JP4418880B2 - Microstructure with micro structure on the surface - Google Patents

Description

  The present invention relates to a fine structure made of a resin and having an uneven structure such as a fine groove or well on a surface.

As for a fine structure having micro unevenness on the surface of a microchannel chip or the like, a structure using various materials such as silicon, glass and resin has been proposed.
In a fine structure using silicon, a method of forming a concavo-convex pattern by etching a silicon wafer cut out from a silicon single crystal is widely used.
Such a method is preferable in terms of high accuracy of the concavo-convex shape, but has a problem that a silicon wafer as a raw material is expensive, a processing machine and processing equipment are extremely expensive, and a processing time is long. In addition, the accuracy of the concavo-convex shape is easily influenced by the processing machine and processing conditions, and the occurrence rate of defective products may be high.

  Glass microstructures basically have the same problems as silicon microstructures, and problems such as cost of raw materials and mechanical equipment, processing time, and defect rate have not been solved.

With respect to the fine structure made of resin, studies using various resins have been made.
In the case of using PDMS (polydimethylsiloxane) as a main component, a method is used in which PDMS into which a reactive group is introduced and a curing agent mixed therein are poured into a mold and heated and solidified.

Since such PDMS microstructures can be fabricated relatively easily at the laboratory level, there have been many research examples so far, and some of them have been commercialized.
However, because the raw materials are expensive and the curing time is long, it is difficult to realize low cost and mass production expected by using a resin in a PDMS microstructure.
In addition, since the structure itself is elastomeric and flexible, it is difficult to maintain accuracy, and when a liquid is flowed at a high pressure in the flow path, problems such as deformation and leakage occur.

A transparent hard resin such as acrylic or polycarbonate is also used for the resin microstructure. Fabrication by a method of forming a concavo-convex pattern on a substrate made of these resins using a laser processing machine, a micro cutting machine or the like is widely performed.
According to these methods, a simple pattern structure can be easily produced, but as the pattern becomes more complicated, the processing time becomes longer, and as a result, the productivity is greatly reduced. Further, since the processing machine is expensive, it is difficult to produce a microstructure having a low price and high mass productivity by such a method.

    In the production of a fine structure using a resin, injection molding which is advantageous in terms of productivity is also used. Production of fine structures by injection molding using polystyrene, acrylic resin, polycarbonate, alicyclic polyolefin, etc. has been carried out, but these resins have problems in transferring fine uneven patterns and releasing products. . In other words, a fine structure having a designed concavo-convex pattern has not been obtained because the corner portion is not filled with resin, a weld line remains, or is deformed at the time of mold release.

In order to solve such problems, we have already invented a novel resin composition excellent in transferability (Patent Document 1). According to the present invention, it has been found that a microchip on which a micro uneven pattern is formed can be obtained.
By optimizing the resin used in this way, it is possible to produce a microstructure by injection molding. However, in normal injection molding, there is an overheating-cooling process, so heat shrinkage affects the dimensional accuracy of the fine shape. To do.

  In order to increase the dimensional accuracy of the micro structure, a resin molding method that does not affect thermal shrinkage is necessary, and as an example, molding with a curable resin using photocuring can be considered. In such molding, a mask exposure method, a method of pouring a curable resin into a mold, or the like is used.

  In the mask exposure method, a mask corresponding to the pattern is placed on a photo-curing resin coated on the substrate with a certain thickness, and after irradiation with light for a certain period of time, the uncured resin is removed. Thus, an uneven structure is produced (see Patent Document 2). Since such a method is only a combination of existing techniques, a concavo-convex structure can be obtained relatively easily, but there are problems such as a limited number of structures that can be manufactured and a decrease in accuracy with a fine structure. That is, in the mask exposure, an oblique wall standing at an arbitrary angle on the substrate or a hole having a different depth cannot normally be produced. In addition, for walls perpendicular to the substrate, light and chemical reactions diffuse in the resin when forming a structure by exposure, which causes wall tilt and flatness, resulting in high dimensional accuracy. It is difficult to obtain a structure. Further, the conventional resins used for such mask exposure hardly have any non-fluorescence, and there is a problem when used for a microchip or the like.

