JP2022050208A - Molding composition, molded body, and method for suppressing gas generation - Google Patents

Abstract

To provide a molding composition and a molded body which can reduce a gas generated by heating and melting a resin in molding processing such as injection molding.SOLUTION: The molding composition contains: a porous coordination polymer containing metal ions and organic ligands; and at least one base material selected from the group consisting of plastic resins, rubbers, and sealing materials. The porous coordination polymer and the base material respectively satisfy the following condition (A) or (B): (A) the radius of the metal ions of the porous coordination polymer is 62×10-12 m or less when the acid dissociation constant of a gas derived from the base material is 16.6 or less; and (B) the radius of the metal ions of the porous coordination polymer is 68×10-12 m or more when the acid dissociation constant of a gas derived from the base material is 17.0 or less.SELECTED DRAWING: Figure 2

Description

The present invention relates to a molding composition and a molded product.

In recent years, when a molded body using a plastic resin is used for applications such as bearings, high accuracy is required. On the other hand, when a molded product using a plastic resin is used for a joint for a water heater or the like, it is required to increase the strength and the accuracy of the sealed portion by reducing voids. In addition, problems such as poor appearance (for example, discoloration and weld) on the surface of the molded body due to the generation of gas derived from the plastic resin, accumulation of the gas component of the mold during molding, and corrosion by the gas are improved. Is required. In addition, when using a molded product, environmental deterioration caused by the generation of gas derived from plastic resin from the molded product, although it is a trace amount (especially at semiconductor-related production sites sensitive to the work environment, the above-mentioned gas such as parts, etc. It is required to improve the problem of environmental deterioration caused by the occurrence). Various studies have been made to improve the problem caused by the generation of gas derived from such plastic resin, but there is still room for improvement.

As a method of suppressing the generation of gas, there is a method of first adding a considerable number of gas vents to the mold and attaching a gas suction device to the molding machine to suppress the generation of gas. When the plastic resin is polyphenyl sulfide (PPS), a volatile gas component is generated by performing a thermal oxidation treatment for heating the polyphenyl sulfide under the condition in which an oxidizing substance is present and performing an oxidative cross-linking treatment. There is a method of greatly reducing the amount (for example, Patent Document 1 and Patent Document 2). However, it cannot be said that the generation of gas can be sufficiently suppressed by either method. In particular, in the above-mentioned oxidative cross-linking treatment method, the degree of thermal oxidation treatment is large, so that when the pellet-shaped PPS after thermal oxidation treatment is melted, a gelled product is formed and another problem such as unstable molding occurs. ..

As another method of suppressing the generation of gas, there is a method of adsorbing the above gas in a plastic resin. Examples of this method include a method of adding a metal compound such as molybdenum and tungsten to a plastic resin (Patent Document 3), a method of adding zinc oxide to a plastic resin (Patent Document 4), and a hydrotalcite substance to plastic. Method of adding to resin (Patent Document 5), method of adding PAN-based carbon fiber to plastic resin (Patent Document 6), method of adding porous zeolite body to plastic resin (Patent Document 7), specific There is a method of adding a porous coordination polymer having a value of Lewis acid value (Patent Document 8). Although the method of adsorbing the gas in the plastic resin has a certain effect, further improvement is required.

Japanese Unexamined Patent Publication No. 63-207827 Japanese Unexamined Patent Publication No. 62-197422 Patent No. 3245253 Re-Table 2005-037924 Publication No. Patent No. 323 535 Japanese Unexamined Patent Publication No. 2017-190426 Japanese Unexamined Patent Publication No. 2016-132710

As described above, the method of suppressing the generation of gas derived from the base material such as plastic resin has a certain effect in any of them, but there is room for further improvement.
Therefore, an object of the present invention is to provide a molding composition and a molded body capable of suppressing the external generation of gas derived from one or more base materials selected from the group consisting of plastic resins, rubbers, and sealing materials. The purpose is to provide.

As a result of diligent research to solve the above problems, the present inventors have combined a porous coordination polymer containing a metal ion having a specific metal ionic radius and an organic ligand with a base material. , The obtained molding composition has been found to be able to solve the above-mentioned problems, and has completed the present invention.
That is, the present invention is as follows.

(1)
The porous coordination polymer containing a metal ion and an organic ligand and one or more base materials selected from the group consisting of plastic resins, rubbers, and sealing materials are contained, and the porous coordination height is high. A molding composition in which the molecule and the base material satisfy the following conditions (A) or (B), respectively.
(A) When the acid dissociation constant of the gas derived from the base material is 15.7 or less, the radius of the metal ion of the porous coordination polymer is 62 × 10 ^-12 m or less.
(B) When the acid dissociation constant of the gas derived from the base material is 16.2 or less, the radius of the metal ion of the porous coordination polymer is 68 × ^10-12 m or more.

(2)
The metal ions are Ag (I), Al (III), Be (II), Ca (II), Cd (II), Ce (III), Co (III), Co (II), Cr (III), Cu (II), Cu (I), Dy (III), Er (III), Eu (III), Fe (III), Fe (II), Ga (III), Gd (III), Ho (III), In (III), Li (I), Mg (II), Mn (III), Mo (III), Nd (III), Ni (II), Sc (III), Sm (III), Sn (II), Tb (III), Tm (III), Ti (IV), V (III), W (IV), Y (III), Yb (III), Zn (II), Pd (II), Au (I), A molding composition which is one or more selected from the group consisting of Tl (I), Hg (I), Pt (I) and Zr (IV).

(3)
A molded product of the above-mentioned molding composition.

(4)
By blending a porous coordination polymer containing a metal ion and an organic ligand into one or more base materials selected from the group consisting of plastic resins, rubbers, and sealing materials, the base material can be used. A method for suppressing the generation of derived gas, wherein the porous coordination polymer and the base material satisfy the following conditions (A) or (B), respectively.
(A) When the acid dissociation constant of the gas derived from the base material is 16.6 or less, the radius of the metal ion of the porous coordination polymer is 62 × 10 ^-12 m or less.
(B) When the acid dissociation constant of the gas derived from the base material is 17.0 or less, the radius of the metal ion of the porous coordination polymer is 68 × ^10-12 m or more.

According to the present invention, it is possible to provide a molding composition and a molded body capable of suppressing the external generation of gas derived from one or more base materials selected from the group consisting of plastic resins, rubbers, and sealing materials. Is.

As an example of analysis by a pyrolysis gas chromatograph, a diagram showing a chromatogram of the analysis result of an aromatic polyamide resin (PA6T). The figure which shows the relationship between the acid dissociation constant of a gas component with a gas adsorption rate of 15% as a threshold, and the ionic radius of a metal ion constituting a porous coordination polymer.

Hereinafter, embodiments for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described. The present embodiment is an example for explaining the present invention, and the present invention is not limited to the embodiment thereof.

The porous coordination polymer containing a metal ion and an organic ligand and one or more base materials selected from the group consisting of plastic resins, rubbers, and sealing materials are contained, and the porous coordination height is high. The molecule and the base material satisfy the following conditions (A) or (B), respectively.
(A) When the acid dissociation constant of the gas derived from the base material is 16.6 or less, the radius of the metal ion of the porous coordination polymer is 62 × 10 ^-12 m or less.
(B) When the acid dissociation constant of the gas derived from the base material is 17.0 or less, the radius of the metal ion of the porous coordination polymer is 68 × ^10-12 m or more.

The molding composition of the present embodiment can suppress the generation of gas derived from the base material to the outside by combining the porous coordination polymer and the base material. More specifically, the gas derived from the base material includes not only the gas generated from the base material, but also components that can be contained as impurities in the base material (for example, a polymerizer at the time of resin synthesis, a catalyst residue), and the base material. Derived from interaction with other materials that may be included in the molding composition (eg, curing agents, inorganic fillers, plasticizers, antioxidants, UV absorbers, light stabilizers, heat stabilizers, flame retardants). It may be gas. The gas referred to here may be, for example, a gas generated by decomposing the above-mentioned components in the process of heat-molding a molding composition containing a base material, and in the form of a molded product, by air contact or the like over time. It may be a gas generated by decomposing the above components. Therefore, when molding is performed using the molding composition of the present embodiment, deterioration of accuracy due to generated gas can be suppressed, deterioration of strength due to voids or the like can be suppressed, environmental deterioration such as cleanliness can be suppressed, and during molding processing. Advantages such as being able to suppress mold corrosion in the above can be obtained. As a result, the molding composition can improve the quality of the molded product and reduce the cost by reducing the frequency of mold maintenance and the like. The type of gas generated from the molding composition is identified by analyzing the gas, and the types of components that can be contained in the base material and other molding compositions that cause the gas generation, and It is possible to determine whether or not the gas is derived from the base material by comprehensively considering the conditions under which the gas is generated.

In this embodiment, the ionic radius of the porous coordination polymer is determined by Diploma Program Chemistry Data, Shannon et al., Acta A 32 (1976) 751., Http://pmsl.planet.sci.kobe- Classified according to the contents described in u.ac.jp/~seto/?page_id=51&lang=ja, etc.

(Porosity Coordination Polymer)
The porous coordination polymer contains metal ions and organic ligands. The porous coordination polymer has, for example, a form in which metal ions are adsorbed on an organic ligand. The organic ligand is, for example, an organic ligand capable of binding to a metal ion. The porous coordination polymer is also referred to as MOF (Metal-Organic Framework) or PCP (Porous Coordination Polymer).
The porous coordination polymer has, for example, a large number of pores in the macropore or mesopore region, and has a uniform pore diameter because the pore diameter (pore diameter) is determined by the crystal structure. .. By controlling the length of the organic ligand and the affinity by the chemical structure, the porous coordination polymer can increase the holding power of the gas generated from the base material and can be finely packed. From the same viewpoint, the average pore diameter of the porous coordination polymer is preferably equal to or larger than the molecular diameter of the generated gas, and the specific surface area of the porous coordination polymer by the BET method is 400 m ² / g or more. Is preferable. The average pore diameter of the porous coordination polymer is obtained from the gas adsorption isotherm by the BET method.

(Metal ions)
From the viewpoint of suppressing the generation of gas derived from the base material to the outside, when the acid dissociation constant of the gas is 16.0 or less, the radius of the metal ion of the porous coordination polymer is 62 × 10 ^-12 m or less. Is. When the acid dissociation constant of the gas derived from the base material is 17.0 or less, the radius of the metal ion of the porous coordination polymer is 68 × ^10-12 m or more.
Examples of metal ions having a metal ionic radius of 62 × 10 ^-12 m or less include Al (III), Be (II), Cr (III), Fe (III), Fe (II), Ga (III), and Ti (IV). ) And so on.
On the other hand, as metal ions having a radius of 68 × ^10-12 m or more, Ag (I), Be (II), Ca (II), Cd (II), Ce (III), Co (III), etc. Co (II), Cu (II), Cu (I), Dy (III), Er (III), Eu (III), Ga (III), Gd (III), Ho (III), In (III), Li (I), Mg (II), Mn (III), Mo (III), Nd (III), Ni (II), Sc (III), Sm (III), Sn (II), Tb (III), Tm (III), V (III), W (IV), Y (III), Yb (III), Zn (II), Pd (II), Au (I), Tl (I), Hg (I), Examples thereof include Pt (I) and Zr (IV).

