JP4852293B2 - Surface modification method for polymer substrate, polymer substrate, and coating member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for surface-modifying a part of the surface of a polymer substrate material selectively (partially), capable of more highly accurately and finely performing the surface modification. <P>SOLUTION: This method for surface-modifying the polymer substrate comprises a process of applying a penetrative substance on a prescribed zone of the surface of a polymer substrate material, a process of forming a coating layer so as to cover the penetrative substance and a process of penetrating the penetrative substance to the polymer substrate material by bringing the surface of coating layer side of the polymer substrate material in contact with a supercritical fluid. Thereby, it is possible to perform the surface modification of the part of surface of the polymer substrate material more highly accurately and finely. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a surface modification method for a polymer substrate using a supercritical fluid, a polymer substrate formed using the method, and a coating member used in the surface modification method.

  In recent years, various processes have been proposed in which a supercritical fluid that has permeability as a gas and at the same time functions as a solvent such as a liquid is used for molding a polymer substrate. For example, a supercritical fluid acts as a plasticizer by penetrating into a thermoplastic resin and can reduce the viscosity of the polymer substrate. Therefore, the supercritical fluid can be used to reduce the polymer base during injection molding. A method for improving fluidity and transferability of a material has been proposed (see, for example, Patent Document 1).

  In addition, various methods for enhancing the function such as improving the wettability of the surface of the polymer substrate by utilizing the function of the supercritical fluid as a solvent have been proposed (see, for example, Patent Documents 2 and 3). ). Patent Document 2 discloses that a fiber surface can be hydrophilized by dissolving polyalkyl glycol in a supercritical fluid and bringing the polyalkyl glycol into contact with the fiber. Patent Document 3 discloses a highly functional surface of a polymer substrate that performs dyeing by contacting a supercritical fluid in which a solute as a functional material is dissolved in advance in a supercritical state, that is, under a high pressure, and the polymer substrate. A batch process for disclosing is disclosed.

  Conventionally, a mask having a hole having a desired shape is provided on the substrate, and a supercritical fluid in which a substance (metal complex) to be deposited on the substrate is dissolved is sprayed from above the mask, and the deposited substance is applied to the substrate surface. A method of forming a pattern of 100 μm or less is also proposed (see, for example, Patent Document 4).

Japanese Patent Laid-Open No. 10-128783 JP 2001-226874 A JP 2002-129464 A JP 2002-313750 A

  The above Patent Documents 1 to 3 are methods for modifying the surface of a polymer substrate using a supercritical fluid as a solvent, and disclose a technique for modifying the entire surface of the polymer substrate. However, it is difficult to selectively and finely modify a part of the polymer substrate surface by the techniques disclosed in Patent Documents 1 to 3 described above. Further, in Cited Document 4, since a substance (solute) is dissolved in a supercritical fluid and sprayed onto a polymer substrate, the following problems may occur.

  There is a strong correlation between the pressure of the supercritical fluid and the solubility of the solute. When the supercritical fluid is discharged to the outside from a container under high pressure filled with the supercritical fluid in which the solute is dissolved, the pressure of the supercritical fluid is rapidly reduced, and the solubility of the solute is significantly reduced. That is, as described in the cited document 4, when a solute is dissolved in a supercritical fluid and sprayed onto a polymer substrate, the solute is precipitated at the time of spraying. Therefore, in the technique described in the cited document 4, the solute can be deposited on the surface of the polymer substrate, but the solute is infiltrated into the inside of the polymer substrate along with the penetration of the supercritical fluid into the polymer substrate. It cannot be modified.

  The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to selectively (partially) selectively part of the surface of a polymer substrate by a simpler method using a supercritical fluid. Another object is to provide a method for modifying a part of the surface of a polymer substrate with high accuracy and finely while modifying.

According to a first aspect of the present invention, there is provided a method for modifying a surface of a polymer substrate using a supercritical fluid, the method comprising adding an osmotic material to a predetermined region on the surface of the polymer substrate, Forming a coating layer that is made of a water-soluble resin and that allows the supercritical fluid to pass therethrough, and bringing the supercritical fluid into contact with the surface of the polymer substrate on the coating layer side to thereby form the osmotic substance. A surface modification method comprising impregnating the polymer base material with a polymer.

  In the surface modification method according to the first aspect of the present invention, when the osmotic substance is added to a predetermined region of the surface of the polymer substrate, the osmotic substance is added to the surface of the polymer substrate in a predetermined pattern. Is preferred.

  The present applicant has previously proposed a technique in which a penetrating substance (organic substance) is applied in advance to the surface of a polymer substrate, and a supercritical fluid is brought into contact with the polymer substrate surface to modify the polymer substrate surface. (Japanese Patent Application No. 2004-129235: hereinafter referred to as Application 1). In Application 1, the following method has been proposed as a method for selectively modifying a part of the surface of the polymer substrate. First, a penetrating substance intended to permeate the surface of the polymer substrate is applied to the entire surface or a wide area of the surface of the polymer substrate, and then a mold surface having a predetermined uneven pattern is brought into close contact with the surface of the polymer substrate. Next, the supercritical fluid flows into the space defined between the mold (concave portion) and the polymer substrate surface, and the applied penetrating material is applied only to the region of the polymer substrate surface into which the supercritical fluid has flowed. Selectively penetrate.

  Further, the present applicant has proposed a method for selectively modifying a part of the surface of the polymer substrate by a simpler method than the method for modifying the surface of the polymer substrate proposed in the above application 1 (Japanese Patent Application No. 2005-128995). : Hereinafter referred to as Application 2). In the application 2, by using an inkjet method or a screen printing method, a penetrating substance is added in a predetermined pattern on a polymer substrate, and a supercritical fluid is brought into contact with the surface of the polymer substrate on the penetrating substance side added, A method for selectively modifying a portion of the polymer substrate surface by impregnating the penetrant into the polymer substrate was proposed.

  As a result of diligent research on the surface modification method of the polymer substrate using the supercritical fluid as described above, the present inventors have found the following. When the supercritical fluid is brought into contact with the polymer substrate to which the osmotic material is added and the osmotic material is allowed to permeate the polymer substrate, a part of the osmotic material may be eluted into the supercritical fluid depending on the contact conditions and the like. Therefore, it has been found that there are cases where the penetrating substance does not penetrate efficiently into the polymer substrate. In the surface modification method of Application 2, when the supercritical fluid is brought into contact with the polymer substrate to which the osmotic material is added in a predetermined pattern, the osmotic material added to the surface of the polymer substrate is eluted into the supercritical fluid. Thus, it was found that bleeding occurred in the pattern. Therefore, the present inventors have further improved the surface modification method of Application 2 based on the above findings, and have reached the surface modification method of the present invention.

  An example of a method for modifying the surface of a polymer substrate according to the first embodiment of the present invention is shown in FIG. In the method for modifying the surface of a polymer substrate according to the first aspect of the present invention, first, as shown in FIG. 2 (a), predetermined regions (all or A substance (penetrating substance) 2 to be permeated is added to a predetermined portion (the penetrating substance 2 is added to the surface of the polymer substrate 1 in a predetermined pattern). Next, as shown in FIG. 2B, a coating agent is added so as to cover the penetrating material 2 to form a coating layer 3. In the example of FIG. 2B, the coating layer 3 is formed over the entire surface of the polymer substrate 1, but the present invention is not limited to this, and the coating layer 3 covers at least the penetrating substance 2. It may be formed in a region where the osmotic substance 2 can be formed, or may be formed on a part of the surface of the polymer substrate that can cover the penetrating substance 2. Further, if necessary, the coating layer 3 can be cured or gelled, which can prevent the coating layer 3 from flowing and flowing out.

  Next, as shown in FIG. 2 (c), the polymer base material 1 on which the coating layer 3 is formed is placed, for example, in a sealed container 4, and a supercritical fluid 5 is introduced into the sealed container 4, thereby polymer base material. The supercritical fluid 5 is brought into contact with the surface of the one coating layer 3 side. Then, the supercritical fluid 5 first penetrates into the coating layer 3, then reaches the penetrating material 2 and dissolves it. The supercritical fluid 5 penetrates into the polymer substrate 1 together with the dissolved osmotic material 2. At this time, although the osmotic substance 2 is dissolved in the supercritical fluid 5 and is in a fluid state, since the osmotic substance 2 is covered with the coating layer 3, the osmotic substance 2 is not scattered from the vicinity of the surface of the polymer substrate 1. By the action of the coating layer 3, the osmotic substance 2 dissolved in the supercritical fluid 5 penetrates into the polymer substrate 1 efficiently and at a high concentration. In addition, since the osmotic material 2 is covered with the coating layer 3, the osmotic material 2 can be permeated without bleeding a predetermined pattern of the osmotic material 2 added on the polymer substrate 1. Therefore, the region of the predetermined pattern to be surface-modified of the polymer substrate 1 can be modified with high accuracy.

  After the osmotic substance 2 is infiltrated into the polymer substrate 1 as described above, the polymer substrate 1 is taken out from the sealed container 4 (state shown in FIG. 2D). Finally, the coating layer 3 coated with the penetrating substance 2 is washed away with a suitable solvent (the state shown in FIG. 2 (e)). At that time, the penetrating substance 2 remaining on the polymer substrate 1 may also be removed.

  In the surface modification method according to the first aspect of the present invention, as a method for selectively (partially) adding a penetrating substance to a predetermined region on the surface of the polymer substrate, the penetrating substance is liquefied and this is applied to a screen printing method or the like. A method of adding by a printing method such as an inkjet method is preferred. As another method, a method of applying a solution containing a penetrating substance after placing a resist mask produced using a metal mask or a photolithography method on a polymer substrate may be employed. Examples of the method of liquefying the osmotic material include a method of softening the osmotic material by heating, a method of dissolving the osmotic material in a predetermined solvent, etc., but it dissolves in the solvent from the point that it is not necessary to adjust the temperature. The method is simple and suitable.

According to a second aspect of the present invention, there is provided a method for modifying a surface of a polymer substrate using a supercritical fluid, wherein a mask layer having openings having a predetermined pattern is formed on the polymer substrate. Forming a layer of an osmotic material in at least an opening of the mask layer, forming a coating layer made of a water-soluble resin and transmitting a supercritical fluid on the layer of the osmotic material , and the polymer There is provided a surface modification method comprising bringing a supercritical fluid into contact with a surface of the substrate on the coating layer side and allowing the penetrating substance to penetrate the polymer substrate through an opening of the mask layer. .

