JP7528580B2 - Patterned film and method for forming same - Google Patents

Description

The present invention relates to a patterned film.

Various methods have been reported for forming patterned films, including methods that use irradiation with active energy rays such as ultraviolet rays or electron beams, and methods that use self-organizing materials such as block copolymers.

JP 2009-260330 A JP 2016-197176 A

The present invention aims to provide a technology that enables the formation of patterned films in a simple manner.

According to a first aspect of the present invention, there is provided a method for forming a pattern film, the method including: providing a first film on a substrate; forming a second film on the first film, the second film being made of an emulsion containing dispersed particles containing a first liquid that is cured by irradiation with active energy rays, and a dispersion medium containing a second liquid that is not cured by irradiation with active energy rays; irradiating at least a portion of another region of the second film with the active energy rays without irradiating at least a portion of the second film with the active energy rays, thereby curing the first liquid in the region irradiated with the active energy rays; drying the second film after the irradiation with the active energy rays to remove at least a portion of the second liquid from the second film, and dissolving at least a portion of the material of the first film in the uncured first liquid contained in the second film; and curing the uncured first liquid in which at least a portion of the material of the first film has been dissolved.

According to a second aspect of the present invention, a method for producing a granular layer comprising: providing a first film on a substrate; forming a second film on the first film, the second film being made of an emulsion containing dispersed particles containing a first liquid that is cured by irradiation with active energy rays, and a dispersion medium containing a second liquid that is not cured by irradiation with the active energy rays; irradiating at least a partial region of the second film with the active energy rays without irradiating at least a partial region of the second film with the active energy rays, thereby forming a granular layer made of a cured product of the dispersed particles in the region irradiated with the active energy rays; and then curing the uncured first liquid.

According to a third aspect of the present invention, there is provided a patterned film formed by the method according to the first or second aspect.

The present invention provides a technology that enables the formation of patterned films in a simple manner.

1A to 1C are cross-sectional views each showing a schematic diagram of a first film forming step in the pattern film forming method according to the first embodiment of the present invention. 4A to 4C are cross-sectional views each showing a schematic diagram of a step of forming a second film in the method of forming a pattern film according to the first embodiment of the present invention. 3A to 3C are cross-sectional views each showing a schematic diagram of an active energy ray irradiation step in the method for forming a pattern film according to the first embodiment of the present invention. 5A to 5C are cross-sectional views each showing a schematic diagram of a removing step of a second liquid in the method for forming a pattern film according to the first embodiment of the present invention. FIG. 4 is a cross-sectional view illustrating a structure obtained after a second liquid removing step in the pattern film forming method according to the first embodiment of the present invention. 3A to 3C are cross-sectional views each showing a schematic diagram of a fixing step in the method for forming a pattern film according to the first embodiment of the present invention. 6A to 6C are cross-sectional views each showing a schematic diagram of a first film forming step in a pattern film forming method according to a second embodiment of the present invention. 6 is a cross-sectional view illustrating a process of forming a second film in the method of forming a pattern film according to the second embodiment of the present invention. FIG. 5 is a cross-sectional view illustrating an example of an active energy ray irradiation step in the method for forming a pattern film according to a second embodiment of the present invention. FIG. 11A to 11C are cross-sectional views each showing a schematic diagram of a process for removing a second liquid in the method for forming a pattern film according to a second embodiment of the present invention. FIG. 11 is a cross-sectional view illustrating a structure obtained after a second liquid removing step in the pattern film forming method according to the second embodiment of the present invention. 6 is a cross-sectional view illustrating a fixing step in the method for forming a pattern film according to a second embodiment of the present invention. FIG. 11A to 11C are cross-sectional views each showing a schematic diagram of a first film forming step in a pattern film forming method according to a third embodiment of the present invention. FIG. 11 is a cross-sectional view illustrating a first active energy ray irradiation step in the method for forming a pattern film according to a third embodiment of the present invention. 13A to 13C are cross-sectional views each showing a schematic diagram of a step of forming a second film in the method of forming a pattern film according to a third embodiment of the present invention. FIG. 13 is a cross-sectional view illustrating a second active energy ray irradiation step in the method for forming a pattern film according to the third embodiment of the present invention. 13A to 13C are cross-sectional views each showing a schematic diagram of a process for removing a second liquid in the method for forming a pattern film according to the third embodiment of the present invention. FIG. 13 is a cross-sectional view illustrating a structure obtained after a second liquid removing step in the method for forming a pattern film according to the third embodiment of the present invention. 13A to 13C are cross-sectional views each showing a schematic diagram of a fixing step in the method for forming a pattern film according to a third embodiment of the present invention. Graph showing particle size distribution of emulsion. Photograph of the patterned film obtained in Test 1. 22 is an enlarged photograph of the pattern film of FIG. 21. Photographs showing a first film forming step in the pattern film forming method of Test 2. Photographs showing a second film forming step in the pattern film forming method of Test 2. Photographs showing an energy ray irradiation step in the pattern film forming method of Test 2. 13 is a photograph showing the film structure 5 minutes after the start of the drying process in the pattern film forming method of Test 2. 13 is a photograph showing the film structure 20 minutes after the start of the drying process in the pattern film forming method of Test 2. 13 is a photograph showing a film structure 30 minutes after the start of a drying process in the pattern film forming method of Test 2. 13 is a photograph showing the film structure 35 minutes after the start of the drying process in the pattern film forming method of Test 2. 13 is a photograph showing the film structure 40 minutes after the start of the drying process in the pattern film forming method of Test 2. 13 is a photograph showing a film structure 60 minutes after the start of a drying process in the pattern film forming method of Test 2. Photograph showing a film structure after a fixing process in the pattern film forming method of Test 2. Photographs showing the first energy ray irradiation step in the pattern film forming method of Test 3. 13 is a photograph showing a liquid storage cell formed in the pattern film forming method of Test 3. Photographs showing the second energy ray irradiation step in the pattern film forming method of Test 3. 13 is a photograph showing a film structure immediately after the start of a drying process in the pattern film forming method of Test 3. 13 is a photograph showing the film structure 15 minutes after the start of the drying process in the pattern film forming method of Test 3. 13 is a photograph showing the film structure 20 minutes after the start of the drying process in the pattern film forming method of Test 3. 13 is a photograph showing the film structure 25 minutes after the start of the drying process in the pattern film forming method of Test 3. 13 is a photograph showing a film structure 30 minutes after the start of a drying process in the pattern film forming method of Test 3. 13 is a photograph showing a film structure 40 minutes after the start of a drying process in the pattern film forming method of Test 3. 13 is a photograph showing a film structure 60 minutes after the start of a drying process in the pattern film forming method of Test 3. 13 is a photograph showing a film structure 120 minutes after the start of a drying process in the pattern film forming method of Test 3.

Embodiments of the present invention will be described in detail below with reference to the drawings. Note that components that perform the same or similar functions are given the same reference numbers throughout the drawings, and duplicate descriptions will be omitted.

[First embodiment]
The method for forming a pattern film according to the first embodiment will be described below in the order of steps. To facilitate understanding of each step, an example of the state of the film in each step is shown in Figures 1 to 6, and these figures will be referred to in the following description.

