JP2019056055A - Molded body, and production method of the same - Google Patents

Abstract

To provide a molded body capable of achieving both of a function derived from the porous nature of a metalorganic structure and an effect by resin composite, and a production method of the same.SOLUTION: A molded body includes: a metalorganic structure, and a surface composed of a composite material containing a resin having a SP value of 15-25 (MPa), where the metalorganic structure is exposed on the surface composed of the composite material, and the ratio of metalorganic structure exposed on the surface found by the following formula (1) is 5-98%. The ratio of a metalorganic structure exposed on the surface=(A/B)×100 (1), where A is an amount (atm%) of a metal atom derived from the metalorganic structure on the surface composed of the composite measured by an X-ray photoelectron spectroscopy method, and B is an amount of metal atom (atm%) in the metalorganic structure.SELECTED DRAWING: None

Description

  The present invention relates to a molded body and a manufacturing method thereof.

A metal-organic complex (Metal-Organic Framework; hereinafter referred to as “MOF”) or a porous coordination polymer (hereinafter also referred to as “PCP”) includes a metal ion and a plurality of coordination. It is a structure having a one-dimensional, two-dimensional, or three-dimensional regular and continuous structure obtained through bond formation by a coordinate bond with an organic ligand having a coordinated functional group (for example, non-patent literature) 1).
For example, zinc nitrate hexahydrate and terephthalic acid (1,4-benzenedicarboxylic acid, also referred to as H ₂ BDC) are reacted by pressurization and heating, or a reaction is performed using a tertiary amine as a catalyst. Then, a structure represented by the composition formula Zn ₄ O (BDC) ₃ is obtained. BDC represents 1,4-benzenedicarboxylate. This structure is a structure in which the structures of the above-described composition formulas are continuously connected in a three-dimensional manner, and is sometimes referred to as MOF-5.

The characteristic of MOF is the vacancies in its structure. The pores can be freely designed in size and shape by changing the metal or organic matter. From this, MOF is expected to be applied to storage of gas and liquid, separation of various substances or filtration. The difference from conventional porous materials such as zeolite and activated carbon is that the size and structure of the pores can be designed according to the structure of the metal species and the organic compound. That is, the MOF can adjust the size, shape, and polarity of the pores according to the molecules to be adsorbed, stored, separated, or filtered.
MOF can also use the metal in the structure as a catalyst. The MOF can be used for various applications such as a magnetic material, an ion conductive material, a sensor, and an optical material by enclosing various materials in the pores. The structure, function, application field, etc. of MOF have been reported by many reviews (for example, Non-Patent Document 2).

  MOF is a rigid organic configuration between metal atoms, metal ions, metal clusters, or metal-containing secondary structural units (hereinafter also referred to as SBU) that have been adjusted in coordination number for MOF formation. In most cases, it consists of a regular structure linked by a ligand. For this reason, MOF has high crystallinity and often takes a single crystal or polycrystalline structure. In addition, the MOF essentially has pores therein. For this reason, MOF crystals are brittle, and when MOF is disposed on the surface of a substrate such as a film or elastic body, it may be damaged by physical contact or impact, or the MOF may be damaged or dropped due to deformation of the substrate. Thus, the function as MOF may be lost.

  Recently, it has been studied to combine MOF with resin. In Non-Patent Document 3, MOF (UiO-66) having zirconium (Zr) as a metal and terephthalic acid as an organic ligand is combined with a styrene-butadiene copolymer (SBS or SBR) or polystyrene (PS). It is described.

CrystEngComm, 2012, 14 volumes, 3001 Science and Technology of Advanced Materials, 16, vol. 2015, paper number 054202 Chemical Communications, 2016, 52, 14376

  However, when MOF and resin are combined by the method of Non-Patent Document 3, the porosity of MOF is sacrificed and the adsorption performance is lowered. As the resin ratio is increased, the flexibility and physical strength are increased, but the adsorption performance is significantly reduced. That is, there is a trade-off relationship between flexibility and physical strength and adsorption performance.

  An object of this invention is to provide the molded object which can satisfy | fill the function derived from the porosity of MOF, and the effect by resin composite, and its manufacturing method.

The present invention has the following aspects.
[1] It has a surface made of a composite material including a metal organic structure and a resin having an SP value of 15 to 25 (MPa) ^1/2 ,
The metal organic structure is exposed on the surface made of the composite material,
The molded object whose metal organic structure body ratio exposed by the surface calculated | required by following formula (1) is 5-98%.
Ratio of metal-organic structure exposed on the surface = (A / B) × 100 (1)
However, A shows the quantity (atm%) of the metal atom derived from the said metal organic structure in the surface which consists of the said composite material measured by X-ray photoelectron spectroscopy,
B represents the amount of metal atoms (atm%) in the metal organic structure.
[2] The molded article according to [1], wherein the surface made of the composite material has an uneven structure.
[3] The molded article according to [2], wherein the uneven structure includes a regular periodic structure.
[4] The molded body according to any one of [1] to [3], wherein a mass ratio of the resin to the metal organic structure is 2/98 to 90/10.
[5] The molded body according to any one of [1] to [4], wherein the metal organic structure has a crystal structure, and a median value of the crystal structure is 10 nm to 500 μm.
[6] The molded product according to [5], wherein the median size of the crystal structure is 50 nm to 100 μm.
[7] The molded product according to [6], wherein a median value of the crystal structure is 500 nm to 20 μm.
[8] A primary molded body having a surface made of a composite material including a metal organic structure and a resin having an SP value of 15 to 25 (MPa) ^1/2 is manufactured.
The manufacturing method of a molded object which gives a physical process to the surface which consists of the said composite material of the said primary molded object, and exposes the said metal organic structure.
[9] The method for producing a molded article according to [8], wherein the physical treatment is at least one selected from the group consisting of corona treatment, plasma treatment, and flame treatment.
[10] The method for producing a molded article according to [8] or [9], wherein a concavo-convex structure is formed on the surface of the primary molded article made of the composite material before or after the physical treatment.

  ADVANTAGE OF THE INVENTION According to this invention, the molded object which can satisfy | fill both the function derived from the porosity of MOF, and the effect by resin composite, and its manufacturing method can be provided.