(Organic ligand)
The organic ligand is preferably a cross-linking ligand capable of cross-linking to a metal ion. Examples of the bridging ligand include 2-methylimidazole, terephthalic acid, 2,5-dihydroxyterephthalic acid, 1,4-naphthalenedicarboxylic acid, 1,3,5-benzenetricarboxylic acid and 4,4'-biphenyldicarboxylic acid. Acid, 4,4 ″ -p-terphenyldicarboxylic acid, isophthalic acid, 1,3,5-benzenetricarboxylic acid, 1,3,5-tri-4-carboxyphenylbenzene, methylimidazole, 4,4′- Biphenyldicarboxyic acid, fumaric acid, naphthalenedicarboxylic acid, hexaazatriphenylene, 2,5-dihydroxybenzoic acid, trimesic acid, 5-cyano-benzenedicarboxylic acid, 5-ethyl-1,3benzodicarboxylic acid, terephenyl-3 , 3', 5,5'-tetracarboxylic acid, 9,10-anthracendicarboxylic acid, imidazole, 2,2'-diamino-4,4'-stilvendicarboxylic acid, 2,2'-dinitro-stylbenzicarboxylic acid, 2,5-Dihydroxyterephthalic acid, 3,3', 5,5'-tetracarboxydiphenylmethane, 1,2,4,5-tetrakis (4-carboxyphenyl) benzene, 4,4', 4 "-s-triazine -2,4,6 trail-Sanbenzoic acid, 2-hydroxyterephthalic acid, biphenyl-3,3', 5,5'-tetracarboxylic acid, biphenyl-3,4,5-tricarboxylic acid, 5-bromoisophthalic acid , Maronic acid, 5-cyano-benzenedicarboxylic acid, 5-ethyl-1,3benzodicarboxylic acid, terephenyl-3,3 ″, 5,5 ″ tetracarboxylic acid, 9,10-anthracendicarboxylic acid, imidazole, 2 , 2'-diamino-4,4-stylbenzicarboxylic acid, 2,2'-dinitro-stilbendicarboxylic acid, 2,5-dihydroxyterephthalic acid, 3,3', 5,5'tetracarboxydiphenylmethane, 1,2, 4,5-Tetrakiss (4-carboxyphenyl) benzene, 4,4', 4 ″ -s-triazine-2,4,6 trail-sanbenzoic acid, 2-hydroxyterephthalic acid, biphenyl-3,3', 5 , 5'-tetracarboxylic acid, biphenyl-3,4', 5'-tricarboxylic acid, 5-bromoisophthalic acid, malonic acid and the like.

In the method for producing a composition for a molded body, after removing residual substances adhering to or existing in the surface and pores of the porous coordination polymer, the porous coordination polymer is used as a base. It is desirable to combine it with the material. If the residual substance is present, the pores may be narrowed or completely blocked by the residual substance, making it difficult to inject the generated gas into the pores of the porous coordination polymer. Examples of the method for removing the residual substance include a method for cleaning the porous coordination polymer with a solvent. Examples of the solvent used for washing include water, methanol, THF, and DMF, and the solvent is preferably water and / or methanol. When the solvent is water and / or methanol, the molecular diameter of the solvent is small, so that the solvent easily enters the pores of the porous coordination polymer, and the residual substance in the pores can be easily removed. Further, in the step of cleaning the residual substance, the porous coordination polymer may be immersed in the solvent for a long time. The soaking time is preferably 12 hours or more, more preferably 24 hours or more. Examples of the method for removing unreacted substances or impurities include a method for removing residual substances by heat treatment. When the unreacted substance or impurities are organic substances and it is desired to remove the organic substances, it is preferable to perform the heat treatment in the air or in an oxygen atmosphere. If the unreacted substance or impurities are volatile substances and it is desired to remove the volatile substances, it is preferable to perform vacuum heat treatment. The heating temperature is preferably 100 to 300 ° C. A method of completely removing the solvent by performing a heat treatment after cleaning with a solvent is preferable.

このとき、酸解離定数 Ka は、溶媒の濃度 [Hsol] を定数内に含めた形で次のように表せる。

http://www.fm.ehcc.kyoto-u.ac.jp/pKa_compilation_Williams_RipinEvans.pdf
上記の文献集および中和滴定や吸光光度計法、キャピラリー電気泳動法により実験的に求めた。酸解離定数は一般的に－１０から４０の範囲の値をとる場合が多い。
また、解離基が存在しない物質の酸解離定数については３０．０と設定した。 (Base material)
The base material is one or more selected from the group consisting of plastic resins, rubbers, and sealing materials. Further, if necessary, an inorganic filler, a plasticizer, a weathering resistance-imparting additive, or the like may be added, and the additive is not particularly limited as long as it is an additive generally blended with the base material. It is possible. The gas derived from the base material is generated from these compounding materials.
As for the acid dissociation constant of gas, if the general formula of acid is HA and the solvent is Hsol, the dissociation equilibrium reaction is as follows.

At this time, the acid dissociation constant Ka can be expressed as follows in the form of including the solvent concentration [Hsol] in the constant.

http://www.fm.ehcc.kyoto-u.ac.jp/pKa_compilation_Williams_RipinEvans.pdf
It was experimentally obtained by the above-mentioned literature collection, neutralization titration, absorptiometry, and capillary electrophoresis. The acid dissociation constant generally takes a value in the range of -10 to 40.
The acid dissociation constant of the substance having no dissociation group was set to 30.0.

(Plastic resin)
The plastic resin includes one kind or two or more kinds of resins. Examples of the resin include thermoplastic resins and thermosetting resins. Examples of the thermoplastic resin include polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polystyrene resin, AS resin, ABS resin, methacrylic resin, polyvinyl alcohol resin, EVA resin, and aromatic polyamide resin. And polyamide resin such as polyamide 66, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polyethylene terephthalate resin, polybutylene terephthalate resin, fluororesin, polyphenylene sulphide resin, polysulfone resin, polyallylate resin, polyetherimide resin, polyether. Examples thereof include a sulfone resin, a polyether ketone resin, a liquid crystal polyester resin, a thermoplastic polyimide resin, and a thermoplastic polyurethane resin. Examples of the thermosetting resin include epoxy resin, unsaturated polyester resin, phenol resin, urea resin, melamine resin, alkyd resin, silicone resin, polyimide resin, polyurethane resin, vinyl ester resin, diallyl phthalate resin, furan resin, and polyaminobismaleimide. Examples thereof include resins, casein resins, epoxy acrylate resins, urethane acrylate resins, polyurea resins, benzoxazine resins, oxetane resins, xylene resins, dicyclopentadiene resins, and episulfide resins. Among these, a polyamide resin such as an aromatic polyamide resin and a polyamide 66 and a polyphenylene sulfide resin are preferable, and an aromatic polyamide resin and a polyphenylene sulfide resin are more preferable, from the viewpoint of further reducing the gas derived from the base material.

(Rubbers)
Examples of rubbers include artificial rubber and natural rubber. Examples of the artificial rubber include polybutadiene, polyisoprene, a random copolymer and block copolymer of styrene-butadiene, a hydrogenated additive of the block copolymer, an acrylonitrile-butadiene copolymer, a butadiene-isoprene copolymer and the like. Diene rubber, ethylene-propylene random copolymer and block copolymer, ethylene-butene random copolymer and block copolymer, copolymer of ethylene and α-olefin, ethylene-acrylic acid, ethylene- Ethylene-unsaturated carboxylic acid copolymer such as methacrylic acid, ethylene-acrylic acid ester, ethylene-unsaturated carboxylic acid ester copolymer such as ethylene-methacrylic acid ester, and a part of unsaturated carboxylic acid is a metal salt. Ethethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymer such as ethylene-acrylic acid-acrylic acid metal salt, ethylene-methacrylic acid-methacrylic acid metal salt, acrylic acid ester-butadiene copolymer butyl acrylate- Acrylic elastic polymers such as butadiene copolymers, copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate, ethylene-propylene-ethylidene norbornene copolymers, ethylene-propylene-hexadien copolymers and the like- Examples thereof include propylene non-conjugated diene ternary copolymers, butylene-isoprene copolymers, chlorinated polyethylenes and modified products thereof. These rubbers may be used alone or in combination of two or more.

(Silicone material)
Examples of the sealing material include silicone-based sealing materials, modified silicone-based sealing materials, polyurethane-based sealing materials (for example, acrylic urentane-based sealing materials), silylated acrylate-based sealing materials, polysulfide-based sealing materials, and polyisobutylene-based sealing materials. And so on. These sealing materials may be used alone or in combination of two or more.

(Inorganic filler)
The molding composition may contain an inorganic filler from the viewpoint of improving the mechanical characteristics. As the inorganic filler, a known inorganic filler is used, and examples thereof include a particulate inorganic filler, a fibrous inorganic filler, and a scaly or plate-shaped inorganic filler. The particulate inorganic filler may be, for example, a particulate inorganic filler having a micron size or a particulate inorganic filler having a nano size. Examples of the particulate inorganic filler having a micron size include calcium carbonate particles, silica particles, glass beads, titanium oxide particles, zinc oxide particles, potassium titanate particles, titania particles, monoclinic titania particles, and calcium phosphate particles. Examples thereof include wallastnite, vermiculite, silas balloon, and glass balloon. Examples of the particulate inorganic filler having a nano size include nanotitanium oxide, nanosilica, carbon black, carbon filler and the like. The inorganic filler may be used alone or in combination of two or more. Among these, the particulate inorganic filler is preferably potassium titanate particles from the viewpoint of further excellent sustained release of the functional sustained release liquid (particularly small animal control agent). The fibrous inorganic filler is preferably a fibrous inorganic filler having an average fiber diameter of 0.05 to 10 μm and an average fiber length of 3 to 150 μm from the viewpoint of not adversely affecting the appearance of the molded body. More preferably, it is a fibrous inorganic filler having an average fiber diameter of 0.1 to 7 μm and an average fiber length of 5 to 50 μm. The fibrous inorganic filler may be, for example, a fibrous inorganic filler having a micron size or a fibrous inorganic filler having a nano size. Examples of the fibrous inorganic filler having a micron size include glass fiber, carbon fiber, stone ink fiber, aramid fiber, vinylon fiber, polyamide fiber, polyester fiber, cotton, linen fiber, kenaf fiber, bamboo fiber, rayon, and steel fiber. , Aluminum fiber, gypsum fiber, potassium tetratate fiber, potassium hexatitrate fiber, potassium octatiate fiber, titania fiber, monoclinic titania fiber, silica fiber, wallastonite, zonotrite and the like. Examples of the fibrous inorganic filler having a nano size include carbon fiber, carbon nanotube, fullerene, cotton fibril, silicon nitride whiskers, alumina whiskers, silicon carbide whiskers, nickel whiskers and the like. These fibrous inorganic fillers may be used alone or in combination of two or more. The scaly or plate-shaped inorganic filler may be, for example, a scaly or plate-shaped inorganic filler having a micron size, or a scaly or plate-shaped inorganic filler having a nano size. Examples of microscopic scale-like or plate-like inorganic fillers include talc, kaolin clay, mica (synthetic mica or natural mica), glass flakes, aragonite, calcium sulfate, aluminum hydroxide, potassium titanate, potassium titanate. Examples thereof include lithium, potassium magnesium titanate, sericite, plate-like alumina, and boron nitride. Examples of the scaly or plate-like inorganic filler having a nano size include organicized montmorillonite, swellable synthetic mica, graphite, graphite and the like. The scaly inorganic filler may be used alone or in combination of two or more. The inorganic filler may be used as it is, and from the viewpoint of improving the interfacial adhesiveness with the resin and further improving the mechanical properties, a silane coupling agent such as aminosilane, epoxysilane, acrylicsilane, or a titanate cup. It may be used in the form of surface treatment with a surface treatment agent such as a ring agent.

