JP2004189798A - Resin substrate for microreactor - Google Patents

Abstract

An object of the present invention is to provide a microreactor resin substrate in which grooves and holes with extremely high precision are formed and a sample or fluid used for analysis is not clogged or leaked.
A microreactor resin substrate comprising a resin-filler composite material, wherein the filler material is an inorganic or polymer material having an aspect ratio of 10 or more, or a composite material having an aspect ratio of 2.5 × 10 ⁴ or more. A resin substrate for a microreactor, which is a polymer material having a refractive index and contains 0.01 to 200 parts by weight of the filler based on 100 parts by weight of the resin.
[Selection diagram] None

Description

【００８２】
表１、２より、実施例１〜２３で作製した樹脂基板はいずれも分析に問題の無い転写性を示したが、比較例１〜４、６〜９で作製した樹脂基板は分析に明らかな問題があった。また、比較例５で作製した樹脂基板は、転写性は優れているものの、透明性は得られていない。この場合、マイクロリアクター基板としての機能は有するものの、検出部として光学系を用いることはできない。
【００８３】
【発明の効果】
本発明によれば、極めて高い精度の溝や孔が形成されたマイクロリアクター用樹脂基板を提供できる。
【図面の簡単な説明】
【図１】転写金型を溶融樹脂に押し当てた場合の充填材の状態を示す模式図である。
【図２】層状珪酸塩の結晶薄片の状態を説明するための模式図である。
【図３】層状珪酸塩の結晶薄片の平均層間距離が６ｎｍ以上の場合のＸ線回折プロファイルである。
【図４】層状珪酸塩の結晶薄片の平均層間距離が６ｎｍ未満の場合のＸ線回折プロファイルである。
【図５】本発明のマイクロリアクター用樹脂基板を平面で切断した切断面を示す模式図である。
【図６】平均粒子径と界面長との関係を示す図である。
【図７】実施例で用いたプレス金型を示す模式図である。
【図８】実施例で用いたプレス金型の入れ子型を示す模式図である。
【図９】実施例で作製した樹脂基板の凸形状を示す断面図である。
【図１０】実施例の転写性評価において樹脂基板の切断方法を示す模式図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a microreactor resin substrate in which grooves and holes with extremely high precision are formed.
[0002]
[Prior art]
2. Description of the Related Art In recent years, researches on separation / concentration, chemical reaction, and analysis of a specimen in a minute area have been actively performed. If sample separation / concentration or chemical reaction is performed in a micro area, the efficiency of heat exchange with the reactor can be greatly improved, and energy costs can be greatly reduced. Further, if various types of reaction steps can be integrated in a microscopic region, combinatorial synthesis can be easily realized. Further, by miniaturizing the analysis system, there are many advantages such as the analysis time can be greatly reduced, and the amount of sample and the amount of waste can be significantly reduced.
[0003]
In the context of recent social changes, low-cost and short-term medical bedside diagnostics, monitoring of environmental pollutants in air, water and soil, food safety inspections, etc. The need for necessary diagnostic / analytical techniques is increasing. For example, in recent years when the number of elderly people is remarkably increasing, the health index values diagnosed by the patient's family near the patient are managed at home, and if the collected data can be transmitted to the hospital regularly, the home medical environment will be improved. It is possible to further increase. Further, if environmental pollutants such as heavy metals, dioxins, and environmental hormones can be easily measured without using expensive and large-scale equipment, it is possible to provide a finer safety environment. In recent years, as the danger to the ecosystem of enormous pollution of water, air and soil has been revealed, it is extremely important to know each and every pollution factor easily and cheaply. The concept of such simple measurement is called “Point of Care (POC)” and is a very important concept in the future society.
[0004]
In order to easily perform such measurement, it is necessary to be able to perform measurement using a small amount of sample, but high sensitivity is required for analysis and detection of a small amount of sample. Conventionally, methods that can be analyzed with a trace amount and high sensitivity include GC-MS and LC-MS, which are separated by capillary gas chromatography (CGC), capillary liquid chromatography (CLC), and detected by a mass spectrometer (MS). Etc. have been widely used. However, there is a problem that expensive and large-scale GC-MS and LC-MS cannot be easily carried. Therefore, there is an extremely high need for the development of an analysis / detection method that can be easily analyzed at the site where measurement is required and that supports “on-site analysis”.
[0005]
On the other hand, grooves or holes are cut in the surface of a chip having a size of several cm to about 10 cm square or less, and a small amount of sample is analyzed in a minute region by utilizing separation, concentration, or reaction in the grooves or holes. An approach has been proposed. This technique is collectively referred to as μTAS (micro or miniaturized total analysis system) or microreactor. The concept of such a microreactor was already introduced in Non-Patent Document 1 in 1990.
[0006]
For a substrate of a chip used in a microreactor, inorganic materials such as glass, quartz, and silicon have been mainly used in view of workability and accuracy. For example, if photolithography technology widely used in semiconductor fine processing technology is used, micron-order grooves can be freely formed on a glass substrate or a silicon substrate. However, when analyzing an enormous number of contaminated sites, it is important that measurement chips be mass-produced and discarded easily and inexpensively, and glass and silicon are expensive. Also, in the medical field, when a glass substrate is used, it is obliged to pay an appropriate processing cost at the time of disposal.
[0007]
Therefore, a microreactor substrate made of resin has been studied. The microreactor resin substrate is superior to glass and the like in terms of cost, disposal as waste, and the like, and is also characterized by being light and not cracking. Furthermore, by performing injection molding or hot press molding using a transfer mold, it is possible to form grooves and holes on the surface with extremely high productivity.
However, extremely high precision is required for the grooves and holes on the surface of the microreactor resin substrate so that samples and fluids used for analysis do not clog or leak.
