JP2022015930A - Method for forming pattern film, pattern film, and structure - Google Patents

Abstract

To provide a technique allowing formation of a pattern film with a simple method.SOLUTION: A method for forming a pattern film of the present invention includes: forming, on a base having a plurality of concave parts, a film composed of an emulsion including dispersion particles including first liquid that is cured by irradiation with an active energy ray and a dispersion medium including second liquid that is not cured by irradiation of the active energy ray; irradiating the film with the active energy ray in a pattern shape to cure the first liquid in an area where the film is irradiated with the active energy ray; after the irradiation with the active energy ray, removing at least a part of the second liquid from the film; and curing the uncured first liquid included in the film from which at least a part of the second liquid is removed.SELECTED DRAWING: None

Description

The present invention relates to a patterned film.

As a method for forming a pattern film, various methods such as a method using irradiation with active energy rays such as ultraviolet rays and electron beams and a method using a self-assembling material such as a block copolymer have been reported.

Japanese Unexamined Patent Publication No. 2009-260330 Japanese Unexamined Patent Publication No. 2016-197176

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

According to the first aspect of the present invention, on a substrate having a plurality of recesses, dispersion particles containing a first liquid that is cured by irradiation with active energy rays and dispersion containing a second liquid that is not cured by irradiation with the active energy rays. Forming a film made of an emulsion containing a medium, irradiating the film with the active energy rays in a pattern, and curing the first liquid in the region irradiated with the active energy rays, and the activity. After irradiation with energy rays, at least a part of the second liquid is removed from the film, and the uncured first liquid contained in the film from which at least a part of the second liquid is removed is cured. A method for forming a patterned film including the energy is provided.

According to the second aspect of the present invention, on a substrate having a plurality of recesses, dispersion particles containing a first liquid that is cured by irradiation with active energy rays and dispersion containing a second liquid that is not cured by irradiation with the active energy rays. A film made of an emulsion containing a medium is formed so that the emulsion does not completely embed the plurality of recesses, and the film is irradiated with the active energy rays in a pattern to obtain the active energy rays. After forming a granular layer made of a cured product of the dispersed particles in the irradiated region and irradiating the activated energy ray, at least a part of the second liquid is removed from the film to obtain the active energy ray. At least a part of the uncured first liquid in the unirradiated region is moved into the gaps in the granular layer and the plurality of recesses, and then the uncured first liquid is transferred. A method for forming a pattern film including curing is provided.

According to the third aspect of the present invention, a first dispersed particle containing a first liquid that is cured by irradiation with a first active energy ray and a second liquid that is not cured by irradiation with the first active energy ray are formed on a substrate. Forming a first film composed of a first emulsion containing a first dispersion medium, irradiating the first film with the first active energy ray to cure the first liquid, and the first. After irradiation with 1 active energy ray, the second liquid is removed from the first film to obtain a porous layer made of a cured product of the first liquid, and the second active energy is placed on the porous layer. A second film composed of a second emulsion containing a second dispersion particle containing a third liquid that is cured by irradiation with a ray and a second dispersion medium containing a fourth liquid that is not cured by irradiation with the second active energy ray is formed. By irradiating the second film with the second active energy ray in a pattern, the third liquid is cured in the region irradiated with the second active energy ray, and the second active energy ray is applied. After the irradiation, at least a part of the fourth liquid is removed from the second film, and the uncured third liquid contained in the second film from which at least a part of the fourth liquid is removed is removed. A method for forming a patterned film, including curing, is provided.

According to the fourth aspect of the present invention, a first dispersed particle containing a first liquid that is cured by irradiation with a first active energy ray and a second liquid that is not cured by irradiation with the first active energy ray are formed on a substrate. A porous material made of a cured product of the first dispersed particles is formed by forming a first film containing the first dispersion medium containing the first dispersion medium and irradiating the first film with the first active energy ray. A second dispersed particle containing a third liquid that is cured by forming a layer, removing the second liquid from the porous layer, and irradiating the porous layer with a second active energy ray. Forming a second film composed of a second emulsion containing a second dispersion medium containing a fourth liquid that is not cured by irradiation with the second active energy ray, and patterning the second active energy ray on the second film. After irradiating in a shape to form a granular layer made of a cured product of the second dispersed particles in the region irradiated with the second active energy ray, and after irradiating the second active energy ray, the second film. At least a part of the fourth liquid is removed from the liquid, and at least a part of the uncured third liquid in the region not irradiated with the second active energy ray is put into the granular layer and the porous layer. A method for forming a pattern film is provided, which comprises moving the liquid and then curing the uncured third liquid.

According to the fifth aspect of the present invention, there is provided a pattern film formed by the method according to any one of the first to fourth aspects.

According to the sixth aspect of the present invention, a substrate having a plurality of recesses, a granular layer partially covering the substrate, and a cured product in which the gaps between the plurality of recesses and the granular layer are at least partially embedded. A structure comprising the above is provided.

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a technique that enables the formation of a patterned film by a simple method.