It is a schematic cross section which shows an example of the molded object of this invention. It is a schematic cross section which shows the other example of the molded object of this invention.

[Molded body]
The molded body of the present invention (hereinafter also referred to as “main molded body”) has a surface (hereinafter referred to as “composite”) composed of a composite material containing MOF and a resin having an SP value of 15 to 25 (MPa) ^1/2. It is also referred to as “material surface”.). The composite material will be described in detail later.
In addition, in this specification and a claim, "-" which shows a numerical range means that the numerical value described before and behind that is included as a lower limit and an upper limit.

As a molded object which has a composite material surface, the following (i) and (ii) are mentioned, for example. However, the molded body is not limited to these.
(I) A molded body made of a composite material.
(Ii) A molded body (laminate) having a base material made of a material other than the composite material and a layer made of the composite material provided on the base material (hereinafter also referred to as “composite material layer”).

The molded body (i) may be a laminated body in which a plurality of composite material layers are laminated.
In the molded article (ii), the material of the base material is not particularly limited, and examples thereof include resin, metal, ceramic, glass, wood, paper, and cloth.
The molded body (ii) may further have another layer between the base material and the composite material layer.

The shape etc. of this molded object are not specifically limited, For example, it may be arbitrary shapes, such as a sheet form, a film form, and a three-dimensional shape. A shape having a large surface area is preferable in that the surface function of the MOF can be further utilized. As an example, a sheet form and a film form can be mentioned.
If the molded body is in a bulk form with a small surface area, or if characteristics such as flexibility are required even in a sheet form or a film form, the base material made of a material other than the composite material, A composite material layer may be provided.

FIG. 1 is a schematic cross-sectional view showing an example of the molded body. The molded body 1 in this example is a sheet made of a composite material. The first surface 1a of the molded body 1 and the second surface 1b on the opposite side are composite material surfaces. Although there is no restriction | limiting in particular in the thickness of the molded object 1, For example, you may be 10 micrometers-10 mm.
FIG. 2 is a schematic cross-sectional view showing another example of the molded body. The molded body 2 in this example is a laminated sheet including a base material 3 and a composite material layer 4 laminated on both surfaces of the base material 3. The first surface 2a of the molded body 2 and the second surface 2b opposite to the first surface 2a are composite material surfaces. Although the thickness in particular of the base material 3 is not restrict | limited, For example, if it gives as an example of a flexible sheet | seat, it may be 10 micrometers-30 mm. Since the thickness of the composite material layer 4 is determined in consideration of the surface function required by the molded body, mechanical properties such as flexibility of the base material, base material followability and adhesion of the composite material layer, etc. For example, it may be 1 μm to 1 mm as an example.
1 to 2 are different from actual ones for convenience of explanation. In the molded body 2, the composite material layer 4 may be laminated only on one side of the substrate 3.

The MOF is exposed on the composite material surface of the molded body. Further, the MOF ratio exposed on the surface (hereinafter also referred to as “surface exposed MOF ratio”) obtained by the following formula (1) of the molded body is 5 to 98%.
The surface exposure MOF ratio is an index indicating the ratio of the portion of the composite material surface where the MOF is exposed. If the surface exposure MOF ratio is not less than the above lower limit value, the functions derived from the porosity of the MOF (adsorption function, etc .; hereinafter also referred to as “MOF function”) are sufficiently developed. If the surface exposure MOF ratio is equal to or less than the above upper limit value, the MOF is hardly damaged or dropped off, and the durability of the MOF function is excellent.
The MOF ratio is preferably 10 to 90%, more preferably 15 to 80%, and still more preferably 46 to 80%.

Surface exposure MOF ratio = (A / B) × 100 (1)
However, A shows the quantity (atm%) of the metal atom derived from MOF in the composite material surface measured by X ray photoelectron spectroscopy (henceforth "XPS"),
B shows the amount of metal atoms (atm%) in MOF.

The amount A of metal atoms by XPS is a ratio to the total atomic weight (100 atm%) of atoms having an atomic weight equal to or higher than lithium as measured by XPS. Details of the method of measuring the amount A of metal atoms are shown in the examples described later.
The amount B of metal atoms in the MOF is a ratio with respect to the total atomic weight (100 atm%) of atoms having an atomic weight equal to or higher than lithium constituting the MOF. The amount B of metal atoms is calculated from the MOF composition formula.
When the composite material includes a plurality of MOFs, the value of B is a weighted average value of the amount of metal atoms in each MOF, with the mass of each MOF as a weight.
The surface exposure MOF ratio can be adjusted by the mass ratio of the MOF and the resin in the composite material, the conditions of physical treatment applied to the composite material surface, and the like.
The surface exposure MOF ratio can be easily confirmed by performing elemental analysis of the composite material surface with an energy dispersive X-ray analysis (EDX) apparatus attached to a scanning electron microscope (SEM). The value by EDX does not necessarily match the value by the above formula (1), but shows the same tendency as the value by the above formula (1). For example, the larger the value by EDX, the larger the value by the above formula (1).

The molded body preferably has an uneven structure on the surface of the composite material.
Examples of the concavo-convex structure include a shape in which a plurality of convex portions or concave portions are arranged in a distributed manner, a shape in which a plurality of ridges or grooves are arranged in parallel (so-called line and space), and a wavy shape. Examples of the shape of the convex portion or the convex portion include a columnar shape, a polygonal columnar shape, a hemispherical shape, a conical shape, and a polygonal pyramid shape.

By having a concavo-convex structure on the composite material surface, the following two effects can be obtained.
One is an increase in surface area. As the MOF in the molded body, the one located on the surface of the molded body exhibits more function. By increasing the surface area, the MOF located on the surface increases, and the MOF in the molded body can be used more effectively.
Another effect is to cause turbulent flow such as gas or liquid on the surface of the molded body. The MOF function includes gas, liquid adsorption, storage, separation, and the like. When the gas or liquid that is the target of adsorption, storage, separation, etc. passes through the surface of the molded body, if the surface of the molded body is flat, the gas or liquid flows as it is. There is a possibility that the concentration of liquid or liquid tends to decrease. If there is a concavo-convex structure on the surface, a turbulent flow of gas or liquid occurs there, and the gas or liquid near the surface is agitated. Thereby, the density | concentration of the gas and liquid used as adsorption | suction, storage, isolation | separation, etc. does not fall on the molded object surface, but effective function expression can be performed.

