JP2007216226A - Micronozzle, its manufacturing method, spotting method, and spotter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a micronozzle, which can simultaneously deliver through a number of delivery ports a number of types of solutions respectively through individual flow passages without contamination between the solutions to form a number of spots at one time and easily, and to provide its manufacturing method, a spotting method and a spotter provided with the micronozzle. <P>SOLUTION: This micronozzle has four or more mutually independent capillary flow passages and a delivery port and an injection port provided in each of the flow passages. The center-to-center distance of adjacent delivery ports is 4 to 10,000 times the diameter of the delivery port. The center-to-center distance of the adjacent injection ports is larger than the center-to-center distance of the adjacent delivery ports, and the diameter of the injection port is larger than the diameter of the delivery port. There are also provided its manufacturing method, a spotting method, and a spotter provided with the micronozzle. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a nozzle having a minute discharge port used for various applications, and simultaneously discharges a plurality of types of liquids from a plurality of discharge ports and coats a plurality of types of coating liquids into a large number of minute dots. The present invention relates to a micro-nozzle that can be manufactured, a manufacturing method thereof, and a spotting method. The present invention also relates to a spotter for manufacturing a microarray or the like in which a large number of probes are fixed as a large number of spots on the surface of a substrate.

  The micro nozzle of the present invention is particularly useful as a spotter nozzle for producing a microarray used as a production apparatus for a so-called DNA chip, immunodiagnostic drug, biosensor, or the like.

  Ink jet method, photochemical method, needle stamp method (contact method), etc. are known as a method of spotting a probe solution onto a substrate, which is a process of microarray production. Yes. However, spotting a very large number of different solutions is quite difficult and only known is the method of forming spots sequentially, or the method of forming a few but a few spots at a time and performing them sequentially. There wasn't.

  It is expected that a desired number of spots can be formed at a time by using a method in which a large number of kinds of solutions are simultaneously ejected from a micro nozzle having a necessary number of ejection ports. A method for supplying a different solution to each discharge port of a nozzle having a nozzle and a specific method for connecting pipes to a large number of minute discharge ports are not known or realized.

  The problem to be solved by the present invention is that a large number of types of coating liquids are simultaneously discharged from a large number of discharge ports through individual flow paths without contamination between the coating liquids, and a large number of spots can be easily and at once. It is an object to provide a micro nozzle that can be formed, a manufacturing method thereof, a spotting method using the micro nozzle, and a spotter equipped with the micro nozzle.

  As a result of intensive studies on means for solving the above problems, the present inventors have found that the above problems can be solved by making the discharge port diameter, the discharge port interval, and the injection port interval have a specific relationship. The nozzle can be easily formed by a structure in which a member having a large number of discharge ports and a member in which a defect portion serving as a capillary channel is formed on the surface or inside is fixed, and these members are Using the active energy ray-curable composition as a raw material, it was found that at least one of them was adhered in a semi-cured state, and it was formed by a method of laminating by irradiating active energy rays again, and the present invention was completed. . In addition, the present inventors store the coating liquid independently in each inlet formed in the shape of a liquid storage tank, without connecting a pump independently to each inlet by using the above-mentioned micro nozzle, It has been found that the above-mentioned problems can be easily solved by contacting, pressing and stamping the micronozzle with an application target, and the present invention has been completed.

That is, the present invention includes a member (A) and a plurality of members (B) stacked on the member (A), and four or more capillary channels and each channel independent of each other. A micro nozzle having a discharge port and an injection port,
(1) The distance between the centers of adjacent discharge ports is 4 to 10,000 times the diameter of the discharge ports,
(2) The distance between the centers of the adjacent injection ports is larger than the distance between the centers of the adjacent discharge ports, and the diameter of the injection port is larger than the diameter of the discharge port,
(3) The member (A) has four or more capillary channels that pass through the member (A) and discharge ports of the channels,
(4) The plurality of members (B)
(i) a cured product of the active energy ray-curable composition, and
(ii) It has a deficient portion that forms a flow path communicating with the discharge port of the member (A) on the surface where the members (B) are laminated and / or the surface laminated with the member (A). The micro nozzle characterized by this is provided.

Further, the present invention is a method of manufacturing the micro nozzle,
(1) A member (A) having four or more capillary flow channels independent of each other that penetrate the member and a discharge port of each flow channel;
(2) A semi-cured product of an active energy ray-curable composition having a flow path that penetrates a member connected to the discharge port of the member (A) or a defect portion that forms a flow path with the member (A). A member (B) made of
(3) Next, the active energy ray is irradiated to cure the member (B) and bond the member (A) and the member (B).
The present invention provides a method for producing a micro nozzle.

The present invention is also a method for producing the micro nozzle,
(1) a member (A) having four or more capillary flow channels independent of each other penetrating the member and a discharge port of each flow channel, and made of a semi-cured product of the active energy ray-curable composition;
(2) Laminating a member (B) having a defective portion forming a flow path with a flow path penetrating a member connected to the discharge port of the member (A) or the member (A);
(3) Next, the active energy ray is irradiated to cure the member (A) and bond the member (A) and the member (B).
The present invention provides a method for manufacturing a micro nozzle.

  In addition, the present invention provides a spotting method in which a coating liquid is applied to a coating object in a spot shape using the micro nozzle. Furthermore, the present invention provides a spotter having the micro nozzle.

The present invention relates to a micro-nozzle capable of easily discharging a large number of kinds of solutions from a large number of discharge ports through individual flow paths without any contamination between the solutions and forming a large number of spots all at once, and a method for manufacturing the same. And a spotting method using the micro nozzle, and a spotter equipped with the micro nozzle. The micro nozzle of the present invention can perform spotting of many different types of solutions at high speed, and can easily supply different coating liquids to the respective discharge ports.
Furthermore, interference of the position of the flow path provided in each layer of the plurality of members (B) can be avoided, and the degree of design freedom can be increased. Further, according to the present invention, it is easy to form a nozzle having a large number of discharge ports, for example, a micro nozzle having discharge ports arranged in a matrix.

  First, the micro nozzle of the present invention will be described. The micro-nozzle of the present invention is a micro-nozzle having a multilayer structure in which a plurality of members are laminated, and having four or more capillary channels independent of each other, and an outlet and an inlet of each channel. The distance between the centers of the adjacent discharge ports is 4 to 10,000 times the diameter of the discharge ports, the distance between the centers of the adjacent injection ports is larger than the distance between the centers of the adjacent discharge ports, and The diameter is larger than the diameter of the discharge port.

  The external shape of the micronozzle of the present invention is not particularly limited, and may be a shape corresponding to the shape of an object to be coated or a device to which the micronozzle of the present invention is attached. For example, in the form of a sheet (including film, ribbon, etc., the same shall apply hereinafter), plate (including convex or concave curved plate, the same shall apply hereinafter), tubular (roller), and other complex shapes. Although it can be, it is preferable that it is the shape which has a surface where the front and back are parallel like a sheet form or plate shape. Furthermore, the surface on which the discharge port is provided (hereinafter sometimes referred to as “nozzle surface”) is a convex curved surface (kamaboko shape) that is a part of a cylinder, and the opposite side is a flat surface. Particularly preferred. At this time, the nozzle surface is preferably a part of a cylinder having a diameter of preferably 5 cm to 10 m, more preferably 10 cm to 1 m. In addition, said shape says the shape of the part except incidental structures, such as the below-mentioned spacer and fixing structure.

By using the micro-nozzles with the above-mentioned curved surface and moving the contact surface sequentially like a roller, spotting one row at a time from one end of the discharge ports arranged in a matrix. Can spot accurately.
Alternatively, it is also preferable to form the entire micro nozzle of the present invention in a flexible sheet shape. High-resolution spotting is achieved by pressing a micro-nozzle formed in a flexible sheet shape from the back of the nozzle with a flexible member to bring the nozzle surface into close contact with the object to be spotted and spotting in that state. Is possible. In addition, a convex structure that acts as a spacer when spotting is provided on the nozzle surface, and when the micro nozzle is brought into contact with an application target (for example, a substrate for microarray), the distance between the discharge port and the application target is made close to a predetermined interval. It is also preferable to maintain the state in order to suppress variation between spots. The spacer preferably has a thickness of 3 to 100 μm, and more preferably 10 to 50 μm.

  The flow path of the micro nozzle of the present invention is formed as a defective portion of a cured product of the active energy ray curable composition constituting the micro nozzle. By forming a cured product of the active energy ray curable composition, the formation thereof is facilitated. However, the micro nozzle of the present invention does not need to be entirely composed of a cured product of the active energy ray curable composition, and part of the micro nozzle may be composed of other materials. It may consist of.

  The flow channel is preferably connected to one injection port and one discharge port corresponding thereto by one non-branched flow channel, but has four or more independent flow channels. In this case, a plurality of, preferably 2 to 10, and more preferably 2 to 4 discharge ports may be communicated with each other in a flow path in which one injection port is branched. Such a micro nozzle is suitable for an application in which a plurality of microarrays are simultaneously manufactured by simultaneously spotting four or more spots on a plurality of coating objects.

  The diameter of the inlet is larger than the diameter of the discharge port, and the distance between the centers of the injection ports is larger than the distance between the centers of the discharge ports. Thereby, the injection | pouring of a several different coating liquid can be performed easily, and the connection of piping for inject | pouring a coating liquid becomes easy. The injection port referred to in the present invention refers to the one in which the other end of the channel is opened on the surface of the micro nozzle, but a pipe may be connected thereto. In this case, the dimension of the surface portion of the micro nozzle is the dimension of the discharge port.

  The micro-nozzle of the present invention has a structure in which discharge ports are opened in the same direction and can be applied in a plurality of dots from a plurality of discharge ports to one application object. For example, if the application target is flat, the surface is flat, if the application target is a convex curved surface, the corresponding concave curved surface, and if the application target has a step, the corresponding step is provided. Each discharge port is formed so as to open on the surface.

  Although the number of discharge ports is four or more, it is usually 4 to 10,000, more preferably 10 to 10,000, and further preferably 30 to 1,000. When the number of discharge ports is 3 or less, the effect of the present invention is hardly exhibited, and when it is excessively large, production becomes difficult.

  The arrangement of the discharge ports is arbitrary, and may be, for example, a linear arrangement, a plurality of lines of a linear arrangement, a matrix arrangement, an alternating arrangement, a circular arrangement, a concentric arrangement, a radial arrangement, etc. It is preferable to have a linear arrangement or a shape (matrix arrangement) arranged in the vertical and horizontal directions. However, the discharge ports in each row may be arranged at the same position, alternately, or obliquely.

  Since the micro nozzle of the present invention is intended for spotting into a plurality of independent spots, the distance between the centers of the discharge ports is 4 times or more, preferably 5 times or more, more preferably 6 times the diameter of the discharge ports. This is larger than the known composite fiber spinning nozzle. Further, the distance between the centers of the discharge ports is 10,000 times or less, preferably 100 times or less, more preferably 10 times or less the diameter of the discharge ports. If it is smaller than this range, it will be difficult to spot independent points. If it is larger than this range, the nozzle size tends to be large.

  The distance between the centers of the discharge ports is arbitrary, and can be, for example, the distance between the centers of the spots of the microarray to be manufactured, but is preferably 2 to 1000 μm, and more preferably 5 to 500 μm. Of course, the distance between the centers does not need to be constant, and may be different in the vertical direction and the horizontal direction.