[0008]
The transfer accuracy of a groove or a hole formed by injection molding or hot press molding to a mold is generally such that the smaller the shape to be transferred, the more likely it is that a problem such as sink or dripping occurs in the formed groove or hole. . This is due to the shrinkage and stress relaxation of the resin, and controlling the shrinkage and stress relaxation characteristics of the resin is a very important issue when manufacturing a resin substrate for a microreactor.
[0009]
[Non-patent document 1]
A. Manz, N .; Graber, H .; M. Widmer: Sens. Actuators, B, 1,244 (1990)
[0010]
[Problems to be solved by the invention]
In view of the above situation, an object of the present invention is to provide a microreactor resin substrate in which grooves and holes with extremely high precision are formed.
[0011]
[Means for Solving the Problems]
The present invention 1 is a resin substrate for a microreactor made of a resin-filler composite material, wherein the filler is an inorganic material or a polymer material having an aspect ratio of 10 or more, or 2.5 × 10 ⁴ A microreactor resin substrate which is a polymer material having the above-mentioned birefringence and contains 0.01 to 200 parts by weight of the filler based on 100 parts by weight of the resin.
[0012]
The present invention 2 is a resin substrate for a microreactor made of a resin-filler composite material, which is 100 μm when observing the interface between the resin and the filler on a cut surface cut in a plane. ² This is a microreactor resin substrate having an interface length per unit of 2 mm or more.
[0013]
In this specification, the term “resin substrate for microreactor” mainly refers to 1) a fine groove that allows a flowable minute sample to flow on the resin substrate surface, and the minute sample reacts on the resin substrate. 2) A resin substrate having a structure for detecting the target substance in the sample, 2) a resin substrate having micropores, and having a structure for detecting the target substance in the sample by reacting a minute amount of the sample in the hole. It has fine grooves on the substrate surface to allow a flowable trace sample to flow, and has a structure in which the trace sample reacts on the resin substrate to synthesize and manufacture the target substance. 4) Flow to the resin substrate surface It means a material having a fine groove for allowing a possible trace sample to flow, and having a structure for purifying or extracting a target substance by passing the trace sample through an adsorption / desorption step on a resin substrate.
Hereinafter, the present invention will be described in detail.
[0014]
The resin substrate for a microreactor of the first invention is made of a resin-filler composite material. The resin is not particularly limited, and any of a thermoplastic resin and a thermosetting resin can be used. Among them, a thermoplastic resin is preferable because the surface can be easily processed by heating. In the case of a thermosetting resin, it is not possible to plasticize by heating and perform surface processing.However, a precursor liquid mixed with a curing agent or the like is introduced into a transfer mold in advance, and cured in place. It is possible to shape the resin surface. In this case, since the precursor liquid is liquid, the shape of the transfer mold can be transferred more faithfully. Generally, a resin which is statically cured exhibits a low coefficient of linear expansion and a low molding shrinkage. The thermosetting resin is not particularly limited, but an epoxy resin is preferred from the viewpoint of cost and handleability.
[0015]
The resin is not particularly limited, but in view of the purpose of providing an inexpensive microreactor resin substrate, for example, polyolefin resin, polystyrene resin, polylactic acid resin, acrylic resin, polycarbonate resin, polyethylene terephthalate An inexpensive resin such as a system resin is suitable.
When a resin substrate for a microreactor is used for chemical analysis, since the target substance is often detected optically, such as absorption spectroscopy or fluorescence analysis, for example, the light transmittance of an acrylic resin, a polycarbonate resin, etc. A resin excellent in the above is preferable.
When a resin substrate for a microreactor is used for chemical analysis, an acidic substance or an alkaline substance is often used as a reactant for detecting a target substance. A resin having excellent alkalinity is preferred. Polyolefin-based resins are suitable for chemical analysis applications in that they hardly emit fluorescence.
[0016]
Further, when the microreactor resin substrate of the present invention 1 is used for embedding into a living body or mounting microorganisms, proteins, enzymes, antibodies, and the like, the resin preferably has no mutagenic properties.
In the present specification, the term mutagenic means that a predetermined mutagenicity test in a mutagenicity test using a microorganism and a chromosome aberration test using a cultured mammalian cell result It means that mutagenicity exceeding the standard is recognized and may cause health disorders.
[0017]
The filler is an inorganic material or a polymer material having an aspect ratio of 10 or more, or 2.5 × 10 ⁴ It is a polymer material having the above birefringence.
When an inorganic material or a polymer material having an aspect ratio of 10 or more is used as the filler, deformation of a minute region after injection molding or hot press molding can be suppressed extremely efficiently. When a filler having an aspect ratio of less than 10 is used, such an effect cannot be obtained.
[0018]
As shown in FIG. 1, the filler having a high aspect ratio easily orients around the grooves and holes when the transfer mold is pressed against the molten resin. When a substance having an aspect ratio is used as the filler, a higher interaction occurs between the long plane of the filler and the resin material. That is, since the resin dimensional deformation rate decreases in the orientation direction of the filler, the resin deformation around the grooves and holes can be more effectively reduced. In addition, since a slip occurs between the resin and the filler during the melt molding, the shear stress with respect to the shear rate decreases. This is also a secondary effect that leads to a reduction in the resin deformation rate.
[0019]
The inorganic material or the polymer material having an aspect ratio of 10 or more preferably has a long side of 500 nm or less and a short side of 50 nm or less. If the size of the filler is on the order of nanometers, the interface length between the resin and the filler is significantly increased, and the deformation of the minute region can be suppressed more efficiently. In addition, when a minute amount of liquid is sent to the fine flow path on the microreactor resin substrate of the present invention, the shape of the flow path wall is extremely important for forming a smooth flow. In view of the fact that the width of the flow path formed on the resin substrate for a microreactor of the present invention 1 is usually about 1 μm, it is possible to avoid the problem that the filler protrudes from the wall of the flow path if the filler has the above size. can do.
In addition, when the long side of the inorganic material or the polymer material having the aspect ratio of 10 or more is 300 nm or less, the obtained microreactor resin substrate has excellent light transmittance in the visible light wavelength region of 400 to 800 nm. It is more preferable because it becomes a material.