  In the method of pouring a curable resin into a mold, a fine structure is prepared by using a mold having a fine concavo-convex structure on the surface, pouring a photocurable resin there, and curing the resin by light irradiation. Since the photo-curing resin used can reduce the resin viscosity before curing, it is generally easy to fill the resin at the tip of the microstructure. In addition, since there is no cooling process after the formation of the structure and there is no volume change due to thermal shrinkage or crystallization, deformation is unlikely to occur, and according to this method, a highly accurate fine structure reflecting the dimensional accuracy of the mold can be formed.

  As described above, in the method of pouring the curable resin into the mold, it is easy to form a fine shape with high accuracy, but most of the problems are found in the mold release after curing. In other words, epoxy compounds and acrylic compounds that are often used as components of photo-curable resins, as they can be seen from the fact that they are also used as adhesives, adhere to metal, glass, and silicon, which are mold materials. Therefore, at the time of mold release, the micro structure of the fine structure is deformed, broken, or the mold is damaged.

  In order to solve such problems, we have so far studied to improve photocurable resins and molds and have devised new molding methods using photocurable resins (Patent Documents 3 and 4). We have devised a molding method for curable resins using polypropylene resins and silicone rubber, which are difficult-to-adhere resins, as a mold to solve the above-mentioned mold release problem, but these molds still have problems in durability and accuracy. Therefore, further improvement is desired. A photo-curable resin that can use a highly durable mold made of ordinary metal, glass, silicon, etc. is considered necessary, but at present it is required for moldability such as releasability and microchips. Nothing that is satisfactory in terms of physical properties such as non-fluorescence is provided.

Japanese Patent No. 3867126 JP 2003-66033 A JP 2006-346905 A JP2007-253071

  In view of the above technical problem, the present invention uses a highly durable mold made of silicon or metal, and can be manufactured by a method capable of obtaining high productivity such as photocuring, is inexpensive, excellent in mass productivity, and has a fine shape. An object of the present invention is to provide a fine structure made of a non-fluorescent material with high accuracy and applicable to a microchip.

The microstructure of the present invention has a uniform liquid when mixed with monomer X having a single polymerizable double bond and polymerized by free radical polymerization, and two or more polymerizable double bonds. A polymer A comprising a monomer Y having a bond and polymerized by free radical polymerization, wherein the weight ratio of the monomer X to the monomer Y is in the range of 90/10 to 55/45; and the monomer X And the monomer Y is a polymer composition mainly composed of a polymer B dissolved or colloidally dispersed in the liquid, and the monomer X has a glass transition temperature of 20 ° C. The photo-curing having a weight ratio of the polymer A and the polymer B in the range of 93/7 to 65/35, and a mixture of the monomer X, the monomer Y, and the polymer B as the main components. The storage elastic modulus at any temperature of 20 ° C. to 25 ° C. after photo-curing the functional resin is 1 to It is in the range of 100MPa,
Monomer X is one of or a mixture of alkyl acrylate, alkyl methacrylate, and a monomer containing at least a moiety having a chemical structure represented by formula (1),
(Equation (1), m is an integer of 2 to 4, n represents an integer of 1 to 10, R represents CH ₃ or H)
Monomer Y is ethylene glycol diacrylate, butanediol diacrylate, 1,6-hexanediol diacrylate, 1,10-decanediol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, allyl acrylate, ethylene dimethacrylate One or a mixture of glycol, butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,10-decanediol dimethacrylate, diethylene glycol methacrylate, polyethylene glycol dimethacrylate, and allyl methacrylate The polymer B is composed of core / shell type polymer fine particles and has a micro uneven structure on the surface.

