JP7211180B2 - Method for forming pattern film and pattern film - Google Patents

Description

The present invention relates to patterned films.

Various methods have been reported as methods for forming a patterned film, such as a method utilizing irradiation of active energy rays such as ultraviolet rays and electron beams, and a method using a self-organizing material such as a block copolymer.

JP 2009-260330 A JP 2016-197176 A

An object of the present invention is to provide a technique that enables formation of a pattern film by a simple method.

According to the first aspect of the present invention, 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 are included on a substrate. forming a film made of an emulsion; irradiating the film with the active energy ray in a pattern to cure the first liquid in the region irradiated with the active energy ray; and irradiating the active energy ray. subsequently removing at least a portion of the second liquid from the film; and curing the uncured first liquid contained in the film from which the at least a portion of the second liquid has been removed. A method of forming a patterned film is provided.

According to the second aspect of the present invention, 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 are included on a substrate. forming a film made of an emulsion; and irradiating the film with the active energy ray in a pattern to form a granular layer made of a cured product of the dispersed particles in the region irradiated with the active energy ray. and removing at least part of the second liquid from the film after irradiation with the active energy ray, and removing at least part of the uncured first liquid from the region not irradiated with the active energy ray. A method is provided for forming a patterned film comprising transferring to a granular layer and curing the uncured first liquid contained in the film from which at least a portion of the second liquid has been removed.

A third aspect of the present invention provides a patterned film formed by the method according to the first or second aspect.

ADVANTAGE OF THE INVENTION According to this invention, the technique which enables formation of a pattern film by a simple method is provided.

