Method for manufacturing resin structure and manufacturing apparatus for resin structure

Abstract

To solve a problem that it is difficult to obtain a resin structure of a high porosity and polymerization rate, since the structure and property of a porous resin change according to polymerization conditions in the production of a resin structure having a porous structure formed when polymerizing a polymerizable compound.SOLUTION: A production method of a resin structure includes a preparation step for preparing a liquid composition containing a polymerizable compound and a solvent, a first irradiation step for irradiating the prepared liquid composition with first active energy rays, and a second irradiation step for irradiating the liquid composition irradiated with the first active energy rays with second active energy rays. The resin structure has a porous structure having a resin skeleton. The porous structure is formed by irradiating the polymerizable compound in the liquid composition with the first active energy rays and the second active energy rays. The irradiation intensity of the second active energy rays is higher than that of the first active energy rays.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a resin structure and a manufacturing apparatus for a resin structure.

Background Art

[0002] Generally, porous resins can be utilized in various applications. For example, by appropriately selecting the shape of pores, the size of pores, and the surface characteristics of the skeleton portion in the porous resin, a separation layer that allows only a specific substance to permeate or blocks it can be provided. As another example, by utilizing the large surface area and void volume of the porous resin, an efficient reaction field or storage field for gases or liquids taken in from the outside can be provided. Therefore, if a liquid composition for forming a porous resin that is excellent in handleability and can be easily applied to various locations can be provided, the range of applications of the porous resin will be greatly expanded.

[0003] As such a liquid composition for forming a porous resin, for example, in Patent Document 1, a porous formation photocurable resin composition containing a photopolymerizable monomer (A), an organic compound (B) incompatible with the photopolymerizable monomer (A), a common solvent (C) compatible with the photopolymerizable monomer (A) and the organic compound (B), and a photoinitiator (D) as essential components is disclosed.

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, in the production of a resin structure in which a porous structure is formed along with the polymerization of a polymerizable compound, since the structure and properties of the porous resin change based on the polymerization conditions, there is a problem that it is difficult to obtain a resin structure having a high porosity and polymerization rate.

Means for Solving the Problems

[0005] The present invention relates to a method for manufacturing a resin structure, including: an application step of applying a liquid composition containing a polymerizable compound and a solvent; a first irradiation step of irradiating the applied liquid composition with a first active energy ray; and a second irradiation step of irradiating the liquid composition irradiated with the first active energy ray with a second active energy ray. The resin structure has a porous structure with a resin as a skeleton, and the porous structure is formed by irradiating the polymerizable compound in the liquid composition with the first active energy ray and the second active energy ray. The irradiation intensity of the second active energy ray is higher than that of the first active energy ray. <,> The polymerizable compound and the solvent are compatible, the porous structure is formed by the incompatibility of the polymer formed during the polymerization of the polymerizable compound in the liquid composition and the solvent, and the applying step is a step of applying the liquid composition to the active material layer formed on the electrode substrate It relates to a method for manufacturing a resin structure, which is characterized by the above.

Effects of the Invention

[0006] According to the present invention, it is possible to provide a manufacturing method and a manufacturing apparatus capable of improving the porosity and the polymerization rate in a resin structure in which a porous structure is formed along with the polymerization of a polymerizable compound.

Brief Description of the Drawings

[0007]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0008] Hereinafter, an embodiment of the present invention will be described.

[0009] <<Method for Manufacturing a Resin Structure>> The manufacturing method of the resin structure of this embodiment includes an application step of applying a liquid composition containing a polymerizable compound and a solvent, a first irradiation step of irradiating the applied liquid composition with a first active energy ray, and a second irradiation step of irradiating the liquid composition irradiated with the first active energy ray with a second active energy ray. Further, the manufacturing method of the resin structure of this embodiment may have a removal step of removing the solvent from the resin structure after the second irradiation step, etc., as necessary.

[0010] <Application step> The application step is a step of applying a liquid composition containing a polymerizable compound and a solvent to an object to be applied such as a substrate. The applied liquid composition preferably forms a liquid composition layer, which is a liquid film of the liquid composition, on the object to be applied. The method of applying the liquid composition is not particularly limited, and examples thereof include various printing methods such as spin coating method, casting method, microgravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, and inkjet printing method. Among these, from the viewpoint of being able to control the position where the liquid composition is applied, a liquid ejection method such as an inkjet printing method is preferable.

[0011] -Liquid composition- The liquid composition contains a polymerizable compound, a solvent, and other components such as a polymerization initiator as necessary. Further, the liquid composition forms a resin structure (hereinafter also referred to as "porous resin") having a porous structure with a resin as a skeleton when cured. In the present disclosure, the liquid composition forms a porous resin, which means not only the case where the porous resin is formed in the liquid composition, but also the case where a precursor of the porous resin (for example, the skeleton portion of the porous resin) is formed in the liquid composition and the porous resin is formed in a subsequent step (for example, a heating step or the like). Further, the liquid composition forming a porous resin means that a part of the components (polymerizable compounds or the like) in the liquid composition are cured (polymerized) to form the skeleton of the porous resin, and other components (solvents or the like) in the liquid composition are not cured and do not form the porous resin.

[0012] --Polymerizable compound-- The polymerizable compound forms a resin by polymerization and forms a porous resin when polymerized in the liquid composition. The resin formed by the polymerizable compound preferably has a network structure formed by the application of active energy rays (for example, irradiation with light, application of heat, etc.). For example, acrylate resin, methacrylate resin, urethane acrylate resin, vinyl ester resin, unsaturated polyester resin, epoxy resin, oxetane resin, vinyl ether resin, and a resin formed by an ene-thiol reaction are preferred. Further, from the viewpoint of easily forming a structure by utilizing highly reactive radical polymerization, acrylate resin, methacrylate resin, urethane acrylate resin formed by a polymerizable compound having a (meth)acryloyl group, and vinyl ester resin formed by a polymerizable compound having a vinyl group are more preferred from the viewpoint of productivity. These may be used alone or in combination of two or more. When two or more are used in combination, the combination of the polymerizable compounds is not particularly limited and can be appropriately selected according to the purpose. For example, for imparting flexibility, it is preferable to mix other resins with urethane acrylate resin as the main component. In the present disclosure, a polymerizable compound having an acryloyl group or a methacryloyl group is referred to as a polymerizable compound having a (meth)acryloyl group.

[0013] The coincidence compound preferably has at least one radically polymerizable functional group. Examples thereof include monofunctional, difunctional, trifunctional or higher radically polymerizable compounds, functional monomers, and radically polymerizable oligomers. Among these, difunctional or higher radically polymerizable compounds are preferred.

[0014] Examples of the monofunctional radically polymerizable compound include 2-(2-ethoxyethoxy)ethyl acrylate, methoxypolyethylene glycol monoacrylate, methoxypolyethylene glycol monomethacrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethyl succinate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-ethylhexyl carbitol acrylate, 3-methoxybutyl acrylate, benzyl acrylate, cyclohexyl acrylate, isoamyl acrylate, isobutyl acrylate, methoxytriethylene glycol acrylate, phenoxytetraethylene glycol acrylate, cetyl acrylate, isostearyl acrylate, stearyl acrylate, styrene monomer, and the like. These may be used alone or in combination of two or more.

[0015] Examples of the difunctional radically polymerizable compound include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, EO-modified bisphenol A diacrylate, EO-modified bisphenol F diacrylate, neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, and the like. These may be used alone or in combination of two or more.

[0016] Examples of the radical polymerizable compound having three or more functional groups include trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, caprolactone-modified trimethylolpropane triacrylate, HPA-modified trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glycerol triacrylate, ECH-modified glycerol triacrylate, EO-modified glycerol triacrylate, PO-modified glycerol triacrylate, tris(acryloxyethyl) isocyanurate, dipentaerythritol hexaacrylate (DPHA), caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, alkyl-modified dipentaerythritol pentaacrylate, alkyl-modified dipentaerythritol tetraacrylate, alkyl-modified dipentaerythritol triacrylate, dimethylolpropane tetraacrylate (DTMPTA), pentaerythritol ethoxytetraacrylate, EO-modified triacrylate phosphate, 2,2,5,5-tetrahydroxymethylcyclopentanone tetraacrylate, and the like. These may be used alone or in combination of two or more.

[0017] The content of the polymerizable compound in the liquid composition is preferably 5.0% by mass or more and 70.0% by mass or less, more preferably 10.0% by mass or more and 50.0% by mass or less, and still more preferably 20.0% by mass or more and 40.0% by mass or less, based on the total amount of the liquid composition. When the content of the polymerizable compound is 70.0% by mass or less, the pore size of the resulting porous resin does not become too small, such as several nm or less, the porous resin has an appropriate porosity, and the tendency of liquid or gas penetration to occur can be suppressed, which is preferable. Further, when the content of the polymerizable compound is 5.0% by mass or more, a three-dimensional network structure of the resin is sufficiently formed to obtain a sufficient porous structure, and the strength of the resulting porous structure also tends to be improved, which is preferable.

