JP2007170469A - Temperature responsive valve and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a temperature responsive valve easy to manufacture as a micro valve which can open/close or switch a flow path, is driven at a small temperature difference and is used for a micro fluid device, and to provide its manufacturing method. <P>SOLUTION: The valve comprises the fine flow path, and a valve element arranged in the fine flow path for opening/closing the fine flow path, switching it or controlling its flow amount. The valve element is formed of a joint body consisting of a temperature responsive gel having a gel-solid transition temperature and a flexible member. It is deformed with a temperature change to open/close the fine flow path, switch it or control its flow amount. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a temperature responsive valve capable of opening / closing, switching, or controlling a flow rate according to a temperature change, and a manufacturing method thereof, and in particular, a microfluidic device, that is, a minute flow channel is formed in a member. The present invention relates to a minute temperature-responsive valve that is incorporated in or connected to a chemical / biochemical microdevice, and a method for manufacturing the same.

  There are various driving methods for valves that perform opening / closing, flow control, and channel switching of microfluidic devices, such as compressed air, mechanical force and displacement, magnetism, temperature, and fluid hydrogen ion concentration (pH). The method is known. Among these, those that can be controlled such as opening and closing by temperature change can be driven in a non-contact manner by laser or infrared rays, and therefore various types of temperature-responsive valves have been studied.

  As a prior document relating to a temperature-responsive valve, Patent Document 1 filed by the present inventors includes a method for producing a gelable porous body using a temperature-sensitive monomer, and a nonwoven fabric containing the porous body. A filtration membrane in which the filtration rate is changed by a change in temperature formed on a liquid-permeable substrate such as is disclosed. The filtration membrane can be used as a temperature responsive valve. However, the filtration membrane disclosed in this document functions only as an open / close valve and a flow rate adjustment valve, and a flow path switching valve cannot be formed. There was a difficulty that had to be handled.

  Further, in Patent Document 2, which is an application of the present inventors, a gel having a capillary channel in a member and facing the channel in the middle of the channel and filled with a temperature-responsive gel A temperature responsive valve having a chamber and a manufacturing method thereof are disclosed (see Patent Document 2). However, since the valve having such a configuration closes the flow path by causing the temperature-responsive gel to swell in the gel chamber due to temperature change, a flow path switching valve cannot be formed. In addition, the transition from the channel open state in which a certain gap is provided in the gel chamber so that the fluid can flow to the channel blockage state in which the gel chamber is substantially filled with the swollen gel, The response speed was also insufficient due to the large change required.

  On the other hand, a so-called bimetal thermostat is known as a switch for distributing / cutting electricity according to a temperature change. In this method, electricity is circulated / cut by utilizing the fact that a plate obtained by joining two kinds of metal plates having different thermal expansion coefficients changes the curvature according to a temperature change. However, if this is used for a fluid on-off valve, the curvature change with respect to the temperature change is slow, so that a large temperature difference is required for opening and closing and switching operations. Also, it has been considerably difficult to produce a minute bimetal and incorporate it into a microfluidic device.

JP-A-62-228215 JP 2002-66999 A

  A problem to be solved by the present invention is a temperature-responsive valve that can be opened and closed and switched, that can be driven with a small temperature difference, and that is easy to manufacture a minute valve that can be used in a microfluidic device. It is in providing the manufacturing method.

  In the present invention, since the valve body constituting the valve is a joined body of a temperature-responsive gel having a gel-solid transition temperature and a flexible member, the temperature-responsive gel is gel- When the solid transition occurs, the valve body is deformed due to a difference in curvature from the joined flexible member. Due to this, even if the volume change of the gel-solid transition of the temperature-responsive gel is a small volume change, it greatly affects the deformation of the valve body, so there is no need to give an excessive temperature change and excellent response speed Therefore, it is possible to open / close or switch the flow path.

  That is, the present invention relates to a valve comprising a fine flow path and a valve body that opens and closes the fine flow path disposed in the fine flow path, and the valve body has a gel-solid transition temperature. There is provided a temperature responsive valve which is composed of a joined body of a flexible member and is deformed by temperature change to open and close a fine flow path.

Furthermore, the present invention is a method of manufacturing the temperature responsive valve,
A temperature-responsive gel is bonded to at least a portion of the film-like flexible member formed with the valve body, and the valve body is formed with a notched portion penetrating the front and back for forming a tongue piece portion at the joint portion. Forming a valve layer having
The valve body layer is sandwiched between two flow path layers having grooves or through-holes constituting a fine flow path so that the grooves or through-holes of the two flow path layers are communicated and isolated by deformation of the valve body. A temperature responsive valve manufacturing method for stacking is provided.

Furthermore, the present invention is a method of manufacturing the temperature responsive valve,
An active energy ray-curable resin composition is applied onto a support, and the active energy rays are irradiated to portions other than the cut-out portions penetrating the front and back for forming the tongue piece portion. Forming a sex member,
The film-like flexible member is coated with an active energy ray-curable temperature-responsive gel-forming composition and applied to a portion other than the portion formed as a notch that penetrates the front and back surfaces for forming the tongue portion. After irradiating the active energy ray, by removing the uncured component of the non-irradiated part, the valve body layer having the valve body is formed,
The valve body layer is sandwiched between two flow path layers having grooves or through-holes constituting a fine flow path so that the grooves or through-holes of the two flow path layers are communicated and isolated by deformation of the valve body. The present invention provides a method for manufacturing a temperature-responsive valve that is laminated.

  The present invention is a temperature responsive valve that can open / close, switch, and adjust flow rate, can be driven with a small temperature difference, and can be easily incorporated into a microfluidic device, and a method for manufacturing the same. Can be provided.

  In addition, the temperature-responsive valve of the present invention can be formed simultaneously or in parallel when manufacturing a microfluidic device having a laminated structure, so that positioning of the valve body is easy, and a complicated process is required. Etc. are not required.

  The temperature-responsive valve of the present invention is a valve composed of a fine channel and a valve body that opens and closes the fine channel disposed in the fine channel, and the valve body has a gel-solid transition temperature. It consists of a joined body of a responsive gel and a flexible member, and is deformed by a temperature change to open and close a fine channel.

[Fine channel]
Examples of the fine flow path constituting the temperature responsive valve of the present invention include high-speed processing, reduction of by-products, and high-speed examination of conditions in the fields of chemical reaction, biochemical reaction and chemical engineering processing. A fine flow path provided in a microfluidic device that is expected to be made into a fluid. Here, the microfluidic device is referred to as a microchannel, a microchannel chip, a chemical IC (IC), a microreactor, a microanalysis chip, a microtas (μ-TAS), and the like, and a fine capillary tube in the member. A device having a flow path of, such as chemical, biochemical, and electrochemical, used for reaction, processing, analysis, detection, and the like.

  The width of the cross section of the micro flow path (if the temperature responsive valve has an outer shape such as a plate or film, the maximum flow path in the long axis direction of the temperature responsive valve in the cross section perpendicular to the flow path The dimension is referred to as the “width” of the flow path, and the maximum flow path dimension in the direction perpendicular to the major axis direction is referred to as the “height” of the flow path. The width and the height may be arbitrary, and are preferably 1 to 1000 μm, more preferably 3 to 500 μm, and most preferably 5 to 300 μm. The height of the channel cross section is also arbitrary, preferably 1 to 3000 μm, more preferably 3 to 1000 μm, and most preferably 5 to 500 μm. Within these ranges, the effects of the present invention are sufficiently exhibited, which is preferable.

The cross-sectional area of the fine channel is preferably 1 μm ² to 1 mm ² , more preferably 10 μm ^{2 to} 0.1 mm ² . When the cross-sectional area of the flow path is 1 μm ² or more, the production is easy and the liquid blocking property is good. Moreover, if it is 1 mm < ² > or less, the pressure | voltage resistance and response speed of a valve | bulb can be ensured favorable.

[Temperature-responsive gel]
The temperature-responsive gel (including those in a solid state or a dry state) having a gel-solid transition temperature constituting the valve body of the present invention is also called a thermosensitive gel, and is between the freezing point and boiling point of the swelling medium. Have a gel-solid transition temperature. Since the degree of swelling of the gel due to temperature changes greatly near the gel-solid transition temperature, by using such a temperature-responsive gel, a valve that can be opened and closed and the flow path can be switched in a narrow temperature range. Can do. The gel-solid transition temperature refers to a phase transition temperature corresponding to a phase separation temperature (also referred to as critical co-solution temperature) in the case of a linear polymer composed of the same monomer. The range of temperature change using the temperature-responsive valve of the present invention does not necessarily need to be in the range across the gel-solid transition temperature. For example, it may be a temperature change within a temperature range equal to or higher than the gel-solid transition temperature, or may be a temperature change within a temperature range equal to or lower than the gel-solid transition temperature. However, it is preferably a temperature change near the gel-solid transition temperature, and more preferably a temperature change across the gel-solid transition temperature. In general, when the gel exhibits a lower critical co-melting temperature (LCST) type gel-solid transition, that is, when the gel is in a gel state at a lower temperature side than the gel-solid transition temperature and becomes a solid state at a higher temperature side, The change in curvature at a certain temperature difference increases, but the response speed decreases. The opposite is true when the upper critical co-melting temperature (UCST) is indicated. Many temperature-responsive aqueous gels are of the LCST type, and many temperature-responsive non-aqueous gels are of the UCST type.

