Liquid composition group, porous resin manufacturing apparatus, and porous resin manufacturing method

Abstract

The present invention provides a liquid composition set, including: a liquid composition X containing a polymerizable compound X and a solvent X; and a liquid composition Y containing a solvent Y. The liquid composition X is used to form a porous resin. A liquid composition Z containing 10.0% by mass of the liquid composition X and 90.0% by mass of the liquid composition Y has a light transmittance of 30% or higher at a wavelength of 550 nm, and the light transmittance is measured while stirring the liquid composition Z. A haze measurement element prepared from the liquid composition Z has a haze increase rate of 1.0% or higher.

Description

Technical Field

[0001] The present invention relates to a liquid composition set, a porous resin manufacturing apparatus, and a porous resin manufacturing method. Background Art

[0002] Generally, porous resins can be used in a variety of applications. As an example, by appropriately selecting the shape and size of the pores of the porous resin, the surface properties of the skeleton part, etc., the porous resin can provide a separation layer that only penetrates or blocks a specific substance. As another example, by utilizing the large surface area and void volume of the porous resin, the porous resin can provide an effective reaction field or storage place for the gas or liquid sucked from the outside. Therefore, if a liquid composition for forming a porous resin with excellent handling and applicability to various places can be provided, the application of the porous resin is greatly expanded.

[0003] As an example of such a liquid composition for forming a porous resin, for example, PTL 1 discloses a porous body-forming photocurable resin composition, which contains a photopolymerizable monomer (A), an organic compound (B) incompatible with the photopolymerizable monomer (A), a common solvent (C) compatible with both the photopolymerizable monomer (A) and the organic compound (B), and a photopolymerization initiator (D) as essential components.

[0004] Citation List

[0005] Patent Literature

[0006]

PTL1

[0007] Technical issues

[0008] However, when a liquid composition for forming a porous resin is used in combination with another liquid composition, there is a concern that if the liquid composition for forming a porous resin comes into contact with the other liquid composition, the resulting resin may be inhibited from becoming porous.

[0009] Solutions to the problem

[0010] The present invention provides a liquid composition set, comprising: a liquid composition X comprising a polymerizable compound X and a solvent X; and a liquid composition Y comprising a solvent Y. The liquid composition X is used to form a porous resin. A liquid composition Z comprising 10.0% by mass of the liquid composition X and 90.0% by mass of the liquid composition Y has a light transmittance of 30% or more at a wavelength of 550 nm, the light transmittance being measured while stirring the liquid composition Z. A haze measurement element prepared from the liquid composition Z has a haze rise rate of 1.0% or more.

[0011] Effects of the Invention

[0012] According to some embodiments of the present invention, there is provided a liquid composition set including a liquid composition for forming a porous resin and another liquid composition, wherein the liquid composition set forms a resin having excellent porosity in a contact region where the liquid composition for forming a porous resin contacts the other liquid composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] The accompanying drawings are intended to illustrate exemplary embodiments of the present invention and should not be interpreted as limiting the scope thereof. Unless otherwise explicitly stated, the accompanying drawings should not be considered to be drawn to scale. In addition, in several views, the same or similar reference numerals represent the same or similar parts.

[0014] [ Figure 1 ]

[0015] Figure 1 1 is a schematic diagram showing a porous resin production apparatus for carrying out a porous resin production method according to an embodiment of the present invention.

[0016] [ Figure 2 ]

[0017] Figure 2 It is a schematic diagram showing a material jetting manufacturing apparatus. DETAILED DESCRIPTION

[0018] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present invention.As used herein, the singular forms "a", "an" and "the" include the plural forms as well, unless the context clearly dictates otherwise.

[0019] In describing the embodiments shown in the drawings, specific terms are used for clarity. However, the invention of this specification is not limited to the specific terms so selected, and it should be understood that each specific element includes all technical equivalents having similar functions, operating in a similar manner and achieving similar results.

[0020] Liquid composition set

[0021] The liquid composition set includes a liquid composition X and a liquid composition Y, and may further include other liquid compositions as required. In the liquid composition set, the liquid composition X and the liquid composition Y each exist independently in a liquid state. The liquid composition set is not limited to the integration of a container filled with the liquid composition X and another container filled with the liquid composition Y. The concept of the liquid composition set includes a case where the liquid composition X and the liquid composition Y are contained in separate containers, respectively, which assumes the combined use of the liquid composition X and the liquid composition Y, or substantially induces the combined use of the liquid composition X and the liquid composition Y. The liquid composition X and the liquid composition Y are liquids of different compositions.

[0022] The liquid composition group includes liquid compositions X and Y. At least one of the liquid compositions X and Y contains a polymerizable compound. When the polymerizable compound is cured (polymerized), a porous resin is formed. Therefore, the liquid composition group is preferably used to form a porous resin. The meaning of "the liquid composition group forms a porous resin" is not particularly limited, as long as the porous resin is formed as a result of using the liquid composition group in a manner that the liquid composition X and the liquid composition Y are in contact with each other. Specifically, for example, the following cases are included in the meaning of "the liquid composition group forms a porous resin". The liquid composition X and the liquid composition Y are applied in a manner that the liquid composition X and the liquid composition Y are in contact with each other, and as a result, a porous resin is formed only in the area where the liquid composition X has been applied and in another area where the liquid composition X and the liquid composition Y are in contact with each other, and a porous resin is not formed in the area where the liquid composition Y has been applied (except for the area where the liquid composition X and the liquid composition Y are in contact with each other). More specifically, for example, the following cases are also included in the meaning of "the liquid composition group forms a porous resin". A material (eg, a polymerizable compound) that forms a porous resin by curing (polymerization) is contained in the liquid composition X but not in the liquid composition Y, and as a result, a porous resin is formed by using the liquid composition set.

[0023] The meaning of “a liquid composition group forms a porous resin” includes a situation where a portion of the components of the liquid composition contained in the liquid composition group (e.g., a polymerizable compound) is solidified (polymerized) to form a porous resin, but the remaining portion of the components of the liquid composition contained in the liquid composition group (e.g., a solvent) is not solidified and does not form a porous resin.

[0024] The liquid composition set includes a liquid composition for forming a porous resin and another liquid composition. The liquid composition set is used to contact the liquid composition for forming a porous resin with another liquid composition. The reason why the liquid composition set of the present invention is preferably used in this case is as follows.

[0025] If the liquid composition for forming a porous resin contacts another liquid composition in the contact area, it is feared that the porosity of the resin formed in the contact area is suppressed. In the case where the liquid composition for forming a porous resin is applied to a porous substrate to form a porous resin on the porous substrate, this fear increases. In this case, when a porous resin is formed on a porous substrate, in order to suppress the penetration of the porous resin forming liquid composition into the porous substrate, it is preferred to apply another liquid composition on the porous substrate in advance. However, if the liquid composition for forming a porous resin contacts another liquid composition, it is feared that the porosity of the resin formed in the contact area is suppressed. In this case, the connectivity between the pores in the porous substrate and the pores in the porous resin is damaged by the resin whose porosity is suppressed due to the formation in the contact area, and the material permeability of the composite porous body including the porous substrate and the porous resin is reduced. Below, the details of the liquid composition group of the present invention that can form a resin with excellent porosity even in the area where the porous resin forming liquid composition contacts another liquid composition are described. Specifically, the details of the liquid composition X as the porous resin-forming liquid composition and the liquid composition Y as another liquid composition will be described.

[0026] Liquid CompositionX

[0027] The liquid composition X is a liquid used in combination with the liquid composition Y. The liquid composition X is preferably applied to the area where the liquid composition Y is applied. The liquid composition X is a liquid that can form a porous resin even if used alone (that is, even if not used in combination with the liquid composition Y). Since the liquid composition group contains the liquid composition X, it can form a porous resin. Hereinafter, the resin formed only by the liquid composition X is referred to as the resin X, and the porous body of the resin X is referred to as the porous resin X. The meaning of "the liquid composition X forms the porous resin X" includes the case where a part of the components of the liquid composition X (for example, the polymerizable compound X) is cured (polymerized) to form the porous resin X, but the other components of the liquid composition X (for example, the solvent X) are not cured and the porous resin X is not formed.

[0028] The liquid composition X contains a polymerizable compound X and a solvent X, and may contain other components such as a polymerization initiator as necessary.

[0029] Polymeric CompoundsX

[0030] The polymerizable compound X forms a resin X by polymerization. When polymerized in the liquid composition X, a porous resin is formed. The resin X formed by the polymerizable compound X is preferably a resin having a mesh structure formed by the application of active energy rays (e.g., light irradiation, heating, etc.). Preferred examples thereof include, but are not limited to, acrylate resins, methacrylate resins, urethane acrylate resins, vinyl ester resins, unsaturated polyester resins, epoxy resins, propylene oxide resins, vinyl ether resins, and resins formed by ene-thiol reactions. In addition, from the perspective of easy formation of structures by free radical polymerization with high reactivity, acrylate resins, methacrylate resins, and urethane acrylate resins formed by polymerizable compounds having (meth) acryloyl groups are more preferred, and from the perspective of productivity, vinyl ester resins formed by polymerizable compounds having vinyl groups are more preferred. These can be used alone or in combination of two or more. When two or more are used in combination, there is no particular limitation on the combination of polymerizable compounds, and they can be appropriately selected according to the purpose. For example, in order to impart flexibility, it is preferred to use a urethane acrylate resin as the main component and mix other resins. In the present application, a polymerizable compound having an acryloyl group or a methacryloyl group is referred to as a polymerizable compound having a (meth)acryloyl group.

[0031] The active energy ray is not particularly limited as long as it can carry out the polymerization reaction of the polymerizable compound X in the liquid composition X and provide the necessary energy, and examples thereof include, but are not limited to, ultraviolet rays, electron beams, α rays, β rays, γ rays, X-rays, etc. Among them, ultraviolet rays are preferred. In particular, when a high-energy light source is used, the polymerization reaction can be carried out even without using a polymerization initiator.

[0032] The polymerizable compound preferably has at least one free radical polymerizable functional group. Examples thereof include, but are not limited to, free radical polymerizable compounds having one, two, or three or more functional groups, functional monomers, and free radical polymerizable oligomers. Among them, free radical polymerizable compounds having two or more functional groups are preferred.

[0033] As a monofunctional free radical polymerizable compound, specific examples include, but are not limited to, 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 carbitone acrylate, 3-methoxybutyl acrylate, benzyl acrylate, cyclohexyl acrylate, isopentyl acrylate, isobutyl acrylate, methoxytriethylene glycol acrylate, phenoxytetraethylene glycol acrylate, cetyl acrylate, isostearyl acrylate, stearyl acrylate, and styrene monomer. These may be used alone or in combination of two or more.

[0034] Specific examples of the bifunctional free radical polymerizable compound include, but are not limited to, 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, and tricyclodecane dimethanol diacrylate. These may be used alone or in combination of two or more.

[0035] As a free radical polymerizable compound with three or more functional groups, specific examples include, but are not limited to, 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, and the like. Acrylate, PO-modified glycerol triacrylate, tri(acryloyloxyethyl) 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 ethoxy tetraacrylate, EO-modified phosphoric acid triacrylate, 2,2,5,5-tetramethylolcyclopentanone tetraacrylate. These may be used alone or in combination of two or more.

[0036] The content of the polymerizable compound X in the liquid composition X is preferably 5.0 mass % or more and 70.0 mass % or less, more preferably 10.0 mass % or more and 50.0 mass % or less, and further preferably 20.0 mass % or more and 40.0 mass % or less, relative to the total amount of the liquid composition X. When the content of the polymerizable compound is 70.0 mass % or less, the size of the pores of the obtained porous body will not be too small to be less than a few nm, and the porous body has an appropriate porosity, which can suppress the tendency that liquid or gas penetration is difficult to occur, and is very suitable. In addition, when the content of the polymerizable compound is 5.0 mass % or more, the three-dimensional network structure of the resin can be fully formed, the porous structure can be fully obtained, and the strength of the obtained porous structure can also be improved, which is very suitable.

[0037] SolventX

[0038] Solvent X (hereinafter referred to as "porogen") is a liquid that is compatible with polymerizable compound X. In addition, solvent X is a liquid that is not compatible with polymer (resin X) (produces phase separation) during the polymerization of polymerizable compound X in liquid composition X. Therefore, in the present invention, the term "solvent X" is different from the commonly used term "solvent" in its meaning. Since liquid composition X contains solvent X, polymerizable compound X forms porous resin X when polymerized in liquid composition X. In addition, a compound that can be dissolved by light or heat to generate free radicals or acids (polymerization initiator described later) is preferred. Solvent X can be used alone or in combination of two or more. In this embodiment, solvent X is not polymerizable.

[0039] The boiling point of the porogen alone or in combination of two or more porogens 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. When the boiling point is 50°C or higher, the vaporization of the porogen near room temperature is suppressed, the handling of the liquid composition X becomes easy, and the content of the porogen in the liquid composition X becomes easy to control. In addition, when the boiling point is 250°C or lower, the time for the drying process of the porogen after polymerization is shortened, and the productivity of the porous resin is improved. In addition, since the amount of the porogen remaining in 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.

[0040] The boiling point of the porogen alone or in combination of two or more porogens is preferably 120° C. or higher at normal pressure.

[0041] Specific examples of porogens include glycols such as diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisopropyl ether, and dipropylene glycol monomethyl ether, esters such as gamma-butyrolactone and propylene carbonate, and amides such as NN dimethyl acetylacetone. Specific examples thereof also include liquids having a relatively large molecular weight, such as methyl myristate, methyl decanoate, methyl myristate, and tetradecane. Specific examples thereof also include liquids such as acetone, 2-ethylhexanol, and 1-bromonaphthalene.

[0042] In the present invention, the liquids exemplified above do not always qualify as porogens. The so-called porogen in the present invention, as described above, refers to a liquid that is compatible with the polymerizable compound X, and is a liquid that is not compatible with (produces phase separation from) the polymer (resin X) in the process of polymerizing the polymerizable compound X in the liquid composition X. In other words, whether a certain liquid qualifies as a porogen depends on the relationship with the polymerizable compound X and the polymer (resin X formed by polymerization of the polymerizable compound X).

[0043] The liquid composition X only needs to contain at least one porogen having the above-mentioned specific relationship with the polymerizable compound X. Therefore, when preparing the liquid composition X, the range of material selection is expanded, and the design of the liquid composition X becomes easy. Since the range of material selection when preparing the liquid composition X is expanded, the corresponding selection range is expanded when the liquid composition is required to have characteristics other than the formation of a porous structure. For example, when the liquid composition X is ejected by an inkjet method, the liquid composition X is required to have ejection stability and the like from a perspective other than the formation of a porous structure. Since the range of material selection is wide, the design of the liquid composition X becomes easy.

[0044] As described above, the liquid composition X of this embodiment only needs to contain at least one porogen having the above-mentioned specific relationship with the polymerizable compound X, and therefore, it may also contain a liquid (non-porogen liquid) that does not have the above-mentioned specific relationship with the polymerizable compound X. However, the content of the liquid (non-porogen liquid) that does not have the above-mentioned specific relationship with the polymerizable compound X is preferably 10.0 mass% or less, more preferably 5.0 mass% or less, and even more preferably 1.0 mass% or less, relative to the total amount of the liquid composition, and it is particularly preferred that the liquid (non-porogen liquid) that does not have the above-mentioned specific relationship with the polymerizable compound X is not contained.

[0045] The content of the porogen in the liquid composition X is preferably 30.0 mass % or more and 95.0 mass % or less, more preferably 50.0 mass % or more and 90.0 mass % or less, and even more preferably 60.0 mass % or more and 80.0 mass % or less, relative to the total amount of the liquid composition. When the content of the porogen is 30.0 mass % or more, the pore size of the obtained porous body will not be too small to be less than a few nm, and the porous body has an appropriate porosity, which can suppress the tendency of liquid or gas penetration to be difficult to occur, and therefore it is very suitable. In addition, when the content of the porogen is 95.0 mass % or less, the three-dimensional network structure of the resin can be fully formed, the porous structure can be fully obtained, and the strength of the obtained porous structure can also be improved, and therefore it is very suitable.