FIG. 3 is a cross-sectional view schematically showing a step of forming a first film made of a first emulsion in the method for forming a pattern film according to an embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing an irradiation step of a first active energy ray in the method for forming a pattern film according to an embodiment of the present invention. FIG. 3 is a cross-sectional view schematically showing a structure obtained after a step of removing a second liquid in the method for forming a pattern film according to an embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing a process of forming a second film composed of a second emulsion in the method for forming a pattern film according to an embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing an irradiation step of a second active energy ray in the method for forming a pattern film according to an embodiment of the present invention. FIG. 3 is a cross-sectional view schematically showing a step of removing a fourth liquid in the method for forming a pattern film according to an embodiment of the present invention. FIG. 3 is a cross-sectional view schematically showing a structure obtained after a step of removing a fourth liquid in the method for forming a pattern film according to an embodiment of the present invention. FIG. 3 is a cross-sectional view schematically showing a curing step of an uncured third liquid in the method for forming a pattern film according to an embodiment of the present invention. In the pattern film forming method similar to the methods of FIGS. 1 to 8 except that the porous layer is omitted, the film immediately after being irradiated with the active energy rays in a pattern and the black layer are placed behind the sample. An optical micrograph taken. In the pattern film forming method similar to the methods of FIGS. 1 to 8 except that the porous layer is omitted, the film 20 minutes after the completion of the patterned irradiation of the active energy rays is placed behind the sample. An optical micrograph taken with a black layer installed. In the pattern film forming method similar to the methods of FIGS. 1 to 8 except that the porous layer is omitted, the film 40 minutes after the completion of the patterned irradiation of the active energy rays is placed behind the sample. An optical micrograph taken with a black layer installed. In the pattern film forming method similar to the method of FIGS. 1 to 8 except that the porous layer is omitted, the film 50 minutes after the completion of the patterned irradiation of the active energy rays is placed behind the sample. An optical micrograph taken with a black layer installed. In the pattern film forming method similar to the methods of FIGS. 1 to 8 except that the porous layer is omitted, the film 60 minutes after the completion of the patterned irradiation of the active energy rays is placed behind the sample. An optical micrograph taken with a black layer installed. In the pattern film forming method similar to the methods of FIGS. 1 to 8 except that the porous layer was omitted, the film 70 minutes after the completion of the patterned irradiation of the active energy rays was placed behind the sample. An optical micrograph taken with a black layer installed. An optical micrograph of the film of FIG. 14 with a white layer placed behind the sample. In the pattern film forming method similar to the methods of FIGS. 1 to 8 except that the porous layer is omitted, the film 120 minutes after the completion of the patterned irradiation of the active energy rays is placed behind the sample. An optical micrograph taken with a black layer installed. An optical micrograph of the film of FIG. 16 with a white layer placed behind the sample. An optical micrograph taken by sputtering gold on the film of FIG. 16. The graph which shows the particle size distribution of an emulsion. The graph which showed the relationship between the penetration depth of an oligomer into a porous layer, and the elapsed time, which was obtained assuming that the void of a porous layer is a capillary tube. The graph which showed the relationship between the permeation volume of an oligomer into a porous layer and the elapsed time, which was obtained assuming that the void of a porous layer is a capillary tube. In the methods of FIGS. 1 to 8, the average particle size of the first dispersed particles and the average particle size of the second dispersed particles are 49.8 μm and 28.1 μm, respectively, and the amount of the first emulsion and the amount of the second emulsion are respectively. An optical micrograph taken by illuminating the film obtained when the particle size is 75 μL with oblique incident light. In the methods of FIGS. 1 to 8, the average particle size of the first dispersed particles and the average particle size of the second dispersed particles are 49.8 μm and 28.1 μm, respectively, and the amount of the first emulsion and the amount of the second emulsion are set respectively. Optical micrographs taken by illuminating the films obtained at 75 μL and 82 μL with oblique incident light. In the methods of FIGS. 1 to 8, the average particle size of the first dispersed particles and the average particle size of the second dispersed particles are 49.8 μm and 28.1 μm, respectively, and the amount of the first emulsion and the amount of the second emulsion are set respectively. Optical micrographs taken by illuminating the films obtained at 75 μL and 90 μL with oblique incident light. In the methods of FIGS. 1 to 8, the average particle size of the first dispersed particles and the average particle size of the second dispersed particles are 49.8 μm and 28.1 μm, respectively, and the amount of the first emulsion and the amount of the second emulsion are set respectively. Optical micrographs taken by illuminating the films obtained at 75 μL and 100 μL with oblique incident light. In the methods of FIGS. 1 to 8, the average particle size of the first dispersed particles and the average particle size of the second dispersed particles are 49.8 μm and 28.1 μm, respectively, and the amount of the first emulsion and the amount of the second emulsion are set respectively. Optical micrographs taken by illuminating the films obtained at 75 μL and 112 μL with oblique incident light. In the methods of FIGS. 1 to 8, the average particle size of the first dispersed particles and the average particle size of the second dispersed particles are set to 28.1 μm and 49.8 μm, respectively, and the amount of the first emulsion and the amount of the second emulsion are respectively. An optical micrograph taken by illuminating the film obtained when the particle size is 75 μL with oblique incident light. In the methods of FIGS. 1 to 8, the average particle size of the first dispersed particles and the average particle size of the second dispersed particles are set to 28.1 μm and 49.8 μm, respectively, and the amount of the first emulsion and the amount of the second emulsion are set respectively. Optical micrographs taken by illuminating the films obtained at 75 μL and 112 μL with oblique incident light. The graph which shows the cross-sectional profile obtained by the three-dimensional shape measurement with respect to the membrane of FIG. 22 and FIG. 27. The graph which shows the cross-sectional profile obtained by the three-dimensional shape measurement with respect to the membrane of FIG. 26 and FIG. 28.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Components that exhibit similar or similar functions are given the same reference numbers throughout the drawings, and duplicate explanations are omitted.

Hereinafter, the method for forming the pattern film will be described in the order of steps. In order to help understanding of each step, an example of the state of the film in each step is shown in FIGS. 1 to 8, and these drawings will be referred to in the following description.

<Preparation of the first emulsion>
First, a first emulsion containing a first dispersion particle containing a first liquid that is cured by irradiation with a first active energy ray and a first dispersion medium containing a second liquid that is not cured by irradiation with a first active energy ray is prepared. do.

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

The first dispersed particles include a first liquid that is cured by irradiation with the first active energy ray. Examples of the first active energy ray include 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 of them can be used. As the first liquid, it is preferable to use an acrylic monomer or an oligomer, or a methacrylic monomer or an oligomer because of the advantages such as a wide range of choices and a large degree of freedom in adjusting the physical properties. As the first liquid, for example, trimethylolpropane triacrylate or the like can be used. The proportion of the monomer and the oligomer in the first liquid is, for example, 30 to 100% by mass.

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

The first dispersion medium contains a second liquid that is not cured by irradiation with the first active energy ray. 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, when the first liquid is a hydrophilic liquid, the second liquid can be a lipophilic liquid, for example, an isoparaffin solvent or a mineral spirit.

According to one example, the average particle size of the first dispersed particles is in the range of 5 μm to 0.5 mm. Here, the "average particle size" is a weight average diameter obtained by measuring the particle size distribution according to the laser diffraction / scattering method. When the first dispersed particles have the above size, the uncured third liquid described later can be efficiently permeated into the gaps between the first cured particles formed by curing the first dispersed particles in a later step. ..

The average particle size of the first dispersed particles may be equal to or different from the average particle size of the second dispersed particles described later. In the latter case, the average particle size of the first dispersed particles may be smaller than the average particle size of the second dispersed particles, but it is preferably larger than the average particle size of the second dispersed particles. When the average particle size of the first dispersed particles is larger than the average particle size of the second dispersed particles, a pattern film having better shape accuracy can be formed. The ratio D1 / D2 of the average particle size D1 of the first dispersed particles to the average particle size D2 of the second dispersed particles is preferably in the range of 0.02 to 20, and preferably in the range of 0.1 to 10. It is more preferable to have.

The proportion of the first dispersed particles in the first emulsion is preferably 25% by mass or more. When the first dispersed particles occupy the above ratio in the first emulsion, the temperature of the region irradiated with the first active energy ray is raised by effectively utilizing the heat of polymerization, so that the first dispersion containing the first liquid is contained. The first aggregate layer can be formed at the same time as destabilizing the dispersed state of the particles. The upper limit of the proportion of the first dispersed particles in the first emulsion is not particularly limited as long as the phase inversion of the first emulsion does not occur. According to one example, this ratio 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. Examples of the alkylphenone-based photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone. The first liquid can contain the photopolymerization initiator in an amount of, for example, 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the monomer and the oligomer.

