WO2022009842A1 - 触媒粒子 - Google Patents

触媒粒子 Download PDF

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Publication number
WO2022009842A1
WO2022009842A1 PCT/JP2021/025326 JP2021025326W WO2022009842A1 WO 2022009842 A1 WO2022009842 A1 WO 2022009842A1 JP 2021025326 W JP2021025326 W JP 2021025326W WO 2022009842 A1 WO2022009842 A1 WO 2022009842A1
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Prior art keywords
catalyst
particles
resin
catalyst particles
parts
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PCT/JP2021/025326
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English (en)
French (fr)
Japanese (ja)
Inventor
英輝 森内
隆之 佐野
友希 神野
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Tomoegawa Co Ltd
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Tomoegawa Paper Co Ltd
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Priority to JP2022535321A priority Critical patent/JP7462756B2/ja
Publication of WO2022009842A1 publication Critical patent/WO2022009842A1/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity

Definitions

  • the present invention relates to catalyst particles.
  • reaction injection molding method In recent years, from the viewpoint of resource saving and energy saving, large-sized molded products manufactured by the reaction injection molding method (RIM method) are becoming widespread as a molding method in which a curing reaction and shaping are simultaneously performed in a mold.
  • reaction injection molding the heat of reaction of the curable resin causes a chain reaction to occur in the entire large molded product, resulting in molding.
  • the amount of resin and catalyst that react as an absolute amount in a part with a large area or volume, so the amount of heat generated is large, the chain reaction can proceed quickly, and good curability. Is shown.
  • a large amount of reacting resin or catalyst cannot be present, so that a sufficient amount of heat cannot be obtained and the curability is lowered.
  • the curing reaction can be uneven between the portion having a large area and volume and the portion having a small area and volume.
  • Patent Document 1 and the like propose a curing catalyst for a thermosetting resin. That is, by encapsulating the low-temperature curing catalyst originally used for curing at low temperature in microcapsules which are resins, the low-temperature curing catalyst and the curable resin are separated up to the melting temperature of the microcapsules. After reaching the melting temperature of the microcapsules, the catalyst can be acted on to quickly cure the curable resin. In this way, the reaction can be controlled by using the latent catalyst.
  • a fast-reactive (fast-curing) catalyst which is generally used at a low temperature, does not have good storage stability when mixed with a curable resin.
  • fast-reactive catalysts have a short so-called pot life. Therefore, the worker has to prepare the composition each time, and the workability is poor. In addition, the surplus composition cannot be stored and must be discarded, which is not preferable in terms of resource saving and environmental problems.
  • a curing catalyst having a long pot life has low reactivity even when heated to a high temperature, resulting in low curing property. As described above, in the curing catalyst, there is a problem of trade-off between pot life and workability, storage stability and the like. In addition, the activity of the catalyst may be lost due to moisture in the air during storage.
  • a method for molding a molding resin using dicyclopentadiene as a main raw material a method using liquid A (dicyclopentadiene + catalyst) and liquid B (dicyclopentadiene + catalytic activator) is known. Specifically, when the liquid A and the liquid B are poured into a molding mold, the two liquids are mixed, and the catalyst in the liquid A and the catalyst activator in the liquid B react with each other to develop a function as a polymerization catalyst. Then, polymerization is started and a molded product can be obtained.
  • the polymerization of dicyclopentadiene proceeds at an extremely high rate when the two liquids are mixed. Therefore, in order to obtain a large-sized molded product, it was necessary to have equipment for quickly introducing dicyclopentadiene, which had started high-speed polymerization, into every corner of the mold.
  • a method for molding a molding resin using addition type silicone as a main raw material a method of initiating a polymerization reaction by adding a platinum catalyst to a silicone main agent to obtain a molded product is known.
  • the main agent, silicone has a high viscosity, and polymerization using a platinum catalyst proceeds rapidly. Therefore, in order to obtain a large-sized molded product, it is necessary to have equipment for quickly introducing the silicone having started high-speed polymerization into every corner of the molding die.
  • the present invention solves the problems of the prior art, and an object of the present invention is to provide catalyst particles whose reaction can be easily controlled.
  • the present inventors have found that the above problems can be solved by using specific catalyst particles containing a catalyst, and have completed the present invention. That is, the present invention is as follows.
  • the present invention (1) is a catalyst particle containing the porous particles and the catalyst liquid held in the pores of the porous particles.
