Pervaporation membrane

Abstract

Provided is a pervaporation membrane which is suitable for suppressing separation of a separation functional layer from a porous support body when the pervaporation membrane is drawn out from a wound body of the pervaporation membrane. This pervaporation membrane is provided with: a separation function layer containing a silicone resin; and a porous support body that supports the separation function layer. In the pervaporation membrane, the peel strength measured by the following test is 0.15 N / 20 mm or more. Testing: cutting the pervaporation membrane to form a test piece with the width of 20mm and the length of 150mm; and peeling off the separation functional layer from the porous support body by using a test piece at a peeling angle of 180 degrees and a stretching speed of 300 mm / min.

Description

Technical Field

[0001] The present invention relates to pervaporation membranes. Background Art

[0002] As a method for obtaining a valuable substance derived from non-petroleum, a method for utilizing fermentation based on microorganisms is known. For example, a method for producing volatile organic compounds (fermentation products) such as alcohol by fermenting carbon sources such as glucose using microorganisms has been developed. The fermentation of the carbon source is carried out, for example, in an aqueous solution. In this method, if the content of the fermentation product in the aqueous solution increases, the fermentation based on microorganisms is sometimes stopped. In order to continuously manufacture the fermentation product based on microorganisms, it is necessary to separate the fermentation product from the aqueous solution.

[0003] As an example of a method for separating a volatile organic compound from an aqueous solution containing the organic compound, a pervaporation method (pervaporation method) using a pervaporation membrane can be cited. The pervaporation method is suitable for separating volatile organic compounds from aqueous solutions containing various substances. Compared with the distillation method, the pervaporation method also tends to suppress energy consumption and carbon dioxide emissions. A specific example of the material of the pervaporation membrane used in the pervaporation method is a silicone resin (for example, Patent Document 1).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent No. 4899122 Summary of the invention

[0007] Problems to be solved by the invention

[0008] From the viewpoint of improving its strength, the pervaporation membrane preferably includes a separation functional layer including a silicone resin and a porous support supporting the separation functional layer. However, according to the research of the inventors of the present application, for example, when a pervaporation membrane including a porous support is manufactured in a roll-to-roll manner and the pervaporation membrane is stored in a wound state, when the pervaporation membrane is pulled out from the wound body of the pervaporation membrane, there is a tendency for the separation functional layer to peel off from the porous support.

[0009] Therefore, an object of the present invention is to provide a pervaporation membrane suitable for suppressing the separation functional layer from being peeled off from a porous support when the pervaporation membrane is pulled out from a wound body of the pervaporation membrane.

[0010] Means for solving problems

[0011] The inventors of the present application have conducted intensive studies and have newly discovered that the peel strength between the separation functional layer and the porous support measured at a peeling angle of 180° can be used as an indicator of peeling occurring when the pervaporation membrane is extracted from a wound body of the pervaporation membrane, thereby completing the present invention.

[0012] The present invention provides a pervaporation membrane, which comprises:

[0013] a separation functional layer comprising a silicone resin; and

[0014] a porous support for supporting the separation functional layer;

[0015] The peel strength measured by the following test is 0.15 N / 20 mm or more.

[0016] Test: The pervaporation membrane was cut into a test piece of 20 mm in width x 150 mm in length. Using the test piece, the separation functional layer was peeled off from the porous support at a peeling angle of 180° and a tensile speed of 300 mm / min.

[0017] Effects of the Invention

[0018] According to the present invention, it is possible to provide a pervaporation membrane suitable for suppressing the separation functional layer from being peeled off from a porous support when the pervaporation membrane is pulled out from a wound body of the pervaporation membrane. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] [ Figure 1A ] is a cross-sectional view schematically showing the pervaporation membrane of Embodiment 1.

[0020] [ Figure 1B ] is a diagram for illustrating the method for manufacturing the permeation vaporization membrane of embodiment 1.

[0021] [ Figure 1C ] is a diagram for illustrating the method for manufacturing the permeation vaporization membrane of embodiment 1.

[0022] [ Figure 2A ] is a cross-sectional view schematically showing the permeation vaporization membrane of Embodiment 2.

[0023] [ Figure 2B ] is a diagram for illustrating a method for manufacturing a permeation vaporization membrane according to a second embodiment.

[0024] [ Figure 2C ] is a diagram for illustrating a method for manufacturing a permeation vaporization membrane according to a second embodiment.

[0025] [ Figure 3 ] is a cross-sectional view schematically showing the permeation vaporization membrane of Embodiment 3.

[0026] [ Figure 4A ] is a cross-sectional view schematically showing the permeation vaporization membrane of embodiment 4.

[0027] [ Figure 4B ] is a diagram for illustrating a method for manufacturing a permeation vaporization membrane according to a fourth embodiment.

[0028] [ Figure 4C ] is a diagram for illustrating a method for manufacturing a permeation vaporization membrane according to a fourth embodiment.

[0029] [ Figure 5 ] is a cross-sectional view schematically showing the permeation vaporization membrane of embodiment 5.

[0030] [ Figure 6 ] is a cross-sectional view schematically showing the permeation vaporization membrane of Embodiment 6.

[0031] [ Figure 7 ] is a schematic cross-sectional view of a membrane separation device equipped with a pervaporation membrane.

[0032] [ Figure 8 ] is a stereoscopic diagram schematically showing a modified example of the membrane separation device.

[0033] [ Fig. 9 ] is a schematic diagram showing an example of a membrane separation system. DETAILED DESCRIPTION

[0034] A pervaporation membrane according to a first aspect of the present invention comprises:

[0035] a separation functional layer comprising a silicone resin; and

[0036] a porous support for supporting the separation functional layer;

[0037] The peel strength measured by the following test is 0.15 N / 20 mm or more.

[0038] Test: The pervaporation membrane was cut into a test piece of 20 mm in width x 150 mm in length. Using the test piece, the separation functional layer was peeled off from the porous support at a peeling angle of 180° and a tensile speed of 300 mm / min.

[0039] In a second aspect of the present invention, for example, in the pervaporation membrane according to the first aspect, the peel strength is 0.5 N / 20 mm or more.

[0040] In the third aspect of the present invention, for example, in the pervaporation membrane according to the first or second aspect, the adhesion between the separation functional layer and the porous support measured by SAICAS (surface and interfacial measuring analysis system) is 0.01 kN / m or more.

[0041] In a fourth aspect of the present invention, for example, in the pervaporation membrane according to any one of the first to third aspects, the porous support has a surface that faces the separation functional layer and has been subjected to a surface modification treatment.

[0042] In a fifth aspect of the present invention, for example, in the pervaporation membrane according to the fourth aspect, the surface modification treatment is a corona treatment.

[0043] In a sixth aspect of the present invention, for example, in the pervaporation membrane according to the fourth or fifth aspect, the silicone resin is formed of a condensed silicone resin composition.

[0044] In a seventh aspect of the present invention, for example, in the pervaporation membrane according to any one of the first to third aspects, the porous support has a primer layer directly in contact with the separation functional layer, and the primer layer is bonded to the silicone resin.

[0045] In an eighth aspect of the present invention, for example, in the pervaporation membrane according to the seventh aspect, the silicone resin is formed of an addition-type silicone resin composition.

[0046] In a ninth aspect of the present invention, for example, in the pervaporation membrane according to any one of the first to fifth aspects, the silicone resin is formed of a silicone resin composition containing polyorganosiloxane.

[0047] The silicone resin composition contains a compound having a reactive group F1 reactive with the polyorganosiloxane and a reactive group F2 reactive with the surface of the porous support opposite to the separation functional layer.

[0048] In a tenth aspect of the present invention, for example, in the pervaporation membrane according to any one of the first to third aspects, the porous support has a surface facing the separation functional layer and including a plurality of openings, and an average diameter of the plurality of openings is 0.5 μm or more.

[0049] In an eleventh aspect of the present invention, for example, in the pervaporation membrane according to the tenth aspect, the surface is bonded to the silicone resin.

[0050] In a twelfth aspect of the present invention, for example, in the pervaporation membrane according to any one of the first to third aspects, the separation functional layer further includes a filler.

[0051] In a thirteenth aspect of the present invention, for example, in the pervaporation membrane according to the twelfth aspect, the filler includes at least one selected from the group consisting of zeolite and silica.

[0052] In a fourteenth aspect of the present invention, for example, in the pervaporation membrane according to any one of the first to third aspects, the porous support has a main body and a microporous layer disposed on the main body, and the microporous layer contains polysulfone.

[0053] In a fifteenth aspect of the present invention, for example, in the pervaporation membrane according to the fourteenth aspect, the silicone resin is formed of a silicone resin composition having a solvent content of 10 wt % (weight %) or less.

[0054] In a sixteenth aspect of the present invention, for example, the pervaporation membrane according to any one of the first to fifteenth aspects is used to separate a volatile organic compound from an aqueous solution containing the organic compound.

[0055] In a seventeenth aspect of the present invention, for example, in the pervaporation membrane according to the sixteenth aspect, the organic compound is a fermentation product produced by a microorganism.

[0056] Hereinafter, the present invention will be described in detail, but the following description is not intended to limit the present invention to specific embodiments.

[0057] <Embodiment of pervaporation membrane>

[0058] The pervaporation membrane of this embodiment comprises a separation functional layer comprising a silicone resin and a porous support body supporting the separation functional layer. The separation functional layer, for example, has a surface directly in contact with the porous support body and a surface exposed to the outside of the pervaporation membrane. The pervaporation membrane, for example, is composed only of the separation functional layer and the porous support body. The pervaporation membrane is typically a membrane (separation membrane) that allows volatile organic compounds C to preferentially permeate from an aqueous solution S comprising organic compounds C.

[0059] The pervaporation membrane of this embodiment has a peel strength A1 of 0.15 N / 20 mm or more as measured by the following Test 1. When the peel strength A1 is as high as this, the separation functional layer can be sufficiently prevented from peeling off from the porous support when the pervaporation membrane is pulled out from the wound body of the pervaporation membrane.

[0060] Test 1: A pervaporation membrane was cut into a test piece of 20 mm in width x 150 mm in length. Using the test piece, the separation functional layer was peeled off from the porous support at a peeling angle of 180° and a tensile speed of 300 mm / min.

[0061] In detail, the above-mentioned test 1 is carried out by the following method. First, the permeation vaporization membrane to be evaluated is cut into a width of 20mm×length of 150mm as a test piece. Then, the surface of the porous support body possessed by the test piece is overlapped as a whole on the acrylic resin test plate via a double-sided tape (for example, No. 5000NS manufactured by Nitto Denko Corporation), and a 2kg roller is reciprocated once to crimp them. The acrylic resin test plate has a size of, for example, 150mm in width×150mm in length. Then, in the direction from one end of the test piece toward the other end, the separation function layer is peeled off from the porous support body by hand for only 90mm. Using a commercially available tensile testing machine, the peeled separation function layer and one end of the test piece are held near the chuck, and the remaining separation function layer is peeled off from the porous support body at a peeling angle of 180° and a tensile speed of 300mm / min. The average value of the peeling force at this time is determined as the peeling strength A1. It should be noted that in the tensile testing machine, the initial distance between the chucks is 150mm. Test 1 was performed in an atmosphere of 25°C.

[0062] The peel strength A1 is preferably 0.2 N / 20 mm or more, and may be 0.3 N / 20 mm or more, 0.4 N / 20 mm or more, 0.5 N / 20 mm or more, 0.6 N / 20 mm or more, 0.7 N / 20 mm or more, 0.8 N / 20 mm or more, and may be 1.0 N / 20 mm or more. The upper limit of the peel strength A1 is not particularly limited, and is, for example, 20 N / 20 mm.

[0063] It should be noted that in the above-mentioned test 1, the following situation exists, that is, since the separation functional layer is fully fixed to the porous support, the separation functional layer cannot be peeled off from the porous support by hand. If it is forcibly peeled off, the separation functional layer will break. It is speculated that this phenomenon is due to the above-mentioned peel strength A1 (N / 20mm) being greater than the fracture strength B1 (N / 20mm) of the separation functional layer. Therefore, in this case, the fracture strength B1 of the separation functional layer can be determined separately, and the peel strength A1 is regarded as a value greater than the fracture strength B1 (that is, peel strength A1 (N / 20mm) ≥ fracture strength B1 (N / 20mm)).

[0064] The breaking strength B1 of the separation functional layer can be determined by the following method. First, a layer having the same composition and thickness as the separation functional layer of the pervaporation membrane is prepared on a release liner, and a self-supporting film of the separation functional layer is prepared by removing the release liner. Next, the self-supporting film of the separation functional layer is cut into a test piece of 20 mm in width and 60 mm in length. The test piece is placed in a commercially available tensile testing machine, and a tensile test is performed under the following measurement conditions.

[0065] ·Measurement conditions

[0066] Temperature: 25℃

[0067] Tensile direction: length direction of the test piece

[0068] Initial distance between chucks: 20mm

[0069] Stretching speed: 300 mm / min

[0070] In the tensile test, the strength B2 (N / mm 2 ). Based on strength B2 (N / mm 2 ), the thickness B3 (mm) of the separation functional layer and the width (20 mm) of the test piece, the breaking strength B1 (N / 20 mm) can be calculated by the following formula.

[0071] Breaking strength B1(N / 20mm)

[0072] = Strength B2 (N / mm 2 )×thickness B3(mm)×20×(1 / 20)

[0073] Furthermore, in the pervaporation membrane of the present embodiment, the adhesion between the separation functional layer and the porous support measured by SAICAS (Surface and Interface Analysis System) is preferably 0.01 kN / m or more.

[0074] In detail, the above-mentioned adhesion can be measured by the following method. First, the permeation vaporization membrane to be evaluated is cut into a test piece with a size of 10 mm in length and 10 mm in width. The test piece is set in SAICAS. In SAICAS, the material of the cutting edge used for cutting is single crystal diamond, the blade width is 1 mm, and the rake angle is 10°. Next, the horizontal movement speed of the cutting edge is set to 10 μm / sec, and the vertical movement speed is set to 0.5 μm / sec, and the test piece is cut with the cutting edge. At the stage where the cutting edge reaches the interface between the separation functional layer and the porous support body, the cutting edge is moved only in the horizontal direction to peel off the separation functional layer from the porous support body. The peeling strength P at this time is calculated by the following formula, and the calculated value obtained can be regarded as the adhesion. It should be noted that in the following formula, F His the load when the cutting edge is moved in the horizontal direction at the interface between the separation functional layer and the porous support, and W is the blade width of the cutting edge.

