JP4353757B2 - Manufacturing method of resin molded product and manufacturing method of mold - Google Patents

Description

  The present invention relates to a method for producing a resin molded product having a desired modeling depth, a resin molded product obtained therefrom, and a method for producing a mold used for producing the resin molded product. In particular, the method of the present invention is useful as a method for producing a resin molded product used for diagnosis, reaction, separation, measurement and the like in the clinical laboratory field, gene processing field, and combinatorial chemistry field.

  Today, as society matures, medical and health values are changing from a narrow range of basic health to seeking a “rich and healthy life”. Against this background of changes in values, medical expenses are increasing, and the number of people at the border between health and disease is increasing. Against this background and because prevention is less burdensome than treatment, it is thought that in the future society, individual consciousness will change in a direction that places importance on preventive medicine rather than therapeutic medicine. . Along with such changes in personal consciousness, in the medical field, especially in the clinical laboratory field, it is possible to perform more rapid examinations and diagnoses near the patient, for example, in the operating room, bedside, or at home. There is a demand for a restraint inspection system and a non-invasive or minimally invasive inspection system that requires a smaller amount of specimen such as blood.

  Further, in order to realize an unconstrained inspection system that enables quick inspection / diagnosis as described above, by reducing the size of a substrate used for inspection / diagnosis, for example, portability of the apparatus is improved. It is necessary to give.

  For example, if the diameter of the flow path can be reduced from 1 mm to 0.1 mm by micromachine technology, not only the amount of the sample is reduced, but also the time required for diagnosis can be reduced to 1/10 or less. Furthermore, if the diameter of the flow path can be miniaturized by micromachine technology, it is expected that the device will have portability and at the same time perform the same function as a conventional large device. In addition, a plurality of channels can be arranged on the same substrate by miniaturizing the flow path, and parallel processing is also expected.

  Miniaturization is expected in the field of combinatorial chemistry, especially in high-throughput screening (HTS) in pharmaceutical development. Combinatorial chemistry is the efficient synthesis and utilization of many compound groups (libraries) using combinations.

  The 96-well plate and 384-well plate used for high-throughput screening can screen a plurality of samples at the same time. For example, the 96-well plate and the 384-well plate contribute to acceleration of drug development by combining with an automatic dispensing device.

  If micro-machine technology makes it possible to reduce the width or diameter of a container from 10 mm to 0.4 mm and the depth from 10 mm to 0.3 mm, for example, 1,000 to 5,000 micro-chips on the same substrate. It can have containers and can be expected to dramatically accelerate drug development.

  Similarly, miniaturization is also expected for use in chemical synthesis / analysis applications in the combinatorial chemistry field, particularly in the chemical industry field.

  With the progress of the global human genome analysis program, the number and types of diseases that can be diagnosed by DNA are steadily increasing, and many of the diseases that have been diagnosed indirectly by biochemical analysis are DNA. At a certain level, it is now possible to make a definitive diagnosis that approaches the cause or mechanism of the disease. As a result, in the future, it is predicted that the board used for diagnosis for drug treatment without side effects suitable for individuals, which is said to be made-to-order medicine, and for the presence or absence of specific diseases by individual will spread to the clinic level in town. ing.

  Precise and inexpensive substrates are expected in order to reduce the amount of sample, shorten the diagnosis time, and make the inspection device portable.

  Commonly used methods for gene-related applications include capillary electrophoresis, microarray method, and gene amplification (PCR: Polymerase Chain Reaction) method that can detect a very small amount of genomic sample more than 100,000 times and detect it with high sensitivity. . In capillary electrophoresis, a sample is introduced into a capillary having a diameter of 100 to 200 μm, separated by electrophoresis, and optically detected. If miniaturization of this capillary diameter becomes possible, it is expected that the diagnosis time will be further increased. Due to the miniaturization of the capillary diameter, a plurality of capillaries can be arranged on the same substrate, and parallel processing is also expected.

  Fluorescence analysis is generally used for microarray detection, and accurate gene expression information cannot be acquired unless detection sensitivity and reproducibility are high. In order to increase detection sensitivity and reproducibility without reducing the array density on the substrate, attempts have been made to increase the area of one array. However, there is a limit to the area that can be expanded on a flat substrate, and there is a limit to improving detection sensitivity and reproducibility without reducing the array density on the substrate. If a substrate having a fine concave or convex shape becomes possible, it is possible to dramatically increase the area and volume of one array, and it is expected to improve detection sensitivity and reproducibility.

  The PCR method amplifies the target DNA by 100,000 times or more in a short time by using a polymerase. If this container can be miniaturized, it is expected to reduce the cost as well as increase the speed and efficiency and reduce the amount of expensive antibodies and substrates used. Furthermore, if it is possible to arrange a plurality of flow paths, a plurality of mixing units, and a plurality of containers on the same substrate by miniaturization, it is expected that the capillary electrophoresis method and the PCR method are performed on the same substrate. .

  Conventional resin molded products have been formed by injection molding, blow molding or press molding using a mold or a metal mold formed by a cutting method.

  However, when producing a metal mold from a mold, there is a limit to the accuracy of the mold, and therefore there is a limitation on the modeling range for a metal mold using the mold. In addition, even when a metal mold is produced by a cutting method, since there is a limit to the cutting tool and the work accuracy using the cutting tool, a resin molded product having a precise and fine shape regardless of which processing method is used. Is not realized.

  As described above, in the case of using a metal mold by a mold or a cutting method, a resin molded product having a precise and fine shape is not realized in any of the processing methods.

