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CN104950050A - Recovered solvent analytical approach and unit, solvent recovery and preparation method, and solution film making method - Google Patents

Recovered solvent analytical approach and unit, solvent recovery and preparation method, and solution film making method Download PDF

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Publication number
CN104950050A
CN104950050A CN201510145679.8A CN201510145679A CN104950050A CN 104950050 A CN104950050 A CN 104950050A CN 201510145679 A CN201510145679 A CN 201510145679A CN 104950050 A CN104950050 A CN 104950050A
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solvent
solvent composition
distillation
recycling design
composition
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CN104950050B (en
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杉山茂久
水岛康博
岸野伸哉
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Fujifilm Corp
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Fujifilm Corp
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • 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
    • B29C41/02—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 definite length, i.e. discrete articles
    • B29C41/12—Spreading-out the material on a substrate, e.g. on the surface of a liquid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/12—Preparation by evaporation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/86—Signal analysis
    • G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Library & Information Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Sampling And Sample Adjustment (AREA)
  • Moulding By Coating Moulds (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

The invention provides a recovered solvent analytical approach and unit, a solvent recovery and preparation method and a solution film making method. The analytical unit (10) obtains a quality ratio of a solvent component in a mixture of a recovered liquid, i.e., a recovered solvent. The analytical unit (10) has a thermostatic chamber (13), a measurer (14), a vaporizing chamber (16), a separation unit (17), a detector (18) and a ratio calculation unit (19b). The measurer (14) samples a sample vaporized in the vaporizing chamber (16) from the recovered solvent. The thermostatic chamber (13) enables temperature of the recovered solvent measured by the measurer (14) to rise through heating so as to adjust to a specific temperature. According to the recovered solvent analytical method provided by the invention, for the recovered solvent, an error can be inhibited and the quality ratio of the solvent component is obtained.

Description

Recycling design analytic approach and unit, solvent recovery preparation method and solution film-forming method
Technical field
The present invention relates to a kind of recycling design analytical approach and unit, solvent recovery preparation method and solution film-forming method.
Background technology
Stacked multiple thin polymer film on the panel of the display device such as liquid crystal display and using.Such as, use Polarizer in a liquid crystal display, Polarizer is made up of the diaphragm of light polarizing film with the two sides being configured at light polarizing film.Sometimes optical compensation films is used as diaphragm.Representative film as diaphragm and optical compensation films has the TAC film using Triafol T (hereinafter referred to as TAC) as component of polymer, and having as light polarizing film with polyvinyl alcohol (PVA) (hereinafter referred to as PVA) and modified PVA is the PVA film of component of polymer.
TAC film is manufactured by solution film-forming method, and in this solution film-forming method, the TAC solution making TAC be dissolved in solvent is delayed at supporting mass upper reaches and peeled and carry out drying.Further, according to as object quality and purposes etc., such as, select the curtain coating modes such as individual layer curtain coating, altogether curtain coating, manufacture the TAC film of single layer structure or sandwich construction thus.Further, consider the dissolubility of TAC and all many condition etc. of film-forming process, the solvent of TAC solution is set to the potpourri of the compound be mixed with as multiple solvent composition, as an example, has the potpourri of methylene chloride and methyl alcohol.Altogether during curtain coating, use multiple TAC solution.As multiple TAC solution, such as, can enumerate the solution that the quality ratio of the solvent composition in potpourri and solvent is different mutually.
Along with the raising of panel quality, also require to improve quality to laminated members such as the various thin polymer films such as TAC film and the stacked Polarizers of thin polymer film.Such as, Polarizer is required to improve the adhesion between TAC film and light polarizing film, not easily peels to make them.For the raising of this adhesion, known to manufacturing TAC film by solution film-forming method, be total to curtain coating by making multiple TAC solution and improve.Specifically, by common curtain coating, the top layer forming the pellicular front adhered to light polarizing film is formed in main film body.For the formation of the 1TAC solution of main film body be set to the potpourri containing methylene chloride for the formation of each solvent of the 2TAC solution on top layer.Further, the solvent for making 2TAC solution is set to the quality ratio of methylene chloride higher than the solvent for making 1TAC solution.Improve former adhesive power thus.Further, now, each solvent of 1TAC solution and 2TAC solution can independently make, but it can be used as benchmark solvent after the solvent of preferred preparation 1TAC solution, adds methylene chloride and prepare the solvent of 2TAC solution in this benchmark solvent.This is because have this great advantages of benchmark solvent guaranteeing jointly to use to manufacture the different multiple film of proterties.
When manufacturing thin polymer film by solution film-forming method, solvent is recovered and recycles.When recycling, solvent is manufacturing the film forming apparatus of film and is circulating for the preparation of reclaiming rear manufacture in the recovery preparation facilities of the solvent of new dope (dope) from film forming apparatus.In dry run in film forming apparatus, solvent evaporation and become gas, by reclaiming this gas and condensation and become liquid.Therefore, when the solvent used in the manufacture of film only has benchmark solvent, the quality ratio of the solvent composition in the recycling design be recovered is roughly the same with the quality ratio of the solvent composition in benchmark solvent.But, when the film manufactured by changing, exist to change into from the situation used solvent being only set to benchmark solvent and be set to this situation etc. of two kinds of the benchmark solvent solvent different from benchmark solvent with the quality ratio of solvent composition.In this case, the quality ratio change of the solvent composition in recycling design, and the quality ratio of the solvent composition in recycling design becomes different from the quality ratio of the solvent composition in benchmark solvent.Such as solution film-forming operation to be changed into the situation of the situation of use 1TAC solution and 2TAC solution manufacture film from the situation only using aforementioned 1TAC solution to manufacture film.So, when the quality ratio change of solvent composition, or recycle this quality ratio recycling design different from benchmark solvent when preparing benchmark solvent, in qualitative control, require the quality ratio of the solvent composition confirmed before use in benchmark solvent.Further, the proterties of this benchmark solvent on many films brings impact, and therefore about quality, the especially mass ratio of solvent composition, must manage with strict benchmark.
But, as the method for the refining of liquid and preparation, qualitative control, use gas chromatograph (GC, Gas Chromatography), and the on-line gas chromatography carrying out online analyzing also is popularized all the time.Such as, described in Japanese Patent Publication 06-166640 publication, Japanese Patent Publication 07-178301 publication, propose in the distillation of benzene and the distillation of the potpourri of liquid that is made up of multiple composition, use on-line gas chromatography to carry out the method for the analysis of benzene and potpourri.And, described in Japanese Patent Publication 2005-199188 publication, Japanese Patent Publication 2007-196171 publication, proposing the distillation column be provided with as the on-line gas chromatography of remote operated analytical equipment can be carried out, also proposed the method using coalescer in order to reduce error.
But, even if obtain the quality ratio of solvent composition to benchmark solvent, also there is the situation that quality is inconsistent.This is because the quality ratio time error recycling design recycled to prepare benchmark solvent being obtained to solvent composition is larger.Even if use the method described in Japanese Patent Publication 2007-196171 publication, consider from this viewpoint of the qualitative control of benchmark solvent that the error of this recycling design or excessive causes the permissible range exceeded in qualitative control.
Summary of the invention
Therefore, the object of the present invention is to provide and a kind ofly suppress error to obtain recycling design analytical approach and unit, solvent recovery preparation method and the solution film-forming method of the quality ratio of solvent composition for potpourri and recycling design.
Recycling design analytical approach of the present invention possesses temperature adjustment step (step A), sampling step (step B), gasification step (step C), separating step (D step), detecting step (E step) and ratio calculation procedure (F step).In step A, make the potpourri as liquid by heating and the recycling design that reclaims heats up and is adjusted to specified temp.In step B, to maintain the state of above-mentioned specified temp, specified quantitative of sampling from recycling design.In step C, made the sample gasification of sampling in step B by heating.In D step, the sample separation of gasification is become each solvent composition.Sample is directed to chromatographic column and utilizes carrier gas to pass through in the chromatography column and separated.Chromatographic column possesses Stationary liquid.Carrier gas is mobile phase.In E step, detect the amount of the solvent composition be separated respectively.In F step, according to each amount detected, calculate the quality ratio of solvent composition.
When the boiling point of recycling design is set to TL DEG C, preferred aforementioned specified temp is more than (TL-30) DEG C and be less than in the scope of TL DEG C.
When repeatedly calculating the quality ratio of solvent composition, preferably repeatedly carry out this series of operation of step A, step B, step C, D step, E step and F step, and aforementioned specified temp in each step A is identical.
In step A, preferably make recycling design by the pipe of constant temperature enclosure, thus recycling design is adjusted to specified temp, described constant temperature enclosure possesses: pipe, guides recycling design; Chamber, the space and space outerpace that surround pipe also separate by containing pipe; And temperature control device, control the internal temperature of chamber.
