TW201941937A - Method for manufacturing laminate - Google Patents

Abstract

The present invention relates to a method for manufacturing a laminate including a metal substrate and a metal organic structure formed thereon, the method including: (step 1a) a step of activating a surface of metal substrate, or (step 1b) a step of modifying a surface of metal substrate to form a metal layer thereon, and (step 2) a step of contacting the metal base material treated in the above step 1a or step 1b with a solution containing at least one metal ion and a solution containing at least one organic ligand to form a metal organic structure on the metal base material.

Description

   Laminated body manufacturing method   

The present disclosure relates to a method for manufacturing a laminated body and a laminated body obtained by the manufacturing method.

A metal organic structure (MOF: Metal Organic Framework) has a porous coordination network structure, and is used as an adsorbent, a catalyst, or the like. The metal organic structure system is formed on the surface of a support and can be used as a laminated body.

A laminated body including a support and a metal-organic structure formed on the surface thereof, and a method for manufacturing the same are described in Patent Document 1, for example. Patent Document 1 contains: (a) a step of blowing a first solution containing at least one kind of metal ions on at least a part of the surface of the support, and (b) blowing a solution containing at least one kind of at least two teeth on at least a part of the surface of the support The step of the second solution of the organic compound, wherein the step (b) may be performed before or after the step (a) or at the same time, and a laminated body is manufactured by a method of forming a porous metal organic structure layer.

    [Prior technical literature]         [Patent Literature]    

Patent Document 1: Japanese Patent Application Publication No. 2014-500143.

The laminated system as described in Patent Document 1 forms a metal organic structure (hereinafter referred to as "MOF") in a state of being superposed on the surface of a substrate belonging to a support. The present inventors have found that in such a laminated body, the adhesion of the MOF layer to the substrate is low, and there is a problem that the MOF layer is peeled from the substrate.

The subject of the present disclosure is to provide a laminated body which has a metal substrate and a metal organic structure formed on the metal substrate while suppressing the separation of the metal organic structure.

This disclosure includes the following aspects.

1. A method for manufacturing a laminate, the laminate system comprising a metal substrate and a metal organic structure formed on the metal substrate, the method for manufacturing the laminate has the following steps: (step 1a) activating the metal substrate A surface step, or (step 1b) a step of modifying the surface of the metal substrate and forming a metal layer thereon; and (step 2) combining the metal substrate treated with the above step 1a or step 1b with a layer containing at least one metal ion The step of contacting a solution with a solution containing at least one organic ligand to form a metal organic structure on a metal substrate.

2. A method for manufacturing a laminate, the laminate system comprising a metal substrate and a metal organic structure formed on the metal substrate, the method for manufacturing the laminate is provided with the following steps: (step 1a) activating a metal substrate Step of forming a metal surface; and (step 2) contacting the surface of the metal substrate with a solution containing at least one metal ion and a solution containing at least one organic ligand to form a metal organic structure on the metal substrate step.

3. The manufacturing method according to the above [1] or [2], wherein the metal constituting the metal base material is Si, Al, Cu, Fe, Ni, Zn, or Fe / Ni / Cr alloy.

4. The manufacturing method according to any one of the above [1] to [3], wherein the step of activating the surface of the metal substrate is performed by treating the surface of the metal substrate with hydrogen fluoride, hydrogen chloride, fluorine, or chlorine.

5. The manufacturing method according to any one of the above [1] to [4], wherein in step 2 above, the metal ion contained in the solution is an ion of Al, Cu, Fe, Mn, or Co.

6. The manufacturing method according to any one of the above [1] to [5], wherein the metal ion system formed on the surface of the metal substrate is the same as the metal ion in the solution.

7. The production method according to any one of the above [1] to [6], wherein the organic ligand is selected from 1,4-benzenedicarboxylic acid, 1,2-benzenedicarboxylic acid, and butylene Oxalic acid, 1,3,5-benzenetricarboxylic acid, 4,4 ', 4 "-(1,3,5-benzenetriyl) parabenzoic acid, 4,4'-bipyridine, triazole, imidazole , 3,3'-bipyrazole, benzimidazole, and 3,5-pyridinedicarboxylic acid.

8. A laminated body obtained by the manufacturing method described in any one of the above [1] to [7].

A laminated body comprising a metal substrate and a metal organic structure formed on the metal substrate, wherein a metal atom on the surface of the metal substrate constitutes a part of the metal organic structure.

10. A laminated body comprising a metal substrate and a metal organic structure formed on the metal substrate, wherein the surface of the metal substrate is modified, and the modified surface has a metal layer, and the metal layer A metal organic structure is formed thereon.

11. A fin composed of the laminated body described in [9] or [10] above.

12. A dehumidifier / humidifier made of the fins described in [11] above.

13. A heat exchanger comprising the fins according to the above [11].

According to the present disclosure, in a multilayer body including a metal substrate and a metal organic structure formed on the metal substrate, peeling of the metal organic structure from the substrate can be suppressed.

The manufacturing method of the present disclosure will be described below.