(Plasticizer)
The molding composition may contain a plasticizer from the viewpoint of further improving the processability and flexibility of the molded product. Examples of the plasticizer include a carboxylic acid ester derivative, a phosphoric acid ester derivative, a phosphazene derivative, a carboxylic acid amide derivative, a sulfonic acid ester derivative, and a sulfonic amide derivative. The plasticizer may be used alone or in combination of two or more.

Examples of the carboxylic acid ester derivative include alkyl esters of various carboxylic acids which may be substituted with hydroxyl groups, nitro groups, amino groups, epoxy groups, halogens and the like, and aromatic esters. Specific examples of the carboxylic acid ester derivative include dimethylphthalate, diethylphthalate, di-n-octylphthalate, diphenylphthalate, benzylphthalate, dimethoxyethylphthalate, and di-epoxyhexahydrophthalate (2-ethylhexyl). , 4,5-Epoxycyclohexahydrophthalate di (7,8-epoxy-2-octenyl), 4,5-epoxycyclohexahydrophthalate di (9,10-epoxyoctadecyl), 4,5-epoxycyclohexyl Diphthalic acid ester derivatives such as di (10,11-epoxyundesyl) sahydrophthalate, di (tetrahydrofurfuroxyethyl), various phthalic acid mixed esters and ethylene oxide adducts of phthalic acid mixed esters, isophthalic acid ester derivatives , Tetrahydrophthalic acid ester derivative, butoxyethyl parahydroxybenzoate, cyclohexyloxyethoxyethoxyethyl parahydroxybenzoate, 2-ethylhexyl parahydroxybenzoate, hydroxybenzoic acid ester of ω-alkyloligoethylene oxide, parahydroxy of undecylglycidyl ether An benzoic acid ester derivative such as an benzoic acid adduct, a propionic acid ester derivative such as thiodipropionic acid di (tetrahydrofurfuroxyethyl), an adipic acid ester derivative, an azelaic acid ester derivative, a sebacic acid ester derivative, a dodecane-2-acid ester. Derivatives, maleic acid ester derivatives, fumaric acid ester derivatives, trimetic acid ester derivatives, tri-citrate (butoxyethoxyethyl), di-n-octyl-mono (nonylphenoxyethyl) citrate, tri-n-octyl citrate, citrus Citrate ester derivatives such as dioctyl acid (tetrahydrofurfuroxyethyl), trimyristyl citrate, triethylcitrate, itacon acid ester derivatives, oleic acid ester derivatives such as tetrahydrofurfuryl oleate, lysinol acid ester derivatives, lactic acid (n- Butyl), lactic acid (2-ethylhexyl), lactic acid (n-butoxyethoxyethyl), lactic acid (n-octoxyethoxyethyl), lactic acid ester derivatives such as lactic acid (n-decyloxyethoxyethyl), di (octoxyethoxyethyl tartrate) Ethyl), tartrate (n-octyl) (nonylphenoxyethyl), tartrate ester derivatives such as di (octoxyethoxyethyl) tartrate, dibutoxye malate Examples thereof include malic acid ester derivatives such as chill, di (n-butoxyethoxyethyl) malate, distearyl malate, octadecenylisononyl malate, and salicylic acid ester derivatives such as salicylic acid adducts of benzyl glycidyl ether.

Examples of the phosphoric acid ester derivative include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri- (2-ethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyldiphenyl phosphate and isodecyl. Included are diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (chloroethyl) phosphate, xylenyl diphenyl phosphate, and tetrakis (2,4-dithiary butylphenyl) 4,4'-biphenylenediphosphonate. ..

式中、ｍは３～２５の整数を示し、Ｒ１、及びＲ２は互いに同一であっても異なっていてもよく、炭素数１～８のアルキル基、あるいは炭素数１～８のアルキル基及び／又はアリル基で置換されていてもよいフェニル基を示す。ホスファゼン誘導体は、式（１）で表される直鎖状ホスファゼン化合物の１種類で構成されてもよく、２種類以上の混合物の形態で構成されていてもよい。 Examples of the phosphazene derivative include a cyclic phosphazene compound represented by the following general formula (1).

In the formula, m represents an integer of 3 to 25, and R1 and R2 may be the same or different from each other, and may be an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms and /. Alternatively, it indicates a phenyl group which may be substituted with an allyl group. The phosphazene derivative may be composed of one kind of the linear phosphazene compound represented by the formula (1), or may be composed of two or more kinds of mixtures.

式中、ｎは３～１０００の整数を示し、Ｒ３、及びＲ４は互いに同一であっても異なっていてもよく、炭素数１～８のアルキル基、あるいは、炭素数１～８のアルキル基及び／又はアリル基で置換されていてもよいフェニル基を示し、Ｘは、基－Ｎ＝Ｐ（ＯＲ^３）_３、基－Ｎ＝Ｐ（ＯＲ^４）_３、基－Ｎ＝Ｐ（Ｏ）（ＯＲ^３）又は基－Ｎ＝Ｐ（Ｏ）（ＯＲ^４）を示し、Ｙは、基－Ｐ（ＯＲ^３）_４、基－Ｐ（ＯＲ^４）_４、基－Ｐ（Ｏ）（ＯＲ^３）_２又は基－Ｐ（Ｏ）（ＯＲ^４）_２を示す。ホスファゼン誘導体は、式（２）で表される直鎖状ホスファゼン化合物の１種類で構成されてもよく、２種類以上の混合物の形態で構成されていてもよい。 Examples of the phosphazene derivative include a linear phosphazene compound represented by the following general formula (2).

In the formula, n represents an integer of 3 to 1000, and R3 and R4 may be the same or different from each other, and may be an alkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms. / Or a phenyl group optionally substituted with an allyl group, where X is group —N = P (OR ³ ) ₃ , group —N = P (OR ⁴ ) ₃ , group —N = P (O) ( OR ³ ) or group-N = P (O) (OR ⁴ ), where Y is group-P (OR ³ ) ₄ , group-P (OR ⁴ ) ₄ , group-P (O) (OR ³ ). ₂ or group-P (O) (OR ⁴ ) ₂ is shown. The phosphazene derivative may be composed of one kind of the linear phosphazene compound represented by the formula (2), or may be composed of two or more kinds of mixtures.

式中、ｒは、０又は１を示し、Ａは２価の基である－ＳＯ_２－、－Ｓ－、－Ｏ－又は－Ｃ（ＣＨ３）２－を示す。 As the phosphazene derivative, the alkyl groups and the like are eliminated from R ¹ , R ² , R ³ and R ⁴ in the formula (1) or the formula (2) by the cross-linking group represented by the following formula (3). It may be a phosphazene compound in which oxygen atoms are crosslinked.

In the formula, r represents 0 or 1, and A represents the divalent group -SO _2- , -S-, -O- or -C (CH3) 2-.

Specific examples of the cyclic phosphazene compound represented by the formula (1) include hexaphenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, decaffenoxycyclopentaphosphazene, hexapropoxycyclotriphosphazene, octapropoxyxycyclotetraphosphazene, and decappropoxy. Cyclopentaphosphazene can be mentioned. Specific examples of the linear phosphazene compound represented by the formula (2) include a chain phosphazene compound in which a propoxy group and / or a phenoxy group is substituted with a chain dichlorophosphazene. Specific examples of the crosslinked structure represented by the formula (3) include 4,4'-sulfonyldiphenylene (bisphenol-S residue), 4,4'-oxydiphenylene group, and 4,4'-thiodiphenylene. Groups and 4,4'-diphenylene groups can be mentioned. These phosphazene derivatives may be substituted with an amino group and / or a phenylamino group at arbitrary positions. These phosphazene derivatives may be used alone or in combination of two or more.

Examples of the carboxylic acid amide derivative include N-cyclohexylbenzoic acid amide and the like. Examples of the sulfonamide derivative include N-methyl-benzenesulfonamide, N-ethyl-benzenesulfonamide, N-butyl-benzenesulfonamide, N-cyclohexyl-benzenesulfonamide, N-ethyl-P-toluenesulfonamide, and the like. Examples thereof include N-butyl-toluenesulfonamide and N-cyclohexyl-toluenesulfonamide.

Examples of the sulfonic acid ester derivative include ethyl benzenesulfonic acid, 2-methoxyethyl methanesulfonic acid, 2,2,2-trifluoroethyl methanesulfonic acid, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, and p. -N-propyl toluenesulfonic acid and the like can be mentioned.

Examples of the sulfonic acid amide derivative include N-methylmethanesulfonic acid amide, p-toluenesulfonic acid amide, p-aminobenzenesulfonamide, o-aminobenzenesulfonamide, m-aminobenzenesulfonamide, and aniline-4-sulfon. Examples thereof include acid amide, 1-aminobenzene-4-sulfonic acid amide, 1-aminobenzene-4-sulfonic acid amide, 4-aminobenzene sulfonic acid amide, p-sulfanyl acid amide and the like.

(Weather resistance imparting additive)
The molding composition may contain a weathering resistance-imparting additive from the viewpoint of further improving the weathering resistance when left outdoors. The weather resistance-imparting additive is selected from the group consisting of antioxidants such as hindered phenolic antioxidants and phosphorus-based antioxidants, ultraviolet-absorbing light stabilizers, hindered amine-based light stabilizers, and carbon. One type can be mentioned.

Examples of the hindered phenolic antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [ 3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], bis- [3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) -butanoic acid ] -Glycolester, Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, Thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,3', 3 ", 5,5', 5" -hexa-tert-butyl-a, a', a "-(Methylene-2,4,6-triyl) tri-p-cresol, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tetrakis [methylene-3-3" (3,5-Di-tert-butyl-4-hydroxyphenyl) propionate] Methan and methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate can be mentioned.

Examples of the phosphorus antioxidant include tris (2,4-di-tert-butylphenyl) phosphite and tris [2-[[2,4,8,10-tetra-tert-butylbenzo [d, f]]. [1,3,2] dioxaphosfefin-6-yl] oxy] ethyl] amine, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diyl Bisphosphonite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol phosphite, bis (2,6-di-tert-butyl-4-phenyl) pentaerythritol phos Examples include fight and bis (2,4-di-tert-butylphenyl) pentaeristol diphosfite.

Examples of the ultraviolet absorber include 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol and 2- (2H-benzotriazole-2-yl). Examples include -4,6-di-tert-pentylphenol, propandioc acid, and [(4-methoxyphenyl) -methylene] -dimethyl ester.

Examples of the hindered amine-based photostabilizer include N, N', N ", N" "-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine)". -4-yl) amino) -triazine-2-yl) -4,7-diazadecan-1,10-diamine, poly [(6- (1,1,3,3-tetramethylbutyl) amino-1,3 , 5-Triazine-2,4-diyl) (2,2,6,6-tetramethyl-4-piperidyl) imino] Hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino) ), Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-disspiro- [5.111 .2] -Heneikosan-21-one, propanic acid, [(4-methoxyphenyl) -methylene]-, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 1,3- Examples include benzenedicarboxyamide, N, N-bis (2,2,6,6-tetramethyl-4-piperidinyl), and 2-ethyl, 2'-ethoxy-oxalanilide.