[0018] --Solvent-- The solvent (also referred to as "porogen" in the following description) is a liquid that is compatible with the polymerizable compound. Further, the solvent is a liquid that becomes incompatible (phase separation occurs) with the polymer (resin) generated during the process of polymerization of the polymerizable compound in the liquid composition. By including the solvent in the liquid composition, when the polymerizable compound is polymerized in the liquid composition, in other words, when the first active energy ray and the second active energy ray are sequentially irradiated in the liquid composition, a porous resin is formed. Further, it is preferably capable of dissolving a compound (a polymerization initiator described later) that generates radicals or an acid by light or heat. The solvent may be used alone or in combination of two or more. Note that the solvent does not have polymerizability.

[0019] The boiling point of a single type of porogen or the boiling point when two or more types are used in combination is preferably 50°C or higher and 250°C or lower, more preferably 70°C or higher and 200°C or lower, at normal pressure. By the boiling point being 50°C or higher, the vaporization of the porogen near room temperature is suppressed, making it easier to handle the liquid composition and easier to control the content of the porogen in the liquid composition. Further, by the boiling point being 250°C or lower, the time in the step of drying the porogen after polymerization is shortened, improving the productivity of the porous resin. Also, since the amount of the porogen remaining inside the porous resin can be suppressed, the quality is improved when the porous resin is used as a functional layer such as a substance separation layer for separating substances or a reaction layer as a reaction field. Further, the boiling point of a single type of porogen or the boiling point when two or more types are used in combination is preferably 120°C or higher at normal pressure.

[0020] Examples of porogens include ethylene glycols such as diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisopropyl ether, and dipropylene glycol monomethyl ether; esters such as γ-butyrolactone and propylene carbonate; amides such as N,N-dimethylacetamide; and the like. Also, liquids with relatively large molecular weights such as methyl myristate, methyl decanoate, methyl myristate, and tetradecane can be mentioned. Further, liquids such as acetone, 2-ethylhexanol, and 1-bromonaphthalene can be mentioned. Note that not all of the above-exemplified liquids always correspond to porogens. As described above, a porogen is a liquid that is compatible with a polymerizable compound and becomes incompatible (phase separation occurs) with the polymer (resin) generated during the process of polymerization of the polymerizable compound in the liquid composition. In other words, whether a certain liquid corresponds to a porogen is determined by its relationship with the polymerizable compound and the polymer (resin formed by polymerization of the polymerizable compound). In addition, since the liquid composition only needs to contain at least one type of porogen having the above specific relationship with the polymerizable compound, the range of material selection during the production of the liquid composition is widened, and the design of the liquid composition becomes easier. By widening the range of material selection during the production of the liquid composition, when there are characteristics required for the liquid composition from viewpoints other than the formation of the porous structure, the range of response is widened. For example, when the liquid composition is ejected by an inkjet method, from viewpoints other than porous formation, it is required that the liquid composition has ejection stability and the like. However, since the range of material selection is wide, the design of the liquid composition becomes easier. Incidentally, since the liquid composition only needs to contain at least one kind of porogen having the above specific relationship with the polymerizable compound, it may additionally contain a liquid (a liquid that is not a porogen) that does not have the above specific relationship with the polymerizable compound. However, the content of the liquid (a liquid that is not a porogen) that does not have the above specific relationship with the polymerizable compound is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, still more preferably 1.0% by mass or less, and particularly preferably not contained, based on the total amount of the liquid composition.

[0021] The content of the porogen in the liquid composition is preferably 30.0% by mass or more and 95.0% by mass or less, more preferably 50.0% by mass or more and 90.0% by mass or less, still more preferably 60.0% by mass or more and 80.0% by mass or less, based on the total amount of the liquid composition. When the content of the porogen is 30.0% by mass or more, the size of the pores of the resulting porous body does not become too small to be several nm or less, the porous body has an appropriate porosity, and the tendency for the penetration of liquids and gases to occur can be suppressed, which is preferable. Also, when the content of the porogen is 95.0% by mass or less, a three-dimensional network structure of the resin is sufficiently formed and a porous structure is sufficiently obtained, and the strength of the resulting porous structure also tends to improve, which is preferable.

[0022] The mass ratio (polymerizable compound: porogen) of the content of the polymerizable compound and the content of the porogen in the liquid composition is preferably 1.0:0.4 to 1.0:19.0, more preferably 1.0:1.0 to 1.0:9.0, still more preferably 1.0:1.5 to 1.0:4.0.

[0023] ---Polymerization-induced phase separation--- The porous resin is formed by polymerization-induced phase separation. Polymerization-induced phase separation refers to a state where the polymerizable compound and the porogen are compatible, but the polymer (resin) formed during the polymerization of the polymerizable compound and the porogen are incompatible (phase separation occurs). Although there are other methods to obtain a porous resin by phase separation, by using the method of polymerization-induced phase separation, a porous body with a network structure can be formed, and thus a porous body with high resistance to chemicals and heat can be expected. In addition, compared with other methods, it also has the advantages of a short process time and easy surface modification.

[0024] Next, the formation process of the porous resin using polymerization-induced phase separation will be described. The polymerizable compound undergoes a polymerization reaction by light irradiation or the like to form a resin. During this process, the solubility of the growing resin in the porogen decreases, and phase separation occurs between the resin and the porogen. Finally, the resin forms a porous structure in which the porogen and the like fill the pores. When this is dried, the porogen and the like are removed, and the porous resin remains. Therefore, in order to form a porous resin having an appropriate porosity, the compatibility between the porogen and the polymerizable compound, and the compatibility between the porogen and the resin formed by the polymerization of the polymerizable compound are considered.

[0025] The compatibility between the porogen and the polymerizable compound is determined as follows. First, the liquid composition is injected into a quartz cell, and while stirring at 300 rpm using a stirrer, the transmittance of light (visible light) at a wavelength of 550 nm of the liquid composition is measured. In the present disclosure, when the light transmittance is 30% or more, it is determined that the polymerizable compound and the porogen are in a compatible state, and when it is less than 30%, it is determined that the polymerizable compound and the porogen are in an incompatible state. The various conditions regarding the measurement of the light transmittance are shown below. · Quartz cell: Special micro cell with screw cap (product name: M25-UV-2) · Transmittance measuring device: USB4000 manufactured by Ocean Optics · Stirring speed: 300 rpm · Measurement wavelength: 550 nm · Reference: Measure the light transmittance at a wavelength of 550 nm with the inside of the quartz cell in an air state and obtain it (transmittance: 100%)

[0026] The compatibility with the resin formed by the polymerization of porogen and the polymerizable compound is judged as follows. First, resin fine particles are uniformly dispersed on an alkali-free glass substrate by spin coating to serve as a gap agent. Subsequently, the substrate coated with the gap agent is bonded to an alkali-free glass substrate not coated with the gap agent with the surface coated with the gap agent sandwiched between them. Next, the liquid composition is filled between the bonded substrates using capillary action to produce an "element for haze measurement before UV irradiation". Subsequently, the element for haze measurement before UV irradiation is irradiated with UV to cure the liquid composition. Finally, the "element for haze measurement" is produced by sealing the periphery of the substrate with a sealant. The various conditions during production are shown below. · Alkali-free glass substrate: Made by Nippon Electric Glass, 40 mm, t = 0.7 mm, OA-10G · Gap agent: Made by Sekisui Chemical, resin fine particle Micropearl GS-L100, average particle diameter 100 μm · Spin coating conditions: Dispersion droplet amount 150 μL, rotation speed 1000 rpm, rotation time 30 s · Filled liquid composition amount: 160 μL · UV irradiation conditions: Use a UV-LED as the light source, light source wavelength 365 nm, irradiation intensity 30 mW / cm 2 , irradiation time 20 s · Sealant: TB3035B (manufactured by Three Bond) Next, the haze value (cloudiness) is measured using the prepared element for measuring haze before UV irradiation and the element for measuring haze. Taking the measured value of the element for measuring haze before UV irradiation as the reference (haze value 0), the increase rate of the measured value (haze value) of the element for measuring haze with respect to the measured value of the element for measuring haze before UV irradiation is calculated. The haze value of the element for measuring haze increases as the compatibility between the resin formed by the polymerization of the polymerizable compound and the porogen decreases, and decreases as the compatibility increases. Also, the higher the haze value, the easier it is for the resin formed by the polymerization of the polymerizable compound to form a porous structure. In the present disclosure, when the increase rate of the haze value is 1.0% or more, it is determined that the resin and the porogen are in an incompatible state, and when it is less than 1.0%, it is determined that the resin and the porogen are in a compatible state. The devices used for the measurement are shown below. · Haze measuring device: Haze meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.

[0027] --Polymerization initiator-- A polymerization initiator is a material that can generate active species such as radicals and cations by energy such as light and heat, and initiate the polymerization of a polymerizable compound. As the polymerization initiator, known radical polymerization initiators, cationic polymerization initiators, base generators, etc. can be used alone or in combination of two or more, and among them, it is preferable to use a photo-radical polymerization initiator.