  The temperature-responsive gel used in the present invention may be an aqueous gel or a non-aqueous gel, but is swollen by a fluid flowing through the temperature-responsive valve to become a temperature-responsive gel. The gel-solid transition temperature can be designed to a suitable value according to the purpose of use by selecting a gel material. The gel-solid transition temperature is basically determined by the characteristics of the monomer constituting the gel, but the type of crosslinking agent, the crosslinking density, the type and copolymerization ratio of the copolymerization monomer, the type of swelling medium and the swelling. Since it is affected by the salt concentration of the medium, it is preferable to adjust the gel-solid transition temperature according to the type of fluid flowing through the temperature-responsive valve.

  Any monomer (hereinafter referred to as “temperature-sensitive monomer”) constituting such a temperature-responsive gel can be used. For example, in the case of an aqueous gel, N-alkyl (meth) is used. N-substituted (meth) acrylamides such as acrylamide and / or N-alkylene (meth) acrylamide, long chain alkyl groups such as myristyl (meth) acrylate, and (meth) acrylates having a long chain alkylene group can be exemplified. .

  Examples of N-alkyl (meth) acrylamide and / or N-alkylene (meth) acrylamide include N-ethylacrylamide, N-isopropylacrylamide, Nn-propylacrylamide, N, N-dimethylacrylamide, N, N- Methylethylacrylamide, N, N-methylisopropylacrylamide, N, N-methyl-n-propylacrylamide, N, N-diethylacrylamide, N, N-cyclopropylacrylamide, N-acryloylpyrrolidine, N-acryloylpiperidine, N, N-cyclopropylmethacrylamide, N, N-diethylmethacrylamide, N-isopropylmethacrylamide, Nn-propylmethacrylamide, N-methacryloylpyrrolidine, N-methacryloylpiperidine It can be mentioned.

  Examples of the (meth) acrylate having a long-chain alkyl group or a long-chain alkylene group include alkyl (meth) acrylates having 9 to 20 carbon atoms. Of these, N-isopropylacrylamide and myristyl (meth) acrylate are preferred because the transition occurs near room temperature. Of course, these thermosensitive monomers can also be made into a copolymer with these or other monomers that do not exhibit temperature sensitivity.

  In the case of non-aqueous gels, many cross-linked polymer-θ solvent combinations exhibit a UCST-type gel-solid transition temperature, for example, cross-linked polystyrene-cyclohexane system. Many alkene-type polymer-aliphatic or aromatic solvent systems also exhibit LCST-type gel-solid transition temperatures. In addition, there are those having two gel-solid transition temperatures of UCST type and LCST type, such as a crosslinked polyisobutylene-benzene system.

  A temperature-responsive gel expands by swelling from a solid state to a gel state. The degree of expansion is arbitrary, but the ratio of the length after swelling to that before swelling is preferably 1.03 to 2, more preferably 1.05 to 1.6. When this value is equal to or greater than the lower limit, the curvature of the valve body can be suitably changed, and the valve can be opened and closed satisfactorily. Further, it is preferable because a large valve body is not required and inconveniences such as an increase in the dead volume of the valve portion hardly occur. It is preferable that it is not more than the above upper limit value because peeling between the gel layer and the other material, gel self-destruction, reduction in pressure resistance of the valve, reduction in durability, and the like hardly occur.

  The amount of dimensional change of the gel due to temperature change depends on the selection of the temperature-sensitive monomer, adjustment of the degree of cross-linking by the addition amount of the cross-linkable monomer, etc. Mixing ratio of monomers (hereinafter referred to as “non-temperature-sensitive monomers”) whose coalescence does not become a temperature-responsive gel, non-swellable polymer, solid particles, non-temperature-sensitive gel It can be adjusted by the amount of particles added. The addition of a non-swellable polymer or the like to the temperature responsive gel can be carried out by a method of adding these to a temperature responsive gel material to cause gelation.

  It is preferable from the viewpoint of productivity that the temperature-responsive gel used in the present invention can be manufactured at room temperature. However, when manufactured at room temperature, a valve body that extends flatly at room temperature is often formed. On the other hand, in the case of a warped shape at room temperature, for example, a method of manufacturing at a temperature other than room temperature, a fluid used for this valve as a solvent (swelling medium) used when forming a temperature-responsive gel A method of using a solvent having a smaller degree of swelling of the temperature-responsive gel, a method of adding crosslinked polymer particles swollen by the fluid used in the valve to the gel-forming material, and a solvent used in forming the temperature-responsive gel (Swelling medium) and non-temperature-responsive gel particles with different degrees of swelling depending on the fluid flowing through the valve can be manufactured by a method of adding to a gel-forming material, a method of forming a warped shape when forming a valve body, etc. I can do it. In this way, in the case of a structure having a valve seat, the shape warped at room temperature is for the valve body to hold down the valve seat at room temperature to prevent leakage in the closed state, or at room temperature. In many cases, it is preferable that the valve body is warped at room temperature so that the body is completely separated from the valve seat and the flow path is completely opened.

The method for forming the temperature-responsive gel is arbitrary. For example,
(I) As a crosslinking polymerization method,
(Ii) a method in which the temperature-sensitive monomer is a cross-linkable monomer, and the temperature-sensitive monomer is cross-linked.
(I-ii) A method in which a temperature-responsive gel material contains a non-crosslinked polymerizable thermosensitive monomer and a crosslinkable polymerizable compound copolymerized with the thermosensitive monomer, and these are copolymerized ,
(II) As a post-crosslinking method,
(II-i) a method of crosslinking a non-crosslinked polymer comprising a thermosensitive monomer, for example, with ionizing radiation,
(II-ii) The temperature-responsive gel material contains a crosslinking agent that crosslinks the non-crosslinked polymer of the temperature-sensitive monomer, such as a light (or heat or water) crosslinking agent, A method of performing a photo (or heat or water) cross-linking reaction of the polymer subsequent to thermal (or photo) polymerization,
Can be illustrated. Among these, the cross-linking polymerization method of (I-ii) is preferable because it is easy to produce. Among them, the cross-linking polymerization is active energy ray cross-linking polymerization, and the formation speed is high, and the below-described porosity can be easily obtained. It is preferable because a gel can be formed. Examples of the active energy rays include rays such as ultraviolet rays, visible rays, and infrared rays; ionizing radiations such as X-rays and gamma rays; and particle rays such as electron beams, ion beams, beta rays, and heavy particle rays.

  When a non-crosslinked polymerizable temperature-sensitive monomer is used, the crosslinked polymerizable compound copolymerized therewith is typically a polyfunctional compound having two or more polymerizable carbon-carbon double bonds in one molecule. A monomer and a polyfunctional oligomer can be mentioned. Examples of such polyfunctional monomers include methylene bisacrylamide, ethylene bisacrylamide, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and polyethylene. Bifunctional such as glycol di (meth) acrylate, 2,2′-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane, 2,2′-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane Monomers, trifunctional monomers such as trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, isocyanurate tri (meth) acrylate, pentaerythritol tetra (meth) acrylate Tetrafunctional monomers etc., dipentaerythritol - 6-functional monomer such as Le hexaacrylate. Of course, it is also possible to use a mixture of these monomers.

  The polyfunctional oligomer that can be cross-linked by irradiation with energy rays may be, for example, an oligomer having a weight average molecular weight of 500 to 50,000 (also referred to as a prepolymer). For example, (meth) acrylic acid ester of an epoxy resin, polyether resin (Meth) acrylic acid ester, polybutadiene resin (meth) acrylic acid ester, polyurethane resin having an acrylic group or methacrylic group at the molecular end, and the like. Of course, these oligomers can also be used by mixing with each other, and can also be used by mixing with monomers.

  The cross-linkable polymerizable compound only needs to be mixed with the temperature-sensitive monomer or have a common solvent. Further, as described later, when forming a porous temperature-responsive gel, one that is compatible with the pore-forming agent can be selected. By selecting the mixing amount and type of the crosslinkable compound, the degree of swelling of the temperature responsive gel and the degree of change thereof can be adjusted. Increasing the crosslink density by increasing the addition amount of the crosslinkable compound or using a crosslinkable compound having a large number of functional groups increases the hardness and strength of the temperature-responsive gel and decreases the amount of dimensional change.

  In the present invention, for the purpose of adjusting the strength, hardness, swelling degree, response temperature, response sensitivity, etc. of the temperature-responsive gel, other polymerization that can be copolymerized with the temperature-sensitive monomer is used for the temperature-responsive gel material. Sexual compounds can also be added.

  Any other polymerizable compound that can be copolymerized with the temperature-sensitive monomer may be any compound that dissolves in the temperature-responsive gel material, and a monofunctional monomer or a monofunctional oligomer can be used. For example, acrylamide, methacrylamide, polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, acrylic acid, methacrylic acid, vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-2-phenylpropane sulfonic acid, 2-acrylamide 2-methylpropanesulfonic acid ethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, phenyl (meth) acrylate, phenyl cellosolve (meth) acrylate, n-vinylpyrrolidone, isobornyl (meth) acrylate, dicyclopentenyl ( Data) acrylate, and di cyclopentenylene b carboxyethyl (meth) acrylate.

  The temperature-responsive gel is preferably porous at least in either a gel state or a solid state (hereinafter, such a gel is referred to as a “porous gel”). The porous gel is a porous body composed of a polymer portion and a void portion, and the polymer portion is formed of a gel or a gelable polymer. More preferably, the porous gel is porous both in a gel state and in a solid state.