[0046] The mass ratio of the content of the polymerizable compound X to the content of the porogen in the liquid composition X (polymerizable compound X:porogen) is preferably 1.0:0.4 to 1.0:19.0, more preferably 1.0:1.0 to 1.0:9.0, and even more preferably 1.0:1.5 to 1.0:4.0.

[0047] Polymerization initiator

[0048] The polymerization initiator is a material that generates active species such as free radicals or cations from energy such as light or heat, and can initiate polymerization of the polymerizable compound X. As the polymerization initiator, a known free radical polymerization initiator, a cationic polymerization initiator, a base generator, etc. can be used alone or in combination of two or more, and among them, a photoradical polymerization initiator is preferably used.

[0049] As the photoradical polymerization initiator, a photoradical generator can be used. For example, a photoradical polymerization initiator such as Michler's ketone or benzophenone known by the trade name IRGACURE or DAROCUR, more specific compounds include benzophenone, acetophenone derivatives, such as α-hydroxy or α-aminoacetophenone, 4-aroyl-1,3-dioxocyclopentyloxy, benzyl ketal, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, diphenyl Ketone, 2-chlorobenzophenone, pp'-dichlorobenzophenone, pp'-bis(diethylamino)benzophenone, Michler's ketone, benzil, benzoin, benzyl dimethyl 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-ketone, 1-(4-isopropylbenzene) benzoin alkyl ethers or esters such as 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-morpholinopropane-1-one, 2-hydroxy-2-methyl-1-phenyl-propane-1-one (DAROCUR 1173), bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-monoacylphosphine oxide, bisacylphosphine oxide or titanocene, fluorescein, anthraquinone, thioxanthone or xanthone, rofen dimer, trihalomethyl compounds or dihalomethyl compounds, active ester compounds, organic boron compounds, etc.

[0050] In addition, a photo-crosslinking radical generator such as a diazide compound may be simultaneously contained. In addition, when the polymerization is performed only by heat, a thermal polymerization initiator such as azobisisobutyronitrile (AIBN) which is a common radical generator may be used.

[0051] In order to obtain a sufficient curing speed, when the total mass of the polymerizable compound X is set to 100.0 mass%, the content of the polymerization initiator is preferably 0.05 mass% or more and 10.0 mass% or less, and more preferably 0.5 mass% or more and 5.0 mass% or less.

[0052] Conditions for producing porous resin X

[0053] The porous resin X as a porous body of the resin X is formed by polymerization-induced phase separation in the liquid composition X. The so-called polymerization-induced phase separation refers to a state in which the porogen is miscible with the polymerizable compound X but is incompatible with the polymer (resin X) generated in the polymerization process of the polymerizable compound X (phase separation). In the method of obtaining a porous body by phase separation, although there are other methods, by using the polymerization-induced phase separation method, a porous body having a mesh structure can be formed, and therefore a porous body having high drug resistance and heat resistance can be produced. Further advantages are that the processing time is shorter and the surface modification is easier than other methods.

[0054] Next, a method of using a porous resin X that induces phase separation by polymerization is described. The polymerizable compound X undergoes a polymerization reaction by light irradiation or the like, thereby generating the resin X. During this process, the solubility of the porogen in the growing resin X decreases, and the resin X and the porogen undergo phase separation. Finally, the resin X forms a porous structure having a mesh structure of a porous structure in which the pores are filled with the porogen or the like. The porogen is removed by drying, and the porous resin X is separated. Therefore, in order to form the porous resin X, a condition indicating the compatibility of the polymerizable compound X and the porogen and another condition indicating the compatibility of the resin X and the porogen are studied.

[0055] Conditions indicating compatibility of polymerizable compound X with porogen

[0056] The condition indicating that the polymerizable compound X and the porogen are compatible is, for example, that the transmittance of the liquid composition X at a wavelength of 550 nm is 30% or more when the liquid composition X is stirred. The measurement procedure for determining whether this condition is satisfied is as follows.

[0057] First, the liquid composition X is injected into a quartz container, and the transmittance of the liquid composition X at a wavelength of 550 nm (i.e., visible light) is measured while stirring the liquid composition X with a stirrer at 300 rpm. When the transmittance is 30% or more, it is judged that the polymerizable compound X and the porogen are in a miscible state, and when the transmittance is less than 30%, it is judged that the polymerizable compound X and the porogen are in an incompatible state. Various conditions for measuring the transmittance are as follows.

[0058] -Quartz container: Special micro container with screw cap (trade name: M25-UV-2)

[0059] - Transmittance measuring device: USB4000, manufactured by Ocean Optics.

[0060] -Stirring speed: 300rpm

[0061] -Measurement wavelength: 550nm

[0062] - Initial conditions: The transmittance of light with a wavelength of 550 nm was measured in the quartz container in the air state (ie, transmittance: 100%).

[0063] Conditions indicating compatibility of resin X with porogen

[0064] The condition indicating that the resin X and the porogen are incompatible (phase separated) is, for example, that the haze increase rate of a haze measuring element produced using the liquid composition X is 1.0% or more. The measurement procedure for determining whether this condition is satisfied is as follows.

[0065] First, on an alkali-free glass substrate, resin particles are evenly dispersed on the substrate by spin coating to serve as a gap agent. Next, the substrate coated with the gap agent and the alkali-free glass substrate not coated with the gap agent are bonded to each other by sandwiching the surface coated with the gap agent. Next, the liquid composition X is filled between the bonded substrates using the capillary phenomenon to produce an "element for measuring haze before UV irradiation". Next, the element for measuring haze before UV irradiation is subjected to UV irradiation to cure the liquid composition X. Finally, the "element for measuring haze" is produced by sealing the surrounding of the substrate with a sealant. The conditions for production are as follows:

[0066] -Alkali-free glass substrate: OA-10G manufactured by Nippon Electric Glass Co., Ltd., 40 mm, t=0.7 mm.

[0067] - Gap agent: Micro-fine resin particles MICROPEARL GS-L100, with an average particle size of 100 μm.

[0068] -Spin coating conditions: dispersion drop amount 150 μL, rotation speed 1000 rpm, rotation time 30 s.

[0069] -Filled liquid composition volume: 160 μL

[0070] -UV irradiation conditions: UV-LED is used as the light source, the wavelength of the light source is 365nm, and the irradiation intensity is 30mW / cm 2 , the irradiation time is 20s.

[0071] - Sealant: TB3035B (made by Three Bond)

[0072] Next, the haze value (blurriness) is measured using the prepared haze measuring element before UV irradiation and the haze measuring element. The measured value of the haze measuring element before UV irradiation is used as a reference (haze value 0), and the increase rate of the measured value (haze value) of the haze measuring element relative to the measured value of the haze measuring element before UV irradiation is calculated. The lower the compatibility between the resin X formed by the polymerization of the polymerizable compound X and the porogen, the higher the haze value of the haze measuring element. On the contrary, the higher the above-mentioned compatibility, the lower the haze value of the haze measuring element. In addition, it is shown that the higher the haze value, the easier it is for the resin X formed by the polymerization of the polymerizable compound X to form a porous structure. In this embodiment, when the increase rate of the haze value is 1.0% or more, it is judged that the resin X and the porogen are in a non-miscible state, and when the increase rate of the haze value is less than 1.0%, it is judged that the resin X and the porogen are in a miscible state. The device used for measurement is as follows:

[0073] -Haze meter NDH5000, manufactured by NIPPON DENSHOKU INDUSTRIES.

[0074] Method for producing liquid composition X

[0075] The liquid composition X is preferably prepared through a step of dissolving a polymerization initiator in the polymerizable compound X, a step of further dissolving a porogen and other components, and a step of stirring them into a uniform solution.

[0076] Physical properties of liquid composition X

[0077] From the viewpoint of workability when applying the liquid composition X, the viscosity of the liquid composition X is preferably 1.0 mPa·s or more and 150.0 mPa·s or less at 25°C, 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. 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 X is applied to an inkjet method. Here, the viscosity can be measured using, for example, a viscometer (device name: RE-550L, manufactured by Toki Sangyo Co., Ltd.).

[0078] Liquid composition Y

[0079] The liquid composition Y is a liquid used in combination with the liquid composition X for forming a porous resin. In order to suppress the diffusion of the liquid composition X and form a porous resin at a desired position, it is preferable to use the liquid composition Y. Specifically, when forming a porous resin on a porous substrate, in order to suppress the penetration of the liquid composition X into the porous substrate, it is preferable to apply the liquid composition Y to the porous substrate before applying the liquid composition X. By suppressing the penetration of the liquid composition X into the porous substrate, it is possible to suppress the formation of a part of the porous resin in the porous substrate, thereby suppressing the reduction of the function of the porous substrate.

[0080] The liquid composition Y contains a solvent Y and optionally other components. It is preferred that the liquid composition Y does not form a porous resin when used alone (i.e., when not used in combination with the liquid composition X). That is, the liquid composition Y preferably does not substantially contain a polymerizable compound. Here, the so-called "substantially does not contain a polymerizable compound" means that no polymerizable compound can be detected by a method commonly known in the art for confirming the presence or absence of a polymerizable compound in the liquid composition Y.

[0081] Solvent Y

[0082] The solvent Y is not particularly limited as long as it satisfies the specific conditions described below in the liquid composition Z containing the liquid composition X and the liquid composition Y. The solvent Y may be used alone or in combination of two or more. In the present invention, unlike the solvent X, the solvent Y is not called a porogen.

[0083] The boiling point of a single solvent Y or a combination of two or more solvents Y at normal pressure is preferably 50°C or higher and 250°C or lower, more preferably 70°C or higher and 200°C or lower. If the boiling point is 50°C or higher, the evaporation of the solvent Y is suppressed near room temperature, the handling of the liquid composition Y becomes easy, and the control of the amount of the solvent Y in the liquid composition Y becomes easy. When the boiling point is 250°C or lower, the time required for drying the solvent Y after the porous resin is formed is shortened, and the productivity is improved. In addition, the amount of the solvent Y remaining in the porous resin can be reduced, thereby improving the quality of the porous resin as a functional layer, such as a separation layer for separating substances or a reaction layer as a reaction field.

[0084] Furthermore, one type of solvent Y alone or a combination of two or more types of solvents Y preferably has a boiling point of 120° C. or higher under normal pressure.

[0085] Examples of solvent Y include, but are not limited to, ethylene glycol such as ethylene glycol monobutyl ether, ketones such as cyclohexanone, esters such as diethyl carbonate, amides such as N,N-dimethylacetamide, and liquids such as ethanol and 1,3-butanediol.

[0086] In the present invention, the above-mentioned liquid is not always used as the solvent Y. As described above, the solvent Y in the present invention is a liquid that satisfies specific conditions described later in the liquid composition Z containing the liquid composition X and the liquid composition Y.

[0087] The content of solvent Y in liquid composition Y is preferably 60.0% by mass or more, more preferably 70.0% by mass or more, further preferably 80.0% by mass or more, and particularly preferably 90.0% by mass or more. The total amount (100% by mass) of liquid composition Y may be solvent Y.

[0088] Physical properties of liquid composition Y

[0089] From the viewpoint of operability when imparting the liquid composition Y, the viscosity of the liquid composition Y is preferably 1.0 mPa·s or more and 150.0 mPa·s or less at 25°C, 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. When the viscosity of the liquid composition Y 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 Y is applied to an inkjet method. Here, the viscosity can be measured using, for example, a viscometer (device name: RE-550L, manufactured by Toki Sangyo Co., Ltd.).

[0090] Liquid composition Z

[0091] Liquid composition Z is a liquid used in a test for showing that even when liquid composition X and liquid composition Y are in contact, a resin formed in a contact region between liquid composition X and liquid composition Y exhibits excellent porosity. Therefore, unlike liquid composition X and liquid composition Y, liquid composition Z itself is not a constituent element of the liquid composition set.

[0092] Liquid composition Z is a liquid composed of a mixture of 10.0 mass % of liquid composition X and 90.0 mass % of liquid composition Y. Therefore, liquid composition Z contains components derived from liquid composition X such as polymerizable compound X, solvent X, and polymerization initiator, and components derived from liquid composition Y such as solvent Y.

[0093] In the present invention, the polymerizable compound contained in the liquid composition Z is referred to as polymerizable compound Z, and the solvent contained in the liquid composition Z is referred to as solvent Z. Therefore, the polymerizable compound Z means at least the polymerizable compound X, and the solvent Z means at least the solvent X and the solvent Y.

[0094] First, the reason for conducting the test under the condition that the resin formed in the contact area where the liquid composition X and the liquid composition Y contacted each other showed excellent porosity using the liquid composition Z will be described.

[0095] When the liquid composition X and the liquid composition Y are used in combination, when the liquid composition X and the liquid composition Y are in contact with each other, the liquid composition X and the liquid composition Y are partially mixed with each other in the contact region (i.e., near the interface between the liquid composition X and the liquid composition Y), and a concentration gradient of the liquid composition X and the liquid composition Y is generated. In order to form a porous resin from the polymerizable compound X contained in the liquid composition X even in the contact region where the concentration gradient is generated, it is necessary to define conditions under which a porous resin can be formed even when the concentration of the component from the liquid composition X is low and the concentration of the component from the liquid composition Y is high. Hereinafter, the conditions under which a porous resin can be formed using a liquid composition Z containing 10.0% by mass of the liquid composition X and 90.0% by mass of the liquid composition Y are described in detail. Hereinafter, the resin formed by the liquid composition Z is referred to as the resin Z, and the porous body of the resin Z is referred to as the porous resin Z.

[0096] Production conditions of porous resin Z

[0097] The porous resin Z as a porous body of the resin Z is formed by polymerization-induced phase separation occurring in the liquid composition Z. The polymerization-induced phase separation refers to a state in which the solvent Z and the polymerizable compound Z are miscible but the polymer (i.e., the resin Z) produced during the polymerization of the polymerizable compound Z is immiscible with the solvent Z (i.e., phase-separated).

[0098] Next, a method for forming a porous resin Z by polymerization-induced phase separation is described. The polymerizable compound Z undergoes a polymerization reaction by light irradiation or the like to generate the resin Z. At this time, the solubility of the solvent Z in the growing resin Z decreases, and the resin Z and the solvent Z undergo phase separation. Finally, the resin Z forms a network porous structure in which the pores are filled with the solvent Z. The solvent Z is removed by drying, and the porous resin Z is separated. Therefore, in order to form the porous resin Z, a condition indicating the compatibility of the polymerizable compound Z and the solvent Z and another condition indicating the compatibility of the resin Z and the solvent Z are considered.

[0099] Conditions indicating compatibility of polymerizable compound Z with solvent Z

[0100] The condition indicating that the polymerizable compound Z is compatible with the solvent Z can be exemplified by the condition that the liquid composition Z shows a transmittance of 30% or more at a wavelength of 550 nm when the transmittance is measured while stirring the liquid composition Z. The measurement procedure for determining whether this condition is satisfied is as follows.

[0101] First, the liquid composition Z is injected into a quartz container, and the transmittance of the liquid composition Z at a wavelength of 550 nm (i.e., visible light) is measured while stirring the liquid composition Z with a stirrer at 300 rpm. When the transmittance is 30% or more, the polymerizable compound Z and the solvent Z are judged to be in a miscible state, and when the transmittance is less than 30%, the polymerizable compound Z and the solvent Z are judged to be in an incompatible state. Various conditions for measuring the transmittance are as follows.

[0102] -Quartz container: Special micro container with screw cap (trade name: M25-UV-2)

[0103] - Transmittance measuring device: USB4000, manufactured by Ocean Optics.

[0104] -Stirring speed: 300rpm

[0105] -Measurement wavelength: 550nm

[0106] - Initial conditions: The transmittance of light with a wavelength of 550 nm was measured in the quartz container in the air state (ie, transmittance: 100%).