<Formation of First Film>
First, a substrate is prepared. Any substrate can be used as the substrate, and for example, a film or a sheet can be used.

Next, a first film is provided on the substrate. The first film is primarily a non-fluid film.

The material of the first film is, for example, a material that does not dissolve in the first liquid until the step of removing the second liquid, or does not exhibit flowability until the step of removing the second liquid. The material of the first film is, for example, a material that exhibits a higher solubility in the first liquid compared to the second liquid. According to one example, the material of the first film is a thermoplastic resin. According to another example, the material of the first film is a thermosetting resin. The material of the first film may be one or more low molecular weight compounds.

In addition to the resin, the material of the first film may further include one or more additives dissolved or dispersed therein. Such additives include, for example, dyes, pigments, metal particles, and magnetic particles.

When an additive is contained in the material of the first film, the proportion of the additive in the material of the first film is preferably in the range of 0.01 to 80% by mass, and more preferably in the range of 0.1 to 70% by mass.

The first film can be formed on the substrate by, for example, coating or printing. Alternatively, the first film may be formed on the support by coating or printing, and then transferred from the support to the substrate. The film formed by coating or printing may be dried as necessary.

The thickness of the first film is in the range of 0.5 to 50 μm in one example, and in the range of 1.0 to 20 μm in another example.

Figure 1 shows a schematic diagram of an example of a state in which a first film is formed on a substrate. In Figure 1, a first film 2 is formed as a continuous film on a substrate 1.

<Preparation of emulsion>
After providing a first film on a substrate, an emulsion is prepared that contains dispersed particles containing a first liquid that is cured by irradiation with active energy rays and a dispersion medium containing a second liquid that is not cured by irradiation with active energy rays. The preparation of this emulsion may be performed before providing the first film on the substrate, or may be performed in parallel with providing the first film on the substrate.

The emulsion may be an oil-in-water (O/W) emulsion or a water-in-oil (W/O) emulsion.

The dispersed particles include a first liquid that is cured by irradiation with active energy rays. Examples of active energy rays include ultraviolet rays, electron beams, and X-rays. The first liquid may be, for example, an acrylic monomer or oligomer, a methacrylic monomer or oligomer, an epoxy monomer or oligomer, or a mixture containing one or more of them. It is preferable to use an acrylic monomer or oligomer, or a methacrylic monomer or oligomer as the first liquid, because of the advantages of a wide range of options and a large degree of freedom in adjusting physical properties. For example, trimethylolpropane triacrylate may be used as the first liquid. The proportion of the monomer and oligomer in the first liquid is, for example, 30 to 100% by mass.

Incidentally, there are more types of lipophilic first liquids that harden when irradiated with active energy rays than there are hydrophilic first liquids. Therefore, O/W emulsions offer greater freedom in material selection than W/O emulsions.

The dispersion medium includes a second liquid that does not harden when exposed to active energy rays. If the first liquid is lipophilic, the second liquid can be a hydrophilic liquid, such as water, a lower alcohol such as methanol or ethanol, or a mixture thereof. On the other hand, if the first liquid is hydrophilic, the second liquid can be a lipophilic liquid, such as an isoparaffinic solvent or mineral spirits.

Although it depends on the size of the pattern to be formed, it is preferable that the first dispersed particles have an average particle size of 0.5 μm to 0.5 mm. Here, the "average particle size" is the weight average diameter obtained by particle size distribution measurement according to the laser diffraction/scattering method. When the first dispersed particles have the above size, the uncured first liquid etc. can be efficiently permeated into the gaps between the particles in a later process.

The proportion of dispersed particles in the emulsion is preferably 25% by mass or more. When the dispersed particles occupy the above proportion in the emulsion, the temperature of the area irradiated with active energy rays can be increased by effectively utilizing the heat of polymerization to destabilize the dispersion state of the dispersed particles containing the first liquid and form an aggregate layer at the same time. The upper limit of the proportion of dispersed particles in the emulsion is not particularly limited as long as it is within a range in which phase inversion of the emulsion does not occur. According to one example, this proportion is 70% by mass or less.

The first liquid may further contain a photopolymerization initiator. As the photopolymerization initiator, a known photopolymerization initiator, for example, an alkylphenone-based photopolymerization initiator, can be used. As an alkylphenone-based photopolymerization initiator, for example, 1-hydroxycyclohexyl phenyl ketone can be mentioned. The first liquid may contain the photopolymerization initiator in an amount of, for example, 0.1 to 10 parts by mass per 100 parts by mass of the total amount of the monomer and oligomer.

When the emulsion is, for example, an O/W type, the dispersed particles may contain a hydrophobe in addition to the first liquid. Examples of hydrophobes include higher alcohols with low solubility in water, such as cetyl alcohol, hexadecane, polymerizable monomers with relatively large molecular weights of the hydrocarbon chain, such as lauryl methacrylate and stearyl methacrylate, hydrophobic dyes, and polymers, such as polymethyl methacrylate and polystyrene. The hydrophobe serves to stabilize the first emulsion. The hydrophobe can be contained in an amount of, for example, 0.1 to 10 parts by mass per 100 parts by mass of the first liquid.

The dispersion medium may further contain a surfactant. For example, a commercially available surfactant for use in emulsion polymerization may be used as the surfactant. For example, a sulfosuccinate type surfactant such as dioctyl sodium sulfosuccinate may be used as the surfactant. The emulsion may contain the surfactant in an amount of, for example, 0.1 to 5.0% by mass based on the total mass of the emulsion.

When the emulsion is an O/W type emulsion, the dispersion medium generally contains a surfactant to ensure emulsification and the stability of the dispersed particles. In addition, this O/W type emulsion can also contain water-soluble polymers, cellulose nanofibers, etc. in the dispersion medium to improve the long-term storage stability of the emulsion. Furthermore, if necessary, this O/W type emulsion can also contain a viscosity modifier or an antifoaming agent in the dispersion medium.

On the other hand, when the emulsion is a W/O type emulsion, in order to prepare a stable emulsion, the dispersion medium may contain a nonionic surfactant or a polymeric dispersion stabilizer having an appropriate hydrophilic-lipophilic balance (HLB) value. If necessary, this W/O type emulsion may also contain an ionic surfactant in the dispersion medium.

Emulsions can be prepared using known emulsification and dispersion techniques, such as paint shakers, ultrasonic homogenizers, colloid mills, homogenizers, and membrane emulsification methods.

<Formation of second film>
Next, a second film made of the emulsion is formed on the first film. Hereinafter, the "second film made of emulsion" is also referred to as a liquid film. Specifically, the liquid film can be formed on the first film by applying the emulsion onto the first film.

The coating method is not particularly limited, but an appropriate coating method such as die coating, comma coating, or curtain coating can be selected depending on the thickness of the liquid film. The thickness of the liquid film can be, for example, 10 to 3000 μm. In addition, when applying a small amount of emulsion to form a liquid film with a small area, a dispenser or the like can be used as necessary.

Figure 2 shows a schematic diagram of an example of a state in which a second film made of an emulsion is formed on a first film. In Figure 2, a second film 3 made of an emulsion composed of dispersed particles 31 and a dispersion medium 32 is formed on the first film 2.

