JP2016161427A - Gel sensor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gel sensor that can easily identify changes with time of a specific stimulus.SOLUTION: The gel sensor includes: a plurality of cells divided by a barrier wall; and stimulus-responding gels in the cells, the cells having a width in a range from 30 μm to 1000 μm, both inclusive, and the height differences in the stimulus-responding gels in the cells being not smaller than 5.5 μm. The stimulus-responding gels are each made of a polymeric material with the crosslinked structure, a solvent, and fine particles with an average particle diameter in the range from 10nm to 1000nm, both inclusive.SELECTED DRAWING: None

Description

  The present invention relates to a gel sensor.

  Polymer gels (stimulus responsive gels) that change volume and color by expanding and contracting in response to a specific stimulus are expected to be used in a wide range of fields such as medical devices and optical element materials. (For example, refer to Patent Document 1).

  However, with a conventional gel sensor using a stimulus-responsive gel, it has been difficult to identify changes over time of a predetermined stimulus.

Japanese Patent No. 4284642

  An object of the present invention is to provide a gel sensor that can easily identify a change over time of a predetermined stimulus.

Such an object is achieved by the present invention described below.
The gel sensor of the present invention comprises a plurality of cells fractionated by a partition,
A stimulus responsive gel disposed in the cell,
The width of the cell is 30 μm or more and 1000 μm or less,
The height difference of the stimulus-responsive gel in the cell is 5.5 μm or more.

  Accordingly, it is possible to provide a gel sensor that can easily identify a change over time of a predetermined stimulus.

  The gel sensor of the present invention preferably has the cell in which the stimulus-responsive gel having a convex surface is disposed.

  In the gel sensor of the present invention, it is preferable that a contact angle of the stimulus-responsive gel having a convex surface with respect to the partition wall is 110 ° or more.

  The gel sensor of the present invention preferably has the cell in which the stimulus-responsive gel having a concave surface is disposed.

  In the gel sensor of the present invention, the contact angle of the stimulation-responsive gel having a concave surface with respect to the partition wall is preferably 70 ° or less.

  In the gel sensor of the present invention, the stimulus-responsive gel may be composed of a material including a polymer material having a crosslinked structure, a solvent, and fine particles having an average particle diameter of 10 nm to 1000 nm. preferable.

  In the gel sensor of the present invention, it is preferable that a stimulus-permeable member having a function of transmitting a predetermined stimulus is provided on the surface side to which the specimen of the stimulus-responsive gel is supplied.

In the gel sensor of the present invention, it is preferable that the stimulus-permeable member is a semipermeable membrane.
In the gel sensor of the present invention, it is preferable that an absorption member that absorbs the sample is provided on the side opposite to the surface to which the sample of the stimulus-responsive gel is supplied.

It is a typical longitudinal cross-sectional view for demonstrating the gel sensor of 1st Embodiment. It is a typical top view of the gel sensor shown in FIG. It is a schematic top view for demonstrating the color change with time of the stimulus responsive gel in the gel sensor of 1st Embodiment, (a) is a figure which shows the state immediately after starting to receive a stimulus, ( (b) is a figure which shows a state when medium time has passed since it started receiving a stimulus, (c) is a figure which shows a state after sufficient time has passed since it started receiving a stimulus. It is a typical longitudinal cross-sectional view for demonstrating the gel sensor of 2nd Embodiment. It is a schematic top view for demonstrating the color change with time of the stimulus-responsive gel in the gel sensor of 2nd Embodiment, (a) is a figure which shows the state immediately after starting to receive a stimulus, (b) is a figure which shows a state when medium time has passed since it started receiving a stimulus, (c) is a figure which shows a state after sufficient time has passed since it started receiving a stimulus. It is a typical top view of the gel sensor in other embodiments, (a) is a top view in case the plane view shape of a cell (accommodating part) is a hexagon, (b) is a cell (accommodating part). It is a top view in case the planar view shape of this is circular.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

《Gel sensor》
Hereinafter, the gel sensor will be described.

[First Embodiment]
First, the gel sensor of the first embodiment will be described.

  1 is a schematic longitudinal sectional view for explaining the gel sensor of the first embodiment, FIG. 2 is a schematic plan view of the gel sensor shown in FIG. 1, and FIG. 3 is a gel of the first embodiment. It is a schematic top view for demonstrating the color change with time of the stimulus responsive gel in a sensor. (A) of FIG. 3 is a diagram showing a state immediately after starting to receive a stimulus, (b) is a diagram showing a state when an intermediate time has elapsed since the start of receiving a stimulus, and (c) It is a figure which shows the state after sufficient time passed after starting to receive a stimulus. In FIG. 3, the hatched portion indicates a portion whose color tone has changed due to a predetermined stimulus. Further, for example, assuming that the relationship of t1 <t2 <t3 is satisfied, (a) in FIG. 3 shows a state after t1 seconds from the start of stimulation, and (b) in FIG. ) Shows a state after t2 seconds after starting to receive the stimulus, and (c) in FIG. 3 shows a state after t3 seconds after starting to receive the stimulus. In the following description, the case where the upper side in FIG. 1 is the observer side (viewpoint side) and the lower side in FIG. 1 is the side to which the specimen is supplied will be mainly described (about FIG. 4 described later). The same).

  The gel sensor 10 includes a stimulus-responsive gel 1 and a housing member 2 that houses the stimulus-responsive gel 1.

  The stimulus-responsive gel 1 reacts at least one of expansion and contraction by responding to a predetermined stimulus.