The weather resistance-imparting additive may be used alone or in combination of two or more. Among these, the weather resistance-imparting additives are pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3]. -(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tris (2,4-di-tert) -Butylphenyl) Phenylphosphite, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite, bis (2,4-di-tert-butyl) Phenyl) pentaerythritol phosphite, 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2-ethyl, 2'-ethoxy-oxalanilide, N, N ′, N ″, N ″ ″-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazine-2- Il) -4,7-diazadecan-1,10-diamine, poly [(6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl) ( 2,2,6,6-Tetramethyl-4-piperidyl) imino] Hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)), 1,3-benzenedicarboxyamide, and One or more selected from the group consisting of N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) can be mentioned.

ここで、式（４）及び（５）中、Ｒはそれぞれ独立にヒンダードフェノール基を示す。 Further, from the viewpoint of further suppressing the generation of gas derived from the base material to the outside, it is selected from the group consisting of the antioxidant represented by the following formula (4) and the antioxidant represented by the following formula (5). It is also possible to include one or more kinds of antioxidants. When such a hindered phenolic antioxidant is added to the molding composition, the oxidation and subsequent decomposition of the base material or the porous coordination polymer due to heating during molding of the molding composition are further suppressed, and the base is further suppressed. It is possible to further reduce the generation of gas derived from the material to the outside. In the present specification, in the formulas (4), (6), (7) and (9), the group having no particular symbol at the binding end indicates a methyl group. For example, in the following formula (4), three groups having no symbol at the bond end are bonded to the benzene ring, but all of them are methyl groups.

Here, in the formulas (4) and (5), R independently represents a hindered phenol group.

In the molding composition of the present embodiment, R is 3,5-di-tert-butyl-4-hydroxyphenyl group or 4-tert-butyl from the viewpoint of further suppressing the generation of gas derived from the base material to the outside. It is preferably a -3-hirodoxy-2,6-dimethylphenyl group. From the same point of view, the antioxidants are 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxy-phenyl) methyl] -1,3,5-triazine-2,4. 6-trione, 1,3,5-tris [(4-tert-butyl-3-hirodoxy-2,6-dimethylphenyl) methyl] -1,3,5-triazine-2,4,6-trione, and 4-[[3,5-bis [(3,5-di-tert-butyl-4-hydroxy-phenyl) methyl] -2,4,6-trimethyl-phenyl] methyl] -2,6-di-tert It is more preferred to be selected from the group consisting of -butyl-phenol. Further, from the same viewpoint, it is particularly preferable that the antioxidant is at least one of the antioxidant represented by the following formula (6) and the antioxidant represented by the following formula (7). From the same viewpoint, it is also preferable to use the above-mentioned preferable antioxidant and a phosphorus-based antioxidant in combination as the antioxidant.

In the molding composition of the present embodiment, from the viewpoint of suppressing the decomposition of the antioxidant itself due to heating during molding of the molding composition and further suppressing the generation of gas derived from the base material to the outside, the antioxidant. The melting point of the above is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, still more preferably 220 ° C. or higher.

When the molding composition of the present embodiment does not contain the above-mentioned antioxidant, the total content of the base material and the porous coordination polymer in the molding composition is 100% by mass of the molding composition. On the other hand, it is preferably 60% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, and further preferably 80% by mass or more and 100% by mass or less. When the total content of the above is within the above range, the generation of gas derived from the base material to the outside is further suppressed, and the physical characteristics required for the product are more effectively imparted to the molding composition. Can be done.

From the viewpoint of further imparting the physical characteristics required for the product to the molding composition, the content of the base material in the molding composition is 100% by mass based on the total of the base material and the porous coordination polymer. It is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more.

From the viewpoint of further suppressing the generation of gas derived from the base material to the outside, the content of the porous coordination polymer is 0.01 with respect to the total 100% by mass of the base material and the porous coordination polymer. It is preferably ~ 15% by mass, more preferably 0.1 to 10% by mass, and even more preferably 0.5 to 5% by mass.

When the molding composition contains a weathering-imparting additive other than the antioxidant, the content of the weathering-imparting additive is preferably 40% by mass or less with respect to 100% by mass of the molding composition. , 30% by mass or less, more preferably 20% by mass or less. When the above content is within the above range, the generation of gas derived from the base material to the outside can be further suppressed, and the physical characteristics required for the product can be more effectively imparted to the molding composition. ..

The molding composition may contain any other component, such as an inorganic filler, a plasticizer, a flame retardant, in an amount that does not interfere with the solution of the problems of the present invention. For example, the content of any other component in the molding composition is 50% by mass with respect to a total of 100 parts by mass of the base material, the porous coordination polymer, and the weathering-imparting additive other than the antioxidant. It is preferably parts or less, more preferably 30 parts by mass or less, and even more preferably 10 parts by mass or less.

When the molding composition of the present embodiment contains the above-mentioned antioxidant, the total content of the base material, the porous coordination polymer, and the antioxidant in the molding composition is 100. It is preferably 60% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, and further preferably 80% by mass or more and 100% by mass or less with respect to the mass%. When the total content of the above is within the above range, the generation of gas derived from the base material to the outside is further suppressed, and the physical characteristics required for the product are more effectively imparted to the molding composition. Can be done.

From the viewpoint of further imparting the physical characteristics required for the product to the molding composition, the content of the base material in the molding composition is 100% by mass in total of the base material, the porous coordination polymer and the antioxidant. On the other hand, it is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more.

From the viewpoint of further suppressing the generation of gas derived from the base material to the outside, the content of the porous coordination polymer is 100% by mass in total of the base material, the porous coordination polymer and the antioxidant. , 0.01 to 15% by mass, more preferably 0.1 to 10% by mass, and even more preferably 0.5 to 5% by mass.

From the same viewpoint, the content of the antioxidant is preferably 0.01 to 10% by mass, preferably 0.01 to 10% by mass, based on 100% by mass of the total of the base material, the porous coordination polymer and the antioxidant. It is more preferably 0.05 to 5% by mass, and even more preferably 0.1 to 3% by mass.

When the molding composition contains a weathering-imparting additive other than the antioxidant, the content of the weathering-imparting additive is preferably 40% by mass or less with respect to 100% by mass of the molding composition. , 30% by mass or less, and particularly preferably 20% by mass or less. When the above content is within the above range, the generation of gas derived from the base material to the outside can be further suppressed, and the physical characteristics required for the product can be more effectively imparted to the molding composition. ..

The molding composition may contain any other component, such as an inorganic filler, a plasticizer, a flame retardant, in an amount that does not interfere with the solution of the problems of the present invention. For example, the content of any other component in the molding composition is 100 parts by mass in total of the base material, the porous coordination polymer, the antioxidant, and the weathering-imparting additive other than the antioxidant. It is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and further preferably 10 parts by mass or less.

(Use)
The molding composition can be used not only by processing it into a molded product having a predetermined shape, but also as it is, for example, as a paint, a sealing agent, a cushioning material or a filling material. The molding composition may be fluidized, semi-fluidized or, for example, by selecting an appropriate plastic resin and appropriately adjusting the amount of the porous coordination polymer added and the amount of the filler, plasticizer, etc. added. A molded body having rubber-like elasticity can be manufactured. Therefore, the present invention also includes a molded product molded from the molding composition of the present embodiment. Those having fluidity can be used, for example, as a paint, and those having semi-fluidity can be used, for example, as a sealing agent. Further, those having rubber-like elasticity can be used, for example, as a cushioning material or a padding. When the molding composition is used as a paint, a sealing agent, a cushioning material or a filling material, a coloring material such as a colorant or a pigment can be added to the matrix resin as needed. In the molding process of the molding composition, for example, injection molding, compression molding, transfer molding, extrusion molding, blow molding, calendar molding, FRP molding, laminated molding, casting molding, solution casting method, vacuum / pneumatic molding, extrusion. Appropriate known molding methods such as composite molding, foam molding, thermal molding, insert molding, and melt impregnation method can be applied. Further, the shape of the molded product as a product is not particularly limited, and may be any shape such as a flat plate shape, a rod shape, a cylindrical shape, a comb shape, and a spherical shape. In addition to molding the molding composition alone, it is also possible to perform two-color or multicolor molding in combination with a metal or the like.

Another embodiment of the present invention comprises a porous coordination polymer containing a metal ion and an organic ligand in one or more base materials selected from the group consisting of plastic resins, rubbers, and sealing materials. It is a method of suppressing the generation of gas derived from the base material by blending, and is a method in which the porous coordination polymer and the base material satisfy the following conditions (A) or (B), respectively. ..
(A) When the acid dissociation constant of the gas derived from the base material is 16.6 or less, the radius of the metal ion of the porous coordination polymer is 62 × 10 ^-12 m or less.
(B) When the acid dissociation constant of the gas derived from the base material is 17.0 or less, the radius of the metal ion of the porous coordination polymer is 68 × ^10-12 m or more.

The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Example 1]
Titanium ion (oxidation number 4, ionic radius 42 pm) was used as the metal ion, and a porous coordination polymer (“MIL-125 (Ti)”) composed of terephthalic acid was used as the organic ligand. A composition for molding is obtained by compounding and mixing 0.5 g of a porous coordination polymer and 50 g of an aromatic polyamide resin (“RA230NK” manufactured by Mitsui Chemicals, Inc.) at 320 ° C. using a laboplast mill device. Was produced.
The prepared molding composition was molded in a heating press at 320 ° C. and 10 MPa under heating conditions to prepare a molded product on a plate having a thickness of 1.0 mm.

[Example 2]
Instead of MIL-125 (Ti), a porous coordination polymer ("Al-PCP-F") composed of aluminum ion (oxidation number 3, ionic radius 54 pm) and fumaric acid as an organic ligand is used. A molded body was produced in the same manner as in Example 1 except for the above.

[Example 3]
Except for using a porous coordination polymer (“Fe-BTC”) composed of iron ion (oxidation number 3, ionic radius 55 pm) and trimesic acid as an organic ligand instead of MIL-125 (Ti). Made a molded body in the same manner as in Example 1.

[Example 4]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of chromium ions (oxidation number 3, ionic radius 63 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 1 except that it was used.

[Example 5]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of nickel ions (oxidation number 2, ionic radius 68 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 1 except that it was used.

[Example 6]
Instead of MIL-125 (Ti), a porous coordination polymer (“Uio-66)” composed of zirconium ion (oxidation number 4, ionic radius 72pm) and terephthalic acid as an organic ligand was used. A molded body was produced in the same manner as in Example 1 except for the above.

[Example 7]
Instead of MIL-125 (Ti), a porous coordination polymer (“Cu-BTC”) composed of copper ion (oxidation number 2, ionic radius 73 pm) and trimesic acid as an organic ligand was used. Made a molded body in the same manner as in Example 1.

[Example 8]
Instead of MIL-125 (Ti), a porous coordination polymer (“Zif-8”) composed of zinc ion (oxidation number 2, ionic radius 74 pm) and 2-imidazole as an organic ligand was used. A molded body was produced in the same manner as in Example 1 except for the above.