FIG. 2 is a cross-sectional view schematically showing an example of a state in which a film made of emulsion is formed on a substrate; FIG. 4 is a cross-sectional view schematically showing an example of a state in which a granular layer made of a cured product of dispersed particles is formed in the region irradiated with ultraviolet rays by pattern irradiation of ultraviolet rays. FIG. 4 is a cross-sectional view schematically showing an example of a state in which dispersed particles coalesce in a non-irradiated region by starting to remove the second liquid from the film; FIG. 10 is a cross-sectional view schematically showing an example of a state in which coalescence of the dispersed particles further progresses in the non-irradiated region, and the coalescence of the dispersed particles permeates and diffuses into a granular layer made of a cured product of the dispersed particles. FIG. 5 is a cross-sectional view schematically showing an example of a state in which the removal of the second liquid is completed and the coalescence of the dispersed particles has completely moved to the granular layer; FIG. 4 is a cross-sectional view schematically showing an example of a state in which an uncured first liquid is cured by irradiating the entire surface with ultraviolet rays; Optical micrograph of the emulsion. The graph which shows the particle size distribution of an emulsion. A photograph showing a state in which an emulsion is filled in a reservoir cell. A photograph showing a state in which a metal mask is placed on a liquid reservoir cell via a spacer. The photograph which shows the state which irradiated the parallel light of the ultraviolet-ray from the metal mask. A photograph showing the state of the film immediately after the end of exposure. A photograph showing the state of the film 1 minute after starting room-temperature drying of the emulsion after exposure. The photograph which shows the state of the film|membrane 5 minutes after starting room temperature drying of an emulsion after exposure. A photograph showing the state of the film 10 minutes after starting room-temperature drying of the emulsion after exposure. A photograph showing the state of the film 15 minutes after starting to dry the emulsion at room temperature after exposure. A photograph showing the state of the film 20 minutes after starting room-temperature drying of the emulsion after exposure. The photograph which shows the state of the film|membrane 30 minutes after starting room temperature drying of the emulsion after exposure. A photograph showing the state of the film 45 minutes after starting room temperature drying of the emulsion after exposure. A photograph showing the state of a sample obtained by starting room-temperature drying of the emulsion after exposure, then exposing the entire surface one minute later, and then removing the residual dispersion medium. A photograph showing the state of a sample obtained by drying the emulsion at room temperature after exposure, then exposing the entire surface 5 minutes later, and then removing the residual dispersion medium. A photograph showing the state of a sample obtained by drying the emulsion at room temperature after exposure, then exposing the entire surface 10 minutes later, and then removing the residual dispersion medium. A photograph showing the state of a sample obtained by starting room-temperature drying of the emulsion after exposure, performing overall exposure 15 minutes later, and then removing the residual dispersion medium. A photograph showing the state of a sample obtained by starting room-temperature drying of the emulsion after exposure, performing overall exposure 20 minutes later, and then removing the residual dispersion medium. A photograph showing the state of a sample obtained by starting room-temperature drying of the emulsion after exposure, performing overall exposure 30 minutes later, and then removing the residual dispersion medium. A photograph showing the state of a sample obtained by starting room-temperature drying of the emulsion after exposure, performing overall exposure 45 minutes later, and then removing the residual dispersion medium. FIG. 10B is a diagram showing an image obtained by measuring the three-dimensional shape of the sample (dried film) of FIG. 10A after aluminum vapor deposition. The figure which shows the image which measured the three-dimensional shape after performing aluminum vapor deposition on the sample (dry film) of FIG. 10B. The figure which shows the image which measured the three-dimensional shape after performing aluminum vapor deposition on the sample (dry film) of FIG. 10C. The figure which shows the image which measured the three-dimensional shape after performing aluminum vapor deposition on the sample (dry film) of FIG. 10D. The figure which shows the image which measured the three-dimensional shape after performing aluminum vapor deposition on the sample (dry film) of FIG. 10E. The figure which shows the image which measured the three-dimensional shape after performing aluminum vapor deposition on the sample (dry film) of FIG. 10F. The figure which shows the image which measured the three-dimensional shape after performing aluminum vapor deposition on the sample (dry film) of FIG. 10G. 4 is a graph showing the relationship between the drying time of the emulsion and the height difference between the irradiated area and the non-irradiated area. A photograph showing the state of the film immediately after exposure. The photograph which shows the state of the film|membrane 2 minutes after starting hotplate drying of emulsion. A photograph showing the state of the film after 2 minutes and 30 seconds from the start of hot plate drying of the emulsion. A photograph showing the state of the film after 2 minutes and 40 seconds from the start of hot plate drying of the emulsion. A photograph showing the state of the film after 3 minutes and 30 seconds from the start of hot plate drying of the emulsion. The photograph which shows the state of the film|membrane 5 minutes after starting hot plate drying of emulsion.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Components having the same or similar functions are denoted by the same reference numerals throughout the drawings, and overlapping descriptions are omitted.

The method for forming the pattern film will be described below in the order of steps. In order to facilitate understanding of each step, examples of the state of the film in each step are shown in FIGS. 1 to 6, and these drawings will be referred to in the following description.

<Preparation of emulsion>
First, 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 is prepared.

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

The dispersed particles contain a first liquid that is cured by irradiation with active energy rays. Active energy rays include, for example, ultraviolet rays, electron beams, and X-rays. As the first liquid, for example, an acrylic monomer or oligomer, a methacrylic monomer or oligomer, an epoxy monomer or oligomer, or a mixture containing one or more thereof can be used. As the first liquid, it is preferable to use acrylic monomers or oligomers or methacrylic monomers or oligomers because of the advantages of a wide range of options and a large degree of freedom in adjusting physical properties. As the first liquid, for example, trimethylolpropane triacrylate can be used. The ratio of monomers and oligomers in the first liquid is, for example, 30 to 100% by mass.

It should be noted that there are more types of liquids that are lipophilic than those that are hydrophilic as liquids that are cured by irradiation with active energy rays. Therefore, the O/W type emulsion has a higher degree of freedom in material selection than the W/O type emulsion.

The dispersion medium contains a second liquid that is not cured by irradiation with 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 mixtures thereof. On the other hand, if the first liquid is a hydrophilic liquid, the second liquid can be a lipophilic liquid such as an isoparaffinic solvent or mineral spirits.

