JP7076783B2 - Members, fluid separators, and compositions - Google Patents

Description

The present invention relates to members, fluid separators, and compositions.

A method of utilizing a member (separation membrane) that selectively permeates a fluid is known in order to separate one of the fluids (gas component or liquid component) from a mixture of two or more kinds of fluids.
As a technique as described above, Patent Document 1 states, "In a gas-liquid separation membrane in which a plurality of vents are formed, the passage of a gas is permitted and the passage of a liquid is blocked by a capillary force. Is a gas-liquid separation membrane characterized by being formed by laser processing independently of each other and having a uniform pore size. "

Japanese Unexamined Patent Application Publication No. 2003-08733

The gas separation membrane is formed by laser processing a plurality of ventilation holes arranged in the membrane, and the manufacturing process is complicated, and moreover, fine processing technology is required, and the manufacturing is large-scale. There was a problem in that it required various equipment.
Therefore, it is an object of the present invention to provide a member that can be manufactured by a simpler method and that can be applied to a fluid separation membrane. It is also an object of the present invention to provide a fluid separation device and a composition.

As a result of diligent studies to achieve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be achieved by the following configurations.

[1] A member obtained by curing a composition containing a curable silicone rubber component and a filler, and the filler extends from the core portion and the core portion in different four axial directions. It has a three-dimensional shape with a needle-shaped portion, and the content mass ratio r of the content of the filler to the total content of the curable silicone rubber component and the filler in the composition is 0. A member used for a separation film for separating one of the fluids from a mixture having 70 or more and containing at least two kinds of fluids .
[2] The member according to [1], wherein the curable silicone rubber component contains an organopolysiloxane having a hydrolyzable group bonded to a silicon atom.
[3] The member according to [1] or [2], wherein r is 0.80 or more.
[4] A separation membrane having the member according to any one of [1] to [3] , an introduction section separated by the separation membrane, and a take-out section are provided, and at least two kinds of the introduction section are provided. A fluid separation device in which a mixture containing the above-mentioned fluid is introduced, and one of the above-mentioned fluids separated from the above-mentioned mixture by the above-mentioned separation membrane is taken out from the above-mentioned extraction section.
[5] A composition containing a curable silicone rubber component and a filler, wherein the filler has a core portion and a needle-shaped portion extending from the core portion in four axial directions. It has a three-dimensional shape, and the content mass ratio r of the content of the filler to the total content of the curable silicone rubber component and the filler in the composition is 0.70 or more, and the above. A composition in which the cured product of the composition is used as a separation membrane for separating one of the fluids from a mixture containing at least two or more fluids .
[6] The composition according to [5], wherein r is 0.80 or more.

According to the present invention, it is possible to provide a member that can be manufactured by a simpler method and can be applied to a fluid separation membrane. Further, according to the present invention, a fluid separation device and a composition can also be provided.

It is a schematic diagram which shows the 1st Embodiment of the fluid separation apparatus which concerns on embodiment of this invention. It is a schematic diagram which shows the 2nd Embodiment of the fluid separation apparatus which concerns on embodiment of this invention. It is a measurement result of the water contact angle of a member. It is explanatory drawing explaining the experimental method which concerns on the confirmation of the gas permeability of a member. It is a measurement result by the mercury intrusion method concerning the member of r = 0.20, and is the figure which shows the relationship of the pore volume with respect to the pore diameter. It is a measurement result by the mercury intrusion method concerning the member of r = 0.30, and is the figure which shows the relationship of the pore volume with respect to the pore diameter. It is a measurement result by the mercury intrusion method concerning the member of r = 0.40, and is the figure which shows the relationship of the pore volume with respect to the pore diameter. It is a measurement result by the mercury intrusion method concerning the member of r = 0.50, and is the figure which shows the relationship of the pore volume with respect to the pore diameter. It is a measurement result by the mercury intrusion method concerning the member of r = 0.60, and is the figure which shows the relationship of the pore volume with respect to the pore diameter. It is a measurement result by the mercury intrusion method concerning the member of r = 0.70, and is the figure which shows the relationship of the pore volume with respect to the pore diameter. It is a measurement result by the mercury intrusion method concerning the member of r = 0.80, and is the figure which shows the relationship of the pore volume with respect to the pore diameter. It is a measurement result by the mercury intrusion method concerning the member of r = 0.90, and is the figure which shows the relationship of the pore volume with respect to the pore diameter. It is the measurement result by the mercury intrusion method which concerns on each member of r = 0.20 to 0.90, and is the figure which summarized the relationship of the pore volume with respect to the pore diameter. It is a figure which shows the relationship of the mode diameter of a pore with respect to r of a member. It is the measurement result by the mercury intrusion method concerning the member of r = 0.20, and is the figure which shows the relationship of the cumulative pore volume with respect to the pore diameter. It is the measurement result by the mercury intrusion method concerning the member of r = 0.30, and is the figure which shows the relationship of the cumulative pore volume with respect to the pore diameter. It is a measurement result by the mercury intrusion method concerning the member of r = 0.40, and is the figure which shows the relationship of the cumulative pore volume with respect to the pore diameter. It is the measurement result by the mercury intrusion method concerning the member of r = 0.50, and is the figure which shows the relationship of the cumulative pore volume with respect to the pore diameter. It is the measurement result by the mercury intrusion method concerning the member of r = 0.60, and is the figure which shows the relationship of the cumulative pore volume with respect to the pore diameter. It is a measurement result by the mercury intrusion method concerning the member of r = 0.70, and is the figure which shows the relationship of the cumulative pore volume with respect to the pore diameter. It is a measurement result by the mercury intrusion method concerning the member of r = 0.80, and is the figure which shows the relationship of the cumulative pore volume with respect to the pore diameter. It is a measurement result by the mercury intrusion method concerning the member of r = 0.90, and is the figure which shows the relationship of the cumulative pore volume with respect to the pore diameter. It is the measurement result by the mercury intrusion method which concerns on each member of r = 0.20 to 0.90, and is the figure which summarized the relationship of the cumulative pore volume with respect to the pore diameter. It is a figure which shows the relationship of the total volume of pores with respect to r. It is a figure which shows the relationship of the porosity with respect to r.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on a representative embodiment of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.