Recycling design analytic unit of the present invention possesses thermoregulation mechanism, sampling unit, gasification mechanism, chromatographic column, detecting device and ratio calculating part.Thermoregulation mechanism is adjusted to specified temp by heating the recycling design reclaimed by the potpourri as liquid.Sampling unit is sampled specified quantitative from recycling design.Sampling unit, while the temperature of the recycling design guided from governor motion is maintained above-mentioned specified temp, is sampled.Gasification mechanism makes the sample of sampling gasify by heating.Chromatographic column is provided with Stationary liquid in inside and carrier gas is directed in this chromatographic column.The sample of gasification is directed in Stationary liquid.Carrier gas is for making sample by the mobile phase of Stationary liquid.Detecting device detects the amount of the solvent composition be separated in the chromatography column respectively.Ratio calculating part, according to each amount detected by test section, calculates the quality ratio of solvent composition.
Solvent recovery preparation method of the present invention possesses recycling step (G step), the 1st distilation steps (H step), temperature adjustment step (I step), sampling step (J step), gasification step (K step), separating step (L step), detecting step (M step), ratio calculation procedure (N step), the 2nd distilation steps (O step), the 1st solvent preparation process (P step) and the 2nd solvent preparation process (Q step).In G step, be made the recycling design of liquid by the solvent evaporated in solution film-forming is reclaimed also condensation with the state of gas.Solution film-forming manufactures film by the polymer solution being dissolved with polymkeric substance in a solvent.Aforementioned solvents is the potpourri of the 1st solvent composition and the 2nd solvent composition.In H step, remove impurity by distillating recovering solvent, thus the potpourri being made the 1st solvent composition and the 2nd solvent composition i.e. solvent distillation.In I step, by heating make solvent distillation be divided into the 1st solvent distillation, the 2nd solvent distillation and the 3rd solvent distillation the wherein the described 1st solvent distillation heat up and be adjusted to specified temp.In J step, to maintain the state of aforementioned specified temp, specified quantitative of sampling from the 1st solvent distillation.In K step, made the sample gasification of sampling in J step by heating.In L step, the sample separation gasified is become the 1st solvent composition and the 2nd solvent composition in K step.Sample is directed to chromatographic column and utilizes carrier gas to pass through in the chromatography column and separated.Chromatographic column possesses Stationary liquid.Carrier gas is mobile phase.In M step, detect each amount of the 1st solvent composition and the 2nd solvent composition be separated in L step.In N step, according to each amount detected in M step, calculate the quality ratio of the 1st solvent composition and the 2nd solvent composition.In O step, by the 2nd solvent distillation by distillation be separated into the 1st solvent composition and the 2nd solvent composition.In P step, by the obtain in O step the 1st solvent composition and the 2nd solvent composition are joined the 3rd in solvent distillation for the preparation of the 1st novel solvent of the solution film-forming after being supplied to.According to the aforementioned quality ratio calculated in N step, determine to join each addition of the 3rd the 1st solvent composition in solvent distillation and the 2nd solvent composition.In Q step, prepare 2nd novel solvent of quality ratio higher than the 1st novel solvent of the 1st solvent composition.2nd novel solvent is prepared by being added in the 1st solvent composition that obtains in O step in a part of point to get from the 1st novel solvent.
When solution film-forming manufactures the film of sandwich construction by the 1st polymer solution being dissolved with polymkeric substance in the 1st solvent and the 2nd polymer solution that is dissolved with polymkeric substance in the quality ratio of the 1st solvent composition is higher than the 2nd solvent of the 1st solvent, above-mentioned solvent recovery preparation method is especially effective.
Solution film-forming method of the present invention possesses casting step (R step), drying steps (S step), recycling step (T step), H step, I step, J step, K step, L step, M step, N step, O step, the 1st solvent preparation process (U step), Q step and polymer solution preparation process (V step).In R step, out form casting films by making the curtain coating supporting mass continuous stream of polymer solution from curtain coating mould to movement.Polymer solution is formed in solvent by dissolution of polymer.Solvent is the potpourri of the 1st solvent composition and the 2nd solvent composition.In S step, be made film by peeling casting films continuously from curtain coating supporting mass and carrying out drying.In T step, be made the recycling design of liquid by the solvent evaporated in R step and S step is reclaimed also condensation with the state of gas.In U step, prepare the 1st novel solvent in solvent distillation by the obtain in O step the 1st solvent composition and the 2nd solvent composition being joined the 3rd.According to the aforementioned quality ratio calculated in N step, determine to join each addition of the 3rd the 1st solvent composition in solvent distillation and the 2nd solvent composition.In V step, the 1st novel polymer solution of the R step after preparation is supplied to and the 2nd novel polymer solution.1st novel polymer solution dissolves novel polymer and prepares in the 1st novel solvent.2nd novel polymer solution dissolves novel polymer and prepares in the 2nd novel solvent.1st novel polymer solution and the 2nd novel polymer solution flow out continuously from curtain coating mould.
According to the present invention, for potpourri and recycling design, error can be suppressed to obtain the quality ratio of solvent composition.
Accompanying drawing explanation
Fig. 1 is the skeleton diagram implementing recycling design analytic unit of the present invention.
Fig. 2 is the cut-open view of the film obtained by implementing the present invention.
Fig. 3 is the cut-open view of Polarizer.
Fig. 4 is the skeleton diagram of solution film-forming equipment.
Fig. 5 is the skeleton diagram of solvent recovery preparation facilities.
Embodiment
As shown in Figure 1, recycling design analytic unit (hereinafter referred to as analytic unit) 10 is for analyzing the recycling design reclaimed from solution film-forming device 62 (with reference to figure 4) described later.Specifically, analytic unit 10 for obtaining the quality ratio of the multiple solvent compositions comprised in the recycling design of potpourri and liquid online, and for differentiating the compound as solvent composition respectively according to the quality ratio of solvent composition.In the present embodiment, the recycling design reclaimed from solution film-forming device 62 (with reference to figure 4) is not be all supplied to analytic unit 10, but such as a point part of getting from recycling design is supplied to analytic unit 10 as aftermentioned.Detailed content about solution film-forming device is aftermentioned by utilizing another accompanying drawing to carry out.Further, in the present embodiment, in solution film-forming device 62, use methylene chloride and methyl alcohol as the solvent composition of the 1st solvent 68 and the 2nd solvent 69 (with reference to figure 4), the solvent composition therefore in recycling design is methylene chloride and methyl alcohol.But each solvent composition of the 1st solvent 68 and the 2nd solvent 69 is not limited thereto, the 1st solvent 68 and the 2nd solvent 69 also can be made up of the solvent composition of more than 3 kinds.Such as, the 1st solvent 68, the 2nd solvent 69 can be the 3 composition systems be made up of methylene chloride, methyl alcohol and n-butyl alcohol or the 4 composition systems etc. be made up of methylene chloride, methyl alcohol, n-butyl alcohol and a small amount of water respectively.
Analytic unit 10 possesses the quantitative portion 15, vaporizer 16, separation unit 17, the detecting device 18 that are made up of constant temperature enclosure 13 and measuring appliance 14 and forms arithmetical unit 19.The structure be made up of vaporizer 16, separation unit 17, detecting device 18 and the discriminating portion 19a described later that forms arithmetical unit 19 is identical with so-called on-line gas chromatography.Quantitative portion 15 is for from guiding in the recycling design of coming the specified quantitative of sampling and supplying to vaporizer 16 as sample.
Constant temperature enclosure 13 for being adjusted to the thermoregulation mechanism of specified temp for making recycling design heat up, and possesses pipe 26, chamber 27 and the 1st temperature control device 28.In order to suppress evaporation, recycling design is preferably to suppress to be directed to constant temperature enclosure 13 in the state of lower temperature as far as possible.In the present embodiment, to suppress the state of the lower temperature of less than 40 DEG C scopes more than 0 DEG C, recycling design is guided to constant temperature enclosure 13.Each end of pipe 26 is configured at the opening being arranged on chamber 27, and one end is set to the entrance of supply recycling design, and the other end is set to the outlet that recycling design flows out.This outlet is connected with measuring appliance 14.Chamber 27 holds the pipe 26 guiding recycling design, and is separated in the space around pipe 26 and space outerpace.1st temperature control device 28 controls inner temperature by heating the inside of chamber 27, makes to be heated up by the recycling design in pipe 26 and be adjusted to than being directed to pipe 26 specified temp (temperature adjustment operation) higher before by this control.Wherein, this specified temp is set to the temperature of the gasification that can suppress recycling design.Pressing mechanism (not shown) is provided with in pipe 26, but also without the need to this pressing mechanism must be arranged.Pressurize in the inside of pressing mechanism to pipe 26, recycling design is directed in pipe 26 with pressurized state thus.So, under the state of pressurizeing to recycling design in pipe 26, aforementioned specified temp is set as the temperature suppressing under pressurised conditions to gasify.