  When the temperature-responsive gel is porous in the solid state, it can be confirmed to be porous by an electron microscope. However, if the temperature-responsive gel is porous in the gel phase state, the measurement is not possible. Have difficulty. However, it is confirmed that the porous structure in the gel phase state is an order of magnitude increase in response speed. That is, by making it porous, the required diffusion distance of the swelling medium at the time of phase change becomes extremely short, so that the response speed of gelation by absorption of the swelling medium and solidification by discharging of the swelling medium increases, It is considered that the response speed such as opening and closing is improved. Therefore, a porous gel that is porous in a gel state and non-porous in a solid state can change the temperature in a temperature range of (gel-solid transition temperature minus 5 ° C.) or higher to obtain a high response speed. Therefore, it is preferable to change the temperature in a temperature range equal to or higher than the gel-solid transition temperature. In addition, a porous gel that is non-porous in a gel state and porous in a solid state value can obtain a high response speed by changing the temperature within a temperature range of (gel-solid transition temperature plus 5 ° C.) or less. Therefore, it is preferable to change the temperature in the temperature range below the gel-solid transition temperature. For a porous gel that is porous in both a gel state and a solid state, it is preferable to change the temperature at a temperature that crosses the gel-solid transition temperature because a high response speed is obtained. More preferably, the temperature is changed to a temperature of minus 5 ° C. or lower and the high temperature side is set to a temperature of (gel-solid transition temperature plus 5 ° C.) or higher.

  The method for producing the porous gel is arbitrary, but for example, it can be produced by the method disclosed in JP-A-5-16076. That is, a temperature-sensitive monomer, a cross-linkable monomer, and a homogeneous mixed solution (hereinafter referred to as a phase separation agent) of a compound compatible with these and incompatible with these copolymers (hereinafter referred to as a phase separation agent) , And may be referred to as “porous gel raw material”), and using this porous gel raw material, a crosslinked polymer is irradiated with energy rays in the same manner as in the above-mentioned normal temperature-responsive gel formation. And forming a porous body by phase separation, and if necessary, the phase separation agent in the pores can be replaced with an aqueous liquid. By this method, when the mixing ratio of the phase separation agent is increased, a porous gel that is porous in both the gel state and the solid state is obtained, and when the phase separation agent is relatively decreased, the gel state is porous and solid state. A porous gel that is non-porous is obtained. In addition, a method of cross-linking polymerization at a temperature that becomes a solid using a swelling agent that becomes a thermosensitive gel as a solvent, for example, in the case of N-isopropylacrylamide, water is used as a phase separation agent at a temperature of 30 ° C. or higher. When the mixing ratio of the phase separation agent is increased by the crosslinking polymerization method, a porous gel that is porous in both the gel state and the solid state is obtained, and when the phase separation agent is relatively small, the gel state is non-porous. A porous gel that is porous in a solid state is obtained.

  As a phase separation agent, a mixture of a temperature-sensitive monomer and a cross-linkable polymerizable monomer is compatible, but the cross-linked polymer formed by irradiating the mixture with energy rays does not swell, and energy. Any material that is inert to the wire can be used without any particular limitation.

  More specifically, water, monohydric or polyhydric alcohols, alkyl esters such as methyl caprate, dialkyl ketones such as diisobutyl ketone, liquid polyethylene glycol, polyethylene glycol monoester, polyethylene glycol monoester Ether, polyethylene glycol sorbitan monoester, polyethylene glycol sorbitan diester, polyethylene glycol sorbitan triester, polyester polyol, oligomers such as polyethylene glycol amine, cellulose acetate, ethyl cellulose, nitrocellulose, hydroxymethyl cellulose, chitosan, polystyrene, polyvinyl chloride, Polycarbonate, polysulfone, polyethersulfone, polyurethane, phenoxy resin, polyarylate, polyacrylate Nitrile, polyacrylic acid esters, polyacrylic acid, polymethyl methacrylate, polyacrylamide, polyethylene glycol, polyvinyl pyrrolidone, polyvinyl methyl ether, polyvinyl alcohol and oligomers or polymers such as a copolymer thereof. The phase-separating agent may be a mixture containing them or a mixture thereof, or may be a mixture of a solvent that swells the cross-linked polymer formed thereon.

  The phase separation agent can be used without being removed depending on the system after forming the polymer by irradiation with energy rays, but can also be removed. The removal can employ any method such as washing, drying, and substitution. However, when the phase separation agent needs to be removed, it is preferable that the phase separation agent is water-soluble because it is easy to remove.

  The viscosity of the porous gel raw material is arbitrary, and in the production method in which it is applied to the valve body and irradiated with active energy rays, it is preferably 1 to 100 PaS because it is easy to apply, In the production method in which the active energy ray is applied to a (temporary) support and subjected to pattern exposure, it is preferably 0.1 to 10 PaS at 25 ° C. because it is easy to apply.

[Flexible member]
The flexible member, which is the other material constituting the valve body, is arbitrary as long as the expansion and contraction characteristics with respect to temperature are different from those of the temperature-responsive gel. For example, organic polymer, metal, glass, crystal and diamond The organic polymer is preferable because it has a suitable Young's modulus and good moldability. It is preferable that the organic polymer is a cross-linked polymer because there is little creep and the reproducibility and stability of the valve operation is improved.
The thickness of the flexible member is arbitrary, but the preferred thickness depends on the tensile elastic modulus, and it is preferable to make it thinner as the tensile elastic modulus is larger. For example, the value of “tensile modulus physical property × thickness” is preferably 0.1 to 10 kPam, more preferably 0.3 to 3 kPam.
The flexible member preferably has a functional group on the surface that can be covalently bonded to the temperature-responsive gel in order to be bonded well to the temperature-responsive gel. Although the method of giving such a functional group is arbitrary, the following method can be illustrated, for example. That is,
(I) The flexible member is formed of a polymer of a monomer copolymerizable with the monomer contained in the temperature-responsive gel material, and the unreacted monomer remains on the surface of the member. How to keep,
(Ii) Thermally polymerizable monomer containing, for example, epoxy, a functional group copolymerizable with the monomer contained in the temperature-responsive gel material, such as a (meth) acryloyl group. Compound) is a polymer formed by thermal polymerization, and the unreacted monomer is left on the surface of the member.
(Iii) The flexible member is treated with a surface treatment agent such as a silane coupling agent having a (meth) acryloyl group in the military, and the surface is co-polymerized with the monomer contained in the temperature-responsive gel material. A method for introducing a polymerizable functional group;
(Iv) The flexible member is formed of a monomer (co) polymer having a functional group such as an epoxy group, an isocyanato group, an aldehyde group, a chloroaldehyde group, or a hydroxyl group in the molecule, while the temperature is The method of using the compound which has the functional group couple | bonded with said functional group in the molecule | numerator, for example in the multisensitive monomer contained in the responsive gel raw material.
At this time, in the above method (i), the flexible member is formed by energy beam in situ polymerization of the (meth) acryloyl group-containing monomer, and in this case, the irradiation amount is insufficient and the incomplete line is formed. It can be created by a method of making it hardened. Further, in the above (i) to (iii), a method of applying a temperature-responsive gel material on the flexible member having the polymerizable functional group and forming a gel by irradiation with energy rays is preferable. It can be joined by covalent bond.

[Valve]
The valve body constituting the temperature responsive valve of the present invention is composed of a joined body of a temperature responsive gel and a flexible member, and the temperature responsive gel undergoes a gel-solid transition due to a temperature change and joined. The valve body can be deformed due to the difference in expansion and contraction with the flexible member, and the channel can be opened and closed or switched.

  What is necessary is just to design suitably the planar shape and dimension of the said valve body by the shape and structure of a flow path so that a flow path can be opened and closed and switched. As the shape, a tongue-like shape can be particularly preferably used. For example, a tongue-like shape having a linear fixed end at one end, a tongue-like shape having a plurality of point-like fixing portions, and a part of the periphery It is a strip shape or a star shape having a plurality of fixed portions, and can be a shape in which a plurality of tongue pieces are gathered. Of these, a tongue-like shape with one end fixed is preferable because it is easy to manufacture and reliable, and the tongue is preferably U-shaped, U-shaped, or trapezoidal. The tongue piece preferably has a width of 1.0 to 2 times, more preferably 1.1 to 1.8 times, most preferably 1.2 to 1.6 times the length at the base which is the fixed end. . By setting it within this range, it is possible to suppress twisting of the valve body, and to ensure reliable and reproducible operations such as opening / closing, switching, flow rate adjustment, and non-returning, and the dimensions do not become excessively large.

  In the valve body, it is preferable that the temperature-responsive gel and the flexible member are laminated in layers. Moreover, even if both members are laminated | stacked on the whole laminated valve body part, the temperature-responsive gel may be laminated | stacked on a part of flexible member, and two types from which temperature responsiveness differs on a flexible member. The above temperature-responsive gel may be laminated.

In addition, when a minute valve is formed, it is necessary to accurately fix the minute valve body at an appropriate position. For this purpose, the valve body is provided on a part of a film-like member. Is preferred. For this purpose, the valve body preferably has a structure comprising a tongue piece provided on a film-like flexible member and a temperature-responsive gel laminated on the tongue piece. Specifically, the following structure is preferable.
(1) A valve member having a fixed portion having a larger area, for example, 10 to 10,000 times as large as the valve body, is formed at the base of the valve body, and only the valve body portion is left, and the fixed portion is temperature responsive. Shape embedded in the valve member.
(2) A tongue-like valve body surrounded by a U-shaped or U-shaped through groove is formed on a part of the film-like flexible member over the entire temperature-responsive valve. shape.

  For example, in the case of (2) above, the gel may be joined after the tongue-shaped portion surrounded by the through groove is formed on the flexible member. It is also possible to form a valve body part by joining a temperature-responsive gel in the form of a tongue piece to a part of this, and form a through-groove around the valve body to form a tongue piece-like valve body. The through groove can be formed by, for example, photolithography, laser cutting machine, mechanical punching, or plasma processing.