[0075] P(kN / m)=F H (kN) / W(m)

[0076] The adhesion between the separation functional layer and the porous support is preferably 0.03 kN / m or more, and may be 0.05 kN / m or more, 0.08 kN / m or more, 0.1 kN / m or more, 0.15 kN / m or more, or 0.2 kN / m or more. The upper limit of the adhesion is not particularly limited, and is, for example, 1 kN / m.

[0077] Furthermore, the pervaporation membrane of this embodiment preferably has a peel strength A2 measured by the following Test 2 that is smaller than the above-mentioned peel strength A1. In this case, when the pervaporation membrane is unwound from the wound body of the pervaporation membrane, the separation functional layer can be further suppressed from peeling off from the porous support.

[0078] Test 2: Two test pieces T1 and T2 with a size of 20 mm in width and 150 mm in length were cut out from the pervaporation membrane. The two test pieces T1 and T2 were overlapped so that the separation functional layer of one test piece T1 was in contact with the porous support of the other test piece T2, and a 2 kg roller was reciprocated once to press them together. The test piece T2 was peeled off from the test piece T1 at a peeling angle of 180° and a tensile speed of 300 mm / min.

[0079] From another aspect, the present invention provides a pervaporation membrane having:

[0080] a separation functional layer comprising a silicone resin; and

[0081] A porous support for supporting the separation functional layer,

[0082] The peel strength A1 measured by the above-mentioned test 1 is greater than the peel strength A2 measured by the above-mentioned test 2.

[0083] In detail, the above-mentioned test 2 is carried out by the following method. First, two test pieces T1 and T2 with a size of 20 mm in width and 150 mm in length are cut out from the permeation vaporization membrane to be evaluated. Then, the surface of the porous support body possessed by the test piece T1 is overlapped on the acrylic resin test plate as a whole via a double-sided tape (for example, No. 5000NS manufactured by Nitto Denko Corporation), and a 2 kg roller is reciprocated once to press them. The acrylic resin test plate has a size of 150 mm in width and 150 mm in length, for example. Then, the two test pieces T1 and T2 are overlapped in a manner that the separation functional layer of the test piece T1 contacts the porous support body of the test piece T2, and a 2 kg roller is reciprocated once to press them. Then, the test piece T2 is peeled off only 90 mm from the test piece T1 by hand in the direction from one end of the test piece T1 toward the other end. Using a commercially available tensile testing machine, the peeled test piece T2 and one end of the test piece T1 were held with a chuck, and the remaining test piece T2 was peeled off from the test piece T1 at a peeling angle of 180° and a tensile speed of 300 mm / min. The average value of the peeling force at this time was determined as the peeling strength A2. It should be noted that in the tensile testing machine, the initial distance between the chucks was 150 mm. Test 2 was conducted in an atmosphere of 25°C.

[0084] The peel strength A2 is, for example, less than 0.15 N / 20 mm, and may be 0.1 N / 20 mm or less, 0.05 N / 20 mm or less, or even 0.01 N / 20 mm or less. The peel strength A2 may be substantially 0 N / 20 mm.

[0085] In this embodiment, when the following Test 3 is performed on the pervaporation membrane, it is preferred that no peeling of the separation functional layer from the porous support body can be visually confirmed. It should be noted that according to the research of the inventors of the present application, the state of the pervaporation membrane (test piece T1) after the Test 3 tends to be well consistent with the state of the pervaporation membrane after the pervaporation membrane is extracted from the wound body of the pervaporation membrane.

[0086] Test 3: Cut out two test pieces T1 and T2 with a size of 20 mm in width and 150 mm in length from the permeation vaporization membrane. Overlap the two test pieces T1 and T2 in such a way that the separation functional layer of one test piece T1 contacts the porous support of the other test piece T2. Fix the test piece T1 with the test piece T2 located above the test piece T1. Place a 300 g weight on one end of the test piece T2. Hold the other end of the test piece T2 and move the test piece T2 horizontally over the test piece T1 at a speed of 10 mm / sec. Visually check whether the separation functional layer of the test piece T1 has peeled off after the test piece T2 has passed.

[0087] In detail, the above-mentioned test 3 is carried out by the following method. First, two test pieces T1 and T2 having a size of 20 mm in width × 150 mm in length are cut out from the permeation vaporization membrane to be evaluated. Then, the surface of the porous support body possessed by the test piece T1 is overlapped as a whole on the acrylic resin test plate via a double-sided tape (for example, No. 5000NS manufactured by Nitto Denko Corporation), and a 2 kg roller is reciprocated once to press them together. The acrylic resin test plate has a size of, for example, 150 mm in width × 150 mm in length. Then, the two test pieces T1 and T2 are overlapped in such a way that the separation functional layer of the test piece T1 contacts the porous support body of the test piece T2, and a 2 kg roller is reciprocated once to press them together.

[0088] Next, with the test piece T2 located above the test piece T1, fix the test piece T1. For example, the test piece T1 is fixed by fixing a test plate made of acrylic resin to an operating table. Next, a 300g weight is placed on one end of the test piece T2 (specifically, one end in the length direction of the test piece T2). The shape of the weight is, for example, cylindrical or columnar. Holding the other end of the test piece T2, move the test piece T2 on the test piece T1 in the horizontal direction (specifically, the length direction of the test piece T2) at a speed of 10mm / sec. For the test piece T1 after the test piece T2 (specifically, one end of the test piece T2 with the weight placed thereon) passes, visually confirm whether the separation functional layer is peeled off. Test 3 is performed in an atmosphere of 25°C.

[0089] Below, use Figures 1A to 6 Embodiments 1 to 6 are described as preferred examples of the present embodiment. The same reference numerals are given to the common elements in Embodiments 1 to 6, and their descriptions are sometimes omitted. The descriptions of Embodiments 1 to 6 are applicable to each other as long as they are not technically contradictory. Furthermore, Embodiments 1 to 6 can also be combined with each other as long as they are not technically contradictory.

[0090] [Implementation Method 1]

[0091] like Figure 1A As shown, the pervaporation membrane 10A of the first embodiment includes a separation functional layer 1 and a porous support 5. The separation functional layer 1 has a surface 1a directly in contact with the porous support 5. The porous support 5 includes, for example, a main body 6 and a microporous layer 7 disposed on the main body 6. In the pervaporation membrane 10A, the microporous layer 7 is located between the main body 6 and the separation functional layer 1, and is directly in contact with each of the main body 6 and the separation functional layer 1. Specifically, the microporous layer 7 has a surface 7a directly in contact with the separation functional layer 1. The peel strength A1 measured in the above-mentioned test 1 corresponds to the peel strength between the surface 1a of the separation functional layer 1 and the surface 7a of the microporous layer 7.

[0092] (Separation Functional Layer)

[0093] The separation functional layer 1 is, for example, a layer that allows the organic compound C to preferentially permeate the aqueous solution S, and is typically a dense layer (non-porous layer) in which no pores are observed when observed at a magnification of 5000 times using a scanning electron microscope (SEM).

[0094] As described above, the separation function layer 1 contains a silicone resin. In Embodiment 1, the silicone resin is formed from a condensed silicone resin composition. As described later, in Embodiment 1, by using a condensed silicone resin composition, the porous support 5 (specifically, the microporous layer 7) can be bonded to the silicone resin formed from the condensed silicone resin composition.

[0095] The condensation type silicone resin composition is a type of silicone resin composition that is cured by a condensation reaction. The condensation type silicone resin composition, for example, comprises a polyorganosiloxane P1 having a silanol (SiOH) group and a silane compound P2 having functional groups such as an alkoxy group, an alkenyl group, an acyloxy group, an amino group, a ketoxime group, and an amide group. The condensation type silicone resin composition may further comprise a curing catalyst or may not comprise a curing catalyst. It should be noted that the condensation type silicone resin composition may be a commercially available silicone resin composition to which a curing catalyst is added.

[0096] The condensation type silicone resin composition can be formed into a silicone resin by, for example, heat treatment to cause the silanol groups of the polyorganosiloxane P1 to react with the functional groups of the silane compound P2 (condensation reaction). In this condensation reaction, the silane compound P2 functions as a crosslinking agent.

[0097] The number of silanol groups in the polyorganosiloxane P1 is, for example, 2 or more. The silanol groups are, for example, located at the ends of the polyorganosiloxane P1. The polyorganosiloxane P1 may have an alkyl group such as a methyl group or an ethyl group, a phenyl group, or the like introduced as a substituent of a side chain.

[0098] The polyorganosiloxane P1 is, for example, a polyalkylalkylsiloxane such as polydimethylsiloxane, polydiethylsiloxane, polymethylethylsiloxane; a polyalkylarylsiloxane; a polyorganosiloxane such as poly(dimethylsiloxane-diethylsiloxane) and a silanol group introduced therein.

[0099] The weight average molecular weight of polyorganosiloxane P1 is, for example, 1000 or more, 10,000 or more, 100,000 or more, 200,000 or more, 300,000 or more, or 400,000 or more. The upper limit of the weight average molecular weight of polyorganosiloxane P1 is not particularly limited, and is, for example, 1,000,000.

[0100] As described above, the silane compound P2 has functional groups such as an alkoxy group, an alkenyloxy group, an acyloxy group, an amino group, a ketoxime group, and an amide group. As an alkoxy group, a methoxy group, an ethoxy group, etc. can be mentioned. As an alkenyloxy group, an isopropenyloxy group, etc. can be mentioned. As an acyloxy group, an acetoxy group, etc. can be mentioned. As an amino group, a dimethylamino group, a diethylamino group, an ethylmethylamino group, etc. can be mentioned. As a ketoxime group, an acetoxime group, a methylethylketoxime group, etc. can be mentioned. As an amide group, an acetamide group, an N-methylacetamide group, an N-ethylacetamide group, etc. can be mentioned. The number of functional groups in the silane compound P2 is, for example, more than 2. In detail, the silane compound P2 preferably contains an alkoxysilyl group as an alkoxy group.

[0101] The silane compound P2 may be a low molecular weight compound having a molecular weight of about 1000 or less, or may be a high molecular weight compound having a polysiloxane skeleton.

[0102] Examples of the curing catalyst include tin catalysts and organic tin catalysts such as dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin dioctoate.

[0103] The condensation type silicone resin composition may contain an organic solvent in addition to the above-mentioned components. Examples of the organic solvent include hydrocarbon solvents such as cyclohexane, n-hexane, and n-heptane; aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and methyl acetate; ketone solvents such as acetone and methyl ethyl ketone; and alcohol solvents such as methanol, ethanol, and butanol. The organic solvent may be used alone or in combination of two or more. The condensation type silicone resin composition may also be a solvent-free type that does not contain an organic solvent or the like.

[0104] The separation functional layer 1 may contain silicone resin as a main component, or may be substantially composed of silicone resin alone. The “main component” refers to the component that is contained in the largest amount by weight in the separation functional layer 1 .

[0105] The thickness of the separation functional layer 1 is, for example, 200 μm or less, 100 μm or less, or 80 μm or less. The thickness of the separation functional layer 1 may be 1.0 μm or more, 10 μm or more, or 30 μm or more.

[0106] (Porous Support)

[0107] As described above, the porous support 5 includes, for example, the main body 6 and the microporous layer 7. The porous support 5 is typically an ultrafiltration membrane.

[0108] In Embodiment 1, the porous support 5 has a surface (surface 7a of the microporous layer 7) that is opposite to the separation functional layer 1 and has been subjected to a surface modification treatment. In other words, a surface modification treatment is applied to the surface 7a of the microporous layer 7. Examples of the surface modification treatment include corona treatment, plasma treatment, excimer treatment, flame treatment, and the like, and corona treatment is preferred.

[0109] The main body 6 is, for example, a fiber structure such as a woven fabric or a nonwoven fabric, and is typically a nonwoven fabric. Examples of the fibers contained in the fiber structure include natural fibers such as wood pulp, cotton, and hemp (e.g., Manila hemp); and chemical fibers (synthetic fibers) such as polyester fibers, rayon, vinylon, acetate fibers, polyvinyl alcohol (PVA) fibers, polyamide fibers, polyolefin fibers, and polyurethane fibers. The main body 6 is, for example, a nonwoven fabric made of polyester fibers. The main body 6 has, for example, an average pore size of 1 μm to 50 μm.

[0110] Examples of the material of the microporous layer 7 include fluororesins such as polyvinylidene fluoride and polytetrafluoroethylene, polyarylethersulfones such as polysulfone and polyethersulfone, and polyimide. The microporous layer 7 has an average pore diameter of, for example, 0.01 μm to 0.4 μm.

[0111] The thickness of the porous support 5 is not particularly limited, and may be, for example, 10 μm or more, 50 μm or more, or 100 μm or more. The thickness of the porous support 5 may be, for example, 300 μm or less, or 200 μm or less.

[0112] (Method for producing pervaporation membrane)

[0113] The pervaporation membrane 10A can be manufactured, for example, by the following method. Figure 1B As shown, the surface 7a of the microporous layer 7 of the porous support 5 is irradiated with active energy rays 15 to perform surface modification treatment. Specific examples of the active energy rays 15 are electron beams, ion beams, plasma beams, ultraviolet rays, etc. Through the surface modification treatment, a plurality of hydroxyl groups are introduced into the surface 7a of the microporous layer 7.

[0114] Next, a coating liquid containing the material of the separation function layer 1 is prepared. The coating liquid is, for example, a silicone resin composition (condensed silicone resin composition). Figure 1C As shown, the coating film 11 is formed by coating the coating liquid on the surface 7a of the microporous layer 7. The separation functional layer 1 is formed by curing the coating film 11, and the pervaporation membrane 10A ( Figure 1A The coating film 11 can be cured at room temperature or under heating.

[0115] When the coating film 11 is cured by heating, the heating conditions of the coating film 11 are not particularly limited. For example, the heating temperature of the coating film 11 may be 80°C or higher, 90°C or higher, 100°C or higher, or 120°C or higher. The higher the heating temperature of the coating film 11, the more fully the curing reaction of the components in the silicone resin composition proceeds. The upper limit of the heating temperature of the coating film 11 is not particularly limited, and is, for example, 200°C. The heating time of the coating film 11 can be appropriately adjusted according to the composition of the silicone resin composition used.

[0116] The pervaporation membrane 10A can be produced in a roll-to-roll method. That is, a long porous support 5 can be pulled out from a roll of porous support 5, and the surface modification treatment and the formation of separation functional layer 1 can be performed while the porous support 5 is transported. Furthermore, the obtained pervaporation membrane 10A can be rolled up to produce a roll of pervaporation membrane 10A. The roll-to-roll method is suitable for mass production of pervaporation membrane 10A.

