Humidifying element and humidifier

Abstract

The invention provides a humidifying element capable of improving humidifying performance. A humidifying element (1) is provided with: a laminate (10) having a porous reinforcing material (11) and a moisture-permeable film (12) laminated on at least one surface (11a) of the porous reinforcing material (11); and a frame (30), in which the laminated body (10) is disposed on the air path side with respect to the frame (30). Furthermore, the laminated body (10) preferably forms a bag-shaped water-holding container so as to cover the air path side of the frame (30), and in the laminated body (10), preferably, the moisture-permeable film (12) is disposed on the frame (30) side with respect to the porous reinforcing material (11).

Description

Technical Field

[0001] The present disclosure relates to a humidifying element and a humidifier. In addition, the present application claims priority based on Japanese Patent Application No. 2022-096880 filed in Japan on June 15, 2022 and Japanese Patent Application No. 2023-090139 filed in Japan on May 31, 2023, and cites the contents thereof. Background Art

[0002] Compared with conventional humidifiers using evaporation plates, moisture permeable membrane humidifiers have higher humidification performance and can perform clean humidification by suppressing the scattering of impurities. On the other hand, in order to exert moisture permeability, special shapes and materials are required, which becomes a cost issue. In addition, due to deformation and damage of the moisture permeable membrane and adhesion / accumulation of scale components, the function is reduced, and there are problems in long-term reliability. Therefore, improvements have been repeatedly made to maintain long-term humidification performance and reduce costs.

[0003] For example, Patent Document 1 discloses a humidifying element that uses a structure on a thin plate bonded to the outside of a thin bag-shaped moisture-permeable membrane. This prevents the moisture-permeable membrane from expanding and does not require other components. The humidifying element is easily reused, thereby reducing costs and providing long-term and stable moisture-permeable performance.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2003-97831 Summary of the invention

[0007] Problems to be solved by the invention

[0008] However, in Patent Document 1, a bag-shaped moisture-permeable film is bonded to the inner side of a component on a thin plate and used. The outlet of water vapor is blocked on the bonding surface of the component on the thin plate, so that the area where water vapor is generated is limited to the hole portion of the component on the thin plate, resulting in a problem that the moisture-permeable performance cannot be fully utilized.

[0009] In addition, as described above, since the moisture permeable membrane cannot fully exert its moisture permeability, in order to exert sufficient humidification performance, a humidifying element with an area larger than the moisture permeable membrane must be used, which has the disadvantage of requiring the humidifier to be larger. Moreover, if the humidifier is larger, there is also the problem of increased cost.

[0010] Therefore, an object of the present disclosure is to provide a humidifying element having excellent humidification performance.

[0011] Solutions for solving problems

[0012] The present inventors have conducted in-depth research to solve the above problems, and found that the following humidifying element can solve the problems of the present disclosure, wherein the humidifying element comprises: a laminate having a porous reinforcing material and a moisture-permeable membrane laminated on at least one surface of the porous reinforcing material; and a frame, wherein the laminate is arranged on the air path side relative to the frame. The present disclosure relates to a substance completed based on these insights.

[0013] That is, the present disclosure provides a humidifying element including: a laminate having a porous reinforcing material and a moisture-permeable membrane laminated on at least one surface of the porous reinforcing material; and a frame, wherein the laminate is arranged on an air passage side with respect to the frame.

[0014] The humidifying element arranges the stack on the air path side of the frame. Even if the area of ​​the stack that can absorb liquid water in the form of water vapor is only a part of the stack, the water vapor will diffuse to the entire stack, and a wide area of ​​the surface on the air path side of the stack can be used as a water vapor volatilization surface, thereby increasing the effective area of ​​the moisture permeable membrane of the stack and exerting high moisture permeability.

[0015] The humidifying element is preferably formed as a bag-shaped water-retaining container in which the stack covers the air passage side of the frame.

[0016] In the laminated body, the moisture permeable film is preferably arranged on the frame side relative to the porous reinforcing material. With the above structure, adhesion and accumulation of scale components can be suppressed, so that the moisture permeability performance can be easily exhibited for a long time.

[0017] Furthermore, the moisture permeable film is preferably a nonporous film. When the moisture permeable film is a nonporous film, it is easy to suppress the scattering of impurities.

[0018] Preferably, the non-porous film contains a thermoplastic resin having a cationic portion, wherein the cationic portion contains a group containing an ammonium ion or a group capable of forming an ammonium ion. By containing a group containing an ammonium ion or a group capable of forming an ammonium ion, the non-porous film can exert a bactericidal effect, thereby inhibiting the attachment / accumulation of miscellaneous bacteria and the like.

[0019] Preferably, the nonporous film contains a thermoplastic resin having a hydrophilic portion, wherein the hydrophilic portion contains a structural unit represented by the following formula (1). The nonporous film can form a water-conducting path in the moisture-permeable film due to the hydrophilic portion having the structural unit, thereby easily exhibiting moisture permeability.

[0020] [Chemical formula 1]

[0021]

[0022] (R1 and R2 each independently represent a hydrogen atom or a methyl group.)

[0023] In addition, it is preferred that the nonporous membrane contains a thermoplastic resin having a hydrophobic portion, wherein the hydrophobic portion contains a structural unit represented by the following formula (2) and / or the following formula (3). By making the nonporous membrane have the hydrophobic portion of the structural unit, the surface of the nonporous membrane can exhibit hydrophobicity.

[0024] [Chemical formula 2]

[0025]

[0026] (R1 represents a hydrogen atom or a methyl group, and R3 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.)

[0027] [Chemical formula 3]

[0028]

[0029] (R1 represents a hydrogen atom or a methyl group, and R4 represents a branched alkyl group having 3 or more carbon atoms.)

[0030] Furthermore, the moisture-permeable film is preferably a hydrophilic porous film.

[0031] It is preferred that the porous film and the porous reinforcing material have different thicknesses.

[0032] In the humidifying element, it is preferred that the stacked body and the frame be bonded together by adhesion or welding.