<Irradiation with active energy rays>
Next, the second film is irradiated with active energy rays in a pattern. As the active energy rays, as described above, for example, ultraviolet rays, electron beams, X-rays, etc. can be mentioned. The pattern irradiation can be carried out, for example, by selectively irradiating the active energy rays through a mask or the like, or by selectively irradiating the laser beam.

By irradiating the active energy rays, the first liquid contained in the dispersed particles is polymerized and hardened in the area of the second film irradiated with the active energy rays (hereinafter also referred to as the irradiated area). This makes it possible to form a porous layer made of the hardened product of the dispersed particles.

Figure 3 shows an example of a state in which a granular layer made of a hardened product of dispersed particles is formed in the area irradiated with ultraviolet light by patterned irradiation of ultraviolet light. As shown in Figure 3, for example, when patterned exposure of ultraviolet light is performed using a mask 5, in the area irradiated with ultraviolet light, the first liquid contained in the dispersed particles 31 is polymerized and hardened, and the dispersed particles 31 become hardened particles 41. These hardened particles 41 aggregate and stack, and as a result, a granular layer 4a made of hardened particles 41 is formed. In the area irradiated with ultraviolet light, the second liquid contained in the dispersion medium 32 does not harden, so the dispersion medium 32 exists in the granular layer 4a, specifically, in the gaps between the hardened particles 41. On the other hand, in the area not irradiated with ultraviolet light (hereinafter also referred to as the non-irradiated area) in Figure 3, the first liquid contained in the dispersed particles 31 remains unhardened.

Regarding the aggregation mechanism of the hardened particles 41 in the irradiated area, the inventor believes that the reason is as follows.

When exposed to active energy rays, the dispersed particles 31 generate heat due to polymerization, which causes the temperature of the irradiated area to rise. This temperature rise causes the surfactant that has been adsorbed to the surface of the dispersed particles 31 to stabilize the dispersion of the dispersed particles 31 to desorb. This causes the surface potential of the dispersed particles 31, where polymerization has progressed, to decrease. As a result, the dispersion of the dispersed particles 31 or their cured particles 41 becomes unstable, and particle aggregation is promoted. In addition, as the particles aggregate and come into contact with each other, polymerization crosslinking may occur between the particles.

This aggregation is completed before the surfactant that has been released due to the temperature rise caused by the heat of polymerization is re-adsorbed onto the particles. This allows the aggregated particles to maintain their aggregated state without being re-dispersed.

The aggregation of the cured particles 41 in the irradiated area may be promoted by incorporating a crosslinking agent into the dispersion medium in advance. This makes it easier for crosslinks to form between the particles when irradiated with active energy rays, thereby promoting the aggregation of the particles.

<Removal of second liquid>
After irradiation with active energy rays, at least a part of the second liquid is removed from the second film. In this step, at least a part of the second liquid may be removed, but the entire second liquid may be removed. The second liquid may be removed, for example, by drying the second film. The drying is preferably performed until the amount of the second liquid is 30% by mass or less of the amount of the second liquid immediately after the formation of the second liquid film, and more preferably until the amount is 5% by mass or less. The second liquid may be removed by leaving the second film at room temperature, but is preferably removed by heating and drying the second film. The heating and drying can be performed, for example, by heating the second film at a temperature in the range of 40 to 100° C. for 0.1 to 1 hour.

In this process, the second liquid is removed to promote the coalescence of the dispersed particles containing the uncured first liquid. Then, at least a portion of the uncured first liquid is moved from the non-irradiated area to the granular layer consisting of the cured product of the dispersed particles. The movement of the uncured first liquid from the non-irradiated area to the granular layer may be performed so that all of it moves to the granular layer, or so that only a portion of it moves to the granular layer.

Furthermore, in this process, at least a portion of the material of the first film is fluidized, dissolved in the unhardened first liquid, or fluidized and dissolved in the unhardened first liquid and transferred to the granular layer. The material of the first film may be transferred to the granular layer in its entirety, or only a portion of it may be transferred to the granular layer.

For example, when the material of the first film is a thermoplastic resin and the second liquid is removed by heating and drying at a temperature equal to or higher than the softening point of the thermoplastic resin, the removal of the second liquid not only advances the coalescence of the dispersed particles containing the uncured first liquid, but also causes the material of the first film to soften (fluidize). At least a portion of the uncured first liquid and at least a portion of the softened material of the first film are absorbed by the granular layer, either at least partially intermixed or not intermixed.

Alternatively, if the material of the first film is a thermosetting resin and the second liquid is removed at a temperature at which the thermosetting resin does not harden, as the coalescence of the dispersed particles containing the uncured first liquid progresses as the second liquid is removed, at least a portion of the thermosetting resin mixes with at least a portion of the uncured first liquid. Then, at least a portion of the uncured first liquid that has mixed with the thermosetting resin and at least a portion of the uncured first liquid that has not mixed with the thermosetting resin are absorbed by the granular layer.

In this method, it is not necessary to carry out a development step, i.e., removal of the uncured first liquid using a developer, after irradiation with active energy rays.

Figures 4 and 5 show schematic examples of changes in the state of the first and second films caused by the removal of the second liquid. Figure 4 shows schematic examples of a state in which coalescence of dispersed particles occurs in non-irradiated areas by starting the removal of the second liquid from the second film. Figure 5 shows schematic examples of a state in which the first liquid constituting the coalescence of dispersed particles mixes with the material of the first film, and the mixture permeates the granular layer made of the hardened dispersed particles.

When a portion of the second liquid contained in the dispersion medium 32 is removed from the second film 3, as shown in FIG. 4, the second liquid that filled the gaps between the particles in the granular layer 4a is reduced in the irradiated area, and the second liquid is reduced in the non-irradiated area, and the dispersed particles 31 coalesce. When the second liquid is reduced, the material of the first film 2 dissolves into the uncured first liquid, for example, due to an increase in the contact area between the material of the first film 2 and the uncured first liquid. Then, as shown in FIG. 5, the mixture 4b of the material of the first film 2 and the uncured first liquid penetrates into the gaps in the granular layer 4a and diffuses into the granular layer 4a. It is believed that this penetration and diffusion proceeds due to capillary forces.

<Establishing the pattern>
Finally, the uncured material contained in the film from which the second liquid has been removed is cured. For example, if the material of the first film is a thermoplastic resin, it is cooled to a temperature lower than its glass transition point, and the entire film is irradiated with active energy rays. Alternatively, if the material of the first film is a thermosetting resin, it is heated to a temperature equal to or higher than its curing temperature, and the entire film is irradiated with active energy rays. Alternatively, the entire film may simply be irradiated with active energy rays. Also, if the material of the first film is a thermosetting resin and the first liquid is cured by heating, the film is heated to a temperature at which both of them are cured. In this way, a pattern film is formed.

