozzle 86.Each additive liquid retention tank 89a, additive liquid retention tank 89b, except storing, also have dissolving function.And, this additive liquid retention tank 89a, additive liquid retention tank 89b are when being put into the required various additives of curtain coating stoste 85 or solvent, make agitating vane 89c rotation, and make additive liquid 93a, the additive liquid 93b that neccessary composition forms with suitable proportion allotment.The various additives that this additive liquid is used and allotment amount thereof are to predetermine for each kind of the film of manufacturing, to the amount that drops into necessary additive and additive in additive liquid retention tank 89a.
As shown in Figure 5, static mixer 82 is a plurality of and form with array configuration by being configured in the 1st element (element) 82b, the 2nd element 82c in the stream 82a of curtain coating stoste 85.The 1st element 82b has with the 2nd element 82c: the angle that change mixes or the element not of the same race of direction.In addition, the kind of element of the same race or configuration number in upright arrangement can suitably not change.By by these each elements 82b, element 82c, and to mixed additive liquid 93a in curtain coating stoste 85.
As shown in Figure 6, dynamic mixer 83 by stator (stator) 83b and rotor (rotator) 83c, mixes being mixed with the curtain coating stoste 85 of additive liquid 93a in pipe arrangement 83a.Rotor 83c is fixed on drive shaft 83d.This rotor 83c by the rotation of drive shaft 83d with respect to stator 83b relativity rotate.Drive shaft 83d is linked to and omits illustrated electric motor.Thus, additive liquid 93a and then be blended in more equably in curtain coating stoste 85.
At the both ends of pipe arrangement 83a, dispose sealing element 83e and labyrinth ring (labyrinth) parts 83f.The outstanding spiral ridge 83g that is formed with of side face at labyrinth ring parts 83f.Labyrinth ring parts 83f is fixed on drive shaft 83d, and 83d rotates integratedly with drive shaft.The spiral of the spiral ridge 83g of left and right labyrinth ring parts 83f towards contrary in left and right.When drive shaft 83d rotates, by each spiral ridge 83g, the curtain coating stoste 85 of invading from sealing element 83e is back in pipe arrangement 83a.Thus, prevent from revealing curtain coating stoste 85 from the gap between drive shaft 83d and sealing element 83e.
As shown in Figure 4, the curtain coating stoste 85 by dynamic mixer 83 is to filter by strainer 84.Separating out CA 30 is when separating out, to remove foreign matter, so the filtration of strainer 84 load is few, thereby filter life is elongated.Thereafter, curtain coating stoste 85 is delivered to casting mold 78, as shown in Figure 3, and curtain coating on curtain coating rotating cylinder (drum) 95 of rotation.
Casting device 73 comprises: casting mold 78, curtain coating rotating cylinder 95 and angle stripper 96, these component configuration are in the 73a of curtain coating chamber.Curtain coating rotating cylinder 95 rotates centered by axle by omitting illustrated drive unit.Curtain coating rotating cylinder is an example of curtain coating supporter.Curtain coating rotating cylinder 95 passes through not shown register, and is set as casting films 97 to carry out cooling temperature.
Utilize the curtain coating step of casting device 73 for example for as described below.Casting mold 78 is to the periphery of the curtain coating rotating cylinder 95 of the rotation curtain coating stoste 85 that flows continuously.On curtain coating rotating cylinder 95, by curtain coating stoste 85, be formed with banded casting films 97.Casting films on curtain coating rotating cylinder 95 97 is by cooling, thereby and self-supporting become can conveyance state.Thereafter, casting films 97 is stripped from curtain coating rotating cylinder 95 by angle stripper 96, and becomes banded moistening film 98.
Between curtain coating chamber 73a and pin tenter 74, dispose cross-over connection portion 99.Cross-over connection portion 99 has carrying roller 99a, and moistening film 98 is delivered to pin tenter 74.Pin tenter 74 has a plurality of needle plates (pin plate).Needle plate connects and keeps the edge, both sides of moistening film 98.Needle plate carrys out the moistening film 98 of conveyance by chain loopy moving.In this conveyance, moistening film 98 is carried to dry wind (drying step).Thus, moistening film 98 is dry and become banded film 100.
In the downstream of pin tenter 74, be provided with side shears (side slitter) 101.Side shears 101 is by edge, the both sides severing of film 100.The edge, both sides of this severing is delivered to crusher (crusher) and pulverizes by blowing.The edge, both sides of pulverizing is dissolved in solvent and forms, and for replacing raw material CA 17 or separating out CA 30, and seeks recycling.
In kiln 75, dispose a plurality of roller 75a, film 100 is wound on and on these rollers, carries out conveyance.The temperature of the environment in kiln 75 or humidity etc. regulate by not shown air conditioning machinery, by making film 100 by promoting dry (drying step) of film 100 in kiln 75.
