JP2016026904A - Joined member and production method of joined member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a joined member joined firmly, and having a fine space excellent in tolerance to a nonpolar solvent; and to provide a production method of the joined member.SOLUTION: In a joined member 1 formed by joining together a first substrate 11 comprising a cycloolefin resin and having a recessed part 20 formed thereon, and a second substrate 12 comprising a cycloolefin resin, and having a fine space 5 formed by the recessed part 20 and the second substrate 12, the first substrate 11 and the second substrate 12 are joined with a paraffinic material, and a hydrophilized layer 11a impermeable to a nonpolar solvent is formed in the recessed part 20.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a joining member having a fine space and a method for manufacturing the joining member.

  As a microreactor or an analysis chip, a flow path plate formed by a joining member obtained by joining two substrates is used. As a method for mass-producing such joining members, a base material made of a resin material is used.

  When a cycloolefin resin is used as a base material, the adhesive and the heat welding require a lot of manufacturing time until joining, and there is a problem that a fine flow path is crushed. Therefore, in Patent Document 1, an optical bonding technique using vacuum ultraviolet light processing has been developed. FIG. 12 is a schematic diagram of a vacuum ultraviolet treatment process in the resin microchannel chemical device 100 disclosed in Patent Document 1. As shown in FIG. 12A, the vacuum ultraviolet light 111 is irradiated from the vacuum ultraviolet light source 110, the vacuum ultraviolet treatment is performed on the bonding surfaces of the two substrates 103 and 104, and the surface modification layers 107 and 108 are formed. Been formed. As shown in FIG. 12B, in the subsequent bonding process, the two base materials 103 and 104 were heated and pressed to be bonded.

  In patent document 2, the technique joined using paraffin which is a nonpolar solvent was developed. FIG. 13 is a partial cross-sectional view of the microchip plate 200 made of the joining member disclosed in Patent Document 2, cut from the thickness direction. A first base material 202 and a second base material 203 made of cycloolefin polymer (cycloolefin resin) are joined together by being heated and pressurized through a paraffin adhesive layer 205, as shown in FIG. Thus, the flow path 204 is formed.

JP 2006-187730 A International Publication No. 2009/131070

  However, in the optical bonding technique using the vacuum ultraviolet treatment, the treated surface is hydrophilized, so that the bonding strength after bonding may be insufficient due to moisture adsorbed after the vacuum ultraviolet treatment. For this reason, there has been a problem that a microreactor or an analysis chip using a bonded substrate with insufficient bonding strength is damaged during use.

  On the other hand, since the cycloolefin resin is not sufficiently resistant to a nonpolar solvent, it is known that cracking and cracking occur when the nonpolar solvent diffuses excessively. In other words, the cycloolefin resin lacks chemical resistance against nonpolar solvents. For this reason, when joining using paraffin which is a nonpolar solvent, it is not preferable to apply more than necessary for joining. However, as shown in FIG. 13, when paraffin is applied to a portion that is not an adhesive portion, the paraffin sometimes remains excessively during heating and pressurization. In such a case, even if it is firmly joined using paraffin, for example, if excessive paraffin adheres to the flow path, cracking or cracking may occur in the base material of the cycloolefin resin. There has been a problem that the inner wall of the channel portion swells and blocks the channel.

  This invention solves the subject mentioned above and provides the manufacturing method of the joining member which has the fine space excellent in the tolerance to a nonpolar solvent while being joined firmly, and a joining member.

  In order to solve this problem, in the present invention, a first base material made of a cycloolefin resin and having a recess formed therein is joined to a second base material made of a cycloolefin resin, and the recess and the second base material are joined together. A joining member having a fine space formed by a base material, wherein the first base material and the second base material are joined by a paraffinic material, and a nonpolar solvent does not penetrate into the concave portion. A hydrophilic layer is formed.

  A paraffinic material that is a nonpolar solvent does not penetrate into the recesses in which the hydrophilic layer is formed. Since the joining part of the 1st substrate and the 2nd substrate is joined by the paraffin type material, joining strength is stabilized and it joins firmly. In addition, the hydrophilic layer formed in the concave portion of the first base material has a property that the nonpolar solvent does not penetrate (diffuse) and repels the nonpolar solvent. That is, the nonpolar solvent hardly diffuses in the concave portion having the hydrophilic layer, and the nonpolar solvent does not stay. Therefore, while the 1st base material and the 2nd base material are joined firmly, the joining member which has the fine space excellent in the tolerance to a nonpolar solvent can be provided.