The present disclosure is a method for manufacturing a laminated body. The laminated system has a metal substrate and a metal organic structure formed on the metal substrate. The method for manufacturing the laminated body has the following steps: (step 1a) activating the surface of the metal substrate Step; (step 1b) a step of modifying the surface of the metal substrate and forming a metal layer thereon; and (step 2) using the metal substrate treated by the above step 1a or step 1b with a solution containing at least one metal ion and The step of forming a metal organic structure on a metal substrate by contacting a solution containing at least one organic ligand.

Step 1a is explained below.

Step 1a is a step of activating the surface of the metal substrate.

First, a metal substrate is prepared.

The metal constituting the metal substrate may be Si, Al, Cu, Fe, Ni, Zn, or an alloy containing these.

The alloy is not particularly limited, and examples thereof include Fe / Ni / Cr alloy and Al / Cu alloy.

In a preferred aspect, the metal constituting the metal substrate is Al.

The shape of the above-mentioned metal substrate is not particularly limited, and may be various shapes depending on the application. As described below, the laminated body of the present disclosure is unlikely to peel off the MOF layer, so it can be used even with a substrate having a complicated shape. For example, in addition to the simple shape such as a plate shape and a rod shape, the shape of the metal substrate may be a wing shape, an uneven shape, a pore structure, and the like for increasing the surface area. Increasing the surface area can maximize the use of the function of the MOF, so it is preferably a fin-like shape, a concave-convex shape, a pore structure, and the like.

Then, the surface of the metal substrate is activated by treating the surface of the metal substrate.

The above treatment is not particularly limited as long as it is a treatment that can activate the surface of the metal substrate, and examples thereof include etching, O ₂ ion treatment, atmospheric piezoelectric slurry treatment, UVO ₃ (ultraviolet-ozone) treatment, and hot water treatment. It is preferable to use an etching process.

The above-mentioned activation refers to a state in which an organic ligand is bonded to the surface of a metal substrate and a metal-organic structure can be formed by the treatment of Step 2 described below. For example, metal substrate surface activation includes the formation of metal ions on the surface of a metal substrate.

The etching can be performed by treating the surface of the metal substrate with an etchant such as hydrogen fluoride, hydrogen chloride, fluorine, or chlorine depending on the type of the metal substrate. Among these, since it can be used as a solution, it is preferable to perform etching using hydrogen fluoride.

The treatment with the etchant on the surface of the metal substrate can be performed by bringing the surface of the metal substrate into contact with the etchant. The etchant used in the treatment may be a gas or a liquid, and is preferably a liquid.

The processing temperature of the etchant is preferably 0 to 50 ° C, more preferably 10 to 30 ° C, and typically room temperature.

The processing time of the etchant is preferably 30 to 60 minutes, and more preferably 15 to 30 minutes.

Next, step 1b will be described.

Step 1b is a step of modifying the surface of the metal substrate and forming a metal layer thereon.

First, a metal substrate is prepared in the same manner as in step 1a.

Next, the surface of the metal substrate is treated and the surface is modified.

Here, "modification" refers to adding a functional group or molecule to the surface of a metal substrate and modifying the surface.

The method of modifying the surface of the metal substrate can be performed, for example, by applying a compound (for example, poly (ethylene glycol) methacrylate, etc.) to be provided to the surface of the metal substrate, and coupling the surface of the metal substrate Both capable compounds (for example, methacryloxyethyl phosphate, etc.) are copolymerized, and the surface of the metal substrate is treated with the obtained copolymer.

In a preferred aspect, the copolymer may be a poly (ethylene glycol) methacrylate / methacrylic acid methacrylate copolymer (polymerization ratio of 99/1 to 80/20, preferably 99 / 1 to 95/5, specifically 97/3) and so on.

Through the above-mentioned treatment, the copolymer is bonded to the metal substrate through the coupling ability portion (derived from the methacryloxyethyl phosphate), and the surface of the metal substrate is modified.

Next, the modified metal substrate is processed to form a metal layer on the modified surface of the metal substrate. The treatment method can be performed by treating the modified metal substrate with a metal ion-containing treatment agent such as an alcohol solution of a metal alkoxide.

For example, when an Al layer is formed on a modified metal substrate, it is treated with an ethanol solution of alumina.

The metal substrate treated in step 1a or step 1b is delivered to step 2. Step 2 is explained below.

Step 2 is a step of forming a metal organic structure on the metal substrate by contacting the surface of the metal substrate treated with a solution containing at least one metal ion and a solution containing at least one organic ligand.

The metal ions contained in the solution are not particularly limited, and for example, metal ions selected from the group consisting of Groups Ia, IIa, IIIa, IVa to VIII, and Ib to VIb. The metal ion is preferably Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ro, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, TI, Si, Ge, Sn, Pb, As, Sb, Bi, La, Ce, Pr, Nd, Pm, Sm, En, Gd, Tb, Dy, Ho, Er, Tm and Yb ions.