Between kiln 75 and take-up mechanism 76, be provided with to film 100 is carried out cooling cooling room 102, film 100 is removed electric pressure neutralizer (except electric pole) and gives roller etc. to the annular knurl that annular knurl (knurling) is given in the edge, both sides of film 100.Take-up mechanism 76 has pressure roller (press roller), and film 100 is batched at volume core.
Secondly, the effect of present embodiment is described.As shown in Figure 1, when CA 30 is separated out in manufacture, to dissolving in case 6, put into raw material CA17 and methylene dichloride 18 and stir by stirrer 6a, and production example as polymer solution concentration be the thin stoste 21 (dissolving step) of 7 quality %.This thin stoste 21 is by strainer 12 (filtration step), and with pressure regulator valve 7b, pressure is adjusted to fixingly, and is delivered to the 1st nozzle 25 of separating out device 8.In present embodiment, the concentration that makes thin stoste 21 is 7 quality %, therefore filters load few, can carry out high-performance filtration.
As shown in Figure 2, from the 1st nozzle 25, to the water surface of separating out in device 8, spray thin stoste 21, thereby this thin stoste 21 spreads on the water surface.The Temperature Setting of hot water 22 is the temperature higher than the boiling point of methylene dichloride 18.Therefore, methylene dichloride in the thin stoste 21 contacting with the water surface 18 is flash evapn by the heat from hot water 22, thus obtain wire separate out CA 30 (polymkeric substance is separated out step).This separates out CA 30 also can make by the Water-heating shower from the 2nd nozzle 26 (shower) methylene dichloride 18 evaporations efficiently.In addition, by agitating vane 27 and from the 2nd nozzle 26, spray hot water 22, and will separate out CA 30, be delivered to relief outlet 8a.
The 1st extrusion roll 33 and the clamping of the 2nd extrusion roll 34 carry and come separate out CA 30, and will separate out CA 30 and carry to discharge portion 9.Now, by extrusion roll 33, extrusion roll 34, clamp and separate out CA 30, separate out hot water contained in CA 30 22 and be stressed out.The hot water 22 of extruding out with the 1st extrusion roll 33 is back to separates out in device 8.In addition, the hot water 22 of extruding out with the 2nd extrusion roll 34, via the overflow recoverer 37, the water recycling pipeline 38 that are formed near relief outlet 8a, and is back to hot-water storage case 39.
The 1st extrusion roll 33 and the 2nd extrusion roll 34 are individually subject to rotation and control.And, for example, under the state stopping in the rotation that makes the 1st extrusion roll 33, by making the 2nd extrusion roll 34 rotations, and make to separate out CA 30 stretchings by the cramping conveyance of the 2nd extrusion roll 34, and disconnect in the cramping position of the 1st extrusion roll 33.The rear end of separating out CA 30 disconnecting, the rotation by the 2nd extrusion roll 34 falls in discharge portion 9.By carrying continuously in this way the CA 30 that separates out to disconnect, and can simultaneously will separate out device 8, remain air-tight state and suppress methylene dichloride 18 to outside leakage, one side will be separated out CA 30 and be delivered to discharge portion 9 from separating out device 8.
By discharge portion 9 the 3rd 42 of CA30 that separate out who cuts off opens, and casts to vibrating dryer 10.When sending from discharge portion 9 while separating out CA 30, after the 3rd 42 is closed, open for the 2nd 41.Thereafter, the 1st extrusion roll 33 rotations, send to discharge portion 9 and will separate out CA 30.Below, by repeating identical step, and the CA 30 that separates out that continuity can be discharged be broken as suitable length, and one side will separate out device 8 and remain air-tight state, and one side will be separated out CA 30 and be delivered to the vibrating dryer 10 of next step.
In vibrating dryer 10, to separating out CA 30, for example apply the vibration of above-below direction, and promote to separate out the dry of water in CA 30.In addition, from pipeline 45 heat air deliveries, making to separate out CA 30 is dried.
Obtain in the above described manner from raw material CA 17, remove foreign matter etc. separate out CA 30.This is separated out CA 30 and compares with raw material CA 17, is easily dissolved in methylene dichloride 18 and other all kinds of SOLVENTS.Can infer that its reason is, in the stage of raw material CA 17, once dissolve, thereby the indissoluble solution in raw material CA 17 partly disappears.This is separated out CA 30 and distinguishes keeping for each kind or the place of production of raw material CA 17.
When switching to the situation of new variety, first, that selects to be suitable for new variety separates out CA 30.In addition, the prescription based on new variety, comes specific solvent and allotment amount thereof etc.Secondly, as shown in Figure 4, separate out CA 30a, separate out CA 30b and solvent 79 and put into and dissolve case 80.Then, by stirrer 80a, these homogeneous are mixed, and make the curtain coating stoste 85 that new variety are used.In addition, the retention tank 89a by additive liquid liquor charging portion 88 is in harmonious proportion the additive liquid 93a that new variety are used, and this additive liquid 93a is delivered to and adds nozzle 86.Then, by adding nozzle 86, on curtain coating stoste 85 center lines, add additive liquid 93a.
