WO2019244922A1 - Composition de moulage et objet moulé - Google Patents

Composition de moulage et objet moulé Download PDF

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Publication number
WO2019244922A1
WO2019244922A1 PCT/JP2019/024266 JP2019024266W WO2019244922A1 WO 2019244922 A1 WO2019244922 A1 WO 2019244922A1 JP 2019024266 W JP2019024266 W JP 2019024266W WO 2019244922 A1 WO2019244922 A1 WO 2019244922A1
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iii
coordination polymer
lewis acid
acid
porous coordination
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PCT/JP2019/024266
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English (en)
Japanese (ja)
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俊介 坪
▲高▼橋　徹
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株式会社ニックス
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Priority to JP2020525764A priority Critical patent/JPWO2019244922A1/ja
Publication of WO2019244922A1 publication Critical patent/WO2019244922A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups

Definitions

  • the present invention relates to a molding composition and a molded article.
  • a method for suppressing the generation of gas there is a method in which a considerable number of gas vents are added to a mold and a gas suction device is attached to a molding machine to suppress generation of gas.
  • the plastic resin is polyphenyl sulfide (PPS)
  • PPS polyphenyl sulfide
  • a thermal oxidation treatment of heating the polyphenyl sulfide under the condition that an oxidizing substance is present is performed, and an oxidative cross-linking treatment is performed to generate volatile gas components.
  • Patent Documents 1 and 2 There are methods for greatly reducing the amount. However, none of these methods can sufficiently suppress the generation of gas.
  • a method of adsorbing the gas in a plastic resin includes, for example, 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 method of adding a hydrotalcite substance to a plastic resin.
  • a method of adding PAN-based carbon fiber to a plastic resin Patent Document 6
  • a method of adding a porous zeolite body to a plastic resin Patent Document 7
  • the method of adsorbing the gas in the plastic resin has a certain effect, but requires further improvement.
  • the method of suppressing generation of gas derived from a base material such as a plastic resin has a certain effect in any case, but there is room for further improvement.
  • an object of the present invention is to provide a molding composition and a molded article capable of suppressing the generation of a gas derived from at least one base material selected from the group consisting of plastic resins, rubbers, and sealing materials to the outside.
  • the purpose is to provide.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, when a porous coordination polymer containing a metal ion having a specific Lewis acid value and an organic ligand is combined with a base material, The present inventors have found that the obtained molding composition can solve the above problems, and have completed the present invention.
  • the present invention is as follows. [1] Including a 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, A molding composition wherein the porous coordination polymer and the base material respectively satisfy the following condition (A) or (B).
  • A) The gas derived from the base material contains a hard Lewis base, the metal ion is a hard Lewis acid, and the Lewis acid value of the porous coordination polymer is 0.15 or more.
  • the gas derived from the base material contains an intermediate or soft Lewis base, the metal ion is an intermediate or soft Lewis acid, and the Lewis acid value of the porous coordination polymer is 0. 28 or more.
  • the above molding composition comprising an antioxidant represented by the following formula (4) and one or more antioxidants selected from the group consisting of an antioxidant represented by the following formula (5).
  • R independently represents a hindered phenol group.
  • R is each independently a 3,5-di-tert-butyl-4-hydroxyphenyl group or a 4-tert-butyl-3-hydroxy-2,6-dimethylphenyl group.
  • 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), V (III), W (IV), Y (III), Yb (III), Zn (II), Pd (II), Au (I), Tl (I), At least one selected from the group consisting of Hg (I), Pt (I) and Zr (IV) The molding composition.
  • a molded article of the molding composition [5] A molded article of the molding composition. [6] By mixing a porous coordination polymer containing a metal ion and an organic ligand into one or more base materials selected from the group consisting of a plastic resin, rubbers, and a sealing material, A method for suppressing the generation of derived gas, A method wherein the porous coordination polymer and the base material satisfy the following condition (A) or (B), respectively. (A) The gas derived from the base material contains a hard Lewis base, the metal ion is a hard Lewis acid, and the Lewis acid value of the porous coordination polymer is 0.15 or more.
  • the gas derived from the base material contains an intermediate or soft Lewis base, the metal ion is an intermediate or soft Lewis acid, and the Lewis acid value of the porous coordination polymer is 0. 28 or more.
  • one or more antioxidants selected from the group consisting of an antioxidant represented by the following formula (4) and an antioxidant represented by the following formula (5), The above method, wherein the generation of derived gas is further suppressed.
  • R independently represents a hindered phenol group.
  • the molding composition and molded object which can suppress generation
  • the present embodiment is an exemplification for describing the present invention, and the present invention is not limited to only the embodiment.
  • the molding composition of the present embodiment includes a porous coordination polymer containing a metal ion and an organic ligand, and one or more base materials selected from the group consisting of a plastic resin, rubbers, and a sealing material. And
  • the porous coordination polymer and the base material satisfy the following condition (A) or (B).
  • (A) The gas derived from the base material contains a hard Lewis base, the metal ion is a hard Lewis acid, and the Lewis acid value of the porous coordination polymer is 0.15 or more.
  • the gas derived from the base material contains an intermediate or soft Lewis base, the metal ion is an intermediate or soft Lewis acid, and the Lewis acid value of the porous coordination polymer is 0. 28 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.
  • the gas derived from the base material includes not only the gas generated from the base material, but also components (eg, a polymerizing agent and a catalyst residue at the time of resin synthesis) that can be contained as impurities in the base material, and the base material.
  • components eg, a polymerizing agent and a catalyst residue at the time of resin synthesis
  • the base material eg, a polymerizing agent and a catalyst residue at the time of resin synthesis
  • Derived from interaction with other materials that can 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 decomposition of the above components in the process of heating and molding the molding composition including the base material, and in the form of a molded body, is caused by air contact or the like over time. It may be a gas generated by decomposition of the above components. For this reason, when molding using the molding composition of the present embodiment, it is possible to suppress a decrease in accuracy due to generated gas, to suppress a decrease in strength due to voids and the like, to suppress environmental degradation such as cleanness, and to perform molding. In this case, advantages such as suppression of mold corrosion can be obtained. As a result, the molding composition can improve the quality of the molded body, and can reduce costs by reducing the frequency of mold maintenance and the like.
