JP2022015953A - Pattern film and method for forming the same - 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: providing a first film on a base; forming, on the first film, a second 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; without irradiating at least one part of the second film with an active energy ray, irradiating at least the other part of the second film with the active energy ray 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 second film and dissolving at least a part of a material of the first film in the uncured first liquid included in the second film; and curing the uncured first liquid in which at least a part of the material of the first film is dissolved.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, a first film is provided on a base material, and on the first film, dispersed particles containing a first liquid that is cured by irradiation with active energy rays, and the active energy rays. The first film is formed of an emulsion containing a dispersion medium containing a second liquid that is not cured by irradiation, and at least a part of the second film is not irradiated with the active energy rays. After irradiating at least a part of the other regions of the two membranes with the active energy rays to cure the first liquid in the regions irradiated with the active energy rays, and after irradiating the active energy rays, the second. At least a part of the second liquid is removed from the membrane, and at least a part of the material of the first membrane is dissolved in the uncured first liquid contained in the second membrane. Provided is a method for forming a pattern film, which comprises curing the uncured first liquid in which at least a part of the material of the film is dissolved.

According to the second aspect of the present invention, the first film is provided on the base material, and the dispersed particles containing the first liquid that is cured by irradiation with the active energy rays on the first film, and the active energy rays. The first film is formed by forming a second film containing an emulsion containing a dispersion medium containing a second liquid that is not cured by irradiation, and without irradiating at least a part of the region of the second film with the active energy rays. By irradiating at least a part of the other regions of the two films with the active energy rays, a granular layer made of a cured product of the dispersed particles is formed in the regions irradiated with the active energy rays, and the active energy rays are formed. After the irradiation, at least a part of the second liquid is removed from the second film, and at least a part of the uncured first liquid in the region not irradiated with the active energy ray is put into the granular layer. A method for forming a pattern film is provided, which comprises moving at least a part of the material of the first film to the granular layer and then curing the uncured first liquid. To.

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

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 process of forming a first film in the method for forming a pattern film according to the first embodiment of the present invention. FIG. 3 is a cross-sectional view schematically showing a process of forming a second film in the method for forming a pattern film according to the first embodiment of the present invention. The cross-sectional view schematically which shows the irradiation process of an active energy ray in the method of forming a pattern film which concerns on 1st Embodiment of this invention. The cross-sectional view which shows schematic the process of removing the 2nd liquid in the method of forming the pattern film which concerns on 1st Embodiment of this 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 the first embodiment of the present invention. The cross-sectional view schematically which shows the fixing process in the method of forming a pattern film which concerns on 1st Embodiment of this invention. FIG. 2 is a cross-sectional view schematically showing a process of forming a first film in the method for forming a pattern film according to a second embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing a process of forming a second film in the method for forming a pattern film according to the second embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing an irradiation process of active energy rays in the method for forming a pattern film according to a second embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing a step of removing a second liquid in the method for forming a pattern film according to a second embodiment of the present invention. FIG. 2 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 a second embodiment of the present invention. The cross-sectional view schematically which shows the fixing process in the method of forming a pattern film which concerns on 2nd Embodiment of this invention. FIG. 3 is a cross-sectional view schematically showing a process of forming a first film in the method for forming a pattern film according to a third embodiment of the present invention. The cross-sectional view schematically which shows the irradiation process of the 1st active energy ray in the method of forming a pattern film which concerns on 3rd Embodiment of this invention. FIG. 3 is a cross-sectional view schematically showing a process of forming a second film in the method for forming a pattern film according to a third embodiment of the present invention. The cross-sectional view schematically which shows the irradiation process of the 2nd active energy ray in the method of forming the pattern film which concerns on 3rd Embodiment of this invention. FIG. 3 is a cross-sectional view schematically showing a step of removing a second liquid in the method for forming a pattern film according to a third 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 a third embodiment of the present invention. The cross-sectional view schematically which shows the fixing process in the method of forming a pattern film which concerns on 3rd Embodiment of this invention. The graph which shows the particle size distribution of an emulsion. A photograph of the pattern film obtained in Test 1. An enlarged photograph showing the pattern film of FIG. 21. The photograph which shows the 1st film formation process in the pattern film formation method of test 2. The photograph which shows the 2nd film formation process in the pattern film formation method of test 2. The photograph which shows the energy ray irradiation process in the pattern film formation method of test 2. A photograph showing the film structure 5 minutes after the start of the drying process in the pattern film forming method of Test 2. A photograph showing the film structure 20 minutes after the start of the drying process in the pattern film forming method of Test 2. A photograph showing the film structure 30 minutes after the start of the drying process in the pattern film forming method of Test 2. A photograph showing the film structure 35 minutes after the start of the drying process in the pattern film forming method of Test 2. A photograph showing the film structure 40 minutes after the start of the drying process in the pattern film forming method of Test 2. A photograph showing the film structure 60 minutes after the start of the drying process in the pattern film forming method of Test 2. A photograph showing the film structure after the fixing step in the pattern film forming method of Test 2. The photograph which shows the 1st energy ray irradiation process in the pattern film formation method of test 3. The photograph which shows the liquid reservoir cell formed in the pattern film formation method of test 3. The photograph which shows the 2nd energy ray irradiation process in the pattern film formation method of test 3. A photograph showing the film structure immediately after the start of the drying process in the pattern film forming method of Test 3. A photograph showing the film structure 15 minutes after the start of the drying process in the pattern film forming method of Test 3. A photograph showing the film structure 20 minutes after the start of the drying process in the pattern film forming method of Test 3. A photograph showing the film structure 25 minutes after the start of the drying process in the pattern film forming method of Test 3. A photograph showing the film structure 30 minutes after the start of the drying process in the pattern film forming method of Test 3. A photograph showing the film structure 40 minutes after the start of the drying process in the pattern film forming method of Test 3. A photograph showing the film structure 60 minutes after the start of the drying process in the pattern film forming method of Test 3. A photograph showing the film structure 120 minutes after the start of the drying process in the pattern film forming method of Test 3.