The material of pipe 26 is set to as stainless SUS316.But, be not limited to SUS316, as long as under aforementioned specified temp can not because of the contact with recycling design deterioration and the material that recycling design can not be made rotten.In addition, the heat transfer coefficient of material is higher, more can shorten the length of pipe 26, and can recycling design be made at short notice to become specified temp, therefore preferably.The length of pipe 26 in chamber 27 is set to 35m.But, be not limited to 35m, carry out changing according to the wall thickness of material, pipe 26 and diameter and aforementioned specified temp.
Chamber 27 can be replaced or together use such as tank etc. with chamber 27.When being set to tank, configure pipe 26 lodging in the water in tank, the recycling design passed through in pipe 26 water via adjusted temperature heats and is adjusted to the specified temp in the scope suppressing gasification.
Measuring appliance 14 as sampling unit also therefrom samples (sampling operation) to guiding the recycling design of coming to carry out measurement from constant temperature enclosure 13.In sampling, as aftermentioned measurement is supplied to the specified quantitative of vaporizer.In the present embodiment, measured amount is located at 0.33 ~ 1 microlitre (0.33 × 10 -9m 3~ 1 × 10 -9m 3) scope in, the volume of the such as measuring tube that this amount is entered by measured sample determines, is therefore not limited to the amount of above-mentioned scope.1st temperature control device 28 is not only connected with chamber 27, is also connected with measuring appliance 14, and measured recycling design is maintained the specified temp regulated in constant temperature enclosure 13.That is, the temperature of the recycling design in measuring appliance 14 is maintained the temperature reached by the intensification in constant temperature enclosure 13 by the 1st temperature control device 28.
Vaporizer 16 guides the gasification process of the sample gasification of coming for making to measure in measuring appliance 14 by heating.Be configured with accommodation section (not shown) in the inside of vaporizer 16, vaporizer 16 has heating arrangements (not shown).Accommodation section is formed as tubulose, and the sample from measuring appliance 14 is passed through.Heating arrangements heats vaporizer 16 inside, becomes more than the temperature of sample gasification to make the temperature of accommodation section.In the present embodiment, in order to accommodation section is heated to 85 DEG C and vaporizer 16 inside is heated to more than 85 DEG C.
As present embodiment, preferred vaporizer 16 possesses aforementioned accommodation section and heating arrangements, and analytic unit 10 possesses the 2nd temperature control device the 31,2nd temperature control device 31 controls vaporizer 16 heating arrangements in order to the temperature controlled in vaporizer 16.The temperature of vaporizer 16 inside remains constant by the heating arrangements controlling vaporizer 16 by the 2nd temperature control device 31.In the present embodiment, the temperature in vaporizer 16 is remained constant 85 DEG C, but is not limited to this temperature.In addition, under the electronic equipment that analytic unit 10 possesses preferably all is placed in stationary temperature environment, this temperature is preferably constant in the scope of less than 20 DEG C more than 10 DEG C.This temperature controls to utilize such as air-conditioning equipment (not shown) etc. to carry out.
The separation circuit of solvent composition contained by separation unit 17 becomes for the sample separation of the state by potpourri and gas, and possess chromatographic column 32, constant temperature enclosure 33 and carrier gas supply unit 34.When containing the material be not contained in the 1st solvent 68 and the 2nd solvent 69 (with reference to figure 4) in recycling design, this material is also separated.Chromatographic column 32 such as the aftermentioned carrier gas 35 utilizing supply to come makes sample pass through and is separated into each solvent composition, and is made up of gc column tube 32a and Stationary liquid 32b.Chromatographic column 32 is the inwall coating Stationary liquid 32b at gc column tube 32a and the so-called capillary column that formed.The material of gc column tube 32a is set to SUS.Stationary liquid 32b keeps in order to each compound such as the 1st solvent composition, the 2nd solvent composition comprised in sample separation.Carrier gas supply unit 34 supplies the carrier gas 35 as mobile phase using constant flow to chromatographic column 32.Carrier gas 35 is selected according to the kind of the compounds such as the solvent composition be separated and Stationary liquid.Such as, helium (He), nitrogen (N can be used 2), hydrogen (H 2) etc., use H in the present embodiment 2.
Aforementioned 2nd temperature control device 31 is not only connected with the heating arrangements of vaporizer 16, is also connected with constant temperature enclosure 33.2nd temperature control device 31 remains constant by the temperature of namely inside of constant temperature enclosure 33 being surrounded the atmosphere of chromatographic column 32, with this via gc column tube 32a control Stationary liquid 32b and the temperature of sample passed through in chromatographic column 32.
The material of gc column tube 32a can be set to glass to replace SUS.Stationary liquid 32b per sample in the kind of the solvent composition that comprises and impurity select.As mentioned above, the chromatographic column 32 of present embodiment is capillary column, but also can replace this, for being filled with the so-called packed column of Stationary liquid in chromatogram column casing.From the viewpoint of the separation progression of per unit length, be preferably capillary column.In addition, only illustrate a chromatographic column 32 and detecting device 18 respectively in FIG, but also can use multiple chromatographic columns 32 and multiple detecting device 18 that Stationary liquid 32b is mutually different, in the present embodiment, also respectively chromatographic column 32 and detecting device 18 are set to multiple.
Detecting device 18 is for detecting the detection operation of the amount of the solvent composition be separated in chromatographic column 32.Detecting device 18 possesses to guide each solvent composition of sequence detection the sensor (not shown) of output detections signal of coming from chromatographic column 32.The signal level of detection signal is corresponding with the amount of the time per unit guiding the solvent composition of coming, and namely the amount of time per unit is more many more raises.Detecting device 18 is by each solvent composition detected by sensor, and the peak area obtained according to carrying out integration to detection signal obtains the amount of solvent composition respectively.The amount of detection signal and calculated each solvent composition is delivered to composition arithmetical unit 19 by detecting device 18.
Composition arithmetical unit 19 possesses discriminating portion 19a and ratio calculating part 19b.Discriminating portion 19a is for differentiating each solvent composition be separated.This discriminating portion 19a is by each solvent composition detected by detecting device 18, measure from sample, import to the retention time of chromatographic column 32 till detection signal demonstrates peak value (Retention Time, retention time), and carry out the discriminating of the compound as solvent composition detected according to retention time.When carrying out this discriminating, such as with respectively the benchmark retention time that differentiated each solvent composition determines intrinsic retention time in advance being compared, determining the solvent composition corresponding with retention time thus.Ratio calculating part 19b calculates the quality ratio (ratio calculation process) of the solvent composition detected according to the amount of each solvent composition obtained by detecting device 18.
In the present embodiment, quality detects as aforementioned quantities by detecting device 18, but also can use the detecting device detected as amount by volume.Now, according to the volume detected, such as, obtain quality by ratio calculating part 19b and carry out calculated mass ratio.When obtaining quality according to volume, according to the kind of the compound as solvent composition differentiated in discriminating portion 19a, such as, obtain quality by the temperature and pressure etc. when being detected by detecting device 18.And, this analytic unit 10 is used in solvent recovery preparation facilities 63 (with reference to figure 5) described later, if the preparing arithmetical unit 112 (with reference to figure 5) and quality can be obtained according to volume of this solvent recovery preparation facilities 63, then can use the detecting device 18 detected as amount by volume, and use the ratio calculating part 19b obtaining volume ratio.
If the solvent composition comprised in known recycling design in advance and the order being directed to the solvent composition detecting device 18 from chromatographic column 32, then do not need discriminating portion 19a, be therefore set to ratio calculating part 19b and replace forming arithmetical unit 19.
The effect of said structure is described.Recycling design is directed in constant temperature enclosure 13, measuring appliance 14, vaporizer 16, separation unit 17 and detecting device 18 successively.Recycling design is directed in the pipe 26 of the constant temperature enclosure 13 being arranged at quantitative portion 15, and flows through the inside of pipe 26 towards measuring appliance 14.Recycling design in pipe 26 is pressurized by aforementioned pressing mechanism, in the present embodiment, is forced into 0.3MPa [gauge].In addition, as this force value, have the mark of " [gauge] " to represent from absolute pressure at end mark and deduct atmospheric gauge pressure.Pipe 26 is contained in chamber 27, and the 1st temperature control device 28 carries out temperature control by carrying out heating to the inside of chamber 27.Therefore, the temperature variation caused by the temperature of chamber 27 outside of pipe 26 is inhibited, and during passing through this pipe 26, the temperature of recycling design becomes specified temp.Further, even if the temperature being supplied to the recycling design of constant temperature enclosure 13 changes, recycling design also can become specified temp by the heating in constant temperature enclosure 13.So, by the 1st temperature control device 28, via chamber 27 and pipe 26, the temperature of recycling design is adjusted to specified temp.Such as, by the temperature of chamber 27 inside is adjusted to 50 DEG C, recycling design is adjusted to 50 DEG C.Regulated by this temperature, compared with not implementing temperature and regulate the situation of operation, the error of the amount of sampling in the sampling operation of rear operation can be suppressed for less, the counting accuracy of the quality ratio of solvent composition is improved.Further, even if repeatedly carry out multiple repairing weld also can suppress error, thus certain amount of can sampling exactly.