  • the gas generated from the molding composition while analyzing the gas to identify the type, the type of components that can be included in the base material or other molding composition that causes the gas, 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.
  • “hard Lewis acid or hard Lewis base”, “intermediate Lewis acid or intermediate Lewis base”, and “soft Lewis acid or soft Lewis base” are Hard and Soft Acids and Bases ( It corresponds to Lewis acids (Lewis bases) classified into hard Lewis acids (Lewis bases), intermediate Lewis acids (Lewis bases), and soft Lewis acids (Lewis bases) classified based on the principle of HSAB). Refers to a concept. More specifically, each Lewis acid or Lewis base is classified based on the contents described in “Chemistry and Education ⁇ 2008, 56, 400-401 ⁇ Hardness / Softness of Acid / Base”.
  • the porous coordination polymer contains a metal ion and an organic ligand.
  • the porous coordination polymer has, for example, a form in which a metal ion is adsorbed on an organic ligand.
  • the organic ligand is, for example, an organic ligand that can bind 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 a macropore or mesopore region, and has a uniform pore diameter because the pore diameter (pore diameter) is determined based on the crystal structure. .
  • the porous coordination polymer can increase the holding power of the gas generated from the base material and can be packed finely by controlling the affinity of the organic ligand by the length and the chemical structure.
  • the average pore diameter of the porous coordination polymer is preferably equal to or more 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 preferred.
  • the average pore diameter of the porous coordination polymer is determined from a gas adsorption isotherm by the BET method.
  • the metal ion is a hard Lewis acid, and the Lewis acid value of the porous coordination polymer is 0.15 or more.
  • the metal ion is an intermediate or soft Lewis acid, and the Lewis acid value of the porous coordination polymer is 0. .28 or more.
  • Lewis acid value (atomic weight of metal atom acting as Lewis acid) / (molecular weight of structural unit of porous coordination polymer)
  • the Lewis acid value is 0.30 or more. (Preferably 0.32 or more, more preferably 0.35 or more).
  • the Lewis acid value is 0.18 or more (preferably 0.20 or more) from the viewpoint of suppressing generation of a gas containing a hard Lewis base derived from the base material to the outside. , More preferably 0.23 or more).
  • the organic ligand is preferably a cross-linkable ligand capable of cross-linking a metal ion.
  • 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-carboxylphenylbenzene, methylimidazole, 4,4 ′ -Biphenyldicarboxylic acid, fumaric acid, naphthalenedicarboxylic acid, hexaazatriphenylene, 2,5-dihydroxybenzoic acid, trimesic acid, 5-cyano-benzenedicarbox
  • the surface of the porous coordination polymer, the residue substance that is attached to or present in the pores is removed, and then the porous coordination polymer is removed. It is desirable to compound the material.
  • the pores may be narrowed or completely closed by the residual substance, and it may be difficult to inject the generated gas into the pores of the porous coordination polymer.
  • the method for removing the residual substance include a method for washing the porous coordination polymer with a solvent.
  • the solvent used for washing include water, methanol, THF, and DMF, and the solvent is preferably water and / or methanol.
  • the solvent is water and / or methanol
  • the solvent has a small molecular diameter, so that the solvent easily enters the pores of the porous coordination polymer, and the residual substances in the pores can be easily removed.
  • the porous coordination polymer may be immersed in the solvent for a long time.
  • the immersion time is preferably at least 12 hours, more preferably at least 24 hours.
  • a method for removing unreacted substances or impurities a method for removing residual substances by heat treatment is given.
  • the heat treatment is preferably performed in air or an oxygen atmosphere.
  • the unreacted substance or the impurity is a volatile substance and it is desired to remove the volatile substance, it is preferable to perform a vacuum heat treatment.
  • the heating temperature is preferably from 100 to 300 ° C. After washing with a solvent, a method of performing a heat treatment to completely remove the solvent is preferable.
  • the base material is at least one selected from the group consisting of plastic resins, rubbers, and sealing materials.
  • the gas derived from the base material contains a hard Lewis base
  • the metal ion is a hard Lewis acid
  • the Lewis acid value of the porous coordination polymer is 0.15 or more
  • the gas derived from the base material is
  • the metal ion contains an intermediate or soft Lewis base
  • the metal ion is an intermediate or soft Lewis acid
  • the Lewis acid value of the porous coordination polymer is 0.28 or more.
  • hard Lewis base examples include H 2 O, HO ⁇ , F ⁇ , MeCO 2 ⁇ , CO 3 2 ⁇ , NO 3 ⁇ , ROH, RO ⁇ , Cl ⁇ , NH 3 , and RNH 2 (where R is a substituent Represents a hydrocarbon group which may have a).
  • Intermediate or soft Lewis bases include R 2 S, RSH, RS ⁇ , I ⁇ , SCN ⁇ , R 3 P, CN ⁇ , CO, C 2 H 4 , C 6 H 6 , H ⁇ , R ⁇ , Br ⁇ , NO 2 ⁇ , C 5 H 5 N, and C 6 H 5 NH 2 (where R represents a hydrocarbon group which may have a substituent) and the like.
  • the plastic resin includes one or more resins.
  • the resin include a thermoplastic resin and a thermosetting resin.
  • the thermoplastic resin 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, 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 sulfide resin, polysulfone resin, polyarylate resin, polyetherimide resin, polyether Examples include a sulfone resin, a polyether ketone resin, a liquid crystal polyester resin, a thermoplastic polyimide resin, and a thermoplastic polyurethane resin.
  • thermosetting resin examples 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.
  • an aromatic polyamide resin a polyamide resin such as polyamide 66, and a polyphenylene sulfide resin are preferable, and an aromatic polyamide resin and a polyphenylene sulfide resin are more preferable.
  • Examples of rubbers include artificial rubber and natural rubber.
  • Examples of the artificial rubber include polybutadiene, polyisoprene, random copolymers and block copolymers of styrene-butadiene, hydrogenated products of block copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers, and the like.
  • sealing material examples include a silicone-based sealing material, a modified silicone-based sealing material, a polyurethane-based sealing material (for example, an acrylic urethane-based sealing material), a silylated acrylate-based sealing material, a polysulfide-based sealing material, and a polyisobutylene-based sealing material. And the like. These sealing materials are used individually by 1 type or in combination of 2 or more types.
