JP5145869B2 - Transportation system and transportation method - Google Patents

Description

  The present invention relates to a transportation system and a transportation method.

In general, external pumps (diaphragm pumps, syringe pumps, peristaltic pumps, gear pumps, etc.) are used for material transport in the microreactor.
An example in which a liquid feeding system is installed in a microreactor using a piezoelectric element (piezoelectric element) or electroosmotic flow is also known.
For example, in Patent Document 1, the volume of a cavity is changed by driving a piezoelectric element, and an injection port that sends and receives a sample to and from a channel is communicated with the injection port via the channel. A microreactor having a discharge port for collecting a sample has been proposed, and Patent Document 2 discloses a plurality of liquid inlets, a mixing channel communicating with the liquid inlets, and a distance from the plurality of liquid inlets. A liquid mixing apparatus comprising: a liquid outlet provided in the mixing path; and an electric field forming means for generating an electroosmotic flow from the plurality of liquid inlets toward the liquid outlet in the liquid accommodated in the mixing path. Wall surface state changing means for locally changing the state of the wall surface of the mixing path in contact with the surface to cause local variation in the velocity field of the liquid flowing through the mixing path, the electric field forming means, A single electric field acting on the liquid contained in the serial mixing path, forming between said plurality of liquid inlet and said liquid outlet, a liquid mixing device according to claim is proposed.

JP 2001-228159 A JP 2004-156964 A

  The present invention is to provide a transport system and a transport method capable of transporting not only a low-viscosity fluid but also a high-viscosity fluid, a semisolid, a solid dispersion, and the like in a microchannel. .

The above problems of the present invention have been solved by means <1> and <5>. The preferred embodiments are shown below together with <2>, <3>, <4>, <6>, <7> and <8>.
<1> A micro flow channel in which at least a part of an inner wall surface is formed of a stimulus-responsive polymer or a crosslinked body that generates a volume change by applying a stimulus, and causing the volume change and propagating the volume change. A transportation system comprising at least a stimulus applying means capable of
<2> The transport system according to <1>, wherein the stimulus-responsive polymer or the crosslinked body is formed with a thickness in a range of 1/10 or more with respect to a flow path diameter.
<3> The stimulus is a chemical reaction, light, heat (temperature change), ion movement in a stimulus-responsive gel, application of an electric field, application of current, change in pH, change in ion concentration, adsorption / desorption of a chemical substance A transport system according to the above <1> or <2> selected from the group consisting of a change in solvent composition and a magnetic field,
<4> The above <1> to <1>, wherein the stimulus is selected from the group consisting of chemical reaction, light, temperature change, electrochemical reaction, migration of ions in a stimulus-responsive polymer or crosslinked body, and application of an electric field. 3> The transport system according to any one of 3>.
<5> A microchannel in which at least a part of an inner wall surface is formed of a stimulus-responsive polymer or a crosslinked body that causes a volume change by applying a stimulus, and a stimulus that causes the volume change and propagates the volume change A step of preparing a transport system including at least an applying unit, a step of filling the microchannel with a fluid, and applying a stimulus to the stimulus-responsive polymer or the crosslinked body by the stimulus applying unit to cause a volume change. And transporting the substance in the microchannel by being able to further propagate the volume change,
<6> The transport method according to <5>, wherein the stimulus-responsive polymer or the crosslinked body is formed with a thickness in a range of 1/10 or more with respect to a flow path diameter.
<7> The stimulus is a chemical reaction, light, heat (temperature change), ion movement in a stimulus-responsive gel, application of an electric field, application of current, change in pH, change in ion concentration, adsorption / desorption of a chemical substance A transport method according to the above <5> or <6>, which is selected from the group consisting of a change in solvent composition and a magnetic field,
<8> The above <5>, wherein the stimulus is selected from the group consisting of chemical reaction, light, temperature change, electrochemical reaction, stimulus-responsive polymer or ion movement in a crosslinked body, and application of an electric field. > To <7> The transport method according to any one of the above.

  According to the present invention, there are provided a transport system and a transport method that can transport not only a low-viscosity fluid but also a high-viscosity fluid, a semi-solid, a solid dispersion, and the like in a microchannel. Can do.

  Hereinafter, the present invention will be described in detail with reference to the drawings.

(Transport system)
In the transport system of the present invention, a stimulus-responsive polymer or cross-linked body (hereinafter referred to as “stimulus-responsive polymer or cross-linked body”) that produces a volume change upon application of a stimulus is referred to as “stimulus-responsive gel”. It is characterized by comprising at least a micro-channel formed at least in part and a stimulus applying means capable of causing the volume change and propagating the volume change.
The stimulus-responsive polymer is a non-crosslinked polymer that absorbs / desorbs (absorbs / releases) a liquid upon application of a stimulus to change the volume (swell / shrink), and the stimulus-responsive crosslinked body includes: It is a polymer crosslinked body that absorbs and desorbs (absorbs / releases) a liquid and gives a volume change (swelling / shrinking) by applying a stimulus.

In the transport system of the present invention, the thickness D of the stimulus-responsive gel formed on at least a part of the inner wall surface of the microchannel is D / L = 1/10 or more with respect to the channel diameter L. Is preferred. Moreover, it is preferable that it is the range of D / L = 1/10 or more and D / L = 9/10 or less, in the range of D / L = 1/5 or more and D / L = 4/5 or less. More preferably, it is more preferably in the range of D / L = 3/10 or more and D / L = 7/10 or less. When the thickness of the stimulus-responsive gel is within the above range, transportation of high-viscosity fluids, semi-solids, solid dispersions, and the like in the microchannel is facilitated, and volume change and propagation of the stimulus-responsive gel is facilitated. The propulsive force generated in the flow direction can be efficiently transmitted to the fluid and the solid matter in the fluid, and efficient transportation becomes possible. Further, when the D / L is 9/10 or less, a sufficient transportation amount can be achieved, and when it is 1/10 or more, a sufficient driving force can be obtained.
The channel diameter is a circle-equivalent diameter (diameter) obtained from the cross-sectional area of the channel cut by a plane perpendicular to the flow direction.

The stimulus applied to the stimulus-responsive gel includes chemical reaction, light, heat (temperature change), ion movement in the stimulus-responsive gel, application of electric field, application of current, change in pH, change in ion concentration, chemistry The adsorption / desorption (absorption / release) of the liquid can be exemplified by the adsorption / desorption of the substance, the change of the solvent composition, the application of a stimulus such as a magnetic field.
Among these, from the viewpoint of simplicity in the stimulus applying means, the stimulus includes chemical reaction, light, temperature change, electrochemical reaction, migration of ions in the stimulus-responsive polymer or crosslinked body, and application of an electric field. Preferably selected from the group, selected from the group consisting of light, temperature change, electrochemical reaction, migration of ions in the stimuli-responsive polymer or crosslinked body, and application of an electric field. Is more preferable.
In addition, since the stimulus can be easily applied from the outside of the microchannel, the stimulus is selected from the group consisting of light, temperature change, migration of ions in the stimulus-responsive polymer or crosslinked body, and application of an electric field. It is preferable that

The stimulus imparting means in the transport system of the present invention can impart stimulus to the stimulus-responsive polymer or crosslinked body, cause a volume change in the stimulus-responsive polymer or crosslinked body, and propagate the volume change. Means.
In the present invention, the term “propagating volume change” refers to moving the volume change in the stimulus-responsive polymer or crosslinked body. In addition, what is propagated is only the volume change of the stimulus-responsive polymer or crosslinked body, and the stimulus-responsive polymer or crosslinked body itself does not move.