Be added with the curtain coating stoste 85 of additive liquid 93a, by static mixer 82 and dynamic mixer 83, mix and after homogenization, be delivered to casting mold 78 (with reference to Fig. 3).So, in present embodiment, when switching kind, the curtain coating stoste 85 of preparation new variety, and when the old curtain coating stoste 85 of displacement, only in the curtain coating stoste stream of adding device 71, new and old stoste is replaced.And, the required stream capacity of displacement of curtain coating stoste 85, with as Patent Document 1 by raw material CA with dissolution with solvents and filter and carry out the concentrated and Production Example of photoflash lamp and compare as the situation of the curtain coating stoste of 20 quality %, become the stream capacity of 1/30 left and right, thereby the replacement amount of the new and old stoste in the time of can making to switch kind is compared and is reduced to 1/30 left and right with situation in the past.
In addition,, because the replacement amount of new and old stoste significantly reduces, therefore can shorten the required activity duration of displacement of new and old stoste, thereby can improve the running efficiency of equipment.So, when switching kind, can individually carry out the switching of separating out CA of curtain coating stoste 85 and the switching of additive liquid, thereby can carry out efficiently kind switching.
In present embodiment, use curtain coating rotating cylinder 95 as supporter, but the present invention is not limited thereto, also can uses casting belt (band).During this situation, making turning axle, be to set up casting belt on 1 pair of rotating cylinder of level, by making rotating cylinder rotation that casting belt is moved.
In present embodiment, by the casting films 97 on curtain coating rotating cylinder 95, carry out cooling cooling gel (gel) change mode, and make casting films 97 become the state that can strip, but the present invention is not limited thereto, also can carry out dry drying mode by the casting films on the supporters such as rotating cylinder or band, and make casting films become the state that can strip.
The film 100 obtaining by the present invention, especially can be used for phase retardation film or polarization board protective film.
More than the width of film 100 is preferably 600mm, more than being more preferred from 1400mm and below 2500mm.In addition, the width of film 100 also can be greater than 2500mm.More than the thickness of film 100 is preferably 15 μ m and below 120 μ m.
(polymkeric substance)
Can be used for polymkeric substance of the present invention as long as be thermoplastic resin; be not particularly limited; for example, enumerate acylated cellulose, contain lactonic ring polymkeric substance (lactone-ring containing polymer), cyclic olefin (cyclic olefin), polycarbonate (polycarbonate) etc.Wherein be preferably acylated cellulose, cyclic olefin, be wherein preferably and contain acetate groups (acetate group), the acylated cellulose of propionic acid ester group (propionate group) and the cyclic olefin obtaining by addition polymerization.
(acylated cellulose)
The acyl group using in acylated cellulose of the present invention (acyl group) is only a kind, or also can use two or more acyl groups.When using two or more acyl groups, one of them is preferably ethanoyl (acetyl group).With carboxylic acid (carboxylic acid), make the ratio of cellulosic hydroxy esterification, the substitution value of acyl group is preferably and meets the whole of following formula (I)～(III).In addition, in following formula (I)～(III), A and B represent the substitution value of acyl group, and A represents the substitution value of ethanoyl, and B is the substitution value of the acyl group of carbonatoms 3～22 in addition.In addition, the 90 quality % that are preferably cellulosetri-acetate (TAC, triacetyl cellulose) are the above and particle below 4mm of 0.1mm above.
(I) 2.0≤A+B≤3.0
(II) 1.0≤A≤3.0
(III) 0≤B≤2.9
Total substitution value A+B of acyl group is preferably more than 2.20 and below 2.90, and You Jia is more than 2.40 and below 2.88.In addition, the substitution value B of the acyl group of carbonatoms 3～22 is more preferred from more than 0.30, and You Jia is more than 0.5.
In addition, about the detailed content of acylated cellulose, be recorded in [0140] paragraph of No. 2005-104148, Japanese Patent Laid-Open to [0195] paragraph.These are recorded and are also applicable to the present invention.In addition, about solvent and plasticizer, deterioration preventing agent, UV light absorber (ultraviolet ray (ultraviolet, UV) agent), optical anisotropy's control agent, hysteresis (retardation) control agent, dyestuff, matting agent (mat agent), stripper, peel off the additives such as promotor, be recorded in detail similarly [0196] paragraph of No. 2005-104148, Japanese Patent Laid-Open to [0516] paragraph.In addition, as the Mierocrystalline cellulose of the raw material of acylated cellulose, also can be from any acquisition of velveteen (linter), paper pulp.
In described embodiment, with respect to raw material CA 17, use methylene dichloride 18 as solvent, by the hot water 22 being heated to more than the boiling point of methylene dichloride 18, make methylene dichloride 18 evaporations, therefore available simple equipment forms and reduces heat energy loss, and make efficiently solvability excellence separate out CA 30.In addition, by using single solvent, and make the recovery of solvent thereafter and recycling become simple.