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.

[First Embodiment]
Hereinafter, the method for forming the pattern film according to the first embodiment will be described in 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 6, and these drawings will be referred to in the following description.

<Formation of the first film>
First, the base material is prepared. As the base material, any base material can be used, and for example, a film or a sheet can be used.

Next, the first film is provided on the base material. The first membrane is mainly a non-fluid membrane.

The material of the first film is, for example, a material that does not dissolve in the first liquid until the step of removing the second liquid, or does not show fluidity until the step of removing the second liquid. The material of the first membrane exhibits higher solubility in the first liquid, for example, as compared to the second liquid. According to one example, the material of the first film is a thermoplastic resin. According to another example, the material of the first film is a thermosetting resin. The material of the first film may be one or more small molecule compounds.

In addition to the above resin, the material of the first film may further contain one or more additives dissolved or dispersed therein. Examples of such additives include dyes, pigments, metal particles, and magnetic particles.

When the additive is contained in the material of the first film, the ratio of the additive to the material of the first film is preferably in the range of 0.01 to 80% by mass, preferably 0.1 to 70% by mass. It is more preferable that it is within the range.

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

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

FIG. 1 schematically shows an example of a state in which the first film is formed on a substrate. In FIG. 1, a first film 2 as a continuous film is formed on the base material 1.

<Preparation of emulsion>
After providing the first film on the substrate, 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. do. The preparation of this emulsion may be performed before the first film is provided on the substrate, or may be performed in parallel with the first film being provided on the substrate.

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

The dispersed particles include a first liquid that is cured by irradiation with active energy rays. Examples of the 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 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 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 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.

Although it depends on the pattern size to be formed, the first dispersed particles preferably have an average particle size of 0.5 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 first liquid or the like can be efficiently permeated into the gaps between the particles in a later step.

The proportion of the dispersed particles in the emulsion is preferably 25% by mass or more. When the dispersed particles occupy the above ratio in the emulsion, the temperature of the region irradiated with the active energy rays is raised by effectively utilizing the heat of polymerization, thereby destabilizing the dispersed state of the dispersed particles containing the first liquid. At the same time, a cohesive layer can be formed. 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 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 emulsion is, for example, O / W type, the 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 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 emulsion can contain the surfactant in an amount of, for example, 0.1 to 5.0% by weight, based on the total mass of the emulsion.

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

On the other hand, when the emulsion is a W / O type emulsion, in order to prepare a stable emulsion, the dispersion medium is a nonionic surfactant having a suitable hydrophilic lipophilic (HLB) value or a polymer-based dispersion stable. Can include agents. If desired, the W / O emulsion can also contain an ionic surfactant in the dispersion medium.

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

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

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 liquid film. The thickness of the liquid film can be, for example, 10 to 3000 μm. Further, when a small amount of emulsion is applied to form a liquid film having a small area, a dispenser or the like can be used as needed.

FIG. 2 schematically shows an example of a state in which a second film made of an emulsion is formed on the first film. In FIG. 2, a second film 3 made of an emulsion composed of a dispersion particle 31 and a dispersion medium 32 is formed on the first film 2.

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

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

FIG. 3 schematically shows an example of a state in which a granular layer made of a cured product of dispersed particles is formed in a region irradiated with ultraviolet rays by pattern irradiation of ultraviolet rays. As shown in FIG. 3, for example, when a pattern exposure of ultraviolet rays is performed using a mask 5, in the region irradiated with ultraviolet rays, the first liquid contained in the dispersed particles 31 is cured by polymerization, and the dispersed particles 31 are cured. Becomes hardened particles 41. These cured product particles 41 are aggregated and laminated, and as a result, a granular layer 4a composed of the cured product particles 41 is formed. Since the second liquid contained in the dispersion medium 32 does not cure in the region irradiated with ultraviolet rays, the dispersion medium 32 exists in the granular layer 4a, specifically, in the gaps between the cured product particles 41. On the other hand, in FIG. 3, in the region not irradiated with ultraviolet rays (hereinafter, also referred to as non-irradiated region), the first liquid contained in the dispersed particles 31 remains uncured.

The present inventor considers the reason for the aggregation mechanism of the cured product particles 41 in the irradiation region as follows.