  In the bonding member of the present invention, the hydrophilic layer is formed over the entire inner surface of the fine space. If a hydrophilic layer is formed over the entire inner surface of the fine space in the concave portion of the first base material and the portion of the second base material corresponding to the concave portion, the nonpolar solvent is difficult to diffuse and the nonpolar solvent is retained. No longer. Therefore, resistance to nonpolar solvents is further improved.

Furthermore, in the joining member of the present invention, the hydrophilic layer is preferably a modified layer that has been modified so that the sum of the polar component of the surface free energy and the hydrogen bonding component is 100 mJ / m ² or more. . If the modified layer is modified so that the total of the polar component of the surface free energy and the hydrogen bonding component of the formed hydrophilic layer is 100 mJ / m ² or more, the nonpolar solvent does not diffuse, so it is nonpolar Resistance to the solvent is further improved. For this reason, even when a nonpolar solvent is allowed to flow into the fine space, the nonpolar solvent does not penetrate and does not swell.

  Moreover, this invention is a manufacturing method of the joining member by which the 1st base material and 2nd base material which consist of cycloolefin resin were joined, Comprising: The said 1st base material and said 2nd base in which the 1st recessed part was formed In order to form a fine space by the step of preparing a material, the step of irradiating a part of the first base material including the first concave portion with ultraviolet light, and the first concave portion and the second base material, Applying a paraffinic material to one or both of the first base material and the second base material, and heating and pressurizing the first base material and the second base material to face each other. It is characterized by that.

  A hydrophilic layer is formed on a part of the first substrate by the step of irradiating with ultraviolet rays. The hydrophilic layer is a region in which the paraffinic material does not permeate even when the paraffinic material is applied to the first base material because the wettability of the paraffinic material is small. Since the paraffinic material does not permeate, the first recess in which the hydrophilic layer is formed is not swollen by the paraffinic material. Therefore, it is suppressed that the fine space formed in the joining member is blocked, and the resistance to the nonpolar solvent is excellent. Furthermore, since the area | region which has not irradiated the ultraviolet-ray of a 1st base material and a 2nd base material is joined by a paraffin type material, the joint strength of a 1st base material and a 2nd base material is stable, and It can be firmly joined. Therefore, it is possible to easily manufacture a joining member having a fine space in which the first base material and the second base material are firmly joined and excellent in resistance to a nonpolar solvent.

  Moreover, in the manufacturing method of the joining member of this invention, it further has the process of irradiating a part including the part corresponding to the said 1st recessed part in a said 2nd base material with an ultraviolet-ray. In addition to the partial region including the first concave portion irradiated with the ultraviolet rays of the first base material, the partial region including the portion corresponding to the first concave portion irradiated with the ultraviolet rays in the second base material is a paraffin type. The other areas are joined by a paraffinic material without the material being applied. The region where the hydrophilic layer is formed by irradiating ultraviolet rays is not swollen by the nonpolar solvent. Therefore, it is possible to easily manufacture a joining member having a hydrophilic layer over the entire inner surface of the fine space formed in the joining member and further improving resistance to a nonpolar solvent.

  Moreover, in the manufacturing method of the joining member of this invention, the 2nd recessed part corresponding to the said 1st recessed part is formed in the said 2nd base material, It is characterized by the above-mentioned. In the second base material, a second concave portion corresponding to the first concave portion irradiated with ultraviolet rays is formed, a part of the region including the second concave portion is not coated with a paraffinic material, and the other region is a paraffinic material. Are joined together. Since it has a 2nd recessed part, the joining member in which the comparatively big fine space was formed can be manufactured easily.

Furthermore, in the step of irradiating with ultraviolet rays, the hydrophilic layer is a modified layer that has been modified so that the sum of the polar component of the surface free energy and the hydrogen bonding component is 100 mJ / m ² or more. Features. If the modified layer is modified so that the total of the polar component of the surface free energy and the hydrogen bonding component of the formed hydrophilic layer is 100 mJ / m ² or more, a nonpolar solvent is allowed to flow into the fine space. Even in such a case, the nonpolar solvent does not penetrate into the hydrophilic layer. Thereby, the joining member which has the fine space excellent in tolerance to a nonpolar solvent can be manufactured reliably.

  According to the joining member of the present invention, the first base material and the second base material are joined by a paraffin-based material, and the hydrophilic layer that does not allow the nonpolar solvent to permeate is formed in the concave portion for forming the fine space. Is formed. Since the first base material and the second base material other than the recesses are joined by a paraffinic material, the joining strength is stable and the joints are firmly joined. Further, the nonpolar solvent is difficult to diffuse in the recess having the hydrophilic layer, and the nonpolar solvent does not stay. Therefore, while the 1st base material and the 2nd base material are joined firmly, the joining member which has the fine space excellent in the tolerance to a nonpolar solvent can be provided.