  The shape of the temperature-responsive gel and the other flexible member in the valve body in the thickness direction is arbitrary, for example, a film shape with a constant thickness, a film shape whose thickness changes into a taper shape, a frame or a support portion However, a film having a certain thickness is preferable because it is easy to produce.

  Although the minimum of the thickness of the said valve body is arbitrary, 1 micrometer or more is preferable, 5 micrometers or more are more preferable, and 10 micrometers or more are still more preferable. The lower limit of the thickness of the valve body is within the above range, and is preferably 1/10 or more of the diameter of the flow path to be opened / closed or switched, that is, the flow path connected to the valve, It is preferable that it is 1/5 or more of the diameter of a flow path. The diameter of the flow path is the diameter of a circle having a corresponding cross-sectional area when the cross-sectional shape of the flow path is other than a circle. By setting the thickness of the valve body to be equal to or greater than this lower limit, it is possible to open / close and switch even in a flow path having a pressure difference, and manufacture is facilitated.

  The upper limit of the thickness of the valve body is also arbitrary, but is preferably 500 μm or less, more preferably 300 μm or less, and most preferably 150 μm or less. The upper limit of the thickness of the valve body is within the above range, and is preferably 10 times or less, more preferably 5 times or less, and most preferably 2 times or less the diameter of the flow path. . By setting it to the upper limit or less, it becomes easy to increase the curvature change of the valve body, so that the valve body can be made small, the formation of a minute valve is facilitated, and the response speed is also increased. In addition, when the thickness of a valve body changes with places, the thickness of the said valve body shall be average thickness.

  The ratio between the thickness of the flexible member and the thickness of the gel layer is arbitrary, but a suitable ratio depends on the hardness of the flexible member. The value of “tensile modulus physical property × thickness” of the flexible member is preferably 1 to 3000 times, more preferably 1 to 1000 times, and most preferably 1 to 300 times that of the gel layer. By setting it above the lower limit of this range, it is easy to obtain a valve body having durability and reproducibility. By setting it below the upper limit of this range, the amount of change in the curvature of the valve body can be increased. However, the Young's modulus of the gel is often several orders of magnitude lower than the Young's modulus of the other material, so if it is difficult to reduce the thickness of the other material to the above range, the thickness of the other material is Is preferably as close to the above range as possible. In general, since it is difficult to measure the tensile modulus of gel, three times the bending rigidity may be used as the tensile modulus.

The valve body used in the present invention has a temperature change of ± 10 ° C. centering on a set temperature (for example, the gel-solid transition temperature), and the curvature is preferably 0.1 (mm ⁻¹ ) or more, more preferably, It is 0.3 (mm ⁻¹ ) or more, and most preferably 0.5 (mm ⁻¹ ) or more. The change range of the curvature may be changed in a positive to positive range, may be changed in a 0 to positive range, or may be changed in a negative to positive range. What is necessary is just to select and use a suitable thing according to the flow path of the microvalve to form, or the shape of a valve seat. Among these. What changes in the negative to positive range is preferable because it has wide applicability to the shape of the flow path and is biased in the direction of pressing the valve seat in the closed state, so that the amount of fluid leakage is reduced.

[Temperature responsive valve]
The temperature-responsive valve according to the present invention can have any configuration as long as the valve body is deformed by temperature change to open, close, switch, or control the flow rate of the fine flow path. A structure in which a valve body is provided in the middle of the flow path of the fine flow path, a structure in which a valve body is provided in a branch portion of a branched fine flow path formed in the same plane, or a layer having a hole or a notch The structure etc. which the valve body layer was provided in the middle of the flow path of the fine flow path by the communicating hole formed by laminating | stacking in multiple layers can be illustrated.

  In particular, a temperature-responsive valve formed by a laminated structure is preferable because a valve body can be easily installed in the middle of the flow path, and a valve body that is deformed by a temperature change can easily close the flow path. As a temperature-responsive valve having such a laminated structure, a joined body of a tongue piece provided on a film-like flexible member and a temperature-responsive gel in which a temperature-responsive gel is laminated on the tongue piece. A valve body layer made of a film-like flexible member having a valve body made of the above and two flow path layers having grooves or through holes constituting a fine flow path, and the grooves or penetrations of the two flow path layers A preferable example is one having a multilayer structure in which two flow path layers are laminated with the valve body layer sandwiched so that the holes communicate and are isolated by deformation of the valve body.

  The temperature responsive valve of the present invention reduces the cross-sectional area of the flow path or allows the flow path to be close to or in contact with at least a part of the members constituting the fine flow path either before or after the temperature change. Is closed to control the flow rate and open / close the flow path. (Hereinafter, of the parts constituting the fine flow path, the part where the valve body approaches or contacts either before or after the temperature change is referred to as a valve seat.)

  In addition, a configuration in which a valve body is provided at a branch portion of a branching micro flow path, for example, the micro flow path has a trifurcated branch flow path, and the valve body is a regular trifurcated branch. A configuration in which one of the channels is closed and the one channel is opened due to a temperature change and the other channel is closed is preferable because the channel can be switched. it can.

  The valve seat is a part that shuts off the flow path or reduces the cross-sectional area of the flow path when pressed by the valve body, and is the periphery of the opening in the flow path. The structure of the valve seat is arbitrary, for example, around the hole formed in a plane, the tip of the tube, the fixed end side of the tongue-like valve body, and the middle of the valve body in contact with the valve body, It may be a peripheral portion in the vicinity of the end of the flow path extending in parallel with the surface. Among these, the peripheral portion in the vicinity of the end portion of the flow path is preferable because the structure is simple and the manufacture is easy. The planar shape of the opening in the channel is also arbitrary and can be designed according to the purpose of use. For example, when the valve of the present invention is a flow control valve, the planar shape of the valve seat is tapered, and when the curvature of the valve body is small, the opening area not pressed by the valve body is small, and the curvature of the valve body is large. A shape in which the opening area gradually increases as it becomes is preferable. Further, for example, when the valve of the present invention is an on-off valve or a flow path switching valve, if the planar shape of the valve seat is shortened in the length direction of the valve body and lengthened in the width direction, the valve body slightly warps. A shape that is fully open at once is preferable.

  The valve chamber is a space in which the valve body is movable, and its structure is arbitrary. It may be a part of the flow path, or may be formed in a shape corresponding to the shape of the valve body. However, it is preferable to use a part of the flow path extending in a direction parallel to the valve body because the structure is simple and the manufacturing is easy.

  The shape and structure of the flow path connected to the valve seat and the flow path connected to the valve chamber are arbitrary, but the groove provided in the film-like member or plate-like member having the groove is laminated with other members. The shape formed by this is preferable because the structure is simple and the manufacture is easy.

  Materials other than the valve body of the temperature responsive valve of the present invention are arbitrary, such as glass, crystals such as quartz, semiconductors such as silicon, metals such as stainless steel, ceramics, carbon, high molecular polymers (hereinafter, It is easy to selectively change the temperature of only a necessary part, for example, only a minute valve body part due to a low electrothermal coefficient, and the heat capacity. Therefore, when the temperature of the entire microfluidic device in which the temperature responsive valve is incorporated is changed, energy saving is preferable.

  The polymer may be a homopolymer or a copolymer, and may be a thermoplastic polymer or a thermosetting polymer. From the viewpoint of productivity, a cured product of a thermoplastic polymer or an energy beam curable composition is preferable.

  Examples of the polymer that can be used for members other than the valve body forming the temperature-responsive valve of the present invention include polystyrene, poly-α-methylstyrene, polystyrene / maleic acid copolymer, polystyrene / acrylonitrile copolymer, and the like. Styrene polymers; Polysulfone polymers such as porsulfone and polyethersulfone; (Meth) acrylic polymers such as polymethyl methacrylate and polyacrylonitrile; Polymaleimide polymers;

Polycarbonate polymers such as bisphenol A polycarbonate, bisphenol F polycarbonate, and bisphenol Z polycarbonate; polyolefin polymers such as polyethylene, polypropylene, and poly-4-methylpentene-1; chlorine-containing heavy compounds such as vinyl chloride and vinylidene chloride Cellulose polymer such as cellulose acetate and methylcellulose;

Polyurethane polymers; Polyamide polymers; Polyimide polymers; Polyether or polythioether polymers such as poly-2,6-dimethylphenylene oxide and polyphenylene sulfide; Polyether ketone polymers such as polyether ether ketone Polyester polymers such as polyethylene terephthalate and polyarylate; epoxy resins; urea resins; phenol resins and the like.

  Among these, a styrene polymer, a (meth) acrylic polymer, a polycarbonate polymer, a polysulfone polymer, and a polyester polymer are preferable from the viewpoint of good adhesiveness.

The energy beam curable compound constituting the energy beam curable composition may be any one such as radical polymerizable, anionic polymerizable, and cationic polymerizable.
The energy ray-curable compound is not limited to those that polymerize in the absence of a polymerization initiator, and those that polymerize with energy rays only in the presence of a polymerization initiator can also be used.

  As such an energy ray-curable compound, those having a polymerizable carbon-carbon double bond are preferable, and among them, a highly reactive (meth) acrylic compound or vinyl ether, or absence of a photopolymerization initiator is preferred. A maleimide compound that cures even underneath is preferred.