Irradiation with active energy rays causes the dispersed particles 31 to generate heat due to polymerization, which raises the temperature of the irradiated region. Due to this temperature rise, the surfactant that has been adsorbed on the surface of the dispersed particles 31 and has stabilized the dispersed particles 31 is desorbed. As a result, the surface potential of the dispersed particles 31 in which the polymerization has proceeded decreases. As a result, the dispersion of the dispersed particles 31 or the cured product particles 41 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 particles 41 in the 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 second liquid>
After irradiation with active energy rays, at least a part of the second liquid is removed from the second membrane. In this step, at least a part of the second liquid may be removed, but all of the second liquid may be removed. The removal of the second liquid can be carried out, for example, by drying the second membrane. Drying is preferably performed until the amount of the second liquid is 30% by mass or less of the amount of the second liquid immediately after forming the second liquid film, and more preferably 5% by mass or less. preferable. The removal of the second 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, the second liquid is removed to allow the coalescence of the dispersed particles containing the uncured first liquid. Then, at least a part of the uncured first liquid is moved from the non-irradiated region to the granular layer made of the cured product of the dispersed particles. The movement of the uncured first liquid from the non-irradiated region to the granular layer may be performed so that all of the uncured first liquid moves to the granular layer, or only a part thereof moves to the granular layer. ..

Further, in this step, at least a part of the material of the first membrane is fluidized, dissolved in the uncured first liquid, or fluidized and dissolved in the uncured first liquid. Move to the granular layer. The transfer of the material of the first film to the granular layer may be performed so that all of the material is transferred to the granular layer, or only a part thereof is transferred to the granular layer.

For example, when the material of the first film is a thermoplastic resin and the second liquid is removed by heating and drying at a temperature equal to or higher than the softening point of the thermoplastic resin, the uncured first film is removed as the second liquid is removed. In addition to the progress of coalescence of dispersed particles containing one liquid, the material of the first film is softened (fluidized). At least a portion of the uncured first liquid and at least a portion of the softened first film material are absorbed by the granular layer with or without at least partial mixing.

Alternatively, when the material of the first film is a thermosetting resin and the second liquid is removed at a temperature at which the thermosetting resin does not cure, the uncured first liquid is removed along with the removal of the second liquid. As the coalescence of the contained dispersed particles progresses, at least a part of the thermosetting resin is mixed with at least a part of the uncured first liquid. Then, at least a part of the uncured first liquid mixed with the thermosetting resin and at least a part of the uncured first liquid not mixed with the thermosetting resin are absorbed by the granular layer. ..

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

4 and 5 schematically show an example of a state change of the first film and the second film caused by the removal of the second liquid. FIG. 4 schematically shows an example of a state in which the coalescence of dispersed particles occurs in the non-irradiated region by starting the removal of the second liquid from the second film. FIG. 5 outlines an example of a state in which the first liquid constituting the union of the dispersed particles is mixed with the material of the first film, and the mixture thereof permeates into the granular layer made of the cured product of the dispersed particles. Is shown.

When a part of the second liquid contained in the dispersion medium 32 is removed from the second film 3, as shown in FIG. 4, the second liquid filling the gaps between the particles in the granular layer 4a decreases in the irradiation region. However, in the non-irradiated region, the second liquid decreases and the dispersed particles 31 coalesce. When the amount of the second liquid decreases, for example, the contact area between the material of the first film 2 and the uncured first liquid increases, so that the material of the first film 2 becomes the uncured first liquid. Dissolves in. Then, as shown in FIG. 5, the mixture 4b of the material of the first film 2 and the uncured first liquid permeates into the gap in the granular layer 4a and diffuses into the granular layer 4a. This penetration and diffusion is thought to proceed by capillary force.

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

FIG. 6 schematically shows an example of a state in which an uncured material is cured by a combination of cooling and full surface irradiation of ultraviolet rays or only full surface irradiation of ultraviolet rays when the material of the first film is a thermoplastic resin. ing. The thermoplastic resin is solidified by cooling, and the uncured first liquid is cured by polymerization when the entire membrane is irradiated with ultraviolet rays. As a result, the cured product phase 4c is formed. Further, in the cured product particles 41 constituting the granular layer 4a, further polymerization proceeds by irradiation with ultraviolet rays.

As a result, a pattern film including the granular layer 4a and the cured product phase 4c, which is a cured product in which the gaps thereof are at least partially embedded, can be obtained.

The curing of the uncured product can be performed after all the uncured first liquid and the material of the first film existing in the non-irradiated region have moved from this region to the granular layer. Alternatively, the curing of the uncured material can be performed when only a part of the uncured first liquid or the material of the first film present in the non-irradiated region moves from this region to the granular layer. .. For example, treatments such as cooling and heating to cure the material of the first membrane and irradiation of the entire membrane with active energy rays before the second liquid is completely removed from the membrane (that is, in the non-irradiated region). The first liquid and the material of the first film may penetrate into the granular layer and diffuse in them). By doing so, it is possible to obtain a pattern film having a thickness in the non-irradiated region and having a thicker irradiated region than the non-irradiated region. When the first film contains two or more components, all of those components may be moved to the granular layer, or only some of the components may be moved to the granular layer.

<Effect>
In the above method, the pattern can be spontaneously (self-organized) formed only by irradiating the film of the emulsion with a pattern of 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 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.