  • the molding composition of the present embodiment can suppress the generation of the gas derived from the base material to the outside.
  • the gas include water, acetic acid, chlorine, chloride, nitrogen dioxide, nitric acid gas, nitrous acid gas, ammonia, a saturated fatty acid represented by CH 3 (CH 2 ) n COOH, and CH 3 (CH 2 ) n CONH.
  • a saturated fatty acid amide represented by 2 (in each formula, n represents an integer, and preferably represents an integer of 4 to 20); a monounsaturated fatty acid represented by C p H q COOH; fatty acids, unsaturated fatty acids such as tri-unsaturated fatty acids, C p H q represented by CONH 2, monounsaturated fatty acid amides, di-unsaturated fatty acid amides, unsaturated fatty acid amides (formula such as tri-unsaturated fatty acid amide Wherein p and q represent integers, and the relationship between p and q depends on the number of unsaturated carbon-carbon bonds, for example, p represents an integer of 5 to 21.
  • Gas, bromine, bromide Gases containing intermediate Lewis base components such as nitrogen oxides, sulfur dioxide, cyclic amides, sulfides (eg, hydrogen sulfide), iodine, cyanide, carbon dioxide, carbon monoxide, ethylene, benzene, aromatic compounds, etc. And a gas containing a soft Lewis base component.
  • intermediate Lewis base components such as nitrogen oxides, sulfur dioxide, cyclic amides, sulfides (eg, hydrogen sulfide), iodine, cyanide, carbon dioxide, carbon monoxide, ethylene, benzene, aromatic compounds, etc.
  • a gas containing a soft Lewis base component containing a soft Lewis base component.
  • the gas generated from the base material will be described as an example in the case where the base material is PPS (polyphenylene sulfide).
  • PPS polyphenylene sulfide
  • PPS is industrially obtained by polycondensation reaction between paradichlorobenzene (p-DCB) and sodium sulfide (Na2S) or sodium hydrosulfide (NaSH) in a polar solvent under high temperature and pressure.
  • p-DCB paradichlorobenzene
  • Na2S sodium sulfide
  • NaSH sodium hydrosulfide
  • various reactions such as a dehydration reaction, a desalination reaction, an exothermic reaction, and a high-temperature pressurization reaction are performed, and the outline thereof is represented by the following reaction formula. Therefore, chlorine remains in PPS as a reaction residue.
  • the sulfur contained in the structure of the PPS is separated by heat by heating at the time of molding, and further oxidized to sulfite ions, sulfate ions, and hydrogen sulfide, and a part of the gas is gasified to form, for example, , Sulfurous acid gas and hydrogen sulfide gas. Further, part of the chlorine remaining in the PPS becomes chlorine gas by heating during molding.
  • the gas generated from the PPS is a sulfur compound classified as an intermediate or soft Lewis base and a chlorine gas classified as a hard Lewis base.
  • a porous coordination polymer whose metal ion is an intermediate or soft Lewis acid and has a Lewis acid value of 0.28 or more is considered to be effective for the adsorption of a sulfur compound as an intermediate or soft Lewis base.
  • a porous coordination polymer in which the metal ion is a hard Lewis acid and the Lewis acid value is 0.15 or more is considered to be effective for the adsorption of chlorine gas, which is a hard Lewis base.
  • a porous coordination polymer adsorbing a gas containing a hard Lewis base and a porous coordination polymer adsorbing a gas containing an intermediate or soft Lewis base are used. It is thought that it is effective to use both.
  • the gas generated from the base material will be described as an example in the case where the base material is an aromatic polyamide resin (hereinafter, also referred to as “aromatic PA resin”).
  • aromatic PA resin aromatic polyamide resin
  • the heating of the aromatic PA resin at the time of molding causes cleavage of the amide group, separation from the denatured chain, separation of the polyamide chain, liberation of ketone, separation of the denatured chain, and the like.
  • the saturated fatty acid represented by CH 3 (CH 2 ) n COOH the saturated fatty acid amide represented by CH 3 (CH 2 ) n CONH 2
  • the saturated fatty acid amide represented by CH 3 (CH 2 ) n CN (Wherein n represents an integer, and preferably represents an integer of 4 to 20), monounsaturated fatty acid, diunsaturated fatty acid, triunsaturated fatty acid represented by C p H q COOH.
  • Unsaturated fatty acids such as unsaturated fatty acids, unsaturated fatty acid amides such as mono-unsaturated fatty acid amides, di-unsaturated fatty acid amides, tri-unsaturated fatty acid amides represented by C p H q CONH 2 , C p H q Unsaturated fatty acid nitriles such as mono-unsaturated fatty acid nitrile, di-unsaturated fatty acid nitrile, and tri-unsaturated fatty acid nitrile represented by CN (wherein p and q represent integers, p and Is dependent on the number of unsaturated carbon-carbon bonds, q is 2p-1 when there is one unsaturated carbon-carbon double bond, and q is two when there are two unsaturated carbon-carbon double bonds.
  • the gas generated from the aromatic PA resin is a saturated fatty acid nitrile represented by CH 3 (CH 2 ) n CN classified into an intermediate or soft Lewis base (where n represents an integer, preferably 4 to 20). ), And unsaturated fatty acid nitriles such as mono-unsaturated fatty acid nitrile, di-unsaturated fatty acid nitrile, and tri-unsaturated fatty acid nitrile represented by C p H q CN (where p and q are integers) And the relationship between p and q depends on the number of unsaturated carbon-carbon bonds.
  • Cyclic amide and aromatic amide polymers and hard Lewis salts Saturated fatty acids represented by CH 3 (CH 2 ) n COOH and saturated fatty acid amides represented by CH 3 (CH 2 ) n CONH 2 (in the formulas, n represents an integer, preferably Represents an integer of 4 to 20), an unsaturated fatty acid such as a mono-unsaturated fatty acid, a di-unsaturated fatty acid, or a tri-unsaturated fatty acid, represented by C p H q COOH, and a C p H q CONH 2 .