  For this reason, there are limits to the accuracy and miniaturization of flow channels and containers when the obtained resin molded products are used in the clinical laboratory field, especially blood tests, urine tests, and biochemical analysis applications. There was a problem that the amount increased. As a result, in the case of using a metal mold by a mold or a cutting method, there is a drawback that the portability of the inspection / diagnosis device cannot be imparted.

  Similarly, there is a limit to miniaturization of containers when resin molded products obtained using molds or metal molds by cutting methods are used for combinatorial chemistry-related applications, especially high-throughput screening applications in pharmaceutical development. , Had the disadvantage that drug development could not be dramatically accelerated (accelerated) and reduced in volume (cost reduced)

  Similarly, when the obtained resin molded products are used for combinatorial chemistry related applications, especially chemical synthesis / analysis applications in the chemical industry, there are limits to the accuracy and miniaturization of the flow path, shortening the chemical synthesis / analysis time. It has the disadvantages that it is impossible to reduce the amount of chemicals used for mixing and reaction, the amount of waste liquid, and the environmental load.

  Similarly, resin molded products obtained using molds and metal molds by cutting methods can be used in gene-related fields, especially capillary electrophoresis, microarray analysis, gene amplification (PCR) amplification, etc. However, there is a limit to miniaturization, and there are disadvantages that the analysis speed cannot be increased and the amount of sample cannot be reduced. As a result, when using a metal mold by a mold or a cutting method, there is a problem that the substrate cannot be reduced in size.

  As a processing method to solve such problems when using a metal mold by a mold or a cutting method, fine processing is performed by wet etching processing or dry etching processing on a glass or silicon substrate applying a semiconductor micro processing technology. The technology to apply is known. However, wet etching is not a precise processing method because it becomes difficult to obtain width (or diameter) accuracy when the modeling depth becomes deeper than 0.5 mm due to the progress of under-etching under the masking material.

  In contrast to wet etching, dry etching is a technique developed from the pattern formation process of Si semiconductor, and its application to various electronic components and compound semiconductors by various plasma source species is being studied. However, this method has excellent fine workability, but the etching rate is as slow as 500 to 2,000 nm / min. For example, when processing with a modeling depth of 0.1 mm, a processing time of 50 minutes or more is required. It was necessary and was not an inexpensive processing method with excellent productivity.

  Further, when the processing time of dry etching is 1 hour or longer, the device electrode becomes heated, and there is a concern about deformation of the substrate or damage to the device. Therefore, it is necessary to take a measure such as temporarily stopping the machining and starting the machining again, and the productivity further decreases.

  A lithography method is known as another method for solving the problem in the case of using a metallic mold by a mold or a cutting method. In this lithography method, first, a resist is coated on a substrate, the resist layer is exposed, and then a resist pattern is formed by development. Then, after depositing a metal structure on the substrate by electroplating according to the resist pattern, a molded product is formed by injection molding using the metal structure as a mold.

  For example, about 50,000 or more molded articles can be obtained from a single metal structure so that laser disks, CD-ROMs, and mini-discs are typical examples of products obtained by this method. Furthermore, the lithography method can be said to be a method with excellent productivity in that it can be manufactured precisely and at a very low cost. In addition, the material that can be handled is different from that of silicon, and it is expected that the material unit price will be low and that it will be used for future application development.

  However, in the lithography method, the modeling depth is centered on 1 to 3 microns so that laser disks, CD-ROMs, and mini-discs can be cited as representative examples. Therefore, the actual situation is that an example having a modeling depth of, for example, 30 microns such as a flow path and a container has not been realized. The reason is that, for example, when a resin molded product is obtained by injection molding, it is difficult to obtain a resin molded product having excellent transferability and mold release property.

  In the case of a laser disk or the like, since the modeling depth is 1 to 3 microns, it was possible to obtain a resin molded product having excellent transferability and releasability even when the metal structure depth direction angle is close to vertical. . However, when trying to obtain a resin molded product having a modeling depth of, for example, 30 microns, such as a flow path and a container at the same vertical angle, a part of the resin remains in the metal structure or the shape is changed. There has been a problem that it is impossible to obtain a resin molded product having excellent properties and releasability.

  A lithography method, in particular, a lithography method using synchrotron radiation as an exposure light source is known (see, for example, Patent Document 1). The high directivity of synchrotron radiation is comparable to laser light, and short-wavelength light that cannot be realized with a laser can clear the diffraction limit that becomes a bottleneck by fine processing. Therefore, when synchrotron radiation light is used as the exposure light source, a thicker layer can be exposed, so that a finer and deeper modeling depth can be obtained as compared with a conventional light source.

However, in the case of exposure processing using synchrotron radiation, the resist layer is exposed in the vertical direction because of its high directivity, so that the pattern of the resulting metal structure is vertical, and is excellent in transferability and releasability. There arises a problem that a resin molded product cannot be obtained. In the case of synchrotron radiation capable of exposing a deeper layer, the phenomenon that the transferability and releasability are impaired becomes more prominent. Thus, in the conventional method for producing a resin molded product, the angle in the depth direction of the metal structure cannot be controlled, so that a resin molded product excellent in transferability and releasability cannot be produced with high productivity. There was a point. The synchrotron radiation facility is a very large facility, and it is not easy to construct and maintain the facility. In particular, since the construction and maintenance of equipment is very expensive, the cost of a molded product obtained by injection molding may be several tens of times higher than that of a molded product obtained by a normal lithography method. is expected.
JP 2001-38738 A

  As described above, the conventional method for producing a resin molded product has a problem that a resin molded product having a desired shape cannot be produced with high productivity because the shape of the metal structure cannot be controlled efficiently.