[0033] Furthermore, in the humidifying element, it is preferable that the stacked body and the frame are bonded to each other with an adhesive.

[0034] The moisture-permeable film is preferably applied so as to cover at least one surface of the porous reinforcing material.

[0035] Furthermore, the present disclosure provides a humidifier equipped with the above-mentioned humidifying element.

[0036] Furthermore, the present disclosure provides an air conditioner equipped with the above-mentioned humidifier.

[0037] Furthermore, the present disclosure provides a ventilation device equipped with the above-mentioned humidifier.

[0038] In addition, the present disclosure provides an air purifier equipped with the above-mentioned humidifier.

[0039] Beneficial Effects

[0040] The humidifying element of the present disclosure can improve the humidification performance. Therefore, when used as a humidifier, the humidifying element of the present disclosure can be miniaturized and is preferably used as a moisture permeable membrane type humidifier. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1It is a cross-sectional schematic diagram showing one embodiment of the humidifying element of the present disclosure. DETAILED DESCRIPTION

[0042] [Humidification element]

[0043] The humidifying element of one embodiment of the present disclosure comprises at least: a laminate having a porous reinforcing material and a moisture permeable membrane provided on at least one surface of the porous reinforcing material; and a frame. In addition, the laminate is arranged on the air path side of the frame. In addition, in the present disclosure, the side of the humidifying element where water flows is referred to as the "water path side", and the side where air flows is referred to as the "air path side". In addition, the moisture permeable membrane can be provided on a single side of the porous reinforcing material, or on both sides.

[0044] In addition, a humidifying element according to another embodiment of the present disclosure comprises at least: a laminate having a porous reinforcing material and a moisture-permeable membrane provided on at least one surface of the porous reinforcing material; and a frame, wherein the laminate preferably forms a bag-shaped water-retaining container in a manner covering the frame.

[0045] In addition, it is preferred that a water supply port and a water discharge port are provided on the humidifying element. The water supply port and the water discharge port may be provided in advance when the frame is manufactured.

[0046] Figure 1 1 is a cross-sectional schematic diagram showing an embodiment of the humidifying element of the present disclosure. The humidifying element 1 comprises: a frame 30 and a laminate 10 attached to the air path side of the frame 30. The frame 30 has a hole 31 connected to the outside. The laminate 10 has a porous reinforcing material 11 and a moisture permeable membrane 12 provided on one surface 11a of the porous reinforcing material 11. The laminate 10 is attached via an adhesive 20 in a manner covering the hole 31 of the frame 30.

[0047] In the humidifying element, by arranging the stacked body on the air path side of the frame, even if the area where the moisture permeable film is in contact with the water path side, that is, the area that can absorb liquid water in the form of water vapor from the hole portion of the frame, is only a part of the moisture permeable film, water vapor can diffuse into the stacked body. Therefore, a wide area of ​​the surface on the air path side of the stacked body can function as a water vapor volatilization surface, the effective area of ​​the moisture permeable film can be increased, and high moisture permeability can be exerted.

[0048] In addition, in the laminate, it is preferred that the moisture-permeable membrane is disposed on the frame side relative to the porous reinforcing material. Figure 1In the humidifying element 1 shown, the moisture permeable membrane 12 is attached to the frame 30 in a manner that blocks the hole 31 in a manner that is located on the frame 30 side relative to the porous reinforcing material 11, that is, on the opposite side of the porous reinforcing material 11. With the above structure, liquid water contacts the above moisture permeable membrane, and the adhesion / deposition of scale components can be suppressed, so that the moisture permeability performance can be easily exerted for a long time.

[0049] <frame>

[0050] The humidifying element is provided with the frame. The frame is preferably arranged on the water path side of the stack, and more preferably the stack can be bonded to form a bag-like shape. The frame may be, for example, a plate, a frame may be bent to form a bag-like structure, or two or more frames may be bonded to form a bag-like structure. That is, the stack may be arranged on both sides of a plate-like frame, or the stack may be arranged in a manner covering the air path side of the bag-like frame.

[0051] In addition, although there are no particular limitations on the outer shape of the frame, it is preferably a substantially rectangular parallelepiped shape from the viewpoint of efficiently arranging the humidifying element.

[0052] The frame is preferably made of a rigid material, for example, resins such as ABS, polyethylene, polypropylene, nylon, POM, PPS, polyvinyl chloride, propylene, polycarbonate, and metals / alloys such as aluminum, stainless steel, and titanium can be used.

[0053] In addition, the manufacturing method of the frame is not particularly limited. When the frame is made of resin, it is preferably made by extrusion molding or injection molding. In addition, the hole portion can be formed by punching the manufactured frame, or two or more frames can be used to form the hole portion, or a mold that pre-forms the hole portion can be used to make it.

[0054] <Laminate>

[0055] The humidifying element includes a laminate including a porous reinforcing material and a moisture-permeable membrane formed on at least one surface of the porous reinforcing material.

[0056] (moisture permeable film)

[0057] The above-mentioned moisture permeable film is a film that does not permeate liquid water but only permeates water vapor. The above-mentioned moisture permeable film can be a non-porous film or a porous film. It should be noted that in the present disclosure, a film that only confirms that the holes below 50nm formed in the above-mentioned moisture permeable film are formed by SEM observation is defined as a non-porous film. In addition, when a plurality of items exceeding 50nm can be confirmed, it is defined as a porous film.

[0058] In order to absorb moisture, the non-porous film preferably comprises a thermoplastic resin. The thermoplastic resin preferably has a hydrophilic portion. In addition, in order to impart hydrophobicity to the surface of the non-porous film and form a water-conducting passage in the non-porous film, it is preferred that a hydrophobic portion is provided in the thermoplastic resin. Therefore, the thermoplastic resin preferably has both a hydrophilic portion and a hydrophobic portion. It is inferred that: in the non-porous film, by forming a structure in which the hydrophilic portion is separated from the hydrophobic portion, the hydrophilic portion functions as a water-conducting passage, enabling more water vapor to pass through, and thus having better moisture permeability.