[0117] In the first embodiment, a plurality of hydroxyl groups are introduced into the surface 7a of the microporous layer 7 by the surface modification treatment. Therefore, when the coating film 11 is subjected to a heat treatment, a part of the silane compound P2 contained in the condensed silicone resin composition reacts with the silanol group of the polyorganosiloxane P1, and also reacts with the hydroxyl groups present on the surface 7a of the microporous layer 7. Thus, the microporous layer 7 can be bonded to the silicone resin formed by the condensed silicone resin composition by a covalent bond. The pervaporation membrane 10A of the first embodiment tends to have a large peel strength A1 due to the bonding between the porous support 5 (microporous layer 7) and the silicone resin.

[0118] (Application of Pervaporation Membrane)

[0119] The permeation vaporization membrane 10A of the present embodiment is suitable for use, for example, in separating organic compound C from an aqueous solution S containing volatile organic compound C. There is no particular limitation on the organic compound C as long as it is volatile. In this specification, the so-called "volatile organic compound" refers to an organic compound having a boiling point of 20°C to 260°C at atmospheric pressure (101.325 kPa). It should be noted that for organic compound C, for example, when the concentration in the aqueous solution is high, an aqueous phase containing water as the main component and an organic phase having a higher content of organic compound C than the aqueous phase are generated. However, organic compound C may not generate an aqueous phase and an organic phase.

[0120] The number of carbon atoms in the organic compound C is not particularly limited, and may be, for example, 10 or less, 8 or less, 6 or less, or 4 or less. The lower limit of the number of carbon atoms in the organic compound C may be 1 or 2. The organic compound C may have, for example, a functional group containing an oxygen atom such as a hydroxyl group, a carbonyl group, an ether group, or an ester group. In the organic compound C, the number of functional groups containing an oxygen atom is typically 1.

[0121] As the organic compound C, for example, alcohol, ketone, ester, etc. can be mentioned, typically alcohol. Alcohol can be an alkyl alcohol consisting of only an alkyl group and a hydroxyl group, or an aryl alcohol containing an aryl group and a hydroxyl group. The alkyl alcohol can be any of linear, branched, and cyclic. As the alkyl alcohol, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, tert-butanol, n-pentanol, etc. can be mentioned. As the aryl alcohol, for example, phenol, etc. can be mentioned.

[0122] The ketone may be a dialkyl ketone consisting only of an alkyl group and a carbonyl group. Examples of the dialkyl ketone include methyl ethyl ketone (MEK) and acetone.

[0123] The ester may be a fatty acid alkyl ester consisting only of an alkyl group and an ester group. Examples of the fatty acid alkyl ester include ethyl acetate and the like.

[0124] It should be noted that the organic compound C is not limited to the above compounds and may be an aromatic hydrocarbon such as benzene, toluene, or xylene.

[0125] The aqueous solution S may contain one organic compound C, or may contain two or more organic compounds C. The content of the organic compound C in the aqueous solution S is, for example, 0.5 wt% or more, 1 wt% or more, 2 wt% or more, or 5 wt% or more. The upper limit of the content of the organic compound C is not particularly limited, and is, for example, 50 wt%.

[0126] The organic compound C may be a fermentation product produced by microorganisms fermenting carbon sources, or may be an alcohol (bioalcohol) produced by microorganisms. That is, the aqueous solution S may be a fermentation liquid containing the organic compound C as a fermentation product. However, the aqueous solution S is not limited to the fermentation liquid, and may also be waste liquid or wastewater discharged from chemical equipment, etc.

[0127] The aqueous solution S may contain other components such as microorganisms that generate fermentation products, carbon sources, nitrogen sources, inorganic ions, etc., in addition to water and organic compounds C. The microorganisms that generate fermentation products are typically bacteria. As carbon sources, polysaccharides such as starch and monosaccharides such as glucose can be cited.

[0128] (Pervaporation membrane characteristics)

[0129] In the pervaporation membrane 10A, the separation coefficient of the organic compound C with respect to water is not particularly limited. As an example, the separation coefficient α of the pervaporation membrane 10A with respect to n-butanol (BuOH) with respect to water is, for example, 10 or more, and may be 15 or more, 20 or more, 25 or more, 30 or more, or 40 or more. The upper limit of the separation coefficient α is, for example, 100.

[0130] The separation coefficient α can be measured by the following method. While a mixed liquid obtained from BuOH and water is in contact with one side of the pervaporation membrane 10A (e.g., the main surface 10a on the separation functional layer side of the pervaporation membrane 10A), the space adjacent to the other side of the pervaporation membrane 10A (e.g., the main surface 10b on the porous support body side of the pervaporation membrane 10A) is depressurized. Thus, a permeating fluid passing through the pervaporation membrane 10A is obtained. The weight ratio of water and the weight ratio of BuOH in the permeating fluid are measured. In the above operation, the content of BuOH in the mixed liquid is 1.0 wt%. The temperature of the mixed liquid in contact with the pervaporation membrane 10A is 30°C. The space adjacent to the other side of the pervaporation membrane 10A is depressurized to 15 hPa. The separation coefficient α can be calculated according to the following formula. In the following formula, X A and X B are the weight ratio of BuOH and the weight ratio of water in the mixed liquid respectively. A and Y B They are respectively the weight ratio of BuOH and the weight ratio of water in the permeated fluid that has permeated the pervaporation membrane 10A.

[0131] Separation coefficient α=(Y A / Y B ) / (X A / X B )

[0132] In the measurement conditions of the separation coefficient α, the flux of BuOH permeating the pervaporation membrane 10A is not particularly limited, and is, for example, 0.01 (g / min / m 2 )~10.0(g / min / m 2 ).

[0133] [Implementation Method 2]

[0134] like Figure 2AAs shown, the pervaporation membrane 10B of the second embodiment includes a separation functional layer 1 and a porous support 5. The porous support 5 includes a main body 6, a microporous layer 7, and a primer layer 8 in this order. In the pervaporation membrane 10B, the primer layer 8 is located between the microporous layer 7 and the separation functional layer 1, and is directly in contact with each of the microporous layer 7 and the separation functional layer 1. Specifically, the primer layer 8 has a surface 8a that is directly in contact with the microporous layer 7 and a surface 8b that is directly in contact with the separation functional layer 1. The peel strength A1 measured in the above-mentioned test 1 corresponds to the peel strength between the surface 1a of the separation functional layer 1 and the surface 8b of the primer layer 8.

[0135] (Separation Functional Layer)

[0136] In the second embodiment, the silicone resin is, for example, a resin formed of an addition-type silicone resin composition. However, depending on the circumstances, the silicone resin may be formed of the condensation-type silicone resin composition or UV-curable silicone resin composition described above in the first embodiment.

[0137] [Addition type silicone resin composition]

[0138] The addition type silicone resin composition is a type of silicone resin composition that is cured by an addition reaction. The addition type silicone resin composition, for example, comprises a polyorganosiloxane P3 having an alkenyl group and a polyorganosiloxane P4 having a hydrosilane (SiH) group. The addition type silicone resin composition preferably further comprises a curing catalyst (hydrosilylation catalyst). It should be noted that the addition type silicone resin composition may be a material in which a curing catalyst is added to a commercially available silicone resin composition. However, the addition type silicone resin composition may not include a curing catalyst.

[0139] The addition-type silicone resin composition can be formed into a silicone resin by, for example, heat-treating the alkenyl group of the polyorganosiloxane P3 and the hydrosilyl group of the polyorganosiloxane P4 to react (hydrosilylation reaction). In the hydrosilylation reaction, the polyorganosiloxane P4 functions as a crosslinking agent.

[0140] Examples of the alkenyl group in the polyorganosiloxane P3 include vinyl and hexenyl groups. The number of alkenyl groups in the polyorganosiloxane P3 is, for example, 2 or more. The alkenyl group is, for example, located at the terminal of the polyorganosiloxane P3.

[0141] The polyorganosiloxane P3 is, for example, a polyorganosiloxane in which an alkenyl group is introduced into the polyorganosiloxane described above with respect to the polyorganosiloxane P1.

[0142] The weight average molecular weight of the polyorganosiloxane P3 is, for example, 1000 or more, 10,000 or more, 100,000 or more, 200,000 or more, 300,000 or more, or 400,000 or more. The larger the weight average molecular weight of the polyorganosiloxane P3, the more the separation characteristics of the pervaporation membrane 10B tend to improve. The upper limit of the weight average molecular weight of the polyorganosiloxane P3 is not particularly limited, and is, for example, 1,000,000.

[0143] The number of hydrosilyl groups in the polyorganosiloxane P4 is, for example, not less than 2. The hydrosilyl group may be located at the terminal of the polyorganosiloxane P4, or may be included in the main chain of the polyorganosiloxane P4.

[0144] Examples of the polyorganosiloxane P4 include polymethylhydrogensiloxane, poly(dimethylsiloxane-methylhydrogensiloxane), and hydrosilyl-terminated polydimethylsiloxane.

[0145] The weight average molecular weight of the polyorganosiloxane P4 is, for example, 100 or more, and may be 10,000 or more. The larger the weight average molecular weight of the polyorganosiloxane P4, the more the separation characteristics of the pervaporation membrane 10B tend to improve. The upper limit of the weight average molecular weight of the polyorganosiloxane P4 is not particularly limited, and is, for example, 1,000,000.

[0146] The weight ratio P4 / P3 of the polyorganosiloxane P4 to the polyorganosiloxane P3 is, for example, 500 wt% or less, 100 wt% or less, 50 wt% or less, 20 wt% or less, 10 wt% or less, or 5 wt% or less. The lower the weight ratio P4 / P3, the more likely the peel strength A1 is to increase. The lower limit of the weight ratio P4 / P3 is, for example, 0.01 wt% or more.

[0147] As a curing catalyst, for example, a platinum-based catalyst can be cited. In other words, the addition-type silicone resin composition may contain a curing catalyst containing platinum. Specific examples of the platinum-based catalyst are chloroplatinic acid, an olefin complex of platinum, an olefin complex of chloroplatinic acid, and the like. As described above, the addition-type silicone resin composition may not contain a curing catalyst.

[0148] The addition type silicone resin composition may contain a compound that generates a catalyst active species that catalyzes an addition reaction when irradiated with active energy rays such as ultraviolet rays (UV). The addition type silicone resin composition containing such a compound can cause an addition reaction by, for example, UV irradiation.

[0149] The addition type silicone resin composition may contain an organic solvent in addition to the above components. Examples of the organic solvent include the organic solvents described above for the condensation type silicone resin composition. The addition type silicone resin composition may be a solvent-free type that contains substantially no solvent such as an organic solvent.

[0150] [UV curable silicone resin composition]

[0151] The UV-curable silicone resin composition is a type of silicone resin composition that is cured by ultraviolet (UV) irradiation. The UV-curable silicone resin composition undergoes a curing reaction, for example, by free radical polymerization, free radical addition, ionic polymerization, and the like. The UV-curable silicone resin composition that undergoes a curing reaction by free radical polymerization, for example, includes a polyorganosiloxane P5 having a double bond (specifically, a carbon-carbon double bond) derived from an alkenyl group, an acryloyl group, and the like. The UV-curable silicone resin composition that undergoes a curing reaction by free radical addition, for example, includes a polyorganosiloxane P5 having a double bond (specifically, a carbon-carbon double bond) derived from an alkenyl group, an acryloyl group, and the like, and a compound P6 having a functional group such as a thiol group that can undergo free radical addition. The UV-curable silicone resin composition that undergoes a curing reaction by ionic polymerization, for example, includes a polyorganosiloxane P7 having a functional group such as an epoxy group that can undergo ionic polymerization, and a compound that produces a catalyst active species that catalyzes ionic polymerization by UV irradiation.

[0152] According to the UV curable silicone resin composition that undergoes a curing reaction by radical polymerization, for example, double bonds contained in alkenyl groups, acryloyl groups, etc. of the polyorganosiloxane P5 undergo a radical polymerization reaction by UV irradiation, thereby forming a silicone resin.

[0153] Examples of the alkenyl group of the polyorganosiloxane P5 include vinyl and hexenyl groups. The number of alkenyl groups in the polyorganosiloxane P5 is, for example, 2 or more. The alkenyl group is, for example, located at the end of the polyorganosiloxane P5. In the polyorganosiloxane P5, as a substituent of the side chain, an alkyl group such as a methyl group or an ethyl group, a phenyl group, etc. may be introduced.

[0154] The polyorganosiloxane P5 is obtained by introducing a substituent having a double bond, such as an alkenyl group or an acryloyl group, into the polyorganosiloxane described above for the polyorganosiloxane P1, for example.

[0155] The weight average molecular weight of polyorganosiloxane P5 is, for example, 1000 or more, 10,000 or more, 100,000 or more, 200,000 or more, 300,000 or more, or 400,000 or more. The upper limit of the weight average molecular weight of polyorganosiloxane P5 is not particularly limited, and is, for example, 1,000,000.

[0156] According to the UV curable silicone resin composition that undergoes a curing reaction by radical addition, for example, by UV irradiation, the functional group capable of radical addition contained in compound P6 is radically added to the double bond contained in the alkenyl group, acryloyl group, etc. of polyorganosiloxane P5. Thus, the radical addition reaction can proceed to form a silicone resin.

[0157] In compound P6, the functional group capable of radical addition is, for example, a thiol group, an alkylthiol group, etc. Examples of the alkylthiol group include mercaptomethyl and mercaptoethyl groups. The number of the functional groups capable of radical addition in compound P6 is, for example, 2 or more.

[0158] Compound P6 may be a polyorganosiloxane containing a functional group capable of free radical addition. The functional group is, for example, located at the end of the polyorganosiloxane. In the polyorganosiloxane, an alkyl group such as a methyl group or an ethyl group, a phenyl group, etc. may be introduced as a substituent of a side chain.

[0159] Compound P6 is, for example, a compound obtained by introducing a functional group capable of radical addition, such as a thiol group, into the polyorganosiloxane described above with respect to polyorganosiloxane P1.

[0160] The weight average molecular weight of compound P6 is, for example, 1000 or more, 10,000 or more, 100,000 or more, 200,000 or more, 300,000 or more, or 400,000 or more. The upper limit of the weight average molecular weight of compound P6 is not particularly limited, and is, for example, 1,000,000.

[0161] According to the UV curable silicone resin composition that undergoes curing reaction by ion polymerization, for example, by UV irradiation, a catalyst active species that catalyzes ion polymerization is generated, and ion polymerizable functional groups contained in the polyorganosiloxane P7 undergo ion polymerization reaction with each other, thereby forming a silicone resin.