  An example of a method for modifying the surface of a polymer substrate according to the second embodiment of the present invention is shown in FIG. In the polymer substrate surface modification method according to the second aspect of the present invention, first, a mask layer 76 is formed on the polymer substrate 41. At this time, as shown in FIG. 8A, a mask layer 76 is formed in a region other than the region 77 to be surface-modified on the polymer base material 41. That is, the mask layer 76 in which the region 77 to be surface-modified on the polymer base material 41 becomes an opening is formed. Next, a layer 72 of a penetrating substance (substance that permeates the polymer base material 41) is formed on the mask layer 76 (state shown in FIG. 8B). At this time, in the example of FIG. 8B, a layer 72 of a penetrating material is formed not only on the region 77 of the polymer base material 41 exposed at the opening of the mask layer 76 but also on the entire surface of the mask layer 76. However, the present invention is not limited to this, and it is sufficient that the osmotic material layer 72 is formed at least in the opening of the mask layer 76, and the osmotic material layer 72 is formed on a region other than the opening of the mask layer 76. May not be formed.

  Next, as shown in FIG. 8C, a coating agent is added on the osmotic material layer 72 to form a coating layer 73. In the example of FIG. 8, since the osmotic material layer 72 is formed over the entire surface of the mask layer 76, the coating layer 73 is also formed over the entire surface of the osmotic material layer 72. The present invention is not limited to this. When the osmotic material layer 72 is formed only in a part of the region including the opening of the mask layer 76, the coating layer 73 may be formed so as to cover the osmotic material layer 72. The coating layer 73 may be formed in a partial region so as to cover the osmotic material layer 72 formed in the partial region, or the coating layer 73 may be formed over the entire surface of the polymer substrate. Also good.

  Next, as shown in FIG. 8D, the polymer base material 41 on which the coating layer 73 is formed is placed in, for example, the sealed container 4, and the supercritical fluid 5 is introduced into the sealed container 4, so that the polymer substrate The supercritical fluid 5 is brought into contact with the surface of the material 41 on the coating layer 73 side. Then, the supercritical fluid 5 first penetrates into the coating layer 73, and then reaches the layer 72 of the penetrating substance to dissolve the substance. At this time, the permeation substance added on the region 77 of the polymer base material 41 exposed at the opening of the mask layer 76 is also dissolved in the supercritical fluid 5. As a result, a part of the osmotic material layer 72 formed on the region 77 of the polymer substrate 41 exposed in the opening of the mask layer 76 is removed from the region 77 on the surface of the polymer substrate 41 together with the supercritical fluid 5. As shown in FIG. 8D, the penetrating substance penetrates only the region 77 on the surface of the polymer base material 41. At this time, although the osmotic material layer 72 is dissolved in the supercritical fluid 5 and is in a fluid state, the osmotic material layer 72 is covered with the coating layer 73 and the mask layer 76, so Do not splash outside. By the action of the coating layer 73 and the mask layer 76, the penetrating substance dissolved in the supercritical fluid 5 penetrates into the polymer substrate 41 efficiently and at a high concentration.

  Next, the polymer base material 41 is taken out from the sealed container 4 (state shown in FIG. 8E). Finally, the coating layer 73, the penetrating material layer 72, and the mask layer 76 on the polymer substrate 41 are washed away with an appropriate solvent (the state shown in FIG. 8F). At this time, the formed film (or layer) on the polymer substrate 41 may be removed in order from the top, but the coating layer 73 and the penetrating material layer 72 on the mask layer 76 are removed by removing the mask layer 76 with a solvent. Are preferably removed together.

  In the surface modification method according to the second aspect of the present invention, any method can be used as a method for forming a mask layer as long as it can form a mask layer having an opening in a region to be surface modified of a polymer substrate. Although the method can be used, in particular, by adhering a mask material such as a liquefied photosensitive resin to a region other than the region to be surface-modified of the polymer substrate by a printing method such as a screen printing method or an ink jet method, and curing it. It is preferable to form a mask layer. As another method for forming the mask layer, a photosensitive resin is applied to the entire surface of the polymer substrate, and then the photosensitive region in the region to be surface-modified on the polymer substrate using a metal mask or a photolithography method is used. It is also possible to form the mask layer by removing the functional resin. Examples of the method for liquefying the mask material include a method for softening the mask material by heating, a method for dissolving the mask material in a predetermined solvent, and the like. A method of dissolving the mask material is simple and preferable.

  In the surface modification method according to the second aspect of the present invention, the mask layer can shield the supercritical fluid, is a material that adheres / adheres to the surface of the polymer substrate, and the supercritical fluid is polymerized. Any material can be used as long as it is a material that can be removed without leaving any damage to the polymer substrate after the treatment to be brought into contact with the substrate. By forming the mask layer with a material having such properties, it is possible to prevent the supercritical fluid from entering the region of the polymer substrate to which the mask layer is adhered / adhered. As the material having such properties, a polymer material can be used, and for example, a photosensitive resin, a thermoplastic resin, a thermosetting resin, and the like are preferable. More specifically, when a thermoplastic resin is used for the polymer substrate, it is preferable to use a positive resist 1805 (manufactured by Shipley Far East). This photosensitive resin material can shield the supercritical fluid, and is a material that adheres / adheres to the surface of the polymer substrate, and when removing it, propanol, butanol, ethanol, methanol, or the like is used. Therefore, even when removing the mask layer, it is possible to perform the treatment without damaging the polymer substrate.

  In the surface modification method according to the second aspect of the present invention, in order to shield the supercritical fluid and suppress damage to the polymer substrate in a region other than the opening of the mask layer, You may provide the base layer which exhibits the said effect between polymer base materials.

  In the surface modification method according to the first and second aspects of the present invention, the coating layer is preferably formed by one method selected from the group consisting of a dipping method, a roll coating method, a screen printing method, and a spray method. . Any method can be used as a method for adding the coating layer on the penetrating substance of the polymer base material as long as it can be added so that at least the added portion of the penetrating substance is coated. These known addition methods can be used. The thickness of the coating layer is arbitrary as long as the supercritical fluid can easily permeate and the permeation material does not diffuse. The thickness of the coating layer depends on the polymer substrate, the permeation material, and the like to be used. It can be set appropriately. In general, the thickness of the coating layer is preferably in the range of 5 μm to 200 μm, and is preferably uniform.

  As a material for the coating layer that can be used in the surface modification method according to the first and second aspects of the present invention, a material that can relatively permeate the supercritical fluid and suppress diffusion of the permeation substance is selected. It is preferable to do. By forming the coating layer with a material having such properties, the supercritical fluid in which the osmotic material is dissolved is guided to the surface of the polymer substrate, and the diffusion of the osmotic material from the surface of the polymer substrate is suppressed. Since the supercritical fluid can be brought into contact with the polymer substrate, the penetrating substance can be efficiently penetrated into the polymer substrate at a high concentration. In the surface modification method according to the first and second aspects of the present invention, it is preferable that the coating layer is formed of a material that is more difficult to dissolve in the supercritical fluid than the penetrating substance.

  As a material for the coating layer having the above properties, for example, various water-soluble resins (water-soluble polymers) can be used. Examples of the water-soluble resin include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate and the like. Further, as other coating layer forming materials, polyethylene oxide, sodium polyacrylate, polyacrylamide, cellulose, polyethylene glycol, polyvinyl pyrrolidone and the like can be used. When the coating layer is formed of a water-soluble resin, the coating layer can be removed by rinsing the polymer substrate with water when the coating layer is removed after the penetrating substance has penetrated the polymer substrate. Therefore, it can be removed without damaging the polymer substrate.

  In the surface modification method according to the first and second aspects of the present invention, a predetermined concavo-convex pattern may be provided by forming, cutting, or the like in the region of the predetermined pattern to be surface-modified of the polymer substrate. In particular, it is preferable that the region of the predetermined pattern of the polymer substrate is formed by a recess, and the recess includes a groove pattern. When a groove pattern is formed on the surface of the polymer substrate, the groove pattern can be used as a guide when adding a penetrating substance to a part of the polymer substrate surface (predetermined pattern).

  As described above, when a penetrating substance is added to the surface of a flat polymer substrate by a screen printing method or an ink jet printing method, a pattern of 100 μm or more can be formed, but a finer pattern is formed. This is difficult at present. However, a concavo-convex pattern having a width or depth of 100 μm or less, more desirably 50 μm or less, and even more desirably 10 μm or less is formed on the surface of the polymer substrate, and the polymer substrate is formed on the concavo-convex pattern portion by, for example, an ink jet method. When the osmotic substance is added to the surface, the osmotic substance is stretched along the concavo-convex pattern portion by capillary action, and a finer pattern of the substance can be formed on the polymer substrate surface.

  In addition, when a penetrating substance is added to the polymer substrate inside the concavo-convex pattern of the polymer substrate, since the osmotic substance enters the concavo-convex pattern, when the supercritical fluid is brought into contact with the polymer substrate surface, the concavo-convex pattern This side wall can suppress elution and diffusion of the osmotic material in the lateral direction (in-plane direction of the polymer substrate), and can suppress bleeding of the osmotic material pattern. Therefore, even a finer penetrating substance pattern can be formed on the polymer substrate surface with high accuracy. The concave / convex pattern formed on the surface of the polymer substrate is preferably a concave pattern such as a groove pattern, but it is also possible to form a convex pattern and use a valley between the convex patterns. Furthermore, the pattern of the substance formed on the polymer substrate may be configured to be used in combination with the pattern of the substance formed on the flat part of the polymer substrate as well as the above-described concave and / or convex portions.

According to a third aspect of the present invention, there is provided a method for modifying a surface of a polymer substrate using a supercritical fluid, wherein the penetrating material is made of a water-soluble resin and allows the supercritical fluid to pass therethrough. Adding a predetermined pattern to the surface, placing the coating film on the polymer substrate, contacting the surface of the polymer substrate on the coating film side with a supercritical fluid, and There is provided a method of surface modification comprising impregnating a polymer substrate.

  In the polymer substrate surface modification method according to the third aspect of the present invention, the coating film is placed on the polymer substrate, and the surface of the coating film to which the penetrating substance is added is disposed on the polymer substrate. It is preferable that the coating film and the polymer substrate are brought into close contact with each other so as to face the surface of the substrate.

  An example of a method for modifying the surface of a polymer substrate according to the third embodiment of the present invention is shown in FIG. In the method for modifying the surface of a polymer substrate according to the third aspect of the present invention, first, a penetrating substance 2 (a substance that penetrates the polymer substrate 1) is predetermined on the coating film 80 by using a printing method such as an inkjet method. Are added in the pattern (state shown in FIG. 9A). In addition, as a forming material of the coating film 80, the material mentioned by description of the forming material of the said coating layer can be used, and it is preferable that it forms with water-soluble resin especially.

  Next, as shown in FIG. 9B, the coating film 80 is provided on the polymer substrate 1 so that the surface of the coating film 80 to which the penetrating substance 2 is added faces the surface of the polymer substrate 1. . At this time, as shown in FIG. 9B, it is desirable that the penetrating substance 2 is adhered to the surface of the polymer substrate 1 by bonding so that the polymer substrate 1 and the coating film 80 are adhered.

