WO2025052769A1 - Production method for hydrogel structure and intermediate of hydrogel structure - Google Patents

Abstract

In order to inhibit a swollen hydrogel from moving during patterning by light irradiation, a production method (M11) for a hydrogel structure includes a patterning step (S14) in which a hydrogel swollen with water is irradiated with light to perform patterning, wherein in the patterning step (S14), at least some of the side surfaces of the hydrogel are supported by a support member formed on the main surface.

Description

Method for producing hydrogel structure and intermediate product of hydrogel structure

The present invention relates to a method for producing a hydrogel structure. The present invention also relates to an intermediate of the hydrogel structure.

Patent Document 1 describes a technology that uses a swollen hydrogel and dehydrates and shrinks the hydrogel, which has been patterned with a spatial distribution of the refractive index, to increase the resolution of the pattern of the spatial distribution of the refractive index compared to when it was patterned. Patent Document 1 calls this technology Implosion Fabrication (ImpFab).

U.S. Pat. No. 1,121,4661

In ImpFab, in the process of patterning the swollen hydrogel, the hydrogel may be surrounded by water. This is a measure to suppress the shrinkage of the volume of the hydrogel that may occur as the hydrogel dehydrates. However, when the hydrogel is surrounded by water, the hydrogel becomes more likely to move on the main surface of the substrate. Such movement of the hydrogel during patterning leads to a decrease in patterning accuracy.

One aspect of the present invention has been made in consideration of the above-mentioned problems, and its purpose is to suppress the movement of swollen hydrogel during patterning by light irradiation.

In order to solve the above problems, a method for producing a hydrogel structure according to one embodiment of the present invention includes a patterning step in which a hydrogel placed on a main surface of a substrate and swollen with water is patterned by irradiating the hydrogel with light, and in the patterning step, at least a portion of the side surface of the hydrogel is supported by a support member formed on the main surface.

In order to solve the above problems, a method for producing a hydrogel structure according to one embodiment of the present invention includes a patterning step in which a hydrogel that covers a main surface of a substrate and is swollen with water is irradiated with light to perform patterning, and a cutting step in which the hydrogel is cut into pieces of a predetermined size.

In order to solve the above problems, an intermediate hydrogel structure according to one embodiment of the present invention is an intermediate hydrogel structure comprising a substrate, a swollen hydrogel placed on the main surface of the substrate, and a sealing member that seals the substrate and the hydrogel together with water, and at least a portion of the side surface of the hydrogel is supported by a support member formed on the main surface.

According to one aspect of the present invention, it is possible to suppress the movement of swollen hydrogel during patterning by light irradiation.

1 is a flowchart of a method for producing a hydrogel structure according to a first embodiment of the present invention. 2A and 2B are a perspective view and a plan view of a substrate at the start of the manufacturing method of the hydrogel structure shown in FIG. 1 . 2A to 2C are plan views of a substrate in each step included in the method for producing the hydrogel structure shown in Figure 1. 5A and 5B are a plan view and a cross-sectional view of an intermediate of a hydrogel structure according to a second embodiment of the present invention. 4A to 4C are schematic diagrams showing a first modified example of a patterning step included in the method for producing the hydrogel structure shown in FIG. 1 . 1. FIG. 4 is a schematic diagram showing a second modified example of the patterning step included in the method for producing the hydrogel structure shown in FIG.

[Embodiment 1]
<Method for producing hydrogel structure>
A method M11 for producing a hydrogel structure according to a first embodiment of the present invention will be described with reference to Fig. 1 to Fig. 3. In the following, the method M11 for producing a hydrogel structure will also be simply referred to as the production method M11.

FIG. 1 is a flowchart of manufacturing method M11. FIG. 2 is a perspective view (left) and a plan view (right) of substrate 11 at the start of manufacturing method M11. FIG. 3 is a plan view of substrate 11 at each step included in manufacturing method M11.

2, the normal direction of the principal surfaces 111, 112 of the substrate 11 is defined as the z-axis direction, and among the in-plane directions of the principal surfaces 111, 112, the directions parallel to each side of the frame 12 are defined as the x-axis direction and the y-axis direction, respectively. The direction from the principal surface 112 toward the principal surface 111 is defined as the z-axis positive direction, and the x-axis positive direction and the y-axis positive direction are defined so as to form a left-handed Cartesian coordinate system together with the z-axis positive direction. This method of defining the Cartesian coordinate system is also common to the Cartesian coordinate system shown in FIG. 3.

As shown in FIG. 1, manufacturing method M11 includes a support formation process S11, a hydrogel formation process S12, a pigment dispersion process S13, a patterning process S14, a cleaning process S15, a deposition process S16, and a shrinkage process S17.

FIG. 2 shows the substrate 11 at the start of manufacturing method M11. FIG. 2 shows a schematic diagram of the substrate 11 and a frame body 12 formed on a main surface 111 of the substrate 11. Therefore, the ratios of the dimensions of the substrate 11 and the frame body 12 in FIG. 2 do not necessarily match the ratios of the dimensions in the actual products.

As shown in FIG. 2, the substrate 11 is a plate-like member having a pair of main surfaces 111, 112 that are parallel to each other. Furthermore, the shape of the substrate 11 is a square when the main surface 111 is viewed in a plan view from the positive direction of the z axis. Note that the shape of the substrate 11 is not limited to a square, and may be a quadrangle such as a rectangle, or may be a circle like a wafer. Furthermore, in the following, when referring to a plan view, this refers to the case where the main surface 111 is viewed in a plan view from the positive direction of the z axis.

The material constituting the substrate 11 is not limited, but is preferably a material that transmits the wavelength of light used as the signal light in the hydrogel structure 10 manufactured by manufacturing method M11 and in the optical composite device including the hydrogel structure 10. Examples of materials constituting the substrate 11 include glass materials such as quartz and semiconductor materials such as silicon. In this embodiment, silicon is used as the material for the substrate 11.

Alignment marks 113 are formed at each of the four corners of the main surface 111. In this embodiment, the shape of the alignment marks 113 is a cross, but the shape is not limited. In this embodiment, the alignment marks 113 are also made of a thin metal film. However, the material is not limited, and may be, for example, a resin such as a photoresist.

(Support formation process)
The support formation step S11 is a step of forming a frame body 12 on the main surface 111 (see FIG. 3). The frame body 12 is an example of a support member formed on the substrate 11. In this embodiment, the frame body 12 is annular (see FIG. 2).

The shape of the outer edge of the frame body 12 is a square in a plan view. The width of each of the four sides constituting the frame body 12 is uniform. Therefore, the shape of the recess 121 formed inside the frame body 12 is also a square in a plan view. The inner wall surface of the frame body 12, which defines the shape of the recess 121, is an example of a wall surface that supports at least a part (all of the side in this embodiment) of the side of the hydrogel swollen in the patterning process S14 described later. The inner wall surface of the frame body 12 can also be said to constitute a part of the side of the support member. The inner wall surface and the outer wall surface of the frame body 12 are formed so as to intersect with the main surface 111 (so as to be perpendicular in this embodiment). The shape of the outer edge of the frame body 12 and the recess 121 when viewed in a plan view is not limited to a square, but may be a quadrangle such as a rectangle, a polygon other than a quadrangle, or a shape without corners such as a circle or an ellipse.