[Example 9]
Instead of MIL-125 (Ti), a porous coordination polymer ("Pt-") composed of platinum ions (oxidation number 2, ionic radius 80pm), 4,4'-bipyridine and ethyleneamine as organic ligands. A molded body was produced in the same manner as in Example 1 except that PCP ”) was used.

[Example 10]
Highly porous coordination composed of lanthanum ion (oxidation number 3, ionic radius 103pm) and 1,3,5-tris (4-carboxyphenyl) benzene as an organic ligand instead of MIL-125 (Ti). A molded product was prepared in the same manner as in Example 1 except that the molecule (“Zif-8”) was used.

[Example 11]
A porous coordination polymer ("Ag-PCP") composed of silver ion (oxidation number 1, ionic radius 115pm) and di-p-xylylene as an organic ligand is used instead of MIL-125 (Ti). A molded body was produced in the same manner as in Example 1 except for the above.

[Example 12]
Titanium ion (oxidation number 4, ionic radius 42 pm) was used as the metal ion, and a porous coordination polymer (“MIL-125 (Ti)”) composed of terephthalic acid was used as the organic ligand. A composition for molding was prepared by compounding and mixing 0.5 g of a porous coordination polymer and 50 g of a polyamide 6 resin (“CM1007” manufactured by Toray Industries, Inc.) at 280 ° C. using a laboplast mill device. ..
The prepared molding composition was molded with a heating press at 280 ° C. and 10 MPa under heating conditions to prepare a molded product on a plate having a thickness of 1.0 mm.

[Example 13]
Instead of MIL-125 (Ti), a porous coordination polymer ("Al-PCP-F") composed of aluminum ion (oxidation number 3, ionic radius 54 pm) and fumaric acid as an organic ligand is used. A molded body was produced in the same manner as in Example 12 except for the above.

[Example 14]
Except for using a porous coordination polymer (“Fe-BTC”) composed of iron ion (oxidation number 3, ionic radius 55 pm) and trimesic acid as an organic ligand instead of MIL-125 (Ti). Made a molded body in the same manner as in Example 12.

[Example 15]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of chromium ions (oxidation number 3, ionic radius 63 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 12 except that it was used.

[Example 16]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of nickel ions (oxidation number 2, ionic radius 68 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 1 except that it was used.

[Example 17]
Instead of MIL-125 (Ti), a porous coordination polymer (“Uio-66)” composed of zirconium ion (oxidation number 4, ionic radius 72pm) and terephthalic acid as an organic ligand was used. A molded body was produced in the same manner as in Example 12 except for the above.

[Example 18]
Instead of MIL-125 (Ti), a porous coordination polymer (“Cu-BTC”) composed of copper ion (oxidation number 2, ionic radius 73 pm) and trimesic acid as an organic ligand was used. Made a molded body in the same manner as in Example 12.

[Example 19]
Instead of MIL-125 (Ti), a porous coordination polymer (“Zif-8”) composed of zinc ion (oxidation number 2, ionic radius 74 pm) and 2-imidazole as an organic ligand was used. A molded body was produced in the same manner as in Example 12 except for the above.

[Example 20]
Instead of MIL-125 (Ti), a porous coordination polymer ("Pt-") composed of platinum ions (oxidation number 2, ionic radius 80pm), 4,4'-bipyridine and ethyleneamine as organic ligands. A molded body was produced in the same manner as in Example 12 except that PCP ”) was used.

[Example 21]
Highly porous coordination composed of lanthanum ion (oxidation number 3, ionic radius 103pm) and 1,3,5-tris (4-carboxyphenyl) benzene as an organic ligand instead of MIL-125 (Ti). A molded product was produced in the same manner as in Example 12 except that the molecule (“Zif-8”) was used.

[Example 22]
A porous coordination polymer ("Ag-PCP") composed of silver ion (oxidation number 1, ionic radius 115pm) and di-p-xylylene as an organic ligand is used instead of MIL-125 (Ti). A molded body was produced in the same manner as in Example 12 except for the above.

[Example 23]
Titanium ion (oxidation number 4, ionic radius 42 pm) was used as the metal ion, and a porous coordination polymer (“MIL-125 (Ti)”) composed of terephthalic acid was used as the organic ligand. 0.5 g of the porous coordination polymer and 50 g of the polyphenylene sulfide resin (“1140A6” manufactured by Polyplastics Co., Ltd.) are compounded and mixed at 300 ° C. using a laboplast mill device to prepare a molding composition. Made.
The prepared molding composition was molded with a heating press at a heating condition of 300 ° C. and 10 MPa to prepare a molded product on a plate having a thickness of 1.0 mm.

[Example 24]
Instead of MIL-125 (Ti), a porous coordination polymer ("Al-PCP-F") composed of aluminum ion (oxidation number 3, ionic radius 54 pm) and fumaric acid as an organic ligand is used. A molded body was produced in the same manner as in Example 23 except for the above.

[Example 25]
Except for using a porous coordination polymer (“Fe-BTC”) composed of iron ion (oxidation number 3, ionic radius 55 pm) and trimesic acid as an organic ligand instead of MIL-125 (Ti). Made a molded body in the same manner as in Example 23.

[Example 26]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of chromium ions (oxidation number 3, ionic radius 63 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 23 except that it was used.

[Example 27]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of nickel ions (oxidation number 2, ionic radius 68 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 23 except that it was used.

[Example 28]
Instead of MIL-125 (Ti), a porous coordination polymer (“Uio-66)” composed of zirconium ion (oxidation number 4, ionic radius 72pm) and terephthalic acid as an organic ligand was used. A molded body was produced in the same manner as in Example 23 except for the above.

[Example 29]
Instead of MIL-125 (Ti), a porous coordination polymer (“Cu-BTC”) composed of copper ion (oxidation number 2, ionic radius 73 pm) and trimesic acid as an organic ligand was used. Made a molded body in the same manner as in Example 23.

[Example 30]
Instead of MIL-125 (Ti), a porous coordination polymer (“Zif-8”) composed of zinc ion (oxidation number 2, ionic radius 74 pm) and 2-imidazole as an organic ligand was used. A molded body was produced in the same manner as in Example 23 except for the above.

[Example 31]
Instead of MIL-125 (Ti), a porous coordination polymer ("Pt-") composed of platinum ions (oxidation number 2, ionic radius 80pm), 4,4'-bipyridine and ethyleneamine as organic ligands. A molded body was produced in the same manner as in Example 23 except that PCP ”) was used.

[Example 32]
Highly porous coordination composed of lanthanum ion (oxidation number 3, ionic radius 103pm) and 1,3,5-tris (4-carboxyphenyl) benzene as an organic ligand instead of MIL-125 (Ti). A molded product was produced in the same manner as in Example 23 except that the molecule (“Zif-8”) was used.

[Example 33]
A porous coordination polymer ("Ag-PCP") composed of silver ion (oxidation number 1, ionic radius 115pm) and di-p-xylylene as an organic ligand is used instead of MIL-125 (Ti). A molded body was produced in the same manner as in Example 23 except for the above.

[Example 34]
Titanium ion (oxidation number 4, ionic radius 42 pm) was used as the metal ion, and a porous coordination polymer (“MIL-125 (Ti)”) composed of terephthalic acid was used as the organic ligand. A composition for molding was prepared by compounding and mixing 0.5 g of a porous coordination polymer and 50 g of ABS resin (“700-314” manufactured by Toray Industries, Inc.) at 240 ° C.
The prepared molding composition was molded with a heating press at 240 ° C. and 10 MPa under heating conditions to prepare a molded product on a plate having a thickness of 1.0 mm.

[Example 35]
Instead of MIL-125 (Ti), a porous coordination polymer ("Al-PCP-F") composed of aluminum ion (oxidation number 3, ionic radius 54 pm) and fumaric acid as an organic ligand is used. A molded body was produced in the same manner as in Example 34 except for the above.

[Example 36]
Except for using a porous coordination polymer (“Fe-BTC”) composed of iron ion (oxidation number 3, ionic radius 55 pm) and trimesic acid as an organic ligand instead of MIL-125 (Ti). Made a molded body in the same manner as in Example 34.

[Example 37]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of chromium ions (oxidation number 3, ionic radius 63 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 34 except that it was used.

[Example 38]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of nickel ions (oxidation number 2, ionic radius 68 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 34 except that it was used.

[Example 39]
Instead of MIL-125 (Ti), a porous coordination polymer (“Uio-66)” composed of zirconium ion (oxidation number 4, ionic radius 72pm) and terephthalic acid as an organic ligand was used. A molded body was produced in the same manner as in Example 34 except for the above.

[Example 40]
Instead of MIL-125 (Ti), a porous coordination polymer (“Cu-BTC”) composed of copper ion (oxidation number 2, ionic radius 73 pm) and trimesic acid as an organic ligand was used. Made a molded body in the same manner as in Example 34.

[Example 41]
Instead of MIL-125 (Ti), a porous coordination polymer (“Zif-8”) composed of zinc ion (oxidation number 2, ionic radius 74 pm) and 2-imidazole as an organic ligand was used. A molded body was produced in the same manner as in Example 34 except for the above.

[Example 42]
Instead of MIL-125 (Ti), a porous coordination polymer ("Pt-") composed of platinum ions (oxidation number 2, ionic radius 80pm), 4,4'-bipyridine and ethyleneamine as organic ligands. A molded body was produced in the same manner as in Example 34 except that PCP ”) was used.

[Example 43]
Highly porous coordination composed of lanthanum ion (oxidation number 3, ionic radius 103pm) and 1,3,5-tris (4-carboxyphenyl) benzene as an organic ligand instead of MIL-125 (Ti). A molded product was produced in the same manner as in Example 34 except that the molecule (“Zif-8”) was used.

[Example 44]
A porous coordination polymer ("Ag-PCP") composed of silver ion (oxidation number 1, ionic radius 115pm) and di-p-xylylene as an organic ligand is used instead of MIL-125 (Ti). A molded body was produced in the same manner as in Example 34 except for the above.

[Example 45]
Titanium ion (oxidation number 4, ionic radius 42 pm) was used as the metal ion, and a porous coordination polymer (“MIL-125 (Ti)”) composed of terephthalic acid was used as the organic ligand. A composition for molding was prepared by compounding and mixing 0.5 g of a porous coordination polymer and 50 g of a polyphenylene oxide resin (“XYRON 100V” manufactured by Asahi Kasei Corporation at 320 ° C.).
The prepared molding composition was molded with a heating press machine under heating conditions of 320 ° C. and 10 MPa to prepare a molded product on a plate having a thickness of 1.0 mm.

[Example 46]
Instead of MIL-125 (Ti), a porous coordination polymer ("Al-PCP-F") composed of aluminum ion (oxidation number 3, ionic radius 54 pm) and fumaric acid as an organic ligand is used. A molded body was produced in the same manner as in Example 45 except for the above.

[Example 47]
Except for using a porous coordination polymer (“Fe-BTC”) composed of iron ion (oxidation number 3, ionic radius 55 pm) and trimesic acid as an organic ligand instead of MIL-125 (Ti). Made a molded body in the same manner as in Example 45.

[Example 48]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of chromium ions (oxidation number 3, ionic radius 63 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 45 except that it was used.

[Example 49]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of nickel ions (oxidation number 2, ionic radius 68 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 45 except that it was used.

[Example 50]
Instead of MIL-125 (Ti), a porous coordination polymer (“Uio-66)” composed of zirconium ion (oxidation number 4, ionic radius 72pm) and terephthalic acid as an organic ligand was used. A molded body was produced in the same manner as in Example 45 except for the above.