[0107] Conditions indicating compatibility of resin Z with solvent Z

[0108] The condition indicating that the resin Z and the solvent Z are immiscible (ie, phase separated) is, for example, a condition that the haze increase rate of a haze measuring element prepared from the liquid composition Z is 1.0% or more. The measurement procedure for determining whether this condition is satisfied is as follows.

[0109] First, on an alkali-free glass substrate, resin particles are evenly dispersed on the substrate by spin coating to serve as a gap agent. Next, the substrate coated with the gap agent and the alkali-free glass substrate not coated with the gap agent are bonded to each other by sandwiching the surface coated with the gap agent. Next, the liquid composition Z is filled between the bonded substrates using the capillary phenomenon to produce an "element for measuring haze before UV irradiation". Next, the element for measuring haze before UV irradiation is subjected to UV irradiation to cure the liquid composition Z. Finally, the "element for measuring haze" is produced by encapsulating the surrounding of the substrate with a sealant. The conditions for production are as follows:

[0110] -Alkali-free glass substrate: OA-10G manufactured by Nippon Electric Glass Co., Ltd., 40 mm, t=0.7 mm.

[0111] - Gap agent: Micro-fine resin particles MICROPEARL GS-L100, with an average particle size of 100 μm.

[0112] -Spin coating conditions: dispersion drop amount 150 μL, rotation speed 1000 rpm, rotation time 30 s.

[0113] -Filled liquid composition volume: 160 μL

[0114] -UV irradiation conditions: UV-LED is used as the light source, the wavelength of the light source is 365nm, and the irradiation intensity is 30mW / cm 2 , the irradiation time is 20s.

[0115] - Sealant: TB3035B (made by Three Bond)

[0116] Next, the haze value (blurriness) is measured using the prepared haze measuring element before UV irradiation and the haze measuring element. The measured value of the haze measuring element before UV irradiation is used as a reference (haze value 0), and the increase rate of the measured value of the haze measuring element (haze value) relative to the measured value of the haze measuring element before UV irradiation is calculated. The lower the compatibility between the resin Z and the solvent Z formed by the polymerization of the polymerizable compound Z, the higher the haze value of the haze measuring element. On the contrary, the higher the above-mentioned compatibility, the lower the haze value of the haze measuring element. In addition, it is shown that the higher the haze value, the easier it is for the resin Z formed by the polymerization of the polymerizable compound Z to form a porous structure. In this embodiment, when the rate of increase of the haze value is 1.0% or more, it is judged that the resin Z and the solvent Z are in a non-miscible state, and when the rate of increase of the haze value is less than 1.0%, it is judged that the resin Z and the solvent Z are in a miscible state. The device used for measurement is as follows:

[0117] -Haze meter NDH5000, manufactured by NIPPON DENSHOKU INDUSTRIES.

[0118] Method for satisfying the production conditions of porous resin Z

[0119] The following describes a method for satisfying the conditions for making the porous resin Z porous. As described above, in order to form the porous resin Z, the compatibility between the polymerizable compound Z and the solvent Z should be high, and the compatibility between the resin Z and the solvent Z should be low. This compatibility can be estimated by the Hansen solubility parameter (HSP) described in detail below.

[0120] Hansen Solubility Parameter (HSP)

[0121] The above miscibility can be predicted by the Hansen Solubility Parameter (HSP). The so-called Hansen Solubility Parameter (HSP) is a useful tool for predicting the miscibility of two substances. It is a parameter discovered by Charles M. Hansen. The Hansen Solubility Parameter (HSP) is expressed by combining the following three parameters (δD, δP, and δH) derived from experiments and theories. The unit of the Hansen Solubility Parameter (HSP) is MPa.0.5 or (J / cm 3 ) 0.5 In this embodiment, (J / cm 3 ) 0.5 .

[0122] δD: Energy derived from London dispersion forces.

[0123] δP: Energy due to dipole interaction.

[0124] δH: Energy derived from hydrogen bonding forces.

[0125] The Hansen solubility parameter (HSP) is a vector represented by (δD, δP, δH), and is plotted in a three-dimensional space (Hansen space) with the three parameters as coordinate axes. The Hansen solubility parameter (HSP) of commonly used substances has a well-known information source such as a database, so the Hansen solubility parameter (HSP) of the desired substance can be obtained by referring to the database. For substances whose Hansen solubility parameter (HSP) is not registered in the database, the Hansen solubility parameter (HSP) can be calculated from the chemical structure of the substance and the Hansen dissolving sphere method described later by using computer software such as Hansen Solubility Parameters in Practice (HSP iP). The Hansen solubility parameter (HSP) of a mixture containing two or more substances is calculated according to the following method: for the Hansen solubility parameter (HSP) of each substance, multiply it by the volume ratio of each substance to the entire mixture, and the vector sum of the obtained values. In the present embodiment, the Hansen solubility parameter (HSP) of the solvent Z obtained based on a known information source such as a database is represented as the "Hansen solubility parameter of the solvent".

[0126] In addition, the relative energy difference (RED) based on the Hansen solubility parameter (HSP) of the solute and the Hansen solubility parameter (HSP) of the solution is expressed as follows:

[0127] Relative energy difference (RED) = Ra / Ro

[0128] In the above formula, Ra represents the interaction distance between the Hansen Solubility Parameter (HSP) of the solute and the Hansen Solubility Parameter (HSP) of the solution, and Ro represents the interaction radius of the solute. The interaction distance Ra between the Hansen Solubility Parameters (HSP) represents the distance between the two substances. The smaller the value, the closer the two substances are in three-dimensional space (Hansen space), indicating that the possibility of mutual dissolution (miscibility) is higher.

[0129] Assuming that the respective Hansen Solubility Parameters (HSP) for the two substances (solute A and solution B) are as follows, Ra can be calculated as follows:

[0130] HSP A =(δD A ,δP A ,δH A )

[0131] HSP B =(δD B ,δP B ,δH B )

[0132] Ra=[4×(δD A -δD B ) 2 +(δP A -δP B ) 2 +(δH A -δH B ) 2 ] 1 / 2

[0133] Ro (interaction radius of the solute) can be determined by the Hansen dissolving sphere method as described below.

[0134] Hansen dissolving ball method

[0135] First, prepare the substance for which Ro is to be obtained and dozens of evaluation solvents with known Hansen solubility parameters (HSP), and conduct a compatibility test of the target substance with each evaluation solvent. In the compatibility test, the Hansen solubility parameters (HSP) of the evaluation solvents showing compatibility and the Hansen solubility parameters (HSP) of the evaluation solvents not showing compatibility are plotted on the Hansen space respectively. Based on the Hansen solubility parameters (HSP) of each evaluation solvent plotted, a virtual sphere (Hansen sphere) is created on the Hansen space, which includes the Hansen solubility parameters (HSP) of the evaluation solvent group showing compatibility and does not include the Hansen solubility parameters (HSP) of the evaluation solvent group not showing compatibility. The radius of the Hansen sphere is the interaction radius Ro of the substance, and the center is the Hansen solubility parameter (HSP) of the substance. The evaluation criteria for compatibility between a substance for which the interaction radius Ro and the Hansen solubility parameter (HSP) are to be determined and an evaluation solvent for which the Hansen solubility parameter (HSP) is known (the criteria for determining whether the substances are compatible) are set by the evaluator himself. The evaluation criteria of this embodiment will be described later.

[0136] Hansen Solubility Parameter (HSP) and Interaction Radius of Polymeric Compounds

[0137] The Hansen solubility parameter (HSP) of the polymerizable compound in this embodiment and the interaction radius of the polymerizable compound are determined by the Hansen dissolving sphere method. As described above, the evaluation criteria for compatibility in the Hansen dissolving sphere method are set by the evaluator himself, so the Hansen solubility parameter (HSP) of the polymerizable compound Z in this embodiment obtained based on the following criteria is expressed as "Hansen solubility parameter C of polymerizable compound Z", and the interaction radius of the polymerizable compound Z is expressed as "interaction radius D of polymerizable compound Z". In other words, the "Hansen solubility parameter C of polymerizable compound Z" and the "interaction radius D of polymerizable compound Z" are different from the "Hansen solubility parameter of the solvent" obtained based on a known information source such as a database, and are obtained based on the Hansen dissolving sphere method including the compatibility evaluation criteria set by the evaluator himself.

[0138] The Hansen solubility parameter C of the polymerizable compound Z and the interaction radius D of the polymerizable compound Z can be obtained according to the following [1-1] and [1-2], from the evaluation of the compatibility of the polymerizable compound Z with the evaluation solvent (based on the evaluation of "measuring the transmittance of the transmittance measuring composition containing the polymerizable compound Z and the evaluation solvent while stirring for light of a wavelength of 550 nm").

[0139] [1-1] Preparation of Composition for Transmittance Measurement

[0140] First, a polymerizable compound Z for which the Hansen solubility parameter (HSP) is to be determined and several dozen evaluation solvents for which the Hansen solubility parameter (HSP) is known are prepared, and the polymerizable compound Z, each evaluation solvent, and a polymerization initiator are mixed in the following ratios to prepare a transmittance measurement composition. The following 21 evaluation solvents are used as the several dozen evaluation solvents for which the Hansen solubility parameter (HSP) is known.

[0141] Transmittance measurement composition ratio

[0142] -Polymerizable compound Z for which Hansen solubility parameter (HSP) is to be determined: 28.0 mass %

[0143] -Hansen solubility parameter (HSP) known evaluation solvent: 70.0 mass%

[0144] -Polymerization initiator (Irgacure 819, manufactured by BASF): 2.0 mass%

[0145] Evaluation solvent set (21 types)

[0146] Ethanol, 2-propanol, trimethylbenzene, dipropylene glycol monomethyl ether, N-methyl 2-pyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether, propylene carbonate, ethyl acetate, tetrahydrofuran, acetone, n-tetradecane, ethylene glycol, diethylene glycol monobutyl ether, diethylene glycol butyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, 2-ethylhexanol, diisobutyl ketone, benzyl alcohol, 1-bromonaphthalene.

[0147] [1-2] Measurement of light transmittance

[0148] The prepared transmittance measurement composition is injected into a quartz container, and the transmittance of the transmittance measurement composition at a wavelength of 550nm (visible light) is measured while stirring at 300rpm using a stirrer. In this embodiment, when the light transmittance is 30% or higher, it is judged that the polymerizable compound Z and the evaluation solvent are in a miscible state, and when it is less than 30%, it is judged that the polymerizable compound Z and the evaluation solvent are in a non-miscible state. The conditions for measuring light transmittance are as follows:

[0149] -Quartz container: Special micro container with screw cap (trade name: M25-UV-2)

[0150] - Transmittance measuring device: USB4000, manufactured by Ocean Optics.

[0151] -Stirring speed: 300rpm

[0152] -Measurement wavelength: 550nm

[0153] - Initial conditions: The transmittance of light with a wavelength of 550 nm was measured in the quartz container in the air state (transmittance: 100%).

[0154] Hansen solubility parameter (HSP) and interaction radius of resin Z formed by polymerization of polymerizable compound Z

[0155] The Hansen solubility parameter (HSP) of the resin Z formed by polymerizing the polymerizable compound Z in the present invention, and the interaction radius of the resin Z formed by polymerizing the polymerizable compound Z are determined by the Hansen dissolving sphere method. As described above, the evaluation criteria for compatibility in the Hansen dissolving sphere method are set by the evaluator himself, and therefore, the Hansen solubility parameter (HSP) of the resin Z formed by polymerizing the polymerizable compound Z of the present invention obtained according to the following criteria is expressed as "Hansen solubility parameter A of resin Z", and the interaction radius of the resin Z formed by polymerizing the polymerizable compound Z is expressed as "interaction radius B of resin Z". In other words, the "Hansen solubility parameter A of resin Z" and the "interaction radius B of resin Z" are different from the "Hansen solubility parameter of the solvent" obtained based on a known information source such as a database, and are obtained based on the Hansen dissolving sphere method including the compatibility evaluation criteria set by the evaluator himself.

[0156] The Hansen solubility parameter A of resin Z and the interaction radius B of resin Z can be obtained according to the following [2-1], [2-2], and [2-3], from the evaluation of the compatibility of resin Z with the evaluation solvent (based on the evaluation of "the increase rate of the haze value (fuzziness) of the haze measuring element prepared using the haze measuring composition containing the polymerizable compound Z and the evaluation solvent").

[0157] [2-1] Preparation of haze measurement composition

[0158] First, a precursor (polymerizable compound Z) of a resin Z for which the Hansen solubility parameter (HSP) is to be determined and several dozen evaluation solvents with known Hansen solubility parameters (HSP) are prepared, and the polymerizable compound Z, each evaluation solvent, and a polymerization initiator are mixed in the ratio shown below to prepare a composition for haze measurement. The following 21 evaluation solvents are used as the several dozen evaluation solvents with known Hansen solubility parameters (HSP).

[0159] Haze measurement composition ratio

[0160] - Resin Z precursor (i.e., polymerizable compound Z) for which Hansen solubility parameter (HSP) is to be determined: 28.0% by mass

[0161] -Hansen solubility parameter (HSP) known evaluation solvent: 70.0 mass%

[0162] -Polymerization initiator (Irgacure 819, manufactured by BASF): 2.0 mass%

[0163] Evaluation solvent set (21 types)

[0164] Ethanol, 2-propanol, trimethylbenzene, dipropylene glycol monomethyl ether, N-methyl 2-pyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether, propylene carbonate, ethyl acetate, tetrahydrofuran, acetone, n-tetradecane, ethylene glycol, diethylene glycol monobutyl ether, diethylene glycol butyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, 2-ethylhexanol, diisobutyl ketone, benzyl alcohol, 1-bromonaphthalene.

[0165] [2-2] Manufacturing of haze measurement element

[0166] On an alkali-free glass substrate, resin particles are uniformly dispersed on the substrate by spin coating to serve as a gap agent. Next, the substrate coated with the gap agent and the alkali-free glass substrate not coated with the gap agent are bonded together by sandwiching the surface coated with the gap agent. Next, the haze measurement composition prepared in [2-1] is filled between the bonded substrates using a capillary phenomenon to produce a "haze measurement element before UV irradiation". Next, the haze measurement element before UV irradiation is subjected to UV irradiation to cure the haze measurement composition. Finally, the "haze measurement element" is produced by sealing the substrate with a sealant. The conditions during production are as follows:

[0167] -Alkali-free glass substrate: manufactured by Nippon Electric Glass Co., Ltd., 40 mm, t=0.7 mm, OA-10G.

[0168] - Gap agent: Micro-fine resin particles MICROPEARL GS-L100, with an average particle size of 100 μm.

[0169] -Spin coating conditions: dispersion drop amount 150 μL, rotation speed 1000 rpm, rotation time 30 s.

[0170] -Amount of the filled haze measurement composition: 160 μL

[0171] -UV irradiation conditions: Use UV-LED as the light source, the wavelength of the light source is 365nm, the irradiation intensity is 30mW / cm2, and the irradiation time is 20s.

[0172] - Sealant: TB3035B (made by Three Bond)

[0173] [2-3] Determination of haze value (blurriness)

[0174] The haze value (blurriness) is measured using the prepared haze measuring element before UV irradiation and the haze measuring element. The measured value of the haze measuring element before UV irradiation is used as a reference (haze value 0), and the increase rate of the measured value of the haze measuring element (haze value) relative to the measured value of the haze measuring element before UV irradiation is calculated. The lower the compatibility between the resin Z formed by the polymerization of the polymerizable compound Z and the evaluation solvent, the higher the haze value of the haze measuring element, and the higher the above-mentioned compatibility, the lower the haze value of the haze measuring element. In addition, the higher the haze value, the easier it is for the resin Z formed by the polymerization of the polymerizable compound Z to form a porous structure. In this embodiment, when the rate of increase of the haze value is 1.0% or more, it is judged that the resin Z and the evaluation solvent are in a non-miscible state, and when the rate of increase of the haze value is less than 1.0%, it is judged that the resin Z and the evaluation solvent are miscible. The device used for measurement is as follows:

[0175] -Haze meter NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.