  As a method for bringing the polymer substrate 1 and the coating film 80 into close contact with each other, it is effective to put water, ethanol, methanol or the like between the polymer substrate 1 and the coating film 80 and bond them together. Specifically, first, a small amount of water, ethanol, methanol or the like is dropped on the surface of the polymer substrate 1, and the coating film 80 is placed on the surface of the polymer substrate 1 so that the surface to which the penetrating substance 2 is added faces the polymer substrate 1. Then, it is preferable that the surface of the coating film 80 is pressed and adhered while gradually avoiding the entry of air from the end of the coating film 80. In such a bonding method, a volatile liquid such as water or alcohol is interposed between the coating film and the polymer substrate, and the two are brought into close contact while preventing air from entering, and then the liquid is volatilized. As the liquid, it is desirable to appropriately select a liquid that does not dissolve or decompose the coating film, the polymer base material, and the penetrating substance.

  Next, as shown in FIG. 9C, the polymer base material 1 to which the coating film 80 is bonded is placed, for example, in a sealed container 4, and the supercritical fluid 5 is introduced into the sealed container 4, so that the polymer The supercritical fluid 5 is brought into contact with the surface of the substrate 1 on the coating film 80 side. Then, the supercritical fluid 5 first penetrates into the coating film 80, and then reaches the penetrating substance 2 and dissolves it. The supercritical fluid 5 penetrates into the polymer substrate 1 together with the dissolved osmotic material 2. At this time, although the osmotic substance 2 is dissolved in the supercritical fluid 5 and is in a fluid state, since the osmotic substance 2 is covered with the coating film 80, the osmotic substance 2 is not scattered from the vicinity of the surface of the polymer substrate 1. Due to the action of the coating film 80, the osmotic substance 2 dissolved in the supercritical fluid 5 penetrates into the polymer substrate 1 efficiently and at a high concentration.

  After the osmotic substance 2 is infiltrated into the polymer base material 1 as described above, the polymer base material 1 is taken out from the sealed container 4 (state shown in FIG. 9D). Finally, the coating film 80 coated with the osmotic material 2 is washed away with a suitable solvent (state shown in FIG. 9 (e)). In the polymer substrate surface modification method according to the third aspect of the present invention described above, a coating film in which a penetrating substance is previously added to the polymer substrate in a predetermined pattern can be supplied as a roll sheet. In some cases, it is possible to realize versatility in manufacturing and cost reduction, such as dealing with various shapes of polymer base materials, and it is possible to improve mass productivity.

  In the example of the polymer substrate surface modification method according to the first to third aspects of the present invention described above, an example in which part of the penetrating substance added to the polymer substrate penetrates the polymer substrate (for example, FIG. 2 (e), FIG. 8 (f) and FIG. 9 (e)) have been described, but the present invention is not limited to this. All penetrating substances added to the polymer substrate may be allowed to penetrate into the polymer substrate. The permeation amount of the permeation substance can be arbitrarily controlled by changing conditions such as the temperature, pressure, contact time and the like of the supercritical fluid to be contacted. It is preferable to adjust the amount of penetration of the substance.

  In the method for modifying the surface of the polymer substrate according to the first to third aspects of the present invention, the supercritical fluid is brought into contact with the surface of the polymer substrate (for example, FIG. 2 (c), FIG. 8 (d) and In FIG. 9 (c)), it is preferable to control the pressure of the supercritical fluid and press the surface of the polymer substrate with the supercritical fluid at an appropriate pressure. This pressing allows the penetrating substance to penetrate deeper into the polymer substrate. Further, as described above, the supercritical fluid acts as a plasticizer on the polymer substrate and softens the polymer substrate surface. Therefore, when the supercritical fluid is brought into contact with the surface of the polymer substrate, or when the polymer substrate surface is pressed with a mold or the like, the penetrating substance is efficiently introduced into the polymer substrate while suppressing deformation of the polymer substrate. Since it can be permeated, a more precise pattern can be formed on the surface of the polymer substrate.

  In the polymer substrate surface modification method according to the first to third aspects of the present invention, the supercritical fluid is preferably carbon dioxide in a supercritical state (hereinafter also referred to as supercritical carbon dioxide). Note that various materials can be used as the supercritical fluid, and nitrogen other than supercritical carbon dioxide (supercritical nitrogen) may be used. Further, as the supercritical fluid, air, water, butane, pentane, methanol or the like in a supercritical state may be used, and any fluid that dissolves the osmotic substance to some extent can be used. In order to improve the solubility of the permeation substance in the supercritical fluid, the supercritical fluid may be mixed with an entrainer, that is, an alcohol such as acetone, methanol, ethanol, or propanol as an auxiliary agent.

  In the polymer substrate surface modification method according to the first to third aspects of the present invention, conditions such as temperature and pressure of the supercritical fluid to be brought into contact with the polymer substrate are arbitrary. In the case of carbon dioxide having a temperature of about 31 ° C. and a pressure of about 7 MPa or more, the temperature is preferably in the range of 35 to 150 ° C. and the pressure is preferably in the range of 10 to 25 MPa. If the temperature or pressure is outside the above ranges, the solubility of the osmotic material in the supercritical fluid and the permeability to the polymer substrate become insufficient.

  In the polymer substrate surface modification method according to the first to third aspects of the present invention, the polymer substrate is selected from the group consisting of polymethyl methacrylate, polycarbonate, wholly aromatic polyamide, wholly aromatic polyester, and amorphous polyolefin. It is preferable that it is formed of one. Moreover, you may use the material which has these as a main component. Furthermore, in the surface modification method of the present invention, various resins other than the above resins may be used as the polymer substrate. For example, polylactic acid, polyamide, polyetherimide, polyamideimide, polyester, polyacetal, polymethylpentene, polytetrafluoroethylene, liquid crystal polymer, styrene resin, polymethylpentene, polyacetal, etc. Various thermoplastic resins such as a polymer alloy mainly composed of the above and those obtained by blending these with various fillers may be used.

  In the polymer substrate surface modification method according to the first to third aspects of the present invention, the osmotic substance is preferably an organic substance, and in particular, the osmotic substance is preferably dissolved in the supercritical fluid. When an organic substance that dissolves in a supercritical fluid is used as the osmotic substance, the organic substance penetrates into the polymer substrate in a state dissolved in the supercritical fluid, so that the organic substance easily penetrates into the polymer substrate. .

  In the polymer substrate surface modification method according to the first to third aspects of the present invention, the penetrating material is preferably a pigment. For example, when an azo dye or an organic pigment material such as a fluorescent dye or phthalocyanine is used as the penetrating substance, the polymer substrate surface can be dyed.

  In the polymer substrate surface modification method according to the first to third aspects of the present invention, the penetrating material is preferably polyethylene glycol, polypropylene glycol, polyalkyl glycol or the like. When these materials are used as the osmotic substance, these materials have hydrophilic groups (OH), so that the surface of the polymer substrate can be hydrophilized. In particular, since polyethylene glycol dissolves in, for example, supercritical carbon dioxide, it easily penetrates into the polymer substrate. Therefore, when polyethylene glycol is used as the penetrating substance, it becomes easy to produce a polymer substrate having a hydrophilic surface. In addition, since polyethylene glycol is excellent in biocompatibility, a polymer substrate hydrophilized using polyethylene glycol is also suitable as a polymer substrate used in biochips, micro TAS (micro total analysis system) and the like. is there. For example, hydrophobization rate of nucleic acid due to the effect of controlling the adhesion of nucleic acids and proteins by hydrophilizing the surface of the polymer base material, which is a hydrophobic material, and by dividing the polymer base surface in the micro-region of hydrophilization-hydrophobization It becomes possible to perform separation by.

  In the method for modifying the surface of a polymer substrate according to the first to third aspects of the present invention, the following penetrating substance may be used. When a hydrophobic ultraviolet stabilizer such as benzophenone or coumarin is used as the penetrating substance, the tensile strength after weathering of the polymer substrate can be improved. In addition, when a fluorinated compound such as a fluorinated organic copper complex is used as the penetrating substance, the frictional property of the polymer substrate can be improved, or a water repellent function can be imparted. Further, when silicon oil is used as the penetrating substance, a water repellent function is exhibited.

  In the surface modification method for a polymer substrate according to the first to third aspects of the present invention, the penetrating material is preferably a metal complex. When an organometallic complex is used as the penetrating substance, electroless plating catalyst nuclei can be formed on the polymer substrate. In this case, it is preferable that the method for modifying the surface of the polymer substrate of the present invention further includes forming a plating layer by electroless plating in the region where the penetrating substance is added.

  In the present invention, the substance that penetrates the surface of the polymer substrate called “penetrating substance” is not limited to various organic substances as described above, and inorganic materials modified with organic compounds can also be used. Any substance can be used as long as it dissolves to some extent in the supercritical fluid. Examples of the inorganic material serving as the base of such a penetrating material include metal alkoxides.

  In the polymer substrate surface modification method according to the first to third aspects of the present invention, it is also possible to use a material that does not dissolve in the supercritical fluid as the penetrating material. When an osmotic substance that does not dissolve in the supercritical fluid is used, the osmotic substance partially added (applied) to the polymer substrate surface when the supercritical fluid is brought into contact with the polymer substrate surface is supercritical. It penetrates into the polymer substrate by the pressure of the fluid. In this case, any material can be used as the material for the osmotic material. However, in consideration of the molecular size of the osmotic material that can easily penetrate into the polymer substrate, a material having a molecular weight of 5000 or less is used. desirable. For example, as the osmotic substance, inorganic materials such as metal fine particles, carbon nanotubes, fullerenes, nanohorns such as nanohorns, titanium oxide, and the like can be used. However, when using these materials, it is desirable to chemically solubilize these inorganic materials and solubilize them in a supercritical fluid.

  In the polymer substrate surface modification method according to the first to third aspects of the present invention, it is preferable that the surface of the polymer substrate on which the penetrating substance permeates has a three-dimensional structure.

  According to the 4th aspect of this invention, the polymer base material surface-modified using any one 1st-3rd surface modification method is provided.

According to a fifth aspect of the present invention, there is provided a coating member for use in surface modification of a polymer substrate with a supercritical fluid, the coating film comprising a water-soluble resin and transmitting the supercritical fluid ; A coating member comprising the penetrating material formed on the coating film is provided.

  According to the surface modification method for a polymer substrate according to the first aspect of the present invention, the coating layer is formed so as to cover the substance (penetrating substance) that permeates the polymer substrate. When the osmotic material penetrates into the polymer base material by contacting the osmotic material, the osmotic material dissolved in the supercritical fluid permeates the polymer base material without scattering from the polymer base surface to the outside, so that the osmotic material is more efficiently Moreover, it can penetrate at a high concentration.

