CN101069780B - Solution condensing device and method - Google Patents
Solution condensing device and method Download PDFInfo
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- CN101069780B CN101069780B CN2007100914525A CN200710091452A CN101069780B CN 101069780 B CN101069780 B CN 101069780B CN 2007100914525 A CN2007100914525 A CN 2007100914525A CN 200710091452 A CN200710091452 A CN 200710091452A CN 101069780 B CN101069780 B CN 101069780B
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Abstract
The invention relates to device and method of solution concentrating, which flash evaporation concentration method avoids the mixture of mucilage and the solvent after condensing separation. Flash evaporation part (54) is located on the bottom of the container (50), and condensation part (55) is located on top. Flash evaporation nozzle (45) is located in the flash evaporation part (54), and nozzle elements (45b) are located in concentrated mucilage (56). The flash evaporation nozzle (45) is divided to eight nozzle elements (45b) by branch part (45a). The velocity of flow of each nozzle element (45b) is lower than 2000 mol/(m2.s). Through reducing the amount of flash evaporation from the nozzle elements (45b), foam of flash evaporation is reduced, and the mixture of mucilage to the condensation part (55) is controlled.
Description
Technical field
The present invention relates to solution condensing device and method, be specifically related to utilize the solution condensing device and the method for flash method concentrated polymer solution.
Background technology
Utilizing solution film-forming method; in the time of Production Example such as cellulose acylate film; polymer solution (below; be called rubber cement (dope)) modulation; in order to shorten dissolution time or to reduce the remaining of dissolved matter not; polymer concentration when carrying out dispersing and dissolving time and again (below, be called the low concentration rubber cement) is reduced to below the concentration of stream when moulding, to be easy to dissolving.The low concentration rubber cement is condensed to the concentration (below, be called the high concentration rubber cement) of regulation by enrichment process, moulds as high concentration rubber cement stream.Concentrating of rubber cement utilized flash concentration method or diaphragm type evaporation concentration method to carry out in the past.Wherein, the flash concentration method; especially adopt the flash concentration method of the spraying flash method of record in the patent documentation 1; as shown in Figure 8; when in container 141, emitting the low concentration rubber cement 147 that is filtered device 152 filtrations from nozzle 148; cause the micronize of liquid, follow the surface area of its evaporated liquor can obtain the high evaporation performance by increase.Vaporized solvent 144b from concentrated latex 144 volatilizations is sent to condenser 149 via pipe arrangement 150, is condensed, reclaims at this.In addition, after the rubber cement 144 that will concentrate is sent into filter 153 as high concentration rubber cement 151, supply with film line.In container 141, be provided with the stirring vane 145 that rotates by motor 146 and overlap 142, in cover 142, flow into medium 143.
But, in the solution condensing device that adopts above-mentioned spraying flash method, since by nozzle 148 above the liquid level 144a of concentrated latex 144, emit low concentration rubber cement 147, therefore there is the adhesion of particles liquid 147a that splashes on the cryosurface 141a, the defective of the skinning 147b of solute formation takes place after the solution drying easily.The generation of this skinning 147b because of the variation along with the ratio of components of solution, produces the pollution in the container 141, so become problem.In addition, in order not make concentrated latex 144 dryings that contact with the container inner face, surface temperature is lower than the boiling point of rubber cement in need making, but in flash concentration method in the past, if surface temperature in reducing, just exist the solvent that gasified from rubber cement 144 (below, being called vaporized solvent) 144b is in inner face condensation again, sneak in the rubber cement 144 dilution rubber cement, the problem that thickening efficiency descends.In addition, in order to make the solvent gasification equably, need enough emit the space and the liquid surface area of liquid, the problem that exists container 141 to maximize.
To this, the inventor, shown in patent documentation 2, proposed in the container that constitutes by flash distillation portion and condensation part, by delivered solution in the solution of nozzle in described flash distillation portion, utilize the solvent of flash method in the condensation of described condensation part, separate the solution condensing device that takes out this chilled solution and utilize the solution that described flash method concentrated from described container from vaporizer.According to this solution condensing device, can suppress skinning, carry out high efficiency concentrating.
Patent documentation 1: No. the 441441st, United States Patent (USP)
Patent documentation 2: the spy opens the 2004-66136 communique
But, in the solution condensing device of patent documentation 2, existing when in concentrated latex, emitting flash gas, concentrated latex splashes from liquid level, is blended in the separated solvent in condensation part the problem that pollutes.In addition, when carrying out flash vaporization in solution, if the solution in the container contacts with the nozzle outer surface of the boiling point that surpasses solution, the solution of contact is boiling just, and solid constituent sticks on the nozzle outer surface.The solid constituent of this adhesion flakes off in container in the solution along with the time changes, and becomes the impurity in the solution.Exist in the lower procedure of this impurity after flash concentration, add the problem of big filter load.In addition, if stop enrichment facility, in this stopped, solvent gas was trapped in the nozzle, at the solution that reaches the dry nozzle interior of nozzle inner surface more than the boiling point, thereby had the problem of plug nozzle.
Summary of the invention
The present invention proposes for addressing the above problem, and its purpose is to provide a kind of solution condensing device and method thereof, can suppress solution sneak into condensation portion from solvent in the generation of impurity in the generation of the pollution that causes and the solution, and prevent plug nozzle.
For achieving the above object; Solution condensing device of the present invention; In the container that is consisted of by flash distillation section and condensation part; Delivered solution the solution in from from the outlet of nozzle to described flash distillation section; Utilize flash method from the solvent of vaporizer by the condensation of described condensation part; Separate the liquid that takes out this condensation and utilize the concentrated solution of described flash method from described container; It is characterized in that; With per 1 outlet of described nozzle quantity of solvent from the final gasification of described solution; Be set at below the amount X by following mathematical expression (1) regulation
The quantity of solvent from the final gasification of described solution of the outlet of per 1 described nozzle is set in below the amount X that is stipulated by following mathematical expression (1),
X＝1.5×(to/tb)×(Pb/Po)(mol/s)............(1)
Wherein, to:273 (K), tb: the boiling point of solution (K), Po:1.01 * 10
5(Pa), Pb: press in the container (Pa).
In addition, the present invention is characterized in that, will be set in 10mol/ (m from the flow velocity of the solution of described jet expansion
2S) above, 2000mol/ (m
2S) below.The present invention is characterized in that, described condensation part has receiver, will be from the gas-liquid interface position of described solution when the height setting of described receiver is H, the relation of described quantity of solvent X and height H is set at:
When X＜0.3 (mol/s), for 0.1m≤H≤2.0m,
When 0.3 (mol/s)≤X≤0.6 (mol/s), for 0.5m≤H≤2m,
When 0.6 (mol/s)＜X, be 1.0m≤H≤2.0m.
In addition, when the area with the gas-liquid interface of described solution is set at S, the relation of described quantity of solvent X and area S is set at:
When X＜0.3 (mol/s), be 0.008m
2≤ S≤7.0m
2,
When 0.3 (mol/s)≤X≤0.6 (mol/s), be 0.7m
2≤ S≤7.0m
2,
When 0.6 (mol/s)＜X, be 1.7m
2≤ S≤7.0m
2
In addition, possess a plurality of described jet expansions, spacing between the open centre of these a plurality of outlets is set in more than the 100mm.In addition, described nozzle possesses pressure-regulating valve outside described container, detects in the nozzle from described pressure-regulating valve to described outlet and presses.In addition, the contact-making surface temperature of solution in described nozzle and the container is set in boiling point+2 ℃ that are lower than solution.Described nozzle has heat insulating member at outer surface.In addition, the inboard benchmark overall heat-transfer coefficient of the nozzle tube wall that described heat insulating member is formed is set in 1.0W/m
2Below.In addition, described heat insulating member is made of heat insulation layer, described heat insulation layer has the double-sleeve structure that is made of interior pipe and outer tube, the gap of pipe and outer tube is set in the above 30mm of 5mm in described, connecting the part of container to the described outlet from described nozzle, in described, in the gap of pipe and outer tube, do not have the gap holding part part.
Solution condensing device of the present invention, it is characterized in that, possesses cool cycles portion, it is made of the cooling end that is used for making the solution that concentrates at described container to turn back to the circulation road of described nozzle and to cool off the solution on this circulation road, described cool cycles portion moves when stopping to the nozzle liquor charging, and the solvent gas that is trapped in the described nozzle is replaced as solution.
Solution concentration method of the present invention, in the container that constitutes by flash distillation portion and condensation part, delivered solution from the outlet of the nozzle solution in described flash distillation portion, utilize the solvent of flash method by the condensation of described condensation part from vaporizer, separate the liquid that takes out this condensation and utilize the concentrated solution of described flash method from described container, described solution concentration method is characterised in that
The quantity of solvent from the final gasification of described solution of the outlet of per 1 described nozzle is set in below the amount X that is stipulated by following mathematical expression (1),
X＝1.5×(to/tb)×(Pb/Po)(mol/s)...............(1)
Wherein, to:273 (K), tb: the boiling point of solution (K), Po:1.01 * 10
5(Pa), Pb: press in the container (Pa).In addition, will be set in 10mol/ (m from the flow velocity of the solution of described jet expansion
2S) above, 2000mol/ (m
2S) below.