[0028] As a photo radical polymerization initiator, a photo radical generator can be used. For example, photo radical polymerization initiators such as Michler's ketone and benzophenone known under the trade names Irgacure and Darocur, and more specific compounds include benzophenone, acetophenone derivatives such as α-hydroxy- or α-aminoacetophenone, 4-aroyl-1,3-dioxolane, benzyl ketal, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, pp'-dichlorobenzophenone, pp'-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzyldimethyl ketal, tetramethylthiuram monosulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, azobisisobutyronitrile, benzoin peroxide, di-tert-butyl peroxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, methyl benzoylformate, benzoin isopropyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin n-propyl, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173), bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one monoacylphosphine oxide, bisacylphosphine oxide or titanocene, fluorene, anthraquinone, thioxanthone or xanthone, rofin dimer, trihalomethyl compound or dihalomethyl compound, active ester compound, organic boron compound, etc. are preferably used., Furthermore, a photocrosslinkable radical generator such as a bisazide compound may be contained simultaneously. In addition, when polymerizing only by heat, a thermal polymerization initiator such as azobisisobutyronitrile (AIBN), which is a normal radical generator, can be used.,

[0029] The content of the polymerization initiator is preferably 0.05% by mass or more and 10.0% by mass or less, more preferably 0.5% by mass or more and 5.0% by mass or less, when the total mass of the polymerizable compounds is 100.0% by mass in order to obtain a sufficient curing rate.,

[0030] --Others-- The liquid composition of the present disclosure may be a non-dispersed composition that does not contain a dispersion in the liquid composition or a dispersed composition that contains a dispersion in the liquid composition, but a non-dispersed composition is preferred. This is because the liquid composition can be used in various application means. For example, it is preferable because it can be stably used even in an inkjet method where maintaining ejection stability is important.,

[0031] -Method for producing liquid composition- The liquid composition is preferably prepared through steps such as dissolving a polymerization initiator in a polymerizable compound, further dissolving a porogen or other components, and stirring to obtain a uniform solution.,

[0032] -Physical properties of liquid composition- The viscosity of the liquid composition is preferably 1.0 mPa·s or more and 150.0 mPa·s or less, more preferably 1.0 mPa·s or more and 30.0 mPa·s or less, and particularly preferably 1.0 mPa·s or more and 25.0 mPa·s or less at 25°C from the viewpoint of workability when applying the liquid composition. When the viscosity of the liquid composition is 1.0 mPa·s or more and 30.0 mPa·s or less, good ejection properties can be obtained even when the liquid composition is applied by an inkjet method. Here, the viscosity can be measured using, for example, a viscometer (device name: RE-550L, manufactured by Toki Sangyo Co., Ltd.).

[0033] <First Irradiation Step> The first irradiation step is a step of irradiating the liquid composition applied in the application step with first active energy rays. The first irradiation step improves the porosity of the finally produced porous resin, thereby improving, for example, the fluid uptake property of a fluid such as a liquid or a gas in the porous resin. Specifically, by irradiating the liquid composition with first active energy rays, a porous precursor having a porous structure that is the basis for forming a porous resin with a high porosity is formed. In the first irradiation step, if a porous precursor is formed, a polymerizable compound may remain as an unreacted component.

[0034] The first active energy rays are not particularly limited as long as they can impart the energy necessary for advancing the polymerization reaction of the polymerizable compound. Examples include ultraviolet rays, electron beams, α-rays, β-rays, γ-rays, X-rays, etc. Among these, ultraviolet rays are preferable. When a particularly high-energy light source is used, the polymerization reaction can proceed without using a polymerization initiator.

[0035] The reason for forming the porous precursor by the first irradiation step will be explained. As described above, when forming a porous resin by polymerization-induced phase separation, the structure and properties of the porous resin change based on the polymerization conditions. For example, when forming a porous resin under conditions where polymerization of a polymerizable compound is promoted by irradiating an active energy ray with a high irradiation intensity to a liquid composition, polymerization proceeds before phase separation sufficiently occurs, and it tends to be difficult to produce a porous resin with a high porosity. Therefore, in the first irradiation step aimed at forming a porous precursor having a porous structure that is the basis for forming a porous resin with a high porosity, the irradiation intensity of the first active energy ray to be irradiated is set not to be too high. Specifically, it is set such that the irradiation intensity of the first active energy ray is lower than the irradiation intensity of the second active energy ray irradiated in a second irradiation step described later, which is aimed at promoting the polymerization reaction of the polymerizable compound as an unreacted component. More specifically, the irradiation intensity of the first active energy ray is preferably 2 1 W / cm or less, more preferably 2 less than 300 mW / cm, and even more preferably 2 less than 100 mW / cm. However, if the irradiation intensity of the first active energy ray is too low, phase separation proceeds excessively, resulting in variations and coarsening of the porous structure. Further, the irradiation time also becomes longer, leading to a decrease in productivity. Therefore, it is preferably 2 10 mW / cm or more, and more preferably 2 30 mW / cm or more. When the first irradiation step is performed while the light source irradiating the first active energy ray and the liquid composition move relative to each other, the irradiation intensity on the surface of the liquid composition continuously changes. The irradiation intensity in such a case represents the average value of the irradiation intensities measured at a plurality of locations uniformly selected from within the region where the first irradiation step is executed.

[0036] The time for irradiating the first active energy ray in the first irradiation step is preferably equal to or longer than the structure determination time at which the porous structure that forms the basis for forming the porous resin with a high porosity is determined. By having the time for irradiating the first active energy ray be equal to or longer than the structure determination time, it is possible to avoid the second irradiation step, which will be described later, from being executed in a state where the formation of the porous structure is insufficient. As a result, it is possible to manufacture a porous resin with a high porosity.

[0037] The structure determination time can be calculated by the following method using a liquid composition. First, resin fine particles are uniformly dispersed on a non-alkali glass substrate by spin coating to serve as a spacer. Subsequently, the substrate coated with the spacer is bonded to another non-alkali glass substrate that is not coated with the spacer so that the surfaces coated with the spacer are sandwiched together. Next, the liquid composition is filled between the bonded elements using capillary action, and finally, the periphery of the substrate is sealed with a sealant to produce an "element for measuring the structure determination time". The various conditions during production are shown below. · Non-alkali glass substrate: manufactured by Nippon Electric Glass, 40 mm, t = 0.7 mm, OA-10G · Spacer: manufactured by Sekisui Chemical, resin fine particle Micropearl GS-L100, average particle diameter 100 μm · Spin coating conditions: dispersion droplet drop volume 150 μL, rotation speed 1000 rpm, rotation time 30 s · Amount of liquid composition filled: 160 μL · Sealant: TB3035B (manufactured by Three Bond) Next, the first active energy ray is irradiated to the produced element for measuring the structure determination time under the same conditions as in the first irradiation step. Using the transmittance of the element before irradiation as a reference, the attenuation of the measured value (transmittance) of the element during irradiation is measured. The attenuation rate is calculated with the transmittance when the attenuation change disappears due to excessive irradiation of the first active energy ray being set to 100%. The attenuation rate increases as the porous structure is formed by polymerization. In the present disclosure, the time required for the attenuation rate of the transmittance to reach 50% from the start of irradiation is defined as the structure determination time. The apparatus used for the measurement is shown below. · Transmittance measurement device: LCD-5200, manufactured by Otsuka Electronics Co., Ltd.

[0038] <Second Irradiation Step> The second irradiation step is a step of irradiating a second active energy ray onto the liquid composition irradiated with the first active energy ray. The second irradiation step promotes the polymerization reaction of the polymerizable compound remaining as an unreacted component in the first irradiation step, thereby improving the polymerization rate of the porous resin, and thereby, for example, improving the strength of the porous resin. Specifically, the polymerization rate of the porous resin is preferably 90% or more. Further, when the porous resin is used as an insulating layer (separator) for an energy storage element, the remaining of the polymerizable compound as an unreacted component can be suppressed, and thereby, the deterioration of battery characteristics (for example, gas generation, etc.) caused by the remaining of the polymerizable compound can be suppressed. In the present disclosure, the "liquid composition irradiated with the first active energy ray" irradiated with the second active energy ray represents an irradiated object or the like generated by irradiating the liquid composition with the first active energy ray in the first irradiation step. Specifically, it is a composite of a porous precursor generated in the first irradiation step, a polymerizable compound as an unreacted component, and a solvent.

[0039] In addition, the second active energy ray is not particularly limited as long as it can impart the energy necessary for promoting the polymerization reaction of the polymerizable compound. For example, ultraviolet rays, electron beams, α-rays, β-rays, γ-rays, X-rays, etc. can be mentioned. Among these, ultraviolet rays are preferable. When a particularly high-energy light source is used, the polymerization reaction can proceed without using a polymerization initiator. Further, the types of the first active energy ray and the second active energy ray may be the same or different, but it is preferable that they are the same, and it is preferable that both are ultraviolet rays. When both the first active energy ray and the second active energy ray are ultraviolet rays, the peak wavelengths may be the same or different, but it is preferable that they are the same.