  Examples of the crosslinkable (meth) acrylic monomer that can be preferably used as the energy ray curable compound include diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexane. Diol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 2,2′-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane,

2,2′-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane, hydroxydipivalic acid neopentyl glycol di (meth) acrylate, dicyclopentanyl diacrylate, bis (acryloxyethyl) hydroxyethyl isocyanurate , Bifunctional monomers such as N-methylenebisacrylamide;

Trifunctional monomers such as trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate; pentaerythritol tetra (meta) ) Tetrafunctional monomer such as acrylate; hexafunctional monomer such as dipentaerythritol hexa (meth) acrylate.

  Moreover, a polymerizable oligomer (referred to as a prepolymer) can also be used as the energy ray curable compound, and examples thereof include those having a weight average molecular weight of 500 to 50,000. Examples of such polymerizable oligomers include (meth) acrylic acid ester of epoxy resin, (meth) acrylic acid ester of polyether resin, (meth) acrylic acid ester of polybutadiene resin, and (meth) acryloyl at the molecular end. Examples thereof include a polyurethane resin having a group.

  Examples of maleimide-based crosslinkable energy ray-curable compounds include 4,4′-methylenebis (N-phenylmaleimide), 2,3-bis (2,4,5-trimethyl-3-thienyl) maleimide, 1,2-bismaleimide ethane, 1,6-bismaleimide hexane, triethylene glycol bismaleimide, N, N′-m-phenylene dimaleimide, m-tolylene dimaleimide, N, N′-1,4-phenylene diene Maleimide, N, N′-diphenylmethane dimaleimide, N, N′-diphenyl ether dimaleimide,

N, N'-diphenylsulfone dimaleimide, 1,4-bis (maleimidoethyl) -1,4-diazoniabicyclo- [2,2,2] octane dichloride, 4,4'-isopropylidenediphenyl dicyanate , N ′-(methylenedi-p-phenylene) dimaleimide, bifunctional maleimide; N- (9-acridinyl) maleimide, and maleimide having a polymerizable functional group other than maleimide group.

  Examples of maleimide-based cross-linkable oligomers include polytetramethylene glycol maleimide alkylates such as polytetramethylene glycol maleimide capriate and polytetramethylene glycol maleimide acetate. Maleimide monomers and oligomers can be copolymerized with each other and / or with compounds having a polymerizable carbon / carbon double bond such as vinyl monomers, vinyl ethers, and acrylic monomers. These compounds can also be used independently and can also be used in mixture of 2 or more types.

  If necessary, a photopolymerization initiator can be added to the energy ray curable composition. The photopolymerization initiator is not particularly limited as long as it is active with respect to the energy beam used and can polymerize the energy beam curable compound. For example, a radical polymerization initiator or an anionic polymerization initiator is used. It may be a cationic polymerization initiator. The photopolymerization initiator may be a maleimide compound.

  Examples of monofunctional maleimide monomers that can be used in combination include N-alkylmaleimides such as N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, and N-dodecylmaleimide; N-fats such as N-cyclohexylmaleimide. N-benzylmaleimide; N-phenylmaleimide, N- (alkylphenyl) maleimide, N-dialkoxyphenylmaleimide, N- (2-chlorophenyl) maleimide, 2,3-dichloro-N- (2,6 -Diethylphenyl) maleimide,

N- (substituted or unsubstituted phenyl) maleimide such as 2,3-dichloro-N- (2-ethyl-6-methylphenyl) maleimide; N-benzyl-2,3-dichloromaleimide, N- (4′-fluoro A maleimide having a halogen such as phenyl) -2,3-dichloromaleimide; a maleimide having a hydroxyl group such as hydroxyphenylmaleimide; a maleimide having a carboxy group such as N- (4-carboxy-3-hydroxyphenyl) maleimide;

A maleimide having an alkoxy group such as N-methoxyphenylmaleimide; a maleimide having an amino group such as N- [3- (diethylamino) propyl] maleimide; a polycyclic aromatic maleimide such as N- (1-pyrenyl) maleimide; And maleimide having a heterocyclic ring such as (dimethylamino-4-methyl-3-coumarinyl) maleimide and N- (4-anilino-1-naphthyl) maleimide.

  Examples of energy rays include rays such as ultraviolet rays, visible rays, and infrared rays; ionizing radiations such as X-rays and gamma rays; and particle rays such as electron rays, ion beams, beta rays, and heavy particle rays. The member may be a polymer blend or a polymer alloy, or may be a foam, a laminate, or another composite. The member may contain other components such as a modifier and a colorant.

  Examples of the modifier include hydrophobizing agents (water repellents) such as silicone oil and fluorine-substituted hydrocarbons; surfactants such as anionic, cationic and nonionic surfactants, inorganic powders such as silica gel, and polyvinylpyrrolidone. Hydrophilic agents such as hydrophilic polymers; plasticizers for adjusting the tensile modulus. Examples of the colorant include arbitrary dyes and pigments, fluorescent dyes and pigments, and ultraviolet absorbers.

  Further, the temperature responsive valve of the present invention is preferably incorporated into a microfluidic device in which another mechanism is formed, and preferably integrated with another member or another mechanism by lamination or adhesion. In addition, a plurality of temperature responsive valves can be formed in one member, and after manufacturing, these can be cut into a plurality of temperature responsive valves.

  As described above, in the temperature responsive valve of the present invention, the valve body constituting the valve is composed of a joined body of a temperature responsive gel having a gel-solid transition temperature and a flexible member. Therefore, when the temperature-responsive gel causes a gel-solid transition, the valve body is deformed due to the difference in expansion and contraction characteristics with the joined flexible member. Due to this, even if the volume change of the gel-solid transition of the temperature-responsive gel is a small volume change, it greatly affects the deformation of the valve body, so there is no need to give an excessive temperature change and excellent response speed Therefore, it is possible to open / close or switch the flow path.

  Moreover, since the temperature-responsive valve of the present invention can be incorporated as a part of a laminated member when forming a flow path having a laminated structure, for example, accurate alignment with a fine flow path is facilitated.

[Method of manufacturing temperature-responsive valve]
The method for producing the temperature responsive valve is not particularly limited as long as it can form the above-described configuration, and a method of appropriately laminating a member that forms a fine flow path and a member that forms a valve body can be suitably used. As such a method, the following method can be illustrated preferably.

(I) A temperature-responsive gel is joined to at least a portion of the film-like flexible member that forms the valve body, and a notch that penetrates the front and back for forming a tongue piece portion is formed in the joint. Forming a valve body layer having the valve body;
The valve body layer is sandwiched between two flow path layers having grooves or through-holes constituting a fine flow path so that the grooves or through-holes of the two flow path layers are communicated and isolated by deformation of the valve body. Manufacturing method of temperature responsive valve to be laminated.

(II) The active energy ray-curable resin composition is applied onto the support, and the active energy rays are irradiated to the part other than the part formed as a notched part penetrating the front and back for forming the tongue part. Forming a flexible member of
The film-like flexible member is coated with an active energy ray-curable temperature-responsive gel-forming composition and applied to a portion other than the portion formed as a notch that penetrates the front and back surfaces for forming the tongue portion. After irradiating the active energy ray, by removing the uncured component of the non-irradiated part, the valve body layer having the valve body is formed,
The valve body layer is sandwiched between two flow path layers having grooves or through-holes constituting a fine flow path so that the grooves or through-holes of the two flow path layers are communicated and isolated by deformation of the valve body. Manufacturing method of temperature responsive valve to be laminated.

  As described above, the joining of the valve body in the above method is preferably performed by a method of forming a temperature-responsive gel on a flexible member having a functional group or a flexible member in an incomplete line-cured state. Can be joined. In particular, an active energy ray-curable temperature-responsive gel-forming composition is applied to a range including a valve body, and a temperature-responsive gel is formed by irradiation with active energy rays to form a film-like flexible member. The method of joining to can be preferably used.

  Moreover, when using an active energy ray-curable temperature-responsive gel-forming composition as the gel-forming material, a porous gel can be suitably formed by including a pore-forming agent in the composition.

[Embodiment]
An embodiment of the temperature responsive valve of the present invention will be described. In addition, the mechanism which has the same function is shown with the same number common to each embodiment.

  As shown in FIGS. 1 and 2, the first aspect of the present invention is a groove (1) that becomes an inflow side flow path (1) on the surface and a valve chamber (2) into which the valve body (15) enters. The valve body (15) is configured as a part surrounded by a plate-like first member (3) having a recess (2) and a notch (4) (hereinafter abbreviated as notch (4)) penetrating the front and back. A film-like second member (6) in which a portion to be a tongue piece (5) is formed, and a plate-like third member (8) having a groove to be an outflow side channel (7) on the surface are laminated. A film-like temperature-responsive gel (9) is joined to the first member (8) side of the tongue piece (5) of the second member to form a valve body (5). .

  One end (left side in FIG. 2) of the inflow side flow path (1) provided in the first member (3) is a communication hole (10) opened in the second member (6) and the third member (8). And is opened to the outside of the temperature-responsive valve, and serves as an inlet (11). The other end (the right side in FIG. 2) of the inflow channel (1) is connected to the valve chamber (2).

  One end (left side in FIG. 2) of the outflow side flow path (7) of the third member (8) is a valve from the base side of the tongue-like valve body (5) provided in the second member (6). The valve body (15) is formed so as to overlap with the body (15), and the portion where the valve body (15) and the third member (8) are in contact functions as the valve seat (12). The other end (right side in FIG. 2) of the outflow side flow path (7) of the third member (8) is connected to the outside of the temperature responsive valve through a communication hole (13) opened in the third member (8). It is open and serves as an outlet (14).