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

Moreover, the proportion of the 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 region irradiated with the active energy ray is raised by effectively utilizing the heat of polymerization, thereby destabilizing the dispersed state of the dispersed particles containing the first liquid. It is possible to form a cohesive layer at the same time. Moreover, the upper limit of the proportion of the dispersed particles in the emulsion is not particularly limited as long as it does not cause phase inversion of the emulsion. According to one example, this proportion is 60% by weight or less.

The first liquid may further contain a photopolymerization initiator. As the photopolymerization initiator, a known photopolymerization initiator such as an alkylphenone photopolymerization initiator can be used. Examples of alkylphenone-based photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone. The first liquid may contain a photopolymerization initiator in an amount of, for example, 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the monomer and oligomer.

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

The dispersion medium may further contain a surfactant. As the surfactant, for example, those commercially available for use in emulsion polymerization can be used. As the surfactant, for example, a sulfosuccinate type surfactant such as dioctyl sodium sulfosuccinate can be used. The emulsion may contain surfactants in an amount of, for example, 0.1 to 5.0% by weight relative to the total weight of the emulsion.

In the case of an O/W emulsion, the dispersion medium generally contains a surfactant in order to ensure emulsification and stability of the dispersed particles. In addition, the O/W emulsion may contain a water-soluble polymer, cellulose nanofibers, etc. in the dispersion medium in order to improve the long-term storage stability of the emulsion. Furthermore, if necessary, the O/W emulsion may contain a viscosity modifier and an antifoaming agent in the dispersion medium.

On the other hand, in the case of a W/O type emulsion, the dispersion medium contains a nonionic surfactant or a polymeric dispersion stabilizer having a suitable hydrophilic-lipophilic balance (HLB) value in order to prepare a stable emulsion. be able to. If necessary, the W/O emulsion may effectively contain an ionic surfactant in the dispersion medium.

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

<Formation of film>
Next, a film made of the above emulsion is formed on the substrate. Hereinafter, "film made of emulsion" is also referred to as liquid film. Specifically, a liquid film can be formed on a substrate by applying the above emulsion onto the substrate. Any base material can be used as the base material, for example, a film or a sheet can be used.

The coating method is not particularly limited, but an appropriate coating method such as die coating, comma coating, or curtain coating can be selected according to the thickness of the liquid film. The thickness of the liquid film can be, for example, 10 to 3000 μm. Moreover, 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.

FIG. 1 schematically shows an example of a state in which a film made of emulsion is formed on a substrate. In FIG. 1, a film 2a made of an emulsion composed of dispersed particles 21a and a dispersion medium 22 is formed on a substrate 1. As shown in FIG.

<Irradiation of active energy rays>
Next, the formed film is irradiated with an active energy ray in a pattern. Examples of active energy rays include ultraviolet rays, electron beams, and X-rays, as described above. Pattern irradiation can be carried out, for example, by selectively irradiating an active energy ray through a mask or by selectively irradiating a laser beam.

Due to the pattern irradiation of the active energy rays, the first liquid contained in the dispersed particles is cured by polymerization in the regions irradiated with the active energy rays (hereinafter also referred to as irradiation regions). Thereby, a granular layer made of a cured product of the dispersed particles can be formed.

FIG. 2 schematically shows an example of a state in which a granular layer made of a cured product of dispersed particles is formed in the region irradiated with ultraviolet rays by pattern irradiation of ultraviolet rays. As shown in FIG. 2, in the region irradiated with the ultraviolet rays, the first liquid contained in the dispersed particles 21a is cured by polymerization, and the dispersed particles 21a become a cured product 21b1 of the dispersed particles. The cured product 21b1 of the dispersed particles aggregates and stacks, and as a result, the granular layer 21b composed of the cured product 21b1 of the dispersed particles is formed. Since the second liquid contained in the dispersion medium 22 is not cured in the region irradiated with the ultraviolet rays, the dispersion medium 22 exists in the granular layer 21b, specifically, in the gaps between the cured products 21b1. On the other hand, in FIG. 2, the first liquid contained in the dispersed particles 21a remains uncured in the regions not irradiated with ultraviolet rays (hereinafter also referred to as non-irradiated regions).