At this, the boiling point of recycling design is set to TL (unit: DEG C).Further, when making it heat up heating recycling design, will not occur the temperature of the upper limit of gas phase, the temperature (being called that liquid phase keeps ceiling temperature) of the upper limit that namely recycling design is only kept by liquid phase is set to TV (unit: DEG C).Liquid phase keeps ceiling temperature TV usually above (TL-30) DEG C and lower than TL.Aforementioned specified temp in constant temperature enclosure 13 is preferably located at more than (TL-30) DEG C and is less than in the scope of TL DEG C, is more preferably less than TV DEG C.This is based on only namely keeping the viewpoint that just can be set to higher temperature in the scope of liquid condition in the scope suppressing gasification.By aforementioned specified temp is located at this scope, can the error of the amount of sampling in the sampling operation of rear operation be suppressed for less, and, because sample all more quickly and reliably becomes gas in vaporizer 16, therefore the counting accuracy of the quality ratio of solvent composition is further enhanced.With regard to aforementioned specified temp during pressurized state, the boiling point under this pressure is obtained as above-mentioned TL, and keep ceiling temperature to obtain as above-mentioned TV the liquid phase under this pressure.Boiling point TL and liquid phase keep ceiling temperature TV such as to make it heat up by heating the recycling design as liquid before the aforementioned specified temp of setting obtaining.In the present embodiment, sample separately from recycling design, and sampled sample is heated and makes it heat up, obtain boiling point TL and liquid phase maintenance ceiling temperature TV thus.
When the multiple solvent compositions comprised in recycling design are azeotropic material, azeotropic point is set to above-mentioned TL, when not being azeotropic material, the boiling point of solvent composition lower for boiling point is set to above-mentioned TL.Methylene chloride in the recycling design of present embodiment and methyl alcohol are azeotropic material, and its azeotropic point is 79.6 DEG C under 0.3MPa [gauge], is set to TL.And, by aforementioned specified temp being adjusted to more than (TL-30) DEG C and the steady temperature be less than in the scope of TL, be less than (TL-30) DEG C and compared with each situation of the temperature of more than TL, the counting accuracy confirming the quality ratio of solvent composition is further enhanced with being set to.Specifically, under confirming each situation being adjusted to 49.6 DEG C, 65 DEG C, 79.5 DEG C under 0.3MPa [gauge], compare with each situation being adjusted to 79.6 DEG C with the situation lower than 49.6 DEG C, the counting accuracy of the quality ratio of solvent composition is reliably improved, and with do not implement compared with thermoregulator situation, the counting accuracy of the quality ratio of solvent composition is improved more reliably.
The liquid phase of the recycling design in present embodiment keeps ceiling temperature TV to be 65 DEG C under 0.3MPa [gauge], aforementioned specified temp is adjusted under 0.3MPa [gauge] stationary temperature in more than 50 DEG C less than 65 DEG C scopes.Thus, confirm compared with not implementing temperature and regulate the situation of operation, the counting accuracy of the quality ratio of solvent composition is largely increased.Specifically, confirm and under 0.3MPa [gauge], to be adjusted to (TV-15) DEG C namely 50 DEG C, 58 DEG C, TV DEG C namely in each situation of 65 DEG C, with do not carry out compared with thermoregulator situation, the counting accuracy of the quality ratio of solvent composition is increased to about 5 times.
The recycling design being adjusted to specified temp is directed to measuring appliance 14 from constant temperature enclosure 13, the specified quantitative of sampling as sample for being supplied to vaporizer 16.The recycling design be directed in measuring appliance 14 becomes specified temp in advance in constant temperature enclosure 13, measures with the state maintaining this temperature, and error therefore can be suppressed to measure exactly, thus specified quantitative of can sampling exactly.Further, even if repeatedly carry out multiple repairing weld, also error can be suppressed, thus certain amount of can sampling exactly.
Sample is all vaporized by heating by vaporizer 16.The sample be directed in vaporizer 16 is adjusted to specified temp by quantitative portion 15 in advance, therefore easily sets the temperature conditions in vaporizer 16, becomes gas by the heating arrangements of vaporizer 16 with specific gasification rate.
By the 2nd temperature control device 31, the temperature in vaporizer 16 remains stationary temperature, and therefore the gasification rate of sample is constant, and therefore detecting device 18 detects the amount of each solvent composition more accurately.
In vaporizer 16, the sample of gasification is directed in chromatographic column 32 with the state of gas, utilizes carrier gas 35 to pass through in chromatographic column 32 inside.Sample, by chromatographic mechanism, is vacillated dynamic downwards with the state being held in Stationary liquid 32b in gc column tube 32a, while be separated into each solvent composition.These each solvent compositions sequentially flow out from chromatographic column 32 faster with translational speed and are sent to detecting device 18.
Start to detect by detecting device 18, the detection signal changed corresponding to the amount of the time per unit of solvent composition is sent to composition arithmetical unit 19.Further, carry out integration by detecting device 18 pairs of detection signals, obtain the peak area of each solvent composition detected thus successively.Further, whenever obtaining peak area, peak area is converted to the amount of solvent composition and is sent to composition arithmetical unit 19.In addition, each solvent composition detected by detecting device 18 is discharged from detecting device 18 and goes out of use.
In discriminating portion 19a, carry out the mensuration of retention time according to the change of detection signal, and according to the retention time determined, differentiate the compound as each solvent composition.Further, for each solvent composition identified, quality ratio is calculated by ratio calculating part 19b according to the gauge of each solvent composition carrying out self-detector 18.Thus, the quality ratio of the solvent composition comprised in solvent can be recycled.By regulating operation via aforementioned temperature, the error of the quality ratio of obtained solvent composition can be suppressed for less.
When repeatedly calculating the quality ratio of solvent composition, repeatedly carrying out temperature and regulating operation, sampling operation, gasification process, separation circuit, detection operation and this series of processes of ratio calculation process.Now, the specified temp in operation is regulated to be set to identical each temperature.That is, regulating the specified temp in operation to be set to the temperature after the 2nd time regulates the specified temp in operation identical with the 1st temperature.Thus, the quality ratio of the solvent composition that each error is inhibited is obtained.In addition, if " identical " relevant with above-mentioned specified temp is strictly identical, then from suppressing the viewpoint of error most preferably, but also can not be strictly identical.
Analytic unit 10 is such as configured in the solvent recovery preparation facilities 63 (with reference to figure 4) of solution film-forming equipment 60 (with reference to figure 4) described later and uses.Film 50 shown in Fig. 2 is the example manufactured by implementing solution film-forming equipment 60 of the present invention.Film 50 is 3-tier architecture, and possesses main film body 52 and be configured at 1 pair of top layer 53 on surface of main film body 52.Although do not observe the border between main film body 52 and top layer 53, depict their border in fig. 2 for convenience of description.In the present embodiment, manufacture the film 50 possessing the 3-tier architecture on main film body 52 and 1 pair of top layer 53, but manufactured film is not limited to this.Such as, also can be possess main film body 52 and only possess the film of 2 Rotating fields on top layer 53 on a surface of main film body 52 and main film body is the film of sandwich construction.
Main film body 52 is made up of cellulose acylate and adjuvant, but also can not comprise adjuvant.1 pair of top layer 53 is made up of mutually the same composition, and specifically, arbitrary top layer 53 is formed by cellulose acylate, particulate and adjuvant, and their ratio also can be set to different from each other.Top layer 53 also can not comprise in particulate and adjuvant at least any one.Adjuvant is the delay inhibitor etc. of the delay of plasticizer, ultraviolet light absorber and control film 50.Particulate plays a role as the Marresistance of raising film 50 and the so-called deluster of sliding or attaching when preventing film 50 overlapping.Particulate is set to give prominence to from pellicular front 50a, makes pellicular front 50a have certain roughness thus, is formed small concavo-convex, but omits diagram in fig. 2.Concavo-convex by this, also mutually can not attach even if film 50 overlaps each other, guarantee film 50 slip each other, and manifest certain Marresistance.As particulate, such as, use silicon dioxide (silicon dioxide, SiO 2).