By making to separate out CA 30, in discharge portion 9, disconnect and will separate out device 8 and remain air-tight state, do not make to leak to machine exterior as the solvent as methylene dichloride 18, and can be used.
In addition, in described embodiment, be made as and make to separate out the formation that CA 30 disconnects in discharge portion 9, and will separate out device 8 and remain air-tight state, but for example by adopting, by separating out the extrusion roll 33 of device 8 and separating out between the case end plate of device 8, remain airtight airtight construction, thereby need not utilize discharge portion 9 to disconnect.During this situation, be preferably in vibrating dryer 10, by cutting unit or roller, clamping disconnected.And then, also can use turning valve described later (rotary valve) 65 (with reference to Fig. 7), separate out the airtight of device 8 or discharge portion 9 and the disconnection of separating out CA 30.
In described embodiment, with respect to raw material CA 17, use methylene dichloride 18 as solvent, by the hot water 22 being heated to more than the boiling point of methylene dichloride 18, make methylene dichloride 18 evaporations, but be not limited to these materials, as long as solvent is good solvent, can use other single solvents or mixed solvent.In addition,, as long as for being heated to the liquid more than boiling point of solvent, be not limited to water, also can use other liquid.In addition, when using the situation of mixed solvent, to usining the mixed solvent that solvent recuperation pipeline 55 reclaims, carry out separation and reclaimed as each solvent, or being recycled as mixed solvent.
In addition, in described embodiment, by flowing of hot water 22, will separate out CA 30 and carry to relief outlet direction, but also can replace this or in addition, by roller or other conveying units, be delivered to relief outlet 8a.
In described the 1st embodiment, by separating out device 8, discharge portion 9, vibrating dryer 10 and discharge portion 46, obtain and separate out CA 30, but in addition, also can form obtain by the device of the 2nd embodiment shown in Fig. 7 and separate out CA 30.In the 2nd embodiment, comprise and separate out device 8, vibratory screening apparatus (vibrating screen) 61, extrusion roll 62, extrusion roll 63, guide plate 64, hot air dryer 66 and pulverizer 67.In addition, in the 2nd embodiment, to the component parts identical with the 1st embodiment, enclose same-sign and omit repeat specification.
Separate out device 8 and the 1st embodiment forms roughly the samely.What separate out that device 8 separates out, separate out CA 30 overflow together with hot water 22, certainly separate out device 8 and be expelled to vibratory screening apparatus 61.In vibratory screening apparatus 61, to sieve main body 61a reception, separate out CA 30.Hot water 22 flows to Recovery of the hot water groove (launder) 61b by sieve main body 61a.Then, by water recycling pipeline 38, be back to hot-water storage case 39 (with reference to Fig. 1).
Sieve main body 61a vibrates by vibrating mechanism 61c.Separate out after CA 30 shakes off moisture on this sieve main body 61a and be sent to extrusion roll 62.Extrusion roll 62, extrusion roll 63 are separated out CA30 and are squeezed moisture from above-below direction clamping.This moisture is back to hot-water storage case 39 (with reference to Fig. 1) through Recovery of the hot water groove 61b, water recycling pipeline 38.In addition, extrusion roll 62, extrusion roll 63 are provided with 2, but these also can be more than 1 or 3.
Separate out in device 8 is configured in identical closed cabinet 59 with vibratory screening apparatus 61.On these closed cabinets 59, be connected with solvent recuperation pipeline 55.The methylene dichloride 18 reclaiming via solvent recuperation pipeline 55 as shown in Figure 1, is back to solvent storage case 14 and is recycled through condenser 56, separator tank 57.In the same manner, on hot air dryer 66 described later and pulverizer 67, be also connected with solvent recuperation pipeline 55, methylene dichloride 18 recycles via solvent recuperation pipeline 55.
The CA 30 that separates out that leaves extrusion roll 63 is guided by guide plate 64, and is delivered to hot air dryer 66 by turning valve 65.Hot air dryer 66 utilizes hot blast that the CA 30 that separates out carrying by turning valve 65 is dried.Dry separate out that CA 30 is delivered to that pulverizer 67 is pulverized and the piece that forms fixed measure.The CA 30 that separates out after pulverizing loads in can elastic container 49.
In addition, in the 1st embodiment, use door 40～door 42, door 47, door 48 to guarantee to separate out the stopping property of device 8 or vibrating dryer 10, but also can replace this, with the turning valve 65 shown in Fig. 7, guarantee these stopping property.