[0162] In the polyorganosiloxane P7, the functional group capable of ion polymerization is, for example, an epoxy group. Examples of the substituent containing the epoxy group include the epoxy group itself, a glycidyl group, a glycidyloxypropyl group, and the like. The number of the functional groups capable of ion polymerization in the polyorganosiloxane P7 is, for example, 2 or more. The functional group capable of ion polymerization is, for example, located at the end of the polyorganosiloxane P7. In the polyorganosiloxane P7, as a substituent of the side chain, an alkyl group such as a methyl group or an ethyl group, a phenyl group, and the like can be introduced.

[0163] The polyorganosiloxane P7 is obtained, for example, by introducing an ion-polymerizable functional group such as an epoxy group into the polyorganosiloxane described above for the polyorganosiloxane P1.

[0164] The weight average molecular weight of polyorganosiloxane P7 is, for example, 1000 or more, 10,000 or more, 100,000 or more, 200,000 or more, 300,000 or more, or 400,000 or more. The upper limit of the weight average molecular weight of polyorganosiloxane P7 is not particularly limited, and is, for example, 1,000,000.

[0165] In addition to the above-mentioned components, the UV-curable silicone resin composition may also contain an organic solvent. Examples of the organic solvent include hydrocarbon solvents such as cyclohexane, n-hexane, and n-heptane; aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and methyl acetate; ketone solvents such as acetone and methyl ethyl ketone; alcohol solvents such as methanol, ethanol, and butanol, etc. The organic solvent may be used alone or in combination of two or more. The UV-curable silicone resin composition may also be a solvent-free type that does not substantially contain an organic solvent or other solvents.

[0166] (Porous Support)

[0167] As described above, the porous support 5 includes, for example, a main body 6, a microporous layer 7, and a primer layer 8. The porous support 5 is typically a support having a primer layer 8 formed on an ultrafiltration membrane. The primer layer 8 functions as a base layer for improving adhesion to the separation functional layer 1. The primer layer 8 has a microporous structure, for example, because it is formed on the surface 7a of the microporous layer 7.

[0168] In the second embodiment, a surface modification treatment is performed on the surface 7a of the microporous layer 7. Examples of the surface modification treatment include the treatments described above with respect to the first embodiment.

[0169] The primer layer 8 is, for example, a layer formed from a composition L containing a compound C1 having a reactive group F1 reactive with a polyorganosiloxane (particularly the polyorganosiloxane P4) contained in the silicone resin composition for forming the separation functional layer 1 and a reactive group F2 reactive with the surface 7 a of the microporous layer 7 .

[0170] In the above-mentioned compound C1, the reactive group F1 is preferably capable of reacting with the hydrosilyl group of the polyorganosiloxane P4, and is typically an alkenyl group. As a specific example of the alkenyl group, the alkenyl group described above for the polyorganosiloxane P3 can be cited. The reactive group F2 is preferably capable of reacting with the hydroxyl group introduced into the surface 7a of the microporous layer 7 by surface modification treatment, and is typically an alkoxy group. As a specific example of the alkoxy group, the alkoxy group described above for the silane compound P2 can be cited. In detail, the reactive group F2 is preferably an alkoxysilyl group.

[0171] The compound C1 is, for example, a silane coupling agent having a reactive group F1. Specific examples of the compound C1 include vinyltrimethoxysilane and the like.

[0172] In addition to the compound C1, the composition L may contain a catalyst that promotes the reaction between the reactive group F1 and the polyorganosiloxane, a catalyst that promotes the reaction between the reactive group F2 and the surface 7 a of the microporous layer 7 , an organic solvent, and the like.

[0173] As described later, the primer layer 8 is prepared, for example, by applying the composition L (coating solution) containing the above-mentioned compound C1 on the surface 7a of the microporous layer 7. The coating thickness at this time is not particularly limited, and is, for example, 1 μm to 100 μm. By drying the coating film obtained by applying the coating solution, a primer layer 8 having a thickness of about 1 / 10 or less of the coating thickness can be obtained.

[0174] (Method for producing pervaporation membrane)

[0175] The pervaporation membrane 10B can be produced, for example, by the following method. First, a laminate having the main body 6 and the microporous layer 7 is prepared. Next, by referring to the method of Embodiment 1, Figure 1B The surface 7a of the microporous layer 7 is subjected to surface modification treatment by the method described above. Next, a composition L (coating solution) containing the above-mentioned compound C1 is prepared and coated on the surface 7a of the microporous layer 7. The obtained coating film is dried to form a primer layer 8, and a porous support 5 ( Figure 2B The drying conditions of the coating film are not particularly limited. For example, the drying temperature is room temperature (25° C.) to 100° C., and the drying time is 10 minutes to 1 day.

[0176] Next, a coating liquid containing the material of the separation function layer 1 is prepared. The coating liquid is, for example, a silicone resin composition (particularly an addition type silicone resin composition). Figure 2C As shown in FIG. 1 , a coating film 11 is formed by applying a coating liquid onto the surface 8b of the primer layer 8. The coating film 11 is cured to form a separation functional layer 1, thereby obtaining a pervaporation membrane 10B ( Figure 2A ). The curing of the coating film 11 can be performed at room temperature or in a heated environment. The curing of the coating film 11 can also be performed by irradiation with active energy rays such as UV. In the case where the coating film 11 is cured by heating, the heating conditions of the coating film 11 are not particularly limited, and the conditions described above in Embodiment 1 can be used.

[0177] The production of the pervaporation membrane 10B can be carried out in a roll-to-roll method. That is, a long laminated body can be pulled out from a roll of the laminated body having the main body 6 and the microporous layer 7, and the surface modification treatment, the formation of the primer layer 8, and the formation of the separation functional layer 1 can be carried out while the laminated body is transported. Furthermore, the obtained pervaporation membrane 10B can be wound up to produce a roll of the pervaporation membrane 10B. The roll-to-roll method is suitable for mass production of the pervaporation membrane 10B.

[0178] In the second embodiment, when the primer layer 8 is formed, the reactive group F2 of the compound C1 reacts with the surface 7a of the microporous layer 7 (specifically, the hydroxyl group introduced into the surface 7a). Thus, the compound C1 can be bonded to the microporous layer 7. In this state, the reactive group F1 is present on the surface of the primer layer 8. Therefore, when the coating film 11 is heat-treated, a part of the polyorganosiloxane (e.g., polyorganosiloxane P4) contained in the silicone resin composition reacts with other polyorganosiloxanes (e.g., polyorganosiloxane P3), and also reacts with the reactive group F1 of the primer layer 8. Thus, the primer layer 8 can be bonded to the silicone resin formed by the silicone resin composition via a covalent bond. Through the bonding of the porous support 5 (primer layer 8) and the silicone resin, in the permeation vaporization membrane 10B of the second embodiment, there is a tendency that the peel strength A1 is large.

[0179] [Implementation method 3]

[0180] like Figure 3 As shown, the pervaporation membrane 10C of the third embodiment includes a separation functional layer 1 and a porous support 5. In the third embodiment, the separation functional layer 1 is formed of a mixture containing a silicone resin composition and the compound C1 described above in the second embodiment. Except for the above, the configuration of the pervaporation membrane 10C of the third embodiment is the same as that of the pervaporation membrane 10A of the first embodiment.

[0181] In Embodiment 3, the silicone resin composition is, for example, an addition-type silicone resin composition. However, depending on the circumstances, the silicone resin composition may also be a condensation-type silicone resin composition or a UV-curable silicone resin composition. It should be noted that in this specification, a mixture comprising a silicone resin composition and compound C1 is sometimes referred to as a silicone resin composition. That is, in Embodiment 3, the silicone resin composition for forming the silicone resin comprises a polyorganosiloxane (particularly a polyorganosiloxane P4) and a compound C1. As described above, compound C1 has reactive groups F1 and F2. Reactive group F1 can react with polyorganosiloxane (particularly polyorganosiloxane P4), and reactive group F2 can react with the surface of the porous support 5 opposite to the separation functional layer 1 (specifically, the surface 7a of the microporous layer 7).

[0182] (Method for producing pervaporation membrane)

[0183] The pervaporation membrane 10C can be produced, for example, by the following method. Figure 1B In the method described, the surface 7 a of the microporous layer 7 of the porous support 5 is subjected to a surface modification treatment.

[0184] Next, a coating solution containing a material for the separation functional layer 1 is prepared. The coating solution is a mixture containing a silicone resin composition (particularly an addition-type silicone resin composition) and a compound C1. The mixture may also contain a catalyst that promotes the reaction between the reactive group F1 of the compound C1 and the polyorganosiloxane, a catalyst that promotes the reaction between the reactive group F2 and the surface 7a of the microporous layer 7, and the like. The content of the compound C1 in the mixture is preferably less than 10wt%, and may be less than 8wt%, less than 5wt%, or less than 1wt%. When the content of the compound C1 is less than 10wt%, it is easy to adjust the peel strength A1 to a sufficiently large value. The lower limit of the content of the compound C1 is, for example, 0.001wt%, may be 0.01wt%, or may be 0.1wt%.

[0185] Next, a coating film is formed by applying the coating liquid onto the surface 7a of the microporous layer 7. The coating film is cured to form the separation functional layer 1, and the permeation vaporization membrane 10C is obtained. The curing of the coating film can be performed at room temperature or in a heated environment. The curing of the coating film can also be performed by irradiation with active energy rays such as UV. When the coating film is cured by heating, the heating conditions of the coating film are not particularly limited, and the conditions described above in Embodiment 1 can be used.

[0186] The production of the pervaporation membrane 10C can be performed in a roll-to-roll method. That is, a long porous support 5 can be pulled out from a roll of porous support 5, and the surface modification treatment and the formation of separation functional layer 1 can be performed while the porous support 5 is transported. Furthermore, the obtained pervaporation membrane 10C can be rolled up to produce a roll of pervaporation membrane 10C. The roll-to-roll method is suitable for mass production of pervaporation membrane 10C.

[0187] In the third embodiment, when the separation functional layer 1 is formed, the reactive group F2 of the compound C1 reacts with the surface 7a of the microporous layer 7 (specifically, the hydroxyl group introduced into the surface 7a). Thus, the compound C1 can be bonded to the microporous layer 7. Furthermore, a part of the polyorganosiloxane (e.g., polyorganosiloxane P4) contained in the silicone resin composition reacts with other polyorganosiloxanes (e.g., polyorganosiloxane P3) and also reacts with the reactive group F1 of the compound C1. Thus, the microporous layer 7 can be bonded to the silicone resin formed by the silicone resin composition via the compound C1. Through the bonding of the porous support 5 (microporous layer 7) and the silicone resin, the permeation vaporization membrane 10C of the third embodiment has a tendency to have a large peel strength A1.

[0188] [Implementation Method 4]

[0189] like Figure 4AAs shown, the pervaporation membrane 10D of the fourth embodiment includes a separation functional layer 1 and a porous support 5. The porous support 5 has only a main body 6 and does not have a microporous layer 7. Except for the above, the configuration of the pervaporation membrane 10D of the fourth embodiment is the same as that of the pervaporation membrane 10A of the first embodiment.

[0190] (Separation Functional Layer)

[0191] In Embodiment 4, the silicone resin is, for example, a resin formed of the addition-type silicone resin composition described above in Embodiment 2. However, depending on circumstances, the silicone resin may be formed of the condensation-type silicone resin composition or UV-curable silicone resin composition described above in Embodiment 1.

[0192] (Porous Support)

[0193] As described above, the porous support 5 has only the main body 6. The main body 6 is, for example, a fiber structure, typically a nonwoven fabric. That is, in the fourth embodiment, the separation functional layer 1 is directly in contact with the fiber structure (specifically, the nonwoven fabric).

[0194] The porous support 5 (main body 6) has a surface 5a opposite to the separation functional layer 1. In detail, the surface 5a faces the separation functional layer 1 side. The surface 5a is, for example, directly in contact with the separation functional layer 1. The surface 5a includes a plurality of openings H1. The openings H1 are, for example, connected to the pores contained in the porous support 5. When the porous support 5 is a fiber structure, the openings H1 are typically gaps between fibers in the surface 5a.

[0195] The average diameter L1 of the plurality of openings H1 is 0.5 μm or more, preferably 1 μm or more, 2 μm or more, 5 μm or more, 8 μm or more, 10 μm or more, 13 μm or more, and may be 15 μm or more. The upper limit of the average diameter L1 is not particularly limited, and may be, for example, 10 mm or less, 1 mm or less, 100 μm or less, or 50 μm or less.

[0196] The average diameter L1 can be determined by the following method. First, a scanning electron microscope (SEM) is used to observe the surface 5a of the porous support 5. The observation of the surface 5a is performed, for example, on the porous support 5 taken out from the pervaporation membrane 10D. It should be noted that the observation of the surface 5a can be performed on the porous support 5 before the pervaporation membrane 10D is produced.

[0197] As an example, when the porous support 5 is a non-woven fabric and the opening H1 is large, the magnification of the SEM is adjusted to about 50 times, and in the obtained SEM image, the opening H1 is determined within a range larger than 2.0 mm in length × 2.5 mm in width. Assuming that the porous support 5 has a microporous layer 7 and the opening H1 is small, the magnification of the SEM is adjusted to about 20,000 times, and in the obtained SEM image, the opening H1 is determined within a range larger than 4.8 μm in length × 6.0 μm in width. In detail, the opening H1 is determined by converting the SEM image into a binary image of the opening H1 and other parts (non-openings) other than the opening H1 using software (e.g., Image J). For each determined opening H1, the area (opening area h) is calculated by image processing. For each opening H1, the diameter of a circle having the same area as the calculated area is regarded as the diameter d of the opening H1. Based on the obtained results, the average diameter L1 can be determined by the following formula. It should be noted that, as shown in the following formula, the average diameter L1 is a weighted average value of the diameters d weighted by the opening area h.

[0198] Average diameter L1 (μm) = Σ {opening area h (μm 2 )×diameter d(μm) / Σopening area h(μm 2 )

[0199] The opening ratio R1 of the surface 5a is not particularly limited, and is, for example, 1 to 30%. The opening ratio R1 can be measured by the following method. First, the surface 5a of the porous support 5 is observed with an SEM by the method described above for the average diameter L1 to determine the opening H1. The ratio of the total area occupied by the opening H1 in the SEM image can be regarded as the opening ratio R1.

[0200] The porous support 5 has a surface opposite to the surface 5a (typically, the main surface 10b on the porous support side of the pervaporation membrane 10D). Like the surface 5a, the surface opposite to the surface 5a includes, for example, a plurality of openings H2. The openings H2 are connected to, for example, pores included in the porous support 5. When the porous support 5 is a fiber structure, the openings H2 are typically gaps between fibers in the surface opposite to the surface 5a.