Specifically, the metal ion may be Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ln ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , Hf ⁴⁺ , V ⁴⁺ , V ³⁺ , V ²⁺ , Nb ³⁺ , Ta ³⁺ , Cr ³⁺ , Mo ³⁺ , W ³⁺ , Mn ³⁺ , Mn ²⁺ , Re ³⁺ , Re ²⁺ , Fe ³⁺ , Fe ²⁺ , Ru ³⁺ , Ru ²⁺ , Os ³⁺ , Os ²⁺ , Co ³⁺ , Co ²⁺ , Rh ²⁺ , Rh ⁺ , Ir ²⁺ , Ir ⁺ , Ni ²⁺ , Ni ⁺ , Pd ²⁺ , Pd ⁺ , Pt ²⁺ , Pt ⁺ , Cu ²⁺ , Cu ⁺ , Ag ⁺ , Au ⁺ , Zn ²⁺ , Cd ²⁺ , Hg ²⁺ , Al ³⁺ , Ga ³⁺ , ln ³⁺ , TI ³⁺ , Si ⁴⁺ , Si ²⁺ , Ge ⁴⁺ , Ge ²⁺ , Sn ⁴⁺ , Sn ²⁺ , Pb ⁴⁺ , Pb ²⁺ , As ⁵⁺ , As ³⁺ , As ⁺ , Sb ^{5 +} , Sb ³⁺ , Sb ⁺ , Bi ⁵⁺ , Bi ³⁺ , Bi ⁺ , La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Pm ³⁺ , Sm ³⁺ , En ³⁺ , Gd ^{3 +} , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Er ³⁺ , Tm ³⁺ or Yb ³⁺ .

These metal ions may be used alone or in combination of two or more. Preferably, the metal ion is one kind.

In a preferred aspect, the above metal ions are Al ³⁺ , Cu ²⁺ , Cu ⁺ , Fe ³⁺ , Fe ²⁺ , Mn ³⁺ , Mn ²⁺ , Co ³⁺ , or Co ²⁺ , preferably Al ³⁺ , Fe ³⁺ .

The metal ions contained in the solution may be the same as or different from the metal ions formed on the surface of the metal substrate, and are preferably the same.

The solution containing the above-mentioned metal ion may be a solution containing the above-mentioned metal ion. The salt may be any of an organic acid salt, an inorganic acid salt, an organic base salt, or an inorganic base salt. The salt is preferably an inorganic acid salt.

Examples of the organic acid salt include monocarboxylic acid salts (e.g., acetate, trifluoroacetate, butyrate, palmitate, stearate, etc.), and polycarboxylic acid salts (e.g., fumarate, cis butyrate). Oxalates, etc.), oxycarboxylates (e.g., lactate, tartrate, citrate, succinate, malonate, etc.), organic sulfonates (e.g., methanesulfonate, toluenesulfonate Acid salt, p-toluenesulfonate, etc.).

Examples of the inorganic acid salt include hydrochloride, sulfate, nitrate, hydrobromide, and phosphate.

In a preferred embodiment, the salt containing metal ions may be an inorganic acid salt, especially a nitrate salt.

The solvent of the metal ion-containing solution may be, for example, ethanol, dimethylformamide, toluene, methanol, chlorobenzene, diethylformamide, dimethylmethane, water, hydrogen peroxide, methylamine, Sodium hydroxide solution, N-methylpyrrolidone ether, acetonitrile, chlorotoluene, triethylamine, ethylene glycol or a mixture thereof.

The metal ion-containing solution is preferably 5 to 20% by mass, and more preferably 5 to 10% by mass.

The metal ion-containing solution may contain a catalyst, an acid, and the like as other components.

The organic ligand is not particularly limited as long as it can form at least two coordination bonds with metal ions on the surface of the metal substrate or metal layer and metal ions contained in the solution.

The coordination bond can be formed, for example, by a functional group capable of forming at least one coordination bond with a metal ion.

Examples of the functional group capable of forming the above-mentioned coordination bond include: -COOH, -CS ₂ H, -NO ₂ , -B (OH) ₂ , -SO ₃ H, -Si (OH) ₃ , -Ge (OH) ₃ , -Sn (OH) ₃ , -Si (SH) ₄ , -Ge (SH) ₄ , -Sn (SH) ₃ , -PO ₃ H, -AsO ₃ H, -AsO ₄ H, -P (SH) ₃ , -As (SH) ₃ , -CH (RSH) ₂ , -C (RSH) ₃ , -CH (RNH ₂ ) ₂ , -C (RNH ₂ ) ₃ , -CH (ROH) ₂ , -C (ROH) ₃ , -CH (RCN) ₃ , and -C (RCN) ₃ . In the above formula, R is a single bond and an alkylene group having 1 to 5 carbon atoms (for example, methylene, ethylidene, n-propylidene, isopropylidene, n-butylidene, isobutylene, tertiary ethylene, etc. Butyl or n-pentyl), a divalent aromatic group having 6 to 14 carbons (for example, phenylene), or a combination of the above-mentioned alkylene and aromatic group (for example, -phenylene-alkylene- Phenylene-). Furthermore, the functional group capable of forming the above-mentioned coordination bond may contain a hetero atom in the heterocyclic ring, preferably a nitrogen atom.