[0059] Examples of the thermoplastic resin include acrylic resins, cellulose resins, polyester resins such as polybutylene terephthalate, polyether resins, polyurethane resins, polyvinyl chloride resins, polyethylene, polystyrene resins, polyamide resins, polyacetal resins, polycarbonate resins, polyphenylene sulfide resins, polyetheretherketone, polyimide resins, polytetrafluoroethylene resins, polycaprolactone, and polylactic acid.

[0060] As described above, the thermoplastic resin preferably has a hydrophilic part and a hydrophobic part, and therefore is preferably a thermoplastic copolymer containing different monomer components.

[0061] The hydrophilic part is preferably composed of a monomer (a) (hereinafter referred to as monomer (a)) unit containing a hydrophilic functional group in a side chain in the structural unit of the copolymer. In addition, the hydrophobic part is preferably composed of a monomer (b) (hereinafter referred to as monomer (b)) unit containing a hydrophobic functional group in a side chain. In addition, the hydrophilic part and the hydrophobic part are preferably formed in the copolymer. In the non-porous film, the copolymer can maintain a core-shell structure in which the hydrophobic part is formed inside and the hydrophilic part is formed outside. In this case, the hydrophilic part and the hydrophobic part can be formed by the core and shell of two or more adjacent copolymers. In addition, the copolymer can also be a core-shell structure before the non-porous film is formed, and the core-shell structure is not maintained when the non-porous film is formed.

[0062] The copolymer preferably contains a structural unit derived from the monomer (a) as a part constituting the hydrophilic part. As the monomer (a), for example, there can be listed: a monomer containing a glycidyl group, a monomer containing a hydrolyzable silyl group, a monomer containing an acetoacetyl group, a monomer containing a hydroxyl group, a monomer containing a carboxyl group, methyl (meth)acrylate, and a monomer having a cationic functional group described later. Among them, preferably a monomer containing a carboxyl group, methyl (meth)acrylate, and a monomer having a cationic functional group described later. The monomer (a) can be used alone or in combination of two or more. It should be noted that "(meth)acrylic acid" in this specification means at least one of "acrylic acid" and "methacrylic acid".

[0063] As said glycidyl group-containing monomer, glycidyl (meth)acrylate, (meth)allyl glycidyl ether, etc. are mentioned, for example.

[0064] Examples of the hydrolyzable silyl group-containing monomer include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri(β-methoxyethoxy)silane, and vinyl methyl dimethoxysilane; and (meth) acryloxy silyl group-containing monomers such as γ-(meth)acryloxypropyl trimethoxysilane, γ-(meth)acryloxypropyl methyl dimethoxysilane, γ-(meth)acryloxypropyl triethoxysilane, and γ-(meth)acryloxypropyl methyl diethoxysilane.

[0065] Examples of the acetoacetyl group-containing monomer include allyl diacetoacetate, acetoacetoxyethyl (meth)acrylate, acetoacetoxyethyl crotonate, acetoacetoxypropyl (meth)acrylate, acetoacetoxypropyl crotonate, and 2-cyanoacetoacetoxyethyl (meth)acrylate.

[0066] Examples of the hydroxyl group-containing monomer include hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0067] Examples of the carboxyl group-containing monomer include acid anhydride monomers such as crotonic acid, maleic acid, and maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamide N-glycolic acid, cinnamic acid, and (meth)acrylic acid.

[0068] Furthermore, as the monomer (a), methyl (meth)acrylate and / or (meth)acrylic acid are particularly preferred. That is, the hydrophilic portion preferably includes a structural unit represented by the following formula (1).

[0069] [Chemical formula 1]

[0070]

[0071] (R1 and R2 each independently represent a hydrogen atom or a methyl group.)

[0072] The content of the monomer (a) is preferably 20 to 70 mol%, more preferably 30 to 70 mol%, and further preferably 40 to 60 mol% relative to the total monomer components constituting the copolymer. By adjusting the content of the monomer (a) within this range, a hydrophilic portion can be formed in the nonporous membrane to easily form a water-conducting path, and the moisture permeability is further improved.

[0073] The copolymer preferably contains a structural unit derived from the monomer (b) as a part constituting the hydrophobic portion. The monomer (b) is not particularly limited, but preferably contains a monomer having a hydrocarbon group with a carbon number of 2 or more, and more preferably, a (meth)acrylate having a hydrocarbon group with a carbon number of 2 or more can be cited. The monomer (b) can be used alone or in combination of two or more.

[0074] Examples of the hydrocarbon group having 2 or more carbon atoms include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded to each other.

[0075] Examples of the aliphatic hydrocarbon group include alkyl, alkenyl, and alkynyl. Examples of the alkyl group include straight or branched alkyl groups such as ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, isooctyl, decyl, dodecyl, and stearyl. Examples of the alkenyl group include straight or branched alkenyl groups such as vinyl, aryl, methallyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, and 5-hexenyl. Examples of the alkynyl group include straight or branched alkynyl groups such as ethynyl and propynyl.

[0076] Examples of the alicyclic hydrocarbon group include cycloalkyl groups having 3 to 12 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclododecyl; cycloalkenyl groups having 3 to 12 carbon atoms such as cyclohexenyl; and bridged hydrocarbon groups having 4 to 15 carbon atoms such as bicycloheptyl and bicycloheptenyl.

[0077] Examples of the aromatic hydrocarbon group include aryl groups having 6 to 14 carbon atoms (particularly aryl groups having 6 to 10 carbon atoms), such as phenyl and naphthyl.

[0078] The hydrocarbon group having 2 or more carbon atoms is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and more preferably a linear or branched alkyl group or an aromatic hydrocarbon group.

[0079] Specifically, the monomer (b) is preferably a monomer capable of forming a structural unit represented by the following formula (2) and / or the following formula (3). That is, the hydrophobic portion preferably includes a structural unit represented by the following formula (2) and / or the following formula (3).

[0080] [Chemical formula 2]

[0081]

[0082] (R1 represents a hydrogen atom or a methyl group, and R3 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.)