  The present invention has been made to solve such problems, and is used for manufacturing a resin molded product capable of manufacturing a resin molded product having a desired shape with high productivity, and the manufacturing thereof. One object is to provide a mold manufacturing method.

  Another object of the present invention is to provide a resin molded product having a desired modeling depth, or a chip suitable for use in the clinical examination field, gene-related field, and combinatorial chemistry field.

  The mold manufacturing method according to the present invention includes a step of forming a resist layer on a substrate, a resist pattern forming step of performing exposure, development, or exposure, heat treatment, and development on the resist layer using a mask, and the substrate Is left in an organic solvent atmosphere to give an inclination angle to the wall surface of the resist pattern, and a metal structure is deposited according to the resist pattern formed on the substrate. Thereby, the metal mold | die which has a desired shape can be manufactured with sufficient productivity.

  In the above mold manufacturing method, the substrate is left in an organic solvent atmosphere, and a solution containing an organic solvent is applied onto the resist pattern on the substrate, instead of applying a tilt angle to the wall surface of the resist pattern. Then, a step of giving an inclination angle to the wall surface of the resist pattern may be included. Thereby, the metal mold | die which has a desired shape can be manufactured with sufficient productivity.

  In the above-described mold manufacturing method, in the resist pattern forming step, the resist layer is formed and exposed a plurality of times until the resist layer is formed into a structure having a desired height or depth. It is desirable to be characterized by repetition.

  In a preferred embodiment of the above-described mold manufacturing method, in the resist pattern forming step, when the formation and exposure of the resist layer are repeated a plurality of times, the mask pattern position of each layer in the exposure is the same position. The method further comprises a mask alignment step for aligning the position of the mask pattern.

  A preferred embodiment of the above-described mold manufacturing method is characterized in that, in the resist pattern forming step, resists having different sensitivities are used for each resist layer when the formation and exposure of the resist layer are repeated a plurality of times. Is.

  A preferred embodiment of the above-described mold manufacturing method is characterized in that the light source used for exposure in the step of forming the resist pattern is an ultraviolet lamp or laser light.

  In a preferred embodiment of the above-described mold manufacturing method, the depth or height of the uneven portion of the resin molded product formed by the step of forming the resin molded product is substantially 5 μm to 500 μm. The method for producing a mold according to any one of claims 1 to 6, wherein

  The method for producing a resin molded product according to the present invention includes a step of producing a mold by the above-described method for producing a mold, and a molded product forming step of forming a resin molded product by the die. Thereby, the resin molded product which has a desired shape can be manufactured with sufficient productivity.

  The resin molded product according to the present invention is a resin molded product obtained by the above-described method for producing a resin molded product.

  A preferred embodiment of the above-described resin molded product has at least one pattern among a flow path pattern, a mixing portion pattern, and a container pattern.

  A preferred embodiment of the above-mentioned resin molded article has at least one pattern among electrodes, heaters, and temperature sensors.

  The chip | tip concerning this invention is a chip | tip for clinical tests obtained by the manufacturing method of the above-mentioned resin molded product.

  The above-described clinical test chip is suitable for any one of a blood test chip, a urine test chip, and a biochemical test chip.

  The chip | tip concerning this invention is a chip | tip for combinatorial chemistry obtained by the manufacturing method of the above-mentioned resin molded product.

  The above-mentioned combinatorial chemistry chip is suitable for a drug development chip or a chemical synthesis / analysis chip.

  The chip according to the present invention is a gene-related chip obtained by the above-described method for producing a resin molded product.

  The aforementioned gene-related chip is suitable for a gene amplification chip.

  The method for producing a resin molded product of the present invention is excellent in mold releasability during molding, and is excellent in terms of mold life and defect rate. Therefore, according to the present invention, a resin molded product having a desired shape can be produced with high productivity.

  Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 shows a manufacturing process of a resin molded product in the present embodiment. The manufacturing apparatus used to realize the present embodiment is widely known, and the description thereof is omitted here. With reference to FIG. 1, the manufacturing method in this Embodiment is demonstrated.

  The resin molded product of this embodiment mainly includes (a) formation of a resist layer on a substrate, (b) exposure of the resist layer using a mask, (c) heat treatment of the resist layer, (d) development of the resist layer, e) The resist pattern substrate is left in an organic solvent atmosphere to form a desired resist pattern. Furthermore, according to the formed resist pattern, a metal structure is deposited on the substrate by plating. A resin molded product is manufactured by forming a resin molded product using the metal structure as a mold.

  (A) The formation of the resist layer on the substrate will be described. The flatness of the resin molded product obtained in the molded product forming step is determined in the process of forming a resist layer on the substrate. That is, the flatness at the time when the resist layer is formed on the substrate is reflected in the flatness of the metal structure, and hence the resin molded product.

  The method for forming the resist layer on the substrate is not limited at all, and generally includes a spin coating method, a dipping method, a roll method, and a dry film resist bonding. Among these, the spin coating method is a method of applying a resist on a rotating glass substrate, and has an advantage of applying the resist to a glass substrate having a diameter of more than 300 mm with high flatness. Accordingly, the spin coating method is preferably used from the viewpoint of realizing high flatness. By this spin coating method, the first resist layer 3 is formed on the entire surface of the substrate 1 as shown in FIG.

  There are two types of resists used: positive resists and negative resists. In any case, since the depth of focus of the resist varies depending on the resist sensitivity and exposure conditions, for example, when a UV exposure apparatus is used, it is desirable to select the type of exposure time and UV output value according to the resist thickness and sensitivity. . When the resist to be used is a wet resist, for example, in order to obtain a predetermined resist thickness by a spin coating method, there are a method of changing the spin coating rotational speed and a method of adjusting the viscosity. A method of changing the spin coat rotational speed is to obtain a desired resist thickness by setting the spin coater rotational speed. The method of adjusting the viscosity is to adjust the viscosity according to the flatness required in actual use because there is a concern that the flatness may decrease when the resist thickness is large or the coating area is increased. .