From the viewpoint of increasing the surface area, it is preferable that the concavo-convex structure has a shape that realizes a surface area 1.2 times or more with respect to a plane having the same size in a top view.
On the other hand, when the surface area becomes extremely large with respect to the plane, the uneven structure is easily broken. Although the specific upper limit depends on the physical properties of the resin, it cannot be generally stated. For example, a line-and-space with a large aspect ratio (height / width) in the height direction such that the surface area is more than 10 times the plane. When formed on the surface, the concavo-convex structure is unstable and easily brittle. Therefore, the surface area of the concavo-convex structure is preferably not more than 10 times the surface area of a plane having the same size as viewed from above.

The concavo-convex structure effective for function expression can be defined by simulation from the direction and speed of the target gas or liquid flow, but the shape in which multiple convex parts are distributed and the direction of the flow Line and space are preferred.
The concavo-convex structure preferably includes a regular periodic structure in that the flow of gas or liquid is easily spread over the entire surface of the composite material. The regular periodic structure is preferable from the viewpoint of easy manufacture.
In the regular periodic structure, a plurality of structures (projections, recesses, ridges, grooves, etc.) having the same size are arranged at a constant pitch and in a certain direction within the surface of the composite material. The arrangement direction of the plurality of structures may be one direction or two or more directions.
The size of the plurality of structures constituting the regular periodic structure is selected according to the target gas or liquid. In terms of formability, the width in the arrangement direction (the diameter of the projections or recesses, the width of the projections or grooves, etc.) is appropriately within the range of 20 nm to 1 mm. The aspect ratio in the height direction is preferably 10 or less from the viewpoint of durability. The pitch can be, for example, 20 nm to 5 mm.

(MOF)
The MOF is not particularly limited as long as it conforms to the definition of MOF. MOF is a structure in which a metal atom (which may be a metal ion) and an organic ligand having two or more coordination functional groups are continuously bonded. The MOF is typically a porous body having a plurality of pores inside. The MOF may include some functional molecules in the pores.

Examples of metal atoms constituting MOF include zinc, cobalt, niobium, zirconium, cadmium, copper, nickel, chromium, vanadium, titanium, molybdenum, and aluminum. However, the metal atoms constituting the MOF are not limited to these. The metal atoms constituting the MOF may be one type or two or more types.
As a metal raw material of MOF, a complex having a metal ion such as Zn ²⁺ , Cu ²⁺ , Ni ²⁺ , Co ²⁺ or a metal-containing secondary structural unit (SBU) is particularly suitable.

The coordinating functional group of the organic ligand is a functional group capable of coordinating to a metal atom, such as a carboxyl group, an imidazole group, a hydroxyl group, a sulfonic acid group, a pyridine group, a tertiary amine group, an amide group, a thioamide group, etc. Is mentioned.
As the organic ligand, one in which two or more coordinating functional groups are substituted with a skeleton having a rigid structure (for example, an aromatic ring, an unsaturated bond, etc.) is typically used.
Examples of organic ligands that can be suitably used in the present invention are shown below. However, the present invention is not limited to this.
1,3,5-tris (4-carboxyphenyl) benzene (BTB), 1,4-benzenedicarboxylic acid (BDC), 2,5-dihydroxy-1,4-benzenedicarboxylic acid (DOBDC), cyclobutyl-1, 4-benzenedicarboxylic acid (CB BDC), 2-amino-1,4-benzenedicarboxylic acid (H2N BDC), tetrahydropyrene-2,7-dicarboxylic acid (HPDC), terphenyl dicarboxylic acid (TPDC), 2,6 -Naphthalenedicarboxylic acid (2,6-NDC), pyrene-2,7-dicarboxylic acid (PDC), biphenyldicarboxylic acid (BPDC), any dicarboxylic acid having a phenyl compound, 3,3 ', 5,5'- Biphenyltetracarboxylic acid, imidazole, benzimidazole, 2-nitroimidazole, cyclobenzui Midazole, imidazole-2-carboxaldehyde, 4-cyanoimidazole, 6-methylbenzimidazole, 6-bromobenzimidazole and the like.

Specific examples of the obtained MOF are listed below, but the present invention is not limited thereto.
MOF-177 represented by Zn ₄ O (1,3,5-benzenetribenzoate) ₂ ; MOF represented by Zn ₄ O (1,4-benzenedicarboxylate) ₃ , also known as IRMOF-I −5; MOF-74 (Mg) represented by Mg ₂ (2,5-dihydroxy-1,4-benzenedicarboxylate); Zn ₂ (2,5-dihydroxy-1,4-benzenedicarboxylate) MOF-74 (Zn) represented by: MOF-505 represented by Cu ₂ (3,3 ′, 5,5′-biphenyltetracarboxylate); Zn ₄ O (cyclobutyl-1,4-benzenedicarboxyl) _Zn 4 O (terphenyl; IRMOF-3 represented by Zn 4 O (2-amino-1,4-benzene _{dicarboxylate) 3; IRMOF-6} represented by the rate) _{Carboxylate) 3} or _Zn 4 O _{(tetrahydropyrene-2,7-dicarboxylate)} IRMOF-11 is represented by _3; IRMOF represented by _Zn 4 O _{(tetrahydropyrene-2,7-dicarboxylate) 3} -8; ZIF-68 represented by Zn (benzimidazolate) (2-nitroimidazolate); ZIF-69 represented by Zn (cyclobenzimidazolate) (2-nitroimidazolate); Zn (benzimidazole) ZIF-7 is expressed by _{rate) 2;} Co (benzimidazolyl _rate) ZIF-9 is expressed by _2; Zn ₂ (ZIF-11 represented by benzimidazolyl rate); Zn (butylimidazolate-2-carboxaldehyde ) ZIF-90 represented by _2; Zn (4-cyano-imidazo rate) (2-nitro-imidazolate) ZIF-82; ZIF-70 represented by Zn (imidazolate) (2-nitroimidazolate); ZIF-79 represented by Zn (6-methylbenzimidazolate) (2-nitroimidazolate); and Zn ZIF-81 represented by (6-bromobenzimidazolate) (2-nitroimidazolate) and the like.