In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes those having no substituent and those having a substituent to the extent that the effect of the present invention is not impaired. It is something to do. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). This is also synonymous with each compound.
Further, in the present specification, "(meth) acrylate" represents both acrylate and methacrylate, or either, and "(meth) acrylic" represents both acrylic and methacrylic, or either. Further, "(meth) acryloyl" represents both or either of acryloyl and methacryloyl.

[Element]
The member according to the embodiment of the present invention is a member obtained by curing a composition containing a curable silicone rubber component and a filler having a predetermined three-dimensional shape, and is the above-mentioned member in the above composition. A member having a mass ratio r (filler / (filler + silicone rubber component)) of the content of the filler to the total content of the curable silicone rubber component and the filler of 0.70 or more. be.

The shape and size of the member are not particularly limited and can be appropriately selected according to the intended use. Among them, a form laminated on a base material (for example, a membrane filter formed on a support) and a membrane filter formed on a support are easy to apply to a fluid separation membrane (hereinafter, also simply referred to as “separation membrane”). It is also preferable that it has a self-supporting membranous form.
When the member has a flat plate shape, the thickness is preferably more than 2000 μm in that it has more excellent mechanical strength and can be easily applied to a separation membrane. The upper limit is not particularly limited, but is generally preferably 1 cm or less.

Although the mechanism by which the effect of the present invention is obtained by the above members is not always clear, the present inventors speculate as follows. It should be noted that the following mechanism is speculative and is included in the scope of the present invention even when the effect of the present invention is obtained by a mechanism other than the mechanism described below.

In general, a member that can be preferably used as a fluid separation membrane, typically a gas-liquid separation membrane, does not allow liquid permeation when in contact with a gas-liquid mixed fluid, while allowing gas permeation. By doing so, a member capable of separating gas and liquid can be mentioned.
When this member is in the form of a membrane, it preferably has pores extending from one main surface of the membrane to the other main surface, and these pores are formed by a fluid to be separated (for example, a gas-liquid separation membrane). If so, it is often a gas) passes through.

For example, it is assumed that the size of the pores of the separation membrane varies and a small amount of pores having a larger pore diameter are present.
At this time, when the gas-liquid mixed fluid is supplied to the main surface on one side of the gas-liquid separation membrane, the pores having a larger pore diameter existing in the separation membrane originally allow only gas to permeate the main surface on the other side. It may allow the liquid to permeate more easily where it should be. That is, it is presumed that the pores having a larger pore diameter are more likely to allow the liquid to permeate.
Further, it is presumed that the pores once permeated with the liquid in this way will become a path (leak path) for the liquid to easily permeate the membrane thereafter. As a result, it is presumed that the separation membrane cannot obtain a sufficient gas-liquid separation function.

Further, when pores having a smaller pore size are present in the separation membrane, the gas permeation rate tends to be lower in the pores, and as a result, the separation efficiency (separation ability) is insufficient for the separation membrane as a whole. Will be.

As described above, if the size of the pores in the member varies, there is a problem that a sufficient function as a separation membrane cannot be obtained.
The member according to the embodiment of the present invention has been studied in view of the above problems, contains a filler having a predetermined three-dimensional shape, and a curable silicone rubber component, and has an r of 0.70 or more. One of the feature points is that it is a member obtained by curing the composition.