[Example 51]
Instead of MIL-125 (Ti), a porous coordination polymer (“Cu-BTC”) composed of copper ion (oxidation number 2, ionic radius 73 pm) and trimesic acid as an organic ligand was used. Made a molded body in the same manner as in Example 45.

[Example 52]
Instead of MIL-125 (Ti), a porous coordination polymer (“Zif-8”) composed of zinc ion (oxidation number 2, ionic radius 74 pm) and 2-imidazole as an organic ligand was used. A molded body was produced in the same manner as in Example 45 except for the above.

[Example 53]
Instead of MIL-125 (Ti), a porous coordination polymer ("Pt-") composed of platinum ions (oxidation number 2, ionic radius 80pm), 4,4'-bipyridine and ethyleneamine as organic ligands. A molded body was produced in the same manner as in Example 45 except that PCP ”) was used.

[Example 54]
Highly porous coordination composed of lanthanum ion (oxidation number 3, ionic radius 103pm) and 1,3,5-tris (4-carboxyphenyl) benzene as an organic ligand instead of MIL-125 (Ti). A molded product was produced in the same manner as in Example 45 except that the molecule (“Zif-8”) was used.

[Example 55]
A porous coordination polymer ("Ag-PCP") composed of silver ion (oxidation number 1, ionic radius 115pm) and di-p-xylylene as an organic ligand is used instead of MIL-125 (Ti). A molded body was produced in the same manner as in Example 45 except for the above.

[Example 56]
Titanium ion (oxidation number 4, ionic radius 42 pm) was used as the metal ion, and a porous coordination polymer (“MIL-125 (Ti)”) composed of terephthalic acid was used as the organic ligand. A composition for molding was prepared by compounding and mixing 0.5 g of a porous coordination polymer and 50 g of a polybutylene terephthalate resin (Mitsubishi Chemical Corporation “5010-CR2”) at 120 ° C.
The prepared molding composition was molded with a heating press at 120 ° C. and 10 MPa under heating conditions to prepare a molded product on a plate having a thickness of 1.0 mm.

[Example 57]
Instead of MIL-125 (Ti), a porous coordination polymer ("Al-PCP-F") composed of aluminum ion (oxidation number 3, ionic radius 54 pm) and fumaric acid as an organic ligand is used. A molded body was produced in the same manner as in Example 56 except for the above.

[Example 58]
Except for using a porous coordination polymer (“Fe-BTC”) composed of iron ion (oxidation number 3, ionic radius 55 pm) and trimesic acid as an organic ligand instead of MIL-125 (Ti). Made a molded body in the same manner as in Example 56.

[Example 59]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of chromium ions (oxidation number 3, ionic radius 63 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 56 except that it was used.

[Example 60]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of nickel ions (oxidation number 2, ionic radius 68 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 56 except that it was used.

[Example 61]
Instead of MIL-125 (Ti), a porous coordination polymer (“Uio-66)” composed of zirconium ion (oxidation number 4, ionic radius 72pm) and terephthalic acid as an organic ligand was used. A molded body was produced in the same manner as in Example 56 except for the above.

[Example 62]
Instead of MIL-125 (Ti), a porous coordination polymer (“Cu-BTC”) composed of copper ion (oxidation number 2, ionic radius 73 pm) and trimesic acid as an organic ligand was used. Made a molded body in the same manner as in Example 56.

[Example 63]
Instead of MIL-125 (Ti), a porous coordination polymer (“Zif-8”) composed of zinc ion (oxidation number 2, ionic radius 74 pm) and 2-imidazole as an organic ligand was used. A molded body was produced in the same manner as in Example 56 except for the above.

[Example 64]
Instead of MIL-125 (Ti), a porous coordination polymer ("Pt-") composed of platinum ions (oxidation number 2, ionic radius 80pm), 4,4'-bipyridine and ethyleneamine as organic ligands. A molded body was produced in the same manner as in Example 56 except that PCP ”) was used.

[Example 65]
Highly porous coordination composed of lanthanum ion (oxidation number 3, ionic radius 103pm) and 1,3,5-tris (4-carboxyphenyl) benzene as an organic ligand instead of MIL-125 (Ti). A molded product was produced in the same manner as in Example 56 except that the molecule (“Zif-8”) was used.

[Example 66]
A porous coordination polymer ("Ag-PCP") composed of silver ion (oxidation number 1, ionic radius 115pm) and di-p-xylylene as an organic ligand is used instead of MIL-125 (Ti). A molded body was produced in the same manner as in Example 56 except for the above.

[Example 67]
Titanium ion (oxidation number 4, ionic radius 42 pm) was used as the metal ion, and a porous coordination polymer (“MIL-125 (Ti)”) composed of terephthalic acid was used as the organic ligand. A composition for molding was prepared by compounding and mixing 0.5 g of a porous coordination polymer and 50 g of a polyvinyl chloride resin (“GR-800-T” manufactured by Shin-Etsu Chemical Co., Ltd.) at 200 ° C. ..
The prepared molding composition was molded with a heating press machine under heating conditions of 200 ° C. and 10 MPa to prepare a molded product on a plate having a thickness of 1.0 mm.

[Example 68]
Instead of MIL-125 (Ti), a porous coordination polymer ("Al-PCP-F") composed of aluminum ion (oxidation number 3, ionic radius 54 pm) and fumaric acid as an organic ligand is used. A molded body was produced in the same manner as in Example 67 except for the above.

[Example 69]
Except for using a porous coordination polymer (“Fe-BTC”) composed of iron ion (oxidation number 3, ionic radius 55 pm) and trimesic acid as an organic ligand instead of MIL-125 (Ti). Made a molded body in the same manner as in Example 67.

[Example 70]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of chromium ions (oxidation number 3, ionic radius 63 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 67 except that it was used.

[Example 71]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of nickel ions (oxidation number 2, ionic radius 68 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 67 except that it was used.

[Example 72]
Instead of MIL-125 (Ti), a porous coordination polymer (“Uio-66)” composed of zirconium ion (oxidation number 4, ionic radius 72pm) and terephthalic acid as an organic ligand was used. A molded body was produced in the same manner as in Example 67 except for the above.

[Example 73]
Instead of MIL-125 (Ti), a porous coordination polymer (“Cu-BTC”) composed of copper ion (oxidation number 2, ionic radius 73 pm) and trimesic acid as an organic ligand was used. Made a molded body in the same manner as in Example 67.

[Example 74]
Instead of MIL-125 (Ti), a porous coordination polymer (“Zif-8”) composed of zinc ion (oxidation number 2, ionic radius 74 pm) and 2-imidazole as an organic ligand was used. A molded body was produced in the same manner as in Example 67 except for the above.

[Example 75]
Instead of MIL-125 (Ti), a porous coordination polymer ("Pt-") composed of platinum ions (oxidation number 2, ionic radius 80pm), 4,4'-bipyridine and ethyleneamine as organic ligands. A molded body was produced in the same manner as in Example 67 except that PCP ”) was used.

[Example 76]
Highly porous coordination composed of lanthanum ion (oxidation number 3, ionic radius 103pm) and 1,3,5-tris (4-carboxyphenyl) benzene as an organic ligand instead of MIL-125 (Ti). A molded product was produced in the same manner as in Example 67 except that the molecule (“Zif-8”) was used.

[Example 77]
A porous coordination polymer ("Ag-PCP") composed of silver ion (oxidation number 1, ionic radius 115pm) and di-p-xylylene as an organic ligand is used instead of MIL-125 (Ti). A molded body was produced in the same manner as in Example 67 except for the above.

[Example 78]
Titanium ion (oxidation number 4, ionic radius 42 pm) was used as the metal ion, and a porous coordination polymer (“MIL-125 (Ti)”) composed of terephthalic acid was used as the organic ligand. 0.5 g of the porous coordination polymer and 50 g of the PTFE resin (“M-12” manufactured by Daikin Industries, Ltd.) were compounded and mixed at 340 ° C. to prepare a molding composition.
The prepared molding composition was molded with a heating press at 340 ° C. and 10 MPa under heating conditions to prepare a molded product on a plate having a thickness of 1.0 mm.

[Example 79]
Instead of MIL-125 (Ti), a porous coordination polymer ("Al-PCP-F") composed of aluminum ion (oxidation number 3, ionic radius 54 pm) and fumaric acid as an organic ligand is used. A molded body was produced in the same manner as in Example 78 except for the above.

[Example 80
Except for using a porous coordination polymer (“Fe-BTC”) composed of iron ion (oxidation number 3, ionic radius 55 pm) and trimesic acid as an organic ligand instead of MIL-125 (Ti). Made a molded body in the same manner as in Example 78.

[Example 81]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of chromium ions (oxidation number 3, ionic radius 63 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 78 except that it was used.

[Example 82]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of nickel ions (oxidation number 2, ionic radius 68 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 78 except that it was used.

[Example 83]
Instead of MIL-125 (Ti), a porous coordination polymer (“Uio-66)” composed of zirconium ion (oxidation number 4, ionic radius 72pm) and terephthalic acid as an organic ligand was used. A molded body was produced in the same manner as in Example 78 except for the above.

[Example 84]
Instead of MIL-125 (Ti), a porous coordination polymer (“Cu-BTC”) composed of copper ion (oxidation number 2, ionic radius 73 pm) and trimesic acid as an organic ligand was used. Made a molded body in the same manner as in Example 78.

[Example 85]
Instead of MIL-125 (Ti), a porous coordination polymer (“Zif-8”) composed of zinc ion (oxidation number 2, ionic radius 74 pm) and 2-imidazole as an organic ligand was used. A molded body was produced in the same manner as in Example 78 except for the above.

[Example 86]
Instead of MIL-125 (Ti), a porous coordination polymer ("Pt-") composed of platinum ions (oxidation number 2, ionic radius 80pm), 4,4'-bipyridine and ethyleneamine as organic ligands. A molded body was produced in the same manner as in Example 78 except that PCP ”) was used.

[Example 87]
Highly porous coordination composed of lanthanum ion (oxidation number 3, ionic radius 103pm) and 1,3,5-tris (4-carboxyphenyl) benzene as an organic ligand instead of MIL-125 (Ti). A molded product was produced in the same manner as in Example 78 except that the molecule (“Zif-8”) was used.

[Example 88]
A porous coordination polymer ("Ag-PCP") composed of silver ion (oxidation number 1, ionic radius 115pm) and di-p-xylylene as an organic ligand is used instead of MIL-125 (Ti). A molded body was produced in the same manner as in Example 78 except that the molded product was formed.

[Example 89]
Titanium ion (oxidation number 4, ionic radius 42 pm) was used as the metal ion, and a porous coordination polymer (“MIL-125 (Ti)”) composed of terephthalic acid was used as the organic ligand. A composition for molding was prepared by compounding and mixing 0.5 g of a porous coordination polymer and 50 g of a polycarbonate resin (“S-3000” manufactured by Mitsubishi Chemical Corporation) at 300 ° C.
The prepared molding composition was molded with a heating press at a heating condition of 300 ° C. and 10 MPa to prepare a molded product on a plate having a thickness of 1.0 mm.

[Example 90]
Instead of MIL-125 (Ti), a porous coordination polymer ("Al-PCP-F") composed of aluminum ion (oxidation number 3, ionic radius 54 pm) and fumaric acid as an organic ligand is used. A molded body was produced in the same manner as in Example 89 except that the molded product was formed.