[0040] The reason for promoting the polymerization reaction of the polymerizable compound remaining as an unreacted component in the first irradiation step by the second irradiation step will be described. As described above, when forming a porous resin by polymerization-induced phase separation, the structure and properties of the porous resin change based on the polymerization conditions. Specifically, the above-described first irradiation step is set so that the irradiation intensity of the first active energy ray to be irradiated is not too high for the purpose of forming a porous precursor having a porous structure that is the basis for forming a porous resin with a high porosity. Therefore, when a polymerizable compound remains as an unreacted component in the first irradiation step, it tends to be difficult to produce a porous resin with a high polymerization rate. Therefore, in the second irradiation step aimed at forming a porous resin with a high polymerization rate, the irradiation intensity of the second active energy ray is set to be higher than the irradiation intensity of the first active energy ray. Specifically, the irradiation intensity of the second active energy ray is preferably 300 mW / cm 2 or more, more preferably 400 mW / cm 2 or more, and even more preferably 1 W / cm 2 or more. When the second irradiation step is performed while the light source irradiating the second active energy ray and the irradiated object (the liquid composition irradiated with the first active energy ray) move relative to each other, the irradiation intensity on the surface of the irradiated object continuously changes. The irradiation intensity in such a case represents the average value of the irradiation intensities measured at a plurality of locations uniformly selected from within the region where the second irradiation step is executed. Further, the irradiation intensity of the second active energy ray is preferably 5 times or more, and more preferably 10 times or more, that of the first active energy ray.

[0041] The method for measuring the polymerization rate in the porous resin is not particularly limited, and examples thereof include a method of measuring by infrared spectroscopy. Specifically, the peak value at 820 to 800 cm -1 corresponding to the out-of-plane bending vibration of =CH, and 1430 to 1400 cm -1The peak value, or the peak value at 1640 - 1620 cm corresponding to C=C -1 is read, and calculated by comparing with the value before irradiation.

[0042] <Removal step> The removal step is a step of removing the solvent from the porous resin after the second irradiation step. The method for removing the solvent is not particularly limited, and examples include a method of removing the solvent from the porous resin by heating. At this time, heating under reduced pressure promotes the removal of the solvent more, and can suppress the remaining of the solvent in the porous resin, so it is preferable.

[0043] <<Manufacturing apparatus for resin structure>> The manufacturing apparatus for the resin structure of the present embodiment includes an applying means for applying a liquid composition containing a polymerizable compound and a solvent, a first irradiation means for irradiating the applied liquid composition with a first active energy ray, and a second irradiation means for irradiating the liquid composition irradiated with the first active energy ray with a second active energy ray. Further, the manufacturing apparatus for the resin structure of the present embodiment may have a removing means for removing the solvent from the resin structure after irradiation by the second irradiation means, etc., if necessary.

[0044] The details of the manufacturing apparatus for the resin structure will be described with reference to FIG. 1. FIG. 1 is a schematic diagram showing an example of the manufacturing apparatus for the resin structure. A porous resin manufacturing apparatus 100, which is an example of the manufacturing apparatus for the resin structure, is an apparatus for manufacturing a porous resin using the above liquid composition. The porous resin manufacturing apparatus 100 includes a printing engineering department 10 that executes a step of applying the liquid composition onto a printing substrate 4, which is an example of a base material, to form a liquid composition layer, a polymerization engineering department 20 and a polymerization engineering department 21 that execute a step of activating the polymerization initiator of the liquid composition layer and obtaining a porous resin 6 by polymerization of the polymerizable compound, and a heating engineering department 30 that executes a step of heating the porous resin 6 to remove the solvent. The porous resin manufacturing apparatus 100 includes a transport section 5 for transporting the printing substrate 4, and the transport section 5 transports the printing substrate 4 at a preset speed in the order of the printing engineering department 10, the polymerization engineering department 20, the polymerization engineering department 21, and the heating engineering department 30.

[0045] <Printing Engineering Department> The printing engineering department 10 includes a printing apparatus 1a which is an example of an applying means for realizing an applying step of applying a liquid composition onto a printing substrate 4, a storage container 1b that stores the liquid composition, and a supply tube 1c that supplies the liquid composition stored in the storage container 1b to the printing apparatus 1a.

[0046] The storage container 1b stores the liquid composition 7. The printing engineering department 10 discharges the liquid composition 7 from the printing apparatus 1a and applies the liquid composition 7 onto the printing substrate 4 to form a liquid composition layer in a thin film shape. Note that the storage container 1b may be configured to be integrated with the porous resin manufacturing apparatus 100, or may be configured to be removable from the porous resin manufacturing apparatus 100. Further, it may be a container used for adding to a storage container integrated with the porous resin manufacturing apparatus 100 or a storage container removable from the porous resin manufacturing apparatus 100.

[0047] The printing apparatus 1a is not particularly limited as long as it can apply the liquid composition 7. For example, any printing apparatus corresponding to various printing methods such as the spin coating method, the casting method, the micro gravure coating method, the gravure coating method, the bar coating method, the roll coating method, the wire bar coating method, the dip coating method, the slit coating method, the capillary coating method, the spray coating method, the nozzle coating method, the gravure printing method, the screen printing method, the flexographic printing method, the offset printing method, the reverse printing method, and the inkjet printing method can be used.

[0048] The storage container 1b and the supply tube 1c can be arbitrarily selected as long as they can stably store and supply the liquid composition 7. The material constituting the storage container 1b and the supply tube 1c preferably has light-shielding properties in the relatively short wavelength region of ultraviolet light and visible light. Thereby, the liquid composition 7 is prevented from being polymerized by external light.

[0049] <Polymerization Engineering Department> As shown in FIG. 1, the polymerization engineering section 20 includes a light irradiation device 2a which is an example of a first irradiation means for polymerizing a polymerizable compound by irradiating a liquid composition with active energy rays such as heat and light, and a polymerization inert gas circulation device 2b for circulating a polymerization inert gas. The light irradiation device 2a irradiates the liquid composition formed by the printing engineering section 10 with light in the presence of a polymerization inert gas to form a porous precursor.

[0050] As shown in FIG. 1, the polymerization engineering section 21 includes a light irradiation device 2c which is an example of a second irradiation means for polymerizing a polymerizable compound by irradiating the liquid composition irradiated with the first active energy rays in the polymerization engineering section 20 with active energy rays such as heat and light, and a polymerization inert gas circulation device 2d for circulating a polymerization inert gas. The light irradiation device 2c irradiates the liquid composition irradiated with the first active energy rays in the polymerization engineering section 20 with light in the presence of a polymerization inert gas to form a porous resin 6.

[0051] The light irradiation devices 2a and 2c are not particularly limited as long as they are appropriately selected according to the absorption wavelength of the photoinitiator contained in the liquid composition layer and can initiate and proceed the polymerization of the compounds in the liquid composition layer. Examples thereof include ultraviolet light sources such as high-pressure mercury lamps, metal halide lamps, hot cathode tubes, cold cathode tubes, and LEDs. However, since light with a shorter wavelength generally has a tendency to reach deeper more easily, it is preferable to select a light source according to the thickness of the porous film to be formed.

[0052] Next, the polymerization inert gas circulation devices 2b and 2d serve to reduce the concentration of polymerization-active oxygen contained in the atmosphere and allow the polymerization reaction of the polymerizable compound near the surface of the liquid composition layer to proceed without being inhibited. Therefore, the polymerization inert gas used is not particularly limited as long as it satisfies the above functions, and examples thereof include nitrogen, carbon dioxide, and argon.

[0053] In addition, considering that an inhibition reduction effect can be effectively obtained as the flow rate of the polymerization inert gas, it is preferable that the O2 concentration is less than 20% (an environment with an oxygen concentration lower than that of the atmosphere), more preferably 0% or more and 15% or less, and even more preferably 0% or more and 5% or less. Further, in order to realize stable polymerization progress conditions, the polymerization inert gas circulation devices 2b and 2d preferably are provided with temperature control means capable of adjusting the temperature.

[0054] <Heating Engineering Department> As shown in FIG. 1, the heating engineering department 30 has a heating device 3a which is an example of a removing means, and heats and dries and removes the solvent remaining in the porous resin 6 formed by the polymerization engineering department 20 and the polymerization engineering department 21 by the heating device 3a. The heating engineering department 30 may carry out the solvent removing step under reduced pressure. In addition, the heating engineering department 30 may heat and dry and remove the photopolymerization initiator remaining in the porous resin 6 by the heating device 3a.

[0055] The heating device 3a is not particularly limited as long as it satisfies the above functions, and examples thereof include an IR heater and a hot air heater. Regarding the heating temperature and the heating time, they can be appropriately selected according to the boiling point of the solvent contained in the porous resin 6 and the formed film thickness.

[0056] <Printing Substrate> As the material of the printing substrate 4, any material can be used regardless of being transparent or opaque. That is, as the transparent substrate, a glass substrate, a resin film substrate such as various plastic films, or a composite substrate thereof, etc., and as the opaque substrate, a silicon substrate, a metal substrate such as stainless steel, or a laminate thereof, etc., various substrates can be used. Note that the printing substrate 4 may be a recording medium such as plain paper, glossy paper, special paper, cloth, etc. Further, as the recording medium, a low-permeability substrate (low-absorbency substrate) may be used. The low-permeability substrate means a substrate having a surface with low water permeability, absorbency, or adsorptivity, and includes materials having a large number of cavities inside but not open to the outside. Examples of the low-permeability substrate include coated paper used for commercial printing and recording media such as cardboard with waste paper pulp blended in the middle and back layers and coated on the surface. Note that the printing substrate 4 may be a porous resin sheet used as an insulating layer for a power storage element or a power generation element.

[0057] Regarding the shape, whether it is a curved surface or has an uneven shape, it can be used as long as it is a substrate applicable to the printing process section 10, the polymerization process section 20, and the polymerization process section 21.