The MOF typically has a crystal structure. Since MOF has a regular structure, it is easy to crystallize and is easily obtained as a single crystal or polycrystal. The crystal may be a single crystal or a polycrystal.
The size of the crystal structure is preferably 10 nm to 500 μm, more preferably 50 nm to 100 μm, and even more preferably 500 nm to 20 μm as a median value. When the median of the size of the crystal structure is within the above range, both the MOF function and the physical and mechanical properties as a composite can be achieved.
When the median of the size of the crystal structure is less than 10 nm, the MOF structural unit constituting the crystal structure is considered to be approximately 3 or less, the surface area ratio is too large in the state of being compounded in the resin, and the pores are It may not be used. On the other hand, when the median size of the crystal structure is more than 500 μm, the interface between the resin and the MOF peels off, reflecting the difference in physical properties (for example, elastic modulus and thermal expansion coefficient) from the resin, resulting in a composite It may be a defective part of the material. Therefore, if the size of the MOF crystal structure in the resin is too small, the function of the MOF is limited. If it is too large, the strength and durability of the composite material may be insufficient.

The median size of the MOF crystal structure is measured by the following method.
An image of the surface of the molded body (composite material surface) is obtained using a scanning electron microscope or an optical microscope. The magnification at this time is a magnification at which the number of crystals (MOF) present in the image is 100 to 200. The maximum diameter of all the crystals present in the obtained image is measured, and the median value (average value of the minimum value and the maximum value) is calculated, and this value is the median value of the crystal structure size of MOF. And

(resin)
The SP value of the resin is 15 to 25 (MPa) ^1/2 and is preferably 16 to 23 (MPa) ^1/2 .
The SP value is the square root of the material cohesive force, and is a specific numerical value depending on the composition and structure of the material. The cohesive strength of the material consists of components of dispersion, polarity and hydrogen bonding. Of these, the dispersion force is relatively small depending on the type of molecule. On the other hand, the polarity and the hydrogen bond are greatly different depending on the functional group of the molecule. In general, a molecule having a large polarity has a large polar interaction between the molecules, and has a large SP value. A molecule capable of hydrogen bonding has high cohesion due to hydrogen bonding, resulting in a large SP value.
When the SP value is within the above range, the MOF and the resin interact moderately, and the interface between the MOF and the resin can be easily peeled off even if stress is applied during or after the production of the composite material or molded article. In addition, since there is no interaction more than necessary, the function of the MOF as a porous body can be fully utilized.

A resin having an SP value of less than 15 (MPa) ^1/2 not only has a weak interaction between the same molecules, but also has a small interaction with other materials. Even if the MOF is combined, the interaction with the MOF is weak and the interface peels off, making it difficult to exhibit sufficient strength as a molded body. In addition, in a resin having an SP value of less than 15 (MPa) ^1/2 , a material having a strong cohesive force such as MOF is difficult to disperse and aggregates. When agglomeration occurs, it is not possible to satisfy the softness, flexibility, and durability that were the aim of the composite.
Examples of the resin having an SP value of less than 15 (MPa) ^1/2 include perfluoro resins such as polytetrafluoroethylene and hydrophobic silicone resins such as dimethylsiloxane.

On the other hand, a resin having an SP value of more than 25 (MPa) ^1/2 includes a polar group and a hydrogen bonding group, and thus strongly interacts with a highly polar MOF. Here, since strong polar groups and hydrogen bonding groups generally have coordinating ability, when MOF and a high SP value resin are combined and heated in a combined state or for a long period of time, they bind and bond to MOF. An exchange may occur and destroy the MOF. Even when a high SP value resin does not break the bond of MOF, the resin surrounds the MOF due to strong interaction with the MOF, making it difficult to utilize the holes of the MOF.
Examples of resins having an SP value of more than 25 (MPa) ^1/2 include hydroxyl group-containing resins such as polyvinyl alcohol and phenol resin, cyano group-containing resins such as polycyanoacrylate and polydinitrile fumarate, and primary grades such as polyvinylamine. Or secondary amino group containing resin is mentioned.

The resin is not particularly limited as long as the SP value is within the above range.
Examples of the resin include a thermoplastic resin and a curable resin. The molecular weight of the thermoplastic resin may be in a range that can be molded, and may be, for example, 5,000 to 1,000,000. Examples of the curable resin include a thermosetting resin and a photocurable resin. In addition, when resin is curable resin, SP value of resin is SP value of curable resin after hardening.
The resin may be a resin whose main chain is composed of carbon atoms, or may be a resin (polyether resin, silicone resin, etc.) containing atoms other than carbon atoms in the main chain.

Specific examples of the resin are shown below. However, the resin used in the present invention is not limited to these. In addition, (meth) acrylate shows an acrylate or a methacrylate.
Polyolefin resins such as polyethylene, polypropylene, polybutadiene, and polyisoprene; poly (meth) acrylate resins such as poly (meth) acrylate methyl, poly (meth) acrylate butyl, and poly (meth) acrylate hexyl; polyvinyl acetate, polyvinyl Polyvinyl ester resins such as butyral; polyvinyl ether resins such as polyvinyl phenyl ether; polyvinyl halide resins such as polyvinyl chloride; polystyrene resins such as polystyrene and polymethylstyrene; polyvinyl ester resins such as polydimethylmaleic acid and polydimethylfumaric acid; Polyamide resin such as nylon 66; polyimide resin; polyester resin such as polyethylene terephthalate; cellulose resin such as cellulose and cellulose acetate; alkyd resin; polyurethane resin ; Polylactic acid; polyethylene oxides, polyoxyalkylene resins, such as polypropylene oxide; polycarbonate resins, epoxy resins, furan resins; backbone aromatic sophisticated polymer; benzoxazine resin. These copolymers, composites, mixtures and the like can also be used.