According to the present invention, a kind of solution condensing device can be provided, it is in the container that is made of flash distillation portion and condensation part, delivered solution from the outlet of the nozzle solution in described flash distillation portion, utilize the solvent of flash method in the condensation of described condensation part from vaporizer, separate the solution that takes out this chilled liquid and utilize flash method to concentrate from described container, wherein, to is set at 273 (K), with tb be set at solution boiling point (K), Po is set at 1.01 * 10
5(Pa), Pb is set at when pressing (Pa) in the container, because below the outlet of each described nozzle is set in amount X by following mathematical expression (1) regulation from the quantity of solvent of described final gasification, so can prevent that solution splashes when flash vaporization, become the spittle, this spittle is blended into the condensation part.Thus, solution can not be blended in the solvent that separated.So, in follow-up evaporation refining step etc., the fault of separating out of solid content can not take place, carry out the refining of solvent easily.
X＝1.5×(to/tb)×(Pb/Po)(mol/s)...............(1)
In addition, by being set in 10mol/ (m from the flow velocity of the solution of nozzle outlet
2S) above, 2000mol/ (m
2S) below, can suppress the generation of the spittle equally and splash, can suppress solution sneaking in the solvent that separated.If be lower than 10mol/ (m
2S), produce bubble in spray nozzle front end portion easily, because the time of contact of bubble and solvent is long, so thickening efficiency descends.In addition, if surpass 2000mol/ (m
2S), then become fierce from splashing of the spittle of liquid level.
By the spacing between the open centre of a plurality of outlets is set in more than the 100mm, can conjointly not increase between bubble, can suppress the generation of the spittle.This spacing is wide more good more, if but increase the gap, owing to cause the increase of container capacity, so, preferably below the above 500mm of 100mm.
Described nozzle possesses pressure-regulating valve outside described container, press by detecting in the nozzle from described pressure-regulating valve to nozzle opening, can judge spray nozzle clogging automatically, seeks corresponding rapidly.In addition, be set in boiling point+2 ℃ that are lower than solution, can be suppressed at the boiling of the solution of nozzle outer surface, can prevent the adhesion of the solid constituent in the solution by contact-making surface temperature with solution in nozzle and the container.
Have heat insulating member by described nozzle at outer surface, the contact-making surface temperature of solution in nozzle and the container can be remained on boiling point+2 ℃ of solution.In addition, the inboard benchmark overall heat-transfer coefficient of the nozzle tube wall by will utilizing described heat insulating member is set in 1.0W/m
2Below the K, can be adiabatic expeditiously.
Described heat insulating member is made of heat insulation layer, and this heat insulation layer has the double-sleeve structure that is made of interior pipe and outer tube, and the clearance gauge of pipe and outer tube in described is fixed in the above 30mm of 5mm.If be lower than 5mm, insulation effect descends, if surpass 30mm, except that volume increased, insulation effect did not change so yet.In addition, by in the part that connects container from nozzle to the jet expansion, do not have the structure of gap holding part part in being formed in the gap of pipe and outer tube, the gap holding part part can not become heat transfer component, can not reduce insulation effect.
By possessing by being used for making the solution that is concentrated by described container to turn back to the circulation road of described nozzle and cooling off the cool cycles portion that the cooling end of the solution on this circulation road constitutes, described cool cycles portion works when stopping to the nozzle liquor charging, the solvent gas that is trapped in the described nozzle is replaced as solution, can in nozzle, not be detained solvent gas, dry on the nozzle inner surface that reaches more than the boiling point, as to adhere to nozzle interior solution, even stopping to the nozzle liquor charging, under the state that interrupts concentrating, can plug nozzle yet.
Description of drawings
Fig. 1 is the skeleton diagram that adopts the rubber cement production line of solution concentration method of the present invention.
Fig. 2 is the cutaway view that solution condensing device of the present invention represented in summary.
The vertical view of the state of the flash distillation nozzle in the solution condensing device that Fig. 3 observes from below.
Fig. 4 is the vertical view of flash distillation nozzle of the part of shortcoming ground expression outer tube.
Fig. 5 is the V-V line cutaway view among Fig. 4.
Fig. 6 is the curve map of the relation of expression filtration yield of filter and pressure ratio.
Fig. 7 is the skeleton diagram of expression film line.
Fig. 8 is the cutaway view that the solution condensing device that utilizes flash vaporization in the past represented in summary.
Among the figure: 10-rubber cement production line, 40-filter, 43-control valve, the 44-solution condensing device, 45-flash distillation nozzle, 45a-branching portion, the 45b-nozzle body, pipe in the 45c-installation portion, 46-, the 47-outer tube, 50-solution condensing device body, 51,52, the 53-overcoat, the 55a-cryosurface, 56-concentrated latex, 56a-liquid level, the 57-solvent, 57a-vaporized solvent, 57b-condensing solvent, 65-level detection sensor, 66-pump, 66a-controller, 67-high concentration rubber cement, 71-secondary filter, 72-Pressure gauge, 73-judgment of clogging portion, 74-cool cycles portion, 80-film line, 91-film.
The specific embodiment
Below, the solute (polymer and additive) and the solvent that constitute the rubber cement that adopts among the present invention are described.Then, the film of the rubber cement manufacture method of solution concentration method of the present invention, the solution film-forming method that adopts this rubber cement, manufacturing, the optics goods of employing film are adopted in explanation successively.In addition, about rubber cement, describe by the example that adopts primary cellulose acetate (below, be called TAC) solution (rubber cement), but the present invention is not limited to this solution.For example, also can with TAC instead of application the present invention in the concentrating of the polymer solution (rubber cement) of other polymer.In addition, also can be used as solute and adopt difficult low molecular compound (monomer) or the oligomer that in solvent, dissolves, after having modulated low concentration solution, utilize solution concentration method of the present invention to concentrate, make highly concentrated solution.
[polymer]
The polymer that adopts among the present invention does not limit especially.As the polymer that adopts among the present invention, as long as can be dissolved in the solvent of the suitable organic or inorganic more than a kind, can be with this solution the supply system film, just not special especially restriction.As example of polymer so, can enumerate polyamide, aromatic polyimide, polyesteramide, polyamide-imide, polyacrylic resin, polymethacrylate resin, mylar, cellulose-based macromolecule, silicones, fluororesin etc. such as cellulose acylate (cellulose acylate), Merlon, polyurethane, polyvinyl alcohol resin, polyacrylonitrile, aromatic polyamide.Preferably, in these polymer, adopt cellulose esters.In addition, in cellulose esters, preferably adopt cellulose acylate, especially preferably use cellulose acetate.In addition, in this cellulose acetate, most preferably using its average degree of acetylation is 57.5～62.5% primary cellulose acetate (TAC).So-called degree of acetylation, represent each cellulose Unit Weight in conjunction with the acetic acid amount.Degree of acetylation is according to the mensuration and the calculating of the degree of acetylation among the ASTM:D-817-91 (test methods of cellulose acetate etc.).In the present invention, use the cellulose acylate particle, have the particle diameter of 0.1～4mm more than the 90 weight % of the particle of use, preferably have 1～4mm.In addition, preferred 95 weight % particle diameter above, that more preferably 97 weight % are above and then preferred 98 weight % are above, most preferably the above particle of 99 weight % has 0.1～4mm.In addition, the particle diameter that has 2～3mm more than the 50 weight % of the preferred particle that uses.Preferred 70 weight % are above, more preferably 80 weight % are above, most preferably the above particle of 90 weight % has the particle diameter of 2～3mm.Preferably, the shape of particle of cellulose acylate has the shape of subglobular as far as possible.
[additive]
As the additive that uses among the present invention, plasticizer, ultra-violet absorber etc. are arranged.As plasticizer; (for example can adopt phosphate system; triphenyl phosphate (below; be called TPP); tricresyl phosphate; tricresyl phosphate base diphenyl ester; the hot phenyl diphenyl ester of phosphoric acid; the biphenyl diphenyl phosphoester (below; be called DBP); trioctyl phosphate; tributyl phosphate etc.); phthalate ester system (for example; diethyl phthalate; DMEP; repefral; dioctyl phthalate etc.); ethyl glycolate system (for example; triacetin; tributyrin; butyl phthalyl butyl alcohol acid esters; ethyl phthalyl ethyl hexanol acid esters (below; be also referred to as ethyl phthalyl glycolic ethyl ester); methyl phthalyl ethyl hexanol acid esters; butyl phthalyl butyl alcohol acid esters etc.); acetate system (for example, dipentaerythritol six acetates; two trimethylolpropanes, four acetates etc.) and other plasticizer.
Also can in rubber cement, add ultra-violet absorber.For example, can adopt Viosorb 110 based compound, BTA based compound, salicylate based compound, benzophenone based compound, cyanoacrylate based compound, nickel complex salt based compound and other ultra-violet absorber.Especially preferred ultra-violet absorber is BTA based compound or benzophenone based compound.In addition, also can be as required, before the modulation of rubber cement or the arbitrary stage after the modulation, in rubber cement, add multiple additives, for example releasing agent, peel off promoter, fluorine based surfactant etc.