The predetermined stimulus to which the stimulus-responsive gel 1 reacts varies depending on the constituent material of the stimulus-responsive gel, but for example, various substances such as protein, sugar, uric acid, lactic acid, various hormones, various ionic substances, various metals, Examples include heat and light.
The constituent material of the stimulus-responsive gel 1 will be described in detail later.

The housing member 2 is a member that houses the stimulus-responsive gel 1.
The housing member 2 has a partition wall 21 and is divided into a plurality of cells 22 by the partition wall.

  In each of the plurality of cells (accommodating portions) 22 constituting the gel sensor 10, the stimulus-responsive gel 1 is accommodated.

  And the cell 22 which comprises the gel sensor 10, and the stimulus-responsive gel 1 satisfy | fill the conditions of a predetermined shape.

  That is, the width of the cell 22 (the width of the stimulus-responsive gel 1 in the cell 22) is 30 μm or more and 1000 μm or less, and the height difference (the maximum height and the minimum height) of the stimulus-responsive gel 1 in the cell 22 Difference) is 5.5 μm or more.

  The width of the cell 22 here means the length of the major axis when the planar shape of the cell 22 is a circle (ellipse or circle), and in the case of a polygon, of the line segments connecting the vertices. The length of the longest line segment.

By satisfying such a condition, the timing of color tone change due to the response to the stimulus can be made sufficiently different at each part in the cell 22 when viewed in plan. In other words, in the portion where the height of the stimulus-responsive gel 1 is low (the portion where the thickness is small), the color change due to the response to the stimulus is recognized at a relatively early timing, whereas the height of the stimulus-responsive gel 1 is high. In a high part (a part having a large thickness), the timing of the color change due to the response to the stimulus is delayed, and a sufficient time difference can be provided for the color change in each part in the cell 22. More specifically, when the stimulus-responsive gel 1 on the side close to the specimen supply side (the lower side in FIG. 1) changes in color at a portion where the height of the stimulus-responsive gel 1 is high (a portion where the thickness is large). Even so, the stimulus-responsive gel 1 on the viewer's viewpoint side (upper side in FIG. 1) does not cause a change in color tone, and the stimulus-responsive gel 1 present on the viewer's viewpoint side The color tone change generated in the stimulus-responsive gel 1 on the side close to the sample supply side (lower side in FIG. 1) is concealed. Thus, if the timing of the color change due to the response to the stimulus is sufficiently different at each part in the cell 22 when viewed in plan, the change over time of the predetermined stimulus can be easily identified. . In addition, the viewing angle characteristics are excellent, and the visibility when observed from an oblique direction is also improved.
On the other hand, if the above relationship is not satisfied, a satisfactory result cannot be obtained.

  For example, if the cell width is less than the lower limit, it is difficult to make the difference in level of the stimulus-responsive gel within the cell sufficiently large, and it is difficult to identify changes over time of a given stimulus. It becomes. Even if the height difference of the stimulus-responsive gel in the cell can be made sufficiently large, if the width of the cell is too small, the change in color tone at each part of the stimulus-responsive gel will appear. It is difficult to identify above, and again, it is difficult to identify changes over time of a given stimulus.

  Further, when the cell width exceeds the upper limit value, for example, the ratio of the flat portion of the surface of the stimulus-responsive gel in the cell becomes large, and it is difficult to identify the change over time of the predetermined stimulus. Become. In addition, for example, by machining or the like, even when the ratio of the flat portion provided on the surface of the stimulus-responsive gel in the cell is sufficiently small, if the width of the cell is too large, The diffusion of the specimen in the cell width direction becomes remarkable, and it becomes difficult to identify the change over time of a predetermined stimulus.

  Moreover, when the height difference of the stimulus-responsive gel in the cell is less than the lower limit value, it is difficult to identify a change with time of a predetermined stimulus.

  Any one of the expansion and contraction states of the stimulus-responsive gel 1 may be used as long as the above conditions are satisfied. However, the stimulus-responsive gel 1 is contracted and the stimulus-responsive gel 1 is expanded. In any state, it is preferable that the above conditions are satisfied. Thereby, the effect mentioned above is exhibited more notably.

  Further, at least some of the plurality of cells 22 included in the gel sensor 10 may satisfy the above-described conditions, but the above-described conditions may be satisfied with 50% or more of the cells 22 on a number basis. More preferably, 80% or more of the cells 22 satisfy the above-described condition, and 90% or more of the cells 22 satisfy the above-described condition.

As described above, the width of the cell 22 (the width of the stimulus-responsive gel 1 in the cell 22) may be 30 μm or more and 1000 μm or less, preferably 40 μm or more and 800 μm or less, and more preferably 50 μm or more and 500 μm or less. Is more preferable.
Thereby, the effects as described above are more remarkably exhibited.

Further, the height difference of the stimulus-responsive gel 1 in the cell 22 may be 5.5 μm or more, but is preferably 7.4 μm or more and 148.1 μm or less, and is 9.3 μm or more and 92.6 μm or less. More preferably.
Thereby, the effects as described above are more remarkably exhibited.

  In the present embodiment, the stimulus-responsive gel 1 in the cell 22 has a convex surface. In other words, the stimulus-responsive gel 1 in the cell 22 is higher in the vicinity of the central portion in the cell width direction than the contact portion with the partition wall 21.