  The monomer X constituting the polymer A is not particularly limited as long as it has a single polymerizable double bond and is polymerized by free radical polymerization. Vinyl monomers, (meth) acrylates, acrylamides Etc. can be used. The monomer X may be a single monomer or a mixture of two or more monomers.

  The monomer X preferably has a high polymerization rate from the viewpoint of increasing the productivity when producing the fine structure, and such a monomer has a (meth) acryloyl group chemical structure. Is preferred. Monomer X is preferably not an aromatic compound from the viewpoint of fluorescence. Examples of the monomer X as described above include (meth) acrylates in which an alkyl group or a cycloalkyl group is bonded to an ester moiety. Examples of such monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, nonyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl Examples include methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, nonyl methacrylate, and cyclohexyl methacrylate.

  The monomer Y constituting the polymer A is not particularly limited as long as it is a monomer that becomes a uniform liquid when mixed with the monomer X and has two or more polymerizable double bonds and is polymerized by free radical polymerization. However, it is preferably not an aromatic compound from the viewpoint of fluorescence. Examples of such monomer Y include ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, di (meth) acrylic acid 1 , 10-decanediol, polyethylene glycol di (meth) acrylate, allyl (meth) acrylate, and the like. Monomer Y may be one type of monomer or a mixture of two or more types of monomers.

  The weight ratio of the monomer X and the monomer Y constituting the polymer A is in the range of 90/10 to 55/45. In the present invention, the problem of mold release at the time of forming a fine structure is solved by reducing the adhesive strength of the resin and imparting elasticity to the resin. In general, it is known that the adhesive strength can be reduced by crosslinking the resin, and therefore monomer Y was added as a crosslinking agent. However, if the ratio of the monomer Y is too large, the elasticity of the resin is lost and the resin Y becomes too hard, so the weight ratio of the monomer X and the monomer Y in the present invention is 90/10 to 55/45. Is in range.

  The polymer B is not particularly limited as long as it is a polymer that is dissolved or colloidally dispersed in a liquid composed of the monomer X and the monomer Y. Poly (meth) acrylates, vinyl polymers, diene-based polymers Polymers, condensation polymers and the like can be used freely.

  The ratio of the polymer A and the polymer B in the polymer composition is not particularly limited. However, when the microstructure is formed, if the amount of the polymer B is small, the shrinkage increases and the dimensional accuracy decreases. If the amount of the polymer B is large, the viscosity of the photocurable resin mainly composed of the monomer X / monomer Y / the polymer B becomes too high to cause a problem during molding. The weight ratio of the combined B is preferably in the range of 93/7 to 65/35.

  Since the polymer composition needs elasticity for releasing as described above, the storage elastic modulus at any temperature of 20 ° C. to 25 ° C. is preferably in the range of 1 to 1100 MPa, and in the range of 5 to 800 MPa. More preferably. Each of the monomer X, the monomer Y and the polymer B is not particularly limited as described above, but the combination of these three components must be selected so that the storage elastic modulus of the polymer composition falls within the above range. Don't be.

  In the monomer X of the present invention, the glass transition temperature of a polymer obtained by polymerizing the monomer X is preferably 20 ° C. or lower, and more preferably 0 ° C. or lower. As described above, since the polymer composition of the present invention needs to have elasticity, the monomer X, which is one of the main components, is preferably in a rubbery state near the room temperature.

The monomer X of the present invention preferably contains at least a monomer having a chemical structure represented by the formula (1).

(Equation (1), m is an integer of 2 to 4, n represents an integer of 1 to 10, R represents CH ₃ or H)
Since the monomer X contains the monomer having the structure of the formula (1), hydrophilicity can be imparted to the fine structure. Therefore, the fine structure can be used as a biochip or the like in the fields of medicine, biochemistry, and biology. It becomes possible to use it more suitably. In order to impart hydrophilicity, the monomer X more preferably contains 20% by weight or more of the monomer having the structure of the formula (1). Examples of monomers having the structure of formula (1) include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl. Methacrylate, 2-methoxyethyl acrylate, 2-methoxypropyl acrylate, 4-methoxybutyl acrylate, 2-methoxyethyl methacrylate, 2-methoxypropyl methacrylate, 4-methoxybutyl methacrylate, hydroxyl-terminated polyethylene glycol monoacrylate, hydroxyl-terminated polyethylene glycol mono Methacrylate, methyl-terminated polyethylene glycol monoacrylate, methyl-terminated polyethylene glycol monomethacrylate And the like.