  • Unsaturated fatty acids such as mono-unsaturated fatty acid amide, di-unsaturated fatty acid amide, and tri-unsaturated fatty acid amide (in the formulas, p and q each represent an integer; Depending on the number of inter-bonds, q is 2p-1 if there is one unsaturated carbon-carbon double bond, q is 2p-3 if there are two unsaturated carbon-carbon double bonds, When there are three unsaturated carbon-carbon double bonds, q is 2p-5 And p represents, for example, an integer of 5 to 21).
  • a porous coordination polymer whose metal ion is an intermediate or soft Lewis acid and whose Lewis acid value is 0.28 or more is effective for the adsorption of the above-mentioned intermediate or soft Lewis base.
  • a porous coordination polymer in which the metal ion is a hard Lewis acid and the Lewis acid value is 0.15 or more is considered to be effective for the adsorption of the hard Lewis base.
  • a porous coordination polymer for adsorbing a gas containing a hard Lewis base and a porous coordination polymer for adsorbing a gas containing an intermediate or soft Lewis base are used. It is considered to be effective to use in combination with a coordination polymer.
  • the molding composition may contain an inorganic filler from the viewpoint of improving mechanical properties.
  • an 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-like inorganic filler.
  • the particulate inorganic filler may be, for example, a micron-sized particulate inorganic filler or a nano-sized particulate inorganic filler.
  • the particulate inorganic filler having a micron size examples include, for example, calcium carbonate particles, silica particles, glass beads, titanium oxide particles, zinc oxide particles, potassium titanate particles, titania particles, monoclinic titania particles, calcium phosphate particles, Examples include wollastonite, vermiculite, shirasu balloon, glass balloon and the like.
  • the nano-sized particulate inorganic filler include nano titanium oxide, nano silica, carbon black, carbon filler and the like.
  • the inorganic filler may be used alone or in combination of two or more. Among them, the particulate inorganic filler is preferably potassium titanate particles from the viewpoint of further improving the sustained release of a function sustained release liquid (particularly, a small animal control agent).
  • the fibrous inorganic filler is preferably a fibrous inorganic filler having an average fiber diameter of 0.05 to 10 ⁇ m and an average fiber length of 3 to 150 ⁇ m, from the viewpoint of not adversely affecting the appearance of the molded article, More preferably, it is a fibrous inorganic filler having an average fiber diameter of 0.1 to 7 ⁇ m and an average fiber length of 5 to 50 ⁇ m.
  • the fibrous inorganic filler may be, for example, a micron-sized fibrous inorganic filler or a nano-sized fibrous inorganic filler.
  • fibrous inorganic filler having a micron size examples include glass fiber, carbon fiber, graphite fiber, aramid fiber, vinylon fiber, polyamide fiber, polyester fiber, cotton, hemp fiber, kenaf fiber, bamboo fiber, rayon, and steel fiber. , Aluminum fiber, gypsum fiber, potassium titanate fiber, potassium hexatitanate fiber, potassium octa titanate fiber, titania fiber, monoclinic titania fiber, silica fiber, wollastonite, zonotolite and the like.
  • nano-sized fibrous inorganic filler examples include carbon fiber, carbon nanotube, fullerene, cotton fibril, silicon nitride whisker, alumina whisker, silicon carbide whisker, nickel whisker, and the like. These fibrous inorganic fillers may be used alone or in combination of two or more.
  • the scaly or plate-like inorganic filler may be, for example, a micron-sized scaly or plate-like inorganic filler, or a nano-sized scaly or plate-like inorganic filler.
  • Examples of the scaly or plate-like inorganic filler having a micron size include talc, kaolin clay, mica (synthetic mica or natural mica), glass flake, aragonite, calcium sulfate, aluminum hydroxide, potassium titanate, potassium titanate Examples include lithium, potassium magnesium titanate, sericite, plate-like alumina, boron nitride, and the like.
  • Examples of the nano-sized scaly or plate-like inorganic filler include organic montmorillonite, swellable synthetic mica, graphite, graphite, and the like. The scaly inorganic filler is 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 adhesion to the resin or further improving the mechanical properties, a silane coupling agent such as aminosilane, epoxysilane, or 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.
  • the molding composition may contain a plasticizer from the viewpoint of further improving the processability and flexibility of the molded article.
  • a plasticizer examples 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 sulfonamide derivative.
  • the plasticizer may be used alone or in combination of two or more.
  • carboxylic acid ester derivatives examples include alkyl esters of various carboxylic acids which may be substituted with a hydroxyl group, a nitro group, an amino group, an epoxy group, a halogen, and the like, and aromatic esters.
  • carboxylic acid ester derivatives include, for example, dimethyl phthalate, diethyl phthalate, di-n-octyl phthalate, diphenyl phthalate, benzyl phthalate, dimethoxyethyl phthalate, di (2-ethylhexyl) 4,5-epoxyhexahydrophthalate 4,5-epoxycyclohexahydrophthalic acid di (7,8-epoxy-2-octenyl), 4,5-epoxycyclohexahydrophthalic acid di (9,10-epoxyoctadecyl), 4,5-epoxycyclohexyl Phthalate ester derivatives such as di (10,11-epoxyundecyl) sahydrophthalate, di (tetrahydrofurfuroxyethyl) phthalate, mixed esters of various phthalic acids and ethylene oxide adducts of mixed esters of phthalic acid, isophthal
  • phosphate derivative examples include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri- (2-ethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, and isodecyl.
  • Examples of the phosphazene derivative include a cyclic phosphazene compound represented by the following general formula (1).
  • m represents an integer of 3 to 25
  • R 1 and R 2 may be the same or different and each have an alkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms. And / or 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 a mixture of two or more kinds.
  • phosphazene derivative for example, a linear phosphazene compound represented by the following general formula (2) may also be mentioned.
  • n an integer of 3 to 1000, and R 3 and R 4 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.
  • Y represents a group -P (OR 3 ) 4 , a group -P (OR 4 ) 4 , a group -P (O) (OR 3 ) 2 or a group -P (O) (OR 4 ) 2 .
  • the phosphazene derivative may be composed of one kind of the linear phosphazene compound represented by the formula (2),
  • phosphazene derivative an alkyl group or the like is eliminated from R 1 , R 2 , R 3 and R 4 in the formula (1) or the formula (2) by a crosslinking group represented by the following formula (3).