  In addition, according to the surface modification method for a polymer substrate according to the first aspect of the present invention, since the osmotic material is covered with the coating layer, the polymer substrate dissolves in the supercritical fluid when it penetrates the polymer substrate. The diffusion of the penetrating material in the in-plane direction of the polymer base material can be suppressed, and bleeding of the pattern of the penetrating material can be suppressed. Therefore, according to the method for modifying the surface of the polymer substrate according to the first aspect of the present invention, the predetermined region on the surface of the polymer substrate can be modified more finely and with high accuracy.

  According to the surface modification method for a polymer substrate according to the second aspect of the present invention, the mask layer and the coating layer are formed so as to cover the osmotic material, so that the osmotic material is brought into contact with the polymer substrate. When penetrating the polymer base material, the penetrating substance dissolved in the supercritical fluid penetrates into the polymer base without scattering from the polymer base surface to the outside, so that the penetrating substance penetrates more efficiently and at a high concentration. be able to.

  Moreover, according to the surface modification method for a polymer substrate according to the second aspect of the present invention, since the mask layer is formed on the side portion of the osmotic material, supercriticality is achieved when the osmotic material penetrates the polymer substrate. Diffusion of the osmotic material dissolved in the fluid in the in-plane direction of the polymer substrate can be suppressed, and bleeding of the osmotic material pattern can be suppressed. Therefore, according to the method for modifying the surface of the polymer substrate according to the second aspect of the present invention, the predetermined region on the surface of the polymer substrate can be modified more finely and with high accuracy.

  According to the method for modifying the surface of a polymer substrate according to the third aspect of the present invention, the supercritical fluid is brought into contact with the polymer substrate in a state where the osmotic material is coated on the coating film. Since the osmotic substance penetrates into the polymer substrate without scattering from the polymer substrate surface to the outside, the osmotic substance can be penetrated more efficiently and at a high concentration.

  In addition, according to the surface modification method for a polymer substrate according to the third aspect of the present invention, since the osmotic substance is covered with the coating film, when the osmotic substance penetrates the polymer substrate, the supercritical fluid is used. Diffusion of the dissolved osmotic material in the in-plane direction of the polymer substrate can be suppressed, and bleeding of the osmotic material pattern can be suppressed. Therefore, according to the method for modifying the surface of a polymer substrate according to the third aspect of the present invention, a predetermined region on the surface of the polymer substrate can be modified more finely and with high accuracy.

  According to the method for modifying the surface of a polymer substrate according to the first to third aspects of the present invention, it is not necessary to use a mold having a fine concavo-convex pattern as proposed in the above application 1, so that the manufacturing cost And the process can be simplified.

  Examples of the surface modification method for a polymer substrate of the present invention and examples of a coating member used in the surface modification method will be specifically described below with reference to the drawings, but the present invention is not limited thereto.

  In Example 1, as shown in FIG. 1, the dye 2 (penetrating substance) is added to the surface of the polymer substrate 1 in a character pattern (“A” and “B”), and the dye 2 is attached only to that portion to the polymer group. A method of modifying the surface by infiltrating the material 1 will be described.

[High pressure equipment used for surface modification]
First, before describing the surface modification method in Example 1, a high-pressure apparatus used in the surface modification method in Example 1 will be described with reference to FIG. FIG. 3 is a schematic configuration diagram of a high-pressure apparatus used in the surface modification method of this example. As shown in FIG. 3, the high-pressure device 100 mainly includes a high-pressure vessel 4, a CO ₂ cylinder 12, a supercritical fluid adjustment device 13, and pipes 16 a and 16 b that connect these components. .

  As shown in FIG. 3, the high-pressure vessel 4 includes a container body 33 having a recess 31 formed on the surface and a lid 34, and an O-ring 32 is provided on the upper surface of the outer wall of the recess 31 of the container body 33. Yes. And as shown in FIG. 3, the recessed part 31 of the container main body 33 is sealed by mounting the lid | cover 34 on the upper surface at the side of the recessed part of the container main body 33, and bolting. Further, as shown in FIG. 3, the high-pressure vessel 4 is formed with a flow path 36 and an introduction port 35 that are in communication with the recess 31 of the vessel body 33. Further, as shown in FIG. 3, the flow path 36 circulates with a pipe 16b through which an external supercritical fluid flows through the inlet 35, and the supercritical fluid generated outside the high-pressure vessel 4 is piped. It is efficiently introduced into the recessed portion 31 of the sealed container body 33 from 16 b through the inlet 35 and the flow path 36. At this time, since the concave portion 31 of the container body 33 is sealed by the lid 34 via the O-ring 32, the supercritical fluid introduced into the concave portion 31 via the introduction port 35 and the flow path 36 is retained in the high pressure vessel 4. There is no leakage to the outside.

As shown in FIG. 3, the supercritical fluid adjustment device 13 mainly includes a booster pump 21 and a buffer tank 17. The CO ₂ cylinder 12 and the supercritical fluid conditioner 13 are connected by a pipe 16a. The CO ₂ gas introduced from the CO ₂ cylinder 12 into the supercritical fluid conditioner 13 via the pipe 16a is supplied by a booster pump 21. And introduced into the buffer tank 17. The introduced CO ₂ gas is boosted to a predetermined pressure in the buffer tank 17 and is adjusted to a predetermined temperature by a heater 14 a provided in the buffer tank 17 (supercritical CO ₂ gas in a supercritical state). Carbon). The supercritical carbon dioxide generated in the buffer tank 17 passes through the pipe 16b whose temperature is adjusted to a predetermined temperature by the temperature controller 14b, and is sealed from the inlet 35 of the high-pressure vessel 4 through the flow path 36. It is introduced into the recess 31.

[Method for surface modification of polymer substrate]
Next, a method for modifying the surface of the polymer substrate in this example will be described with reference to FIG. First, a polymer substrate 1 having a flat surface was prepared. As the polymer substrate 1, a polycarbonate resin having a glass transition temperature Tg of about 130 ° C. was used. Subsequently, the pigment | dye 2 was added to the surface of the polymer base material 1 by the screen printing method by the predetermined pattern (character pattern). In this example, in order to evaluate the effect of partial surface modification, alphabets “A” and “B” were formed as the pattern of the dye 2 as shown in FIG. Moreover, as the pigment | dye 2 added to the polymer base material 1, the alcohol solution of dye Blue35 represented by the following chemical formula was used. At this time, the pigment solution was added so that the coating thickness was about 15 μm. Next, the polymer substrate 1 coated with the dye 2 was dried at 70 ° C. for 1 hour, and then cooled at room temperature for 1 hour.

  As described above, a polymer substrate 1 in which the dye 2 was added to the surface as shown in FIG. 1 in a predetermined character pattern was obtained. FIG. 2 (a) shows a schematic cross-sectional view of the polymer substrate 1 at this time. At this point, the dye 2 is simply applied on the polymer substrate 1, and the dye 2 is a polymer. It does not penetrate into the substrate 1.

  Next, a coating layer 3 was formed on the polymer substrate 1 so as to cover the dye 2 formed in the character pattern (state of FIG. 2B). Specifically, the coating layer 3 was formed as follows. In this example, polyvinyl alcohol was used as a material for forming the coating layer 3. First, polyvinyl alcohol was applied to the entire surface of the polymer substrate 1 on which the dye 2 was added by spin coating. At this time, the coating thickness was about 100 μm. Next, the polymer substrate 1 coated with polyvinyl alcohol was dried at 70 ° C. for 1 hour, and then cooled at room temperature for 1 hour. In this way, the coating layer 3 was formed on the polymer substrate 1. Even at this point, since the dye 2 added on the polymer substrate 1 is only covered with the coating layer 3, the dye 2 does not penetrate into the polymer substrate 1.

Next, the polymer substrate 1 was installed at the bottom of the recess 31 of the high-pressure vessel 4. Thereafter, the recess 34 in the high-pressure vessel 4 was sealed by placing the lid 34 on the vessel body 33 and tightening the bolts. Next, the supercritical fluid was introduced into the recess 31 in the high-pressure vessel 4 as follows. First, the CO ₂ gas cylinder 12 CO ₂ gas through the booster pump 21 of the supercritical fluid regulator 13 is introduced into the buffer tank 17. The introduced CO ₂ gas is pressurized and heated in the buffer tank 17 to generate supercritical CO ₂ (supercritical carbon dioxide). In this example, supercritical carbon dioxide having a temperature of 40 ° C. and a pressure of 15 MPa was generated. Next, the valve 15 b is opened, and the supercritical carbon dioxide adjusted to a predetermined pressure in the buffer tank 17 is sealed in the high-pressure vessel 4 through the inlet 35 and the flow path 36. It was introduced into 31 and allowed to stay (state of FIG. 2 (c)).

  The piping 16b connecting the supercritical fluid adjusting device 13 and the high-pressure vessel 4 is adjusted to a predetermined temperature by a temperature adjusting device 14b (for example, a hot water circulation type temperature adjusting device). Accordingly, the temperature of the supercritical carbon dioxide passing through the pipe 16b can be adjusted. Therefore, it is possible to adjust the temperature in the recess 31 of the high-pressure vessel 4 into which supercritical carbon dioxide is introduced by the temperature control device 14b.

  When supercritical carbon dioxide introduced into the recess 31 of the high-pressure vessel 4 comes into contact with the polymer base 1 from the coating layer 3 side, the supercritical carbon dioxide first penetrates into the coating layer 3. Next, the supercritical carbon dioxide reaches the dye 2 coated on the coating layer 3, and the dye 2 is dissolved in the supercritical carbon dioxide. And the pigment | dye 2 melt | dissolved in the supercritical carbon dioxide permeate | transmits the inside of the polymer base material 1 with a supercritical carbon dioxide. At this time, the dye 2 is dissolved in supercritical carbon dioxide and is in a fluid state. However, since the dye 2 is coated on the coating layer 3, the dye 2 is prevented from diffusing from the surface of the polymer substrate 1 to the outside. can do. As a result, compared with the case where the coating layer 3 is not formed, the dye 2 can be efficiently penetrated into the polymer substrate 1 at a high concentration. Moreover, when the coating layer 3 is formed so as to cover the dye 2 added in a predetermined pattern on the polymer substrate 1 as in this embodiment, the dye 2 in the in-plane direction of the polymer substrate 1 is formed. Since diffusion can be suppressed, bleeding of the pattern of the dye 2 is suppressed. Therefore, it is possible to form a finer pattern with higher definition than when the coating layer 3 is not formed.