The stimulus applying means that can be used in the present invention is not particularly limited as long as it is a means that can give a stimulus that causes a volume change in the stimulus-responsive gel and can propagate the volume change. Appropriate means may be selected according to the type of stimulus to be applied.
As the stimulus applying means, for example, a device capable of applying a stimulus such as light or heat and changing the position where the stimulus is applied, or a means for filling a fluid containing a vibration-reactive reagent in the microchannel The device group which provides irritation | stimulation to the whole microchannel part in which irritation | stimulation responsive gel was provided, the means etc. which control the part which irritate | stimulates these apparatuses with a control apparatus are mentioned.
The stimulus application by the stimulus application means may be continuous, intermittent, pulsed, or gradually changing, and transports the fluid in the microchannel. If it is possible, there is no particular limitation.
Moreover, there is no restriction | limiting in particular in the part which gives irritation | stimulation by a irritation | stimulation means, and even if it provides only one place or several places in the stimulus responsive gel part of a microchannel, it gives uniformly to the whole. Alternatively, it may be gradually changed.

More specifically, the following means can be preferably exemplified.
When using the Belozov-Jabochinsky reaction, which is a chemical reaction, as a stimulus, there is a means for containing a catalyst in a stimulus-responsive gel and filling a solution containing malonic acid, sodium bromate and an acid into a microchannel. It can be illustrated.
In the case where light is used as a stimulus, a means for producing a micro flow path with a transparent base material that transmits light and moving spot irradiation by a known light source in the flow direction of the flow path can be exemplified.
In the case of using a temperature change as a stimulus, a means for irradiating a known laser to heat and moving the irradiation in the flow direction of the flow path can be exemplified.
In the case where an electrochemical reaction is used as the stimulus, a means for producing a micro flow channel having a plurality of electrodes along the flow channel and controlling the electrochemical reaction (oxidation-reduction reaction) at each electrode of the micro flow channel can be exemplified. .
In the case of using the movement of ions in the stimulus-responsive gel as a stimulus, a micro flow channel having a plurality of electrodes is prepared along the flow channel, and the positive / negative of the applied voltage is propagated through each electrode of the micro flow channel. A means for controlling localization can be exemplified.
In the case of using the application of an electric field as a stimulus, a means for producing a microchannel having a plurality of electrodes along the channel and appropriately changing the positive / negative of the electric field in each electrode of the microchannel can be exemplified.

FIG. 1 is a schematic diagram showing an example in which a micro-channel in which a stimulus-responsive polymer or a crosslinked body is formed on at least a part of an inner wall surface, and the stimulus-responsive polymer or the crosslinked body undergoes a volume change by applying a stimulus. It is sectional drawing.
In FIG. 1, the microchannel in which the stimulus-responsive polymer or the crosslinked body is formed on at least a part of the inner wall surface changes in order as shown in FIGS. 1 (A), 1 (B), and 1 (C). It is the figure which showed a mode that it goes.
FIG. 1A is a cross-sectional view in the flow channel direction of a part of the micro flow channel 10 in which the stimulus-responsive polymer or the crosslinked body 12 is formed on the inner wall surface 14. The microchannel 10 is formed by a microchannel-forming substrate portion 16 made of a known substrate. In addition, the microchannel 10 is filled with a fluid containing a liquid that can be absorbed and discharged by the stimulus-responsive polymer such as water or the crosslinked body 12.
FIG. 1B shows that a stimulus is applied to a part of the microchannel 10 shown in FIG. 1A by a stimulus applying means (not shown). The portion to which the stimulus is applied is schematically represented as the stimulus applying portion 18.
As shown in FIG. 1 (B), by applying a stimulus to a part of the microchannel 10 filled with a fluid containing a liquid that can be absorbed and discharged by the stimulus-responsive polymer such as water or the crosslinked body 12, The stimulus-responsive polymer or crosslinked body 12 of the portion to which the stimulus is applied absorbs the liquid and swells, and changes as shown in the diagram shown in FIG. In FIG. 1 (B), the stimulus-responsive polymer or crosslinked body 12 of the portion to which the stimulus is applied swells, and the swollen portion 20 is formed. In addition, the stimulus-responsive polymer or crosslinked body 12 in the portion where no stimulus is applied is not particularly changed, and becomes a non-swelled portion 22.
In FIG. 1, the stimulation-responsive polymer or crosslinked body 12 is exemplified as one that swells upon application of stimulus, but if the stimulus-responsive polymer or crosslinked body 12 that contracts upon application of stimulus is used. Needless to say, a contraction portion is formed in FIG.
In addition, the fluid filled in the microchannel 10 may be a liquid that can be absorbed and discharged by the stimuli-responsive polymer or the cross-linked body 12 and can swell and contract even if it is not water.

FIG. 2 shows an example in which a micro flow channel in which a stimulus-responsive polymer or crosslinked body is formed on at least a part of the inner wall surface is used to propagate the volume change of the stimulus-responsive polymer or crosslinked body by applying a stimulus. It is a schematic cross section.
The microchannel 10 in which the stimulus-responsive polymer or the crosslinked body 12 is formed on the inner wall surface 14 is formed by a microchannel-forming base material portion 16 made of a known base material. A fluid containing a liquid that can be absorbed and discharged by the stimuli-responsive polymer or cross-linked body 12 is filled.
By applying a stimulus to one or more portions of the microchannel 10 filled with the liquid using a stimulus applying means (not shown), the stimulus-responsive polymer or crosslinked body 12 of the portion to which the stimulus has been applied is provided. The liquid is absorbed and swells to form swollen portions 20a and 20b. Furthermore, the swelling portions 20a and 20b can also be moved gradually by gradually moving the stimulus applying portions 18a and 18b in the flow direction while continuing to apply the stimulus.

As described above, by moving the swelling portions 20a and 20b, that is, by propagating the volume change of the stimulus-responsive polymer or the crosslinked body, the transport system of the present invention is not only a low-viscosity fluid but also a high-viscosity fluid. Fluids, semi-solids, and solid dispersions can also be transported.
This is because the force that changes the volume when the stimulus-responsive polymer or crosslinked body swells or contracts is very strong.