[0083] [Chemical formula 3]

[0084]

[0085] (R1 represents a hydrogen atom or a methyl group, and R4 represents a branched alkyl group having 3 or more carbon atoms.)

[0086] In the above formula (2), the bonding position of R3 may be any of the hydrocarbons constituting the benzene ring. Examples of monomers capable of forming the structural unit represented by the above formula (2) include styrene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, and the like.

[0087] Examples of the monomer capable of forming the structural unit represented by the formula (3) include isopropyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0088] The content of the monomer (b) is preferably 20 mol% to 70 mol%, more preferably 30 mol% to 70 mol%, and further preferably 40 mol% to 60 mol% relative to the total monomer components constituting the copolymer. By preparing the content of the monomer (b) within this range, water repellency can be exerted, and a water-conducting path can be easily formed by forming a hydrophobic portion in the non-porous film, and the moisture permeability is more excellent.

[0089] The above-mentioned thermoplastic resin preferably has a cationic part. In this case, the cationic part may be present in the above-mentioned hydrophilic part and / or the above-mentioned hydrophobic part, or may be present in other places. In addition, the above-mentioned thermoplastic resin preferably has a cationic part in the hydrophilic part. The above-mentioned cationic part is preferably a cationic functional group or a group that can generate a cationic functional group. The above-mentioned group that can generate a cationic functional group refers to a group that does not have a cationic functional group at the stage of the above-mentioned thermoplastic resin, but generates a cationic functional group at the stage of forming the above-mentioned non-porous membrane and when used. In addition, the above-mentioned cationic functional group may also be a zwitterionic functional group that has both cations and anions. Therefore, the above-mentioned thermoplastic resin may have an anionic part. In addition, the above-mentioned thermoplastic resin preferably does not have an anionic part.

[0090] As the above-mentioned cationic functional group, for example, a nitrogen-containing group can be listed. As the above-mentioned nitrogen-containing group, a group containing ammonium ions or a group capable of forming ammonium ions can be listed. Here, the above-mentioned group capable of forming ammonium ions refers to a group that is not ionized at the stage of the above-mentioned thermoplastic resin, and forms an ionized body at the stage of forming the above-mentioned non-porous membrane and when used. As the above-mentioned group containing ammonium ions and the group capable of generating ammonium ions, for example, cyclic groups containing nitrogen atoms such as primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium groups, imino groups (-NH- groups and =NH groups), amidine groups, imino groups, hydrazine groups, amide groups, imide groups, pyridyl groups, etc. can be listed. In addition, as the above-mentioned zwitterionic functional group, for example, a quaternary ammonium-containing group can be listed. As the above-mentioned quaternary ammonium-containing group, for example, a betaine group, a phosphorylcholine group, etc. can be listed. Among the above thermoplastic resins, from the viewpoint of exerting antibacterial properties and preventing bacteria from flying from the nonporous film, groups capable of generating ammonium ions after the nonporous film is formed are preferred, and groups capable of generating quaternary ammonium groups (quaternary ammonium groups, imide groups) are more preferred.

[0091] When the thermoplastic resin is the copolymer, the copolymer preferably contains a structural unit derived from a monomer having a cationic functional group in a side chain. Examples of the monomer having a cationic functional group include monomers having the nitrogen-containing group as a functional group. Examples of the monomer having the nitrogen-containing group as a functional group include amide group-containing monomers, amino group-containing monomers, and imide group-containing monomers. Examples of the amide group-containing monomer include: N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-dipropyl (meth)acrylamide, N,N-diisopropyl (meth)acrylamide, N,N-di(n-butyl) (meth)acrylamide, N,N-di(tert-butyl) (meth)acrylamide and the like N,N-dialkyl (meth)acrylamide; N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-butyl (meth)acrylamide, N-n-butyl (meth)acrylamide and the like N-alkyl (meth)acrylamide; N-vinylacetamide, N-(2-hydroxyethyl) (meth)acrylamide, N- N-hydroxyalkyl (meth)acrylamide such as amine, N-(2-hydroxypropyl) (meth)acrylamide, N-(1-hydroxypropyl) (meth)acrylamide, N-(3-hydroxypropyl) (meth)acrylamide, N-(2-hydroxybutyl) (meth)acrylamide, N-(3-hydroxybutyl) (meth)acrylamide, and N-(4-hydroxybutyl) (meth)acrylamide; N-alkoxyalkyl (meth)acrylamide such as N-methoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide, and N-butoxymethyl (meth)acrylamide; and N,N-dimethylaminopropyl (meth)acrylamide and N-(meth)acryloyl morpholine. In addition, examples of amino group-containing monomers include substituted or unsubstituted amino group-containing (meth)acrylates such as aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and tert-butylaminoethyl (meth)acrylate. In addition, examples of monomers containing an imide group include N-(meth)acryloyloxymethylene succinimide, N-(meth)acryloyl-6-oxyhexamethylene succinimide, N-(meth)acryloyl-8-oxyhexamethylene succinimide, N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide, N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, and N-laurylitaconimide. The above monomers having a cationic functional group may be used alone or in combination of two or more.

[0092] The content of the monomer having a cationic functional group is preferably 0.5 mol% to 10 mol%, more preferably 1 mol% to 7 mol%, and further preferably 2 mol% to 5 mol% relative to all monomer components constituting the copolymer. By preparing the content of the monomer having a cationic functional group within this range, repulsion with scale components can be exerted, and adhesion / accumulation of scale components to the non-porous membrane can be suppressed.

[0093] In addition, the above-mentioned copolymer may also contain a structural part derived from a crosslinking agent. As the above-mentioned crosslinking agent, as long as it is a compound that can be crosslinked with the side chain of the monomer constituting the above-mentioned copolymer, there is no particular limitation. For example, a difunctional body preferably has two reactive functional groups. From the viewpoints of increasing the width of the density of the crosslinking density in the polymer, adjusting the mechanical properties, etc., a trifunctional or higher crosslinking agent can be used. As the above-mentioned crosslinking agent, for example, difunctional or higher epoxy-containing compounds, difunctional or higher isocyanate-containing compounds, etc. can be listed. In the above-mentioned copolymer, from the aspect of being able to generate quaternary ammonium ions after the crosslinking reaction with the functional group formed in the side chain, it is particularly preferred to contain difunctional or higher epoxy-containing compounds.