  The shape of the discharge port is arbitrary, and may be a circle, a hexagon, a rectangle, a slit, or the like, but is preferably a circle or a rectangle. The diameter of the discharge port is preferably 1 to 500 μm, more preferably 1 to 300 μm, and most preferably 3 to 200 μm. However, if the cross-section is not a circle, it is expressed by the diameter of a circle having the same cross-sectional area. If it is too small, the production becomes difficult, and the discharge speed decreases. If it is too large, formation of a minute spot becomes impossible.

  The discharge port may be formed on a flat surface of the micro nozzle, a curved surface, an upper plane of a trapezoidal convex structure, or a cylinder in which the periphery of the discharge port is higher in a wall shape than these surfaces It may be in the shape. In particular, when the target site to be applied is the bottom of a groove-like recess, the discharge port is formed on the upper plane of the above-mentioned trapezoidal convex structure that is high enough to reach the bottom of the groove. Or it is preferable that it is formed in the said cylindrical shape.

  The micro-nozzle of the present invention is (1) a member (hereinafter referred to as “member (A)”) having four or more capillary channels that pass through the member and discharge ports of the channels. (2) The flow path in the member made of a cured product of the active energy ray-curable composition and communicating with the discharge port of the member (A), or the flow path is formed on the surface laminated with the member (A) And a member formed by laminating a member (hereinafter referred to as a member (B)) having a defect portion.

  Hereinafter, the micro nozzle according to the present invention will be described in the case where the micro nozzle is composed of the member (A) and the member (B). However, the description is the same for other structures. Further, in the present specification, the member (A) expresses the top and bottom, the height, and the like in a posture in which the opening (nozzle surface) of the discharge port is placed downward.

  First, the member (A) having four or more independent capillary channels penetrating the members and the discharge ports of the channels will be described. The discharge port is provided as an opening of a hole-like flow path that penetrates through the member (A) (the flow path formed in the member (A) may be referred to as “flow path (A)”). ing. The diameter and shape of the flow path (A) may be constant or different in the depth direction. Further, the direction in which the holes are pierced is not necessarily perpendicular to the nozzle surface of the member (A), and the plurality of flow paths (A) may not be parallel to each other.

  The outer shape of the member (A) can take any shape depending on the shape of the micro nozzle, but can be the same as the preferred shape of the micro nozzle of the present invention described above. Among them, for example, a planar shape, a trapezoidal shape, and a shape having a convex portion serving as a spacer on the surface are preferable.

  The member (A) is preferably formed so that the whole or the nozzle surface is formed smaller than the member (B), and for example, when used in a contact type, only the vicinity of the discharge port is in contact with the application object. In particular, when the target site to be spotted is the bottom of the groove-shaped recess, the width of the member (A) is smaller than the width of the groove of the application object, instead of the member (A) being a trapezoid. The thickness is preferably a thickness corresponding to the depth of the groove.

  Although the thickness of a member (A) is arbitrary, 0.5-500 micrometers is preferable and 3-100 micrometers is still more preferable. If the thickness is too small, it becomes difficult to manufacture, and if it is too large, it becomes difficult to form fine discharge ports, and the discharge amount during use is reduced, so that spot formation at high speed becomes impossible. As will be described later, when the member (A) is formed of a hydrophobic material and the member (B) is formed of a hydrophilic material, the thickness of the member (A) is preferably thinner. The member (A) may have a defective portion that becomes a flow path when laminated with the member (B) on the upper surface, that is, the back surface of the nozzle surface.

  The member (A) may be made of any material, and may be, for example, glass, crystals such as quartz, metals such as stainless steel, semiconductors such as silicon, ceramics, carbon, polymers, and the like. The member (A) may be a composite formed of different materials, for example, a laminate, but the whole is composed of the same material, or a laminate of thin film-like members as described below. It is preferable because it is easy to manufacture.

  Among these materials, a polymer is preferable because the nozzle surface is easily made hydrophobic. The polymer may be a homopolymer or a copolymer, and may be a thermoplastic polymer or a thermosetting polymer. From the standpoint of productivity, the polymer is a cured product of an active energy ray-curable composition (hereinafter, the active energy ray-curable composition constituting the member (A) may be referred to as “composition (A)”). Preferably there is.

  The material constituting the nozzle surface of the member (A) preferably has a contact angle with water of 45 degrees or more, more preferably 55 to 110 degrees, and most preferably 60 to 95 degrees ( Hereinafter, such surface characteristics are referred to as “hydrophobic”). If the contact angle with water is less than this range, the nozzle surface is wetted by the liquid introduced into each discharge port, which tends to induce spot spread and contamination between liquids.

  There is no inconvenience due to the fact that the contact angle of the nozzle surface with water itself is high and may be 180 degrees, for example, but if the contact angle of the nozzle surface is increased, the inner surface of the hole formed in the member (A), that is, The inner surface of the flow path (A) having the discharge port as an opening tends to be high at the same time, making it difficult to control the discharge pressure. The smaller the contact angle of the inner surface of the channel (A), the better, preferably 90 degrees or less, and more preferably 70 degrees or less.

  From this point, it is also preferable that the member (A) is a composite composed of a plurality of layers, a very thin layer is formed of a hydrophobic material, and the inner layer is formed of a hydrophilic material. Alternatively, the member (A) is preferably formed into a thin film and laminated with the hydrophilic member (B). From the viewpoint of durability, the member (A) is preferably made of a material having high hardness or a material having high wear resistance at least at the portion that becomes the nozzle surface.

  Examples of the polymer that can be used for the member (A) include polystyrene, poly-α-methylstyrene, a copolymer of polystyrene and maleic acid, a styrene polymer such as a copolymer of polystyrene and acrylonitrile, and porsulfone. , Polysulfone polymers such as polyethersulfone, (meth) acrylic polymers such as polymethyl methacrylate and polyacrylonitrile, polymaleimide polymers,

  Polycarbonate polymers, polyolefin polymers, chlorine-containing polymers such as vinyl chloride and vinylidene chloride, cellulose polymers such as cellulose acetate and methyl cellulose, polyurethane polymers, polyamide polymers, polyimides Polymers, fluoropolymers, polyether or polythioether polymers such as poly-2,6-dimethylphenylene oxide, polyphenylene sulfide,

  Examples thereof include polyether ketone polymers such as polyether ether ketone, polyester polymers such as polyethylene terephthalate and polyarylate, epoxy resins, urea resins, and phenol resins. Among these, a styrene polymer, a (meth) acrylic polymer, a polycarbonate polymer, a polysulfone polymer, and a polyester polymer are preferable from the viewpoint of good adhesion to the member (B).

  The polymer that can be used for the member (A) is also preferably a cured product of an active energy ray-curable composition (hereinafter referred to as “composition (A)”). Forming the member (A) with a cured product of the composition (A) is easy to control the flexibility, hydrophobicity, etc., and easily adhere to the member (B). preferable. The composition (A) is the same as the composition (B) described later except that the ratio between preferred hydrophilicity and hydrophobicity and the preferred hardness are different.

  The method of forming the discharge port and the flow path (A) is arbitrary, and drill drilling, laser drilling, lithography (etching), photolithography (refers to patterning hardening using active energy rays or patterning decomposition using active energy rays; the same applies hereinafter), Micro stereolithography can be used. Among these, a method in which the composition (A) is used as the material of the member (A), and the discharge port and the flow path (A) are simultaneously formed by on-site polymerization of the member (A) by photolithography. Is preferred.

  Subsequently, the flow path is formed on the surface of the member made of the cured product of the active energy ray-curable composition and connected to the discharge port of the member (A), or on the surface laminated with the member (A). The member (B) having a defect portion will be described. Hereinafter, the member (B) will be described with reference to the simple schematic diagrams shown in FIG. 8 and FIG. 9 as an example. The members (B) (22) and (23) are laminated and fixed to the members (A) and (21), so that one end of each of the channels (28, 28 ', 28 ") of the member (A). , 28 ′ ″), and the other end is connected to the surface of the member (B) (23) as a capillary (27, 27 ′, 27 ″, 27 ′ ″). 25, 26, 25 ′, 26 ′, 25 ″, 26 ″, 25 ′ ″, 26 ′ ″) (hereinafter, only one of the four systems will be shown and described as necessary). Have

  The flow path may be formed as a capillary inside the member (B), and a defect portion (25) is provided on the surface, and the surface of the member (B) (22) having the defect portion is formed on the member ( A) By being laminated on the member (A) on the (21) side, the capillary channel (25) is formed on the side surface of the defect portion (25) and the surface laminated with the members (A) (21). It may be formed. The member (B) may have both a defect part (25) and a capillary channel (Example 1, FIGS. 1-7).

  The channels (25, 26) are channels for supplying liquid to be discharged to the channels (A) (28) connected to the discharge port (24), and preferably have a diameter larger than the diameter of the discharge port. By doing so, flow path resistance is reduced and high speed spotting is possible. The other end of the channel is opened as an inlet (27) in the members (B) and (23) or between the members (A) and (B).

  The center-to-center distance of the injection port (27) is greater than the center-to-center distance of the discharge port (24), and the ratio of “the center-to-center distance of the injection port / the center-to-center distance of the discharge port” is greater than 1, Preferably, 5 to 100 is more preferable, and 10 to 50 is most preferable. In the present invention, this ratio can be made large. If this ratio is too small, the effect of the present invention will not be exhibited, and if it is too large, the nozzle will become excessively large, resulting in inconvenience.

  By making the center-to-center distance of the inlet larger than the center-to-center distance of the discharge port, a large-diameter flow path can be formed to reduce pressure loss, and piping can be easily connected to the large-diameter inlet. The liquid supply to the inlet becomes easy.

  The cross-sectional area of the flow path (25, 26) is arbitrary, but is preferably larger than the area of the discharge port, and is the smallest at the portion in contact with the member (A) (21) and the largest at the injection port (27). Is more preferable. With such a structure, the flow path resistance can be reduced.

  In addition, it is preferable that the flow paths (25, 25 ′, 25 ″, 25 ′ ″) have the same length in order to equalize the pressure loss of the flow paths, or the flow paths (25, 25 ′). , 25 ″, 25 ′ ″) by adjusting the cross-sectional area, it is also preferable to equalize the pressure loss between the flow paths.

  The injection port (27) may be opened on any surface of the member (A), the member (B), or both, and is opened between the members (A) (21) and the members (B) (22). However, it is preferable that the member (B) is open on the surface opposite to the member (A).

  The positional relationship between the discharge ports (24, 24 ′, 24 ″, 24 ′ ″) and the injection ports (27, 27 ′, 27 ″, 27 ′ ″) is arbitrary, and is, for example, drawn radially from the discharge ports. An injection port is formed at the other end of the flow channel, and a shape having a discharge port group near the center of the nozzle, or an injection port is formed at the other end of the flow channel drawn in one direction from the discharge port. The shape may be such that the group and the inlet group are separated. When the discharge ports are arranged in a matrix, it is preferable that the injection ports have an enlarged matrix arrangement that is arranged on the upper surface of the member (B) in the same order as the discharge ports.