FIG. 3 is an enlarged schematic cross-sectional view of an example of a microchannel in which a stimulus-responsive polymer or a crosslinked body is formed on at least a part of an inner wall surface and a plurality of electrodes are arranged.
The microchannel 10 in which the stimulus-responsive polymer or the crosslinked body 12 is formed on the inner wall surface 14 is formed by a microchannel-forming base material portion 16 made of a known base material, and is opposed to the microchannel 10. A plurality of pairs of electrodes 24 are provided in the flow direction of the flow path so as to face the two surfaces. Further, the stimulus-responsive polymer or cross-linked body 12 on the inner wall surface of the microchannel in FIG. 3 represents a state that is not particularly given as stimulus.
For example, in the case of using an electrochemical reaction, migration of ions in a stimulus-responsive gel, or application of an electric field as the stimulus, a stimulus-responsive polymer or cross-link is formed on at least a part of the inner wall surface as shown in FIG. A microchannel in which a body is formed and a plurality of electrodes are arranged can be suitably used.
There are no particular restrictions on the shape, number, size, arrangement, etc. of the electrodes provided in the microchannel, and they may be provided as necessary. For example, as shown in FIG. 3, a plurality of pairs of electrodes may be arranged above and below the inner wall surface of the microchannel, or a plurality of pairs of electrodes may be arranged on the top, bottom, left and right of the inner wall surface of the microchannel. Alternatively, electrodes may be arranged on the entire upper and lower surfaces of the inner wall surface of the microchannel, and a ring-shaped electrode may be provided around the microchannel. Moreover, an electrode may be installed so that it may be exposed in a flow path in the inner wall face of a micro flow path, or it may be installed without exposing as needed.
Moreover, what is necessary is just to control a voltage and an electric current as needed for the electrode provided in the microchannel. Moreover, when an electrode is provided, it may or may not be energized in the microchannel according to the stimulus required for the stimulus-responsive gel.

When the transport system of the present invention has a micro-channel in which a stimulus-responsive gel is modified by chemical bonding on at least a part of the inner wall, the amount of the stimulus-responsive gel used can be easily adjusted to the required amount. This is preferable because it is excellent in terms of cost. Further, by modifying the stimulus-responsive gel on the inner wall by chemical bonding, it is possible to prevent the stimulus-responsive gel from dropping and peeling from the inner wall due to repeated swelling and shrinkage of the stimulus-responsive gel and external force.
The chemical bond is more preferably a covalent bond.
The transport system of the present invention may use only one kind of stimulus-responsive gel or a plurality of kinds. Moreover, the transportation system of the present invention may use only one kind of stimulus-responsive gel or a plurality of kinds of stimuli-responsive gels in one microchannel.

  The stimulus-responsive gel that can be used in the present invention includes, for example, chemical reaction, light, heat (temperature change), ion movement in the stimulus-responsive gel, application of electric field, application of current, change in pH, ion concentration. The liquid is adsorbed (absorbed / released) and changed in volume (swelled / contracted) by applying a stimulus such as a change in water, adsorption / desorption of a chemical substance, a change in solvent composition, and a magnetic field.

The chemical reaction can be exemplified by a vibrational reaction, preferably a vibrational reaction accompanied by redox, and more preferably a Belousov-Zhabotinskii reaction (BZ reaction).
A material having a functional group that reversibly expresses a redox reaction is preferably used as a stimulus-responsive gel that responds by a chemical reaction, particularly a redox reaction.

In the case of using a stimulus-responsive gel that responds to a stimulus by the Belozov-Jabochinsky reaction, it is preferable to have a catalyst in the stimulus-responsive gel.
Examples of the catalyst include Group 3 to Group 11 transition metal catalysts, which are preferably a catalyst containing ruthenium, cerium, iron, and manganese, and more preferably a catalyst containing ruthenium.
In addition, the catalyst may be simply contained in the stimulus-responsive gel or may be bound to the stimulus-responsive gel through a chemical bond.
The content of the catalyst is preferably 0.1% by weight or more and 50% by weight or less with respect to the stimulus-responsive gel.

The stimuli-responsive gel that responds to stimuli by the application of light is preferably a cross-linked product of a hydrophilic polymer compound having a group that is ionically dissociated by light, such as a triarylmethane derivative or a spirobenzopyran derivative. And a cross-linked product of a copolymer of a triarylmethane leuco derivative and (meth) acrylamide.
In addition, as a stimulus-responsive gel that responds to a stimulus by application of light, a cross-linked product of a polymer compound having a group that causes cis-trans isomerization by light, such as a compound having an azo group (particularly, an azobenzene structure) is preferable. Examples thereof include a crosslinked product of a copolymer of (meth) acryloyl group-containing azobenzene and (meth) acrylamide.

  As a stimulus-responsive gel that responds to a stimulus by heat (temperature change), a polymer with LCST (lower critical eutectic temperature) that has the property of aggregating by a hydrophobic interaction and precipitating from an aqueous solution above a certain temperature. Cross-linked body, cross-linked body of polymer having UCST (upper critical eutectic temperature), polymer gel having polymer chain hydrogen-bonded to each other, or two-component polymer IPN body to hydrogen-bond to each other (inter-penetration) Network structure), semi-IPN bodies, polymer gels having cohesive side chains such as crystallinity, and the like are preferable. Among these, LCST gel using hydrophobic interaction is particularly preferable. LCST gel shrinks at high temperature, and UCST gel, IPN gel, semi-IPN gel, and crystalline gel have the property of swelling at high temperature.

Specific examples of gels that shrink at high temperatures include cross-linked N-alkyl-substituted (meth) acrylamides such as poly-N-isopropylacrylamide, N-alkyl-substituted (meth) acrylamide and (meth) acrylic acid and salts thereof, Or a crosslinked product of a copolymer of two or more components such as (meth) acrylamide or (meth) acrylic acid alkyl ester, a crosslinked product of polyvinyl methyl ether, a crosslinked product of an alkyl-substituted cellulose derivative such as methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, etc. Etc. Among these, poly N-isopropyl (meth) acrylamide is preferable.
On the other hand, specific compounds of gels that swell at high temperature include IPN bodies, semi-IPN bodies and partially neutralized bodies (acrylic) composed of crosslinked poly (meth) acrylamide and crosslinked poly (meth) acrylic acid. In which the acid unit is partially chlorinated), a cross-linked copolymer of poly (meth) acrylamide as a main component and a poly (meth) acrylic acid cross-linked IPN, semi-IPN, and their parts Japanese style and so on. More preferably, a crosslinked product of poly N-alkyl-substituted alkylamide, an IPN product of a crosslinked product of poly (meth) acrylamide and a crosslinked product of poly (meth) acrylic acid, a semi-IPN product, and a partially neutralized product thereof. Can be mentioned.

  In addition, as the crystalline gel, a crosslinked product of a copolymer of (meth) acrylic acid ester and (meth) acrylic acid having a long-chain alkyl group such as octyl group, decyl group, lauryl group, stearyl group, or the like Salt. The temperature (phase transition temperature) showing the volume change of the thermoresponsive polymer gel can be variously designed depending on the structure and composition of the polymer gel. The preferred phase transition temperature is within the boiling point or freezing point of the solvent, more preferably in the range of −30 ° C. to 300 ° C., still more preferably in the range of −10 ° C. to 150 ° C., and particularly preferably 0. It is the range of 60 degreeC or more.