Figure 6 shows a schematic example of a state in which the uncured material is cured by a combination of cooling and full-surface irradiation with ultraviolet light or by full-surface irradiation with ultraviolet light alone when the material of the first film is a thermoplastic resin. The thermoplastic resin solidifies by cooling, and the uncured first liquid is cured by polymerization when the entire film is irradiated with ultraviolet light. As a result, a cured material phase 4c is formed. Furthermore, in the cured material particles 41 that make up the granular layer 4a, further polymerization proceeds due to ultraviolet light irradiation.

This results in a patterned film having a granular layer 4a and a hardened phase 4c that is a hardened material that at least partially fills the gaps between the granular layer 4a.

The uncured material can be cured after all of the uncured first liquid or the material of the first film present in the non-irradiated area has moved from this area to the granular layer. Alternatively, the uncured material can be cured when only a part of the uncured first liquid or the material of the first film present in the non-irradiated area has moved from this area to the granular layer. For example, the cooling and heating processes for curing the material of the first film and the irradiation of the entire film with active energy rays may be performed before the second liquid is completely removed from the film (i.e., at a stage in the middle of the first liquid and the material of the first film in the non-irradiated area penetrating the granular layer and diffusing therein). In this way, a pattern film having a thickness in the non-irradiated area and a thicker irradiated area than the non-irradiated area can be obtained. In addition, when the first film contains two or more components, all of the components may be moved to the granular layer, or only a part of the components may be moved to the granular layer.

＜Effects＞
In the above method, the emulsion film is irradiated with active energy rays in a pattern, and then the second liquid is simply removed, so that the pattern can be formed spontaneously (in a self-organizing manner). In the above method, it is not necessary to provide a guide pattern on the substrate in advance, and no development process is required. Therefore, the above method is a simple method.

Furthermore, while conventional techniques could achieve pattern sizes of, for example, a line width of several nm to several hundred μm and a height difference of several nm to several hundred μm, the above method can achieve a wide range of pattern sizes. For example, the above method can form a pattern film with a large line width or height difference, for example, a line width on the order of microns to millimeters and a height difference on the order of microns to millimeters. As an example, the above method can form a pattern film with a line width in the range of 10 μm to 5 mm and a height difference in the range of 10 μm to 2 mm.

The above method also provides excellent control over the shape and size of the pattern, making it possible to form pattern films of various shapes and sizes.

Furthermore, in the above method, a second film made of an emulsion is formed on the first film, and at least a portion of the material of the first film is transferred to a particulate layer obtained from a portion of the second film. Therefore, the first film does not have to be capable of forming a pattern by itself in a self-organizing manner. Therefore, according to the above method, a patterned film in which the composition of the hardened particles 41 and the hardened phase 4c are different can be obtained.

[Second embodiment]
The method for forming a pattern film according to the second embodiment will be described below in the order of steps. To facilitate understanding of each step, examples of the state of the film at each step are shown in Figs. 7 to 12, and these figures will be referred to in the following description.

<Formation of First Film>
First, a substrate is prepared. As the substrate, the substrate described in the first embodiment can be used.

Next, a first film is provided on the substrate. The first film is provided only on a partial region of the substrate. Other than providing the first film only on a partial region of the substrate, the matters relating to the first film are the same as those described in the first embodiment.

Figure 7 shows a schematic example of a state in which the first film is formed only on a partial region of the substrate. In Figure 7, the first film 2 is formed as a continuous film on the substrate 1. The first film 2 partially covers one main surface of the substrate 1.

<Formation of second film>
Next, a second film made of an emulsion is formed. The second film is formed on at least a part of the first film and on another part of the region of the substrate, i.e., on at least one of the regions of the substrate where the first film is not provided. Other than forming the second film in this manner, the matters related to the second film are the same as those described in the first embodiment.

Figure 8 shows a schematic diagram of an example of a state in which a second film made of an emulsion is formed on a first film. In Figure 8, a second film 3 made of an emulsion composed of dispersed particles 31 and a dispersion medium 32 is formed on at least a portion of the first film 2 and on at least a portion of the region of the substrate 1 where the first film 2 is not provided.

<Irradiation with active energy rays>
Next, the second film is irradiated with active energy rays in a pattern. The active energy rays are irradiated to at least a part of the region of the second film that is located on the first film and at least a part of the region of the second film that is not located on the first film. Other than the irradiation with active energy rays in this manner, the matters related to the irradiation with active energy rays are the same as those described in the first embodiment.

Figure 9 shows an example of a state in which a granular layer made of a hardened product of dispersed particles is formed in the area irradiated with ultraviolet light by patterned irradiation of ultraviolet light. As shown in Figure 9, for example, when patterned exposure of ultraviolet light is performed using a mask 5, the dispersed particles 31 are hardened to become hardened particles 41 in the area irradiated with ultraviolet light, and a granular layer 4a made of these hardened particles 41 is formed. The ultraviolet light is irradiated to at least a part of the area of the second film 3 located on the first film 2 and at least a part of the area of the second film 3 not located on the first film 2. Therefore, the granular layer 4a includes a part located on the first film 2 (hereinafter also referred to as the first part) and a part not located on the first film 2 (hereinafter also referred to as the second part).

<Removal of second liquid>
After irradiation with active energy rays, at least a portion of the second liquid is removed from the second film by the same method as described in the first embodiment.

In the first portion of the granular layer located on the first film, the material of the first film and the uncured first liquid that are located near the first portion move. On the other hand, in the second portion of the granular layer that is not located on the first film, since the first film is not present near this portion, for example, only the uncured first liquid that is located near the second portion moves. Alternatively, in addition to the uncured first liquid that is located near the second portion moving to the second portion, a smaller amount of the material of the first film moves compared to the first portion.

Figures 10 and 11 show schematic examples of changes in the state of the first and second films caused by the removal of the second liquid. Figure 10 shows schematic examples of a state in which the coalescence of dispersed particles occurs in the non-irradiated region by starting the removal of the second liquid from the second film. Figure 11 shows schematic examples of a state in which a part of the first liquid constituting the coalescence of dispersed particles mixes with the material of the first film, the mixture permeates a part of the granular layer made of the hardened dispersed particles, and another part of the first liquid permeates the other part of the granular layer without mixing with the material of the first film.

When a portion of the second liquid contained in the dispersion medium 32 is removed from the second film 3, as shown in FIG. 10, the amount of the second liquid that filled the gaps between the particles in the granular layer 4a decreases in the irradiated area, while the amount of the second liquid decreases in the non-irradiated area, and the dispersed particles 31 coalesce.

When the second liquid decreases, in addition to coalescence of the dispersed particles 31 occurring near the first film 2, the material of the first film 2 dissolves into the uncured first liquid, for example, due to an increase in the contact area between the material of the first film 2 and the uncured first liquid. Then, as shown in FIG. 11, the mixture 4b of the material of the first film 2 and the uncured first liquid permeates into the gaps in the granular layer 4a and diffuses into the granular layer 4a.

On the other hand, at a position sufficiently far from the first film 2, when the second liquid decreases, the dispersed particles 31 coalesce, but the material of the first film 2 does not dissolve in the uncured first liquid. Therefore, as shown in FIG. 11, only the uncured first liquid 4d penetrates into the gaps in the granular layer 4a and diffuses into the granular layer 4a.