[Example 91]
Except for using a porous coordination polymer (“Fe-BTC”) composed of iron ion (oxidation number 3, ionic radius 55 pm) and trimesic acid as an organic ligand instead of MIL-125 (Ti). Made a molded body in the same manner as in Example 89.

[Example 92]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of chromium ions (oxidation number 3, ionic radius 63 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 89 except that it was used.

[Example 93]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of nickel ions (oxidation number 2, ionic radius 68 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 89 except that it was used.

[Example 94]
Instead of MIL-125 (Ti), a porous coordination polymer (“Uio-66)” composed of zirconium ion (oxidation number 4, ionic radius 72pm) and terephthalic acid as an organic ligand was used. A molded body was produced in the same manner as in Example 89 except for the above.

[Example 95]
Instead of MIL-125 (Ti), a porous coordination polymer (“Cu-BTC”) composed of copper ion (oxidation number 2, ionic radius 73 pm) and trimesic acid as an organic ligand was used. Made a molded body in the same manner as in Example 89.
[Example 96]

Instead of MIL-125 (Ti), a porous coordination polymer (“Zif-8”) composed of zinc ion (oxidation number 2, ionic radius 74 pm) and 2-imidazole as an organic ligand was used. A molded body was produced in the same manner as in Example 89 except for the above.

[Example 97]
Instead of MIL-125 (Ti), a porous coordination polymer ("Pt-") composed of platinum ions (oxidation number 2, ionic radius 80pm), 4,4'-bipyridine and ethyleneamine as organic ligands. A molded body was produced in the same manner as in Example 89 except that PCP ”) was used.

[Example 98]
Highly porous coordination composed of lanthanum ion (oxidation number 3, ionic radius 103pm) and 1,3,5-tris (4-carboxyphenyl) benzene as an organic ligand instead of MIL-125 (Ti). A molded product was produced in the same manner as in Example 89 except that the molecule (“Zif-8”) was used.

[Example 99]
A porous coordination polymer ("Ag-PCP") composed of silver ion (oxidation number 1, ionic radius 115pm) and di-p-xylylene as an organic ligand is used instead of MIL-125 (Ti). A molded body was produced in the same manner as in Example 89 except that the molded product was formed.

[Example 100]
Titanium ion (oxidation number 4, ionic radius 42 pm) was used as the metal ion, and a porous coordination polymer (“MIL-125 (Ti)”) composed of terephthalic acid was used as the organic ligand. A composition for molding was prepared by compounding and mixing 0.5 g of a porous coordination polymer and 50 g of a polyacetal resin (“M-90-44” manufactured by Polyplastics Co., Ltd.) at 210 ° C.
The prepared molding composition was molded with a heating press at 210 ° C. and 10 MPa under heating conditions to prepare a molded product on a plate having a thickness of 1.0 mm.

[Example 101]
Instead of MIL-125 (Ti), a porous coordination polymer ("Al-PCP-F") composed of aluminum ion (oxidation number 3, ionic radius 54 pm) and fumaric acid as an organic ligand is used. A molded body was produced in the same manner as in Example 100 except for the above.

[Example 102]
Except for using a porous coordination polymer (“Fe-BTC”) composed of iron ion (oxidation number 3, ionic radius 55 pm) and trimesic acid as an organic ligand instead of MIL-125 (Ti). Made a molded body in the same manner as in Example 100.

[Example 103]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of chromium ions (oxidation number 3, ionic radius 63 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 100 except that it was used.

[Example 104]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of nickel ions (oxidation number 2, ionic radius 68 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 100 except that it was used.

[Example 105]
Instead of MIL-125 (Ti), a porous coordination polymer (“Uio-66)” composed of zirconium ion (oxidation number 4, ionic radius 72pm) and terephthalic acid as an organic ligand was used. A molded body was produced in the same manner as in Example 100 except for the above.

[Example 106]
Instead of MIL-125 (Ti), a porous coordination polymer (“Cu-BTC”) composed of copper ion (oxidation number 2, ionic radius 73 pm) and trimesic acid as an organic ligand was used. Made a molded body in the same manner as in Example 100.

[Example 107]
Instead of MIL-125 (Ti), a porous coordination polymer (“Zif-8”) composed of zinc ion (oxidation number 2, ionic radius 74 pm) and 2-imidazole as an organic ligand was used. A molded body was produced in the same manner as in Example 100 except for the above.

[Example 108]
Instead of MIL-125 (Ti), a porous coordination polymer ("Pt-") composed of platinum ions (oxidation number 2, ionic radius 80pm), 4,4'-bipyridine and ethyleneamine as organic ligands. A molded body was produced in the same manner as in Example 100 except that PCP ”) was used.

[Example 109]
Highly porous coordination composed of lanthanum ion (oxidation number 3, ionic radius 103pm) and 1,3,5-tris (4-carboxyphenyl) benzene as an organic ligand instead of MIL-125 (Ti). A molded product was produced in the same manner as in Example 100 except that the molecule (“Zif-8”) was used.

[Example 110]
A porous coordination polymer ("Ag-PCP") composed of silver ion (oxidation number 1, ionic radius 115pm) and di-p-xylylene as an organic ligand is used instead of MIL-125 (Ti). A molded body was produced in the same manner as in Example 100 except for the above.

[Example 111]
Titanium ion (oxidation number 4, ionic radius 42 pm) was used as the metal ion, and a porous coordination polymer (“MIL-125 (Ti)”) composed of terephthalic acid was used as the organic ligand. A composition for molding was prepared by compounding and mixing 0.5 g of a porous coordination polymer and 50 g of a urethane-based elastomer (“Elaston C80A” manufactured by BASF) at 280 ° C.
The prepared molding composition was molded with a heating press at 280 ° C. and 10 MPa under heating conditions to prepare a molded product on a plate having a thickness of 1.0 mm.

[Example 112]
Instead of MIL-125 (Ti), a porous coordination polymer ("Al-PCP-F") composed of aluminum ion (oxidation number 3, ionic radius 54 pm) and fumaric acid as an organic ligand is used. A molded body was produced in the same manner as in Example 111 except for the above.

[Example 113]
Except for using a porous coordination polymer (“Fe-BTC”) composed of iron ion (oxidation number 3, ionic radius 55 pm) and trimesic acid as an organic ligand instead of MIL-125 (Ti). Made a molded body in the same manner as in Example 111.

[Example 114]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of chromium ions (oxidation number 3, ionic radius 63 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 111 except that it was used.

[Example 115]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of nickel ions (oxidation number 2, ionic radius 68 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 111 except that it was used.

[Example 116]
Instead of MIL-125 (Ti), a porous coordination polymer (“Uio-66)” composed of zirconium ion (oxidation number 4, ionic radius 72pm) and terephthalic acid as an organic ligand was used. A molded body was produced in the same manner as in Example 111 except for the above.

[Example 117]
Instead of MIL-125 (Ti), a porous coordination polymer (“Cu-BTC”) composed of copper ion (oxidation number 2, ionic radius 73 pm) and trimesic acid as an organic ligand was used. Made a molded body in the same manner as in Example 111.

[Example 118]
Instead of MIL-125 (Ti), a porous coordination polymer (“Zif-8”) composed of zinc ion (oxidation number 2, ionic radius 74 pm) and 2-imidazole as an organic ligand was used. A molded body was produced in the same manner as in Example 111 except for the above.

[Example 119]
Instead of MIL-125 (Ti), a porous coordination polymer ("Pt-") composed of platinum ions (oxidation number 2, ionic radius 80pm), 4,4'-bipyridine and ethyleneamine as organic ligands. A molded body was produced in the same manner as in Example 111 except that PCP ”) was used.

[Example 120]
Highly porous coordination composed of lanthanum ion (oxidation number 3, ionic radius 103pm) and 1,3,5-tris (4-carboxyphenyl) benzene as an organic ligand instead of MIL-125 (Ti). A molded product was produced in the same manner as in Example 111 except that the molecule (“Zif-8”) was used.

[Example 121]
A porous coordination polymer ("Ag-PCP") composed of silver ion (oxidation number 1, ionic radius 115pm) and di-p-xylylene as an organic ligand is used instead of MIL-125 (Ti). A molded body was produced in the same manner as in Example 111 except for the above.

[Example 122]
Titanium ion (oxidation number 4, ionic radius 42 pm) was used as the metal ion, and a porous coordination polymer (“MIL-125 (Ti)”) composed of terephthalic acid was used as the organic ligand. A composition for molding was prepared by compounding and mixing 0.5 g of a porous coordination polymer and 50 g of EPDM rubber (“JSR EP331” manufactured by JSR Corporation at 180 ° C.).
The prepared molding composition was molded in a heating press at 180 ° C. and 10 MPa under heating conditions to prepare a molded product on a plate having a thickness of 1.0 mm.

[Example 123]
Instead of MIL-125 (Ti), a porous coordination polymer ("Al-PCP-F") composed of aluminum ion (oxidation number 3, ionic radius 54 pm) and fumaric acid as an organic ligand is used. A molded body was produced in the same manner as in Example 122 except for the above.

[Example 124]
Except for using a porous coordination polymer (“Fe-BTC”) composed of iron ion (oxidation number 3, ionic radius 55 pm) and trimesic acid as an organic ligand instead of MIL-125 (Ti). Made a molded body in the same manner as in Example 122.

[Example 125]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of chromium ions (oxidation number 3, ionic radius 63 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 122 except that it was used.

[Example 126]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of nickel ions (oxidation number 2, ionic radius 68 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 122 except that it was used.

[Example 127]
Instead of MIL-125 (Ti), a porous coordination polymer (“Uio-66)” composed of zirconium ion (oxidation number 4, ionic radius 72pm) and terephthalic acid as an organic ligand was used. A molded body was produced in the same manner as in Example 122 except for the above.

[Example 128]
Instead of MIL-125 (Ti), a porous coordination polymer (“Cu-BTC”) composed of copper ion (oxidation number 2, ionic radius 73 pm) and trimesic acid as an organic ligand was used. Made a molded body in the same manner as in Example 122.

[Example 129]
Instead of MIL-125 (Ti), a porous coordination polymer (“Zif-8”) composed of zinc ion (oxidation number 2, ionic radius 74 pm) and 2-imidazole as an organic ligand was used. A molded body was produced in the same manner as in Example 122 except for the above.

[Example 130]
Instead of MIL-125 (Ti), a porous coordination polymer ("Pt-") composed of platinum ions (oxidation number 2, ionic radius 80pm), 4,4'-bipyridine and ethyleneamine as organic ligands. A molded body was produced in the same manner as in Example 122 except that PCP ”) was used.

[Example 131]
Highly porous coordination composed of lanthanum ion (oxidation number 3, ionic radius 103pm) and 1,3,5-tris (4-carboxyphenyl) benzene as an organic ligand instead of MIL-125 (Ti). A molded product was prepared in the same manner as in Example 122 except that the molecule (“Zif-8”) was used.

[Example 132]
A porous coordination polymer ("Ag-PCP") composed of silver ion (oxidation number 1, ionic radius 115pm) and di-p-xylylene as an organic ligand is used instead of MIL-125 (Ti). A molded body was produced in the same manner as in Example 122 except for the above.

