JP2000042402A - Liquid transport device and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the swelling of a base material by providing a non-porous liquid flow channel subjected to hydrophilizing treatment to be specified in its contact angle with water to the surface of the base material and preventing the hydrophilized part of the liquid flow channel from becoming a groove shape. SOLUTION: A non-porous liquid flow channel subjected to hydrophilizing treatment so that the surface of the part thereof to be made hydrophilic so as to become 45 deg. or less in its contact angle with water is made hydrophilic by copolymerizing a polymerizable compd. in a photopolymerizable compsn. and a part of a hydrophilic polymerizable compd. in a hydrophilic layer forming material, a harmful liquid flow channel and other part are provided to the surface of a base material in a demarcated state to form a hydrophobic part of which the contact angle with water is 60 deg. or higher. The hydrophilized part of the demarcated liquid flow channel is formed so that the depth thereof is 1/10 or less the width thereof or unevenness is not generated or a groove shape forming a projected part is not substantially formed. By this constitution, a liquid to be transported is prevented from overflowing the flow channel and can be stably transported.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a microreactor (microreactor); an integrated DNA analyzer; a microelectrophoresis apparatus; a microchromatography; for medical testing, biochemistry, environmental analysis, and biotechnology. More specifically, the present invention relates to a liquid transport device useful as a component such as a biosensor, etc., and more specifically, to transfer a liquid such as a reaction stock solution, a diluent, a reaction product solution, a test stock solution, a buffer solution, or a developing solution to a target site. Related to a liquid transport device.

[0002]

2. Description of the Related Art It is known that a hydrophilic porous film is adhered or formed on a glass or plastic substrate and used as a liquid flow path.

In the case of forming a fine liquid flow path, it is also known that a groove is formed in a plastic base material such as metal silicon, glass, or polymethyl methacrylate, and this is used as a liquid flow path. (Eg, analytical chemistry, such as R.M.M.Cormick,
1997, 69, 2626).

[0004]

The method of bonding or forming a hydrophilic porous film on a substrate and using it as a liquid flow path is a method in which the width of the flow path is several mm to several cm. Is a preferable method, but when the flow path width is as fine as 1 mm or less, there are drawbacks that the formation is difficult and the flow rate becomes extremely small.

On the other hand, a method of forming a thin groove in a substrate is limited to a method of low productivity such as etching when the substrate is made of an inorganic substance such as metallic silicon or glass. In addition, plastic substrates that are excellent in productivity and can be injection-molded are generally hydrophobic, and particularly in the case of aqueous solutions containing salts, they tend to become droplets due to the cohesive force, and the flow path width is reduced. It was difficult to stably flow in the groove as the diameter became smaller. In order to solve this disadvantage, it is conceivable to make only the inside of the groove hydrophilic. However, it was actually quite difficult to make only the inside of the narrow groove hydrophilic. When a hydrophilic polymer is used as the base material, problems such as a liquid flowing out to a portion other than the groove, a component of the hydrophilic polymer being eluted in an aqueous solution to be sent, and a swelling of the hydrophilic polymer have occurred. Was.

[0006] The problem to be solved by the present invention is that the liquid to be transported does not overflow out of the flow path or become droplets, and the base material constituting the liquid transport device does not swell, and It is an object of the present invention to provide a liquid transport device in which a material component does not elute into a liquid to be transported, which has high productivity and is inexpensive.

[0007]

Means for Solving the Problems As a result of diligent studies on a method for solving the above-mentioned problems, the present inventor has found that a non-porous liquid stream subjected to hydrophilization treatment is applied to the surface of a substrate made of a hydrophobic polymer. If a liquid path is formed on the surface of the substrate and the liquid flow path is formed in a planar shape, the liquid flow path is formed in a specific relationship between the contact angle of the substrate with water and the contact angle of the hydrophilic treatment portion with water. They have found that they function as flow channels, and have completed the present invention.

That is, in order to solve the above-mentioned problems, the present invention provides (I) a non-porous liquid flow path which has been hydrophilized on a surface of a substrate so that the contact angle with water is 45 ° or less. And (2) a liquid transport device having a hydrophobic part having a contact angle with water of 60 degrees or more that fractionates the harmful liquid flow path and the other part, wherein the part is subjected to a hydrophilic treatment. Is not substantially groove-shaped.

In order to solve the above-mentioned problems, the present invention provides a photopolymerizable composition (a ') containing (II) a hydrophobic polymerizable compound (a) and a photopolymerization initiator in an arbitrary shape. After shaping the obtained uncured excipient, excluding the portion to be hydrophilized, polymerizing and curing the portion other than the portion to be hydrophilized by irradiating an energy ray, and then polymerizing the hydrophilic polymerizable compound Irradiating them with a hydrophilic layer-forming material (b ') containing no photopolymerization initiator and irradiating them with an actinic ray, thereby polymerizing and curing the uncured portion of the excipient. At the interface between the uncured portion of the excipient and the hydrophilic layer-forming material (b '), the polymerizable compound (a) in the photopolymerizable composition (a') and the hydrophilic layer-forming material (b ') Copolymerization with a part of the hydrophilic polymerizable compound (b) in the A method for producing a liquid transport device for hydrophilizing a surface of a part, wherein a hydrophobic polymerizable compound (a) is polymerized and cured by an energy ray or an actinic ray used in the presence or absence of a polymerization initiator. It is possible and the hydrophilic polymerizable compound (b) can be polymerized by the actinic light used in the presence of a polymerization initiator,
In the absence of a polymerization initiator, a hydrophobic polymerizable compound (a), a hydrophilic polymerizable compound (b) and an actinic ray satisfying the condition that they are not polymerized by the actinic ray used are used. And a method for manufacturing a liquid transport device.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid transport device of the present invention comprises: (1) a non-porous liquid flow channel which has been subjected to hydrophilic treatment so that the contact angle with water is 45 ° or less; A) a liquid transport device having a hydrophobic part having a contact angle with water of 60 degrees or more, wherein the liquid flow path and the other part are fractionated.
The hydrophilized portion is not substantially groove-shaped.

That is, in the liquid transport device of the present invention, the hydrophilic portion and the hydrophobic portion are formed on the surface of the substrate having substantially no irregularities. Are formed to flow over a substantially non-grooved substrate surface. In the present invention, “not substantially groove-shaped” means that the depth of the hydrophilized portion is one width of the width of the portion.
/ 10 or less, no irregularities, or convex. In the liquid transport device of the present invention, the hydrophilization section does not need to be concave, but depending on the hydrophilization method, μ may be used.
m or less. Therefore, in the liquid transport of the present invention, even if the liquid flow path has such a dent due to the etching, the width of the liquid flow path may be as small as one.
If it is / 10 or less, it is not excluded.

The liquid flow path of the liquid transport device of the present invention may be convex with respect to the surface of the substrate. this is,
For example, it may occur when a liquid channel is formed by coating a hydrophilic polymer. In this case, the height of the liquid channel is not particularly limited, but the thickness is preferably not more than 1/3 of the width.

In the liquid transport device of the present invention, the liquid flows in contact with and over the liquid flow path. For example, as in the case where the flow path is formed of a porous material, the flow is thick. It does not flow through the road layer. When the liquid flows over the liquid flow path, the liquid flow path is substantially flat or convex, so that the liquid flows over the flow path while being raised on the surface of the base material.