The present inventor considers the reason for the aggregation mechanism of the cured product 21b1 in the irradiated area as follows.

Irradiation of the active energy rays causes the dispersed particles 21a to generate heat due to polymerization, which raises the temperature of the irradiated region. Due to this temperature rise, the surfactant adsorbed on the surface of the dispersed particles 21a to stabilize the dispersion of the dispersed particles 21a is desorbed. As a result, the surface potential of the dispersed particles 21a in which the polymerization has progressed is lowered. As a result, the dispersion of the dispersed particles 21a or the cured product 21b1 thereof becomes unstable, promoting aggregation of the particles. In addition, polymerization and cross-linking may occur between particles during the process of particles aggregating and coming into contact with each other.

Moreover, this aggregation is completed before the surfactant desorbed due to the temperature rise due to the heat generated by the polymerization is re-adsorbed to the particles. Thereby, the aggregated particles maintain their aggregation state without being re-dispersed.

Aggregation of the cured product 21b1 in the irradiated area may be promoted by adding a cross-linking agent to the dispersion medium in advance. This facilitates the formation of cross-links between particles during irradiation with active energy rays, and as a result, promotes aggregation of the particles.

<Removal of Second Liquid>
At least part of the second liquid is removed from the film after the irradiation with the active energy ray. At least part of the second liquid may be removed in this step, but all of the second liquid may be removed. Removal of the second liquid can be performed, for example, by drying the membrane. Drying is preferably performed until the amount of the second liquid is 30% by mass or less, more preferably 5% by mass or less, of the amount of the second liquid immediately after forming the liquid film. The removal of the second liquid may be carried out by leaving the film at room temperature, but is preferably carried out by heating and drying the film. Heat drying can be performed by heating the film at a temperature within the range of 40 to 100° C. for 0.1 to 1 hour, for example. By removing the second liquid, at least part of the uncured first liquid can be moved from the region not irradiated with the active energy ray to the granular layer composed of the cured dispersed particles.

In this step, the removal of the second liquid causes at least a portion of the uncured first liquid to migrate from the non-irradiated areas to the granular layer of cured dispersed particles. The movement of the uncured first liquid from the non-irradiated areas to the granular layer may be performed so that all of it moves to the granular layer, or only a portion of it moves to the granular layer. .

In this method, it is not necessary to perform the development step, that is, the removal of the uncured first liquid using a developer after the irradiation of the active energy ray.

3 to 5 schematically show an example of the film state change caused by the removal of the second liquid. FIG. 3 schematically illustrates an example of a situation in which coalescence of dispersed particles has occurred in non-irradiated areas by initiating removal of the second liquid from the membrane. FIG. 4 schematically shows an example of a state in which the coalescence of the dispersed particles further progresses in the non-irradiated region, and the coalescence of the dispersed particles permeates and diffuses into the granular layer composed of the cured product of the dispersed particles. ing. FIG. 5 schematically shows an example of a state in which the removal of the second liquid is completed and the coalescence of the dispersed particles has completely moved to the granular layer.

When part of the second liquid contained in the dispersion medium 22 is removed from the film 2a, as shown in FIG. In the non-irradiated area, as the second liquid decreases, the dispersed particles 21a coalesce to form a coalesced body 21a'. Then, as shown in FIG. 4, the uncured first liquid that forms these coalesced bodies 21a' permeates the gaps in the granular layer 21b and diffuses into the granular layer 21b. This permeation and diffusion are thought to proceed by capillary forces. When the removal of the second liquid is completed, the transfer of the uncured first liquid from the non-irradiated areas to the granular layer 21b is completed. As a result, for example, the structure shown in FIG. 5 is obtained. When the second liquid is completely removed from the film, the liquid remaining in the film is, for example, only the liquid that constitutes the dispersed particles 21a or their combined bodies 21a'.

<Pattern fixation>
Finally, the uncured first liquid contained in the film from which the second liquid has been removed is cured. Curing of the uncured first liquid can be performed, for example, by irradiating the entire film with active energy rays. A pattern film is thus formed.