[0020]
On the other hand, 2.5 × 10 ⁴ When a polymer material having the above-described birefringence is used, deformation of a minute region after injection molding or hot press molding can be suppressed very efficiently. The polymer material having such an orientation structure can be generally formed by a technique such as stretch molding. The stretched polymer exhibits a low linear expansion coefficient and a low molding shrinkage in the orientation direction, as low as the inorganic material, due to the anisotropy developed by stretching. If such a material is filled, deformation of a minute region after injection molding or hot press molding can be suppressed extremely efficiently due to the interaction force between the oriented portion and the matrix material. Also, 2.5 × 10 ⁴ If the filler is a polymer material having the above birefringence, even if the aspect ratio is less than 10, slip occurs between the resin and the filler at the time of melt molding. Lower. This is also a secondary effect that leads to a reduction in the resin deformation rate.
[0021]
2.5 × 10 above ⁴ The polymer material having the above-mentioned birefringence is not particularly limited, and examples thereof include stretch-formed fibers. In addition, the above 2.5 × 10 ⁴ As a polymer material having the above birefringence, a liquid crystal polymer can also be used. Since the liquid crystal polymer exhibits a liquid crystal structure in a molten state, it can be easily molecularly oriented, and exhibits a low linear expansion coefficient and a molding shrinkage rate in the alignment direction due to the developed anisotropy.
[0022]
2.5 × 10 above ⁴ When the major axis of the polymer material having the above birefringence is 300 nm or less, the obtained microreactor resin substrate becomes a material having excellent light transmittance in the visible light wavelength region of 400 to 800 nm. preferable.
[0023]
When the filler is made of an inorganic material, an appropriate surface treatment may be applied. Generally, when the primary particle diameter is smaller than 500 nm, the particles are likely to aggregate due to an increase in particle surface energy. In most cases, resins have hydrophobic properties as compared with inorganic materials, and when different materials have different hydrophilic-hydrophobic degrees, fillers made of inorganic materials tend to aggregate. Therefore, by modifying the surface of the filler made of an inorganic material with an appropriate surface treatment agent, aggregation of the filler can be effectively suppressed.
The surface treatment agent is not particularly limited, but examples thereof include fatty acids such as stearic acid; coupling agents such as silane coupling agents and titanate coupling agents; and long-chain alkyl amino acids such as aminododecanoic acid. .
[0024]
Further, in order to prevent aggregation of the filler made of an inorganic material, an acid component may be blended with the above resin. The acid component is not particularly limited. For example, maleic acid, acrylic acid, carboxylic acid and the like are preferable. The method for blending the acid component is not particularly limited, and examples thereof include a method of blending a polymer material containing a large amount of an acid component, a method of grafting an acid component to a resin, and the like.
[0025]
The filler is not particularly limited, and examples thereof include fibrous substances such as glass fibers and carbon fibers; whisker-like substances such as wollastonite, carbon pitch, and silica pitch; and layered silicates. Among them, layered silicates are preferable because they can be mined naturally and can be produced at low cost by synthesis.
The above-mentioned layered silicate means a silicate mineral having exchangeable cations between layers. Usually, fine flaky crystals having a thickness of about 1 nm and an average aspect ratio of about 20 to 200 are aggregated by ionic bonding. What we do.
[0026]
The layered silicate is not particularly restricted but includes, for example, smectite clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite, natural mica such as vermiculite and halloysite, and swelling mica (swelling mica). Synthetic mica such as mica), and natural and synthetic ones can be used. Among them, swellable smectite-based viscous minerals and / or swellable mica are preferred.
[0027]
Generally, a crystal flake of a layered silicate is, for example, a tetrahedron in which four oxygen ions are coordinated around ions such as silicon, and six oxygen atoms around ions such as aluminum, like montmorillonite shown in FIG. It is composed of an octahedron to which ions are coordinated and OH groups, and each of the crystal flakes is linked by ionic bonding force by arrangement of cations such as sodium and calcium on the crystal surface (B). As described above, since a structure having a stronger intra-layer bonding force than an interlayer bonding force is used, a structure having a high aspect ratio can be easily formed by applying an appropriate shearing force or the like.
[0028]
The layered silicate is preferably one in which ions such as sodium and calcium on the crystal surface (B) are ion-exchanged with a cationic surfactant. Thereby, the layered crystal surface (B) is made non-polar, and the dispersibility of the layered silicate in the non-polar resin is improved.
[0029]
The layered silicate is preferably dispersed in the resin such that the average interlayer distance of the layered silicate detected by X-ray diffraction measurement is 6 nm or more. If the phyllosilicate is highly dispersed in the resin, the relative area between the phyllosilicate and the resin will increase dramatically, and the mutual friction force between the phyllosilicate and the resin will further improve dimensional stability. Injection molded articles or hot press molded articles can be provided. In general, the interlayer attraction of the layered silicate becomes extremely small when the interlayer distance becomes 6 nm or more, and thus the layered silicate is finely dispersed in the resin. Therefore, by setting the average interlayer distance to 6 nm or more, the deformation of the minute region of the resin-filler composite material after injection molding or hot press molding can be suppressed extremely efficiently. When the layered silicate is aggregated with each other due to the ionic bonding force, that is, when the interlayer distance is less than 6 nm, the modification effect by the addition of the layered silicate becomes very small.
Note that the average interlayer distance of the layered silicate refers to the distance between the 001 planes of the flaked crystal of the layered silicate, that is, the distance between the centers of the two flaked crystals in FIG. FIG. 3 shows an X-ray diffraction profile when the average interlayer distance is 6 nm or more, and FIG. 4 shows an X-ray diffraction profile when the average interlayer distance is less than 6 nm. In FIG. 3, although a small diffraction peak appears at the position of the interlayer distance of 2 nm, the broad diffraction line of 6 nm or more indicates that most of the interlayer distance is 6 nm or more.