  When the temperature-responsive gel (9) has a lower critical co-melting temperature (LCST) type gel-solid transition temperature, the valve body (15) of the first aspect is higher than the vicinity of the transition temperature. On the side, the shrinkage of the temperature-responsive gel (9) warps downward in FIG. 2, and the valve body (15) enters the valve chamber (2) and separates from the valve seat (12), thereby causing the inflow side flow path (1). And the outflow channel (7) communicate with each other. On the contrary, a force that expands and warps upward in FIG. 2 is generated on the low temperature side near the transition temperature, and the valve body (15) is urged in the direction of pressing the valve seat (12) to block the flow path. . When the temperature-responsive gel has an upper critical co-melting temperature (UCST) type gel-solid transition temperature, the relationship between temperature and operation is reversed.

  The method of forming the grooves of the first member (3) and the third member (8) is arbitrary. For example, a method of directly forming a member having grooves by injection molding or stereolithography, photolithography having an etching process, mechanical A method of forming a groove in a member by cutting, laser processing, plasma processing, etc., bonding of a film-like or plate-like member (3b) (8b) having a through groove and another member (3a) (8a), By applying the active energy ray-curable resin composition on the member, and performing selective exposure and washing, a film-like member (3b) (8b) having a through groove is formed and another member (3a) at the same time. A method of bonding to (8a) can be exemplified.

  The fixing method of the first member (3), the second member (6), and the third member (8) is also arbitrary. Adhesion with an adhesive, thermal fusion, ultrasonic fusion, incompletely cured polymer is used. Adhesion that is completely cured by contact can be used.

  In the above description, the inflow side and the outflow side are provided for convenience, but the inflow side and the outflow side in the above description may be used in opposite directions. In this case, however, the force for blocking the flow path is weaker than in this example. The temperature responsive valve according to the first aspect can be used as an open / close valve. When the temperature responsive gel (9) has an LCST type gel-solid transition temperature, the temperature responsive valve (9) has a lower temperature than the vicinity of the transition temperature. When the valve has a UCST-type gel-solid transition temperature, it becomes a check valve on the higher temperature side than the transition temperature, and always on the lower temperature side. Can be used as an open valve.

  As a variation of the first aspect, when the end of the third member (8) on the side of the outflow side flow path (7) that overlaps the valve element (15) is formed in a tapered shape that gradually decreases toward the tip, It can be used as a flow control valve whose flow path resistance changes according to the curvature change of the body.

  In the second aspect of the present invention, as shown in FIG. 3, the second member (6) has the same shape as the second member (6) of the first aspect having the tongue piece (5). And a member (6b) that is the same as the member (6a) except that the tongue piece (5) is missing, and that the temperature-responsive gel (9) is formed on the member (6a). The same as the first aspect except that the tongue (5) is coated on the third member (8) side by the same thickness as the member (6b). In this 2nd aspect, since the temperature-responsive gel (9) is formed in the back surface of the valve body (15) compared with the 1st aspect, the temperature-responsive valve of this 2nd aspect is against temperature change. Thus, the operation reverse to that of the first mode valve is performed.

  As shown in FIGS. 4 and 5, the third aspect of the present invention is a plate-shaped first having a groove serving as the inflow side flow channel (1) and a groove serving as the outflow side flow channel (7) on the surface. A portion that becomes a tongue piece (5) is formed as a portion surrounded by the member (16) and the notch (4), and has a film-like second member (6), and a concave portion that becomes a valve chamber (2) on the surface. A plate-like third member (17) is laminated and fixed, and a temperature-responsive gel (9) is coated on the third member (17) side of the tongue piece (5) of the second member to coat the valve body (15 ).

  One end (the left side in FIG. 5) of the inflow channel (1) of the first member (16) is connected to the second member (6) and the third member (17) through a communication hole (10). It opens to the outside of the temperature responsive valve to serve as an inlet (11), and the other end (right side in FIG. 5) of the inflow side flow path (1) is provided around the valve body (5) of the second member (6). It is formed to the position where it communicates with the notch (4).

  Further, one end (left side in FIG. 5) of the outflow side flow path (7) of the first member (16) overlaps the valve body (15) from the base side of the valve body (15). The portion where the valve body (15) and the first member (16) are in contact functions as the valve seat (12). The other end (the right side in FIG. 5) of the outflow side channel (7) opens out of the temperature-responsive valve through a communication hole (13) opened in the second member (6) and the third member (17). The outlet (14). The first member (16) is formed with a recessed valve chamber (2) having a size that allows the valve body (15) to enter. The valve chamber (2) communicates with the inflow side flow path (1) of the first member (3) through a notch (4) provided in the second member (6).

  When the temperature-responsive gel (9) has an LCST type gel-solid transition temperature, the temperature-responsive valve according to the second aspect of the present invention is expanded at a temperature lower than the vicinity of the transition temperature. As a result, the valve body (15) generates a force that warps downward in FIG. 5, and is biased in the direction of pressing the valve seat (12) to block the flow path. On the other hand, on the higher temperature side near the transition temperature, the valve body (15) warps upward in FIG. 5 due to the shrinkage of the temperature-responsive gel, and the valve body (15) moves away from the valve seat (12) into the valve chamber (2). By entering, the inflow side flow path (1) and the outflow side flow path (7) communicate with each other. When the temperature-responsive gel (9) has a UCST type gel-solid transition temperature, the relationship between the temperature and the operation is reversed.

  In the above description, the inflow side and the outflow side are provided for convenience, but the inflow side and the outflow side in the above description may be used in opposite directions. In this case, however, the force for blocking the flow path is weaker than in this example. The temperature-responsive valve according to the third aspect can be used as an open / close valve. When the temperature-responsive gel (9) has an LCST type gel-solid transition temperature, the temperature-responsive valve (9) can be used at a lower temperature than the vicinity of the transition temperature. When the valve has a UCST-type gel-solid transition temperature, it becomes a check valve on the higher temperature side than the transition temperature, and always on the lower temperature side. Can be used as an open valve.

  As a variation of the third aspect, if the end of the first member (16) on the valve body (15) side of the outflow side flow path (7) is formed into a tapered shape that gradually decreases toward the tip, the valve body ( It can be used as a flow rate control valve whose flow path resistance changes according to the curvature change of 7).

  In the third aspect, each member may be composed of a plurality of members as in the first aspect. For example, the first member (16) is a joined body of a film-like or plate-like member (16b) having a through groove and another member (16a), like the first member (3) in the first embodiment. May be.

  In the fourth aspect of the present invention, as shown in FIG. 5, the second member (6) includes a member (6a) having the same structure as the second member (6) in the third aspect, and a tongue piece ( 5) A member (6b) similar to the member (6a) is formed except that it is missing, and the temperature-responsive gel (9) is formed on the tongue (5) of the member (6a). The same as the third aspect except that the first member (3) is coated with the same thickness as the member (6b). In this 4th aspect, since the temperature-responsive gel (9) is formed in the back surface of the valve body (15) compared with the 3rd aspect, the temperature-responsive valve of this 4th aspect is against temperature change. Thus, the operation reverse to that of the first mode valve is performed.

  As shown in FIGS. 7 and 8, the fifth aspect of the present invention is a flow path switching valve having one inflow port and two outflow ports, and a groove serving as an inflow side flow channel (1) on the surface. And a plate-like first member (22) having a groove serving as a first outflow channel (21), and a film-like shape in which a portion to be a tongue piece (5) is formed as a portion surrounded by a notch (4) The second member (6), the film-like third member (23) provided with a through-hole serving as the valve chamber (2), the valve chamber (2) and the second outflow side flow path (24) communicate with each other. A film-like fourth member (26) provided with a communication hole (25) and a plate-like fifth member (27) having a groove serving as a second outflow channel (24) on the surface are laminated. The third member side (23) of the tongue (5) of the second member (6) is coated with a temperature-responsive gel (9).

  One end (left side in FIG. 8) of the inflow channel (1) of the first member (22) is the second member (6), the third member (23), the fourth member (26), and the fifth member. (27) is opened to the outside of the temperature-responsive valve through the communication hole (10) provided as the inlet (11), and the other end (right side in FIG. 8) is provided around the valve body (5). It is formed up to the position where it communicates with the notch (4). One end (left side in FIG. 8) of the first outflow side flow path (21) provided in the first member (22) is overlapped with the valve body (15) from the base side of the valve body (15). It is formed to the center part of the body (15), and the part where the valve body (15) and the first member (22) are in contact functions as the valve seat (28) on the first outflow side. The other end (right side in FIG. 8) of the first outflow side channel (21) is opened in the second member (6), the third member (23), the fourth member (26), and the fifth member (27). It opens to the outside of this temperature-responsive valve through the formed communication hole (31) and serves as a first outlet (32).

  The through hole (12) of the third member (23) is formed in a size that allows the valve body (15) to enter and serves as a valve chamber (2). The hole (25) provided in the fourth member (26) is smaller than the valve body (15) and is provided at a position closed by the valve body (15). The valve body (15) and the fourth member ( 26) The contact portion with the surface functions as a valve seat (29) on the second outflow side. One end (left side in FIG. 8) of the second outflow channel (24) provided in the fourth member (26) continues to the second outflow side valve seat (33) of the fourth member (26). The other end (right side in FIG. 8) of the second outflow side channel (24) is connected to the communication hole (25), and this temperature response is made through the communication hole (33) opened in the fifth member (27). The second outlet (34) is opened outside the control valve.

  In the fifth aspect, each member may be composed of a plurality of members, as in the first aspect. For example, the first member (22) is a joined body of a film-like or plate-like member (22b) having a through groove and another member (22a), like the first member (3) in the first embodiment. May be.