[0201] The average diameter L2 of the plurality of openings H2 is 0.5 μm or more, preferably 1 μm or more, 2 μm or more, 5 μm or more, 8 μm or more, 10 μm or more, 13 μm or more, and may be 15 μm or more. The upper limit of the average diameter L2 is not particularly limited, and may be, for example, 10 mm or less, 1 mm or less, 100 μm or less, or 50 μm or less. The average diameter L2 can be determined by the method described above for the average diameter L1.

[0202] The average diameter L2 may be the same as the average diameter L1 described above, or may be a value greater than the average diameter L1. As an example, the ratio L2 / L1 of the average diameter L2 (μm) to the average diameter L1 (μm) is, for example, 0.3 to 30. The ratio L2 / L1 is, for example, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, 5 or less, or 3 or less. The ratio L2 / L1 is, for example, 0.3 or more, 0.5 or more, or 0.8 or more.

[0203] The aperture ratio R2 of the surface opposite to the surface 5a is not particularly limited, and is, for example, 1 to 30%. The aperture ratio R2 can be measured by the method described above for the aperture ratio R1. The aperture ratio R2 may be the same as the aperture ratio R1, or may be a value higher than the aperture ratio R1. As an example, the absolute value |R2-R1| of the difference between the aperture ratio R2 (%) and the aperture ratio R1 (%) is, for example, less than 30%, less than 20%, less than 10%, or less than 5%.

[0204] In the fourth embodiment, the porous support 5 does not have a microporous layer, so there is a tendency that the air permeability is high when used alone. As an example, the air permeability in the thickness direction of the porous support 5 is represented by the air permeability (Gurley permeability) obtained by the air permeability measurement B method (Gurley method) specified in JIS L1096: 2010, for example, it is 50 seconds / 100mL or less, it can be 30 seconds / 100mL or less, 10 seconds / 100mL or less, and it can also be 5 seconds / 100mL or less. The lower limit of the Gurley air permeability of the porous support 5 is not particularly limited, for example, it is 0.1 seconds / 100mL.

[0205] In Embodiment 4, the surface 5a of the porous support 5 is treated with a molecular bonding agent. The molecular bonding agent includes a molecular bonding compound (hereinafter referred to as "compound C2") and an organic solvent, water or other solvent as required. Compound C2 has a reactive group F3 that can react with the surface 5a of the porous support 5, and a reactive group F4 that can react with the silicone resin contained in the separation functional layer 1. The reactive group F4 can react not only with the silicone resin, but also with the surface 5a of the porous support 5.

[0206] The reactive group F3 is, for example, at least one selected from the group consisting of an amino group, an azido group, a mercapto group, an isocyanate group, a urea group, and an epoxy group, and is typically an azido group. The reactive group F4 is, for example, at least one selected from the group consisting of a silanol group and a group G that generates a silanol group by a hydrolysis reaction. A specific example of the group G is an alkoxysilyl group.

[0207] Compound C2 is represented by, for example, the following formula (1).

[0208] R A -ZR B (1)

[0209] In formula (1), R A represents a reactive group F3 or a monovalent substituent having one or more reactive groups F3, R B represents a reactive group F4, and Z represents a divalent organic group.

[0210] In formula (1), Z includes an alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 2 to 20 carbon atoms which may have a substituent, an alkynylene group having 2 to 20 carbon atoms which may have a substituent, and an arylene group having 6 to 20 carbon atoms which may have a substituent.

[0211] Examples of the alkylene group having 1 to 20 carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene, and are preferably methylene, ethylene, and propylene, and more preferably propylene. Examples of the alkenylene group having 2 to 20 carbon atoms include vinylene, propenylene, butenylene, and pentenylene. Examples of the alkynylene group having 2 to 20 carbon atoms include ethynylene and propynylene. Examples of the arylene group having 6 to 20 carbon atoms include o-phenylene, m-phenylene, p-phenylene, 2,6-naphthylene, and 1,5-naphthylene.

[0212] Examples of the substituent which the alkylene group, alkenylene group and alkynylene group may have include halogen atoms such as fluorine atom and chlorine atom; alkoxy groups such as methoxy group and ethoxy group; alkylthio groups such as methylthio group and ethylthio group; and alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group.

[0213] Examples of the substituent which the arylene group may have include a cyano group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; an alkyl group such as a methyl group or an ethyl group; an alkoxy group such as a methoxy group or an ethoxy group; and an alkylthio group such as a methylthio group or an ethylthio group.

[0214] The above-mentioned substituents may be bonded to any position in the groups such as the alkylene group, the alkenylene group, the alkynylene group and the arylene group, and a plurality of substituents may be bonded to the same element or different elements.

[0215] As R A For example, groups represented by the following formulae (2) to (4) are mentioned.

[0216] [Chemical formula 1]

[0217]

[0218] In formulae (2) to (4), * represents a bond with Z in formula (1). 1 represents a divalent hydrocarbon group having 1 to 10 carbon atoms. 2 and R 3 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 4 and R 5 Each independently represents a reactive group F3 or a group represented by the above formula (2). 4 and R 5 In the case of a group represented by formula (2), in formula (2), * represents a bond to a carbon atom constituting a triazine ring in formula (4). 6 represents a single bond, or -N(R 7 )- is a divalent group. 7 It represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0219] In formula (2), as R 1 , preferably a divalent hydrocarbon group having 2 to 6 carbon atoms. 1 For example, there can be mentioned an alkylene group or an arylene group having 1 to 10 carbon atoms, and specifically, there can be mentioned an alkylene group such as ethylene and trimethylene; and an arylene group such as o-phenylene, m-phenylene and p-phenylene.

[0220] In formula (2), R 2 and R 3 Each of R is independently preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. 2 and R 3 , for example, alkyl, alkynyl or aryl groups having 1 to 20 carbon atoms can be mentioned, and specifically, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl can be mentioned; alkenyl groups such as vinyl, 1-propenyl, 2-propenyl, isopropenyl, 3-butenyl, 4-pentenyl and 5-hexenyl can be mentioned; alkynyl groups such as ethynyl, propargyl and butynyl can be mentioned; and aryl groups such as phenyl, 1-naphthyl and 2-naphthyl can be mentioned.

[0221] In formula (4), R 4 and R 5 The reactive groups F3 are preferably identical to one another.

[0222] In formula (4), R 6 represents a single bond, or -N(R 7 )- is a divalent group. 7 The hydrocarbon group may be any of the above R 2 and R 3 The hydrocarbon group is the same as the group described above.6 Preferably it represents -NH-.

[0223] R A Preferred is the group represented by formula (4) among the groups represented by formulas (2) to (4), and more preferred is the group represented by formula (4) in which R 4 or R 5 is an azido group or a group represented by the above formula (2).

[0224] As R A For example, a group represented by the following formula (5) can be mentioned.

[0225] [Chemical formula 2]

[0226]

[0227] In formula (5), * represents a bond with Z in formula (1). 1 ~R 3 and R 6 are the same as those described above for formulae (2) and (4). 1 ~R 3 They can be the same or different from each other.

[0228] In formula (1), R B The group may be a group represented by the following formula (6).

[0229] -Si(X) a (Y) 3-a (6)

[0230] In formula (6), X represents a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms, and Y represents a hydrocarbon group having 1 to 20 carbon atoms. a represents an integer of 1 to 3.

[0231] In the formula (6), X includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, etc., preferably ethoxy. Y includes R in the formula (2): 2 and R 3 The hydrocarbon group is not the group described above.

[0232] R B Preferably, X represents a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms, and a is 3. More preferably, X represents a hydroxyl group or an ethoxy group, and a is 3.

[0233] As R AExamples of the amino compound C2 include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, [3-(N,N-dimethylamino)propyl]trimethoxysilane, [3-(phenylamino)propyl]trimethoxysilane, trimethyl[3-(triethoxysilyl)propyl]ammonium chloride, and trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride.

[0234] As R A Examples of the compound C2 which is an azido group include (11-azidoundecyl)trimethoxysilane and (11-azidoundecyl)triethoxysilane.

[0235] As R A Examples of the compound C2 which is a mercapto group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyldimethoxymethylsilane.

[0236] As R A Examples of the compound C2 having an isocyanate group include 3-(trimethoxysilyl)propyl isocyanate and 3-(triethoxysilyl)propyl isocyanate.

[0237] As R A Examples of the ureido compound C2 include 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane.

[0238] As R A Examples of the compound C2 which is an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane.

[0239] As R A The compound C2 is a monovalent substituent having one or more reactive groups F3, for example, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and compounds represented by the following formulas (1-1) to (1-9).

[0240] [Chemical formula 3]

[0241]

[0242] [Chemical formula 4]

[0243]

[0244] (1-1): N,N'-bis(2-aminoethyl)-6-(3-trihydroxysilylpropyl)amino-1,3,5-triazine-2,4-diamine

[0245] (1-2): N,N'-bis(2-aminoethyl)-6-(3-trimethoxysilylpropyl)amino-1,3,5-triazine-2,4-diamine

[0246] (1-3): N,N'-bis(2-aminoethyl)-6-(3-triethoxysilylpropyl)amino-1,3,5-triazine-2,4-diamine

[0247] (1-4): N,N'-bis(2-aminomethyl)-6-(3-trihydroxysilylpropyl)amino-1,3,5-triazine-2,4-diamine

[0248] (1-5): N,N'-bis(2-aminomethyl)-6-(3-trimethoxysilylpropyl)amino-1,3,5-triazine-2,4-diamine

[0249] (1-6): N,N'-bis(2-aminomethyl)-6-(3-triethoxysilylpropyl)amino-1,3,5-triazine-2,4-diamine

[0250] (1-7): 6-(3-trihydroxysilylpropyl)amino-1,3,5-triazine-2,4-diazide

[0251] (1-8): 6-(3-trimethoxysilylpropyl)amino-1,3,5-triazine-2,4-diazide

[0252] (1-9): 6-(3-triethoxysilylpropyl)amino-1,3,5-triazine-2,4-diazide

[0253] Compound C2 is preferably a compound represented by the above formulae (1-1) to (1-9), and more preferably a compound represented by formula (1-1) or (1-9).

[0254] (Method for producing pervaporation membrane)

[0255] The pervaporation membrane 10D can be manufactured, for example, by the following method. Figure 4BAs shown, a separation functional layer 1 is produced on a release liner 12. The separation functional layer 1 can be produced by coating a coating liquid containing a material for the separation functional layer 1 on the release liner 12 and curing the resulting coating film. The coating liquid is, for example, a silicone resin composition (particularly an addition-type silicone resin composition). The curing of the coating film can be carried out at room temperature or in a heated environment. The curing of the coating film can also be carried out by irradiation with active energy rays such as UV. When the coating film is cured by heating, the heating conditions of the coating film are not particularly limited, and the conditions described above in Embodiment 1 can be used. With respect to the surface 1a of the separation functional layer 1, the reference to Embodiment 1 can be used. Figure 1B The surface modification was carried out by the method described above.

[0256] As the release liner 12, for example, films containing resins; paper; sheets containing metal materials such as aluminum and stainless steel, etc. can be cited. Sheets containing metal materials tend to have high heat resistance. From the perspective of excellent surface smoothness, the release liner 12 is preferably a film containing resins. In the release liner 12, as polymers contained in the resin, polyolefins such as polyethylene, polypropylene, polybutene, polybutadiene, and polymethylpentene can be cited; polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyvinyl chloride, vinyl chloride copolymers; polyurethanes; ethylene-vinyl acetate copolymers, etc. are preferred, and polyethylene terephthalate is particularly preferred.

[0257] The surface of the release liner 12 may be subjected to a release treatment. The release treatment can be performed, for example, by applying a release treatment agent to the surface of the release liner 12. Examples of the release treatment agent include silicone-based release treatment agents, long-chain alkyl-based release treatment agents, fluorine-based release treatment agents, and molybdenum sulfide-based release treatment agents. The release treatment agent may be used alone or in combination of two or more. The release liner 12 is preferably a film made of polyethylene terephthalate (PET) subjected to a release treatment.

[0258] The thickness of the release liner 12 is not particularly limited, and is, for example, 5 to 100 μm, and preferably 10 to 50 μm.

[0259] Next, a molecular binder (coating liquid) containing the above-mentioned compound C2 is prepared. The molecular binder is coated on the surface 5a of the porous support 5. As a result, the reactive groups F3 and F4 of the compound C2 react with the surface 5a of the porous support 5 (specifically, the hydroxyl groups present on the surface 5a). The compound C2 reacts with the surface 5a, thereby bonding the compound C2 to the surface 5a. In this state, the reactive group F4 exists on the surface 5a. That is, by using the treatment of the molecular binder, the reactive group F4 can be introduced into the surface 5a of the porous support 5.

[0260] Next, the porous support 5 is disposed on the separation functional layer 1 so that the surface 5a of the porous support 5 coated with the molecular binder is in contact with the separation functional layer 1 ( Figure 4C ), and heat drying is performed. Thus, the reaction between the reactive groups F4 present on the surface 5a and the resin (especially the silicone resin) contained in the separation functional layer 1 proceeds.

[0261] The drying temperature of the molecular binder is, for example, 40 to 150° C., and may be 60° C. or higher, or 70° C. or higher. The drying temperature of the molecular binder may be 150° C. or lower, or 90° C. or lower.

[0262] It should be noted that the heat drying of the molecular binder can be performed at the stage where the molecular binder is coated on the surface 5a of the porous support 5. In this case, the process of coating the molecular binder and drying it can be repeated multiple times. Thus, the density of the reactive groups F4 in the surface 5a can be increased. When the above process is repeated multiple times, different types of molecular binders can be used according to the process.

[0263] As another example, when the reactive group F3 is an azido group, the reaction between the reactive group F3 and the surface 5 a of the porous support 5 tends to proceed easily by irradiating the surface 5 a with ultraviolet rays.

[0264] The release liner 12 is removed after the reactive group F4 reacts with the silicone resin, thereby obtaining the pervaporation membrane 10D.

[0265] The pervaporation membrane 10D can be produced in a roll-to-roll method. That is, a long strip of release liner 12 can be pulled out from a roll of release liner 12, and separation functional layer 1 can be formed, porous support 5 can be arranged, and release liner 12 can be removed while the release liner 12 is conveyed. Furthermore, the obtained pervaporation membrane 10D can be wound up to produce a roll of pervaporation membrane 10D. The roll-to-roll method is suitable for mass production of pervaporation membrane 10D.

[0266] In Embodiment 4, surface 5a of porous support 5 can be bonded to silicone resin contained in separation functional layer 1 via compound C2. Since surface 5a of porous support 5 is bonded to silicone resin, pervaporation membrane 10D of Embodiment 4 tends to have a large peel strength A1.

