WO2020255925A1

WO2020255925A1 - Method for forming pattern, method for manufacturing substrate with pattern, and method for manufacturing sintered body with pattern

Info

Publication number: WO2020255925A1
Application number: PCT/JP2020/023437
Authority: WO
Inventors: 不二夫津守; 和樹徳丸; 宮田　剛志
Original assignee: 国立大学法人九州大学
Priority date: 2019-06-19
Filing date: 2020-06-15
Publication date: 2020-12-24
Also published as: JPWO2020255925A1; WO2020255433A1

Abstract

One aspect of the present disclosure provides a method for forming a pattern, the method comprising: a step for pressing a mold onto a resin layer to form a transfer pattern; and a step for deforming the resin layer along the direction orthogonal to the pressing direction.

Description

Pattern formation method, pattern base material manufacturing method, and patterned sintered body manufacturing method

The present disclosure relates to a pattern forming method, a method for producing a patterned base material, and a method for producing a patterned sintered body.

Imprint processing is known as one of the microfabrication technologies. The imprint process is a process of forming a transfer pattern on the surface of the resin layer by pressing a mold having a predetermined pattern against the resin layer and transferring the pattern. In Non-Patent Document 1, a technique for forming a multilayer structure by imprint processing is studied.

However, if the pattern of the pressing mold is complicated or the aspect ratio is large, the transfer pattern may collapse during peeling after the transfer pattern is formed, or the pattern of the mold may be sufficiently filled with the resin layer. However, it may be difficult to form the expected transfer pattern. In addition, it is not possible to die-cut a shape such as an overhang whose size is different between the upper part and the lower part of the pattern and the width of the upper part is larger than the width of the lower part, and a pattern having an overhang shape is manufactured by imprint technology. That is difficult.

Imprint processing technology that can form special patterns such as patterns with a large aspect ratio and patterns with overhangs by simple methods, imprint processing that can form complex transfer patterns It is useful if there is technology. Further, it is useful if there is a method for producing a patterned base material using the technique.

An object of the present disclosure is to provide a pattern forming method capable of easily forming a pattern having a large aspect ratio or the like. Another object of the present disclosure is to provide a method for producing a patterned substrate, which can easily produce a patterned substrate having a pattern having a large aspect ratio or the like. Another object of the present disclosure is to provide a method for producing a patterned sintered body, which can easily produce a sintered body having a pattern having a large aspect ratio or the like.

One aspect of the present disclosure is a pattern forming method comprising a step of pressing a mold against a resin layer to provide a transfer pattern and a step of deforming the resin layer along a direction orthogonal to the pressing direction. I will provide a.

In the above pattern forming method, after a transfer pattern is provided on the resin layer by imprinting, the pattern possessed by the mold is formed by deforming the resin layer having the transfer pattern along a direction orthogonal to the pressing direction of the transfer pattern. It is possible to easily form a pattern having a large aspect ratio or the like.

The resin layer may have a plurality of layers.

The resin layer may have a first resin layer and a second resin layer.

The first resin layer may have a pattern on the surface of the first resin layer on the side of the second resin layer.

The step of providing the transfer pattern may be a step of providing the transfer pattern by heating the resin layer and the mold so as to face each other.

The step of providing the transfer pattern may be a step of providing the transfer pattern by irradiating the resin layer with light while pressing the resin layer and the mold while facing each other.

After deforming the resin layer, the resin layer may be further provided with a step of irradiating the resin layer with heat or light.

One aspect of the present disclosure is a step of pressing a mold against a resin layer containing a polymer to form a transfer pattern, and a step of deforming the resin layer along a direction orthogonal to the pressing direction. Provided is a method for producing a patterned base material.

In the method for producing a patterned base material, a transfer pattern is provided on the resin layer by imprinting, and then the resin layer having the transfer pattern is deformed along a direction orthogonal to the pressing direction of the transfer pattern. It is possible to easily provide a patterned base material having a pattern having an aspect ratio larger than that of the mold on the base material.

One aspect of the present disclosure is that the resin layer is pressed against the stacking direction of the laminate having the elastic base material and the resin layer provided on the base material and containing the polymer. A method for producing a patterned base material, which comprises a step of forming a transfer pattern on a surface opposite to the base material side and a step of deforming the resin layer along a direction orthogonal to the laminating direction. I will provide a.

In the method for producing a patterned base material, a transfer pattern is provided by imprinting on a resin layer on a stretchable base material, and then the transfer pattern is pressed in the direction of pressing by using the stretchability of the base material. By deforming the resin layer having a transfer pattern along the orthogonal directions, it is possible to easily provide a patterned base material having a pattern having a large aspect ratio or the like on the base material.

The step of deforming the resin layer may be a step of deforming the resin layer by shrinking the base material along a direction orthogonal to the laminating direction.

The step of deforming the resin layer may be a step of forming a pattern having a larger aspect ratio than the transfer pattern by shrinking the base material along a direction orthogonal to the laminating direction.

The base material may contain at least one selected from the group consisting of elastic bodies, photoresponsive gels, and temperature responsive gels. When the base material contains the above-mentioned materials, the transfer pattern can be more easily deformed.

The base material may contain a silicone resin.

The resin layer may have a plurality of layers.

The resin layer may have a first resin layer and a second resin layer.

The first resin layer is located between the second resin layer and the base material, and even if the first resin layer has a pattern on the surface opposite to the base material side. Good.

The recessed aspect ratio of the above type may be 5 to 10.

The polymer may contain at least one selected from the group consisting of thermoplastic polymers and thermosetting polymers.

The polymer may contain polyvinyl alcohol.

The polymer may have a polymerizable functional group.

The resin layer may contain inorganic particles in addition to the polymer.

The inorganic particles may contain at least one selected from the group consisting of magnesium oxide, titanium oxide, zirconium oxide, iron oxide, aluminum oxide, silicon oxide, silicon nitride, aluminum nitride, silicon carbide, hydroxyapatite and ferrite. ..

The resin layer may contain a polymerizable compound in addition to the polymer.

The above-mentioned polymerizable compound may contain at least one selected from the group consisting of photopolymerizable compounds and thermally polymerizable compounds.