[0058] <<Resin structure>> The film thickness of the resin structure (porous resin) having a porous structure with a resin formed by the liquid composition as the skeleton is not particularly limited, but considering the curing uniformity during polymerization, it is preferably 0.01 μm or more and 500 μm or less, more preferably 0.01 μm or more and 100 μm or less, still more preferably 1 μm or more and 50 μm or less, and particularly preferably 10 μm or more and 20 μm or less. When the film thickness is 0.01 μm or more, the surface area of the obtained porous resin becomes large, and the functions of the porous resin can be sufficiently obtained. Also, when the film thickness is 500 μm or less, unevenness of light or heat used during polymerization in the film thickness direction is suppressed, and a uniform porous resin in the film thickness direction can be obtained. By producing a uniform porous resin in the film thickness direction, structural unevenness of the porous resin can be suppressed, and a decrease in the permeability of liquids or gases can be suppressed. Note that the film thickness of the porous resin is appropriately adjusted according to the application in which the porous resin is used. For example, when the porous resin is used as an insulating layer for a power storage element, it is preferably 10 μm or more and 20 μm or less. The porous resin to be formed is not particularly limited. From the viewpoint of ensuring good permeability to liquids and gases, it preferably has a three-dimensional branched network structure of a cured resin as a skeleton and has a co-continuous structure (also referred to as a monolith structure) in which a plurality of pores in the porous resin are continuously connected. That is, the porous resin preferably has a large number of pores, and it is preferable that one pore has connectivity with other pores around it and spreads three-dimensionally. When the pores communicate with each other, the infiltration of liquids and gases can occur sufficiently, and functions such as substance separation and reaction fields can be efficiently expressed. Note that air permeability is one of the physical properties obtained by having a co-continuous structure. The air permeability of the porous resin is preferably measured in accordance with JIS P8117 and is preferably 500 seconds / 100 mL or less, more preferably 300 seconds / 100 mL or less. At this time, the air permeability is measured using, for example, a Gurley densometer (manufactured by Toyo Seiki Seisakusho). The cross-sectional shape of the pores of the porous resin to be formed may be various shapes and various sizes such as a substantially circular shape, a substantially elliptical shape, and a substantially polygonal shape. Here, the size of the pore refers to the length of the longest part in the cross-sectional shape. The size of the pore can be determined from a cross-sectional photograph taken with a scanning electron microscope (SEM). Regarding the size of the pores of the porous resin, although not particularly limited, it is preferably 0.01 μm or more and 10 μm or less from the viewpoint of the permeability of liquids and gases. Also, the porosity of the porous resin is preferably 30% or more, more preferably 50% or more. The method for setting the size and porosity of the pores of the porous resin within these ranges is not particularly limited, and examples include a method of adjusting the content of the polymerizable compound in the liquid composition to the above range, a method of adjusting the content of the porogen in the liquid composition to the above range, and a method of adjusting the irradiation conditions of active energy rays.

[0059] <<Uses of the resin structure>> <For use in energy storage elements or power generation elements> A resin structure (porous resin) having a porous structure with a resin formed using the above liquid composition as a skeleton can be used, for example, as an insulating layer for a power storage element or a power generation element. When used for these applications, for example, it is preferable to form an insulating layer (separator) by applying the liquid composition onto an active material layer previously formed on an electrode substrate. As the insulating layer for a power storage element or a power generation element, for example, it is known to use a film-like porous insulating layer having pores or a porosity of a predetermined size. On the other hand, when the above liquid composition is used, the pores and porosity can be appropriately changed by appropriately adjusting the content of the polymerizable compound, the content of the porogen, the irradiation conditions of the active energy ray, etc., and the design freedom in terms of the performance of the power storage element and the power generation element can be improved. In addition, since the above liquid composition can be applied by various application methods, for example, it can be applied by an inkjet method, and the design freedom in terms of the shape of the power storage element and the power generation element can be improved. Note that the insulating layer is a member that separates the positive electrode and the negative electrode and ensures ionic conductivity between the positive electrode and the negative electrode. Also, in the present disclosure, when referring to the insulating layer, it is not limited to a layered shape. Note that the above liquid composition can be applied onto an insulating layer (first insulating layer) for a power storage element or a power generation element to additionally form an insulating layer (second insulating layer) composed of a porous resin layer. By forming the second insulating layer on the first insulating layer, various functions such as heat resistance, impact resistance, and high-temperature shrinkage resistance of the entire insulating layer can be added or improved.

[0060] The electrode substrate is not particularly limited as long as it is a conductive substrate, and it can generally be suitably used for secondary batteries, capacitors, especially lithium-ion secondary batteries, which are energy storage devices, such as aluminum foil, copper foil, stainless steel foil, titanium foil, and etched foils obtained by etching them to form fine holes, and perforated electrode substrates used for lithium-ion capacitors. In addition, carbon paper fibrous electrodes used in power generation devices such as fuel cells, which are made into a non-woven or woven flat shape, or those having fine holes among the above-mentioned perforated electrode substrates can also be used. Furthermore, in the case of a solar device, in addition to the above electrodes, those in which a transparent semiconductor thin film such as indium-titanium-based oxide or zinc oxide is formed on a flat substrate such as glass or plastics, or those in which a conductive electrode film is thinly vapor-deposited can be used.

[0061] The active material layer is formed by dispersing a powdery active material or catalyst composition in a liquid, applying, fixing, and drying such a liquid on the electrode substrate. Usually, printing using spraying, dispenser, die coater, or dip coating is used, and it is formed by drying after application.

[0062] The positive electrode active material is not particularly limited as long as it is a material capable of reversibly occluding and releasing alkali metal ions. Typically, an alkali metal-containing transition metal compound can be used as the positive electrode active material. For example, as the lithium-containing transition metal compound, composite oxides containing at least one element selected from the group consisting of cobalt, manganese, nickel, chromium, iron, and vanadium and lithium can be mentioned. For example, lithium-containing transition metal oxides such as lithium cobalt oxide, lithium nickel oxide, and lithium manganese oxide, olivine-type lithium salts such as LiFePO4, chalcogen compounds such as titanium disulfide and molybdenum disulfide, and manganese dioxide can be mentioned. The lithium-containing transition metal oxide is a metal oxide containing lithium and a transition metal or a metal oxide in which a part of the transition metal in the metal oxide is substituted by a different element. Examples of the different element include Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, B, etc., and among them, Mn, Al, Co, Ni, and Mg are preferable. The different element may be one kind or two or more kinds. These positive electrode active materials can be used alone or in combination of two or more kinds. Examples of the above active material in a nickel-hydrogen battery include nickel hydroxide.

[0063] The negative electrode active material is not particularly limited as long as it is a material capable of reversibly occluding and releasing alkali metal ions. Typically, a carbon material containing graphite having a graphite-type crystal structure can be used as the negative electrode active material. Examples of such carbon materials include natural graphite, spherical or fibrous artificial graphite, non-graphitizable carbon (hard carbon), graphitizable carbon (soft carbon), etc. Examples of materials other than carbon materials include lithium titanate. Also, from the viewpoint of increasing the energy density of a lithium-ion battery, high-capacity materials such as silicon, tin, silicon alloys, tin alloys, silicon oxide, silicon nitride, and tin oxide can also be suitably used as the negative electrode active material.

[0064] Examples of the above active material in a nickel-hydrogen battery as the hydrogen storage alloy include AB2-type or A2B-type hydrogen storage alloys.

[0065] Examples of binders for the positive electrode or negative electrode include PVDF, PTFE, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, methyl polyacrylate, ethyl polyacrylate, hexyl polyacrylate, polymethacrylic acid, methyl polymethacrylate, ethyl polymethacrylate, hexyl polymethacrylate, polyvinyl acetate, polyvinyl pyrrolidone, polyether, polyethersulfone, hexafluoropolypropylene, styrene butadiene rubber, carboxymethyl cellulose, etc. In addition, copolymers of two or more materials selected from tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and hexadiene may be used. Also, two or more selected from these may be mixed and used. Examples of conductive agents included in the electrode include carbon blacks such as natural graphite and artificial graphite, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black, conductive fibers such as carbon fibers and metal fibers, metal powders such as carbon fluoride and aluminum, conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, and organic conductive materials such as phenylene derivatives and graphene derivatives.

[0066] In a fuel cell, the active material generally used is a catalyst for the cathode electrode and the anode electrode, which is obtained by supporting metal fine particles such as platinum, ruthenium, or a platinum alloy on a catalyst carrier such as carbon. To support the catalyst particles on the surface of the catalyst carrier, for example, the catalyst carrier is suspended in water, and a precursor of the catalyst particles (chloroplatinic acid, dinitrodiaminoplatinum, platinic chloride, platinum chloride, platinum bis(acetylacetonate), dichlorodiammineplatinum, dichlorotetraammineplatinum, ruthenium chloroplatinate, iridium chloride, rhodium chloride, ferric chloride, cobalt chloride, chromium chloride, gold chloride, silver nitrate, rhodium nitrate, palladium chloride, nickel nitrate, iron sulfate, copper chloride, etc., containing alloy components) is added and dissolved in the suspension. An alkali is added to form a metal hydroxide, and a catalyst carrier supported on the surface of the catalyst carrier is obtained. By applying such a catalyst carrier onto an electrode and reducing it in a hydrogen atmosphere or the like, an electrode with catalyst particles (active material) coated on the surface is obtained.