[solvent]
As the solvent that adopts among the present invention, halogenated hydrocarbons, ester class, ketone, ethers, alcohols etc. are arranged, but do not limit especially.Solvent is not so long as the purity of commercially available product just needs special restriction.Solvent, (100 weight %) uses separately, alcohol, ketone, ester, the use of ether ground that also can mixed carbon number 1～6.Example about spendable solvent, (for example can enumerate halogenated hydrocarbons, carrene, chloroform etc.), the ester class (for example, methyl acetate, toluic acid salt (ホ Le メ one foretells), ethyl acetate, amyl acetate, butyl acetate etc.), ketone (for example, acetone, butanone, cyclohexanone etc.), ethers (for example, dioxane, dioxolane, tetrahydrofuran, diethyl ether, methyl-t-butyl ether etc.), alcohols (for example, methyl alcohol, ethanol etc.) etc.In addition, the preferred used solvent of processed in advance.In addition,, consider, preferably adopt methyl acetate from this point of environmental protection as the solvent that adopts among the present invention.Can adopt methyl acetate separately, also can be used as the mixed solvent that is mixed with other solvent and use.In addition, owing to the invention is characterized in the generation that suppresses skinning, so for the combination of the solvent and the solute of easy generation skinning, i.e. its effect is brought into play in the combination of solvent that solubility is low and solute especially.Especially when adopting TAC, be under the situation of main solvent, more can obtain significant effect at methyl acetate with the solvability difference as polymer.
[rubber cement manufacture method]
Fig. 1 represents can be used for the rubber cement production line 10 of solution concentration method of the present invention, but the rubber cement production line that adopts in the solution concentration method of the present invention is not limited to illustrated mode.The manufacturing process of rubber cement is, at first opens valve 12, from solvent tank 11 to dissolving tank 13 delivery solvent.Then, while measure to dissolving tank 13 and send into the TAC that is contained in the meter 14.
In addition, carry out the switching manipulation of valve 16, send into the additive solution of aequum from additive tank 15 to dissolving tank 13.Additive except that the method for sending into as solution, for example, is under the situation of liquid at additive at normal temperatures, also can send into dissolving tank 13 with the state of this liquid.In addition, be under the situation of solid at additive, also can adopt meter to send into dissolving tank 13.The kind of additive is not limited to a kind.In such cases, also can adopt the method for multiple additives of in additive tank 15, packing into, or adopt a plurality of additive tank, by method of sending into to dissolving tank of pipe arrangement etc. independently separately.
The order of pressing solvent, TAC, plasticizer drops into to dissolving tank 13, the change but ordering in launching also can suit.For example, also can measure TAC, it is sent into dissolving tank 13 after, carry the solvent of preferred amounts.In addition, not necessarily must send into additive to dissolving tank 13 in advance, also can be in follow-up operation, additive package in the rubber cement that has mixed TAC and solvent.
The stirring vane 19a that dissolving tank 13 has overcoat 17, be made of blade and the core shift shaft 19b of dissolvers formula.Medium is circulated in overcoat 17, with the adjustment of the solvent in the dissolving tank 13 etc. to uniform temperature.In addition, by motor 18a rotation stirring vane 19a, by motor 18b rotation core shift shaft 19b.By stirring vane 19a, the solute in the dissolving tank 13 is dissolved in the solvent, obtain thick solvent soln 20.
The solvent of gasification is liquefied by condenser 25, and turns back to modulation jar 21.Based on flow value by flowmeter 27, regulate the liquor charging flow of the thick solvent soln 20 of pump 26, reach optimised quantity.About analyzer 28, for example can adopt near infrared ray industrial analysis instrument.Utilize this analyzer 28 can measure the ratio of components of the low concentration rubber cement 30 before concentrating.About heater 29, adopt the multi tube heat exchanger that possesses the silent oscillation blender.Adjust heating-up temperature based on the value of measuring with thermometer 31.In addition, each numerical value of low concentration rubber cement 30 before concentrating is preferably in scope as described below, that is: the survival gas amount the when viscosity when polymer concentration is 30 ℃ of 5 weight %～30 weight %, temperature is 30 ℃ of 0.1Pas～100Pas, temperature is that 10mg/L～500mg/L, temperature are 50 ℃～180 ℃, but also is not limited to these number ranges.
If the temperature with the low concentration rubber cement 30 of thermometer 31 instrumentations reaches normal value,, utilize transfer valve 32 to switch streams just by the indication of thermometer 31.Low concentration rubber cement 30, is sent from flash distillation nozzle 45 in solution condensing device 44 through filter 40, Pressure gauge 41, thermometer 42 and control valve 43 by transfer valve 32, and flash vaporization becomes the high concentration rubber cement.About adopting the solution concentration method of the present invention of solution condensing device 44,, describe in detail in the back with reference to Fig. 2～Fig. 5.In addition, the manufacture method of the low concentration rubber cement before concentrating is not limited to described method.For example, in Fig. 1, adopt rubber cement production line 10 to carry out continuously, but also can be to make the low concentration rubber cement, make its flash vaporization in solution condensing device 44 with intermittence unit with batch (-type).
[solution concentration method]
As shown in Figure 2, solution condensing device 44 possesses container 50 and covers the 1st overcoat the 51, the 2nd overcoat the 52, the 3rd overcoat 53 of this container 50.On each overcoat 51～53, be provided with independently pipe arrangement, via each pipe arrangement feeding medium.By the circulation of this medium, the each several part of container 50 is controlled under the suitable temperature conditions.Container 50 is made of with the condensation part 55 that is located at its top flash distillation portion 54.Medium is used as cooling usefulness by be used as heating usefulness in overcoat 51,52 in overcoat 53, heating flash evaporation portion 54, cooling condensation portion 55.Flash distillation portion 54 and condensation part 55 can as the device body combination, also can be used as an integral manufacturing after doing as another system.
Fig. 3 is illustrated in the configuration example in the container 50 of flash distillation nozzle 45, is the vertical view from following observation flash distillation nozzle 45.Fig. 4 is the diagram of the branching portion 45a of expression flash distillation nozzle 45, and the part of outer tube 47 is shown to shortcoming.Fig. 5 is the V-V line cutaway view among Fig. 4.As Fig. 3～shown in Figure 5, the dual structure of pipe 46 and outer tube 47 in flash distillation nozzle 45 forms.In pipe 46 and outer tube 47, in the present embodiment, adopts 47d at the bottom of 7 T font branch tube parts (T type pipe) 46a, 47a or L font tube parts (union elbow) 46b, 47b, pipe 46c, 47c, the pipe, pressure-reducing valve etc., integrated by welding formation.Branching portion 45a has 8 nozzle bodies (outlet) 45b.Each nozzle body 45b is configured to be arranged in 2 * 4.
Fixed flange on the bottom of flash distillation nozzle 45 is as installation portion 45c.This installation portion 45c can be installed on the installation portion 50a of container 50 sides.
The radical of nozzle body 45b or configuration example are decided according to the capacity of container 50 or the liquor charging amount of low concentration rubber cement 30.The number of nozzle body 45b or configuration example are not limited to the mode of illustrated example, and change can suit.For example, can change to 2 * 4 configuration example, also can form 3 * 4 or 4 * 4 configuration example.In addition, also can replace array configurations, form the ring-type configuration.Under the situation of ring-type configuration, be not limited to single configuration, also can dispose dual or multiplely.In addition, about the material of interior pipe 46 and outer tube 47, can adopt SUS304, SUS316, SUS316L, Hasiteluoyi hastelloy (Ha ス テ ロ ィ C) (registration mark), titanium etc.
In the present embodiment, by 8 nozzle body 45b are set, can with from the flow-control of the low concentration rubber cement 30 of each nozzle body 45b at 2000mol/ (m
2S) below.Thus, can carry out flash vaporization expeditiously, the spittle can not fly into condensation part 55 from liquid level (gas-liquid interface) 56a of concentrated latex 56 simultaneously, can suppress concentrated latex 56 sneaking into to condensation part 55.In addition, if surpass 2000mol/ (m from the flow of the low concentration rubber cement 30 of each nozzle body 45b
2S), concentrated latex 56 becomes the spittle from liquid level 56a easily and flies up, because of this spittle concentrated latex is sneaked into condensation part 55.In addition, if the flow of solution is lower than 10mol/ (m
2S), then because easily at spray nozzle front end portion growth bubble, prolong the time of contact of bubble and solution, so thickening efficiency descends, can not carry out high efficiency flash vaporization.
Do not limit especially a plurality of nozzle body 45b in spacing P1, P2 in the heart, but preferably below the above 500mm of 100mm, more preferably in the scope below the above 400mm of 150mm.If be lower than 100mm, increase from the bubble of nozzle body 45b is continuous each other, be easy to generate the spittle, each spittle splashes on the cryosurface 55a easily.Therefore, concentrated latex 56 sneaking in chilled solvent taken place.In addition, if spacing P surpasses 500mm,, cause the increase of container capacity, so not preferred though prevent the effect raising that the spittle takes place and prevents to disperse.
As Fig. 4 and shown in Figure 5, the interior pipe 46 of flash distillation nozzle 45 and outer tube 47 constitute by welding T type pipe joint 46a, 47a or union elbow 46b, 47b, tube parts such as pipe 46c, 47c, do not dispose the formation of liner in being formed between pipe 46 and the outer tube 47.That is, only a front end and the flash distillation nozzle 45 at each nozzle body 45b connects on the installation portion 45c of containers 50, pipe 46 and outer tube 47 in the welding, owing to do not have gap holding part part such as liner, so can not conduct heat from this part.In the gap of interior pipe 46 and outer tube 47, enclose or feed argon gas etc.In addition, also can form vacuum as required.In addition, the gap holding part part of also can packing in such cases, preferably is set in 0.01W/mK with its coefficient of overall heat transmission.