  The injection port (27) has a structure for connecting to a mechanism for feeding the discharge liquid, for example, a piezo element, an ink jet driving mechanism such as a heating mechanism, for example, a conical structure of the inlet, and a convexity around the inlet. It may be molded into a cylindrical structure, an O-ring holding structure, etc., or a mechanism for connecting pipes, such as a hose port, screw hole, luer fitting (standard connector that can fix a syringe with about 1/4 rotation) Further, an O-ring holding structure or the like may be provided, or the pipe may be fixedly connected.

  Alternatively, the injection port (27) may have a well shape. In the case of a well shape, the liquid is fed only by movement due to its own weight or capillary phenomenon without a special liquid feeding mechanism. A pipe for applying pressure by a water column, a mercury column, an oil column or the like may be connected to the well, or a pressurizing mechanism using a pressure gas or the like may be provided. Further, the member (B) may be provided with other structures, for example, an inkjet drive mechanism such as a piezo element or a heating mechanism, a diaphragm pump, a base diaphragm valve, a filtration mechanism connected to a flow path, or the like. good.

  The outer shape of the member (B) is arbitrary as long as it can be laminated and fixed in close contact with the member (A), and is similar to the shape shown in the case of the member (A). Although the height (thickness) of a member (B) is arbitrary, Preferably it is 10 micrometers-30 mm, More preferably, it is 100 micrometers-10 mm. If the thickness is too small, it becomes difficult to produce, and if it is too large, it becomes difficult to form a fine flow path, and the discharge amount during use decreases, so that spot formation at high speed becomes impossible. In the present specification, the height and the like of the member (B) are expressed by the posture of being laminated on the member (A) placed with the nozzle face down.

  The member (B) is formed of a cured product of an active energy ray-curable composition (hereinafter referred to as “composition (B)”). By forming with the hardened | cured material of a composition (B), formation of the structure which has a flow path inside becomes easy, and control, such as hydrophilic property and a softness | flexibility, becomes easy.

  The member (B) is preferably composed of a laminate in which a plurality of members each formed of a cured product of the composition (B) are laminated. As an example of the member (B) made of such a laminate, a member (B1) having an inlet and a flow path in the member connected to the inlet, a member (A), and a member (B1) are laminated. And a member (B2) having a defect portion forming a flow path with the formed surface or a flow path in the member.

  More specifically, the member (B) is formed by laminating two members (member 22 and member 23), and the layer constituting the member (B) becomes a capillary channel (25). It is preferable that it has (25).

  When the member (B) is a laminate, the lamination direction of the members constituting the member (B) may be parallel to the contact surface with the members (A) (21) or may be laminated at other angles. The members (A) and (21) are preferably laminated in parallel with the contact surface.

  Hereinafter, the member (B) is a laminate, and a plurality of members (22, 23) constituting the member (B) are formed in parallel with the contact surface with the member (A), with the nozzle surface facing downward. A description will be given in a state where the members are stacked and fixed on the members (A) and (21) placed on the surface. Such a structure has, for example, a defective portion (25) formed of a defective portion of the layer constituent material in the member (22), and the member (22) is another member (23) (or one is a member ( A) and (21) may be sandwiched and laminated so that the defect (25) becomes a capillary channel (25).

  The defect part (25, 26) may be linear, for example, or may have any shape that forms a cross section of the flow path (26) passing through the member (23) up and down (in the thickness direction). When the defect is linear, the line is not limited to a straight line, and may be an arbitrary line such as a curve or a zigzag. In this case, the flow path is formed in the member (22) in parallel with the member (22).

  When the defect portion (25, 26) has a shape that is a cross section of the flow path, it is preferably a circle, but may be any shape such as a rectangle or a slit. In this case, it is also possible to form a channel formed by slanting by laminating the position of the missing portion of each member little by little.

  When the member (22) is in contact with the member (A) (21), the defect portion (25) is provided at a position connected to the flow path (A) (28), and the member (B) includes a plurality of members (B). When the members are stacked and come into contact with another member (23) constituting the member (B), the member is provided so as to be connected to the defective portion (26) provided in the other member (23). The formed flow path may be opened as an injection port (27) at the edge of the member forming the member (B) (that is, the side surface of the nozzle), or the member (23) (23) ( That is, you may open to the back surface of a nozzle.

  In addition, when the member (B) is formed by laminating a plurality of members, the number of members having the linear defect portion (25) may be one layer, but when the number of nozzles is large, the linear shape It is preferable to form a flow path parallel to the contact surface of the member (A) and the member (B) in the multiple layers by laminating a large number of layers having a defect (Example 1 and FIGS. 1 to 7). . Specifically, the member (B) includes (1) a member (B1 ′) having an inlet and a flow path in the member connected to the inlet, and (2) members constituting the member (B). A member (B3 ′) having a defective portion forming a flow path on the surface where the layers are stacked, a flow path in the member, and (3) a surface where the members (A) and (B3 ′) are stacked. What has the defect | deletion part which forms a flow path, and the member (B2 ') which has the flow path in a member is mentioned. In that case, you may form this member (B3 ') by laminating | stacking many members, and it is preferable that the number of this member (B3') is 2-40, and it is further 4-30. preferable.

  In the member (B2 ′), a member having a linear defect part and a member having a hole defect part are alternately laminated (Example 1 and FIGS. 1 to 7), and the flow path provided in each layer. This is preferable because it avoids position interference and increases the degree of freedom in design. In this case, the number of members having linear defects is preferably 2 to 20, and more preferably 3 to 15. If it is less than this, it will be difficult to form a nozzle having a large number of discharge ports, and if it is too much, it will be difficult to produce.

  In the matrix arrangement in which the discharge ports are arranged in a matrix and the injection ports are enlarged (for example, in Example 1 and FIGS. 1 to 7), the member (B2) includes a plurality of members having a defect portion that becomes a flow path. It is preferable that a flow path formed in a layer close to the member (A) communicates with the outer discharge port, and a member farther from the member (A) takes charge of the discharge port closer to the center. Therefore, when manufacturing a micro nozzle having 2N rows of discharge ports when N is a natural number, it is preferable to have a member having a defective portion that becomes a horizontal flow path laminated on the N layer.

  For the part where the shape of the defect part (25) is linear and the linear defect part becomes a flow path, the width of the defect part (25) becomes the width of the flow path, and the member (22) having the defect part Is the height of the flow path. When the member (B) is composed of a plurality of members, the thickness of each member is preferably 1 to 1000 μm. In addition, when the shape of the defect is a hole (26) and the hole-shaped defect becomes a cross section of the flow path (26), the diameter is preferably 1 to 1000 μm, more preferably 10 to 500 μm. It is.

  If it is thinner or smaller than this, it becomes difficult to produce, and the liquid supply speed to the discharge port is insufficient. If it is thicker or larger than this, the nozzle becomes excessively large. However, this is not the case when the defective portion serving as the flow path has another structure such as the well (26) at the same time.

  The member (B) (22) and the member (A) (21) are laminated by connecting the discharge port (24) or the flow paths (A) (28) and the flow path (25) to form the member (A) Any method can be used as long as the relative position of the member (B) is fixed, for example, screwing, caulking, fitting, compression by other members, etc., adhesion, adhesion, fusion, surface dissolution and drying. Integration by polymerization, integration by polymerization, and the like.

  Examples of the adhesion include use of a solvent-type adhesive, use of a solventless adhesive, and use of a melt-type adhesive. Examples of the fusion include fusion by heat, ultrasonic waves, and high frequencies. The integration by dissolution and drying may be performed by solvent application or solvent absorption on the surface of the member to be fixed. In the integration by polymerization, the member to be fixed is formed as a semi-cured product of the active energy ray-curable composition, and the active energy ray is further irradiated and cured in a state in which the member is in close contact with the other member, and simultaneously bonded. A method is mentioned. Among these, integration by polymerization using an active energy ray-curable composition is preferable because it does not block fine voids and has high productivity.

  When the member (B) is composed of a plurality of members, the fixing method of each member constituting the member (B) is arbitrary, but the same method as the fixing method of the member (A) and the member (B) Can be used. Among them, integration by polymerization using the composition (B) is preferable because it does not block fine voids and has high productivity.

  In the case where the member to be fixed does not have a defective portion, as another preferable fixing method, a member to be bonded by insufficiently irradiating active energy rays in a state where the composition (B) is spread on the liquid surface It is also preferable to form a cured product or semi-cured product and adhere it in the same manner as above. When it is necessary to provide a defect portion in the member, the defect portion can be formed by laser drilling after fixing.

  The liquid for developing the composition (B) is arbitrary, and examples thereof include water (including an aqueous solution, the same applies hereinafter), silicon oil, mercury, halogenated naphthalene, and the like, but water is preferred. It is also preferable to add a solvent to the composition (B). In the liquid level development, the composition (B) may be dropped or flown down from the liquid level, or may be extruded into the liquid.

  When member (B) consists of a plurality of members, each member may be formed continuously. For example, an active energy ray is patterned and irradiated to the uncured layer of the composition (B), and the member (B) formed on the composition (B) is removed without removing the uncured composition (B) in the non-irradiated portion. The second layer of B2) is formed (or the member (B1) is submerged to a depth corresponding to the thickness of the member (B2) below the liquid surface of the composition (B)), and active energy rays are patterned on the member (B2). A method (micro stereolithography) of irradiating and repeating this process can also be adopted.

  At this time, in order to prevent the active energy rays irradiated with patterning from curing only the surface layer and not to cure the non-irradiated part of the lower layer, the active energy ray absorption rate of the composition (B) is increased to lower the lower layer. For example, a method using active energy rays that are easily absorbed, such as an electron beam, and a method that focuses only on the surface layer using an optical system having a large aperture ratio.

  The composition (B) forms a cured resin by irradiation with active energy rays and contains an active energy ray-curable compound. The composition (B) may be an active energy ray-curable compound alone, a mixture of plural kinds of active energy ray-curable compounds, or may contain a third component. The active energy ray-curable compound is arbitrary as long as it is cured by active energy rays, and may be any one such as radical polymerizable, anionic polymerizable, and cationic polymerizable.

  The active energy ray-curable compound is not limited to those that polymerize in the absence of a polymerization initiator, and those that polymerize with active energy rays only in the presence of a polymerization initiator can also be used. The active energy ray-curable compound is preferably an addition polymerizable compound, and preferably has a polymerizable carbon-carbon double bond as the active energy ray-polymerizable functional group. ) A maleimide compound that cures even in the absence of an acrylic compound, vinyl ether, or photopolymerization initiator is preferred.

  Furthermore, the active energy ray-curable compound is preferably a compound that is polymerized to form a crosslinked polymer in that the shape retention is high in a semi-cured state and the strength after curing is also high. Therefore, a compound having two or more polymerizable carbon-carbon double bonds in one molecule (hereinafter, “having two or more addition polymerizable functional groups in one molecule” is referred to as “multifunctional”. More preferably).

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

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

  Trifunctional monomers such as trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, and pentaerythritol tetra (meth) Examples thereof include a tetrafunctional monomer such as acrylate and a hexafunctional monomer such as dipentaerythritol hexa (meth) acrylate.