  According to the method for manufacturing a joining member of the present invention, the first base material is formed with a hydrophilic layer that is irradiated with ultraviolet light to a part including the first concave portion for forming a fine space and does not penetrate a nonpolar solvent. The paraffinic material is applied to one or both of the first base material and the second base material and bonded to the second base material. Thereby, since a 1st base material and a 2nd base material are joined by a paraffin type material, joining strength is stabilized and it can join firmly. On the other hand, the hydrophilic layer does not swell because no paraffinic material remains. For this reason, it is suppressed that the fine space formed in the joining member is blocked. Therefore, it is possible to easily manufacture a joining member having a fine space in which the first base material and the second base material are firmly joined and excellent in resistance to a nonpolar solvent.

It is a perspective view which shows the joining member of embodiment of this invention. It is a top view which shows the joining member of embodiment of this invention. It is the schematic cross section cut | disconnected by the III-III line | wire of FIG. It is explanatory drawing which shows the manufacturing process for manufacturing the joining member of FIG. It is a schematic cross section which shows the 1st modification of embodiment of this invention. It is explanatory drawing which shows the 2nd modification of the manufacturing process of this invention. It is explanatory drawing which shows the 1st modification of the manufacturing process of this invention. It is a schematic cross section which shows the 2nd modification of embodiment of this invention. It is explanatory drawing which shows the joint strength in an Example. It is explanatory drawing which shows the joint strength in an Example. It is explanatory drawing which shows the surface free energy in an Example. It is a schematic diagram of the process of the vacuum ultraviolet-ray process in the conventional resin microchannel chemical device, (a) is a schematic cross section of a vacuum ultraviolet-ray process, (b) is a schematic cross section of a joining process. It is the fragmentary sectional view which cut | disconnected the microchip plate by the conventional joining member from the thickness direction.

  Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings. For easy understanding, various dimensions in the drawings are appropriately changed.

  Below, the joining member 1 in this embodiment is demonstrated using FIGS. 1-3. FIG. 1 is a perspective view showing a joining member 1 according to an embodiment of the present invention. FIG. 2 is a plan view showing the joining member 1 according to the embodiment of the present invention. 3 is a schematic cross-sectional view taken along line III-III in FIG.

  As shown in FIGS. 1 and 2, the joining member 1 has a minute space 5 formed on the joining surface between the first base material 11 and the second base material 12. The minute space 5 has a rectangular cross section with a width of 100 μm and a depth of 40 μm, and is extended from the Y2 side to the Y1 side and branched on the Y1 side as shown in FIG. A through hole 6 penetrating in the Z1 direction is connected to the end of the minute space 5. The through-hole 6 is a portion that serves as an inflow port and an outflow port for fluid when the fine space 5 is used as a flow path.

  The first base material 11 is made of a cycloolefin resin, and is formed into a rectangular thin plate by injection molding. Similarly, the 2nd base material 12 consists of cycloolefin resin, and is shape | molded by the rectangular thin plate shape by injection molding. As shown in FIG. 3, a recess 20 is formed in the first base material 11. In the recess 20, a hydrophilic layer 11 a is formed. The hydrophilic layer 11a is a modified layer in which the irradiated surface of the cycloolefin resin as a base material is modified by being irradiated with vacuum ultraviolet light. The thickness of the hydrophilic layer 11a is estimated to be on the order of 1 μm, but is schematically shown in FIG.

  The hydrophilization layer 11a is a layer having hydrophilicity in the sense that it has a high affinity for water molecules, and the hydrophilicity can be simply evaluated by the wettability of water. The hydrophilic layer 11a has good wettability with water, low affinity with oils such as lipids and nonpolar solvents, and poor oil wettability, that is, has a property of repelling oils such as nonpolar solvents.

  The cycloolefin resin used for the first base material 11 and the second base material 12 is, for example, trade names ZEONEX and ZEONOR made by ZEON Corporation, trade name APPEL made by Mitsui Chemicals, trade name ARTON made by Nippon Synthetic Rubber, Nippon Kasei Kogyo Co., Ltd. The product name Optrez made by Polyplastics and the product name Topas made by Polyplastics can be used.