Secondly, to separating out the preferred process form of CA 30, describe.From the CA 30 that separates out of vibrating dryer 10 or hot air dryer 66 discharges, be cotton-shaped, (bulk density) is low and light for loose density.In this cotton-shaped processing of separating out acylated cellulose throw out (cellulose acylate floc, CAF) 31, this cotton-shaped acylated cellulose throw out 31 of separating out is because gently easily dispersing.In addition,, while preparing stoste in membrane equipment, the volume of the cotton-shaped CAF of separating out 31 using enlarges markedly.Therefore, there is the size that makes the unfavorable condition of environmental degradation and the transporter of the cotton-shaped CAF of separating out 31 because dispersing or dissolve the various devices such as case 80 to become large unfavorable condition.For eliminating described problem, the granular acylated cellobiose crude granule (cellulose acylate particle, CAP) 32 of separating out that the cotton-shaped CAF of separating out 31 is formed to granule (pellet), fritter (tablet) etc. with tablets press is to improve loose density.Thus, can make to prepare the equipment size of stoste roughly the same with situation in the past, also can use existing installation.In addition, for separating out CA 30, according to its form, cotton-shaped person is called to the cotton-shaped CAF of separating out 31, granule or fritter even-granular person are called to the granular CAP of separating out 32, separately use both.In addition, the cotton-shaped CAF 31 that separates out is because loose density is low light, easily disperse and volume becomes large and is difficult to and processes, but easily carry out to the dissolving of solvent etc.Therefore, can be with the situation of cotton-shaped processing time, also can be used as the cotton-shaped CAF of separating out 31 and process.
Fig. 8 is the sketch chart of granulating equipment.When the situation with online (on line) granulation, from the vibrating dryer 10 of Fig. 1 or the hot air dryer 66 of Fig. 7 or pulverizer 67 any, the cotton-shaped CAF of separating out 31 is delivered to thick drying machine 110.Till thick drying machine 110 is slightly dried to by the cotton-shaped CAF of separating out 31 amount of moisture that is suitable for granulation (thick drying step).The cotton-shaped CAF 31 that separates out from thick drying machine 110, is delivered to wet type tablets press 112 by quantitative feeder (feeder) 111.Wet type tablets press 112 is separated out CAF 31 extrusion moldings by cotton-shaped, and forms the granular CAP of separating out 32 (wet type granulation step).
The granular CAP of separating out 32 is delivered to vibrating dryer 113 (final drying machine).Vibrating dryer 113 1 is faced the granular CAP of separating out 32 and is applied vibration, one side is by the hot blast that adds more than 0.1m/sec and below 1m/sec, and the granular CAP of separating out 32 is dried to amount of moisture becomes (final drying step) more than 0.1% and till below 3%.Vibrating dryer 113 is the formation substantially the same with the vibrating dryer 10 shown in Fig. 2.
Granulation also can be the either method of wet type granulation and dry type granulation, but is preferably the wet type prilling process of continous way and granulation efficiently.
For carrying out wet type granulation, must make target amount of moisture is more than 20% and 150% following (dry basis) degree.Below, about amount of moisture, omit the record of dry basis, but with dry basis, represent when being called the situation of amount of moisture.The quality of separating out CA 30 as determinand is being made as to MB, and when making to separate out CA 30 roughly the quality after complete drying is made as the situation of MA, the value of this amount of moisture is for { the percentage that try to achieve (MB-MA)/MA} * 100.At vibrating dryer 10 or hot air dryer 66 or pulverizer 67 is discharged and the amount of moisture of the cotton-shaped CAF of separating out 31 of dehydration is 200% left and right, by thick drying machine 110, making amount of moisture is more than 20% and 150% following degree.Certainly, can make the cotton-shaped CAF of separating out 31 be dried to more than 20% and during the situation of the amount of moisture of 150% following degree, can omit thick drying machine 110 with vibrating dryer 10 or hot air dryer 66.
With regard to cotton-shaped, separate out with regard to CAF 31 thick dry, as long as for can carry out dry method, can use either method.You Jia is the thick drying machine 110 of the indirect heating modes such as the few paddle dryer that disperses (paddle dryer), rotary kiln (rotary kiln) of low, the cotton-shaped CAF of separating out 31 of wind speed.Equally also can use the thick drying machine of the direct heating mode that adopts the vibrating dryer that wind speed is low.But when being the situation of vibrating dryer, improving drying efficiency and if improve wind speed, have dispersing of the cotton-shaped CAF of separating out 31 to become many, thereby catching apparatus becomes large shortcoming.
The cotton-shaped CAF of separating out 31 is slightly being dried and is making amount of moisture become the time point more than 20% and below 150%, using wet type tablets press (for example logical (DALTON) company in island F-5 type processed wet type tablets press) 112 to carry out granulation.This wet type tablets press 112 makes roller in the upper rotation of dish-shape die (disc die), and the cotton-shaped CAF of separating out 31 is held between dish-shape die and roller, from the hole of dish-shape die, with 15MPa to 20MPa pressurization, pushes.At the back side of dish-shape die, be provided with cutter formula cutting unit (knife cutter), the molding of extruding is cut to suitable length, and granulation is the granular CAP 32 that separates out.
The loose density of the cotton-shaped CAF of separating out 31 is the degree more than 0.03 and below 0.05, and with respect to this, the loose density of the granular CAP of separating out 32 is more than 0.1, more than loose density is compared with the cotton-shaped CAF of separating out 31 and improved one digit number.Therefore, easily process, stoste Preparation equipment etc. also can be used existing installation.