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

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

  1,4-bis (maleimidoethyl) -1,4-diazoniabicyclo- [2,2,2] octane dichloride, 4,4'-isopropylidenediphenyl dicyanate N, N '-(methylenedi-p-phenylene And bifunctional maleimide such as dimaleimide, and maleimide having a maleimide group and a polymerizable functional group other than the maleimide group such as N- (9-acridinyl) maleimide. Maleimide monomers can be copolymerized with compounds having polymerizable carbon / carbon double bonds such as vinyl monomers, vinyl ethers, and acrylic monomers.

  These active energy ray-curable compounds can be used alone or in admixture of two or more. The active energy ray-polymerizable active energy ray-curable compound can also be a mixture of a polyfunctional monomer and a monofunctional monomer for the purpose of adjusting the viscosity, increasing the adhesiveness or tackiness in a semi-cured state, and the like. .

  Examples of the monofunctional (meth) acrylic monomer include methyl methacrylate, alkyl (meth) acrylate, isobornyl (meth) acrylate, alkoxy polyethylene glycol (meth) acrylate, phenoxydialkyl (meth) acrylate, and phenoxy polyethylene glycol (meth) acrylate. , Alkylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, hydroxyalkyl (meth) acrylate,

  Glycerol acrylate methacrylate, butanediol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxypropyl acrylate, ethylenoxide-modified phthalic acid acrylate, w-cargoxiaprolactone monoacrylate 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxyethyl succinic acid,

  Acrylic acid dimer, 2-acryloyloxypropyrihexahydrogen phthalate, fluorine-substituted alkyl (meth) acrylate, chlorine-substituted alkyl (meth) acrylate, sulfonic acid soda ethoxy (meth) acrylate, sulfonic acid-2-methylpropane-2 -Acrylamide, phosphate ester group-containing (meth) acrylate,

  Sulfonic acid ester group-containing (meth) acrylate, silano group-containing (meth) acrylate, ((di) alkyl) amino group-containing (meth) acrylate, quaternary ((di) alkyl) ammonium group-containing (meth) acrylate, (N -Alkyl) acrylamide, (N, N-dialkyl) acrylamide, achloroylmorpholine and the like.

  Examples of monofunctional maleimide monomers include N-alkylmaleimides such as N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide and N-dodecylmaleimide, N-alicyclicmaleimides such as N-cyclohexylmaleimide, and the like. N-benzylmaleimide, N-phenylmaleimide, N- (alkylphenyl) maleimide, N-dialkoxyphenylmaleimide, N- (2-chlorophenyl) maleimide,

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

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

  The composition (B) preferably contains an amphiphilic polymerizable compound that can be copolymerized with the active energy ray-curable compound that is an essential component of the composition. By containing an amphiphilic compound, it becomes possible to form a surface that is hard to swell the cured product in water, is hydrophilic, and has a low adsorptivity to biological components.

  The amphiphilic polymerizable compound contains both a hydrophilic group and a hydrophobic group in the molecule, and is copolymerized with the active energy ray-curable compound contained in the active energy ray-curable composition by irradiation with active energy rays. It has a polymerizable functional group that can be used. When the active energy ray-curable compound is a compound having two or more polymerizable carbon-carbon unsaturated bonds in one molecule, the amphiphilic polymerizable compound is one or more polymerizable in one molecule. A compound having a carbon-carbon unsaturated bond is preferred.

  The amphiphilic polymerizable compound need not be a crosslinked polymer, but may be a compound that becomes a crosslinked polymer. The amphiphilic polymerizable compound is also one that is uniformly compatible with the active energy ray curable compound. The term “compatible” in this case means that the phase separation does not occur macroscopically, and includes a state where micelles are formed and stably dispersed.

  An amphiphilic polymerizable compound is a compound having a hydrophilic group and a hydrophobic group in a molecule and compatible with both water and a hydrophobic solvent. Even in this case, the term “compatible” means that the phase is not macroscopically separated, and includes a state where micelles are formed and stably dispersed. The amphiphilic polymerizable compound has a solubility in water of 0.5% or more at 0 ° C. and a solubility in cyclohexane: toluene = 5: 1 (mass ratio) mixed solvent at 25 ° C. of 25% by mass. % Or more is preferable.

  As used herein, the term “solubility” means, for example, that the solubility is 0.5% or more by mass percentage means that at least 0.5% by mass of a compound can be dissolved, and the mass percentage is 0.00. Although 5% of the compound does not dissolve in the solvent, the compound in which only a small amount of the solvent can be dissolved is not included in the compound. If at least one of the solubility in water or the solubility in cyclohexane: toluene = 5: 1 (mass ratio) mixed solvent is lower than these values, it is difficult to satisfy both high surface hydrophilicity and water resistance. Become.

  When the amphiphilic polymerizable compound has a nonionic hydrophilic group, particularly a polyether-based hydrophilic group, the balance between hydrophilicity and hydrophobicity is 11 in terms of Griffin's HLB value (HLB value). What is-16 is preferable, and what is 11-15 is still more preferable. Outside this range, it is difficult to obtain a molded product having high hydrophilicity and water resistance, or the combination and mixing ratio of the compounds for obtaining it are extremely limited, and the performance of the molded product is poor. It tends to be stable.

  The hydrophilic group possessed by the amphiphilic polymerizable compound is arbitrary, for example, a cationic group such as an amino group, a quaternary ammonium group or a phosphonium group, an anionic group such as a sulfone group, a phosphoric acid group or a carbonyl group; It may be a nonionic group such as a polyethylene glycol group or an amide group, or a zwitterionic group such as an amino acid group. The amphiphilic polymerizable compound is a compound having, as a hydrophilic group, preferably a polyether group, particularly preferably a polyethylene glycol chain having a repeating number of 6 to 20.

  Examples of the hydrophobic group of the amphiphilic polymerizable compound include an alkyl group, an alkylene group, an alkylphenyl group, a long chain alkoxy group, a fluorine-substituted alkyl group, and a siloxane group. The amphiphilic polymerizable compound is preferably a compound having an alkyl group or alkylene group having 6 to 20 carbon atoms as a hydrophobic group. The alkyl group or alkylene group having 6 to 20 carbon atoms may be contained in the form of, for example, an alkylphenyl group, an alkylphenoxy group, an alkoxy group, or a phenylalkyl group.

  The amphiphilic polymerizable compound is preferably a compound having a polyethylene glycol chain having 6 to 20 repeats as a hydrophilic group and an alkyl group or alkylene group having 6 to 20 carbon atoms as a hydrophobic group. Among these amphiphilic polymerizable compounds, nonylphenoxypolyethylene glycol (n = 8 to 17) (meth) acrylate and nonylphenoxypolypropylene glycol (n = 8 to 17) (meth) acrylate are particularly preferable.

  The preferred ratio of the active energy ray-curable compound and the amphiphilic polymerizable compound varies depending on the types and combinations of the active energy ray-curable compound and the amphiphilic polymerizable compound, but 1 part by mass of the other active energy ray-curable compounds. On the other hand, it is preferable that it is 0.1 mass part or more of an amphiphilic polymerizable compound, and it is still more preferable that it is 0.2 mass part or more. If it is less than this value, it becomes difficult to form a highly hydrophilic surface.

  Further, the ratio of the amphiphilic polymerizable compound is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less, relative to 1 part by mass of the other active energy ray-curable compound. When the ratio of the amphiphilic polymerizable compound to 1 part by mass of the active energy ray-curable compound is more than 5 parts by mass, the polymer tends to be swellable with respect to water, and the polymer constituting the wetted part gels. It tends to become a thing.

  By appropriately selecting the mixing ratio of the active energy ray-curable compound and the amphiphilic polymerizable compound, a cured product that does not gel in a wet state and exhibits high hydrophilicity and low adsorptivity can be produced. As the hydrophilicity of the amphiphilic polymerizable compound is relatively strong, for example, the higher the HLB value of griffin, the smaller the preferred addition amount.

  In the composition (B), a photopolymerization initiator, a polymerization retarder, a polymerization inhibitor, a solvent, a thickener, a modifier, a colorant and the like can be mixed and used as necessary. The photopolymerization initiator that can be mixed and used as necessary in the composition (B) is active with respect to the active energy ray used in the present invention, and can polymerize the active energy ray-curable compound. If it is a thing, there will be no restriction | limiting in particular, For example, it may be a radical polymerization initiator, an anionic polymerization initiator, and a cationic polymerization initiator.

  Examples of such photopolymerization initiators include acetophenones such as p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and the like. Ketones such as benzophenone, 4,4′-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone,

  Examples thereof include benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether, benzyl ketals such as benzyldimethyl ketal and hydroxycyclohexyl phenyl ketone, and azides such as N-azidosulfonylphenylmaleimide. Moreover, polymeric photoinitiators, such as a maleimide type compound, can be mentioned.

  When the photopolymerization initiator is mixed and used in the composition (B), in the case of a non-polymerizable photopolymerization initiator, 0.005 to 20% is preferable as a mass percentage, and the range is 0.1 to 5%. Is particularly preferred. The photopolymerization initiator may be polymerizable, for example, a polyfunctional or monofunctional maleimide monomer exemplified as an active energy ray-polymerizable active energy ray-curable compound. The usage amount in this case is not limited to the above.

  As the polymerization retarder and polymerization inhibitor that can be contained in the composition (B), active energy ray polymerizable compounds such as α-methylstyrene and 2,4-diphenyl-4-methyl-1-pentene are polymerized. Examples thereof include vinyl monomers having a low speed and hindant phenols such as tert-butylphenol. When using light rays as the active energy rays, it is preferable to use a polymerization retarder and / or a polymerization inhibitor and a photopolymerization initiator in combination in order to improve patterning accuracy.

  Examples of the thickener that can be mixed and used in the composition (B) as needed include chain polymers such as polystyrene. Examples of the modifier that can be mixed and used in the composition (B) as necessary include, for example, hydrophobic compounds such as silicone oil and fluorine-substituted hydrocarbon that function as a water repellent and a release agent; Examples thereof include water-soluble polymers such as polyvinyl pyrrolidone and polyethylene glycol that function as an adsorption inhibitor. Examples of the colorant that can be mixed and used in the composition (B) as needed include arbitrary dyes and pigments, fluorescent dyes, and ultraviolet absorbers.

  The present invention also provides a production method capable of preferably producing the micro nozzle of the present invention. The first micro-nozzle manufacturing method of the present invention comprises a member (A) having four or more independent capillary channels penetrating the members and discharge outlets of the channels, and the member (A). Laminating a member (B) made of a semi-cured material of an active energy ray curable composition having a defective portion forming a channel with the member (A) or a member in the member connected to the discharge port. Then, the active energy ray is irradiated to cure the member (B), and the member (A) and the member (B) are adhered to each other. Hereinafter, for simplification of description, the coating includes casting unless otherwise specified. Moreover, a coating film shall contain a casting.

  In the first production method of the present invention, first, an active energy ray-curable composition (composition (B)) for forming a member (B) is coated on a temporary support, and an uncured coating is applied. It is preferable to form a film.

  The temporary support used in the production method of the present invention is capable of coating or casting the composition (B) thereon, and after curing the composition (B), It can be removed by any method such as peeling, dissolution, or decomposition. The shape of the temporary support is not particularly limited, and a shape corresponding to the purpose of use can be adopted.