The member according to the embodiment of the present invention is obtained by curing the above composition, and the obtained member has a predetermined three-dimensional shape in the binder obtained by curing the curable silicone rubber component. The filler is dispersed.
Since the filler having a three-dimensional shape, which will be described later, is dispersed in the member, it is presumed that the filler tends to be porous.
Further, when the above composition is cured, the fillers are packed more densely due to the curing shrinkage of the curable silicone rubber component, but the filler having a specific three-dimensional shape, which will be described later, has a certain structure or more. It is presumed that it is difficult to pack tightly, and as a result, the obtained pore diameter is presumed to be more uniform.
As a result, the member according to the embodiment of the present invention has more pores, and the half width of the pore diameter distribution of each pore is smaller (in other words, the distribution is sharper). When applied to a separation membrane, excellent separation ability can be obtained. Hereinafter, each component of the member according to the embodiment of the present invention will be described in detail.

〔Composition〕
The member according to the embodiment of the present invention is a member obtained by curing a composition containing a curable silicone rubber component and a filler having a specific three-dimensional shape (hereinafter, also referred to as “specific filler”). be.
In the above composition, the content mass ratio r of the content of the filler to the total content of the curable silicone rubber component and the filler is 0.70 or more. When the content mass ratio is 0.70 or more, it is presumed that the obtained member has a sufficient amount of pores so as to exhibit sufficient separation ability as a separation membrane.

In general, the pores in a member have an open hole and an obturator foramen (independent pores), and the open hole also has a through pore that communicates with the front and back of the member and an inlet pore (there is no outlet) that does not. ) (Reference: Measurement method and physical properties of porous body, Masashi Goto, Gypsum & Lime No., 240 p299, 1992).
The numerical value obtained by the mercury intrusion method described later is the value of the pores, and in the present specification, the volume ratio of the total volume of the pores to the total volume of the members is defined as "porosity (volume%)".
This porosity represents the amount of pores in the member, i.e., according to the definition above, the sum of the through pores and the non-penetrating pores. The larger the amount of the pores (that is, the higher the porosity), the better the function as the separation membrane.

The content mass ratio r is preferably 0.80 or more, and more preferably 0.90 or more, in that a member having a more excellent effect of the present invention can be obtained.
The upper limit of the content mass ratio r is not particularly limited, but is generally preferably less than 1.0.
In this specification, the content mass ratio r can be calculated from the charged amount of each component, and means a numerical value obtained by rounding down the third decimal place.
A combustion type total organic carbon analysis (TOC) method can be used as a method for calculating the content mass ratio r from the member. That is, the content mass ratio r can be calculated by quantifying the amount of carbon dioxide generated from the curable silicone rubber component in advance and measuring the proportion of the curable silicone rubber component contained.

<Curable silicone rubber component>
The curable silicone component is a component that cures to become a binder, and is intended as a solvent-free solid content. Further, the curable silicone rubber component exhibits curability. According to the above composition containing a curable silicone component, a member having a surface showing high water repellency can be obtained.

The contact angle (static contact angle) of the surface of the member obtained by curing the above composition containing the curable silicone component and the filler described below with respect to water is not particularly limited, but is preferably 120 ° or more. , 130 ° or more is more preferable, 140 ° or more is further preferable, and 150 ° or more is particularly preferable.
In addition, in this specification, a static contact angle with respect to water means a water contact angle measured by the method described in an Example.

The curable silicone component is not particularly limited, and examples thereof include a reaction-curable silicone rubber composition.
Examples of the reaction-curing type silicone rubber composition include a condensation type silicone rubber composition and an addition polymerization type silicone rubber composition, and known silicone rubber compositions can be used without particular limitation.
Among them, a condensation type silicone rubber composition is preferable, and a room temperature curing type silicone rubber composition is more preferable, in that a member having a more excellent effect of the present invention can be easily obtained.

Specific examples of the reaction-curable silicone rubber composition include a silicone rubber composition containing an organopolysiloxane having a reactive functional group.
Examples of the reactive functional group include a hydroxy group (silanol group), an alkoxy group (alkoxysilyl group), a mercapto group, an epoxy group, an ethylenically unsaturated group (vinyl group, (meth) acrylic group, etc.) and the like. Can be mentioned.