  In addition to the specific examples illustrated above, a gel showing a plurality of phase transition points in accordance with temperature changes can be suitably used as the stimulus-responsive gel that responds to a stimulus by heat. Specifically, an IPN (interpenetrating network structure) or semi-IPN of a crosslinked product of polyalkyl-substituted (meth) acrylamide such as poly-N-isopropyl (meth) acrylamide and a crosslinked product of poly (meth) acrylic acid Examples include the body. These gels are known to exhibit two phase transition points of swelling-shrinking-swelling with increasing temperature.

  It is also preferable to include an ionic functional group in the polymer gel for the purpose of increasing the volume change amount of the stimulus-responsive gel that responds to the stimulus by heat. Examples of the ionic functional group include carboxylic acid, sulfonic acid, ammonium group, and phosphoric acid group. The ionic functional group copolymerizes monomers having these functional groups when preparing the gel, and impregnates the synthesized stimuli-responsive gel with the monomer to polymerize it into the IPN or semi-IPN form. The functional group in the gel can be contained by a method such as partial conversion by a chemical reaction such as hydrolysis or oxidation reaction.

  Examples of stimuli-responsive gels that respond to stimuli by electrochemical reactions include ferrocene derivatives, metal complexes such as cobalt cenium and ruthenium, transition metals, fullerene derivatives, porphyrins, expanded porphyrins, pyrrole compounds, phenothiazines, viologen derivatives, phenothiazine derivatives, Thiophene compounds, aniline compounds, carbazole derivatives, tetrathiafulvalene derivatives, diamine compounds, phthalocyanine compounds, hydrazone compounds, oxadiazole derivatives, perylene derivatives, naphthalene derivatives, etc. Other porphyrins, redox proteins, etc. Examples thereof include a gel structure having an ecologically derived substance or the like as a functional group, and a polymer such as polypyrrole or polyaniline that is oxidized and reduced by a polymer matrix.

  The stimulus-responsive gel that responds to the stimulus by the movement of ions in the stimulus-responsive gel includes a polyether derivative, a polypyrrole derivative, a fluorine-based ion exchange resin derivative, a polyester derivative, a polyimine derivative, a polymer gel impregnated with an ionic liquid, Examples thereof include polymers containing them.

  As a stimulus-responsive gel that responds to a stimulus by applying an electric current or an electric field, a CT complex (charge transfer complex) of a cationic polymer gel and an electron-accepting compound is preferable, and amino-substituted (meta) such as dimethylaminopropyl (meth) acrylamide is used. ) Crosslinked product of acrylamide; Crosslinked product of amino-substituted alkyl ester of (meth) acrylic acid such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and dimethylaminopropyl acrylate; Crosslinked product of polystyrene; Crosslinked product of polyvinylpyridine A crosslinked product of polyvinyl carbazole; a crosslinked product of polydimethylaminostyrene, and in particular, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate Over DOO, dialkylaminoalkyl such as diethylaminoethyl (meth) acrylate (meth) acrylate-based polymer is preferable. These may be used in combination with electron accepting compounds such as benzoquinone, 7,7,8,8-tetracyanoquinodimethane (TCNQ), tetracyanoethylene, chloranil, trinitrobenzene, maleic anhydride and iodine. it can.

  As the stimulus-responsive gel that responds to a stimulus by a change in pH, an electrolyte polymer gel is preferable. A cross-linked product of poly (meth) acrylic acid or a salt thereof, (meth) acrylic acid and (meth) acrylamide, or hydroxyethyl (meth) ) Copolymers and salts of copolymers with acrylates, alkyl (meth) acrylates, etc. Crosslinks and salts of polymaleic acid, maleic acid and (meth) acrylamide, hydroxyethyl (meth) acrylate, (meth) Cross-linked products of copolymers with alkyl acrylates and their salts, cross-linked products of polyvinyl sulfonic acids and vinyl sulfonic acids with (meth) acrylamide, hydroxyethyl (meth) acrylate, (meth) acrylic acid alkyl esters, etc. Cross-linked copolymer, cross-linked polyvinyl benzene sulfonic acid and its salts, vinyl Cross-linked products and salts of copolymers of rubenzene sulfonic acid and (meth) acrylamide, hydroxyethyl (meth) acrylate, alkyl (meth) acrylate, etc., cross-linked products and salts of polyacrylamide alkyl sulfonic acid, acrylamide Cross-linked products and salts of copolymers of alkylsulfonic acid and (meth) acrylamide, hydroxyethyl (meth) acrylate, alkyl (meth) acrylic acid, etc., cross-linked products of polydimethylaminopropyl (meth) acrylamide and hydrochloric acid thereof Salt, dimethylaminopropyl (meth) acrylamide and (meth) acrylic acid, (meth) acrylamide, hydroxyethyl (meth) acrylate, cross-linked products of methacrylic acid alkyl esters, etc. Salt, polydimethylamino Cross-linked product of propyl (meth) acrylamide and polyvinyl alcohol, quaternized product or salt thereof, cross-linked product or salt of composite of polyvinyl alcohol and poly (meth) acrylic acid, cross-linked product of carboxyalkyl cellulose salt Examples thereof include partial hydrolysates of crosslinked products of poly (meth) acrylonitrile and salts thereof.

  The change in pH is due to electrode reaction such as electrolysis of liquid or oxidation-reduction reaction of a compound to be added, oxidation-reduction reaction of conductive polymer, and addition or desorption of a chemical substance that changes pH. It is preferable.

  As the stimulus-responsive gel that responds to the stimulus by changing the ion concentration, an ionic polymer material (polymer gel) similar to the stimulus-responsive gel caused by the pH change can be used. The change in the ion concentration is preferably due to the addition of salt or the like, the use of an ion exchange resin, or the like.

  As the stimuli-responsive gel that responds to stimuli by adsorption and desorption of chemical substances, strong ionic polymer gels are preferable. Examples thereof include crosslinked products of polyvinyl sulfonic acid, vinyl sulfonic acid and (meth) acrylamide, and hydroxyethyl (meth). Cross-linked products of copolymers with acrylates, alkyl (meth) acrylates, cross-linked products of polyvinyl benzene sulfonic acid, vinyl benzene sulfonic acid and (meth) acrylamide, hydroxyethyl (meth) acrylate, alkyl (meth) acrylate Cross-linked products of copolymers with esters, cross-linked products of poly (meth) acrylamide alkyl sulfonic acid, (meth) acrylamide alkyl sulfonic acid and (meth) acrylamide, hydroxyethyl (meth) acrylate, (meth) acrylic acid alkyl ester Co-weight with Are like the body of the cross-linked product, in particular, polyacrylamide alkylsulfonic acid polymer is preferably used.