The cellulose acylate on main film body 52 and top layer 53 is set to TAC.But each cellulose acylate on main film body 52 and top layer 53 is not limited thereto.Such as, also the cellulose acylate of main film body 52 can be set to cellulose diacetate (DAC), the cellulose acylate on top layer 53 is set to TAC.Further, in the present embodiment, each component of polymer on main film body 52 and top layer 53 is all set to cellulose acylate, as long as but can be made the polymkeric substance of film by solution film-forming method.As other polymkeric substance, such as, there are cyclic polyolefin, acrylic acid etc.
Can be made up of two top layers 53 mutually the same composition, and its ratio is mutually different.Further, also can be in two top layers 53, only have a top layer to comprise the form of particulate.
The thickness T10 of film 50 is set to 60 μm, and the thickness T12 of main film body 52 is set to 54 μm, and the thickness T13 on top layer 53 is set to 3 μm.But each thickness is not limited to this, as long as thickness T10 is more than 10 μm in the scope of less than 80 μm, thickness T12 is more than 9 μm in the scope of less than 70 μm, and thickness T13 is more than 1 μm in the scope of less than 10 μm.
This film 50 may be used for Polarizer.As shown in Figure 3, Polarizer 56 possesses light polarizing film 57 and is configured at the film 50 on two faces of light polarizing film 57.Film 50 plays a role as the diaphragm for the protection of light polarizing film 57.Film 50 plays a role as the diaphragm with optical compensation function when having optical compensation function.Film 50 is by solution film-forming equipment 60 (with reference to figure 4) described later, form top layer 53 by the 2nd dope 67 (with reference to figure 4), in described 2nd dope 67, employ the solvent of quality ratio higher than the 1st dope 66 (with reference to figure 4) for the formation of main film body 52 of methylene chloride.Therefore, with the film of the single layer structure only manufactured by the 1st dope 66 with do not use the 2nd dope 67 and the film forming the sandwich construction on top layer is compared, film 50 stronger with the adhesion of light polarizing film 57.
As shown in Figure 4, implement solution film-forming equipment 60 of the present invention and possess dope preparation facilities 61, solution film-forming device 62 and solvent recovery preparation facilities 63.Dope preparation facilities 61 is the 1st dope 66 as the 1st polymer solution and the 2nd dope 67 as the 2nd polymer solution of component of polymer for the preparation of TAC77.That is, dope preparation facilities 61 is for the preparation of the polymer solution preparation section of each polymer solution for making film 50.Dope preparation facilities 61 possesses dissolving portion 72,73 and mixing through part 74.
If supply TAC77 and the 1st solvent 68, then dissolving portion 72 these potpourris are heated and in stirring at least any one.Thus, dissolving portion 72 makes TAC77 be dissolved in the 1st solvent 68.Dissolving portion 73 is set to the structure identical with dissolving portion 72, if supply TAC77 and the 2nd solvent 69, then by heat and in stirring at least any one, TAC77 is dissolved in the 2nd solvent 69.
In the present embodiment, the 1st solvent 68 and the 2nd solvent 69 are set to respectively the potpourri of methylene chloride and methyl alcohol.1st solvent 68 be the 2nd solvent 69 and manufacture other films dope various solvents each preparation in the benchmark solvent that uses.As aftermentioned, by adding methylene chloride in the 1st solvent 68, methylene chloride becomes higher than the 1st solvent 68 relative to the quality ratio of methyl alcohol the 2nd solvent 69.Quality ratio in 1st solvent 68 and methylene chloride: methyl alcohol is specifically set to 833: 155, this quality ratio in the 2nd solvent is set to 870: 130.But, methylene chloride in 1st solvent 68 and the 2nd solvent 69: methyl alcohol is not limited to this, if make the quality ratio of the methylene chloride in the 2nd solvent 69 higher than the quality ratio of the methylene chloride in the 1st solvent 68 in the scope being located at 833: 155 ~ 900: 100, then reliably can obtain the raising effect of former adhesive power.In addition, the scope of above-mentioned quality ratio comprises each quality ratio of lower limit and the upper limit.Further, also exist and the 1st solvent 68 and the 2nd solvent 69 be set to the situation of the 3 composition systems also adding n-butyl alcohol and be set to the situation of the 4 composition systems adding minor amount of water in this 3 composition system.
If supply TAC77, the 2nd solvent 69 and particulate 78, then mix through part 74 and their potpourri is such as stirred, make TAC77 be dissolved in the 2nd solvent 69 thus, and particulate 78 is disperseed.In order to make particulate 78 effectively and reliably disperse, ultrasonic oscillator is set at mixing through part 74, and by this ultrasonic oscillator, ultrasound wave is applied to the potpourri of TAC77, the 2nd solvent 69 and particulate 78.The particle dispersion liquid 79 obtained adds in the TAC solution obtained in dissolving portion 73, is stirred by stirring machine (not shown), until particulate 78 is dispersed to uniform state.In the TAC solution obtained by dissolving portion 72 and the TAC solution being dispersed with particulate 78 equably, add adjuvant 80 respectively, thus become the 1st dope 66 of use the 1st solvent 68 and use the 2nd dope 67 of the 2nd solvent 69.In addition, the 1st prepared dope 66 and the 2nd dope 67 can temporarily be stored in respectively to be preserved in container etc.
Solution film-forming device 62 for being manufactured the solution film-forming operation of film 50 by the 1st dope 66 and the 2nd dope 67, and by curtain coating mould 81, travelling belt 82, roller 83,84, stenter 85, roller drying section 86, reeling end 87 and angle stripper 89 etc. form.
Curtain coating mould 81, travelling belt 82 and roller 83,84 is for forming the casting films 88 by the 1st dope 66 and the 2nd dope 67 overlap continuously.Travelling belt 82 is for being formed as the curtain coating supporting mass of the circulation of ring-type.Travelling belt 82 is wound in the side face between roller 83 and roller 84.In roller 83 and roller 84 at least any one has drive division (not shown), circumferentially rotated by drive division.By this rotation, move along its length with the travelling belt 82 of circumferential contact.Be configured at curtain coating mould 81 on travelling belt 82 to be clamped the state of the 1st dope 66 and overlap by the 2nd dope 67, flow out the 1st dope 66 and the 2nd dope 67 continuously.In addition, in the present embodiment, be provided with gas supply part (not shown) opposedly with the curtain coating face of the formation casting films 88 of travelling belt 82.This gas supply part ejection gas promotes the drying of passed through casting films 88.Angle stripper 89 is for stripping the casting films 88 being dried to and can transmitting degree.When stripping, utilizing angle stripper 89 tread support membrane 50, remaining fixing with the position that strips that casting films 88 is peeled from travelling belt 82.In addition, cylinder (not shown) also can be used to replace travelling belt 82 and roller 83,84.
Stenter 85, while utilize the clip 85a as holding member to keep each sidepiece of film 50, promotes the drying of film 50.Stenter 85, while utilize clip 85a to keep each sidepiece of film 50 to transmit along its length, is given the tension force on Width, the width of film 50 is widened.Gas supply part 85b dry gas being flowed to carry out near film 50 to supply is possessed in this stenter 85.Also pin can be used to replace clip 85a.Clip 85a is by clamping film 50, and pin runs through film 50 by through-thickness and keeps film 50 respectively.
Roller drying section 86 is for transmitting film 50 while promote drying.The direction of transfer that roller drying section 86 possesses along film 50 is arranged with multiple multiple roller 86a, air conditioner (not shown) and chamber (not shown).In multiple roller 86a, have the driven roller circumferentially rotated, film 50 is sent to downstream by the rotation of this driven roller.Air conditioner is connected with the condenser 91 (with reference to figure 5) of solvent recovery preparation facilities 63, and the atmosphere of the chamber interior of absorption roller drying section 86, and attracted gas is delivered to condenser 91.If be removed the gas of the 1st solvent 68, the 2nd solvent 69 and moisture from condenser 91 supply, be then again send into chamber interior after the temperature of object using this gas regulation.Thus, the temperature and humidity of chamber interior is remained constant.Can arrange between stenter 85 with roller drying section 86 and have and the mutually isostructural stenter of stenter 85 (not shown).
Reeling end 87 coils into web-like by supplying the microscler film 50 of coming from roller drying section 86.In addition, cooling chamber (not shown) can be set between roller drying section 86 and reeling end 87.This cooling chamber was cooled to room temperature before batching the film 50 by inside.
In solution film-forming device 62, owing to carrying out drying to casting films 88 and film 50, therefore the 1st solvent 68 and the 2nd solvent 69 gasify as solvent gas.1st solvent 68 of gasification in solution film-forming device 62 and the 2nd solvent 69 reclaim as solvent gas by solvent recovery preparation facilities 63, and for the preparation of the 1st solvent 68 newly supplied to solution film-forming device 62 and the 2nd solvent 69.In addition, about the detailed content of solvent recovery preparation facilities 63, aftermentioned by utilizing another accompanying drawing to carry out.