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

The first 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 sodium dioctyl sulfosuccinate can be used. The first emulsion can contain the surfactant in an amount of, for example, 0.1 to 5.0% by mass, based on the total mass of the first emulsion.

When the first emulsion is an O / W type emulsion, the first dispersion medium generally contains a surfactant in order to ensure emulsification and stability of the first dispersed particles. Further, in order to improve the long-term storage stability of the first emulsion, the O / W type emulsion may contain a water-soluble polymer, cellulose nanofibers, or the like in the first dispersion medium. Further, if necessary, the O / W type emulsion may contain a viscosity modifier and an antifoaming agent in the first dispersion medium.

On the other hand, when the first emulsion is a W / O type emulsion, in order to prepare a stable emulsion, the first dispersion medium is a nonionic surfactant or a polymer having a suitable hydrophilic lipophilic (HLB) value. A system dispersion stabilizer can be included. If desired, the W / O emulsion may also contain an ionic surfactant in the first dispersion medium.

The first emulsion can be prepared by utilizing known emulsification / dispersion techniques such as paint shaker, ultrasonic homogenizer, colloid mill, homogenizer, membrane emulsification method and the like.

<Formation of the first film>
Next, a first film composed of the first emulsion is formed on the substrate. Hereinafter, the "first film composed of the first emulsion" is also referred to as a first liquid film. Specifically, the first liquid film can be formed on the substrate by applying the first emulsion on the substrate. As the base material, any base material can be used, and for example, a film or a sheet can be used.

The coating method is not particularly limited, but an appropriate coating method, for example, a die coat, a comma coat, or a curtain coat can be selected depending on the thickness of the first liquid film. The thickness of the first liquid film can be, for example, 10 to 3000 μm. Further, when a small amount of the first emulsion is applied to form a first liquid film having a small area, a dispenser or the like can be used as needed.

FIG. 1 schematically shows an example of a state in which a first film made of a first emulsion is formed on a substrate. In FIG. 1, a first film 2a1 made of a first emulsion composed of a first dispersion particle 21a1 and a first dispersion medium 22a1 is formed on a base material 1.

<Irradiation of the first active energy ray>
Next, the formed first film is irradiated with the first active energy ray. As described above, examples of the first active energy ray include ultraviolet rays, electron beams, and X-rays.

The first active energy ray may irradiate the entire first film or may irradiate the first film in a pattern. The pattern irradiation can be performed, for example, by irradiating the first active energy ray regioselectively through a mask or the like, or by irradiating the laser beam regioselectively. Here, as an example, the first active energy ray is applied to the entire first film.

In the region of the first film irradiated with the first active energy ray (hereinafter, also referred to as the first irradiation region) by the irradiation with the first active energy ray, the first liquid contained in the first dispersed particles is cured by polymerization. do. This makes it possible to form a porous layer made of a cured product of the first dispersed particles.

FIG. 2 schematically shows an example of a state in which a porous layer made of a cured product of the first dispersed particles is formed by irradiation with ultraviolet rays. As shown in FIG. 2, in the region irradiated with ultraviolet rays, the first liquid contained in the first dispersed particles 21a1 is cured by polymerization, and the first dispersed particles 21a1 become a cured product 21b1. These cured products 21b1 are aggregated and laminated, and as a result, a porous layer 2b1 made of the cured product 21b1 is formed. On the other hand, since the second liquid contained in the first dispersion medium 22a1 does not cure, the first dispersion medium 22a1 exists in the porous layer 2b1, specifically, in the gap between the cured products 21b1. On the other hand, in FIG. 2, in the region not irradiated with ultraviolet rays, the first liquid contained in the first dispersed particles 21a1 remains uncured.

Aggregation of the cured product 21b1 in the first irradiation region may be promoted by preliminarily blending a cross-linking agent in the first dispersion medium. This facilitates the formation of crosslinks between the particles during irradiation with the first active energy ray, and as a result, the aggregation of the particles is promoted.

<Removal of second liquid>
After irradiation with the first active energy ray, the second liquid is removed from the porous layer. The removal of the second liquid can be carried out, for example, by drying the porous layer. The removal of the second liquid may be carried out by leaving the porous layer at room temperature, but it is preferably carried out by heating and drying the porous layer. The heat drying can be performed, for example, by heating the porous layer at a temperature in the range of 40 to 100 ° C. for 0.1 to 1 hour.

FIG. 3 schematically shows an example of a porous layer from which the second liquid has been removed. The porous layer 2b1 shown in FIG. 3 is composed of an aggregate of the cured product 21b1. The porous layer 2b1 has a gap between the cured products 21b1.

<Preparation of second emulsion>
While forming the porous layer as described above, it contains a second dispersed particle containing a third liquid that is cured by irradiation with a second active energy ray, and a fourth liquid that is not cured by irradiation with a second active energy ray. A second emulsion containing the second dispersion medium is prepared. The preparation of the second emulsion may be carried out in parallel with the formation of the porous layer, may be carried out prior to the formation of the porous layer, or may be carried out after the formation of the porous layer.

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

The second dispersed particle contains a third liquid that is cured by irradiation with a second active energy ray.
Examples of the second active energy ray include ultraviolet rays, electron beams, and X-rays. The second active energy ray may be the same as or different from the first active energy ray.

As the third 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 of them can be used. As the third liquid, it is preferable to use an acrylic monomer or an oligomer, or a methacrylic monomer or an oligomer because of the advantages such as a wide range of choices and a large degree of freedom in adjusting the physical properties. As the third liquid, for example, trimethylolpropane triacrylate or the like can be used. The proportion of the monomer and the oligomer in the third liquid is, for example, 30 to 100% by mass. The third liquid may be the same as or different from the first liquid.

The third liquid, which is cured by irradiation with the second active energy ray, has more lipophilic ones than hydrophilic ones. Therefore, the O / W type emulsion has a higher degree of freedom in material selection than the W / O type emulsion.

The second dispersion medium contains a fourth liquid that is not cured by irradiation with a second active energy ray. If the third liquid is lipophilic, the fourth 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, when the third liquid is a hydrophilic liquid, the fourth liquid can be a lipophilic liquid, for example, an isoparaffin solvent or a mineral spirit.

The second dispersed particles preferably have an average particle size of 0.5 μm to 0.5 mm, although it depends on the pattern size to be formed. When the second dispersed particles have the above size, the uncured third liquid can be efficiently permeated into the gaps between the particles in a later step.