[0176] Relative energy difference (RED) based on the Hansen solubility parameters (HSP) of resin Z and solvent Z

[0177] As described above, a haze measuring element is prepared using a haze measuring composition containing a polymerizable compound Z and an evaluation solvent, and the relative energy difference (RED) is calculated according to the following formula 1 from the Hansen solubility parameter A of the resin Z polymerized by the polymerizable compound Z determined based on the rate of increase of the haze value (cloudiness) of the haze measuring element, the interaction radius B of the resin Z, and the Hansen solubility parameter of the solvent Z. The relative energy difference (RED) is preferably 1.00 or higher, more preferably 1.10 or higher, further more preferably 1.20 or higher, and particularly preferably 1.30 or higher.

[0178] Relative Energy Difference (RED) =

[0179] (Distance between the Hansen solubility parameter A of resin Z and the Hansen solubility parameter of solvent Z) / interaction radius B of resin Z (Formula 1)

[0180] When the relative energy difference (RED) based on the Hansen solubility parameter (HSP) of the resin Z and the solvent Z is 1.00 or higher, the resin Z and the solvent Z formed by polymerization of the polymerizable compound Z in the liquid composition are easily phase-separated, and a porous resin is more easily formed, and therefore, it is very suitable.

[0181] Relative energy difference (RED) based on the Hansen solubility parameter (HSP) of polymerizable compound Z and solvent Z

[0182] As described above, while stirring the transmittance measuring composition containing the polymerizable compound Z and the evaluation solvent, the transmittance of the transmittance measuring composition at a wavelength of 550 nm is measured, and the relative energy difference (RED) is calculated according to the following formula 2 from the Hansen solubility parameter C of the polymerizable compound Z determined based on the transmittance of the light, the interaction radius D of the polymerizable compound Z determined based on the compatibility between the polymerizable compound Z and the evaluation solvent, and the Hansen solubility parameter of the solvent Z. The relative energy difference (RED) is preferably 1.05 or less, more preferably 0.90 or less, further more preferably 0.80 or less, and particularly preferably 0.70 or less.

[0183] Relative Energy Difference (RED) =

[0184] (Distance between the Hansen solubility parameter C of polymerizable compound Z and the Hansen solubility parameter of solvent Z) / interaction radius D of polymerizable compound Z (Formula 2)

[0185] When the relative energy difference (RED) based on the Hansen solubility parameter (HSP) of the polymerizable compound Z and the solvent Z is 1.05 or less, the polymerizable compound Z and the solvent Z are likely to show compatibility, and as it approaches 0, the compatibility is better. Therefore, by making the relative energy difference (RED) 1.05 or less, a liquid composition having high dissolution stability such that the polymerizable compound Z does not precipitate over time after being dissolved in the solvent Z can be obtained.

[0186] Porous resin manufacturing device and porous resin manufacturing method

[0187] Figure 1 It is a schematic diagram showing a porous resin production apparatus for realizing the porous resin production method of the present invention.

[0188] Porous resin manufacturing device

[0189] The porous resin manufacturing device 100 is a device for manufacturing a porous resin using the above-mentioned liquid composition and liquid composition Y. The porous resin manufacturing device 100 includes a printing processing unit 10, a polymerization processing unit 20, and a heating processing unit 30. The printing processing unit 10 performs a process of applying the liquid composition X and the liquid composition Y to the printing substrate 4, respectively, to form layers of the liquid composition X and the liquid composition Y, respectively. The polymerization processing unit 20 performs a polymerization process of activating the polymerization initiator in the liquid composition X layer and polymerizing the polymerizable compound to obtain a porous resin precursor 6. The heating processing unit 30 performs a heating process of heating the porous resin precursor 6 to obtain a porous resin. The porous resin manufacturing device 100 also includes a conveying unit 5 for conveying the printing substrate 4. The conveying unit 5 conveys the printing substrate 4 through the printing processing unit 10, the polymerization processing unit 20, and the heating processing unit 30 in sequence at a predetermined speed.

[0190] Printing Processing Unit

[0191] The printing processing unit 10 includes a printing device 1a, a storage container 1b, and a supply pipe 1c. The printing device 1a is an imparting device that performs an imparting process of imparting the liquid composition X and the liquid composition Y to the printing substrate 4, respectively. The storage container 1b respectively contains the liquid composition X and the liquid composition Y. The supply pipe 1c supplies the liquid composition X and the liquid composition Y contained in the storage container 1b to the printing device 1a. The imparting device includes an imparting device X for imparting the liquid composition X and an imparting device Y for imparting the liquid composition Y. The imparting process includes an imparting process X for imparting the liquid composition X and an imparting process Y for imparting the liquid composition Y.

[0192] The storage container 1b contains the liquid composition X and the liquid composition Y (in Figure 1 In the printing process unit 10, the liquid composition X and the liquid composition Y are simply expressed as liquid composition 7). In the printing process unit 10, the printing device 1a discharges the liquid composition X and the liquid composition Y, respectively, and applies the liquid composition X and the liquid composition Y to the printing substrate 4, respectively, to form thin film layers of the liquid composition X and the liquid composition Y, respectively. In the present invention, the applying step Y is first performed, and then the applying step X is performed. After the applying step Y, the applying step X is preferably performed in a manner that the liquid composition X is applied to an area overlapping at least a part of the area where the liquid composition Y is applied.

[0193] The storage container 1b may be integrated with the porous resin manufacturing apparatus 100 or may be detachable from the porous resin manufacturing apparatus 100. In addition, the storage container 1b may be used to supply the liquid composition to another storage container integrated with the porous resin manufacturing apparatus 100 or another storage container detachable from the porous resin manufacturing apparatus 100.

[0194] The printing device 1a is not particularly limited as long as it can impart the liquid composition X and the liquid composition Y. Specific examples thereof include, but are not limited to, any printing device corresponding to various printing methods such as spin coating, casting, micro-gravure coating, gravure coating, rod coating, roller coating, wire rod coating, dip coating, slit coating, capillary coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, offset printing, reverse printing, and inkjet printing.

[0195] The storage container 1b and the supply pipe 1c may be selected arbitrarily as long as they can respectively reliably store and supply the liquid composition X and the liquid composition Y. The storage container 1b and the supply pipe 1c are preferably made of a material having light-shielding properties in a relatively short wavelength region such as the ultraviolet region and the visible light region. In this case, the liquid composition X is prevented from starting to polymerize due to external light.

[0196] Aggregate Processing Unit

[0197] like Figure 1 As shown, the polymerization processing unit 20 includes a light irradiator 2a and a polymerization inert gas circulator 2b. The light irradiator 2a is a curing device that performs a curing treatment to cure the liquid composition by irradiating active energy rays such as heat and light. The polymerization inert gas circulator 2b circulates the polymerization inert gas. The light irradiator 2a irradiates light to the layer of the liquid composition X and the layer of the liquid composition Y formed by the printing processing unit 10 in the presence of the polymerization inert gas, so that photopolymerization starts in the layer of the liquid composition X, and a porous resin precursor 6 is obtained.

[0198] The light irradiator 2a is appropriately selected according to the absorption wavelength of the photopolymerization initiator, and is not particularly limited as long as it can initiate and carry out the polymerization of the polymerizable compound contained in the layer of the liquid composition X. Specific examples thereof include, but are not limited to, ultraviolet light sources such as high-pressure mercury lamps, metal halide lamps, hot cathode tubes, cold cathode tubes, and LEDs (light-emitting diodes). However, since light with a shorter wavelength generally tends to easily reach deep parts, it is preferred to select a light source according to the thickness of the porous film to be formed.

[0199] When the emission intensity of the light source of the light irradiator 2a is too strong, polymerization proceeds rapidly before sufficient phase separation occurs, making it difficult to obtain a porous structure. On the contrary, when the emission intensity is too weak, phase separation proceeds beyond the micron level, and porous deviation or coarsening is likely to occur. In addition, there is a tendency for the irradiation time to become longer and the productivity to decrease. Therefore, the luminous intensity is preferably 10mW / cm 2 or higher and 1W / cm 2 or lower, more preferably 30 mW / cm 2 or higher and 300mW / cm 2 or lower.

[0200] The polymerization inert gas circulation device 2b plays the role of reducing the concentration of polymerization-active oxygen contained in the atmosphere, and allowing the polymerization reaction of the polymerizable compound X near the surface of the layer of the liquid composition X to proceed without hindering it. Therefore, the polymerization inert gas used is not particularly limited as long as it satisfies the above function, and its specific examples include, but are not limited to, nitrogen, carbon dioxide, and argon.

[0201] In addition, as the flow rate, it is preferably 0 2 The concentration is less than 20% (lower than atmospheric oxygen concentration), more preferably 0% or more and 15% or less, and even more preferably 0% or more and 5% or less. In addition, the polymerization inert gas circulation device 2b is preferably provided with a temperature controller capable of adjusting the temperature in order to achieve stable polymerization conditions.

[0202] Heating treatment unit

[0203] like Figure 1 As shown, the heat treatment unit 30 has a heater 3a. The heat treatment unit 30 performs a solvent removal process, and the heater 3a heats the solvent X and the solvent Y remaining in the porous resin precursor 6 formed by the polymerization treatment unit 20 to dry and remove them. As a result, a porous resin is formed. The heat treatment unit 30 can perform the solvent removal process under reduced pressure.

[0204] The heat treatment unit 30 also performs a polymerization promotion process and an initiator removal process. In the polymerization promotion process, the heater 3a heats the porous resin precursor 6 to further promote the polymerization reaction performed by the polymerization treatment unit 20. In the initiator removal process, the heater 3a heats the photopolymerization initiator remaining in the porous resin precursor 6 to dry and remove it. The polymerization promotion process and the initiator removal process are not necessarily performed during the solvent removal process, and may be performed before or after the solvent removal process.

[0205] After the solvent removal process, the heat treatment unit 30 also performs a polymerization completion process of heating the porous resin under reduced pressure. The heater 3a is not particularly limited as long as it performs the above-mentioned function. Examples thereof include, but are not limited to, an IR (infrared) heater and a hot air heater.

[0206] The heating temperature and time can be appropriately selected according to the boiling points of the solvent X and the solvent Y contained in the porous resin precursor 6 or the thickness of the film to be formed.

[0207] Printing substrate

[0208] As the material of the printing substrate 4, any material can be used regardless of whether it is transparent or opaque. That is, as a transparent substrate, a glass substrate, a resin film substrate such as various plastic films, or a composite substrate thereof can be used, and as an opaque substrate, a metal substrate such as a silicon substrate, stainless steel, or various substrates such as a laminate of these substrates can be used.

[0209] The printing substrate 4 may be a recording medium such as ordinary paper, glossy paper, special paper, cloth, etc. In addition, as a recording medium, it may be a low permeability substrate (low absorption substrate). The so-called low permeability substrate refers to a substrate having a surface with low water permeability, absorption, or adsorption, and also includes a material that has many cavities inside but is not open to the outside. As a low permeability substrate, there can be listed coated paper used for commercial printing, waste paper pulp arranged in the middle layer and back layer and a coating applied to the surface of the cardboard, etc.

[0210] As described above, the printed substrate 4 is preferably a porous substrate. This is because the effect of the present invention is more significant when a porous substrate is used. As specific examples of porous substrates, active material layers used in storage elements, porous sheets used as insulating layers in storage elements or power generation elements, etc. can be cited, but are not limited to these.

[0211] In addition, regarding the shape, even if it is a curved surface or has a concave-convex shape, as long as it is a substrate applicable to the printing process unit 10 and the polymerization process unit 20, it can be used.

[0212] Porous resin

[0213] The film thickness of the porous resin formed by the liquid composition group is not particularly limited, but in consideration of the uniformity of hardening 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, further 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 larger, and the function based on the porous resin can be fully obtained. In addition, when the film thickness is 500 μm or less, the unevenness of light or heat used during polymerization can be suppressed in the film thickness direction, and a porous resin uniform in the film thickness direction can be obtained. By making a porous resin uniform in the film thickness direction, the structural unevenness of the porous resin can be suppressed, and the permeability of liquid or gas can be suppressed. The film thickness of the porous resin is appropriately adjusted according to the purpose of using the porous resin. For example, when a 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.

[0214] The porous resin formed is not particularly limited, but from the perspective of ensuring good permeability of liquid or gas, it is preferred to have a three-dimensional branched mesh structure of a cured product of the resin as a skeleton, and have a co-continuous structure (also called a monolithic structure) in which a plurality of pores in the porous resin are continuously connected. That is, the porous resin preferably has a plurality of pores, and has connectivity between one pore and other pores around it, and diffuses three-dimensionally. The pores are connected, so that the infiltration of liquid or gas can occur sufficiently, and the function of material separation or reaction field can be effectively exerted.

[0215] As one of the physical properties obtained by having a co-continuous structure, air permeability can be cited. The air permeability of the porous resin is measured, for example, according to JIS P8117, and 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, for example, using a Gurley type meter (manufactured by Toyo Seiki Seisakusho).

[0216] The cross-sectional shape of the pores of the formed porous resin can be various shapes and sizes such as approximately circular, approximately elliptical, and approximately polygonal. Here, the size of the pores refers to the length of the longest part of the cross-sectional shape. The size of the pores can be obtained from a cross-sectional photograph taken with a scanning electron microscope (SEM). There is no particular restriction on the size of the pores of the porous resin, but from the perspective of the permeability of liquid or gas, it is preferably 0.01 μm or more and 10 μm or less. In addition, as the porosity of the porous resin, it is preferably 30% or more, and more preferably 50% or more. There is no particular restriction on the method of setting the size and porosity of the pores of the porous resin to the above range. For example, there can be cited a method of adjusting the content of the polymerizable compound X in the liquid composition X to the above range, a method of adjusting the content of the porogen in the liquid composition X to the above range, and a method of adjusting the irradiation conditions of the active energy ray.

[0217] Applications of porous resin

[0218] Storage element use or power generation element use

[0219] The porous resin formed using the liquid composition set of the present invention can be used, for example, as an insulating layer for a storage element or a power generation element. In other words, the liquid composition set of the present invention can be used as a liquid composition set for manufacturing an insulating layer in a storage element or a power generation element. When used for these purposes, it is preferred that, for example, the insulating layer (spacer) is formed by sequentially applying the liquid composition Y and the liquid composition X to the active material layer preformed on the electrode substrate.

[0220] As an insulating layer for a storage element or a power generation element, for example, a thin film-shaped porous insulating layer having pores or porosity of a certain size is used, which is well known. On the other hand, when using the liquid composition group of the present invention, by appropriately adjusting the content of the polymerizable compound X, the content of the porogen, the irradiation conditions of the active energy ray, etc., the pores or porosity can be appropriately changed, and the design freedom in terms of the performance of the storage element and the power generation element can be improved. In addition, the liquid composition group of the present invention can be developed by a variety of imparting methods, for example, it can be imparted by inkjet, which can improve the design freedom of the shape surface of the storage element and the power generation element. The liquid composition group of the present invention imparts the liquid composition X to the area of ​​the liquid composition Y to which the active material layer has been imparted, so that the porous resin formed by curing the liquid composition X will not excessively enter the active material layer. Thus, the reduction in the function of the active material layer can be suppressed. In addition, since the resin formed in the contact area between the liquid composition X and the liquid composition Y is excellent in porosity, the reduction in the function of the insulating layer (i.e., the separator) is also suppressed.

[0221] The insulating layer is a component that separates the positive electrode from the negative electrode and ensures ion conductivity between the positive electrode and the negative electrode. In addition, when the insulating layer is indicated in this application, it is not limited to a layered shape.