FIG. 6 schematically shows an example of a state in which the uncured first liquid is cured by irradiating the entire surface with ultraviolet rays. As shown in FIG. 6, when the entire film is irradiated with ultraviolet rays, the uncured first liquid is cured by polymerization. As a result, a polymerized phase 21b2 is formed. Further, in the cured product 21b1 forming the granular layer 21b, further polymerization progresses due to ultraviolet irradiation. As a result, the pattern film 2b composed of the cured product 21b1 of the dispersed particles and the polymerized phase 21b2 is formed.

As mentioned above, the curing of the uncured first liquid can take place after all of the uncured first liquid present in the non-irradiated areas has migrated from these areas into the granular layer. Alternatively, curing of the uncured first liquid can also take place when only a portion of the uncured first liquid present in the non-irradiated areas migrates from these areas into the granular layer. For example, irradiation of the entire film with active energy rays is performed before the second liquid is completely removed from the film (that is, the first liquid in the non-irradiated area penetrates the granular layer and diffuses into the granular layer). An intermediate stage, such as the stage in FIG. 4, may be performed. In this way, it is possible to obtain a pattern film having a thickness in the non-irradiated regions and the irradiated regions being thicker than the non-irradiated regions.

<effect>
In the above method, patterns can be formed spontaneously (in a self-organizing manner) simply by pattern-irradiating an emulsion film with active energy rays and then removing the second liquid. The above method does not require a guide pattern to be provided on the substrate in advance, nor does it require a development step. Therefore, the above method is a simple method.

In addition, the pattern size that can be realized by the conventional technique is, for example, a line width of several nanometers to several hundreds of micrometers and a height difference of several nanometers to several hundred micrometers. It is possible. For example, according to the above method, it is possible to form a pattern film having a large line width or height difference, for example, a pattern film having a line width of micro-order to milli-order or a height difference of micro-order to milli-order. . According to one example, according to the above method, a pattern film having a line width in the range of 10 μm to 5 mm and a pattern film having a height difference in the range of 10 μm to 2 mm can be formed.

Furthermore, the above method is excellent in controllability of pattern shape and size, and can form pattern films of various shapes and sizes.

<Preparation of emulsion>
An O/W emulsion was prepared using the following materials.
Monomer or oligomer: trimethylolpropane triacrylate Photoinitiator: α-hydroxyketone (IRGACURE (registered trademark) 184 manufactured by BASF)
Surfactant: sodium dioctyl sulfosuccinate (Sunmorin (registered trademark) OT-70 manufactured by Sanyo Chemical Industries)
Second Liquid: Water First, 2.60 g of surfactant was dissolved in 90 mL of the second liquid. Next, a first liquid prepared by pre-dissolving 3.75 g of a photoinitiator in 75 mL of trimethylolpropane triacrylate was added dropwise to this solution while lightly stirring with a propeller to prepare a coarse droplet dispersion. bottom. A 20 mL aliquot was taken from this droplet dispersion and transferred to a 50 mL brown vial. Next, the brown vial containing the liquid droplet dispersion was mounted on a paint shaker PC1171 manufactured by Asada Iron Works Co., Ltd., and emulsified by shaking for 30 seconds. This gave an emulsion with a particle size distribution (average particle size: 87.3 μm). For the particle size distribution, the weight average diameter was measured by a measuring system comprising a particle size distribution measuring device Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. and a liquid circulation pump Microtrac USVR also manufactured by Nikkiso Co., Ltd. attached. The resulting emulsion is composed of dispersed particles (hereinafter also referred to as emulsion droplets) containing the first liquid and a dispersion medium containing the second liquid. An optical microscope photograph of the prepared emulsion is shown in FIG. 7, and the particle size distribution is shown in FIG.

<Formation of film>
Five layers of masking tape manufactured by 3M with a width of 20 mm and a thickness of 80 μm were pasted along the long side of the surface of a microscope slide glass, and the central portion was cut out in a rectangular shape, resulting in a depth of 400 μm. , a cell having a liquid reservoir with an area of 10 mm x 30 mm (hereinafter referred to as a liquid reservoir cell) was produced.