  • the present invention (2) is a catalyst particle in which the catalyst particle according to the invention (1) is covered with a resin.
  • the present invention (3) is a catalyst particle having a resin microcapsule as an outer shell, and the resin microcapsule is a catalyst particle containing a catalyst or a catalyst solution.
  • the present invention (4) is a catalyst particle containing a resin particle (A) and a catalyst contained in the resin particle (A).
  • the present invention (5) is a catalyst particle in which a part or all of the surface of the catalyst particle according to any one of the inventions (1) to (4) is covered with inorganic particles.
  • the present invention (6) is a catalyst particle in which a part or all of the surface of the catalyst particle according to any one of the inventions (2) to (5) is further covered with the resin (B).
  • FIG. 1 is a front view, a side view, and a cross-sectional view of the casting container used for the reactivity evaluation.
  • Catalyst particles are generally substances that do not show activity under normal environmental conditions such as room temperature and room light, but show activity directly or indirectly by external stimuli such as heating and light irradiation, but are limited thereto. Not done.
  • the catalyst particles of the present invention include, for example, a case where the elements constituting the catalyst particles change with time to exhibit activity as a catalyst.
  • the catalyst particles of the present invention are, for example, catalyst particles composed of a catalyst and a solvent contained in resin microcapsules (sometimes abbreviated as microcapsules), the solvent in which the catalyst is dissolved permeates the resin microcapsules. It also includes those in which the reaction is started by contact between the catalyst dissolved in the solvent and the reactant when reaching the outside.
  • directly refers to the case where an external stimulus directly activates the catalyst.
  • indirectly means that a component other than the catalyst (resin microcapsules, resin, solvent, etc.) is changed by an external stimulus, and as a result, the catalyst is activated. For example, it means that the resin microcapsules are melted by heat or light, and the reaction is started when the catalyst comes into contact with the reactants.
  • the resin microcapsules cover fine particles or droplets and are processed into fine capsules.
  • the method for measuring the average particle size (volume average particle size) of catalyst particles, porous particles, resin microcapsules, resin particles, inorganic particles and the like can be measured by an apparatus using a laser diffraction method.
  • the catalyst particles according to the first embodiment are catalyst particles containing the porous particles and the catalyst liquid held in the pores of the porous particles.
  • Porous particles are particles having a large number of pores on the surface of the particles.
  • the material of the porous particles is not particularly limited, and may be inorganic porous particles or organic porous particles.
  • the inorganic porous particles include amorphous silica, anhydrous silica, aluminum silicate, magnesium silicate, zinc silicate, calcium silicate, titanium oxide, aluminum oxide, magnesium oxide, calcium carbonate, calcium sulfate, barium sulfate, and the like.
  • examples thereof include magnesium hydroxide, hydrotalcite, zeolite, calcium silicate, kaolin, talc, bentonite and the like.
  • the organic porous particles include polyethylene resin powder, acrylic resin powder, styrene-acrylic resin powder, polyamide resin powder, urea resin powder, ion exchange resin powder and the like.
  • the porous particles may have an airgel-like form, a hollow form, or the like. These can be used alone or in combination of two or more.
  • the porous particles are preferably silica-based particles.
  • the shape of the porous particles can be appropriately changed depending on the use of the catalyst particles and is not particularly limited, and examples thereof include an amorphous shape, a spherical shape, a polyhedral shape, a fibrous shape, a plate shape, and a flat shape.
  • an amorphous shape a spherical shape, a polyhedral shape, a fibrous shape, a plate shape, and a flat shape.
  • the particle size (volume average particle size) of the porous particles is not particularly limited, but is preferably 1 mm or less, more preferably 500 um or less, still more preferably 100 um or less, and most preferably 50 um or less. By reducing the particle size, the specific surface area that contributes to the reaction can be increased.
  • the pore volume of the porous particles can be appropriately changed depending on the use of the catalyst particles and the like, and is not particularly limited, but is preferably 10 mL / 100 g or more, more preferably 30 mL / 100 g or more, still more preferably 70 ml / 100 g or more. Most preferably, it is 100 ml / 100 g or more.
  • Such pore volume can be measured according to the BET method (krypton gas).
  • 3Flex manufactured by Micromeritics is used, and Smart VacPrep manufactured by Micromeritics is used as the pretreatment device.