[0030]
The lower limit of the amount of the filler is 0.01 part by weight and the upper limit is 200 parts by weight based on 100 parts by weight of the resin. If the amount is less than 0.01 part by weight, the effect on the dimensional stability cannot be exerted. If the amount exceeds 200 parts by weight, the transparency of the obtained microreactor resin substrate decreases due to scattering by the filler. A preferred lower limit is 1 part by weight, and a preferred upper limit is 20 parts by weight.
[0031]
The present invention 2 is a resin substrate for a microreactor made of a resin-filler composite material, which is 100 μm when observing the interface between the resin and the filler on a cut surface cut in a plane. ² This is a microreactor resin substrate having an interface length per unit of 2 mm or more. Here, the interface length means the total length per unit area of the resin and the filler observed on the cut surface.
FIG. 5 shows a cross section of the microreactor resin substrate of the present invention 2 cut in a plane, and FIG. 6 shows the relationship between the average particle diameter and the interface length. From FIG. 6, it can be seen that the interface length is dramatically increased especially when the average particle diameter is 150 nm or less. The interface length at an average particle diameter of 150 nm is 100 μm ² When the interface length exceeds 2 mm, the area of the interface between the resin and the filler increases dramatically. If the area of the interface between the resin and the filler increases, the interaction between the resin and the filler increases, and the coefficient of linear thermal expansion and the rate of dimensional change of the resin-filler composite material can be reduced.
The resin and the filler used for the microreactor resin substrate of the second aspect of the present invention can be the same as those of the microreactor resin substrate of the first aspect of the present invention.
[0032]
In the microreactor resin substrates of the first and second aspects of the present invention, the minimum value of the light transmittance in the wavelength region of 400 to 800 nm is preferably 50% or more. If it is less than 50%, the light transmittance in the visible light wavelength region will be poor. When the microreactor resin substrates of the present invention 1 and 2 are used for analysis and detection of a substance, the fact that optical detection methods such as absorbance measurement and fluorescence measurement can be used means that the detection mechanism is simple. It is preferred in that respect. Having a light transmittance in a visible light wavelength region is an important characteristic when a microreactor is used as an analysis system. In addition, since the resin substrate for a microreactor of the present invention has transparency, it is possible to directly observe the flow state, color development, and the like of the microfluid using an optical microscope or the like.
[0033]
The cross-sectional shape of the groove of the resin substrate for a microreactor of the present invention 1 and the present invention 2 is not particularly limited, and includes a polygonal shape such as a triangle, a square, and a rectangle; and a circular shape such as a semicircle and a semi-ellipse. . Further, grooves having different shapes may be combined.
A preferred lower limit of the width of the groove is 1 μm, a preferred upper limit is 3000 μm, a preferred lower limit of the depth is 0.1 μm, a preferred upper limit is 2000 μm, and a preferred lower limit of the cross-sectional area is 0.1 μm. ² The preferable upper limit is 6 million μm. ² It is. If the groove is small, the foreign matter in the sample may cause the capillary to be clogged or the flow may be disturbed. Larger grooves require more sample.
[0034]
In a μTAS or a microreactor using the microreactor resin substrate of the present invention 1 and the present invention 2, a very small sample of about 10 pL to 100 μL is used. In order to perform such a trace component analysis or quantitative analysis, it is necessary to flow more evenly over the formed groove, and in that respect, it is required that the dimensional accuracy of the groove be excellent. Generally, when a trace component is analyzed using μTAS or a microreactor, the size of the groove volume is proportional to the detection amount of the target chemical substance. Furthermore, the variation in the groove volume disturbs the uniformity of the flow of the fluid flowing in the groove, so that the variation in the detection amount of the target chemical substance is further increased. In general, when performing quantitative analysis of a target chemical substance, it is desired that the analysis accuracy is high even for simple analysis. Therefore, when attempting to transfer grooves using a mold having a convex shape, it is necessary to faithfully transfer the convex shape in order to obtain a meaningful detection result.
[0035]
The method for producing the microreactor resin substrate of the present invention 1 and the present invention 2 is not particularly limited, and a method of kneading the above resin and filler by a conventionally known method, for example, a method of injection molding or hot press molding and the like. Is mentioned.
[0036]
The resin substrate for a microreactor according to the first aspect of the present invention is made of a resin-filler composite material in which a resin having a specific property is blended with a resin. By using a resin-filler composite material in which a filler is blended with the above interface length, the shrinkage characteristics and stress relaxation characteristics of the resin can be effectively controlled. Can be suppressed very efficiently, and grooves and holes with extremely high precision can be formed. In addition, since the molding shrinkage is low, even if flow paths of complicated figures including straight lines and curves are joined with different microreactor resin substrates, deviation between flow paths can be minimized.
[0037]
The resin substrate for a microreactor of the present invention 1 and the present invention 2 can be used as a substrate having fine grooves through which a small amount of sample capable of flowing on the surface or a substrate having fine reaction holes for detecting a predetermined target substance. It can be suitably used. In the groove of the microreactor resin substrate, design and arrange the sampling part of the liquid sample, the merging part of the liquids with different components, the dilution part, the concentration part, the reaction part, the separation part, and the detection part as appropriate, and cover with a suitable material. Alternatively, a microreactor or a μTAS chip can be obtained by sealing to prevent liquid leakage.
[0038]
Further, as a means for sending the liquid, for example, a liquid sending means using a pump liquid sending or an electroosmotic flow can be added. When the above-mentioned electroosmotic flow is used as a liquid sending means, a flow path portion mainly for electrophoretic separation can be formed. In the case where liquid is supplied by any liquid supply means such as a pump liquid supply or an electroosmotic flow, one channel portion may have a plurality of purposes. In the microreactor resin substrate, the flow path may consist of only a flow path part mainly for one operation, but a plurality of flow path parts mainly for different operations may be used. Because of the combined flow path, it is possible to provide a device capable of performing not only qualitative analysis but also advanced analysis involving quantitative analysis and reaction.