  The polymer B of the present invention is preferably composed of core / shell type polymer fine particles. By using such a polymer B, the photocurable resin mainly composed of the monomer X, the monomer Y, and the polymer B of the present invention is suppressed in viscosity increase and easy to handle. . Furthermore, the core-shell type polymer fine particles of the polymer B of the present invention preferably have a generated stress of 100 MPa or less, more preferably 20 MPa or less in a stretched 100% strain state. As described above, the polymer composition constituting the fine structure needs to be given elasticity in order to improve the releasability, and therefore the polymer B is preferably flexible.

Although there is no restriction | limiting in particular in the particle diameter of this core-shell particle, Considering that it is easy to use emulsion polymerization as a manufacturing method, a particle diameter exists in the range of 0.01-10 micrometers, and it is easy to use it.
The polymer used for the shell of the core-shell particle is not particularly limited, but considering the ease of using emulsion polymerization as a production method and the generation of fluorescence, a (meth) acrylate polymer such as polymethyl methacrylate and its Examples thereof include a copolymer, polyvinyl acetate, and a copolymer thereof.
The polymer used for the core of the core-shell particle is not particularly limited, but considering the ease of using emulsion polymerization as a production method and the generation of fluorescence, a (meth) acrylate polymer such as polybutyl acrylate and its Examples thereof include a copolymer, polyvinyl acetate, and a copolymer thereof.

  The core-shell type polymer fine particles are preferably cross-linked at least in order to maintain the shape. As a result, the polymer B can stably form a dispersed phase in the polymer composition constituting the microstructure, and can function well as an elastic body when flexible. There is no restriction | limiting in particular about the monomer which forms bridge | crosslinking, Divinyl monomers, di (meth) acrylates, allyl (meth) acrylate, etc. are mentioned.

In the fine structure of the present invention, the concave and convex shape of the fine structure on the surface is composed of one or a plurality of concave portions and / or convex portions, the concave portion is not deep, and the convex protrusion height is in the range of 0.1 μm to 500 μm. The recess opening width or protrusion protruding width or the diameter of the contact circle of the recess or protrusion is in the range of 0.1 μm to 500 μm, and the recess does not deepen, the protrusion protruding height and the recess opening width or protrusion protruding width or recess or protrusion The ratio of the tangent circle diameter of the part is 1/100 to 10/1.
Considering that the microstructure of the present invention can be applied to bio-applications that handle cells, bacteria, proteins, DNA, etc., optical applications such as optical devices, and analysis / synthesis applications such as lab-on-chip, etc. The dimension range of was displayed.

  The microstructure of the present invention is preferably produced by pouring a photocurable resin mainly composed of the monomer X, the monomer Y and the polymer B into a mold and solidifying by photopolymerization. In the present invention, since it aims at providing a fine structure by a method capable of obtaining high productivity and dimensional accuracy, production by photopolymerization using a template is preferable.

You may add a photoinitiator to the photocurable resin used for preparation of the microstructure of this invention. There is no restriction | limiting in particular about a photoinitiator, It can select and use freely from photoinitiators, such as a benzoin ether type | system | group, a ketal type | system | group, an acetophenone type, a benzophenone type, and a thioxanthone type.
In addition, the photocurable resin may be freely mixed with a monomer, a polymer, an inorganic filler, or the like as long as the effects of the present invention are not impaired.
The light irradiation device used for photopolymerization is not particularly limited, and a device equipped with a high-pressure mercury lamp, a metal halide lamp, a UV discharge tube, or the like can be used freely.
It is more preferable that the photocurable resin is cured in a nitrogen atmosphere from the viewpoint of polymerizability.