Among them, the curable silicone rubber component preferably contains an organopolysiloxane having a hydrolyzable group bonded to a silicon atom, in that a member having a more excellent effect of the present invention can be obtained.
Organopolysiloxane having a hydrolyzable group bonded to a silicon atom is cured by a condensation reaction, and water and / or alcohol is desorbed at the time of curing, so that the curing shrinkage is generally larger in many cases. When an organopolysiloxane having a hydrolyzable group bonded to such a silicon atom is used, the specific fillers are sufficiently in contact with each other, and pores having a more uniform pore size can be easily obtained.

For example, when the organopolysiloxane has an alkoxysilyl group, the silicone rubber composition containing the organopolysiloxane includes a partially hydrolyzed partial hydrolyzate of the alkoxysilyl group, and the entire hydrolyzed product. It may contain hydrolysates and condensates in which some of them are condensed.
More specifically, examples of the organopolysiloxane include diorganopolysiloxane having hydroxyl groups at both ends of the molecular chain.

Further, the reaction-curable silicone rubber composition may contain components other than organopolysiloxane. In the following, other components will be described.
However, in the present specification, the solvent is not included as a component constituting the reaction-curable silicone rubber composition.
Generally, a commercially available curable silicone rubber (dispersion) liquid may contain a solvent.
However, the curable silicone rubber component in the present specification means a solid content, and therefore, when a commercially available curable silicone rubber (dispersion) liquid as described above is used as the curable silicone rubber component, it is "curable". As the "silicone rubber component", the solid content of the commercially available curable silicone rubber liquid as described above is regarded as the "curable silicone rubber component", and the content mass ratio r is calculated.

The other components are not particularly limited, and examples thereof include at least one silane additive selected from the group consisting of a silane compound, a partial hydrolyzate of a silane compound, and a condensate of a silane compound.
The silane additive is a compound capable of reacting with an organopolysiloxane having a hydroxy group (silanol group) (typically, a diorganopolysiloxane having a hydroxy group at the end of the molecular chain).
The diorganopolysiloxane having hydroxy groups at both ends of the molecular chain and the silane additive can be cured by chemically reacting with each other at room temperature or heating.
The reaction-curable silicone rubber composition is preferably, for example, a moisture-curable silicone rubber composition that cures at room temperature.

In the organopolysiloxane having a reactive functional group, the organic group other than the reactive functional group bonded to the Si atom is not particularly limited, but for example, a methyl group, an ethyl group, an n-propyl group, and an isopropyl. Alkyl groups such as groups; aryl groups such as phenyl groups and trill groups; cycloalkyl groups such as cyclohexyl groups; some or all of the hydrogen atoms bonded to the carbon atoms of these groups are halogen atoms and cyano groups. Examples thereof include groups substituted with such as. When there are a plurality of bonded organic groups, they may be the same or different.

The number of repetitions of the siloxane bond is not particularly limited, but an integer of 5 or more is preferable. The reaction-curable silicone rubber composition may contain one kind of organopolysiloxane alone or two or more kinds together.

The kinematic viscosity of the organopolysiloxane is not particularly limited, but in general, 0.000025 to 0.5 m ² / s (25 to 500,000 cSt) is preferable at 25 ° C., and 0.001 to 0.1 m ² / s (1000). ~ 100,000 cSt) is more preferable.

Among the silane additives, the silane compound may be a polyfunctional silane compound having a hydrolyzable group, and from the viewpoint of enhancing the water repellency of the member, the silane compound represented by the following formula (1) is used. preferable.
(R ₁ ) _m SiX _n (1)

In the above formula, R ₁ represents a methyl group, a vinyl group, or a phenyl group. X represents an alkoxy group having 1 to 5 carbon atoms, a methylethylketooxime group, a propenyloxy group, or an acetoxy group.
m represents 0 or 1. n represents 3 or 4. However, when m is 0, n is 4, and when m is 1, n is 3.

Specific examples of the silane compound represented by the above formula (1) include methyltri (methylethylketooxym) silane, vinyltri (methylethylketooxym) silane, methyltripropenyloxysilane, vinyltripropenyloxysilane, phenyltripropenyloxysilane, and methyl. Examples thereof include triacetoxysilane, vinyl triacetoxysilane, and tetraalkoxysilane (alkoxy groups include, for example, methoxy group and ethoxy group).
The reaction-curing silicone rubber composition may contain one kind of silane additive alone or two or more kinds together.

When the reaction-curable silicone rubber composition contains an organopolysiloxane having a reactive functional group and a silane additive, the content of the silane additive is not particularly limited, but the organopoly having a reactive functional group is not particularly limited. It is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of siloxane.