As resin, 1 type may be used independently and 2 or more types may be used together.
When two or more kinds of resins are used in combination, if the SP value of the whole of the two or more kinds of resins is within the range of 15 to 25 (MPa) ^1/2 , the SP value by itself is 15 (MPa) ^1/2. Less than or 25 (MPa) ^1/2 resin may be included.

  Several types of SP values are known. The SP value in the present invention is a Hansen solubility parameter. The SP value can be known from documents such as Polymer Handbook (4th edition, 1999, page VII / 675). If the molecular structure is known, it can be estimated from the type of functional group.

(Composite material)
The composite material includes the above-described MOF and resin. The composite material may further contain other components as needed within a range not impairing the effects of the present invention.

In the composite material, the blending ratio of MOF and resin is determined in consideration of the MOF function desired for the molded body.
The mass ratio of resin to MOF (resin / MOF) is preferably 2/98 to 90/10, more preferably 5/95 to 70/30, and still more preferably 10/90 to 50/50. When the resin / MOF is 2/98 or more, the function as a so-called binder is sufficient to hold the MOF by the resin, and the MOF caused by physical contact or impact on the composite material surface, deformation of the composite material surface, etc. Less likely to break or drop off. Moreover, the moldability of the composite material is excellent. When the resin / MOF is 90/10 or less, the MOF function is easily exhibited because the absolute amount of MOF is sufficiently large and the MOF is not easily surrounded by the resin.
The total content of MOF and resin may be, for example, 30 to 100% by mass with respect to the total mass of the composite material.

There is no restriction | limiting in particular as another component. For example, a surfactant or a dispersing agent may be used to assist mixing of the MOF and the resin. In order to improve the durability of the composite material, an antioxidant, an ultraviolet ray inhibitor and the like may be used. In order to enhance the decorating properties of the molded body, dyes, pigments, surface smoothing agents, lubricants, and the like may be used.
In addition, it is preferable to use those additives that do not interfere with the function of MOF. Therefore, it is preferable to use after evaluating the reactivity and interaction between MOF and the additive in advance.
In general, inorganic fine particles are often added to a resin for the purpose of an extender or a reinforcing agent. However, in the composite of MOF and resin, the addition of inorganic fine particles other than MOF affects the amount of MOF added, so it is preferable to determine the amount added with sufficient consideration of the effect on the MOF function.

  This molded object can be manufactured with the manufacturing method of the molded object shown below, for example.

[Method for producing molded article]
The method for producing a molded body of the present invention includes a step of manufacturing a primary molded body having a composite material surface (molding step), a step of performing physical treatment on the composite material surface of the primary molded body and exposing MOF (surface physical treatment). Process).
The manufacturing method of the molded object of this invention can further include the process (surface shaping | molding process) of forming an uneven structure in the composite material surface of a primary molded object before or after a surface physical treatment process as needed. . When the surface shaping step is performed after the surface physical treatment step, the surface physical treatment step may be performed again after the surface shaping step.

(Molding process)
As a method for producing the primary molded body, for example, a method in which MOF and a resin are combined and molded may be mentioned. As a method of combining the MOF and the resin, a known method of combining the inorganic additive and the resin may be used.
The most common composite method is a method of adding MOF crystals to a resin solution in which a resin is dissolved in a solvent. In this case, the primary molded body can be manufactured as follows.

First, MOF crystals and other components as necessary are added to the resin solution, and this mixture is stirred using a stirring means such as a stirring blade, a homogenizer, a bead mill, and a revolving type stirring and degassing apparatus. Disperse in to obtain a dispersion.
When obtaining a dispersion, a stirring method in which MOF crystals are broken more than necessary is not preferable. Agitation means such as an ultrasonic homogenizer and a ball mill that generate strong physical force and shear force are used in consideration of the strength of MOF.

Next, this dispersion is applied to a substrate or cast into a mold to obtain a desired form, and then the solvent is volatilized.
Here, the coating method of the dispersion liquid on the substrate is not particularly limited, and a known coating method may be used. For example, a roll coater, a bar coater, letterpress printing, intaglio printing or the like can be used for application to a flat surface or film. Application to the bulk or molded body can be performed by spraying, ink jetting, dip coating, electrostatic coating, or the like.
Further, the method for volatilizing the solvent is not particularly limited, and a known drying method such as drying by heat, drying by reduced pressure, or air drying may be used.
Thereby, a composite material molded body (sheet or the like) in which MOF is dispersed in the resin is formed. When a composite material molded body is obtained by applying to a base material, the laminate of the base material and the composite material molded body may be used as it is as a primary molded body, or the composite material molded body is peeled off from the base material as a primary molded body. Also good.

Another composite method includes a method of adding MOF to a thermoplastic resin and kneading under heating. In this case, a primary molded body is obtained by molding the obtained kneaded material.
The kneading method is not particularly limited. For example, a known kneading apparatus such as a kneader or a roll press can be used. You may use the kneading apparatus in a shaping | molding apparatus as it is. In this case, a lubricant or the like may be used as necessary.
The molding method is not particularly limited. For example, a known molding method can be used as a molding method of the thermoplastic resin such as press molding, injection molding, and extrusion molding.
In this method, since heat and shear force are applied to the MOF, it is preferable to examine in advance whether the MOF can withstand the stress.

MOF can be synthesized by a known method. A commercial product may be used as long as the desired MOF is commercially available. A plurality of methods for synthesizing MOF are known, and the method for synthesizing MOF used in the present invention is not particularly limited. Typical methods for synthesizing MOF are solution method and hydrothermal method. In addition, solid phase synthesis method (mechanochemical method), microwave method, ultrasonic method and the like are known.
The solution method is a method in which a solution of metals (metal complex or metal-containing secondary structure) and an organic ligand solution are mixed in the presence of a catalyst as necessary.
At this time, when the solvent of the metal solution and the solvent of the organic ligand solution are difficult to mix, the MOF synthesis reaction occurs at the interface. At this time, if the reaction system is allowed to stand, a relatively large MOF crystal may grow on the interface.
When the solvent of the metal solution and the solvent of the organic ligand solution are easily miscible, or when these solvents are the same solvent, the reaction occurs everywhere, so that fine crystals or polycrystals are formed. can get.
The hydrothermal method is a method in which a solution in which a metal and an organic ligand are dissolved in a solvent is sealed in a pressure vessel and heated to a temperature equal to or higher than the boiling point of the solvent to react at a high temperature and high pressure. It is preferably used when a low-reactivity product is reacted.
When the above materials (metals, organic ligands, etc.) are used and synthesized by these synthesis methods, various MOFs are synthesized according to the materials used. By selecting and combining metals and organic ligands, or using a plurality of metals and organic ligands in combination, MOF is synthesized with a high degree of design freedom.