One aspect of the present disclosure is to press a mold against a stacking direction of a laminate having a stretchable base material and a resin layer provided on the base material and containing a polymer and inorganic particles. , A step of forming a transfer pattern on the surface of the resin layer opposite to the base material side, and a step of deforming the resin layer by shrinking the base material along a direction orthogonal to the laminating direction. The present invention provides a method for producing a patterned sintered body, which comprises a step of firing the resin layer to form a sintered body of the inorganic particles.

In the method for producing a sintered body with a pattern, a transfer pattern is provided by imprinting on a resin layer on a stretchable base material, and then the transfer pattern is pressed using the stretchability of the base material. By deforming the resin layer having the transfer pattern along the direction orthogonal to the above, a resin layer having a pattern having a large aspect ratio or the like is formed on the base material, and then the resin layer is fired to form a pattern. A sintered body can be easily provided.

According to the present disclosure, it is possible to provide a pattern forming method capable of easily forming a pattern having a large aspect ratio or the like. According to the present disclosure, it is also possible to provide a method for producing a patterned substrate, which can easily produce a patterned substrate having a pattern having a large aspect ratio or the like. According to the present disclosure, it is also possible to provide a method for producing a patterned sintered body, which can easily produce a sintered body having a pattern having a large aspect ratio or the like.

FIG. 1 is a schematic diagram for explaining an example of a pattern forming method. FIG. 2 is a schematic diagram for explaining another example of the pattern forming method. FIG. 3 is a schematic diagram for explaining another example of the pattern forming method. FIG. 4 is a schematic diagram for explaining another example of the pattern forming method. FIG. 5 is an optical micrograph showing a part of the patterned substrate produced in the examples. FIG. 6 is an electron micrograph showing a part of the patterned base material produced in the examples. FIG. 7 is an electron micrograph showing a part of the patterned base material produced in the examples.

Hereinafter, embodiments of the present disclosure will be described with reference to the drawings in some cases. However, the following embodiments are examples for explaining the present disclosure, and are not intended to limit the present disclosure to the following contents. Unless otherwise specified, the positional relationship such as up, down, left, and right shall be based on the positional relationship shown in the drawings. The dimensional ratio of each element is not limited to the ratio shown in the drawings.

Unless otherwise specified, the materials exemplified in this specification may be used alone or in combination of two or more. The content of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component in the composition are present, unless otherwise specified. ..

<Pattern formation method>
One embodiment of the pattern forming method is a method including deforming the transfer pattern formed by the imprint method in the in-plane direction. The pattern forming method includes, for example, a step of pressing a mold against the resin layer to provide a transfer pattern, and a step of deforming the resin layer along a direction orthogonal to the pressing direction.

FIG. 1 is a schematic diagram for explaining an example of a pattern forming method. The pattern forming method shown in FIG. 1 includes a first step of preparing the base material 2 ((a) of FIG. 1), a second step of stretching the base material 2 ((b) of FIG. 1), and the base material. In the third step ((c) of FIG. 1) of providing the laminate of the first resin layer 4 and the second resin layer 6 on 2, the mold 52 is pressed from the second resin layer 6 side of the laminate. Then, by removing the mold 52, a fourth step ((d) and (e) of FIG. 1) of providing a transfer pattern on the first resin layer 4 and the second resin layer 6 and the base material A resin having a transfer pattern along a direction orthogonal to the pressing direction of the first resin layer 4 and the second resin layer 6 by removing the force that stretched 2 and shrinking the base material 2. It has a fifth step ((f) of FIG. 1) of deforming the layer.

The base material 2 is deformable in order to deform the transfer pattern formed on the resin layer by the imprint method in the in-plane direction. FIG. 1 shows an example in which a stretchable base material (for example, an elastic body) is used as the base material 2, but for example, if it can supply a force for deforming the resin layer after forming a transfer pattern. Often, it may be a material that shrinks by supplying light or heat after forming a transfer pattern. In this case, the first step and the second step can be omitted. The base material 2 may contain, for example, at least one selected from the group consisting of elastic bodies, photoresponsive gels, and temperature responsive gels. When the base material 2 contains the above-mentioned material, the resin layer having the transfer pattern can be easily deformed later.

The base material 2 may be made of a material having a high elastic modulus. Since the base material 2 is made of a material having a high elastic modulus, the stress at the time of stretching can be improved, and more sufficient force is supplied to deform the resin layer having the transfer pattern in a later step. be able to. The base material 2 may contain, for example, a silicone resin, a urethane resin, a natural rubber, a styrene-butadiene rubber, a butadiene rubber, an isoprene rubber, or the like.

The shape of the base material 2 is not particularly limited, but may be, for example, a plate shape. The thickness of the base material 2 and the elastic modulus of the base material 2 are not particularly limited as long as they can be deformed (for example, deformed by expansion and contraction). The upper limit of the thickness of the base material 2 may be, for example, 1 mm or less, 0.5 mm or less, or 0.3 mm or less. The lower limit of the thickness of the base material 2 may be, for example, 0.1 mm or more. When the resin layer is deformed in a later step by utilizing the expansion and contraction of the base material 2, when the lower limit of the thickness of the base material 2 is set within the above range, the base material 2 is shrunk and the resin layer is deformed. Therefore, sufficient force can be supplied to the resin layer. Further, by setting the lower limit of the thickness of the base material 2 within the above range, a sufficient thickness can be maintained even after the base material 2 is stretched, and the workability of the subsequent process can be improved. it can. The thickness of the base material 2 may be adjusted within the above range, and may be, for example, 0.1 to 1 mm or 0.1 to 0.5 mm.

The degree of stretching of the base material 2 (stretching ratio) in the step of stretching the base material 2 may be adjusted in a subsequent step according to the degree of deformation of the resin layer having the transfer pattern. The lower limit of the draw ratio of the base material 2 may be, for example, 1.5 times or more, 1.7 times or more, 2.0 times or more, 2.5 times or more, or 3.0 times or more. The upper limit of the draw ratio of the base material 2 may be, for example, 8.0 times or less, 6.0 times or less, 5.0 times or less, or 4.0 times or less. The draw ratio of the base material 2 may be adjusted within the above range, and may be, for example, 1.5 to 8.0 times or 1.7 to 6.0 times.