The reaction-curable silicone rubber composition may contain a catalyst, if necessary.
Examples of the catalyst include tin carboxylates such as tin naphthenate, tin caprylate, and tin oleate; dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin dioleate, diphenyltin diacetate, and dibutyl oxide. Tin compounds such as tin, dibutyltin dimethoxydo, dibutylbis (triethoxysiloxy) tin, and dibutyltin benzylmalate; tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexoxy) titanium, dipropoxybis ( Acetylacetona) Titanium and a titanium acid ester or titanium chelate compound such as titanium isopropoxyoctylene glycol; an organic sulfonic acid compound such as dodecylbenzene sulfonic acid; and the like can be mentioned.

As the curable silicone component, a moisture-curable silicone rubber composition (silicone rubber component) is preferable, and the curing reaction type is at least one condensation reaction selected from the group consisting of dehydration, dealcoholization, and deoxime. It is more preferable to have a one-component moisture-curable silicone rubber composition which is a dehydration or dealcohol type condensation reaction.

<Specific filler>
The composition contains a filler (specific filler) having a three-dimensional shape having a core portion and a needle-shaped portion extending from the core portion in four different axial directions. The content of the specific filler in the composition is not particularly limited as long as it satisfies the range of the content mass ratio r in relation to the curable silicone component, but a member having a better effect of the present invention can be obtained. In terms of points, 70 to 99% by mass is preferable, 80% by mass or more is more preferable, and 90% by mass or more is further preferable with respect to the total mass of the solid content of the composition.
The composition may contain one kind of the specific filler alone, or may contain two or more kinds together. When the composition contains two or more kinds of specific fillers, the total content thereof is preferably within the above range.

In the present specification, the specific filler is not particularly limited as long as it has a three-dimensional shape having a core portion and a needle-shaped portion extending from the core portion in four different axial directions, but is more excellent in the present invention. When considering a regular tetrahedron having the core as the center of gravity in terms of obtaining a member having an effect, each needle-shaped portion extends in the directions of four vertices of the regular tetrahedron having the core as the center of gravity. The shape is preferable.
The specific filler has a three-dimensional shape generally called "tetrapod-like" (a three-dimensional shape having a core portion and a needle-shaped portion extending from the core portion in four different axial directions).

The shape of the needle-shaped portion is not particularly limited, but the aspect ratio is preferably 3 or more. Further, the lengths of the four needle-shaped portions are not particularly limited, but are preferably substantially the same.

The length of the needle-shaped portion is not particularly limited, but the average length is preferably 1 to 50 μm, more preferably 5 to 30 μm.

The material of the specific filler is not particularly limited, and examples thereof include organic substances, inorganic substances, and composites thereof. Examples of the complex include a complex having a coating layer containing an organic substance on a substrate containing an inorganic substance.
Inorganic substances include metal oxides such as alumina, potassium titanate, wollastonite, zinc oxide, and aluminum borate; simple metals such as chromium, copper, iron, and nickel; silicon carbide, graphite, and nitride. Examples thereof include inorganic oxides other than metals such as silicon, and the above-mentioned composites. Among them, a metal oxide is preferable as the inorganic substance in that a member having a more excellent effect of the present invention can be obtained, and it is more preferable that each of the needle-shaped portions is a single crystal of the metal oxide. ..

<Other ingredients>
The composition may contain a curable silicone rubber component and other components other than the specific filler. Examples of other components include solvents.

(solvent)
The composition preferably contains a solvent. Since the composition contains a solvent, it is easy to obtain a member in which the specific filler is more uniformly dispersed.
The content of the solvent in the composition is not particularly limited, but it is generally preferable to adjust the solid content of the composition to 1 to 30% by mass.
The composition may contain one kind of solvent alone or two or more kinds together. When the composition contains two or more kinds of solvents, it is preferable that the total content of the two or more kinds of solvents is within the above range.

The solvent is not particularly limited, but for example, aliphatic or aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cyclopentane, octane, heptane, cyclohexane, white spirit; dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol. Ethers such as monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; butyl acetate, propyl acetate, benzyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, etc. Ethers; ketones such as ethyl isobutyl ketone and methyl isobutyl ketone; alcohols such as n-butanol and propyl alcohol can be mentioned. These solvents may be used alone or in combination of two or more.
Among them, the composition uses at least one solvent selected from the group consisting of aliphatic or aromatic hydrocarbons and esters as a solvent in that a member having a more excellent effect of the present invention can be obtained. It is preferable to contain it.

The composition may contain components other than the above as long as the effects of the present invention are not impaired. The components other than the above are not particularly limited, but for example, fillers other than the specific filler, pigments, solvents, antisettling agents, antifoaming agents, curing accelerators, ultraviolet absorbers, antioxidants, surface conditioners, etc. Examples thereof include viscosity modifiers, leveling agents, dispersants, plasticizers, preservatives and the like, and known components can be used for all of them.