  For example, in the case of the spin coat method, the thickness of the resist layer applied at one time is preferably in the range of 10 to 50 μm, more preferably in the range of 20 to 50 μm in consideration of maintaining high flatness. desirable. In order to obtain a desired resist layer thickness while maintaining high flatness, a plurality of resist layers can be formed. When multiple resist layers are formed to obtain the desired resist layer thickness by spin coating, it is easy to obtain a resist pattern having an inclination angle by making a difference in the solubility of each layer in an organic solvent. It may become. When a positive resist is used for the resist layer, it is possible to make a difference in solubility in an organic solvent by adjusting the temperature and time in baking (solvent drying). For example, by making the baking time of the upper layer shorter than that of the lower layer, the inclination angle of the upper layer can be made wider.

  When a positive resist is used for the resist layer, if the baking time (solvent drying) is excessively advanced, the resist will be hardened and it will be difficult to form a pattern in subsequent development. It is preferable to select appropriately such as shortening the time. When a negative resist, especially a chemically amplified negative resist, is used for the resist layer, the crosslink density is changed by adjusting the temperature and time in the heat treatment (crosslinking) after exposure (ring opening), so that It becomes possible to make a difference in solubility. For example, by making the heat treatment time for the upper layer shorter than that for the lower layer, the crosslink density of the upper layer can be made lower than that of the lower layer, and the inclination angle of the upper layer can be made wider.

  (B) The exposure of the resist layer using a mask will be described. The mask A3 used in the step shown in FIG. 1 (a) is not limited at all, and examples thereof include an emulsion mask and a chrome mask. In the resist pattern forming step, the width, depth, container interval, and container width (or diameter), depth dimension, and accuracy of the flow path depend on the mask used. The dimensions and accuracy are also reflected in the resin molded product. Therefore, in order to make each dimension and accuracy of the resin molded product predetermined, it is necessary to define the size and accuracy of the mask. The method for increasing the accuracy of the mask is not limited at all. For example, the laser light source used for mask pattern formation can be changed to one having a shorter wavelength, but the equipment cost is high, and the mask manufacturing cost is high. Since the cost is high, it is desirable to appropriately define the resin molded product according to the accuracy required for practical use. Thereby, as shown in FIG. 1A, the first resist layer 2 is selectively exposed by the mask A3.

  The material of the mask is preferably quartz glass from the viewpoint of temperature expansion coefficient and UV transmission / absorption performance, but is relatively expensive. Therefore, it is desirable to appropriately define the resin molded product according to the accuracy required for practical use. In order to obtain a resist pattern as designed, it is necessary that the pattern design (transmission / shading part) of the mask used for exposure is reliable, and simulation using CAE analysis software is one of the solutions.

  The light source used for the exposure is preferably an ultraviolet lamp or a laser light source whose equipment cost is low. Although synchrotron radiation has a deep exposure depth, the cost of such equipment is high, and the price of the resin molded product is substantially high, which is not industrially practical.

  Since exposure conditions such as exposure time and exposure intensity vary depending on the material and thickness of the resist layer, it is preferable to adjust appropriately according to the pattern to be obtained. In particular, adjustment of the exposure conditions is important because it affects the dimensions and accuracy of the pattern such as the width, depth, container interval, container width (or diameter), and depth of the flow path. Since the depth of focus varies depending on the type of resist, for example, when a UV exposure apparatus is used, it is desirable to select the exposure time and the UV output value according to the thickness and sensitivity of the resist.

  (C) The heat treatment of the resist layer will be described. As heat treatment after exposure, heat treatment called annealing is known in order to correct the shape of the resist pattern. Here, it is performed only when a chemically amplified negative resist is used for the purpose of chemical crosslinking. The chemically amplified negative resist is mainly composed of a two-component system or a three-component system, and, for example, an epoxy group at the end of a chemical structure is opened by light at the time of exposure, and is subjected to a crosslinking reaction by heat treatment. . When the heat treatment time is, for example, 100 μm, the crosslinking reaction proceeds in several minutes under the condition of a set temperature of 100 ° C.

  If the amount of heat treatment (temperature, time) of the resist layer increases too much, chemical crosslinking proceeds and the resist pattern surface is deformed or cracked. If the resist thickness to be set is not 100 microns or more, the heat treatment time It is preferable to select as appropriate, such as shortening. Further, if the chemical crosslinking proceeds too much, it becomes difficult to obtain an inclined pattern when the resist pattern substrate, which is the subsequent step, is left in an organic solvent atmosphere. preferable.

  (D) The development of the resist layer will be described. For the development in the step shown in FIG. 1B, it is preferable to use a predetermined developer corresponding to the resist used. Development conditions such as development time, development temperature, and developer concentration are preferably adjusted as appropriate according to the resist thickness and pattern shape. For example, if the development time is too long in order to obtain the required depth, the container interval and the container width (or diameter) become larger than predetermined dimensions, so it is preferable to set conditions appropriately. As shown in FIG. 1B, a resist pattern 4 is formed by developing the resist layer.