The third step is a step of providing the first resin layer 4 and the second resin layer 6 on the base material 2. The first resin layer 4 and the second resin layer 6 may be formed by sticking a separately prepared resin layer on the base material 2, and the composition for forming the resin layer is formed on the base material 2. It may be formed by applying a solution containing the mixture. The first resin layer 4 and the second resin layer 6 may be the same as or different from each other. Hereinafter, the first resin layer 4 and the second resin layer 6 may be collectively referred to as a resin layer in some cases.

The first resin layer 4 and the second resin layer 6 may contain, for example, a polymer, or may be made of a polymer. The polymer may be, for example, a thermoplastic polymer, a thermosetting polymer, or the like. The polymer may be, for example, a photocurable polymer or the like. The polymer can be selected according to the method of forming a transfer pattern on the resin layer by the imprint method. For example, when the step of providing the transfer pattern is a step of providing the transfer pattern by heating the resin layer and the mold while pressing them against each other, the polymer may include a thermoplastic polymer or a thermosetting polymer. Further, for example, when the step of providing the transfer pattern is a step of providing the transfer pattern by irradiating the resin layer with light while pressing the resin layer and the mold against each other, the polymer may contain a photocurable polymer. .. The polymer may also have polymerizable functional groups. The polymerizable functional group may be, for example, a glycidyl group, a hydroxyl group, a carboxy group, an ethylenically unsaturated group or the like. When the first resin layer 4 and the second resin layer 6 are different, the second resin layer 6 preferably contains, for example, an acid-soluble polymer or an alkali-soluble polymer.

Examples of the thermoplastic polymer include polyolefins such as polyvinyl alcohol, polyethylene and polypropylene, poly (meth) acrylic acid alkyl esters such as polyvinyl chloride, polyurethane and polymethyl methacrylate, polystyrene, polylactic acid, and polyethylene terephthalate. Examples include polyester. Examples of the thermosetting polymer include epoxy resin, phenol resin, melamine resin and the like. Examples of the photocurable polymer include polymers having a photopolymerizable functional group.

The upper limit of the thickness of the first resin layer 4 may be, for example, 5 mm or less, 3 mm or less, 1 mm or less, 500 μm or less, 100 μm or less, or 50 μm or less. By setting the upper limit of the thickness of the first resin layer 4 within the above range, the distribution of the force applied to the resin layer in the thickness direction when the resin layer having the transfer pattern is deformed in a later step is distributed. It can be reduced and the deformation of the resin layer can be controlled more easily. The lower limit of the thickness of the first resin layer 4 may be, for example, 25 μm or more, or 30 μm or more. By setting the lower limit of the thickness of the first resin layer 4 within the above range, the handleability can be further improved. The thickness of the first resin layer 4 may be adjusted within the above range, and may be, for example, 25 μm to 5 mm or 25 to 100 μm.

The second resin layer 6 may be removed in a later step if necessary. By removing the second resin layer 6, for example, it becomes easy to form a pattern having a large aspect ratio. The thickness of the second resin layer 6 may be smaller than the thickness of the first resin layer 4. The upper limit of the thickness of the second resin layer 6 may be, for example, 20 μm or less, 15 μm or less, or 10 μm or less. By setting the upper limit value of the second resin layer 6 within the above range, it becomes easier when the second resin layer 6 is removed in a later step. The lower limit of the thickness of the second resin layer 6 may be, for example, 0.1 μm or more, 0.5 μm or more, 1 μm or more, 3 μm or more, or 5 μm or more. By setting the lower limit of the thickness of the second resin layer 6 within the above range, it is possible to prevent the first resin layers 4 from being fused with each other when the resin layer having a pattern is deformed in a later step. be able to. The thickness of the second resin layer 6 may be adjusted within the above range, and may be, for example, 1 to 25 μm or 5 to 10 μm.

FIG. 1 shows an example in which the resin layer is formed from a plurality of layers, but the resin layer may be one layer and may include two or more layers. When two or more layers are included, at least one of the layers constituting the resin layer may be, for example, a resin composition layer, an inorganic layer, and a composite layer. That is, the resin layer may include a first resin layer and a second resin layer, may include a resin composition layer and an inorganic layer, and may include a resin composition layer and a composite layer. When the resin layer includes two or more layers, the material of each layer may be the same or different. The inorganic layer includes, for example, metal oxides such as magnesium oxide, titanium oxide, zirconium oxide, iron oxide, aluminum oxide and silicon oxide, nitrides such as silicon nitride and aluminum nitride, carbides such as silicon carbide, and calcium phosphate such as hydroxyapatite. , Ferrite, and at least one selected from the group consisting of amorphous carbon (carbon black, etc.) and the like, and the inorganic layer may be made of these materials. Examples of the composite layer include a layer in which inorganic particles are dispersed in a resin serving as a binder. The material of the inorganic particles in the composite layer is, for example, magnesium oxide, titanium oxide, zirconium oxide, iron oxide, aluminum oxide, metal oxides such as silicon oxide, carbides such as silicon carbide, and amorphous carbon (carbon black, etc.). It may be at least one selected from the group consisting of the above. When the resin layer contains a composite layer, it can exhibit a function according to the material of the inorganic particles contained in the composite layer. When the resin layer contains a composite layer, the inorganic particles can be sintered and a sintered body having a desired pattern can be obtained by forming a resin layer having a transfer pattern and then firing the resin layer.

The first resin layer 4 and the second resin layer 6 may be formed on the base material 2 by using the slurry containing the polymer and the solvent. More specifically, the polymer is dissolved or dispersed in a solvent to prepare a slurry, which is applied onto the substrate 2 to form a coating film, and then the solvent content in the coating film is reduced. The first resin layer 4 and the second resin layer 6 can be formed by using the method of forming the resin layer. The slurry may contain other components in addition to the polymer and solvent. As the other components, for example, the above-mentioned inorganic particles, plasticizers, polymerizable compounds and the like can be used. Examples of the plasticizer include glycerin, polyethylene glycol, phthalate ester and the like. The polymerizable compound may include, for example, at least one selected from the group consisting of photopolymerizable compounds and thermopolymerizable compounds. Examples of the photopolymerizable compound include (meth) acrylate and styrene. Examples of the thermopolymerizable compound include bisphenol A and the like.