[0267] [Implementation method 5]

[0268] like Figure 5As shown, a pervaporation membrane 10E of the fifth embodiment includes a separation functional layer 1 and a porous support 5. In the pervaporation membrane 10E, the separation functional layer 1 includes a substrate 2 containing a silicone resin and a filler 3 dispersed in the substrate 2. Except for the above, the configuration of the pervaporation membrane 10E of the fifth embodiment is the same as that of the pervaporation membrane 10A of the first embodiment.

[0269] (Separation Functional Layer)

[0270] As described above, in the pervaporation membrane 10E, the separation functional layer 1 further includes the filler 3. All or part of the filler 3 is buried in the matrix 2. In the matrix 2, all the fillers 3 may be separated from each other or partially aggregated.

[0271] In Embodiment 5, the silicone resin contained in the substrate 2 is, for example, a resin formed of the addition-type silicone resin composition described above in Embodiment 2. However, depending on circumstances, the silicone resin may be formed of the condensation-type silicone resin composition or UV-curable silicone resin composition described above in Embodiment 1.

[0272] The filler 3 includes, for example, an inorganic material such as zeolite, silica, and bentonite. The filler 3 includes, for example, at least one selected from the group consisting of zeolite and silica, and preferably includes silica. The filler 3 including silica tends to have excellent hydrolysis resistance compared to the filler 3 including zeolite. Furthermore, according to the filler 3 including silica, the free volume of the silicone resin contained in the substrate 2 tends to increase. If the free volume of the silicone resin increases, the separation characteristics of the pervaporation membrane 10E, especially the separation coefficient α of BuOH relative to water, tends to be improved.

[0273] Silica generally refers to silicon dioxide. Filler 3 may be a silica filler containing silicon dioxide as a main component. The silica filler, for example, does not have a crystalline structure. The silica filler, for example, can be made by reacting metallic silicon with oxygen. The silica filler can be made by a sol-gel method, a sedimentation method, an aqueous solution wet method, etc. Filler 3 may be substantially composed only of silicon dioxide.

[0274] However, the filler 3 may also contain zeolite. As the zeolite contained in the filler 3, for example, high-silicon zeolite having a high ratio of silica to alumina and silica zeolite not containing alumina can be cited. As the filler 3 containing high-silicon zeolite, HSZ (registered trademark) manufactured by Tosoh Corporation, HiSiv (registered trademark) manufactured by Union Showa Co., Ltd., USKY manufactured by Union Showa Co., Ltd., and Zeoal (registered trademark) manufactured by Nakamura Superhard Co., Ltd. can be used.

[0275] The filler 3, in particular the silica filler, for example, does not have micropores with a diameter of 2 nm or less. However, the filler 3 may also have mesopores with a diameter of 2 nm to 50 nm, or macropores with a diameter of 50 nm or more.

[0276] The filler 3, especially the silica filler, preferably has a surface modified by a modifying group containing a hydrocarbon group. In other words, the filler 3 is preferably surface-modified by the modifying group. The surface-modified filler 3 has high dispersibility in the silicone resin and is suitable for suppressing the generation of cracks in the case of preparing the separation functional layer 1, etc.

[0277] The number of carbon atoms of the hydrocarbon group contained in the modifying group is not particularly limited, and is, for example, 1 to 25. The number of carbon atoms of the hydrocarbon group may be 5 or less. The hydrocarbon group may be linear, branched, or cyclic. Examples of the hydrocarbon group include alkyl groups such as methyl and ethyl groups.

[0278] The modifying group may further include a silicon atom, and a hydrocarbon group may be bonded to the silicon atom. The modifying group may include at least one selected from the group consisting of an organosilyl group and a polyorganosiloxane group. As the organosilyl group, for example, triorganosilyl groups such as trimethylsilyl groups; diorganosilyl groups such as dimethylsilyl groups, etc. may be cited. As the polyorganosiloxane group, dimethylpolysiloxane groups, etc. may be cited.

[0279] The surface modification using the modifying group can be performed, for example, by reacting a hydroxyl group present on the surface of the filler 3 with a known silane coupling agent.

[0280] Specific examples of surface-modified silica fillers include "AEROSIL (registered trademark) RX series" (RX50, RX200, RX300, etc.), "AEROSIL (registered trademark) RY series" (RY50, RY200, RY200S, etc.), "AEROSIL (registered trademark) NY series" (NY50, NY50L, etc.), "AEROSIL (registered trademark) NAX series" (NAX50, etc.), and "AEROSIL (registered trademark) R series" (R972, R974, R976, etc.) manufactured by Japan Aerosil Co., Ltd.

[0281] As for filler 3, from the viewpoint of dispersibility in silicone resin, it is preferred that the surface of filler 3 is sufficiently modified by modifying groups. In other words, it is preferred that the number of hydroxyl groups present on the surface of filler 3 is small. Whether filler 3 is sufficiently surface-modified by modifying groups can be judged, for example, based on the pH of the dispersion of filler 3 and the Hansen solubility parameter (HSP value) of filler 3. It should be noted that the Hansen solubility parameter is obtained by dividing the solubility parameter introduced by Hildebrand into three components: dispersion term δD, polar term δP, and hydrogen bond term δH. The details of the Hansen solubility parameters are disclosed in "Hansen Solubility Parameters; A Users Handbook (CRC Press, 2007)" and the like.

[0282] In this embodiment, the pH of the dispersion of filler 3 measured by the following test 4 is, for example, 4.0 to 9.0, or 6.0 to 8.0. The pH of the dispersion is preferably neutral (near pH 7.0). When the pH of the dispersion is neutral, it can be said that the filler 3 is sufficiently surface-modified by the modifying group, and the number of hydroxyl groups present on the surface is small.

[0283] Test 4: A dispersion was prepared by mixing water, methanol and filler 3, and the pH of the dispersion was measured. Here, the content of filler 3 in the dispersion was 4 wt %, the weight ratio of water to methanol was 1:1, and the temperature of the dispersion was 25°C.

[0284] The shape of the filler 3 is, for example, particulate. In this specification, "particulate" includes spherical, ellipsoidal, scaly and fibrous shapes. The filler 3 can also be in powder form. The average particle size of the filler 3 is not particularly limited, for example, it is less than 50μm, it can be less than 20μm, less than 10μm, less than 1μm, less than 500nm, less than 100nm, less than 50nm, less than 30nm, and can also be less than 20nm. The separation functional layer 1 containing the filler 3 with a small average particle size is easy to disperse the stress applied to the separation functional layer 1, and tends to have high adhesion with the porous support body 5. The lower limit of the average particle size of the filler 3 of the separation functional layer 1 is not particularly limited, for example, it is 1nm, and it can be 5nm.

[0285] The average particle size of the filler 3 can be determined, for example, by the following method. First, a cross section of the separation functional layer 1 is observed using a transmission electron microscope. In the obtained electron microscope image, the area of ​​a specific filler 3 is calculated by image processing. The diameter of a circle having the same area as the calculated area is regarded as the particle size (particle diameter) of the specific filler 3. The particle sizes of any number (at least 50) of fillers 3 are calculated separately, and the average value of the calculated values ​​is regarded as the average particle size of the filler 3.

[0286] The content of the filler 3 in the separation functional layer 1 is, for example, 1 wt% or more, and may be 5 wt% or more, 10 wt% or more, 20 wt% or more, 30 wt% or more, or 40 wt% or more. The upper limit of the content of the filler 3 in the separation functional layer 1 is not particularly limited, and is, for example, 70 wt% or less, and may be less than 50 wt%. When the content of the filler 3 is less than 50 wt%, there is a tendency to fully suppress the generation of defects such as cracks during the production of the separation functional layer 1. The content of the matrix 2 in the separation functional layer 1 is not particularly limited, and is, for example, 30 wt% to 99 wt%, and may be 30 wt% to 90 wt%.

[0287] The surface area D1 of the filler 3 per unit weight of the matrix 2 is not particularly limited, and is, for example, 5 m 2 / g or more, can be 10m 2 / g or more, 20m 2 / g or more, 30m 2 / g or more, 40m 2 / g or more, and can also be 50m 2 The upper limit of the surface area D1 is not particularly limited, but is, for example, 100 m 2 The surface area D1 can be determined based on the BET specific surface area D2 (m 2 / g), the weight W1 (g) of the substrate 2 contained in the separation functional layer 1, and the weight W2 (g) of the filler 3 contained in the separation functional layer 1 are calculated according to the following formulas.

[0288] D1(m 2 / g)=D2(m 2 / g)×W2(g) / W1(g)

[0289] (Porous Support)

[0290] The porous support 5 includes, for example, a main body 6 and a microporous layer 7. In the fifth embodiment, the surface 7a of the microporous layer 7 does not need to be subjected to a surface modification treatment.

[0291] (Method for producing pervaporation membrane)

[0292] The permeation vaporization membrane 10E can be produced, for example, by the following method. First, a coating liquid containing a material for the separation functional layer 1 is prepared. The coating liquid is a mixture containing a silicone resin composition (especially an addition-type silicone resin composition) and a filler 3. Next, a coating film is formed by applying the coating liquid onto the surface 7a of the microporous layer 7. The separation functional layer 1 is formed by curing the coating film, thereby obtaining the permeation vaporization membrane 10E. The curing of the coating film can be carried out at room temperature or in a heated environment. The curing of the coating film can also be carried out by irradiation with active energy rays such as UV. In the case where the coating film is cured by heating, the heating conditions of the coating film are not particularly limited, and the conditions described above in Implementation Example 1 can be adopted.

[0293] The pervaporation membrane 10E can be produced in a roll-to-roll method. That is, a long porous support 5 can be pulled out from a roll of porous support 5, and separation functional layer 1 can be formed while the porous support 5 is transported. Furthermore, the obtained pervaporation membrane 10E can be rolled up to produce a roll of pervaporation membrane 10E. The roll-to-roll method is suitable for mass production of pervaporation membrane 10E.

[0294] In Embodiment 5, separation functional layer 1 includes filler 3. Filler 3 can disperse stress applied to separation functional layer 1 and improve adhesion with porous support 5. Therefore, pervaporation membrane 10E of Embodiment 5 tends to have a large peel strength A1.

[0295] [Implementation Method 6]

[0296] like Figure 6 As shown, the pervaporation membrane 10F of the sixth embodiment includes a separation functional layer 1 and a porous support 5. The porous support 5 includes a main body 6 and a microporous layer 7 disposed on the main body 6, and the microporous layer 7 includes polysulfone. Except for the above, the configuration of the pervaporation membrane 10F of the sixth embodiment is the same as that of the pervaporation membrane 10A of the first embodiment.

[0297] (Separation Functional Layer)

[0298] In Embodiment 6, the silicone resin is, for example, a resin formed from the addition type silicone resin composition described above in Embodiment 2. However, depending on circumstances, the silicone resin may be formed from the condensation type silicone resin composition or UV curable silicone resin composition described above in Embodiment 1.

[0299] In Embodiment 6, the silicone resin composition forming the silicone resin preferably has a low content of a solvent such as an organic solvent. According to the silicone resin composition having a low content of a solvent, when the permeation vaporization membrane 10F is produced, it is possible to suppress the microporous layer 7 including polysulfone from coming into contact with the silicone resin composition and dissolving. The content of the solvent in the silicone resin composition is, for example, 40 wt % or less, 20 wt % or less, or 10 wt % or less. The silicone resin composition may also be a solvent-free type that does not contain a solvent.

[0300] (Porous Support)

[0301] As described above, the porous support 5 includes a main body 6 and a microporous layer 7 disposed on the main body 6, and the microporous layer 7 includes polysulfone. The microporous layer 7 may include polysulfone as a main component, or may be substantially composed of polysulfone only. In the sixth embodiment, the surface 7a of the microporous layer 7 may not be subjected to a surface modification treatment.

[0302] (Method for producing pervaporation membrane)

[0303] The permeation vaporization membrane 10F can be produced, for example, by the following method. First, a porous support body 5 having a main body 6 and a microporous layer 7 containing polysulfone is prepared. Next, a coating liquid containing a material for the separation functional layer 1 is prepared. The coating liquid is, for example, a silicone resin composition (especially an addition-type silicone resin composition). Next, a coating film is formed by applying the coating liquid on the surface 7a of the microporous layer 7. By curing the coating film, a separation functional layer 1 is formed to obtain a permeation vaporization membrane 10F. The curing of the coating film can be carried out at room temperature or in a heated environment. The curing of the coating film can also be carried out by irradiation with active energy rays such as UV. In the case where the coating film is cured by heating, the heating conditions of the coating film are not particularly limited, and the conditions described above in Implementation Example 1 can be adopted.

[0304] The pervaporation membrane 10F can be produced by a roll-to-roll method. That is, a long porous support 5 can be pulled out from a roll of porous support 5, and separation functional layer 1 can be formed while the porous support 5 is transported. Furthermore, the obtained pervaporation membrane 10F can be rolled up to produce a roll of pervaporation membrane 10F. The roll-to-roll method is suitable for mass production of pervaporation membrane 10F.

[0305] According to the research of the inventors of the present application, polysulfone has high affinity with silicone resin. Therefore, in Embodiment 6, microporous layer 7 made of polysulfone and separation functional layer 1 made of silicone resin have high adhesion. Therefore, in pervaporation membrane 10F of Embodiment 6, there is a tendency that peel strength A1 is large.

[0306] <Embodiment of membrane separation device>

[0307] like Figure 7 As shown in FIG. 1 , the membrane separation device 20 of the present embodiment includes a pervaporation membrane 10A and a tank 22. It should be noted that the membrane separation device 20 may include a Figure 2A to Figure 6 The tank 22 includes the pervaporation membranes 10B to 10F described above. The tank 22 includes a first chamber 23 and a second chamber 24. The first chamber 23 functions as a supply space to which a supply fluid (specifically, the aqueous solution S described above) is supplied. The second chamber 24 functions as a permeation space to which a permeation fluid S1 is supplied. The permeation fluid S1 is obtained by the aqueous solution S passing through the pervaporation membrane 10A.

[0308] Pervaporation membrane 10A is disposed inside tank 22. Pervaporation membrane 10A partitions first chamber 23 and second chamber 24 inside tank 22. Pervaporation membrane 10A extends from one of a pair of wall surfaces of tank 22 to the other.

[0309] The first chamber 23 has an inlet 23a and an outlet 23b. The second chamber 24 has an outlet 24a. The inlet 23a is an opening for supplying the aqueous solution S to the supply space (the first chamber 23). The outlet 24a is an opening for discharging the permeated fluid S1 from the permeation space (the second chamber 24). The outlet 23b is an opening for discharging the aqueous solution S (non-permeated fluid S2) that has not permeated the permeation vaporization membrane 10A from the supply space (the first chamber 23). Each of the inlet 23a, the outlet 23b, and the outlet 24a is formed, for example, on the wall surface of the tank 22.