  The 2nd base material 12 is joined to the 1st base material 11 so that the minute space 5 can be formed with the recessed part 20 in which the hydrophilization layer 11a was formed, and the 2nd base material 12. FIG. The first base material 11 and the second base material 12 other than the region where the fine space 5 is formed are joined by a paraffin-based material to form a joint portion 30.

  In this embodiment, the 1st base material 11 and the 2nd base material 12 are joined by n-heptadecane (n-Heptadecane), and the junction part 30 is formed. Immediately before joining the first base material 11 and the second base material 12 made of cycloolefin resin, n-heptadecane is applied, and the first base material 11 and the second base material 12 are bonded together via n-heptadecane. Are joined. In this case, the joining part 30 has almost no thickness.

n-Heptadecane is a material of the chemical formula C ₁₇ H ₃₆ and is a paraffinic material that is a typical kind of nonpolar solvent. In the present specification, the paraffinic material is a hydrocarbon-based nonpolar solvent composed almost of dispersed components, and is a generic name including molecules of C ₂₀ H ₄₂ or less. Nonpolar solvents have the property of low wettability to hydrophilic materials. Therefore, n-heptadecane, which is a nonpolar solvent, does not adhere to the recess 20 where the hydrophilic layer 11a is formed by irradiation with vacuum ultraviolet light.

  In addition, the paraffinic material applicable to the junction part 30 is not limited to n-heptadecane.

The material that can be used for the joint 30 is preferably a nonpolar solvent. Here, the nonpolar solvent includes not only a solvent whose surface free energy is composed only of a dispersed component but also a solvent containing a polar component of 5% or less, preferably 1% or less. Typical nonpolar solvents are hydrocarbon paraffin (chemical formula C _n H _{2n + 2} ), naphthene (chemical formula C _n H _2n ), and the like. The number average molecular weight of paraffin and naphthene is within the range of 100 to 1000, preferably within the range of 200 to 600, and the average carbon number is about 7 to 72, preferably with the paraffinic material applied to the present invention. Is about 16-45.

  The cycloolefin resin used for the first base material 11 and the second base material 12 has chemical resistance in the polar solvent, but does not have chemical resistance in the nonpolar solvent. For example, when a cycloolefin polymer resin is oiled, it becomes brittle and cracks occur. This was a phenomenon difficult to overcome for cycloolefin polymer resins. Therefore, the cycloolefin resin microreactor is weak against nonpolar solvents such as oil and cannot be used for the synthesis of emulsion from the viewpoint of chemical resistance. In the flow path plate by the joining member 1 of the present embodiment, the microreactor that synthesizes an emulsion or the like because the hydrophilic layer 11a having resistance to a nonpolar solvent is formed in the fine space 5 in which chemical resistance is required. It can also be applied to.

<Manufacturing method>
Next, the manufacturing method of this invention is demonstrated using FIG. FIG. 4 is an explanatory view showing a manufacturing process for manufacturing the joining member of FIG. 3.

  As shown to Fig.4 (a), the 1st base material 11 and the 2nd base material 12 are prepared, and the 1st recessed part 21 (recessed part 20) is formed in the 1st base material 11 by injection molding.

  Next, as shown in FIG. 4B, a process of irradiating the first recess 21 with vacuum ultraviolet light from the light source 60 through the opening of the mask material 51 is performed. It is preferable that the light source 60 and the first base material 11 have a space of about 1 mm to 10 mm, and the mask material 51 is in close contact with the first base material 11 (semi-contact). The mask material 51 is a metal mask provided with an opening by etching a metal plate, or a photomask obtained by patterning a light shielding film on a synthetic quartz substrate that transmits vacuum ultraviolet light. Or you may form by the same method from another material. By the step of irradiating the vacuum ultraviolet light, the hydrophilic layer 11a in which the nonpolar solvent does not penetrate into the first recess 21 of the first base material 11 can be formed. The hydrophilic layer 11a is a modified layer of cycloolefin resin.

  As shown in FIG. 4 (c), the paraffinic material 31 is applied to the other region except the first recess 21 where the hydrophilic layer 11a is formed by the step of applying the paraffinic material 31 to the surface. Is done. The paraffinic material 31 is a hydrocarbon-based nonpolar solvent composed of almost dispersed components, for example, n-heptadecane. At this time, the paraffinic material 31 that is a nonpolar solvent is not applied to the first recess 21. Subsequently, as shown in FIG. 4D, bonding is performed by a process of heating and pressurizing the first base material 11 and the second base material 12 facing each other. Thereby, the fine space 5 can be formed by the first concave portion 21 and the second base material 12 of the first base material 11.