Next, 112 μL of the emulsion is sampled with a micropipette, and this is developed and filled in a liquid reservoir cell to prepare an emulsion film (i.e., liquid film) having a thickness of about 375 μm as a calculated value considering specific gravity. bottom. FIG. 9A shows a photograph showing the state in which the emulsion is filled in the reservoir cell.

<Irradiation of UV rays>
A 0.25 mm-thick copper mask having striped openings with a pitch of 2 mm was placed on the liquid film via a 1 mm-thick aluminum spacer so as not to come into contact with the liquid surface. FIG. 9B shows a photograph showing the state in which the copper mask is installed. Next, using a UV parallel light exposure machine (UVC-2502S manufactured by SAN-EI ELECTRONIC), ultraviolet light with an illuminance of 4.6 mW/cm ² is irradiated from the mask for 8 seconds, so that the liquid film has an integrated light amount of 36. An exposure of 0.8 mJ/cm ² was given. FIG. 9C shows a photograph showing a state in which the liquid film is irradiated with ultraviolet rays. As a result, the first liquid was polymerized in the region irradiated with the ultraviolet rays to form a granular layer made of a cured product of the dispersed particles.

<Drying of membrane>
Then, the film after exposure to ultraviolet light was naturally dried at room temperature for 45 minutes (23° C., 57% RH). Photographs showing the state of the membrane during the drying process are shown in Figures 9D-9K. Immediately after exposure, an agglomerated pattern has already been formed in the irradiated area (see FIG. 9D), and as drying progresses, uncured emulsion droplets in the non-irradiated area coalesce and break, forming a granular layer in the irradiated area. (See Figures 9E to 9K). It can be seen from FIGS. 9D and 9I that the uncured emulsion droplets in the non-irradiated areas coalesce as drying progresses and change into larger droplets. As a result, coalescence of the dispersed particles containing the unpolymerized first liquid was promoted in the regions not irradiated with ultraviolet rays, and the coalesced particles were moved to the granular layer to form an uneven pattern.

Furthermore, in order to quantitatively grasp the formation process of the concave-convex pattern due to drying, the uncured emulsion in the non-irradiated area was exposed to UV light with an integrated light intensity of 36.8 mJ/ ^cm2 for each elapsed drying time. The liquid droplets were also subjected to a curing treatment to fix the uneven structure in the liquid film at that time. Subsequently, by removing the remaining water (second liquid) of the dispersion medium by drying at room temperature for 2 hours, uneven pattern samples with different drying elapsed times were produced. Finally, as temporary adhesion, the entire surface was exposed to ultraviolet light with an integrated light amount of 138 mJ/cm ² . Photographs of the uneven pattern samples are shown in FIGS. 10A to 10G.

In order to measure the height difference between the irradiated area and the non-irradiated area in the samples shown in FIGS. After that, the three-dimensional shape was measured using a one-shot 3D shape measuring machine VR3100 manufactured by Keyence Corporation. The images are shown in FIGS. 11A-11G. The images shown in FIGS. 11A to 11G are stretched three times in the depth direction of the film to enhance the three-dimensional effect. Also, FIG. 12 shows n=5 average values of the measured values of the height difference between the irradiated area and the non-irradiated area. From the results of FIG. 12, a pattern appeared immediately after exposure, and there was a height difference of about 200 μm at the initial stage after 1 minute of drying. was obtained. It should be noted that the height difference is slightly reduced after 5 minutes of drying. This is because some of the emulsion droplets in the non-irradiated area gathered at the edge fall back into the original non-irradiated area when the exposure is finished.

<Pattern fixation>
Finally, the entire surface of the film on which pattern formation was completed was exposed to ultraviolet light with an integrated light amount of 276 mJ/cm ² . This fixed the pattern. The line width of the pattern film as an average value of n=5 was 2.46 mm, and the height difference was 390 μm.