In this embodiment, hydrogel is used as the material that constitutes the frame body 12. However, the material of the frame body 12 is not limited to this, and may be a resin, a metal, or an oxide.

When a hydrogel is used as the material for forming the frame body 12, the composition of the polymer that forms the hydrogel may be the same as the composition of the polymer that forms the hydrogel that forms the hydrogel structure, but it is preferable that the composition is different from the polymer. In other words, the hydrogel that forms the frame body 12 is preferably different from the hydrogel that forms the hydrogel structure. Here, the hydrogel that forms the frame body 12 preferably has a higher crosslink density than the hydrogel that forms the hydrogel structure. The crosslink density refers to the density of crosslinking points for the monomers that form the hydrogel, and is defined as "the number of crosslinking points/the number of monomer units." The crosslinking point refers to a point that bonds two or more main chains of the polymer that forms the hydrogel. The crosslinking point can be composed of, for example, a compound having two or more bonding parts such as diamine, or a monomer having two or more polymerization parts such as diacrylate, but is not limited to this. The crosslinking density of the hydrogel that forms the frame body 12 is preferably two or more times, more preferably five or more times, and most preferably ten or more times, the crosslinking density of the hydrogel that forms the hydrogel structure. The upper limit of the crosslink density of the hydrogel that constitutes the frame 12 is 1000 times or less based on the crosslink density of the hydrogel that constitutes the hydrogel structure.

Furthermore, when a hydrogel is used as the material constituting the frame body 12, the frame body 12, which is an example of a support member, is preferably made of a water retention agent. Examples of water retention agents include acrylic polymers having at least one of acrylic acid, acrylamide, polyvinyl alcohol, and PEG structures in the side chain, and copolymers of these acrylic polymers. Such acrylic polymers and copolymers of acrylic polymers are a form of hydrogel, and are widely used as water-absorbent polymers.

In addition, in this embodiment, the frame 12 is patterned by forming a film made of hydrogel and then using a photolithography method, but this is not limited to this.

In this embodiment, the length of each side of the square that forms the inner edge of the frame 12 is 10 mm. However, the length of each side is not limited to this and can be designed appropriately depending on the purpose of the hydrogel structure. The length of each side can be, for example, 1 mm or more and 100 mm or less.

In this embodiment, the height of the frame 12 is 1 mm. However, the height is not limited to this and can be designed appropriately depending on the contents of the hydrogel formation process S12 described below. The height can be 50 μm or more and 5 mm or less.

(Substrate processing process)
The manufacturing method M11 may further include a substrate treatment step (not shown in FIG. 1 ) performed before a hydrogel formation step S12 described later. The substrate treatment step may be performed before or after the support formation step S11.

The substrate treatment process is a process of performing a hydrophilic treatment on a partial area of the main surface 111 of the substrate 11. By carrying out the substrate treatment process, the force generated between the partial area of the main surface 111 and the partial area of the swollen hydrogel 13 can be made greater than the force generated between the area of the main surface 111 other than the partial area and the area of the swollen hydrogel 13 other than the partial area.

In one embodiment of manufacturing method M11, a sliding treatment may be performed in addition to the substrate treatment process. The sliding treatment is a treatment that reduces the force generated between the main surface 111 and the swollen hydrogel 13 in areas of the main surface 111 included in the recess 121 other than the partial area. In other words, it is a treatment that improves the sliding at the interface between the main surface 111 and the swollen hydrogel 13. Examples of the sliding treatment include a hydrophobic treatment and a water-repellent treatment. A specific example of the water-repellent treatment is the formation of a film or coating of a fluorine-based resin.

In the substrate processing step, a photoresist film is formed as a mask on the main surface 111 except for the aforementioned partial area. This mask can be appropriately formed using a microfabrication method such as photolithography or electron beam lithography.

Specific examples of hydrophilic treatments include acid treatment, plasma treatment, and ozone treatment. When these hydrophilic treatments are performed on the partial region, oxygen is exposed in a dense state in the partial region. Therefore, the partial region can utilize the force of hydrogen bonds to bond a hydrogel, which will be described later, to the main surface 111.

This configuration provides the following advantages in each process after the swollen hydrogel 13 is formed inside the recess 121 in the hydrogel formation process S12 described below. That is, it is possible to reduce the possibility that the hydrogel 13 will shift position or that the swollen hydrogel 13 will protrude outside the recess 121.

As a variation of the substrate processing step, the partial region may be subjected to a chemical treatment. Here, chemical treatment refers to a process of modifying the ends of the silicon constituting the surface of the partial region with a compound that bonds the substrate 11 with the swollen hydrogel described below.

Examples of compounds used in this chemical treatment include various compounds called silane coupling agents. In addition, it is preferable that the silane coupling agent contains at least one of a functional group capable of interacting with the hydrogel and a functional group capable of forming a covalent bond with the hydrogel.

Examples of silane coupling agents include chlorosilanes, alkoxysilanes, tetraethyl orthosilicate (TEOS), 3-aminopropyltriethoxysilane (APTS), and vinyltrimethoxysilane. The amino group contained in APTS can interact with the hydrogel. The methylene group contained in vinyltrimethoxysilane can form a covalent bond with the hydrogel by breaking the double bond. Therefore, the partial region can utilize the force of bonding via the compound to bond the hydrogel (described below) to the main surface 111.

In this embodiment, the case where the hydrophilic treatment is applied to the partial area of the main surface 111 has been described. However, the partial area to be hydrophilic treated can also be set on the inner wall surface of the frame body 12 instead of the main surface 111. In this case, the partial area on the inner wall surface of the frame body 12 is bonded to a partial area of the hydrogel 13 described below. Even with this configuration, it is possible to reduce the possibility that the hydrogel 13 will shift in position or that the swollen hydrogel 13 will protrude outside the recess 121.

(Hydrogel formation process)
The hydrogel formation step S12 is a step of forming a swollen hydrogel 13 at least inside the recesses 121 of the main surface 111 (see FIG. 3 ). In the hydrogel formation step S12, the inside of the recesses 121 is filled with a monomer that is a raw material for the swollen hydrogel 13, and the monomer is polymerized to obtain the swollen hydrogel 13.

In a modified example of the hydrogel formation process S12, a small piece of contracted hydrogel that has been preformed to a predetermined shape and dimensions can be placed in the recess 121, and water can be supplied to the small piece to cause it to swell, thereby obtaining a swollen hydrogel 13. The predetermined shape and dimensions of the contracted hydrogel can be determined appropriately based on the contraction rate (or expansion rate) of the hydrogel.

The material constituting the hydrogel 13 is not limited as long as it swells by absorbing moisture and shrinks by releasing moisture. Examples of materials constituting the hydrogel 13 include (meth)acrylates having a carboxylic acid unit in the side chain, (meth)acrylamides having an amide group in the side chain, (meth)acrylates having an amino group in the side chain, and PEGs having a polyethylene glycol chain in the side chain or main chain (hereinafter referred to as "acrylates, etc."). Preferred examples of materials constituting the hydrogel 13 include polymers and copolymers of acrylates, etc. Examples of materials constituting the hydrogel 13 include materials described in Patent Document 1 (e.g., FIG. 1A) and materials described in International Publication WO2022/176376 (e.g., FIG. 2).