  In this case, the chemical substance includes a surfactant, for example, a cationic interface such as an alkylpyridine salt such as n-dodecylpyridinium chloride, an alkylammonium salt, a phenylammonium salt, and a phosphonium salt such as tetraphenylphosphonium chloride. An activator can be preferably used.

  In addition, as a stimulus-responsive gel that responds to a stimulus by adsorption / desorption of a chemical substance, a phenylboronic acid simple substance that is a stimulus-responsive gel that responds to a stimulus by adsorption / desorption of a diol compound, sugar, or a polyhydric alcohol compound such as a nucleotide. And a crosslinked product of a copolymer of a monomer and an ethylenically unsaturated monomer. Examples of such a stimulus-responsive gel include stimuli-responsive gels described in JP-A-7-304971, JP-A-11-322761, and JP-A-2000-309614.

Examples of the phenylboronic acid monomer include 4- (dihydroxyborono) styrene, 3- (meth) acrylamide phenylboronic acid, N- (4′-vinylbenzyl) -4-phenylboronic acid carboxamide 3-((meta ) Acrylamidylglycylamide) phenylboronic acid, 3- (meth) acrylamide-2-trifluoromethylphenylboronic acid, 3- (meth) acrylamide-4-pentafluoroethylphenylboronic acid, 3- (meth) acrylamide -6-heptafluoropropylphenylboronic acid, 3-((meth) acrylamidylglycylamide) -6-heptafluoropropylphenylboronic acid, 3- (meth) acrylamide-4,6-bis (heptafluoropropyl) Phenylboronic acid, 3- (meth) acrylamide-2- (1, 1,2,2,3,3-hexafluoropropyl) phenylboronic acid, 3- (meth) acrylamide-4- (1-chloro-1,1,2,2,3,3-hexafluoropropyl) phenyl boron Preferred examples include acid and 3- (meth) acrylamide-6- (perfluoro-1,4-dimethyl-2,5-dioxaoctyl) phenylboronic acid.
Preferred examples of the ethylenically unsaturated monomer include N-alkyl-substituted (meth) acrylamide, (meth) acrylamide, hydroxyethyl (meth) acrylate, (meth) acrylic acid alkyl ester, and (meth) acrylic acid. .

  Most polymer gels can be cited as stimuli-responsive gels that respond to stimuli by changes in solvent composition, and swelling and shrinkage can be caused by using good and poor solvents in the polymer gel. .

  Examples of the stimuli-responsive gel that responds to a stimulus by applying a magnetic field include cross-linked polyvinyl alcohol containing ferromagnetic particles and a magnetic fluid, but the gel itself is particularly suitable if it is a gel that responds to a magnetic field stimulus. It is not limited, and any material may be used as long as it is included in the category of gel.

The stimulus-responsive gel that can be used in the present invention may be synthesized using a crosslinking agent. A well-known thing can be used as said crosslinking agent.
The amount of the crosslinking agent used in the stimulus-responsive gel is preferably 0.01% by weight or more and 10% by weight or less, and 0.1% by weight or more and 1.0% by weight with respect to the weight of the whole monomer. The following is more preferable. Within the above range, not only the self-supporting property is excellent, but a sufficient volume change amount can be obtained, and further, the stimulation-responsive gel can be easily modified on the inner wall surface of the microchannel.

Although the maximum volume change amount of the stimulus-responsive gel is not particularly limited, it is preferably as high as possible. The volume ratio at the time of maximum swelling and at the time of minimum contraction is more preferably 3 or more, and particularly preferably 5 or more.
Furthermore, the absorption amount of the liquid at the time of the maximum swelling of the stimulus-responsive gel is preferably in the range of (the mass of the liquid absorbed by the stimulus-responsive gel / the mass of the stimulus-responsive gel when dried) = 5 or more and 500 or less. If it is 5 or more, the volume change of the stimulus-responsive gel can be sufficiently taken, and if it is 500 or less, the gel strength can be sufficiently secured, which is preferable.

  In the stimuli-responsive gel, various stabilizers such as ultraviolet absorbers and light stabilizers can be copolymerized or bonded within a range that does not impair the properties. For example, it is preferable to copolymerize or bond a hindered amine or hindered phenol compound or a compound having a light stabilizing function. The amount of copolymerization or binding of these compounds is preferably in the range of 0.01% by weight to 5% by weight with respect to the stimulus-responsive gel.

The fluid that can be flowed to the transportation system of the present invention does not have to be a complete liquid, and may contain a solid or a gas depending on the intended use, and its composition, concentration, etc., should be selected as necessary. Can do. In particular, the transport system of the present invention is capable of transporting highly viscous fluids, semi-solids and / or solid dispersions that cannot generally be transported through microchannels. The high-viscosity fluid includes, for example, a fluid having a viscosity of 1,000 cs (centistokes) or more that generally cannot be transported through the micro-channel, although it varies depending on the flow velocity, the channel cross-sectional area, and the length. .
The fluid is not particularly limited as long as it contains a compound necessary for the stimulus-responsive gel used to swell and contract, but includes an organic solvent or an aqueous medium such as water or alcohols. Is preferable, it is more preferable that an aqueous medium is included, and it is further preferable that water is included.
Moreover, as a semi-solid and / or solid dispersion, generally, a dispersion containing 5 wt% to 95 wt% of a semi-solid and / or solid cannot be transported in a microchannel. Can be mentioned.

The microchannel is a microscale channel. That is, the width of the flow path (flow path diameter) is 5,000 μm or less, preferably 10 μm or more and 1,000 μm or less, more preferably 30 μm or more and 500 μm or less. Further, the depth of the flow path is about 10 μm or more and 500 μm or less. Furthermore, although the length of the flow path depends on the shape of the flow path to be formed, it is preferably in the range of 5 mm to 400 mm, more preferably in the range of 10 mm to 200 mm.
Moreover, there is no restriction | limiting in particular about the shape of a microchannel, What is necessary is just to make it a desired shape. As the cross-sectional shape of the microchannel, for example, the cross-sectional shape in a direction perpendicular to the flow direction can be a desired shape such as a circle, an ellipse, or a polygon.

In the transport system of the present invention, examples of the material forming the microchannel include metals, ceramics, glass, fused silica, silicone, resin, and the like, in addition to the stimulus-responsive gel, with glass being preferred. In the case where the stimulus-responsive gel is modified on the inner wall of the microchannel, it is preferable that the material is glass or resin because the modification to the inner wall is easy.
The material is preferably glass from the viewpoints of low cost, transparency, workability, and the like.