In the liquid transport device of the present invention, the hydrophobic portion has a contact angle with water (hereinafter referred to as a “contact angle with water”).
Is sometimes referred to as “water contact angle”) is 60 degrees or more. The contact angle referred to in the present invention refers to a stationary angle. If the water contact angle is less than 60 degrees, overflow or bleeding of the liquid from the flow path is likely to occur, which is not preferable. The water contact angle of the hydrophobic portion also has a relationship with the water contact angle of the hydrophilized liquid flow path portion, but is generally preferably higher, preferably 75 ° or more, and more preferably 90 ° or more. It is even more preferred. The upper limit may be 180 degrees. However, if the contact angle of the hydrophobic portion with water is too high, it is often difficult to reduce the water contact angle of the portion subjected to the hydrophilic treatment.
0 degrees or less is preferable. Further, it is preferable that the difference in water contact angle between the hydrophobic portion and the hydrophilic portion serving as the liquid flow path is large.

The base material is not particularly limited as long as a liquid can flow thereon, and may be, for example, a polymer, glass, ceramic, metal, semiconductor, or the like. In addition, the shape is not particularly limited, and may take a shape according to the purpose of use. For example, a film shape (including a sheet shape), a plate shape, a coating film shape, a stick shape, a tubular shape, a cylindrical shape, and other complicated shapes Although it may be a molded product of any shape, it is preferably in the form of a film or a coating from the viewpoint of ease of molding. Further, the base material may be in a form integrated with another support. In this case, the material of the support is arbitrary, and may be, for example, plastic, polymer, glass, ceramic, metal, paper, cloth, nonwoven fabric, injection molded product, or the like. When the substrate is a coating film, it is used in a state of being integrated with the support. Further, after a plurality of liquid flow paths are formed on one base material, a plurality of devices can be cut out.

Although the dimensions of the liquid flow path are arbitrary depending on the purpose of use, the liquid transport device of the present invention is suitable as a small device, and the flow path width is preferably in the range of 3 μm to 10 mm, and more preferably in the range of 30 μm to 10 μm. A range of 1 mm is particularly preferred. The length of the liquid flow path is arbitrary and may be determined according to the purpose of use. Of course, the liquid flow path does not need to be straight,
Any shape may be used. Other functional parts connected to the liquid flow path, for example, a liquid holding unit such as a liquid reservoir or a reaction tank,
It can be formed with the same structure as the liquid channel in the present invention, and an inlet, an outlet, an electrophoresis column, an electrode, and other structures may be formed.

The method of transporting liquid in the liquid transport device of the present invention is not particularly limited.
For example, gravity potential, centrifugal force, cohesive force, surface tension, voltage, ultrasonic waves, and the like can be used. When a voltage is used as the driving force for transporting the liquid, electrodes are provided at both ends of the liquid flow path. The electrode can be formed of a conductive substance such as carbon, metal, or conductive polymer by any method such as vacuum evaporation, sputtering, printing, coating, bonding, and pressing.

One embodiment of the liquid transport device of the present invention is: (1) a substrate (A ') composed of a hydrophobic polymer (A) and having a contact angle with water of 60 ° or more; A liquid transport device having a non-porous liquid flow path on the surface of a material (A ′) that has been subjected to a hydrophilic treatment so that the contact angle with water is 45 ° or less.

The substrate (A ') constitutes the above-mentioned hydrophobic portion, and the water contact angle is the same as that described above for the hydrophobic portion of the liquid transport device of the present invention.

In the present invention, the water contact angle of the base material (A ') is a value measured using a molded product made of the polymer (A) and having a smooth surface, and the molded product is obtained by melt molding. Preferably, there is. The polymer that cannot be melt-molded may be a molded product having a smooth surface made of the polymer (A) with a film formed by a solvent casting method or on-site polymerization. Take the value measured on the surface.

As the substrate (A '), any material can be used, whether organic or inorganic, as long as it exhibits a water contact angle of 60 degrees or more, but is preferably a polymer having good moldability.
For example, it can be implemented by being composed of a hydrophobic polymer (A).

Examples of the polymer (A) include styrene polymers such as polystyrene, high-impact polystyrene, poly-α-methylstyrene, polystyrene / maleic acid copolymer, and polystyrene / acrylonitrile copolymer; Polysulfone-based polymers such as polyethersulfone; poly (meth) acrylate-based polymers such as polymethyl methacrylate and polyacrylonitrile; polycarbonate-based polymers;
Cellulose polymers such as cellulose acetate and methyl cellulose; polyurethane polymers; chlorine-containing polymers such as vinyl chloride and vinylidene chloride; polyamide polymers; polyimide polymers; polyolefin polymers such as polyethylene and polypropylene; fluorine-containing polymers such as polyvinylidene fluoride. Polyether or polythioether polymers such as polyphenylene oxide and polyphenylene sulfide; and polyester polymers such as polyethylene terephthalate and polyarylate. Of course, the polymer (A) may be a homopolymer or a copolymer. The polymer (A) may be a thermoplastic polymer or a thermosetting polymer, but is preferably a thermoplastic polymer or a photocurable crosslinked polymer having a high curing rate from the viewpoint of productivity.

As the polymer (A), those having a water contact angle of 60 ° or more are preferably used. However, even if the material has a water contact angle of less than 60 °, selection of the molding method and the base material (A ′) Any material that can make the water contact angle of the substrate (A ′) 60 degrees or more by water-repellent treatment of the surface and blending with a hydrophobic compound, even if the water contact angle is less than 60 degrees. Can be used. The substrate (A ') may be composed of a blend or an alloy, or may be a composite such as a laminate or a surface-repellent treated body. Further, additives such as a modifier, a colorant, and an inorganic substance may be added to the base material (A '). By adding a water repellent material as a modifier to the base material (A '), a polymer having a water contact angle of less than 60 degrees can also be used.

Examples of the modifier that can be added to the base material (A ') include silicone oil, a fluorinated hydrocarbon, and a fluororesin powder that function as a water repellent.

The coloring agent which can be added to the substrate (A ') includes any dye, pigment and fluorescent dye.

Examples of the inorganic substance which can be added to the base material (A ') include clay, calcium sulfate, calcium carbonate and the like.

The shape of the substrate (A ') of the present invention is not particularly limited, and may be a shape according to the purpose of use, for example, a film (including a sheet), a plate, a coating, a stick, a tube, or the like. Although it may be a cylindrical or other complicated shaped product, it is preferably a film or a coating from the viewpoint of ease of molding. Further, the base material (A ′) may be in a form integrated with another support or the like. In this case, the material of the support is arbitrary, and examples thereof include a polymer, glass, ceramic, metal, and semiconductor. The shape of the support is a film (sheet), plate, bar, paper, cloth, nonwoven fabric, Injection molded products are exemplified. When the substrate (A ') is a coating film formed by photo-curing, it is preferable that the substrate (A') is integrated with the support. In addition, it is also possible to form a plurality of devices by forming a plurality of liquid flow paths on one base material and then cutting them.