In the fourth step, first, the resin layer is heated while pressing the mold 52 from the side of the second resin layer 6 against the first resin layer 4 and the second resin layer 6 formed as described above. .. By the fourth step, the pattern corresponding to the mold 52 is transferred onto the resin layer.

The mold 52 may be made of, for example, a metal or a resin material, but is preferably made of a resin material because a mold having a plurality of patterns can be easily prepared. Examples of the resin material constituting the mold 52 include polyimide, silicone resin, and the like.

Mold 52 has a recess. The mold 52 may have a plurality of recesses. In FIG. 1D, the plurality of recesses of the mold 52 all have the same shape, but the plurality of recesses may be different from each other. In FIG. 1D, the shape of the concave portion in the cross section of the mold 52 in the thickness direction is substantially triangular, but may be, for example, semicircular, trapezoidal, rectangular, or the like. In FIG. 1D, the cross section of the mold 52 having a plurality of recesses in the thickness direction has a sinusoidal shape, but may be, for example, a rectangular wave shape, and does not necessarily have to have a constant period. Absent. When the recess of the mold 52 is rectangular, the lower limit of the aspect ratio of the recess may be, for example, 0.1 or more, 0.5 or more, or 1 or more. The upper limit of the aspect ratio of the recess may be, for example, 10 or less, or 9 or less. The aspect ratio of the recess may be adjusted within the above range, and may be, for example, 0.1 to 10 or 0.1 to 9. The aspect ratio in the present specification means the ratio of the depth to the width in the rectangular concave cross section, and is a numerical value obtained by dividing the value corresponding to the depth by the value corresponding to the width.

The pressure at the time of pressing the mold 52 in the fourth step may be adjusted according to the material or the like constituting the resin layer. The lower limit of the pressure may be, for example, 0.5 MPa or more, 1.0 MPa or more, 3 MPa or more, or 5 MPa or more. By setting the lower limit of the pressure within the above range, the resin layer can be sufficiently filled in the recesses of the mold 52. The upper limit of the pressure may be, for example, 100 MPa or less, 50 MPa or less, 30 MPa or less, 20 MPa or less, or 10 MPa or less. By setting the upper limit value of the pressure within the above range, deformation and avoidance of the mold 52 can be more sufficiently suppressed. The pressure may be adjusted within the above range, for example, 5 to 50 MPa, or 10 to 20 MPa.

In the fourth step, the resin layer is heated while pressing the mold 52. The heating temperature at this time may be adjusted according to the material or the like constituting the resin layer. The lower limit of the heating temperature may be, for example, 80 ° C. or higher, 90 ° C. or higher, 100 ° C. or higher, or 150 ° C. or higher. By setting the lower limit of the heating temperature within the above range, it is possible to facilitate the transfer of the pattern to the resin layer. The upper limit of the heating temperature may be, for example, less than 200 ° C., 180 ° C. or lower, or 160 ° C. or lower. By setting the upper limit of the heating temperature within the above range, deterioration of the resin layer due to heat can be further suppressed. The temperature may be adjusted within the above range, for example, 80 to 180 ° C, or 100 to 160 ° C.

The heating time for heating the resin layer in the fourth step may be, for example, 10 seconds to 5 minutes, 20 seconds to 3 minutes, 30 seconds to 1.5 minutes, or 30 to 60 seconds.

In the fourth step, for example, the resin layer may be heated and humidified before pressing the mold 52. Moldability can be improved by heating and humidifying the resin layer. The heating may be, for example, 25 to 35 ° C. The above humidification is performed by adjusting the relative humidity of the environment to which the resin layer is exposed. The lower limit of the relative humidity may be 40% RH or more, 50% RH or more, 60% RH or more, 70% RH or more, 80% RH or more, or 85% RH or more. By setting the lower limit of the relative humidity within the above range, the moldability of the resin layer can be further improved. The upper limit of the relative humidity may be, for example, 100% RH or less, or 90% RH or less. By setting the upper limit of the relative humidity within the above range and adjusting the water content of the resin layer, the softening of the resin layer can be made appropriate, and the transfer pattern can be more sufficiently suppressed from being disrupted. Can be done. The time for heating and humidifying the resin layer may be adjusted according to the thickness of the resin layer (total thickness of the first resin layer 4 and the second resin layer 6), and is, for example, 0.5 hours. It may be 1 hour or more, or 1.5 hours or more. The time for heating and humidifying the resin layer may be, for example, 3 hours or less.

In the fifth step, the force applied to maintain the base material 2 in the stretched state is removed, and the base material 2 is contracted to press the resin layer having the transfer pattern formed in the above step. This is a step of deforming along a direction orthogonal to the direction of (the direction indicated by the arrow (f) in FIG. 1). By including this step, it is possible to form a pattern that is difficult to form using the mold 52.

The patterned base material 10 is obtained in the fifth step. The pattern on the patterned base material 10 can also be a pattern having a larger aspect ratio than the transfer pattern transferred by the mold 52.

The above pattern forming method may further include other steps. Examples of other steps include a step of deforming the resin layer and then irradiating the resin layer with heat or light. When the pattern forming method further includes a step of irradiating the resin layer with heat or light after deforming the resin layer, the transfer pattern can be more sufficiently fixed.