  When the stimulus-responsive gel 1 in the cell 22 has such a surface shape, the viewing angle characteristic is particularly excellent, for example, the visibility when observed from an oblique direction is particularly excellent. it can.

  The stimulus-responsive gel 1 having a convex surface is formed by, for example, subjecting the partition wall 21 to a lyophobic treatment (for example, a fluorine-based plasma treatment or a liquid-repellent film (for example, a fluorine-based resin such as PTFE). And the like can be suitably formed.

  The contact angle of the stimulus-responsive gel 1 having a convex surface with respect to the partition wall 21 is preferably 110 ° or more, more preferably 115 ° or more and 175 ° or less, and 120 ° or more and 170 ° or less. Is more preferable.

  Thereby, the surface shape of the stimulus-responsive gel 1 can be more stably controlled while increasing the height difference of the stimulus-responsive gel 1 in the cell 22. As a result, it is possible to more suitably identify a change over time of a predetermined stimulus and to make the viewing angle characteristics particularly excellent.

  Although the shape of the cell 22 is not particularly limited, in the configuration shown in FIG. 2, the planar shape of the cell 22 is a rectangle (square). As shown in FIG. 2, the width of the cell 22 is the length of the diagonal line L.

  Thereby, the visibility of the stimulus-responsive gel 1 is improved, and changes over time of the stimulus can be identified more suitably. Further, the flexibility and durability of the gel sensor 10 can be made particularly excellent.

  The plurality of cells 22 may have the same conditions or different conditions. For example, the size and shape of the cells 22 and the height difference of the stimulus-responsive gel 1 in each cell 22 may be different. Moreover, the stimulus-responsive gel 1 accommodated in the plurality of cells 22 may have the same composition or may have different compositions.

  The gel sensor 10 has only to have a plurality of cells 22, but preferably has 10 or more and 1000000 or less cells, and preferably has 20 or more and 100000 or less cells. More preferred.

  Thereby, the visibility of the stimulus-responsive gel 1 can be made particularly excellent while effectively suppressing an increase in size of the gel sensor 10.

  Examples of the constituent material of the partition wall 21 include polyolefins such as polyethylene, polypropylene, polybutadiene, and ethylene-vinyl acetate copolymer, polyvinyl chloride, polyurethane, polystyrene, polymethyl methacrylate, polycarbonate, polyamide, polyethylene terephthalate, and polybutylene terephthalate. Acrylic resins such as polyester and polymethyl methacrylate, ABS resin, AS resin, ionomer, polyacetal, polyphenylene sulfide, polyether ether ketone, natural rubber, butyl rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, silicone rubber, fluorine Various rubber materials such as rubber; Silicone materials such as dimethylpolysiloxane; Polyurethane, polyester, polyamid System, olefin, various thermoplastic elastomers such as styrene and the like.

  The thickness of the partition wall 21 (thickness in the horizontal direction in FIG. 1) is not particularly limited, but is preferably 2 μm or more and 300 μm or less, and more preferably 5 μm or more and 100 μm or less.

  Accordingly, the area ratio occupied by the stimulus-responsive gel 1 when the gel sensor 10 is viewed in plan is sufficiently large, and the strength of the gel sensor 10 is improved while the visibility of the stimulus-responsive gel 1 is particularly excellent. The durability and the like can be made particularly excellent.

  In addition, in each site | part, the thickness of the partition 21 may be constant and may have the site | part from which the thickness of the partition 21 differs.

  Moreover, in the gel sensor 10 of this embodiment, the stimulus permeable member 3 having a function of transmitting a predetermined stimulus is provided on the surface (the lower surface in FIG. 1) to which the specimen of the stimulus responsive gel 1 is supplied. It has been.

  Thereby, while being able to hold | maintain the stimulus responsive gel 1 suitably in the target site | part, it can suppress more effectively that the stimulus responsive gel 1 deform | transforms unintentionally by external force, etc. While making the durability of the sensor 10 particularly excellent, the specimen can be stably supplied to the stimulus-responsive gel 1 and the predetermined stimulus can be detected more stably.

The shape of the stimulus-permeable member 3 is not particularly limited, but is preferably a film.
Thereby, while the effect mentioned above is exhibited more notably, thickening of the gel sensor 10 etc. can be suppressed more effectively.

  As the stimulus permeable member 3, a member having a function of transmitting a predetermined stimulus (stimulus to be detected) can be used. For example, a semipermeable membrane such as cellophane can be preferably used.

  Thereby, the effect mentioned above is exhibited more notably. In addition, since the semipermeable membrane such as cellophane has stable characteristics and is easily available, the gel sensor 10 can be provided more stably while making the quality stability of the gel sensor 10 particularly excellent. can do.

  The thickness of the stimulus-permeable member 3 is preferably 10 μm or more and 500 μm or less, and more preferably 20 μm or more and 300 μm or less.

  Thereby, the effect by providing the stimulus-permeable member 3 as described above can be more remarkably exhibited while effectively suppressing the thickening of the gel sensor 10 and the like.

  Moreover, in the gel sensor 10 of this embodiment, the absorption member 4 which absorbs a test substance is provided in the surface (upper surface in FIG. 1) side opposite to the surface to which the test substance of the stimulus responsive gel 1 is supplied. Yes.

  Thereby, for example, when the specimens are sequentially supplied (when supplied continuously or intermittently), the specimen supplied previously is efficiently discharged from the stimulus-responsive gel 1 and newly supplied. Since the specimen can be supplied to the stimulus-responsive gel 1, the change in the amount of stimulus over time can be known more accurately. In other words, it is possible to effectively suppress the detection of the accurate stimulus amount from being disturbed by mixing the previously supplied specimen and the newly supplied specimen. In addition, when an excessive sample is supplied, the gel sensor 10 can be prevented from being wetted excessively by the overflowing sample.