  For example, it may be a sheet shape (including film shape, ribbon shape, belt shape), plate shape, coating film shape, roll shape, and other complicated shapes, but the composition (B) is applied thereon. From the viewpoint of easy work or casting, and easy irradiation of active energy rays, the surface to be bonded is a flat surface or a quadratic curved surface with a curved surface, particularly flexible. A sheet shape is preferred.

  The temporary support may be a composite, such as a coating formed on some support. The temporary support may also be printed with cells, drawings, alignment symbols and the like. The material of the temporary support is not particularly limited as long as the above conditions are satisfied, and examples thereof include polymers (polymers), metals, glasses, crystals such as quartz, ceramics, and semiconductors such as silicon. Among these, a polymer and a metal are particularly preferable.

  The polymer used for the temporary support may be a homopolymer, a copolymer, a thermoplastic polymer, or a thermosetting polymer. . From the viewpoint of productivity, a thermoplastic polymer or an active energy ray-curable crosslinked polymer is preferable.

  When removal of the temporary support is due to peeling, it is difficult to dissolve in many types of compositions (B), and it is easy to peel from the cured product. A chlorine-containing polymer, a fluorine-containing polymer, a polythioether polymer, a polyether ketone polymer, or a polyester polymer is preferably used.

  When the temporary removal of the support is by dissolution, for example, water-soluble resins such as polyvinyl pyrrolidone and polyethylene glycol, alkali-soluble resins such as carboxyl group-containing resins, amino groups and quaternary ammonium An acid-soluble resin such as a salt-containing resin is preferably used.

  The temporary support may be composed of a polymer blend or a polymer alloy, may be a laminate or other complex, and may be a surface-treated product. Furthermore, the temporary support may contain additives such as modifiers, colorants, fillers, reinforcements and the like. Surface treatment is for the purpose of preventing dissolution by the composition (B), for the purpose of facilitating the peeling of the composition (B) from the cured product, and for the purpose of improving the wettability of the composition (B). Could be

  The surface treatment method is arbitrary, for example, corona treatment, plasma treatment, ultraviolet treatment, electron beam treatment, sulfonation treatment, fluorination treatment, primer treatment with a silane coupling agent, physical treatment such as surface graft polymerization, rubbing, etc. Etc.

  When the composition (B) is thinly coated thereon, the temporary support is preferably wetted by the composition (B) or weak in repelling power. That is, the contact angle with the composition (B) to be used is preferably 90 degrees or less, more preferably 45 degrees or less, and most preferably 25 degrees or less.

  In the case where the temporary support is a material having a low surface energy, for example, polyolefin, fluoropolymer, polyphenylene sulfide, polyether ether ketone, etc., the composition used by the surface treatment of the adhesive surface of the temporary support. It is preferable to reduce the contact angle with the object (B).

  However, it is necessary to select the degree of treatment so that the cured composition (B) does not adhere so firmly that it cannot be peeled off by the surface treatment. As these surface treatment methods, for example, corona discharge treatment, plasma treatment, ultraviolet treatment, primer treatment and the like are preferable. In addition to the surface treatment, the wettability can be controlled by selecting a modifier to be blended with the temporary support.

  Examples of the modifier that can be contained in the temporary support include, for example, hydrophobizing agents (water repellents) such as silicon oil and fluorine-substituted hydrocarbons, water-soluble polymers, surfactants, and inorganic substances such as silica gel. Examples thereof include a hydrophilizing agent such as powder. Examples of the colorant that can be contained in the temporary support include arbitrary dyes and pigments, fluorescent dyes and pigments, and ultraviolet absorbers. Examples of the reinforcing material that can be contained in the temporary support include inorganic powders such as clay, organic and inorganic fibers, and woven fabrics.

  Although the thickness of the uncured coating film applied to the temporary support varies slightly due to shrinkage during curing, etc., since it is generally the thickness of the cured product layer, the preferred thickness of the coating film is the microscopic thickness of the present invention. It is substantially the same as the thickness of the member (B) in the nozzle. The composition (B) to be applied may be the same as or different from the composition (A) constituting the member (A).

  As a method for coating the composition (B) on the temporary support, any coating method that can be applied on the support can be used. For example, spin coating, roller coating, casting Method, dipping method, spray method, bar coater method, XY applicator method, screen printing method, letterpress printing method, gravure printing method, extrusion from nozzles and casting. Further, when the composition (B) is applied particularly thinly, it is also possible to employ a method in which the solvent is volatilized after the composition (B) is coated with a solvent.

  The part (B) which becomes a flow path in the member (B) connected to the discharge port of the member (A) on the uncured coating film of the composition (B) coated on the temporary support, the member ( A) and another member (B) constituting the member (B) (the member B2 or the member B2 ′) and a portion that becomes a defective portion that forms a flow path on a surface laminated with the surface, or a portion that becomes an injection port ( That is, these are portions that become defective portions) and are irradiated with active energy rays to semi-harden the composition (B) of the irradiated portion, while the active energy ray non-irradiated portions of the composition (B) are This is left as an uncured portion (hereinafter, this operation may be referred to as “patterning exposure” or simply “exposure”).

  The term “half-curing” as used herein refers to curing to such an extent that the composition (B) becomes non-flowable or difficult to flow and unreacted active energy ray-polymerizable functional groups remain. Such a semi-cured state can be obtained by irradiating an amount of the active energy ray that is insufficient for complete curing. If the irradiation amount of the active energy ray is too small and the degree of curing is insufficient, the selectivity for removing the uncured portion becomes insufficient, and the resin defect portion having the desired shape cannot be formed. ), The composition (B) enters the member (A) or the defective portion of the member (B) to block the formed flow path or cause fluctuations in the cross-sectional area of the flow path.

  On the other hand, when the irradiation amount is excessive and the degree of curing is excessive, the semi-cured coating film loses flexibility and the adhesiveness is lowered, resulting in incomplete adhesion. The optimum degree of semi-curing can be determined optimally by simple experiments with the system used.

  The shape of the pattern in the patterning exposure, that is, the shape of the portion to be a defective portion is the flow path in the member (B) connected to the discharge port of the member (A), the member (A) and the member (B) It is the shape used as the defect | deletion part which forms a flow path in the surface laminated | stacked with the member (B), or an injection port. In addition to the discharge port and the flow path, the defect portion can be simultaneously formed with other structures, such as an injection port, as necessary.

  Examples of active energy rays that can be used in the present invention include rays such as ultraviolet rays, visible rays, infrared rays, laser rays, and radiated rays, ionizing radiations such as X-rays, gamma rays, and radiated rays, electron beams, ion beams, beta rays, A particle beam such as a heavy particle beam may be mentioned. Among these, ultraviolet rays and visible light are preferable from the viewpoint of handleability and curing speed, and ultraviolet rays are particularly preferable.

  For the purpose of accelerating the curing and complete the curing, it is preferable to irradiate active energy rays 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.

  An exposure method, that is, a method of irradiating active energy rays to a portion other than a portion that becomes a defective portion is arbitrary. The photolithographic technique can be used.

  In the first production method of the micro nozzle of the present invention, after exposure, the uncured composition (B) in the non-irradiated part is removed to form a defective part (hereinafter, this operation may be referred to as “development”). is there). The developing method is arbitrary, and methods such as blowing with compressed air, absorption with filter paper, flushing with a non-solvent liquid flow such as water, dissolution with solvent, volatilization, decomposition, etc. can be used. Of these, the non-solvent liquid flow or the solvent dissolution is preferred. The flushing and dissolution can be arbitrarily selected from ultrasonic cleaning, shaking in a liquid, and cleaning with a discharge liquid or a spray liquid.

  The size of the defect formed by patterning exposure and development is not necessarily the same as the size of the non-exposed portion of the active energy ray (non-exposed portion), and may be larger or smaller than the size of the non-exposed portion of the active energy ray. In some cases. That is, it may vary depending on the type and irradiation amount of active energy rays, the reactivity of active energy ray-curable compounds, the type and addition amount of active energy ray polymerization initiators, the addition amount of polymerization inhibitors and retarders, the development method, etc. . For example, when the amount of irradiation light is large, the size of the defect portion tends to be smaller than the size of the non-exposed portion.

  The semi-cured coating film of the composition (B) coated on the temporary support is brought into contact with the member (A) after development, and further irradiated with active energy rays in that state, so that the composition (A) The semi-cured coating film is further cured and adhered to the member (A). However, when the semi-cured coating film of the composition (B) is further cured, the cured coating film of the composition (B) is adhered to the member (A) with sufficient strength, and the cured product layer of the composition (B). It is meant that the temporary support is cured to such an extent that it can be removed. Therefore, it is not always necessary to cure until the polymerizable reactive group disappears completely.

  The active energy ray irradiation in this step is limited to such an extent that the temporary support can be removed but the polymerizable reactive group in the composition (B) has not completely disappeared. It is also preferable to increase the strength for fixing the member. For example, in the same manner as the formation of the member (B) after removing the temporary support, for example, a structure such as a spacer is fixedly formed on the surface of the member (B).

  As the active energy ray that can be used for curing for fixing in this step, the active energy ray used in the step of semi-curing the composition (B) can be used, but the same as that used for the semi-curing. Need not be.

  After adhering the member (B) to the member (A), the member (B) is transferred to the member (A) by removing the temporary support from the member (B). The method for removing the temporary support is arbitrary, and may be peeling, dissolution, decomposition, melting, volatilization, etc., but peeling is preferable from the viewpoint of high productivity, and peeling in a liquid such as water is also preferable.

  Further, when the member (B) is composed of a plurality of members, after forming the member from the composition (B) in the same manner as described above, the composition (B) is further formed on the member in the same manner as described above. It can manufacture by repeatedly forming the other member which comprises a member (B). That is, after forming the member (B1) from the composition (B), the member (B2) comprising the same or different composition (B) as the member (B1) on the member (B1) in the same manner as described above. The method of forming and laminating is mentioned. Moreover, after forming the said member (B1 ') from a composition (B), it is the member which consists of the same or different composition (B) as a member (B1') further on this member (B1 ') similarly to the above. (B3 ′) is repeatedly formed at least once, and further, a member (B2 ′) made of the same or different composition (B) as the member (B1 ′) or (B3 ′) is formed on the member (B3 ′). The method of laminating is mentioned.

  At this time, when the member (B) is composed of a plurality of members, a linear flow path that is independent of each member is formed by arranging the missing portions that become the flow paths of the respective members so that the positions do not overlap when viewed from above. It can be formed, but when the positions overlap, an independent two-stage channel can be formed by sandwiching a member having a hole-like channel that becomes a vertical channel between the members. . The member to be transferred and bonded may not have a defect portion. In this case, the defect portion can be formed by laser ablation after lamination adhesion.

  When the member (B) includes a plurality of members, the order of forming the members is arbitrary, and may be from the side in contact with the member (A) or from the opposite side of the member (A). Further, after the member (A) is laminated with the member (B2) or the member (B2 ′) which is a part of the member (B), the member (B2) or the member (B2 ′) is further The member (B1) or the member (B3 ′) may be laminated.

  The method for producing a second micro-nozzle according to the present invention comprises four or more capillary channels that pass through members and discharge ports of the channels, and semi-curing of the active energy ray-curable composition. A member (A) made of a material and a member (B) having a defective portion that forms a flow path with the flow path in the member connected to the discharge port of the member (A) or the member (A). Then, the active energy ray is irradiated to cure the member (A), and the member (A) and the member (B) are bonded to manufacture the micro nozzle of the present invention.