  When the temperature-responsive gel has an LCST type gel-solid transition temperature, the temperature-responsive valve according to the fifth aspect is expanded by expansion of the temperature-responsive gel (9) at a temperature lower than the vicinity of the transition temperature. The body (15) generates a force that warps downward in FIG. 8, closes the valve seat (28) on the first outflow side, and shuts off the inflow side channel (1) and the first outflow side channel (21). In addition, the valve body (15) is separated from the second outflow side valve seat (29), and the inflow side flow path (1) and the second outflow side flow path (24) are connected.

  On the other hand, the valve body (15) warps upward in FIG. 8 due to the shrinkage of the temperature-responsive gel (9) on the higher temperature side than the vicinity of the transition temperature, and moves away from the valve seat (28) on the first outflow side. The flow path (1) and the first outflow side flow path (21) communicate with each other, and enter the valve chamber (2) to press the second outflow side valve seat (29) to thereby connect the inflow side flow path (1) and the first flow path. 2. Shut off the outflow channel (24). When the temperature-responsive gel has a UCST type gel-solid transition temperature, the relationship between the temperature and the operation is reversed.

  In the above description, the inflow side and the outflow side are provided for the sake of convenience. However, the inflow side and the outflow side in the above description are used in opposite directions, and two inflow ports and one outflow port are used. It may be used as a flow path switching valve having

  Controls such as opening and closing of the temperature responsive valve, flow path switching, and flow rate adjustment of the present invention can be performed by adjusting the temperature of at least the valve body portion of the temperature responsive valve. The temperature adjustment method and the temperature adjustment mechanism to be used are arbitrary. For example, heating by an electric heater incorporated in a temperature responsive valve, heating or cooling by an incorporated heat medium passage or refrigerant passage, incorporated or contacted Examples thereof include heating and cooling by a Peltier element, heating and cooling by contact with a temperature-adjusted solid, liquid, or gas, heating by an electromagnetic wave such as a laser beam, infrared rays, and microwaves, and heating by an ultrasonic wave. In the present invention, the temperature control region may be the entire microfluidic device in which the temperature responsive valve is incorporated, as long as other parts can be used. The temperature adjustment mechanism may be incorporated in the temperature responsive valve of the present invention or may be an external mechanism, but is provided in a housing that holds the microfluidic device in which the temperature responsive valve is incorporated. It is preferable that the microfluidic device portion can be replaced and used.

  For example, when this temperature responsive valve is used as an automatic flow path switching valve of an adsorption / desorption separation device, the entire microfluidic device in which this temperature responsive valve is incorporated is a temperature controlled solid, A method of contacting with a liquid or gas is preferred. In addition, when a plurality of temperature-responsive valves are incorporated in one microfluidic device and controlled independently, a method of contacting a temperature-controlled solid in the vicinity of each valve chamber or a method using a Peltier element is simple. It is preferable.

  The temperature-responsive valve of the present invention can open and close a minute flow path and adjust the flow rate with a simple structure. The temperature-responsive valve of the present invention requires an independent liquid pump for each microfluidic device or for each independent flow path system incorporated in one microfluidic device when used for reaction, analysis, inspection, etc. However, since the stock solution is supplied at a common pressure and the flow rate of each device can be adjusted and distributed / blocked by this valve, it is easy to process a large number simultaneously and in parallel, and work efficiency can be improved.

In addition, the temperature responsive valve of the present invention adjusts the flow rate of each flow path while supplying a stock solution at a common pressure even in applications where multiple fluids flow through a single microfluidic device such as mixing, reaction, extraction, and filtration. The device can be simplified.
Furthermore, when the flow path switching valve is constituted by the temperature responsive valve of the present invention, it can be widely used for general applications of the flow path switching valve in the microfluidic device such as sample injection of a micro liquid chromatograph.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example and a comparative example, this invention is not limited to the range of these Examples. In the following examples, “part” represents “part by mass” unless otherwise specified.

[Energy beam irradiation equipment]
A light source unit for a multi-light 200 type exposure apparatus manufactured by USHIO INC., In which a 200w metal halide lamp was incorporated, was used. The ultraviolet intensity is 50 mw / cm 2.

[Preparation of energy beam curable composition]
[Composition (x-1)]
60 parts of a trifunctional urethane acrylate oligomer having an average molecular weight of about 2000 (“Unidic V-4263” manufactured by Dainippon Ink & Chemicals, Inc.) as a cross-linkable polymerizable compound, 1,6-hexanediol diacrylate (Daiichi Kogyo Seiyaku) 20 parts of “New Frontier HDDA” manufactured by Co., Ltd., 20 parts of nonylphenoxypolyethylene glycol (n = 17) acrylate (“N-177E” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 1-hydroxy as an ultraviolet polymerization initiator 5 parts of cyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Geigy Inc .; photopolymerization initiator) and 2,4-diphenyl-4-methyl-1-pentene (manufactured by Kanto Chemical Co., Inc .; polymerization retarder) as a polymerization retarder ) Prepare an energy ray curable composition (x-1) by uniformly mixing 0.1 parts. It was.

  The ultraviolet ray cured film of the present energy beam curable composition (x-1) has a tensile elastic modulus of about 580 MPa and an elongation at break of about 7.3%.

[Preparation of temperature-responsive gel material]
[Porous gel material (y-1)]
95 parts of N-isopropylacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.) as a temperature-sensitive monomer, 5 parts of a trifunctional urethane acrylate oligomer having an average molecular weight of about 2000 as a crosslinking polymerizable monomer, and a photopolymerization initiator 5 parts of the above 1-hydroxycyclohexyl phenyl ketone, 25 parts of polyvinylpyrrolidone having a molecular weight of 40,000 (manufactured by Wako Pure Chemical Industries, Ltd.) as a pore-forming agent, and 50 parts of crosslinked polyvinylpyrrolidone powder (manufactured by Hanai Chemical Co., Ltd.), 110 parts of N, N-dimethylacetamide (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed to prepare a gel material (y-1).

  Poly-N-isopropylacrylamide aqueous gel is known to have an LCST-type gel-solid transition temperature around 32 to 37 degrees.

[Example 1]
In this example, the temperature responsive valve of the first aspect will be described in more detail.
[Production of temperature-responsive valve]
<Third member>
As shown in FIGS. 1 and 2, the active energy ray-curable resin composition (x-1) is applied to an acrylic plate (8a) having a size of 75 mm × 25 mm × 1 mm, and is passed through a photomask. (7) Irradiate ultraviolet rays to portions other than the portion to be formed, and wash and remove the uncured resin composition of the non-irradiated portion with a 50% aqueous ethanol solution, thereby curing the acrylic plate (8a) and the cured resin composition (x -1) A third member (8) which is a laminated fixed body of a cured film (8b) and has a groove (7) serving as an outflow channel (7) as a through groove (defect) of the cured film (8b). )created. Thereafter, a hole was drilled at the end of the groove (7) to be the outflow side channel (7) of the third member to form a communication hole (13) and an outlet (14).

<Second member and valve body>
Using a polypropylene sheet having a thickness of 60 μm as a temporary support (not shown), applying the active energy ray-curable resin composition (x-1) thereto, and forming a notch (4) through a photomask Except for the part other than the active energy ray-curable resin composition (x-1), the irradiation part is semi-cured by irradiating ultraviolet rays by an amount insufficient for complete curing, and the uncured resin of the non-irradiated part The composition was washed and removed with a 50% aqueous ethanol solution to form a second member (6) having a notch (4) and a portion to be a tongue piece (5) surrounded by the cutout (4). As shown in FIG. 2 (a), this is aligned and laminated on the third member (8), and the second member (6) is cured by irradiating with ultraviolet rays. Joined.

  Thereafter, the temporary support (not shown) is peeled off, the porous temperature-responsive gel material (y-2) is applied to the tongue piece (5) of the second member (6), and the valve body (5 ) Were irradiated with ultraviolet rays, coated with a temperature-responsive gel (9), and thoroughly washed with water to obtain a valve body (15).

<First member>
The active energy ray-curable resin composition (x-1) is applied to the same temporary support (not shown) as used for the production of the second member (6) and is insufficient for complete curing. The irradiated part was semi-cured by irradiating ultraviolet rays in an amount to form a member (3a).

  Next, the active energy ray-curable resin composition (x-1) is further applied thereon, and the ultraviolet rays are completely applied to the portions other than the portion that becomes the inflow side flow path (1) and the valve chamber (2) through the photomask. By irradiating only an insufficient amount for curing, the irradiated part is semi-cured, and the uncured resin composition of the non-irradiated part is washed and removed with a 50% aqueous ethanol solution to form the inflow side flow path (1). A member (3b) having a groove (1) and a recess (valve chamber 2) connected thereto was formed and simultaneously joined to the member (3a) to form a first member (3).

  As shown in FIGS. 2 (a) and 2 (b), these are aligned and laminated on the joined body of the second member (6) and the third member (8), and irradiated with ultraviolet rays to irradiate the third member (8 ) Is cured and simultaneously joined to the second member (6) and the third member (8), and then a hole is drilled to a depth communicating with the inflow channel (1) from the third member side. A hole (10) and an inlet (11) were formed to produce a temperature responsive valve.

[Dimensions of each part]
The produced temperature-responsive valve has a plate shape of length 75 mm × width 25 mm × thickness 1.45 mm, the first member (3) is 300 μm thick, the second member (6) is 50 μm thick, and the third member. Is 1100 μm thick, the inflow channel (1) is 300 μm wide, 20 mm long, 200 μm deep, the valve chamber (2) is 6 mm wide, 5 mm long, 200 μm deep, the tongue piece (5) is 5 mm wide, Length 4mm, thickness 50μm, notch (4) width 200μm, temperature-responsive gel (9) width 5mm, length 4mm, thickness 100μm, valve element (15) width 5mm, length 4mm, thickness The outlet side flow path (7) has a width of 300 μm, a length of 25 mm, a depth of 100 μm, and the connecting holes (10) and (13) both have a diameter of 500 μm.