FIG. 2 is a schematic diagram for explaining another example of the pattern forming method. The pattern forming method shown in FIG. 2 includes a first step of preparing the base material 2 ((a) of FIG. 2), a second step of stretching the base material 2 ((b) of FIG. 2), and the base material. In the third step ((c) of FIG. 2) of providing the laminate of the first resin layer 4 and the second resin layer 6 on 2, the mold 52 is pressed from the second resin layer 6 side of the laminate. Then, by removing the mold 52, a fourth step ((d) and (e) of FIG. 2) of providing a transfer pattern on the first resin layer 4 and the second resin layer 6 and the base material A resin having a transfer pattern along a direction orthogonal to the pressing direction of the first resin layer 4 and the second resin layer 6 by removing the force that stretched 2 and shrinking the base material 2. It has a fifth step ((f) of FIG. 2) of deforming the layer. The pattern forming method shown in FIG. 2 is basically the same as the pattern forming method shown in FIG. 1 except that the concave shape of the mold 52 is different from that shown in FIG. 1, and the pattern forming method shown in FIG. 1 is formed. The content described for the method can be applied.

The mold 52 shown in FIG. 2D has a plurality of recesses having a quadrangular cross-sectional shape. In addition to the pattern forming method shown in FIG. 2, the resin layer having the transfer pattern is deformed as shown in FIG. 2 (f) by adjusting the distance between the recesses (distance from the adjacent recesses). The shape to be formed can be adjusted. In the example shown in FIG. 2, since the shape of the transfer pattern is rectangular, the volume of the second resin layer 6 when the resin layer is deformed greatly differs depending on the position. In the upper portion of the convex portion of the transfer pattern, there is a gap between the convex portion and the adjacent convex portion, and the resin layer can be easily moved when the resin layer is deformed. However, since the lower portion of the convex portion of the transfer pattern (on the base material 2 side) is deformed while compressing the first resin layer 4 and the second resin layer 6, the first resin layer 4 and the second resin layer 6 are deformed. The components constituting the resin layer 6 are pushed upward of the convex portion of the transfer pattern, and as a result, the first resin layer 4 can be deformed so as to form an overhang inside the second resin layer 6. The shape of the overhang can be adjusted according to the moldability of the first resin layer 4 and the second resin layer 6 such as viscoelasticity.

According to the above-mentioned pattern forming method, a patterned base material can be obtained. That is, the present disclosure provides a method for producing a patterned substrate. One embodiment of the method for producing a patterned base material is a step of pressing a mold against a resin layer containing a polymer to form a transfer pattern, and the resin layer being pressed along a direction orthogonal to the pressing direction. It has a step of transforming. Further, another embodiment of the method for producing a patterned base material is based on a stacking direction of a laminate having a stretchable base material and a resin layer provided on the base material and containing a polymer. A step of pressing a mold to form a transfer pattern on a surface of the resin layer opposite to the base material side, and a step of deforming the resin layer along a direction orthogonal to the laminating direction. Have.

In the above description, one embodiment of the pattern forming method and the method for manufacturing a patterned base material has been described with an example in which a resin layer is provided on the elastic base material. However, another embodiment of the pattern forming method and the method for producing a patterned base material has, for example, providing a resin layer having a transfer pattern on a base material different from the stretchable base material, and having a transfer pattern. A method including peeling the resin layer from the base material and sticking it on a stretchable base material from the first resin layer side, and deforming the resin layer by deforming the stretchable base material. It may be. Further, when the resin layer having a transfer pattern is attached onto a stretchable base material, an adhesive may be used, and the viewpoint of improving the followability of the resin layer to the deformation of the stretchable base material. Therefore, it is preferable to use an adhesive. As the adhesive, for example, a polyvinyl alcohol-based adhesive or the like can be used.

When at least the first resin layer contains inorganic particles, the patterned base material obtained by the above-mentioned pattern forming method and the patterned base material obtained by the above-mentioned method for producing the patterned base material are further fired. Thereby, it can be used for producing a sintered body of the above-mentioned inorganic particles. The obtained sintered body can have a shape that is difficult to form by the conventional imprint method. That is, the above-mentioned pattern forming method and the method for producing a patterned base material can also be used to produce a sintered body having a shape that is difficult to produce by a conventional imprint method.

One embodiment of the method for producing a patterned sintered body is based on a stacking direction of a laminate having a stretchable base material and a resin layer provided on the base material and containing a polymer and inorganic particles. By pressing the mold to form a transfer pattern on the surface of the resin layer opposite to the base material side, and by shrinking the base material along a direction orthogonal to the laminating direction. It includes a step of deforming the resin layer and a step of firing the resin layer to form a sintered body of the inorganic particles. As a method for producing a patterned sintered body, for example, the base material may be peeled from the resin layer and then the resin layer may be fired to form a sintered body of the inorganic particles.

3 and 4 are schematic views for explaining another example of the pattern forming method. In the example shown below, a pattern is provided on the surface of the first resin layer and then a second resin layer is provided, or the first resin layer is on the second resin layer side of the first resin layer. This is an example corresponding to the case where the surface of the surface has a pattern. According to such a method, a pattern having a more complicated shape can be formed. In the pattern forming method shown in FIGS. 3 and 4, the first resin layer 4 is viewed from the first resin layer 4 side with respect to the laminate having the base material 2 and the first resin layer 4 provided on the base material 2. Steps of forming the first transfer pattern by pressing one mold 52 ((a) and (b) in FIG. 3), a second resin on the first resin layer 4 having the first transfer pattern. In the step of providing the layer 6 ((c) in FIG. 3), the second mold 54 is pressed from the side of the second resin layer 6 and the second mold 54 is removed to form the second transfer pattern. In the steps ((a) and (b) of FIG. 4), the first resin layer 4 and the second resin layer 6 are pressed along the direction orthogonal to the pressing direction by compressing and shrinking the base material 2. A step of deforming a resin layer having a transfer pattern ((c) in FIG. 3), and a lamination including a first resin layer and a second resin layer while peeling off the base material 2 or removing the base material 2 by thermal decomposition. It has a step ((d) of FIG. 3) of firing a body to form a sintered body 20 of inorganic particles.

The method for producing the patterned sintered body has been described as an example in which the base material 2 is compressed and shrunk instead of being stretched in advance, but the intention is not limited to this. That is, also in the method for producing the patterned sintered body, a method of pre-stretching the base material 2 may be adopted in the same manner as described in the above-mentioned pattern forming method and the above-mentioned method for producing the patterned base material. ..