  When the thickness of the entire resist layer increases, there is a concern that the width (or diameter) of the surface becomes wider than the width (or diameter) of the bottom of the resist in the development process. When a plurality of resist layers are formed, it may be preferable to form resists having different sensitivities in stages in forming each resist layer. In this case, for example, the sensitivity of the resist near the surface is made higher than that near the bottom. More specifically, BMR C-1000PM manufactured by Tokyo Ohka Kogyo Co., Ltd. can be used as a resist with high sensitivity, and PMER-N-CA3000PM manufactured by Tokyo Ohka Kogyo Co., Ltd. can be used as a resist with low sensitivity. In addition, the sensitivity may be adjusted by changing the drying time of the resist. For example, when BMR C-1000PM manufactured by Tokyo Ohka Kogyo Co., Ltd. is used, when drying the resist after spin coating, the drying time for the first layer is 40 minutes at 110 ° C., and the drying time for the second layer is 20 minutes at 110 ° C. By setting the minute, the sensitivity of the first layer can be increased.

  (E) The leaving of the resist pattern substrate in an organic solvent atmosphere will be described. The purpose of leaving the resist pattern substrate in a solvent atmosphere is to form a vertical resist pattern into an inclined pattern. Usually, when contact exposure is performed using UV parallel light, the resist pattern is a vertical pattern as shown in FIG. In particular, when a chemically crosslinked negative resist is used, the vertical pattern is maintained due to alkali resistance even after development.

  For example, as shown in FIG. 1C, the inclined pattern is formed by preparing a pedestal 10 on a metal tray 6 and placing a resist pattern substrate on the pedestal. Then, the organic solvent 5 is immersed in the bottom of the tray, or an open container having the organic solvent 5 is set on the bottom of the tray, and the tray is sealed with a metallic lid.

  The inclination angle of the resist pattern is preferably set according to the molding conditions, the resin material, the addition amount of the release agent, etc., but is provided particularly when the molding depth of the resin molded product to be obtained is 10 μm or more. Preferably, the necessity is further increased when the thickness is 20 μm or more. The inclination angle of the resist pattern is preferably 50 ° to 90 °, more preferably 60 ° to 87 °, from the shape of the resin molded product. Although the organic solvent to be used is not particularly specified, the same material as the solvent used as a solvent for the resist is preferable, and it is generally preferable to use thinner. If the vapor concentration of the organic solvent is too low, an inclined pattern will not be formed. Conversely, if it is too high, not only the pattern inclination but also the flatness of the resist surface may be impaired. Is preferably selected according to the tray volume and the area of the resist pattern substrate.

  Similarly, as a method of forming an inclined pattern, an inclined pattern may be formed by applying an organic solvent or a resist of the same brand on the resist pattern and allowing it to stand for a certain period of time. This method is efficient because the slope can be obtained in a shorter time than leaving in a steam atmosphere. As an example, when an inclined pattern is obtained by leaving in a solvent atmosphere for 1 hour, the inclined pattern can be obtained in about 1/3 of 20 minutes in solvent coating.

  Examples of a method for obtaining a molded product having a uniform depth and accuracy such as a flow path, a mixing unit, and a container include a method of changing the resist type (negative type and positive type) used in resist coating, a metal structure And a method of polishing the surface of the substrate. When a plurality of resist layers are formed to obtain a desired molding depth, the resist layers are exposed and developed at the same time, or after forming and exposing one resist layer, a resist layer is further formed. The two resist layers can be developed at the same time.

  The metal structure forming step will be described in more detail. The metal structure forming step is a process of obtaining a metal structure by depositing metal along the resist pattern obtained in the resist pattern forming step and forming an uneven surface of the metal structure along the resist pattern. .

  As shown in FIG. 1D, in this step, the conductive film 7 is formed in advance along the resist pattern. Although the formation method of the conductive film 7 is not specifically limited, Preferably, vapor deposition, sputtering, etc. can be used. Examples of the conductive material used for the conductive film 7 include gold, silver, platinum, and copper. After the conductive film 7 is formed, a metal structure 8 is formed by depositing metal along the pattern by plating. As a result, the configuration shown in FIG. The plating method for depositing the metal is not particularly limited, and examples thereof include electrolytic plating and electroless plating. The metal to be used is not particularly limited, and nickel, nickel having a modified crystal structure, nickel-cobalt alloy, copper, and gold can be used, and nickel is preferably used from the viewpoint of economy and durability.

  The thickness of the metal structure 8 is generally 0.3 mm to 0.5 mm when an optical disk is taken as an example. In consideration of the deformation of the metal structure 8 at the time of injection molding, a metal structure 8 having a further increased thickness, for example, a metal structure 8 having a thickness of 5 to 10 mm, may be produced. In this case, if the stress of the metal material is high, there is a concern that warping may occur in the metal structure 8, and therefore it is preferable to use nickel. The metal structure 8 may be polished according to the surface state. However, since there is a concern that dirt adheres to the modeled object, it is preferable to perform ultrasonic cleaning after polishing. Further, the metal structure may be surface-treated with a release agent or the like in order to improve the surface state. In addition, the inclination angle in the depth direction of the metal structure 8 is desirably 50 ° to 90 °, more desirably 60 ° to 87 °, from the shape of the resin molded product.

  An example of the step of forming the metal structure 8 without forming the conductive film 7 is an electroless plating method. In particular, when the resist pattern is fine or has a high aspect ratio structure, it is difficult for the conductive film to be deposited on the pattern inclined portion, and as a result, current conduction is poor in electrolytic plating, and the conductive film is likely to be peeled off. The electroless plating method can be expected to increase the production efficiency of the metal structure without such a concern. After depositing a metal by electroless plating, a metal structure having a desired thickness may be completed by electrolytic plating. As shown in FIG. 1F, the metal structure deposited by plating is separated from the resist pattern.