As another method for producing a primary molded body, MOF, a polymerizable monomer (or a crosslinkable material), and other components as necessary are mixed, and the polymerizable monomer in the resulting composition is mixed. A method of forming a composite material by polymerizing (or cross-linking) a body (or a crosslinkable material) to obtain a composite material can be mentioned. After molding the composition, the polymerizable monomer (or crosslinkable material) in the composition may be polymerized (or crosslinked).
The mixing of the MOF and the polymerizable monomer (or crosslinkable material) or the like depends on the viscosity of the polymerizable monomer (or crosslinkable material) or the like, but is the same method as the mixing of the resin solution and MOF described above. It can be carried out. Polymerization (or crosslinking) may be performed in the presence of an initiator. When the curable resin is liquid, the use of a solvent may be omitted.
For example, MOF is dispersed in a styrene monomer, and styrene is radically polymerized. Thereby, a composite material in which MOF is dispersed in polystyrene is obtained. Since polystyrene is thermoplastic, it can be molded into a desired shape by hot pressing after polymerization.
Alternatively, a composite material is obtained by dispersing MOF in an epoxy resin before curing (for example, a mixture of bisphenol A diglycidyl ether and methylhexahydrophthalic anhydride), forming the desired form by coating or casting, and then curing by heating. A molded body (primary molded body) is obtained. Here, a thermosetting epoxy resin is taken as an example, but a photocurable material (for example, a polyfunctional acrylate) can also be used.

As another method for producing a primary molded body, metals (metal complex, metal-containing secondary structure, etc.) and organic ligands as raw materials for MOF, and other components as necessary are added to the resin solution. There is a method of synthesizing MOF in a resin solution to form a desired form by coating or casting, and then volatilizing the solvent.
As the resin, a resin having an organic ligand structure (for example, terephthalic acid polyether) may be used. In this case, it is not necessary to add an organic ligand separately.
When MOF is synthesized in a resin solution in this way, the resin and MOF can be combined without applying a large stress. Therefore, this method can be suitably used particularly when fragile MOF is combined with a resin.
In this method, unreacted metals and organic ligands may remain in the composite material molded body. Therefore, it is preferable to confirm that there is no problem even if these unreacted substances are removed from the composite material molded body by a solvent extraction method or the like or remain in the composite material molded body.

As another method for producing a primary molded body, a polymerizable monomer (or a crosslinkable material), a metal and an organic ligand as raw materials for MOF, and other components as necessary are mixed. A method of forming a composite material by polymerizing (or cross-linking) a polymerizable monomer (or cross-linkable material) and synthesizing MOF in the obtained composition to obtain a composite material can be mentioned. After molding the composition, polymerization (or crosslinking) of the polymerizable monomer (or crosslinkable material) in the composition and synthesis of MOF may be performed. The polymerization (or crosslinking) of the polymerizable monomer (or crosslinkable material) and the synthesis of MOF may be performed simultaneously or sequentially.
In this method, resin and MOF are synthesized simultaneously or sequentially. By using this method, a highly dispersed composite material can be obtained without stress. On the other hand, in this method, it is necessary to consider the influence of the MOF raw material on the polymerization reaction (or cross-linking reaction), and conversely the influence of the polymerizable monomer (or cross-linkable material) and initiator on the MOF synthesis reaction. For this reason, there are limitations on the system to be combined. In addition, it is necessary to consider the removal and influence of residual monomers and unreacted MOF raw materials from the composite material molded body.

  As described above, there are a wide variety of methods for producing a primary molded body. Not only the examples given above, but any known composite material forming method or molding method may be used as long as the MOF is not impaired.

(Surface physical treatment process)
In the surface physical treatment step, physical treatment is performed on the composite material surface of the primary molded body.
In order to exhibit a composite effect (flexibility, durability, moldability, adhesion to a substrate, cohesiveness, etc.) due to the resin, a certain amount of resin is required. In this case, a part of the MOF is buried in the resin. In this case, the MOF function is not fully exhibited.
By physically treating the composite material surface of the primary molded body and removing the resin film on the surface layer, the buried MOF is exposed to the surface, and the surface exposed MOF ratio of the composite material surface increases. As a result, the MOF function is fully exhibited. For example, by performing physical processing, the gas adsorption function is greatly improved.

A physical processing method will not be restrict | limited especially if it does not give a damage to a molded object, A well-known method can be used.
In order to expose the MOF, it is only necessary to remove the resin thin film existing on the MOF, so that a relatively mild physical treatment is preferable. Examples of such physical treatment include corona treatment, plasma treatment, and flame treatment. These treatments can be suitably used for performing only surface activation without causing fatal damage to the molded body.
However, the physical treatment is not limited to these methods, and a physical surface roughening method such as sandblasting, a method of applying strong electrical stress such as arc discharge, and the like can be used depending on the purpose.
It is preferable that the specific processing conditions are set while actually processing and confirming the molded body.