<Manufacturing method of composition>
The method for producing the above composition is not particularly limited, and each component already described may be mixed. The mixing order of each component is not particularly limited, but for example, when the composition contains a solvent, the solvent and the curable silicone rubber component are mixed in advance to obtain a mixed solution, and the filler is dispersed in the mixed solution. It may be a method of making it.
When a commercially available curable silicone rubber (dispersion) liquid is used as the curable silicone rubber component, the composition may be obtained by mixing other components with the curable silicone rubber (dispersion) liquid.

[Manufacturing method of parts]
The method for producing the member according to the embodiment of the present invention is not particularly limited, and the composition already described may be cured.
The method for curing the composition is not particularly limited, but for example, the composition is applied onto a substrate to obtain a composition layer, and energy (typically) is applied to the composition layer as required. Is heat energy) and may be cured.

Among them, the member according to the embodiment of the present invention is preferably a member obtained by the following manufacturing method in that a member having more excellent mechanical strength can be obtained.
That is, it is a method for manufacturing a member, which comprises a step a of injecting the composition already described into a mold and a step b of curing the composition in the mold. In the following, each step will be described in detail.

<Step a>
Step a is a step of injecting the above composition into a mold. This step is a step of injecting the composition into a mold, and the method of injecting the composition is not particularly limited, and a known method can be applied.
Further, the shape of the mold is not particularly limited, and may be appropriately selected according to the shape of the desired member. Further, this step may further include a step of degassing the composition, and specific examples thereof include a method of maintaining the composition in a reduced pressure state after pouring into a mold.

<Step b>
Step b is a step of curing the composition in the mold. The curing method can be appropriately selected according to the curing conditions of the curable silicone component. For example, when the composition contains a condensation-type room-temperature curable silicone component, the composition can be cured by maintaining the mold into which the composition is injected at room temperature in the atmosphere. ..

When the composition contains a solvent, the method for producing the member according to the above embodiment may further include a step of removing the solvent in the composition. The method for removing the solvent in the composition is not particularly limited, and examples thereof include a method for removing (evaporating) the solvent together with the curing of the composition in step b.

The member according to the embodiment of the present invention has a feature that the water contact angle on the surface is large, a sufficient amount of pores are provided, and the pore size distribution of the pores is uniform. It can be preferably used as a separation membrane (in other words, a fluid separation membrane) for separating one of the fluids from the mixture containing the fluid.

[Fluid separator]
The fluid separation device according to the embodiment of the present invention includes a separation membrane provided with the members already described, an introduction portion separated by the separation membrane, and a take-out portion, and the introduction portion includes at least two or more kinds of fluids. This is a fluid separation device in which one of the fluids separated from the mixture by the separation membrane is taken out from the take-out unit into which the mixture containing the above is introduced.

(First Embodiment)
FIG. 1 is a schematic diagram showing a first embodiment of the fluid separation device according to the embodiment of the present invention. The fluid separation device 10 includes an introduction unit 11 and an extraction unit 12, and the introduction unit 11 and the extraction unit 12 are separated by a separation membrane 13.
The introduction unit 11 of the fluid separation device 10 has an introduction port 14 into which the mixture is introduced, and a concentrate outlet 15 from which the concentrate is taken out after a part of the components are taken out from the mixture. .. Further, the take-out unit 12 has a separate take-out outlet 16 for taking out the fluid that has passed through the separation membrane 13.
In the following description, a method of separating a gas from a gas-liquid mixed fluid using the above-mentioned fluid separation device 10 will be described as an example, but as a mixture applicable to the fluid separation device according to the embodiment of the present invention. May be a gas-liquid mixed fluid (gas-liquid two-phase flow) or a liquid-liquid two-phase flow (typically, a mixed fluid of water and oil).

The mixture (gas-liquid mixed fluid) is introduced from the introduction port 14 into the introduction portion 11 along the F1 direction, and _a part of the components permeate the separation membrane 13 along the _F3 direction. At this time, the gas in the mixture moves (separates) to the extraction unit 12 along the _F3 direction.
At this time, it is typically preferable that the pressure on the introduction portion 11 side is higher than that on the take-out portion 12. The take-out portion 12 side may be depressurized.
The separated fluid (gas in the above example) is taken out of the fluid separation device 10 from the separation outlet 16.

On the other hand, a part of the components (gas in the above example) is removed from the mixture to form a concentrate, and the concentrate is taken out of the fluid separation device 10 from the concentrate outlet 15.