<Establishing the pattern>
Finally, the uncured material contained in the film from which the second liquid has been removed is cured. This fixing step is performed in the same manner as described in the first embodiment.

The first liquid and the material of the first film are present in the first portion of the granular layer. On the other hand, in the second portion of the granular layer, only the first liquid is present, or in addition to the first liquid, the material of the first film is present in a smaller amount (relative amount to the first liquid) than in the first portion. Therefore, in the pattern film obtained in this manner, the hardened phase formed in the first portion has a higher relative amount of hardened material of the first film material to the hardened material of the first liquid compared to the hardened material of the first liquid, compared to the hardened material phase formed in the second portion.

Figure 12 shows a schematic diagram of an example of the state in which the uncured material is cured by cooling and irradiating the entire surface with ultraviolet light when the material of the first film is a thermoplastic resin.

In the first portion, the thermoplastic resin solidifies by cooling, and the uncured first liquid is cured by ultraviolet light irradiation. As a result, a cured phase 4c is formed. On the other hand, in the second portion, there is no thermoplastic resin, and the uncured first liquid is cured by ultraviolet light irradiation. As a result, a cured phase 4e is formed. Then, in the cured particles 41 that make up the granular layer 4a, further polymerization proceeds due to ultraviolet light irradiation.

This results in a pattern film having a first pattern portion 4A and a second pattern portion 4B, where the first pattern portion 4A includes a part of the granular layer 4a and a hardened material phase 4c that is a hardened material that at least partially fills the gaps therebetween, and the second pattern portion 4B includes another part of the granular layer 4a and a hardened material phase 4e that is a hardened material that at least partially fills the gaps therebetween.

＜Effects＞
In this embodiment, the same effect as in the first embodiment can be obtained. In addition, in this embodiment, the hardened phase formed in the first portion and the hardened phase formed in the second portion can have different compositions. That is, according to this embodiment, it is possible to form a more complicated structure.

[Third embodiment]
The method for forming a pattern film according to the third embodiment will be described below in the order of steps. To facilitate understanding of each step, an example of the state of the film at each step is shown in Fig. 13 to Fig. 19, and these figures will be referred to in the following description.

<Formation of First Film>
First, a substrate is prepared. As the substrate, the same substrate as described in the first embodiment can be used.

Next, a first film is provided on the substrate. The first film may be provided over the entire region of the substrate, or may be provided over only a portion of the region of the substrate.

The material for the first film contains a resin that is cured by irradiation with the first active energy ray. Examples of the first active energy ray include ultraviolet light, electron beams, and X-rays. The resin that is cured by irradiation with the first active energy ray can be, for example, the resin described for the first liquid in the first embodiment. The material for the first film can further contain a solvent such as an organic solvent. Other matters related to the first film are the same as those described in the first and second embodiments.

Figure 13 shows a schematic diagram of an example of a state in which a first film is formed on a substrate. In Figure 13, a first film 2 is formed as a continuous film on a substrate 1.

<Irradiation of first active energy ray>
Next, the first film is irradiated with a first active energy ray in a pattern. The first active energy ray is irradiated to one or more regions of the first film, and is not irradiated to one or more other regions of the first film. The first active energy ray is irradiated to cure the resin contained in the first film in the region irradiated with the first active energy ray (hereinafter also referred to as the first irradiated region). For example, the degree of polymerization of the resin in the first irradiated region is made higher than the degree of polymerization of the resin in the region of the first film not irradiated with the first active energy ray (hereinafter also referred to as the first non-irradiated region).

Figure 14 shows a schematic example of a state in which a first irradiated region and a first non-irradiated region are formed in the first film by patternwise irradiation of ultraviolet light to the first film. As shown in Figure 14, for example, when patternwise exposure to ultraviolet light is performed using a first mask 5A, the resin contained in the first film 2 does not harden in the first non-irradiated region 2A that is not irradiated with ultraviolet light, and the resin contained in the first film 2 hardens in the first irradiated region 2B that is irradiated with ultraviolet light.

<Formation of second film>
Next, a second film made of an emulsion is formed on the first film in the same manner as described in the first embodiment.

The second film may be formed so as to cover the entire first film, or may be formed so as to cover only a portion of the first film. In the latter case, the second film is formed, for example, so as to cover at least a portion of the first non-irradiated region and at least a portion of the first irradiated region.

Figure 15 shows a schematic diagram of an example of a state in which a second film made of an emulsion is formed on a first film. In Figure 15, the second film 3 is formed so as to cover at least a part of the first non-irradiated area 2A and at least a part of the first irradiated area 2B.

<Irradiation with second active energy ray>
Next, the second film is irradiated with the second active energy ray in a pattern. The matters related to the irradiation of the second active energy ray are the same as those described in the first embodiment. Note that the region of the second film that is not irradiated with the second active energy ray and the region that is irradiated with the second active energy ray are referred to as the second non-irradiated region and the second irradiated region, respectively.

Figure 16 shows an example of a state in which a granular layer made of a hardened product of dispersed particles is formed in the second irradiation area irradiated with ultraviolet light by patterned irradiation of ultraviolet light. As shown in Figure 16, for example, when patterned exposure of ultraviolet light is performed using the second mask 5B, the dispersed particles 31 are hardened to become hardened particles 41 in the second irradiation area irradiated with ultraviolet light, and a granular layer 4a made of these hardened particles 41 is formed. For example, ultraviolet light is irradiated to a part of the area of the second film 3 located on the first non-irradiated area 2A and a part of the area of the second film 3 located on the first irradiation area 2B. Therefore, the granular layer 4a includes a part located on the first non-irradiated area 2A (hereinafter also referred to as the third part) and a part located on the first irradiation area 2B (hereinafter also referred to as the fourth part).

<Removal of second liquid>
After the irradiation with the second active energy rays, at least a part of the second liquid is removed from the second film by the same method as described in the first embodiment.

The uncured material of the first film and the uncured first liquid that are located near the third portion move to the third portion of the granular layer located on the first non-irradiated region. On the other hand, since there is no uncured material of the first film near the fourth portion of the granular layer located on the first irradiated region, for example, only the uncured first liquid that is located near the fourth portion moves to the fourth portion. Alternatively, in addition to the uncured first liquid that is located near the fourth portion moving to the fourth portion, a smaller amount of the uncured material of the first film moves to the fourth portion compared to the third portion.

Figures 17 and 18 show schematic examples of changes in the state of the first and second films caused by the removal of the second liquid. Figure 17 shows schematic examples of a state in which the coalescence of dispersed particles occurs in the second non-irradiated region by starting the removal of the second liquid from the second film. Figure 18 shows schematic examples of a state in which a portion of the first liquid constituting the coalescence of dispersed particles mixes with the uncured material of the first film, the mixture permeates a portion of the granular layer made of the cured material of the dispersed particles, and another portion of the first liquid permeates another portion of the granular layer without mixing with the uncured material of the first film.

When a portion of the second liquid contained in the dispersion medium 32 is removed from the second film 3, as shown in FIG. 17, the amount of the second liquid that filled the gaps between the particles in the granular layer 4a decreases in the second irradiated region, and the amount of the second liquid decreases in the second non-irradiated region, and the dispersed particles 31 coalesce.