The liquid transport device of the present invention has a non-porous liquid channel formed on the surface of the substrate (A '), which has been subjected to a hydrophilization treatment so that the contact angle with water is 45 degrees or less. is there. The method of hydrophilizing the flow channel portion is arbitrary, and examples thereof include plasma treatment, plasma polymerization, corona discharge treatment, chemical modification of the surface, graft polymerization of a hydrophilic compound on the surface, and coating of a hydrophilic polymer. Among these hydrophilic treatment methods, corona discharge treatment and chemical modification of the surface with a hydrophilic compound are methods that do not substantially generate surface irregularities, but plasma treatment, sulfonation treatment, and nitration treatment are: Due to the etching of the surface, the hydrophilized portion may become concave with a depth of less than 1 μm. In the plasma polymerization, the graft polymerization of a hydrophilic compound on the surface, and the coating method of the hydrophilic polymer, the hydrophilized portion has a convex shape with respect to the surface.

The plasma treatment or plasma polymerization is preferably carried out in the presence of oxygen; acetone, organic acids and other oxygen-containing compounds; and nitrogen-containing compounds such as amines. Also, normal pressure plasma processing is possible.

The coating of a hydrophilic polymer is a method of applying a solution of a soluble polymer on a substrate in an arbitrary pattern by printing or the like. Examples of soluble polymers that can be used include polyhydroxymethyl methacrylate, polyvinyl alcohol, sulfonated cellulose, and sulfonated polysulfone.

When the hydrophilic polymer is not chemically bonded to the substrate as in the coating method, the hydrophilic polymer may elute during use. In order to prevent this, it is preferable to use a crosslinked polymer as the hydrophilic polymer. The layer made of a hydrophilic cross-linked polymer can be easily formed by a method of cross-linking after coating, or a coating of a hydrophilic cross-linkable polymerizable compound and cross-linking polymerization. Hydrophilic polymer coatings are preferred because they provide a high degree of hydrophilicity. When the coating of the hydrophilic polymer is performed by on-site polymerization of a hydrophilic polymerizable compound, the polymerization rate can be increased by using a polymerizable compound having a carbon-carbon unsaturated double bond as the hydrophilic polymerizable compound. It is preferable because it becomes higher.

As a method of chemical modification of the surface, for example,
Introduction of hydroxyl group, carboxyl group, amino group, amide group, etc. by halogenation and its substitution reaction; concentrated sulfuric acid, fuming sulfuric acid,
Sulfonation by contact with persulfate; nitration by contact with concentrated nitric acid, fuming nitric acid and the like, and introduction of a hydroxyl group or amino group by substitution or reduction thereof; photochemical reaction using azide or the like.

As a method for graft polymerization of a hydrophilic polymerizable compound, for example, a method in which a substrate is subjected to corona treatment, plasma treatment, radiation treatment or the like, followed by contact with a hydrophilic addition polymerizable compound, or photopolymerization is used. Methods used, and the like.

Among these, in the graft polymerization of a hydrophilic polymerizable compound, a layer composed of a hydrophilic polymer is formed by covalently bonding a layer of a hydrophilic polymer to a hydrophobic polymer (A) constituting a base material (A '). This is preferable because there is no danger that the hydrophilic layer will be peeled off or the components of the hydrophilic layer will elute. Further, as the hydrophilic polymerizable compound, it is preferable to use a polymerizable compound having a carbon-carbon unsaturated double bond because the polymerization rate is increased.

As the hydrophilic polymerizable compound, for example,
What is illustrated as a hydrophilic polymerizable compound (b) in the manufacturing method of this invention mentioned later is mentioned.

In the liquid transport device of the present invention, only the flow path portion needs to be made hydrophilic by the hydrophilic treatment, and the other portions need not be made hydrophilic. However, in the method of contacting with a hydrophilic addition polymerizable compound after corona treatment, plasma treatment, radiation treatment, or the like, a protective layer is formed in a portion other than the channel portion, and after the hydrophilic treatment, the protective layer is removed. There is a need to. Examples of the method for forming the protective layer include methods such as printing of a polymer solution; coating of the entire surface and etching of a portion not requiring protection; and photolithography. The hydrophilization treatment method requiring formation and removal of such a protective layer has a problem of low production efficiency. On the other hand, coating of a hydrophilic polymer, surface modification with a hydrophilic compound, and graft polymerization of a hydrophilic compound on the surface are:
A method with high productivity such as a patterning method by printing or energy beam irradiation can be used, and the degree of hydrophilization is high, which is a preferable method. In both of these methods, a thin liquid channel on the order of μm can be formed by using a patterning method by irradiation with energy rays. In the printing method, when a flow path having a width of about 0.3 to 3 mm is formed, productivity is high and this is a preferable method.
The formation of thinner channels is much more difficult.

In the above description, a method for forming a hydrophilic portion on a hydrophobic substrate later has been described.
The liquid transport device of the present invention can also be manufactured by a method of forming a hydrophobic portion on a hydrophilic substrate later.

That is, using a hydrophilic substrate having a water contact angle of 45 ° or less, the surface other than the portion to be a liquid flow path is subjected to a hydrophobic treatment (water repellent treatment) so that the water contact angle is 60 ° or more. Thereby, a hydrophilic liquid channel can be formed on the surface of the hydrophobic substrate. When the substrate is a polymer, the water contact angle is 4
When a polymer having a temperature of 5 degrees or less is used, inconveniences such as swelling due to an aqueous liquid generally occur. However, when an inorganic material such as glass, silica, silicon, or ceramic is used as the base material, the water contact angle can be increased by selecting the type of the material or forming a fine unevenness on the surface.
It can be less than 5 degrees.

The method of the hydrophobic treatment is optional.
Fluorine treatment, plasma treatment, plasma polymerization, chemical modification of the surface, graft polymerization of a hydrophobic compound onto the surface, coating of a hydrophobic polymer, and the like are included.

The plasma treatment and the plasma polymerization are performed, for example,
Hydrophobization can be achieved by performing plasma treatment or plasma polymerization in the presence of a fluoride such as carbon tetrafluoride, a chloride such as tetrachloroethane, or a hydrocarbon such as methane or benzene.

Examples of the chemical modification of the surface include halogenation such as fluorination, chlorination, and bromination, and alkylation by a substitution reaction thereof; and a photochemical reaction using an azide compound.

The coating of a hydrophobic polymer is a method of applying a solution of a soluble polymer on a substrate in an arbitrary pattern by printing or the like. Examples of the soluble polymer that can be used include, among the materials exemplified as the hydrophobic polymer (A), a polymer that is soluble in a solvent.

Examples of the graft polymerization of a hydrophobic compound onto a surface include a method in which a substrate is subjected to a surface treatment such as a corona treatment, a plasma treatment, or a radiation treatment, and then contacted with a hydrophobic addition polymerizable compound; And a surface grafting method utilizing the same.

Among these, the method of contacting with a hydrophobic addition-polymerizable compound after corona treatment, plasma treatment, radiation treatment, or the like, comprises forming a protective layer in the flow path portion, performing hydrophobic treatment, and then protecting the protective layer. Need to be removed. The formation of the protective layer includes a method of printing a polymer solution; a method of etching and removing an unprotected portion after coating the entire surface; and a photolithography.

The liquid transport device of the present invention can be used by covering the liquid transport device with a non-contact cover in order to prevent evaporation of the liquid during use. It is also preferable to integrate the liquid transport device of the present invention with the cover.