  Further, by having the absorbing member 4, for example, when the supply of the liquid sample is stopped, when the supply amount of the sample is remarkably reduced, or when the use environment of the gel sensor 10 is low humidity, the stimulus responsiveness is obtained. Drying of the gel 1 can be effectively suppressed. As a result, it is possible to stably detect a predetermined stimulus with high reliability over a relatively long time even in an environment where the stimulus-responsive gel 1 is likely to be dried.

In particular, in the illustrated configuration, the absorbing member 4 is provided so as to cover the entire gel sensor 10 when the gel sensor 10 is viewed in plan.
Thereby, the effects as described above can be more remarkably exhibited.

  Examples of preferable constituents of the absorbent member 4 include cellulose materials and water-absorbing polymers, and cellulose materials are particularly preferable. Since such a material has moderate hydrophilicity, for example, when the specimen contains water (for example, body fluid such as sweat), it absorbs the specimen suitably, and in the absorbed specimen The contained water can be suitably evaporated.

  The thickness of the absorbing member 4 is preferably from 0.1 mm to 2.0 mm, and more preferably from 0.2 mm to 1.5 mm.

  Thereby, the effect by providing the absorbing member 4 as described above can be more remarkably exhibited while effectively suppressing the increase in the thickness of the gel sensor 10 and the decrease in the visibility of the reaction result to the stimulus. .

In the illustrated configuration, the gel sensor 10 is in the form of a sheet.
Thereby, while making the quantity of the stimulus responsive gel 1 comparatively small, it can be made to contact with a test substance more efficiently and a predetermined stimulus can be easily detected. Moreover, the detection accuracy of a predetermined stimulus can be made particularly excellent.

  The thickness of the gel sensor 10 is preferably 0.2 mm or greater and 7.0 mm or less, and more preferably 0.3 mm or greater and 5.5 mm or less.

  Thereby, while suppressing the thickening of the gel sensor, the stability, durability, and reliability of the shape of the gel sensor 10 can be made particularly excellent, and the change over time of a predetermined stimulus can be further improved. It can be suitably identified.

  Next, with reference to FIG. 3, the color change with time of the stimulus-responsive gel 1 in the gel sensor 10 of the present embodiment will be specifically described.

  As described above, in the gel sensor 10 of the present embodiment, the stimulus-responsive gel 1 in the cell 22 has a convex surface, and is near the center of the cell 22 when the gel sensor 10 is viewed in plan. Compared with, the height of the stimulus-responsive gel 1 is lower in the vicinity of the outer peripheral portion.

  For this reason, at the initial stage where the predetermined stimulation is started (when t1 seconds have elapsed after receiving the predetermined stimulation), only the portion near the outer peripheral portion of the cell 22 is included in the stimulus-responsive gel 1 in the cell 22. The color tone changes (see FIG. 3A).

  After that, when the time has elapsed since the start of receiving a predetermined stimulus (when t2 seconds have elapsed after receiving the predetermined stimulus), the region of the stimulus-responsive gel 1 whose color tone has changed is near the outer periphery of the cell 22 From the center to the vicinity of the center (see FIG. 3B).

  Furthermore, when a sufficient amount of time has elapsed since the start of receiving the predetermined stimulus (when t3 seconds have elapsed after receiving the predetermined stimulus), the central portion of the cell 22 where the convex top is present (the central portion when viewed in plan) ) Until the stimulus-responsive gel 1 changes in color, and the entire stimulus-responsive gel 1 in the cell 22 is recognized as having changed in color.

  For example, when the stimulus-responsive gel 1 is blue when not receiving a predetermined stimulus, and red when receiving a predetermined stimulus, the initial stage (predetermined when a predetermined stimulus is started) When t1 seconds have elapsed since the stimulation was received (see (a) of FIG. 3), only a part of the visible part of the stimulus-responsive gel 1 in the cell 22 is changed to red, and the other parts are Presents a blue color. In such a state, the viewer recognizes the color as bluish purple due to the color mixture.

  Thereafter, when the time since the start of the predetermined stimulus has elapsed (when t2 seconds have elapsed since the predetermined stimulus was received; see FIG. 3B), the ratio of the portion that has turned red increases, and the blue portion The ratio of decreases. In such a state, the viewer recognizes it as reddish purple due to color mixing.

  Further, when a sufficient amount of time has elapsed since the start of receiving a predetermined stimulus (when t3 seconds have elapsed since the predetermined stimulus was received; see FIG. 3C), the stimulus-responsive gel 1 when viewed in plan view The whole color changes to red.

  In this way, the color tone of the gel sensor 10 sequentially changes from blue, blue-purple, red-purple, and red along with the elapsed time after receiving a predetermined stimulus. Because of this, it is possible to easily identify changes over time of a predetermined stimulus.

<Constituent material of stimulus-responsive gel>
Next, the constituent material of the stimulus responsive gel 1 will be described.

  The stimulus-responsive gel 1 may be composed of any material as long as it responds to a predetermined stimulus, but usually contains a polymer material having a crosslinked structure and a solvent. It is composed of

(Polymer material)
The polymer material constituting the stimulus-responsive gel 1 is an important component for detecting a specific stimulus, and its structure varies depending on the type of stimulus to be detected.