[0039]
On the other hand, from the viewpoint of the productivity of the microreactor or the μTAS chip, at least one plate-like member is a flat plate having a groove through which a liquid flows on the surface, and this flat plate and the other plate or the film-like member are replaced by the flat plate. It is preferable to adopt a capillary structure produced by laminating the grooves inside. Further, it is also possible to adopt a structure in which a capillary is formed by attaching an elastic film on a resin substrate. It is also possible to adopt a structure consisting only of a flat plate (plate-like member) having a groove through which liquid flows on the surface, with the upper surface of the groove kept open.
[0040]
The obtained microreactor or μTAS chip can be used for bedside diagnosis at medical sites, on-site analysis of environmental pollutants, and the like. As the bedside diagnosis, for example, the outpatient can be notified of the test results of blood components and the like on the day of the consultation and can select a therapeutic drug and a treatment method based on the results. Examples of the on-site analysis of environmental pollutants include quantitative and qualitative analysis of pollutants in rivers and harmful substances in waste. An advantage of this is that an analysis that had conventionally been required to be brought back and used with a large measuring device such as a GC-MS can be performed at a contamination site without bringing it back.
[0041]
The substance to be detected by the microreactor or the μTAS chip is not particularly limited, but includes, for example, environmental pollutants such as environmental hormones, VOCs, heavy metals, and dioxins; biological components contained in blood, cerebrospinal fluid, saliva, urine, and the like; And biological components derived from tissues and mucous membranes; proteins such as bacteria and viruses as infection sources; nucleic acids such as DNA and RNA; allergens and various antigens.
[0042]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
[0043]
(Example 1)
In a small extruder TEX30 manufactured by Nippon Steel Works, polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., grade: LG) and glass fiber (unitika glass fiber, unitika) are adjusted to have a weight ratio of 100/10. The mixture was fed, melt-kneaded at a set temperature of 200 ° C., and the extruded strand was pelletized with a pelletizer. The obtained pellet was press-molded into a 1.5 mm-thick plate to obtain a plate for resin substrate production.
[0044]
The press mold was preheated at 180 ° C. with a manual press. About 4 g of the obtained resin substrate manufacturing plate was placed on this mold core, and the press mold was heated to 180 ° C. When it was confirmed that the temperature of the press mold reached 180 ° C., the pressure was 980 N / cm. ² For 30 seconds to transfer-mold a rectangular groove in the material. The press mold was transferred to a cooling press, and the pressure was 980 N / cm. ² Then, it was confirmed that the mold temperature had dropped to room temperature, and the press mold was taken out of the cooling press. The resin substrate to which the groove was transferred was taken out of the mold core.
[0045]
The press die used is shown in FIG. The clearance of the press die is 1 mm, and the thickness of the molded resin substrate is 1 mm. The press mold is provided with a nest for evaluation in which the flow path shown in FIG. 8 is drawn, and a rectangular projection having a height of 50 μm and a width of 50 μm formed by cutting as shown in FIG. Are engraved, and a resin substrate having the cross-sectional shape shown in FIG. 9 is obtained by pressing.
[0046]
(Example 2)
Same as Experimental Example 1 except that as a combination of a resin and a filler, 100 parts by weight of polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., grade: LG) and 10 parts by weight of talc (manufactured by Nippon Talc, general-purpose talc) were used. A resin substrate was produced by the method described in (1).
[0047]
(Example 3)
As a combination of a resin and a filler, a resin 100 in which polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., grade: LG) and acid-modified polymethyl methacrylate (manufactured by Yushi Kabushiki Kaisha, grade: Modeper A8200) are blended in a ratio of 95: 5. A resin substrate was produced in the same manner as in Experimental Example 1, except that 10 parts by weight of montmorillonite (manufactured by Southern Clay Co., Cloisite 20A) was used.
[0048]
(Example 4)
As a combination of a resin and a filler, a resin 100 in which polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., grade: LG) and acid-modified polymethyl methacrylate (manufactured by Yushi Kabushiki Kaisha, grade: Modeper A8200) are blended in a ratio of 95: 5. A resin substrate was produced in the same manner as in Experimental Example 1, except that 10 parts by weight and 10 parts by weight of synthetic mica (manufactured by Corp Chemical Co., Ltd., MAE) were used.
[0049]
(Example 5)
Resin 100 in which polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., grade: LG) and acid-modified polymethyl methacrylate (manufactured by Yushi Kabushiki Kaisha, grade: Modeper A8200) are combined at a ratio of 95: 5 as a combination of resin and filler. A resin substrate was produced in the same manner as in Experimental Example 1, except that 50 parts by weight and 50 parts by weight of synthetic mica (manufactured by Corp Chemical Co., Ltd., MAE) were used.
[0050]
(Example 6)
As a combination of a resin and a filler, a resin 100 in which polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., grade: LG) and acid-modified polymethyl methacrylate (manufactured by Yushi Kabushiki Kaisha, grade: Modeper A8200) are blended in a ratio of 95: 5. A resin substrate was prepared in the same manner as in Experimental Example 1, except that 5 parts by weight and 5 parts by weight of synthetic mica (manufactured by Corp Chemical Co., Ltd., MAE) were used.
[0051]
(Example 7)
A resin substrate was produced in the same manner as in Experimental Example 1 except that 100 parts by weight of polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., grade: LG) and 10 parts by weight of fine powder PET filler were used as a combination of the resin and the filler. Was prepared.
The fine powder PET filler is biaxially stretched at a stretching temperature of 200 ° C. by stretching a PET film having a thickness of 100 μm (PET-G, manufactured by Toray Synthetic Film Co., Ltd.) 10 times in the longitudinal direction and 8 times in the transverse direction. Annealed at 220 ° C. while holding, was finely cut by a film cutter to obtain.