As said glass, common things, such as soda glass, quartz glass, borosilicate glass, crystal glass, can be used, for example. Moreover, as a glass transition point of glass, it is more preferable that they are 500 degreeC or more and 600 degrees C or less.
The resin is preferably a resin having impact resistance, heat resistance, chemical resistance, transparency, and the like that is suitable for the reaction to be performed and unit operation, and specifically, polyester resin, styrene resin, acrylic resin, styrene / acrylic resin. Preferred examples include resins, silicone resins, epoxy resins, diene resins, phenol resins, terpene resins, coumarin resins, amide resins, amideimide resins, butyral resins, urethane resins, ethylene / vinyl acetate resins, and more preferably methyl. Acrylic resin such as methacrylate resin, and styrene resin. Further, the resin is preferably a resin having a glass transition point, and the glass transition point of the resin is preferably in a range of 90 ° C. or higher and 150 ° C. or lower, and in a range of 100 ° C. or higher and 140 ° C. or lower. More preferably.

The method for forming the microchannel in the present invention is not particularly limited, and may be manufactured by a known method. Alternatively, a stimulus-responsive gel may be provided in the microchannel using a commercially available device having a microchannel.
An example of a commercially available device having a microchannel is an integrated glass chip manufactured by Micro Chemical Engineering Co., Ltd.
Moreover, the following method is mentioned preferably as a formation method of the microchannel in this invention.

  As a method of forming a microchannel in which a stimulus-responsive gel is modified on the inner wall surface of the microchannel, it is also referred to as a step of manufacturing or preparing a device in which the microchannel is formed (hereinafter referred to as “channel manufacturing or preparing step”). ), A step of modifying a reactive group on the inner wall of the microchannel (hereinafter also referred to as “inner wall modification step”), and a reaction of the stimulus-responsive gel precursor composition with the reactive group, A production method including a step of forming a stimulus-responsive gel on the inner wall of the road (hereinafter also referred to as “gel formation step”) can be preferably exemplified.

There is no restriction | limiting in particular as a formation method of the micro flow path in the said flow path preparation or a preparation process, For example, a well-known method can be used. The microchannel can be produced by, for example, a fine processing technique. Examples of fine processing methods include, for example, a method using LIGA technology using X-rays, a method using a resist portion as a structure by a photolithography method, a method of etching a resist opening, a micro discharge processing method, a laser processing method There is a mechanical micro cutting method using a micro tool made of a hard material such as diamond. These techniques may be used alone or in combination.
Among these, when using a resin, it is preferable to use a mechanical micro cutting method.
Moreover, when using the device which has a commercially available microchannel, it is preferable that the said device is a product made from resin or glass from the point that modification | denaturation of a stimulus responsive gel is easy.

  The method for modifying the reactive group on the inner wall in the inner wall modifying step is not particularly limited. However, when the substrate of the microchannel device is glass, for example, a silane compound having a reactive group is applied to the inner wall surface. For example, when the substrate is a resin, a method of reacting a compound having at least a group capable of reacting with a functional group in the resin and a reactive group on the inner wall surface is exemplified.

The gel forming step is a step of reacting the stimulus-responsive gel precursor composition and the reactive group to form a microchannel in which the inner wall and the stimulus-responsive gel are bonded by a covalent bond.
The stimulus-responsive gel precursor composition can contain a monomer, a crosslinking agent, a reaction initiator, a solvent, and the like for forming a stimulus-responsive gel according to a desired stimulus-responsive gel. .
The reactive group can be appropriately selected according to a desired stimulus-responsive gel. For example, when a stimulus-responsive gel is formed by a radical polymerization reaction, the reactive group is preferably a radical polymerizable group. When a stimulus-responsive gel is formed by a cationic polymerization reaction, the reactive group is A cationically polymerizable group is preferred.
Preferred examples of the reactive group include an ethylenically unsaturated group that is a radical polymerizable group and a cyclic ether group that is a cationic polymerizable group. From the viewpoint of reactivity and the like, a vinyl group, an epoxy group, an oxetanyl group, and the like. Is more preferable.

The transport system of the present invention may have one microchannel or two or more microchannels provided with a stimulus-responsive gel on at least the inner wall of the microchannel as required. May have a micro flow path without a branch, a merging portion, or a stimulus-responsive gel.
Moreover, the transport system of the present invention may have a site having functions such as reaction, mixing, separation, purification, analysis, and washing depending on the application.
Further, the transportation system of the present invention may be provided with a liquid feeding port for feeding a fluid to the transportation system, a collection port for collecting the fluid from the transportation system, etc., if necessary.

  In addition, the transportation system of the present invention may be combined in plural according to its use, and also has a device having functions such as reaction, mixing, separation, purification, analysis, washing, liquid feeding device, recovery device, Other microchannel devices or the like may be combined.

  The transport method of the present invention includes a microchannel in which at least a part of an inner wall surface is formed of a stimulus-responsive polymer or a cross-linked body that causes a volume change by applying a stimulus, the volume change, and the volume change A step of preparing a transportation system including at least a stimulus applying means capable of propagating the liquid (hereinafter also referred to as “preparation step”), and a step of filling the microchannel with a fluid (hereinafter referred to as “filling step”). And the step of transporting the substance in the microchannel by applying a stimulus to the stimulus-responsive polymer or crosslinked body by the stimulus applying means, causing a volume change, and further propagating the volume change. (Hereinafter also referred to as “transport process”).

As the transportation system in the transportation method of the present invention, the transportation system of the present invention described above can be suitably used, and the preferred embodiments in the transportation system are also the same.
The fluid that fills the microchannel in the transport step is not particularly limited as long as the stimuli-responsive polymer or crosslinked body can absorb and discharge, swell and contract. In addition, the fluid that fills the microchannel in the transporting process may not be a fluid containing a substance that is transported by the transporting method of the present invention, and another microfluid may be initially filled in the microchannel.
For example, it is also preferable that another fluid is first filled in the microchannel, and a fluid containing a substance to be transported by the transport method of the present invention is introduced into the microchannel in accordance with the progress of transport in the transport process. .
The substance in the microchannel may contain a solid, liquid, or gas depending on the intended use, and its composition, concentration, etc. can be selected as necessary.
Further, the substance in the microchannel is mixed, dissolved, or dissolved in a fluid containing a compound that can be absorbed and discharged by the stimulus-responsive polymer or the crosslinked body in the microchannel and can swell and contract. It is contained in a dispersed state.
In particular, the transport method of the present invention can transport high-viscosity fluids, semisolids and / or solid dispersions that cannot generally be transported through microchannels.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all.

(Example 1: Stimulation by Belozov-Jabochinsky reaction (BZ reaction))
A 10% trichlorovinylsilane isooctane solution was allowed to flow through a glass microreactor having a cylindrical channel having a diameter of 100 μm, and vinyl groups were introduced into the inner wall of the channel. Thereafter, it was washed with methanol.
A methanol solution of N-isopropylacrylamide, tris (2,2′-bipyridine) ruthenium (II) complex, methylenebisacrylamide and azobis (isobutyronitrile) was flowed into the flow channel, and the monomer was attached to the inner wall of the flow channel. Later, the gel was modified on the inner wall of the flow path by heating to 60 ° C. It was confirmed by microscopic observation that the gel having a thickness of 25 μm was modified.
Malonic acid, sodium bromate and nitric acid 0.06M, 0.08M and 0.09M respectively
When the aqueous solution was filled in the flow channel, it was confirmed by microscopic observation that the gel on the inner wall of the flow channel propagated the swelling and shrinkage behavior autonomously. Here, a slurry was prepared such that titanium oxide particles (particle size: 5 μm) were added to the mixed solvent and the weight ratio thereof was 30%. When the slurry was introduced to the channel inlet with a Teflon (registered trademark) tube and a coupler and pressurized with a syringe pump, the slurry containing titanium oxide particles was 10 μL / hr due to the propagation of the volume change of the gel in the channel. Transported at a flow rate.