  The polymer material constituting the stimulus-responsive gel 1 is not particularly limited, and can be selected depending on the component to be detected.

  Various polymer materials for detecting a specific stimulus in the stimulus-responsive gel 1 are known. For example, such a known polymer material can also be used.

Hereinafter, specific examples of the polymer material constituting the stimulus-responsive gel 1 will be described.
As a polymeric material which comprises the stimulus responsive gel 1, what was obtained by making a monomer (monomer), a polymerization initiator, a crosslinking agent etc. react is used, for example.

  Examples of the monomer include acrylamide, N-methylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminopropylacrylamide, various quaternary salts, and acryloyl. Morpholine, N, N-dimethylaminoethyl acrylate quaternary salts, acrylic acid, various alkyl acrylates, methacrylic acid, various alkyl methacrylates, 2-hydroxyethyl methacrylate, glycerol monomethacrylate, N-vinylpyrrolidone, acrylonitrile, styrene, polyethylene glycol Diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, poly Lopylene glycol diacrylate, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, 2-hydroxy-1-acryloxy-3 -Methacryloxypropane, 2,2-bis [4- (acryloxypolypropoxy) phenyl] propane, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol di Methacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxydiethoxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxypolyethoxy) ) Phenyl] propane, trimethylolpropane trimethacrylate, tetramethylolmethane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, dipentaerythritol hexaacrylate, N, N′-methylenebisacrylamide, N, N′-methylenebismethacrylamide, diethylene glycol diallyl ether, divinylbenzene and the like can be mentioned.

  In addition, examples of the functional group capable of interacting with a sugar include a boronic acid group (particularly, a phenylboronic acid group). Therefore, a monomer having a boronic acid group may be used. Examples of such boronic acid group-containing monomers include acryloylaminobenzeneboronic acid, methacryloylaminobenzeneboronic acid, 4-vinylbenzeneboronic acid, and the like.

  Moreover, when detecting an ionic substance (especially one containing calcium ions) as a stimulus (specific component), as a monomer, 4-acrylamidobenzo 18-crown-6-ether, acryloylaminobenzocrown ether, methacryloyl Crown ether group-containing monomers (particularly, benzocrown ether group-containing monomers) such as aminobenzocrown ether and 4-vinylbenzocrown ether can be suitably used.

  When detecting an ionic substance such as sodium chloride as a stimulus (specific component), as a monomer, 3-acrylamidophenylboronic acid, vinylphenylboronic acid, acryloyloxyphenylboronic acid, N-isopropylacrylamide ( NIPAAm), ethylenebisacrylamide, N-hydroxyethylacrylamide and the like can be suitably used. In particular, when detecting an ionic substance such as sodium chloride as a stimulus (specific component), the monomer is selected from the group consisting of 3-acrylamidophenylboronic acid, vinylphenylboronic acid and acryloyloxyphenylboronic acid. A combination of one or more monomers and one or more monomers selected from the group consisting of N-isopropylacrylamide (NIPAAm), ethylenebisacrylamide and N-hydroxyethylacrylamide Are preferably used.

  When lactic acid is detected as a stimulus (specific component), as monomers, 3-acrylamidophenylboronic acid, vinylphenylboronic acid, acryloyloxyphenylboronic acid, N-isopropylacrylamide (NIPAAm), ethylene bis Acrylamide, N-hydroxyethylacrylamide and the like can be preferably used. In particular, when lactic acid is detected as a stimulus (specific component), one or two monomers selected from the group consisting of 3-acrylamidophenylboronic acid, vinylphenylboronic acid, and acryloyloxyphenylboronic acid are used as monomers. It is preferable to use a combination of at least one monomer and one or more monomers selected from the group consisting of N-isopropylacrylamide (NIPAAm), ethylenebisacrylamide and N-hydroxyethylacrylamide. .

  The polymerization initiator can be appropriately selected depending on, for example, the polymerization mode. Specifically, hydrogen peroxide, persulfate such as potassium persulfate, sodium persulfate, ammonium persulfate, etc. Agents, such as 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (N, N'-dimethyleneisobutylamidine) dihydrochloride, 2,2'-azobis {2-methyl -N- [1,1, -bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 4, 4′-azobis (4-cyanovaleric acid), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4′-dimethylvaleronitrile), benzophenone, 2,2-di Toxi-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1 -[4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, a compound that generates a radical by ultraviolet light, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxypropoxy) -3,4-dimethyl-9H-thioxanthone-9-one mesochloride, 2-methyl-1 [4- (methylthio) Phenyl] -2-morpholinopropane-1,2-benzyl- -Dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (py-1-yl) titanium, 1,3-di ( Substances obtained by mixing peroxyesters such as t-butylperoxycarbonyl) benzene and 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone with thiopyrylium salts, merocyanine, quinoline and styrylquinoline dyes Examples include compounds that generate radicals by light having a wavelength of 360 nm or more such as hydrogen peroxide or persulfate, for example, a combination of a reducing substance such as sulfite and L-ascorbic acid, an amine salt, and the like. It can also be used as a redox initiator.

  As the crosslinking agent, a compound having two or more polymerizable functional groups can be used. Specifically, ethylene glycol, propylene glycol, trimethylolpropane, glycerin, polyoxyethylene glycol, polyoxypropylene glycol, polyglycerin. N, N'-methylenebisacrylamide, N, N-methylene-bis-N-vinylacetamide, N, N-butylene-bis-N-vinylacetamide, tolylene diisocyanate, hexamethylene diisocyanate, allylated starch, allylated Cellulose, diallyl phthalate, tetraallyloxyethane, pentaerythritol triallyl ether, trimethylolpropane triallyl ether, diethylene glycol diallyl ether, triallyl trimellitate, etc. .