[0067] In the case of a solar cell or the like, the active material includes oxide semiconductor layers such as tungsten oxide powder, titanium oxide powder, SnO2, ZnO, ZrO2, Nb2O5, CeO2, SiO2, and Al2O3. The semiconductor layer has a dye supported thereon, and examples of the dye include ruthenium tris-type transition metal complexes, ruthenium bis-type transition metal complexes, osmium tris-type transition metal complexes, osmium bis-type transition metal complexes, ruthenium cis-diaqua-bipyridyl complexes, phthalocyanine, porphyrin, and organic-inorganic perovskite crystals.

[0068] <White ink application> The above liquid composition is whitened by forming a porous resin and then removing the porogen. Therefore, it is preferably used, for example, as a white ink to be applied on a recording medium. In the present disclosure, the white ink is not particularly limited as long as it can form a white image, and it includes those that are transparent or of a color other than white at the time of ink application.

[0069] As white ink, those that exhibit white by containing an inorganic pigment such as titanium oxide as a coloring material are generally known. However, such white ink has problems of being prone to sedimentation due to the large specific gravity of the coloring material and being inferior in storage stability and ejection stability. In that regard, the white ink composed of the above liquid composition can exhibit white without containing a white coloring material such as a pigment or a dye as a component other than the liquid composition, so that the storage stability and the ejection stability can be improved. Note that the white ink of the present embodiment may contain a white coloring material, but preferably does not substantially contain a white coloring material. When not substantially containing a white coloring material, the content of the white coloring material is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, still more preferably 0.01% by mass or less, even more preferably below the detection limit, and particularly preferably not contained, based on the mass of the white ink. Thus, since the white ink does not substantially contain a white coloring material, the weight of the white image formed by the white ink can be reduced, and it can be suitably used, for example, as white ink for aircraft painting, white ink for automobile painting, etc.

[0070] In addition, as white ink, those containing a plurality of types of polymerizable compounds and becoming cloudy by phase separation of these polymers during curing are also known. However, such white ink exhibits white by phase separation of the polymers and does not exhibit white by an air layer, so there is a problem of inferior whiteness. In this regard, when the liquid composition of the present embodiment is used as white ink, since white is exhibited by a porous resin having pores as an air layer, high whiteness can be exhibited. Note that white is a color called "white" in common social perception, and the whiteness can be evaluated by measuring, for example, the lightness (L * ) with a spectrophotometric densitometer such as X-Rite939. For example, when it is applied at 100% duty or more or in an amount sufficient to sufficiently cover the surface of the recording medium, the lightness (L * ) and chromaticity (a * , b * ) are such that 70 ≦ L * ≦ 100, -4.5 ≦ a *≤2, -6≤b * Preferably, it shows a range of ≤2.5.

[0071] In addition, since the white ink of the present embodiment forms a layer composed of a porous resin when applied onto a recording medium, it may be used as a primer ink for producing an underlayer (primer layer) that improves the fixability of another ink (such as an ink containing a coloring material) applied later. Generally, when using a low-permeability substrate or non-permeability substrate such as coated paper, glass substrate, resin film substrate, or metal substrate as the recording medium, there is a problem that the fixability of the ink to the substrate decreases. In this regard, when using the white ink (primer ink) of the present embodiment, since the fixability of the white ink (primer ink) to the low-permeability substrate or non-permeability substrate is high, the fixability of another ink applied later onto the underlayer can be improved. Also, even if another ink applied later (such as an ink containing a coloring material) is a permeable ink (such as an aqueous ink) that is difficult to use on a low-permeability substrate or non-permeability substrate, the coloring material can be fixed on the surface of the porous resin while the ink components penetrate and diffuse into the porous resin. In addition, since the white ink (primer ink) forms a white receiving layer, it can conceal the color and transparency of the recording medium and also improve the image density of another ink (such as an ink containing a coloring material) applied later.

[0072] <Stereolithography application> Since the above liquid composition can form a porous resin layer having a layer thickness in the height direction, a three-dimensional object can be fabricated by laminating a plurality of such porous resin layers. Generally, in stereolithography, distortion of the three-dimensional object due to curing shrinkage is an issue. In this regard, the stereolithography composition containing the liquid composition of the present embodiment forms a porous body having a network structure with polymerization-induced phase separation, so that the internal stress during polymerization is relaxed by the network structure, and distortion of the fabricated object due to curing shrinkage is suppressed.

[0073] Next, a shaping apparatus and a shaping method for shaping a three-dimensional object will be described with reference to FIG. 2. FIG. 2 is a schematic diagram showing an example of a shaping apparatus using the material jetting method. The shaping apparatus shown in FIG. 2 includes a discharging means (an example of an applying means) for discharging a liquid composition by an inkjet method or the like, and a curing means (an example of a first irradiating means and a second irradiating means) for irradiating the discharged liquid composition with active energy rays to cure it. The apparatus shapes a three-dimensional object by sequentially repeating the discharging by the discharging means and the curing by the curing means. Further, the shaping method realized by the shaping apparatus shown in FIG. 2 includes a discharging step (an example of a discharging step) of discharging a liquid composition by an inkjet method, and a curing step (an example of a first irradiating step and a second irradiating step) of irradiating the discharged liquid composition with active energy rays to cure it. The method shapes a three-dimensional object by sequentially repeating the discharging step and the curing step. This shaping apparatus and shaping method will be specifically described. The shaping apparatus 39 shown in FIG. 2 uses a head unit (movable in the AB direction) in which inkjet heads are arranged to discharge a first three-dimensional shaping composition from the shaping object discharge head unit 30 and a second three-dimensional shaping composition having a composition different from that of the first three-dimensional shaping composition from the support discharge head units 31 and 32, and laminates them while curing these three-dimensional shaping compositions with the adjacent ultraviolet irradiation means 33 and 34. More specifically, for example, after discharging the second three-dimensional shaping composition from the support discharge head units 31 and 32 onto the shaping object support substrate 37, irradiating it with active energy rays to solidify it to form a first support layer having a reservoir portion, discharging the first three-dimensional shaping composition from the shaping object discharge head unit 30 into the reservoir portion, and irradiating it with active energy rays to solidify it to form a first shaping object layer. This process is repeated a plurality of times while lowering the stage 38 movable in the vertical direction according to the number of laminations, thereby laminating the support layer and the shaping object layer to manufacture the three-dimensional object 35. Thereafter, the support laminate portion 36 is removed as necessary. In FIG. 2, only one shaping object discharge head unit 30 is provided, but two or more can also be provided.

[0074] <Carrier application> When the above liquid composition is mixed with a functional substance to form a porous resin, a carrier having the functional substance supported on the surface of the porous resin can be produced. Here, the surface of the porous resin means not only the outer surface of the porous resin but also the inner surface communicating with the outside. Thus, since the functional substance can be supported in the voids communicating with the outside, the surface area capable of supporting the functional substance increases.

[0075] When the composition for forming a carrier of the present embodiment is used, the pores and porosity can be changed by appropriately adjusting the content of the polymerizable compound, the content of the porogen, the irradiation conditions of the active energy ray, etc., and the degree of freedom in designing the performance of the carrier can be improved. Further, since the composition for forming a carrier of the present embodiment can be applied by various application methods, for example, it can be applied by an inkjet method, and the degree of freedom in designing the shape of the carrier can be improved. Specifically, the carrier can be uniformly formed not only on a flat surface but also on a curved surface, and the labor of adjusting the shape by cutting the carrier according to the shape of the object can be omitted. Further, by ejecting by an inkjet method to form droplets, and irradiating the active energy ray to the droplets in flight or the independent droplets attached to the substrate, a carrier having a particle shape can also be formed.

[0076] The functional substance is a substance that directly or indirectly exhibits a predetermined function, and preferably a substance whose function increases or improves as the area supported on the porous resin increases, and the function is exhibited when the supported functional substance is located on the outer surface and / or the inner surface communicating with the outside (in other words, a substance whose function is suppressed when located on the inner surface not communicating with the outside) is more preferable. Further, the functional substance may be a substance dissolved or dispersed in the liquid composition, but is preferably a dispersed substance. Examples of the functional substance include, but are not particularly limited to, photocatalysts, physiologically active substances, and the like.

[0077] A photocatalyst is a substance that exhibits photocatalytic activity when irradiated with light in a specific wavelength range (excitation light having energy equal to or greater than the band gap between the valence band and the conduction band of the photocatalyst). By exhibiting the photocatalytic activity, the photocatalyst can exert various effects such as antibacterial action, deodorizing and odor-removing action, and decomposition action of harmful substances such as volatile organic compounds (VOCs).