In a preferred aspect, the functional group capable of forming the above-mentioned coordination bond may be -COOH, -NO ₂ and the like.

It is preferable that the said organic ligand has the said functional group so that it may become bidentate or more. In this organic ligand, the part other than the functional group is not particularly limited as long as the organic ligand can form a coordination bond with a metal ion.

In one aspect, the organic ligand is derived from a saturated or unsaturated aliphatic compound, an aromatic compound, or an aliphatic aromatic compound.

The aliphatic portion of the above-mentioned aliphatic compound or aliphatic aromatic compound may be linear, branched, or cyclic. When the aliphatic portion is cyclic, it may have a plural ring. The aliphatic portion of the above-mentioned aliphatic compound or aliphatic aromatic compound preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and for example, has 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. In a preferred aspect, the aliphatic portion is derived from methane, adamantane, acetylene, ethylene or butadiene.

The aromatic part of the above-mentioned aromatic compound or aliphatic aromatic compound may have one or more rings, and for example, may have 2, 3, 4 or 5 rings. The rings may or may not be condensed. The aromatic part of the above-mentioned aromatic compound or aliphatic aromatic compound preferably has 1, 2 or 3 rings, and more preferably 1 or 2 rings. In addition, each ring of the compound may have at least one kind of hetero atom in the ring, for example, N, O, S, B, P, Si, Al, and preferably N, O, or S. The aromatic part of the aromatic compound or the aliphatic aromatic compound is preferably a ring containing 1 or 2 carbon atoms. When there are two aromatic moieties, the two rings may be condensed or not. In a preferred aspect, the aromatic moiety is derived from benzene, naphthalene, biphenyl, bipyridyl or pyridyl.

In one aspect, the organic ligand is derived from a dicarboxylic acid, a tricarboxylic acid, or a tetracarboxylic acid.

啉-2,3-二羧酸、6-氯喹

啉-2,3-二羧酸、4,4’-二胺基苯基甲烷-3,3’-二羧酸、喹啉-3,4-二羧酸、7-氯-4-羥基喹啉-2,8-二羧酸、二醯亞胺二羧酸、吡啶-2,6-二羧酸、2-甲基咪唑-4,5-二羧酸、噻吩-3,4-二羧酸、2-異丙基咪唑-4,5-二羧酸、四氫吡喃-4,4-二羧酸、苝-3,9-二羧酸、苝二羧酸、Pluriol E200-二羧酸、3,6-二氧雜辛烷二羧酸、3,5-環己二烯-1,2-二羧酸、辛烷二羧酸、戊烷-3,3-二羧酸、4,4’-二胺基-1,1’-聯苯基-3,3’-二羧酸、4,4’-二胺基聯苯基-3,3’-二羧酸、聯苯胺-3,3’-二羧酸、1,4-雙(苯基胺基)苯-2,5-二羧酸、1,1’-聯萘基二羧酸、7-氯-8-甲基喹啉-2,3-二羧酸、1-苯胺基-蒽醌-2,4’-二羧酸、聚四氫呋喃250-二羧酸、1,4-雙(羧甲基)哌

-2,3-二羧酸、7-氯喹啉-3,8-二羧酸、1-(4-羧基)苯基-3-(4-氯)苯基吡唑啉-4,5-二羧酸、1,4,5,6,7,7-六氯-5-降莰烯-2,3-二羧酸、苯基茚烷二羧酸、1,3-二苄基-2-側氧基咪唑啶-4,5-二羧酸、1,4-環己烷二羧酸、萘-1,8-二羧酸、2-苯甲醯基苯-1,3-二羧酸、1,3-二苄基-2-側氧基咪唑亞烷基(oxoimidazolidinylidene)-4,5-cis-二羧酸、2,2’-聯喹啉-4,4’-二羧酸、吡啶-3,4-二羧酸、3,6,9-三氧雜十一烷二羧酸、羥基二苯 基酮二羧酸、Pluriol E300-二羧酸、Pluriol E400-二羧酸、Pluriol E600-二羧酸、吡唑-3,4-二羧酸、2,3-吡

二羧酸、5,6-二甲基-2,3-吡

二羧酸、4,4’-二胺基(二苯基醚)二醯亞胺二羧酸、4,4’-二胺基二苯基甲烷二醯亞胺二羧酸、4,4’-二胺基(二苯基碸)二醯亞胺二羧酸、1,4-萘二羧酸、2,6-萘二羧酸、1,3-金剛烷二羧酸、1,8-萘二羧酸、2,3-萘二羧酸、8-甲氧基-2,3-萘二羧酸、8-硝基-2,3-萘二羧酸、8-磺基-2,3-萘二羧酸、蒽-2,3-二羧酸、2’,3’-二苯基-對三聯苯基-4,4”-二羧酸、(二苯基醚)-4,4’-二羧酸、咪唑-4,5-二羧酸、4(1H)-側氧基二氫苯并噻喃-2,8-二羧酸、5-第三丁基-1,3-苯二羧酸、7,8-喹啉二羧酸、4,5-咪唑二羧酸、4-環己烯-1,2-二羧酸、三十六烷二羧酸、十四烷二羧酸、1,7-庚烷二羧酸、5-羥基-1,3-苯二羧酸、2,5-二羥基-1,4-二羧酸、吡