So, can constitute heat insulation layer by the double-sleeve structure that constitutes by interior pipe 46 and outer tube 47.The gap of pipe 46 and outer tube 47 in not limiting especially, but preferably in the above 30mm of 5mm.If the gap is lower than 5mm, then difficulty is guaranteed thermal insulation, if surpass 30mm, because the overall volume of flash distillation nozzle 45 increases, insulation effect does not improve so yet, causes waste.So, by forming the heat insulation layer of the double-sleeve structure that constitutes by interior pipe 46 and outer tube 47, can make the contact-making surface temperature of the solution in nozzle 45 and the container 50 be lower than boiling point+2 ℃ of solution.Especially, by utilizing heat insulating member that the inboard benchmark overall heat-transfer coefficient of the tube wall of nozzle 45 is set in 1.0W/m
2Below the K, can suppress from the heat transfer of the nozzle interior solution that surpasses boiling point heating to nozzle outer surface.Can prevent the adhesion of the solids in the solution that the boiling of solution causes.In addition, preferably the outer surface of outer tube and the contact-making surface of concentrated latex are formed more than polishing grinding 200 orders.Thus, can not hinder solution, can suppress from the heat transfer of nozzle surface heating to solution along the flowing of nozzle surface.
In addition, also can replace having insulation effect, medium is circulated between interior pipe 46 and outer tube 47.In addition, also the gap can be formed triplen, the medium of temperature of in interior side clearance and outer side clearance, having distinguished varying cyclically, with intermediate space as heat insulation layer.In addition, also can replace forming double-sleeve structure or multiple tubular construction, the material of not invading with the solvent of rubber cement applies processing to nozzle outer surface in addition.
As shown in Figure 2, preferred, the height H of the upper end-face edge of the side plate 58a from liquid level 56a to described receiver 58 is based on the quantity of solvent X that is drawn by described mathematical expression (1), by following provisions.
When X＜0.3 (mol/s), for 0.1m≤H≤2.0m,
When 0.3 (mol/s)≤X≤0.6 (mol/s), for 0.5m≤H≤2m,
When 0.6 (mol/s)＜X, be 1.0m≤H≤2.0m.
If height H less than setting, then causes solution sneaking in condensing solvent easily, in addition, if height H is greater than setting, then because the condensation number of vaporized solvent on the internal tank wall increases dilution concentrated solution, thereby thickening efficiency decline.
In addition, preferred, the area S of the liquid level shown in Fig. 3 section line is based on the quantity of solvent X that is drawn by described mathematical expression (1), by following provisions.
When X＜0.3 (mol/s), be 0.008m
2≤ S≤7.0m
2,
When 0.3 (mol/s)≤X≤0.6 (mol/s), be 0.7m
2≤ S≤7.0m
2,
When 0.6 (mol/s)＜X, be 1.7m
2≤ S≤7.0m
2
If the area of liquid level is less than setting, the then influence of the inner wall of receptor easily links to each other from the bubble of nozzle generation is easy each other, and solution spills from liquid level easily.In addition, if area S greater than setting, the mobile mixing of the solution in the container dies down, and CONCENTRATION DISTRIBUTION takes place easily.
As shown in Figure 1, between control valve 43 and flash distillation nozzle 45, Pressure gauge 72 is installed,,, can monitors the obstruction of flash distillation nozzle 45 by judgment of clogging portion 73 monitor pressures by signal based on this Pressure gauge 72.That is, when the detected pressures by Pressure gauge 72 is lower than certain value, judge that by judgment of clogging portion 73 flash distillation nozzle 45 stops up, and sends warning.
In addition, between pump 66 and flowmeter 70, be provided with cool cycles portion 74.Cool cycles portion 74 is made of cooler 75, the static mixer 76 that is configured in its downstream, transfer valve 77a, 77b, 77c and flow control valve 77d.This cool cycles portion 74 when interrupting flash vaporization, makes high concentration rubber cement 67 circulations from container 50, sends into flash distillation nozzle 45.In addition, be no more than the mode of boiling point+2 ℃ of solution, come the rubber cement of self-pumping 66 by cooler 75 coolings with rubber cement by flash distillation nozzle 45. Transfer valve 77a, 77b, 77c, when interrupting flash vaporization, carry out handover operation, make the high concentration rubber cement of just carrying 67 turn back to flash distillation nozzle 45, between flash distillation nozzle 45 and container 50, make 67 circulations of high concentration rubber cement via this cool cycles portion 74 towards film line 80.By having so cool cycles portion 74, interrupting under the situation of flash vaporization for the moment, can suppress because of solvent gas is trapped in the nozzle 45, reach the solution of the dry nozzle interior of the above nozzle inner surface of boiling point and the obturation of nozzle 45 takes place.
Preferably, pressure when solution condensing device 44 is sent into (flash vaporization) low concentration rubber cement 30, scope at saturated vapor pressure (MPa)～its saturated vapor pressure (MPa)+5 (MPa) of its temperature of the solvent that constitutes low concentration rubber cement 30 can concentrate concentrated latex expeditiously.If below saturated vapor pressure, cause the boiling of solvent sometimes, skinning etc. takes place.In addition, if the temperature of solution is reduced to below the boiling point, be used for the shortage of heat of flash vaporization, condensation efficiency descends.In addition,, then additionally need the pressure-resistance structure of equipment if more than saturated vapor pressure (MPa)+5 (MPa), unfavorable on cost etc.But the present invention is not limited thereto scope.
If solvent (below, the be called vaporized solvent) 57a of gasification reaches the cryosurface 55a of condensation part 55, become liquid (below, be called condensing solvent) 57b with regard to condensation.Condensing solvent 57b, the surface tension by cryosurface 55a forms spherical or wetting expansion, falls downwards along cryosurface 55a by gravity, is stored in the receiver 58.Be stored in the solvent 57 in the receiver 58,, reclaim by recycling can 63 by pipe arrangement 60, control valve 61, flowmeter 62.Then, solvent 57 is admitted to evaporation purification apparatus 64, by after refining, can be used as solvent and utilizes.In addition, the Pressure gauge 59 that is used to measure the pressure in it is installed in container 50, carry out the temperature control of the control of flash vaporization amount of low concentration rubber cement or flash distillation portion 54, condensation part 55 etc. based on its value, so that the pressure in the container 50 remain under certain pressure.In addition, for the surface tension that makes cryosurface 55a reaches preferred value, preferably form the material of the inwall of container 50 by SUS304, SUS316, SUS316L, Hasiteluoyi hastelloy (registration mark), titanium (チ タ Application) (registration mark) etc.In addition,, can utilize the surface tension of cryosurface not make condensate liquid drop on flash distillation portion ground and reclaim condensate liquid, therefore more preferably this structure if on aggegation face 55a, be provided with towards the prominent bar or the groove of the direction of withdrawal liquid.
The liquid level 56a of concentrated latex 56 is measured by level detection sensor 65, its value is sent to the controller 66a that is installed on the pump 66.By the liquor charging amount of controller 66a adjustment pump 66, extract high concentration rubber cements 67 out from solution condensing device 44 simultaneously.Preferably, determine the capacity of container 50 according to the flow of concentrated latex 56, so that mean residence time was 0.5 minute～40 minutes scope.In such cases, preferred, in container 50, the volume of gas (gas saturation) is 3%～60%.In addition, the gas saturation, from the volume of gas and solution and (Vg) and the volume of solution (VL), by { (Vg-VL)/Vg} * 100 (%) definition.If in these scopes, just in container 50, store low concentration rubber cement 30 as concentrated latex 56, can be used as solvent 57 and take out the vaporized solvent 57a that produces from concentrated latex 56 expeditiously, in addition, also guarantee the position that is provided with of solution condensing device 44 easily.In addition, according to the present invention, because the average time that concentrated latex 56 is detained in solution condensing device 44 is very short, the scope at 0.5 minute～20 minutes is so can cause the sex change of rubber cement hardly.In addition, in the present invention, solutions employed enrichment facility 44 is not limited to each above-mentioned number range.
As shown in Figure 2, the part 56b that liquid level 56a and container 50 join is the position that skinning takes place in the easiest change because of liquid level 56a.Therefore, preferred, adopt 2 overcoats 51,52 that are installed in the flash distillation portion 54, more strictly carry out temperature control.That is, the medium of the 1st overcoat 51, the mode that gasifies easily with concentrated latex 56 flows heat medium.The medium of the 2nd overcoat 52 is if adopt the solvent in the concentrated latex 56 not reach the heat medium of the temperature of vapor liquid equilibrium in container 50, even also suppress gasification owing to adhere to vaporized solvent 57a, so the misgivings of skinning do not take place.In addition, in the present invention, from mixed solvent modulation rubber cement the time, be benchmark with the minimum solvent of vapor liquid equilibrium temperature.Mobile cooling medium in the 3rd overcoat 53 is to reach the temperature of condensation easily on cryosurface 55a, liquefaction vaporized solvent 57a.
By so changing medium by each overcoat, can keep the internal face of container 50 with a plurality of temperature conditions, can carry out concentrating of rubber cement expeditiously.Specifically be, employing reaches the medium of the 1st overcoat 51 of fiducial temperature in 20 ℃～70 ℃ the scope, reaches the medium of the 2nd overcoat 52 of fiducial temperature in 10 ℃～60 ℃ the scope, reach the medium of the 3rd overcoat of fiducial temperature in-10 ℃～20 ℃ the scope, by the amplitude of fluctuation with the temperature of these media be set at ± 1 ℃, can suppress the variation of the concentrated condition of rubber cement.In addition, expression divides 3 subregion changing temperature conditions in Fig. 2, but the present invention also is not limited to 3 subregions, also can divide 2 subregions or 4 above changing temperature conditions of subregion.