The Implosion Fabrication (ImpFab) technology described in Patent Document 1 can be applied to the hydrogel formation process S12 and the subsequent pigment dispersion process S13, washing process S15, deposition process S16, and shrinkage process S17. Therefore, only a brief explanation of these processes will be given.

(Pigment dispersion process)
The pigment dispersion step S13 is a step carried out before the patterning step S14, and is a step of dispersing a pigment inside the swollen hydrogel 13.

(Patterning process)
The patterning step S14 is a step of patterning the hydrogel 13 by irradiating the hydrogel 13 placed on the main surface 111 and swollen with light to bond a dye to the swollen hydrogel 13. In the patterning step S14, at least a part of the side surface of the swollen hydrogel 13 is supported by the inner wall surface of the frame 12. In this embodiment, as shown in the plan view of the hydrogel formation step S12 in FIG. 3, the side surface of the swollen hydrogel 13 is surrounded by the inner wall surface of the frame 12, and the entire side surface of the swollen hydrogel 13 is supported by the inner wall surface of the frame 12.

In addition, in this embodiment, the dye is bonded to the hydrogel 13 using a two-photon absorption method. By carrying out the patterning step S14, when the main surface 111 is viewed in plan, the hydrogel 13 has regions in which the content of the bound dye has a spatial distribution and regions in which the dye is not bound.

(Washing process)
The cleaning process S15 is a process carried out after the patterning process S14, and is a process for cleaning out the pigment dispersed inside the hydrogel 13 swollen by the pigment dispersion process S13, which is not bound to the swollen hydrogel 13.

(Deposition process)
The deposition step S16 is a step of further modifying the dye bonded to the inside of the swollen hydrogel 13 with functional particles or molecules. Examples of these include fine metal particles (e.g., nanoparticles), fluorescent particles, proteins, DNA, etc. In this embodiment, gold nanoparticles are modified with the dye.

The deposition step S16 may further include a step of further growing the modified particles, or a step of reacting the modified molecules with a further compound. In this embodiment, the particle size of the metal particles is increased by depositing silver on the surface of the above-mentioned gold nanoparticles.

The metal particles contained in the hydrogel 13 change the refractive index of the hydrogel 13. Therefore, when signal light is incident on the hydrogel 13 and passes through the hydrogel 13, the amount of phase modulation in the signal light can be increased. This amount of phase modulation depends on the amount of metal particles contained in the hydrogel 13. Therefore, it can be said that this amount of phase modulation depends on the amount of pigment contained in the hydrogel 13, and further, on the amount of light irradiated to each area of the hydrogel 13 in the patterning process S14.

The area patterned in the patterning step S14 (area irradiated with light) where the dye has a spatial distribution becomes an optically effective area 132 where the amount of phase modulation is spatially distributed by carrying out the deposition step S16 (see the plan view of the patterning step S14 in FIG. 3). On the other hand, the area not patterned in the patterning step S14 (area not irradiated with light) where the dye is not bonded becomes an optically ineffective area 133 where the amount of phase modulation is constant. In this way, when the main surface 111 is viewed in a plan view, the swollen hydrogel 13 has an optically effective area 132 where the amount of phase modulation has a spatial distribution, and an optically ineffective area 133 where the amount of phase modulation is constant.

In addition, by appropriately selecting particles or molecules to modify the dye in the deposition process S16, it is possible to impart a spatial distribution of absorptance to the optically effective region 132. In this way, the optically effective region 132 is a region in which at least one of the absorptance and the amount of phase modulation has a spatial distribution, and the optically ineffective region 133 is a region in which the absorptance and the amount of phase modulation are constant.

In the plan view of the patterning step S14 and the contraction step S17 in Fig. 3, the center of gravity P _C of the swollen hydrogel 13 and the center of gravity P _C of the contracted hydrogel 13 are respectively illustrated by open circles. The center of gravity P _C is the intersection of two diagonals of the square-shaped hydrogel 13. In this embodiment, the contraction rate of the hydrogel 13 is set to 1/2. However, the contraction rate of the swollen hydrogel 13 is not limited to 1/2. This contraction rate can be appropriately designed depending on the selection of the material constituting the swollen hydrogel 13.

(Shrinkage process)
The contraction step S17 is a step of contracting the swollen hydrogel 13 (see the plan view of the contraction step S17 in FIG. 5 ). As described above, the contraction rate of the hydrogel 13 is 1/2, so that the length of each side of the hydrogel 13 is contracted to 1/2.

As described above, by carrying out manufacturing method M11, a hydrogel structure 10 is produced (see the plan view of contraction step S17 in FIG. 3). In one aspect of the present invention, a post-processing step, which will be described later, may be carried out after carrying out contraction step S17. By carrying out the post-processing step, an optical composite device including the hydrogel structure 10 is produced.

(Post-processing)
The manufacturing method M11 may include post-processing steps not shown in Fig. 1. The post-processing steps include a lamination step, an alignment step, and a bonding step.

The post-processing step uses the hydrogel structure 10 produced by manufacturing method M11, a light source module, and a light detection module.

As described above, the hydrogel structure 10 is manufactured by the manufacturing method M11. In this embodiment, the center of gravity P _C shown in the plan view of the contraction step S17 in FIG. 3 coincides with the optical axis A ₁ of the hydrogel 13 in the hydrogel structure 10.

The light source module is a light source that irradiates signal light to be incident on the hydrogel 13 of the hydrogel structure 10. The light source module includes a substrate and a light-emitting device provided on the main surface of the substrate. The light-emitting device may be a light-emitting diode, a laser diode, or a liquid crystal panel.

In this embodiment, the shape and dimensions of the substrate of the light source module are the same as those of substrate 11. Furthermore, an alignment mark is formed at each of the four corners of the main surface of the substrate. The shape of the alignment marks is the same as that of alignment mark 113. Furthermore, the position of each alignment mark on the main surface of the substrate corresponds to the position of each alignment mark 113 on main surface 111. Therefore, when the substrate 11 and the substrate of the light source module are overlapped so that their outer edges coincide with each other in a plan view, each alignment mark 113 and each alignment mark of the light source module are perfectly overlapped.

The light source module may further include an optical system provided downstream of the light emitting device. This optical system can be used to collimate the signal light emitted by the light emitting device.

In this embodiment, the optical axis of the light emitting device in the light source module corresponds to the optical axis _A1 of the hydrogel 13. Therefore, when the outer edge of the substrate 11 and the outer edge of the substrate of the light source module are overlapped so as to coincide with each other in a plan view, the optical axis _A1 and the optical axis of the light source module are perfectly overlapped.

The light detection module is a photodetector that detects signal light emitted by the light emitting device of the light source module and transmitted through the hydrogel 13 of the hydrogel structure 10. The light detection module includes a substrate and a light receiving device 33 provided on the main surface of the substrate. A specific example of the light receiving device is a photodiode.