The proportion of the second dispersed particles in the second emulsion is preferably 25% by mass or more. When the second dispersed particles occupy the above ratio in the second emulsion, the temperature of the region irradiated with the second active energy ray is raised by effectively utilizing the heat of polymerization, so that the second dispersion containing the third liquid is contained. It is possible to destabilize the dispersed state of particles and at the same time form an aggregated layer. Further, the upper limit of the ratio of the second dispersed particles in the second emulsion is not particularly limited as long as the phase inversion of the second emulsion does not occur. According to one example, this ratio is 70% by mass or less.

The third 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. Examples of the alkylphenone-based photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone. The third liquid can contain the photopolymerization initiator in an amount of, for example, 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the monomer and the oligomer.

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

The second 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 sodium dioctyl sulfosuccinate can be used. The second emulsion can contain the surfactant in an amount of, for example, 0.1 to 5.0% by mass, based on the total mass of the second emulsion.

When the second emulsion is an O / W type emulsion, the second dispersion medium generally contains a surfactant in order to ensure emulsification and stability of the second dispersed particles. Further, in order to improve the long-term storage stability of the second emulsion, the O / W type emulsion may contain a water-soluble polymer, cellulose nanofibers, or the like in the second dispersion medium. Further, if necessary, the O / W type emulsion can also contain a viscosity modifier and an antifoaming agent in the second dispersion medium.

On the other hand, when the second emulsion is a W / O type emulsion, in order to prepare a stable emulsion, the second dispersion medium is a nonionic surfactant or a polymer having a suitable hydrophilic lipophilic (HLB) value. A system dispersion stabilizer can be included. If desired, the W / O emulsion can also contain an ionic surfactant in the second dispersion medium.

The second emulsion can be prepared by utilizing known emulsification / dispersion techniques such as paint shaker, ultrasonic homogenizer, colloid mill, homogenizer, membrane emulsification method and the like.

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

The coating method is not particularly limited, but an appropriate coating method, for example, a die coat, a comma coat, or a curtain coat can be selected depending on the thickness of the second liquid film. The thickness of the second liquid film can be, for example, 10 to 3000 μm. Further, when a small amount of the second emulsion is applied to form a second liquid film having a small area, a dispenser or the like can be used if necessary.

When the cured product of the first dispersed particles is hydrophilic, the third liquid is hydrophilic, and the fourth liquid is hydrophobic, the second emulsion does not penetrate into the porous layer at this stage. Even when the cured product of the first dispersed particles is hydrophobic, the third liquid is hydrophobic, and the fourth liquid is hydrophilic, the second emulsion is difficult to penetrate into the porous layer at this stage. When the cured product of the first dispersed particles is hydrophilic, the third liquid is hydrophobic, and the fourth liquid is hydrophilic, a part of the fourth liquid permeates the porous layer at this stage. However, the third liquid does not penetrate the porous layer and therefore the second emulsion hardly penetrates the porous layer. Even when the cured product of the first dispersed particles is hydrophobic, the third liquid is hydrophilic, and the fourth liquid is hydrophobic, a part of the fourth liquid permeates the porous layer at this stage. There is a possibility, but the third liquid does not penetrate the porous layer, and therefore the second emulsion hardly penetrates the porous layer.

FIG. 4 schematically shows an example of a state in which a second film composed of a second emulsion is formed on a porous layer. In FIG. 4, a second film 2a2 made of a second emulsion composed of a second dispersion particle 21a2 and a second dispersion medium 22a2 is formed on the porous layer 2b1.

<Irradiation of the second active energy ray>
Next, the formed second film is irradiated with the second active energy ray in a pattern. As described above, examples of the second active energy ray include ultraviolet rays, electron beams, and X-rays. The pattern irradiation can be performed, for example, by irradiating the second active energy ray regioselectively through a mask or the like, or by irradiating the laser beam regioselectively.

In the region irradiated with the second active energy ray (hereinafter, also referred to as the second irradiation region) by the pattern irradiation of the second active energy ray, the third liquid contained in the second dispersed particles is cured by polymerization. This makes it possible to form a granular layer made of a cured product of the second dispersed particles.

FIG. 5 schematically shows an example of a state in which a granular layer made of a cured product of the second dispersed particles is formed in a region irradiated with ultraviolet rays by pattern irradiation of ultraviolet rays. As shown in FIG. 5, in the region irradiated with ultraviolet rays, the third liquid contained in the second dispersed particles 21a2 is cured by polymerization, and the second dispersed particles 21a2 become the cured product 21b2. These cured products 21b2 are aggregated and laminated, and as a result, a granular layer 2b2 made of the cured product 21b2 is formed. Since the fourth liquid contained in the second dispersion medium 22a2 does not cure in the region irradiated with ultraviolet rays, the second dispersion medium 22a2 exists in the granular layer 2b2, specifically, in the gap between the cured products 21b2. .. On the other hand, in FIG. 5, in the region not irradiated with ultraviolet rays (hereinafter, also referred to as non-irradiated region), the third liquid contained in the second dispersed particles 21a2 remains uncured.

The present inventor considers the reason for the aggregation mechanism of the cured product 21b2 in the second irradiation region as follows.

Irradiation with the second active energy ray causes the second dispersed particles 21a2 to generate heat due to polymerization, whereby the temperature of the second irradiation region rises. Due to this temperature rise, the surfactant that has been adsorbed on the surface of the second dispersed particles 21a2 and has stabilized the second dispersed particles 21a2 is desorbed. As a result, the surface potential of the second dispersed particles 21a2 in which the polymerization has proceeded decreases. As a result, the dispersion of the second dispersed particles 21a2 or the cured product 21b2 thereof becomes unstable, and the aggregation of the particles is promoted. In addition, there is a possibility that polymerization cross-linking may occur between the particles in the process of agglomeration of the particles and contact between the particles.

In addition, this aggregation is completed before the surfactant desorbed due to the temperature rise due to the heat of polymerization is re-adsorbed on the particles. As a result, the agglomerated particles maintain their agglomerated state without being redispersed.

Aggregation of the cured product 21b2 in the second irradiation region may be promoted by preliminarily blending a cross-linking agent in the dispersion medium. This facilitates the formation of crosslinks between the particles when irradiated with active energy rays, and as a result, the aggregation of the particles is promoted.

<Removal of 4th liquid>
After irradiation with the second active energy ray, at least a part of the fourth liquid is removed from the second membrane. In this step, at least a part of the fourth liquid may be removed, but all of the fourth liquid may be removed. The removal of the fourth liquid can be carried out, for example, by drying the second membrane. Drying is preferably performed until the amount of the fourth liquid is 30% by mass or less of the amount of the fourth liquid immediately after forming the second liquid film, and more preferably 5% by mass or less. preferable. The removal of the fourth liquid may be carried out by leaving the second film at room temperature, but it is preferably carried out by heating and drying the second film. The heat 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 step, by removing the fourth liquid, at least a part of the uncured third liquid is moved from the non-irradiated region to the granular layer composed of the cured product of the second dispersed particles. The movement of the uncured third liquid from the non-irradiated region to the granular layer may be performed so that all of the uncured third liquid moves to the granular layer, or only a part thereof moves to the granular layer. .. If only part of the uncured third liquid moves from the irradiated area to the granular layer, the other part of the uncured third liquid can be absorbed by the porous layer.