The stimulus-responsive gel 1 may include a plurality of different polymer materials.
The content of the polymer material in the stimulus-responsive gel 1 is preferably 0.7% by mass or more and 36.0% by mass or less, and more preferably 2.4% by mass or more and 27.0% by mass or less. preferable.

(solvent)
When the stimulus-responsive gel 1 contains a solvent, the above-described polymer material can be suitably gelled.

  As the solvent, various organic solvents and inorganic solvents can be used. More specifically, for example, water; various alcohols such as methanol and ethanol; ketones such as acetone; ethers such as tetrahydrofuran and diethyl ether; dimethylformamide Amides such as: Chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; Cycloaliphatic hydrocarbons such as cyclohexane and methylcyclohexane; Aromatics such as benzene, toluene and xylene In particular, those containing water are preferable.

The stimulus-responsive gel 1 may include a plurality of different components as solvents.
The content of the solvent in the stimulus-responsive gel 1 is preferably 30% by mass to 95% by mass, and more preferably 50% by mass to 90% by mass.

(Fine particles)
The stimulus-responsive gel 1 only needs to contain a polymer material having a crosslinked structure and a solvent, but may further contain fine particles.

  The fine particles contribute to the expression of the structural color due to Bragg reflection, and when the stimulus-responsive gel 1 contains fine particles, when a predetermined stimulus (specific component) is given to the stimulus-responsive gel 1, Since the structural color or the change of the structural color due to the colloidal crystal is easily visually recognized, the specific component can be detected more easily. In addition, since the structural color or the structural color change due to the colloidal crystal is easily visually recognized, for example, the predetermined stimulus (specific component) can be quantified more easily and more accurately by the color tone. .

  Fine particles are composed of inorganic materials such as silica and titanium oxide; polystyrene, polyester, polyimide, polyolefin, poly (meth) acrylate methyl, polyethylene, polypropylene, polyethersulfone, nylon, polyurethane, polyvinyl chloride, polychlorinated Examples thereof include organic materials (polymers) such as vinylidene, and the fine particles are preferably silica fine particles. Thereby, the stability of the shape of the fine particles can be made particularly excellent, and the durability and reliability of the stimulus-responsive gel 1 can be made particularly excellent. Silica fine particles are relatively easy to obtain as those having a sharp particle size distribution (monodispersed fine particles), which is advantageous from the viewpoint of stable production and supply of the stimulus-responsive gel 1.

  The shape of the fine particles is not particularly limited, but is preferably spherical. Thereby, the structural color or the change of the structural color due to the colloidal crystal is visually recognized, and the specific component can be detected more easily.

  The average particle diameter of the fine particles is not particularly limited, but is preferably 10 nm or more and 1000 nm or less, and more preferably 20 nm or more and 500 nm or less.

  Thereby, when a predetermined stimulus (specific component) is given to the stimulus-responsive gel 1, the structural color or the change of the structural color due to the colloidal crystal is more easily visually recognized. Detection can be performed more easily and more reliably. In addition, since the structural color or the structural color change due to the colloidal crystal is more easily recognized, for example, the predetermined stimulus (specific component) can be quantified more easily and more accurately depending on the degree of the color change. Can be done.

  In the present specification, the average particle diameter means a volume-based average particle diameter. For example, a dispersion obtained by adding a sample to methanol and dispersing for 3 minutes with an ultrasonic disperser is a Coulter counter particle size distribution measuring instrument. It can be determined by measuring with a 50 μm aperture (for example, TA-II type manufactured by COULTER ELECTRONICS INC).

The stimulus-responsive gel 1 may include a plurality of different types of fine particles.
The content of the fine particles in the stimulus-responsive gel 1 is preferably 1.6% by mass or more and 36% by mass or less, and more preferably 4.0% by mass or more and 24% by mass or less.

(Other ingredients)
The stimulus-responsive gel 1 may contain components other than those described above (other components).

  Examples of such components include oxidation inhibitors, ultraviolet absorbers, fungicides, antibacterial agents, deodorants, and refreshing components.

  The gel sensor 10 may be manufactured by any method. For example, in the cell 22 surrounded by the partition wall 21 of the housing member 2, a liquid containing the stimulus-responsive gel 1 or a precursor thereof may be used. It can form by providing using an inkjet method or a dispenser. At this time, by applying the surface treatment described above to the surface of the partition wall 21, the stimulus-responsive gel 1 having a desired surface shape can be easily formed. At this time, by providing the stimulus-permeable member 3 on the surface opposite to the surface to which the liquid is applied, the stimulus-responsive gel 1 diffuses unintentionally and flows out of the cell 22. This can be effectively prevented. Thus, the target gel sensor 10 can be obtained by installing the absorption member 4 after forming the stimulus-responsive gel 1 having a predetermined shape.

  Note that the stimulus-responsive gel 1 may have a predetermined surface shape by, for example, post-processing machining or laser processing. Moreover, you may form as what has a predetermined | prescribed surface shape using the shaping | molding die of a predetermined | prescribed shape.

[Second Embodiment]
Next, the gel sensor of the second embodiment will be described.