The effect of said structure is described.The TAC77 that the TAC77 of the 1st dope 66 is sent to dissolving portion the 72,2nd dope 67 is sent to dissolving portion 73 and mixing through part 74.In dissolving portion 72, TAC77 is dissolved in the 1st solvent 68 and becomes TAC solution.The 1st dope 66 is obtained by adding adjuvant 80 in this TAC solution.Further, in dissolving portion 73, TAC77 is dissolved in the 2nd solvent 69 and becomes TAC solution.In mixing through part 74, TAC77 is dissolved in the 2nd solvent 69 and particulate 78 disperses and becomes particle dispersion liquid 79.After adding particle dispersion liquid 79 in from the TAC solution in dissolving portion 73, add adjuvant 80, the 2nd dope 67 can be obtained thus.
1st dope 66 and the 2nd dope 67 are sent to curtain coating mould 81 continuously.Flow out the 1st dope 66 and the 2nd dope 67 continuously from curtain coating mould 81 to the travelling belt 82 movement, formed continuously with the casting films 88 (curtain coating operation) of the overlapping 3-tier architecture of the order of the 2nd dope 67, the 1st dope 66, the 2nd dope on travelling belt 82 thus.Casting films 88 carries out drying by pressure fan, and is stripped from travelling belt 82 by angle stripper 89 with the state comprising the 1st solvent 68 and the 2nd solvent 69, thus is made film 50.In addition, the film 50 when stripping is for remaining the so-called moistening film of the 1st solvent 68 and the 2nd solvent 69.If travelling belt 82 carries out circulating and from the casting position stripping position and be back to curtain coating the 1st dope 66, the 2nd dope 67, then the 1st dope 66 that curtain coating is new again and the 2nd dope 67.
The casting films 88 utilizing angle stripper 89 to strip i.e. film 50 is directed to stenter 85.In stenter 85, film 50 is transmitted, while by promoting dry from the dry gas of gas supply part 85b, and by the time changing width of clip 85a in regulation.
Film 50 is directed to roller drying section 86 from stenter 85, dried during chamber (not shown) inside by this roller drying section 86.As above, from travelling belt 82 peel continuously casting films 88 and formed microscler film 50 by stenter 85 and roller drying section 86 dried (drying process).Dry film 50 is directed to reeling end 87, coils into web-like.Further, the atmosphere in solution film-forming device 62 is sent to solvent recovery preparation facilities 63 with the state comprising the solvent gas be made up of the 1st solvent 68 of evaporation from casting films 88 and film 50 and the 2nd solvent 69 and is removed solvent gas.Such as, in the present embodiment, be provided with the chamber etc. of roller drying section 86 as above in the chamber (not shown) of the transmission path of the film 50 in the chamber (not shown) surrounding curtain coating mould 81 and travelling belt 82 and covering stenter 85, the atmosphere of these chambers is sent to the state comprising solvent gas and reclaims preparation facilities 63 and be removed solvent gas.The gas being removed solvent gas is sent to solution film-forming device 62 again.Solvent gas is recovered by solvent recovery preparation facilities 63, and is supplied to dope preparation facilities 61 after being made the 1st new solvent 68 and the 2nd solvent 69.
Above-mentioned example is the example being manufactured film 50 by the common curtain coating of the 1st dope 66 and the 2nd dope 67, but also can replace to use the successively curtain coating of multiple curtain coating mould.
As shown in Figure 5, solvent recovery preparation facilities 63 by condenser 91, the 1st distillation column 92, the 2nd distillation column 93, the 1st ~ 3rd analytic unit 101 ~ 103, flowmeter 105 ~ 108, extractor 111, prepare arithmetical unit 112 and the 1st ~ 6th tank body 121 ~ 126 etc. and form.Condenser 91 is for being made the recycling design 131 of liquid by solvent gas, the atmosphere of solution film-forming device 62 is sent in this condenser 91.Containing solvent gas in this atmosphere, this atmosphere reclaims with the state of gas and cools by condenser 91, makes the solvent gas condensation comprised in gas to be made the recycling design 131 (recovery process) of liquid thus.
1st tank body 121 and the 2nd tank body 122 are for accumulating recycling design 131.1st tank body 121 accumulates the recycling design 131 brought continuously from condenser 91.The recycling design 131 of such as specified quantitative was sent to the 2nd tank body 122 from the 1st tank body 121 in the specific moment.In addition, recycling design 131 can be sent from the 1st tank body 121 continuously to the 2nd tank body 122.The recycling design 131 of the 2nd tank body 122 is sent to the 1st distillation column 92.
1st distillation column 92 is for deimpurity 1st distillation process of being made a return journey by distillating recovering solvent 131.Impurity is the material beyond each solvent composition of using in the 1st solvent 68 and the respective composition of the 2nd solvent 69.In present embodiment, this impurity is water.In the present embodiment, be not separated the solvent composition comprised in the 1st solvent 68 and the 2nd solvent 69 in the 1st distillation column 92, the solvent distillation 132 therefore obtained by this distillation is the potpourri of the 1st solvent 68 and the 2nd solvent 69.Therefore, solvent distillation 132 is the potpourri of methylene chloride and methyl alcohol, and the quality ratio of methylene chloride and methyl alcohol is different from the 1st solvent 68, and, be also different from the 2nd solvent 69.In addition, as mentioned above, when the 1st solvent 68 and the 2nd solvent 69 are the 3 composition system also comprising n-butyl alcohol, 1 butanols and the potpourri of water and the potpourri of methylene chloride and methyl alcohol are distinguished by the 1st distillation column 92.Now, the potpourri of n-butyl alcohol and water can be directed to refining plant (not shown) and isolate n-butyl alcohol, and the n-butyl alcohol be separated is supplied to the 3rd tank body 123 and the 4th tank body 124 uses.Further, as mentioned above, when the 1st solvent 68 and the 2nd solvent 69 are the 4 composition system also comprising n-butyl alcohol and water, same refining plant can be utilized to be separated the potpourri of n-butyl alcohol and water, and be supplied to the 3rd tank body 123 and the 4th tank body 124 uses.Utilize and described laterly prepare the quantity delivered being supplied to the 3rd tank body 123 and the 4th tank body 124 that arithmetical unit 112 calculates n-butyl alcohol and water.
Solvent distillation 132 is divided into the 1st ~ 3rd solvent distillation these 3 kinds.1st solvent distillation be sent to the 1st analytic unit the 101,2nd solvent distillation be sent to the 2nd distillation column the 93,3rd solvent distillation be sent to the 4th tank body 124.Specifically, first, from solvent distillation 132, point to get the 2nd solvent distillation, point to get the 2nd surplus after solvent distillation and be sent to the 3rd tank body 123 and accumulated.Lodge in a wherein part in the 3rd tank body 123 as the 1st solvent distillation and be sent to the 1st analytic unit 101.Point to get surplus in the 1st the 3rd tank body 123 after solvent distillation as the 3rd solvent distillation and the 4th tank body 124 that is sent to for the preparation of the 1st solvent 68.
1st analytic unit 101 has the structure identical with the analytic unit 10 shown in Fig. 1, and for via the recycling design after the 1st distillation process namely solvent distillation 132 carry out the discriminating of each compound as comprised solvent composition, and obtain the quality ratio of solvent composition.When comprising impurity, also carry out the discriminating of this impurity and the quality ratio obtained relative to solvent composition.Lodge in a wherein part in the 3rd tank body 123 as the 1st solvent distillation and be sent to the 1st analytic unit 101, going out of use by after detecting device 18 (with reference to figure 1).In the present embodiment, can identify solvent distillation 132 by the 1st analytic unit 101 and be made up of two kinds of solvent compositions, the 1st compound as the 1st solvent composition is methylene chloride, and the 2nd compound as the 2nd solvent composition is methyl alcohol.Further, methylene chloride is calculated: the quality ratio of methyl alcohol is 838: 150.This result of calculation exports as detection signal to preparing arithmetical unit 112 by the 1st analytic unit 101, and is exported as detection signal to the 2nd distillation column 93 by identification result.
Prepare the detection signal of arithmetical unit 112 according to the 1st analytic unit 101, by flowmeter 105 calculated flow rate, and control according to this result of calculation the flow flowing to the 4th tank body 124 via flowmeter 105 from the 3rd tank body 123 of the 3rd solvent distillation.