If in the gas phase scope of absolute pressure partly of container 50, carry out at 500hPa～1100hPa, then can carry out come-up and separation expeditiously from the gas in the concentrated latex 56 (bubble), thereby preferred this scope, but the present invention is not limited thereto scope.In addition, adopt near-infrared industrial analysis instrument 69, analyze the ratio of components of high concentration rubber cement 67, confirm to reach ratio of components as purpose.In addition, high concentration rubber cement 67 after by flowmeter 70, secondary filter 71, is adopted by film line 80.In addition, in secondary filter 71, be provided with not shown Pressure gauge.In addition, the analyzer 28,69 that the present invention is used is not limited near infrared ray industrial analysis instrument.For example, also can adopt known analyzers such as ultrasonic propagation velocity analyzer.
Preferably, high concentration rubber cement 67 after concentrating, in the survival gas amount of the viscosity of polymer concentration when being 30 ℃ of 12 weight %～40 weight %, temperature when being 30 ℃ of 1Pas～200Pas, temperature is that 1mg/L～200mg/L, temperature are in each number range of 20 ℃～60 ℃, but also is not limited to these number ranges.In addition, when once having carried out solution concentration method of the present invention, because the difference of the polymer concentration of high concentration rubber cement 67 and the polymer concentration of low concentration rubber cement 30 is at 1 weight %～15 weight %, can concentrate expeditiously, suppress the rubber cement quality badness simultaneously, so preferred this scope, but also be not limited to these number ranges.
As previously mentioned, preferred, the viscosity of the low concentration rubber cement before concentrating is the low viscosity of 0.1Pas～100Pas at 30 ℃, to be easy to carry out the liquor charging in rubber cement production line 10., if, adopt film line 80 shown in Figure 7 to make film,,, prolong drying time so, need to prolong stream and mould band in order to obtain having the film of self-supporting because the quantity of solvent in the gel mould 89 is big with the original state of this low concentration rubber cement 30.Therefore, concentrate by adopting solution concentration method of the present invention, (preferred 1Pas～200Pas), can improve the viscosity of gel mould tackifys.Therefore, can shorten the time that gel mould becomes the film with self-supporting, can seek to reduce cost, seek device and miniaturization simultaneously.
The flow of low concentration rubber cement 30 is measured by the flowmeter 27 (with reference to Fig. 1) in the downstream that is installed in pump 26, regulates the liquor charging amount according to this measured value.In addition, the high concentration rubber cement 67 after concentrating is detected by level detection sensor 65, based on this value controller 66a control pump 66, so that liquid level (with reference to Fig. 2) 56a reaches fixing.
When filter 40 is carried low concentration rubber cement 30, if the filtration yield (constant speed is filtered the solid constituent amount before concentrating) that will reach till the regulation filter pressure is set at V0, then, the filtration yield (concentrate the back constant speed and filter the solid constituent amount) that reaches the solid constituent of regulation filter pressure is set at V1 when secondary filter 71 is carried high concentration rubber cement 67.At this moment, preferably press the filter life rate of change of formula (1) calculating below 50%.
Filtration yield rate of change (%)=(V0-V1)/V0} * 100 ... (1)
Specifically be, the flow constant speed of low concentration rubber cement 30 is in the scope of 60kg/hr～1200kg/hr, and the flow constant speed of high concentration rubber cement 67 is in the scope of 59kg/hr～1190kg/hr.In addition, measure filter 40 and reach regulation filter pressure (P
L) till filtration yield V0 and secondary filter 71 reach decide filter pressure (P
H) till filtration yield V1.In addition, in the present invention, the preceding constant speed that concentrates of preferred filter 40 is filtered solid constituent amount V0, at 100kg/m
2～20000kg/m
2Scope.In addition, the concentrated back constant speed of preferred secondary filter 71 is filtered solid constituent amount V1, at 60kg/m
2～20000kg/m
2Scope.In addition, preferred, the regulation filter pressure (P of filter 40
L) at the scope of 0.5MPa～2.0MPa, the regulation filter pressure (P of secondary filter 71
H) in the scope of 0.5MPa～3.0MPa.In addition, the performance of the filter 40,71 that the present invention is used is not limited to described each number range.
By controlling these terms and conditions, can be suppressed at the generation of the skinning in the container 50, can confirm that skinning sneaks into the variation of the filtration load of the secondary filter 71 that causes.About filtering load, adopt Fig. 6 explanation.The transverse axis of Fig. 6 is represented the concentrated back filtration yield V1 (g/cm of secondary filter
2).In addition, the longitudinal axis represent secondary filter with respect to initial stage pressure (P
o) running the time pressure (P
H) pressure ratio (P
H/ P
o).Experimental data with zero graphic representation adopts solution concentration method of the present invention to obtain connects with solid line.In addition, with the experimental data that △ graphic representation adopts the secondary filter 153 in the downstream that is located at the used device 140 of previously described solution concentration method in the past to carry out, with dashed lines connects.As can be seen from Figure 6, in the present invention, owing to suppressed the generation of the skinning in device 140, so do not produce rapid pressure oscillation.But, in method in the past, a large amount of skinning takes place in device 140, this skinning is sneaked in the high concentration rubber cement, causes the obstruction of the filter (not shown) of secondary filter 153, and pressure ratio sharply rises.In the past, if produce so obstruction of filter, tackled by switching to another not shown secondary filter.But owing to switch secondary filter, because of following the flow change of replacement, difficulty is carried out the continuous manufacturings of high concentration rubber cement uniformly such as ratio of components.In addition, the loss of the residual rubber cement in the filter also increases.In addition, need the unnecessary solvent that is used to clean, time.But, according to the present invention, owing to can increase filtration yield V1, thus can prolong the time of switching secondary filter significantly.
[solution film-forming method]
Film line shown in Fig. 7 80.The rubber cement that described high concentration rubber cement 67 is housed is connected with stream mold 84 with filter 83 via pump 82 with jar 81.In addition, stirring vane 85 by motor (not shown) rotation is installed in jars 81, high concentration rubber cement 67 is kept evenly at rubber cement.High concentration rubber cement 67 for this stage also can mix additives such as plasticizer, ultra-violet absorber.
Below stream mold 84, be provided with and be wrapped in the stream of rotation on the roller 86,87 and mould and be with 88, this stream is moulded and is with 88, along with rotating roller 86,87 with not shown drive unit rotation and rotating.High concentration rubber cement 67 is carried with jar 81 from rubber cement by pump 82, after removing impurity by filter 83, is admitted to stream mold 84.Mould at stream and be with 88 upper reaches to mould high concentration rubber cement 67 by stream mold 84, form gel mould 89.Mould on one side and be with 88 to transmit gel moulds 89 with stream, on one side slowly gelation mould from stream by angle stripper 90 and to be with 87 to peel off, formation film 91 to having self-supporting.
Deliver to the film 91 of dry section 93 from stenter 92, be wound onto on a plurality of rollers 94, while transmit dry.Dried film 91 after district's 95 coolings that are cooled, is wound onto on the up-coiler 96.In addition, 95 films of sending 91 from the cooling zone also can be cut edge before coiling and be handled or additional annular knurl.
In the present embodiment, illustrated that the individual layer stream that adopts single stream mold moulds method, but solution film-forming method of the present invention is not limited to individual layer stream and moulds method.For example, also can adopt the mold of manifold stream, or have the stream mold of feeding section, a cocurrent flow is moulded multilayer ground system film.In addition, also can adopt a plurality of stream molds, utilize one by one stream to mould the legal system film.
The solvent that adopts among the present invention in the front and back of solution concentration, can change composition, also can not change composition.For example, when having changed composition, by (for example, n-butanols, methyl alcohol etc. dissolving solute in) the mixed solvent, obtain the low concentration rubber cement containing high boiling solvent.Mould when stripping at stream, need Weak solvents such as methyl alcohol or n-butanols, but these solvents worsen the dissolubility of rubber cement.So, preferably in the low concentration rubber cement, contain less as far as possible, concentrating back raising ratio.Utilize the low boiling point solvent of concentration method of the present invention to gasify easily, the easy residual characteristics of high boiling solvent.
In addition, preferred when the used solvent of the present invention adopts mixed solvent, combination is the good solvent and the insoluble Weak solvent of dissolving solute easily.When making the low concentration rubber cement,, adopt the ratio of components of good solvent high in order to seek to shorten dissolution time.In addition, when solute adopts polymer, how not make the Weak solvent swelling dissolve polymer.By adopting solution concentration method of the present invention, remove good solvent selectively, can obtain the high relatively high concentration rubber cement of ratio of components of Weak solvent.If adopt film line shown in Figure 7 80, stream is moulded this high concentration rubber cement, obtains the gel mould 89 of polymer swelling on stream is moulded with 88 easily, can shorten the time that becomes the film 91 with self-supporting.
[film and goods]
From the film 91 that obtains, adopt 5cm at 5 places at its width
2Sample.Under crossed polarizer, observe these samples, the mean value of the quantity of fleck defect is set in below a reference value.In addition, also reach below a reference value each condition of regulation rubber cement manufacture method, solution concentration method, solution film-forming method in order to make from the film of low concentration rubber cement 30 system films.Thus, can confirm to suppress the generation of the skinning in the container 50.For example,, among the present invention, a reference value being defined as, the above impurity of size 20 μ m is 0/5cm
2, the impurity that is lower than 20 μ m more than the 10 μ m is 10/5cm
2, the impurity that is lower than 10 μ m more than the 5 μ m is 10/5cm
2Learn, as long as reach this below a reference value from the film of low concentration rubber cement, high concentration rubber cement system film respectively, just can be manufactured on practical on the unconverted rubber cement of characteristic during the manufacturing rubber cement.In addition, the film that can not had problems expeditiously from this high concentration rubber cement.In addition, in the present invention, described a reference value is not limited to described value, also can change, so that have necessary performance as the film of purpose.