  The molded product forming step will be described in more detail. The molded product forming step is a process of forming a resin molded product 9 using the metal structure 8 as a mold, as shown in FIG. The method for forming the resin molded product 9 is not particularly limited, and examples thereof include injection molding, press molding, monomer cast molding, solvent cast molding, roll transfer method by extrusion molding, and the like, from the viewpoint of productivity and mold transferability. Injection molding is preferably used. When the resin molded product 9 is formed by injection molding using a metal structure having a predetermined dimension as a mold, the shape of the metal structure 8 can be reproduced as a resin molded product with a high transfer rate. As a method for confirming the transfer rate, an optical microscope, a scanning electron microscope (SEM), a transmission electron microscope (TEM), or the like can be used.

  When forming the resin molded product 9 by using the metal structure 8 as a mold, for example, by injection molding, 10,000 to 50,000, or 200,000 resin molded products can be obtained with one metal structure 9. It is possible to greatly eliminate the cost burden for manufacturing the metal structure. Further, the time required for one cycle of injection molding is as short as 5 to 30 seconds, which is extremely efficient in terms of productivity. If a molding die capable of simultaneously forming a plurality of resin molded products in one cycle of injection molding is used, productivity can be further improved. In the molding method, the metal structure may be used as a metal mold, or the metal structure may be set in a metal mold prepared in advance.

  The resin material used for forming the resin molded product is not particularly limited. For example, acrylic resin, polylactic acid, polyglycolic acid, styrene resin, acrylic / styrene copolymer resin (MS resin), polycarbonate resin Resins, polyester resins such as polyethylene terephthalate, polyvinyl alcohol resins, ethylene / vinyl alcohol copolymer resins, thermoplastic elastomers such as styrene elastomers, silicone resins such as vinyl chloride resin polydimethylsiloxane, etc. .

  These resins are one kind of lubricants, light stabilizers, heat stabilizers, antifogging agents, pigments, flame retardants, antistatic agents, mold release agents, antiblocking agents, ultraviolet absorbers, antioxidants and the like as necessary. Or 2 or more types can be contained.

  The resin molded product obtained by the molding method will be described in more detail. FIG. 2 shows an example of a resin molded product that can be manufactured using the manufacturing method of the present embodiment. FIG. 2A is a top view of the resin molded product, and FIG. 2B is a cross-sectional view of the resin molded product. The resin molded product of FIG. 2 is provided with a plurality of recesses in the substrate, and these recesses serve as a flow path 11 for blood or the like. This flow path 11 is formed in the cross direction, and becomes a mixing portion 12 where a plurality of flow paths 11 intersect. Furthermore, the resin molded product has a heater, a temperature sensor, and an electrode (not shown). The heater and the temperature sensor are arranged on the flow path. Metal parts such as electrodes or heaters can be formed by sputtering or vapor deposition. A temperature sensor is provided for temperature control required for heating or reaction treatment. About each dimension and precision of such a resin molded product, it is desirable to adjust suitably according to said each process according to the numerical value required in actual use. It is preferable that each dimension of the flow path, the mixing unit, the container, and the like in the resin molded product is within the following range.

  The minimum value of the width of the flow path 11 of the resin molded product is derived from the mask processing accuracy, and it can be further miniaturized industrially by using a laser beam having a short wavelength such as X-ray or laser. Presumed to be. However, the object of the present invention is to provide a precise and inexpensive resin molded product 7 widely in the medical field, the industrial field, and the biotechnology field, and in particular, in a chip used for clinical examination, combinatorial chemistry, or gene related. Since it is suitable, it is preferable that a width | variety is 5 micrometers or more from a viewpoint easy to reproduce industrially. In addition, in the use of unstandardized multi-product small-lot resin molded products 7, the width is preferably 5 μm or more from the viewpoint of providing a precise and inexpensive container. The maximum value of the width of the flow path is not particularly limited, but is preferably 300 μm or less in order to shorten the diagnosis time by miniaturization, enable a plurality of processes, and impart portability to the apparatus.

  The minimum value of the depth of the flow path of the resin molded product is preferably 5 μm or more in order to have a function as a flow path. The maximum value of the depth of the channel is not particularly limited, but in applications such as chemical analysis and DNA diagnosis, the diagnosis time can be shortened by reducing the width of the channel, and multiple processes can be performed to make the device portable. In order not to impair such advantages, the thickness is preferably 300 μm or less, and more preferably 200 μm or less.

  The minimum value of the length of the flow path of the resin molded product is preferably 5 mm or more in order to have functions of sample introduction and separation (analysis) in applications such as chemical analysis and DNA diagnosis. The maximum value of the length of the flow path is not particularly limited, but in applications such as chemical analysis and DNA diagnosis, shortening the length of the flow path shortens the diagnosis time and enables multiple processing, thereby making the device portable. In order not to impair the advantage of imparting, it is preferably 300 mm or less. The minimum value of the container interval of the resin molded product is derived from the mask processing accuracy, and it is speculated that it can be miniaturized industrially by using laser light with a short wavelength such as X-ray and laser. Is done. However, the object of the present invention is to provide precise and inexpensive containers widely in the medical field, industrial field, biotechnology field, etc., and is particularly suitable for chips used for clinical tests, combinatorial chemistry, or genetics. Since it is a thing, it is preferable that a container space | interval is 5 micrometers or more from a viewpoint easy to reproduce industrially.