[0310] The membrane separation device 20 is suitable for a flow-through (continuous) membrane separation method. However, the membrane separation device 20 can also be used for a batch-type membrane separation method.

[0311] (Method for operating membrane separation device)

[0312] The operating method of the membrane separation device 20 is implemented as follows, for example. First, the aqueous solution S is supplied to the first chamber 23 of the membrane separation device 20 through the inlet 23a. Thereby, the aqueous solution S can be brought into contact with one surface (for example, the main surface 10a) of the pervaporation membrane 10A.

[0313] Next, while the aqueous solution S is in contact with one side of the pervaporation membrane 10A, the space adjacent to the other side (e.g., the main side 10b) of the pervaporation membrane 10A is decompressed. Specifically, the pressure in the second chamber 24 is reduced through the outlet 24a. The decompression in the second chamber 24 can be performed, for example, by a decompression device such as a vacuum pump. The pressure in the second chamber 24 is, for example, 50 kPa or less, and can be 20 kPa or less, 10 kPa or less, 5 kPa or less, 3 kPa or less, or 2 kPa or less. It should be noted that, in this specification, "pressure" refers to absolute pressure unless otherwise specified.

[0314] By reducing the pressure in the second chamber 24, a permeated fluid S1 having a high content of organic compound C can be obtained on the other side of the pervaporation membrane 10A. In other words, the permeated fluid S1 is supplied to the second chamber 24. In the second chamber 24, the permeated fluid S1 is typically a gas. The permeated fluid S1 is discharged to the outside of the membrane separation device 20 through the outlet 24a.

[0315] On the other hand, the content of the organic compound C in the aqueous solution S gradually decreases from the inlet 23a to the outlet 23b of the first chamber 23. The aqueous solution S (non-permeable fluid S2) treated in the first chamber 23 is discharged to the outside of the membrane separation device 20 through the outlet 23b. The non-permeable fluid S2 is typically a liquid.

[0316] As described above, the pervaporation membrane 10A can preferentially permeate the organic compound C contained in the aqueous solution S. Therefore, the permeated fluid S1 obtained by operating the membrane separation device 20 has a higher content of organic compound C than the aqueous solution S supplied to the membrane separation device 20 .

[0317] <Modification of membrane separation device>

[0318] The membrane separation device 20 may be a spiral membrane element, a hollow fiber membrane element, a coil-type membrane element in which a plurality of pervaporation membranes are stacked, a plate-and-frame membrane element, or the like. Figure 8 A spiral type membrane element is shown. Figure 8 The membrane separation device 25 includes a central tube 26 and a stack 27. The stack 27 includes the pervaporation membrane 10A (or the pervaporation membranes 10B to 10F).

[0319] The central tube 26 has a cylindrical shape. A plurality of holes or slits are formed on the surface of the central tube 26 for allowing the permeating fluid S1 to flow into the interior of the central tube 26. Examples of the material of the central tube 26 include resins such as acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polyphenylene ether resin (PPE resin), and polysulfone resin (PSF resin); and metals such as stainless steel and titanium. The inner diameter of the central tube 26 is, for example, in the range of 20 to 100 mm.

[0320] Laminated body 27 includes, in addition to pervaporation membrane 10A, feed-side flow path material 28 and permeate-side flow path material 29. Laminated body 27 is wound around core tube 26. Membrane separation device 25 may further include an exterior material (not shown).

[0321] As the supply side flow path material 28 and the permeate side flow path material 29, for example, a net, woven fabric or knitted fabric made of a resin obtained from polyethylene, polypropylene, polyethylene terephthalate (PET), polyphenylene sulfide (PPS) or ethylene-chlorotrifluoroethylene copolymer (ECTFE) can be used.

[0322] The membrane separation device 25 can be operated, for example, by the following method. First, the aqueous solution S is supplied to one end of the wound stack 27. The internal space of the central tube 26 is depressurized. As a result, the permeated fluid S1 that has permeated the pervaporation membrane 10A of the stack 27 moves into the interior of the central tube 26. The permeated fluid S1 passes through the central tube 26 and is discharged to the outside. The aqueous solution S (non-permeated fluid S2) treated in the membrane separation device 25 is discharged to the outside from the other end of the wound stack 27.

[0323] <Embodiment of membrane separation system>

[0324] like Fig. 9 As shown in FIG. 1 , the membrane separation system 100 of the present embodiment includes the membrane separation device 20 described above. Figure 8 The membrane separation device 25 described above is used instead of the membrane separation device 20.

[0325] The membrane separation system 100 further includes a membrane separation device 20 and a tank 30. The tank 30 stores an aqueous solution S to be supplied to the membrane separation device 20. The tank 30 may be a fermentation tank for producing an organic compound C by fermentation of a carbon source by microorganisms.

[0326] The membrane separation system 100 further includes an aqueous solution supply path 70, a non-permeated fluid discharge path 71, and a permeated fluid discharge path 72. The aqueous solution supply path 70 is a path for supplying the aqueous solution S from the tank 30 to the membrane separation device 20 during operation, and is connected to the outlet 31 of the tank 30 and the inlet 23a of the membrane separation device 20. The aqueous solution supply path 70 is provided with, for example, a pump 50 for controlling the flow rate of the aqueous solution S.

[0327] The non-permeated fluid discharge path 71 is a path for discharging the non-permeated fluid S2 from the membrane separation device 20 during operation, and is connected to the outlet 23b of the membrane separation device 20. For example, a pump 51 for controlling the flow rate of the non-permeated fluid S2 is arranged in the non-permeated fluid discharge path 71. It should be noted that the pump 51 may not be arranged in the non-permeated fluid discharge path 71. The non-permeated fluid discharge path 71 may be connected to the inlet 32 ​​of the tank 30, and may be configured so that the non-permeated fluid S2 is delivered to the tank 30 during operation. That is, during operation, the non-permeated fluid S2 may be mixed with the aqueous solution S in the tank 30 and circulated in the aqueous solution supply path 70 and the non-permeated fluid discharge path 71. When the non-permeated fluid S2 is delivered to the tank 30, the aqueous solution S and the non-permeated fluid S2 are mixed in the tank 30, and the content rate of the organic compound C in the aqueous solution S is reduced. When the tank 30 is a fermentation tank, the fermentation stop by the microorganisms can be suppressed by reducing the content rate of the organic compound C in the aqueous solution S, thereby continuously producing the fermented product.

[0328] The permeate fluid discharge path 72 is a path for discharging the permeate fluid S1 from the membrane separation device 20 during operation, and is connected to the outlet 24a of the membrane separation device 20. For example, a decompression device 52 is arranged in the permeate fluid discharge path 72. The decompression device 52 can reduce the pressure in the permeate space of the membrane separation device 20. The decompression device 52 is preferably a vacuum device such as a vacuum pump. The vacuum pump is typically a gas-transporting vacuum pump, and a reciprocating vacuum pump, a rotary vacuum pump, etc. can be cited. As a reciprocating vacuum pump, a diaphragm type and a swing piston type vacuum pump can be cited. As a rotary vacuum pump, there can be cited: a liquid seal pump; an oil rotary pump (rotary pump); a mechanical booster pump; various dry pumps such as roots type, claw type, screw type, turbine type, and vortex type. The pump as the decompression device 52 can also be provided with a variable speed mechanism for changing the rotation speed, etc. An example of a variable speed mechanism is an inverter that drives the motor of the pump. By controlling the rotation speed of the pump, etc. using a variable speed mechanism, the pressure of the permeate space of the membrane separation device 20 can be appropriately adjusted.

[0329] A heat exchanger for cooling the permeated fluid S1 may be further arranged in the permeated fluid discharge path 72. The gas permeated fluid S1 can be condensed by the heat exchanger. The heat exchanger is, for example, a gas-liquid heat exchanger that performs heat exchange between a cooling medium such as an antifreeze liquid and the gas permeated fluid S1. The heat exchanger may be located between the membrane separation device 20 and the pressure reducing device 52 (on the upstream side of the pressure reducing device 52), or between the pressure reducing device 52 and the recovery unit 40 described later (on the downstream side of the pressure reducing device 52).

[0330] The membrane separation system 100 further includes a recovery unit 40. The recovery unit 40 recovers the permeated fluid S1 sent from the membrane separation device 20 and can store the permeated fluid S1. The recovery unit 40 is, for example, a tank storing the permeated fluid S1. The inlet 41 of the recovery unit 40 is connected to a permeated fluid discharge path 72.

[0331] The membrane separation system 100 may further include a controller 60 for controlling the various components of the membrane separation system 100. The controller 60 is, for example, a DSP (Digital Signal Processor) including an A / D conversion circuit, an input / output circuit, an operation circuit, a storage device, etc. The controller 60 stores a program for properly operating the membrane separation system 100.

[0332] Unless otherwise specified, each path of the membrane separation system 100 is constituted by, for example, a pipe made of metal or resin.

[0333] Example

[0334] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0335] (Example 1)

[0336] First, RS-50 (a laminate of a PVDF microporous layer and a PET nonwoven fabric) manufactured by Nitto Denko Corporation was prepared as a porous support. The surface of the microporous layer of the porous support was subjected to a corona treatment. The corona treatment was performed at an output power of 0.16 kW, a worktable moving speed of 3 m / min, and a discharge amount of 200 W·min / m 2 implemented under the conditions of.

[0337] Next, 62 g of toluene (special grade, manufactured by FUJIFILM Wako Pure Chemical Corporation) as a diluent solvent and 3 g of a tin catalyst (YC6831, manufactured by Momentive Performance Materials Japan LLC) as a curing catalyst were added to 100 g of a silicone resin composition (YSR3022, manufactured by Momentive Performance Materials Japan LLC, toluene·MEK solution, solid content 30 wt%) to prepare a coating liquid (condensed silicone resin composition). The coating liquid was applied onto the microporous layer of the porous support to obtain a coating film (thickness 500 μm).

[0338] Next, the coated film was heated at 90° C. for 20 minutes to be cured, thereby producing a separation functional layer having a thickness of 50 μm. Thus, the pervaporation membrane of Example 1 was obtained.

[0339] (Example 2)

[0340] First, RS-50 (a laminate of a PVDF microporous layer and a PET nonwoven fabric) manufactured by Nitto Denko Co., Ltd. was prepared, and the surface of the microporous layer was subjected to corona treatment. The corona treatment was performed at an output power of 0.16 kW, a table moving speed of 3 m / min, and a discharge amount of 200 W·min / m 2 . Then, a composition containing vinyltrimethoxysilane as compound C1 (Shin-Etsu Silicones, Primer No. 4) was diluted to 10 times with toluene (FUJIFILM Wako Pure Chemical Corporation, special grade), and applied on the microporous layer with a coating thickness of 50 μm to obtain a coating film. The coating film was dried at 25° C. for 20 minutes to form a primer layer with a thickness of about 0.1 μm. Thus, a porous support having a main body, a microporous layer and a primer layer was obtained.

[0341] Next, 54 g of toluene (special grade, manufactured by FUJIFILM Wako Pure Chemical Corporation) as a diluent solvent and 1 g of a platinum catalyst (CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) as a curing catalyst were added to 100 g of a silicone resin composition (manufactured by Shin-Etsu Chemical Co., Ltd., KS-847T, toluene solution, solid content 30 wt%) to prepare a coating solution (addition type silicone resin composition). The coating solution was applied onto the primer layer of the porous support to obtain a coating film (thickness 500 μm).

[0342] Next, the coated film was heated at 90° C. for 20 minutes to be cured, thereby producing a separation functional layer having a thickness of 50 μm. Thus, a pervaporation membrane of Example 2 was obtained.

[0343] (Example 3)

[0344] First, RS-50 (a laminate of a PVDF microporous layer and a PET nonwoven fabric) manufactured by Nitto Denko Corporation was prepared as a porous support. The surface of the microporous layer of the porous support was subjected to a corona treatment. The corona treatment was performed at an output power of 0.16 kW, a worktable moving speed of 3 m / min, and a discharge amount of 200 W·min / m 2 implemented under the conditions.

[0345] Next, 54 g of toluene (Fujifilm Wako Pure Chemical Corporation, special grade) as a diluent solvent, 1 g of a platinum catalyst (Shin-Etsu Chemical Co., Ltd., CAT-PL-50T) as a curing catalyst, and 5 g of a composition containing vinyltrimethoxysilane as compound C1 (Shin-Etsu Silicones, Primer No. 4) were added to 100 g of a silicone resin composition (Shin-Etsu Chemical Co., Ltd., KS-847T, toluene solution, solid content 30 wt%) to prepare a coating liquid (addition type silicone resin composition). The coating liquid was applied onto the microporous layer of the porous support to obtain a coating film (thickness 500 μm).

[0346] Next, the coated film was heated at 90° C. for 20 minutes to be cured, thereby producing a separation functional layer having a thickness of 50 μm. Thus, a pervaporation membrane of Example 3 was obtained.

[0347] (Example 4)

[0348] First, 54 g of toluene (special grade, manufactured by FUJIFILM Wako Pure Chemical Corporation) as a diluent solvent and 1 g of a platinum catalyst (CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) as a curing catalyst were added to 100 g of a silicone resin composition (KS-847T, manufactured by Shin-Etsu Chemical Co., Ltd., toluene solution, solid content 30 wt%) to prepare a coating solution (addition type silicone resin composition). Next, the coating solution was applied onto a release liner (MRE38, manufactured by Mitsubishi Chemical Corporation) to obtain a coating film (thickness 500 μm).

[0349] Next, the coating film was heated at 90°C for 20 minutes to cure, thereby preparing a separation functional layer with a thickness of 50 μm. The surface of the prepared separation functional layer was subjected to corona treatment. The corona treatment was carried out at an output power of 0.16 kW, a worktable moving speed of 3 m / min, and a discharge amount of 200 W·min / m 2 implemented under the conditions of.

[0350] Next, a PET nonwoven fabric is prepared as a porous support. An aqueous solution containing a molecular bonding compound (Sulfur Chemical Laboratory Inc., N,N'-bis(2-aminoethyl)-6-(3-trihydroxysilylpropyl)amino-1,3,5-triazine-2,4-diamine) at a content of 0.5wt% is applied to the surface of the porous support, and the porous support is arranged on the separation functional layer in such a manner that the surface treated with the aqueous solution is in contact with the separation functional layer, and heated at 90°C for 10 minutes. Thus, the surface of the porous support is bonded to the silicone resin contained in the separation functional layer via the molecular bonding compound. By removing the release liner, the permeation vaporization membrane of Example 4 is obtained.

