JP2012072007A - Gas generating agent, and micropump - Google Patents

Abstract

A gas generating agent capable of improving the output of a micropump and a micropump having a high output are provided.
A gas generating agent contains an aliphatic polyether having an azidomethyl group and a hydroxyl group, and a binder.
[Selection] Figure 1

Description

  The present invention relates to a gas generating agent used in a microfluidic device and a micropump using the same.

  In recent years, analyzers using microfluidic devices have come to be used as analyzers that are small and have excellent portability. In the analysis apparatus using the microfluidic device, the sample can be fed, diluted, analyzed, and the like in the microchannel.

  For example, Patent Document 1 below has a substrate in which a gas generation chamber connected to a microchannel is defined, and a gas generation agent containing an azo compound and a binder resin is accommodated in the gas generation chamber. Micropumps have been proposed. In this micro pump, gas is generated from the gas generating agent by supplying thermal energy to the gas generating agent, and the pump function is manifested by supplying the gas to the micro flow path.

  In Patent Document 2 below, a pumping function is provided to a microfluidic device by providing a gas generation layer so as to cover the main surface of the substrate on which a microchannel opening on one main surface is formed. Is described. Patent Document 2 exemplifies various azo compounds and azide compounds as gas generating agents to be contained in the gas generating layer.

JP 2009-84128 A JP 2010-107515 A

  In recent years, there have been increasing demands for forming a multistage dilution series in a microfluidic device, and for measuring a plurality of samples with one microfluidic device. In order to satisfy such a demand, the structure of the microfluidic device is becoming more and more complicated. As the structure of the microfluidic device becomes complicated, the output required for the micropump increases and the driving time increases.

  The present invention has been made in view of such a point, and an object of the present invention is to provide a gas generating agent capable of improving the output of the micropump and extending its driving time and a micropump having a high output. is there.

  As a result of earnest research, the present inventors can improve the output of the micropump by using a gas generating agent containing an aliphatic polyether having an azidomethyl group and a hydroxyl group and a binder among various azo compounds and azide compounds. I found. As a result, the present inventors came to make this invention.

  That is, the gas generating agent according to the present invention relates to a gas generating agent used in a micropump for supplying gas to a microchannel of a microfluidic device. The gas generating agent according to the present invention contains an aliphatic polyether having an azidomethyl group and a hydroxyl group and a binder.

  In the present invention, “microfluidic device” refers to a device having a microchannel. The “microchannel” refers to a channel formed in a shape and dimension that develops a so-called micro effect in the liquid flowing through the microchannel. Specifically, the term “microchannel” means that the liquid flowing through a microchannel is strongly affected by surface tension and capillary action, and has a different shape from that of a liquid flowing through a normal channel. It refers to the flow path that is formed.

  On the specific situation with the gas generating agent which concerns on this invention, content of aliphatic polyether exists in the range of 10 weight part-1000 weight part with respect to 100 weight part of binders.

  In another specific aspect of the gas generating agent according to the present invention, the aliphatic polyether contains at least one of compounds represented by the following formulas (1), (2), and (3).

  In another specific aspect of the gas generant according to the present invention, the binder is an acrylic resin.

  In still another specific aspect of the gas generating agent according to the present invention, the gas generating agent further includes 0.01 to 50 parts by weight of a photosensitizer with respect to 100 parts by weight of the aliphatic polyether.

  The micropump according to the present invention includes a substrate on which a microchannel is formed, and a gas generating material that supplies gas to the microchannel. The gas generating material includes a gas generating agent containing an aliphatic polyether having an azidomethyl group and a hydroxyl group, and a binder. That is, in the micropump according to the present invention, the gas generating material includes the gas generating agent according to the present invention. Therefore, the micropump according to the present invention has a high output and a long driving time.

  In a specific aspect of the micropump according to the present invention, the microchannel is open on the surface of the substrate, and the gas generating material is placed on the surface of the substrate so as to cover the opening of the microchannel. Is provided. In this case, it is not necessary to provide a gas generation chamber in the substrate. Accordingly, the substrate can be reduced in size and the substrate can be easily manufactured.