-2,3-二羧酸、呋喃-2,5-二羧酸、1-壬烯-6,9-二羧酸、二十烯二羧酸、4,4’-二羥基二苯基甲烷-3,3’-二羧酸、1-胺基-4-甲基-9,10-二側氧基-9,10-二氫蒽-2,3-二羧酸、2,5-吡啶二羧酸、環己烯-2,3-二羧酸、2,9-二氯芙歐品紅(fluorubine)-4,11-二羧酸、7-氯-3-甲基喹啉-6,8-二羧酸、2,4-二氯二苯基酮-2’,5’-二羧酸、1,3-苯二羧酸、2,6-吡啶二羧酸、1-甲基吡咯-3,4-二羧酸、1-苄基-1H-吡咯-3,4-二羧酸、蒽醌-1,5-二羧酸、3,5-吡唑二羧酸、2-硝基苯-1,4-二羧酸、庚烷-1,7-二羧酸、環丁烷-1,1-二羧酸、1,14-十四烷二羧酸、5,6-脫氫降莰烷-2,3-二羧酸、5-乙基-2,3-吡啶二羧酸及樟腦二羧酸。 Examples of the dicarboxylic acid include oxalic acid, succinic acid, tartaric acid, maleic acid, 1,4-butanedicarboxylic acid, 1,4-butenedicarboxylic acid, and 4-oxopyran-2 1,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid Acid, acetylene dicarboxylic acid, 1,2-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butanedicarboxylic acid Ene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, terephthalic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, Quinoline-2,4-dicarboxylic acid, quinine

Porphyrin-2,3-dicarboxylic acid, 6-chloroquine

Porphyrin-2,3-dicarboxylic acid, 4,4'-diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquine Porphyrin-2,8-dicarboxylic acid, diammonium dicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid Acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, pyrene-3,9-dicarboxylic acid, pyrene dicarboxylic acid, Pluriol E200-dicarboxylic acid Acid, 3,6-dioxaoctane dicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octane dicarboxylic acid, pentane-3,3-dicarboxylic acid, 4 , 4'-diamino-1,1'-biphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, benzidine- 3,3'-dicarboxylic acid, 1,4-bis (phenylamino) benzene-2,5-dicarboxylic acid, 1,1'-binapthyl dicarboxylic acid, 7-chloro-8-methyl Quinoline-2,3-dicarboxylic acid, 1-anilino-anthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran 250-dicarboxylic acid, 1,4-bis (carboxymethyl) piperidine

-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1- (4-carboxy) phenyl-3- (4-chloro) phenylpyrazoline-4,5-di Carboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindane dicarboxylic acid, 1,3-dibenzyl-2- Pendant imidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzylidenebenzene-1,3-dicarboxylic acid , 1,3-dibenzyl-2-oxoimidazole alkylidene (oxoimidazolidinylidene) -4,5-cis-dicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, Pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, hydroxydiphenylketone dicarboxylic acid, Pluriol E300-dicarboxylic acid, Pluriol E400-dicarboxylic acid, Pluriol E600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyridine

Dicarboxylic acid, 5,6-dimethyl-2,3-pyridine

Dicarboxylic acid, 4,4'-diamino (diphenyl ether) diamidodicarboxylic acid, 4,4'-diaminodiphenylmethane diamidodicarboxylic acid, 4,4 ' -Diamino (diphenylphosphonium) diamidoimine dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-adamantane dicarboxylic acid, 1,8- Naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 8-methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3-naphthalenedicarboxylic acid, 8-sulfo-2, 3-naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2 ', 3'-diphenyl-p-terphenyl-4,4 "-dicarboxylic acid, (diphenyl ether) -4, 4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4 (1H) -side oxydihydrobenzothiane-2,8-dicarboxylic acid, 5-third butyl-1,3 -Benzene dicarboxylic acid, 7,8-quinoline dicarboxylic acid, 4,5-imidazole dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, trioxane dicarboxylic acid, tetradecane Dicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, 2,5-dihydroxy-1,4-dicarboxylic acid, pyridine

-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosene dicarboxylic acid, 4,4'-dihydroxydiphenylmethane -3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridine Dicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluoine-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8 -Dicarboxylic acid, 2,4-dichlorodiphenyl ketone-2 ', 5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1-methylpyrrole- 3,4-dicarboxylic acid, 1-benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2-nitro Benzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 5,6-dehydrogenation Norbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid and camphor dicarboxylic acid.