[0094] Examples of the epoxy group-containing compound include bisphenol A and epichlorohydrin type epoxy compounds, polyethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, N,N,N',N'-tetraglycidyl-m-xylene diamine (e.g., trade name "TETRAD-X", manufactured by Mitsubishi Gas Chemical Co., Ltd.), and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (e.g., trade name "TETRAD-C", manufactured by Mitsubishi Gas Chemical Co., Ltd.).

[0095] The amount of the crosslinking agent used is preferably 1 to 60 mol parts relative to the total amount (100 mol parts) of the reactive side chains of the copolymer, more preferably 2 to 30 mol parts, and further preferably 4 to 15 mol parts. By preparing the amount of the crosslinking agent used within this range, a water-conducting path can be easily formed in the nonporous film, making it easy to make the moisture permeability excellent.

[0096] The weight average molecular weight of the thermoplastic resin is not particularly limited, but is preferably 20,000 to 2,000,000, more preferably 30,000 to 1,500,000, further preferably 50,000 to 1,000,000, and particularly preferably 70,000 to 500,000. The weight average molecular weight is a value calculated based on polystyrene conversion by gel permeation chromatography (GPC).

[0097] The thickness of the nonporous film is preferably 0.5 μm to 5 μm, more preferably 1 μm to 4 μm. If the thickness is 0.5 μm or more, the film forming property becomes good, the gas barrier property can be improved, and the moisture permeability can be further improved. If the thickness is 5 μm or less, it is easy to form a thin film, sufficient moisture permeability can be maintained, and the humidifier can be miniaturized, and the economic efficiency is also excellent.

[0098] The nonporous film may contain other components than the thermoplastic resin within a range that does not impair the effects of the laminate.

[0099] The nonporous film may contain, for example, an anti-blocking agent, a release agent, an antiseptic, a leveling agent, etc. as other components, etc. The content of the other components is preferably 0.1 to 10 parts by mass, more preferably 0.15 to 3 parts by mass, and particularly preferably 0.2 to 2 parts by mass, relative to the total amount (100 parts by mass) of the thermoplastic resin.

[0100] The above-mentioned copolymer has a hydrophilic part and a hydrophobic part, causing the above-mentioned non-porous membrane to have a structure in which the hydrophilic part and the hydrophobic part are separated on the surface. The maximum diameter of the hydrophilic part in the above-mentioned non-porous membrane surface is preferably less than 50nm, more preferably less than 20nm. If the maximum diameter of the above-mentioned hydrophilic part is less than 50nm, the material with a size exceeding 50nm is not easy to penetrate the above-mentioned non-porous membrane, and the above-mentioned non-porous membrane can be used as a barrier film (barrier film) that does not allow materials (such as viruses, etc.) above 50nm to penetrate. The diameter of the above-mentioned hydrophilic part is evaluated by the following method. By using the adhesion measurement mode of a scanning probe microscope (SPM), the part with high adsorption force (hydrophilic part) and the part with low adsorption force (hydrophobic part) are digitized by adhesion, and processed using image analysis software, the diameter of the hydrophilic part can be calculated in the form of equivalent circle diameter. In addition, the above-mentioned maximum diameter is the diameter with the largest diameter in the diameter (equivalent circle diameter) of the hydrophilic part calculated as described above.

[0101] In addition, the moisture permeable film may be a porous film. In addition, the porous film is preferably a hydrophilic porous film. By making the porous film a hydrophilic porous film, it is easy to be compatible with water and easy to exert moisture permeability.

[0102] As the material forming the above-mentioned hydrophilic porous membrane, for example, organic substances such as cellulose resin, polyamide resin, polyimide resin, and polyamide-imide resin, inorganic substances such as metal, glass, and ceramics, etc. can be listed. Among them, from the viewpoint that the above-mentioned moisture permeable membrane can be made into a film at a lower temperature on the above-mentioned porous reinforcing material, and excellent in moisture permeability, it is preferably an organic substance. The above-mentioned material can also be fibrous such as metal fiber and inorganic fiber. The material forming the above-mentioned hydrophilic porous membrane can be only one kind, or it can be more than two kinds.

[0103] Examples of the hydrophilic porous membrane include a resin porous membrane, an inorganic porous membrane, a metal porous membrane, and a fibrous substrate.

[0104] The average pore size of the porous membrane is preferably 0.1 μm to 10 μm. In addition, the porosity of the porous membrane is preferably 40% to 90% by volume. By setting the average pore size and / or porosity within the above range, a stable membrane structure is easily formed, and only water vapor is efficiently permeated.

[0105] The thickness of the porous membrane is preferably different from the thickness of the porous reinforcing material. In addition, the thickness of the porous membrane is preferably thinner than the porous reinforcing material. If such a structure is provided, it is easy to improve moisture permeability. In addition, as the thickness of the porous membrane, it is preferably 0.5 μm to 15 μm, more preferably 1 μm to 12 μm.

[0106] The moisture-permeable film is preferably a layer formed by coating. Since it is formed by coating, it can be easily produced.

[0107] (porous reinforcement material)

[0108] Preferably, the porous reinforcing material is an element that serves as a support for the moisture-permeable film and has excellent moisture permeability.

[0109] The material forming the porous reinforcing material may be any one of a hydrophilic material and a hydrophobic material, but is preferably a hydrophobic material. If the hydrophobic material is used, when the composition for forming a moisture permeable film is applied, the composition does not penetrate into the porous reinforcing material, so in the porous reinforcing material, there is no need for a guide substrate for preventing the composition from flowing down from the surface opposite to the coating film forming surface.