Up to the step of obtaining the patterned base material 10 in the method for manufacturing the patterned sintered body, the contents described above for the pattern forming method and the above-mentioned method for manufacturing the patterned base material can be applied. For example, a method for forming a first transfer pattern on the first resin layer 4 in a method for producing a patterned sintered body, and a method for forming a second transfer pattern on the first resin layer 4 and the second resin layer 6. As the method, the conditions of the above-mentioned pattern forming method and the above-mentioned transfer pattern forming method described in the method for producing a patterned substrate may be adopted, respectively.

The recess of the second mold 54 is larger than the recess of the first mold 52. The width of the recess of the second mold 54 may be, for example, 5 times or more, 10 times or more, 15 times or more, or 20 times or more based on the width of the recess of the first mold 52. The width of the recess of the second mold 54 may be, for example, 50 times or less, or 40 times or less, based on the width of the recess of the first mold 52.

In the method for producing a sintered body with a pattern, after forming a transfer pattern on the resin layer, the laminate containing the first resin layer and the second resin layer is fired. At this time, the firing temperature can be adjusted according to the type and content of the inorganic particles contained in the resin layer, the type of the polymer, and the like. The lower limit of the firing temperature may be, for example, 100 ° C. or higher, 200 ° C. or higher, 500 ° C. or higher, 700 ° C. or higher, or 800 ° C. or higher. The upper limit of the firing temperature is, for example, 1900 ° C or lower, 1800 ° C or lower, 1700 ° C or lower, 1600 ° C or lower, 1500 ° C or lower, 1400 ° C or lower, 1300 ° C or lower, 1200 ° C or lower, 1100 ° C or lower, 1000 ° C or lower, or It may be 900 ° C. or lower. The firing temperature can be adjusted within the above range, and may be, for example, 100 to 1900 ° C, 500 to 1900 ° C, or 500 to 1500 ° C.

When the obtained sintered body is ceramics and glass, the firing temperature can be specifically 800 to 1900 ° C, 800 to 1600 ° C, or 800 to 1300 ° C. When the obtained sintered body is a sintered body made of metal, the firing temperature can be specifically 500 to 1500 ° C., 500 to 1200 ° C., or 500 to 900 ° C. When metal nanoparticles or the like are used as the inorganic particles, the firing temperature can be set low, and for example, it can be set to about 200 ° C.

The firing atmosphere is not particularly limited, but may be, for example, an inert gas atmosphere, a reducing gas atmosphere, or a mixed gas atmosphere of an inert gas and a reducing gas. Examples of the inert gas include nitrogen, argon and the like. Examples of the reducing gas include hydrogen, methane, ammonia and the like.

Although some embodiments of the present disclosure have been described above, the present disclosure is not limited to the above embodiments. Further, the contents of the description of the above-described embodiment can be applied to each other.

Hereinafter, the contents of the present disclosure will be described in more detail with reference to Examples and Comparative Examples. However, the present disclosure is not limited to the following examples.

(Example 1)
[Preparation of composition for forming resin layer]
In a container, alumina powder (manufactured by Taimei Chemicals Co., Ltd., product name: TM-DAR, average grain shape: 0.1 μm, purity 99.99%) and polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., degree of polymerization: 500). ) And glycerin (manufactured by Wako Pure Chemical Industries, Ltd.) as a plasticizer were measured so as to have a volume ratio of 43:30:27. After further adding pure water to the container, the obtained aqueous solution was stirred and defoamed using a stirring defoaming device (manufactured by Photochemical Co., Ltd., product name: SK-350T) to obtain a slurry. When preparing the above-mentioned slurry, in order to prevent agglomeration of the alumina powder, first, the alumina powder and pure water were mixed in two steps. Further, polyvinyl alcohol was used as a 20% by volume aqueous solution.

[Formation of resin layer]
As a base material, a silicone film (manufactured by AS ONE Corporation, product name: 6-9085-14) having a rubber hardness (durometer hardness) of 47, a length of 80 mm, a width of 80 mm, and a thickness of 0.3 mm was prepared. Both sides of the silicone film were irradiated with ultraviolet rays at an illuminance of 18 mW / cm ² for 3 minutes to hydrophilize the surface of the substrate. Then, the silicone film was stretched 1.5 times, and while maintaining this stretched state, the slurry prepared as described above was applied onto the silicone film by the doctor blade method to form a coating film. The coating film was heated at 80 ° C. for 60 seconds to reduce the water content, thereby forming a first resin layer having a thickness of 100 μm.

Next, a dispersed aqueous solution of hydrophilic carbon black (manufactured by Tokai Carbon Co., Ltd., product name: Aqua-Black162) was diluted 40-fold with pure water, and this was applied onto the first resin layer to form a coating film. An inorganic layer was formed by removing water from the water.

The slurry used to form the first resin layer was applied onto the inorganic layer to form a coating film. The coating film was heated at a temperature of 80 ° C. for 60 seconds to reduce the water content, thereby forming a second resin layer having a thickness of 20 μm.

[Formation of transfer pattern]
First, the prepared resin layer was allowed to stand for 1 hour in an environment of temperature: 30 ° C. and humidity: 70% RH. Next, a polyimide mold of 10 mm × 10 mm (depth of recess: 46 μm, pitch: 150 μm) was prepared, and while pressing the resin layer from the second resin layer side with a pressure of 7.5 MPa, Temperature: A transfer pattern was formed by heating at 80 ° C. for 60 seconds.

[Deformation of resin layer with transfer pattern]
The mold is peeled off from the resin layer having the transfer pattern, and the base material is gradually contracted while weakening the force applied to maintain the stretched state of the base material, thereby following this and deforming the resin layer. did. The transfer pattern in which the compression ratio of the base material was 1.5 was observed based on the state in which the stretched state of the base material was maintained. Here, the compression ratio means a value obtained by L ₁ / L ₀ when the initial length of the base material is L ₀ and the length after stretching is L ₁ . A cross section showing a part of the transfer pattern in each state was observed with an optical microscope. The results are shown in FIG. 5 (b).