2nd distillation column 93 for by distill the 2nd solvent distillation carry out the 2nd distillation process that is separated by each comprised solvent composition.2nd distillation column 93 possesses recording unit, operational part and distillation column main body (all not shown), and pre-recorded in recording unit have with the boiling point of each compound and measure corresponding multiple distillation conditions (distillation pattern).The evaporation latent heat of the compound that consideration should be separated and specific heat etc. and determine distillation condition.If input the detection signal from the 1st analytic unit 101, then operational part carries out specific according to this detection signal to the distillation condition for being separated by each solvent composition.Distillation column controls as specific distillation condition by operational part, distillation column main body to the 2nd solvent distillation distill.But, when comprised solvent composition is known, can there is no recording unit, as long as be the distillation condition corresponding with comprised solvent composition by distillation column main body control yet.By this distillation, the 2nd solvent distillation be separated into comprised solvent composition and methylene chloride 133 and methyl alcohol 134.This methylene chloride 133 and methyl alcohol 134 use with trimming purposes when preparing the 1st solvent 68 respectively, and methylene chloride 133 also uses with interpolation purposes when preparing the 2nd solvent 69.
Extractor 111 is for refining methylene chloride 133.Methylene chloride 133 and methyl alcohol 134 are azeotropic material, containing methyl alcohol in the methylene chloride 133 therefore obtained in the 2nd distillation column 93.Such as in the present embodiment, methyl alcohol is contained in methylene chloride relative to the ratio that the quality of methylene chloride is 92: 8 with the quality of methyl alcohol.Therefore, as present embodiment, methylene chloride 133 uses extractor 111 to carry out refining removing methyl alcohol.Extractor 111 is separated by 2 of aqueous phase and oil phase from the methylene chloride of oil phase side, isolates the methyl alcohol of aqueous phase side.In addition, in the present embodiment, use hexane as the extract of oil phase.The methylene chloride be separated is sent to the 5th tank body 125 and is accumulated.In addition, extractor 111 suitably can be arranged according to the kind of compound etc.
The methylene chloride 133 used in interpolation when trimming and preparation the 2nd solvent 69 of the 1st solvent 68 uses the methylene chloride in the 5th tank body 125 after via the extraction process based on extractor 111.When methylene chloride 133 in 5th tank body 125 uses in the fine setting of the 1st solvent 68, control flow by flowmeter 106 and be supplied to aforementioned 4th tank body 124, when using in the interpolation when preparation the 2nd solvent 69, control flow by flowmeter 108 and mix with a point part of getting from the 1st solvent 68.The control of the flow undertaken by flowmeter 106,108 is by aftermentioned.
In addition, the methylene chloride 133 in the 5th tank body 125 supplies the preparation of the 1st solvent 68 and the 2nd solvent 69, therefore preferably grasps purity exactly as far as possible.Therefore, preferably as present embodiment, the 2nd analytic unit 102 is arranged at solvent recovery preparation facilities 63, and obtains the purity of methylene chloride by the 2nd analytic unit 102.2nd analytic unit 102 has the structure identical with the analytic unit 10 shown in Fig. 1, and calculates with the quality ratio of impurity as the purity of methylene chloride 133.This result of calculation exports as detection signal to preparing arithmetical unit 112 by the 2nd analytic unit 102.Prepare arithmetical unit 112 according to this detection signal, calculate each flow by flowmeter 106 and flowmeter 108, and according to this result of calculation control flow check gauge 106 and flowmeter 108 respectively.Thus, the flow and as the flow of the aftermentioned flow direction from the 1st solvent 68 in a point part of getting that flow to the 4th tank body 124 from the 5th tank body 125 of methylene chloride 133 is controlled.In addition, in the present embodiment, the purity calculating methylene chloride 133 is more than 99 quality %.
The methyl alcohol 134 obtained by the distillation based on the 2nd distillation column 93 lodges in the 6th tank body 126, controls flow and be supplied to aforementioned 4th tank body 124 by flowmeter 107.This methyl alcohol 134 uses to finely tune purposes when preparing the 1st solvent 68 as benchmark solvent, therefore preferably grasps purity exactly as far as possible.Therefore, as present embodiment, preferably the 3rd analytic unit 103 is arranged at solvent recovery preparation facilities 63, and obtains the purity of methyl alcohol by the 3rd analytic unit 103.3rd analytic unit 103 has the structure identical with the analytic unit 10 shown in Fig. 1, and calculates with the quality ratio of impurity as the purity of methyl alcohol 134.This result of calculation exports as detection signal to preparing arithmetical unit 112 by the 3rd analytic unit 103.Prepare arithmetical unit 112 according to this detection signal, by flowmeter 107 calculated flow rate, and control according to this result of calculation the flow flowing to the 4th tank body 124 via flowmeter 107 from the 6th tank body 126 of methyl alcohol 134.In addition, in the present embodiment, the purity calculating methyl alcohol 134 is more than 99 quality %.
As mentioned above, the 3rd solvent distillation be sent in the 4th tank body 124, and in the 3rd solvent distillation, add methylene chloride 133 and methyl alcohol 134 with the addition determined.In addition, during when the 1st solvent 68 is 3 composition system of methylene chloride 133, methyl alcohol and water with for 4 composition system of methylene chloride 133, methyl alcohol, n-butyl alcohol and water, n-butyl alcohol and water are also added into the 3rd in solvent distillation with the addition determined.So, the 1st solvent 68 (the 1st solvent preparation section) can be obtained.Prepare arithmetical unit 112 calculate and determine the 3rd operational throughput of solvent distillation and each addition of methylene chloride 133 and methyl alcohol 134.Preparing the quality ratio of the pre-recorded methylene chloride 133 having a 1st prepared solvent and methyl alcohol 134 in arithmetical unit 112.As mentioned above, if prepare arithmetical unit 112 to input detection signal from the 1st ~ 3rd analytic unit 101 ~ 103 respectively, then itself and the aforementioned quality ratio to have recorded are contrasted, and calculate the 3rd operational throughput of solvent distillation and each addition of methylene chloride 133 and methyl alcohol 134 carried to the 4th tank body 124.In addition, also there is each addition calculating methylene chloride 133 and methyl alcohol 134 is the situation of zero.Such as, in the present embodiment, the methylene chloride recorded of the 1st solvent 68: the quality ratio of methyl alcohol is 833: 155, and the operational throughput calculating the 3rd solvent distillation is 70kg/min, the addition of methylene chloride 133 is 1.7kg/min, and the addition of methyl alcohol 134 is 0.25kg/min.
In addition, in the present embodiment, also exist except the 3rd solvent distillation, methylene chloride 133 and methyl alcohol 134, also the recycling design 131 in the 1st tank body 121 is supplied to the situation of the 4th tank body 124.Such as making the 1st solvent 68 containing the situation of the water of specified quantitative.Therefore, in the present embodiment, a point part of getting from the recycling design 131 in the 1st tank body 121 is supplied to the 1st analytic unit 101, carries out the calculating of the discriminating of each solvent composition and the quality ratio of solvent composition.This result of calculation exports to as detection signal by the 1st analytic unit 101 prepares arithmetical unit 112, prepares arithmetical unit 112 according to the flow of this detection signal control flow check to the recycling design 131 in the 4th tank body 124.
Further, from the solvent in the 4th tank body 124, point get a part, this part is supplied to the 1st analytic unit 101, carries out the calculating of quality ratio of comprised methylene chloride, methyl alcohol, water.If input the detection signal of result of calculation from the 1st analytic unit 101, then prepare arithmetical unit 112 to control as follows: calculate the flow joining the 3rd in the solvent in the 4th tank body 124 solvent distillation, methylene chloride 133, methyl alcohol 134, recycling design 131 in order to be made the 1st solvent 68 further according to this detection signal, and these are sent to the 4th tank body 124.So, the solvent in the 4th tank body 124, by repeatedly detecting the quality ratio of solvent composition and being finely tuned, therefore can obtain the 1st solvent 68 that the quality ratio of solvent composition is constant.Also can add to finely tune purposes new methylene chloride, methyl alcohol, butanols and the pure water such as bought in the 4th tank body 124.Each addition is now calculated by preparing arithmetical unit 112.
Divide from the 1st obtained solvent 68 and get a part, divide the remainder after getting to be supplied to dope preparation facilities 61.Further, with the flow controlled as described above by flowmeter 108, send methylene chloride 133 here from the 5th tank body 125 and be added into from the 1st solvent 68 points of parts of getting, thus, the 2nd solvent 69 (the 2nd solvent preparation section) can be obtained.The 2nd solvent 69 obtained is supplied to dope preparation facilities 61.
By above method, even the recycling design 131 that the quality ratio of solvent composition is different from the 1st solvent 68 and the 2nd solvent 69, the quality ratio that the 1st new solvent 68 and the 2nd solvent 69 also can be prepared into solvent composition keeps constant respectively.And, even if by the manufacturing process of film from being changed into by the situation using the dope of the 1st solvent 68 and the 2nd solvent 69 to manufacture film respectively by the situation only using the dope of the 1st solvent 68 to manufacture film, the quality ratio that the 1st new solvent 68 also can be prepared into solvent composition keeps constant.Further, even if the quality ratio of the solvent composition in recycling design 131 changes in time, the quality ratio that the 1st new solvent 68 also can be prepared into solvent composition keeps constant.