[0110] As the material forming the above-mentioned porous reinforcing material, for example, organic substances such as polyolefin resins, cellulose resins, polycarbonate resins, polyamide resins, polyimide resins, polyamide-imide resins, and fluorine resins, inorganic substances such as metals, glass, and ceramics, etc. can be listed. Among them, since the above-mentioned moisture permeable film can be made into a film at a lower temperature on the above-mentioned porous reinforcing material, in addition, from the viewpoint of excellent moisture permeability and water resistance, it is preferably an organic substance, and as the above-mentioned organic substance, a polyolefin resin is particularly preferably used. The above-mentioned material can also be fibrous such as metal fibers and inorganic fibers. The material forming the above-mentioned porous reinforcing material can be only one kind, or it can be more than two kinds.

[0111] Examples of the porous reinforcing material include a resin porous film, an inorganic porous film, a metal porous film, and a fibrous substrate.

[0112] The polyolefin resin is a polymer (including an olefin elastomer) composed of an olefin as an essential monomer component, that is, a polymer containing at least a structural unit derived from an olefin in a molecule (in one molecule). The olefin is not particularly limited, and examples thereof include α-olefins such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene.

[0113] Examples of the polyolefin resin include polymers containing ethylene as an essential monomer component (polyethylene resins), polymers containing propylene as an essential monomer component (polypropylene resins), ionomers, and amorphous cyclic olefin polymers.

[0114] The porosity of the porous reinforcing material is not particularly limited, but is preferably 30% to 90% by volume, and more preferably 40% to 70% by volume. If the porosity is 30% by volume or more, the moisture permeability becomes better. When the porosity is 90% by volume or less, the supporting performance of the moisture permeable membrane becomes better.

[0115] The thickness of the porous reinforcing material is not particularly limited, but from the viewpoint of being able to fully support the moisture permeable membrane, it is preferably 5 μm or more, more preferably 10 μm or more. In addition, considering excellent moisture permeability and economy, the thickness of the porous reinforcing material is preferably 50 μm or less, more preferably 30 μm or less.

[0116] From the viewpoint of being able to easily form the moisture-permeable film, it is preferred that the porous reinforcing material has a surface (for example, Figure 1 The surface 11a shown in the figure is subjected to hydrophilization treatment. In particular, when a hydrophobic material is used as the material forming the above-mentioned porous reinforcing material, the above-mentioned hydrophilization treatment is preferably implemented. As the above-mentioned hydrophilization treatment, corona discharge treatment, plasma treatment, etc. can be listed. Through these hydrophilization treatments, carboxyl, hydroxyl or carbonyl can be generated on the porous reinforcing material surface, and the composition used to form the above-mentioned moisture permeable film is easy to wet and expand on the porous reinforcing material surface, and the above-mentioned moisture permeable film is easily formed. In addition, thus, the adhesion of the above-mentioned porous reinforcing material and the above-mentioned moisture permeable film is improved. In addition, when the above-mentioned porous reinforcing material formed by the hydrophobic substrate is kept as a winding body, the form in which one face of the above-mentioned porous reinforcing material contacts with the other face in the winding body, but because a hydrophilic face contacts with the other face of the hydrophobic face, adhesion can be prevented.

[0117] The surface tension of the surface of the porous reinforcing material on the side where the moisture permeable film is formed is preferably 35 dyn / cm to 55 dyn / cm, and more preferably 37 dyn / cm to 50 dyn / cm. When the surface tension is 35 dyn / cm or more, it is easy to apply the composition for forming the moisture permeable film, and it is easy to form the moisture permeable film. If the surface tension is 55 dyn / cm or less, the composition for forming the moisture permeable film can be easily wetted and expanded without excessively, and the moisture permeable film can be easily formed on the surface of the porous reinforcing material. It should be noted that when the surface of the porous reinforcing material is hydrophilized, the surface on the side where the moisture permeable film is formed is the surface to which the hydrophilization treatment is applied.

[0118] The surface tension of the interior of the porous reinforcing material (i.e., the interior of the region where the moisture permeable film is not formed) is preferably less than 35dyn / cm, more preferably less than 33dyn / cm. If the surface tension is less than 35dyn / cm, the composition for forming the moisture permeable film can be inhibited from penetrating into the interior of the porous reinforcing material, and the moisture permeable film is easily formed on the surface of the porous reinforcing material. It should be noted that, in the case where the surface of the porous reinforcing material is hydrophilized, the interior of the porous reinforcing material is the interior of the region where the hydrophilization treatment is not performed. In addition, the surface tension of the interior can be obtained by measuring the cross section obtained by cutting the porous reinforcing material.

[0119] <Adhesive>

[0120] In the above-mentioned humidifying element, the above-mentioned frame and the above-mentioned laminate are preferably bonded by an adhesive. In addition, the above-mentioned frame and the above-mentioned laminate can be directly welded by a known or conventional method. By bonding the above-mentioned frame to the above-mentioned laminate, the damage and expansion of the above-mentioned laminate can be suppressed, and the moisture permeability can be easily exerted for a long time. It should be noted that in Figure 1 In the humidifying element 1 shown, the laminated body 10 is bonded to the frame 30 via the adhesive 20 on the moisture-permeable membrane 12 side.

[0121] From the viewpoint of bonding the moisture-permeable film to the frame, the adhesive is preferably an adhesive containing a modified polyolefin resin, and more preferably an adhesive containing an acid-modified polyolefin resin. The adhesive may be one type or two or more types.

[0122] (Method for producing laminated body)

[0123] The laminate can be made by forming the above-mentioned moisture permeable film on at least one surface of the above-mentioned porous reinforcing material using a known or customary method. For example, the above-mentioned moisture permeable film can be directly formed on one surface of the above-mentioned porous reinforcing material, or the above-mentioned moisture permeable film can be temporarily formed on other supports and then transferred (laminated) to one surface of the above-mentioned porous reinforcing material, thereby forming the above-mentioned moisture permeable film on the porous reinforcing material. Among them, from the viewpoint of excellent adhesion between the above-mentioned moisture permeable film and the above-mentioned porous reinforcing material, the former method is preferred.

[0124] The surface of the porous reinforcing material on the side where the moisture-permeable membrane is provided may be subjected to a hydrophilic treatment. Examples of the hydrophilic treatment include the above-mentioned treatments.