Examples of the tricarboxylic acid include 2-hydroxy-1,2,3-propane tricarboxylic acid, 7-chloro-2,3,8-quinoline tricarboxylic acid, 1,2,3- or 1,2, 4-benzenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphinofluorenyl-1,2,4-butanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 4, 4 ', 4 ”-(1,3,5-benzenetriyl) benzoic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo -1H-pyrrolo [2,3-F] quinoline-2,7,9-tricarboxylic acid, 5-ethylfluorenyl-3-amino-6-methylbenzene-1,2,4-tri Carboxylic acid, 3-amino-5-benzylidene-6-methylbenzene-1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid, and rosintricarboxylic acid acid).

Examples of the above tetracarboxylic acid include 1,1-dioxide pyrene [1,12-BCD] thiophene-3,4,9,10-tetracarboxylic acid and pyrene-3,4,9,10-tetracarboxylic acid. Acid or fluorene tetracarboxylic acid such as (fluorene-1,12-fluorene) -3,4,9,10-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid or meso-1,2 Butanetetracarboxylic acid such as 1,3,4-butanetetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxane 18 Ethane-2,3,11,13-tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6- Hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, diphenyl Cyclopentane tetracarboxylic acids such as ketone tetracarboxylic acid, 3,3 ', 4,4'-diphenyl ketone tetracarboxylic acid, tetrahydrofuran tetracarboxylic acid, and cyclopentane-1,2,3,4-tetracarboxylic acid acid.

In one aspect, the organic ligand is derived from a heterocyclic ring that can form a coordination bond through a ring heteroatom. Examples of the heterocyclic ring include the following heterocyclic rings. The heterocyclic ring may be unsubstituted or substituted.

In a preferred aspect, the organic ligand is selected from 1,4-benzenedicarboxylic acid, 1,2-benzenedicarboxylic acid, maleic acid, 1,3,5-benzenetricarboxylic acid, 4 , 4 ', 4 ”-(1,3,5-benzenetriyl) benzoic acid, 4,4'-bipyridine, triazole, imidazole, 3,3'-bipyrazole, benzimidazole, and , 5-pyridinedicarboxylic acid.

These organic ligands may be used alone or in combination of two or more.

In addition, in the present specification, "derived from" means to include, in addition to a specific compound itself, a partially protonated form or a fully protonated form of the compound.

The solvent of the organic ligand-containing solution may be, for example, ethanol, dimethylformamide, toluene, methanol, chlorobenzene, diethylformamide, dimethylmethylene, water, hydrogen peroxide, and formazan. Amine, sodium hydroxide solution, N-methylpyrrolidone ether, acetonitrile, chlorotoluene, triethylamine, or ethylene glycol or a mixture of these.

The solvent containing the metal ion solution and the solvent containing the organic ligand solution may be the same or different, and preferably the same.

The organic ligand-containing solution is preferably 5 to 30% by mass, and more preferably 10 to 20% by mass.

The organic ligand-containing solution may contain a catalyst, a base, and the like as other components.

The method for bringing the surface of the metal substrate treated in step 1a or step 1b into contact with a solution containing at least one metal ion and a solution containing at least one organic ligand is not particularly limited as long as a metal organic structure can be formed on a metal substrate. limited.

For example, the treatment may be performed by immersing the metal substrate in a metal ion solution and an organic ligand solution, or by applying a metal ion solution and an organic ligand to the surface of the metal substrate using a spray or the like. Solution.

The above-mentioned treatment may be performed by separately contacting the metal substrate with the solution of the metal ion and the solution of the organic ligand, or simultaneously.

In one aspect, the metal substrate may be brought into contact with a mixed solution of a solution of a metal ion and a solution of an organic ligand.

In other aspects, the metal substrate may be contacted with a solution of an organic ligand, and then contacted with a solution of a metal ion.

In other aspects, the metal substrate can be contacted with a solution of metal ions, and then contacted with a solution of an organic ligand.

In other aspects, the metal substrate can be contacted with the solution of the metal ion and the solution of the organic ligand several times. At this time, the solution of the metal ion and the solution of the organic ligand may be used with the same solution, or different solutions may be used. For example, a solution of a certain metal ion is initially used (for example, a solution containing the same metal ion as the metal of the metal substrate), and then a solution of other metal ions is used.

In this treatment, the treatment temperature is preferably 10 to 100 ° C, and more preferably 20 to 40 ° C.

In this treatment, the treatment time is preferably 15 to 120 minutes, and more preferably 60 to 120 minutes.

As described above, a metal organic structure layer can be formed on the surface of the metal substrate through step 1a or step 1b and step 2.

The thickness of the obtained metal-organic structure layer is not particularly limited, and may be, for example, 1 μm to 10 mm, preferably 100 μm to 5 mm, and more preferably 500 μm to 2 mm.

The formation of the metal organic structure can be confirmed by X-ray diffraction, X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) observation, and the like.

In the method of the present disclosure, the above-mentioned steps 1a, 1b, and 2 may appropriately include post-processing.

For example, heat treatment may be performed after the contact treatment in step 2.