  Moreover, since the minimum value of a container space | interval may be determined, for example by the positioning accuracy of a blood test apparatus, it is preferable to select suitably according to the specification of an apparatus. In addition, even in non-standardized multi-product small lot applications, the thickness is preferably 5 μm or more from the viewpoint of providing a precise and inexpensive container. The maximum value of the container interval is not particularly limited, but is preferably 10,000 μm or less in order to allow a plurality of processes by reducing the size of the container and to impart portability to the apparatus. For the above reasons, the container width (or diameter) of the resin molded product is preferably a minimum value of 5 μm or more and a maximum value of 10,000 μm or less. The minimum value of the container depth of the resin molded product is not particularly limited, but is preferably 10 μm or more in order to have a function as a container. The maximum value of the container depth is, for example, that it is possible to obtain a deeper shape by applying a resist multiple times, using an exposure light source such as an X-ray beam to obtain a sufficient depth of focus, etc. Guessed. However, the object of the present invention is to provide precise and inexpensive containers widely in the medical field, industrial field, and biotechnology field, and the depth is preferably 1000 μm or less from the viewpoint of being easily reproduced industrially.

  The minimum value of the flatness of the resin molded product is preferably 1 μm or more from the viewpoint of easy industrial reproduction. For example, the maximum value of the flatness of the resin molded product is preferably 200 μm or less from the viewpoint of not hindering use of the molded product bonded to another substrate. The dimensional accuracy of the width and depth of the flow path of the resin molded product is preferably within a range of ± 0.5 to 10% from the viewpoint of being easily reproduced industrially. The container interval, container width (or diameter), and depth dimensional accuracy of the resin molded product are preferably within a range of ± 0.5 to 10% from the viewpoint of easy industrial reproduction.

  The dimensional accuracy with respect to the thickness of the resin molded product is preferably within a range of ± 0.5 to 10% from the viewpoint of easy industrial reproduction. Although the thickness of the resin molded product is not particularly defined, it is preferably in the range of 0.2 to 10 mm in consideration of breakage at the time of take-out in injection molding, breakage at the time of handling, deformation, and distortion. The dimension of the resin molded product is not particularly limited, but when forming a resist pattern by a lithography method, for example, when forming a resist layer by a spin coat method, it can be collected from a range of 400 mm in diameter depending on the application. It is preferable to select appropriately.

  The use of the resin molded product obtained by the present invention is not limited to a specific use. For example, for DNA diagnosis, medical use such as a specimen container, antibody container, and reagent container, industrial use such as a light-related front plate, cell treatment, etc. It is suitable for biotechnological applications and automated chemical analysis of reaction vessels. In the medical field, especially for applications that require biocompatibility such as antithrombogenicity (antiplatelet adhesion) and elimination of harmfulness in cytotoxicity tests, materials with known antithrombogenic effects are used. It is preferable to perform a treatment. As a method for improving biocompatibility by surface treatment, for example, after forming a molded product by injection molding, after depositing a SiO2 film by sputtering, the biocompatibility is imparted by growing the SiO2 film by thermal oxidation. There are methods.

  After forming a resin molded product, when it is used for biochemical analysis, DNA diagnosis, etc. in the medical field, especially in the clinical laboratory field, processing such as heating, reaction, and signal detection is required on the resin molded product. There is a case. As a method of performing heating or reaction treatment on a resin molded product, for example, a method of forming an electrode pattern by sputtering and applying a voltage from an apparatus or a heater can be considered. In addition, when temperature control is required when performing heating or reaction processing, for example, a temperature sensor may be arranged. When performing signal detection, for example, it is conceivable to arrange a photodiode.

  In the medical field, especially in the clinical laboratory field, when used in the biochemical analysis, DNA diagnosis field, etc., a molded product expected to shorten the time required for diagnosis by miniaturizing the flow path can be obtained by the present invention. This is achieved by using a molded resin product. The resin molded product obtained in this form is precise and inexpensive, and in biochemical analysis, DNA diagnostic fields, etc., especially in operating rooms, bedsides, homes, town clinics, etc. It is particularly effective.

  The resin molded product obtained according to this embodiment is precise and inexpensive, and the molded product can be used repeatedly. However, when defects such as contamination and deformation of the substrate surface occur, the cost is minimized. Therefore, even if it is discarded and a new one is used, it is particularly effective in applications where work efficiency such as elimination of labor and shortening of processing time is important. The resin molded product obtained in this form is precise and inexpensive, and can be widely applied in the field of automatic chemical analysis such as combinatorial chemistry in addition to the medical field, industrial field, and biotechnology field. Particularly, the miniaturization of the sample amount can greatly reduce the amount of waste liquid at the time of disposal, and is particularly effective from the viewpoint of environmental protection.

  In addition, when a metal structure and a resin molded product are manufactured by the manufacturing method according to the present invention, the metal structure and the resin molded product are left in an organic solvent atmosphere or an organic solvent is applied to a resist pattern. In some cases, the resist pattern edge portion may have a rounded slope, but there is no practical problem.

The resin molded product obtained according to this embodiment can exhibit high accuracy and the like as compared with conventional molded products. In addition, since the resin molded product is precise and can be formed at a low cost, it is particularly effective when applied to industrially used applications that can exhibit the advantage of minimizing the manufacturing cost. It is.
Example 1

  A method for forming a resin molded product according to the present invention will be described more specifically below with reference to FIG. First, a first resist coating based on an organic material (“PMER N-CA3000PM” manufactured by Tokyo Ohka Kogyo Co., Ltd.) was performed on the substrate 1. Then, after forming the first resist layer 2, the substrate and the desired container The alignment was performed with the mask A3 processed into the mask pattern, and then the first resist layer was exposed to UV light using a UV exposure apparatus (Canon "PLA-501F" wavelength 365 nm, exposure amount 300 mJ / cm2). Then, the first resist layer 2 is heat-treated using a hot plate (100 ° C. × 4 minutes).