The average diameter of the fine powder PET filler measured by laser diffraction was 5 μm, the aspect ratio was about 12, and the birefringence was 5 × 10 ⁵ Met.
[0052]
(Example 8)
As a combination of a resin and a filler, a resin 100 in which polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., grade: LG) and acid-modified polymethyl methacrylate (manufactured by Yushi Kabushiki Kaisha, grade: Modeper A8200) are blended in a ratio of 95: 5. A resin substrate was prepared in the same manner as in Experimental Example 1, except that 10 parts by weight of silica and 10 parts by weight of silica (manufactured by Nippon Aerosil Co., Ltd., grade: R972) were used.
[0053]
(Example 9)
As a combination of a resin and a filler, a resin 100 in which polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., grade: LG) and acid-modified polymethyl methacrylate (manufactured by Yushi Kabushiki Kaisha, grade: Modeper A8200) are blended in a ratio of 95: 5. A resin substrate was prepared in the same manner as in Experimental Example 1, except that 10 parts by weight of silica and 10 parts by weight of silica (manufactured by Nippon Aerosil Co., Ltd., grade: R972) were used.
[0054]
(Example 10)
A resin substrate was prepared in the same manner as in Experimental Example 1 except that 100 parts by weight of polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., grade: LG) and 10 parts by weight of highly stretched polyethylene terephthalate were used as a combination of a resin and a filler. Produced.
As the highly stretched polyethylene terephthalate, a 10 μm-thick biaxially stretched PET film (manufactured by Toray Industries, Inc., Lumirror) finely cut by a film cutting machine was used. The average diameter of the highly stretched polyethylene terephthalate measured by laser diffraction is 80 μm, the aspect ratio is about 10, and the birefringence is 5.0 × 10. ⁴ Met.
[0055]
(Example 11)
A resin substrate was prepared in the same manner as in Experimental Example 1 except that 100 parts by weight of polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., grade: LG) and 10 parts by weight of highly stretched polyethylene terephthalate were used as a combination of a resin and a filler. Produced.
As the highly stretched polyethylene terephthalate, a biaxially stretched PET film (Lumirror, manufactured by Toray Industries, Inc.) having a thickness of 20 μm was finely cut by a film cutting machine. The average diameter of high-stretched polyethylene terephthalate measured by laser diffraction is 60 μm, the aspect ratio is about 3, and the birefringence is 2.8 × 10 ⁴ Met.
[0056]
(Example 12)
A resin substrate was prepared in the same manner as in Experimental Example 1 except that 100 parts by weight of polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., grade: LG) and 10 parts by weight of a liquid crystal polymer were used as a combination of a resin and a filler. did.
As for the liquid crystal polymer, a spinning nozzle was attached to the tip of an extruder TEX30 manufactured by Nippon Steel Corp., and an extruded liquid crystal polymer (manufactured by Polyplastics, grade: Vectra A410) was drawn at a linear speed of 500 m / min. The fiber was oriented in advance by spinning and then cut into a fine shape.
The average diameter of the liquid crystal polymer measured by laser diffraction is 70 μm, the aspect ratio is about 9, and the birefringence is 3.3 × 10 ⁴ Met.
[0057]
(Example 13)
Resin 100 in which polymethyl methacrylate (manufactured by Sumitomo Chemical Co., grade: LG) and acid-modified polymethyl methacrylate (manufactured by Yushi Kagaku Co., grade: Modepar A8200) are mixed at a ratio of 80:20 as a combination of resin and filler. A resin substrate was prepared in the same manner as in Experimental Example 1, except that 10 parts by weight of synthetic mica (manufactured by Corp Chemical Co., MAE) was used.
[0058]
(Example 14)
Resin 100 in which polymethyl methacrylate (manufactured by Sumitomo Chemical Co., grade: LG) and acid-modified polymethyl methacrylate (manufactured by Yushi Kagaku Co., grade: Modeper A8200) are mixed at a ratio of 70:30 as a combination of a resin and a filler. A resin substrate was prepared in the same manner as in Experimental Example 1, except that 10 parts by weight of synthetic mica (manufactured by Corp Chemical Co., MAE) was used.
[0059]
(Example 15)
Resin 100 in which polymethyl methacrylate (manufactured by Sumitomo Chemical Co., grade: LG) and acid-modified polymethyl methacrylate (manufactured by Yushi Kagaku Co., grade: Modeper A8200) are mixed at a ratio of 70:30 as a combination of a resin and a filler. A resin substrate was produced in the same manner as in Experimental Example 1, except that the weight part and 150 parts by weight of synthetic mica (manufactured by Corp Chemical Co., Ltd., MAE) were used.
[0060]
(Example 16)
Resin 100 in which polymethyl methacrylate (manufactured by Sumitomo Chemical Co., grade: LG) and acid-modified polymethyl methacrylate (manufactured by Yushi Kagaku Co., grade: Modeper A8200) are mixed at a ratio of 70:30 as a combination of a resin and a filler. A resin substrate was produced in the same manner as in Experimental Example 1, except that 10 parts by weight of montmorillonite (Cloisite 20A, manufactured by Southern Clay) was used.
[0061]
(Example 17)
Resin 100 in which polymethyl methacrylate (manufactured by Sumitomo Chemical Co., grade: LG) and acid-modified polymethyl methacrylate (manufactured by Yushi Kagaku Co., grade: Modeper A8200) are mixed at a ratio of 70:30 as a combination of a resin and a filler. A resin substrate was prepared in the same manner as in Experimental Example 1 except that 10 parts by weight of synthetic smectite (manufactured by Corp Chemical Co., SAN) was used.
[0062]
(Example 18)
As a combination of a resin and a filler, 100 parts by weight of a resin obtained by mixing a polypropylene resin (manufactured by Nippon Polychem, grade: EA9) and an acid-modified polypropylene (manufactured by Sanyo Chemical Co., grade: Umex 1001) in a ratio of 80:20; A resin substrate was prepared in the same manner as in Experimental Example 1 except that 10 parts by weight of synthetic mica (manufactured by Corp Chemical Co., Ltd., MAE) was used.