(Surface shaping process)
In the surface shaping step, an uneven structure is formed on the composite material surface of the primary molded body.
There is no restriction | limiting in particular in the formation method of an uneven structure, A general method can be used. Examples thereof include a method of transferring a concavo-convex structure by pressing a mold having a concavo-convex structure on the surface to the composite material surface under heating, a method of laser cutting the composite material surface, and the like. When the primary molded body is manufactured by casting, an uneven structure may be formed in advance on the mold.
When forming a fine concavo-convex structure with a pitch of less than 1 μm, it is preferable to use a nanoimprint technique. Nanoimprint technology can be broadly classified into thermal nanoimprint technology that heats and presses the mold, optical nanoimprint that casts and hardens a photocurable resin in a transparent mold, and molding that is targeted for relief plates such as silicone. There is a micro contact printing for attaching a body and printing on a necessary part, and any method can be suitably used in the present invention.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, as for the compound used in an Example, a solvent, etc., all the commercial products (Wako Pure Chemical Industries Ltd. make) unless otherwise indicated. “Room temperature” is a temperature of 23 ± 5 ° C.
The SP values in the examples were taken from the Polymer Handbook (4th edition, 1999, page VII / 675).
The method for measuring the surface exposure MOF ratio and the BET specific surface area is as follows. The center value of the size of the crystal structure of MOF was measured by the above-described measurement method using SEM.

(Surface exposure MOF ratio)
An XPS apparatus (manufactured by Kratos) was used, and the approximate center portion of the molded body (laminated body or sheet) was cut into a 10 mm square and a thickness of 5 mm under the following conditions to obtain a measurement sample. The amount A (atm%) of metal atoms (Zn or Zr) on the measurement target surface was measured using a 1 × 2 mm range near the center of the cut composite material surface. From this value and the amount B (atm%) of the metal atom (Zn or Zr) of the MOF used in the compact, the surface exposure MOF ratio (%) was calculated by the above formula (1).
XPS measurement conditions: Using an X-ray source AlKα (monochrome), a wide spectrum and a narrow spectrum of an assumed element are measured, and atm% is calculated from these results.

(BET specific surface area)
The BET specific surface area was measured as an index of the adsorption performance of the molded body. The BET specific surface area is a specific surface area measured by the BET method using nitrogen as an adsorption gas. The measurement was performed using a BET specific surface area meter (manufactured by Shimadzu Corporation).

(Synthesis Example 1: Synthesis of MOF-5)
Dissolve 5.7 g of terephthalic acid in 400 mL of dimethylformamide (hereinafter also referred to as “DMF”), add an equivalent amount of triethylamine (8.5 mL) to this solution, and stir at room temperature for 10 minutes. -A triethylamine solution was obtained. Separately, 23.1 g of zinc nitrate hexahydrate was added to 500 mL of DMF and dissolved to obtain a zinc nitrate solution. A zinc nitrate solution was added dropwise to the terephthalic acid-triethylamine solution over 15 minutes at room temperature while stirring. After completion of the addition, stirring was continued for another 2.5 hours at room temperature to obtain a reaction solution. The precipitate in the reaction solution was collected by filtration, dispersed again in 250 mL of DMF, and stirring was continued overnight at room temperature. Next, the precipitate was collected again by filtration, dispersed in 350 mL of chloroform (without stabilizer), and further washed for 1 day with stirring at room temperature. The washing treatment with chloroform was further repeated 3 times. The precipitate in chloroform was decanted and then precipitated with a centrifuge (2500 rpm, 3 minutes). The obtained precipitate was dried under reduced pressure at room temperature (using an oil pump), and further dried at 120 ° C. for 6 hours. 5.25 g of powder of MOF-5 (Zn atom amount B: 9.3 atm%) was obtained. The structure of MOF-5 was confirmed with a powder X-ray scattering device (manufactured by Shimadzu Corporation). When the obtained MOF-5 was observed with a scanning electron microscope (manufactured by JEOL), the center value of the size of the crystal structure was 2.5 μm.

(Synthesis Example 2: Synthesis of MOF-74)
2.4 g of 2,5-dihydroxyterephthalic acid was dissolved in 200 mL of DMF to obtain a phthalic acid solution. Separately, 9.3 g of zinc nitrate hexahydrate was dissolved in 200 mL of DMF to obtain a zinc solution. The phthalic acid solution was added dropwise to the zinc solution with stirring at room temperature over 10 minutes. After completion of the addition, stirring was continued at room temperature for another 20 hours to obtain a reaction solution. Crystals in the reaction solution were precipitated with a centrifuge (same conditions as in Synthesis Example 1). The obtained crystals were washed 3 times with 200 mL of DMF, then 3 times with 200 mL of methanol, dispersed again in 200 mL of methanol, and stirred overnight at room temperature. The crystals in methanol were separated with a centrifuge, and the obtained crystals were dried under reduced pressure at room temperature for 8 hours, then dried at 110 ° C. for 12 hours, then dried at 260 ° C. for 12 hours, and MOF− 2.9 g of powder of 74 (Zn) (Zn atom amount B: 12.5 atm%) was obtained. The structure of MOF-74 was confirmed with a powder X-ray scattering apparatus. The center value of the size of the crystal structure was 8.5 μm.

(Synthesis Example 3: Synthesis of UiO-66)
10.6 g of zirconium tetrachloride and 6.8 g of terephthalic acid were dissolved in 1000 mL of DMF at room temperature. This solution was heated and stirred at 120 ° C. for 24 hours under a nitrogen atmosphere to obtain a reaction solution. The reaction solution was cooled to room temperature, the precipitate in the reaction solution was collected by filtration, washed with DMF and chloroform and dried in the same manner as MOF-5 in Synthesis Example 1, and UiO-66 (Zr atom amount B: 0). .70 atm%) powder 3.4 g was obtained. The structure of UiO-66 was confirmed with a powder X-ray scattering apparatus. The center value of the size of the crystal structure was 0.8 μm.