  In FIG. 4C, instead of applying the paraffinic material 31 to the surface of the first base material 11, a paraffinic material may be applied to the surface of the second base material 12. In this case, since the portion corresponding to the first recess 21 in the second base material 12 is coated with a paraffin-based material, the applied paraffin-based material corresponds to the first recess 21 in the second base material 12. It penetrates into the parts that do. Moreover, since this part is not modified, the solvent resistance to the nonpolar solvent remains the cycloolefin resin used.

  According to this manufacturing method, the first base material 11 is formed with the hydrophilic layer 11a in which a nonpolar solvent does not penetrate by irradiating a part including the first recess 21 for forming the fine space 5 with ultraviolet rays, A paraffinic material 31 is applied to the first substrate 11, heated and pressurized, and joined to the second substrate 12. Thereby, since the 1st base material 11 and the 2nd base material 12 are joined by paraffinic material 31, joining strength is stabilized and it can join firmly. On the other hand, the hydrophilic layer 11a does not swell because the paraffinic material 31 does not remain. For this reason, it is suppressed that the fine space 5 formed in the joining member 1 is closed. For this reason, even when the nonpolar solvent flows into the fine space, the nonpolar solvent does not penetrate and does not swell. Therefore, it is possible to easily manufacture the joining member 1 having the fine space 5 excellent in resistance to the nonpolar solvent while the first base material 11 and the second base material 12 are firmly joined. it can.

  In addition, it is preferable that the hydrophilic layer which a nonpolar solvent does not osmose | permeate also in the through-hole 6 is formed. By irradiating the side wall of the through hole 6 with ultraviolet rays, a hydrophilic layer can be formed also in the through hole 6.

(First modification)
Hereinafter, a first modification will be described with reference to FIGS. FIG. 5 is a schematic cross-sectional view showing a first modification. FIG. 6 shows a manufacturing method according to the first modification.

  As shown in FIG. 5, the 2nd base material 12 has the hydrophilic layer 12a formed.

  The 1st base material 11 is the same until the process of irradiating the vacuum ultraviolet light of FIG.4 (b). As shown in FIG. 6B, the second base material 12 is added with a step of irradiating the portion corresponding to the first concave portion 21 (the concave portion 20) with the vacuum ultraviolet light of the light source 60 through the opening of the mask material 52. The The mask material 52 is formed in the same manner as the mask material 51.

  Further, as shown in FIG. 6C, the paraffinic material 32 is applied to the region where the hydrophilic layer 12a is not formed by the step of applying the paraffinic material 32 to the surface of the second substrate 12. Is done. At this time, the paraffinic material 32 which is a nonpolar solvent is not applied to the hydrophilic layer 12a. Subsequently, as shown in FIG. 6D, bonding is performed by a process of heating and pressurizing the first base material 11 and the second base material 12 facing each other. Thereby, the fine space 5 can be formed by the first concave portion 21 and the second base material 12 of the first base material 11.

  According to this manufacturing method, the first base material 11 is irradiated with ultraviolet rays to a part including the first concave portion 21 to form the hydrophilic layer 11 a, and further corresponds to the first concave portion 21 in the second base material 12. The hydrophilic layer 12a is formed by irradiating the portion to be irradiated with ultraviolet rays. Subsequently, a paraffinic material 32 is applied to the second base material 12, heated and pressurized, and joined to the first base material 11. Thereby, since the 1st base material 11 and the 2nd base material 12 are joined by paraffinic material 32, joining strength is stabilized and it can join firmly. On the other hand, the hydrophilic layers 11a and 12a do not swell because the paraffinic material 32 does not remain. This joining member 2 has hydrophilic layers 11a and 12a over the entire inner surface of the formed fine space 5, and the solvent resistance to a nonpolar solvent is improved as compared with the cycloolefin resin used. For this reason, it is suppressed that the fine space 5 formed in the joining member 2 is blocked. Therefore, in the joining member 2 produced by this production method, the first base material 11 and the second base material 12 are firmly joined, and the fine space 5 having resistance to a nonpolar solvent is formed. Yes.

  6C, instead of applying the paraffinic material 32 to the surface of the second substrate 12, the paraffinic material is applied to the surface of the first substrate 11 as shown in FIG. Material 31 may be applied. Alternatively, paraffinic materials 31 and 32 may be applied to the joint surfaces of both the first base material 11 and the second base material 12.

(Second modification)
Hereinafter, a second modification will be described with reference to FIGS. FIG. 7 is a schematic cross-sectional view showing a second modification. FIG. 8 shows a manufacturing method of the second modification.