In this embodiment, the shape and dimensions of the substrate of the light detection module are the same as those of substrate 11. Furthermore, an alignment mark is formed at each of the four corners of the main surface of the substrate. The shape of the alignment marks is the same as that of alignment mark 113. Furthermore, the position of each alignment mark on the main surface of the substrate corresponds to the position of each alignment mark 113 on main surface 111. Therefore, when the substrate 11 and the substrate of the light detection module are overlapped so that their outer edges coincide with each other in a plan view, each alignment mark 113 and each alignment mark of the light detection module are perfectly overlapped.

In this embodiment, the optical axis of the light receiving device in the light detection module corresponds to the optical axis _A1 of the hydrogel 13. Therefore, when the outer edge of the substrate 11 and the outer edge of the substrate of the light detection module are overlapped with each other so that they coincide with each other in a plan view, the optical axis _A1 and the optical axis of the light detection module are perfectly overlapped with each other.

Using the hydrogel structure 10, light source module, and light detection module configured in this manner, each step of the post-processing process is carried out as follows.

The lamination process is a process of stacking the hydrogel structure 10, the light source module, and the light detection module. At this point, the substrates have only been stacked, so the alignment between the substrates has not been adjusted.

Although not shown in FIG. 2, spacers that define the distance between the substrates may be interposed between the substrate of the light source module and substrate 11, and between substrate 11 and the substrate of the light detection module.

The alignment process is a process of adjusting the alignment of the substrate of the light source module, the substrate 11, and the substrate of the light detection module so that the optical axis _A1 , the optical axis of the light source module, and the optical axis of the light detection module coincide with each other. As a method for adjusting this alignment, an existing adjustment method can be appropriately used.

The bonding process is a process of bonding the substrate of the light source module to substrate 11, and bonding substrate 11 to the substrate of the light detection module, with the optical axes of the above-mentioned components aligned. In this embodiment, the substrates are bonded together using a resin adhesive. However, the bonding means for bonding the substrates together is not limited to such adhesives and can be selected as appropriate.

As described above, an optical composite device including a hydrogel structure 10 is manufactured by carrying out manufacturing method M11, which includes a post-treatment process.

<Application examples of the hydrogel structure 10>
As described above, the optically effective region 132 in which at least one of the absorptance and the phase modulation amount has a spatial distribution is formed in the swollen hydrogel 13 included in the hydrogel structure 10. The optically effective region 132 configured in this manner can be made to function in the same manner as the optical diffraction element illustrated in FIG. 10 of International Publication WO2022/176555.

In addition, in the patterning step S14 of manufacturing method M11, the swollen hydrogel 13 is patterned using the two-photon absorption method, so that a multi-stage optical diffraction element can be formed inside one hydrogel 13. Therefore, the hydrogel 13 not only functions as a single-stage optical diffraction element, but also functions as an optical computing device equipped with a multi-stage optical diffraction element.

The optical composite device also includes a light source module and a light detection module in addition to the hydrogel structure 10 containing the contracted hydrogel 13. Therefore, the optical composite device is an optical computing system that compactly integrates a light source that inputs signal light to the optical computing device and a light detector that detects the signal light output from the optical computing device. In addition, in the optical composite device, the alignment of each substrate in the hydrogel structure 10, the light source module, and the light detection module can be easily adjusted, so that each optical axis in the optical computing system can be easily aligned.

As described above, one aspect of the present invention includes an optical diffraction element including a substrate 11 and a contracted hydrogel 13 having an optically effective area 132 in which at least one of the absorbance and the amount of phase modulation has a spatial distribution.

[Embodiment 2]
<Intermediate of hydrogel structure>
An intermediate 5 according to a second embodiment of the present invention and an intermediate 6, which is a modified example thereof, will be described with reference to Fig. 4. Fig. 4 is a plan view of the intermediate 5 and the intermediate 6. Fig. 4 also shows a cross-sectional view of the intermediate 5. This cross-sectional view is obtained by viewing a cross section taken along line A-A' shown in the plan view of the intermediate 5. Both the intermediate 5 and the intermediate 6 are intermediates for producing a hydrogel structure such as the hydrogel structure 10. The method for determining the orthogonal coordinate system shown in Fig. 4 is the same as the method for determining the orthogonal coordinate system shown in Fig. 1.

The intermediate body 5 includes a hydrogel structure 50, a sealing member 54, and water 55. The hydrogel structure 50 includes a substrate 51, a frame 52, and a swollen hydrogel 53.

The substrate 51 corresponds to the substrate 11 of the hydrogel structure 10 described in the first embodiment. However, in this embodiment, a silicon wafer is used as the substrate 51. In the hydrogel structure 10, the substrate 11 is configured so that one swollen hydrogel 13 is placed on the main surface 111 (see the plan view of the hydrogel formation step S12 in FIG. 3). In contrast, in the hydrogel structure 50, the substrate 51 is configured so that multiple swollen hydrogels 53 can be placed on one main surface. In the intermediate body 5 manufactured in this manner, at least a part (all of it in this modified example) of the side surface of the hydrogel 53 is supported by the inner surface (one aspect of the wall surface) of the frame body 52.

Furthermore, four alignment marks 513 are formed on the main surface of the substrate 51. The alignment marks 513 correspond to the alignment marks 113 formed on the main surface 111 of the substrate 11.

A frame 52 is formed on the main surface of the substrate 51 so as to avoid the area where the four alignment marks 513 are formed. The frame 52 is made of hydrogel like the frame 12. However, unlike the frame 12, the frame 52 is required to define the positions of multiple swollen hydrogels 53. Therefore, as shown in the plan view of the intermediate body 5 in Figure 4, the frame 52 has 48 recesses formed in a grid pattern so that 48 swollen hydrogels 53 can be placed on it. Therefore, unlike the frame 12, which is annular, the shape of the frame 52 is a lattice pattern. All of these 48 recesses have the same shape and dimensions, and are formed periodically in each of the x-axis and y-axis directions.

In each recess, a swollen hydrogel 53 similar to the swollen hydrogel 13 is placed. That is, the hydrogel structure 50 has 48 swollen hydrogels 53. As described above, since the 48 recesses of the frame body 52 are formed periodically, the centers of gravity of the 48 swollen hydrogels 53 contained in those recesses are also arranged periodically.

The sealing member 54 seals the substrate 51 and the multiple swollen hydrogels 53 together with the water 55. In this embodiment, the sealing member 54 is composed of two resin sheets. Each sheet is rectangular in plan view, and is formed into a bag shape by fusing the areas along the outer edges. In this way, by sealing the hydrogel structure 50 together with the sealing member 54, the hydrogel structure 50 can be stored without the swollen hydrogels 53 shrinking due to dehydration.

Note that the sealing member 54 is not limited to the bag-like shape shown in FIG. 4, as long as it can seal the hydrogel structure 50 and the sealing member 54. The sealing member 54 may be shaped like a wafer tray that holds wafers one by one, or like a wafer case that holds multiple wafers together.