  FIG. 4 is a schematic longitudinal sectional view for explaining the gel sensor of the second embodiment, and FIG. 5 is a diagram for explaining the color change over time of the stimulus-responsive gel in the gel sensor of the second embodiment. It is a schematic plan view, (a) is a diagram showing a state immediately after starting to receive a stimulus, (b) is a diagram showing a state when a medium time has passed since starting to receive a stimulus. (C) is a figure which shows the state after sufficient time passed since it started to receive a stimulus. In FIG. 5, the hatched portion indicates a portion where the color tone has changed due to a predetermined stimulus. Further, for example, assuming that the relationship of t1 <t2 <t3 is satisfied, (a) in FIG. 5 shows a state after t1 seconds from the start of stimulation, and (b) in FIG. ) Shows a state after t2 seconds after starting to receive the stimulus, and (c) in FIG. 5 shows a state after t3 seconds after starting to receive the stimulus. In the following description, differences from the above-described embodiment will be mainly described, and description of similar matters will be omitted.

  As shown in FIG. 4, in the gel sensor 10 of this embodiment, the surface shape of the stimulus-responsive gel 1 accommodated in the cell 22 is different from that of the above-described embodiment. That is, in the above-described embodiment, the surface has the convex stimulus-responsive gel 1 in the cell 22, whereas in this embodiment, the stimulus-responsive gel 1 in the cell 22 has the surface It has a concave shape. In other words, the stimulus-responsive gel 1 in the cell 22 is lower in the vicinity of the central portion in the cell width direction than in the contact portion with the partition wall 21.

  Since the stimuli-responsive gel 1 in the cell 22 has such a surface shape, the color change occurs from the vicinity of the center of the cell 22 when the gel sensor 10 is viewed in plan, and thus the color change is more easily performed. Can be identified.

  For example, the stimulus-responsive gel 1 having a concave surface is subjected to lyophilic treatment (for example, ultraviolet irradiation treatment or plasma treatment in an environment containing an oxidizing substance such as ozone) or a hydrophilic coating on the partition wall 21. It is possible to form it suitably.

  The contact angle with respect to the partition wall 21 of the stimulus-responsive gel 1 having a concave surface is preferably 70 ° or less, more preferably 5 ° or more and 65 ° or less, and 10 ° or more and 60 ° or less. Is more preferable.

  Thereby, the surface shape of the stimulus-responsive gel 1 can be more stably controlled while increasing the height difference of the stimulus-responsive gel 1 in the cell 22. As a result, it is possible to more suitably identify the change over time of the predetermined stimulus.

  Next, with reference to FIG. 5, the color change with time of the stimulus-responsive gel 1 in the gel sensor 10 of the present embodiment will be specifically described.

  As described above, in the gel sensor 10 of the present embodiment, the stimulus-responsive gel 1 in the cell 22 has a concave shape on the surface, and the vicinity of the outer periphery of the cell 22 when the gel sensor 10 is viewed in plan view. Compared to the above, the height of the stimulus-responsive gel 1 is low near the center.

  For this reason, in the initial stage where the predetermined stimulation is started (when t1 seconds have elapsed after receiving the predetermined stimulation), only the site near the central portion of the cell 22 is included in the stimulus-responsive gel 1 in the cell 22. The color tone changes (see FIG. 5A).

  After that, when a time has elapsed since the start of receiving a predetermined stimulus (when t2 seconds have elapsed after receiving the predetermined stimulus), the region of the stimulus-responsive gel 1 whose color tone has changed is near the center of the cell 22 It expands toward the outer periphery (see FIG. 5B).

  Further, when a sufficient time has elapsed since the start of receiving a predetermined stimulus (when t3 seconds have elapsed after receiving the predetermined stimulus), the stimulus-responsive gel reaches the outer periphery of the cell 22 (the outer periphery when viewed in plan). 1 changes in color tone, and the entire stimulus-responsive gel 1 in the cell 22 is recognized as having changed color tone (see FIG. 5C).

  The gel sensor may include a stimulus-responsive gel having a convex surface and a stimulus-responsive gel having a concave surface.

  Thereby, the effect by providing the stimulus-responsive gel whose surface is convex and the effect by providing the stimulus-responsive gel whose surface is concave can be made compatible.

《Use of gel sensor》
Since the gel sensor 10 can easily detect a predetermined stimulus (for example, a specific component), for example, whether or not a specific substance is contained in the test object (specimen) or in the test object. It can be used as a sensor for measuring the concentration of a specific substance contained.

  Moreover, since the specific component taken in the stimulus-responsive gel 1 can be easily detected, it can also be suitably used as a separation / extraction means for separating / extracting the specific substance contained in the test object. That is, at the stage where the amount of the specific component incorporated into the stimulus-responsive gel is saturated or is likely to be saturated, contact with the test object can be stopped and replaced with another gel sensor as necessary. As a result, the specific component can be recovered from the test object without waste.

More specific uses of the gel sensor 10 include, for example, sensors for biological substances (for example, various cells such as cancer cells and blood cells, proteins such as antibodies (including glycoproteins), etc.), body fluids or extracorporeal secretion. Sensor for components (eg, lactic acid, uric acid, sugar, etc.) contained in substances (eg, blood, saliva, sweat, urine, etc.), means for separating / extracting biological substances (especially trace biological substances such as hormones), Separation / extraction means for metals (especially rare metals and precious metals), sensors for antigens (allergic substances) such as pollen, means for separation / extraction of toxic substances, harmful substances, environmental pollutants, sensors for viruses, bacteria, soil Sensors for components contained in wastewater, sensors for components contained in waste liquid (including wastewater), sensors for components contained in food, components contained in water (for example, salt contained in brackish waters, rivers, paddy fields, etc.) The sensor, and the cell culture monitoring and the like.
The gel sensor 10 is preferably used in close contact with the skin of a living body.