In the method for producing a liquid transport device according to the present invention, the photopolymerizable composition (a ') containing the hydrophobic polymerizable compound (a) and the photopolymerization initiator can be formed into an arbitrary shape. The obtained uncured shaped product is irradiated with energy rays except for the portion to be hydrophilized, thereby polymerizing and curing the portion other than the portion to be hydrophilized to obtain a hydrophobic polymer (A). Then, by irradiating them with a hydrophilic layer-forming material (b ') containing a hydrophilic polymerizable compound (b) and containing no photopolymerization initiator, and irradiating them with active light, The uncured portion of the excipient is polymerized and cured to form a hydrophobic polymer (A), and at the interface between the uncured portion of the excipient and the hydrophilic layer-forming material (b '),
The polymerizable compound (a) in the photopolymerizable composition (a ') and the hydrophilic polymerizable compound (b) in the hydrophilic layer forming material (b')
A method for producing a liquid transport device in which a layer of a hydrophilic polymer (B) is formed on the surface of a portion to be hydrophilized by copolymerizing a part of It is polymerizable and curable by actinic light used in the presence or absence of a polymerization initiator, and the hydrophilic polymerizable compound (b) is polymerizable by actinic light used in the presence of a polymerization initiator. However, in the absence of a polymerization initiator, a hydrophobic polymerizable compound (a), a hydrophilic polymerizable compound (b) and an actinic ray which satisfy the condition that they are not polymerized by the actinic ray used are used. It is characterized by the following.

The hydrophobic polymerizable compound (a) used in the production method of the present invention, whether organic or inorganic, is polymerized by energy rays and actinic rays to produce a polymer having a water contact angle of 60 ° or more. As long as it is radical polymerizable,
Any polymer such as anionic polymerizable polymer and cationic polymerizable polymer may be used, but a polymer having a high polymerization rate, addition polymerizable, or ring-opening polymerizable is preferable. Such a hydrophobic polymerizable compound (a) may be one that polymerizes not only in the absence of a photopolymerization initiator but also one that polymerizes only in the presence of a photopolymerization initiator.

As such a hydrophobic polymerizable compound (a), a compound having a polymerizable carbon-carbon double bond is preferable. Among them, a (meth) acrylic compound having high reactivity and a photopolymerization starter are preferred. Maleimide compounds that cure even in the absence of agents are preferred.

Examples of the (meth) acrylic monomer that can be used as the hydrophobic polymerizable compound (a) include, for example, ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, and 2-ethylhexyl ( (Meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 3-methacryloxypropyl tris (trimethylsiloxy) silane, trifluoro Ethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth)
Acrylate, methyl-2-chloroacrylate, 3-
Monofunctional monomers such as chloro-2-hydroxypropyl (meth) acrylate; diethylene glycol di (meth) acrylate, neopentyl glycol di (meth)
Acrylate, 1,6-hexanediol di (meth) acrylate, 2,2′-bis (4- (meth) acryloyloxy polyethyleneoxyphenyl) propane,
Bifunctional monomers such as 2'-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane; trifunctional monomers such as trimethylolpropane tri (meth) acrylate and trimethylolethanetri (meth) acrylate; pentaerythritol tetra ( Tetrafunctional monomers such as (meth) acrylate; and hexafunctional monomers such as dipentaerythritol hexa (meth) acrylate. These compounds can be used alone or as a mixture of two or more.

Further, as the hydrophobic polymerizable compound (a), a polymerizable oligomer (also referred to as a prepolymer) having a weight average molecular weight of 500 to 50,000, preferably a (meth) acrylic oligomer can be used. The (meth) acrylic oligomer that can be used as the hydrophobic polymerizable compound (a) has a weight average molecular weight of 500 to 500.
00 are preferred, and such oligomers include:
For example, (meth) acrylate of epoxy resin,
Examples include (meth) acrylic acid esters of polyether resins, (meth) acrylic acid esters of polybutadiene resins, and polyurethane resins having a (meth) acryloyl group at a molecular terminal. These oligomers can be used alone, can be used by mixing two or more kinds, or can be used by mixing with a monomer. In order to sufficiently increase the strength and hardness of the formed base material, it is preferable that the polymerized / cured product of the photopolymerizable composition (a ′) is a crosslinked polymer, and therefore, the photopolymerizable resin composition (A ′) preferably contains a so-called polyfunctional monomer and / or oligomer having two or more polymerizable functional groups such as (meth) acryloyl groups in one molecule.

Examples of the maleimide-based monomer which can be used as the hydrophobic polymerizable compound (a) include, for example, maleimide, N-cyclohexylmaleimide, N-butylmaleimide, N-ethylmaleimide, N-methylmaleimide, N-benzylmaleimide Monofunctional maleimides such as
4,4′-methylenebis (N-phenylmaleimide),
2,3-bis (2,4,5-trimethyl-3-thienyl) maleimide, 1,6-bismaleimidehexane,
And bifunctional maleimides such as 1,2-bismaleimideethane. These maleimide-based monomers can be used alone, or two or more can be used as a mixture. These maleimide-based monomers include vinyl ethers, acrylic monomers and / or
Alternatively, it can be used as a mixture with another polymerizable compound such as an oligomer.

In the production method of the present invention, the photopolymerizable composition (a ′) is substantially in a shaped state from contact with the hydrophilic layer-forming material (b ′) until photopolymerization and curing. Must be able to be held. Therefore, the hydrophobic polymerizable compound (a), which is a main component of the photopolymerizable composition (a '), does not dissolve in the hydrophilic layer-forming material (b'), or the photopolymerizable composition It is preferable that (a ') has a high viscosity. For the same purpose, after the photopolymerizable composition (a ′) is shaped and before it is brought into contact with the hydrophilic layer-forming material (b ′), the photopolymerizable composition (a ′) is completely removed. It is also possible to irradiate an actinic ray in such an amount that it does not cure to incompletely cure the excipient to increase its viscosity or gel.

The photopolymerization initiator, which is an essential component of the photopolymerizable composition (a '), is active with respect to the actinic ray used in the present invention, and has a hydrophobic polymerizable compound (a) and a hydrophilic polymerizable compound. There is no particular limitation as long as the polymerizable compound (b) can be polymerized, and examples thereof include a radical polymerization initiator, an anionic polymerization initiator, and a cationic polymerization initiator. Such photopolymerization initiators include, for example, p
-Tert-butyltrichloroacetophenone, 2,2'-
Acetophenones such as diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzophenone, 4,4'-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethyl Thioxanthone, 2-
Ketones such as isopropylthioxanthone; benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether; and benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone.

The photopolymerization initiator is a photopolymerizable composition (a ')
Can be used in a state of being dissolved or dispersed in
It is preferably one that dissolves in the photopolymerizable composition (a ′). The photopolymerization initiator concentration in the photopolymerizable composition (a ') is preferably in the range of 0.01 to 20% by weight,
A range of 10% by weight is particularly preferred.

Other components can be added to the photopolymerizable composition (a ') in a dissolved or non-dissolved state. Other components, for example, thickeners, modifiers, fillers,
Reinforcing materials, coloring agents, and the like are included.

Examples of the thickener that can be added to the photopolymerizable composition (a ′) include linear polymers soluble in the photopolymerizable composition (a ′); clays, zeolites, activated carbon, and titanium oxide. , Aluminum oxide, inorganic powders such as silica gel, and the like.