  The second manufacturing method of the micro nozzle of the present invention is the same as that of the member (A) except that the composition (A) is used instead of the composition (B) described in the first manufacturing method. Forming a cured coating film, laminating it on the member (B), further irradiating active energy rays to advance the curing of the member (A), and bonding the member (A) and the member (B) is there.

  In the second manufacturing method of the micro nozzle according to the present invention, the defect formed as the non-irradiation part of the active energy ray is a defect part serving as a flow path or a defect part serving as an injection port. The defect portion that becomes the flow path may be a linear defect portion that forms a flow path that flows in a direction parallel to the resin layer, or a hole-like shape that penetrates the resin layer that flows in a direction perpendicular to the resin layer. It can be a defect. In the development, the uncured composition (A) in the non-exposed part is not completely removed, and a groove shape in which the bottom of the defect part does not reach the surface of the support can be used. It is possible to form such a groove-like defect and provide a through-hole at a necessary site by laser drilling or the like, but it is preferable to form a flow path penetrating the front and back by development.

  Next, the spotting method of the present invention will be described. The spotting method of the present invention is a method of applying (spotting) a coating solution to a coating object in a spot shape using the micro nozzle of the present invention, and is 4 or more, preferably 10 to 10,000, more preferably 30 in one operation. A method of spotting ~ 3000, most preferably 50 ~ 1000 different solutions simultaneously. Of course, as a plurality of different solutions, coating solutions having the same components and compositions can be used. In the spotting method of the present invention, the contact between the micro nozzle and the application target includes contact through a spacer, and the contact between the discharge port and the application target includes contact through the spacer. Make it not exist.

  The arrangement of spots to be spotted simultaneously is arbitrary, but a row arrangement or a matrix arrangement is preferable. The microarray manufacturing method of the present invention can manufacture one microarray by a single spotting operation. However, when the number of spots to be formed is particularly large, a single microarray is manufactured by a plurality of spotting operations. You may do it. In that case, a method of using a plurality of micro nozzles and spotting them on the substrate sequentially or in an arbitrary order is preferable.

  The spotting method of the present invention is a method in which a coating liquid is simultaneously ejected from each ejection port using the micro nozzle according to the present invention, and is applied (spotted) to a coating object in a dot shape. By discharging at the same time, high-speed spotting becomes possible, and the apparatus for discharging the coating liquid becomes simple.

  In the spotting method of the present invention, it is preferable to apply the coating liquid by bringing an object to be applied close to or in contact with the nozzle surface from a substantially vertical direction, and then separating it again in a substantially vertical direction. By applying by this method, it is possible to apply the dots so that the shapes and dimensions are uniform, particularly the dot shapes are circles. The distance between the micro nozzle and the object to be coated may be controlled by moving the micro nozzle or by moving the object to be coated.

  The spotting method of the present invention can employ a method in which a micro nozzle is brought close to an application object by stamping, contacting, pressing, or non-contacting. Even in stamping, contact, and pressing, when the micro nozzle has a spacer on the nozzle surface or when using another spacer, the discharge port should not touch the object to be coated and be close to a specific interval. become. By providing a spacer, the distance between the discharge port and the object to be coated can be easily kept constant. Even if the spotting speed is increased, the spot size can be made uniform and the reproducibility can be improved, and the spotting speed is improved. .

  The positional relationship between the top and bottom or the left and right of the micro nozzle and the object to be coated is arbitrary, but when spotting is stamping or pressing and the supply of the discharge liquid described below is due to gravity, the nozzle is moved from the top to the bottom. It is preferable to move to and stamp or press.

  For example, when adhering a liquid ejected from a discharge port into a hemispherical shape (hereinafter, a shape in which a part of a sphere is cut off by a plane is referred to as a “hemispherical shape”) The ejection liquid may be extruded, or the ejection liquid may be brought into proximity after being extruded, or at the same time. In the case of using a pump, it is preferable to perform spotting quantitatively by pushing out at a constant speed and bringing an object to be applied in close proximity at regular time intervals.

  The distance between the discharge port and the application target during spotting is preferably 0.2 to 10 times the diameter of the discharge port, more preferably 0.5 to 3 times the diameter of the discharge port. By setting this range, the spot shape, position, and spot interval can be accurately controlled, and the spotting speed is improved.

  However, when the supply of the discharge liquid described later is due to gravity or capillary action and the supply speed is slowed, it is preferably 0 to 3 times the diameter of the discharge port, more preferably the diameter of the discharge port. 0 to 1 times. That is, a method in which a discharge port is brought into contact with an object to be coated without providing a spacer is preferable because a small spot can be formed although the spotting speed is slow. In any of the spotting methods of the present invention, in any case, the distance between the discharge port and the application target is preferably smaller than the diameter when the amount of the coating liquid to be spotted is made spherical. That is, there is a moment when the coating liquid does not fly in the air and adheres to the object to be coated, but adheres to both the micro nozzle and the object to be coated.

  Although the supply method of the discharge liquid to the discharge port in this coating method is arbitrary, it is preferable that the supply is spontaneous by gravity or capillary action. This can be carried out, for example, by injecting the discharge liquid into a liquid storage tank-shaped injection port. A pipe filled with a coating liquid or other liquid may be attached to the injection port, and the supply speed of the coating liquid may be increased by the liquid column pressure, or the discharge liquid may be extruded into a hemisphere from the discharge port. When an appropriate liquid column height is selected, the discharge liquid can be stabilized in a hemispherical form from the discharge port. Further, by adjusting the liquid column opening, the amount of the hemispherical discharge liquid can be adjusted, and the spot size can be adjusted. This supply method is preferable because the apparatus for spotting can be simplified and it is not necessary to connect a pipe to each inlet even when a large number of spots are formed simultaneously.

  Further, the supply of the discharge liquid to the discharge port may be a supply by a pump or the like. Accordingly, it is possible to adopt a method of extruding the liquid from the discharge port into a hemispherical shape and adhering it to the application object close to the discharge port. In this method, pumps such as syringe pumps, gear pumps, squeezing pumps, diaphragm pumps, diaphragms by piezoelectric elements, electromagnetic actuators, pneumatic actuators, etc. and extrusion by pulsed compression in the middle of flexible piping, Pressurization such as opening and closing of valves and compressed air can be used.

  In order to prevent spots from spreading due to bleeding after the spotting operation, or when the microarray manufacturing method of the present invention is a stamp type, that is, a method in which the nozzle surface is in contact with the object to be coated, the amount of spotting is controlled. Therefore, it is also preferable to adjust the viscosity of the liquid to be spotted. The viscosity is preferably 5 to 500 mPa · s (cps), more preferably 10 to 100 mPa · s.

  The method for adjusting the viscosity is arbitrary, but a method in which a water-soluble polymer or oligomer is added to the coating solution and dissolved is preferable. The water-soluble polymer or oligomer is optional, and a polymer or oligomer having a nonionic, cationic or anionic hydrophilic group can be used. However, a compound having a nonionic hydrophilic group can interact with the biochemical substance to be plotted. For example, polyethylene glycol, polyvinyl pyrrolidone, poly (N-substituted) acrylamide, polyvinyl alcohol, polyhydroxymethyl styrene, and the like can be preferably used because of their small action.

  The diameter of the applied spot varies greatly depending on the surface characteristics of the object to be applied, such as bleeding after spotting, but also depends on the size and shape of the discharge port of the micro nozzle. Therefore, the diameter of the micro nozzle discharge port is preferably 1/10 to 1/2 of the diameter of the target spot. The distance between the centers of the spots is determined by the distance between the centers of the discharge ports of the micro nozzle. It is preferable to dry immediately after spotting for the purpose of preventing spot deformation due to bleeding and contamination with adjacent spots. The drying method is arbitrary, but hot air drying, infrared drying, and vacuum drying are preferable.

  When time and temperature are required to dry, such as chemically bonding components in the coating solution to the application target, moisturizing or warming is also preferable. The spotting method of the present invention can produce one microarray by a single spotting operation. However, when the number of spots to be formed is particularly large, a plurality of micronozzles are used to apply to a coating object. It is also preferable to produce a single microarray by spotting in any order.

  The spotter of the present invention (apparatus for applying a coating liquid to a coating object in the form of dots) has the above-described micro nozzle. It is an apparatus having a mechanism for spotting according to the sequence of the spotting method according to the present invention. The spotter of the present invention is optional except that it has a mechanism for mounting a micro nozzle, a mechanism for holding an object to be coated, and a mechanism for discharging a coating liquid from the micro nozzle.

  Examples of the mechanism for discharging the coating liquid from the micro nozzle include a mechanism for contacting, pressing, or stamping the micro-swell on the object to be coated, a mechanism for applying an impact while the micro nozzle is in contact with the object to be coated, Elements, heating elements, electromagnetic actuators, pneumatic actuators, valve opening / closing, mechanisms that push the coating liquid in a pulsed manner by pressure due to impacts in the middle of flexible piping, pumps such as syringe pumps, gear pumps, iron pumps, and compressed air A pressure mechanism such as can be used.

  The spotter of the present invention preferably has a mechanism capable of changing the distance between the micro nozzle and the object to be coated and making contact or setting at a predetermined distance.

  The spotter of the present invention preferably has a drying device. The method of the drying apparatus is arbitrary, but hot air drying, infrared drying, and vacuum drying are preferable. In the case where time and temperature are required to dry, such as chemically bonding components in the coating solution to the application target, the spotter of the present invention preferably has a moisturizing mechanism and a warming mechanism.

  The spotter of the present invention can manufacture one microarray by a single spotting operation. However, when the number of spots to be formed is particularly large, a plurality of micronozzles are mounted, and an object to be coated is applied. It is also preferable to use a spotting device in an arbitrary order to produce a single microarray. Alternatively, it is also preferable that the apparatus is equipped with a plurality of micro-nozzles, and a plurality of micro-arrays are manufactured simultaneously by spotting on a plurality of substrates.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example, this invention is not limited to the range of these Examples. In the following examples, “part” represents “part by mass” and “%” represents mass percentage unless otherwise specified.

<Active energy rays>
Using a multi-light 200 type light source unit manufactured by USHIO INC., Ultraviolet light having an intensity at 365 nm of 50 mW / cm ² was irradiated in a nitrogen atmosphere.

<Measurement method>
The measurements in the examples were performed by the following method.
(Measurement of tensile modulus and elongation at break)
The sheet-like sample was cut into a strip shape having a width of 10 mm and a length of 100 mm to obtain a measurement sample. These samples were subjected to measurement after being left in a room of 24 ± 1 ° C. and humidity of 55 ± 5% for 16 hours or more. “Strograph V1-C” manufactured by Toyo Seiki Seisakusho was used as a tensile tester, and measurement was performed at an interval of 80 mm between grips and a tensile speed of 20 mm / min in an atmosphere of 24 ± 1 ° C. and humidity of 55 ± 5%.

[Measurement of solubility of polymerizable compound in water]
A mixed solution of 0.5 part of polymerizable compound (b) and 99.5 parts of water at 0 ° C. was prepared, stirred vigorously, allowed to stand at 0 ° C. for 24 hours, and then visually checked for phase separation. did.