Film by described solution film-forming method system film can be used as polaroid protective film.By on the two sides of the polarizing coating that forms by polyvinyl alcohol etc., pasting this polaroid protective film, can form polarizer.In addition, also can be as the optical compensating film of on film, pasting optical compensating gage, at the light function system films such as antireflection film of film superimposed layer antiglare layer.Also can constitute the part of liquid crystal watch showing device from these goods.
[embodiment]
Below, embodiment describes the present invention in detail by way of example, but mode of the present invention is not limited thereto.In addition, in explanation, press embodiment 1 and describe in detail,,, omit explanation for the place identical with embodiment 1 about comparative example 1,2.
[embodiment 1]
As shown in Figure 1, be in the stainless steel dissolving tank 13 of 10000L at internal volume, fully the raw material of the rubber cement shown in the note under the dispersed with stirring adopts meter 14 simultaneously, slowly adds TAC powder (laminar), is encased in integral body and reaches 7000kg.In addition, solvent is carrene, methyl alcohol, ethanol and 1-butanols, all utilizes its moisture content below 0.2 weight %.
In embodiment 1,, adopt raw material shown in the note down as the raw material of rubber cement.
TAC particle (being viscosity 305mPas, the average grain diameter 1.5mm of 6 quality % in degree of exchange 2.83, viscometric degree of polymerization 320, moisture content 0.4 quality %, the dichloromethane solution, the powder of datum drift 0.5mm) 17 weight portions
Carrene 63 weight portions
Methyl alcohol 5 weight portions
Ethanol 5 weight portions
1-butanols 5 weight portions
Plasticizer (dipentaerythritol six acetates) 1.2 weight portions
Plasticizer (TPP) 1.2 weight portions
UV agent a:(2,4-pair-(n-octylsulfo)-6-(4-hydroxyl-3,5-two-tert-butyl benzene amido)-1,3,5-triazines 0.2 weight portion
UV agent b:2-(2 '-hydroxyl-3 ', 5 '-two-tert-butyl benzene)-5-chlorobenzotriazole
0.2 weight portion
UV agent c:2-(2 '-hydroxyl-3 ', 5 '-two-tert-aminobenzene)-5-chlorobenzotriazole
0.2 weight portion
C
12H
25OCH
2CH
2OP (=O) (OK)
20.4 weight portion
Particulate (silica (particle diameter 20nm), Mohs' hardness about 7)
0.05 weight portion
By the beginning temperature with dispersion is 20 ℃, and finally reaching temperature is that the media in the overcoats 17 are adjusted on 35 ℃ of ground, has obtained the thick solvent soln 20 of TAC swelling.Thick solvent soln 20 is sent into modulation jars 21, is utilizing pump 26 when heater 29 passes on liquid, adopt near infrared ray industrial analysis instrument (Yokogawa Motor corporate system, HR-800 type) 28, instrumentation the composition of low concentration rubber cement 30, TAC concentration is 17 weight % as a result.In addition, by heater 29 low concentration rubber cement 30 is warmed up to 80 ℃.
By the indication of thermometer 31, after the temperature of the outlet of heat exchanger 29 reaches 80 ℃, switch transfer valve 32, via filter 40, Pressure gauge 41, thermometer 42, from flash distillation nozzle 45 flash vaporization low concentration rubber cement 30 to solution condensing device 44.The flash distillation nozzle adopts by having the flash distillation nozzle 45 of 8 nozzle body 45b as Fig. 3～branching portion 45a shown in Figure 5.In addition, regulate low concentration rubber cement 30 respectively, make temperature reach 80 ℃ of (utilizing thermometer 42 to measure), pressure and reach 1.1MPa (utilizing Pressure gauge 41 to measure) by heat exchanger 29 and control valve 43.In addition, the flow set of low concentration rubber cement 30 is 100L/min, and its viscosity is 20Pas (temperature of rubber cement is made as 30 ℃, utilizes rotary viscosimeter to measure), the molten gas flow (30 ℃, measured value during 101.3kPa) of depositing that contains in the low concentration rubber cement 30 is 150mg/L.
The material of container 50 adopts SUS316L.Adopting the capacity in the container 50 is 5000L, and the heap(ed) capacity of concentrated latex 56 is 3000L (being generally 2000L), and the surface area of cryosurface 55a is the container of 9m2.By utilizing level detection sensor 65 to detect liquid level 56a on one side, on one side by controller 66a control pump 66,56a remains on certain height with liquid level.The capacity of the concentrated latex 56 of this moment is 2000L.In addition, in the 3rd overcoat 53, feed 7 ℃ cooling water.At this moment, the refrigerant inlet temperature is 7 ℃, and the refrigerant outlet temperature is 10 ℃, and refrigerant flow is 1m
3/ min.Vaporized vaporized solvent 57a in cryosurface 55a is condensate in container 50 is as condensing solvent 57b.Condensing solvent 57b, 55a flows down along cryosurface, leans on the gravity liquor charging from receiver 58 by pipe arrangement 60, by control valve 61 make flow keep stable on one side, be collected in the recycling can 63 on one side.
(gas phase absolute pressure in the device body: 1010hPa), the vibration of liquid level 56a is controlled flash vaporization in ± mode 20mm below so that force down about 1kPa by the pressure ratio atmosphere of the gas phase in the container 50 of Pressure gauge 59 instrumentations.About sending into the medium in the 2nd overcoat 52 that is installed in the flash distillation portion 54, the employing temperature is 35 ℃ a water, and the inner wall temperature that device body is met liquid portion is set in 35 ℃.The vibration of the discharge pressure during with flash vaporization in interior mode, adopts control valve 43 to regulate at ± 0.1MPa.With the flow in flowmeter 27, the 70 instrumentation rubber cement production lines 10 change, with reach ± mode below 1% adjusted conveying liquid.
As Fig. 3～shown in Figure 5, flash distillation nozzle 45 as interior pipe 46, constitutes overcoat with the pipe of 80A as outer tube 47 ground with the pipe of 50A, makes it to 8 nozzle body 45b branches.In the gap of interior pipe 46 and outer tube 47, inject air, become the air adiabatic layer.The flow that is equivalent to vaporized solvent is 0.65mol/s.In addition, the inboard benchmark overall heat-transfer coefficient of nozzle surface is 0.5W/m
2K.
Utilize near-infrared industrial analysis instrument 69 to measure the TAC concentration of the high concentration rubber cement 67 that obtains, the result is 21 weight %.In addition, the temperature of high concentration rubber cement is that 38 ℃, viscosity are 60Pas (temperature of rubber cement is set at 30 ℃, utilizes rotary viscosimeter to measure).From the extraction flow of solution condensing device 44 is 84L/min.In addition, the boiling point of this high concentration rubber cement is 40 ℃, and the molten gas flow (measuring under 30 ℃, 101.3kPa) of depositing is 20mg/L.The mean residence time of the rubber cement in the device body is 25min.Reach authorized pressure (P at filter 40
L) during 1.0MPa, filtering solid constituent amount V0 is 1500kg/m
2In addition, reach authorized pressure (P at secondary filter 71
H) during 2.0MPa, filtering solid constituent amount V1 is 1400kg/m
2The filtration yield rate of change is 7%, has measured the solids contaminant capacity in the condensing solvent, and the result is 20ppm.Mensuration is to be undertaken by the condensing solvent at 120 ℃ of 8 hours heating 100mL, has measured the weight of residue.It is no problem when the distillation of condensing solvent is refining.In addition,, the medium of chilled high concentration rubber cement is turned back to flash distillation nozzle 45, utilize cool cycles portion 74 to make the circulation cooling of its circulation by cool cycles portion 74 shown in Figure 1.Can not stop up by this circulation cooling nozzle in condensation stops.
(manufacturing of film)
Measured the length of delay (Rth) of the thickness direction of the film 91 that obtains, the result is 15nm.Learn the film that utilizes solution film-forming method of the present invention to obtain, optical characteristics excellence.In addition, the Rth of so-called thickness direction is by note formula (2) expression down.
Rth＝{(nx+ny)/2-nz}×d…………(2)
Nx in the described formula, ny, nz, the refractive index of the thickness direction of expression horizontal (width of film), vertical (stream of film is moulded direction), film is to adopt ellipsometer (polarization parsing instrument), with the value of wavelength 632.nm mensuration respectively.In addition, d represents the average thickness (nm) of film.
[comparative example 1]
Replace the flash distillation nozzle 45 among the embodiment 1, do not have the nozzle body of branching portion 45a to be 1 flash distillation nozzle of employing, and do not have the nozzle body of heat insulating construction.In addition, form the structure that does not have cool cycles portion 74.In addition, carried out flash vaporization by the condition identical with embodiment.The low concentration rubber cement is 11000mol/ (m to the flow of flash distillation nozzle
2S).Its result sneaks into the solid constituent of 2000ppm in condensing solvent, the fault of separating out of solids takes place in the distillation refining step.In addition, when the continuous running of having carried out 500 hours, the solid content of on nozzle outer surface, adhering, the solids of peeling off is sneaked in the concentrated latex 56.Its result, the filtration solid constituent amount V0 when secondary filter 71 reached authorized pressure (2.0MPa) by 500 hours is 1400kg/m
2, the filtration yield rate of change is 7%, but after 500 hours, filters solid constituent amount V0 and drop to 720kg/m
2, the filtration yield rate of change is 52%.In addition, when the running that repeats enrichment facility stops, in 10 times in the obstruction of 1 time ratio generation nozzle.