Further, in the above method, a second film made of an emulsion is formed on the first film, and at least a part of the material of the first film is transferred to a granular layer obtained from a part of the second film. Therefore, the first film may not be able to form a pattern by itself in a self-organizing manner. Therefore, according to the above method, a pattern film having a different composition between the cured product particles 41 and the cured product phase 4c can be obtained.

[Second Embodiment]
Hereinafter, the method for forming the pattern film according to the second embodiment will be described in 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. 7 to 12, and these drawings will be referred to in the following description.

<Formation of the first film>
First, the base material is prepared. As the base material, the one described in the first embodiment can be used.

Next, the first film is provided on the base material. The first film is provided only in a part of the base material. The matters relating to the first film are the same as those described in the first embodiment, except that the first film is provided only in a part of the region of the base material.

FIG. 7 schematically shows an example of a state in which the first film is formed only in a partial region of the base material. In FIG. 7, a first film 2 as a continuous film is formed on the base material 1. The first film 2 partially covers one main surface of the base material 1.

<Formation of the second film>
Next, a second film made of an emulsion is formed. The second film is formed on at least a portion of the first film and on at least one other region of the substrate, i.e., a region of the substrate where the first film is not provided. .. Except for forming the second film in this way, the matters relating to the second film are the same as those described in the first embodiment.

FIG. 8 schematically shows an example of a state in which a second film made of an emulsion is formed on the first film. In FIG. 8, the dispersed particles 31 and the dispersion medium 32 are formed on at least a part of the first film 2 and on at least a part of the region of the base material 1 where the first film 2 is not provided. A second film 3 made of the constituent emulsion is formed.

<Irradiation of active energy rays>
Next, the second film is irradiated with active energy rays in a pattern. The activation energy ray irradiates at least a part of the region of the second membrane located on the first membrane and at least a part of the region of the second membrane not located on the first membrane. Except for irradiating the active energy rays in this way, the matters relating to the irradiation of the active energy rays are the same as those described in the first embodiment.

FIG. 9 schematically shows an example of a state in which a granular layer made of a cured product of dispersed particles is formed in a region irradiated with ultraviolet rays by pattern irradiation of ultraviolet rays. As shown in FIG. 9, for example, when the pattern exposure of ultraviolet rays is performed using the mask 5, the dispersed particles 31 are cured to become the cured product particles 41 in the region irradiated with the ultraviolet rays, and the cured product particles 41 are used. Granular layer 4a is formed. The ultraviolet rays irradiate at least a part of the region of the second film 3 located on the first film 2 and at least a part of the second film 3 not located on the first film 2. Therefore, the granular layer 4a includes a portion located on the first film 2 (hereinafter, also referred to as a first portion) and a portion not located on the first film 2 (hereinafter, also referred to as a second portion). It will be.

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

Of the material of the first film and the uncured first liquid, those located in the vicinity of the first portion move to the first portion of the granular layer located on the first film. On the other hand, since the first film does not exist in the vicinity of this portion in the second portion of the granular layer that is not located on the first film, for example, the second portion of the uncured first liquid Only those located in the vicinity move. Alternatively, in addition to the movement of the uncured first liquid located in the vicinity of the second part to the second part, the material of the first film moves in a smaller amount as compared with the first part. do.

10 and 11 schematically show an example of a state change of the first film and the second film caused by the removal of the second liquid. FIG. 10 schematically shows an example of a state in which the coalescence of dispersed particles occurs in the non-irradiated region by starting the removal of the second liquid from the second film. In FIG. 11, a part of the first liquid constituting the coalescence of the dispersed particles is mixed with the material of the first film, and the mixture thereof permeates a part of the granular layer made of the cured product of the dispersed particles. However, an example of a state in which the other part of the first liquid has penetrated into the other part of the granular layer without being mixed with the material of the first film is shown schematically.

When a part of the second liquid contained in the dispersion medium 32 is removed from the second film 3, as shown in FIG. 10, in the irradiation region, the second liquid filling the gaps between the particles in the granular layer 4a decreases. However, in the non-irradiated region, the second liquid decreases and the dispersed particles 31 coalesce.

When the second liquid decreases, in addition to the coalescence of the dispersed particles 31 in the vicinity of the first film 2, for example, the contact area between the material of the first film 2 and the uncured first liquid increases. The material of the first film 2 is dissolved in the uncured first liquid due to the above. Then, as shown in FIG. 11, the mixture 4b of the material of the first film 2 and the uncured first liquid permeates into the gap in the granular layer 4a and diffuses into the granular layer 4a.

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

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

The first liquid and the material of the first film are present in the first portion of the granular layer. On the other hand, in the second part of the granular layer, only the first liquid is present, or in addition to the presence of the first liquid, the amount of the material of the first film is smaller than that of the first part (first part). It exists in a relative amount with respect to one liquid). Therefore, in the pattern film thus obtained, the cured product phase formed in the first portion is a cured product of the material of the first film with respect to the cured product of the first liquid as compared with the cured product phase generated in the second portion. The relative amount of is large.