  In the second modification, although the cross-sectional shape of the second base material 12 is different, the same reference numerals are used because the materials are the same.

  As shown in FIG. 7, the second base 12 is formed with a second recess 22 corresponding to the first recess 21. In the second base material 12, a second concave portion 22 corresponding to the first concave portion 21 irradiated with ultraviolet rays is formed. The second concave portion 22 is not coated with a paraffinic material 32, and other regions are paraffinic material 32. Are joined together.

  Since it has the 2nd recessed part 22, it is suitable when forming the comparatively large fine space 5. FIG.

  As shown to Fig.8 (a), the 2nd recessed part 22 corresponding to the 1st recessed part 21 is formed in the 2nd base material 12 by injection molding.

  Next, as shown in FIG. 8B, a process of irradiating the first recess 21 with vacuum ultraviolet light from the light source 60 through the opening of the mask material 51 is performed. It is preferable that the light source 60 and the first base material 11 have a space of about 1 mm to 10 mm, and the mask material 51 is in close contact with the first base material 11 (semi-contact). The mask material 51 is a metal mask provided with an opening by etching a metal plate, or a photomask obtained by patterning a light shielding film on a synthetic quartz substrate that transmits vacuum ultraviolet light. Or you may form by the same method from another material. By the step of irradiating the vacuum ultraviolet light, the hydrophilic layer 11a in which the nonpolar solvent does not penetrate into the first recess 21 of the first base material 11 can be formed. The hydrophilic layer 11a is a modified layer of cycloolefin resin. Further, the second substrate 12 irradiates the second recess 22 with the vacuum ultraviolet light of the light source 60 through the opening of the mask material 52. The mask material 52 is formed in the same manner as the mask material 51. By the step of irradiating the vacuum ultraviolet light, the hydrophilic layer 12a in which the nonpolar solvent does not penetrate into the second recess 22 of the second substrate 12 can be formed. The hydrophilic layer 12a is a modified layer of cycloolefin resin.

  As shown in FIG. 8 (c), the paraffinic material is applied to other regions except for the first concave portion 21 where the hydrophilic layer 11a is formed by the step of applying the paraffinic material 31 to the surface of the first base material 11. The material 31 is applied. At this time, the paraffinic material 31 that is a nonpolar solvent is not applied to the first recess 21. Moreover, the paraffinic material 32 is apply | coated to the area | region other than the 2nd recessed part 22 in which the hydrophilic layer 12a was formed by the process of apply | coating the paraffinic material 32 to the surface of the 2nd base material 12. FIG. At this time, the paraffinic material 32 that is a nonpolar solvent is not applied to the second recess 22. Subsequently, as shown in FIG. 8D, bonding is performed by a process of heating and pressurizing the first base material 11 and the second base material 12 facing each other. Thereby, the fine space 5 can be formed by the first concave portion 21 of the first base material 11 and the second concave portion 22 of the second base material 12.

  According to this manufacturing method, the first base material 11 is irradiated with ultraviolet rays to a part including the first recess 21 to form the hydrophilic layer 11 a, and further includes the second recess 22 in the second base material 12. A hydrophilic layer 12a is formed by irradiating a part with ultraviolet rays. Subsequently, the paraffinic material 31 is applied to the first base material 11, and the paraffinic material 32 is applied to the second base material 12, and the first base material 11 and the second base material 11 are heated and pressurized. The base material 12 is joined. Thereby, since the 1st base material 11 and the 2nd base material 12 are joined by the paraffinic materials 31 and 32, joining strength is stabilized and it can join firmly. On the other hand, the hydrophilic layers 11a and 12a do not swell because the paraffinic materials 31 and 32 do not remain. The joining member 3 has hydrophilic layers 11a and 12a over the entire inner surface of the formed fine space 5, and the solvent resistance to a nonpolar solvent is improved as compared with the cycloolefin resin used. For this reason, it is suppressed that the fine space 5 formed in the joining member 3 is blocked. Therefore, in the joining member 3 produced by this production method, the first base material 11 and the second base material 12 are firmly joined, and the fine space 5 having resistance to a nonpolar solvent is formed. Yes.

  Hereinafter, according to an embodiment of the present invention, the bonding strength of the bonding member and the resistance of the hydrophilic layer to the nonpolar solvent will be described.

  As the first base material 11 and the second base material 12, a trade name ZEONEX 480R manufactured by Nippon Zeon Co., Ltd. is used, and the thickness of the base material is 1 mm. The size of the manufactured sample for destructive testing is 70 mm × 30 mm. The recess 20 had a length of 10 mm, a width of 100 μm, and a depth of 40 μm, was formed by a molding die, and was arranged at a substantially central portion of the sample.