(Example 2 and Example 3)
A transfer pattern is formed in the same manner as in Example 1 except that the draw ratio of the silicone film as the base material is changed to 1.7 times (Example 2) or 2.0 times (Example 3). did. In Example 2, the cross section of the transfer pattern was observed at a position where the compression ratio of the base material was 1.7, and in Example 3, the transfer pattern was observed at a position where the compression ratio of the base material was 2.0. The results are shown in FIGS. 5 (c) and 5 (d), respectively.

FIG. 5 is an optical micrograph showing a part of a cross section of the patterned base material manufactured in the examples. FIG. 5 shows a cross-sectional photograph of the first resin layer 4a and the second resin layer 6a. FIG. 5A is a cross-sectional photograph showing a part of the transfer pattern in a state where the stretched state of the base material is maintained. (B), (c) and (d) of FIG. 5 are cross-sectional photographs showing a part of the transfer pattern when the compression ratios of the base materials are 1.5, 1.7 and 2.0, respectively. It was confirmed that the transfer pattern formed on the resin layer was deformed according to the compression ratio of the base material. For example, focusing on the first resin layer 4a, the height and width of the pattern are larger and the width is smaller than the pattern imprinted by the polyimide mold, and the pattern is deformed into a pattern having a large aspect ratio. You can check it.

(Example 4)
[Formation of first resin layer]
As a base material, a silicone film (manufactured by AS ONE Corporation, product name: 6-9085-14) having a rubber hardness (durometer hardness) of 47, a length of 80 mm, a width of 80 mm, and a thickness of 0.3 mm was prepared. Both sides of the silicone film were irradiated with ultraviolet rays at an illuminance of 18 mW / cm ² for 3 minutes to hydrophilize the surface of the substrate. Then, the silicone film was stretched 1.5 times, and while maintaining this stretched state, the slurry prepared in Example 1 was applied onto the silicone film by the doctor blade method to form a coating film. The coating film was heated at a temperature of 80 ° C. for 60 seconds to reduce the water content, thereby forming a first resin layer having a thickness of 100 μm.

[Formation of the first transfer pattern]
The prepared first resin layer was allowed to stand for 1 hour in an environment of temperature: 30 ° C. and humidity: 70% RH. Next, a polyimide mold of 10 mm × 10 mm (depth of recess: 10 μm, pitch: 10 μm) was prepared, and while pressing with a pressure of 7.5 MPa from the first resin layer side, the temperature was 80 ° C. The first transfer pattern was formed by heating for 60 seconds.

[Formation of second resin layer]
First, polymethylmethacrylate (manufactured by Sigma Aldrich, PMMA, number average molecular weight: 350,000 or less), thickener (manufactured by Meisei Chemical Works, Ltd., product name: Alcox EP-10, ethylene oxide and propylene oxide) A mixed solution was prepared by mixing and dissolving the random copolymer) and the solvent (Acetone manufactured by Wako Pure Chemical Works, Ltd.) so as to have a mass ratio of 9: 1: 90.

As described above, the mixed solution was spin-coated on the first resin layer on which the first transfer pattern was formed to reduce the acetone content, thereby forming a second resin layer having a thickness of 20 μm. A resin layer composed of two layers, a first resin layer and a second resin layer, was obtained.

[Formation of second transfer pattern]
The resin layer prepared as described above was allowed to stand for 1 hour in an environment of temperature: 30 ° C. and humidity of 70% RH. Next, a polyimide mold of 10 mm × 10 mm (depth of recess: 46 μm, pitch: 150 μm) was prepared, and while being pressed from the second resin layer side at a pressure of 7.5 MPa, at a temperature of 80 ° C. A second transfer pattern was formed by heating for 60 seconds. A part of the cross section of the transfer pattern was observed with an electron microscope. The results are shown in FIG. In the electron micrograph shown in FIG. 6, the first resin layer 4b and the second resin layer 6b can be confirmed, and even after the second transfer pattern is formed, the first resin layer 4b It can be confirmed that the fine pattern is maintained on the second resin layer 6b side of the above.

(Example 5)
[Formation of first resin layer]
A polyethylene terephthalate film (PET film) was prepared, and the slurry prepared in Example 1 was applied onto the PET film by the doctor blade method to form a coating film. The coating film was heated at a temperature of 80 ° C. for 60 seconds to reduce the water content, thereby forming a first resin layer having a thickness of 100 μm.

[Formation of the first transfer pattern]
The prepared first resin layer was allowed to stand for 1 hour in an environment of temperature: 30 ° C. and humidity: 70% RH. Next, a 20 mm × 20 mm mold made of silicone resin (depth of recess: 10 μm, pitch: 10 μm) was prepared, and while pressing with a pressure of 7.5 MPa from the first resin layer side, the temperature: 80 ° C. The first transfer pattern was formed by heating in.

[Formation of second resin layer]
A 10% by mass aqueous solution of polyvinyl alcohol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., molecular weight 1500) was dropped onto the first resin layer provided with the first transfer pattern, and a liquid film was formed by spin coating. .. Then, it is heated to a temperature of 60 ° C. by an oven to reduce the amount of water, thereby forming a second resin layer having a thickness of 10 μm, which is composed of two layers, a first resin layer and a second resin layer. A resin layer was obtained.

[Formation of second transfer pattern]
The resin layer prepared as described above was allowed to stand for 1 hour in an environment of temperature: 30 ° C. and humidity of 70% RH. Next, a 20 mm × 20 mm mold made of polyimide (depth of recess: 46 μm, pitch: 150 μm) was prepared, and while pressing with a pressure of 7.5 MPa from the second resin layer side, the temperature was 80 ° C. A second transfer pattern was formed by heating for 60 seconds.

[Deformation of resin layer with transfer pattern]
As a base material, a silicone film (manufactured by AS ONE Corporation, product name: 6-9085-14) having a rubber hardness (durometer hardness) of 47, a length of 25 mm, a width of 40 mm, and a thickness of 0.3 mm was prepared. A polyvinyl alcohol-based adhesive was applied onto the silicone film stretched so that the stretch ratio was 2.0 times. The resin layer provided with the second transfer pattern described above was separated from the PET film, and the resin layer was adhered onto the base material so that the first resin layer was in contact with the silicone film side. Then, after allowing to stand indoors for 30 minutes, it was allowed to stand for 1 hour in an environment of temperature: 30 ° C. and humidity: 90% RH.