The amount of moisture of the granular CAP of separating out 32 is more than 20% and below 150%, for preserving, and is preferably so that the mode that amount of moisture becomes more than 0.1% and below 3% is finally dried.In this is finally dry, the granular loose density of separating out CAP 32 is high, therefore, when being subject to intense impact, has destroyed worry.Thus, be preferably, the drying means by low impact is dried, in order to avoid destroy the granular CAP of separating out 32.
As the drying means of low impact, as vibrating dryer 113, with the direct-fired method of hot blast, can not destroy granulation product, thereby better.On the other hand, in the indirect heating mode that the outer wall of paddle dryer or rotary kiln etc. is heated, there is the destroyed situation of the granular CAP of separating out 32, therefore not good enough as final drying means.
By be the degree more than 0.03 and below 0.05 from loose density in the above described manner the cotton-shaped CAF of separating out 31, forming loose densitys is that more than 0.1 the granular CAP of separating out 32 to 0.5 degree improves loose density, thereby can improve treatment characteristic, can easily prepare stoste.And, by improving loose density, can use existing stoste dissolution equipment, the viewpoint of slave unit efficiency is better.In addition, by vibrating dryer 113, being finally dried, is that drying granular more than 0.1% and below 3% is separated out CAP 32a and form amount of moisture, can become thus and be suitable for the amount of moisture preserved.
[embodiment 1]
Following table 1 represents the result that the raw material CA (comparative example 1) that separates out CA (embodiment 1) and used in the past by the inventive method purifying is compared.In embodiment 1; solubility limit (solid concentration) when investigation is dissolved in the mixed solvent of methylene dichloride and methyl alcohol (methanol) by acylated cellulose; in comparative example 1, approximately 17% is the limit, becomes approximately 24% in embodiment 1, thereby judge solubility limit, improves.In addition, as necessary processing procedure, essential heating enrichment step in comparative example 1, and do not need this step at embodiment 1, with the dissolving that only utilizes dissolving case to carry out, just can reach.In curtain coating step thereafter, embodiment 1 and comparative example 1 are all to carry out curtain coating under the state of approximately 20% solid concentration.
[table 1]
Figure BDA00003490075700271
[embodiment 2]
With the equipment shown in Fig. 3 to the curtain coating stoste of described embodiment 1, carry out curtain coating and obtain film with the curtain coating stoste (solid concentration is approximately 20%) of comparative example 1.About the curtain coating stoste masking with embodiment 1 and (embodiment 2), with 1 curtain coating stoste as a comparative example and not filtrate masking and (comparative example 2), with 1 curtain coating stoste and filtrate masking as a comparative example and (comparative example 3), for every kind of size of foreign matter, and 1 square millimeter of (mm) (mm of the film that separately inquiry agency obtains 2) in the number of foreign matter number.
In investigation, do not reach the small size foreign matter of 10 μ m, more than 10 μ m and while not reaching number separately on per unit area of the middle size foreign matter of 30 μ m and large size foreign matters more than 30 μ m, in the not filtration stoste of comparative example 2, foreign matter contained in raw material CA directly appears in goods, small size foreign matter is 5 front and back, middle size foreign matter is 30 front and back, and large size foreign matter is 10 front and back.When take the situation that the result of this comparative example 2 is benchmark (100%), in embodiment 2, under arbitrary size, the number of the foreign matter number of per unit area is compared and is approximately below 3% with comparative example 2.In addition,, in the complete stoste of filtration of comparative example 3, each size foreign matter is approximately 10% level.According to above result, can judge as embodiment 2, from the film that the curtain coating stoste that was once dissolved in solvent and carried out filtering obtains, there is hardly foreign matter.
Auxiliary agent median size when table 2 represents that investigation is implemented auxiliary agent and filtered, with the result of relation of filtering the absolute filtration diameter of gained according to this particle diameter.If auxiliary agent median size is diminished to become the mode of 60 μ m, 20 μ m, 10 μ m, corresponding to this, absolute filtration diameter also diminishes to become the mode of 15 μ m, 10 μ m, 5 μ m, thereby can judge also, can remove less foreign matter.
[table 2]
Figure BDA00003490075700281
Table 3 represent the investigation polymkeric substance separation method (embodiment 3) that utilizes hot water contact of the present invention, with the result of utilizing the polymkeric substance separation method (comparative example 4) of warm air drying.Thermal conductivity in comparative example 4 (W/mK) is 0.03, and with respect to this, thermal conductivity in embodiment 3 (W/mK) is 0.66, with regard to take with regard to the efficiency that warm air drying is benchmark, with respect to warm air drying, becomes the high-level efficiency of 22 times.In addition, while being made as the situation of 300 μ m thickness in comparative example 4, contact area (square metre (m 2)/kilogram (kg, kilogram) stoste) be 2.26, while being made as the situation of diameter 300 μ m in embodiment 3, contact area (square metre (m 2)/kilogram stoste) be 15.4, for take for the efficiency that warm air drying is benchmark, with respect to warm air drying, become the efficiency of 6.8 times.Therefore, if in addition comprehensive to these, can judge becomes 22 * 6.8 times, with respect to warm air drying, makes efficiency improve approximately 150 times, thus hot water contact compare with warm air drying before this, rate of drying is significantly improved.