  The living body skin generally has a complicated uneven shape, but the gel sensor is excellent in conformity of the shape, and therefore can be suitably adhered to the living body skin. Also, when used in close contact with the skin of a living body (for example, when detecting a component contained in sweat during exercise as a stimulus (specific component)), it is assumed that a large external force such as vibration or impact is applied to the gel sensor. However, even when such a relatively large external force is applied, the specific component (predetermined stimulus) can be accurately detected and can be easily identified. Therefore, when the gel sensor is used in close contact with the skin of a living body, the effect is more remarkably exhibited.

  In addition, the gel sensor can suitably cope with a reduction in size and weight. Therefore, it is suitable for use in the method as described above.

  Further, for example, by detecting lactic acid contained in sweat as a stimulus (specific component), the load on the user (athlete or the like) can be examined. In particular, according to the above-described gel sensor, it is possible to identify a change over time of a predetermined stimulus. For example, in order to prevent a load on the user (athlete, etc.) over an excessively long time, the gel sensor display Can warn the user or the like.

  The gel sensor 10 may be applied to a detection device combined with a detection device that detects a change in the form (for example, volume, color tone, etc.) of the stimulus-responsive gel.

  Thereby, for example, when it is difficult to identify the change in the form of the stimulus-responsive gel 1 with the naked eye (for example, when the color tone change or the volume change is minute, the reflected light whose wavelength changes is in the visible light region. Appropriately responds even when the detection of stimulus (for example, quantitative detection requiring high accuracy, detection of trace components, etc.) is required with higher accuracy. I can.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to these.

  For example, in the above-described embodiment, the case where the gel sensor has a sheet shape has been representatively described. However, the shape of the gel sensor is not limited to this, and for example, a plate shape, a block shape, and a string shape Any shape such as a cylinder or a particle may be used.

  The gel sensor may have a configuration other than that described above. For example, you may provide the adhesive layer for sticking in a predetermined position.

  Moreover, the gel sensor should just have the some cell fractionated by the partition, and the stimulus responsive gel arrange | positioned in a cell, and does not need to be provided with another structure.

  In the above-described embodiment, the case where the planar shape of the cell is rectangular has been described as a representative example. However, the shape of the cell is not limited to this and may be any shape. For example, as shown in FIG. 6A, the planar shape of the cell may be a hexagon. Thereby, for example, a plurality of cells can be arranged on the honeycomb, and the mechanical strength of the gel sensor can be made particularly excellent while increasing the area ratio occupied by the stimulus-responsive gel. In this case, the cell width refers to the length of the diagonal line M in FIG.

  Further, as shown in FIG. 6B, the planar shape may be an ellipse (including a perfect circle). There is a possibility that air bubbles may be mixed when introducing the gel into the cell, but by making the planar shape circular, the possibility of bubbles remaining in the corners of the cell is reduced compared to the case where the planar shape is polygonal. be able to. In this case, the cell width refers to the major axis N shown in FIG.

  In addition, the sensor may be configured such that a part of the constituent members is configured to be replaceable, or configured to be removable and remountable. For example, the absorbent member may be replaceable or configured to be removable and remountable. Thereby, even when a large amount of solid content (for example, a specific component) adheres to the absorbent member, the sensor can be used by replacing the absorbent member, removing it, and washing it. For this reason, the life of the sensor can be extended.

DESCRIPTION OF SYMBOLS 10 ... Gel sensor 1 ... Stimulus response gel 2 ... Accommodating member 21 ... Partition 22 ... Cell (accommodating part)
3 ... Stimulus permeable member 4 ... Absorbing member

Claims (9)

A plurality of cells fractionated by a partition;
A stimulus responsive gel disposed in the cell,
The width of the cell is 30 μm or more and 1000 μm or less,
A gel sensor characterized in that the height difference of the stimulus-responsive gel in the cell is 5.5 μm or more.   The gel sensor according to claim 1, wherein the gel sensor has the cell in which the stimulus-responsive gel having a convex surface is arranged.   The gel sensor according to claim 2, wherein a contact angle of the stimulus-responsive gel having a convex surface with respect to the partition wall is 110 ° or more.   The gel sensor according to any one of claims 1 to 3, wherein the gel sensor has the cell in which the stimulus-responsive gel having a concave surface is arranged.   The gel sensor according to claim 4, wherein a contact angle of the stimulus-responsive gel having a concave surface with respect to the partition wall is 70 ° or less.   6. The stimuli-responsive gel is made of a material containing a polymer material having a crosslinked structure, a solvent, and fine particles having an average particle size of 10 nm to 1000 nm. The gel sensor according to item.   The gel sensor according to any one of claims 1 to 6, wherein a stimulus-permeable member having a function of transmitting a predetermined stimulus is provided on a surface side to which the specimen of the stimulus-responsive gel is supplied.   The gel sensor according to claim 7, wherein the stimulus-permeable member is a semipermeable membrane.   The gel sensor according to any one of claims 1 to 8, wherein an absorption member that absorbs the sample is provided on a surface opposite to a surface to which the sample of the stimulus-responsive gel is supplied.

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