The fine structure of the present invention can be a fine structure composite plate in which a plate made of glass, plastic, or metal is attached to a surface having no fine structure.
By using a fine structure composite plate, the fine structure is reinforced in strength, or can be easily used in an analyzer such as a scanner, and convenience is improved.

  The method for attaching the plate to the fine structure is not particularly limited, and a method of attaching the plate with an adhesive after the preparation of the fine structure can be used freely. Also, when producing a microstructure, a photocurable resin is placed on a mold, a plate is placed on the mold, photocured and then released, and the microstructure and the plate are integrated. A composite plate may be made. In addition, it is more preferable that the plate used in that case is surface-treated with a monomer or a silane coupling agent having a polymerizable double bond so that adhesion to the photocurable resin is good.

  The microstructure and the microstructure composite plate of the present invention can be used as a microchannel chip, a microchannel chip, a microwell array chip, and a cell culture plate.

  Since the resin molded body having a fine structure of the present invention has a fine structure with high accuracy in size and shape by using a material having elasticity and non-adhesiveness, by utilizing the present invention, It becomes possible to provide a microchip or the like having a microchannel or a microwell having an accurate shape, which has been difficult to provide with resins until now. Since the resin molded body having a fine structure of the present invention is also excellent in hydrophilicity, it can be more suitably used as a biochip, a cell culture plate or the like in the fields of medicine, biochemistry, biology and the like. Further, the resin molded body having a fine structure of the present invention can be suitably used as an optical component or the like by utilizing the high precision of dimensions and shape.

The following were used as raw materials for the production of the microstructure of the present invention.
As monomers having one polymerizable double bond, n-butyl acrylate (polymer glass transition temperature: −50 ° C.), 2-methoxyethyl acrylate (polymer glass transition temperature) manufactured by Wako Pure Chemical Industries, Ltd. : -50 ° C), Nippon Kasei's 4-bidoxybutyl acrylate (glass transition temperature of polymer: -30 ° C), Bremermer PME-100 (polyethylene glycol moiety) which is a methyl group-terminated polyethylene glycol monomethacrylate made by Nippon Oil & Fats. The degree of polymerization was about 2) and PME-200 (the degree of polymerization of the polyethylene glycol moiety was about 4).
As monomers having two or more polymerizable double bonds, Blenmer PDE-100, which is diethylene glycol dimethacrylate manufactured by NOF Corporation, 1,6-hexanediol dimethacrylic acid manufactured by Wako Chemical, and Wako Pure Chemical Industries, Ltd. Allyl methacrylate was used.
As the polymer, Kuraray Parapet SA-NW201 (core-shell type polymer fine particle, stress generated at 100% strain of 11 MPa) was used.
As the photopolymerization initiator, Ciba DAROCUR 1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one) manufactured by Ciba Specialty Chemicals was used.