  In another specific aspect of the micropump according to the present invention, the base material further includes a gas generation chamber in which the microchannel is opened, and the gas generation material is disposed in the gas generation chamber. . According to this configuration, the gas generated from the gas generating material can be efficiently guided to the microchannel.

  The gas generating agent according to the present invention contains an aliphatic polyether having an azidomethyl group and a hydroxyl group. Therefore, by using the gas generating agent according to the present invention, it is possible to increase the output of the micropump and increase the driving time.

1 is a schematic cross-sectional view of a micropump according to a first embodiment. It is a schematic sectional drawing of the micropump which concerns on 2nd Embodiment. It is a schematic sectional drawing of the micropump used in order to evaluate the output of a micropump in an Example and a comparative example.

  Hereinafter, a preferred embodiment in which the present invention is implemented will be described using the micropumps 1 and 2 shown in FIGS. 1 and 2 as examples. However, the micropumps 1 and 2 are merely examples. The present invention is not limited to the micropumps 1 and 2 at all.

(First embodiment)
FIG. 1 is a schematic cross-sectional view of the micropump according to the first embodiment.

  A micropump 1 shown in FIG. 1 is a pump for supplying gas to a microchannel of a microfluidic device. The micropump 1 is used in a state where the microchannel 11 of the micropump 1 is connected to the microchannel of the microfluidic device. The micropump 1 may be formed integrally with the microfluidic device or may be formed separately. When the micropump 1 is formed separately from the microfluidic device, the micropump 1 and the microfluidic device may be used by being bonded together by connecting both microchannels, or connecting a pipe or the like You may connect and use both microchannels using a member.

  The micropump 1 includes a base material 10. As long as the base material 10 has low reactivity with the liquid or gas flowing through the microchannel 11 and has sufficient mechanical durability against the pressure applied when the liquid flows through the microchannel 11. In particular, it is not limited. The base material 10 can be formed of, for example, resin, glass, ceramic, or the like. Examples of the resin preferably used for forming the substrate 10 include an organic siloxane compound and a polymethacrylate resin. Specific examples of the organic siloxane compound include polydimethylsiloxane (PDMS) and polymethylhydrogen siloxane.

  A microchannel 11 is formed in the base material 10. The microchannel 11 is open to the surface 10 a of the substrate 10.

  A gas generating layer 12 as a gas generating material is formed on the surface 10a. The gas generation layer 12 covers the opening 11 a of the microchannel 11. For this reason, the gas generated from the gas generation layer 12 when an external stimulus such as light or heat is applied to the gas generation layer 12 is supplied into the microchannel 11 from the opening 11a.

  The gas generation layer 12 is preferably provided so that the gas generated in the gas generation layer 12 is suitably supplied to the microchannel 11. Therefore, the gas generating layer 12 is preferably adhered or bonded to the substrate 10. In this case, the gas generating layer 12 and the substrate 10 may be adhered or adhered using an adhesive or an adhesive, or the gas generating layer 12 and the substrate 10 may be adhered or adhered to at least one surface. The gas generating layer 12 and the base material 10 may be directly adhered or bonded by providing the function.

  The thickness of the gas generation layer 12 is not particularly limited. The thickness of the gas generation layer 12 can be about 10-200 micrometers, for example.

  The surface of the gas generation layer 12 opposite to the substrate 10 is covered with a gas barrier layer 13. The gas barrier layer 13 is a layer that suppresses the gas generated in the gas generation layer 12 from flowing out to the side opposite to the substrate 10 and efficiently supplies the gas to the microchannel 11 side. For this reason, it is preferable that the gas barrier layer 13 has a low permeability of the gas generated in the gas generation layer 12.

  Specifically, the gas barrier layer 13 is made of, for example, polyacryl, polyolefin, polycarbonate, vinyl chloride resin, ABS resin, polyethylene terephthalate (PET) resin, nylon resin, urethane resin, polyimide resin, and glass. Is preferred.

  In addition, the thickness of the gas barrier layer 13 is preferably, for example, 25 μm to 100 μm, and more preferably 50 μm to 100 μm.