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

In the first part, the thermoplastic resin is solidified by cooling, and the uncured first liquid is cured by ultraviolet irradiation. As a result, the cured product phase 4c is formed. On the other hand, in the second part, the thermoplastic resin does not exist, and the uncured first liquid is cured by ultraviolet irradiation. As a result, the cured product phase 4e is formed. Then, in the cured product particles 41 constituting the granular layer 4a, further polymerization proceeds by irradiation with ultraviolet rays.

As a result, the first pattern portion 4A and the second pattern portion 4B are provided, and the first pattern portion 4A is a cured product phase 4c which is a cured product in which a part of the granular layer 4a and a gap thereof are at least partially embedded. In the second pattern portion 4B, a pattern film containing the other part of the granular layer 4a and the cured product phase 4e which is a cured product in which the gap is at least partially embedded can be obtained.

<Effect>
Also in this embodiment, the same effect as that of the first embodiment can be obtained. Further, in the present embodiment, the composition can be different between the cured product phase generated in the first portion and the cured product phase generated in the second portion. That is, according to this embodiment, it is possible to form a more complicated structure.

[Third Embodiment]
Hereinafter, the method for forming the pattern film according to the third embodiment will be described in 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. 13 to 19, and these drawings will be referred to in the following description.

<Formation of the first film>
First, the base material is prepared. As the base material, the one described in the first embodiment can be used.

Next, the first film is provided on the base material. The first film may be provided in the entire region of the base material, or may be provided only in a partial region of the base material.

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

FIG. 13 schematically shows an example of a state in which the first film is formed on the substrate. In FIG. 13, a first film 2 as a continuous film is formed on the base material 1.

<Irradiation of the first active energy ray>
Next, the first membrane is irradiated with the first active energy ray in a pattern. The first active energy ray irradiates one or more regions of the first membrane and does not irradiate the other one or more regions of the first membrane. By irradiation with the first active energy ray, the resin contained in the first film is cured in the region irradiated with the first active energy ray (hereinafter, also referred to as the first irradiation region). For example, the degree of polymerization of the resin in the first irradiation region is compared with the degree of polymerization of the resin in the region of the first film not irradiated with the first active energy ray (hereinafter, also referred to as the first non-irradiation region). Make it high.

FIG. 14 schematically shows an example of a state in which a first irradiated region and a first non-irradiated region are formed on the first film by pattern irradiation of the first film with ultraviolet rays. As shown in FIG. 14, for example, when the pattern exposure of ultraviolet rays is performed using the first mask 5A, the resin contained in the first film 2 is not cured in the first non-irradiated region 2A where the ultraviolet rays are not irradiated. In the first irradiation region 2B irradiated with ultraviolet rays, the resin contained in the first film 2 is cured.

<Formation of the second film>
Next, a second film made of an emulsion is formed on the first film. The matters concerning the second film are the same as those described in the first embodiment.

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

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

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

FIG. 16 schematically shows an example of a state in which a granular layer made of a cured product of dispersed particles is formed in a second irradiation region irradiated with ultraviolet rays by pattern irradiation of ultraviolet rays. As shown in FIG. 16, for example, when the pattern exposure of ultraviolet rays is performed using the second mask 5B, the dispersed particles 31 are cured into the cured product particles 41 in the second irradiation region irradiated with the ultraviolet rays. A granular layer 4a composed of cured product particles 41 is formed. The ultraviolet rays irradiate, for example, a part of the region of the second film 3 located on the first non-irradiated region 2A and a part of the second film 3 located on the first irradiated region 2B. .. Therefore, the granular layer 4a includes a portion located on the first non-irradiated region 2A (hereinafter, also referred to as a third portion) and a portion located on the first irradiation region 2B (hereinafter, also referred to as a fourth portion). Will be included.

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

Of the uncured material of the first film and the uncured first liquid, those located in the vicinity of the third portion move to the third portion of the granular layer located on the first non-irradiated region. .. On the other hand, in the fourth portion of the granular layer located on the first irradiation region, there is no uncured material of the first film in the vicinity of this portion, so that, for example, the uncured first liquid Of these, only those located near the fourth part move. Alternatively, in addition to the movement of the uncured first liquid located near the fourth portion to the fourth portion, the uncured material of the first film material is compared with the third portion. Move in a small amount.

17 and 18 schematically show an example of a state change of the first film and the second film caused by the removal of the second liquid. FIG. 17 schematically shows an example of a state in which the coalescence of dispersed particles occurs in the second non-irradiated region by starting the removal of the second liquid from the second film. In FIG. 18, a part of the first liquid constituting the union of the dispersed particles is mixed with the uncured material of the first film material, and the mixture thereof is a granular layer composed of the cured product of the dispersed particles. An example of a state in which a part of the first liquid has penetrated into another part of the granular layer without being mixed with the uncured material of the material of the first film is shown. ing.

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

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

On the other hand, in the vicinity of the first irradiation region 2B, when the second liquid decreases, the dispersed particles 31 coalesce, but the uncured material of the first film 2 does not exist, so that the first liquid is used. Does not dissolve. Therefore, as shown in FIG. 18, only the uncured first liquid 4d permeates the gaps in the granular layer 4a and diffuses into the granular layer 4a.