  • 1 g of a sample is collected in an analysis cell, degassed under reduced pressure at 200 ° C. for 6 hours with the pretreatment device, and the specific surface area is analyzed by the krypton gas adsorption method.
  • the specific surface area of the porous particles can be appropriately changed depending on the use of the catalyst particles and the like, and is not particularly limited.
  • the specific surface area of the porous particles when accelerating the reaction is preferably 200 m 2 / g or more, more preferably 500 m 2 / g or more, and further preferably 1000 m 2 / g or more.
  • the upper limit of the specific surface area of the porous particles in this case is, for example, 2,500 m 2 / g. In promoting the reaction, when the specific surface area is within the above range, the area serving as a reaction field increases, so that the time until the heating reaction is shortened.
  • the specific surface area of the porous particles when the reaction is delayed is preferably 20 m 2 / g or more, more preferably 50 m 2 / g or more, still more preferably 100 m 2 / g or more, and most preferably 300 m 2 / g or more. ..
  • the upper limit of the specific surface area of the porous particles in this case is, for example, 1000 m 2 / g.
  • the pores of the porous particles are not particularly limited, and include dents (indicating a depth of 10 to 80% of the diameter) and through holes.
  • the pores of the porous particles vary depending on the diameter of the porous particles themselves, but are preferably pores having a diameter of, for example, about 2 nm to 1 mm.
  • the catalyst solution is a composition obtained by dissolving the catalyst in a solvent or dispersing it in a dispersion medium.
  • a composition (catalyst solution or catalyst dispersion) containing a catalyst and a solvent or a dispersion medium is expressed as a catalyst solution.
  • the catalyst solution may contain a solvent for the catalyst and a dispersion medium for the catalyst at the same time.
  • a catalyst in the present specification it may indicate a solid catalyst (for example, powder) other than the catalyst liquid.
  • the catalyst is not particularly limited and can be selected according to the use of the catalyst particles.
  • examples of the catalyst include a thermosetting catalyst, a photocuring catalyst, a urethanization catalyst, and a ring-opening metathesis polymerization catalyst. These can be used alone or in combination of two or more.
  • the solvent or dispersion medium is not particularly limited, and the use of the catalyst particles, the solubility of the catalyst in the solvent, the dispersion degree of the catalyst in the dispersion medium, and other constituent components (porous particles, the outer shell of the resin microcapsules described later, etc.). It can be selected according to the material and the like. For example, a highly hydrophilic solvent such as water, methanol, or ethanol may be used. These can be used alone or in combination of two or more.
  • the content ratio of the catalyst and the solvent or the dispersion medium is not particularly limited, but for example, the catalyst: solvent or dispersion medium can be 1: 10000 to 1: 1000, and 1: 100 to 1. 1:10 is preferable.
  • the content ratio of the catalyst and the solvent or the dispersion medium is in such a range, the effect that the curing is completed promptly after the curing reaction is started can be obtained.
  • the catalyst solution may contain other components (for example, a coloring material (carbon, pigment), a UV absorber, a flame retardant material, an antioxidant, etc.) as long as the effect of the present invention is not impaired.
  • the method for producing the catalyst particles is not particularly limited.
  • the porous particles and the catalyst liquid can be put into a stirring container and stirred with a paint shaker or the like to impregnate the pores of the porous particles with the catalyst solution or the catalyst dispersion liquid to produce the catalyst particles.
  • can. By putting the catalyst liquid prepared in advance into the stirring container, the catalyst liquid contained in the porous particles can be made homogeneous, but the catalyst and the solvent / dispersion medium are separately placed in the stirring container. You may put it in.
  • the surface of the porous particles or the surface of the catalyst particles may be melted or softened by hot air or thermal spraying (plasma) to be deformed.
  • the opening diameter of the pores on the surface of the porous particles is adjusted without changing the internal space of the porous particles (that is, the amount of the catalyst liquid that the porous particles can hold), and the catalyst exuded from the porous particles.
  • the amount of liquid can also be adjusted.
  • the catalyst particles are the catalyst particles containing the porous particles having pores and the catalyst liquid, and the surface of the porous particles in a state where the catalyst liquid is filled in the pores is porous. It is preferable that the catalyst particles are obtained by heating the quality particles to a melting temperature or a softening temperature or higher.
  • the surface of the pores of the porous particles which is obtained by melting or softening the surface of the porous particles whose constituent is resin, is covered while maintaining the internal space of the porous particles (the pores are closed).