[0063]
(Example 19)
As a combination of a resin and a filler, 100 parts by weight of a resin in which a polystyrene resin (manufactured by Asahi Kasei Corporation, grade: G8259) and an acid-modified polystyrene (manufactured by Yushi Kagaku Co., Ltd., grade: Modeper A8100) were mixed at a ratio of 80:20, and synthesized. A resin substrate was prepared in the same manner as in Experimental Example 1, except that 10 parts by weight of mica (manufactured by Corp Chemical, MAE) was used.
[0064]
(Example 20)
As a combination of a resin and a filler, a polylactic acid resin (manufactured by Shimadzu Corp., grade: Lacty9030, MFR = 5.5) and an acid-modified polystyrene (manufactured by Yushi Kabushiki Kaisha, grade: Modeper A8100) were blended at a ratio of 80:20. A resin substrate was prepared in the same manner as in Experimental Example 1, except that 100 parts by weight of resin and 10 parts by weight of synthetic mica (manufactured by Corp Chemical Co., Ltd., MAE) were used and the transfer molding temperature was 210 ° C.
[0065]
(Example 21)
As a combination of a resin and a filler, a polycarbonate resin (manufactured by Teijin Chemicals Ltd., grade: L-1250Z100, MFR = 5.5) and an acid-modified polystyrene (manufactured by Yushi Kagaku Co., grade: Model A8100) were used in a ratio of 80:20. Using 100 parts by weight of the compounded resin and 10 parts by weight of synthetic mica (manufactured by Corp Chemical Co., Ltd., MAE), a resin substrate was produced in the same manner as in Experimental Example 1 except that the transfer molding temperature was 270 ° C.
[0066]
(Example 22)
As a combination of a resin and a filler, 100 parts by weight of a resin in which a polyethylene terephthalate resin (manufactured by Unitika Ltd., Unitika Polyester) and an acid-modified polystyrene (manufactured by Yushi Kabushiki Kaisha, grade: Modiper A8100) are mixed at a ratio of 80:20; A resin substrate was produced in the same manner as in Experimental Example 1, except that 10 parts by weight of synthetic mica (manufactured by Corp Chemical Co., Ltd., MAE) was used and the transfer molding temperature was 270 ° C.
[0067]
(Example 23)
A glycidyl ether type epoxy resin of bisphenol A (Adeka Resin EP-4100, manufactured by Asahi Denka Kogyo Co., Ltd.), a curing agent polyoxypropylene diamine (Eahi Denka Kogyo, EH260), and montmorillonite (Southern Clay Co., Cloisite20A) Was stirred and mixed in a container until it became homogeneous at a weight ratio of 10/3/1 to prepare a liquid precursor.
[0068]
The press die used in Example 1 was preheated to 75 ° C. by a manual press. About 4 g of the prepared liquid precursor was placed in the mold core, and the mold was heated to 75 ° C. After confirming that the mold temperature reached 75 ° C., the material was pressured to 980 N / cm. ² For 3 hours, then the mold temperature was raised to 125 ° C., and the pressure was further increased for 3 hours to transfer-mold a rectangular groove. The press mold was transferred to a cooling press, and the pressure was 980 N / cm. ² After confirming that the mold temperature had dropped to room temperature, the press mold was removed from the cooling press. The resin substrate to which the groove was transferred was taken out of the mold core.
[0069]
(Comparative Example 1)
A resin substrate was prepared in the same manner as in Experimental Example 1, except that polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., grade: LG) was used as the resin, and no filler was used.
[0070]
(Comparative Example 2)
As the resin, a mixture of polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., grade: LG) and acid-modified polymethyl methacrylate (manufactured by Yushi Kabushiki Kaisha, grade: Modeper A8200) in a ratio of 70:30 is used. A resin substrate was produced in the same manner as in Experimental Example 1 except that the resin substrate was not used.
[0071]
(Comparative Example 3)
Experimental Example 1 except for using 10 parts by weight of polymethyl methacrylate (manufactured by Sumitomo Chemical Co., grade: LG) and 10 parts by weight of silica (manufactured by Nippon Aerosil, grade: R972) as a combination of resin and filler. A resin substrate was manufactured in the same manner.
[0072]
(Comparative Example 4)
Resin 300 in which polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., grade: LG) and acid-modified polymethyl methacrylate (manufactured by Yushi Kabushiki Kaisha, grade: Modeper A8200) are combined at a ratio of 95: 5 as a combination of resin and filler. A resin substrate was prepared in the same manner as in Experimental Example 1, except that 10 parts by weight of synthetic mica (manufactured by Corp Chemical Co., MAE) was used.
[0073]
(Comparative Example 5)
Resin 10 in which polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., grade: LG) and acid-modified polymethyl methacrylate (manufactured by Yushi Kagaku Co., grade: Modeper A8200) are combined at a ratio of 70:30 as a combination of a resin and a filler. A resin substrate was produced in the same manner as in Experimental Example 1 except that 300 parts by weight of synthetic mica (MAE, manufactured by Corp Chemical) was used.
[0074]
(Comparative Example 6)
Experimental Example 1 except that as a combination of a resin and a filler, 100 parts by weight of polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., grade: LG) and 10 parts by weight of silica (manufactured by Nippon Aerosil Co., Ltd., grade: R972) were used. A resin substrate was produced in the same manner as in the above.
[0075]
(Comparative Example 7)
Same as Experimental Example 1 except that as a combination of a resin and a filler, 100 parts by weight of polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., grade: LG) and 10 parts by weight of montmorillonite (manufactured by Southern Clay, Cloisite 20A) were used. A resin substrate was produced by the method described in (1).