This movement occurs when the cured product of the first dispersed particles is hydrophilic and the third liquid is hydrophilic, or when the cured product of the first dispersed particles is hydrophobic and the third liquid is hydrophobic. In some cases, it progresses especially quickly. However, when the cured product of the first dispersed particles is hydrophilic and the third liquid is hydrophobic, or when the cured product of the first dispersed particles is hydrophobic and the third liquid is hydrophilic. Even so, the above movements can occur.

In this method, it is not necessary to perform a developing step after irradiation with the second active energy ray, that is, removal using an uncured third liquid developer.

6 and 7 schematically show an example of the state change of the second film caused by the removal of the second liquid. FIG. 6 schematically shows an example of a state in which the second dispersed particles are united in the non-irradiated region by starting the removal of the fourth liquid from the second film. FIG. 7 schematically shows an example of a state in which the union of the second dispersed particles permeates into the porous layer made of the cured product of the first dispersed particles and the granular layer made of the cured product of the second dispersed particles. ing.

When a part of the fourth liquid contained in the second dispersion medium 22a2 was removed from the second film 2a2, as shown in FIG. 6, in the second irradiation region, the gaps between the particles in the granular layer 2b2 were filled. 4 The liquid decreases, and in the non-irradiated region, the fourth liquid decreases and the second dispersed particles 21a2 coalesce. Then, as shown in FIG. 7, the united integrated 21a2'in which the second dispersed particles 21a2 are united, that is, the uncured third liquid partially permeates into the gaps in the granular layer 2b2 and is formed in the granular layer 2b2. It diffuses inward, and another part penetrates into the gap in the porous layer 2b1 and diffuses into the porous layer 2b1. This penetration and diffusion is thought to proceed by capillary force. When the removal of the fourth liquid is completed, the transfer of the uncured third liquid from the non-irradiated region to the granular layer 2b2 and the porous layer 2b1 is completed. As a result, for example, the structure shown in FIG. 7 is obtained. When the fourth liquid is completely removed from the second film, the liquid remaining in the film is, for example, only the liquid constituting the combined 21a2'of the second dispersed particles 21a2.

<Fixing of pattern>
Finally, the uncured third liquid contained in the film from which the fourth liquid has been removed is cured. Curing of the uncured third liquid can be performed, for example, by irradiating the entire membrane with a second active energy ray. As a result, a pattern film is formed.

FIG. 8 schematically shows an example of a state in which an uncured third liquid is cured by irradiating the entire surface with ultraviolet rays. As shown in FIG. 8, when the entire film is irradiated with ultraviolet rays, the uncured third liquid is cured by polymerization. As a result, the polymerization phase 21b2'is formed. Further, in the cured product 21b2 constituting the granular layer 2b2, further polymerization proceeds by irradiation with ultraviolet rays. Further, even in the cured product 21b1 constituting the porous layer 2b1, further polymerization proceeds by irradiation with ultraviolet rays.

As a result, the porous layer 2b1 which is a base having a plurality of recesses, the granular layer 2b2 partially covering the base, and the gaps between the recesses and the granular layer 2b2 provided by the porous layer 2b1 are at least partially separated from each other. A structure having a polymerization phase 21b2'which is an embedded cured product can be obtained. In this structure, the porous layer 2b1 and a part of the polymerization phase 21b2'conform the first layer 2B1, and the other part of the granular layer 2b2 and the polymerization phase 21b2' forms the first layer 2B1. It constitutes the second layer 2B2 as a partially covered pattern film.

As described above, the curing of the uncured third liquid can be performed after all of the uncured third liquid existing in the non-irradiated region has moved from this region to the granular layer and the porous layer. .. Alternatively, the curing of the uncured third liquid may be performed when only a part of the uncured third liquid existing in the non-irradiated region moves from this region to the granular layer and the porous layer. can. For example, irradiation of the entire membrane with the second active energy ray is performed before the fourth liquid is completely removed from the membrane (that is, the third liquid in the non-irradiated region permeates the granular layer and the porous layer, and the inside thereof. You may go to the stage in the middle of spreading with. By doing so, it is possible to obtain a pattern film having a thickness in the non-irradiated region and a thicker second irradiated region than the non-irradiated region.

<Effect>
In the above method, the film of the second emulsion formed on the substrate having a plurality of recesses is irradiated with a pattern of the second active energy ray, and then the pattern is spontaneously (self-made) by simply removing the fourth liquid. Can be organized). The above method does not require a guide pattern to be provided on the substrate in advance and does not require a developing step. Therefore, the above method is a simple method.

Further, the pattern size that can be realized by the conventional technique is, for example, a line width of several nm to several hundred μm or a height difference of several nm to several hundred μm. However, according to the above method, a wide range of pattern sizes can be realized. It is possible. For example, according to the above method, it is possible to form a pattern film having a large line width and height difference, for example, a pattern film having a line width from micro-order to millimeter order and a height difference from micro-order to millimeter order. .. According to one example, according to the above method, it is possible to form 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.

Further, the above method is excellent in controllability of the shape and size of the pattern, and can form a pattern film having various shapes and sizes. In particular, in this method, the film of the second emulsion is formed not on a flat substrate but on a substrate having a plurality of recesses. Therefore, as described below, a pattern film having excellent shape accuracy is formed. Can be done.

When forming a high-density pattern, for example, when forming a line-and-space pattern in which the ratio of the line width to the space width is large, the coalescence caused by the removal of the fourth liquid described with reference to FIGS. 6 and 7 The amount of the third liquid constituting 21a2'is small. Therefore, even when the base is flat, that is, when the base cannot absorb the third liquid, the granular layer 2b2 can absorb almost the entire amount of the third liquid in the non-irradiated region. Therefore, it is possible to form a pattern film having excellent shape accuracy.

On the other hand, when forming a low-density pattern, for example, when forming a line-and-space pattern in which the ratio of the line width to the space width is small, the removal of the fourth liquid described with reference to FIGS. 6 and 7 is performed. The amount of the third liquid constituting the combined 21a2'generated by the above is large. Therefore, when the substrate is flat, that is, when the substrate cannot absorb the third liquid, the granular layer 2b2 can absorb only a part of the third liquid in the non-irradiated region, and the remaining third liquid , May remain in the non-irradiated area. Therefore, in this case, it may not be possible to form a pattern film having excellent shape accuracy.