The modifier which can be added to the photopolymerizable composition (a ') includes, for example, silicone oil, fluorinated hydrocarbon, and fluororesin powder which function as a water repellent.

Examples of fillers and reinforcing agents that can be added to the photopolymerizable composition (a ′) include organic and inorganic staples; clays, zeolites, activated carbon, titanium oxide, aluminum oxide, and silica gel. Powder, and the like.

Examples of the coloring agent that can be added to the photopolymerizable composition (a ′) include any dye, pigment, and fluorescent dye.

The method for shaping the photopolymerizable composition (a ') is not particularly limited. For example, a method such as application by a coater, spraying, dipping, or the like; extrusion from a nozzle; When shaping the photopolymerizable composition (a '), use of a support that is integrated with the photopolymerizable composition (a') or that can be removed after the photopolymerizable composition (a ') is cured. Is also possible. When it is necessary to apply the photopolymerizable composition (a ') thinly and uniformly, a method of applying a solvent to the photopolymerizable composition (a') and then volatilizing the solvent is used. Can also be adopted. The solvent in this case may be any solvent as long as it can dissolve the photopolymerizable composition (a '). However, a solvent having high volatility is preferable because it is necessary to dry the coated body. Examples of such a solvent include alcohols such as methanol, ethanol, and propanol;
Ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether; esters such as ethyl acetate; hydrocarbons such as hexane and toluene; chlorinated solvents such as dichloromethane and dichloroethane.

The uncured excipient of the photopolymerizable composition (a ') is polymerized and cured by irradiating an energy beam except for a portion having an arbitrary shape to be hydrophilized, by applying energy rays. .

The energy ray is not particularly limited as long as it can polymerize and cure the photopolymerizable composition (a ′). Examples of the energy ray include ultraviolet rays, visible rays, infrared rays, electron rays, X rays, and γ rays. No. The energy ray used in this step may be the same as or different from the actinic ray used in the subsequent step, but is preferably the same, and in terms of polymerization and curing speed, And visible light are preferable, and ultraviolet light is particularly preferable. For the purpose of accelerating the polymerization curing speed and performing the polymerization completely, it is preferable to perform the irradiation of the energy ray in a low oxygen concentration atmosphere. The low oxygen concentration atmosphere is preferably a nitrogen stream, a carbon dioxide stream, an argon stream, a vacuum or a reduced pressure atmosphere.

In this step, it is necessary to irradiate an energy beam except for a portion of the shaped product of the photopolymerizable composition (a ') to be made hydrophilic. The method is arbitrary. For example, a photolithography method of masking and irradiating an unnecessary irradiation portion or scanning an energy beam can be used.

After polymerizing and curing the portion other than the portion to be hydrophilized, the excipient is brought into contact with a hydrophilic layer forming material (b ') containing a hydrophilic polymerizable compound (b), Is irradiated with actinic rays.

The hydrophilic polymerizable compound (b) used in the production method of the present invention is a polymerizable compound which gives a polymer having a water contact angle of 45 ° or less, and the production method of the present invention. When irradiated with the actinic ray used in (1), polymerization occurs when a photopolymerization initiator is present, but does not polymerize when no photopolymerization initiator is present. It is preferable that the hydrophilic polymerizable compound (b) be compatible with water at an arbitrary ratio.

When the hydrophilic polymerizable compound (b) is polymerized by the actinic ray used in the present invention in the absence of a photopolymerization initiator, the polymer not bonded to the surface of the support molded product Is increased, the use efficiency of the hydrophilic polymerizable compound (b) is deteriorated, and the exchange frequency of the hydrophilic layer forming material (b ') is increased, so that the productivity tends to decrease. Is not preferred.

Whether the hydrophilic polymerizable compound (b) is polymerized in the absence of a photopolymerization initiator or not depends on the actinic ray used. The selection range of the hydrophilic polymerizable compound (b) can be expanded by selecting the wavelength and intensity of the actinic ray used in the present invention.

From the viewpoint of improving the productivity, the hydrophilic polymerizable compound (b) is an addition polymerizable compound having a high polymerization rate,
For example, a polymerizable compound having a carbon-carbon unsaturated double bond is preferable, and a compound having a (meth) acryloyl group is particularly preferable.

Examples of the hydrophilic group in the molecule of the hydrophilic polymerizable compound (b) include nonionic hydrophilic groups such as polyethylene glycol group, hydroxyl group, sugar-containing group, amide group and pyrrolidone group; carboxyl group, sulfone Groups, anionic hydrophilic groups such as phosphoric acid groups; cationic hydrophilic groups such as amino groups and ammonium groups; amino acid residues; and zwitterionic groups such as phosphoric acid / ammonium ion groups. Of course, these derivatives may be used, for example, amino group, amide group, ammonium group, pyrrolidone group N
Substituents are mentioned. The hydrophilic polymerizable compound (b) is
It may have one or more hydrophilic groups in the molecule, or may have a plurality of types of hydrophilic groups.
When the liquid transport device of the present invention is of a type in which liquid is transported by an electric field, the hydrophilic polymerizable compound (b) having an anionic or cationic group improves the liquid transport rate. It is preferable because it can be used.

Examples of the hydrophilic polymerizable compound having a polyethylene glycol group include phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, and phenoxynonaethylene glycol (meth). ) Acrylate,
Phenoxy (polyethylene glycol) (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth)
Acrylate, methoxy nonaethylene glycol (meth) acrylate, methoxytetradecaethylene glycol (meth) acrylate, methoxytrieicosaethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol Mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, nonaethylene glycol mono (meth) acrylate, tetradecaethylene glycol mono (meth) acrylate, trieicosaethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, methoxydiethylene glycol (meth) Acrylate, and the like.

Examples of the hydrophilic polymerizable compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
2-hydroxybutyl (meth) acrylate, 2-hydroxypentyl (meth) acrylate, 2-hydroxyhexyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth)
Acrylate, glycerol di (meth) acrylate,
Triglycerol di (meth) acrylate, 2-hydroxy-3-phenoxypropylene (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyliphthalate, glycerol mono (meth)
Acrylate, and the like.

Examples of the hydrophilic polymerizable compound having a sugar structure include monosaccharides such as glucose, galactose and mannose and (meth) acrylates of derivatives thereof; disaccharides such as maltose, cellobiose, lactose and sucrose; (Meth) acrylates of the following: oligosaccharides such as scrodextrin and (meth) acrylates of these derivatives; polysaccharides such as starch and heparin and (meth) acrylates of these derivatives.

Examples of the hydrophilic polymerizable compound having an amide group include acrylamide; N-ethyl (meth)
Acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-
N-alkylacrylamides such as cyclopropyl (meth) acrylamide; N-methyl-N-ethyl (meth)
Acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-
Methyl-N-isopropyl (meth) acrylamide, N
N, N-dialkylacrylamides such as -methyl-NN-propyl (meth) acrylamide; N- (meth)
Acryloylmorpholine, N- (meth) acryloylpyrrolidine, N- (meth) acryloylpiperidine, N-
Vinyl-2-pyrrolidone, N-methylenebisacrylamide, N-methoxypropyl (meth) acrylamide,
N-isopropoxypropyl (meth) acrylamide,
N-ethoxypropyl (meth) acrylamide, N-1
-Methoxymethylpropyl (meth) acrylamide, N
-Methoxyethoxypropyl (meth) acrylamide,
N-1-methyl-2-methoxyethyl (meth) acrylamide, N-methyl-NN-propyl (meth) acrylamide, N- (1,3-dioxolan-2-yl)
(Meth) acrylamide, and the like.