  Next, the release valve 24 in the supercritical fluid adjusting device 13 is opened to open the concave portion 31 in the high-pressure vessel 4 to the atmosphere, and then the polymer substrate 1 is taken out from the high-pressure vessel 4 (the state shown in FIG. 2D) ). At this time, after supercritical carbon dioxide in the high-pressure vessel 4 was discharged, the polymer substrate 1 was taken out by opening the high-pressure vessel 4 after returning to room temperature. Next, the polymer substrate 1 was washed with water to remove the coating layer 3, and the polymer substrate 1 was further washed with isopropyl alcohol to remove the dye 2 remaining on the surface of the polymer substrate 1.

  The polymer base material 1 in a state in which the character pattern of the dye 2 as shown in FIG. That is, it was possible to obtain a polymer substrate 1 made of a polycarbonate resin partially surface-modified with the dye 2.

[Comparative Example 1]
In Comparative Example 1, after the dye 2 was added to the polymer substrate 1 by screen printing, a coating layer was not formed, and the surface modification treatment described above (the dye 2 was brought into contact with the supercritical fluid to form the polymer substrate 1). The polymer base material (hereinafter referred to as the polymer base material of Comparative Example 1) was also produced without performing the treatment. In addition, the same material as Example 1 was used for the polymer base material 1 and the pigment | dye 2.

[Comparative Example 2]
In Comparative Example 2, after the dye 2 was added to the polymer substrate 1 by screen printing, the coating layer 3 was not formed, and the surface modification treatment (contact with the supercritical fluid and the dye 2 was performed in the same manner as in Example 1. The polymer base material 1 was permeated) to prepare a polymer base material (hereinafter referred to as the polymer base material of Comparative Example 2). In addition, the same material as Example 1 was used for the polymer base material 1 and the pigment | dye 2.

[Evaluation of adhesion]
The adhesion of the dye 2 formed on the surface of the polymer substrate 1 obtained in Example 1 and Comparative Examples 1 and 2 was evaluated. Specifically, the evaluation was performed by immersing the polymer substrate 1 in isopropyl alcohol, which is a good solvent for the pigment material (dye). As a result, when the polymer base material of Comparative Example 1 was immersed in isopropyl alcohol, the dye was eluted and the printing disappeared. However, in the polymer base material 1 produced in Example 1 and Comparative Example 2, the disappearance of the color of the printed portion (character pattern portion) was not observed. This is because the pigment base material of Comparative Example 1 does not penetrate into the base material and is easily eluted, whereas in Example 1 and Comparative Example 2, the surface modification treatment described above ( The treatment of allowing the dye 2 to permeate the polymer base material 1 by contacting with the supercritical fluid) makes the dye 2 permeate into the polymer base material 1 at a high concentration and makes the dye difficult to elute. It is thought that this is because.

[Cross-section structure]
In the polymer base material produced in Example 1 and Comparative Examples 1 and 2, the state of permeation of the penetrating substance (dye) into the polymer base material surface was analyzed. Specifically, the concentration distribution of the dye in the thickness direction of the polymer substrate in the portion to which the dye of the polymer substrate of Example 1 and Comparative Examples 1 and 2 was added was examined. As a measuring method, the polymer base material was dug from the surface by sputtering, and the change in the relative content of the dye was measured using ESCA (Electron Spectroscopy for Chemical Analysis). The results are shown in FIG. In FIG. 4, the horizontal axis represents the depth position in the thickness direction of the polymer substrate, and the vertical axis represents the relative value of the pigment content on an arbitrary scale. In FIG. 4, white square marks are measurement results of Example 1, black circle marks are measurement results of Comparative Example 1, and white circle marks are measurement results of Comparative Example 2. The position 0 on the horizontal axis is the outermost surface of the polymer substrate. That is, in the characteristic of FIG. 4, the depth position of the base material becomes deeper toward the right side in the drawing. As apparent from FIG. 4, it was found that the dye penetrated from the vicinity of the outermost surface of the polymer substrate to a depth of about 500 nm in the polymer substrate produced in Example 1. On the other hand, in the polymer base material produced in Comparative Example 1, as apparent from FIG. 4, the penetration of the dye into the polymer base material was hardly observed. Moreover, in the polymer base material produced in Comparative Example 2, the dye penetrated from the vicinity of the outermost surface of the polymer base material to a depth of about 400 nm. The penetration amount of the dye was about 60% in the case of Example 1. Met. That is, from the comparison of the penetration amount of the dye between Example 1 and Comparative Example 2 in FIG. 4, by coating the dye with the coating layer as in Example 1, the dye penetrates deeper into the polymer substrate, and It was found to penetrate at high concentration. This is because by covering the dye with the coating layer, diffusion of the dye to the outside during contact with the supercritical fluid is suppressed, and the dye efficiently penetrates into the polymer substrate.

[Evaluation of pattern bleeding]
Further, the degree of bleeding of the dye pattern (character pattern) formed on the surface of the polymer substrate produced in Example 1 and Comparative Examples 1 and 2 was evaluated visually. As a result, no bleeding was observed in the polymer substrate 1 of Example 1, but bleeding was observed in the polymer substrate of Comparative Example 2. From this result, as in Example 1, by coating the pigment with a coating layer, diffusion of the pigment in the in-plane direction of the polymer substrate 1 is suppressed when contacting the supercritical fluid, and bleeding of the pigment pattern is suppressed. I understood that I could do it. That is, as in Example 1, it was found that a high-definition dye pattern with less bleeding could be formed on a polymer substrate by coating the dye with a coating layer. In Comparative Example 1, since the surface modification treatment was not performed using the supercritical fluid, the dye remained added by screen printing, and no bleeding was observed.

  In Example 2, an example in which the surface modification method of the present invention is applied to a plate used for biochemical analysis or the like called micro TAS will be described. A schematic configuration of the micro TAS produced in this example is shown in FIG.

  In the micro TAS 40 of this example, a pattern 42 of the penetrating material 43 as shown in FIG. As the polymer substrate 41, a polymer substrate made of polymethyl methacrylate resin (product name: Delpet 560F, manufactured by Asahi Kasei Kogyo Co., Ltd.) having a glass transition temperature Tg of about 100 ° C. was used. As the penetrating substance 43 forming the pattern 42, polyethylene glycol (PEG) having an average molecular weight of about 1000 was used. That is, in this example, a surface modification treatment is performed to hydrophilize the surface region to which PEG 43 has been added by adding PEG 43 (organic substance) to a predetermined region on the surface of the polymer substrate 1 and bringing it into contact with the supercritical fluid. went.

  As shown in FIG. 5A, the pattern 42 of the PEG 43 includes a circular portion 42a into which a liquid sample is injected, and a flow path 42b extending from the circular portion 42a along the longitudinal direction of the polymer substrate 41. The three branch channels 42c separated from the middle of the channel 42b, and three small circular portions into which the reagent formed at the tip of each of the three branch channels 42c is injected. In this example, the diameter of the circular portion 42a is 5 mm, the diameter of the small circular portion 42d is 2 mm, and the widths of the channel 42b and the small channel 42c are 300 μm. In this example, the surface of the polymer substrate 1 is a flat surface. The pattern 42 of PEG 43 was added on the polymer substrate 41 by screen printing. At this time, PEG43 softened by heating to 60 ° C. was added to the surface of the polymer substrate 41 by screen printing. As described above, a predetermined pattern 42 of PEG 43 was formed on the surface of the polymer substrate 41.

  Next, polyvinyl alcohol was applied on the polymer base material 41 by a screen printing method so as to cover the PEG 43 on which the pattern 42 was printed, and dried to form a coating layer on the PEG 43. At this point, since the predetermined pattern 42 of PEG 43 is formed on the polymer base material 41 and the PEG 43 is simply covered with the coating layer (for example, the state shown in FIG. 2B), PEG 43 does not penetrate into the polymer substrate 41.

  Next, the polymer base material 41 on which the pattern 42 of the PEG 43 is formed by screen printing and the coating layer is formed thereon is placed in the concave portion 31 of the high-pressure vessel 4 used in Example 1, and the inside of the high-pressure vessel 11 Was sealed. Next, in the same manner as in Example 1, the surface of the polymer base material 41 was brought into contact with supercritical carbon dioxide, and PEG 43 was permeated into the polymer base material 41. At this time, supercritical carbon dioxide having a pressure P = 15 MPa and a temperature of 50 ° C. was introduced and retained in the high-pressure vessel 4, and the state was maintained for 30 minutes after the pressure P of the supercritical carbon dioxide was stabilized. . At this time, when the supercritical carbon dioxide comes into contact with the polymer base material 41 from the coating layer side, the supercritical carbon dioxide first penetrates into the coating layer. Next, supercritical carbon dioxide reaches PEG 43 covered with the coating layer, and PEG 43 is dissolved in supercritical carbon dioxide. Then, PEG 43 dissolved in supercritical carbon dioxide penetrates into the polymer substrate 41 together with the supercritical carbon dioxide. At this time, the PEG 43 is dissolved in supercritical carbon dioxide and is in a fluid state, but since the PEG 43 is covered with the coating layer, the PEG 43 can be prevented from diffusing from the surface of the polymer substrate 41 to the outside. . As a result, the PEG 43 can be efficiently penetrated into the polymer base material 41 at a high concentration as compared with the case where the coating layer is not formed. Further, as in this embodiment, when a coating layer is formed on the polymer base material 41 so as to cover the PEG 43 added in a predetermined pattern, the diffusion of the PEG 43 in the in-plane direction of the polymer base material 41 is suppressed. Therefore, the bleeding of the pattern of PEG43 is suppressed. Therefore, it is possible to form a finer pattern with higher definition than when the coating layer is not formed.

  Next, the inside of the high-pressure vessel 4 was opened to the atmosphere in the same manner as in Example 1, and the polymer base material 41 was taken out from the high-pressure vessel 4. Thereafter, the polymer substrate 41 was washed with water to remove the coating layer. In this way, it was possible to obtain a micro TAS 40 made of polymethyl methacrylate resin in which PEG 43 permeated only into the pattern 42 portion on the surface of the polymer substrate 41, that is, only the portion to which PEG 43 was added was surface-modified. In the micro TAS 40 produced in this example, only the surface portion (the pattern 42 portion) of the polymer base material 41 into which the PEG 43 has penetrated is hydrophilized.

[Comparative Example 3]
In Comparative Example 3, PEG (penetrating substance) was added to the polymer substrate by screen printing, and then the coating layer was not formed. Also, the surface modification treatment described above (contacting with the supercritical fluid to bring PEG into the polymer substrate) The micro TAS (hereinafter, referred to as the micro TAS of Comparative Example 3) was produced without performing the treatment. In addition, the same material as Example 2 was used for the polymer base material and PEG.