When the second liquid decreases, in addition to coalescence of the dispersed particles 31 occurring near the first non-irradiated region 2A, the uncured material of the first film 2 dissolves in the uncured first liquid due to, for example, an increase in the contact area between the material of the first film 2 and the uncured first liquid. Then, as shown in FIG. 18, the mixture 4b of the uncured material of the first film 2 and the uncured first liquid permeates into the gaps in the granular layer 4a and diffuses into the granular layer 4a.

On the other hand, in the vicinity of the first irradiation region 2B, when the second liquid decreases, the dispersed particles 31 coalesce, but since there is no uncured material of the first film 2, the particles do not dissolve in the first liquid. Therefore, as shown in FIG. 18, only the uncured first liquid 4d penetrates into the gaps in the granular layer 4a and diffuses into the granular layer 4a.

<Establishing the pattern>
Finally, the uncured material contained in the film from which the second liquid has been removed is cured. This fixing step is performed in the same manner as described in the first embodiment.

In the third portion of the granular layer, the first liquid and the uncured material of the first film are present. On the other hand, in the fourth portion of the granular layer, only the first liquid is present, or in addition to the first liquid, the uncured material of the first film is present in a smaller amount (relative amount to the first liquid) than in the third portion. Therefore, in the pattern film obtained in this manner, the cured material phase that occurs in the third portion has a larger relative amount of the cured material of the first film to the cured material of the first liquid compared to the cured material of the first liquid, compared to the cured material phase that occurs in the fourth portion.

Figure 19 shows a schematic diagram of an example of the state in which the uncured material is cured by irradiating the entire surface with ultraviolet light when the material of the first film is an ultraviolet curable resin.

In the third portion, the uncured first liquid and the uncured material of the first film are cured by UV irradiation. As a result, a cured phase 4c is formed. On the other hand, in the fourth portion, there is no uncured material of the first film, and the uncured first liquid is cured by UV irradiation. As a result, a cured phase 4e is formed. Then, in the cured particles 41 that make up the granular layer 4a, further polymerization proceeds due to UV irradiation.

This results in a pattern film having a first pattern portion 4A and a second pattern portion 4B, the first pattern portion 4A including a part of the granular layer 4a and a cured material phase 4c that is a cured product that at least partially fills the gaps therebetween, and the second pattern portion 4B including another part of the granular layer 4a and a cured material phase 4e that is a cured product that at least partially fills the gaps therebetween. This also results in a structure having the substrate 1, the above-mentioned pattern film, and a cured material layer (first irradiation region 2B) interposed between the substrate 1 and the second pattern portion 4B.

＜Effects＞
In this embodiment, the same effect as in the first embodiment can be obtained. In addition, in this embodiment, the composition of the hardened phase generated in the third portion and the hardened phase generated in the fourth portion can be made different. Furthermore, in this embodiment, for example, the portion of the first film located near the third portion can be eliminated, and the portion located near the fourth portion can be left. That is, according to this embodiment, it is possible to form a more complicated structure.

[1] Test 1
In this test, a pattern film was formed by the method described with reference to FIGS.

<Preparation of first film-forming coating solution>
A coating liquid for forming a first film was prepared using the following materials.
Polymethyl methacrylate type macromonomer: Macromonomer AA-6 (Toagosei Co., Ltd.)
Blue dye: Kayaset Blue N
Solvent: n-butyl acetate 10 g of n-butyl acetate and 1 g of macromonomer AA-6 were charged into a vial, and a shaking treatment was performed under heating at 70°C. As a result, macromonomer AA-6 was dissolved in n-butyl acetate. Next, 0.003 g of Kayaset Blue N was added to this solution, and a shaking treatment was performed without heating. In this manner, a coating liquid for forming a first film was obtained.

<Preparation of emulsion>
An O/W type emulsion was prepared using the following materials.
Trimethylolpropane triacrylate: Light Acrylate TMP-A (Kyoeisha Chemical Co., Ltd.)
Photopolymerization initiator: Lunacure 200 (DKSH Japan Co., Ltd.)
Surfactant: Sanmorin OT-70 (86.7% aqueous solution) (Sanyo Chemical Industries, Ltd.)
Second liquid: Water (distilled water)
A 50 mL brown vial was charged with 0.375 g of a photopolymerization initiator (Lunacure 200), 0.259 g of a surfactant (Sunmorin OT-70), and 7.5 g of trimethylolpropane triacrylate (Light Acrylate TMP-A) in this order, and a rotary mixing process was performed on a ball mill roll. Next, 9 g of distilled water was added to obtain a mixed solution that serves as a precursor of the emulsion. After that, this mixed solution was subjected to an emulsification dispersion process for 30 seconds using a paint shaker. Next, the vial was rotary mixed for 1 hour. In this manner, an emulsion was obtained.

The particle size distribution of this emulsion was measured. Here, the weight average diameter was measured using a measurement system consisting of a particle size distribution measuring device, Microtrac MT3300EXII, manufactured by Nikkiso Co., Ltd., equipped with a liquid circulation pump, Microtrac USVR, also manufactured by Nikkiso Co., Ltd.

Figure 20 is a graph showing the results of particle size distribution measurement of the emulsion. As a result of this particle size distribution measurement, the average particle size of the dispersed particles in the emulsion was 87.3 μm.

<Formation of First Film>
The above coating solution was dropped onto the surface of a microscope slide glass using a dropper, and the film was spread. The film was then dried by heating for 10 minutes in a convection oven set at 70° C. In this manner, a first film having a thickness of 7.6 μm was obtained.

<Formation of second film>
Five layers of 20 mm wide, 80 μm thick masking tape (manufactured by 3M) were attached to the surface of a microscope slide glass prepared separately along the long side direction, and the center of the tape was cut out into a rectangular shape measuring 10 mm×20 mm.

Next, the laminate was peeled off from the slide glass and attached onto the first film. In this way, a cell having a liquid reservoir with the first film at the bottom (hereinafter referred to as a liquid reservoir cell) was produced.

Next, 75 μL of emulsion was collected using a micropipette. This was spread and filled into a liquid storage cell, resulting in a second membrane made of emulsion with a thickness of approximately 375 μm, calculated taking into account the specific gravity.

<Irradiation with active energy rays>
Next, a photomask having a line and space pattern with a line width and space width of 2 mm each was placed on the second film so as not to come into contact with the second film. Next, a metal halide UV light source (LS-165UV manufactured by Sumita Optical Glass Co., Ltd.) was used, and the ultraviolet light emitted from a fiber light guide connected to it was converted into nearly parallel light by a biconvex quartz lens, which was then irradiated from above the mask, thereby exposing the film to an integrated light amount of 40 mJ/ ^cm2 . The photomask was then removed from the slide glass.

<Drying of film and fixing of pattern>
The UV-exposed film was then dried by heating in a convection oven set at 70° C. for 5 minutes.
Next, the entire film was irradiated with ultraviolet light using the above-mentioned exposure device, thereby providing an integrated light amount of 250 mJ/cm ² .