[Use test]
A fitting (not shown) was bonded to the inlet (11) of the produced temperature-responsive valve, and connected to a glass tube (not shown) having an inner diameter of 10 mm via a soft vinyl chloride tube (not shown). When colored water is put up with the glass tube standing, pressure of 300 mm water column is applied to the inlet (11), and the temperature responsive valve is placed on the temperature control plate adjusted to 45 ° C, the colored water flows through the flow path. Then flowed out of the outlet (14). When the temperature-responsive valve was placed on a temperature control plate adjusted to 25 degrees with the colored water flowing, the colored water flow was cut off after about 3 seconds. Next, when the temperature responsive valve was placed again on the temperature control plate adjusted to 45 ° C., the colored water again flowed after 2 seconds.

[Example 2]
In this example, the temperature responsive valve of the second aspect will be described in more detail.
[Production of temperature-responsive valve]
<Third member>
In the same manner as in Example 1, the same third member (7) as in Example 1 was produced.

<Second member>
<Second member and valve body>
Using a polypropylene sheet having a thickness of 60 μm as a temporary support (not shown), applying the active energy ray-curable resin composition (x-1) thereto, and forming a notch (4) through a photomask Except for the part that is not sufficiently cured to irradiate with ultraviolet rays, the irradiated part is semi-cured, and the uncured resin composition of the non-irradiated part is washed away with 50% aqueous ethanol to remove the notched part. A member (6a) having (4) and a tongue piece (5) surrounded thereby was formed.

  The active energy ray-curable resin composition (x-1) is applied on the member (6a), and is completely cured to a portion other than the portion formed of the notch (4) and the valve body (5) through a photomask. Insufficient amount of ultraviolet light is irradiated to semi-cure the irradiated part, and the uncured resin composition of the non-irradiated part is washed and removed with a 50% aqueous ethanol solution to remove the member (6b) from the member (6a). It formed in the shape joined on the top and was set as the 2nd member (6).

  Next, the porous temperature-responsive gel material (y-2) is applied to the tongue piece (5) of the member (6a) by the same thickness as that of the member (6b), and the portion to be the valve body (5) is irradiated with ultraviolet rays. Then, the temperature-responsive gel (9) was coated and sufficiently washed with water to obtain a valve body (5). As shown in FIG. 3 (a), this is aligned and laminated on the third member (8), and the second member (6) is cured by irradiating with ultraviolet rays. Joined. Thereafter, the temporary support (not shown) was peeled off from the second member (6).

<First member>
In exactly the same manner as in Example 1, the same first member (7) as in Example 1 was joined to the third member (7) -second member (6) assembly, and the temperature-responsive valve of the second mode was obtained. Produced.

[Dimensions of each part]
The manufactured temperature-responsive valve has the members (6a) and (6b) both having a thickness of 50 μm and the second member (6) having a thickness of 100 μm, and the temperature-responsive gel (9) having a thickness of 50 μm. The same as in Example 1 except that the thickness of the entire plate-like valve is 1.5 mm. .

[Use test]
When the test similar to Example 1 was done, colored water flowed through the flow path at 25 degreeC, and flowed out from the outflow port (14). When the temperature-responsive valve was placed on a temperature control plate adjusted to 45 ° C. while the colored water was flowing, the colored water flow was cut off after about 3 seconds. Next, when the temperature responsive valve was placed on the temperature control plate adjusted to 25 degrees, the colored water again flowed after 5 seconds.

It is an assembly schematic diagram of the temperature-responsive valve of the first aspect of the present invention. (A) A schematic plan view of the temperature-responsive valve according to the first aspect of the present invention, (b) a side cross-section in a state where the valve body is urged to warp downward in section A of (b) above. Schematic diagram, (c) A side cross-sectional schematic diagram of the state in which the valve body is warped upward in part A of (b) above. (A) a schematic plan view of the temperature-responsive valve according to the first aspect of the present invention, (b) a schematic side sectional view of the valve body warped downward in section B of (b) above, (c) above It is a side cross-sectional schematic diagram of the state which is energizing so that the valve body may warp upwards in the B section of (A). It is an assembly schematic diagram of the temperature-responsive valve of the third aspect of the present invention. (A) A schematic plan view of the temperature-responsive valve according to the third aspect of the present invention, (b) a cross-sectional side view in a state in which the valve body is biased to warp downward in part C of (b) above. Schematic view, (c) A side cross-sectional schematic view of the state in which the valve body is warped upward in section C of (b) above. (A) A schematic plan view of a temperature-responsive valve according to the fourth aspect of the present invention, (b) a cross-sectional side view in a state where the valve body is biased to warp downward in the D part of (b) above. Schematic diagram, (C) A side cross-sectional schematic diagram showing a state in which the valve body is warped upward in D section of (A) above. It is an assembly schematic diagram of the temperature-responsive valve according to the fifth aspect of the present invention. (B) a schematic plan view of the vicinity of the valve body of the temperature-responsive valve of the fifth aspect of the present invention; (b) the valve body in section E of (b) above is biased to warp downward. FIG. 4 is a side cross-sectional schematic diagram of a state, (c) a side cross-sectional schematic diagram of a state in which the valve body is warped upward in the E portion of (a) above.

Explanation of symbols

1: Inflow side channel, groove 2: Valve chamber 3: First member in the first and second modes 4: Notch portion 5: Tongue piece 6: Second member 7: Outflow side channel 8: First mode and 3rd member in 2nd aspect 9: Temperature-responsive gel 10: Communication hole 11: Inflow port 12: Valve seat 13: Communication hole 14: Outflow port 15: Valve body 16: 1st in 3rd aspect and 4th aspect Member 17: Third member 21 in the third aspect and the fourth aspect 21: First outflow side flow path 22: First member 23 in the fifth aspect: Third member 24 in the fifth aspect 24: Second outflow side flow path 25 : Communication hole 26: fourth member 27 in the fifth aspect 27: fifth member 28 in the fifth aspect 28: first outlet valve seat 29: second outlet valve seat 31: communication hole 32: first outlet 33 : Communication hole 34: Second outlet

Claims (10)

A valve composed of a microchannel and a valve body that opens, closes, switches, or controls the flow rate of the microchannel disposed in the microchannel, and the valve body is a temperature-responsive gel having a gel-solid transition temperature. A temperature responsive valve comprising a joined body with a flexible member and deforming due to a temperature change to open, close, switch or control a flow rate of a fine flow path. The said valve body consists of a joined body of the tongue piece part provided in the film-like flexible member, and the temperature-responsive gel laminated | stacked on this tongue piece part. Temperature responsive valve. A film-like flexible member having a valve body comprising a tongue piece provided on a film-like flexible member and a temperature-responsive gel in which a temperature-responsive gel is laminated on the tongue piece. A valve layer comprising:
It consists of two flow path layers having grooves or through holes that make up the fine flow path,
3. The multi-layer structure according to claim 2, wherein the two flow path layers have a multilayer structure in which the valve body layers are sandwiched so that the grooves or through holes of the two flow path layers are communicated and separated by deformation of the valve body. Temperature responsive valve. The fine channel has a trifurcated branch channel, and the valve element closes one of the regular trident branch channels and opens the one channel due to temperature change. The temperature responsive valve according to claim 1, wherein the other one flow path is closed. The temperature-responsive valve according to any one of claims 1 to 4, wherein the temperature-responsive gel is a gel made of a cured product of an active energy ray-curable resin composition. The temperature-responsive valve according to any one of claims 1 to 5, wherein the temperature-responsive gel is a porous body in a solid state. It is a manufacturing method of the temperature responsive valve according to claim 1,
A temperature-responsive gel is bonded to at least a portion of the film-like flexible member formed with the valve body, and the valve body is formed with a notched portion penetrating the front and back for forming a tongue piece portion at the joint portion. Forming a valve layer having
The valve body layer is sandwiched between two flow path layers having grooves or through-holes constituting a fine flow path so that the grooves or through-holes of the two flow path layers are communicated and isolated by deformation of the valve body. And a temperature-responsive valve manufacturing method. An active energy ray-curable temperature-responsive gel-forming composition is applied to a range in which the temperature-responsive gel is bonded to the film-like flexible member including the valve body, and active energy ray irradiation is performed. The method for producing a temperature responsive valve according to claim 7, wherein a temperature responsive gel is formed by bonding to a film-like flexible member. It is a manufacturing method of the temperature responsive valve according to claim 1,
An active energy ray-curable resin composition is applied onto a support, and the active energy rays are irradiated to portions other than the cut-out portions penetrating the front and back for forming the tongue piece portion. Forming a sex member,
The film-like flexible member is coated with an active energy ray-curable temperature-responsive gel-forming composition and applied to a portion other than the portion formed as a notch that penetrates the front and back surfaces for forming the tongue portion. After irradiating the active energy ray, by removing the uncured component of the non-irradiated part, the valve body layer having the valve body is formed,
The valve body layer is sandwiched between two flow path layers having grooves or through-holes constituting a fine flow path so that the grooves or through-holes of the two flow path layers are communicated and isolated by deformation of the valve body. And a temperature-responsive valve manufacturing method. The method for producing a temperature-responsive valve according to claim 8 or 9, wherein the active energy ray-curable temperature-responsive gel-forming composition contains a pore-forming agent.

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