  • a phosphazene compound in which oxygen atoms are cross-linked may be used.
  • r represents 0 or 1
  • A represents a divalent group —SO 2 —, —S—, —O—, or —C (CH 3 ) 2 —.
  • cyclic phosphazene compound represented by the formula (1) examples include hexaphenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, decafenoxycyclopentaphosphazene, hexapropoxycyclotriphosphazene, octapropoxycyclocyclotetraphosphazene, and decapropoxy. And cyclopentaphosphazene.
  • linear phosphazene compound represented by the formula (2) include a linear phosphazene compound in which a linear dichlorophosphazene is substituted with a propoxy group and / or a phenoxy group.
  • crosslinked structure represented by the formula (3) examples include 4,4′-sulfonyldiphenylene (bisphenol-S residue), 4,4′-oxydiphenylene group, and 4,4′-thiodiphenylene And 4,4'-diphenylene groups.
  • These phosphazene derivatives may have an amino group and / or a phenylamino group substituted at an arbitrary position. These phosphazene derivatives may be used alone or in combination of two or more.
  • carboxylic acid amide derivatives include, for example, N-cyclohexylbenzoic acid amide.
  • the sulfonamide derivative include N-methyl-benzenesulfonamide, N-ethyl-benzenesulfonamide, N-butyl-benzenesulfonamide, N-cyclohexyl-benzenesulfonamide, N-ethyl-P-toluenesulfonamide, Examples include N-butyl-toluenesulfonamide and N-cyclohexyl-toluenesulfonamide.
  • sulfonic acid ester derivatives examples include ethyl benzenesulfonate, 2-methoxyethyl methanesulfonate, 2,2,2-trifluoroethyl methanesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, p-toluenesulfonate, -N-propyl toluenesulfonate and the like.
  • sulfonic acid amide derivative examples include N-methylmethanesulfonic acid amide, p-toluenesulfonic acid amide, p-aminobenzenesulfonamide, o-aminobenzenesulfonamide, m-aminobenzenesulfonamide, aniline-4-sulfone
  • acid amide 1-aminobenzene-4-sulfonic acid amide, 1-aminobenzene-4-sulfonamide, 4-aminobenzenesulfonic acid amide, and p-sulfanilic acid amide.
  • the molding composition may contain a weather resistance imparting additive from the viewpoint of further improving the weather resistance when left outdoors.
  • the weatherability-imparting additive is selected from the group consisting of antioxidants such as hindered phenolic antioxidants and phosphorus-based antioxidants, ultraviolet light absorbing light stabilizers, hindered amine light stabilizers, and carbon. One type is mentioned.
  • hindered phenolic antioxidants 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 ] -Glycol ester, 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-
  • Examples of the phosphorus-based antioxidant include tris (2,4-di-tert-butylphenyl) phosphite and tris [2-[[2,4,8,10-tetra-tert-butylbenzo [d, f]].
  • Examples of the ultraviolet absorber include 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol and 2- (2H-benzotriazol-2-yl) phenol -4,6-di-tert-pentylphenol, propandioic acid, and [(4-methoxyphenyl) -methylene] -dimethyl ester.
  • hindered amine light stabilizer examples include, for example, N, N ′, N ′′, N ′ ′′-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethyl) Piperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-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-dispiro- [5.1.
  • the weatherability imparting additive is used alone or in combination of two or more.
  • the weatherability-imparting additives 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)], tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tris (2,4-di-tert) -Butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, bis (2,4-di-tert-butyl) Phenyl) pentaerythritol pho
  • the molding composition of the present embodiment is an antioxidant represented by the following formula (4) and an oxidant represented by the following formula (5) from the viewpoint of further suppressing generation of a gas derived from the base material to the outside. It preferably contains one or more antioxidants selected from the group consisting 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 Generation of gas derived from the material to the outside can be further reduced.
  • a group having no particular symbol at the bonding end indicates a methyl group.
  • R independently represents a hindered phenol group.
  • R is a 3,5-di-tert-butyl-4-hydroxyphenyl group or 4-tert-butyl from the viewpoint of further suppressing generation of a gas derived from the base material to the outside. It is preferably a -3-hydroxy-2,6-dimethylphenyl group.
  • the antioxidant is 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-hydroxy-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 More preferably, it is selected from the group consisting of -butyl-phenol.
  • the antioxidant is particularly preferably 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.
  • the antioxidant Is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and further preferably 220 ° C. or higher.
  • the molding composition of the present embodiment does not contain the above antioxidant, the total content of the base material and the porous coordination polymer in the molding composition is reduced to 100% by mass of the molding composition.
  • 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, further preferably 80% by mass or more and 100% by mass or less.
  • the total content is within the above range, the generation of a gas derived from the base material to the outside is further suppressed, and the physical properties required for the product are more effectively imparted to the molding composition. Can be.
  • the content of the base material in the molding composition is based on 100% by mass of the total of the base material and the porous coordination polymer. It is preferably at least 50% by mass, more preferably at least 70% by mass, even more preferably at least 90% by mass.
  • the content of the porous coordination polymer is 0.01% with respect to 100% by mass of the total of the base material and the porous coordination polymer. It is preferably from 15 to 15% by mass, more preferably from 0.1 to 10% by mass, even more preferably from 0.5 to 5% by mass.
  • the content of the weather resistance-imparting additive is preferably 40% by mass or less based on 100% by mass of the molding composition. , 30% by mass or less, more preferably 20% by mass or less.
  • the content is within the above range, generation of a gas derived from the base material to the outside can be further suppressed, and the physical properties required for the product can be more effectively imparted to the molding composition. .
  • the molding composition may contain other optional components such as an inorganic filler, a plasticizer, and a flame retardant in an amount that does not hinder the solution of the problem of the present invention.
  • the content of other optional components in the molding composition is 50 parts by mass with respect to a total of 100 parts by mass of the base material, the porous coordination polymer, and the weatherability-imparting additive other than the antioxidant. Parts by weight or less, more preferably 30 parts by weight or less, even more preferably 10 parts by weight or less.
  • the total content of the base material, the porous coordination polymer, and the antioxidant in the molding composition is 100% of the molding composition. 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, even more preferably 80% by mass or more and 100% by mass or less.