Example 1
1 g of polyethyl acrylate (manufactured by Sigma-Aldrich, SP value 19.2 (MPa) ^1/2 ) was dissolved in 20 mL of tetrahydrofuran (hereinafter also referred to as “THF”). To this, 2 g of MOF-74 (Zn) powder was added and dispersed using a self-revolving stirring and degassing apparatus (manufactured by Shinky Corporation) to obtain a dispersion.
The dispersion was applied to a first surface of a 100 μm-thick surface hydrophilized polyethylene terephthalate (hereinafter also referred to as “PET”) film (manufactured by Teijin) with an applicator (manufactured by Tester Sangyo) at a thickness of 100 μm. After drying at room temperature for 2 hours, it was placed in an 80 ° C. oven and dried for 3 hours. As a result, a 6 μm thick cloudy MOF-containing film was obtained on the surface-hydrophilized PET film. Next, a laminate in which a MOF-containing film is formed in the same manner as described above on the second surface opposite to the first surface of the surface-hydrophilized PET film, and the MOF-containing film is laminated on both sides of the surface-hydrophilized PET film. Got. This laminate had a BET specific surface area of 620 m ² / g and a surface exposed MOF ratio of 45%.
When both surfaces of this laminate were treated with a corona treatment device (corona treatment), the BET specific surface area was 880 m ₂ / g and the surface exposure MOF ratio was 65%.
Further, a metal roll having a line-and-space structure with a pitch of 20 μm and a depth of 10 μm on the surface was pressed on both surfaces of this laminate, and the surface was shaped at 120 ° C., and then corona-treated again, resulting in a BET specific surface area. Was 1030 m ² / g, and the surface exposure MOF ratio was 69%.

(Example 2)
1 g of polyethylene (manufactured by Sigma-Aldrich, SP value 16.2 (MPa) ^1/2 ) and ² g of UiO-66 powder were placed in a heating table kneader (manufactured by Imoto Seisakusho) and kneaded at 220 ° C. for 30 minutes. . The obtained cloudy resin composite was pressed at 240 ° C. with a desktop press (manufactured by Imoto Seisakusho) to obtain a 100 μm thick sheet. This sheet had a BET specific surface area of 320 m ² / g and a surface exposed MOF ratio of 30%.
When this sheet was placed in a vacuum plasma apparatus and irradiated with argon plasma on both sides (argon plasma treatment), the BET specific surface area was 520 m ² / g and the surface exposed MOF ratio was 49%.
Furthermore, the metal roll used in Example 1 was pressed on each side of the sheet, surface-shaped at 240 ° C., and then subjected to argon plasma treatment again. As a result, the BET specific surface area was 630 m ² / g, and the surface exposed MOF The ratio was 55%.

(Example 3)
3 g of MOF-5 powder is added to 1 g of Epicoat 828 (manufactured by Sigma-Aldrich) and 1 g of methylhexahydrophthalic anhydride, 5 mL of DMF is further added, and the mixture is kneaded with a revolving type stirring deaerator. Got.
This mixture was applied to a 100 μm thick polyimide film (manufactured by DuPont) at a thickness of 30 μm using an applicator, and heated at 80 ° C. for 3 hours, 180 ° C. for 2 hours, and 220 ° C. for 1 hour. Thereby, the sheet | seat containing an epoxy resin (The hardened | cured material by the methyl hexahydrophthalic anhydride of Epicoat 828, SP value 22.2 (MPa) <^1/2> ) and MOF-5 was obtained on the polyimide film.
When the obtained sheet was peeled from the polyimide film, it became a 18um turbid light brown hard single sheet. This sheet had a BET specific surface area of 1200 m ² / g and a surface exposed MOF ratio of 27%.
When both surfaces of this sheet were treated with a flame treatment apparatus (flame treatment), the BET specific surface area was 1480 m ² / g and the surface exposure MOF ratio was 33%.
In addition, when trying to shape the surface of the sheet with the metal roll used in Example 1, the sheet was damaged. Therefore, separately, a sheet was prepared and flame-treated in the same manner as described above, and then a decoration process for forming a line and space structure with a width of 50 μm and a thickness of 5 μm was performed on each side of the sheet by laser cutting. As a result, the BET specific surface area of the sheet was 1650 m ² / g, and the surface exposed MOF ratio was 34%.

  As described above, the BET specific surface area was remarkably increased by physically treating the surface of the molded body. Furthermore, the BET specific surface area was further increased by imparting a concavo-convex structure to the surface.

According to the present invention, it is possible to provide flexibility, durability, and moldability as a resin while providing the molded body surface with an MOF function (adsorption performance and the like).
This molded product has excellent MOF function and durability, and can be used for molecular adsorption, storage, separation, sustained release of medicines and fragrances, magnetic materials, ion conductive materials, sensors, optical materials, etc. It is.

1, 2 Molded bodies 1a, 2a First surface (surface made of composite material)
1b, 2b 2nd surface (surface which consists of composite materials)
2 Molded body 3 Base material 4 Composite material layer

Claims (10)

A surface composed of a composite material including a metal organic structure and a resin having an SP value of 15 to 25 (MPa) ^1/2 ;
The metal organic structure is exposed on the surface made of the composite material,
The molded object whose metal organic structure body ratio exposed by the surface calculated | required by following formula (1) is 5-98%.
Ratio of metal-organic structure exposed on the surface = (A / B) × 100 (1)
However, A shows the quantity (atm%) of the metal atom derived from the said metal organic structure in the surface which consists of the said composite material measured by X-ray photoelectron spectroscopy,
B represents the amount of metal atoms (atm%) in the metal organic structure.   The molded body according to claim 1, wherein the surface made of the composite material has an uneven structure.   The shaped body according to claim 2, wherein the uneven structure includes a regular periodic structure.   The molded body according to any one of claims 1 to 3, wherein a mass ratio of the resin to the metal organic structure is 2/98 to 90/10.   The molded object according to any one of claims 1 to 4, wherein the metal organic structure has a crystal structure, and a median value of the size of the crystal structure is 10 nm to 500 µm.   The molded product according to claim 5, wherein the median value of the size of the crystal structure is 50 nm to 100 μm.   The molded product according to claim 6, wherein the median value of the size of the crystal structure is 500 nm to 20 μm. Producing a primary molded body having a surface made of a composite material including a metal organic structure and a resin having an SP value of 15 to 25 (MPa) ^1/2 ;
The manufacturing method of a molded object which gives a physical process to the surface which consists of the said composite material of the said primary molded object, and exposes the said metal organic structure.   The method for producing a molded body according to claim 8, wherein the physical treatment is at least one selected from the group consisting of corona treatment, plasma treatment, and flame treatment.   The manufacturing method of the molded object of Claim 8 or 9 which forms an uneven structure in the surface which consists of the said composite material of the said primary molded object before or after performing the said physical treatment.

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