[table 3]

Claims (31)

1. a polymer purification method, is characterized in that comprising:
Dissolving step, makes polymer dissolution in solvent and obtains polymers soln;
Filtration step, filters described polymers soln; And
Polymkeric substance is separated out step, and making described polymers soln through described filtration step be dispersed in described polymkeric substance and described solvent is liquid more than non-intermiscibility and the boiling point that is heated to described solvent, makes described solvent evaporation and separates out described polymkeric substance.
2. polymer purification method according to claim 1, is characterized in that:
The polymer solution concentration of described dissolving step is more than 2 quality % and below 19 quality %.
3. polymer purification method according to claim 1 and 2, is characterized in that:
The filtering precision of described filtration step is more than 2 μ m and below 30 μ m.
4. polymer purification method according to claim 1 and 2, is characterized in that:
Described solvent is single solvent.
5. polymer purification method according to claim 3, is characterized in that:
Described solvent is single solvent.
6. polymer purification method according to claim 4, is characterized in that:
Described polymkeric substance is acylated cellulose, and described solvent is methylene dichloride, and described liquid is water.
7. polymer purification method according to claim 5, is characterized in that:
Described polymkeric substance is acylated cellulose, and described solvent is methylene dichloride, and described liquid is water.
8. polymer purification method according to claim 6, is characterized in that:
At described polymkeric substance, separate out in step, more than the temperature of acylated cellobiose cellulose solution is 20 ℃ and below 120 ℃, more than the temperature of described water is 40 ℃ and below 100 ℃.
9. polymer purification method according to claim 7, is characterized in that:
At described polymkeric substance, separate out in step, more than the temperature of acylated cellobiose cellulose solution is 20 ℃ and below 120 ℃, more than the temperature of described water is 40 ℃ and below 100 ℃.
10. according to the polymer purification method described in any one in claim 1 to 2, it is characterized in that comprising:
Thick drying step, after described polymkeric substance is separated out step, is slightly dried the polymkeric substance of separating out;
Wet type granulation step, carries out granulation by wet type to the polymkeric substance of separating out through described thick drying step; And
Final drying step, is finally dried the polymkeric substance of separating out through described wet type granulation step.
11. polymer purification methods according to claim 3, is characterized in that comprising:
Thick drying step, after described polymkeric substance is separated out step, is slightly dried the polymkeric substance of separating out;
Wet type granulation step, carries out granulation by wet type to the polymkeric substance of separating out through described thick drying step; And
Final drying step, is finally dried the polymkeric substance of separating out through described wet type granulation step.
12. polymer purification methods according to claim 4, is characterized in that comprising:
Thick drying step, after described polymkeric substance is separated out step, is slightly dried the polymkeric substance of separating out;
Wet type granulation step, carries out granulation by wet type to the polymkeric substance of separating out through described thick drying step; And
Final drying step, is finally dried the polymkeric substance of separating out through described wet type granulation step.
13. polymer purification methods according to claim 5, is characterized in that comprising:
Thick drying step, after described polymkeric substance is separated out step, is slightly dried the polymkeric substance of separating out;
Wet type granulation step, carries out granulation by wet type to the polymkeric substance of separating out through described thick drying step; And
Final drying step, is finally dried the polymkeric substance of separating out through described wet type granulation step.
14. polymer purification methods according to claim 6, is characterized in that comprising:
Thick drying step, after described polymkeric substance is separated out step, is slightly dried the polymkeric substance of separating out;
Wet type granulation step, carries out granulation by wet type to the polymkeric substance of separating out through described thick drying step; And
Final drying step, is finally dried the polymkeric substance of separating out through described wet type granulation step.
15. polymer purification methods according to claim 7, is characterized in that comprising:
Thick drying step, after described polymkeric substance is separated out step, is slightly dried the polymkeric substance of separating out;
Wet type granulation step, carries out granulation by wet type to the polymkeric substance of separating out through described thick drying step; And
Final drying step, is finally dried the polymkeric substance of separating out through described wet type granulation step.
16. polymer purification methods according to claim 8, is characterized in that comprising:
Thick drying step, after described polymkeric substance is separated out step, is slightly dried the polymkeric substance of separating out;
Wet type granulation step, carries out granulation by wet type to the polymkeric substance of separating out through described thick drying step; And
Final drying step, is finally dried the polymkeric substance of separating out through described wet type granulation step.
17. polymer purification methods according to claim 10, is characterized in that:
In described thick drying step, the amount of moisture that makes to separate out polymkeric substance is more than 20% and below 150%,
In described final drying step, the amount of moisture that makes to separate out polymkeric substance is more than 0.1% and below 3%.