[0078] Examples of photocatalysts include metal oxides such as anatase-type or rutile-type titanium(IV) oxide (TiO2), tungsten(III) oxide (W2O3), tungsten(IV) oxide (WO2), tungsten(VI) oxide (WO3), zinc oxide (ZnO), iron(III) oxide (Fe2O3), strontium titanate (SrTiO3), bismuth(III) oxide (Bi2O3), bismuth vanadate (BiVO4), tin(II) oxide (SnO), tin(IV) oxide (SnO2), tin(VI) oxide (SnO3), zirconium oxide (ZrO2), cerium(II) oxide (CeO), cerium(IV) oxide (CeO2), barium titanate (BaTiO3), indium(III) oxide (In2O3), copper(I) oxide (Cu2O), copper(II) oxide (CuO), potassium tantalate (KTaO3), potassium niobate (KNbO3); metal sulfides such as cadmium sulfide (CdS), zinc sulfide (ZnS), indium sulfide (InS); metal selenides such as cadmium selenate (CdSeO4), zinc selenide (ZnSe); metal nitrides such as gallium nitride (GaN), etc. Among them, it is preferably contains at least one selected from titanium(IV) oxide (TiO2), tin(IV) oxide (SnO2), tungsten(III) oxide (W2O3), tungsten(IV) oxide (WO2), and tungsten(VI) oxide (WO3), and more preferably contains anatase-type titanium(IV) oxide (TiO2).

[0079] A physiologically active substance is an active ingredient used to exert a physiological effect on a living body. Examples include low-molecular compounds such as pharmaceutical compounds, food compounds, and cosmetic compounds, as well as high-molecular compounds including biological macromolecules such as proteins like antibodies and enzymes, and nucleic acids such as DNA and RNA. Further, the "physiological effect" is an effect resulting from the physiological activity of a physiologically active substance at a target site. For example, it is to bring about quantitative and / or qualitative changes or effects on a living body, tissue, cell, protein, DNA, RNA, etc. Also, "physiological activity" means that a physiologically active substance acts on a target site (e.g., a target tissue, etc.) to cause changes or effects. As the target site, for example, it is preferably a receptor present on the cell surface or inside the cell. In this case, a signal is transmitted to the cell by the physiological activity of the physiologically active substance binding to a specific receptor, and as a result, a physiological effect is exerted. The physiologically active substance may be a substance that is converted into a mature form by an enzyme in the living body and then binds to a specific receptor to exert a physiological effect. In this case, in the present application, the substance before being converted into the mature form is also included in the physiologically active substances. Note that the physiologically active substance may be a substance produced by a living organism (human or non-human organism) or an artificially synthesized substance. When a particulate carrier is formed using a liquid composition containing such a physiologically active substance, in order to exert a desired physiological effect, it can be used as a particle for delivering the physiologically active substance to a target site, that is, a particle used in a drug delivery system (DDS), or as a sustained-release particle that continuously releases the drug over a long period. Also, when a sheet-like carrier is formed using a liquid composition containing a physiologically active substance, it can be used as a sustained-release sheet that continuously releases the drug over a long period.

[0080] <Surface modification use> The outer surface of the porous resin formed by the above liquid composition has fine irregularities derived from the porosity, and thus the wettability can be controlled. Specifically, when the resin constituting the porous resin is hydrophilic, it is possible to impart a higher hydrophilicity than the hydrophilicity on the planar surface formed by the resin to the outer surface of the porous resin. Further, when the resin constituting the porous resin is water-repellent, it is possible to impart a higher water-repellency than the water-repellency on the planar surface formed by the resin to the outer surface of the porous resin. Therefore, by applying a surface-modifying liquid containing the liquid composition of the present embodiment to the surface of an object, a surface-modifying layer can be formed, and the wettability of the surface of the object can be easily modified.

[0081] Further, when the liquid composition of the present embodiment is used, by appropriately adjusting the content of the polymerizable compound, the content of the porogen, the irradiation conditions of the active energy ray, etc., the irregularities (irregularities derived from pores and porosity) on the outer surface of the porous material can be changed, and the degree of freedom in design in terms of the performance of the surface-modifying layer can be improved. Further, since the liquid composition of the present embodiment can be applied by various application methods, for example, it can be applied by an inkjet method, and the degree of freedom in design in terms of the shape of the surface-modifying layer can be improved. Specifically, the surface-modifying layer can be uniformly formed not only on a flat surface but also on a curved surface.

[0082] <Separation layer use or reaction layer use> When the porous resin formed from the above liquid composition is permeable to fluids such as liquids and gases, the porous resin can be used as a fluid flow path. When the porous resin can be used as a fluid flow path, the porous resin can be used for applications such as a separation layer for separating a predetermined substance from a fluid and a reaction layer (microreactor) for providing a minute reaction field to a fluid. In other words, the liquid composition of the present embodiment is preferably included in a composition for forming a separation layer or a composition for forming a reaction layer. The porous resin used for these applications preferably allows a fluid to permeate uniformly and efficiently inside the porous resin. In this regard, since the porous resin formed from the liquid composition of the present embodiment has pores formed by phase separation, the voids are continuously connected to each other and have a structure that allows a fluid to permeate uniformly and efficiently. Note that the case where the porous resin is permeable to fluids such as liquids and gases is not particularly limited. For example, the air permeability measured in accordance with JIS P8117 is preferably 500 seconds / 100 mL or less, and more preferably 300 seconds / 100 mL or less. At this time, the air permeability is measured using, for example, a Gurley densometer (manufactured by Toyo Seiki Seisakusho). Note that separation means being able to remove or concentrate a predetermined substance contained in a fluid mixture. Further, the removal is not limited to the case where a predetermined substance is completely removed from the fluid mixture, and may be the case where a partial amount is removed. Note that a reaction field means a place where a predetermined chemical reaction proceeds when a predetermined substance contained in a fluid passes through.

[0083] When used for a separation layer, the above liquid composition preferably contains a polymerizable compound having a functional group capable of interacting with a predetermined substance contained in a fluid. When a porous resin is formed using the liquid composition, functional groups capable of interacting with a predetermined substance are arranged on the surface (inner surface and outer surface) of the porous resin, and the separation of the predetermined substance can be effectively performed. The polymerizable compound having a functional group capable of interacting with a predetermined substance contained in the fluid may be part or all of the polymerizable compounds contained in the liquid composition. In the present application, the functional group capable of interacting with a predetermined substance includes not only the case where the functional group itself can interact with the predetermined substance, but also the case where it can interact with the predetermined substance by additionally performing graft polymerization.

[0084] When used for a reaction layer, the above liquid composition preferably contains a polymerizable compound having a functional group that provides a reaction field for a fluid. When a porous resin is formed using the liquid composition, functional groups that provide a reaction field for a fluid are arranged on the surface (inner surface and outer surface) of the porous resin, and a reaction field can be effectively provided. The polymerizable compound having a functional group that provides a reaction field for a fluid may be part or all of the polymerizable compounds contained in the liquid composition. In the present application, the functional group that provides a reaction field for a fluid includes not only the case where the functional group itself can provide a reaction field, but also the case where it can provide a reaction field by additionally performing graft polymerization.

[0085] The above separation layer and reaction layer are formed, for example, by filling a container capable of forming a fluid inlet and a fluid outlet such as a glass tube with the liquid composition and curing it. Further, by printing the liquid composition on a substrate by an inkjet method or the like, a separation layer and a reaction layer having a flow path of a desired shape formed of a porous resin can be produced (drawn). Since the flow paths of the separation layer and the reaction layer can be printed, separation layers and reaction layers with flow paths that can be appropriately changed according to the purpose can be provided.

[0086] In addition, when the composition for forming a separation layer and the composition for forming a reaction layer of the present embodiment are used, the pores and porosity of the porous resin can be changed by appropriately adjusting the content of the polymerizable compound, the content of the porogen, the irradiation conditions of active energy rays, etc., and the degree of freedom in designing the performance of the separation layer and the reaction layer can be improved.

Examples

[0087] Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples at all.

[0088] <Adjustment of liquid composition> The materials were mixed at the ratios shown below to prepare a liquid composition. · Tricyclodecane dimethanol diacrylate (Daicel Ornex Co., Ltd.): 29.0% by mass · Tetradecane (manufactured by Kanto Chemical Co., Inc.): 70.0% by mass · Irgacure184 (manufactured by BASF): 1.0% by mass

[0089] In the adjusted liquid composition, when the light transmittance at a wavelength of 550 nm was measured by the above method while stirring, it was 30% or more. Also, when the haze value increase rate in the haze measurement element produced using the adjusted liquid composition was measured by the above method, it was 1.0% or more. In addition, when the viscosity of the adjusted liquid composition at 25°C was measured by the above method, it was 1.0 mPa·s or more and 30.0 mPa·s or less.

[0090] <Manufacture of resin structure> (Example 1) - Application step - First, the adjusted liquid composition was filled into the resin structure manufacturing apparatus shown in FIG. 1. In the printing engineering section 10, the liquid composition was applied from the printing apparatus 1a onto the conveyed printing substrate 4 to form a continuous film of the liquid composition such that the thickness of the porous resin formed after the removal process described later would be 20 μm. As the printing apparatus 1a, an inkjet head (GEN5 head, manufactured by Ricoh Printing Systems Co., Ltd.) was used. As the printing substrate 4, a glass substrate sputtered with 8-μm-thick ITO and an electrode substrate laminated with an active material layer manufactured by the following method were used. Note that the ejection of the liquid composition from the inkjet head was stable, and no non-ejecting nozzles or ejected curves were observed.