(Second Embodiment)
FIG. 2 is a schematic diagram showing a second embodiment of the fluid separation device according to the embodiment of the present invention. The fluid separation device 20 includes an introduction unit 21 and an extraction unit 22, and the introduction unit 21 and the extraction unit 22 are separated by a separation membrane 23.
The introduction unit 21 of the fluid separation device 20 includes an introduction port 24 into which the mixture is introduced. Further, the take-out unit 22 has a separate take-out port 25 for taking out the fluid that has passed through the separation membrane 23.
In the following description, a method of separating a gas from a gas-liquid mixed fluid by using the above-mentioned fluid separation device 20 will be described as an example, but as a mixture applicable to the fluid separation device according to the embodiment of the present invention, the method will be described. , Not limited to the above.

The mixture (gas-liquid mixed fluid) is introduced from the introduction port 24 into the introduction section 21 along the _F5 direction, and a part of the component permeates the separation membrane 23 along the _F7 direction. At this time, the gas in the mixture moves (separates) to the extraction unit 22 along the _F7 direction.
At this time, it is typically preferable that the pressure on the introduction section 21 side is higher than that on the take-out section 22.
The separated fluid (gas in the above example) is taken out of the fluid separation device 20 from the separation outlet 25 ( _F6 direction).

On the other hand, a part of the components (gas in the above example) is removed from the mixture to become a concentrate, and the concentrate is taken out of the fluid separator 20 from the introduction port 24 along the _F8 direction.

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.

The following materials were prepared.

A:
Zinc oxide having a tetrapod shape (Panasonic, average fiber length (needle-shaped part): about 10 μm, "Panatetra WZ-0501 (trade name)", corresponds to a specific filler)

B:
RTV (Room Temperature Vulcanizing) Silicone (Toray, 1 component / alcohol type, "HC2100 (trade name)", solid content 96.7% by mass)

C:
Organic solvent (ethyl acetate or hexane)

[Example 1]
(Preparation of composition D1)
0.43 g of B component and 12 ml of C component were mixed in a glass container for about 1 minute to obtain a mixed solution. Next, 1 g of component A was added to the mixed solution, and the mixture was stirred for about 10 minutes to obtain composition D1 (white dispersion). The content mass ratio r in the composition D1 was 0.70.

(Preparation of composition E1)
0.43 g of B component and 3 ml of C component were mixed in a glass container for about 1 minute to obtain a mixed solution. Next, 1 g of component A was added to the mixed solution, and the mixture was stirred for about 1 minute to obtain composition E1 (white dispersion). The mass r contained in the composition E1 was 0.70.

(Creation of member 1)
A coating film-like member was prepared using the composition D1. That is, the composition D1 is placed in a spray can, stirred sufficiently so that Panatetra does not settle, and then sprayed on a support (polyethylene terephthalate, glass, stainless steel, aluminum foil, paper, and cotton), coated, and dried. And formed a film-like member on the support. The water contact angle of the obtained member was measured by the method described later.

(Creation of member 2)
The above composition E1 was injected into a sample tube bottle (Malem No. 3, internal volume 10 ml, corresponding to a mold) and air-dried at room temperature to cure the composition to prepare a monolith-like member. The obtained member (disk type, diameter: 21 mm, thickness: 4 mm) was taken out by breaking the sample tube bottle.

[Examples 2 and 3]
Examples 2 and Examples were carried out in the same manner as in Example 1 except that the contents of the curable silicone rubber component and the filler were adjusted so that the content mass ratio r in the obtained member was as shown in Table 1. The member of Example 3 (coating film-like and monolith-like) was obtained.

[Comparative Examples 1 to 5]
The members of Comparative Examples 1 to 5 (members of Comparative Examples 1 to 5) in the same manner as in Example 1 except that the contents of the silicone rubber and the filler were adjusted so that the content mass ratio r in the obtained member was as shown in Table 1. A coating film-like and a monolith-like form) were obtained.

<Measurement of water contact angle>
The water contact angle (static water contact angle) at 20 ° C. was measured for the coating film-like members of Examples 1 to 3 and Comparative Examples 1 to 5. For the measurement, "contact angle meter DropMaster series DMs-401" manufactured by Kyowa Interface Science Co., Ltd. was used. The results are shown in Table 1 and FIG.
According to FIG. 3, it was confirmed that each of the members of Examples 1 to 3 had a water contact angle of about 150 ° on the surface thereof and had excellent water repellency.

<Confirmation of gas permeability>
A glass container with an opening was prepared and filled with ammonia water. Next, the monolith-shaped members of Examples 1 to 3 were arranged on the glass container so as to cover the opening. Next, a droplet of the aqueous phenolphthalein solution was placed on the member. As a result, the droplet slowly turned red in about 1 minute. The experimental method is shown in FIG.
From the above, it was found that the members of Examples 1 to 3 can be applied to the fluid separation membrane.