[0076]
(Comparative Example 8)
A resin substrate was produced in the same manner as in Experimental Example 1 except that 100 parts by weight of polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., grade: LG) and 10 parts by weight of PET filler were used as a combination of a resin and a filler. .
As the filler, a PET film (PET-G, manufactured by Toray Synthetic Film Co., Ltd.) having a film thickness of 100 μm was finely cut by a film cutting machine and used as a filler. The average diameter of the filler as measured by laser diffraction measurement was 200 μm, the aspect ratio was about 2, and the birefringence was 5 × 10.
[0077]
(Comparative Example 9)
A resin substrate was prepared in the same manner as in Experimental Example 1 except that 100 parts by weight of polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., grade: LG) and 10 parts by weight of low-stretched polyethylene terephthalate were used as a combination of a resin and a filler. Produced.
The low-stretch polyethylene terephthalate is biaxially stretched from a PET film (PET-G, manufactured by Toray Synthetic Film Co., Ltd.) with a thickness of 100 μm at a stretching temperature of 200 ° C. by 1.5 times in the longitudinal direction and 1.2 times in the lateral direction. A film obtained by performing an annealing treatment at 220 ° C. while maintaining the tension was finely cut by a film cutting machine.
The average diameter of low-stretched polyethylene terephthalate measured by laser diffraction is 50 μm, the aspect ratio is about 1.2, and the birefringence is 5 × 10 ² Met.
[0078]
The resin substrates prepared in Examples 1 to 23 and Comparative Examples 1 to 9 were evaluated by the following methods.
The results are shown in Table 1.
[0079]
(Evaluation of transferability)
The resin substrate is cut at portions 1, 2 and 3 shown in FIG. 10, and the cross-sectional shapes of the grooves 11, 12, 13, 14, 21, 22, 31, and 32 are changed by an optical microscope (VHP40) manufactured by Keyence Corporation. And whether or not the convex shape of the mold surface was faithfully transferred was evaluated according to the following criteria.
◎: Especially faithfully transcribed
〇: Faithfully transcribed to the extent that there is no problem in the analysis of the target substance
×: Clearly problematic in analysis of target substance
[0080]
(Transparency evaluation)
The light transmittance of visible light in a wavelength range of 400 to 800 nm was measured with a visible light spectrophotometer (U-3500) manufactured by Hitachi, Ltd., and evaluated according to the following criteria.
◎: The total light transmittance was 90% or more.
〇: Total light transmittance of 50 or more and less than 90%
X: The total light transmittance was less than 50%.
[0081]
[Table 1]

[0082]
From Tables 1 and 2, all of the resin substrates prepared in Examples 1 to 23 showed transferability with no problem in analysis, whereas the resin substrates prepared in Comparative Examples 1 to 4 and 6 to 9 were clear in analysis. There was a problem. Further, the resin substrate produced in Comparative Example 5 was excellent in transferability but was not obtained in transparency. In this case, although it has a function as a microreactor substrate, an optical system cannot be used as a detection unit.
[0083]
【The invention's effect】
According to the present invention, it is possible to provide a microreactor resin substrate in which grooves and holes with extremely high precision are formed.
[Brief description of the drawings]
FIG. 1 is a schematic diagram showing a state of a filler when a transfer mold is pressed against a molten resin.
FIG. 2 is a schematic diagram for explaining a state of a crystal flake of a layered silicate.
FIG. 3 is an X-ray diffraction profile when the average interlayer distance of a crystal flake of a layered silicate is 6 nm or more.
FIG. 4 is an X-ray diffraction profile when the average interlaminar distance of a crystal flake of a layered silicate is less than 6 nm.
FIG. 5 is a schematic view showing a cut surface obtained by cutting the resin substrate for a microreactor of the present invention in a plane.
FIG. 6 is a diagram showing a relationship between an average particle diameter and an interface length.
FIG. 7 is a schematic view showing a press die used in the example.
FIG. 8 is a schematic diagram showing a nesting type of a press die used in an example.
FIG. 9 is a cross-sectional view illustrating a convex shape of the resin substrate manufactured in the example.
FIG. 10 is a schematic view showing a method for cutting a resin substrate in the evaluation of transferability in Examples.

Claims (10)

A resin substrate for a microreactor comprising a resin-filler composite material,
The filler is an inorganic material or a polymer material having an aspect ratio of 10 or more, or a polymer material having a birefringence of 2.5 × 10 ⁴ or more,
A resin substrate for a microreactor, comprising 0.01 to 200 parts by weight of the filler based on 100 parts by weight of the resin. The microreactor resin substrate according to claim 1, wherein the inorganic material or the polymer material having an aspect ratio of 10 or more has a long side of 500 nm or less and a short side of 50 nm or less. A resin substrate for a microreactor comprising a resin-filler composite material,
A resin substrate for a microreactor, wherein an interface length per 100 μm ² is 2 mm or more when an interface between a resin and a filler is observed on a cut surface cut in a plane. 4. The resin substrate for a microreactor according to claim 1, wherein a minimum value of light transmittance in a wavelength region of 400 to 800 nm is 50% or more. The resin substrate for a microreactor according to claim 1, wherein the filler is a layered silicate. The microreactor resin substrate according to claim 5, wherein the layered silicate is a swellable smectite-based viscous mineral and / or swellable mica. 7. The microreactor resin substrate according to claim 5, wherein the layered silicate is dispersed in the resin such that the average interlayer distance detected by X-ray diffraction measurement is 6 nm or more. The resin substrate for a microreactor according to claim 1, 2, 3, 4, 5, 6, or 7, wherein the filler has a long side or a long diameter of 300 nm or less. The resin substrate for a microreactor according to claim 1, 2, 3, 4, 5, 6, 7, or 8, wherein the resin is a thermoplastic resin. The resin is at least one selected from the group consisting of a polyolefin-based resin, an acrylic-based resin, a polycarbonate-based resin, and an epoxy-based resin. 10. The resin substrate for a microreactor according to claim 8, 8 or 9.

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