[0222] The liquid composition set of the present invention is applied to the insulating layer (first insulating layer) for storage elements or power generation elements, and an insulating layer (second insulating layer) composed of a porous resin layer can be additionally formed. By forming the second insulating layer on the first insulating layer, the heat resistance, impact resistance, high temperature shrinkage resistance and other functions of the insulating layer as a whole can be increased or improved.

[0223] The electrode substrate is not particularly limited as long as it is a conductive substrate. Aluminum foil, copper foil, stainless steel foil, titanium foil, and electrode substrates with etched foils with micropores can be used. They can be appropriately used in secondary batteries and capacitors that are generally used as power storage devices. Among them, lithium-ion secondary batteries in particular can also use electrode substrates with holes for lithium-ion capacitors. In addition, carbon paper fiber electrodes used in power generation devices such as fuel cells can be used in a non-woven or woven plane, and electrode substrates with micropores in the above-mentioned holed electrode substrates can also be used. Furthermore, in the case of solar energy devices, in addition to the above-mentioned electrodes, electrode substrates with transparent semiconductor films such as indium / titanium oxides or zinc oxides formed on flat substrates such as glass or plastics, and electrode substrates formed by thinly evaporating conductive electrode films can also be used.

[0224] The active material layer is formed by dispersing a powdered active material and a catalyst composition in a liquid, applying and fixing the resulting liquid on an electrode substrate, and drying it. It is usually formed by printing using a spray, a dispenser, a die coating, or a pull coating, and then drying after coating.

[0225] There are no particular restrictions on the positive electrode active material as long as it is a material that can reversibly absorb and release alkali metal ions. As a typical example, a transition metal compound containing an alkali metal can be used as a positive electrode active material. For example, as a lithium-containing transition metal compound, a composite oxide containing at least one element selected from the group consisting of cobalt, manganese, nickel, chlorine, iron and vanadium and lithium can be listed. For example, lithium-containing transition metal oxides such as lithium cobalt oxide, lithium nickel oxide, and lithium manganese oxide, LiFePO 4 Olivine-type lithium salts such as lithium sulfide, chalcogen compounds such as titanium disulfide and molybdenum disulfide, manganese dioxide, etc. Lithium-containing transition metal oxides are metal oxides containing lithium and transition metals, or metal oxides in which a part of the transition metal in the metal oxide is replaced by a heterogeneous element. As heterogeneous elements, for example, Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, B, etc. can be listed, among which Mn, Al, Co, Ni and Mg are preferred. The heterogeneous elements can be used alone or in combination of two or more. These positive electrode active materials can be used alone or in combination of two or more. As the above-mentioned active materials used in nickel-hydrogen batteries, nickel hydroxide, etc. can be listed.

[0226] There are no particular restrictions on the negative electrode active material as long as it is a material that can reversibly absorb and release alkali metal ions. As a typical example, a carbon material containing graphite having a graphite-type crystal structure can be used as the negative electrode active material. As such a carbon material, natural graphite, spherical or fibrous artificial graphite, difficult-to-graphitize carbon (hard carbon), easy-to-graphitize carbon (soft carbon), etc. can be listed. As materials other than carbon materials, lithium titanate can be listed. In addition, from the perspective of improving the energy density of lithium-ion batteries, high-capacity materials such as silicon, tin, silicon alloys, tin alloys, silicon oxide, silicon nitride, tin oxide, etc. can also be appropriately used as negative electrode active materials.

[0227] As the above-mentioned active material in the nickel-hydrogen battery, as a hydrogen storage alloy, an AB2 series or A2B series hydrogen storage alloy is exemplified.

[0228] The binder of the positive electrode or the negative electrode may be PVDF, PTFE, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamide-imide, polyacrylonitrile, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polyhexyl acrylate, polymethacrylic acid, polymethyl methacrylate, polyethyl methacrylate, polyhexyl methacrylate, polyvinyl acetate, polyvinyl pyrrolidone, polyether, polyether sulfone, hexafluoropolypropylene, styrene butadiene rubber, carboxymethyl cellulose, etc. In addition, a copolymer 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 also be used. In addition, as the conductive agent contained in the electrode, graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, etc., conductive fibers such as carbon fibers or 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, organic conductive materials such as phenylene derivatives and graphene derivatives, etc. can be used.

[0229] The active material in the fuel cell is generally used as a catalyst for the cathode electrode or the anode electrode, and metal particles such as platinum, ruthenium, or platinum alloy are supported on a catalyst carrier such as carbon. In order to make the catalyst particles supported on the surface of the catalyst carrier, for example, the catalyst carrier is suspended in water, and the precursor of the catalyst particles (such as chloroplatinic acid, dinitrodiaminoplatinum, platinum chloride, platinous chloride, diacetylacetonate platinum, dichlorodiamineplatinum, dichlorotetraamineplatinum, platinous sulfate, ruthenic acid chloride, iridic acid chloride, rhodic acid chloride, ferrous chloride, cobalt chloride, chromium chloride, gold chloride, silver nitrate, rhodium nitrate, palladium chloride, nickel nitrate, ferric sulfate, cupric chloride, etc. containing alloy components, etc.) are added to dissolve it in the suspension, and alkali is added to generate a metal hydroxide, and at the same time, a catalyst carrier is obtained so that the metal hydroxide is supported on the surface of the catalyst carrier. The catalyst carrier is coated on the electrode substrate and reduced in a hydrogen atmosphere to obtain an electrode with catalyst particles (active material) coated on the surface.

[0230] In solar cells and other occasions, the active material can be SnO in addition to tungsten oxide powder and titanium oxide powder. 2 、ZnO、ZrO 2 , Nb 2 O 5 、CeO 2 、SiO 2 、Al 2 O 3The dye is carried on the semiconductor layer by an oxide semiconductor layer such as ruthenium-tri-type transition metal complex, ruthenium-bi-type transition metal complex, osmium-tri-type transition metal complex, osmium-bi-type transition metal complex, ruthenium-cis-dihydrate-bipyridine complex, phthalocyanine and porphyrin, organic-inorganic perovskite crystal compounds, etc.

[0231] Solvent X, solvent Y, and electrolyte for use in energy storage devices

[0232] When the porous resin formed by the liquid composition group is used as an insulating layer for an electric storage element, it is preferable that the solvent X and the solvent Y are also used as components contained in the electrolyte constituting the electric storage element. In other words, the electrolyte preferably contains a solution of the solvent X, the solvent Y, and the electrolyte described later. Not only for forming the porous resin, but also by selecting appropriate solvents X and Y as components contained in the electrolyte, the process of removing the solvent X and the solvent Y by a heating process after forming the porous resin and the process of impregnating the porous resin with another electrolyte can be omitted.

[0233] When the heating process can be omitted, damage to the porous resin and damage to components other than the porous resin (e.g., electrode substrate or active material layer) that may be caused by heating can be suppressed. In particular, by suppressing damage to the porous resin, short circuits of the storage element or uneven reactions when the storage element is driven can be suppressed, further improving the performance of the storage element.

[0234] In addition, when the step of removing solvent X and solvent Y by heating is performed, some solvent X and solvent Y may remain in the porous body. Such residual solvent X and solvent Y may generate gas due to an unexpected side reaction inside the storage element, thereby reducing the performance of the storage element. However, by selecting solvent X and solvent Y as components contained in the electrolyte (for example, making it difficult to reduce the performance of the storage element due to side reactions, etc.), the performance reduction can be suppressed.

[0235] When the porous resin is used as an insulating layer for a storage element, the solvent X and the solvent Y are preferably selected appropriately to suppress decomposition reaction or gas generation when the storage element is used (during charging and discharging). For example, propylene carbonate, ethyl methyl carbonate, dimethyl carbonate, ethylene carbonate, acetonitrile, γ-butyrolactone, sulfolane, dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, polyethylene glycol, alcohols, and mixtures thereof can be used. Among them, at least one selected from propylene carbonate, ethyl methyl carbonate, dimethyl carbonate, and ethylene carbonate is preferably used.

[0236] It is preferred that the boiling points of solvent X and solvent Y, which are removed by heating or the like after the porous resin is formed, be higher than those of solvent X and solvent Y, which are removed by heating or the like. Due to the high boiling point, the vaporization of solvent X and solvent Y during the production is suppressed, and the composition of the electrolyte is suppressed from changing from the initially assumed composition. Specifically, it is preferably 80°C or higher, more preferably 85°C or higher, and even more preferably 90°C or higher. The boiling point of propylene carbonate is 240°C, the boiling point of ethyl methyl carbonate is 107°C, the boiling point of dimethyl carbonate is 90°C, and the boiling point of ethylene carbonate is 244°C.

[0237] As described above, even when the functional solvent X and solvent Y are used as components contained in the electrolyte solution constituting the electric storage element, Figure 1 The porous resin production apparatus 100 in the embodiment preferably does not include the heat treatment unit 30 .

[0238] As described above, the electrolyte is a component used when the porous resin formed from the liquid composition group is used as an insulating layer for a storage element. Examples of the electrolyte include solid electrolytes that are soluble in solvent X and solvent Y and liquid electrolytes such as ionic liquids. By including an electrolyte in the liquid composition X or the liquid composition Y, the solvent X, solvent Y, and electrolyte that constitute the remaining components after the porous resin is formed can function as an electrolyte for the storage element. As a result, the step of removing the solvent X and the solvent Y by a heating step or the like after the porous resin is formed and the step of impregnating the porous resin with another electrolyte can be omitted.

[0239] When the heating process can be omitted, damage to the porous resin and damage to components other than the porous resin (e.g., electrode substrate or active material layer) that may be caused by heating can be suppressed. In particular, by suppressing damage to the porous resin, short circuits of the storage element or uneven reactions when the storage element is driven can be suppressed, further improving the performance of the storage element.

[0240] In addition, even if the step of removing solvent X and solvent Y by the heating step is performed, some solvent X and solvent Y may remain in the porous body. Such residual solvent X and solvent Y may generate gas due to an unexpected side reaction inside the storage element, thereby reducing the performance of the storage element. However, by selecting solvent X and solvent Y as components contained in the electrolyte (for example, making it difficult to reduce the performance of the storage element due to side reactions, etc.), the performance reduction can be suppressed.

[0241] As the solid electrolyte, there is no particular limitation as long as it can be dissolved in solvent X and solvent Y. For example, inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, acid supporting salts, and alkali supporting salts can be used. More specifically,

[0242] LiClO 4 ,LiBF 4 ,LiAsF 6 ,LiPF 6 ,LiCF 3 SO 3 ,LiCF 3 COO, KCl, NaClO 3 ,NaCl,NaBF 4 ,NaSCN,KBF 4 ,Mg(ClO 4 ),Mg(BF 4 ) 2 wait.

[0243] As the liquid electrolyte, various ionic liquids containing a cationic component and an anionic component can be cited. The ionic liquid is preferably a liquid that can maintain a liquid state in a wide temperature range including room temperature.

[0244] Examples of the cationic component include imidazole derivatives such as N,N-dimethylimidazolium salt, N,N-methylethylimidazolium salt, and N,N-methylpropylimidazolium salt; aromatic salts such as pyridinium derivatives such as N,N-dimethylpyridinium salt and N,N-methylpropylpyridinium salt; and aliphatic quaternary ammonium compounds such as tetraalkylammonium such as trimethylpropylammonium salt, trimethylhexylammonium salt, and triethylhexylammonium salt.

[0245] As the anion component, for example, from the viewpoint of stability in the atmosphere, a fluorine-containing compound is preferred, and examples thereof include BF 4 - CF 3 SO 3 - PF 4 - ,(CF 3 SO 2 ) 2 N - , B(CN 4 ) - wait.

[0246] The electrolyte content is not particularly limited and can be appropriately selected according to the purpose, but in the electrolyte, it is preferably 0.7 mol / L or more and 4.0 mol / L or less, more preferably 1.0 mol / L or more and 3.0 mol / L or less, and from the perspective of taking both the capacity and output of the storage element into consideration, it is more preferably 1.0 mol / L or more and 2.5 mol / L or less.

[0247] White ink use

[0248] The liquid composition of the present invention is whitened by removing solvent X and solvent Y after forming a porous resin, and therefore, for example, can be used as a liquid composition for imparting a white image to a recording medium. In the present application, the so-called liquid composition for imparting a white image is not particularly limited as long as it can form a white image, and the ink also includes substances other than white (for example, transparent substances or colors other than white). In addition, in the present application, the liquid composition for imparting a white image is also referred to as white ink.

[0249] As is known to all, white inks present white color by containing inorganic pigments such as titanium oxide as coloring materials. However, since the coloring material of such white inks is high in specific gravity, sedimentation is easily generated, and there is a problem of poor storage stability and discharge stability. In this regard, the white ink of the present invention can present white color even if it does not contain white coloring materials such as pigments or dyes, and thus can improve storage stability and discharge stability. The white ink of the present invention may contain white coloring materials, but preferably does not contain white coloring materials substantially. In the case of substantially not containing white coloring materials, the content of white coloring materials is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, further preferably 0.01% by mass or less, more preferably the detection limit or less, and particularly preferably does not contain white coloring materials relative to the mass of the white ink. In this way, since the white ink does not substantially contain white coloring materials, the white image formed by the white ink can be reduced, and for example, it can be suitably used as white ink for aircraft painting, white ink for automobile painting, etc.

[0250] In addition, it is well known that white ink contains a variety of polymerizable compounds, and these polymers will phase separate when hardened, resulting in white turbidity. However, such white ink appears white due to the phase separation between polymers, not the air layer, so there is a problem of poor whiteness. In this regard, when the liquid composition group of the present invention is used as a white ink, it appears white through the porous resin with pores that serve as an air layer, so it can exert a high whiteness. The so-called white is the color that is called "white" in social concepts. The whiteness can be measured by, for example, using a spectrophotometer such as X-Rite939 to measure the lightness (L * ) evaluation, for example, when 100% or more or a sufficient amount of coverage is applied to the surface of the recording medium, the brightness (L * ) and chromaticity (a * ,b * ) is preferably in the following range:

[0251] 70≤L * ≤100

[0252] -4.5≤a * ≤2

[0253] -6≤b * ≤2.5

[0254] In addition, since the white ink of the present invention forms a layer composed of a porous resin when applied to a recording medium, it can also be used as a primer ink that makes a base layer (base layer) that fixes other inks (inks containing colorants, etc.) applied thereafter.

[0255] In general, when a low-permeability substrate or non-permeability substrate such as coated paper, glass substrate, resin film substrate, or metal substrate is used as a recording medium, there is a problem that the fixability of the ink to the substrate is reduced. In this regard, when the white ink (underlying ink) of the present invention is used, since the white ink (underlying ink) has a high fixability to the low-permeability substrate or non-permeability substrate, the fixability of another ink applied later on the base layer can be improved. In addition, even if the other ink applied later (ink containing a colorant, etc.) is a permeable ink (water-based ink, etc.) that is difficult to use for a low-permeability substrate or a non-permeable substrate, the ink components can be diffused into the porous resin, so that the colorant is fixed on the surface of the porous resin.

[0256] In addition, since the white ink (base ink) forms a white receiving layer, the color or transparency of the recording medium can be concealed, so that the image density of other inks (ink containing color materials, etc.) applied later can be improved.

[0257] Three-dimensional modeling application

[0258] The liquid composition set of the present invention can form a porous resin layer having a layer thickness in the height direction, and therefore, by laminating the porous resin layer in multiple layers, a three-dimensional object can be formed. That is, the liquid composition set of the present invention can be used as a liquid composition set for forming a three-dimensional object. Generally speaking, in three-dimensional molding, the deformation of the three-dimensional object caused by hardening and shrinkage is a problem. In this regard, the liquid composition set of the present invention forms a porous body having a mesh structure with phase separation induced by polymerization, and therefore, the mesh structure relaxes the internal stress during polymerization, and suppresses the deformation of the object caused by hardening and shrinkage.