  In the present embodiment, the gas generating layer 12 as the gas generating material contains a gas generating agent. In the present embodiment, the gas generating agent is a photoresponsive gas generating agent that generates gas when irradiated with light.

  The gas generating agent includes a binder resin, an aliphatic polyether having an azidomethyl group and a hydroxyl group, and a photosensitizer. Thus, since the gas generating agent of the present embodiment includes an aliphatic polyether having an azidomethyl group and a hydroxyl group having a high nitrogen content, the micropump 1 has a high output and a long driving time.

  Examples of the aliphatic polyether having an azidomethyl group and a hydroxyl group that are suitably used include aliphatic polyethers represented by the following formula (1), formula (2), and formula (3). Two or more of the aliphatic polyethers represented by formula (1), formula (2), and formula (3) may be mixed and used.

  Among the aliphatic polyethers represented by the above formula (1), formula (2), and formula (3), the aliphatic polyether represented by formula (3) is more preferably used. Output can be further increased.

  Further, the aliphatic polyether having an azidomethyl group and a hydroxyl group may be a compound containing two or more structures represented by formula (4) or formula (5).

  In the compound represented by the formula (1), for example, polyepichlorohydrin (PECH) (Epichromer H, Daiso Corporation) is substituted with azide with sodium azide (190-14901, Wako Pure Chemical Industries, Ltd.). Can be synthesized.

  Examples of the compound represented by the formula (2) include 3,3-bischloromethyloxetane (B1395, Tokyo Chemical Industry Co., Ltd.), di-methylformamide (20673, Wako Pure Chemical Industries, Ltd.), di- 3,3-bis obtained by reacting with sodium azide (190-14901, Wako Pure Chemical Industries, Ltd.) under a solvent such as methyl sulfoxide (042-17095, Wako Pure Chemical Industries, Ltd.) Azidomethyloxetane can be synthesized by ring-opening polymerization.

  The compound represented by the formula (3) can be synthesized, for example, as follows. That is, after dissolving the reaction catalyst in diglycerin, epichlorohydrin is subjected to addition reaction to produce a terminal hydroxyl group-containing aliphatic polyether having a chloromethyl group in the side chain. Next, this polyether and sodium azide can be synthesized by reacting them in dimethylformamide (see, for example, Japanese Patent Publication No. 7-508).

  The content of the aliphatic polyether having an azidomethyl group and a hydroxyl group in the gas generating agent is not particularly limited, but is preferably 10 to 1000 parts by weight, for example, 20 parts by weight with respect to 100 parts by weight of the binder. It is more preferably ~ 800 parts by weight, further preferably 50 parts by weight to 400 parts by weight, still more preferably 30 parts by weight to 90 parts by weight, and 40 parts by weight to 80 parts by weight. Particularly preferred.

  If the content of the aliphatic polyether having an azidomethyl group and a hydroxyl group is too small, the gas generation amount becomes too small, and the output of the micropump 1 may not be sufficiently increased. On the other hand, if the content of the aliphatic polyether having an azidomethyl group and a hydroxyl group is too large, the rigidity of the gas generating layer 12 becomes too low, or the adhesive force of the gas generating layer 12 to the base material 10 becomes too low. There is. In particular, in this embodiment, since the gas generation layer 12 contains the binder resin as described above, the adhesive force between the gas generation layer 12 and the substrate 10 can be further increased.

  Specific examples of the binder preferably used include polymer materials such as poly (meth) acrylate, polyester, polyethylene, polypropylene, polystyrene, polyether, polyurethane, polycarbonate, polyamide, and polyimide. Of these, poly (meth) acrylate is preferred because the gas generation efficiency is further enhanced.

  The binder content in the gas generating agent is not particularly limited, but is preferably in the range of 10 wt% to 70 wt%, for example, and more preferably in the range of 20 wt% to 60 wt%. preferable. If the binder content is too small, the rigidity of the gas generating layer 12 may be too low. On the other hand, when the content of the binder is too large, the content of the glycidyl azide polymer in the gas generating agent may be too small, and the gas generating ability of the gas generating layer 12 may be too low.