[Measurement of solubility of polymerizable compound in hydrophobic solvent]
Prepare a mixed solvent of cyclohexane and toluene consisting of 62.5 parts of cyclohexane and 12.5 parts of toluene, mix 25 parts of the polymerizable compound (b) and 75 parts of a mixed solvent of cyclohexane and toluene and stir vigorously at 25 ° C. Then, after standing at 25 ° C. for 24 hours, the presence or absence of phase separation was visually determined.

[Measurement of contact angle with water]
After leaving the sample at a temperature of 25 ± 1 ° C. and a humidity of 55 ± 5% for 24 hours, using a contact angle meter CA-X manufactured by Kyowa Interface Science, with the same temperature and humidity as described above, with a stabilization time of 3 minutes. It was measured.

<Preparation of active energy ray-curable composition>
The preparation method of the active energy ray curable composition used in the Example was shown below.
[Preparation of Composition A1]
As active energy ray-curable compounds, 10 parts of a trifunctional urethane acrylate oligomer ("Unidic V4263" manufactured by Dainippon Ink & Chemicals, Inc.) and dicyclopentanyl diacrylate ("R-" manufactured by Nippon Kayaku Co., Ltd.) 684 ") 90 parts, 0.5 part of 2,4-diphenyl-4-methyl-1-pentene (manufactured by Kanto Chemical Co., Ltd.) as a polymerization retarder, and 1-hydroxycyclohexyl phenyl ketone (Ciba Geigy Corporation) as an ultraviolet polymerization initiator 5 parts of “Irgacure 184” manufactured by the manufacturer was mixed to prepare Composition A1.

[Composition B1]
As a cross-linkable active energy ray-curable compound, 60 parts of a trifunctional urethane acrylate oligomer (“Unidic V4263” manufactured by Dainippon Ink & Chemicals, Inc.) and 1,6-hexanediol diacrylate (Daiichi Kogyo) 20 parts of “New Frontier HDDA” manufactured by Pharmaceutical Co., Ltd., nonylphenoxypolyethylene glycol (n = 17) acrylate (“N-177E” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., HLB value) as an amphiphilic polymerizable compound = 14.64, soluble in both water or a mixed solvent of cyclohexane and toluene), and 20 parts of 2,4-diphenyl-4-methyl-1-pentene (manufactured by Kanto Chemical Co., Inc.) as a polymerization retarder. 5 parts, and 1-hydroxycyclohexyl phenyl ketone (“Ilva” manufactured by Ciba Geigy) as a photopolymerization initiator Cure 184 ") 5 parts to prepare a composition B1 was homogeneously mixed.

[Example 1]
(Production of members)
As a temporary support, on the corona-treated surface of a polypropylene biaxially stretched sheet (“FOR” manufactured by Futura Chemical Co., Ltd., thickness 30 μm, single-sided corona treatment) (hereinafter referred to as OPP sheet) (not shown), The composition A1 is applied using a 50 μm bar coater, and the part other than the part formed with the discharge port (2) and the flow path (A) (13) of the member (A) shown in FIG. UV light was irradiated to the part of the film for 2 seconds to form a semi-cured coating film that lost fluidity, and the uncured composition A1 of the non-irradiated part was immersed in a 50% aqueous solution of ethanol for more than 5 seconds. Formed on a temporary support by forming discharge ports (2) and channels (A) (13) arranged in a matrix of 4x4 with a diameter of 100 µm and a center-to-center distance of 300 µm. The member A1 (1) having a thickness of 35 μm was formed.

  The use of a 250 μm bar coater in place of the 50 μm bar coater, the use of the composition B1 in place of the composition A1, and the pattern of the photomask forming a defect having the shape shown in FIG. In the same manner as above, an OPP sheet was used as a temporary support (not shown), and a member (B) having a thickness of about 185 μm formed on the cured product of the composition B1 thereon. The first layer (3) was formed. The first layer (3) of the member (B) is provided at a position where the distance between the outer rows is 10 mm from the position (4) corresponding to the outer two rows of the discharge ports (2) of the member A1 (1). A line-shaped defect portion (6) having a line width of 150 μm to be a lateral flow path reaching the four holes × 2 rows of hole-shaped defect portions (5) having a diameter of 1 mm is formed. In addition, a hole-shaped defect portion (7) having a diameter of 200 μm is provided at a position corresponding to 4 × 2 rows inside the discharge port (2) of the member A1 (1).

  Separately, in the same manner as the first layer (3) of the member (B), the member (B) first layer (3) has the shape shown in FIG. 3 except that it does not have a linear defect (6). ), The hole-like defect portions (4 ′) provided at positions corresponding to the outer 4 × 2 rows of the discharge ports (2) of the member A1 (1), corresponding to the inner 4 × 2 rows. 4 × 2 rows provided at positions corresponding to the hole-shaped defect portion (7 ′) provided at the position and the hole-shaped defect portion (5) of the first layer (3) of the member (B). A second layer (8) of the member (B) having a shape shown in FIG. 3 provided with a hole-like defect (5 ′) having a diameter of 1 mm was formed.

  Separately, in the same manner as the first layer (3) of the member (B), from the position (7 ″) corresponding to the two rows of outlets on the center side of the member A1, the shape shown in FIG. A line-shaped defect portion (10) having a line width of 150 μm and a member (4 × 2 rows of hole-shaped defect portions (9 ″) provided at a position where the center-to-center distance is 6 mm; B) 4 × 2 rows of hole-shaped defect portions (5 ″) having a diameter of 1 mm provided at positions corresponding to the hole-shaped defect portions (5 ′) of the second layer (8) of B) A third layer (11) of the member (B) having the shape shown in FIG. 4 was formed.

  Separately, the third layer (11) of the member (B) is the same as the other layers of the member (B) except that the coating thickness of the composition (B) is 2 mm and the ultraviolet irradiation is 10 seconds. ) In the positions corresponding to the hole-like defect portions (5 ″) and (9 ″) of 1), a layer provided with hole-like defect portions (5 ′ ″) and (9 ′ ″) having a diameter of 1 mm is formed. Then, the surrounding area was excised together with the temporary support leaving a range of 12 mm × 12 mm to form the fourth layer (12) of the member (B) having the shape shown in FIG.

(Adhesion of parts)
The fourth layer (12) of the member (B) and the third layer (11) of the member (B) are brought into close contact with each other, and the third layer of the member (B) is placed in a nitrogen atmosphere. By irradiating ultraviolet rays from the layer (11) side for 3 seconds, the composition (B) forming these layers was cured, and the two members were bonded. Then, a temporary support (not shown) is peeled from the third layer (11) of the member (B), and a 12 mm × 12 mm portion in contact with the fourth layer (12) of the member (B) is removed. The surrounding area was excised.

  In the same manner, the second layer (8) constituting the member (B), the first layer (3) constituting the member (B), and the member A1 (1) are sequentially bonded to the member (B). 6), the temporary support (not shown) of the fourth layer (12) is also peeled off and the periphery is excised, and the whole is irradiated with ultraviolet rays for 60 seconds to be completely cured. And the micro nozzle [D1] having the shape shown in FIG. 7 was produced.

  That is, this micro nozzle has a flow path (6) extending in a horizontal direction (that is, a direction parallel to the nozzle surface) between the member (A) and the member (B), and the member (B). There are also flow paths (10) extending in the horizontal direction, and these, flow paths (4 ') and (7, 7') extending in the vertical direction in the member (B), and the member (B ) In the vertical direction (5, 5 ′, 5 ″, 5 ′ ″) and (9 ″, 9 ′ ″) and the channel (A) in the member (A) (13) ), The discharge port (2) and the injection ports (5 ′ ″, 9 ′ ″) are connected to each other. Further, the flow paths (5, 5 ′, 5 ″, 5 ′ ″) and (9 ″, 9 ′ ″) are in a well shape.

  Further, a brass bar (not shown) having a diameter of 2 mm is vertically bonded with an epoxy adhesive on the member (B) of the portion corresponding to the area where the discharge port (2) at the center is formed on the micro nozzle. Glued to.

(Material characteristic test)
Separately, the OPP film used for the above member preparation was used as a temporary support, and the composition (A) 1 or B1 was applied thereon, and cured by irradiation with the same ultraviolet rays as described above for 60 seconds. The coated film was peeled off from a typical support to prepare a sheet-like molded product having a thickness of 185 μm, and a tensile test and a contact angle measurement were performed. As a result, the cured product of composition (A) 1 had a tensile modulus of 1.6 GPa, an elongation at break of 2.8%, and a contact angle with water of 81 degrees. The composition (B) cured product had a tensile elastic modulus of 580 MPa, an elongation at break of 7.2%, and a contact angle with water of 13 degrees.

(Spotting test)
Sixteen wells of micro nozzles manufactured using a syringe with an aqueous solution containing 0.01% of fluorescein (manufactured by Wako Pure Chemical Industries) and 1% polyethylene glycol (manufactured by Suwa Chemical Co., Ltd.) having an average molecular weight of about 2000 ( When 5 ′ ″) and (9 ′ ″) are fully filled, the solution spontaneously enters the flow path and reaches the nozzle surface, but does not drip from the discharge port (2) or wet the nozzle surface. There wasn't.

  The micro nozzle [D1] was pressed against an OHP sheet for ink jet printing with a brass rod in a stamping manner, and immediately thereafter, the OHP sheet was dried with hot air using a hair dryer. When black light was irradiated under a microscope, 16 spots of fluorescence were observed.

[Example 2]
(Production of micro nozzle)
The discharge ports are arranged in a matrix of 10 rows × 10 columns, the number of resin layers having linear flow paths, and the number of resin layers having hole-shaped flow paths provided therebetween are 5 layers. In the same manner as in Example 1 except that the micro nozzle is formed in a shape that is a part of a cylinder having a diameter of about 1 m and the member (A) side is convex, the discharge port has a diameter of 100 μm and a center-to-center distance of 300 μm. The linear flow path in the layer is 150 μm wide, the height is about 185 μm, the vertical flow path through the layer is 200 μm in diameter, and the diameter of the inlet used as a well is 1 mm. A hole micro nozzle [D2] was produced. Further, a brass square bar (not shown) having a diameter of 4 mm × 4 mm was vertically bonded with an epoxy adhesive to a portion on the micro nozzle [D2], which is opposite to the area where the central outlet is formed. .

(Spotting test)
When spotting was performed in the same manner as in Example 1 except that spotting was performed by rolling the nozzle surface on the OHP sheet, fluorescence of 100 spots was observed.

Example 3
(Production of micro nozzle)
100 discharge ports are formed in one row, the resin layer having a linear flow path is 5 layers each having 20 flow paths, and a hole shape provided between the layers The number of resin layers having a plurality of flow paths is five, the injection ports used as wells are provided in 20 holes × 5 rows, and the nozzle surface of the micro nozzle is a cylinder with a diameter of about 30 cm. The discharge port is 100 μm in diameter, the center-to-center distance is 300 μm, and the linear flow path in the layer is 150 μm in width, except that it is a part (however, the discharge port is in the same plane). A 100-hole micro nozzle [D3] having an outer dimension of 15 mm × 50 mm, having a height of about 185 μm, a vertical channel passing through the layer of 200 μm in diameter, and a well diameter of 1 mm was produced.