After that, the silicone film was gradually shrunk to deform the resin layer, and a cross section showing a part of the transfer pattern was observed with an electron microscope. The results are shown in FIG. 7 (c). In the electron micrograph shown in FIG. 7, the first resin layer 4c and the second resin layer 6c can be confirmed. FIG. 7A is an electron micrograph of observing a cross section of the resin layer when the second resin layer is formed, and FIG. 7B is an age-old resin layer forming the second transfer pattern. It is an electron micrograph which observed the cross section of. More specifically, FIG. 7 (c) is obtained by shrinking the silicone film until the compression ratio of the silicone film is 1.5, based on the state where the draw ratio of the silicone film is 2.0. It is an electron micrograph which observed the cross section of the resin layer.

2 ... base material, 4 ... first resin layer, 6 ... second resin layer, 10 ... patterned base material, 20 ... sintered body, 52 ... mold (first mold), 54 ... second mold ..

Claims

The process of pressing the mold against the resin layer to provide a transfer pattern,
A pattern forming method comprising a step of deforming the resin layer along a direction orthogonal to the pressing direction.
The pattern forming method according to claim 1, wherein the resin layer has a plurality of layers.
The pattern forming method according to claim 1 or 2, wherein the resin layer has a first resin layer and a second resin layer.
The pattern forming method according to claim 3, wherein the first resin layer has a pattern on the surface of the first resin layer on the side of the second resin layer.
The pattern according to any one of claims 1 to 4, wherein the step of providing the transfer pattern is a step of providing the transfer pattern by heating the resin layer and the mold while pressing them against each other. Forming method.
Any one of claims 1 to 5, wherein the step of providing the transfer pattern is a step of providing the transfer pattern by irradiating the resin layer with light while pressing the resin layer and the mold against each other. The pattern forming method described in the section.
The pattern forming method according to any one of claims 1 to 6, further comprising a step of irradiating the resin layer with heat or light after deforming the resin layer.
The process of forming a transfer pattern by pressing the mold against the resin layer containing the polymer,
A method for producing a patterned base material, comprising a step of deforming the resin layer along a direction orthogonal to the pressing direction.
The mold is pressed against the stacking direction of the laminate having the elastic base material and the resin layer provided on the base material and containing the polymer, and the base material side of the resin layer is The process of forming a transfer pattern on the opposite surface and
A method for producing a patterned base material, comprising a step of deforming the resin layer along a direction orthogonal to the laminating direction.
The manufacturing method according to claim 9, wherein the step of deforming the resin layer is a step of deforming the resin layer by shrinking the base material along a direction orthogonal to the laminating direction.
The step of deforming the resin layer is a step of forming a pattern having a larger aspect ratio than the transfer pattern by shrinking the base material along a direction orthogonal to the stacking direction, according to claim 9 or 10. The manufacturing method described.
The production method according to any one of claims 9 to 11, wherein the base material contains at least one selected from the group consisting of an elastic body, a photoresponsive gel, and a temperature-responsive gel.
The production method according to any one of claims 9 to 12, wherein the base material contains a silicone resin.
The production method according to any one of claims 9 to 13, wherein the resin layer has a plurality of layers.
The production method according to any one of claims 9 to 14, wherein the resin layer has a first resin layer and a second resin layer.
The first resin layer is located between the second resin layer and the base material.
The production method according to claim 15, wherein the first resin layer has a pattern on a surface opposite to the base material side.
The manufacturing method according to any one of claims 9 to 16, wherein the concave portion of the mold has an aspect ratio of 5 to 10.
The manufacturing method according to any one of claims 9 to 17, wherein the step of providing the transfer pattern is a step of providing the transfer pattern by heating the resin layer and the mold so as to face each other.
Any one of claims 9 to 18, wherein the step of providing the transfer pattern is a step of providing the transfer pattern by irradiating the resin layer with light while pressing the resin layer and the mold against each other. The manufacturing method described in the section.
The production method according to any one of claims 9 to 19, further comprising a step of irradiating the resin layer with heat or light after deforming the resin layer.
The production method according to any one of claims 9 to 20, wherein the polymer comprises at least one selected from the group consisting of a thermoplastic polymer and a thermosetting polymer.
The production method according to any one of claims 9 to 21, wherein the polymer contains polyvinyl alcohol.
The production method according to any one of claims 9 to 22, wherein the polymer has a polymerizable functional group.
The production method according to any one of claims 9 to 23, wherein the resin layer contains inorganic particles in addition to the polymer.
Claimed that the inorganic particles include at least one selected from the group consisting of magnesium oxide, titanium oxide, zirconium oxide, iron oxide, aluminum oxide, silicon oxide, silicon nitride, aluminum nitride, silicon carbide, hydroxyapatite and ferrite. Item 24. The production method according to Item 24.
The production method according to any one of claims 9 to 25, wherein the resin layer contains a polymerizable compound in addition to the polymer.
The production method according to claim 26, wherein the polymerizable compound contains at least one selected from the group consisting of a photopolymerizable compound and a thermopolymerizable compound.
The base of the resin layer is pressed against the stacking direction of the laminate having the stretchable base material and the resin layer provided on the base material and containing the polymer and inorganic particles. The process of forming a transfer pattern on the surface opposite to the material side,
A step of deforming the resin layer by shrinking the base material along a direction orthogonal to the laminating direction.
A method for producing a patterned sintered body, comprising a step of firing the resin layer to form a sintered body of the inorganic particles.
28. The manufacturing method according to claim 28, wherein the step of deforming the resin layer is a step of deforming the resin layer by shrinking the base material along a direction orthogonal to the laminating direction.
28 or 29, wherein the step of deforming the resin layer is a step of forming a pattern having a larger aspect ratio than the transfer pattern by shrinking the base material along a direction orthogonal to the laminating direction. The manufacturing method described.