[Comparative Example 4]
In Comparative Example 4, PEG (penetrating substance) was added to a polymer substrate by screen printing, and then a surface modification treatment (contact with a supercritical fluid was performed in the same manner as in Example 2 without forming a coating layer. To the polymer base material) to produce micro TAS (hereinafter referred to as micro TAS of Comparative Example 4). In addition, the same material as Example 2 was used for the polymer base material and PEG.

[Evaluation of wettability]
The wettability (degree of hydrophilization) on the surface of the micro TAS 40 of Example 2 and Comparative Examples 3 and 4 produced as described above was evaluated. As a result, in the micro TAS of Comparative Example 3, the contact angle of water on the surface portion to which PEG was added was about 55 °, whereas the micro TAS 40 of Example 2 (microsurface subjected to surface modification treatment) In TAS), the contact angle of water on the surface to which PEG was added was about 10 °. Note that the contact angle of Comparative Example 3 is substantially equal to the value of the polymer substrate itself. This indicates that when water is brought into contact with the PEG formed on the polymer substrate of Comparative Example 3, PEG is dissolved in water, and the PEG pattern does not function as a flow path. I understood that. On the other hand, in the micro TAS of Comparative Example 4, the contact angle of water on the surface to which PEG was added was about 10 °, which was the same result as Example 2.

  From the above results, the wettability of the part to which PEG was added was greatly improved by performing surface modification treatment (contact with supercritical carbon dioxide) like the micro TAS 40 produced in Example 2 and Comparative Example 4. It was found that it was improved (hydrophilicity was improved).

  Moreover, when the micro TAS 40 of Example 2 was immersed in water for 24 hours and then the wettability was confirmed again, the contact angle of water hardly changed. Further, after the micro TAS 40 of Example 2 was left in the atmosphere for 10 months, and the wettability of the region to which PEG was added was confirmed, the contact angle of water was 13 °, and good wettability was maintained. I found out. This is considered to be because wettability is stably maintained because PEG penetrates into the polymer substrate at a high concentration.

[Evaluation of flow path pattern]
A small amount of water was dropped on the surface of the micro TAS produced in Example 2 and Comparative Examples 3 and 4, and the degree of bleeding of the formed channel pattern was visually evaluated. As a result, no blur was observed in the micro TAS of Example 2, but blur was observed in the micro TAS of Comparative Example 4. From this result, as in Example 2, by covering the flow path pattern formed of PEG with the coating layer, diffusion of PEG in the in-plane direction of the polymer substrate during contact with the supercritical fluid is suppressed. It was found that the blurring of the road pattern can be suppressed. That is, as in Example 2, it was found that a high-definition PEG flow path pattern with less bleeding can be formed on a polymer substrate by coating PEG with a coating layer. In Comparative Example 3, since the surface modification treatment was not performed using the supercritical fluid, the flow path pattern of PEG remains as it was added by screen printing. Although not observed, as time passed, PEG was dissolved in water and bleeding of the flow path occurred. As time passed, the bleeding further increased.

  Moreover, with respect to the micro TAS of Example 2 and Comparative Examples 3 and 4, water droplets were dropped in the vicinity of the circular portion formed on the micro TAS, and the state of water traveling through the flow path was observed. When water droplets were dropped near the circular portion 42a formed on the micro TAS 40 manufactured in Example 2, it was confirmed that the water was transferred along the flow passage 42b and the branch flow passage 42c and reached the small circular portion 42d. did it. On the other hand, in the micro TAS of Comparative Example 3, water droplets did not propagate along the flow path. In addition, in the micro TAS of Comparative Example 4, it was observed that the dropped water droplets propagated along the flow path formed of PEG, but the water droplet flow was not smooth compared to Example 2, and the water droplets propagated. It took a long time. This is thought to be because, in the micro TAS of Comparative Example 4, the PEG flow path pattern is blotted, so that the side surface of the flow path is uneven, and this unevenness hinders the propagation of water droplets. That is, from this result, like the micro TAS of Example 2, the surface modification treatment after covering the channel pattern formed with PEG with the coating layer suppresses the bleeding of the channel pattern, and the liquid It turned out that the flow path pattern which is easy to flow can be formed.

  In Example 3, as in Example 2, an example in which the surface modification method of the present invention is applied to a micro TAS will be described. However, in this example, a surface modification method suitable for forming a finer penetrating material pattern on the polymer substrate than in Example 2 will be described.

  A schematic configuration diagram of the micro TAS produced in this example is shown in FIG. In the micro TAS 50 of this example, as shown in FIGS. 6A and 6B, the pattern of PEG formed on the surface of the polymer substrate 51 of the micro TAS produced in Example 2 on the surface of the polymer substrate 51 and A similar groove pattern 52 was formed, and PEG 53 (penetrating substance) was added in the groove pattern. In the micro TAS 50 of this example, the dimensions of the groove pattern 52 are as follows. The diameter of the circular part 52a is 5 mm, the widths of the flow path 52b and the branch flow path 52c are both 100 μm, the diameter of the small circular diameter part 52d is 2 mm, and the depths of the circular part 52a, the small circular diameter part 52d and the groove pattern 52 are In either case, the thickness was 100 μm. In this example, PMMA (polymethylmethacrylate) resin is used as the polymer substrate 51, and PEG (polyethylene glycol) 53 is used as the penetrating substance added to the inside of the groove pattern 52. The micro TAS 50 of this example was manufactured as follows.

  First, a mold having an uneven pattern opposite to the groove pattern 52 formed on the polymer substrate 51 is prepared, and the groove pattern 52 as shown in FIG. 6 is formed on the surface by injection molding using the mold. The formed polymer substrate 51 was produced. In this example, the concavo-convex pattern on the mold is formed by precision machining, but the concavo-convex pattern may be formed on the mold by applying a lithography method.

  Next, as shown in FIG. 6A, PEG 53 was added by the inkjet method along the groove pattern 52 of the polymer substrate 51 formed by the above-described method. At this time, the PEG 53 heated to 60 ° C. and softened was discharged from the ink jet head and added to the inside of the groove pattern 52 formed on the surface of the polymer substrate 51. If PEG 53 protrudes from the groove pattern 52 in this step, it is preferable to remove the unnecessary PEG 53 by wiping with water or alcohol.

  Next, polyvinyl alcohol was applied on the polymer substrate 51 and dried so as to cover the PEG 53 added to the inside of the groove pattern 52, thereby forming a coating layer on the PEG 53. Next, in the same manner as in Example 2, supercritical carbon dioxide was brought into contact with the surface of the polymer substrate 51, and PEG 53 was permeated into the groove pattern portion 52 of the polymer substrate 51 to perform surface modification (hydrophilization). did). Thus, the micro TAS50 of this example was obtained.

  In the micro TAS of this example, the side surface and the upper surface of PEG 53 added to the inside of the groove pattern 52 are surrounded by the side wall and the coating layer of the groove pattern 52 (because they are in a covered state). Can be prevented from diffusing from the groove pattern 52 to the outside, and can be efficiently penetrated into the polymer substrate 51 at a high concentration. In addition, when the micro TAS is manufactured by the method as described above, the penetrating substance can be added on the polymer substrate with a pattern of 100 μm or less, and the micro TAS in which only the finer pattern portion is surface-modified is manufactured. Can do.

  Further, the wettability of the micro TAS 50 produced in this example was evaluated in the same manner as in Example 2. As a result, the same result as in Example 2 was obtained. That is, it was confirmed that the wettability was improved only in the pattern portion infiltrated with PEG, became hydrophilic, and was stably maintained.

  In Example 4, an example in which the polymer surface modification method of the present invention is applied to a three-dimensionally shaped polymer base material will be described. Specifically, in this example, when circuit wiring is performed on a module substrate of a one-chip type lens module that integrally includes a lens and an image sensor that detects image formation by the lens as an electrical signal, An example in which the polymer surface modification method is applied will be described.

  A schematic configuration of the lens module manufactured in this example is shown in FIG. As shown in FIGS. 7A and 7B, the lens module 60 manufactured in this example includes a polymer base 61, a lens 62, and an image sensor 63. One surface 61a (upper surface in FIG. 7A) of the polymer base 61 is a substantially flat surface, and the other surface 61b (lower surface in FIG. 7A) is a concave solid surface. . As shown in FIG. 7A, the lens 62 is mounted integrally with the polymer base 61 on the central portion of the flat surface 61a of the polymer base 61, and the image sensor 63 has a concave three-dimensional surface 61b. It is installed on the bottom 61e. And in the lens module 60 of this example, as shown in FIG.7 (b), the some solid wiring 64 which connects the upper part 61d and the bottom part 61e of the concave solid surface 61b of the polymer base material 61 is formed. The three-dimensional wiring 64 is necessary for mounting the image sensor on the concave three-dimensional surface 61 b of the polymer base 61. In order to simplify the description, detailed wiring patterns such as the number of wirings are omitted in FIG.

  As the polymer substrate 61, a polymer substrate made of amorphous polyolefin having a glass transition temperature Tg of about 145 ° C. was used.

  The three-dimensional wiring 64 was formed of a Cu film. The manufacturing method of the three-dimensional wiring 64 is as follows. First, a plating base is formed in a region corresponding to the wiring pattern on the concave three-dimensional surface 61b of the polymer substrate 61. Specifically, a hexane solution of bis (acetylacetonato) palladium metal complex (penetrating substance) is added to the wiring pattern portion on the concave three-dimensional surface 61b of the polymer substrate 61 by an ink jet printing method.

  Next, polyvinyl alcohol was applied on the three-dimensional surface 61b of the polymer substrate 61 and dried so as to cover the wiring pattern portion to which the bis (acetylacetonato) palladium metal complex was added. In this example, polyvinyl alcohol was applied by a spray method. As a result, a coating layer was formed on the wiring pattern portion.

  Next, in the same manner as in Example 2, the supercritical carbon dioxide is brought into contact with the polymer substrate 61 and the metal complex added to the wiring pattern portion of the concave three-dimensional surface 61b is permeated into the polymer substrate 61 and stabilized. When the metal complex is infiltrated into the polymer substrate 61 as described above, the metal complex added to the wiring pattern portion penetrates into the polymer substrate 61 together with the supercritical carbon dioxide in a state of being covered with the coating layer. The metal complex can be prevented from diffusing to the outside of the wiring pattern portion, can be efficiently penetrated into the polymer substrate 61 at a high concentration, and a high-definition wiring pattern without bleeding Can be formed. Metal complexes that can be dissolved in supercritical carbon dioxide and reduced to become plating nuclei include platinum dimethyl (cyclooctadiene), bis (cyclopentadienyl) nickel, bis (acetylacetonate) palladium, hexafluoroacetyl. Acetonato palladium or the like can also be used.