[comparative example 2]
In comparative example 2, adopt solution condensing device in the past 140 shown in Figure 8, made high concentration rubber cement 144 by flash vaporization low concentration rubber cement.The capacity of the rubber cement 144 in the container 141 is 7000L, and the area of cryosurface 141a is 12m
2, material is SUS316.By the condition identical with embodiment 1, charging feedstock in dissolving tank obtains low concentration rubber cement 147.Low concentration rubber cement 147 is 80 ℃ of temperature, pressure 1.1MPa, and flow is 2.5L/min, and viscosity is 20Pas (temperature of rubber cement is set at 30 ℃, utilizes rotary viscosimeter to measure), and the molten gas flow of depositing is 150mg/L.The TAC concentration of low concentration rubber cement 147 is 17 weight %.About overlapping 142 medium 143, the employing temperature is 35 ℃ a water, and the temperature that meets liquid portion is set at 35 ℃.In addition, after utilizing filter 152 to filter low concentration rubber cement 147, make it towards liquid level 144a flash vaporization.The absolute pressure of the gas phase in the container 141 of this moment is 1200hPa.
The TAC concentration of the high concentration rubber cement 151 that obtains is 21 weight %.In addition, the temperature of high concentration rubber cement 151 is that 38 ℃, viscosity are that 60Pas (temperature of rubber cement is set at 30 ℃, utilizes rotary viscosimeter to measure), boiling point are 40 ℃, moltenly deposit that mean residence time is 83min in the device body that gas flow is 10mg/L, rubber cement.From the extraction flow of solution condensing device 140 is 84L/min.In addition, after utilizing secondary filter 153 to filter, make film.Measured the length of delay (Rth) of the thickness direction of the film that obtains, the result is 16nm.In addition, in the running of rubber cement production line, reach authorized pressure (P at filter 152
L) during 1.0MPa, filtering solid constituent amount V0 is 1500kg/m
2In addition, reach authorized pressure (P at secondary filter 153
H) during 2.0MPa, filtering solid constituent amount V1 is 700kg/m
2The filtration yield rate of change is 53%, and a large amount of skinning take place in container 141.
[making of antireflection film and evaluation]
Adopt the film of pressing embodiment 1 system film, made antireflection film, carried out its evaluation.
(the antiglare layer modulation of coating liquid A)
In the mixed solvent of butanone/cyclohexanone=50 weight %/50 weight % of 439g; dissolved the mixture (DPHA of dipentaerythritol five acrylate and dipentaerythritol acrylate; Japan's chemical drug (strain) system) 125g, two (4-methacryl thiophenyl) sulfide (MPSMA, Sumitomo refine (strain) system) 125g.In the solution that obtains, be added in the solution that has dissolved Photoepolymerizationinitiater initiater (ィ Le ガ キ ュ ァ 907, チ バ ガ ィ ギ one society's system) 5.0g and light sensitizer (power ヤ キ ュ ァ one DETX, Japanese chemical drug (strain) system) 3.0g in the butanone of 49g.By applying this solution, the refractive index of carrying out the overlay that ultraviolet curing obtains is 1.60.In addition, in this solution, add crosslinked polystyrene particle (trade name: SX-200H, comprehensive chemistry (strain) system of the grinding) 10g of average grain diameter 2 μ m, use high speed agitator, after the 5000rpm stirring, disperseing 1 hour, polypropylene filter made device with aperture 30 μ m filters, and modulates the coating liquid A of antiglare layer.
(the antiglare layer modulation of coating liquid B)
In the mixed solvent of cyclohexanone 104.1g, butanone 61.3g, with gas blender stir on one side, dura mater coating liquid (デ ソ ラ ィ ト KZ-7886A, JSR (strain) system) 217.0g that contains zirconia and disperse thing added on one side.Refractive index by coating, the overlay that obtains of this solution of ultraviolet curing is 1.61.In addition, add crosslinked polystyrene particle (trade name: SX-200H, comprehensive chemistry (strain) system of the grinding) 5g of average grain diameter 2 μ m in this solution, using high speed agitator, after the 5000rpm stirring, disperseing 1 hour, polypropylene filter made device with aperture 30 μ m filters, and modulates the coating liquid B of antiglare layer.
(the antiglare layer modulation of coating liquid C)
Mixture (DPHA with dipentaerythritol five acrylate and dipentaerythritol acrylate, Japan's chemical drug (strain) system) 91g, contain zirconia and disperse dura mater coating liquid (デ ソ ラ ィ ト KZ-7115, JSR (strain) system) 199g of thing and contain dura mater coating liquid (デ ソ ラ ィ ト KZ-7161, JSR (strain) system) 19g that zirconia disperses thing, be dissolved in the mixed solvent of butanone/cyclohexanone=54 weight %/46 weight % of 52g.In the solution that obtains, add Photoepolymerizationinitiater initiater (ィ Le ガ キ ュ ァ 907, チ バ ガ ィ ギ one corporate system) 10g.Refractive index by coating, the overlay that obtains of this solution of ultraviolet curing is 1.61.In addition, interpolation, dispersed with stirring liquid 29g in this solution, this dispersion liquid is by in the mixed solvent of butanone/cyclohexanone=54 weight %/46 weight % of 80g, use high speed agitator, crosslinked polystyrene particle (trade name: SX-200H with 1 hour dispersed with stirring average grain diameter 2 μ m of 5000rpm, comprehensive chemistry (strain) system of grinding) 20g forms, and the polypropylene filter made device with aperture 30 μ m filters then, modulates the coating liquid C of antiglare layer.
(the hard membrane layer modulation of coating liquid D)
Added the solution that in the cyclohexanone of the butanone of 62g and 88g, is dissolved with ultra-violet solidified dura mater constituent (デ ソ ラ ィ ト KZ-7689,72 weight %, JSR (strain) system) 250g.Refractive index by coating, the overlay that obtains of this solution of ultraviolet curing is 1.53.In addition, filter this solution, modulate the coating liquid D of hard membrane layer with the polypropylene filter made device of aperture 30 μ m.
(the low-index layer modulation of coating liquid)
In heat cross-linking fluoropolymer (TN-049, JSR (strain) system) 20093g of refractive index 1.42, add, stir the MEK-ST (SiO of average grain diameter 10nm～20nm, solid component concentration 30 weight %
2The MEK of colloidal sol (butanone) disperses thing, daily output chemistry (strain) system) 8g, and butanone 100g, the polypropylene filter made device with aperture 1 μ m filters then, modulates low-index layer with coating liquid.
Pressing on the thick TAC film of 80 μ m that embodiment 1 makes, adopt excellent coater to apply described hard membrane layer with applying liquid D, after 120 ℃ of dryings, adopt the air cool metal halide lamp (ァ ィ グ ラ Off ィ ッ Network ス (strain) system) of 160W/cm, irradiation illumination 400mW/cm
2, exposure 300mJ/cm
2Ultraviolet ray, overlay is solidified, form the hard membrane layer of thick 2.5 μ m., apply above-mentioned antiglare layer with coating liquid A thereon, use the condition drying identical, carry out ultraviolet curing, form the antiglare layer of the about 1.5 μ m of thickness with above-mentioned hard membrane layer with excellent coater.In addition, apply above-mentioned low-index layer with coating liquid with excellent coater thereon, after 80 ℃ of dryings,, form the low-index layer of thick 0.096 μ m in addition 120 ℃ of heat cross-linkings 10 minutes.To the antireflection film that obtains, carried out the evaluation of the following stated.
(1) specular reflectivity and accumulative total (Plot branch) reflectivity
Go up installation adapter ARV-474 at spectrophotometer V-550 (Japanese beam split (strain) system), wavelength zone at 380nm～780nm, measure the specular reflectivity of the angle of emergence-5 ° in 5 ° of the incidence angles, calculate the average reflectance of 450nm～650nm, estimated antireflection.As long as specular reflectivity is below 5%, in the practicality with regard to no problem.In addition, the accumulative total reflectivity is by going up at spectrophotometer V-550 (Japanese beam split (strain) system) adapter ILV-471 to be installed, at the wavelength zone of 380nm～780nm, measure the accumulative total reflectivity in 5 ° of the incidence angles, calculated the average reflectance of 450nm～650nm.As long as accumulative total reflectivity below 10%, in the practicality with regard to no problem.
(2) turbidity
Adopt turbidimetry MODEL 1001DP (Japanese electric look industry (strain) system), measured the turbidity of the antireflection film that obtains.As long as turbidity is below 15%, in the practicality with regard to no problem.
(3) pencil hardness evaluation
As the index of traumatic resistance, carried out the pencil hardness evaluation of record in JIS K 5400.Behind 2 hours damping antireflection films under 25 ℃ of temperature, the humidity 60%RH, adopt the test pencil of the 3H of regulation among the JIS S 6006, under the load of 1kg, carried out in the evaluation of n=5, fully finding damage (zero), 1 or 2 damage (△) has been arranged in the evaluation of n=5, the evaluation that damages (*) these 3 stages more than 3 has been arranged in the evaluation of n=5.