The recess 20 was irradiated with vacuum ultraviolet light (SUS05 manufactured by USHIO INC., Wavelength 172 nm, output 10 mW / cm ² ). At this time, the space | interval of a light source and the 1st base material 11 was 5 mm, and irradiation time was 5 minutes.

  Subsequently, n-heptadecane is applied to the first base material 11, and the first base material 11 and the second base material 12 are bonded to each other, and a pressure of 1.65 MPa is applied in the surface direction to heat at 70 degrees Celsius. Bonding for 5 minutes was performed.

  In the examples thus prepared, it was not observed that the substrates were peeled off before the substrates were destroyed. Moreover, the malfunction that the fine space 5 formed by the recessed part 20 and the 2nd base material 12 was obstruct | occluded was not observed.

  Moreover, the effect of joining via n-heptadecane was confirmed by the experiment of the following comparative example.

Vacuum ultraviolet light (SUS05 manufactured by Ushio, wavelength 172 nm, output 10 mW / cm ² ), the distance between the light source and the first substrate is 5 mm, and vacuum ultraviolet light is bonded to the first substrate 11 and the second substrate 12. Irradiation was performed over the entire surface. A number of samples with different irradiation times for irradiation with vacuum ultraviolet light were prepared, and bonding via n-heptadecane was performed on the substrate surface irradiated with vacuum ultraviolet light, and the respective bonding strengths were measured. The bonding area of this measurement sample was 26 mm × 26 mm. The results are shown in FIGS.

  FIG. 9 is a graph summarizing the relationship between the irradiation time of vacuum ultraviolet light performed immediately before coating and the measured bonding strength of the sample coated and bonded with n-heptadecane. FIG. 10 shows vacuum ultraviolet rays in samples in which the bonding strengths of Comparative Example 2 in which n-heptadecane was applied and bonded after irradiation with vacuum ultraviolet light and Comparative Example 3 in which bonding was performed only by irradiation with vacuum ultraviolet light were measured. It is the graph which put together the relationship with the irradiation time of light. As shown in FIG. 9, the bonding strength of Comparative Example 1 (bonding through n-heptadecane on the base material surface not irradiated with vacuum ultraviolet light) was 300N. On the other hand, the bonding strength of Comparative Example 2 in FIGS. 9 and 10 (bonding via n-heptadecane on the substrate surface irradiated with vacuum ultraviolet light for an irradiation time of 1 minute or more) is 50 N or less. there were. As shown in FIG. 10, in Comparative Example 3 using only vacuum ultraviolet light, the bonding strength increases as the irradiation time increases. However, the irradiation time is 4 minutes to 5 minutes, and the bonding strength using vacuum ultraviolet light (Comparative Example 1). And the bonding strength (comparative example 2) via n-heptadecane on the surface of the substrate irradiated with vacuum ultraviolet light substantially coincided. That is, it means that the junction via n-heptadecane cannot be obtained in an irradiation time of 4 minutes or more.

  This is because n-heptadecane cannot be attached to a cycloolefin resin having a hydrophilic layer modified by irradiation with vacuum ultraviolet light, and bonding with vacuum ultraviolet light (the hydrophilic layer of the first substrate 11 and the second group) This is considered to be due to the direct bonding with the hydrophilic layer of the material 12. In other words, compared to bonding using vacuum ultraviolet light, bonding using a paraffin-based material provides a large bonding strength (Comparative Example 1), but bonding using a paraffin-based material and bonding using vacuum ultraviolet light are performed simultaneously. It is not done. Rather, it means that the substrate surface irradiated with vacuum ultraviolet light is in a conflicting bonding condition in which bonding via a paraffinic material cannot be performed.