  Further, an acrylic plate (not shown) having a width of 50 mm, a thickness of 2 mm, and a height of 30 mm is vertically bonded with an epoxy adhesive to a portion of the nozzle member (B) corresponding to the area where the discharge port is formed. did.

(Spotting test)
When spotting was performed in the same manner as in Example 1, fluorescence of 100 spots was observed. Further, when spotting operation was performed 100 times at a distance of 500 μm between the centers, 10,000 spots were formed.

Example 4
(Production of micro nozzle)
In the same manner as in Example 1 except that the distance between the centers of the discharge ports and the injection ports, the dimensions of the flow paths, and the thicknesses of the respective layers are different, the discharge port has a diameter of about 10 μm and the center-to-center distance is 30 μm. The linear flow path is about 20 μm near the connection with the discharge port, the other part is about 100 μm, the height is about 35 μm, and the vertical flow path that penetrates the layer is about the diameter near the connection with the discharge port. A 16-hole micro nozzle [D4] having an outer dimension of 5 mm × 5 mm, having a diameter of 20 μm, the other part having a diameter of 100 μm, and a well diameter of 1 mm was produced. Further, a stainless steel rod having a diameter of 1 mm was vertically bonded with an epoxy adhesive to a portion of the micro nozzle facing the area where the discharge port was formed.

(Spotting test)
When spotting was performed in the same manner as in Example 1, fluorescence of 16 spots was observed.

[Reference Example 1]
(Production of micro nozzle)
Six discharge ports are formed in one row, a resin layer having a linear flow path is a single layer provided with six flow paths, and three injection holes are used as wells. × Except for being provided in two rows, in the same manner as in Example 1, the discharge port has a diameter of 200 μm, the center-to-center distance of 500 μm, the linear flow path in the resin layer has a width of 150 μm, a height of about 185 μm, a well A micro nozzle precursor having a diameter of 1.6 mm was prepared.

  A polystyrene plate (Dainippon Ink Chemical Co., Ltd.) having outer dimensions of 25 mm × 75 mm × 3 mm, in which six wells each having a diameter of 1.6 mm are formed at the injection port on the member (B) side of the micro nozzle precursor. Kogyo Co., Ltd.) was bonded to Composition A1 using ultraviolet rays.

  Further, as a temporary support, the composition A1 was applied to the corona-treated surface of the same OPP sheet (not shown) used in Example 1 using a 50 μm bar coater, and a photomask was used. The part that forms the spacer is irradiated with ultraviolet rays for 2 seconds to form a semi-cured coating film that has lost its fluidity, and the uncured composition A1 in the non-irradiated part is removed by blowing off with compressed air. The micronozzle precursor was brought into close contact with the discharge port forming surface and irradiated with ultraviolet rays for 30 seconds to cure the semi-cured spacer and simultaneously adhere to the member (A), and then peel the OPP sheet. By the above operation, rectangular spacers of 500 μm × 500 μm and a thickness of about 25 μm are arranged on both sides of the row of discharge ports, each with a distance of 1 mm from the line passing through the center of each discharge port, and arranged in two rows of 7 each. A 6-hole nozzle [D5] having an outer dimension of 25 mm × 75 mm and having an interval between rectangles arranged at 500 μm was produced.

(Spotting test)
The use of a micro nozzle [D5], the use of an aldehyde group-fixed slide glass [Tele Chem International Inc., Organoaldehyde SMA] of 25 mm × 75 mm and 1 mm thickness as an application target, And a fluorescently labeled DNA fragment having an amino group (Espec Oligo Service, 5′-C6 amino group-3′-FITC-26 base oligonucleotide) and a microspotting solution [Tele Chem International Inc. Spotting was carried out in the same manner as in Example 1 except that the 1/1 mixed solution was used. The object to be coated was held at 50 ° C. for 1 hour, then washed with water, dried with hot air, and observed with a fluorescence microscope (manufactured by Olympus). As a result, six fluorescent spots having a diameter of about 600 μm were observed.

[Reference Example 2]
(Production of micro nozzle)
A polyethylene tube having an outer diameter of 1.6 mm and an inner diameter of 0.5 mm is bonded to each well of the injection port of the micro nozzle [D5] produced in Reference Example 1 with a cyanoacrylate adhesive (manufactured by Toagosei Chemical Co., Ltd., Aron Alpha +). The micro nozzle [D6] was obtained.

(Production of spotter)
A pedestal having a mechanism for fixing a coating object at a fixed position by a positioning pin and vacuum, a pedestal movable up and down, a television camera fixed to the pedestal, and observing a spot forming part to be coated through a hole provided in the pedestal ( Sony), a spotter having an image monitor for projecting an image captured by the TV camera, a micro-nozzle mounting mechanism for holding the micro-nozzle [D6] in a fixed position by a positioning pin and vacuum, and a six-unit macro syringe pump A six-unit micro syringe pump (manufactured by KD Scientific Co., Ltd., IC-) filled with the same fluorescent soldier labeled DNA fragment-containing solution as used in Reference Example 1 at the other end of each tube of the micro nozzle [D6]. 3260 type) micro syringes.

(Spotting test)
Using the same aldehyde candy fixed slide glass as used in Reference Example 1 as the application target, place it horizontally above the pedestal and raise the pedestal until the spacer of the micro nozzle [D6] contacts the slide glass of the application target I let you. Next, when a fluorescently labeled DNA fragment-containing solution was introduced from each syringe of the 6-series microsyringe pump into the micro nozzle at a rate of 1 μL / min (set value), the DNA solution was slowly discharged from the discharge port of the micro nozzle, resulting in a hemispherical shape. It swelled and adhered to the surface of the object to be coated. At that time, the syringe pump was stopped and the pedestal was lowered and separated from the micro nozzle. When this coating object was treated in the same manner as in Reference Example 1 and observed with a fluorescence microscope, six fluorescent spots having a diameter of about 500 μm and a diameter equal to those in Reference Example 1 were observed.

It is a schematic diagram of the top view of the member (A) of the micro nozzle produced in Examples 1 and 4. It is a schematic diagram of the top view of the 1st layer which comprises the member (B) of the micro nozzle produced in Example 1 and 4. FIG. It is a schematic diagram of the top view of the 2nd layer which comprises the member (B) of the micro nozzle produced in Example 1 and 4. FIG. It is a schematic diagram of the top view of the 3rd layer which comprises the member (B) of the micro nozzle produced in Example 1 and 4. FIG. It is a schematic diagram of the top view of the 4th layer which comprises the member (B) of the micro nozzle produced in Example 1 and 4. FIG. It is a schematic diagram of a plan view of the micro nozzle produced in Examples 1 and 4. It is a schematic diagram of the elevation view of the micro nozzle produced in Examples 1 and 4. In the figure, continuous cavities serving as discharge ports, flow paths (A), flow paths, wells, and injection ports are shown in white. It is a schematic diagram of the top view of the micro nozzle used for description of this invention. It is a schematic diagram of the elevation view of the micro nozzle used for description of this invention.

Explanation of symbols

1: Member (A)
2: discharge port 3: member (B) first layer 4: position 4 ′ corresponding to the discharge port on the outer side of the member (A): hole-like defect portion, flow path 4 ″: hole-like defect portion, Channel 5: Hole-like defect portion, channel, well 5 ′: Hole-like defect portion, channel, well 5 ″: Hole-like defect portion, channel, well 5 ′ ″: Hole-like defect portion , Channel, well, inlet 6: linear defect 7: hole defect 7 ': hole defect 7 ": position corresponding to defect (7') 8: member (B) No. Double layer 9 ″: Hole-like defect portion, flow path, well 9 ′ ″: Hole-like defect portion, flow path, well, inlet 10: Linear defect portion 11: Member (B) third layer 12 : Member (B) fourth layer 13: flow path (A)
21: Member (A)
22: member (B) first layer 23: member (B) second layer 24, 24 ′, 24 ″, 24 ′ ″: discharge port 25, 25 ′, 25 ″, 25 ′ ″: linear defect Part, groove, flow path 26, 26 ′, 26 ″, 26 ′ ″: hole-like defect, flow path, well 27, 27 ′, 27 ″, 27 ′ ″: inlet 28, 28 ′, 28 ", 28 '": Channel (A)

Claims (7)

Four or more capillary channels having a member (A) and a plurality of members (B) stacked on the member (A), and outlets and inlets of each channel A micro nozzle having
(1) The distance between the centers of adjacent discharge ports is 4 to 10,000 times the diameter of the discharge ports,
(2) The distance between the centers of the adjacent injection ports is larger than the distance between the centers of the adjacent discharge ports, and the diameter of the injection port is larger than the diameter of the discharge port,
(3) The member (A) has four or more capillary channels that pass through the member (A) and discharge ports of the channels,
(4) The plurality of members (B)
(i) a cured product of the active energy ray-curable composition, and
(ii) It has a deficient portion that forms a flow path communicating with the discharge port of the member (A) on the surface where the members (B) are laminated and / or the surface laminated with the member (A). Micro nozzle characterized by The plurality of members (B)
(1) having a member (B2) in contact with the member (A), and a member (B1) laminated on the member (B2);
(2) The member (B1) has a flow path that penetrates the injection port and the member (B1) connected to the injection port.
(3) The member (B2) is
(i) a defective portion that forms a flow path by being laminated with the member (A) and a defective portion that forms a flow path by being laminated with the member (B1), or
(ii) a flow path passing through the member (B2),
The micro nozzle according to claim 1, comprising: The plurality of members (B)
(1) having a member (B2) in contact with the member (A), a member (B3) laminated on the member (B2), and a member (B1) laminated on the member (B3);
(2) The member (B1) has a flow path that penetrates the injection port and the member (B1) connected to the injection port.
(3) The member (B2) is
(i) a defective portion that forms a flow path by being laminated with the member (A) and a defective portion that forms a flow path by being laminated with the member (B3), or
(ii) having a flow path penetrating the member (B2);
(4) The member (B3) includes a defective portion that forms a flow path by stacking the members, and a flow path that penetrates the member (B3).
The micro nozzle according to claim 1, comprising: It is a manufacturing method of the micro nozzle of Claim 1,
(1) A member (A) having four or more capillary flow channels independent of each other that penetrate the member and a discharge port of each flow channel;
(2) A semi-cured product of an active energy ray-curable composition having a flow path that penetrates a member connected to the discharge port of the member (A) or a defect portion that forms a flow path with the member (A). A member (B) made of
(3) Next, the active energy ray is irradiated to cure the member (B) and bond the member (A) and the member (B).
A manufacturing method of a micro nozzle characterized by the above-mentioned. It is a manufacturing method of the micro nozzle of Claim 1,
(1) a member (A) having four or more capillary flow channels independent of each other penetrating the member and a discharge port of each flow channel, and made of a semi-cured product of the active energy ray-curable composition;
(2) Laminating a member (B) having a defective portion forming a flow path with a flow path penetrating a member connected to the discharge port of the member (A) or the member (A);
(3) Next, the active energy ray is irradiated to cure the member (A) and bond the member (A) and the member (B).
A manufacturing method of a micro nozzle characterized by the above-mentioned. A spotting method in which a coating solution is applied to a coating object in the form of dots using the micro nozzle according to claim 1. A spotter having the micro nozzle according to claim 1.

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