  A pattern may be formed by further applying a resist layer on the first resist layer 2. In this case, a second resist layer is formed by applying a second resist coating based on an organic material (“PMER N-CA3000PM” manufactured by Tokyo Ohka Kogyo Co., Ltd.) on the substrate 1. After forming the second resist layer Then, alignment between the substrate and the mask B processed into a mask pattern of a desired container was performed.

  Next, the second resist layer was exposed to UV light using a UV exposure apparatus (Canon “PLA-501F” wavelength 365 nm, exposure amount 100 mJ / cm 2), and then using a hot plate (100 ° C. × 8 minutes). The second resist layer was heat treated. The substrate having the resist layer was developed to form a resist pattern on the substrate (developer: “PMER developer P-7G” manufactured by Tokyo Ohka Kogyo Co., Ltd.). Note that a step of applying a resist layer, aligning a mask, and forming a resist pattern by exposure and development may be further repeated. Thereby, a metal structure having a desired depth can be formed.

  Next, as shown in FIG. 1C, the substrate 1 is placed on a pedestal 10 prepared in a metal tray 6. Then, the organic solvent 5 is immersed in the bottom of the tray, or an open container having the organic solvent 5 is set on the bottom of the tray, and the tray is sealed with a metallic lid. Use thinner as the organic solvent and leave the container in an organic solvent atmosphere (please let us know if you have any specific examples of organic solvents).

  Then, as shown in FIG. 1D, vapor deposition or sputtering was performed on the substrate surface having the resist pattern to deposit a conductive film 7 made of silver on the surface of the resist pattern. In this step, platinum, gold, copper, etc. can be deposited in addition. Next, as shown in FIG. 1E, the substrate having the resist pattern was immersed in a plating solution and electroplated to obtain a metal structure 8 made of Ni according to the resist pattern. In this step, copper, gold, etc. can be deposited in addition. The metal structure 8 is separated from the substrate 1 as shown in FIG. As shown in FIG. 1 (g), the obtained metal structure 8 was used as a mold, and a plastic material was filled into the Ni structure by injection molding to obtain a plastic molded body 9.

In accordance with the manufacturing method described above, the resist coating is repeated twice to form a first resist layer, and exposure and heat treatment are performed. Further, the resist coating is repeated once to form a second resist layer, and exposure and heat treatment are performed. A resin molded product having a flow path depth of 50 μm was produced on a substrate having a width of 70 mm × length of 50 mm and a thickness of 1.5 mm as shown in FIG.
Example 2

According to the manufacturing method described above, the resist coating is repeated three times to form the first resist layer, and exposure and heat treatment are performed. Further, the resist coating is repeated once to form the second resist layer, and the exposure and heat treatment are performed. A resin molded product having a flow path depth of 100 μm was produced on a substrate having a width of 70 mm × length of 50 mm and a thickness of 1.5 mm as shown in FIG.
Example 3

  According to the manufacturing method described above, the resist coating is repeated three times to form the first resist layer, and exposure and heat treatment are performed. Further, the resist coating is repeated once to form the second resist layer, and the exposure and heat treatment are performed. A resin molded product having a flow path depth of 300 μm was produced on a substrate having a width of 70 mm × length of 50 mm and a thickness of 1.5 mm as shown in FIG.

In the Example of this invention, it is a schematic diagram which shows the process of forming a resin molded product. It is a figure which shows the structure of the resin molded product concerning Example 1. FIG. It is a figure which shows the structure of the resin molded product concerning Example 2. FIG. It is a figure which shows the structure of the resin molded product concerning Example 3. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 board | substrate, 2 1st resist layer, 3 mask A, 4 resist pattern, 5 organic solvent 6 metal tray, 7 electroconductive film, 8 metal structure, 9 resin molded product, 10 base 11 flow path, 12 mixing part

Claims (7)

Forming a resist layer on the substrate;
A resist pattern forming step of exposing and developing the resist layer using a mask;
Leaving the substrate in an organic solvent atmosphere to give an inclination angle to the wall surface of the resist pattern; and depositing a metal structure according to the resist pattern formed on the substrate;
In the resist pattern forming step, when a resist layer is repeatedly formed and exposed multiple times, a mold manufacturing method using resists having different sensitivities for each resist layer.   2. The method of manufacturing a mold according to claim 1, wherein the substrate is left in an organic solvent atmosphere and an organic solvent is contained on the resist pattern of the substrate in place of the step of providing an inclination angle to the wall surface of the resist pattern. A method for manufacturing a mold, comprising applying a solution to give an inclination angle to a wall surface of the resist pattern.   2. The resist pattern forming step is characterized in that the resist layer is repeatedly formed and exposed a plurality of times until the resist layer is formed into a structure having a desired height or depth. Or the manufacturing method of the metal mold | die of 2.   In the resist pattern forming step, when the resist layer formation and exposure are repeated a plurality of times, a mask alignment step for aligning the mask pattern is further performed so that the mask pattern position of each layer in the exposure is the same position. The mold manufacturing method according to claim 3, further comprising:   5. The mold manufacturing method according to claim 1, wherein a light source used for exposure in the step of forming the resist pattern is an ultraviolet lamp or a laser beam.   6. The gold according to claim 1, wherein the depth or height of the concavo-convex portion of the resin molded product formed by the step of forming the resin molded product is substantially 5 μm to 500 μm. Mold manufacturing method. A step of producing a mold by the method of producing a mold according to claim 1;
A method for producing a resin molded product, comprising: a molded product forming step of forming a resin molded product with the mold.

Images