<Modification of the intermediate of the hydrogel structure>
In the above-described hydrogel structure 50, the frame 52 is used to define the positions of the multiple swollen hydrogels 53. However, in the intermediate 6, which is a modified example of the intermediate 5, the swollen hydrogel is formed so as to cover the main surface of the substrate, making it possible to omit the frame 52. In this modified example, a configuration in which the frame 52 is omitted will be described.

The intermediate 6 includes a hydrogel structure 60, a sealing member 64, and water 65. The sealing member 64 and the water 65 correspond to the sealing member 54 and the water 55, respectively, and therefore will not be described here.

The hydrogel structure 60 includes a substrate 61 and a swollen hydrogel 63. The substrate 61 and the alignment marks 613 formed on the main surface of the substrate 61 correspond to the substrate 51 and the alignment marks 513 formed on the main surface of the substrate 51, respectively, and therefore will not be described here.

In the hydrogel structure 60, no frame is formed on the main surface of the substrate 61. Therefore, in the hydrogel formation step S12, a solid film of swollen hydrogel is formed over the entire main surface of the substrate 61. In other words, the swollen hydrogel covers the main surface of the substrate 61.

In addition, in the manufacturing method M11 for manufacturing the hydrogel structure 60, after the hydrogel formation step S12, a cutting step is performed in which the swollen hydrogel of the solid film is cut into swollen hydrogels 63 having a predetermined shape and size. As shown in the plan view of the intermediate 6 in FIG. 4, a plurality of swollen hydrogels 63 are obtained by making lattice-shaped cut lines 62 in the swollen hydrogel of the solid film. The number of swollen hydrogels 63 in the hydrogel structure 60 is 48, which is the same as the number of swollen hydrogels 53 in the hydrogel structure 50. In the intermediate 6 manufactured in this manner, at least a part of the side of the hydrogel 63 (all of it in this modified example) is supported by the side of the adjacent swollen hydrogel 63 (one aspect of the wall surface).

The manufacturing method M11 for manufacturing the hydrogel structure 60 includes a patterning step S14 and a cutting step, similar to the manufacturing method M11 shown in FIG. 1. In this manufacturing method M11, it does not matter whether the patterning step S14 or the cutting step is performed first.

[Modification of the patterning process]
Hereinafter, a first modified example and a second modified example of the patterning step S14 included in the manufacturing method M11 of the hydrogel structure shown in FIG. 1 will be described with reference to FIG. 5 and FIG. 6, respectively. FIG. 5 and FIG. 6 are schematic diagrams showing a first modified example and a second modified example of the patterning step S14, respectively. More specifically, FIG. 5 is a plan view and a cross-sectional view of the hydrogel structure 70 patterned in the first modified example, and FIG. 6 is a cross-sectional view of the hydrogel structure 70 patterned in the second modified example. In addition, in the cross-sectional views of FIG. 5 and FIG. 6, the z-axis direction is exaggerated in order to make the structure in the z-axis direction easier to understand. In addition, the method of determining the orthogonal coordinate system shown in FIG. 5 and FIG. 6 is the same as the method of determining the orthogonal coordinate system shown in FIG. 1.

<First Modification>
The medium to be patterned in the first modified example is a hydrogel structure 70 (see FIG. 5). The hydrogel structure 70 includes a substrate 71, an alignment mark 713, a frame 72, a plurality of swollen hydrogels 73, and a dam 74. The hydrogel structure 70 is a modified example of the hydrogel structure 50 shown in FIG. 4. That is, (1) substrate 71, (2) alignment mark 713, (3) frame 72, and (4) swollen hydrogel 73 in the hydrogel structure 70 correspond to (1) substrate 51, (2) alignment mark 513, (3) frame 52, and (4) swollen hydrogel 53 in the hydrogel structure 50, respectively. Therefore, here, explanations regarding the substrate 71, the alignment mark 713, the frame 72, and the swollen hydrogel 73 are omitted.

Note that, as shown in the cross-sectional view of FIG. 5, a configuration is adopted in which the height of the swollen hydrogel 73 (the length from the main surface 711 of the substrate 71 to the top end of the swollen hydrogel 73) exceeds the height of the frame body 72 (the length from the main surface 711 to the top end of the frame body 72). However, the relationship between the height of the swollen hydrogel 73 and the height of the frame body 72 is not limited to this and can be determined as appropriate.

The dam 74 is a wall-like member formed to surround the frame 72 (including the inner wall surface surrounding the swollen hydrogel 73) when the main surface 711 of the substrate 71 is viewed in plan. As shown in the plan view of FIG. 5, the dam 74 is formed in a ring shape along the outer edge of the substrate 71. Also, as shown in the cross-sectional view of FIG. 5, the dam 74 is formed to intersect with the main surface 711, and its bottom surface is in close contact with the main surface 711 without any gaps.

In this modified example, as shown in the cross-sectional view of FIG. 5, the height of the weir 74 (the length from the main surface 711 to the top end of the weir 74) is preferably higher than the height of the frame body 72. With this configuration, water is poured into the inner region 741 (i.e., inside the frame body 72) surrounded by the weir 74, and the water is stored in the inner region 741. Since the water level stored in the inner region 741 exceeds the height of the frame body 72, water can be supplied to the swollen hydrogel 73 via the frame body 72. Here, the water level means the depth of the water stored in the inner region 741 in the region where surface tension is not acting (i.e., the region where the surface is horizontal). If the substrate 71 is placed so that the main surface 711 is horizontal in the patterning step S14, the water level can be said to be uniform.

Moreover, it is more preferable that the height of the weir 74 is higher than the height of each of the frame body 72 and the swollen hydrogel 73. With this configuration, when water is poured into the inner region 741, the water level exceeds the height of the frame body 72 and the swollen hydrogel 73, so that water can be directly supplied to the swollen hydrogel 73. Furthermore, since the water level exceeds the height of the frame body 72 and the swollen hydrogel 73, a water immersion lens can be used as the objective lens 81 described later (see the cross-sectional view of FIG. 5). Furthermore, since a large amount of water can be stored in the inner region 741, even if the water supply device 82 described later is not used, it is possible to prevent the swollen hydrogel 73 from shrinking due to dehydration over a long period of time.

The material constituting the weir 74 may be a material that allows water to penetrate when water is poured into the inner region 741, but is preferably a material that can store water for a predetermined period of time. It is more preferable that this material is a material that does not allow water to penetrate. This configuration makes it possible to prevent the water stored in the inner region 741 from leaking outside the weir 74.

In this embodiment, resin is used as the material that constitutes the dam 74. However, the material of the dam 74 is not limited to this, and may be a metal or an oxide (e.g., glass).

As shown in the cross-sectional view of FIG. 5, in a first modified example of the patterning process S14, water is stored in the inner region 741 of the weir 74. Here, the exposure device used in the patterning process S14 includes an objective lens 81 and a water supply device 82.

The objective lens 81 constitutes part of the optical system of an exposure device that performs patterning on the swollen hydrogel 73 by irradiating the swollen hydrogel 73 with light. In this modified example, a water immersion lens is used as the objective lens 81. When using a water immersion lens as the objective lens 81 in this manner, it is preferable that the height of the weir 74 exceeds the working distance of the objective lens 81. With this configuration, when interposing water between the swollen hydrogel 73 and the exit surface of the objective lens 81, there is no need to rely on the surface tension of the water, and the exit surface of the objective lens 81 can be reliably immersed in water.