Examples of the hydrophilic polymerizable compound having a carboxyl group include 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, and 2- (meth) acryloyloxyethyl succinic acid. , W-carboxycaprolactone mono (meth) acrylate, and the like.

Examples of the hydrophilic polymerizable compound having a sulfone group include sodium sulfonic acid methacrylate, sulfonic acid-2-methylpropane-2-acrylamide, styrenesulfonic acid, and 2-acrylamide-
2-methylpropanesulfonic acid, 2-acrylamide-
2-phenylpropanesulfonic acid, sodium (meth) acryloyloxyethylsulfonate, ammonium (meth) acryloyloxyethylsulfonate, allylsulfonic acid, methallylsulfonic acid, vinylsulfonic acid, styrenesulfonic acid, sodium sulfonic acid methacrylate, And the like.

Examples of the hydrophilic polymerizable compound having a phosphate group include mono (2-acryloyloxyethyl) phosphate and bis (methacryloxyethyl) phosphate.

Examples of the hydrophilic polymerizable compound having an amino group include dimethylaminoethyl methacrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N -(Bismethoxymethyl) carbamyloxyethyl methacrylate, N-methoxymethylcarbamyloxyethyl methacrylate, and the like.

Examples of the monomer and / or oligomer having an ammonium group include quaternary dimethylaminoethyl methacrylate, diallyldimethylammonium, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxypropyltrimethylammonium chloride and the like. Is mentioned.

The hydrophilic layer-forming material (b ') contains a hydrophilic polymerizable compound (b) as an essential component,
It may be a liquid or a gas (vapor), but is preferably a liquid from the viewpoint of productivity and effects, and is a hydrophilic polymerizable compound (b) from the viewpoint of easy control of the amount of hydrophilic groups bonded. More preferably, the solution comprises a solvent. The solvent is not particularly limited as long as it can dissolve the hydrophilic polymerizable compound (b), but does not absorb the actinic light used and does not dissolve the photopolymerizable composition (a '). Is preferred. The solvent does not need to completely dissolve the hydrophilic polymerizable compound (b), and a part of the hydrophilic polymerizable compound (b) may be dispersed. Such a solvent is preferably water, a water-soluble solvent, a liquid surfactant or a mixture thereof, and in order to obtain a molded article having excellent surface hydrophilicity, water or a solvent containing water as a main component is used. It is more preferred that there be. If necessary, a surfactant may be added to the hydrophilic layer forming material (b ') in order to promote the dissolution or dispersion of the hydrophilic polymerizable compound (b).

Examples of the water-soluble solvent include methanol, ethanol, propanol, ethylene glycol,
Alcohol solvents such as glycerin; organic acids such as acetic acid; ketone solvents such as acetone; amide solvents such as formamide.

The surfactant which can be added to the hydrophilic layer forming material (b ') as required is any surfactant, for example, sodium alkylaryl sulfonate, sodium alkyl sulfonate, sulfosuccinic acid Anionic surfactants such as sodium ester esters and sodium higher fatty acids; cationic surfactants such as higher amine halides, alkylpyridinium halides, and quaternary ammonium salts; polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, and sorbic acid Nonionic surfactants such as fatty acid esters and fatty acid monoglycerides; amphoteric surfactants such as amino acids;
And the like.

When used as a solution, the concentration of the hydrophilic polymerizable compound (b) in the hydrophilic layer forming material (b ') depends on the required hydrophilicity, reactivity at the interface, and control of the amount of the hydrophilic group bonded. From the viewpoints of post-washing and the like, the range is preferably 0.5 to 80% by weight, and particularly preferably 3 to 50% by weight.

The method of contacting the uncured excipient of the photopolymerizable resin composition (a ') with the material for forming a hydrophilic layer (b') is arbitrary. (B ') immersion, casting or spraying of the hydrophilic layer forming material (b') onto the surface of the shaped object, contact between the shaped object and the foam of the hydrophilic layer forming material (b '), light Examples of the method include co-extrusion of the polymerizable composition (a ') and the hydrophilic layer-forming material (b') and multi-layer coating. Above all, immersion of the excipient into the hydrophilic layer forming material (b ') is preferred. The contact between the uncured excipient of the photopolymerizable composition (a ') and the hydrophilic layer-forming material (b') is caused by forming a hydrophilic layer on the uncured portion of the photopolymerizable composition (a '). It is necessary that the material (b ') makes contact, but it is not necessary that the portion cured by irradiation with energy rays prior to the contact makes contact. However, for simplification of the process, it is preferable to bring the entire shaped article into contact.

When the uncured shaped material obtained by shaping the photopolymerizable composition (a ′) is irradiated with light while being in contact with the material (b ′) for forming a hydrophilic layer, the shaped material is The active species such as radicals, anions, and cations generated inside or on the surface of the polymerize the hydrophobic polymerizable compound (a), and polymerize these generated active species or the hydrophobic polymerizable compound (a). These active species in the chain also induce the polymerization of the hydrophilic polymerizable compound (b) contained in the hydrophilic layer forming material (b ') on the surface of the excipient.
That is, in the polymerization reaction, the hydrophobic polymerizable compound (a) and the hydrophobic polymerizable compound (a) are mixed with each other on the contact surface between the formed material and the hydrophilic layer forming material (b). Between the hydrophilic polymerizable compounds (b) in the hydrophilic layer forming material (b ') phase near the contact surface and between the polymerizable compounds (b) and the hydrophobic polymerizable compound (a) And a hydrophilic polymerizable compound (b) to form a block copolymer. Therefore, the hydrophilic polymerizable compound (b) or its polymer does not exist inside the substrate formed by curing the excipient, and the hydrophilic polymerizable compound (b)
Alternatively, the polymer is bound only to the surface of the substrate.
The amount of the polymer composed of the hydrophilic polymerizable compound (b) bonded to the surface of the substrate is determined by the concentration of the hydrophilic polymerizable compound (b) in the hydrophilic layer forming material (b '), the reaction temperature It can be adjusted by the photopolymerization initiator concentration in the photopolymerizable composition (a '), the light intensity and the like. The hydrophilic polymerizable compound (b) fixed on the surface of the substrate may be the hydrophilic polymerizable compound (b) itself or an oligomer.

In the production method of the present invention, the hydrophilic polymerizable compound (b) is a base material in which a part of the used amount is a cured product of a shaped product of the photopolymerizable composition (a ′). And the remaining hydrophilic polymerizable compound (b) remains uncured in the hydrophilic layer-forming material (b ').

In the manufacturing method of the present invention, a hydrophilic liquid flow path is formed only at a necessary portion of the surface by using a method such as printing or photolithography, and the other portion has a hydrophobic surface. Can be easily manufactured.