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

In the third portion of the granular layer, the first liquid and the uncured material of the first film are present. On the other hand, in the fourth portion of the granular layer, only the first liquid is present, or in addition to the presence of the first liquid, the uncured material of the first film is more than the third portion. It is present in a small amount (relative to the first liquid). Therefore, in the pattern film thus obtained, the cured product phase formed in the third portion is a cured product of the material of the first film with respect to the cured product of the first liquid as compared with the cured product phase generated in the fourth portion. The relative amount of is large.

FIG. 19 schematically shows an example of a state in which the uncured material is cured by the entire surface irradiation of ultraviolet rays when the material of the first film is an ultraviolet curable resin.

In the third part, the uncured first liquid and the uncured material of the first film are cured by ultraviolet irradiation. As a result, the cured product phase 4c is formed. On the other hand, in the fourth part, there is no uncured material of the first film, and the uncured first liquid is cured by ultraviolet irradiation. As a result, the cured product phase 4e is formed. Then, in the cured product particles 41 constituting the granular layer 4a, further polymerization proceeds by irradiation with ultraviolet rays.

As a result, the first pattern portion 4A and the second pattern portion 4B are provided, and the first pattern portion 4A is a cured product phase 4c which is a cured product in which a part of the granular layer 4a and a gap thereof are at least partially embedded. In the second pattern portion 4B, a pattern film containing the other part of the granular layer 4a and the cured product phase 4e which is a cured product in which the gap is at least partially embedded can be obtained. Further, as a result, a structure including the base material 1, the above-mentioned pattern film, and the cured product layer (first irradiation region 2B) interposed between the base material 1 and the second pattern portion 4B can be obtained. ..

<Effect>
Also in this embodiment, the same effect as that of the first embodiment can be obtained. Further, in the present embodiment, the composition can be different between the cured product phase generated in the third portion and the cured product phase generated in the fourth portion. Further, in the present embodiment, for example, in the first film, the portion located in the vicinity of the third portion can be eliminated and the portion located in the vicinity of the fourth portion can be left. That is, according to this embodiment, it is possible to form a more complicated structure.

[1] Test 1
In this test, a pattern film was formed by the method described with reference to FIGS. 1 to 6.

<Preparation of coating liquid for forming the first film>
The following materials were used to prepare a coating liquid for forming the first film.
Polymethylmethacrylate type macromonomer: macromonomer AA-6 (Toagosei Co., Ltd.)
Blue dye: Kayaset Blue N
Solvent: 10 g of n-butyl acetate and 1 g of macromonomer AA-6 were charged in a vial of n-butyl acetate and shaken under heating at 70 ° C. As a result, the macromonomer AA-6 was dissolved in n-butyl acetate. Next, 0.003 g of Kayaset Blue N was added to this solution, and the mixture was shaken without heating. As described above, a coating liquid for forming the first film was obtained.

<Preparation of emulsion>
An O / W type emulsion was prepared using the following materials.
Trimethylolpropane Triacrylate: Light Acrylate TMP-A (Kyoeisha Chemical Co., Ltd.)
Photopolymerization Initiator: Lunarure 200 (DKSH Japan Co., Ltd.)
Surfactant: Sanmorin OT-70 <86.7% aqueous solution> (Sanyo Chemical Industries, Ltd.)
Second 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 emulsion. Then, this mixed solution was subjected to an emulsification / dispersion treatment for 30 seconds using a paint shaker. Subsequently, rotary mixing of the vial was performed for 1 hour. As described above, an emulsion was obtained.

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

<Formation of the first film>
The above coating liquid was dropped onto the surface of a slide glass for a microscope using a dropper, and this was developed into a film. It was then dried by heating in a convection oven set at 70 ° C. for 10 minutes. As described above, a first film having a thickness of 7.6 μm was obtained.

<Formation of the second 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 a separately prepared microscope slide glass along the long side direction. Then, the central portion thereof was cut out in a rectangular shape of 10 mm × 20 mm.

Next, this laminate was peeled off from the slide glass and attached onto the above-mentioned first film. As described above, a cell having a liquid reservoir provided with a first film on the bottom (hereinafter referred to as a liquid reservoir cell) was produced.

Then, a 75 μL emulsion was collected by a micropipette. By developing and filling this in a liquid reservoir cell, a second film made of an emulsion having a thickness of about 375 μm as a calculated value considering the specific gravity was obtained.

<Irradiation of active energy rays>
Next, a photomask having a line-and-space pattern of 2 mm in each of the line width and the space width was placed on the second film so as not to come into contact with the second film. Next, using a metal halide UV light source (LS-165UV manufactured by Sumita Optical Glass, Inc.), the ultraviolet rays emitted from the fiber light guide connected to this light source are made almost parallel light by a biconvex quartz lens, and this is irradiated from above the mask. , The film was exposed to an integrated light amount of 40 mJ / cm ² . After that, the photomask was removed from the slide glass.

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

Optical photographs of the structure thus obtained are shown in FIGS. 21 and 22. In FIG. 21, a first film and a laminated body having a window are sequentially provided on the slide glass. A line and space pattern is formed in the window. FIG. 22 is an enlarged optical photograph showing a line and space pattern in a window. The colored part of the pattern in the window is the line part. The line portion contains a granular layer and a combined emulsion component of a non-irradiated portion in which a first film component containing a blue dye is dissolved.