In the method described with reference to FIGS. 1 to 8, the porous layer 2b1 is formed as a base having a plurality of recesses. Therefore, even if the granular layer 2b2 can absorb only a part of the third liquid in the non-irradiated region, the excess third liquid can be absorbed by the porous layer 2b1. Therefore, according to this method, it is possible to form a pattern film having excellent shape accuracy.

<Modification example>
In the method described with reference to FIGS. 1 to 8, a porous layer made of a cured product of the second dispersed particles is formed in order to provide a base having a plurality of recesses. The porous layer may be formed by another method instead of the method using the first emulsion. Further, if at least the surface region of the base material is porous, the porous layer may not be formed. Further, the base having a plurality of recesses may be a base having a plurality of grooves on the surface.

In any case, the width or diameter of each of the recesses on the surface of the substrate is preferably in the range of 5 μm to 300 μm, and more preferably in the range of 10 μm to 200 μm. Further, on the surface of the base, the average distance between the centers of the adjacent recesses is preferably in the range of 10 μm to 500 μm, and more preferably in the range of 20 μm to 350 μm.

[1] Test 1
In this test, a pattern film was formed by the same method as described with reference to FIGS. 1 to 8 except that the porous layer was not formed, and the shape accuracy thereof was examined.

<Preparation of emulsion>
An O / W type emulsion was prepared as a second emulsion using the following materials.
Trimethylolpropane Triacrylate: Light Acrylate TMP-A (Kyoeisha Chemical Co., Ltd.)
Photopolymerization Initiator: Lunarure200 (DKSH Japan Co., Ltd.)
Surfactant: Sanmorin OT-70 <86.7% aqueous solution> (Sanyo Chemical Industries, Ltd.)
Fourth liquid: water (distilled water)
In a brown vial with a capacity of 50 mL, 0.375 g of a photopolymerization initiator (Lunacure200), 0.259 g of a surfactant (Sammorin OT-70), and 7.5 g of trimethylolpropane triacrylate (light acrylate TMP-A) are added. They were charged in order and subjected to rotary mixing treatment on a ball mill roll. Then, 9 g of distilled water was added to obtain a mixed solution as a precursor of the second emulsion. Then, this mixed solution was subjected to emulsification and dispersion treatment using a homogenizer. Subsequently, rotary mixing of the vial was performed for 30 minutes. As described above, the second emulsion was obtained.

<Formation of liquid film>
Five layers of 3M masking tape having a width of 20 mm and a thickness of 80 μm were attached to the surface of the microscope slide glass along the long side direction. Then, the central portion thereof was cut out in a rectangular shape, thereby producing a cell having a liquid reservoir having a depth of 400 μm and an area of 10 mm × 30 mm (hereinafter referred to as a liquid reservoir cell).
Next, 112 μL of emulsion was collected by a micropipette. By developing and filling this in a liquid reservoir cell, a film (that is, a second liquid film) made of a second emulsion having a thickness of about 375 μm as a calculated value considering the specific gravity was prepared.

<Irradiation of energy rays>
Next, a copper mask having a thickness of 0.25 mm and having a slit-shaped opening having a width of 2 mm was placed on the second liquid film so as not to come into contact with the liquid surface via an aluminum spacer having a thickness of 1 mm. Next, using a UV parallel light exposure machine (UVC-2502S manufactured by SAN-EI ELECTRONIC), the liquid film is irradiated with ultraviolet rays having an illuminance of 4.6 mW / cm ² for 8 seconds to achieve an integrated light amount of 36. An exposure of .8 mJ / cm ² was given. As a result, the third liquid was polymerized in the region irradiated with ultraviolet rays to form a granular layer made of a cured product of the second dispersed particles.

<Drying the membrane>
Next, the film after exposure to ultraviolet rays was naturally dried (23 ° C., 57% RH) for 45 minutes at room temperature. The photographs showing the state of the film in the drying process are shown in FIGS. 9 to 18. As shown in FIG. 9, an agglutination pattern was formed in the irradiation region immediately after the exposure. Then, as shown in FIGS. 9 to 18, as the drying progresses, the uncured emulsion droplets coalesce in the non-irradiated region, and a part of the third liquid constituting them is in the irradiated region. It penetrated and was absorbed into the granular layer (aggregated layer of cured emulsion droplets). However, the rest of the third liquid in the non-irradiated region was not absorbed by the granular layer, forming an amorphous layer adjacent to the granular layer. Thus, in this test, no patterned film having a shape corresponding to the opening of the copper mask was obtained.

[2] Test 2
In this test, a pattern film was formed by the same method as described with reference to FIGS. 1 to 8. Then, the influence of the average particle size of the first and second dispersed particles on the shape accuracy of the pattern film was investigated.

<Preparation of emulsion>
Emulsions E1 and E2 were prepared by the same method as in Test 1 except that the shaft rotation speeds in the emulsification and dispersion treatment using a homogenizer were 4000 rpm and 5000 rpm, respectively. The room temperature during this emulsification / dispersion treatment was 24.8 ° C.

The particle size distribution of these emulsions E1 and E2 was measured. Here, the weight average diameter was measured by a measurement system equipped with Nikkiso Co., Ltd.'s particle size distribution measuring device Microtrac MT3300EXII and Nikkiso Co., Ltd.'s liquid circulation pump Microtrac USVR.

FIG. 19 is a graph showing the results of particle size distribution measurements performed on emulsions E1 and E2. In FIG. 19, the curve C1 represents the particle size distribution of the emulsion E1 and the curve C2 represents the particle size distribution of the emulsion E2. As a result of this particle size distribution measurement, the average particle size of the dispersed particles in the emulsion E1 was 49.8 μm, and the average particle size of the dispersed particles in the emulsion E2 was 28.1 μm.

<Preparation of sample 1>
75 μL of emulsion E1 was collected by a micropipette. By developing and filling this in a liquid reservoir cell prepared by the same method as in Test 1, a film made of a first emulsion having a thickness of about 187.5 μm as a calculated value considering the specific gravity (that is, that is). The first liquid film) was formed.

Next, by irradiating the entire first liquid film with ultraviolet rays having an illuminance of 4.6 mW / cm ² for 30 seconds, the first liquid film was exposed to an integrated light amount of 138 mJ / cm ² . As a result, the first liquid was polymerized in the region irradiated with ultraviolet rays to form a porous layer made of a cured product of the first dispersed particles.

Next, the liquid reservoir cell on which the porous layer was formed was placed on a hot plate heated to 80 ° C. with a spacer in between. As the spacer, a spacer having a distance of 1 mm from the hot plate to the liquid reservoir cell was used. In this state, heating and drying was performed for 10 minutes. As described above, the porous layer was dried.