In the above example, reclaim the 1st solvent 68 and the 2nd solvent 69 and in the 1st dope 66 being again used for it being supplied to curtain coating mould 81 and the 2nd dope 67, but in the 1st new solvent 68 and the 2nd new solvent 69 the 1st dope 66 that also may be used for being supplied to other curtain coating moulds different from curtain coating mould 81 and the 2nd dope 67.Above-mentioned example is the example for recycling the recycling design reclaimed from solution film-forming operation, but the recycling design in the present invention is not limited to the recycling design from solution film-forming operation.Also can be such as recycle the situation of the potpourri be made up of the organic compound of multiple liquid and the situation etc. of the recycling organic compound of liquid and the potpourri of water.Further, solvent is not limited to the solvent for dissolve polymer, also can be the solvent for dissolving oligomer and monomer.

Claims (9)

1. a recycling design analytical approach, it possesses following steps:
(A) potpourri as liquid is made by heating and the recycling design that reclaims heats up and is adjusted to specified temp;
(B) to maintain the state of described specified temp, specified quantitative of sampling from described recycling design;
(C) the sample gasification of sampling in the step B is made by heating;
(D) the described sample separation of gasification is become each solvent composition, described sample is directed to chromatographic column and utilizes carrier gas to pass through in described chromatographic column and separated, and described chromatographic column possesses Stationary liquid, and described carrier gas is mobile phase;
(E) amount of the described solvent composition be separated is detected respectively; And
(F) according to each amount detected, the quality ratio of described solvent composition is calculated.
2. recycling design analytical approach according to claim 1, wherein,
When the boiling point of described recycling design is set to TL DEG C, described specified temp is more than (TL-30) DEG C and be less than in the scope of TL DEG C.
3. recycling design analytical approach according to claim 1 and 2, wherein,
When repeatedly calculating the quality ratio of described solvent composition, repeatedly carry out described step A, described step B, described step C, described D step, described E step and this series of operation of described F step, and described specified temp in each described step A is identical.
4. recycling design analytical approach according to claim 1 and 2, wherein,
In the step A, make described recycling design by the described pipe of constant temperature enclosure, thus described recycling design is adjusted to described specified temp, described constant temperature enclosure possesses: pipe, guides described recycling design; Chamber, holds described pipe and is separated in the space and space outerpace that surround described pipe; And temperature control device, control the internal temperature of described chamber.
5. recycling design analytical approach according to claim 3, wherein,
In the step A, make described recycling design by the described pipe of constant temperature enclosure, thus described recycling design is adjusted to described specified temp, described constant temperature enclosure possesses: pipe, guides described recycling design; Chamber, holds described pipe and is separated in the space and space outerpace that surround described pipe; And temperature control device, control the internal temperature of described chamber.
6. a recycling design analytic unit, it possesses following:
Thermoregulation mechanism, is adjusted to specified temp by heating the recycling design reclaimed by the potpourri as liquid;
Sampling unit, specified quantitative of sampling from described recycling design, described sampling unit is maintained described specified temp, while sample by guiding the temperature of the described recycling design of coming from described governor motion;
Gasification mechanism, makes the sample of sampling gasify by heating;
Chromatographic column, inside is provided with Stationary liquid and carrier gas is directed in described chromatographic column, and the described sample of gasification is directed in described Stationary liquid, and described carrier gas is for making described sample by the mobile phase of described Stationary liquid;
Detecting device, detects the amount of the solvent composition be separated in described chromatographic column respectively; And
Ratio calculating part, according to each amount detected by described test section, calculates the quality ratio of described solvent composition.
7. a solvent recovery preparation method, it possesses following steps:
(G) recycling design of liquid is made by the solvent evaporated in solution film-forming is reclaimed also condensation with the state of gas, described solution film-forming manufactures film by the polymer solution being dissolved with polymkeric substance in a solvent, and described solvent is the potpourri of the 1st solvent composition and the 2nd solvent composition;
(H) impurity is removed by the described recycling design of distillation, thus the potpourri being made described 1st solvent composition and described 2nd solvent composition i.e. solvent distillation;
(I) by heating make described solvent distillation be divided into the 1st solvent distillation, the 2nd solvent distillation and the 3rd solvent distillation the wherein the described 1st solvent distillation heat up and be adjusted to specified temp;
(J) to maintain the state of described specified temp, specified quantitative of sampling from the described 1st solvent distillation;
(K) the sample gasification of sampling in described J step is made by heating;
(L) the described sample separation gasified in described K step is become described 1st solvent composition and described 2nd solvent composition, described sample is directed to chromatographic column and utilizes carrier gas to pass through in described chromatographic column and separated, described chromatographic column possesses Stationary liquid, and described carrier gas is mobile phase;
(M) each amount of described 1st solvent composition and described 2nd solvent composition be separated in described L step is detected;
(N) according to each amount detected in described M step, the quality ratio of described 1st solvent composition and described 2nd solvent composition is calculated;
(O) by the described 2nd solvent distillation by distillation be separated into described 1st solvent composition and described 2nd solvent composition;
(P) by described 1st solvent composition obtained in described O step and described 2nd solvent composition are joined the described 3rd in solvent distillation for the preparation of the 1st new described solvent of the described solution film-forming after being supplied to, according to the described quality ratio calculated in described N step, determine to join each addition of the described 3rd described 1st solvent composition in solvent distillation and described 2nd solvent composition; And
(Q) prepare the 2nd new described solvent of quality ratio higher than described 1st novel solvent of described 1st solvent composition, described 2nd novel solvent is prepared by being added in described 1st solvent composition that obtains in described O step in a part of point to get from described 1st novel solvent.
8. solvent recovery preparation method according to claim 7, wherein,
Described solution film-forming by be dissolved with in solvent described in the 1st described polymkeric substance the 1st described in polymer solution and described 1st solvent composition quality ratio higher than described 1st solvent the 2nd described in be dissolved with in solvent described polymkeric substance the 2nd described in polymer solution manufacture the described film of sandwich construction.
9. a solution film-forming method, it possesses following steps:
(R) by making the curtain coating supporting mass continuous stream of polymer solution from curtain coating mould to movement out form casting films, described polymer solution is formed in solvent by dissolution of polymer, and described solvent is the potpourri of the 1st solvent composition and the 2nd solvent composition;
(S) film is made by peeling described casting films continuously from described curtain coating supporting mass and carry out drying;
(T) recycling design of liquid is made by the described solvent evaporated in described R step and described S step is reclaimed also condensation with the state of gas;
(H) impurity is removed by the described recycling design of distillation, thus the potpourri being made described 1st solvent composition and described 2nd solvent composition i.e. solvent distillation;
(I) by heating make described solvent distillation be divided into the 1st solvent distillation, the 2nd solvent distillation and the 3rd solvent distillation the wherein the described 1st solvent distillation heat up and be adjusted to specified temp;
(J) to maintain the state of described specified temp, specified quantitative of sampling from the described 1st solvent distillation;
(K) the sample gasification of sampling in described J step is made by heating;
(L) the described sample separation gasified in described K step is become described 1st solvent composition and described 2nd solvent composition, described sample is directed to chromatographic column and utilizes carrier gas to pass through in described chromatographic column and separated, described chromatographic column possesses Stationary liquid, and described carrier gas is mobile phase;
(M) each amount of described 1st solvent composition and described 2nd solvent composition be separated in described L step is detected;
(N) according to each amount detected in described M step, the quality ratio of described 1st solvent composition and described 2nd solvent composition is calculated;
(O) by the described 2nd solvent distillation by distillation be separated into described 1st solvent composition and described 2nd solvent composition;
(U) the 1st new described solvent is prepared in solvent distillation by described 1st solvent composition obtained in described O step and described 2nd solvent composition being joined the described 3rd, according to the described quality ratio calculated in described N step, determine to join each addition of the described 3rd described 1st solvent composition in solvent distillation and described 2nd solvent composition;
(Q) prepare the 2nd new described solvent of quality ratio higher than described 1st novel solvent of described 1st solvent composition, described 2nd novel solvent is prepared by being added in described 1st solvent composition that obtains in described O step in a part of point to get from described 1st novel solvent; And
(V) the 1st new described polymer solution and the 2nd new described polymer solution of the described R step after being supplied to is prepared, described 1st novel polymer solution dissolves new described polymkeric substance and prepares in described 1st novel solvent, described 2nd novel polymer solution dissolves new described polymkeric substance and prepares in described 2nd novel solvent, and described 1st novel polymer solution and described 2nd novel polymer solution flow out continuously from curtain coating mould.
CN201510145679.8A 2014-03-31 2015-03-30 Recycling design analytic approach and unit, solvent recovery the preparation method and solution film-forming method Expired - Fee Related CN104950050B (en)

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