Optical photographs of the structure thus obtained are shown in Figures 21 and 22. In Figure 21, a first film and a laminate having a window are sequentially provided on a slide glass. A line and space pattern is formed within the window. Figure 22 is an optical photograph showing an enlarged view of the line and space pattern within the window. The colored portion of the pattern within the window is the line portion. The line portion contains a granular layer and a coalesced emulsion component of the non-irradiated portion in which the first film component containing the blue dye has been dissolved.

[2] Test 2
In this test, a pattern film was formed by the same method as that described with reference to FIGS.

<Formation of First Film>
Five layers of 20 mm wide, 80 μm thick masking tape manufactured by 3M were attached to the surface of a microscope slide along its long side. The center of the tape was then cut out into a rectangular shape measuring 10 mm x 20 mm to prepare a cell having a liquid reservoir (hereinafter referred to as a liquid reservoir cell). Next, three straight lines parallel to each other and extending in the length direction of the slide were drawn on the opening surface (surface of the slide glass) of the liquid reservoir cell including the masking tape layer using a black oil-based pen. In this manner, a first film consisting of an ink layer was obtained. FIG. 23 is an optical photograph of the structure thus obtained. A line and space pattern consisting of an ink layer was provided on the bottom of the liquid reservoir cell.

<Formation of second film>
75 μL of emulsion was collected using a micropipette. The emulsion was the same as that used in Test 1. This emulsion was spread and filled in a liquid storage cell to obtain a second membrane made of emulsion with a thickness of about 375 μm, calculated taking into account the specific gravity.

Figure 24 shows an optical photograph of the structure obtained in this way. The line and space pattern at the bottom of the reservoir cell appears blurred because the reservoir cell is filled with emulsion.

<Irradiation with active energy rays>
Next, a photomask having a line-and-space pattern with a line width and a space width of 2 mm each was placed on the second film so as not to come into contact with the second film. The photomask was placed so that the length direction of the line portions and space portions was perpendicular to the length direction of the line portions and space portions of the line-and-space pattern provided on the bottom of the liquid-reservoir cell, as shown in the optical photograph in FIG.

Next, a light source head unit (HOYA CANDEO OPTRONICS H-1VH4-V1) was connected to a UV-LED irradiator controller (HOYA CANDEO OPTRONICS EXECURE-H-1VCII), and a UV exposure system equipped with a uniform irradiation lens unit (HOYA CANDEO OPTRONICS HDL-21) was used to irradiate the mask with ultraviolet light at an illuminance of 10.7 mW/cm ² for 5 seconds, thereby exposing the film to an integrated light amount of 53.5 mJ/cm ^2. The photomask was then removed from the slide glass.

<Drying of film and fixing of pattern>
Next, the film after the ultraviolet exposure was allowed to dry naturally in an environment at a temperature of 23.6° C. and a relative humidity of 27%.
Thereafter, the entire film was irradiated with ultraviolet light using the above-mentioned exposure device, to give an integrated light amount of 642 mJ/cm ^2. This allowed the pattern to be fixed.

The structure of the film during the drying process is shown in the optical photographs of Figures 26 to 31. The structure of the film after fixing is shown in the optical photograph of Figure 32.

As shown in Figures 26 to 32, in the non-irradiated region near the first film, part of the material of the first film was dissolved in the first liquid. Then, the first liquid moved from the non-irradiated region to the granular layer of the irradiated region, and with this movement, the material of the first film that had dissolved in the first liquid also moved to the granular layer of the irradiated region. On the other hand, in the irradiated region, the material of the first film did not dissolve in the first liquid to the same extent as in the non-irradiated region.

[3] Test 3
In this test, a pattern film was formed by the same method as that described with reference to FIGS.

<Preparation of first film-forming coating solution>
A coating liquid for forming a first film was prepared using the following materials.
Polymethyl methacrylate type macromonomer: Macromonomer AA-6 (Toagosei Co., Ltd.)
Trimethylolpropane triacrylate: Light Acrylate TMP-A (Kyoeisha Chemical Co., Ltd.)
Diphenyl(2,4,6-trimethylbenzyl)phosphine oxide: Lucirin (registered trademark) TPO (BASF Japan Ltd.)
Blue dye: Kayaset Blue N
Solvent: n-butyl acetate 100 g of n-butyl acetate, 7 g of macromonomer AA-6, 3 g of light acrylate TMP-A, 0.6 g of Lucirin TPO, and 0.2 g of Kayaset Blue N were charged into a sealed container that blocks ultraviolet light. Next, the container was rotated at room temperature to mix and dissolve these components. In this manner, a coating liquid for forming a first film was obtained.

<Formation of First Film>
Three layers of 20 mm wide, 80 μm thick masking tape (manufactured by 3M) were attached to the surface of a microscope slide along its long side. The center of the tape was then cut out into a square shape measuring 20 mm x 20 mm. In this manner, a cell having a liquid reservoir (hereinafter referred to as the first liquid reservoir cell) was prepared.

Next, 75 μL of the above coating liquid was collected using a micropipette. This was spread and filled into the first liquid storage cell, and then allowed to dry naturally for 24 hours in a light-shielded room temperature environment. In this way, a first film was obtained that was tack-free and had a thickness of about 7 μm in the center.

<Irradiation of first active energy ray>
The laminate forming the first liquid storage cell was peeled off from the slide glass. Next, a photomask having a line and space pattern with a line width and a space width of 2 mm and 1 mm, respectively, was placed on the first film so as to be in close contact with the first film. Here, as shown in FIG. 33, the photomask was placed on the slide glass so that the length direction of the line portion and the space portion was parallel to the length direction of the slide glass.

Next, a light source head unit (HOYA CANDEO OPTRONICS H-1VH4-V1) was connected to a UV-LED irradiator controller (HOYA CANDEO OPTRONICS EXECURE-H-1VCII), and a UV exposure system equipped with a uniform irradiation lens unit (HOYA CANDEO OPTRONICS HDL-21) was used to irradiate ultraviolet light with an illuminance of 16.3 mW/cm ² from above the mask for 60 seconds, thereby exposing the first film to an integrated light amount of 978 mJ/cm ^2. In this manner, a latent image was recorded on the first film. Thereafter, the photomask was removed from the slide glass.

<Formation of second film>
Five layers of 20 mm wide, 80 μm thick masking tape (manufactured by 3M) were attached to the surface of a microscope slide glass prepared separately along the long side direction, and the center of the tape was cut out into a rectangular shape measuring 10 mm×20 mm.

Next, this laminate was peeled off from the slide glass and attached onto the slide glass on which the first film had been formed. In this way, a cell having a liquid reservoir with the first film at the bottom (hereinafter referred to as the second liquid reservoir cell) was produced.

Figure 34 is an optical photograph of the structure obtained in this manner. Here, as shown in the optical photograph in Figure 34, the length direction of the second liquid storage cell was parallel to the length direction of the slide glass.

Next, 75 μL of emulsion was collected using a micropipette. The emulsion used was the same as that used in Test 1. This was spread and filled into the second liquid storage cell, resulting in a second membrane made of emulsion with a thickness of approximately 375 μm, calculated taking into account the specific gravity.