(Example 2: stimulation by light)
Filled with 0.1M chlorodimethylvinylsilane isooctane solution in a glass micro-channel (Microchip Co., Ltd. standard chip, ICC-IR01, groove width 200 μm, groove depth 90 μm, channel length 60 mm) and sealed It left still for 10 hours in the state, and modified the vinyl group on the glass surface. After discharging the solution, it was washed with hexane and methanol.
Acrylamide 12 parts by weight, 4-acryloylaminoazobenzene 2 parts by weight, cross-linking agent N, N′-methylenebisacrylamide (BIS) (manufactured by Wako Pure Chemical Industries, Ltd.) 0.02 parts by weight, initiator acetaminophenone ( 0.2 parts by weight of Wako Pure Chemical Industries, Ltd.) was dissolved in 51.7 parts by weight of dioxane, and sufficiently substituted with nitrogen. When this solution was coated on the inner wall of a microchannel modified with a vinyl group, and photopolymerization was performed by irradiating UV light, a microchannel whose inner wall was covered with a polymer gel was obtained. It was confirmed by microscopic observation that the gel having a thickness of 20 μm was modified.
When the obtained microchannel was filled with water, the coated gel was in a contracted state. By moving the spot irradiation of 366 nm light using a high-pressure mercury lamp and a color filter in the direction of the flow path, the gel was swollen due to the trans → cis transition of the azobenzene group, and the swelling of the gel propagated in a wave shape. Here, a slurry in which titanium oxide particles were added to water and the weight ratio thereof was 30% was prepared. The slurry was introduced to the inlet of the channel with a Teflon (registered trademark) tube and coupler, pressurized with a syringe pump, and the spot irradiation of 366 nm light was moved in the direction of the channel. Due to the propagation, the slurry containing the titanium oxide particles was transported at a flow rate of 10 μL / hr.

(Example 3: stimulation by temperature change)
Filled with 0.1M chlorodimethylvinylsilane isooctane solution in a glass micro-channel (Microchip Co., Ltd. standard chip, ICC-IR01, groove width 200 μm, groove depth 90 μm, channel length 60 mm) and sealed It left still for 10 hours in the state, and modified the vinyl group on the glass surface. After discharging the solution, it was washed with hexane and methanol.
Acrylamide 12 parts by weight, cross-linking agent N, N'-methylenebisacrylamide (BIS) (Wako Pure Chemical Industries, Ltd.) 0.02 parts by weight, initiator acetaminophenone (Wako Pure Chemical Industries, Ltd.) 0 .2 parts by weight were dissolved in 51.7 parts by weight of dioxane and fully purged with nitrogen. This solution was coated on the inner wall of a microchannel modified with a vinyl group, irradiated with UV light for photopolymerization, and washed to obtain a microchannel whose inner wall was covered with acrylamide gel.
This flow path was filled with 3% by weight of an aqueous acrylic acid solution containing 0.5 mM benzoyl peroxide and dimethylaniline, and a polymerization reaction was carried out for 2 hours. After polymerization, excess polyacrylic acid and unreacted substances were washed away with pure water. The polyacrylamide / polyacrylic acid semi-IPN (interpenetrating polymer networks) gel was coated on the microchannel wall by the above operation. This gel swells at high temperatures and shrinks at low temperatures. It was confirmed by microscopic observation that the gel having a thickness of 30 μm was modified.
When the obtained microchannel was filled with water, the coated gel was in a contracted state at room temperature. By moving the laser in the direction of the flow path, the swelling of the gel propagated in a wave shape. Here, titanium oxide particles were added to water to prepare a slurry in which the weight ratio of titanium oxide particles was 30%. The slurry was introduced to the inlet of the channel with a Teflon (registered trademark) tube and coupler and pressurized with a syringe pump. When the laser was moved in the direction of the channel, oxidation occurred due to the propagation of the volume change of the gel in the channel. The slurry containing titanium particles was transported at a flow rate of 10 μL / hr.

(Example 4: Stimulation by electrochemical reaction)
A 0.5 M sulfuric acid aqueous solution is filled in a glass micro-channel (groove width 1,000 μm, groove depth 1,000 μm, channel length 50 mm) in which microelectrodes (working electrodes) are arranged on the channel wall surface. 1.9 V (vs. SCE) was applied and anodized (5 minutes). Thereafter, sweeping was repeated in the range of -0.1 to 1.1 V (vs. SCE) until the cyclic rectilinear voltammogram became steady, then held at 1.1 V and left until the current value became constant. By the above operation, a hydroxyl group could be introduced onto the electrode. The flow path was washed, filled with an isooctane solution of 0.1 M chlorodimethylvinylsilane and allowed to stand in a sealed state for 10 hours to modify vinyl groups on the glass surface and electrode surface. After discharging the solution, it was washed with hexane and methanol.
12 parts by weight of N-isopropylacrylamide, 2 parts by weight of vinylferrocene, 0.02 parts by weight of the crosslinking agent N, N′-methylenebisacrylamide (BIS) (manufactured by Wako Pure Chemical Industries, Ltd.), initiator acetaminophenone (Wako Pure) 0.2 parts by weight of Yakuhin Kogyo Co., Ltd.) was dissolved in 50 parts by weight of N, N′-dimethylformamide, and thoroughly substituted with nitrogen. This solution is filled in a micro flow path whose inner wall is modified with a vinyl group, photopolymerized by irradiating UV light, and washed with water to cover the inner wall with a polymer gel as shown in FIG. A flow path was obtained. By microscopic observation, it was confirmed that the gel having a thickness of 200 μm was modified.
The resulting microchannel coated gel was in a contracted state. A slurry was prepared such that titanium oxide particles were added and the weight ratio was 30%. The slurry is introduced to the channel inlet with a Teflon (registered trademark) tube and coupler, pressurized with a syringe pump, the electrode potential at the channel inlet is applied to +5 V to swell the local gel, and then the gel is run at 0 V. When this cycle was contracted and propagated far from the inlet, the slurry containing titanium oxide particles was transported at a flow rate of 5 μL / hr due to the propagation of the volume change of the gel in the flow path.