  • the total content is within the above range, the generation of a gas derived from the base material to the outside is further suppressed, and the physical properties required for the product are more effectively imparted to the molding composition. Can be.
  • 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. Is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more.
  • the content of the porous coordination polymer is based on 100% by mass of the total of the base material, the porous coordination polymer, and the antioxidant. , Preferably from 0.01 to 15% by mass, more preferably from 0.1 to 10% by mass, even more preferably from 0.5 to 5% by mass.
  • the content of the antioxidant is 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 from 0.05 to 5% by mass, and even more preferably from 0.1 to 3% by mass.
  • the content of the weather resistance-imparting additive is preferably 40% by mass or less based on 100% by mass of the molding composition. , 30% by mass or less, and particularly preferably 20% by mass or less.
  • the content is within the above range, generation of a gas derived from the base material to the outside can be further suppressed, and the physical properties required for the product can be more effectively imparted to the molding composition. .
  • the molding composition may contain other optional components such as an inorganic filler, a plasticizer, and a flame retardant in an amount that does not hinder the solution of the problem of the present invention.
  • the content of other optional components in the molding composition is 100 parts by mass in total of the base material, the porous coordination polymer, the antioxidant, and the weatherability-imparting additive other than the antioxidant.
  • the amount is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 10 parts by mass or less.
  • the molding composition can be used not only after being processed into a molded article having a predetermined shape but also as it is, for example, as a paint, a sealing agent, a cushion material, or a filler.
  • the molding composition for example, by selecting an appropriate plastic resin, and by appropriately adjusting the addition amount of the porous coordination polymer and the filler, the addition amount of the plasticizer, etc., fluidity, semi-fluidity or A molded article having rubber-like elasticity can be produced.
  • the present invention also includes a molded article molded from the molding composition of the present embodiment. Those having fluidity can be used, for example, as paints, and those having semi-fluidity can be used, for example, as sealing agents.
  • those having rubber-like elasticity can be used, for example, as cushioning materials and padding.
  • a coloring material such as a colorant or a pigment can be added to the matrix resin as needed.
  • injection molding, compression molding, transfer molding, extrusion molding, blow molding, calendar molding, FRP molding, lamination molding, casting molding, solution casting, vacuum / pressure molding, extrusion Appropriate known molding methods such as composite molding, foam molding, thermoforming, insert molding, and melt impregnation can be applied.
  • the shape of the molded product which may be any shape such as a flat plate, a rod, a cylinder, a comb, and a sphere.
  • two-color or multicolor molding in combination with a metal or the like can also be performed.
  • a porous coordination polymer containing a metal ion and an organic ligand is added to one or more base materials selected from the group consisting of plastic resins, rubbers, and sealing materials.
  • the gas derived from the base material contains a hard Lewis base, the metal ion is a hard Lewis acid, and the Lewis acid value of the porous coordination polymer is 0.15 or more.
  • the gas derived from the base material contains an intermediate or soft Lewis base, the metal ion is an intermediate or soft Lewis acid, and the Lewis acid value of the porous coordination polymer is 0. 28 or more.
  • one or more antioxidants selected from the group consisting of an antioxidant represented by the following formula (4) and an antioxidant represented by the following formula (5) are further compounded. By doing so, it is preferable to further suppress the generation of gas derived from the base material.
  • R independently represents a hindered phenol group.
  • Example 1-1 and 2-1 A porous coordination polymer (“Cu-PCP”, composed of Cu 2+ (kind of Lewis acid: intermediate Lewis acid)) as a metal ion and 1,3,5-benzenetricarboxylic acid as an organic ligand Surface area: 1509 m 2 / g, Lewis acid value: 0.28) was used.
  • Cu-PCP composed of Cu 2+ (kind of Lewis acid: intermediate Lewis acid)) as a metal ion and 1,3,5-benzenetricarboxylic acid as an organic ligand Surface area: 1509 m 2 / g, Lewis acid value: 0.28) was used.
  • Example 1-1 An example using a polyphenylene sulfide resin is referred to as Example 1-1, and an example using an aromatic polyamide resin is referred to as Example 2-1.
  • Example 1-2 and 2-2 instead of Cu-PCP, a porous coordination polymer (Ni 2+ (kind of Lewis acid: intermediate Lewis acid)) as a metal ion and 1,3,5-benzenetricarboxylic acid as an organic ligand (A molded body was produced in the same manner as in Examples 1-1 and 2-1 except that “Ni-PCP”, specific surface area: 1080 m 2 / g, Lewis acid value: 0.39) was used.
  • An example using a polyphenylene sulfide resin is Example 1-2
  • an example using an aromatic polyamide resin is Example 2-2.
  • Example 1-3 and 2-3 instead of Cu-PCP, a porous coordination polymer composed of Cu 2+ (a kind of Lewis acid: intermediate Lewis acid) as a metal ion and 1,3,5-benzenetricarboxylic acid as an organic ligand ( A molded product was produced in the same manner as in Examples 1-1 and 2-1 except that “C300” of BASF product, specific surface area: 1500 m 2 / g, Lewis acid value: 0.31) was used.
  • An example using a polyphenylene sulfide resin is referred to as Example 1-3, and an example using an aromatic polyamide resin is referred to as Example 2-3.
  • Example 1-4 and 2-4 instead of Cu-PCP, a porous coordination polymer composed of Zn 2+ (a kind of Lewis acid: intermediate Lewis acid) as a metal ion and 2-methylimidazole as an organic ligand (“Z1200 of BASF”) And a specific surface area of 1300 m 2 / g, and a Lewis acid value of 0.28), except that a molded article was produced in the same manner as in Examples 1-1 and 2-1.
  • An example using a polyphenylene sulfide resin is described as Example 1-4, and an example using an aromatic polyamide resin is described as Example 2-4.
  • Example 1-5 and 2-5 instead of Cu-PCP, a porous coordination polymer (“Cr 3+” ) composed of Cr 3+ (a kind of Lewis acid: hard Lewis acid) as a metal ion and 1,3,5-benzenetricarboxylic acid as an organic ligand -PCP ", specific surface area: 1350 m 2 / g, Lewis acid value: 0.22), except that molded articles were produced in the same manner as in Examples 1-1 and 2-1.