(4) contact angle determination
As the index of the stain resistance on surface, behind 2 hours damping antireflection films under 25 ℃ of temperature, the humidity 60%RH, measure the contact angle with water, as the index of fingerprint tack.Contact angle is as long as in 90 °～180 ° scope, in the practicality with regard to no problem.
(5) tone
By specular light spectrum from described mensuration, calculate L* value, a* value, the b* value of expression with respect to the CIE1976L*a*b* colour space of the tone of the normal reflection light of 5 ° of incident lights of CIE reference light source D65, estimated catoptrical tone.About tone, as long as in space separately, be 0～+ 15, a* is 0～+ 20, b* is-30～0 scope at L*, in the practicality with regard to no problem.
(6) coefficient of kinetic friction is measured
Index as surface smoothness is estimated with the coefficient of kinetic friction.The coefficient of kinetic friction, adopt under 25 ℃, relative humidity 60%RH 2 hours damping antireflection films after, measure machine by the HEIDON-14 dynamic friction, the value of under the condition of φ 5mm stainless steel steel ball, load heavy 100g, speed 60cm/min, measuring.As long as the coefficient of kinetic friction is below 0.15, in the practicality with regard to no problem.
(7) anti-dazzle property evaluation
The antireflection film of making is shone upon the exposed fluorescent lamp (8000cd/m of no barrier
2), by the profile of not making fluorescent lamp fully clear (◎), a little understand fully the profile (zero), fluorescent lamp of fluorescent lamp fuzzy but can contour identification (△), the fluorescent lamp benchmark of fuzzy (*) hardly, estimated the fog-level of this reflection image.
(8) the planar evaluation of overlay
The surface of the overlay of visualization antireflection film is by overlay surface smoothing (◎), overlay surface smoothing but find that weak concavo-convex and clear view having (△), see concavo-convex on the overlay surface and this 4 stages of many places discovery impurity (*) have estimated that it is planar to impurity appears in small amount of impurities (zero), overlay surface.
Then, adopt the film of embodiment 1, antiglare layer is used instead of antiglare layer with coating liquid A apply liquid B, made the identical antireflection film of other condition.In addition, antiglare layer with applying liquid A instead of antiglare layer coating liquid C, has also been made the identical antireflection film of other condition.All antireflection films to making have all carried out described evaluation.Gather in the table 1 its result is shown.
Table 1
Draw from table 1, by the antireflection film that forms from the film that adopts the rubber cement solution film-forming that solution concentration method of the present invention obtains, anti-dazzle property, antireflection excellence, and a little less than the tone reflect that in addition the result of evaluation of film rerum naturas such as pencil hardness, fingerprint tack, the coefficient of kinetic friction is also good.
[making of polarizer and evaluation]
Polarizer is by extending polyvinyl alcohol, and the two sides of the polarizer of absorption iodine utilizes the polyethenol series adhesive film that obtains by embodiment 1 of fitting to make.This polarizer 500 hours have been exposed under 60 ℃, the atmosphere of 90%RH.
Obtain parallel transmitance Yp, the craspedodrome transmitance Yc of visible area by spectrophotometer, determined degree of polarization P based on following formula.
P＝((Yp-Yc)/(Yp+Yc)
1/2)×100(％)
All polarizers that adopt the film formation of making from embodiment 1, degree of polarization has been found sufficient durability all more than 99.6%.Thereby draw, from adopting the film of the rubber cement solution film-forming that solution concentration method of the present invention obtains, be preferred for polaroid protective film (polarizer protection film), the optical characteristics excellence of the polarizer of making.
Then, adopt the film of pressing embodiment 1 system film, made anti-dazzle sexual reflex and prevented polarizer.When adopting this polarizer to make antireflection layer is configured in the liquid crystal indicator on top layer, owing to there be not mirroring of outer light, thus excellent contrast can be obtained, because anti-dazzle property and reflection image is not eye-catching, have excellent visual identity, fingerprint appearance (is Zhied Pattern and is paid) also good.Thereby draw, utilize the film of solution concentration method system film of the present invention, have excellent character as the optical functional film, preferably the part as liquid crystal indicator adopts this film.
Claims (12)
1. solution condensing device, in the container that constitutes by flash distillation portion and condensation part, delivered solution from the outlet of the nozzle solution in described flash distillation portion, utilize the solvent of flash method by the condensation of described condensation part from vaporizer, separate the liquid that takes out this condensation and utilize the concentrated solution of described flash method from described container, described solution condensing device is characterised in that
The quantity of solvent from the final gasification of described solution of the outlet of per 1 described nozzle is set in below the amount X that is stipulated by following mathematical expression (1),
X＝1.5×(to/tb)×(Pb/Po)mol/s............(1)
Wherein, to:273, tb: the boiling point of solution, the unit of to and tb is K,
Po:1.01 * 10
5Pa, Pb: press Pa in the container,
Described condensation part has receiver, will be from the gas-liquid interface position of described solution when the height gage of described receiver is decided to be H, the relation of described quantity of solvent X and height H is set at:
When X＜0.3mol/s, for 0.1m≤H≤2.0m,
When 0.3mol/s≤X≤0.6mol/s, for 0.5m≤H≤2m,
When 0.6mol/s＜X, be 1.0m≤H≤2.0m.
2. solution condensing device as claimed in claim 1 is characterized in that, will be set in 10mol/ (m from the flow velocity of the solution of described jet expansion
2S) above, 2000mol/ (m
2S) below.
3. solution condensing device as claimed in claim 1 or 2 is characterized in that, when the area with the gas-liquid interface of described solution is set at S, the relation of described quantity of solvent X and area S is set at:
When X＜0.3mol/s, be 0.008m
2≤ S≤7.0m
2,
When 0.3mol/s≤X≤0.6mol/s, be 0.7m
2≤ S≤7.0m
2,
When 0.6mol/s＜X, be 1.7m
2≤ S≤7.0m
2
4. solution condensing device as claimed in claim 1 or 2 is characterized in that, possesses a plurality of described jet expansions, and spacing is set in more than the 100mm between the open centre of these a plurality of outlets.
5. solution condensing device as claimed in claim 1 or 2 is characterized in that described nozzle possesses pressure-regulating valve outside described container, detects in the nozzle from described pressure-regulating valve to described outlet and presses.
6. solution condensing device as claimed in claim 1 or 2 is characterized in that, the contact-making surface temperature of solution is set in boiling point+2 ℃ that are lower than solution in described nozzle and the container.
7. solution condensing device as claimed in claim 6 is characterized in that described nozzle has heat insulating member at outer surface.
8. solution condensing device as claimed in claim 7 is characterized in that, the inboard benchmark overall heat-transfer coefficient of the nozzle tube wall that described heat insulating member forms is set in 1.0W/m
2Below.
9. as claim 7 or 8 described solution condensing devices, it is characterized in that, described heat insulating member is made of heat insulation layer, described heat insulation layer has the double-sleeve structure that is made of interior pipe and outer tube, the gap of pipe and outer tube is set in the above 30mm of 5mm in described, to the described outlet, in the gap of interior pipe and outer tube, only enclosing has air or argon gas in the part that connects container from described nozzle.
10. solution condensing device as claimed in claim 1 or 2, it is characterized in that, possesses cool cycles portion, this cool cycles portion is made of the cooling end that is used for making the solution that concentrates at described container to turn back to the circulation road of described nozzle and to cool off the solution in this circulation road, described cool cycles portion moves when nozzle is carried liquid stopping, and solvent gas and the solution that is trapped in the described nozzle is replaced as the solution that is cooled.
11. solution concentration method, in the container that constitutes by flash distillation portion and condensation part, delivered solution from the outlet of the nozzle solution in described flash distillation portion, utilize the solvent of flash method by the condensation of described condensation part from vaporizer, separate the liquid that takes out this condensation and utilize the concentrated solution of described flash method from described container, described solution concentration method is characterised in that
The quantity of solvent from the final gasification of described solution of the outlet of per 1 described nozzle is set in below the amount X that is stipulated by following mathematical expression (1),
X＝1.5×(to/tb)×(Pb/Po)(mol/s)............(1)
Wherein, to:273, tb: the unit of the boiling point of solution, to and tb is K,
Po:1.01 * 10
5Pa, Pb: press Pa in the container.
12. solution concentration method as claimed in claim 11 is characterized in that, will be set in 10mol/ (m from the flow velocity of the solution of described jet expansion
2S) above, 2000mol/ (m
2S) below.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006098549 | 2006-03-31 | ||
| JP2006098549A JP2007268452A (en) | 2006-03-31 | 2006-03-31 | Solution concentration device and method |
| JP2006-098549 | 2006-03-31 |
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|---|---|
| CN101069780A CN101069780A (en) | 2007-11-14 |
| CN101069780B true CN101069780B (en) | 2010-11-10 |
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| JP2009119346A (en) * | 2007-11-13 | 2009-06-04 | Mitsui Chemicals Polyurethanes Inc | Flash tank, depressurizing device, and polyisocyanate manufacturing apparatus |
| CN102553279B (en) * | 2012-01-16 | 2014-03-26 | 哈尔滨工程大学 | High pressure flash drum |
| CN115140710B (en) * | 2022-05-21 | 2023-12-29 | 山东东鑫金属材料有限公司 | Concentrated regeneration facility of hydrochloric acid |
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