The preparation of the emulsion, the formation of the film, the irradiation method and conditions of the ultraviolet rays were the same as in Example 1, and the pattern was produced by changing only the drying conditions.

Immediately after the pattern exposure, the liquid reservoir cell was dried by heating on a hot plate heated to 100° C. using a spacer while being suspended in the air by 1 mm. Photographs showing changes in the liquid film over time are shown in FIGS. 13A to 13F. Drying was completed in about 5 minutes, and a pattern similar to that of Example 1 was formed, with a height difference of 397 μm and a line width of 2.28 mm at n=5 average. Heating accelerates the evaporation of water and at the same time lowers the viscosity of uncured emulsion droplets in the non-irradiated areas, thereby increasing the rate of permeation and absorption into the granular layer in the irradiated areas, thereby quickly completing pattern formation.
The claims as originally filed for the present application are described below as embodiments.
[1] A film 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 is formed on a substrate. and
irradiating the film with the active energy ray in a pattern to cure the first liquid in the region irradiated with the active energy ray;
removing at least a portion of the second liquid from the film after irradiation with the active energy ray;
curing the uncured first liquid contained in the film from which at least a portion of the second liquid has been removed;
A method of forming a patterned film comprising:
[2] Forming, on a substrate, a film 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. and
irradiating the film with the active energy ray in a pattern to form a granular layer made of a cured product of the dispersed particles in the region irradiated with the active energy ray;
After the irradiation with the active energy ray, at least part of the second liquid is removed from the film, and at least part of the uncured first liquid is removed from the region not irradiated with the active energy ray into the granular form. moving to a layer; and
curing the uncured first liquid contained in the film from which at least a portion of the second liquid has been removed;
A method of forming a patterned film comprising:
[3] When only a part of the uncured first liquid present in the region not irradiated with the active energy ray moves from this region to the granular layer, the film contains The method of [2], wherein the uncured first liquid is cured.
[4] The method according to any one of [1] to [3], including curing the uncured first liquid contained in the film before completely removing the second liquid from the film. the method of.
[5] The method according to any one of [1] to [4], wherein the dispersion medium further contains a surfactant.
[6] The method according to any one of [1] to [5], wherein the emulsion is an oil-in-water emulsion.
[7] The method according to [6], wherein the dispersed particles further include hydrohove.
[8] A pattern film formed by the method according to any one of [1] to [7].

DESCRIPTION OF SYMBOLS 1... Base material 2a... Film 2b... Pattern film 21a... Dispersed particles 21a'... Union of dispersed particles 21b... Granular layer 21b1... Cured product of dispersed particles 21b2... Polymer phase 22... Dispersion medium .

Claims (8)

forming, on a substrate, a film 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 the film with the active energy ray in a pattern to cure the first liquid in the region irradiated with the active energy ray;
removing at least part of the second liquid from the film by drying after the irradiation with the active energy ray;
subsequently curing the uncured first liquid contained in the film from which at least part of the second liquid has been removed; forming, on a substrate, a film 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 the film with the active energy ray in a pattern to form a granular layer made of a cured product of the dispersed particles in the region irradiated with the active energy ray;
After the irradiation with the active energy ray, at least part of the second liquid is removed from the film, and at least part of the uncured first liquid is removed from the region not irradiated with the active energy ray into the granular form. moving to a layer; and
and curing the uncured first liquid contained in the film from which at least part of the second liquid has been removed. When only part of the uncured first liquid existing in the region not irradiated with the active energy ray moves from this region to the granular layer, the uncured liquid contained in the film 3. The method of claim 2, wherein the first liquid is cured. 4. A method according to any one of the preceding claims, comprising curing the uncured first liquid contained in the film before completely removing the second liquid from the film. 5. The method of any one of claims 1-4, wherein the dispersion medium further comprises a surfactant. 6. The method of any one of claims 1-5, wherein the emulsion is an oil-in-water emulsion. 7. The method of claim 6, wherein said dispersed particles further comprise hydrophobes. A patterned film formed by the method according to any one of claims 1 to 7 , wherein the second liquid is completely removed .

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