[0091] --Manufacture of the electrode substrate laminated with the active material layer-- 97.0 parts by mass of graphite particles (average particle size 10 μm) as the active material, 1.0 part by mass of cellulose as the thickener, and 2.0 parts by mass of an acrylic resin as the binder were uniformly dispersed in water to obtain an active material dispersion. This dispersion was applied to a 8-μm-thick copper foil serving as the electrode substrate, and the obtained coating film was dried at 120°C for 10 minutes and then pressed to obtain an electrode substrate laminated with a 60-μm-thick active material layer.

[0092] -First irradiation process- Next, the printed substrate 4 after the application process was conveyed into the polymerization engineering section 20 in which nitrogen was filled by the polymerization inert gas circulation device 2b so that the oxygen concentration was 0%, and UV irradiation was performed for 3 seconds from the light irradiation device 2a at an irradiation intensity of 30 mW / cm 2 . The light irradiation device 2a was a UV-LED, and the peak wavelength was 365 nm. Note that when the structure determination time was calculated by the above method using the adjusted liquid composition, it was 1.2 seconds. In Example 1, the time (3 seconds) for irradiating the first active energy ray was equal to or longer than the structure determination time (1.2 seconds).

[0093] -Second irradiation process- Next, the printed substrate 4 after the first irradiation step is conveyed into the polymerization step 21 filled with nitrogen by the polymerization inert gas circulation device 2d so that the oxygen concentration becomes 0%, and 400 mW / cm 2 UV irradiation was performed for 3 seconds at the irradiation intensity of. The light irradiation device 2c was a UV-LED, and the peak wavelength was 365 nm.

[0094] -Removal Step- Furthermore, the printed substrate 4 after the second irradiation step was conveyed into the heating step 30 heated to 120°C by the heating device 3a, and the remaining solvent etc. was removed in the atmosphere to produce a white porous resin having a co-continuous structure.

[0095] (Example 2) In Example 1, a porous resin was produced in the same manner as in Example 1 except that the UV irradiation time in the first irradiation step was changed to 5 seconds and the UV irradiation time in the second irradiation step was changed to 1 second.

[0096] (Example 3) In Example 1, a porous resin was produced in the same manner as in Example 1 except that the UV irradiation time in the first irradiation step was changed to 1 second and the UV irradiation time in the second irradiation step was changed to 5 seconds.

[0097] (Comparative Example 1) In Example 1, a porous resin was produced in the same manner as in Example 1 except that the UV irradiation time in the first irradiation step was changed to 6 seconds and the second irradiation step was not performed.

[0098] (Comparative Example 2) In Example 1, a porous resin was produced in the same manner as in Example 1 except that the first irradiation step was not performed and the UV irradiation time in the second irradiation step was changed to 6 seconds.

[0099] Next, the porosity and polymerization rate of the produced porous resin were evaluated by the following methods. The evaluation results are shown in Table 1.

[0100] [Porosity] An unsaturated fatty acid (commercial butter) was filled into a porous resin formed on an electrode substrate on which a living material layer was laminated. After osmium staining, the internal cross-sectional structure was cut out with a FIB, and the porosity in the porous resin was measured using SEM. The measurement results of the porosity of the porous resin were evaluated based on the following evaluation criteria. (Evaluation Criteria) a+: The porosity is 50% or more. a: The porosity is 30% or more and less than 50%. b: The porosity is less than 30%.

[0101] [Degree of Polymerization] The degree of polymerization in the porous resin formed on the glass substrate sputtered with ITO was measured by infrared spectroscopy. The polymerization rate was calculated by reading the peak value at 820 - 800 cm corresponding to the out-of-plane bending vibration of =CH and comparing it with the value before irradiation. The measurement results of the polymerization rate of the porous resin were evaluated based on the following evaluation criteria. -1 (Evaluation Criteria) (Evaluation Criteria) a: The polymerization rate is 90% or more. b: The polymerization rate is less than 90%.

[0102] [Table 1]

[0103] From the results of Comparative Example 1, it can be seen that it is difficult to produce a porous resin with a high polymerization rate when the second irradiation step is not performed. From the results of Comparative Example 2, it can be seen that it is difficult to produce a porous resin with a high porosity when the first irradiation step is not performed. [Explanation of Reference Signs]

[0104] 1a: Printing device 1b: Storage container 1c: Supply tube 2a: Light irradiation device 2b: Polymerization inert gas circulation device 2c: Light irradiation device 2d: Polymerization inert gas circulation device 3a: Heating device 4: Printing substrate 5: Conveying unit 6: Porous resin 7: Liquid composition 10: Printing engineering department 20: Polymerization engineering department 21: Polymerization engineering department 30: Heating engineering department

Prior art documents

Patent documents

[0105]

Patent Document 1

Claims

1. An application step of applying a liquid composition containing a polymerizable compound and a solvent; A first irradiation step of irradiating the applied liquid composition with a first active energy ray; A second irradiation step of irradiating the liquid composition irradiated with the first active energy ray with a second active energy ray, which is a method for manufacturing a resin structure, The resin structure has a porous structure with a resin as a skeleton, The porous structure is formed by irradiating the polymerizable compound in the liquid composition with the first active energy ray and the second active energy ray, The irradiation intensity of the second active energy ray is higher than the irradiation intensity of the first active energy ray, The polymerizable compound and the solvent are compatible, The porous structure is formed by the polymer and the solvent in the liquid composition becoming incompatible during the polymerization process of the polymerizable compound, The application step is a step of applying the liquid composition to an active material layer formed on an electrode substrate, and a method for manufacturing a resin structure characterized by this.

2. The method for manufacturing a resin structure according to claim 1, wherein the time for irradiating the first active energy ray in the first irradiation step is equal to or longer than the structure determination time calculated using the liquid composition.

3. The irradiation intensity of the first active energy ray is 1 W / cm ２ The method for producing a resin structure according to any one of claims 1 to 2, wherein the irradiation intensity is 1 W / cm or less.

4. The irradiation intensity of the first active energy ray is 10 mW / cm2 or more, and the method for manufacturing a resin structure according to any one of claims 1 to 3.

5. The irradiation intensity of the second active energy ray is 300 mW / cm ２ The method for producing a resin structure according to any one of claims 1 to 4, wherein the above conditions are satisfied.

6. The first active energy ray and the second active energy ray are irradiated by an LED, and the method for manufacturing a resin structure according to any one of claims 1 to 5.

7. The peak wavelengths of the first active energy ray and the second active energy ray are the same, and the method for manufacturing a resin structure according to any one of claims 1 to 6.

8. The irradiation intensity of the second active energy ray is 5 times or more that of the irradiation intensity of the first active energy ray, and the method for manufacturing a resin structure according to any one of claims 1 to 7.

9. The method for manufacturing a resin structure according to any one of claims 1 to 8, including a removal step of removing the solvent from the resin structure after the second irradiation step.

10. The removal step is a step of removing the solvent from the resin structure by heating, and the method for manufacturing a resin structure according to any one of claims 1 to 9.

11. The transmittance of light at a wavelength of 550 nm of the liquid composition measured while stirring the liquid composition is 30% or more, The method for producing a resin structure according to any one of claims 1 to 10, wherein the haze value increase rate in a haze measurement element filled with the liquid composition between two non-alkali glass substrates is 1.0% or more. (Note that the haze value increase rate is based on the measured value of the haze measurement element before UV irradiation, and is the ratio of the measured value of the haze measurement element after UV irradiation under the condition that the polymerizable compound contained in the haze measurement element can be polymerized to the measured value of the haze measurement element before UV irradiation.)

12. The method for producing a resin structure according to any one of claims 1 to 11, wherein the resin structure has a co-continuous structure in which a plurality of pores are continuously connected.

13. The method for producing a resin structure according to any one of claims 1 to 12, wherein the porosity of the resin structure is 30% or more.

14. The method for producing a resin structure according to any one of claims 1 to 13, wherein the thickness of the resin structure is 0.01 μm or more and 500 μm or less.

15. The method for producing a resin structure according to any one of claims 1 to 14, wherein the polymerization rate of the resin structure is 90% or more.

16. The method for producing a resin structure according to any one of claims 1 to 15, wherein the applying step is a step of discharging the liquid composition by an inkjet method.

17. The method for producing a resin structure according to any one of claims 1 to 16, wherein the viscosity of the liquid composition is 1.0 mPa·s or more and 150.0 mPa·s or less at 25°C.

18. The method for producing a resin structure according to any one of claims 1 to 17, wherein the viscosity of the liquid composition is 1.0 mPa·s or more and 30.0 mPa·s or less at 25°C.

19. An applying means for applying a liquid composition containing a polymerizable compound and a solvent, A first irradiation means for irradiating the applied liquid composition with a first active energy ray, A resin structure manufacturing apparatus including a second irradiation means for irradiating the liquid composition irradiated with the first active energy ray with a second active energy ray, wherein The resin structure has a porous structure having a resin as a skeleton, The porous structure is formed by irradiating the polymerizable compound in the liquid composition with the first active energy ray and the second active energy ray. The irradiation intensity of the second active energy ray is higher than that of the first active energy ray. The polymerizable compound and the solvent are compatible. The porous structure is formed by the incompatibility of the polymer produced in the process of polymerization of the polymerizable compound in the liquid composition and the solvent. The applying means is an apparatus for manufacturing a resin structure, which is means for applying the liquid composition to an active material layer formed on an electrode substrate.

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