  • the structure is judged to be a structure in which the surface of the porous particles is coated with a resin.
  • the structure in which the surface of the porous particles is coated with the resin will be described later.
  • the catalyst particles can be used in any application that can be used as a catalyst. For example, it can be used for resin molding (casting, RIM molding, film molding) and the like. Further, the catalyst particles are catalysts by changing the specific densities of the catalyst liquid and the particles themselves in each pore constituting the porous particles and changing the ratio between the catalyst liquid and the voids (filling ratio of the catalyst liquid). The specific gravity of the particles themselves can be controlled. Therefore, in a system containing a catalyst, if you want to start the reaction from relatively below the container, use particles that easily settle (heavy specific gravity), and if you want to start the reaction from relatively above the container, float. It is possible to control the reaction site in the height direction of the vessel by using easy (light specific gravity) particles and by using both of them in combination.
  • the catalyst particles (hereinafter, referred to as the I catalyst particles) which indispensably contain the porous particles having pores and the catalyst liquid held in the pores of the porous particles are referred to as the first catalyst particles. ) was explained.
  • the second embodiment various catalyst particles that do not require porous particles will be described.
  • catalyst particles according to the second embodiment a form including a catalyst particle main body portion and a coating portion covering at least a part of the catalyst particle main body portion is shown, and the catalyst particle main body portion and the coating portion are shown.
  • the entire catalyst particles (total of the catalyst particle main body and the coating) after being coated with the catalyst particles are not particularly distinguished, and both are expressed as "catalyst particles”.
  • the catalyst particles according to the II embodiment relate to the catalyst particles capable of more reliably controlling the reaction, similarly to the catalyst particles according to the I embodiment.
  • the catalyst particles according to the second embodiment have a particularly high thermal potential and are configured so that the reaction can be initiated by an intended reaction initiation trigger such as the reaction temperature in the thermal latent catalyst. That is, when the catalyst particles according to the second embodiment are thermal latent catalysts, the reaction does not start due to factors other than temperature until the curing temperature (for example, the melting temperature of the microcapsules) is reached, and the temperature is cured. It is possible to obtain highly reliable catalyst particles in which the reaction is started only by controlling the temperature.
  • the catalyst particles according to the second embodiment can be expressed as follows.
  • Invention (i) Catalyst particles with resin microcapsules as the outer shell,
  • the resin microcapsules are catalyst particles comprising a catalyst and a solvent or a dispersion medium.
  • the invention (ii) is The catalyst particles of the invention (i), wherein a part or all of the surface of the resin microcapsules is further covered with inorganic particles.
  • the invention (iii) is The catalyst particles include the resin particles (A) and the catalyst contained in the resin particles (A), and are characterized in that a part or all of the surface of the catalyst particles is covered with inorganic particles. These are catalyst particles.
  • the invention (iv) is Catalyst particles with resin microcapsules,
  • the resin microcapsules contain a catalyst and contain a catalyst.
  • the catalyst particles are characterized in that a part or all of the surface of the resin microcapsules is covered with inorganic particles.
  • Invention (v) is The catalyst particle catalyst particles are characterized in that a part or all of the surface of the catalyst particles according to any one of the inventions (i) to (iv) is further covered with the resin (B).
  • the invention (vi) is The catalyst particles include the resin particles and the catalyst contained in the resin particles (A).
  • the catalyst particles are characterized in that a part or all of the surface of the catalyst particles is covered with the resin (B).
  • the invention (vii) is Catalyst particles with resin microcapsules as the outer shell,
  • the resin microcapsules contain a catalyst and contain a catalyst.
  • the catalyst particles are characterized in that a part or all of the surface of the resin microcapsules is covered with the resin (B).
  • the invention (A) is a catalyst particle, characterized in that the I-th catalyst particle is covered with a resin.
  • the invention (B) is a catalyst particle in which a part or the whole of the surface of the catalyst particle of the first catalyst particle or the catalyst particle of the invention (A) is covered with the inorganic particle.
  • the invention (C) is a catalyst particle in which a part or all of the surface of the catalyst particle I, the catalyst particle of the invention (A), or the catalyst particle of the invention (B) is further covered with the resin (B). be.
  • the catalyst particles of the first embodiment are catalyst particles having a resin microcapsule as an outer shell, and the resin microcapsules are characterized by containing a catalyst and a solvent or a dispersion medium. That is, the catalyst particles of the first embodiment can also be expressed as particles having a resin microcapsule and a catalyst liquid contained in the resin microcapsule.