  After allowing the metal complex to penetrate into the polymer substrate 61, the polymer substrate 61 is washed with water to remove the coating layer formed of polyvinyl alcohol, and the polymer substrate 61 is washed with ethanol to remove the polymer base. The metal complex remaining on the material 61 was removed. Next, the polymer substrate 61 was immersed in a reducing agent (sodium borohydride) to reduce the metal complex to form metal fine particles. In this manner, a plating base was formed in a region corresponding to the wiring pattern on the concave three-dimensional surface 61b of the polymer substrate 61.

  Next, Cu was plated on the concave three-dimensional surface 61b side of the polymer substrate 61 by electroless plating. At this time, the Cu film grows only in a portion (plating base portion) where the metal complex has permeated and the surface is modified. In this example, a 10 μm thick Cu film was formed. Thus, the three-dimensional wiring 64 made of the Cu film was formed on the three-dimensional surface 61b of the polymer base 61 as shown in FIG. As described above, when the polymer substrate to which the surface modification method of the present invention is applied has a three-dimensional structure as in this embodiment, the three-dimensional portion (uneven portion) penetrates by performing pattern printing by the ink jet method. Substances can be added. Therefore, by using the surface modification method of the present invention, wiring to a three-dimensional part, which has been impossible in the past, can be made possible.

[Comparative Example 5]
In Comparative Example 5, the metal complex was left added to the region corresponding to the wiring pattern on the three-dimensional surface of the polymer base material, and no coating layer was formed on the polymer base material. The reduction treatment and Cu electroless plating were performed without performing (the treatment of bringing the metal complex into contact with the supercritical fluid in contact with the supercritical fluid) (hereinafter referred to as the lens module of Comparative Example 5). However, in Comparative Example 5, a plating film could not be formed on the wiring pattern portion. In Comparative Example 5, since the surface modification treatment is not performed, the metal complex does not penetrate into the polymer base material and is only on the surface of the polymer base material. It is considered that the adhesion with the plating base was poor and the plating film was not formed on the plating base.

[Comparative Example 6]
In Comparative Example 6, after the metal complex was added onto the polymer substrate by the inkjet method, the surface modification treatment (contact with the supercritical fluid was performed in the same manner as in Example 4 without forming the coating layer). The lens module (hereinafter referred to as the lens module of Comparative Example 6) was manufactured by performing a treatment for permeating the polymer substrate.

[Evaluation of adhesion]
Next, the adhesion of the solid wiring of the lens modules produced in Example 4 and Comparative Example 6 was evaluated. Specifically, a peeling test using an adhesive tape was performed on the three-dimensional wiring formed on the three-dimensional surface of the polymer substrate. As a result, it was found that in any lens module, the three-dimensional wiring is difficult to peel off and the adhesion is greatly improved. Further, when the adhesion of the three-dimensional wiring was confirmed after leaving the lens module after the surface modification treatment in the atmosphere for 10 months, it was found that it was difficult to peel off and good adhesion was maintained. From the above results, it is possible to form a three-dimensional wiring with good adhesiveness by performing a treatment for bringing the metal complex into the polymer substrate by contacting with a supercritical fluid as in Example 4 and Comparative Example 6. I understood.

[Evaluation of wiring pattern bleeding]
The degree of bleeding of the three-dimensional wiring pattern formed on the surface of the lens module produced in Example 4 and Comparative Example 6 was visually evaluated. As a result, no blur was observed in the lens module of Example 4, but blur was observed in the lens module of Comparative Example 6. From this result, by covering the wiring pattern portion to which the metal complex is added with the coating layer as in Example 4, the diffusion of the metal complex in the in-plane direction of the polymer substrate during contact with the supercritical fluid is suppressed. It was found that bleeding of the wiring pattern can be suppressed. That is, as in Example 4, it was found that a high-definition wiring pattern with less bleeding can be formed on the polymer substrate by covering the wiring pattern portion to which the metal complex has been added with the coating layer.

  In Example 5, a micro TAS (FIG. 5) having the same structure as that of Example 2 was produced by a surface modification method different from that of Example 2. The micro TAS polymer substrate, penetrant, and pattern formed on the polymer substrate prepared in this example were the same as in Example 2. The surface modification method of the micro TAS in this example will be described with reference to FIG.

  First, the mask layer 76 was formed on the polymer substrate 41 as follows. A mask material was attached to an area other than the pattern portion 77 such as a flow path of PEG (penetrating substance) to be formed on the polymer substrate 41 by an ink jet printing method. In this example, a photosensitive resin (SU-10 manufactured by Kayaku Microchem Co., Ltd.) was used as the mask material, and the coating thickness of the photosensitive resin was about 1 μm. Next, the polymer base material 41 to which the photosensitive resin was adhered was dried at 70 ° C. for 1 hour and further cooled at room temperature for 1 hour. Next, the mask material was cured by irradiating the mask material with ultraviolet rays to form a mask layer 76. Thus, the mask layer 76 having the pattern portion 77 of the PEG 43 as an opening was formed on the polymer base material 41 (state shown in FIG. 8A). As the material for the mask layer 76, any material can be used as long as it can shield the supercritical fluid and adheres / adheres to the surface of the polymer substrate 41.

  Next, a PEG layer 72 that permeates the polymer substrate 41 was formed on the mask layer 76. Specifically, PEG (average molecular weight 1000) heated to 60 ° C. was applied onto the mask layer 76 and the opening 77 of the mask layer 76 as shown in FIG. In this example, as shown in FIG. 8B, the example in which the PEG layer 72 is applied over the entire surface of the mask layer 76 has been described, but the present invention is not limited to this. In the surface modification method of this example, PEG must be applied to the opening 77 of the mask layer 76, but PEG may not be applied to other regions on the mask layer 76.

  Next, polyvinyl alcohol was applied so as to cover the PEG layer 72 and dried. At this time, polyvinyl alcohol was applied to a thickness of 0.5 μm to form a coating layer 73 on the PEG layer 72 (state shown in FIG. 8C). At this point, since the PEG layer 72 is only covered with the mask layer 76 and the coating layer 73, the PEG does not penetrate into the polymer substrate 41.

  Next, the polymer base material 41 having the coating layer 73 formed on the PEG layer 72 was placed in the recess 31 of the high-pressure vessel 4 used in Example 1, and the inside of the high-pressure vessel 4 was sealed. Next, supercritical carbon dioxide 5 having a pressure P1 of 15 MPa and a temperature of 50 ° C. was introduced into the high-pressure vessel 4 and retained. And after the pressure of the supercritical carbon dioxide 5 was stabilized, the state was maintained for 30 minutes. At this time, a part of the PEG layer 72 formed in the opening 77 of the mask layer 76 together with the supercritical carbon dioxide 5 is brought into contact with the supercritical carbon dioxide on the surface of the polymer substrate 41. It penetrates from the surface of the polymer base material 41 exposed at the opening of the inside (state of FIG. 8D).

  In the micro TAS of this example, the side surface and the top surface of the PEG added on the polymer substrate 41 are surrounded by the side wall of the mask layer 76 and the coating layer 72 (because they are covered). , PEG can be prevented from diffusing from the top of the polymer substrate 41 to the outside, and can be efficiently penetrated into the polymer substrate 41 at a high concentration. Further, in the micro TAS of this example, since the mask layer 76 is formed on the side of the PEG, the in-plane of the PEG polymer substrate 41 dissolved in the supercritical fluid when the PEG penetrates the polymer substrate 41. Diffusion in the direction can be suppressed, and bleeding of the PEG flow path pattern can be suppressed.

  When supercritical carbon dioxide is brought into contact with the polymer substrate (step of FIG. 8 (d)), supercritical carbon dioxide also comes into contact with a region other than the opening, but a mask layer is formed in this region. Therefore, PEG does not penetrate into the polymer substrate in this region (the surface of the polymer substrate in this region is not modified).

  Next, after PEG was infiltrated into a predetermined region of the polymer substrate 41, the inside of the high-pressure vessel 4 was opened to the atmosphere in the same manner as in Example 1, and the polymer substrate 41 was taken out from the high-pressure vessel 4 (FIG. 8 (e) ) State). Next, the mask layer 73 and the PEG layer 72 remaining on the polymer substrate 41 were washed away with water, and the mask layer 76 was washed away with sodium hydroxide (state shown in FIG. 8F). In this way, it was possible to obtain micro TAS 40 made of polymethyl methacrylate resin in which PEG penetrated only into the pattern 42 portion on the surface of the polymer substrate 41, that is, only the portion to which PEG was added was surface-modified. In the micro TAS 40 manufactured in this example, as in Example 2, only the surface portion (42 portions of the pattern) of the polymer base material 41 infiltrated with PEG is hydrophilized.

  Further, the wettability of the micro TAS produced in this example was evaluated in the same manner as in Example 2. As a result, the same result as in Example 2 was obtained. That is, it was confirmed that the wettability was improved only in the pattern portion infiltrated with PEG, the surface was made hydrophilic, and the wettability was stably maintained for a long time. In addition, when water droplets were dropped near the circular portion 42a formed on the micro TAS produced in this example, the water was transmitted along the flow channel 42b and the branch flow channel 42c, as in Example 2, to form a small circle. It was confirmed that it reached the portion 42d.

  In Example 6, instead of directly adding the substance to be infiltrated as in Examples 1 to 5 above to the polymer substrate, a sheet-shaped transfer member prepared separately from the polymer substrate (hereinafter, The osmotic material is added in a predetermined pattern on the coating film), and then the coating film is placed on the polymer substrate, and then the supercritical fluid is brought into contact with the polymer substrate so that the osmotic material is brought into contact with the polymer substrate. Surface modification was carried out by permeating into the surface.

  In this example, as shown in FIG. 1, a polymer base material that has been surface-modified by allowing a dye 2 (penetrating substance) to permeate the surface of the polymer base material 1 with a character pattern (“A” and “B”). Produced. As the polymer substrate 1, a polycarbonate resin having a glass transition temperature Tg of about 130 ° C. was used as in Example 1. A method for modifying the surface of the polymer substrate in this example will be described with reference to FIG.

  First, a coating film 80 made of polyvinyl alcohol solidified into a sheet shape was prepared. The thickness of the coating film 80 was 100 μm.

  Subsequently, the pigment | dye 2 penetrate | infiltrated into a polymer base material was added to the surface of the coating film 80 with the predetermined pattern with the inkjet printing method. In this example, the alphabet “A” and “B” character patterns are finally formed on the polymer substrate 1 as shown in FIG. 1, so when the dye 2 is added to the surface of the coating film 80. The dye 2 was added on the coating film 80 in a pattern (hereinafter also referred to as a reversal pattern) obtained by reversing the character pattern. Moreover, as the pigment | dye 2 added to the coating film 80, the alcohol solution of dye Blue35 represented by Chemical formula (1) was used like Example 1. FIG. The coating thickness of the dye solution was added so as to be about 15 μm. Next, the coating film 80 coated with the dye 2 was sufficiently dried at room temperature. In this way, a coating film 80 made of polyvinyl alcohol to which the dye 2 was added in an inverted pattern of the character pattern was obtained (state of FIG. 9A).