[0259] Secondly, use Figure 2 A modeling device and a modeling method for modeling a three-dimensional modeling object are described. Figure 2 This is a schematic diagram showing an example of a molding device using a material injection method. Figure 2 The molding device includes a discharge device (an example of a dispensing device) for discharging liquid composition X and liquid composition Y by inkjet method, and a curing device for irradiating the discharged liquid composition X with active energy rays to harden it, and the discharge by the discharge device and the curing by the curing device are repeated sequentially to shape a three-dimensional object. Figure 2 The modeling method implemented in the modeling device includes a discharge process (an example of a discharge process) of discharging a liquid composition X and a liquid composition Y by inkjet method, and a curing process of irradiating the discharged liquid composition X with active energy rays to harden it. By sequentially repeating the discharge process and the curing process, a three-dimensional modeling object is formed.

[0260] The molding device and molding method are described in detail. Figure 2 The modeling device 39 uses a head unit (movable in the AB direction) equipped with an inkjet head, discharges a first three-dimensional modeling composition from the modeling head unit 30, discharges a second three-dimensional modeling composition different in composition from the first three-dimensional modeling composition from the support head units 31 and 32, and stacks the three-dimensional modeling compositions while curing them in the adjacent ultraviolet irradiation devices 33 and 34. More specifically, for example, after the second three-dimensional modeling composition is discharged from the support head units 31 and 32 onto the modeling object support substrate 37, and is cured by irradiating it with active energy rays to form a first support layer having a storage portion, the first three-dimensional modeling composition is discharged from the modeling head unit 30 toward the storage portion, and is cured by irradiating it with active energy rays to form a first modeling object layer, so that the above process is consistent with the number of stacking layers, and the movable table 38 in the vertical direction is lowered while repeating the above process multiple times to stack the support layer and the modeling object layer to produce a three-dimensional modeling object 35. Then, the support stacking portion 36 is removed as needed. Figure 2In the embodiment, only one discharge head unit 30 for the molded object is provided, but two or more discharge head units may be provided.

[0261] Laminated body application

[0262] By applying the liquid composition group of the present invention to various objects such as substrates, porous resin layers can be laminated on various objects such as substrates. In other words, the liquid composition group of the present invention is preferably used as a liquid composition group for forming a laminate, which is used to form a laminate having an object such as a substrate and a porous resin layer formed on the object. Specifically, as described above, liquid composition groups for storage elements or power generation elements, liquid composition groups for white ink, and liquid composition groups for three-dimensional modeling can be cited. By applying the liquid composition group for storage elements or power generation elements to the active material layer, the porous resin layer as an insulating layer is laminated, by applying the liquid composition group for white ink to the recording medium, the porous resin layer as a white image is laminated, and by applying the liquid composition group for three-dimensional modeling to the porous resin layer after the curing process, the porous resin layer as the set layer of the three-dimensional modeling object is laminated. In general, when laminating an object such as a substrate, since there is an interface between the object and the layer, when the adhesion of the interface is weak, it is easy to cause peeling between the object and the layer. In particular, when layers are formed by polymerization reaction and laminated, the polymer is easily deformed during polymerization, which can easily cause the object and the layer to peel off. In this regard, when the liquid composition set of the present invention is used for laminated bodies, phase separation is initiated by polymerization to form a porous body with a mesh structure. Therefore, the internal stress during polymerization can be relaxed by the mesh structure, and the deformation of the molded object caused by hardening shrinkage can be suppressed. As a result, the peeling of the object and the layer can be suppressed, which is very suitable.

[0263] Purpose of carrier

[0264] When the liquid composition group of the present invention is mixed with a functional substance to form a porous resin, a carrier on which the functional substance is carried on the surface of the porous resin can be produced. In other words, the liquid composition group of the present invention can be used as a liquid composition group for forming a carrier for producing a carrier on which a functional substance is carried. Here, the surface of the porous resin includes not only the external surface of the porous resin but also the internal surface connected to the outside. In this way, the functional substance can be carried in the gap connected to the outside, and therefore, the surface area on which the functional substance can be carried increases.

[0265] When the liquid composition set for forming a carrier of the present invention is used, the pores or porosity can be changed by appropriately adjusting the content of the polymerizable compound X, 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 increased. In addition, since the liquid composition set for forming a carrier of the present invention can be developed using a variety of imparting methods, it can be imparted, for example, by inkjet, which can increase the degree of freedom in designing the shape of the carrier. Specifically, not only a flat surface but also a relatively curved surface can be uniformly formed, and the operation of cutting the carrier according to the shape of the object can be omitted. In addition, by ejecting droplets by inkjet to form droplets, and irradiating the flying droplets or independent droplets attached to the substrate with active energy rays, a carrier with a particle shape can also be formed.

[0266] Functional substances are substances that directly or indirectly exert a predetermined function, preferably substances whose function increases or improves as the area on which they are carried on the porous resin increases, and more preferably substances that can exert the function by placing the carried functional substance on the external surface and / or the internal surface connected to the outside (in other words, substances whose function is suppressed when located on the internal surface that is not connected to the outside). In addition, the functional substance may be a substance that is dispersed even if it is dissolved in the liquid composition X or the liquid composition Y, but a dispersed substance is preferred. As an example of a functional substance, there is no particular limitation, and photocatalysts, physiologically active substances, etc. can be listed.

[0267] Photocatalysts are substances that exhibit photocatalytic activity by irradiating light in a specific wavelength region (excitation light with energy above the band gap between the valence band and the conductive band of the photocatalyst). By exhibiting this photocatalytic activity, photocatalysts can exert various effects such as antibacterial action, deodorization, deodorization, and decomposition of harmful substances such as volatile organic compounds (VOCs).

[0268] Examples of the photocatalyst include anatase-type or rutile-type titanium (IV) oxide (TiO 2 ), tungsten(III) oxide (W 2 O 3 ), tungsten(IV) oxide (WO 2 ), tungsten oxide (VI) (WO 3 )、ZnO、Iron(III)Oxide(Fe 2 O 3 ), SrTiO 3 ), Bismuth(III) oxide (Bi 2 O 3 ), bismuth vanadate (BiVo 4 )、tin(II) oxide (SnO )、tin(IV) oxide (SnO 2), tin(VI) oxide (SnO 3 )、ZrO 2 ), cerium (II) oxide (CeO), cerium (IV) oxide (CeO 2 ), barium titanate (BaTiO 3 )、Indium(III) oxide 2 O 3 ), copper(I) oxide (Cu 2 O), copper (II) oxide (CuO), potassium tantalate (KTaO 3 ), potassium niobate (KNbO 3 ) and other metal oxides; metal sulfides such as cadmium sulfide (CdS), zinc sulfide (ZnS), indium sulfide (InS); cadmium selenate (CdSeO 4 ), metal selenides such as zinc selenide (ZnSe); metal nitrides such as gallium nitride (GaN), etc., preferably containing titanium (IV) oxide (TiO 2 ), tin(IV) oxide (SnO 2 ), tungsten(III) oxide (W 2 O 3 ), tungsten(IV) oxide (WO 2 ), tungsten oxide (VI) (WO 3 ), more preferably anatase titanium (IV) oxide (TiO 2 ).

[0269] Physiologically active substances are effective ingredients used to make organisms exert physiological effects. For example, low molecular weight compounds containing pharmaceutical compounds, food compounds, cosmetic compounds, etc. can be listed. In addition, high molecular weight compounds containing proteins such as antibodies and enzymes and biopolymers such as nucleic acids such as DNA and RNA can also be listed. In addition, the so-called "physiological effect" refers to the effect produced by the physiological activity of the physiologically active substance at the target site, for example, the change and influence of the amount and / or quality of the organism, tissue, cell, protein, DNA, RNA, etc. In addition, the so-called "physiological activity" refers to the physiologically active substance acting on the target site (for example, target tissue, etc.) to give changes and influences. As the target site, receptors such as those present on the cell surface or in the cell are preferred. At this time, the physiologically active substance transmits the signal to the cell through the physiological activity of binding to a specific receptor, and as a result, exerts a physiological effect. The physiologically active substance can be a substance that converts the enzyme in the organism into a mature form and binds to a specific receptor to exert a physiological effect. In this case, in this application, the substance before the conversion to the mature form is also included in the physiologically active substance. Physiologically active substances can be either substances produced by organisms (human beings or organisms other than humans) or artificially synthesized substances. When a liquid composition containing such a physiologically active substance is used to form a granular carrier, in order to exert the desired physiological effect, it can be used as particles for delivering the physiologically active substance to the target site, that is, particles for drug delivery systems (DDS), and sustained-release particles for long-term sustained release of drugs. In addition, when a liquid composition X or liquid composition Y containing a physiologically active substance is used to form a sheet carrier, it can be used as a sustained-release sheet for long-term sustained release of drugs.

[0270] Surface modification applications

[0271] The outer surface of the porous resin formed by the liquid composition group of the present invention forms fine concavoconvexities originating from the porosity, thereby controlling the wettability. Specifically, when the resin constituting the porous resin is hydrophilic, the outer surface of the porous resin can be given a hydrophilic function higher than the hydrophilicity of the planar surface formed by the resin. In addition, when the resin constituting the porous resin is water-repellent, the outer surface of the porous resin can be given a water-repellent function higher than the water-repellent of the planar surface formed by the resin. Therefore, for the surface of the object, by giving the surface modification liquid containing the liquid composition group of the present invention, a surface modification layer can be formed, thereby making it easy to change the wettability of the surface of the object.

[0272] In addition, when using the liquid composition set of the present invention, by appropriately adjusting the content of the polymerizable compound X, the content of the porogen, the irradiation conditions of the active energy ray, etc., the unevenness of the porous external surface (undulations derived from pores or porosity) can be changed, and the design freedom of the performance of the surface modification layer can be increased. In addition, the liquid composition set of the present invention can be developed by a variety of imparting methods, for example, by inkjet, which can increase the design freedom of the shape of the surface modification layer. Specifically, the surface modification layer can be uniformly formed not only on a flat surface but also on a curved surface.

[0273] Separation layer use or reaction layer use

[0274] When the porous resin formed by the liquid composition group of the present invention is capable of permeating fluids such as liquids or gases, the porous resin can be used as a flow path for the fluid. In cases where the porous resin can be used as a flow path for the fluid, the porous resin can be used as a separation layer for separating a specified substance from the fluid, as a reaction layer (microreactor) for providing a micro reaction field to the fluid, and the like. In other words, the liquid composition group of the present invention can be used as a liquid composition group for forming a separation layer or a liquid composition group for forming a reaction layer. The porous resin used for the above-mentioned purposes is preferably capable of uniformly and effectively permeating the fluid inside the porous resin. In this regard, the porosity of the porous resin formed by the liquid composition group of the present invention is formed due to phase separation, so the gaps are continuously connected and have a structure that allows uniform and effective permeation of the fluid.

[0275] The porous resin is not particularly limited to the case where a fluid such as a liquid or a gas can pass through it, but for example, the air permeability measured according to JIS P8117 is preferably 500 seconds / 100 mL or less, and more preferably 300 seconds / 100 mL or less. In this case, the air permeability is measured using, for example, a Gurley type meter (manufactured by Toyo Seiki Seisakusho).

[0276] The term "separation" means the ability to remove or concentrate a predetermined substance contained in a fluid mixture. In addition, "removal" is not limited to the case where the predetermined substance is completely removed from the fluid mixture, but may also be the case where a partial amount is removed.

[0277] The so-called "reaction field" refers to a place where a specified chemical reaction occurs when a specified substance contained in a fluid passes through.

[0278] When used for separation layer applications, the liquid composition X of the present invention preferably contains a polymerizable compound X having a functional group that can interact with a predetermined substance contained in the fluid. If a porous resin is formed using a liquid composition group containing the liquid composition X, a functional group that can interact with a predetermined substance can be provided on the surface (internal surface and external surface) of the porous resin, thereby effectively separating the predetermined substance. The polymerizable compound X having a functional group that can interact with a predetermined substance contained in the fluid can be a part of the polymerizable compound X contained in the liquid composition, or it can be all of it. In the present application, the so-called "functional group that can interact with a predetermined substance" includes the case where the functional group itself can interact with the predetermined substance, and also includes the case where the functional group can interact with the predetermined substance by additional graft polymerization.

[0279] When used for the reaction layer, the liquid composition X of the present invention preferably contains a polymerizable compound X having a functional group that provides a reaction field to the fluid. If a porous resin is formed using a liquid composition group containing the liquid composition X, the functional group that provides a reaction field to the fluid can be provided on the surface (internal surface and external surface) of the porous resin to effectively provide a reaction field. The polymerizable compound X having a functional group that provides a reaction field to the fluid can be a part of the polymerizable compound X contained in the liquid composition, or it can be all of it. In the present application, the so-called "functional group that provides a reaction field to the fluid" includes the case where the functional group itself can provide a reaction field, and also includes the case where the reaction field can be provided by additional graft polymerization.

[0280] The separation layer and the reaction layer are formed by, for example, filling the liquid composition X and the liquid composition Y into a container such as a glass tube that can form a fluid inlet and a fluid outlet, and hardening them. In addition, by printing the liquid composition X and the liquid composition Y relative to the substrate in an inkjet manner, a separation layer and a reaction layer having a flow path of a desired shape formed by a porous resin can also be produced (drawn). Since the flow path of the separation layer and the reaction layer can be printed, a separation layer and a reaction layer whose flow path can be appropriately changed can be provided according to the purpose.

[0281] In addition, when using the separation layer forming composition set and the reaction layer forming composition set of the present invention, the content of the polymerizable compound X, the content of the porogen, the irradiation conditions of the active energy rays, etc. can be appropriately adjusted to change the pores or porosity of the porous resin, thereby increasing the design freedom in terms of the performance of the separation layer and the reaction layer.

[0282] Example

[0283] A further understanding of the present disclosure may be obtained by reference to the specific examples provided below, which are provided for purposes of illustration only and are not intended to limit the present invention.

[0284] Calculation of Hansen Solubility Parameter C and Interaction Radius D of Polymeric Compounds

[0285] Follow the steps below to calculate the Hansen solubility parameter C and interaction radius D for the following two polymeric compounds.

[0286] -Polymerizable compound P1: tricyclodecane dimethanol diacrylate (manufactured by DAICEL-ALLNEX LTD.)

[0287] -Polymerizable compound P2: ε-caprolactone-modified tris-(2-acryloyloxyethyl)isocyanurate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0288] Preparation of composition for permeability measurement

[0289] First, a polymerizable compound for which the Hansen solubility parameter C and the interaction radius D are to be calculated and the following 21 evaluation solvents whose Hansen solubility parameters (HSP) are known are prepared, and the polymerizable compound, each evaluation solvent, and a polymerization initiator are mixed at the ratio shown below to prepare a transmittance measurement composition.

[0290] Composition ratio for transmittance measurement

[0291] Polymerizable compound for which Hansen solubility parameter C is to be obtained: 28.0 mass %

[0292] Hansen solubility parameter (HSP) known evaluation solvent: 70.0 mass%

[0293] Polymerization initiator (Irgacure 819, manufactured by BASF): 2.0 mass%

[0294] Evaluation solvent set (21 types)

[0295] Ethanol, 2-propanol, trimethylbenzene, dipropylene glycol monomethyl ether, N-methyl 2-pyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether, propylene carbonate, ethyl acetate, tetrahydrofuran, acetone, n-tetradecane, ethylene glycol, diethylene glycol monobutyl ether, diethylene glycol butyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, 2-ethylhexanol, diisobutyl ketone, benzyl alcohol, 1-bromonaphthalene.

[0296] Measurement of light transmittance (compatibility evaluation)

[0297] The prepared transmittance measurement composition is injected into a quartz container, and the transmittance of the transmittance measurement composition at a wavelength of 550nm (visible light) is measured while stirring at 300rpm using a stirrer. In the present invention, when the light transmittance is 30% or higher, it is judged that the polymerizable compound and the evaluation solvent are in a miscible state, and when it is less than 30%, it is judged that the polymerizable compound and the evaluation solvent are in a non-miscible state. The conditions for measuring light transmittance are as follows:

[0298] -Quartz container: Special micro container with screw cap (trade name: M25-UV-2)

[0299] - Transmittance measuring device: USB4000, manufactured by Ocean Optics.