  • An example using a polyphenylene sulfide resin is referred to as Example 1-5
  • an aromatic polyamide resin is referred to as Example 2-5.
  • Example 1-6 and 2-6 instead of Cu-PCP, a porous coordination polymer composed of Fe 3+ (a kind of Lewis acid: hard Lewis acid) as a metal ion and 1,3,5-benzenetricarboxylic acid as an organic ligand (BASF product) (F300), specific surface area: 1300 m 2 / g, Lewis acid value: 0.21), and a molded article was produced in the same manner as in Examples 1-1 and 2-1.
  • An example using a polyphenylene sulfide resin is referred to as Example 1-6
  • an aromatic polyamide resin is referred to as Example 2-6.
  • Example 1-7 and 2-7 instead of Cu-PCP, a porous coordination polymer composed of Mg 2+ (kind of Lewis acid: hard Lewis acid) as a metal ion and formic acid as an organic ligand (“M050” from BASF, specific surface area: A molded body was produced in the same manner as in Examples 1-1 and 2-1 except that 400 m 2 / g, Lewis acid value: 0.21) was used.
  • An example using a polyphenylene sulfide resin is Example 1-7
  • an example using an aromatic polyamide resin is Example 2-7.
  • Example 1-8 and 2-8 instead of Cu-PCP, a porous coordination polymer (BASF) composed of Al 3+ (a type of Lewis acid: hard Lewis acid) as a metal ion and 1,3,5-benzenetricarboxylic acid as an organic ligand A molded article was produced in the same manner as in Examples 1-1 and 2-1 except that the product “MIL110”, specific surface area: 1400 m 2 / g, Lewis acid value: 0.18) was used.
  • An example using a polyphenylene sulfide resin is referred to as Example 1-8, and an example using an aromatic polyamide resin is referred to as Example 2-8.
  • Example 1-9 and 2-9 A porous coordination polymer (“Cu-PCP”, composed of Cu 2+ (kind of Lewis acid: intermediate Lewis acid)) as a metal ion and 1,3,5-benzenetricarboxylic acid as an organic ligand Surface area: 1509 m 2 / g, Lewis acid value: 0.28) was used.
  • a hindered phenolic antioxidant represented by the above formula (6) (lower melting point: 159 ° C., upper melting point: 162 ° C., “CY-1790” manufactured by Solbay) was used.
  • a porous coordination polymer 0.25 g of an antioxidant and 50 g of a polyphenylene sulfide resin (“1140A6” manufactured by Polyplastics Co., Ltd.) or 0.5 g of a porous coordination polymer And 0.25 g of an antioxidant and 50 g of an aromatic polyamide resin (“RA230NK” manufactured by Mitsui Chemicals, Inc.) are kneaded at 250 ° C. for 10 minutes in a Labo Plastomill to obtain a molding composition.
  • the formed molding composition was molded with a heating press under the conditions of heating and pressurizing at 250 ° C. and 10 MPa to produce a plate-shaped molded body having a thickness of 1.0 mm.
  • An example using this is Example 1-9, and an example using an aromatic polyamide resin is Example 2-9.
  • Example 1-10 and 2-10 instead of CY-1790, a mixture of a hindered phenol-based antioxidant represented by the above formula (6) and a phosphite-based antioxidant (lower melting point: 166 ° C, upper melting point: 171 ° C, “solvay product” A molded article was produced in the same manner as in Examples 1-9 and 2-9 except that CY-2777 ") was used.
  • An example using a polyphenylene sulfide resin is Example 1-10
  • an example using a C aromatic polyamide resin is Example 2-10.
  • Example 1-11 and 2-11 A hindered phenolic antioxidant represented by the above formula (7) (lower melting point: 218 ° C., upper melting point: 223 ° C., “IRGANOX3114” manufactured by BASF) was used in place of CY-1790. A molded article was produced in the same manner as in Examples 1-9 and 2-9. An example using a polyphenylene sulfide resin is Example 1-11, and an example using an aromatic polyamide resin is Example 2-11.
  • Example 1-12 and 2-12 A hindered phenolic antioxidant represented by the following formula (9) (lower melting point: 240 ° C, upper melting point: 245 ° C, “IRGANOX1330” manufactured by BASF) was used in place of CY-1790. A molded article was produced in the same manner as in Examples 1-9 and 2-9. An example using a polyphenylene sulfide resin is Example 1-12, and an example using an aromatic polyamide resin is Example 2-12.
  • Example 1-13 and 2-13 Instead of using a hindered phenol-based antioxidant represented by the above formula (7) (lower melting point: 220 ° C., upper melting point: 223 ° C., ADEKA product “AO-20”) in place of CY-1790 A molded article was produced in the same manner as in Examples 1-9 and 2-9.
  • An example using a polyphenylene sulfide resin is referred to as Example 1-13, and an example using an aromatic polyamide resin is referred to as Example 2-13.
  • Example 1-14 and 2-14 Instead of using a hindered phenolic antioxidant represented by the above formula (9) (lower melting point: 243 ° C., upper melting point: 245 ° C., ADEKA product “AO-330”) instead of CY-1790 A molded article was produced in the same manner as in Examples 1-9 and 2-9.
  • An example using a polyphenylene sulfide resin is Example 1-14, and an example using an aromatic polyamide resin is Example 2-14.
  • Comparative Examples 1-1 and 2-1 A molded body was produced in the same manner as in Examples 1-1 and 2-1 except that mesoporous silica H53 (manufactured by AGC S-I-Tech Co., Ltd.) was used instead of the porous coordination polymer.
  • mesoporous silica H53 manufactured by AGC S-I-Tech Co., Ltd.
  • An example using a polyphenylene sulfide resin is referred to as Comparative Example 1-1
  • an example using an aromatic polyamide resin is referred to as Comparative Example 2-1.
  • Comparative Examples 1-2 and 2-2 A molded body was produced in the same manner as in Examples 1-1 and 2-1 except that zeolite F-9 (manufactured by Tosoh Corporation) was used instead of the porous coordination polymer.
  • An example using the polyphenylene sulfide resin is referred to as Comparative Example 1-2, and an example using the aromatic polyamide resin is referred to as Comparative Example 2-2.