[0125] The moisture-permeable film can be formed by applying (coating) the composition for forming the moisture-permeable film onto the porous reinforcing material or the other support, and removing the solvent from the obtained coating film by heating or the like.

[0126] Since the porous reinforcing material is subjected to the hydrophilization treatment to suppress blocking, it can be produced by a roll-to-roll method in which a moisture-permeable film is formed on the porous reinforcing material previously made into a roll and then the roll is made into a roll again.

[0127] The above-mentioned composition can be made by a known or customary method. For example, the above-mentioned copolymer can be made by dissolving or dispersing it in a solvent and mixing additives such as preservatives as needed. As the above-mentioned solvent, water and / or a water-soluble solvent are preferred. It can be inferred that when water or a water-soluble solvent is used, the above-mentioned copolymer is dispersed in the composition in a core-shell shape with a hydrophobic portion on the inside and a hydrophilic portion on the outside. By using such a composition, the hydrophilic portion and the hydrophobic portion are separated when the coating is dried, and a moisture permeable film is formed in a state with a water-conducting channel. In addition, it can be inferred that the hydrophobic portion becomes a state of being firmly bonded to each other, and water resistance becomes better.

[0128] Examples of the water-soluble solvent include aliphatic water-soluble alcohols such as methanol, ethanol, n-propanol, and isopropanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; and the like. The water-soluble solvent may be used alone or in combination of two or more.

[0129] The ratio (concentration) of the copolymer in the composition in which the copolymer is dissolved or dispersed is not particularly limited, and is preferably 0.5 to 5% by mass, more preferably 1 to 4% by mass, and further preferably 1.5 to 3% by mass. When the concentration is 5% by mass or less, the thickness of the coating layer becomes thicker, so the film thickness of the moisture permeable film after drying is further uniformed. Thus, a moisture permeable film with excellent gas barrier properties and further thin filmization can be formed, and as a result, the moisture permeability is further improved. In addition, if the concentration is within the above range, the coating property is excellent, and in addition, a moisture permeable film with excellent moisture permeability and gas barrier properties is easily formed.

[0130] It should be noted that the coating (applying) of the above-mentioned composition can also utilize a known coating method. For example, coating machines such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater can also be used. By such coating formation, a moisture permeable film is easily formed.

[0131] The heating temperature when removing the solvent from the coating is preferably 35°C to 90°C, more preferably 40°C to 85°C, and further preferably 45°C to 80°C. The heating time can be appropriately used for a suitable time, for example, 5 seconds to 20 minutes, preferably 5 seconds to 10 minutes, and more preferably 10 seconds to 5 minutes. The composition can be used to form a moisture permeable film at a low temperature of 90°C or less (especially 80°C or less), so it is easy to form a film. In addition, a polyolefin resin with excellent moisture permeability can be used as a porous reinforcing material.

[0132] The laminated body in which the above-mentioned moisture-permeable film is formed on at least one surface of the above-mentioned porous reinforcing material by the above-mentioned method has excellent moisture permeability. In addition, the above-mentioned laminated body has a structure in which the hydrophilic part and the hydrophobic part are separated, and thus can also be used as a barrier film with moisture permeability. In the case where the diameter of the above-mentioned hydrophilic part is small, since it is a barrier film with the above-mentioned moisture permeability, small-sized substances with hydrophilicity (such as water vapor) are allowed to pass through the hydrophilic part, and large-sized substances (such as viruses) are not allowed to pass through the hydrophilic part, thereby separating the two.

[0133] [Method for manufacturing humidifying element]

[0134] The humidifying element can be manufactured by arranging the stacked body on the air passage side of the frame. In addition, the humidifying element is preferably a humidifying element in which a bag-shaped water-retaining container is formed by covering the frame with the stacked body.

[0135] The frame may be a plate-shaped or bag-shaped frame produced by extrusion molding, a plate-shaped frame produced by injection molding, or a bag-shaped structure produced by laminating two or more plate-shaped frames. In addition, the hole portion may be provided after the bag-shaped frame is produced, or a frame with the hole portion provided in advance may be produced.

[0136] In addition, it is preferred that a part or the whole of the contact portion between the laminate and the frame is bonded. The method of bonding to the frame is not particularly limited, and bonding can be performed by bonding using the above-mentioned adhesive, welding using ultrasonic welding, high-frequency welding, thermal welding, etc.

[0137] The humidifying element having the stacked body disposed on the air path side of the frame can be manufactured by the above method. The humidifying element has the stacked body disposed on the air path side of the frame structure, and the water of the liquid passing into the water path side of the humidifying element is absorbed by the stacked body in the form of water vapor, diffuses in the stacked body, and can release water vapor from the stacked body as a whole to the air path side.

[0138] In addition, a humidifier can be manufactured by mounting a plurality of humidifying elements with the stacked body disposed on the air path side of the frame. Such a humidifier can use humidifying elements with improved humidification performance compared with the past, so that the humidifier can be miniaturized while still having the same performance, and is also excellent in terms of cost.

[0139] Therefore, the humidifier can be suitably used in applications such as air conditioners, ventilators, and air purifiers.

[0140] Each scheme disclosed in this specification may also be combined with any other feature disclosed in this specification. Each configuration and combination of configurations in each embodiment is an example, and appropriate addition, omission, substitution and other changes of configurations may be made within the scope of the present disclosure. In addition, each invention disclosed in this disclosure is not limited by the embodiment, but only by the claims.

[0141] In the conventional humidifying element, the stack is formed on the water path side of the frame, and water vapor cannot be released to the outside from the portion where the frame and the stack are in contact, so the entire surface of the stack cannot be effectively utilized, and the humidification performance is insufficient. On the other hand, the humidifying element of the present disclosure has a stack including a moisture-permeable film formed on the air path side of the frame, so that the absorbed water vapor diffuses in the stack and can be released from the entire surface of the stack, which can further improve the humidification performance.

[0142] Modifications of the invention disclosed herein will be described below.