  The photosensitizer is not particularly limited as long as it is a compound that promotes the decomposition of the gas generating agent by transferring energy to the gas generating agent that generates gas when irradiated with light. Specific examples of the photosensitizer include, for example, thioxanthone, benzophenone, acetophenones, Michler's ketone, benzyl, benzoin, benzoin ether, benzyldimethyl ketal, benzoylbenzate, α-acyloxime ester, tetramethylthiuram monosulfide, aliphatic Amines, amines containing aromatic groups, piperidine like nitrogen part of the ring system, allylthiourea, o-tolylthiourea, sodium diethyldithiophosphate, soluble sulfinic acid soluble salts, N, N -Disubstituted p-aminobenzonitrile compounds, tri-n-butylphosphine, N-nitrosohydroxylamine derivatives, oxazolidine compounds, tetrahydro-1,3-oxazine compounds, formaldehyde or acetaldehyde and di Condensates of Min, anthracene and derivatives thereof, xanthine, N- phenylglycine, phthalocyanine, naphthocyanine, cyanine dyes porphyrin and derivatives thereof such as thiocyanine like. These photosensitizers may be used independently and 2 or more types may be used together.

  The blending ratio of the photosensitizer is not particularly limited as long as the photosensitizing action can be obtained. For example, 100 parts by weight of the aliphatic polyether having an azidomethyl group and a hydroxyl group that generate gas when irradiated with light. The photosensitizer is preferably contained in the range of 0.01 to 50 parts by weight, more preferably 1 to 10 parts by weight. If the amount of photosensitizer is too small, sufficient sensitizing action tends to be difficult to obtain. If the amount of photosensitizer is too large, photodecomposition of the gas generating agent may be suppressed.

  The gas generating agent may further contain a crosslinking agent. By including a crosslinking agent in the gas generating agent, the shape stability of the gas generating layer 12 as the gas generating material can be improved. Specific examples of the crosslinking agent include isocyanate compounds.

(Second Embodiment)
FIG. 2 is a schematic cross-sectional view of the micropump according to the second embodiment.

  In the said 1st Embodiment, the example which provides the gas generation layer 12 on the surface 10a of the base material 10 as a gas generation material was demonstrated. However, the present invention is not limited to this configuration.

  For example, like the micropump 2 shown in FIG. 2, a gas generation chamber 14 in which the microchannel 11 is opened is formed inside the base material 10, and for example, a tablet-like gas is formed in the gas generation chamber 14. You may arrange | position the tablet 12a which is a generating material.

Example 1
An acrylic copolymer (weight average molecular weight 700,000) of 96.5 parts by weight of 2-ethylhexyl acrylate, 3 parts by weight of acrylic acid, and 0.5 parts by weight of 2-hydroxyethyl acrylate was produced. Next, 100 parts by weight of the acrylic copolymer, 200 parts by weight of ethyl acetate as a solvent, 3 parts by weight of an isocyanate compound (trade name Coronate L45 manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, an azidomethyl group and By mixing 100 parts by weight of GAP4006 (manufactured by NOF Corporation) as an aliphatic polyether having a hydroxyl group and 3.5 parts by weight of diethylthioxanthone (manufactured by Ciba Specialty Chemicals, DETX-S) as a photosensitizer. A generator was obtained.

  Next, a gas generating film composed of the PET film and the gas generating layer 12 is formed by applying a gas generating agent on a polyethylene terephthalate (PET) film having a thickness of 50 μm to which an anchor treatment has been applied, and drying. Produced. The thickness of the gas generation layer after drying was about 100 μm. In this embodiment, the PET film constitutes the gas barrier layer 13.

  Next, as shown in FIG. 3, since the gas generating film 17 has adhesiveness, the base material 10 in which the microchannels 11 that are open on both the main surfaces 10 a and 10 b are formed. A micropump was produced by pasting on the surface 10a using self-adhesive force.

  In the present embodiment, the base material 10 was formed from an acrylic plate. The cross-sectional shape of the microchannel 11 was a 0.5 mm square shape. The length of the microchannel 11 was 800 mm. The tip of the microchannel 11 was opened to the atmosphere.