However, when the patterning step S14 is performed in a state where the water level in the inner region 741 is lower than the height of the swollen hydrogel 73 and the upper end of the swollen hydrogel 73 is exposed to air, a lens used with its exit surface in contact with air (a so-called dry lens) can also be used as the objective lens 81. Note that even if the water level in the inner region 741 is lower than the height of the swollen hydrogel 73, a water immersion lens can also be used as the objective lens 81. That is, as will be described later as one aspect of the first modified example, water is interposed between the exit surface of the objective lens 81 and the swollen hydrogel 73 to which light is irradiated.

Furthermore, the water supply device 82 is an example of a means for constantly or intermittently supplying water to the swollen hydrogel 73 placed in the inner region 741. Therefore, in this modified example, water is constantly or intermittently supplied to the swollen hydrogel 73. In this modified example, a dropper is used as an example of the water supply device 82 (see the cross-sectional view of FIG. 5). However, the water supply device 82 is not limited to a dropper, and may be a syringe or a pump. Furthermore, the water supply device 82 may be a manual device in which the amount of water supplied is controlled by an operator, or may be an automatic device controlled by a computer.

Furthermore, it is preferable that the water supply device 82 is configured to supply an amount of water close to the amount of water evaporating per unit time in the inner region 741. Moreover, it is more preferable that the water supply device 82 is configured to supply an amount of water equal to the amount of water evaporating per unit time. Examples of water supply devices capable of continuously supplying a small amount of water per unit time include a microsyringe pump, a microfeeder, a dosing pump, and a tube pump.

As described above, in the first modified example, a configuration is adopted in which water is supplied from a water supply device 82 so that water is continuously present between the exit surface of the objective lens 81 used for light irradiation and the swollen hydrogel 73 that is irradiated with light.

In the first modified example, the height of the weir 74 is configured to be higher than the height of the frame 72 and to exceed the working distance of the objective lens 81. With this configuration, water can be interposed between the exit surface of the objective lens 81, which is a water immersion lens, and the swollen hydrogel 73 on which patterning is performed (i.e., irradiated with light) without substantially using the surface tension of water. However, in one aspect of the first modified example, water can also be interposed between the exit surface and the swollen hydrogel 73 on which patterning is performed by using the surface tension of water. In this case, the height of the weir 74 may be lower than the working distance, or may be lower than the height of the frame 72, or the weir 74 may even be omitted.

As described above, when the surface tension of water is utilized in the patterning step S14, it is preferable that the water supply device 82 supplies water so that water continues to be present between the exit surface of the objective lens 81 and the swollen hydrogel 73 irradiated with light. To achieve this, it is preferable that the position where the water supply device 82 supplies water is in the vicinity of the objective lens 81 or on the side of the objective lens 81, and that the timing and amount of water supplied by the water supply device 82 are appropriately set. When the water supply device 82 supplies water to the side of the objective lens 81, the supplied water flows down the side of the objective lens 81 and reaches between the exit surface of the objective lens 81 and the swollen hydrogel 73 irradiated with light. According to one aspect of the first modified example, it is possible to prevent the water present between the exit surface and the swollen hydrogel 73 from drying up. Therefore, even if the patterning process S14 is performed for a long period of time, the objective lens 81 can be appropriately used as a water immersion lens.

As described above, in the first modified example and one aspect thereof, the water between the exit surface and the irradiated swollen hydrogel 73 may or may not utilize surface tension. In other words, the water level may be located either above or below the exit surface. In addition, the water between the exit surface and the irradiated swollen hydrogel 73 may be (1) in a puddle-like state (as shown in FIG. 5) that uniformly covers the entire main surface, or (2) in a droplet-like state (not shown) that covers only a part of the main surface in the region including the swollen hydrogel 73 that is irradiated with light in the patterning step S14. In the former case, the depth of the water from the main surface is uniform. On the other hand, in the latter case, the depth of the water from the main surface (i.e., the thickness of the water droplet from the main surface) is not uniform, but has a distribution according to the surface tension. In the latter case, it is preferable that the water covers the surface of the frame body 72. By covering the surface of the frame 72 with water, it is possible to reliably reduce dehydration not only in the swollen hydrogel 73 that is irradiated with light in the patterning process S14, but also in the swollen hydrogel 73 that is not irradiated with light.

<Second Modification>
The medium to be patterned in the second modified example is the hydrogel structure 70, as in the first modified example (see FIG. 6), and therefore a description of the hydrogel structure 70 will be omitted here.

The exposure device used in this modified example includes a chamber 83 and a humidifier 84 in addition to the configuration of the exposure device used in the first modified example (see Figure 6).

The chamber 83 is an example of a box that separates an internal space 831 from an external space 832, which is a space other than the internal space 831. The chamber 83 accommodates at least an objective lens 81 of the optical system of the exposure apparatus and a medium to be patterned (the hydrogel structure 70 in this modified example) in the internal space 831. The chamber 83 is preferably airtight so as not to leak water vapor introduced from a humidifier 84, which will be described later, and to maintain a high relative humidity H _I in the internal space 831. An example of such a box other than a chamber is a glove box.

The humidifier 84 increases the relative humidity of the atmosphere by releasing water vapor. The method by which the humidifier 84 releases water vapor is not limited. In this modified example, the humidifier 84 is placed in the external space 832 of the chamber 83, and the water vapor released from the humidifier 84 is introduced into the internal space 831. However, the humidifier 84 may also be placed in the internal space 831 and configured to release water vapor directly into the internal space 831.

As described above, the chamber 83 is airtight, and water vapor is introduced into the internal space 831. Therefore, in this modification, the relative humidity H _I of the internal space 831 accommodating the hydrogel structure 70 exceeds the relative humidity H _O of the external space 832. This configuration makes it possible to reduce the amount of evaporation per unit time of the water 75 stored in the dam 74 during the period in which patterning is being performed. Moreover, the relative humidity H _I is preferably 90% RH or higher, and more preferably 100% RH.

In this modified example, since the amount of evaporation per unit time can be reduced, the water supply device 82 shown in FIG. 5 can be omitted. In addition, since a large amount of water vapor exists in the internal space 831 in this modified example, this water vapor can be used to maintain the hydrogel 73 in a swollen state. Therefore, in this modified example, the dam 74 provided on the main surface 711 of the substrate 71 can be omitted. Even in this case, a water immersion lens can be used as the objective lens 81 by using the surface tension of water to place water droplets between the swollen hydrogel 73 and the exit surface of the objective lens 81.

Furthermore, as explained in the first modified example, when the patterning step S14 is performed in a state where the upper end of the swollen hydrogel 73 is exposed to air, it is preferable to use, as the objective lens 81, a lens that is used with its exit surface in contact with air (a so-called dry lens).