  After preparing the coating film 80 to which the pigment | dye 2 was added as mentioned above, the coating film 80 was stuck to the polymer base material 1 surface as follows. When bringing them into close contact, it is effective to interpose water, ethanol, methanol or the like between the polymer substrate 1 and the coating film 80. In this example, first, a small amount of water was adhered to the surface of the polymer substrate 1, and the coating film 80 was placed thereon. At this time, the surface of the coating film 80 to which the dye 2 was added was placed so as to face the surface of the polymer substrate 1 to which water adhered. Next, the surface of the coating film 80 was pressed while gradually avoiding the ingress of air from the end of the coating film 80 to bring the coating film 80 into close contact with the polymer substrate 1 and then sufficiently dried at room temperature (see FIG. 9 (b) state). At this point, since the coating film 80 to which the dye 2 has been added is only brought into close contact with the polymer substrate 1, the dye 2 does not penetrate into the polymer substrate 1.

  Next, the polymer substrate 1 is placed in the high-pressure vessel 4 used in Example 1, and the supercritical carbon dioxide 5 is brought into contact with the polymer substrate 1 from the coating film 80 side in the same manner as in Example 1 to obtain the dye 2 Was permeated in a predetermined pattern (character pattern) (state shown in FIG. 9C). In the case of the present embodiment, the supercritical carbon dioxide 5 passes through the coating film 80 and then dissolves the dye 2 added to the coating film 80 and permeates into the polymer substrate 1. At this time, the dye 2 is dissolved in the supercritical carbon dioxide 5 and is in a fluid state. However, since the dye 2 is coated on the coating film 80, the dye 2 may diffuse from the surface of the polymer substrate 1 to the outside. It is suppressed. By this action, many dyes 2 can efficiently penetrate into the polymer substrate 1 at a high concentration. Moreover, the said effect | action suppresses the bleeding of the pattern of the pigment | dye 2. FIG. Therefore, in this example, a finer pattern can be formed with high definition.

  Next, the inside of the high-pressure vessel 4 was opened to the atmosphere in the same manner as in Example 1, and the polymer substrate 1 was taken out from the high-pressure vessel 4 (state shown in FIG. 9D). Next, it was washed with water in the same manner as in Example 1 to remove the coating film 80 (state shown in FIG. 9 (e)). Thus, the polymer base material 1 in a state in which the character pattern of the dye 2 as shown in FIG. 1 penetrated into the polymer base material 1 was obtained. That is, a polymer substrate made of a polycarbonate resin in which the dye 2 penetrates the polymer substrate 1 in a predetermined pattern could be obtained.

  When the same evaluation as in Example 1 was performed on the polymer substrate produced in this example, the same result was obtained. That is, the dye penetrated from the surface of the polymer substrate into the interior at a high concentration, and the dye was modified so that it was difficult to peel off.

  As described above, in the polymer substrate surface modification method of the present embodiment, the penetrating substance is permeated in a state where the penetrating substance such as a pigment added to a predetermined portion of the polymer base surface is covered with the coating film. , The osmotic material can be prevented from diffusing into the supercritical fluid. Thereby, the osmotic substance can be efficiently infiltrated into the polymer substrate at a high concentration, and the osmotic substance can be infiltrated with a high-definition pattern. Furthermore, in the method for modifying the surface of the polymer substrate of this example, a coating film (sheet-like transfer member) is prepared separately from the polymer substrate, and printed with a penetrating substance that penetrates the polymer substrate in a predetermined pattern. Therefore, for example, a coating film to which a penetrating substance is added in a predetermined pattern can be manufactured consistently as a roll-shaped transfer member. Therefore, the method for modifying the surface of the polymer substrate of the present embodiment can realize versatility in production and cost reduction, such as adapting to polymer substrates of various shapes, and mass productivity. Can be improved.

  In the above Examples 1 to 6, when the supercritical fluid was brought into contact with the polymer substrate, bolting was performed in order to maintain the sealed state in the high-pressure vessel, but the present invention is not limited to this, and any arbitrary Means may be used. For example, a rotary lid seal mechanism or the like can be used. Further, a method of attaching a die to the press device and sealing the mating surfaces with a pressing force may be employed.

  According to the surface modification method for a polymer substrate of the present invention and the coating member used in the method, a predetermined region (region of a predetermined pattern) on the polymer substrate can be easily surface-modified. In particular, since surface modification can be easily performed even in a fine region of 100 μm or less, the surface modification method for a polymer substrate of the present invention is a micro TAS or biochip that requires surface modification with a fine pattern. Or, it is particularly suitable for manufacturing a three-dimensional wiring device or the like.

FIG. 1 is a perspective view of the polymer substrate produced in Example 1. FIG. FIGS. 2A to 2E are diagrams showing the procedure of the surface modification method of Example 1. FIG. FIG. 3 is a schematic configuration diagram of the high-pressure apparatus used for surface modification of the polymer base material in Example 1. FIG. 4 is a graph showing the distribution of the pigment content in the depth direction of the polymer substrate produced in Example 1. 5A and 5B are schematic configuration diagrams of the micro TAS manufactured in Example 2, FIG. 5A is a perspective view, and FIG. 5B is a cross-sectional view taken along line AA ′ in FIG. is there. 6 is a schematic configuration diagram of the micro TAS manufactured in Example 3, FIG. 6A is a perspective view, and FIG. 6B is a cross-sectional view along BB ′ in FIG. 6A. is there. 7 is a schematic configuration diagram of a lens module manufactured in Example 4, FIG. 7A is a cross-sectional view along CC ′ in FIG. 7B, and FIG. 7B is a three-dimensional surface side. FIG. 8A to 8F are diagrams showing the procedure of the surface modification method of Example 5. FIG. FIGS. 9A to 9E are diagrams showing the procedure of the surface modification method of Example 6. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Polymer base material 2 Osmotic substance 3 Coating layer 5 Supercritical carbon dioxide 76 Mask layer 80 Coating film

Claims (29)

A method for surface modification of a polymer substrate using a supercritical fluid,
Adding an osmotic material to a predetermined region of the surface of the polymer substrate;
Forming a coating layer made of a water-soluble resin and permeable to a supercritical fluid so as to cover the osmotic material;
A surface modification method comprising: bringing a supercritical fluid into contact with a surface of the polymer substrate on the coating layer side to allow the penetrating substance to penetrate into the polymer substrate.   2. The surface modification method according to claim 1, wherein the penetrating substance is added to the surface of the polymer base material in a predetermined pattern when the penetrating substance is added to a predetermined region of the surface of the polymer base material. .   3. The surface modification method according to claim 1, wherein the penetrating substance is added to the surface of the polymer substrate by a screen printing method or an ink jet method. A method for surface modification of a polymer substrate using a supercritical fluid,
Forming a mask layer having openings in a predetermined pattern on the polymer substrate;
Forming a layer of penetrating material in at least the opening of the mask layer;
Forming a coating layer made of a water-soluble resin and transmitting a supercritical fluid on the osmotic material layer;
A surface modification method comprising: bringing a supercritical fluid into contact with the surface of the polymer substrate on the coating layer side and allowing the penetrating substance to penetrate into the polymer substrate through an opening of the mask layer.   The surface modification method according to claim 4, wherein the mask layer is formed by a printing method.   6. The surface modification method according to claim 4, wherein the mask layer is formed of a polymer material.   The surface according to any one of claims 1 to 6, wherein the coating layer is formed by one method selected from the group consisting of a dipping method, a roll coating method, a screen printing method, and a spray method. Modification method.   The surface modification method according to claim 1, wherein the coating layer is made of a material that is less soluble in the supercritical fluid than the penetrating substance.   Furthermore, the surface modification method as described in any one of Claims 2-8 including preparing the polymer base material in which the area | region of the said predetermined pattern was formed in the recessed part. The surface modification method according to claim 9, wherein the recess includes a groove pattern .   A method for surface modification of a polymer substrate using a supercritical fluid,
  Adding a penetrating substance in a predetermined pattern to the surface of the coating film made of a water-soluble resin and transmitting a supercritical fluid;
  Installing the coating film on the polymer substrate;
  A surface modification method comprising bringing a supercritical fluid into contact with the surface of the polymer substrate on the coating film side and allowing the penetrating substance to penetrate into the polymer substrate.   The coating film and the polymer substrate are disposed such that the coating film is placed on the polymer substrate such that the surface of the coating film on which the penetrating substance is added faces the surface of the polymer substrate. The method for surface modification according to claim 11, further comprising: bonding.   The surface modification method according to claim 11 or 12, wherein the coating film is formed of a material that is less soluble in the supercritical fluid than the penetrating substance.   The surface modification method according to any one of claims 1 to 13, wherein the supercritical fluid is carbon dioxide in a supercritical state.   The polymer base material is formed of one selected from the group consisting of polymethyl methacrylate, polycarbonate, wholly aromatic polyamide, wholly aromatic polyester, and amorphous polyolefin. The surface modification method described in 1.   16. The surface modification method according to claim 1, wherein the penetrating substance is an organic substance.   The surface modification method according to claim 1, wherein the osmotic substance is dissolved in the supercritical fluid.   The surface modification method according to claim 16 or 17, wherein the penetrating substance is a pigment.   18. The surface modification method according to claim 16, wherein the penetrating substance is polyethylene glycol.   The surface modification method according to claim 16 or 17, wherein the penetrating substance is a metal complex.   21. The surface modification method according to claim 20, further comprising forming a plating layer by electroless plating in the region to which the penetrating substance is added.   The surface modification method according to any one of claims 1 to 21, wherein the surface of the polymer substrate on which the penetrating substance is permeated has a three-dimensional structure.   The polymer base material surface-modified using the surface modification method as described in any one of Claims 1-22.   A coating member provided on a polymer substrate when the polymer substrate is surface-modified with a supercritical fluid,
  A coating film made of a water-soluble resin and permeable to a supercritical fluid;
  A coating member comprising the penetrating substance formed on the coating film.   The coating member according to claim 24, wherein the penetrating substance is formed on the coating film in a predetermined pattern.   The coating member according to claim 24 or 25, wherein the penetrating substance is an organic substance.   27. The coating member according to claim 24, wherein the coating film is formed of a material that is less soluble in the supercritical fluid than the penetrating substance.   The surface modification method according to any one of claims 1 to 22, wherein the coating layer or the coating film is formed of polyvinyl alcohol.   The coating member according to any one of claims 24 to 27, wherein the coating film is formed of polyvinyl alcohol.

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