The 18. 1 kinds cotton-shaped polymkeric substance of separating out, is characterized in that:
By the polymer purification method described in any one in claim 1 to 9, obtain.
19. 1 kinds of granular polymkeric substance of separating out, is characterized in that:
By the polymer purification method described in any one in claim 10 to 17, obtain.
20. 1 kinds of solution film-forming methods, is characterized in that comprising:
The 1st step, is used and to have the 1st polymers soln manufacturing installation that dissolves case and pump, and what make to obtain by the polymer purification method described in any one in claim 1 to 17 separates out polymer dissolution in solvent, and makes the polymers soln that the 1st kind is used;
The 2nd step, use has the 2nd polymers soln manufacturing installation that dissolves case and pump, what make to obtain by the polymer purification method described in any one in claim 1 to 17 separates out polymer dissolution in solvent, and make, forms the polymers soln that the 2nd different kind of polymers soln used from described the 1st kind is used;
Add step, the polymers soln to an acquisition from described the 1st step and described the 2nd step, adds the additive liquid that is mixed with additive on line;
Curtain coating step, using the polymers soln that is added with described additive liquid as curtain coating stoste, forms casting films and flow to curtain coating supporter from casting mold; And
Drying step, peels off described casting films be dried from described curtain coating supporter; And
From any one the polymers soln from described the 1st step and described the 2nd step, switch to any another the polymers soln in described the 1st step and described the 2nd step, and continuity ground carries out kind switching.
21. solution film-forming methods according to claim 20, is characterized in that:
Described interpolation step is to use a plurality of additive liquid retention tanks, makes the additive liquid that additive liquid that described the 1st kind uses and described the 2nd kind are used,
The additive liquid that the additive liquid that described the 1st kind is used and described the 2nd kind are used switches and carries, and carries out adding on line.
22. 1 kinds of polymer purification equipment, is characterized in that comprising:
Dissolve case, make polymer dissolution in solvent and obtain polymers soln;
Strainer, filters described polymers soln;
Polymkeric substance is separated out device, and taking in described polymers soln is liquid more than non-intermiscibility and the boiling point that is heated to described solvent, the polymers soln to described liquid dissemination from described dissolving case; And
Retrieving arrangement, separates out at described polymkeric substance the polymkeric substance that device is separated out from described liquids recovery.
23. polymer purification equipment according to claim 22, is characterized in that:
It is more than 2 quality % and below 19 quality % that described dissolving case makes described polymer solution concentration.
24. according to the polymer purification equipment described in claim 22 or 23, it is characterized in that:
The filtering precision of described strainer is more than 2 μ m and below 30 μ m.
25. according to the polymer purification equipment described in claim 22 or 23, it is characterized in that:
Described solvent is single solvent.
26. polymer purification equipment according to claim 25, is characterized in that:
Described polymkeric substance is acylated cellulose, and described solvent is methylene dichloride, and described liquid is water.
27. polymer purification equipment according to claim 26, is characterized in that:
The temperature of separating out the acylated cellobiose cellulose solution that device scatters by described polymkeric substance be 20 ℃ above and below 120 ℃, the temperature of described water be 40 ℃ above and below 100 ℃.
28. according to the polymer purification equipment described in claim 22 or 23, it is characterized in that comprising:
Thick drying machine, is slightly dried the polymkeric substance of separating out reclaiming with described retrieving arrangement;
Wet type tablets press, carries out granulation by wet type to the polymkeric substance of separating out through described thick drying machine; And
Final drying machine, is finally dried the polymkeric substance of separating out through described wet type tablets press.
29. polymer purification equipment according to claim 28, is characterized in that:
The amount of moisture that described thick drying machine makes to separate out polymkeric substance is more than 20% and below 150%,
The amount of moisture that described final drying machine makes to separate out polymkeric substance is more than 0.1% and below 3%.
30. 1 kinds of solution film-forming equipment, is characterized in that comprising:
According to the polymer purification equipment described in any one in claim 22 to 29;
A plurality of dissolvers, have separating out the dissolving case of polymer dissolution in solvent and transporting the pump from the polymers soln of described dissolving case of making to obtain from described polymer purification equipment;
Adding set, have store additive liquid a plurality of additive liquid retention tanks, from described a plurality of additive liquid retention tanks optionally feeding additive liquid liquor charging portion and the additive from described liquor charging portion is mixed in from addition portion on the line the polymers soln of described dissolver;
Casting device, using the polymers soln that is added with described additive liquid as curtain coating stoste, is cast to mobile curtain coating supporter, and forms casting films on described curtain coating supporter; And
Film dryer part, is dried the described casting films of peeling off from described casting device.
31. solution film-forming equipment according to claim 30, is characterized in that:
Described adding set is used a plurality of additive liquid retention tanks, makes the additive liquid that additive liquid that the 1st kind uses and the 2nd kind are used,
The additive liquid that the additive liquid that described the 1st kind is used and described the 2nd kind are used switches and carries, and carries out adding on line.
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