[2] Test 2
In this test, a pattern film was formed by the same method as described with reference to FIGS. 7 to 12.

<Formation of the first 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, a cell having a liquid reservoir (hereinafter referred to as a liquid reservoir cell) was produced by cutting out the central portion into a rectangular shape of 10 mm × 20 mm. Next, using a black oil-based pen, three straight lines parallel to each other on the opening surface (slide glass surface) of the liquid reservoir cell containing the masking tape layer, each extending in the length direction of the slide glass. I drew. As described above, the first film composed of the ink layer was obtained. FIG. 23 is an optical photograph of the structure thus obtained. A line-and-space pattern consisting of an ink layer is provided at the bottom of the liquid reservoir cell.

<Formation of the second film>
A 75 μL emulsion was collected by micropipette. As this emulsion, the same emulsion used in Test 1 was prepared. By developing and filling this in a liquid reservoir cell, a second film made of an emulsion having a thickness of about 375 μm as a calculated value considering the specific gravity was obtained.

FIG. 24 is an optical photograph of the structure thus obtained. Since the liquid reservoir cell is filled with an emulsion, the line-and-space pattern provided at the bottom of the liquid reservoir cell looks blurry.

<Irradiation of active energy rays>
Next, a photomask having a line-and-space pattern of 2 mm in each of the line width and the space width was placed on the second film so as not to come into contact with the second film. As shown in the optical photograph of FIG. 25, the length direction of the line portion and the space portion of the photomask is the length direction of the line portion and the space portion of the line and space pattern provided at the bottom of the liquid reservoir cell. It was installed so as to be orthogonal.

Next, a light source head unit (HOYA CANDEO OPTRONICS H-1VH4-V1) is connected to a UV-LED irradiator controller (HOYA CANDEO OPTRONICS EXECURE-H-1VCII), and a uniform irradiation lens unit (HOYA CANDEO OPTRONICS) is connected to this. Using a UV exposure system equipped with HDL-21) manufactured by the company, the film is exposed to an integrated light amount of 53.5 mJ / cm ² by irradiating the film with ultraviolet rays having an illuminance of 10.7 mW / cm ² for 5 seconds. Gave. After that, the photomask was removed from the slide glass.

<Drying of film and fixing of pattern>
Next, the film after exposure to ultraviolet rays was naturally dried in an environment having a temperature of 23.6 ° C. and a relative humidity of 27%.
Then, the entire film was exposed to ultraviolet rays using the above-mentioned exposure machine to give an exposure with an integrated light amount of 642 mJ / cm ² . As a result, the pattern was fixed.

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

As shown in FIGS. 26 to 32, in the vicinity of the first film in the non-irradiated region, a part of the material of the first film was dissolved in the first liquid. Then, the first liquid moved from the non-irradiated region to the granular layer in the irradiated region, and along with this movement, the material of the first film dissolved in the first liquid also moved to the granular layer in the irradiated region. On the other hand, in the irradiated area, the material of the first film did not dissolve in the first liquid as much as in the non-irradiated area.

[3] Test 3
In this test, a pattern film was formed by the same method as described with reference to FIGS. 13 to 19.

<Preparation of coating liquid for forming the first film>
The following materials were used to prepare a coating liquid for forming the first film.
Polymethylmethacrylate type macromonomer: macromonomer AA-6 (Toagosei Co., Ltd.)
Trimethylolpropane Triacrylate: Light Acrylate TMP-A (Kyoeisha Chemical Co., Ltd.)
Diphenyl (2,4,6-trimethylbenzyl) phosphine oxide: Lucirin® TPO (BASF Japan Ltd.)
Blue dye: Kayaset Blue N
Solvents: n-butyl acetate 100 g n-butyl acetate, 7 g macromonomer AA-6, 3 g light acrylate TMP-A, 0.6 g Lucirin TPO and 0.2 g Kayaset Blue N. It was placed in a closed container that blocks ultraviolet rays. The vessel was then rotated at room temperature to mix and dissolve these components. As described above, a coating liquid for forming the first film was obtained.

<Formation of the first film>
Three 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 square shape of 20 mm × 20 mm. As described above, a cell having a liquid reservoir (hereinafter referred to as a first liquid reservoir cell) was produced.

Then, 75 μL of the above coating liquid was collected by a micropipette. This was developed and filled in the first liquid reservoir cell, and further, it was naturally dried for 24 hours in a light-shielded room temperature environment. As described above, a first film that was tack-free and had a central portion having a thickness of about 7 μm was obtained.

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

Next, a light source head unit (HOYA CANDEO OPTRONICS H-1VH4-V1) is connected to a UV-LED irradiator controller (HOYA CANDEO OPTRONICS EXECURE-H-1VCII), and a uniform irradiation lens unit (HOYA CANDEO OPTRONICS) is connected to this. By irradiating the first film with ultraviolet rays with an illuminance of 16.3 mW / cm ² for 60 seconds using a UV exposure system equipped with HDL-21) manufactured by the company, the first film is exposed to an integrated light amount of 978 mJ / cm ² . Gave. As described above, a latent image was recorded on the first film. After that, the photomask was removed from the slide glass.