Examples of the actinic rays to be irradiated in a state where the shaped material of the photopolymerizable composition (a ′) and the material for forming the hydrophilic layer (b ′) are in contact with each other include ultraviolet rays, visible rays and infrared rays.
Among these actinic rays, from the viewpoint of polymerization and curing speed,
Ultraviolet light and visible light are preferred, and ultraviolet light is particularly preferred.
Radiation such as electron beam, X-ray and gamma ray is not suitable because it forms a polymer of a hydrophilic polymerizable compound (b) that does not bond to the substrate. Also, the polymerization / curing speed was increased,
For the purpose of complete curing, it is also preferable to perform irradiation in a low oxygen atmosphere or to remove oxygen dissolved in the hydrophilic layer forming material (b '). The active light irradiation site is
Only the uncured portion in the excipient of the photopolymerizable composition (a ') is sufficient, but irradiation may be performed on other portions as well. From the viewpoint of productivity, it is preferable to irradiate the entire shaped article.

[0088]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the scope of these examples. In the following examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.

[Example 1] Hydrophobic polymerizable compound (a)
70 parts of a urethane acrylate oligomer having an average of three acryloyl groups in one molecule (“Unidick V-4263” manufactured by Dainippon Ink and Chemicals, Inc.) and 1,6-hexanediol diacrylate (Nippon Kayaku) A mixture of 30 parts of “Kayarad HDDA” manufactured by Co., Ltd. was used, and “Irgacure 18 was used as a photopolymerization initiator.
4 "(a photopolymerization initiator manufactured by Ciba Geigy) and 2 parts,
These are uniformly mixed, and the photopolymerizable composition (a'-1)
I got

On the other hand, sodium sulfonate methacrylate ("MS-2N" manufactured by Nippon Emulsifier Co., Ltd.) was used as the hydrophilic polymerizable compound (b-1), and its 30%
An aqueous solution was prepared and used as a hydrophilic layer forming material (b'-1).

After applying the photopolymerizable composition (a'-1) to a glass plate with a bar coater having a thickness of 250 μm, a width of 0.5 mm and a length of 20 mm for forming a liquid flow path were formed on the coating.
Line and 5m to be a reservoir connected to both ends of the line
m × 5 mm square part, all corners are 0.5 mm
A dumbbell-shaped photomask rounded with R is placed in a non-contact state, and a Multilight 2 manufactured by Ushio Inc.
20 mW / cm ² using a light source unit for a 00 type exposure apparatus
For 30 seconds. In the obtained product, the masking portion was uncured and the irradiated portion was cured. Thereafter, the member was converted to a hydrophilic layer forming material (b′-
1) Submerged in a bat having a depth of 10 mm, irradiated with the same ultraviolet rays as above for 90 seconds, taken out, washed with water, peeled off from a glass plate, and air-dried to form a transparent film as a whole. Was manufactured.

The contact angle of water on the surface of the liquid transport device was measured using a CA-D type contact angle meter manufactured by Kyowa Kagaku Co., Ltd., and the contact angle of the dumbbell-type hydrophilic portion was 7 degrees. The water contact angle of the other parts was 78 degrees.

This liquid transport device was placed horizontally in a wet box (a box in which the relative humidity was kept at almost 100%), and distilled water was put on the entire dumbbell-shaped hydrophilic portion using a pipette. The water on the hydrophobic part was also attracted to the hydrophilic part, so that only the dumbbell-shaped hydrophilic part was in water. Then, when water in one of the liquid reservoirs was absorbed by a filter paper and removed, distilled water was removed from the other liquid reservoir by a width of 0.1 mm.
It moved to one liquid reservoir through a 5 mm hydrophilized liquid flow path. When the same test was performed using a phosphate buffer solution (PBS) instead of distilled water, similar results were obtained.

Example 2 A liquid transport device having an electrode was manufactured by bonding a copper wire to each of the two reservoirs of the liquid transport device manufactured in Example 1 and using a conductive carbon paste. .

Water was placed on the liquid transport device in the same manner as in Example 1, and a DC voltage of 100 volts was applied between the electrodes. As a result, the water moved from the positive-side liquid reservoir to the negative-side liquid reservoir. .

Example 3 In Example 1, methoxypolyethylene glycol 400 acrylate ("A" of Shin-Nakamura Chemical Co., Ltd.) was used as the hydrophilic polymerizable compound (b-2) in place of sodium sulfonate methacrylate.
M-90G ”), except that a liquid transport device was manufactured in the same manner as in Example 1.

The water contact angle was measured in the same manner as in Example 1. As a result, the water-treated portion was 16 °, and the other portions were 78 °.

A liquid transport test was performed using this liquid transport device in the same manner as in Example 1, and the same results as in Example 1 were obtained.

Example 4 In Example 1, instead of the hydrophilic layer-forming material (b'-1), the hydrophilic layer-forming material (b'-4) was replaced by sodium sulfonate methacrylate (Nippon Emulsifier Co., Ltd.). "MS-2N" made by company) 1
A liquid transport device was manufactured in the same manner as in Example 1 except that a 0% aqueous solution was used.

The water contact angle was measured in the same manner as in Example 1. As a result, the coated portion was 23 ° and the other polystyrene portions were 9 °.
It was 0 degrees.

Using this liquid transport device, a liquid transport test was conducted in the same manner as in Example 1, and the same results as in Example 1 were obtained for distilled water. In the case of the phosphate buffer solution, when the remaining amount of liquid in the other reservoir became extremely small, the solution was interrupted in the flow path and was not completely sent, but was not particularly problematic.

[Example 5] 17.6 parts of hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2 parts of 10 ethylene oxide-modified bisphenol A diacrylate ("BPE-10" manufactured by Shin-Nakamura Chemical Co., Ltd.), and light 0.4 parts of "Irgacure 184" (manufactured by Ciba Geigy) as a polymerization initiator and 80 parts of 2-butanone were mixed to prepare a hydrophilic polymerizable solution. The hydrophilic polymerizable solution prepared in this manner was coated with a writing pen to a thickness of 0.2 m.
m on a biaxially oriented polystyrene sheet (manufactured by Dainippon Ink and Chemicals, Inc.) with a width of about 0.3
mm, a 15 mm long wire, and a 5 mm × 5 mm square portion to be a liquid reservoir connected to both ends of the wire, applied in a dumbbell shape, dried by applying an air current, and the same as in Example 1. The liquid transport device was manufactured by irradiating 40 mW / cm ² ultraviolet rays for 60 seconds using an ultraviolet irradiation apparatus.

According to the cross-sectional observation with a scanning electron microscope, the hydrophilic polymer applied to the liquid flow path portion has a width of about 3
The thickness was 30 μm and the thickness was about 14 μm.

The water contact angle was measured in the same manner as in Example 1. As a result, the applied portion was 31 ° and the other polystyrene portions were 9 °.
It was 0 degrees.

Using this liquid transport device, a liquid transport test was performed in the same manner as in Example 1, and the same results as in Example 1 were obtained with respect to distilled water. In the case of the phosphate buffer solution, when the remaining amount of the other reservoir became small, the liquid was interrupted in the flow path and was not completely sent, but it was not particularly problematic.

Example 6 In Example 1, the ethylene oxide-modified bisphenol A diacrylate (4-ethylene oxide-modified bisphenol A diacrylate) was used in place of the hydrophobic polymerizable compound (a-1) in place of the hydrophobic polymerizable compound (a-6). "B" manufactured by Daiichi Kogyo Co., Ltd.
PE-4 ") A liquid transport device was produced in the same manner as in Example 1 except that 98 parts were used.