Next, the hydrophilic layer formed on the cycloolefin resin (trade name ZEONEX 480R manufactured by Nippon Zeon Co., Ltd.) as a base material was evaluated by measuring the surface free energy with respect to the irradiation time for irradiation with vacuum ultraviolet light. FIG. 11 shows the results of measuring the surface free energy of each sample with different irradiation times for irradiation with vacuum ultraviolet light over the entire surface of the substrate. After preparing many samples with different irradiation times for irradiation with vacuum ultraviolet light and measuring the contact angle with three liquids of water, 1-bromonaphthalene, and ethylene glycol, each surface using Kitazaki and Hata theory Free energy dispersive component, polar component and hydrogen bond component were calculated. The cycloolefin resin that has not been irradiated with vacuum ultraviolet light has almost no polar component of surface free energy, and is non-polarized only composed of a dispersed component. It can be seen that when the vacuum ultraviolet light is irradiated, the polar component of the surface free energy increases from 0 to 300 mJ / m ² . There was a phenomenon that the polar component of the surface free energy became 100 mJ / m ² or less when the irradiation time was between 1 minute and 4 minutes. This is because immediately after irradiation with vacuum ultraviolet light, organic substances adsorbed on the substrate surface volatilize due to decomposition or the like and the surface free energy increases, but the formation of a modified layer in which the cycloolefin resin is modified progresses so much. This is because it is not.

According to the evaluation results shown in FIGS. 9 to 11, if the sum of the polar component of the surface free energy and the hydrogen bonding component is 100 mJ / m ² or more, the wettability of water is high and the wettability of the nonpolar solvent is high. Considered low.

  The cycloolefin resin originally has a surface free energy composed only of a dispersed component, and has no chemical resistance to a nonpolar solvent. Therefore, there has been a problem that the nonpolar solvent penetrates and swells. Since the modified layer in which the cycloolefin resin is modified has a polar component and a hydrogen bonding component, a nonpolar solvent does not adhere to the modified layer, and therefore a paraffinic material such as n-heptadecane, which is a nonpolar solvent, is a cycloolefin. It will not diffuse into the resin. That is, the hydrophilic layer formed on the cycloolefin resin has resistance to a nonpolar solvent. For this reason, even when the nonpolar solvent is allowed to flow into the fine space, the nonpolar solvent does not penetrate and does not swell.

As shown in FIG. 11, the total of the polar component of the surface free energy and the hydrogen bond component is rapidly modified to 100 mJ / m ² or more in the irradiation time of vacuum ultraviolet light of 5 minutes or more. Therefore, it hydrophilic layer, the sum of the polar component and hydrogen bond component of surface free energy 100 mJ / m ² or more, preferably modified layer modified so that 150 mJ / m ² or more Is preferred. That is, the sum of the polar component and hydrogen bond component of surface free energy of the formed hydrophilic layer is 100 mJ / m ² or more, in particular, if the 150 mJ / m ² or more, the paraffinic material which is non-polar solvent It cannot be attached.

  Regardless of the formation conditions of the hydrophilic layer described in this example, even when the wavelength and output of the vacuum ultraviolet light are different, the total of the polar component of the surface free energy of the formed hydrophilic layer and the hydrogen bonding component If it is the above-mentioned measured value, the formed joining member has the same effect.

1, 2, 3 Joining member 5 Fine space 6 Through-hole 11 1st base material 12 2nd base material 11a, 12a Hydrophilization layer 20 Recessed part 21 1st recessed part 22 2nd recessed part 30 Joining part 31, 32 Paraffin type material

Claims (7)

The 1st base material which consists of cycloolefin resin and the recessed part was formed, and the 2nd base material which consists of cycloolefin resin are joined, and it has the fine space formed by the said recessed part and the said 2nd base material A member,
The first base material and the second base material are joined by a paraffinic material,
A bonding member, wherein a hydrophilic layer that does not allow a nonpolar solvent to permeate is formed in the recess.   The joining member according to claim 1, wherein the hydrophilic layer is formed over the entire inner surface of the fine space. 3. The bonding according to claim 2, wherein the hydrophilic layer is a modified layer that is modified so that a sum of a polar component of surface free energy and a hydrogen bonding component is 100 mJ / m ² or more. Element. A method for producing a joined member in which a first base material and a second base material made of cycloolefin resin are joined,
Preparing the first base material on which the first recess is formed and the second base material;
Irradiating part of the first base material including the first recess with ultraviolet rays;
In order to form a fine space by the first recess and the second base material, a paraffinic material is applied to one or both of the first base material and the second base material, and the first base A step of heating and pressurizing the material and the second base material,
The manufacturing method of the joining member characterized by having.   The method for manufacturing a joining member according to claim 4, further comprising a step of irradiating a part of the second base material including a portion corresponding to the first concave portion with ultraviolet rays.   The method for manufacturing a joining member according to claim 5, wherein a second recess corresponding to the first recess is formed in the second base material. In the step of irradiating with ultraviolet rays, the hydrophilic layer is a modified layer that has been modified so that the sum of the polar component of the surface free energy and the hydrogen bonding component is 100 mJ / m ² or more. The manufacturing method of the joining member in any one of Claim 4 thru | or 6.