The monomer having one polymerizable double bond, the monomer having two or more polymerizable double bonds, a polymer, and a photopolymerization initiator are described in Example 1 of FIG. A sample was selected and weighed into a glass sample tube with the weight part of FIG. 1 and mixed, and then stirred in a dark place at room temperature until the polymer was dissolved and uniformly dispersed. Next, as shown in FIG. 2, the mixture is formed on a mold (prepared by dry etching a silicon substrate in 1 of FIG. 2 and having a microstructure serving as a mold on the upper surface in the figure). A photo-curable resin (2 in FIG. 2) is placed, and a glass plate is further formed thereon (3 in FIG. 2 and immersed in 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) for 12 hours or more until just before use) The photocurable resin was spread over the entire upper surface of the mold. The mold, photocurable resin, and glass plate thus prepared were placed in a nitrogen atmosphere, and an ultraviolet lamp (LUV-16 manufactured by ASONE CORPORATION) was placed at a height of 2 cm from the top surface of the slide glass as shown in FIG. 22W) and ultraviolet irradiation for 30 minutes, the mold was removed and a fine structure was obtained on a glass plate.
Using the stamper 1 (a stamper for line and space production, which can produce a structure in which grooves having a width of 1 μm and a depth of 3 μm are arranged at an interval of 1 μm) as a mold, the microstructure obtained as described above FIG. 4 shows the result of observation of the concavo-convex structure of 1a with a scanning electron microscope from above the pattern surface. In this molded product, no unfilled or deformed resin was observed at the edge of the boundary between the groove of the pattern surface and the resin, and a fine structure faithfully transferring the stamper structure as a whole was recognized.
Using the stamper 2 (a stamper for producing a well array, which can produce a structure in which holes with a diameter of 12 μm and a depth of 15 μm are arranged in a square lattice pattern at intervals of 25 μm) as a template, FIG. 5 shows the result of optical microscopic observation of the concavo-convex structure of the structure 1b from above the pattern surface. In this molded body, no resin filling or deformation near the hole entrance was observed, and a fine structure faithfully transferring the stamper structure as a whole was recognized.
Using the photocurable resin used in this example, a 25 mm × 5 mm × 1 mm strip sample was prepared by photocuring, and the storage elastic modulus was measured. The storage elastic modulus was obtained by measuring dynamic viscoelasticity at a frequency of 10 Hz and 22 ° C. using a Mettler DMA861, and the value was 160 MPa.
(Examples 2 to 12)

From the monomer having one polymerizable double bond, the monomer having two or more polymerizable double bonds, a polymer, and a photopolymerization initiator, Examples 2 to 12 in FIG. What was described was selected, and a photocurable resin was prepared in the same manner as in Example 1 with the weight parts shown in FIG. 1 to form a microstructure. When the microstructures 2a to 12a and the microstructures 2b to 12b produced using the stamper 1 and the stamper 2 as molds under the conditions of Examples 2 to 12 were observed with a microscope in the same manner as in Example 1, all the fine structures were observed. Regarding the structure, the same structure as that shown in FIGS. 4 and 5 was observed, and a fine structure faithfully transferring the stamper structure was confirmed.
When the storage elastic modulus was measured like Example 1 using the photocurable resin of Examples 2-12, the value shown in FIG. 1 was obtained.
(Comparative Example 1)

The monomer having one polymerizable double bond, the monomer having two or more polymerizable double bonds, a polymer, and a photopolymerization initiator are described in Comparative Example 1 in FIG. One was selected and a photocurable resin was prepared in the same manner as in Example 1 with the weight parts shown in FIG. However, with the blending amount of the monomer having two or more polymerizable double bonds in this comparative example, the adhesiveness of the cured resin is extremely high, and the mold (from the above-mentioned) It was impossible to remove the stamper 2). If an excessive force was applied to remove the stamper 2), the silicon mold was broken and a fine structure could not be obtained.
(Comparative Example 2)

The monomer having one polymerizable double bond, the monomer having two or more polymerizable double bonds, a polymer, and a photopolymerization initiator are described in Comparative Example 2 in FIG. One was selected, and a photocurable resin was prepared in the same manner as in Example 1 with the parts by weight shown in FIG. FIG. 6 shows the result of observation with an optical microscope in the same manner as in Example 1 for the microstructure c1 produced using the stamper 3 having the same uneven structure as the stamper 2 as a template. As shown in FIG. 6, in the microstructure of this comparative example, an abnormal structure was observed around the formed hole, and such a structure was generated when the resin was scraped by friction with the mold at the time of mold release. It was estimated. In this comparative example, it is expected that such an abnormal structure was generated because the amount of the monomer having two or more polymerizable double bonds was too much to crosslink and the resulting resin became brittle. .
(Comparative Example 3)