〔summary〕
The method for producing a hydrogel structure according to the first aspect of the present invention includes a patterning step in which a hydrogel placed on a main surface of a substrate and swollen with water is patterned by irradiating the hydrogel with light, and in the patterning step, at least a portion of the side surface of the hydrogel is supported by a support member formed on the main surface.

With the above configuration, the hydrogel has limited freedom of movement in the in-plane direction of the main surface because at least a portion of the side surface is supported by the support member. Therefore, this manufacturing method can suppress the movement of the swollen hydrogel during patterning by light irradiation.

In the method for producing a hydrogel structure according to the second aspect of the present invention, in addition to the configuration of the method for producing a hydrogel structure according to the first aspect described above, a configuration is adopted in which, in the patterning step, the swollen hydrogel is supported by the wall surface of the support member, and the wall surface is formed so as to intersect with the main surface.

The above configuration can reliably suppress the movement of the swollen hydrogel during patterning by light irradiation.

In the method for producing a hydrogel structure according to the third aspect of the present invention, in addition to the configuration of the method for producing a hydrogel structure according to the first or second aspect described above, a configuration is adopted in which the side surface is surrounded by the support member in the patterning step.

The above configuration makes it possible to suppress the movement of the swollen hydrogel in all directions during patterning by light irradiation.

In the method for producing a hydrogel structure according to the fourth aspect of the present invention, in addition to the configuration of the method for producing a hydrogel structure according to the third aspect described above, a configuration is adopted in which, in the patterning step, all of the side surfaces are supported by the support member.

The above configuration makes it possible to reliably suppress the movement of the swollen hydrogel in all directions during patterning by light irradiation.

In the method for producing a hydrogel structure according to the fifth aspect of the present invention, in addition to the configuration of the method for producing a hydrogel structure according to any one of the first to fourth aspects described above, the support member is made of a water retention agent.

With the above configuration, moisture can be supplied to the hydrogel from the support member made of a water retention agent during the patterning process. Therefore, this manufacturing method can suppress the shrinkage of the swollen hydrogel.

In the method for producing a hydrogel structure according to the sixth aspect of the present invention, in addition to the configuration of the method for producing a hydrogel structure according to the fifth aspect described above, the water retention agent is a hydrogel different from the swollen hydrogel and has a higher crosslink density than the swollen hydrogel.

With the above configuration, the hydrogel constituting the support member has a higher crosslink density than the swollen hydrogel, so the support member can firmly support the swollen hydrogel.

The method for producing a hydrogel structure according to the seventh aspect of the present invention employs the same configuration as the method for producing a hydrogel structure according to any one of the first to sixth aspects described above, and further employs a configuration in which water is supplied to the swollen hydrogel either constantly or intermittently in the patterning step.

The above configuration makes it possible to suppress the contraction of the swollen hydrogel for a long period of time. Therefore, even when performing complex patterning that requires a long period of time, it is possible to suppress the contraction of the swollen hydrogel.

In the method for producing a hydrogel structure according to the eighth aspect of the present invention, in addition to the configuration of the method for producing a hydrogel structure according to any one of the first to seventh aspects described above, in the patterning step, (1) the substrate, the swollen hydrogel, and the support member are contained in the internal space of a box, and (2) the relative humidity of the internal space is higher than the relative humidity of the external space, which is a space other than the internal space.

The above configuration makes it possible to suppress the shrinkage of the swollen hydrogel.

In the method for producing a hydrogel structure according to the ninth aspect of the present invention, in addition to the configuration of the method for producing a hydrogel structure according to any one of the first to eighth aspects described above, a dam is formed that surrounds the support member and has a height from the main surface that is higher than that of the support member when the main surface is viewed in plan, and water is stored inside the dam during the patterning process.

The above configuration makes it possible to suppress the contraction of the swollen hydrogel for a long period of time. Therefore, even when performing complex patterning that requires a long period of time, it is possible to suppress the contraction of the swollen hydrogel.

In the method for producing a hydrogel structure according to the tenth aspect of the present invention, in addition to the configuration of the method for producing a hydrogel structure according to the ninth aspect described above, the height of the weir exceeds the working distance of the objective lens used for light irradiation in the patterning process, and in the patterning process, the exit surface of the objective lens is immersed in water stored inside the weir.

With the above configuration, a water immersion lens can be used as the objective lens used for light irradiation in the patterning process.

In the method for producing a hydrogel structure according to the eleventh aspect of the present invention, in addition to the configuration of the method for producing a hydrogel structure according to any one of the first to tenth aspects described above, a configuration is adopted in which water is supplied in the patterning step so that water is continuously present between the exit surface of the objective lens used for light irradiation and the swollen hydrogel irradiated with the light.

With the above configuration, the amount of water between the exit surface and the swollen hydrogel that is irradiated with light (i.e., the swollen hydrogel that is the target of patterning) is reduced through the patterning process, making it possible to prevent the exit surface from being exposed.

The method for producing a hydrogel structure according to the twelfth aspect of the present invention employs a configuration including a patterning step in which a hydrogel that covers the main surface of a substrate and is swollen with water is patterned by irradiating the hydrogel with light, and a cutting step in which the hydrogel is cut into pieces of a predetermined size.

According to the above configuration, the hydrogel swollen with water covers the main surface. Therefore, compared to when the swollen hydrogel is formed only on a part of the main surface, the swollen hydrogel is less likely to move in the in-plane direction of the main surface. Note that in this manufacturing method, it does not matter which process, the patterning process or the cutting process, is performed first. Even if the cutting process is performed before the patterning process, the sides of the cut hydrogels are in contact with each other, so the degree of freedom of movement in the in-plane direction of the main surface is limited compared to when the swollen hydrogel is formed only on a part of the main surface.

In addition, the method for producing a hydrogel structure according to the thirteenth aspect of the present invention further includes, in addition to the configuration of the method for producing a hydrogel structure according to any one of the first to twelfth aspects described above, a pigment dispersion step performed before the patterning step and a washing step performed after the patterning step, in which the pigment dispersion step is a step of dispersing a pigment inside the swollen hydrogel, the patterning step is a step of bonding the pigment to the swollen hydrogel by irradiating the swollen hydrogel with the light, and the washing step is a step of washing the pigment that is not bonded to the swollen hydrogel among the pigments dispersed inside by the pigment dispersion step.

The method for producing a hydrogel structure according to one aspect of the present invention can be suitably applied to ImpFab.

The intermediate hydrogel structure according to the fourteenth aspect of the present invention is an intermediate hydrogel structure comprising a substrate, a swollen hydrogel placed on the main surface of the substrate, and a sealing member that seals the substrate and the hydrogel together with water, and is configured such that at least a portion of the side surface of the hydrogel is supported by a support member formed on the main surface.

The intermediate of the hydrogel structure according to one embodiment of the present invention has the same effect as the method for producing the hydrogel structure according to one embodiment of the present invention.

[Summary 2]
A method for producing a hydrogel structure according to a first aspect of the present invention includes patterning a hydrogel placed on a main surface of a substrate and swollen with water by irradiating the hydrogel with light, and supporting a side surface of the hydrogel by a frame formed on the main surface of the substrate when patterning the hydrogel.