<Measurement of pore size distribution by mercury injection method>
The pore size distributions of the monolithic members of Examples 1 to 3 and Comparative Examples 1 to 5 were measured by the mercury intrusion method. For the measurement, "Pore distribution measuring device Autopore IV 9520 type" manufactured by Shimadzu Corporation-Micromeritex Co., Ltd. was used. The results are shown in FIGS. 5 to 25.
Table 1 shows the total volume of pores (mL / g), median diameter (μm), mode diameter (μm), pore ratio (% by volume), and pore diameter uniformity (half) obtained from the above measurements. The results of the price range (μm) are described together.

The mercury intrusion method is an analysis method in which pressure is applied to the pores to infiltrate mercury, and the volume and specific surface area of the pores are obtained from this pressure and the amount of infused mercury. Further, from the analysis result, it is possible to calculate the diameter of the opening obtained from the relationship between the volume of the opening and the specific surface area when the opening is assumed to be a cylinder.
Here, the porosity and the uniformity of the pore diameter were evaluated according to the following criteria, and are described in Table 1.

(Porosity)
The evaluation criteria for porosity (% by volume) are as follows. As a member used for the fluid separation membrane (separation membrane), A is the most excellent, and A to D are in the order of superiority.

A Porosity exceeded 75% by volume.
B Porosity exceeded 65% by volume and was 75% by volume or less.
C Porosity exceeded 55% by volume and was 65% by volume or less.
D Porosity was 55% by volume or less.

(Homogeneity of hole diameter)
For the uniformity of the pore diameter, the half width in the pore diameter distribution was calculated, and the value was evaluated according to the following criteria. As a member used for the fluid separation membrane (separation membrane), AA is the most excellent, and AA to C are in the order of superiority.

The AA half width was less than 1.4 μm.
A Half width was 1.4 μm or more and less than 1.9 μm.
The half width at half maximum was 1.9 μm or more and less than 2.4 μm.
The full width at half maximum was 2.4 μm or more.

In Table 1, "-" indicates that no measurement or calculation was performed.

From the results shown in Table 1, the members of Examples 1 to 3 have a sufficient amount of pores and their pore diameters have excellent uniformity, and therefore, when applied to a fluid separation membrane. It was presumed that sufficient performance could be obtained, and it was confirmed that the member had the desired effect of the present invention.
On the other hand, it was found that the members of Comparative Examples 1 to 4 had almost no holes, or even if they were found, the amount was insufficient, and the members did not have the desired effect of the present invention. Further, it was found that the member of Comparative Example 5 did not have the desired effect of the present invention because the amount of holes opened was insufficient and the uniformity of the hole diameter was also insufficient.

Further, from the results shown in Table 1, the member of Example 2 has more openings than the member of Example 1, and the obtained openings have more excellent uniformity. Had had. Therefore, it was found that the member of Example 2 had better separation ability when applied to the fluid separation membrane as compared with the member of Example 1.
Further, from the results shown in Table 1, the member of Example 3 had the same amount of pores as the member of Example 2, but had better hole diameter uniformity. rice field. Therefore, it was found that the member of Example 3 had an even better separation ability when applied to the fluid separation membrane as compared with the member of Example 2.

10, 20 Fluid Separator 11, 21 Introducing Unit 12, 22 Extraction Unit 13, 23 Separation Membrane 14, 24 Introducing Port 15 Concentrate Outlet 16, 25 Separation Outlet

Claims (6)

A member obtained by curing a composition containing a curable silicone rubber component and a filler.
The filler has a three-dimensional shape having a core portion and a needle-shaped portion extending from the core portion in four different axial directions.
The content mass ratio r of the content of the filler to the total content of the curable silicone rubber component and the filler in the composition is 0.70 or more .
A member used for a separation membrane for separating one of the fluids from a mixture containing at least two or more kinds of fluids . The member according to claim 1, wherein the curable silicone rubber component contains an organopolysiloxane having a hydrolyzable group bonded to a silicon atom. The member according to claim 1 or 2, wherein r is 0.80 or more. A separation membrane comprising the member according to any one of claims 1 to 3 .
It is provided with an introduction part and a take-out part separated by the separation membrane.
A mixture containing at least two kinds of fluids is introduced into the introduction section.
A fluid separation device in which one of the fluids separated from the mixture by the separation membrane is taken out from the take-out unit. A composition containing a curable silicone rubber component and a filler.
The filler has a three-dimensional shape having a core portion and a needle-shaped portion extending from the core portion in four different axial directions.
The content mass ratio r of the content of the filler to the total content of the curable silicone rubber component and the filler in the composition is 0.70 or more .
A composition in which the cured product of the composition is used as a separation membrane for separating one of the fluids from a mixture containing at least two or more fluids . The composition according to claim 5, wherein r is 0.80 or more.

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