According to the method of the present disclosure, a laminated body capable of suppressing the separation of the metal organic structure from the metal substrate can be obtained. The present disclosure is not bound by any theory, but the reason for suppressing peeling is speculated as follows. It is speculated that when step 1a is performed, metal ions derived from the metal substrate are formed on the surface of the metal substrate in step 1a, and metal organic structures are formed using the metal ions as a starting point in step 2. In other words, it can be said that the atoms on the surface of the metal substrate constitute a part of the metal organic structure, and the metal substrate and the metal organic structure are integrated. In addition, when step 1b is performed, the surface of the metal substrate is modified in step 1b, and then a metal layer is formed, and a metal organic structure is formed with the metal ions of the metal layer as a starting point. That is, it is presumed that the metal-organic structure is formed so as to be integrated with the metal layer, and the metal substrate is in a state where the organic-metal structure is maintained by the modified surface. In other words, the metal substrate, the metal layer, and the organometallic structure can be said to be integrated. That is, in the multilayer body of the present disclosure, the metal substrate and the organometallic structure are directly bonded or through the metal layer to form an integrated state.

The present disclosure includes a laminate obtained by the manufacturing method of the present disclosure.

In one aspect, the present disclosure includes a multilayer body formed of a metal substrate and a metal organic structure formed on the metal substrate, and formed on the metal substrate in a manner integral with the metal substrate. There are metal organic structures.

In one aspect, the present disclosure includes a laminated body having a metal substrate and a metal organic structure formed on the metal substrate. The metal atoms on the surface of the metal substrate constitute a part of the metal organic structure. .

In one aspect, the present disclosure includes a laminated body having a metal substrate and a metal organic structure formed on the metal substrate. The surface of the metal substrate is modified, and the modified surface has a metal layer. A metal organic structure is formed on the metal layer. In the laminated body, it is preferable that the metal substrate and the metal layer are chemically bonded by a modified portion, and the metal atoms of the metal layer constitute a part of the metal-organic structure.

In the laminated body of the present disclosure, the adhesion between the metal substrate and the metal organic structure is high. Therefore, the laminated body of the present disclosure is suitable for applications requiring durability, such as humidity control applications. In addition, the laminated body of the present disclosure is unlikely to cause peeling of the metal-organic structure layer, so it can also be applied to a substrate having a complicated shape. From this point of view, it can be said that it is suitable for the shape of fins, etc., and in order to increase the surface area, humidity control or heat exchange of a complicated shape is required.

Therefore, the present disclosure includes a fin composed of the laminated body of the present disclosure.

In addition, the present disclosure includes a dehumidifier and humidifier, which are formed with fins composed of the laminated body of the present disclosure.

In addition, the present disclosure includes a heat exchanger having fins composed of the laminated body of the present disclosure.

    (Example)    

Example 1

An Al test piece was prepared as a metal substrate. In the pretreatment, the metal substrate was ultrasonically washed in acetone for 30 minutes, and then immersed in HFE7200 and dried.

Next, each metal substrate was immersed in an HF solution for 30 minutes, and then the metal substrate was impregnated with an aqueous solution (50 mL) of Al (NO ₃ ) ₃ ‧H ₂ O (5.43 g, 25 mmol). An aqueous solution (80 mL) of NaOH (6.0 g, 3 eq, 150 mmol) and terephthalic acid (8.3 g, 50 mmol) was added and heated at 100 ° C. for 12 hours.

The post-treatment is performed by washing the surface of the metal substrate with methanol and heating and drying at 70 ° C. to form a metal-organic structure layer on the metal substrate.

Example 2

A metal organic structure layer was formed on the surface of the metal substrate in the same manner as in Example 1 except that an Fe test piece was used as the metal substrate.

Example 3

A metal organic material was formed on the surface of the metal substrate in the same manner as in Example 1 except that the surface of the metal substrate was irradiated with UV-O ₃ (UV-ozone irradiation device manufactured by TECHNOVISION Co., Ltd.) for 10 minutes. Structure layer.

Example 4

A metal organic structure layer was formed on the surface of the metal substrate in the same manner as in Example 3, except that an Fe test piece was used as the metal substrate.

Example 5

Poly (ethylene glycol) methacrylate (manufactured by Sigma-Aldrich, hereinafter referred to as "PEGMA") (19.4 g), methacrylic acid ethoxyethyl phosphate (manufactured by Toho Chemical Industry, below) were fed into a branch test tube. (Referred to as "PPME") (0.6 g) and isopropyl ether (hereinafter referred to as "IPA") (80 g), nitrogen was exhausted for 10 minutes, and heated to 70 ° C. Next, azobisisobutyronitrile (hereinafter referred to as "AIBN") (0.1161 g) was added and reacted for 6 hours to obtain a solution of PEG-PPME polymer (polymerization ratio 97/3) (resin solid content concentration 0.5% by weight). .

An Al test piece was prepared as a metal substrate. In the pretreatment, the metal substrate was ultrasonically washed in acetone for 30 minutes, and then immersed in HFE7200 and dried. Next, the metal substrate was immersed in the PEGMA / PPMA polymer solution obtained above, and then left in the air (20 ° C, humidity 30%) for one day and night to obtain a PEG-coated substrate.