From the monomers, polymers, and photopolymerization initiators having two or more polymerizable double bonds, those described in Comparative Example 3 in FIG. 1 are selected, and one polymerizable double bond is obtained. Using methyl methacrylate (manufactured by Kuraray Co., Ltd., glass transition temperature of polymer: 120 ° C.) as a monomer having a photocurable resin in the same manner as in Example 1 with the weight parts shown in FIG. I tried to shape the body. However, since methyl methacrylate is used in this comparative example, the rigidity of the cured resin is extremely high, and the mold (the stamper 4 having the concavo-convex structure similar to the stamper 2) is removed from the fine structure in the mold release process after the ultraviolet irradiation. It was impossible, and if an excessive force was applied to remove the silicon mold, the silicon mold was broken and a fine structure could not be obtained.
When the storage elastic modulus was measured in the same manner as in Example 1 using the photocurable resin of this comparative example, an extremely high value was obtained as shown in FIG.

  The fine structure having a micro concavo-convex structure on the surface provided by the present invention makes use of the material characteristics such as high structural accuracy and hydrophilicity, and uses a microchannel chip, a microchannel chip, a microwell array chip, a cell culture As a plate or the like, it can be widely used for analysis, inspection, diagnosis, synthesis and the like. In addition, it can be used as an optical component or a micromachine component because of its high structural accuracy.

The material used for an Example and a comparative example, its combination, and the storage elastic modulus of the produced molded object are shown. It is process drawing which showed a part of shaping | molding method of a microstructure. It is process drawing which showed a part of shaping | molding method of a microstructure. It is a photograph of the result of having observed the fine structure of Example 1 by the scanning electron microscope. It is a photograph of the result of observing the microstructure of Example 1 with an optical microscope. It is a photograph of the result of observing the microstructure of Comparative Example 2 with an optical microscope.

Claims (3)

Monomer X having one polymerizable double bond and polymerized by free radical polymerization and when mixed with monomer X, it becomes a uniform liquid and has two or more polymerizable double bonds by free radical polymerization. It consists of a monomer Y to be polymerized, a polymer A in which the weight ratio of monomer X and monomer Y is in the range of 90/10 to 55/45, and monomer X and monomer Y. The polymer composition is mainly composed of a polymer B which is dissolved or colloidally dispersed in a liquid. The monomer X has a glass transition temperature of 20 ° C. or less of the polymer obtained by polymerizing the monomer. After photocuring a photocurable resin having a weight ratio with the polymer B in the range of 93/7 to 65/35 and mainly composed of a mixture of the monomer X, the monomer Y and the polymer B The storage elastic modulus at any temperature of 20 ° C. to 25 ° C. is in the range of 1 to 1100 MPa. Ri,
Monomer X is one of or a mixture of alkyl acrylate, alkyl methacrylate, and a monomer containing at least a moiety having a chemical structure represented by formula (1),
(Equation (1), m is an integer of 2 to 4, n represents an integer of 1 to 10, R represents CH ₃ or H)
Monomer Y is ethylene glycol diacrylate, butanediol diacrylate, 1,6-hexanediol diacrylate, 1,10-decanediol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, allyl acrylate, ethylene dimethacrylate One or a mixture of glycol, butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,10-decanediol dimethacrylate, diethylene glycol methacrylate, polyethylene glycol dimethacrylate, and allyl methacrylate ,
The polymer B is composed of core / shell polymer fine particles,
A fine structure having a micro uneven structure on a surface.   The concave / convex shape of the fine structure on the surface consists of one or a plurality of concave portions and / or convex portions, the concave portion is not deep and the convex protrusion height is in the range of 0.1 μm to 500 μm, and the concave opening width or convex protrusion The ratio of the width or the contact circle diameter of the recess or the protrusion is in the range of 0.1 μm to 500 μm, and the depth of the recess or the protrusion protrusion height and the opening width of the recess or protrusion protrusion width or the contact circle diameter of the recess or protrusion The fine structure according to claim 1, wherein is 1/100 to 10/1. 3. A microstructure composite plate, wherein a plate made of any one of glass, plastic, and metal is attached to a surface of the microstructure having no microstructure according to claim 1 or 2.