The method for producing a hydrogel structure according to the second aspect of the present invention is the method for producing a hydrogel structure according to the first aspect, in which supporting the side surface of the hydrogel includes supporting the hydrogel with a wall surface of the frame formed so as to intersect with the main surface of the substrate.

The method for producing a hydrogel structure according to the third aspect of the present invention is the method for producing a hydrogel structure according to the first aspect, in which supporting the side surface of the hydrogel includes surrounding the side surface of the hydrogel with the frame body.

The method for producing a hydrogel structure according to the fourth aspect of the present invention is the method for producing a hydrogel structure according to the third aspect, in which supporting the side surface of the hydrogel includes supporting the entire side surface of the hydrogel with the frame.

The method for producing a hydrogel structure according to the fifth aspect of the present invention is the method for producing a hydrogel structure according to the first aspect, in which the frame is made of a water retention agent.

The method for producing a hydrogel structure according to the sixth aspect of the present invention is the method for producing a hydrogel structure according to the fifth aspect, in which the water retention agent is a hydrogel different from the swollen hydrogel and has a higher crosslink density than the swollen hydrogel.

The method for producing a hydrogel structure according to the seventh aspect of the present invention is the method for producing a hydrogel structure according to the first aspect, and further comprises supplying water to the hydrogel either constantly or intermittently when patterning the hydrogel.

The method for producing a hydrogel structure according to the eighth aspect of the present invention is the method for producing a hydrogel structure according to the first aspect, and further comprises accommodating the substrate, the hydrogel, and the frame in the internal space of a box when patterning the hydrogel, and setting the relative humidity of the internal space higher than the relative humidity of an external space other than the internal space.

The method for producing a hydrogel structure according to the ninth aspect of the present invention is the method for producing a hydrogel structure according to the first aspect, further comprising forming a dam that surrounds the frame when the main surface of the substrate is viewed in a plan view and has a height from the main surface of the substrate greater than that of the frame, and storing water inside the dam when patterning the hydrogel.

The method for producing a hydrogel structure according to the tenth aspect of the present invention is the method for producing a hydrogel structure according to the ninth aspect, in which the height of the weir exceeds the working distance of an objective lens used when irradiating the hydrogel with light, and when patterning the hydrogel, the exit surface of the objective lens is immersed in water stored inside the weir.

The method for producing a hydrogel structure according to an eleventh aspect of the present invention is the method for producing a hydrogel structure according to the first aspect, and further comprises supplying water so that water is continuously present between the hydrogel and the exit surface of an objective lens used to irradiate the hydrogel with light when patterning the hydrogel.

The method for producing a hydrogel structure according to the twelfth aspect of the present invention includes patterning the hydrogel by irradiating light onto the hydrogel that covers the main surface of a substrate and is swollen with water, and cutting the hydrogel into pieces of a predetermined size.

The method for producing a hydrogel structure according to the thirteenth aspect of the present invention is the method for producing a hydrogel structure according to the first aspect, further comprising dispersing a dye inside the hydrogel before patterning the hydrogel, patterning the hydrogel includes bonding the dye to the hydrogel by irradiating the hydrogel with the light, and the method further comprises washing out the dye that is not bonded to the hydrogel from among the dyes dispersed inside the hydrogel after patterning the hydrogel.

The method for producing a hydrogel structure according to the 14th aspect of the present invention is the method for producing a hydrogel structure according to the 12th aspect, further comprising dispersing a dye inside the hydrogel before patterning the hydrogel, patterning the hydrogel includes bonding the dye to the hydrogel by irradiating the hydrogel with the light, and the method further comprises washing out the dye that is not bonded to the hydrogel from among the dyes dispersed inside the hydrogel after patterning the hydrogel.

The intermediate hydrogel structure according to the fifteenth aspect of the present invention comprises a substrate, a swollen hydrogel placed on the main surface of the substrate, and a sealing member that seals the substrate and the hydrogel together with water, and the side of the hydrogel is supported by a frame on the main surface of the substrate.

[Additional Notes]
The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

10 Hydrogel structure 11 Substrate 111, 112 Main surface 113 Alignment mark 12 Frame 13 Hydrogel

Claims (14)

A patterning step is performed by irradiating light to a hydrogel placed on a main surface of a substrate and swollen with water,
In the patterning step, at least a part of a side surface of the hydrogel is supported by a support member formed on the main surface.
A method for producing a hydrogel structure comprising the steps of: In the patterning step, the swollen hydrogel is supported by a wall surface of the support member, and the wall surface is formed so as to intersect with the main surface.
The method for producing the hydrogel structure according to claim 1 . In the patterning step, the side surface is surrounded by the support member.
The method for producing the hydrogel structure according to claim 1 or 2. In the patterning step, the entire side surface is supported by the support member.
The method for producing a hydrogel structure according to claim 3 . The support member is made of a water retention agent.
The method for producing the hydrogel structure according to any one of claims 1 to 4. The water retention agent is a hydrogel different from the swollen hydrogel and has a higher crosslink density than the swollen hydrogel.
The method for producing a hydrogel structure according to claim 5 . In the patterning step, water is constantly or intermittently supplied to the swollen hydrogel.
A method for producing the hydrogel structure according to any one of claims 1 to 6. In the patterning step, (1) the substrate, the swollen hydrogel, and the support member are accommodated in an internal space of a box, and (2) the relative humidity of the internal space is higher than the relative humidity of an external space other than the internal space.
A method for producing the hydrogel structure according to any one of claims 1 to 7. a dam is formed so as to surround the support member when the main surface is viewed in plan, and the dam has a height from the main surface that is higher than that of the support member;
In the patterning step, water is stored inside the dam.
A method for producing the hydrogel structure according to any one of claims 1 to 8. the height of the dam exceeds a working distance of an objective lens used for light irradiation in the patterning step,
In the patterning step, an exit surface of the objective lens is immersed in water stored inside the weir.
The method for producing a hydrogel structure according to claim 9 . In the patterning step, water is supplied so that water is continuously present between an exit surface of an objective lens used for light irradiation and the swollen hydrogel irradiated with light.
The method for producing the hydrogel structure according to any one of claims 1 to 10. a patterning step of irradiating light onto the hydrogel that covers the main surface of the substrate and is swollen with water to perform patterning;
A cutting step of cutting the hydrogel into pieces of a predetermined size.
A method for producing a hydrogel structure comprising the steps of: Further comprising a dye dispersion step carried out before the patterning step, and a cleaning step carried out after the patterning step,
The pigment dispersion step is a step of dispersing a pigment inside the swollen hydrogel,
the patterning step is a step of binding the dye to the swollen hydrogel by irradiating the swollen hydrogel with light,
The washing step is a step of washing the pigment that is dispersed in the inside of the hydrogel by the pigment dispersion step and is not bound to the swollen hydrogel.
A method for producing the hydrogel structure according to any one of claims 1 to 12. An intermediate of a hydrogel structure comprising a substrate, a swollen hydrogel placed on a main surface of the substrate, and a sealing member for sealing the substrate and the hydrogel together with water, wherein at least a part of a side surface of the hydrogel is supported by a support member formed on the main surface.
An intermediate for a hydrogel structure, characterized in that

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