By collecting 75 μL of emulsion E2 with a micropipette, dropping it on a porous layer, and developing it, a membrane composed of a second emulsion having a thickness of about 187.5 μm as a calculated value considering specific gravity (that is, a first film). A two-component film) was formed.

Next, a copper mask having a thickness of 0.25 mm and having a slit-shaped opening having a width of 2 mm was placed on the second liquid film so as not to come into contact with the liquid surface via an aluminum spacer having a thickness of 1 mm. Next, using a UV parallel light exposure machine (UVC-2502S manufactured by SAN-EI ELECTRONIC), ultraviolet rays with an illuminance of 4.6 mW / cm ² are irradiated from the mask for 8 seconds, whereby the integrated light amount is applied to the second liquid film. An exposure of 36.8 mJ / cm ² was given. As a result, the third liquid was polymerized in the region irradiated with ultraviolet rays to form a granular layer made of a cured product of the second dispersed particles.

Then, the liquid reservoir cell on which the granular layer was formed was placed on a hot plate heated to 80 ° C. with a spacer in between. As the spacer, a spacer having a distance of 1 mm from the hot plate to the liquid reservoir cell was used. In this state, heating and drying was performed for 10 minutes. As described above, the granular layer was dried.

Finally, the entire laminated structure including the porous layer and the granular layer was irradiated with ultraviolet rays having an illuminance of 4.6 mW / cm ² for 90 seconds, thereby giving an exposure of an integrated light amount of 414 mJ / cm ² . .. The pattern was fixed as described above to obtain Sample 1.

<Preparation of sample 2>
Sample 2 was prepared by the same method as that of Sample 1 except that the amount of Emulsion E2 was changed from 75 μL to 82 μL.

<Preparation of sample 3>
Sample 3 was prepared by the same method as that of Sample 1 except that the amount of Emulsion E2 was changed from 75 μL to 90 μL.

<Preparation of sample 4>
Sample 4 was prepared by the same method as that of Sample 1 except that the amount of Emulsion E2 was changed from 75 μL to 100 μL.

<Preparation of sample 5>
Sample 5 was prepared by the same method as that of Sample 1 except that the amount of Emulsion E2 was changed from 75 μL to 112 μL.

<Preparation of sample 6>
Except that 75 μL emulsion E2 was used instead of 75 μL emulsion E1 to form the first liquid film, and 75 μL emulsion E1 was used instead of 75 μL emulsion E2 to form the second liquid film. , Sample 6 was prepared by the same method as that of Sample 1.

<Preparation of sample 7>
Except that 75 μL emulsion E2 was used instead of 75 μL emulsion E1 to form the first liquid film and 112 μL emulsion E1 was used instead of 75 μL emulsion E2 to form the second liquid film. , Sample 7 was prepared by the same method as that of Sample 1.

<Results expected from the mechanism>
The shape accuracy of the pattern film is affected by the rate of movement of the third liquid to the porous layer or the granular layer, that is, the time change of the permeation volume, which has been described with reference to FIGS. 6 and 7. The emulsions used to prepare the samples 1 to 7 are only emulsions E1 and E2. The emulsions E1 and E2 have the same composition and different average particle sizes of the dispersed particles. The average particle size of the dispersed particles affects the change in permeation volume over time. Therefore, in this test, it is considered that it is the average particle size of the dispersed particles that affects the shape accuracy of the pattern film.

In general, the following formula (1) called the Lucas-Washburn formula is often used for the analysis of liquid permeation into the porous body. Here, L _p is the penetration depth of the liquid, t is the time, e is the capillary radius, γ is the surface tension of the liquid, η is the viscosity of the liquid, and cos θ is the liquid and the capillary surface. The contact angle with.

From the formula (1), it can be seen that the permeation rate of the liquid into the voids of the porous body increases as the capillary radius e increases. A porous body obtained from an emulsion having a large average particle size of dispersed particles has a larger void diameter than a porous body obtained from an emulsion having a small average particle size of dispersed particles. The voids in the porous body can be regarded as a collection of capillaries. Therefore, in Samples 1 to 5, it is expected that the pattern film has higher shape accuracy as compared with Samples 6 and 7.

When one of the emulsions E1 and E2 was used as the first emulsion and the other was used as the second emulsion, a simulation was performed on the permeation depth and permeation volume of the third liquid into the porous body over time. .. This will be described below.

When calculating the time change of the liquid penetration depth _Lp from the equation (1), the capillary radius e, the surface tension γ of the liquid, the viscosity η of the liquid, and the contact angle cos θ between the liquid and the capillary surface are obtained. Need to keep.

The viscosity of trimethylolpropane triacrylate is 100 mPa · s (25 ° C.) according to the catalog value. Therefore, this catalog value is used as the viscosity η of the liquid. Further, the contact angle cosθ between the liquid and the capillary surface is assumed to be 1 because the trimethylolpropane triacrylate and the cured product thereof are composed of the same oligomer component.

There is a relationship of McLeod represented by the following formula (2) between the surface tension γ _L of the liquid and the density. Here, C is a substance-specific constant, ρ _L is the density of the saturated liquid (g / cm ³ ), and ρ _V is the density of the saturated steam (g / cm ³ ).

The constant C is a value determined by the chemical structure and is defined by the following equation (3) as Parachor. Here, M is a molecular weight.

The liquid used (trimethylolpropane triacrylate) is an oligomer, and the density ρ _V of the saturated vapor is much smaller than the density ρ _L of the saturated liquid. Therefore, the density ρ _V of the saturated vapor can be ignored, and the following equation (4) can be derived from the equation (3).

For trimethylolpropane triacrylate, the surface tension γ _L was estimated to be 37.0 mN / m by adding the addition factors to the atomic group of paracol. The molecular weight of trimethylolpropane triacrylate was 296.3, and the density ρ _L of the saturated liquid was 1.11 (g / mL).

Assuming that the packing of the particles in the porous body formed by agglomeration of the particles is hexagonal close-packed, the filling rate is 74.05% by volume and the porosity is 25.95% by volume. Here, for the sake of simplicity, it is assumed that the particle filling in the porous body is hexagonal close-packed, and each of the particle-filled portion and the void portion is cylindrical. Based on the above assumptions, the following equation (6) was derived from the following equation (5). Here, f is the radius of the cylinder when it is assumed that the particle filling portion has a cylindrical shape. e is the radius of the cylinder when the void portion is assumed to be a cylinder. L is the length of the cylinder.

Assuming that the radius f is 1/2 of the average particle size of the dispersed particles in the emulsion, the radii f and e shown in Table 1 below are calculated from the formula (6) for the porous bodies obtained from the emulsions E1 and E2. can do.

The equation (1) can be converted into the following equation (7).