Next, aluminum oxide (75 mg) was added to ethanol (10 mL) and subjected to ultrasonic treatment for 1 hour to obtain an aluminum oxide / ethanol solution. Next, the PEG-coated substrate obtained above was washed three times with ethanol to remove water, and then immersed in the alumina-butoxide / ethanol solution and subjected to ultrasonic treatment for 1 hour.

Next, the metal substrate was immersed in an aqueous solution (50 mL) of Al (NO ₃ ) ₃ ‧H ₂ O (5.43 g, 25 mmol), and dissolved in NaOH (6.0 g, 3 eq, 150 mmol) and terephthalic acid (8.3 g, 50 mL) of 80 mL of an aqueous solution was heated at 100 ° C. for 12 hours. Thereafter, the surface was washed with methanol, and heated and dried at 70 ° C. to form a metal-organic structure layer on the metal substrate.

Comparative Example 1

A metal-organic structure layer was formed on the surface of the metal substrate in the same manner as in Example 1 except that the metal substrate was not immersed in HF.

Comparative Example 2

In addition, a complex is formed from Al (NO ₃ ) ₃ and terephthalic acid. The obtained complex and urethane resin as a binder are mixed, and a metal substrate is impregnated therein, thereby forming a metal on the surface of the metal substrate. Organic structure layer.

Endurance test

The laminated bodies obtained in Examples 1 to 5 and Comparative Examples 1 to 2 were immersed in warm water at 70 ° C. for 1,500 hours. Thereafter, the surface was visually observed for MOF peeling. Moreover, the weight change rate of the base material before and after immersion was calculated | required. The results are shown in the table below.

From the above results, it can be seen that, before the metal-organic structure is formed, the laminated system disclosed by the activation of the metal surface shows less peeling and higher adhesion.

    (Industrial availability)    

The laminated system having a metal substrate and a metal organic structure formed on the metal substrate of the present disclosure is suitable for use as an adsorbent, a catalyst, and the like.

Claims (13)

    A method for manufacturing a laminated body. The aforementioned laminated system has a metal substrate and a metal organic structure formed on the metal substrate. The method for manufacturing the laminated body has the following steps: (step 1a) activating the surface of the metal substrate Step, or (step 1b) a step of modifying the surface of the metal substrate and forming a metal layer thereon; and (step 2) combining the metal substrate treated by the above step 1a or step 1b with a solution containing at least one metal ion and The step of forming a metal organic structure on a metal substrate by contacting a solution containing at least one organic ligand.         A method for manufacturing a laminated body. The aforementioned laminated system has a metal substrate and a metal organic structure formed on the metal substrate. The method for manufacturing the laminated body has the following steps: (step 1a) activating the surface of the metal substrate Steps; and (step 2) a step of contacting the surface of the metal substrate with a solution containing at least one metal ion and a solution containing at least one organic ligand to form a metal organic structure on the metal substrate.         The manufacturing method according to item 1 or 2 of the scope of patent application, wherein the metal constituting the aforementioned metal substrate is Si, Al, Cu, Fe, Ni, Zn, or Fe / Ni / Cr alloy.         The manufacturing method according to any one of claims 1 to 3, wherein the step of activating the surface of the metal substrate is performed by treating the surface of the metal substrate with hydrogen fluoride, hydrogen chloride, fluorine, or chlorine.         The manufacturing method according to any one of claims 1 to 4, wherein in step 2 above, the metal ions contained in the solution are ions of Al, Cu, Fe, Mn, or Co.         The manufacturing method according to any one of claims 1 to 5, wherein the metal ion system formed on the surface of the metal substrate by the activation of the step 1a is the same as the metal ion in the solution.         The manufacturing method according to any one of claims 1 to 6, wherein the organic ligand is selected from 1,4-benzenedicarboxylic acid, 1,2-benzenedicarboxylic acid, and maleic acid Diacid, 1,3,5-benzenetricarboxylic acid, 4,4 ', 4 "-(1,3,5-benzenetriyl) parabenzoic acid, 4,4'-bipyridine, triazole, imidazole, 3,3'-bipyrazole, benzimidazole, and 3,5-pyridinedicarboxylic acid.         A laminated body is obtained by the manufacturing method described in any one of claims 1 to 7 of the scope of patent application.         A laminated body is a metal substrate and a metal organic structure formed on the metal substrate, wherein the metal atoms on the surface of the metal substrate constitute a part of the metal organic structure.         A laminated body is a metal substrate and a metal organic structure formed on the metal substrate, wherein the surface of the metal substrate is modified, and the modified surface has a metal layer on the metal layer. A metal organic structure is formed.         A fin is composed of a laminated body described in item 9 or 10 of the scope of patent application.         A dehumidifier / humidifier is a product having fins as described in item 11 of the scope of patent application.         A heat exchanger is one having the fins described in item 11 of the scope of patent application.