As a result of measuring the water contact angle in the same manner as in Example 1, the water contact angle of the surface other than the dumbbell-shaped hydrophilic portion was 69.
And the water contact angle of the liquid reservoir was 7 degrees.

Using this liquid transport device, a liquid transport test was conducted in the same manner as in Example 1. As a result, the liquid transport test was performed in the same manner as in Example 1 as long as the level of distilled water or the phosphate buffer solution in the reservoir was not so high. As a result, when the liquid level was too high, the liquid was more likely to overflow from the flow channel than in Example 1. However, it was easy to control the liquid level of the liquid reservoir so as not to overflow from the flow path.

[Example 7] In Example 1, instead of the hydrophobic polymerizable compound (a-1), 10 ethylene oxide-modified bisphenol A diacrylate (hydrophobic polymerizable compound (a-7)) was used. A liquid transport device was manufactured in the same manner as in Example 1 except that 98 parts of "BPE-10" manufactured by Daiichi Kogyo Co., Ltd. was used.

As a result of measuring the water contact angle in the same manner as in Example 1, the water contact angle of the surface other than the dumbbell-shaped hydrophilic portion was 62.
And the water contact angle of the liquid reservoir was 7 degrees.

A liquid transport test was performed using this liquid transport device in the same manner as in Example 1, and the same results as in Example 1 were obtained in the range where the level of distilled water or the phosphate buffer solution in the reservoir was low. However, when the liquid level was set too high, the liquid tended to overflow from the flow path as compared with Examples 1 and 6. However, it was relatively easy to control the liquid level so as not to overflow from the flow path.

[Comparative Example 1] In Example 1, a 5% aqueous solution of methoxypolyethylene glycol 400 acrylate (“AM-90G” manufactured by Shin-Nakamura Chemical Co., Ltd.) was used instead of the hydrophilic layer forming material (b′-1). A liquid transport device was manufactured in the same manner as in Example 1, except that was used.

As a result of measuring the water contact angle in the same manner as in Example 1, the water contact angle of the surface other than the dumbbell-shaped hydrophilic portion was 78.
And the water contact angle of the liquid reservoir was 50 degrees.

A liquid transport test was performed using this liquid transport device in the same manner as in Example 1. When the amount of distilled water or the phosphate buffer solution in the reservoir was reduced, the liquid was interrupted in the flow path, and the liquid was transferred. I can no longer do it. On the other hand, when a little more liquid was placed in the liquid reservoir so that the liquid was not interrupted in the flow path, the liquid overflowed from the flow path. That is, in the device obtained in Comparative Example 1, it was difficult to control the liquid level, and it was difficult to feed the liquid stably.

[Comparative Example 2] In Example 1, 95 parts of 10 ethylene oxide-modified bisphenol A diacrylate (manufactured by Daiichi Kogyo Co., Ltd., BPE-10) and hydroxyethyl methacrylate were used as the hydrophobic polymerizable compound (a). A liquid transport device was manufactured in the same manner as in Example 1 except that 5 parts of a mixture (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

The water contact angle was measured in the same manner as in Example 1. As a result, the hydrophilic portion was 7 degrees and the other portions were 51 degrees.

Using this liquid transport device, a continuous transport test was conducted in the same manner as in Example 1. When placing distilled water on the liquid flow path, even if distilled water is carefully placed on the liquid flow path so as not to protrude from the flow path using a syringe, the distilled water tends to protrude from the flow path. Did not. When the liquid level in the liquid reservoir slightly increased, the liquid overflowed from the flow path. That is, in the device obtained in Comparative Example 2, it was difficult to control the liquid level, and it was very difficult to stably feed the liquid.

[0118]

According to the liquid transport device of the present invention, the liquid to be transported overflows out of the flow path, and the liquid transport device can generate liquid droplets as compared with the conventional product in which a groove is formed in the base material by etching or the like. It can be transported stably without becoming. Further, in the liquid transport device of the present invention, the base material does not swell, and the base material components do not elute into the liquid. Further, the liquid transport device of the present invention has high productivity and can be manufactured at low cost.

Continued on the front page F-term (reference) 4D075 AB01 AE04 AE17 BB42X BB42Z BB46X BB46Z CA36 CA37 CB11 DA04 DB01 DB13 DB18 DB20 DB31 DC16 DC30 EA06 EA21 EB07 EB13 EB14 EB15 EB19 EB22 EB35 AB04 AEBEBEBA EB39 AB04 EB38 4G068 AA01 AB11 AC20 AD50 4G075 AA30 AA39 CA33 CA54 EC21 EE12 FB02 FB03 FB04 FB06 FB12 FC11 FC20

Claims (7)

[Claims] 1. The method according to claim 1, wherein (1) the contact angle with water is 4
A nonporous liquid flow path that has been hydrophilized to 5 degrees or less, and (2) a hydrophobic part having a contact angle with water of 60 degrees or more, which separates the liquid flow path from other parts, A liquid transport device comprising: a liquid transport device characterized in that the hydrophilized portion is not substantially groove-shaped. 2. The liquid transport device according to claim 1, wherein electrodes are provided at both ends of the liquid flow path. 3. A substrate (A ′) comprising (1) a hydrophobic polymer (A) and having a contact angle with water of 60 ° or more, and (2) a surface of the substrate (A ′), The liquid transport device according to claim 1, further comprising a non-porous liquid flow channel that has been subjected to a hydrophilic treatment so that a contact angle with water is 45 degrees or less. 4. The liquid transport device according to claim 1, wherein the liquid channel is a layer made of a hydrophilic polymer (B). 5. The liquid transport according to claim 4, wherein the layer composed of the hydrophilic polymer is a layer composed of the hydrophilic polymer (B) covalently bonded to the hydrophobic polymer (A) constituting the base material (A ′). device. 6. The liquid transport device according to claim 4, wherein the hydrophilic polymer (B) is an addition polymer of a polymerizable compound having a carbon-carbon unsaturated double bond. 7. A photopolymerizable composition (a ′) containing a hydrophobic polymerizable compound (a) and a photopolymerization initiator is shaped into an arbitrary shape, and the obtained uncured shaped product is obtained. Irradiating an energy beam except for a portion to be hydrophilized to polymerize and cure the portion other than the portion to be hydrophilized, and then containing a hydrophilic polymerizable compound (b) and containing no photopolymerization initiator; By irradiating these with the active layer-forming material (b ') while irradiating them with an actinic ray, the uncured portion of the excipient is polymerized and cured, and the uncured portion of the excipient and the hydrophilic layer At the interface with the forming material (b '), the polymerizable compound (a) in the photopolymerizable composition (a') and the hydrophilic polymerizable compound (b) in the hydrophilic layer forming material (b ') are A liquid transport device that hydrophilizes the surface of the part to be hydrophilized by copolymerizing with a part The production method, wherein the hydrophobic polymerizable compound (a) is polymerized by an energy ray or an actinic ray used in the presence or absence of a polymerization initiator.
The curable and hydrophilic polymerizable compound (b) can be polymerized by the active light used in the presence of the polymerization initiator, but polymerized by the active light used in the absence of the polymerization initiator. A method for producing a liquid transport device, comprising using a hydrophobic polymerizable compound (a), a hydrophilic polymerizable compound (b), and an actinic ray that satisfy the condition of not performing.