<Irradiation with second active energy ray>
Next, a photomask having a line and space pattern with a line width and a space width of 2 mm each was placed on the second film so as not to come into contact with the second film. The photomask was placed so that the length direction of the line portion and space portion was perpendicular to the length direction of the second liquid-reservoir cell, as shown in the optical photograph of FIG.

Next, a light source head unit (HOYA CANDEO OPTRONICS H-1VH4-V1) was connected to a UV-LED irradiator controller (HOYA CANDEO OPTRONICS EXECURE-H-1VCII), and a UV exposure system equipped with a uniform irradiation lens unit (HOYA CANDEO OPTRONICS HDL-21) was used to irradiate the mask with ultraviolet light at an illuminance of 10.7 mW/cm ² for 5 seconds, thereby exposing the film to an integrated light amount of 53.5 mJ/cm ^2. The photomask was then removed from the slide glass.

<Drying of film and fixing of pattern>
Next, the film after the ultraviolet exposure was naturally dried in an environment of a temperature of 24° C. and a relative humidity of 38%. Thereafter, the entire film was exposed to ultraviolet light using the above-mentioned exposure machine, thereby providing an integrated light amount of 642 mJ/cm ^2. This allowed the pattern to be fixed.

The structure of the film during the drying process is shown in the optical photographs of Figures 36 to 43. As shown in the optical photographs of Figures 36 to 43, as the film dries, the uncured material contained in the first non-irradiated area dissolves into the first liquid, and the first liquid migrates from the second non-irradiated area to the granular layer in the second irradiated area.
The invention as originally claimed is set forth below.
[1]
Providing a first film on a substrate;
forming a second film on the first film, the second film being made of an emulsion containing dispersed particles containing a first liquid that is cured by irradiation with active energy rays and a dispersion medium containing a second liquid that is not cured by irradiation with active energy rays;
irradiating at least a portion of the second film with the active energy rays without irradiating at least a portion of the second film with the active energy rays, thereby curing the first liquid in the portion irradiated with the active energy rays;
removing at least a portion of the second liquid from the second film after the irradiation of the active energy rays, and dissolving at least a portion of a material of the first film in the uncured first liquid contained in the second film;
hardening the unhardened first liquid in which at least a portion of the material of the first film has been dissolved;
A method for forming a patterned film comprising the steps of:
[2]
Item 2. The method according to item 1, wherein the material includes a thermoplastic resin, and the uncured first liquid contained in the second film dissolves at least a portion of the material that has been heated and made fluid.
[3]
Providing a first film on a substrate;
forming a second film on the first film, the second film being made of an emulsion containing dispersed particles containing a first liquid that is cured by irradiation with active energy rays and a dispersion medium containing a second liquid that is not cured by irradiation with active energy rays;
irradiating at least a part of the second film with the active energy rays without irradiating at least a part of the second film with the active energy rays, thereby forming a granular layer made of a cured product of the dispersed particles in the part irradiated with the active energy rays;
After the irradiation of the active energy rays, at least a portion of the second liquid is removed from the second film to move at least a portion of the uncured first liquid in the area not irradiated with the active energy rays into the granular layer, and at least a portion of the material of the first film into the granular layer.
Then, the uncured first liquid is cured.
A method for forming a patterned film comprising the steps of:
[4]
4. The method according to claim 3, wherein the material comprises a thermoplastic resin, and at least a portion of the material that has been heated and fluidized is transferred to the particulate layer.
[5]
5. The method according to any one of items 1 to 4, wherein the first film is provided only on a partial region of the substrate, the second film is formed on at least a portion of the first film and on another partial region of the substrate, and the active energy rays are irradiated to at least a portion of a region of the second film that is located on the first film and at least a portion of a region of the second film that is not located on the first film.
[6]
4. The method according to claim 1 or 3, wherein the material contains a resin that is cured by irradiation with active energy rays, and the method further comprises irradiating the first film with the active energy rays in a pattern before forming the second film, thereby curing the resin in a region irradiated with the active energy rays.
[7]
Item 7. The method according to any one of items 1 to 6, wherein the emulsion is an oil-in-water emulsion.
[8]
Item 8. A patterned film formed by the method according to any one of Items 1 to 7.

DESCRIPTION OF SYMBOLS 1... Base material, 2... First film, 2A... First non-irradiation area, 2B... First irradiation area, 3... Second film, 4A... First pattern part, 4B... Second pattern part, 4a... Granular layer , 4b... Mixture, 4c... Cured product phase, 4d... First liquid, 4e... Cured product phase, 5... Mask, 5A... First mask, 5B... Second mask, 31... Dispersion particle, 32... Dispersion medium, 41 ...Cured material particles.

Claims (8)

Providing a first film on a substrate;
forming a second film on the first film, the second film being made of an emulsion containing dispersed particles containing a first liquid that is cured by irradiation with active energy rays and a dispersion medium containing a second liquid that is not cured by irradiation with active energy rays;
irradiating at least a portion of the second film with the active energy rays without irradiating at least a portion of the second film with the active energy rays, thereby curing the first liquid in the portion irradiated with the active energy rays;
After the irradiation of the active energy rays, the second film is dried to remove at least a portion of the second liquid from the second film, and at least a portion of a material of the first film is dissolved in the uncured first liquid contained in the second film.
and curing the uncured first liquid in which at least a portion of the material of the first film is dissolved. The method according to claim 1, wherein the material includes a thermoplastic resin, and the uncured first liquid contained in the second film dissolves at least a portion of the material that has been heated and made fluid. Providing a first film on a substrate;
forming a second film on the first film, the second film being made of an emulsion containing dispersed particles containing a first liquid that is cured by irradiation with active energy rays and a dispersion medium containing a second liquid that is not cured by irradiation with active energy rays;
irradiating at least a part of the second film with the active energy rays without irradiating at least a part of the second film with the active energy rays, thereby forming a granular layer made of a cured product of the dispersed particles in the part irradiated with the active energy rays;
After the irradiation of the active energy rays, the second film is dried to remove at least a portion of the second liquid from the second film, thereby moving at least a portion of the uncured first liquid in the area not irradiated with the active energy rays into the granular layer , and at least a portion of the material of the first film is fluidized, dissolved in the uncured first liquid, or fluidized and dissolved in the uncured first liquid, thereby moving at least a portion of the material of the first film into the granular layer;
and then curing the uncured first liquid. The method according to claim 3, wherein the material includes a thermoplastic resin, and at least a portion of the material that has been heated and fluidized is transferred to the granular layer. The method according to any one of claims 1 to 4, wherein the first film is provided only on a partial region of the substrate, the second film is formed on at least a portion of the first film and on another partial region of the substrate, and the active energy rays are irradiated to at least a portion of the region of the second film that is located on the first film and at least a portion of the region of the second film that is not located on the first film. The method according to claim 1 or 3, wherein the material includes a resin that is cured by irradiation with active energy rays, and further includes irradiating the first film with the active energy rays in a pattern before forming the second film, thereby curing the resin in the area irradiated with the active energy rays. The method according to any one of claims 1 to 6, wherein the emulsion is an oil-in-water emulsion. A patterned film formed by the method according to any one of claims 1 to 7.