[0300] -Stirring speed: 300rpm

[0301] -Measurement wavelength: 550nm

[0302] - Initial conditions: The transmittance of light with a wavelength of 550 nm was measured in the quartz container in the air state (transmittance: 100%).

[0303] Table 1 shows the results of the evaluation of the compatibility between the polymerizable compound and the evaluation solvent according to the following evaluation criteria.

[0304] Evaluation Benchmarks

[0305] a: The polymerizable compound and the evaluation solvent are miscible

[0306] b: The polymerizable compound and the evaluation solvent are not miscible

[0307] Table 1

[0308]

[0309] Calculation by Hansen's dissolving sphere method

[0310] In the compatibility evaluation, the Hansen solubility parameters (HSP) of the evaluation solvents showing compatibility and the Hansen solubility parameters (HSP) of the evaluation solvents not showing compatibility are plotted on the Hansen space. Based on the plotted Hansen solubility parameters (HSP) of each evaluation solvent, a virtual sphere (Hansen sphere) including the Hansen solubility parameters (HSP) of the evaluation solvent group showing compatibility and the Hansen solubility parameters (HSP) of the evaluation solvent group not showing compatibility is created on the Hansen space. The center of the Hansen sphere is calculated as the Hansen solubility parameter C, and the radius of the Hansen sphere is calculated as the interaction radius D.

[0311] Calculated Hansen solubility parameter C and interaction radius D

[0312] The calculated Hansen solubility parameter C and interaction radius D of the polymerizable compound are as follows:

[0313] -Polymerizable compound P1: Hansen solubility parameters C (17.21, 8.42, 7.98), interaction radius D (11.8).

[0314] -Polymerizable compound P2: Hansen solubility parameters C (18.51, 9.04, 4.75), interaction radius D (9.5).

[0315] Calculation of Hansen Solubility Parameter A and Interaction Radius B of Resins Formed by Polymerization of Polymerizable Compounds

[0316] Follow the steps below to calculate the Hansen solubility parameter A and interaction radius B in the resin formed by the polymerization of the following two polymerizable compounds.

[0317] Polymerizable compound P1: tricyclodecane dimethanol diacrylate (manufactured by DAICEL-ALLNEX LTD.)

[0318] Polymerizable compound P2: ε-caprolactone-modified tris-(2-acryloyloxyethyl)isocyanurate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0319] Preparation of haze measurement composition

[0320] First, a precursor (polymerizable compound) of a resin for which the Hansen solubility parameter A and the interaction radius B are to be calculated and the following 21 evaluation solvents whose Hansen solubility parameters (HSP) are known are prepared, and the polymerizable compound, each evaluation solvent, and a polymerization initiator are mixed in the ratio shown below to prepare a composition for haze measurement.

[0321] Haze measurement composition ratio

[0322] Precursor of the resin for which Hansen solubility parameter A is to be obtained (polymerizable compound): 28.0 mass %

[0323] Hansen solubility parameter (HSP) known evaluation solvent: 70.0 mass%

[0324] Polymerization initiator (Irgacure 819, manufactured by BASF): 2.0 mass%

[0325] Evaluation solvent set (21 types)

[0326] Ethanol, 2-propanol, trimethylbenzene, dipropylene glycol monomethyl ether, N-methyl 2-pyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether, propylene carbonate, ethyl acetate, tetrahydrofuran, acetone, n-tetradecane, ethylene glycol, diethylene glycol monobutyl ether, diethylene glycol butyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, 2-ethylhexanol, diisobutyl ketone, benzyl alcohol, 1-bromonaphthalene.

[0327] Manufacturing of haze measuring element

[0328] On an alkali-free glass substrate, resin particles are evenly dispersed on the substrate by spin coating to serve as a gap agent. Next, the substrate coated with the gap agent and the alkali-free glass substrate not coated with the gap agent are bonded together by sandwiching the surface coated with the gap agent. Next, the prepared haze measurement composition is filled between the bonded substrates using the capillary phenomenon to produce a "haze measurement element before UV irradiation". Next, the haze measurement element before UV irradiation is subjected to UV irradiation to cure the haze measurement composition. Finally, the "haze measurement element" is produced by encapsulating the surrounding of the substrate with a sealant. The conditions during production are as follows:

[0329] -Alkali-free glass substrate: manufactured by Nippon Electric Glass Co., Ltd., 40 mm, t=0.7 mm, OA-10G.

[0330] - Gap agent: Micro-fine resin particles MICROPEARL GS-L100, with an average particle size of 100 μm.

[0331] -Spin coating conditions: dispersion drop amount 150 μL, rotation speed 1000 rpm, rotation time 30 s.

[0332] -Amount of the filled haze measurement composition: 160 μL

[0333] -UV irradiation conditions: Use UV-LED as the light source, the wavelength of the light source is 365nm, the irradiation intensity is 30mW / cm2, and the irradiation time is 20s.

[0334] - Sealant: TB3035B (made by Three Bond)

[0335] Determination of haze value (compatibility evaluation)

[0336] The haze value (blurriness) is measured using the prepared haze measuring element before UV irradiation and the haze measuring element. The measured value of the haze measuring element before UV irradiation is used as a reference (haze value 0), and the increase rate of the measured value of the haze measuring element (haze value) relative to the measured value of the haze measuring element before UV irradiation is calculated. In this embodiment, when the increase rate of the haze value is 1.0% or more, it is judged that the resin and the evaluation solvent are in a non-miscible state, and when the increase rate of the haze value is less than 1.0%, it is judged that the resin and the evaluation solvent are miscible. The device used for measurement is as follows:

[0337] -Haze meter NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.

[0338] Table 2 shows the results of the evaluation of compatibility between the resin obtained by polymerizing the polymerizable compound and the evaluation solvent according to the following evaluation criteria.

[0339] Evaluation Benchmarks

[0340] a: The resin formed by the polymerization of the polymerizable compound is incompatible with the evaluation solvent

[0341] b: The resin formed by the polymerization of the polymerizable compound is miscible with the evaluation solvent

[0342] Table 2

[0343]

[0344] Calculation by Hansen's dissolving sphere method

[0345] In the measurement of haze value (haze) (compatibility evaluation), the Hansen solubility parameter (HSP) of the evaluation solvent showing compatibility and the Hansen solubility parameter (HSP) of the evaluation solvent not showing compatibility are plotted on the Hansen space. Based on the plotted Hansen solubility parameter (HSP) of each evaluation solvent, a virtual sphere (Hansen sphere) including the Hansen solubility parameter (HSP) of the evaluation solvent group showing compatibility and the Hansen solubility parameter (HSP) of the evaluation solvent group not showing compatibility is created on the Hansen space. The center of the Hansen sphere is calculated as the Hansen solubility parameter A, and the radius of the Hansen sphere is calculated as the interaction radius B.

[0346] Calculated Hansen solubility parameter A and interaction radius B

[0347] The calculated Hansen solubility parameter A and interaction radius B of the resin formed by polymerization of the polymerizable compound are as follows:

[0348] -The resin formed by the polymerization of polymerizable compound P1: Hansen solubility parameters A (20.02, 5.22, 6.15), interaction radius B (8.3).

[0349] -The resin formed by the polymerization of the polymerizable compound P2: Hansen solubility parameters A (19.89, 10.47, 7.32), interaction radius B (8.2).

[0350] Example 1

[0351] The materials were mixed in the following ratios to prepare liquid composition X and liquid composition Y. In this example, liquid composition Y, which is the liquid applied first, is also referred to as pre-coating liquid, and liquid composition X, which is the liquid applied later, is also referred to as post-coating liquid.

[0352] Liquid composition X (post-coating liquid)

[0353] -Polymerizable compound X (polymerizable compound P1): 28.0 mass %

[0354] -Solvent X (2-propanol): 70.0 mass%

[0355] -Polymerization initiator (Irgacure 819 (manufactured by BASF)): 2.0 mass%

[0356] Liquid composition Y (pre-coating liquid)

[0357] -Solvent Y (ethanol): 100.0 mass%

[0358] Next, a liquid composition Z containing 10.0 mass % of the liquid composition X and 90.0 mass % of the liquid composition Y is adjusted. When the polymerizable compound contained in the liquid composition Z is set to the polymerizable compound Z, and the solvent contained in the liquid composition Z is set to the solvent Z, the polymerizable compound Z is the polymerizable compound P1 (tricyclodecane dimethanol diacrylate), and the solvent Z is a mixed liquid of the solvent X (2-propanol) and the solvent Y (ethanol). Therefore, the Hansen solubility parameter C of the polymerizable compound Z is the same as the Hansen solubility parameter C of the polymerizable compound P1, and the interaction radius D of the polymerizable compound Z is the same as the interaction radius D of the polymerizable compound P1. The Hansen solubility parameter A of the resin Z is the same as the Hansen solubility parameter A of the resin polymerized by the polymerizable compound P1, and the interaction radius B of the resin Z is the same as the interaction radius B of the resin polymerized by the polymerizable compound P1. When the Hansen solubility parameter of the solvent X is expressed as HSP X , the Hansen solubility parameter of solvent Y is expressed as HSP Y When the Hansen solubility parameter of solvent Z is expressed as HSP Z .

[0359] HSP X =(δD X ,δP X ,δH X )

[0360] HSP Y =(δD Y ,δP Y ,δH Y )

[0361] HSP Z =0.1(δD X ,δP X ,δH X )+0.9(δD Y ,δP Y ,δH Y )

[0362] The relative energy difference (RED) calculated based on the following formula 2 from the Hansen solubility parameter C of the polymerizable compound Z, the interaction radius D of the polymerizable compound Z, and the Hansen solubility parameter of the solvent Z was 0.972.

[0363] Relative Energy Difference (RED) =

[0364] (Distance between the Hansen solubility parameter C of the polymerizable compound and the Hansen solubility parameter of the solvent) / "Interaction radius D of the polymerizable compound" (Formula 2)

[0365] The relative energy difference (RED) calculated based on the following formula 1 from the Hansen solubility parameter A of the resin Z, the interaction radius B of the resin Z, and the Hansen solubility parameter of the solvent Z was 1.905.

[0366] Relative Energy Difference (RED) =

[0367] (Distance between the Hansen solubility parameter A of the resin and the Hansen solubility parameter of the solvent) / "Interaction radius B of the resin" (Formula 1)

[0368] The viscosity of the liquid composition X and the liquid composition Y at 25° C. measured using a viscometer (device name: RE-550L, manufactured by Toki Sangyo Co., Ltd.) was 30.0 mPa·s or less.

[0369] Various Examples and Comparative Examples

[0370] In each of the Examples and Comparative Examples, liquid composition X and liquid composition Y were prepared in the same manner as in Example 1 except that the composition was changed according to Tables 3 and 4. In Tables 3 and 4, the unit of each numerical value of the composition is "mass %". In Tables 3 and 4, the relative energy difference (RED) calculated based on Formula 2 (expressed as "RED of polymerizable compound Z and solvent Z" in Tables 3 and 4) with respect to the liquid composition Z in Example 1, and the relative energy difference (RED) calculated based on Formula 1 (expressed as "RED of resin Z and solvent Z" in Tables 3 and 4) are also shown.

[0371] The viscosity at 25°C of the liquid compositions X and Y of Examples 1 to 11 was 30.0 MPa·s or less as measured using a viscometer (device name: RE-550L, manufactured by Toki Sangyo Co., Ltd.) except for the liquid composition Y of Example 7. The viscosity at 25°C of the liquid composition Y of Example 7 was 30.0 MPa·s or more and 100.0 MPa·s or less.

[0372] Table 3

[0373]

[0374] Table 4

[0375]

[0376] In Examples 1 to 11, the light transmittance and haze change rate of the liquid composition X were evaluated.

[0377] Light transmittance

[0378] In each of Examples and Comparative Examples, the light transmittance of the prepared liquid composition X was measured as follows.

[0379] First, the prepared liquid composition X is poured into a quartz container, and the transmittance of light (i.e., visible light) at a wavelength of 550 nm of the liquid composition X is measured while stirring at 300 rpm using a stirrer. In the examples and comparative examples, when the transmittance of light is 30% or more, it is judged that the polymerizable compound X and the porogen are in a miscible state, and when it is less than 30%, it is judged that the polymerizable compound X and the porogen are in a non-miscible state. The conditions for measuring the light transmittance are as follows:

[0380] -Quartz container: Special micro container with screw cap (trade name: M25-UV-2)

[0381] - Transmittance measuring device: USB4000, manufactured by Ocean Optics.

[0382] -Stirring speed: 300rpm

[0383] -Measurement wavelength: 550nm

[0384] - Initial conditions: The transmittance of light with a wavelength of 550 nm was measured in the quartz container in the air state (transmittance: 100%).

[0385] The measurement results of light transmittance are shown in Table 5 according to the following evaluation criteria.

[0386] Evaluation Benchmarks

[0387] a: The light transmittance is 30% or higher.

[0388] b: The light transmittance is less than 30%.

[0389] Haze change rate

[0390] In each of the Examples and Comparative Examples, a haze measurement cell was prepared using the liquid composition X, and the haze value was measured.

[0391] Preparation of haze measurement element

[0392] First, on an alkali-free glass substrate, resin particles are evenly dispersed on the substrate by spin coating to serve as a gap agent. Next, the substrate coated with the gap agent and the alkali-free glass substrate not coated with the gap agent are bonded to each other by sandwiching the surface coated with the gap agent. Next, the prepared liquid composition X is filled between the bonded substrates using the capillary phenomenon to produce an "element for measuring haze before UV irradiation". Next, the element for measuring haze before UV irradiation is subjected to UV irradiation to cure the liquid composition X. Finally, the "element for measuring haze" is produced by encapsulating the surrounding of the substrate with a sealant. The conditions during production are as follows:

[0393] -Alkali-free glass substrate: manufactured by Nippon Electric Glass Co., Ltd., 40 mm, t=0.7 mm, OA-10G.

[0394] - Gap agent: Micro-fine resin particles MICROPEARL GS-L100, with an average particle size of 100 μm.

[0395] -Spin coating conditions: dispersion drop amount 150 μL, rotation speed 1000 rpm, rotation time 30 s.

[0396] -Filled liquid composition X amount: 160 μL

[0397] -UV irradiation conditions: Use UV-LED as the light source, the wavelength of the light source is 365nm, the irradiation intensity is 30mW / cm2, and the irradiation time is 20s.

[0398] - Sealant: TB3035B (made by Three Bond)

[0399] Determination of haze value

[0400] Next, the haze value (ambiguity) is measured using the prepared haze measuring element before UV irradiation and the haze measuring element. The measured value of the haze measuring element before UV irradiation is used as a reference (haze value 0), and the increase rate of the measured value of the haze measuring element (haze value) relative to the measured value of the haze measuring element before UV irradiation is calculated. In the examples and comparative examples, when the increase rate of the haze value is 1.0% or more, it is judged that the resin X and the porogen are incompatible, and when the increase rate of the haze value is less than 1.0%, it is judged that the resin X and the porogen are compatible. The device used for measurement is as follows:

[0401] -Haze meter NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.

[0402] Table 5 shows the measurement results of the haze increase rate according to the following evaluation criteria.

[0403] Evaluation Benchmarks

[0404] a: The rate of increase in haze value is 1.0% or more.

[0405] b: The rate of increase in haze value is less than 1.0%.

[0406] Table 5

[0407]

[0408] As can be seen from Table 5, the light transmittance of the liquid compositions X of Examples 1 to 11 is 30% or more, and the haze increase rate is 1.0% or more. Under these conditions, the liquid compositions X of Examples 1 to 11 can form porous resins alone.

[0409] In each of the Examples and Comparative Examples, the liquid composition Z was evaluated for light transmittance and haze change rate.