  • Comparative Examples 1-3 and 2-3 A molded article was produced in the same manner as in Examples 1-1 and 2-1 except that molecular sieve HUA (manufactured by Union Showa KK) was used instead of the porous coordination polymer.
  • An example using a polyphenylene sulfide resin is referred to as Comparative Example 1-3, and an example using an aromatic polyamide resin is referred to as Comparative Example 2-3.
  • Comparative Examples 1-7 and 2-7 A molded article was produced in the same manner as in Examples 1-1 and 2-1 except that the porous coordination polymer was not used.
  • An example using a polyphenylene sulfide resin is referred to as Comparative Example 1-7, and an example using an aromatic polyamide resin is referred to as Comparative Example 2-7.
  • test pieces (tool steel, SKD-11) for confirming the presence or absence of corrosion were put in a test tube, sealed, and allowed to stand in a 300 ° C. environment for 3 hours.
  • Table 1 shows the results. ⁇ : marked effect ⁇ : effective ⁇ : little effect XX: no effect
  • a fatty acid nitrile represented by CH 3 (CH 2 ) n CN (wherein n represents an integer of 4 to 20), an aromatic amine, a cyclic amide, or an aromatic amide polymer is used as an intermediate or soft Lewis.
  • a fatty acid represented by CH 3 (CH 2 ) n COOH and a fatty acid amide represented by CH 3 (CH 2 ) n CONH 2 (in each formula, n represents an integer of 4 to 20) are hard.
  • the components were classified as Lewis bases, and each component was integrated. Table 2 shows the results.
  • test pieces (tool steel, SKD-11) for confirming the presence or absence of corrosion were put in a test tube, sealed, and allowed to stand in a 300 ° C. environment for 3 hours.
  • Table 2 shows the results. ⁇ : marked effect ⁇ : effective ⁇ : little effect XX: no effect
  • test pieces (tool steel, SKD-11) for confirming the presence or absence of corrosion were put in a test tube, sealed, and allowed to stand in a 300 ° C. environment for 3 hours.
  • Table 3 shows the results. ⁇ : marked effect ⁇ : effective ⁇ : little effect XX: no effect
  • a saturated fatty acid nitrile represented by CH 3 (CH 2 ) n CN (where n represents an integer of 4 to 20)
  • a monounsaturated fatty acid nitrile represented by C p H q CN Unsaturated fatty acid nitriles such as saturated fatty acid nitriles and tri-unsaturated fatty acid nitriles (wherein the relationship between p and q depends on the number of unsaturated carbon-carbon bonds, and when there is one unsaturated carbon-carbon double bond, , Q is 2p-1, q is 2p-3 when there are two unsaturated carbon-carbon double bonds, and q is 2p-5 when there are three unsaturated carbon-carbon double bonds.
  • P represents an integer of 5 to 21), an aromatic amine, a cyclic amide, or an aromatic amide polymer as an intermediate or soft Lewis base, and a saturated fatty acid represented by CH 3 (CH 2 ) n COOH; CH 3 (CH 2) saturated fatty acids represented by n CONH 2 Bromide (in both formulas, n is an integer of 4-20), represented by C p H q COOH, monounsaturated fatty acids, di-unsaturated fatty acids, unsaturated fatty acids such as tri-unsaturated fatty acids and, Unsaturated fatty acids such as monounsaturated fatty acid amide, diunsaturated fatty acid amide, and triunsaturated fatty acid amide represented by C p H q CONH 2 (in the formulas, p and q represent unsaturated carbon Depending on the number of inter-bonds, q is 2p-1 if there is one unsaturated carbon-carbon double bond, q is 2p-3 if there are two unsatur
  • test pieces (tool steel, SKD-11) for confirming the presence or absence of corrosion were put in a test tube, sealed, and allowed to stand in a 300 ° C. environment for 3 hours.
  • Table 4 shows the results. ⁇ : marked effect ⁇ : effective ⁇ : little effect XX: no effect
  • the molding composition of the present embodiment is suitably used as a material for precision molded articles applied to OA equipment, storage media devices such as hard disks, semiconductor-related devices, motor devices, infrastructure devices such as water-supply members, and the like.

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Abstract

La présente invention concerne une composition de moulage comprenant un polymère de coordination poreux comportant un ion métallique et un ligand organique et un ou plusieurs matériaux de base choisis dans le groupe constitué par les résines plastiques, les caoutchoucs et les matériaux d'étanchéité, le polymère de coordination poreux et les matériaux de base satisfaisant les exigences (A) ou (B). (A) Un gaz dérivé des matériaux de base comprend une base de Lewis dure, l'ion métallique est un acide de Lewis dur, et le polymère de coordination poreux possède une valeur d'acide de Lewis de 0,15 ou plus. (B) Un gaz dérivé des matériaux de base comprend une base de Lewis moyenne ou molle, l'ion métallique est un acide de Lewis moyen ou mou, et le polymère de coordination poreux possède une valeur d'acide de Lewis de 0,28 ou plus.
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WO2023153070A1 (fr) * 2022-02-08 2023-08-17 パナソニックＩｐマネジメント株式会社 Agent de désulfuration
WO2024038835A1 (fr) * 2022-08-16 2024-02-22 パナソニックＩｐマネジメント株式会社 Agent de désulfuration
WO2024053339A1 (fr) * 2022-09-09 2024-03-14 パナソニックＩｐマネジメント株式会社 Adsorbant et procédé pour l'utiliser

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JP2017074590A (ja) * 2011-09-05 2017-04-20 株式会社クラレ 吸着材
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JP2016516116A (ja) * 2013-04-09 2016-06-02 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 銅系金属有機骨格を有するポリアミドの安定化
JP2016196559A (ja) * 2015-04-03 2016-11-24 株式会社クラレ 多孔性金属錯体ペレットの製造方法

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Publication number Priority date Publication date Assignee Title
WO2023153070A1 (fr) * 2022-02-08 2023-08-17 パナソニックＩｐマネジメント株式会社 Agent de désulfuration
WO2024038835A1 (fr) * 2022-08-16 2024-02-22 パナソニックＩｐマネジメント株式会社 Agent de désulfuration
WO2024053339A1 (fr) * 2022-09-09 2024-03-14 パナソニックＩｐマネジメント株式会社 Adsorbant et procédé pour l'utiliser

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