[Example 133]
Titanium ion (oxidation number 4, ionic radius 42 pm) was used as the metal ion, and a porous coordination polymer (“MIL-125 (Ti)”) composed of terephthalic acid was used as the organic ligand. A composition for molding was prepared by compounding and mixing 0.5 g of a porous coordination polymer and 50 g of SBR rubber (“JSR HPR850” manufactured by JSR Corporation) at 150 ° C.
The prepared molding composition was molded with a heating press at a heating condition of 150 ° C. and 10 MPa to prepare a molded product on a plate having a thickness of 1.0 mm.

[Example 134]
Instead of MIL-125 (Ti), a porous coordination polymer ("Al-PCP-F") composed of aluminum ion (oxidation number 3, ionic radius 54 pm) and fumaric acid as an organic ligand is used. A molded body was produced in the same manner as in Example 133 except for the above.

[Example 135]
Except for using a porous coordination polymer (“Fe-BTC”) composed of iron ion (oxidation number 3, ionic radius 55 pm) and trimesic acid as an organic ligand instead of MIL-125 (Ti). Made a molded body in the same manner as in Example 133.

[Example 136]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of chromium ions (oxidation number 3, ionic radius 63 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 133 except that it was used.

[Example 137]
Instead of MIL-125 (Ti), a porous coordination polymer (“Mil-101 (Cr)”) composed of nickel ions (oxidation number 2, ionic radius 68 pm) and terephthalic acid as an organic ligand is used. A molded body was produced in the same manner as in Example 133 except that it was used.

[Example 138]
Instead of MIL-125 (Ti), a porous coordination polymer (“Uio-66)” composed of zirconium ion (oxidation number 4, ionic radius 72pm) and terephthalic acid as an organic ligand was used. A molded body was produced in the same manner as in Example 133 except for the above.

[Example 139]
Instead of MIL-125 (Ti), a porous coordination polymer (“Cu-BTC”) composed of copper ion (oxidation number 2, ionic radius 73 pm) and trimesic acid as an organic ligand was used. Made a molded body in the same manner as in Example 133.

[Example 140]
Instead of MIL-125 (Ti), a porous coordination polymer (“Zif-8”) composed of zinc ion (oxidation number 2, ionic radius 74 pm) and 2-imidazole as an organic ligand was used. A molded body was produced in the same manner as in Example 133 except for the above.

[Example 141]
Instead of MIL-125 (Ti), a porous coordination polymer ("Pt-") composed of platinum ions (oxidation number 2, ionic radius 80pm), 4,4'-bipyridine and ethyleneamine as organic ligands. A molded body was produced in the same manner as in Example 133 except that PCP ”) was used.

[Example 142]
Highly porous coordination composed of lanthanum ion (oxidation number 3, ionic radius 103pm) and 1,3,5-tris (4-carboxyphenyl) benzene as an organic ligand instead of MIL-125 (Ti). A molded product was prepared in the same manner as in Example 133 except that the molecule (“Zif-8”) was used.

[Example 143]
A porous coordination polymer ("Ag-PCP") composed of silver ion (oxidation number 1, ionic radius 115pm) and di-p-xylylene as an organic ligand is used instead of MIL-125 (Ti). A molded body was produced in the same manner as in Example 133 except for the above.

[Comparative Example 1]
A molded product was prepared in the same manner as in Example 1 except that the porous coordination polymer was not used.

[Comparative Example 2]
A molded product was produced in the same manner as in Example 12 except that the porous coordination polymer was not used.

[Comparative Example 3]
A molded product was produced in the same manner as in Example 23 except that the porous coordination polymer was not used.

[Comparative Example 4]
A molded product was produced in the same manner as in Example 34 except that the porous coordination polymer was not used.

[Comparative Example 5]
A molded product was produced in the same manner as in Example 45 except that the porous coordination polymer was not used.

[Comparative Example 6]
A molded product was produced in the same manner as in Example 56 except that the porous coordination polymer was not used.

[Comparative Example 7]
A molded product was produced in the same manner as in Example 67 except that the porous coordination polymer was not used.

[Comparative Example 8]
A molded product was produced in the same manner as in Example 78 except that the porous coordination polymer was not used.

[Comparative Example 9]
A molded product was produced in the same manner as in Example 89 except that the porous coordination polymer was not used.

[Comparative Example 10]
A molded product was produced in the same manner as in Example 100 except that the porous coordination polymer was not used.

[Comparative Example 11]
A molded product was produced in the same manner as in Example 111 except that the porous coordination polymer was not used.

[Comparative Example 12]
A molded product was produced in the same manner as in Example 122 except that the porous coordination polymer was not used.

[Comparative Example 13]
A molded product was produced in the same manner as in Example 133 except that the porous coordination polymer was not used.

(Evaluation of gas adsorption rate)
The gas adsorption rate of the prepared samples of Examples and Comparative Examples was evaluated by the following method.
Using a pyrolysis gas chromatograph mass spectrometer (product name "7890A / 5975C" manufactured by Agilent Technologies), heat at the same temperature as the kneading temperature of each resin or rubber, and separate the generated gas components for mass spectrometry. did. The results of mass spectrometry were collated with the library to identify the generated gas components. The amount of generated gas was calculated from the height of each peak in the chromatogram. An example of the main chromatogram is shown in FIG. In this analysis, out of the substances whose gas components could be identified by mass spectrometry, substances up to 90% of the total gas generation amount were targeted.

なお、発生するガスを吸着し、ガス発生量を低減させることが出来る合否判断の下限値として、ガス吸着率15%以上と設定した。 The gas adsorption rate was calculated from the following formula.

The gas adsorption rate was set to 15% or more as the lower limit of the pass / fail judgment that can adsorb the generated gas and reduce the amount of gas generated.

As a result of diligently examining the physical property values of the gas component and the porous coordination polymer generated when the resin and rubber are melted from the obtained results, the following relationship was found for the acid dissociation constant of the gas component.

First, Tables 1 to 5 show the prepared examples and comparative examples. Table 6 shows the gas components generated from each resin and the amount of gas in the comparative example as a reference. The gas adsorption rate calculated from the above formula is shown in Tables 7 to 19 for each resin. In Examples 1 to 143, the relationship between the acid dissociation constant of the gas component having a gas adsorption rate of 15% or more and the ionic radius of the porous coordination polymer is shown in FIG. Further, FIG. 2 shows the relationship between the acid dissociation constant of the gas component having a gas adsorption rate of less than 15% and the ionic radius of the porous coordination polymer. From FIG. 2, it was found that in each of the examples, the acid dissociation constant of the gas component and the ionic radius have the following relationship when the adsorption rate of each gas component is 15% or more.
Condition (A) When the acid dissociation constant of the generated gas component is 16.61 or less, a combination of porous coordination polymers having metal atoms having an ionic radius of 62 pm or less is effective.
Condition (B) When the acid dissociation constant of the generated gas component is 17.00 or more, a combination of porous coordination polymers having metal atoms having an ionic radius of 69 pm or more is effective.

The above condition portion is shaded in FIG. 2.
Further, from FIG. 2, a combination having a gas adsorption rate of less than 15%, which is an inappropriate combination that does not satisfy the above conditions, is a portion that does not correspond to the shaded portion.

Adsorption of a substance to the porous coordination polymer is considered to be due to the adsorbed substance being retained in the pores of the porous coordination polymer. In particular, it is considered that the intermolecular force between the metal atom and the adsorbed substance is involved in the retention of the adsorbed substance. It is considered that two types of forces, the inductive effect and the resonance effect, act on the adsorption by the intermolecular force. The bond in which the inductive effect is involved is a polarization bond, which occurs in a substance in which charge bias occurs. We focused on the acid dissociation constant as a measure of the charge bias of the adsorbed material. The acid dissociation constant is a numerical value of the dissociation reaction in which hydrogen ions are released from the acid. When the value is low, the spread of electrons becomes large and the charge is biased. The charge bias depends on the electronegativity, which is the strength at which electrons are attracted. When the ionic radius of the metal atom constituting the porous coordination polymer is small, the electronegativity becomes large. Therefore, it is considered that a porous coordination polymer having a metal atom having a large electronegativity is effective for an adsorbed substance having a wide electron orbit. On the other hand, the bonds involved in the resonance effect are caused by electron delocalization. Therefore, it can be considered as a substance in which the charge bias does not occur, such as a substance having a large acid dissociation constant, and since the charge bias does not occur, the spread of electrons also becomes small. Therefore, it is considered effective that the porous coordination polymer to be adsorbed is a metal atom having a small electronegativity of the metal atom constituting the porous coordination polymer and having a weak ionic radius to attract electrons. ..

上記表６の各マス目には、記号、物質名、酸解離定数、発生ガス量を順に記載している。


下記表７から表１９のガス吸着率（％）欄の各物質名の後には酸解離定数を記載している。

Therefore, in order to reduce the gas generated when the resin and rubber are melted, the acid dissociation constant of the gas component satisfying the above conditions (A) and (B) and the ionic radius of the metal atom of the porous coordination polymer are used. It is required to be.

Symbols, substance names, acid dissociation constants, and generated gas amounts are listed in order in each cell of Table 6 above.


The acid dissociation constant is described after each substance name in the gas adsorption rate (%) column of Tables 7 to 19 below.

The molding composition of the present embodiment is suitably used as a material for a precision molded body applied to an OA device, a storage medium device such as a hard disk, a semiconductor-related device, a motor device, an infrastructure device such as a water supply member, and the like.

Claims (4)

The porous coordination polymer containing a metal ion and an organic ligand and one or more base materials selected from the group consisting of plastic resins, rubbers, and sealing materials are contained, and the porous coordination height is high. A molding composition in which the molecule and the base material satisfy the following conditions (A) or (B), respectively.
(A) When the acid dissociation constant of the gas derived from the base material is 16.6 or less, the radius of the metal ion of the porous coordination polymer is 62 × 10 ^-12 m or less.
(B) When the acid dissociation constant of the gas derived from the base material is 17.0 or less, the radius of the metal ion of the porous coordination polymer is 68 × ^10-12 m or more. The metal ions are Ag (I), Al (III), Be (II), Ca (II), Cd (II), Ce (III), Co (III), Co (II), Cr (III), Cu (II), Cu (I), Dy (III), Er (III), Eu (III), Fe (III), Fe (II), Ga (III), Gd (III), Ho (III), In (III), Li (I), Mg (II), Mn (III), Mo (III), Nd (III), Ni (II), Sc (III), Sm (II)
I), Sn (II), Tb (III), Ti (IV) Tm (III), V (III), W (IV), Y (III), Yb (III), Zn (II), Pd (II) The molding composition according to claim 1, wherein the composition is one or more selected from the group consisting of Au (I), Tl (I), Hg (I), Pt (I) and Zr (IV). The molded product of the molding composition according to any one of claims 1 and 2. By blending a porous coordination polymer containing a metal ion and an organic ligand into one or more base materials selected from the group consisting of plastic resins, rubbers, and sealing materials, the base material can be used. A method for suppressing the generation of derived gas, wherein the porous coordination polymer and the base material satisfy the following conditions (A) or (B), respectively.
(A) When the acid dissociation constant of the gas derived from the base material is 16.6 or less, the radius of the metal ion of the porous coordination polymer is 62 × 10 ^-12 m or less.
(B) When the acid dissociation constant of the gas derived from the base material is 17.0 or less, the radius of the metal ion of the porous coordination polymer is 68 × ^10-12 m or more.

Images