[0410] In each of the Examples and Comparative Examples, the porosity (porous property) of the resin formed in the contact region between the liquid composition X and the liquid composition Y of the liquid composition set (ie, near the interface between the liquid composition X and the liquid composition Y) was evaluated.

[0411] Light transmittance

[0412] In each of Examples and Comparative Examples, the light transmittance of the prepared liquid composition Z was measured as described below.

[0413] First, the prepared liquid composition Z is injected into a quartz container, and the transmittance of light (i.e., visible light) at a wavelength of 550 nm of the liquid composition Z is measured while stirring at 300 rpm using a stirrer. In the embodiments and comparative examples, when the transmittance of light is 30% or higher, it is judged that the polymerizable compound Z and the solvent Z are in a miscible state, and when it is less than 30%, it is judged that the polymerizable compound Z and the solvent Z are in a non-miscible state. The conditions for measuring the light transmittance are as follows:

[0414] -Quartz container: Special micro container with screw cap (trade name: M25-UV-2)

[0415] - Transmittance measuring device: USB4000, manufactured by Ocean Optics.

[0416] -Stirring speed: 300rpm

[0417] -Measurement wavelength: 550nm

[0418] - Initial conditions: The transmittance of light with a wavelength of 550 nm was measured in the quartz container in the air state (transmittance: 100%).

[0419] The measurement results of light transmittance are shown in Table 6 according to the following evaluation criteria.

[0420] Evaluation Benchmarks

[0421] a: The light transmittance is 30% or higher.

[0422] b: The light transmittance is less than 30%.

[0423] Haze change rate

[0424] In each of the Examples and Comparative Examples, a haze measurement cell was prepared using the liquid composition Z, and the haze value was measured.

[0425] Preparation of haze measurement element

[0426] First, on an alkali-free glass substrate, resin particles are evenly dispersed on the substrate by spin coating to serve as a gap agent. Next, the substrate coated with the gap agent and the alkali-free glass substrate not coated with the gap agent are bonded to each other by clamping the surface coated with the gap agent. Next, the prepared liquid composition Z is filled between the bonded substrates using the capillary phenomenon to produce an "element for measuring haze before UV irradiation". Next, the element for measuring haze before UV irradiation is subjected to UV irradiation to cure the liquid composition Z. Finally, the "element for measuring haze" is produced by encapsulating the surrounding of the substrate with a sealant. The conditions for production are as follows:

[0427] -Alkali-free glass substrate: manufactured by Nippon Electric Glass Co., Ltd., 40 mm, t=0.7 mm, OA-10G.

[0428] - Gap agent: Micro-fine resin particles MICROPEARL GS-L100, with an average particle size of 100 μm.

[0429] -Spin coating conditions: dispersion drop amount 150 μL, rotation speed 1000 rpm, rotation time 30 s.

[0430] -Filled liquid composition Z volume: 160 μL

[0431] -UV irradiation conditions: Use UV-LED as the light source, the wavelength of the light source is 365nm, the irradiation intensity is 30mW / cm2, and the irradiation time is 20s.

[0432] - Sealant: TB3035B (made by Three Bond)

[0433] Determination of haze value

[0434] Next, the haze value (blurriness) is measured using the prepared haze measuring element before UV irradiation and the haze measuring element. The measured value of the haze measuring element before UV irradiation is used as a reference (haze value 0), and the increase rate of the measured value of the haze measuring element (haze value) relative to the measured value of the haze measuring element before UV irradiation is calculated. In the embodiments and comparative examples, when the increase rate of the haze value is 1.0% or more, it is judged that the resin Z and the solvent Z are in a state of non-miscible, and when the increase rate of the haze value is less than 1.0%, it is judged that the resin Z and the solvent Z are in a state of miscible. The device used for measurement is as follows:

[0435] -Haze meter NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.

[0436] The results of the haze increase rate measurements based on the following evaluation criteria are shown in Table 6. Liquid composition Z whose components were judged to be incompatible in the evaluation of light transmittance was not evaluated and is indicated in Table 6 by "-".

[0437] Evaluation Benchmarks

[0438] a: The rate of increase in haze value is 1.0% or more.

[0439] b: The rate of increase in haze value is less than 1.0%.

[0440] The porosity of the resin formed in the contact area

[0441] First, in each of the Examples and Comparative Examples, a porous resin was formed using a liquid composition set (i.e., liquid composition X and liquid composition Y). Specifically, 5 mL of liquid composition Y was added to a glass dish having a diameter of 5 cm, 20 μL of liquid composition X was dripped onto liquid composition Y, and then a porous resin was formed using a liquid composition set (i.e., liquid composition X and liquid composition Y). 2 The cured product was irradiated with ultraviolet light in an atmosphere to produce a cured product. The cured product was held with tweezers and placed on a substrate so that the surface of the cured product on the contact area side was facing upward, and heated at 100°C for 1 minute using a hot plate to remove solvent X and solvent Y to form a porous resin. The UV irradiation conditions were as follows.

[0442] -Light source: UV-LED (FJ800, manufactured by Phoseon Technology)

[0443] -Light source wavelength: 365nm

[0444] - Irradiation intensity: 30mW / cm 2

[0445] - Irradiation time: 20s

[0446] -UV irradiation measurement instrument: UV integrated light meter UIT-250, manufactured by Ushio Electric Co., Ltd.

[0447] Then, the surface of the porous resin on the contact region side was observed by SEM. The porosity of the resin formed in the contact region according to the following evaluation criteria is shown in Table 6. For the liquid composition group that was judged as incompatible with the components in the liquid composition Z in the above-mentioned transmittance evaluation, no evaluation was performed and it was indicated by "-" in Table 6.

[0448] Evaluation Benchmarks

[0449] a: Pores having a pore diameter of 0.01 μm or more and 10 μm or less were observed.

[0450] b: No pores having a pore diameter of 0.01 μm or more and 10 μm or less were observed.

[0451] The porous resins produced using the liquid composition groups of Examples 1 to 11 according to the evaluation in the above "Porosity of the resin formed in the contact area" all have a porosity of 30.0% or more and a co-continuous structure in which multiple pores in the resin are continuously connected to each other.

[0452] Table 6

[0453]

[0454] From the results of Table 3, Table 4 and Table 6, it can be seen that when the relative energy difference (RED) calculated by Formula 2 is 1.05 or less, the compatibility between the polymerizable compound Z and the solvent Z in the liquid composition Z is high. In addition, this result shows that when the relative energy difference (RED) calculated based on Formula 1 is 1.00 or more, the compatibility between the resin Z and the solvent Z in the liquid composition Z is low.

[0455] This indicates that by using a liquid composition set containing the liquid composition X and the liquid composition Y in an appropriate combination, even in a contact region where the liquid composition X and the liquid composition Y come into contact, a resin having excellent porosity is formed in the contact region.

[0456] Preparation of electric storage element using liquid composition set

[0457] Preparation of negative electrode

[0458] 97.0 parts by mass of graphite particles (average particle size 10 μm) as negative electrode active material, 1.0 parts by mass of cellulose as thickener, and 2.0 parts by mass of acrylic resin as binder were uniformly dispersed in water to prepare a negative electrode active material dispersion. The dispersion was applied to a copper foil with a thickness of 8 μm as a negative electrode substrate, and the obtained coating was dried at 120°C for 10 minutes and then pressed to form an electrode composite material part with a thickness of 60 μm. The electrode composite material part was cut into sheets of 50 mm × 33 mm to prepare a negative electrode.

[0459] Preparation of positive electrode

[0460] 94.0 parts by mass of mixed particles of nickel, cobalt and aluminum as positive electrode active materials, 3.0 parts by mass of Ketjen black as a conductive aid, and 3.0 parts by mass of polyvinylidene fluoride resin as a binder were uniformly dispersed in N-methylpyrrolidone as a solvent to prepare a positive electrode active material dispersion. The dispersion was coated on a 15 μm thick aluminum foil as an electrode substrate, and the coating was dried at 120°C for 10 minutes and then pressed to form an electrode composite material part with a thickness of 50 μm. The electrode composite material part was cut into a sheet of 43 mm × 29 mm to prepare a positive electrode.

[0461] Preparation of spacers

[0462] The liquid composition X and the liquid composition Y contained in the liquid composition set of Example 1 were installed in an inkjet discharge device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). The liquid composition Y was discharged onto the negative electrode prepared above to form a solid image-like coating area. Immediately thereafter, the liquid composition X was discharged to form a solid image-like coating area so as to overlap with the above-formed coating area on the negative electrode. Immediately thereafter, the liquid composition X was discharged to form a solid image-like coating area so as to overlap with the above-formed coating area on the negative electrode. 2In the atmosphere, UV (light source: UV-LED (FJ800, manufactured by Phoseon Technology), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 The coated area was irradiated with 1% 20% ion (irradiation time: 20 s) to cure. Then, the cured product was heated at 120° C. for 1 minute using a hot plate to remove solvent X and solvent Y, thereby obtaining a negative electrode integrated with the porous resin and functioning as a separator.

[0463] Preparation of energy storage elements

[0464] Next, the negative electrode integrated with the porous resin and the positive electrode prepared above are placed opposite to each other, an electrolyte is injected, and a laminated outer packaging material is used as an outer packaging to seal the storage element. As the electrolyte, the following solution is used: for a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) (a mixture with a mass ratio of "EC:DMC = 1:1"), LiPF is added as an electrolyte 6 , so that the concentration becomes 1.5 mol / L.

[0465] The above embodiments are illustrative and do not limit the present invention. Therefore, according to the above teachings, many other modifications and variations are possible. For example, the elements and / or features of different illustrative embodiments can be combined with each other and / or replace each other within the scope of the present invention.

[0466] This application is based on and claims the benefit of priority of Japanese Patent Application No. 2020-197906 filed in the Japan Patent Office on November 30, 2020, and the entire disclosure of which is incorporated herein by reference.

[0467] Reference numerals list

[0468] 1a Printing device

[0469] 1b Storage container

[0470] 1c Supply pipe

[0471] 2a Light irradiator

[0472] 2b Polymerization inert gas circulator

[0473] 3a Heater

[0474] 4. Printing substrate

[0475] 5 conveyor unit

[0476] 6Porous resin precursor

[0477] 7 Liquid Composition

[0478] 10 Printing Processing Units

[0479] 20 Aggregation Processing Units

[0480] 30 Heating treatment units

Claims

1. A liquid composition group, comprising: Liquid composition X containing a polymerizable compound X and a solvent X, wherein the polymerizable compound X has a (meth)acryloyl group and is a polymerizable compound capable of polymerizing by active energy; and Liquid composition Y containing a solvent Y, wherein, The liquid composition X is used to form a porous resin, wherein the liquid composition Y is applied to a porous substrate, and the liquid composition X is applied to an area where the liquid composition Y has been applied to inhibit the penetration of the liquid composition X into the porous substrate, wherein, a liquid composition Z containing 10.0% by mass of the liquid composition X and 90.0% by mass of the liquid composition Y has a light transmittance of 30% or higher at a wavelength of 550 nm, and the light transmittance is measured while stirring the liquid composition Z, wherein, a haze measurement element prepared from the liquid composition Z has a haze increase rate of 1.0% or higher, wherein the solvent X is a liquid that is compatible with the polymerizable compound X but is not compatible with the resin X during the polymerization of the polymerizable compound X to form resin X in the liquid composition X, and wherein the liquid composition Y does not contain a polymerizable compound.

2. The liquid composition group according to claim 1, wherein, While stirring the liquid composition X, the light transmittance of the liquid composition X at a wavelength of 550 nm is measured to be 30% or higher, The haze increase rate of a haze measurement element manufactured from the liquid composition X is 1.0% or higher.

3. The liquid composition group according to claim 1 or 2, wherein, The polymerizable compound Z polymerizes to form resin Z, and the relative energy difference (RED) of the resin Z is 1.00 or higher, wherein, the relative energy difference of the resin Z is calculated by the following formula (1): Relative energy difference (RED)= ("The Hansen solubility parameter A of resin Z" - "The Hansen solubility parameter of solvent Z") / "The interaction radius B of resin Z" Formula (1) wherein the solvent Z is contained in the liquid composition Z and contains the solvent X and the solvent Y.

4. The liquid composition group according to any one of claims 1 to 2, wherein the liquid composition Z contains a polymerizable compound Z, the polymerizable compound Z contains the polymerizable compound X, and the relative energy difference (RED) of the polymerizable compound Z is 1.05 or lower, wherein, The relative energy difference of the polymerizable compound Z is calculated by the following formula (2): Relative energy difference (RED)= ("The Hansen solubility parameter C of polymerizable compound Z" - "The Hansen solubility parameter of solvent Z") / "The interaction radius D of polymerizable compound Z" Formula (2) wherein the solvent Z is contained in the liquid composition Z and contains the solvent X and the solvent Y.

5. The liquid composition group according to any one of claims 1 to 2, wherein, The polymeric compound X accounts for 10.0 to 50.0% by mass of the liquid composition X, and the solvent X accounts for 50.0 to 90.0% by mass of the liquid composition X.

6. The liquid composition group according to any one of claims 1 to 2, wherein, the liquid composition X and the liquid composition Y each independently have a viscosity of 1.0 to 150.0 mPa·s at 25°C.

7. The liquid composition group according to any one of claims 1 to 2, wherein, the porous resin has pores with a pore diameter of 0.01 to 10 µm.

8. The liquid composition group according to any one of claims 1 to 2, wherein, the porous resin has a porosity of 30% or higher.

9. The liquid composition group according to any one of claims 1 to 2, wherein, the porous resin has a co-continuous structure formed by continuously connecting a plurality of pores.

10. A method for manufacturing a porous resin, comprising: applying the liquid composition Y; applying the liquid composition X to the region where the liquid composition Y has been applied; and curing the applied liquid composition X, wherein, the liquid composition Z containing 10.0% by mass of the liquid composition X and 90.0% by mass of the liquid composition Y has a light transmittance of 30% or higher at a wavelength of 550 nm, and the light transmittance is measured while stirring the liquid composition Z, wherein the haze measurement element prepared from the liquid composition Z has a haze increase rate of 1.0% or higher, wherein, when applying the liquid composition Y, the liquid composition Y is applied to the porous substrate to inhibit the penetration of the liquid composition X into the porous substrate, wherein the liquid composition X contains a polymeric compound X and a solvent X, wherein the polymeric compound X has a (meth)acryloyl group or a vinyl group, and the solvent X is a liquid that is compatible with the polymeric compound X but is not compatible with the resin X during the polymerization of the polymeric compound X to form the resin X in the liquid composition X, wherein the liquid composition Y does not contain a polymeric compound, and wherein the porous substrate includes an active material layer, and the active material layer is an active material layer for an electricity storage element or a power generation element.

11. The method for manufacturing a porous resin according to claim 10, wherein the liquid composition Y contains a solvent Y, wherein the liquid composition Z contains a polymeric compound Z, the polymeric compound Z contains the polymeric compound X, and the relative energy difference (RED) of the polymeric compound Z is 1.05 or lower, wherein, the relative energy difference of the polymeric compound Z is calculated by the following formula (2): Relative energy difference (RED) = ("Distance between the Hansen solubility parameter C of the polymeric compound Z" and "Hansen solubility parameter of the solvent Z") / "Interaction radius D of the polymeric compound Z" Formula (2); and wherein the polymeric compound Z polymerizes to form the resin Z, and the relative energy difference (RED) of the resin Z is 1.00 or higher, Among them, the relative energy difference of the resin Z is calculated by the following formula (1): Relative Energy Difference (RED) = ("Distance between the Hansen solubility parameter A of resin Z" and "Hansen solubility parameter of solvent Z") / "Interaction radius B of resin Z" Formula (1) Wherein the solvent Z is contained in the liquid composition Z and contains the solvent X and the solvent Y.

12. The method for manufacturing a porous resin according to any one of claims 10 to 11, wherein, When applying the liquid composition X, the liquid composition X is applied by an inkjet method.

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