[0143] [Note 1]

[0144] A humidifying element includes: a laminate having a porous reinforcing material and a moisture-permeable membrane laminated on at least one surface of the porous reinforcing material; and a frame, wherein the laminate is arranged on an air passage side with respect to the frame.

[0145] [Note 2]

[0146] The humidifying element according to Supplementary Note 1, wherein the stacked body forms a bag-shaped water retaining container so as to cover the air passage side of the frame.

[0147] [Note 3]

[0148] The humidifying element according to Supplementary Note 1 or 2, wherein in the stacked body, the moisture-permeable membrane is arranged on the frame side relative to the porous reinforcing material.

[0149] [Note 4]

[0150] The humidifying element according to any one of Supplementary Notes 1 to 3, wherein the moisture-permeable film is a non-porous film.

[0151] [Note 5]

[0152] The humidifying element according to Supplementary Note 4, wherein the nonporous film contains a thermoplastic resin having a cationic portion, and the cationic portion contains a group containing an ammonium ion or a group capable of forming an ammonium ion.

[0153] [Note 6]

[0154] The humidifying element according to Appendix 4 or 5, wherein the nonporous film contains a thermoplastic resin having a hydrophilic portion, and the hydrophilic portion contains a structural unit represented by the following formula (1).

[0155] [Chemical formula 1]

[0156]

[0157] (R1 and R2 each independently represent a hydrogen atom or a methyl group.)

[0158] [Note 7]

[0159] The humidifying element according to any one of Appendixes 4 to 6, wherein the nonporous film contains a thermoplastic resin having a hydrophobic portion, and the hydrophobic portion contains a structural unit represented by the following formula (2) and / or the following formula (3).

[0160] [Chemical formula 2]

[0161]

[0162] (R1 represents a hydrogen atom or a methyl group, and R3 represents an alkyl group having 1 to 2 carbon atoms.)

[0163] [Chemical formula 3]

[0164]

[0165] (R1 represents a hydrogen atom or a methyl group, and R4 represents a branched alkyl group having 3 or more carbon atoms.) [Supplementary Note 8]

[0166] The humidifying element according to any one of Supplementary Notes 1 to 3, wherein the moisture-permeable membrane is a hydrophilic porous membrane.

[0167] [Note 9]

[0168] The humidifying element according to Supplementary Note 8, wherein the hydrophilic porous membrane and the porous reinforcing material have different thicknesses.

[0169] [Note 10]

[0170] The humidifying element according to any one of appendixes 1 to 9, wherein the stacked body and the frame are bonded together by adhesion or welding.

[0171] [Note 11]

[0172] The humidifying element according to any one of appendixes 1 to 9, wherein the stacked body is bonded to the frame with an adhesive.

[0173] [Note 12]

[0174] The humidifying element according to any one of Supplementary Notes 1 to 11, wherein the moisture-permeable film is applied so as to cover at least one surface of the porous reinforcing material.

[0175] [Note 13]

[0176] A humidifier comprising the humidifying element according to any one of Supplementary Notes 1 to 12.

[0177] [Note 14]

[0178] An air conditioner equipped with the humidifier as described in Supplementary Note 13.

[0179] [Note 15]

[0180] A humidifier equipped with the humidifier as described in Supplementary Note 13.

[0181] [Note 16]

[0182] An air purifier equipped with the humidifier as described in Appendix 13.

[0183] Description of Reference Numerals

[0184] 1: Humidification element;

[0185] 10: laminate;

[0186] 11: Porous reinforcement material;

[0187] 11a: One surface of the porous reinforcement material;

[0188] 12: Moisture permeable membrane;

[0189] 20: Adhesive;

[0190] 30: frame;

[0191] 31: Hole.

Claims

1. A humidifying element comprising: a laminate having a porous reinforcing material and a moisture-permeable membrane laminated on at least one surface of the porous reinforcing material; and a frame, wherein: The stacked body is arranged on the air path side with respect to the frame.

2. The humidifying element according to claim 1, wherein: The stacked body forms a bag-shaped water-retaining container so as to cover the air passage side of the frame.

3. The humidifying element according to claim 1 or 2, wherein: In the laminated body, the moisture-permeable membrane is arranged on the frame side with respect to the porous reinforcing material.

4. The humidifying element according to claim 1 or 2, wherein: The moisture permeable membrane is a non-porous membrane.

5. The humidifying element according to claim 4, wherein: The nonporous film contains a thermoplastic resin having a cationic portion containing a group containing an ammonium ion or a group capable of forming an ammonium ion.

6. The humidifying element according to claim 4, wherein: The nonporous film contains a thermoplastic resin having a hydrophilic portion, wherein the hydrophilic portion contains a structural unit represented by the following formula (1): In the formula, R1 and R2 each independently represent a hydrogen atom or a methyl group.

7. The humidifying element according to claim 4, wherein: The nonporous film contains a thermoplastic resin having a hydrophobic portion, wherein the hydrophobic portion contains a structural unit represented by the following formula (2) and / or the following formula (3), In formula (2), R1 represents a hydrogen atom or a methyl group, and R3 represents an alkyl group having 1 to 2 carbon atoms. In formula (3), R1 represents a hydrogen atom or a methyl group, and R4 represents a branched alkyl group having 3 or more carbon atoms.

8. The humidifying element according to claim 1 or 2, wherein: The moisture permeable membrane is a hydrophilic porous membrane.

9. The humidifying element according to claim 8, wherein: The hydrophilic porous membrane and the porous reinforcing material have different thicknesses.

10. The humidifying element according to claim 1 or 2, wherein: The stacked body and the frame are bonded together by adhesion or welding.

11. The humidifying element according to claim 1 or 2, wherein: The laminate is bonded to the frame by an adhesive.

12. The humidifying element according to claim 1 or 2, wherein: The moisture-permeable film is applied so as to cover at least one surface of the porous reinforcing material.

13. A humidifier equipped with the humidifying element according to claim 1 or 2.

14. An air conditioner equipped with the humidifier according to claim 13.

15. A ventilation device equipped with the humidifier according to claim 13.

16. An air purifier equipped with the humidifier according to claim 13.

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