(Comparative Example 1)
Other than using 40 parts by weight of 2,2′-azobis (N-butyl-2-methylpropionamide) (manufactured by Wako Pure Chemical Industries, Ltd., VAM110) instead of 100 parts by weight of the aliphatic polyether having an azidomethyl group and a hydroxyl group. Produced a gas generating film in the same manner as in Example 1 to produce a micropump.

(Comparative Example 2)
100 parts by weight of 2,2′-azobis (N-butyl-2-methylpropionamide), 100 parts by weight of an acrylic copolymer prepared in the same manner as in Example 1, 200 parts by weight of ethyl acetate, and isocyanate type An attempt was made to mix 3 parts by weight of a compound (manufactured by Nippon Polyurethane, trade name Coronate L45) and 3.5 parts by weight of diethylthioxanthone (manufactured by Ciba Specialty Chemicals, DETX-S). However, 2,2′-azobis (N-butyl-2-methylpropionamide) was not dissolved in the acrylic copolymer, and a gas generating film could not be obtained.

(Evaluation of micro pump output characteristics)
The outputs of the micropumps produced in Example 1 and Comparative Example 1 were evaluated in the following manner. First, 1 μl of water is injected into the microchannel 11 from the opening 11b, and then the opening 11b is sealed with a single-sided tape 16 comprising a 30 μm thick acrylic adhesive layer and a 30 μm thick polyethylene terephthalate substrate. did. In this state, UV light having a wavelength of 380 nm was irradiated using an LED, and the moving time and moving distance of the water droplet 15 were measured every 10 seconds. From the result, the moving speed of the water droplet 15 was calculated. Moreover, the movement time which can maintain 90% of the maximum value of movement speed was calculated as a stable time, and the movement time which can maintain 60% was calculated as duration. The results are shown in Table 1 below.

(Adhesive strength test)
The gas generating film produced in each of Example 1 and Comparative Example 1 was cut to a width of 25 mm and adhered to a clean surface of an acrylic resin plate with a 2 kg rubber roller. And according to JISZ0237, 180 degree peeling force in 25 degreeC was measured with the pulling speed of 300 m / min, and average adhesive force was computed. In addition, Shimadzu autograph (AG-IS) was used as a test apparatus. The results are shown in Table 1 below.

  From the results shown in Table 1 above, it can be seen that the use of an aliphatic polyether having an azidomethyl group and a hydroxyl group as a gas generating component can enhance the adhesive force between the base material and the gas generating material. It can also be seen that the maximum gas generation amount per unit time and the driving time can be increased.

DESCRIPTION OF SYMBOLS 1, 2 ... Micro pump 10 ... Base material 10a, 10b ... Main surface 11 of base material ... Micro flow path 11a, 11b ... Opening 12 ... Gas generation layer 12a ... Tablet 13 ... Gas barrier layer 14 ... Gas generation chamber 15 ... Water droplet 16 ... Seal 17 ... Gas generating film

Claims (8)

A gas generating agent used in a micropump for supplying gas to a microchannel of a microfluidic device,
A gas generating agent comprising an aliphatic polyether having an azidomethyl group and a hydroxyl group, and a binder.   The gas generating agent according to claim 1, wherein the content of the aliphatic polyether is in the range of 10 to 1000 parts by weight with respect to 100 parts by weight of the binder. The gas generating agent according to claim 1 or 2, comprising at least one of compounds represented by the following formulas (1), (2) and (3) as the aliphatic polyether.

  The gas generating agent according to claim 4, wherein the binder is an acrylic resin.   The gas generating agent according to any one of claims 1 to 4, further comprising 0.01 to 50 parts by weight of a photosensitizer with respect to 100 parts by weight of the aliphatic polyether. A substrate on which a microchannel is formed;
A gas generating material for supplying gas to the microchannel;
With
The gas generating material is a micropump including a gas generating agent containing an aliphatic polyether having an azidomethyl group and a hydroxyl group, and a binder. The microchannel is open on the surface of the substrate,
The micropump according to claim 6, wherein the gas generating material is provided on a surface of the base material so as to cover an opening of the microchannel. The base is further formed with a gas generation chamber in which the microchannel is open,
The micro pump according to claim 6, wherein the gas generating material is disposed in the gas generating chamber.

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