From the formula (7) and the above values, the relationship between the penetration depth _Lp and the elapsed time shown in FIG. 20 can be obtained. In FIG. 20, curves C3 and C4 show the above-mentioned relationships obtained for the porous bodies obtained from the emulsions E1 and E2, respectively.

Further, the relationship between the permeation volume _Ve and the elapsed time can be expressed by the following equation (8). Here, the permeation volume _Ve is the volume of the liquid that permeates into one capillary tube having a cylindrical shape.

From the formulas (7) and (8) and the above values, the relationship between the permeation volume _Ve shown in FIG. 21 and the elapsed time can be obtained. In FIG. 21, curves C5 and C6 show the above-mentioned relationships obtained for the porous bodies obtained from the emulsions E1 and E2, respectively.

As shown in FIGS. 20 and 21, the porous body obtained from the emulsion E1 is expected to permeate the third liquid at a higher rate than the porous body obtained from the emulsion E2. Therefore, in Samples 1 to 5, it is expected that the pattern film has higher shape accuracy as compared with Samples 6 and 7.

<Image of laminated structure>
Using a digital camera (HOZAN L-835) equipped with a zoom lens (HOZAN L-815), each of Samples 1 to 7 is illuminated from diagonally above, and each laminated structure is illuminated from diagonally above right. I photographed the surface of. The images thus obtained are shown in FIGS. 22 to 28.
As is clear from the comparison between FIGS. 22 to 28 and FIGS. 9 to 18, when the porous layer is formed, a pattern film having more excellent shape accuracy is formed as compared with the case where the porous layer is omitted. We were able to.

<Three-dimensional shape measurement>
For each of Samples 1 to 7 obtained by sputtering gold on the laminated structure, a three-dimensional image and a cross-sectional profile of the surface of the laminated structure were obtained using a one-shot 3D shape measuring machine manufactured by KEYENCE. Some of the results are shown in FIGS. 29 and 30 and Table 2.

In FIG. 29, curves C7 and C8 represent cross-sectional profiles obtained for Samples 1 and 6, respectively. Also, in FIG. 30, curves C9 and C10 represent cross-sectional profiles obtained for samples 5 and 7, respectively.

As is clear from the comparison of the results obtained for Samples 1 and 6 and the comparison of the results obtained for Samples 5 and 7, the average particle size of the first dispersed particles is compared with the average particle size of the second dispersed particles. When it was larger, the maximum inclination in the cross-sectional profile was larger than when the average particle size of the first dispersed particles was smaller than the average particle size of the second dispersed particles. This result is consistent with the above results expected from the mechanism.

1 ... base material, 2a1 ... first film, 2a2 ... second film, 2b1 ... porous layer, 2b2 ... granular layer, 2B1 ... first layer, 2B2 ... second layer, 21a1 ... first dispersed particles, 21a2 ... first 2 dispersed particles, 21a2'... coalesced, 21b1 ... cured product, 21b2 ... cured product, 21b2' ... polymer phase, 22a1 ... first dispersion medium, 22a2 ... second dispersion medium, C1 ... curve, C2 ... curve, C3 ... Curve, C4 ... curve, C5 ... curve, C6 ... curve, C7 ... curve, C8 ... curve, C9 ... curve, C10 ... curve.

Claims (10)

A film composed 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 having a plurality of recesses. To form and
The film is irradiated with the active energy rays in a pattern, and the first liquid is cured in the region irradiated with the active energy rays.
After irradiation with the active energy rays, at least a part of the second liquid is removed from the membrane, and
A method for forming a pattern film, which comprises curing the uncured first liquid contained in the film from which at least a part of the second liquid has been removed. A film composed 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 having a plurality of recesses. The emulsion is formed so as not to completely fill the plurality of recesses.
The film is irradiated with the active energy rays 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 rays.
After irradiation with the active energy rays, at least a part of the second liquid is removed from the membrane, and at least a part of the uncured first liquid in the region not irradiated with the active energy rays is granulated. Moving into the gaps in the layer and into the plurality of recesses,
After that, a method for forming a pattern film, which comprises curing the uncured first liquid. The method according to claim 1 or 2, wherein the substrate is porous. A first dispersion medium containing a first liquid that is cured by irradiation with the first active energy ray and a second liquid that is not cured by irradiation with the first active energy ray is contained on the substrate. Forming a first film consisting of one emulsion,
Irradiating the first film with the first active energy ray to cure the first liquid, and
After irradiation with the first active energy ray, the second liquid is removed from the first membrane to obtain a porous layer made of a cured product of the first liquid.
On the porous layer, a second dispersion particle containing a third liquid that is cured by irradiation with a second active energy ray and a second dispersion medium containing a fourth liquid that is not cured by irradiation with the second active energy ray. Forming a second film consisting of a second emulsion containing
The second membrane is irradiated with the second active energy ray in a pattern, and the third liquid is cured in the region irradiated with the second active energy ray.
After irradiation with the second active energy ray, at least a part of the fourth liquid is removed from the second membrane, and
A method for forming a pattern film, which comprises curing the uncured third liquid contained in the second film from which at least a part of the fourth liquid has been removed. A first dispersion medium containing a first liquid that is cured by irradiation with the first active energy ray and a second liquid that is not cured by irradiation with the first active energy ray is contained on the substrate. Forming a first film consisting of one emulsion,
By irradiating the first film with the first active energy ray to form a porous layer made of a cured product of the first dispersed particles,
Removing the second liquid from the porous layer and
On the porous layer, a second dispersion particle containing a third liquid that is cured by irradiation with a second active energy ray and a second dispersion medium containing a fourth liquid that is not cured by irradiation with the second active energy ray. Forming a second film consisting of a second emulsion containing
The second film is irradiated with the second active energy ray in a pattern to form a granular layer made of a cured product of the second dispersed particles in the region irradiated with the second active energy ray.
After irradiation with the second active energy ray, at least a part of the fourth liquid is removed from the second membrane, and at least the uncured third liquid in the region not irradiated with the second active energy ray. To move a part into the granular layer and the porous layer,
After that, a method for forming a pattern film, which comprises curing the uncured third liquid. The method according to claim 4 or 5, wherein the first dispersed particles have a larger average particle size than the second dispersed particles. The method according to any one of claims 4 to 6, wherein each of the first emulsion and the second emulsion is an oil-in-water emulsion. Irradiation of the first active energy ray is performed on at least a part of the region of the second membrane to be irradiated with the first active energy ray and a region of the second membrane not irradiated with the first active energy ray. The method according to any one of claims 4 to 7, wherein at least a part thereof is located on the porous layer. A pattern film formed by the method according to any one of claims 1 to 8. A base with multiple recesses and
A granular layer partially covering the substrate and
A structure including a cured product in which the plurality of recesses and gaps between the granular layers are at least partially embedded.

Images