[0351] (Example 5)

[0352] First, 15 g of silica filler (AEROSIL RX50, manufactured by Japan Aerosil Co., Ltd.), 87 g of toluene (special grade, manufactured by FUJIFILM Wako Pure Chemical Corporation) as a diluent, and 0.5 g of a platinum catalyst (CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) as a curing catalyst were added to 50 g of a silicone resin composition (manufactured by Shin-Etsu Chemical Co., Ltd., KS-847T, toluene solution, solid content 30 wt%) to prepare a coating liquid (addition type silicone resin composition). The silica filler has a surface modified with a trimethylsilane (TMS) group. Next, a coating film (thickness 500 μm) was obtained by applying the coating liquid onto a porous support. As a porous support, RS-50 (a laminate of a PVDF microporous layer and a PET nonwoven fabric) manufactured by Nitto Denko Corporation was used. The coating film was formed on the PVDF microporous layer of RS-50.

[0353] Next, the coating film was heated at 90° C. for 20 minutes to cure, thereby preparing a separation functional layer having a thickness of 50 μm. The content of the filler in the separation functional layer was 50 wt %. Thus, the pervaporation membrane of Example 5 was obtained.

[0354] (Example 6)

[0355] The pervaporation membrane of Example 6 was obtained by the same method as in Example 5 except that a high-silica zeolite filler (HiSiv3000 manufactured by UNION Showa Co., Ltd.) was used instead of the silica filler.

[0356] (Example 7)

[0357] First, as a porous support, a laminate of a microporous layer made of polysulfone and a nonwoven fabric made of PET is prepared. Then, 50 g of a silicone resin composition (KE-1935B made by Shin-Etsu Chemical Co., Ltd.) is added to 50 g of a silicone resin composition (KE-1935A made by Shin-Etsu Chemical Co., Ltd.) to prepare a coating liquid (addition type silicone resin composition). The coating liquid is a solvent-free type that does not contain a solvent. Next, a coating film (thickness 70 μm) is obtained by applying the coating liquid on the microporous layer of the porous support.

[0358] Next, the coating film was heated at 150° C. for 10 minutes to cure, thereby producing a separation functional layer having a thickness of 50 μm. Thus, a pervaporation membrane of Example 7 was obtained.

[0359] (Example 8)

[0360] First, as a porous support, RS-50 (a laminate of a PVDF microporous layer and a PET nonwoven fabric) manufactured by Nitto Denko Corporation was prepared. Next, 54 g of toluene (special grade manufactured by FUJIFILM Wako Pure Chemical Corporation) as a diluent and 1 g of a platinum catalyst (CAT-PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.) as a curing catalyst were added to 100 g of a silicone resin composition (KS-847T manufactured by Shin-Etsu Chemical Co., Ltd.) to prepare a coating liquid (addition type silicone resin composition). The coating liquid was applied onto the microporous layer of the porous support to obtain a coating film (thickness 500 μm).

[0361] Next, the coated film was heated at 90° C. for 20 minutes to be cured, thereby producing a separation functional layer having a thickness of 50 μm. Thus, a pervaporation membrane of Example 8 was obtained.

[0362] (Example 9)

[0363] A pervaporation membrane of Example 9 was obtained by the same method as in Example 7 except that 40 g of a silicone resin composition (KE-106 manufactured by Shin-Etsu Chemical Co., Ltd., main agent) containing polyorganosiloxane P4 having a hydrosilyl group and 10 g of a silica filler (AEROSIL RX50 manufactured by Nippon Aerosil Co., Ltd.) were added to 40 g of a silicone resin composition (KE-106 manufactured by Shin-Etsu Chemical Co., Ltd., main agent) containing polyorganosiloxane P3 having an alkenyl group to prepare a coating liquid (addition type silicone resin composition). In Example 9, the coating liquid was a solvent-free type containing no solvent. It should be noted that polyorganosiloxane P4 functions as a crosslinking agent.

[0364] (Example 10)

[0365] A coating liquid (addition-type silicone resin composition) was prepared by the same method as in Example 7 except that 40 g of a silicone resin composition (KE-106F manufactured by Shin-Etsu Chemical Co., Ltd., main agent) containing polyorganosiloxane P3 having alkenyl groups (manufactured by Shin-Etsu Chemical Co., Ltd.) was added with 4 g of a silicone resin composition (CAT-106F manufactured by Shin-Etsu Chemical Co., Ltd., curing agent) containing polyorganosiloxane P4 having hydrosilyl groups and 10 g of a silica filler (AEROSIL RX50 manufactured by Japan Aerosil Co., Ltd.) to obtain a permeation vaporization membrane of Example 10. In Example 10, the coating liquid was a solvent-free type containing no solvent. It should be noted that polyorganosiloxane P4 functions as a crosslinking agent. The weight ratio of polyorganosiloxane P4 to polyorganosiloxane P3, P4 / P3, was 10 wt%.

[0366] (Example 11)

[0367] To 45 g of a silicone resin composition (Sylgard 184 manufactured by Dow Corning Toray Co., Ltd., main agent) containing a polyorganosiloxane P3 having an alkenyl group, 4.5 g of a silicone resin composition (Sylgard 184 manufactured by Dow Corning Toray Co., Ltd., curing agent) containing a polyorganosiloxane P4 having a hydrosilyl group and 5 g of a silica filler (AEROSIL RX50 manufactured by Japan Aerosil Co., Ltd.) were added to prepare a coating liquid (addition-type silicone resin composition). Except for this, the permeation vaporization membrane of Example 11 was obtained by the same method as Example 7. In Example 11, the coating liquid is a solvent-free type that does not contain a solvent. It should be noted that the polyorganosiloxane P4 functions as a cross-linking agent. The weight ratio of the polyorganosiloxane P4 to the polyorganosiloxane P3 is 10 wt%.

[0368] (Example 12)

[0369] A pervaporation membrane of Example 12 was obtained by the same method as in Example 11 except that the weight ratio P4 / P3 of polyorganosiloxane P4 to polyorganosiloxane P3 was changed to 3.3 wt %.

[0370] (Example 13)

[0371] The pervaporation membrane of Example 13 was obtained by the same method as in Example 12 except that no silica filler was used.

[0372] [Sealing force]

[0373] The adhesion between the separation functional layer and the porous support was measured by SAICAS using the above-mentioned method for the produced pervaporation membrane.

[0374] [Test 3]

[0375] The pervaporation membrane thus produced was subjected to the above-mentioned Test 3 (roll-out simulation test) to visually confirm whether or not the separation functional layer was peeled off from the porous support.

[0376] [Peel strength A1]

[0377] The above-mentioned test 1 was carried out on the produced pervaporation membrane to measure the peel strength A1. As a tensile testing machine, Autograph AGS-50NX manufactured by Shimadzu Corporation was used. It should be noted that for Examples 1 to 4, the separation functional layer was sufficiently fixed to the porous support body, and the separation functional layer could not be peeled off from the porous support body by hand. When an attempt was made to peel it off forcibly, the separation functional layer broke. In response to this, the breaking strength B1 of the separation functional layer was determined by the above-mentioned method. As described above, the peel strength A1 can be regarded as a value greater than the breaking strength B1.

[0378] [PV performance]

[0379] The separation coefficient α of n-butanol (BuOH) relative to water was measured for the produced pervaporation membrane by the following method. First, the pervaporation membrane was cut into a size of 74 mm in diameter to form a flat film test piece. The test piece was placed in an intermittent membrane separation device (unit). A mixed liquid obtained by n-butanol (BuOH) and water was supplied to the supply space of the unit. The content of BuOH in the mixed liquid was 1.0 wt%.

[0380] Next, the cell was immersed in a water bath, and the temperature of the mixed liquid was adjusted to 30°C. Next, the mixed liquid was stirred using a stirrer disposed in the cell, while the pressure in the permeation space was reduced to 15 hPa. Thus, the mixed liquid permeated through the pervaporation membrane to obtain a gaseous permeation fluid. The gaseous permeation fluid was cooled by a cooling trap using liquid nitrogen to condense the permeation fluid. The composition of the liquid permeation fluid was analyzed using gas chromatography, and the separation coefficient α was calculated based on the obtained results.

[0381] [Immersion test]

[0382] The pervaporation membrane was subjected to an immersion test by the following method. First, a mixed liquid obtained from n-butanol and water was prepared. The content of n-butanol in the mixed liquid was 1.0 wt %, and the temperature of the mixed liquid was 80° C. The pervaporation membrane was immersed in the mixed liquid for 3 weeks. For the pervaporation membrane after immersion, it was visually confirmed whether the separation functional layer was peeled off from the porous support.

[0383] [Table 1]

[0384]

[0385] [Table 2]

[0386]

[0387] The abbreviations in Tables 1 and 2 are as follows.

[0388] YSR3022: Silicone resin composition (Momentive Performance Materials Japan LLC, YSR3022)

[0389] KS847T: Silicone resin composition (manufactured by Shin-Etsu Chemical Co., Ltd., KS-847T)

[0390] KE1935: Silicone resin composition (manufactured by Shin-Etsu Chemical Co., Ltd., KE-1935)

[0391] Primer No. 4: a composition containing vinyltrimethoxysilane (manufactured by Shin-Etsu Silicones, Primer No. 4)

[0392] RX50: silica filler (manufactured by Japan Aerosil Co., Ltd., AEROSIL RX50, surface modification group: trimethylsilane (TMS) group)

[0393] HiSiv3000: Filler made of high-silicon zeolite (manufactured by UNION Showa Co., Ltd., HiSiv3000)

[0394] RS50: Laminated body of PVDF microporous layer and PET nonwoven fabric (manufactured by Nitto Denko Corporation, RS-50)

[0395] Molecular bonding compound: Sulfur Chemical Laboratory Inc., N,N'-bis(2-aminoethyl)-6-(3-trihydroxysilylpropyl)amino-1,3,5-triazine-2,4-diamine

[0396] KE106: Silicone resin composition (manufactured by Shin-Etsu Chemical Co., Ltd., KE-106)

[0397] KE106F: Silicone resin composition (manufactured by Shin-Etsu Chemical Co., Ltd., KE-106F)

[0398] Sylgard 184: Silicone resin composition (manufactured by Dow Corning Toray Co., Ltd., Sylgard 184)

[0399] As can be seen from Tables 1 and 2, in Examples 1 to 7 and 9 to 13, the peel strength A1 was 0.15 N / 20 mm or more. In these pervaporation membranes, when Test 3 (roll-out simulation test) was performed, no peeling of the separation functional layer from the porous support was visually confirmed. Based on this result, it is inferred that when a roll is made using the pervaporation membranes of Examples 1 to 7 and 9 to 13 and the pervaporation membrane is pulled out from the roll, the peeling of the separation functional layer from the porous support is sufficiently suppressed. On the other hand, with respect to the pervaporation membrane of Example 8 having a peel strength A1 of less than 0.15 N / 20 mm, when Test 3 was performed, peeling of the separation functional layer from the porous support was confirmed.

[0400] For Examples 5 and 10, an operation of making a pervaporation membrane in a roll-to-roll manner was actually carried out. In detail, the pervaporation membrane was made by the following method. First, a roll of the porous support used in the above examples was prepared, and a long strip of the porous support was pulled out from the roll. The porous support was conveyed at a linear speed of 0.8 m / min and a tension of 20 N while being coated with the coating liquid used in the above examples, and the porous support was heated and cured, thereby obtaining a pervaporation membrane. The obtained pervaporation membrane was wound up to make a roll. The pervaporation membrane was pulled out from the roll, and the presence or absence of the separation functional layer peeling off from the porous support was visually confirmed. As a result, for Examples 5 and 10, no peeling of the separation functional layer from the porous support was visually confirmed, and the peeling was sufficiently suppressed.

[0401] Furthermore, the results of the immersion test showed that the pervaporation membranes of Examples 1 to 7 and 9 to 13 were less likely to have the separation functional layer peeled off from the porous support even when the operation of separating volatile organic compounds from an aqueous solution containing the organic compounds was performed for a long time.

[0402] Industrial Applicability

[0403] The pervaporation membrane of the present embodiment is suitable for separating volatile organic compounds from an aqueous solution containing the organic compounds.

Claims

1. A permeation vaporization membrane having: a separation functional layer comprising a silicone resin; and a porous support for supporting the separation functional layer, The peel strength measured by the following test is 0.15N / 20mm or more, Test: The pervaporation membrane was cut into a test piece of 20 mm in width and 150 mm in length; the separation functional layer was peeled off from the porous support using the test piece at a peeling angle of 180° and a tensile speed of 300 mm / min.

2. The pervaporation membrane according to claim 1, wherein: The peel strength is greater than 0.5 N / 20 mm.

3. The pervaporation membrane according to claim 1, wherein: The adhesion between the separation functional layer and the porous support measured by SAICAS (Surface and Interface Analysis System) is 0.01 kN / m or more.

4. The pervaporation membrane according to claim 1, wherein: The porous support has a surface that faces the separation functional layer and has been subjected to a surface modification treatment.

5. The pervaporation membrane according to claim 4, wherein: The surface modification treatment is corona treatment.

6. The pervaporation membrane according to claim 4, wherein: The silicone resin is formed from a condensation-type silicone resin composition.

7. The pervaporation membrane according to claim 1, wherein: The porous support has a primer layer directly in contact with the separation function layer. The primer layer is bonded to the silicone resin.

8. The pervaporation membrane according to claim 7, wherein: The silicone resin is formed from an addition-type silicone resin composition.

9. The pervaporation membrane according to claim 1, wherein: The organic silicone resin is formed from an organic silicone resin composition containing polyorganosiloxane, The silicone resin composition includes a compound having a reactive group F1 that can react with the polyorganosiloxane and a reactive group F2 that can react with the surface of the porous support opposite to the separation functional layer.

10. The pervaporation membrane according to claim 1, wherein: The porous support has a surface facing the separation functional layer and including a plurality of openings, The average diameter of the plurality of openings is 0.5 μm or more.

11. The pervaporation membrane according to claim 10, wherein: The surface is bonded to the silicone resin.

12. The pervaporation membrane according to claim 1, wherein: The separation function layer further comprises a filler.

13. The pervaporation membrane according to claim 12, wherein: The filler includes at least one selected from the group consisting of zeolite and silica.

14. The pervaporation membrane according to claim 1, wherein: The porous support has a main body and a microporous layer disposed on the main body. The microporous layer includes polysulfone.

15. The pervaporation membrane according to claim 14, wherein: The silicone resin is formed from a silicone resin composition having a solvent content of 10 wt % or less.

16. The pervaporation membrane of claim 1, used for separating volatile organic compounds from an aqueous solution containing the organic compounds.

17. The pervaporation membrane of claim 16, wherein: The organic compound is a fermentation product produced by microorganisms.

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