(Example 5: Stimulation by migration of ions in stimulus-responsive polymer or crosslinked body)
Nafion 20% solution (manufactured by DuPont) in a glass micro-channel (groove width 1,000 μm, groove depth 1,000 μm, channel length 50 mm) with microelectrodes (working electrodes) arranged on the channel wall Then, a Nafion film was coated on the inner wall surface of the channel. A phenanthroline gold complex aqueous solution was allowed to flow through this flow channel, and after adsorbing this, a sodium sulfate aqueous solution was flowed to obtain a micro flow channel as shown in FIG. 3 whose inner wall was covered with a polymer gel. It was confirmed by microscopic observation that the polymer film having a thickness of 250 μm was modified.
Titanium oxide particles were added to water to prepare a slurry in which the weight ratio of titanium oxide particles was 30%. The slurry is introduced to the channel inlet with a Teflon (registered trademark) tube and a coupler, pressurized with a syringe pump, the electrode potential at the channel inlet is applied to -5V to expand the local Nafion film, and then + 5V to Nafion. When the membrane was contracted and this cycle was propagated far from the entrance, the slurry containing titanium oxide particles was transported at a flow rate of 3 μL / hr by the propagation of the volume change of the Nafion membrane in the flow path.

(Example 6: Stimulation by application of electric field)
A 0.5 M sulfuric acid aqueous solution is filled in a glass micro-channel (groove width 1,000 μm, groove depth 1,000 μm, channel length 50 mm) in which microelectrodes (working electrodes) are arranged on the channel wall surface. 1.9 V (vs. SCE) was applied and anodized (5 minutes). Thereafter, sweeping was repeated in the range of -0.1 to 1.1 V (vs. SCE) until the cyclic rectilinear voltammogram became steady, then held at 1.1 V and left until the current value became constant. By the above operation, a hydroxyl group could be introduced onto the electrode. The channel was washed, filled with an isooctane solution of 0.1 M chlorodimethylvinylsilane, and allowed to stand in a sealed state for 10 hours to modify the vinyl group on the glass surface and electrode surface. After discharging the solution, it was washed with hexane and methanol.
12 parts by weight of N-isopropylacrylamide, 2 parts by weight of acrylic acid and 1.5-fold molar amount of triethylamine, 0.02 part by weight of crosslinking agent N, N′-methylenebisacrylamide (BIS) (manufactured by Wako Pure Chemical Industries, Ltd.) In addition, 0.2 part by weight of the initiator acetaminophenone (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 50 parts by weight of water and sufficiently substituted with nitrogen. This solution is filled in a microchannel whose inner wall is modified with a vinyl group, photopolymerized by irradiating UV light, and the inner wall is covered with a polymer gel when washed off. was gotten. By microscopic observation, it was confirmed that the gel having a thickness of 200 μm was modified.
When all the working electrodes of the obtained microchannel were held at −20 V, the coated gel was in a contracted state. Titanium oxide particles were added to water to prepare a slurry in which the weight ratio of titanium oxide particles was 30%. The slurry is introduced to the channel inlet with a Teflon (registered trademark) tube and coupler, pressurized with a syringe pump, the electrode potential at the channel inlet is applied to +20 V to swell the local gel, and then the gel is -20 V. The slurry containing titanium oxide particles was transported at a flow rate of 10 μL / hr due to the propagation of the volume change of the gel in the flow path when the cycle was propagated from the entrance to the far side.

(Comparative Example 1)
A glass microreactor having a cylindrical channel with a diameter of 1,000 μm was used. A slurry was prepared so that the weight ratio of titanium oxide particles / water was 30%, and the slurry was pressurized with a syringe pump (PHD2000, manufactured by Harvard) and injected into the flow path of the microreactor. However, the movement of the slurry in the flow channel could not be confirmed.

(Comparative Example 2)
A glass microreactor having a cylindrical channel with a diameter of 1,000 μm was used. An aqueous solution prepared by adding polyacrylic acid to a microchannel filled with water and having a kinematic viscosity of 1,000 cs (centistokes) is pressurized with a syringe pump (PHD2000, manufactured by Harvard), and the inside of the microreactor channel Attempted injection. However, the movement of the aqueous solution in the flow channel could not be confirmed.

FIG. 5 is a schematic cross-sectional view showing an example in which a micro-channel in which a stimulus-responsive polymer or a crosslinked body is formed on at least a part of an inner wall surface, and the stimulus-responsive polymer or the crosslinked body undergoes a volume change by applying a stimulus. . It is a schematic cross-sectional view showing an example in which a micro flow channel in which a stimulus-responsive polymer or a crosslinked body is formed on at least a part of the inner wall surface is used to propagate the volume change of the stimulus-responsive polymer or the crosslinked body by applying a stimulus. is there. FIG. 5 is a schematic cross-sectional view showing an enlarged part of an example of a microchannel in which a stimulus-responsive polymer or a crosslinked body is formed on at least a part of an inner wall surface and a plurality of electrodes are arranged.

Explanation of symbols

10 Microchannel 12 Stimulus-responsive polymer or cross-linked body (stimulus-responsive gel)
14 Micro-channel inner wall surface 16 Micro-channel-forming base material portion 18, 18a, 18b Stimulation applying portion 20, 20a, 20b Swelling portion 22 Non-swelling portion 24 Electrode

Claims (8)

A microchannel formed by binding a stimulus-responsive gel that generates a volume change by applying a stimulus to at least a part of the inner wall surface by chemical bonding ;
Bei example the stimulus applying means in which the cause volume change, and can be propagated through the volume change,
The stimulus is a stimulus selected from the group consisting of chemical reaction, light, temperature change, electrochemical reaction, migration of ions in a stimulus-responsive polymer or cross-linked body, and application of an electric field. system.   The transport system according to claim 1, wherein the stimulus-responsive gel is formed with a thickness in a range of 1/10 or more with respect to a flow path diameter.   The transport system according to claim 1 or 2, wherein the stimulus is a stimulus selected from the group consisting of light, temperature change, stimulus-responsive polymer or ion movement in a crosslinked body, and application of an electric field.   The transport system according to claim 1, wherein the chemical bond is a covalent bond. A micro flow path formed by combining a chemically bonded to at least a portion of the inner wall surface of the stimuli-responsive polymer or crosslinked product produces a change in volume by stimulating causes the volume change, and the volume change Providing a transport system comprising at least a stimulating means capable of propagating;
Filling the microchannel with a fluid; and
The Grant stimulus to the stimulus responsive polymer or crosslinked by stimulating means causes a change in volume, by further propagate the volume change, seen including the step of transporting the material microchannel,
The stimulus is a stimulus selected from the group consisting of chemical reaction, light, temperature change, electrochemical reaction, migration of ions in a stimulus-responsive polymer or cross-linked body, and application of an electric field. Method.   The transport method according to claim 5, wherein the stimuli-responsive polymer or crosslinked body is formed with a thickness in the range of 1/10 or more with respect to the channel diameter. The transport method according to claim 5 or 6, wherein the stimulus is a stimulus selected from the group consisting of light, temperature change, stimulus-responsive polymer or ion migration in a crosslinked body, and application of an electric field .   The transport method according to claim 5, wherein the chemical bond is a covalent bond.

Images