<Formation of the second 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 a separately prepared microscope slide glass along the long side direction. Then, the central portion thereof was cut out in a rectangular shape of 10 mm × 20 mm.

Next, this laminate was peeled off from the slide glass and attached onto the slide glass on which the first film was formed. As described above, a cell having a liquid reservoir provided with a first film on the bottom (hereinafter referred to as a second liquid reservoir cell) was produced.

FIG. 34 is an optical photograph of the structure thus obtained. Here, as shown in the optical photograph of FIG. 34, the length direction of the second liquid reservoir cell is parallel to the length direction of the slide glass.

Then, a 75 μL emulsion was collected by a micropipette. As this emulsion, the same emulsion used in Test 1 was prepared. By developing and filling this in a second liquid reservoir cell, a second film made of an emulsion having a thickness of about 375 μm as a calculated value considering the specific gravity was obtained.

<Irradiation of the second active energy ray>
Next, a photomask having a line-and-space pattern of 2 mm in each of the line width and the space width was placed on the second film so as not to come into contact with the second film. As shown in the optical photograph of FIG. 35, the photomask was installed so that the length direction of the line portion and the space portion was orthogonal to the length direction of the second liquid reservoir cell.

Next, a light source head unit (HOYA CANDEO OPTRONICS H-1VH4-V1) is connected to a UV-LED irradiator controller (HOYA CANDEO OPTRONICS EXECURE-H-1VCII), and a uniform irradiation lens unit (HOYA CANDEO OPTRONICS) is connected to this. Using a UV exposure system equipped with HDL-21) manufactured by the company, the film is exposed to an integrated light amount of 53.5 mJ / cm ² by irradiating the film with ultraviolet rays having an illuminance of 10.7 mW / cm ² for 5 seconds. Gave. After that, the photomask was removed from the slide glass.

<Drying of film and fixing of pattern>
Next, the film after exposure to ultraviolet rays was naturally dried in an environment having a temperature of 24 ° C. and a relative humidity of 38%. Then, the entire film was exposed to ultraviolet rays using the above-mentioned exposure machine to give an exposure with an integrated light amount of 642 mJ / cm ² . As a result, the pattern was fixed.

The structure of the film during the drying process is shown in the optical photographs of FIGS. 36 to 43. As shown in the optical photographs of FIGS. 36 to 43, as the film dries, the uncured material contained in the first non-irradiated region is dissolved in the first liquid, and the second non-irradiated region is used as the first liquid. 2 The transfer of the first liquid to the granular layer in the irradiated area occurred.

1 ... Substrate, 2 ... 1st film, 2A ... 1st non-irradiated area, 2B ... 1st irradiation area, 3 ... 2nd film, 4A ... 1st pattern part, 4B ... 2nd pattern part, 4a ... Granular layer 4b ... mixture, 4c ... cured phase, 4d ... first liquid, 4e ... cured phase, 5 ... mask, 5A ... first mask, 5B ... second mask, 31 ... dispersed particles, 32 ... dispersion medium, 41 … Hardened particles.

Claims (8)

Providing a first film on the substrate and
A second 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 the first film. To form and
Without irradiating at least a part of the region of the second film with the active energy ray, irradiating at least a part of the other region of the second film with the active energy ray and irradiating the active energy ray. Curing the first liquid in the region
After irradiation with the active energy rays, at least a part of the second liquid is removed from the second film, and at least a part of the material of the first film is contained in the uncured second film. Dissolving in the first liquid and
A method for forming a pattern film, which comprises curing the uncured first liquid in which at least a part of the material of the first film is dissolved. The method according to claim 1, wherein the material contains a thermoplastic resin, and at least a part of the material that has been heated and fluidized is dissolved in the uncured first liquid contained in the second film. .. Providing a first film on the substrate and
A second 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 the first film. To form and
Without irradiating at least a part of the region of the second film with the active energy ray, irradiating at least a part of the other region of the second film with the active energy ray and irradiating the active energy ray. To form a granular layer made of a cured product of the dispersed particles in the formed region,
After irradiation with the active energy rays, at least a part of the second liquid is removed from the second membrane, and at least a part of the uncured first liquid in the region not irradiated with the active energy rays is said. In addition to moving into the granular layer, at least a part of the material of the first film is moved to the granular layer.
After that, a method for forming a pattern film, which comprises curing the uncured first liquid. The method according to claim 3, wherein the material contains a thermoplastic resin, and at least a part of the material that has been heated and fluidized is transferred to the granular layer. The first film is provided only on a part of the substrate, and the second film is formed on at least a part of the first film and on another part of the substrate. The active energy rays are applied to at least a part of the region of the second membrane located on the first membrane and at least a part of the region of the second membrane not located on the first membrane. The method according to any one of claims 1 to 4. The material contains a resin that is cured by irradiation with active energy rays, and the first film is irradiated with the active energy rays in a pattern before the second film is formed, and the active energy rays are irradiated. The method according to claim 1 or 3, further comprising curing the resin in the region. The method according to any one of claims 1 to 6, wherein the emulsion is an oil-in-water emulsion. A pattern film formed by the method according to any one of claims 1 to 7.

Images