  • the material of the resin microcapsules can be formed so as to include the catalyst and the solvent or the dispersion medium, and is not particularly limited as long as it has the property of activating the catalyst by an external stimulus or the like.
  • the property that the catalyst is activated by an external stimulus or the like is, for example, in a catalyst having thermal potential, when the resin microcapsules reach a predetermined temperature, the resin microcapsules melt and the reactant and the catalyst. Is a property that allows contact. In addition to thermal potential, optical potential and the like can be mentioned. Further, the case where the internal catalyst permeates the outside of the resin microcapsules or the resin microcapsules swell due to the contained solvent or dispersion medium activates the catalyst.
  • the material of the resin microcapsules include natural or synthetic organic polymers (including carbon atoms) produced by addition or condensation polymerization.
  • the polymer is a homopolymer or random and block copolymer produced by free radical, ion, coordination, or condensation polymerization of one or more polymerizable monomers.
  • examples include polyolefins, styrene polymers, polyethers, polyureas, acrylic polymers, polyurethanes, polyesters, polyamides, polysiloxanes, polyvinyl alcohols, cellulose derivatives, polypeptides, polypeptides, polynucleotides and the like, as well as mixtures thereof. Be done.
  • polystyrene-based polymers Preferred are styrene-based polymers, polyolefins, and mixtures thereof. Particularly preferred is polyolefin.
  • Polymers can be produced by bulk, solution, suspension, or emulsion polymerization.
  • the polymer may be a hydrocarbon or may contain functional groups such as halogens, hydroxyl groups, amines, phosphines, phosphine oxides, arsine, sulfur, sulfur oxides, alkoxys, silanes, siloxys and carboxys. Examples thereof include polyurea resin, polystyrene resin, cyclopentadiene resin, norbornene resin, nylon and its derivatives. These materials can be used alone or in combination of two or more.
  • the shape of the resin microcapsules is not particularly limited, but may be substantially spherical or substantially ellipsoidal.
  • the average particle size of the resin microcapsules is not particularly limited, but can be 10 nm to 5 mm, preferably 1 ⁇ m to 100 ⁇ m. When the average particle size of the resin microcapsules is within such a range, it is easy to control the curing rate.
  • the thickness of the outer shell (capsule wall) of the resin microcapsules can be 1 nm to 100 ⁇ m, preferably 100 nm to 50 ⁇ m. When the thickness of the outer shell (capsule wall) of the resin microcapsules is within the range, it is easy to control the curing rate.
  • the average particle size of the catalyst particles of this embodiment is not particularly limited, but may be 10 nm to 5 mm, preferably 1 ⁇ m to 100 ⁇ m. When the average particle size of the catalyst particles is within such a range, the catalyst particles can be easily uniformly dispersed in the solvent or the dispersion medium, and the variation in the curing reaction can be suppressed.
  • the method for producing the catalyst particles (mainly the microencapsulation method) of the first embodiment is not particularly limited, and a known method can be used.
  • a method for producing catalyst particles a physical method, a physicochemical method, and a chemical method can be mentioned.
  • various methods researched and reported in the fields of pharmaceuticals and the like can be used.
  • a method in which a metal catalyst is dissolved in a polymer solution, stirred and cooled, and then a poor solvent for the polymer in which the metal catalyst is dispersed and introduced is added to cure the swollen polymer to form microcapsules (microcapsules).
  • Nanoparticles in Medicine and Polymer; CRC Press: Boca Ratton, 1992) and the like can be used.
  • Retaining the solvent or dispersion medium in the microcapsules can be achieved by omitting the drying step.
  • These production methods can be arbitrarily selected depending on the combination of the catalyst, the solvent or the dispersion medium, the material of the resin microcapsule outer shell, and the like.
  • a known method using a liquid as a core substance can be used, and examples thereof include a Centrifugal extrusion method and a vibration nozzle method.
  • the core selvation method can be used.
  • an interfacial polymerization method for example, an interfacial polymerization method, an in situ polymerization method, a suspension polymerization method and the like can be used.
  • a predetermined amount of the catalyst is weighed in a stirring container (for example, 1 part by mass), a predetermined amount of a solvent or a dispersion medium (for example, 99 parts by mass) is added, and the mixture is stirred with a paint shaker for 30 minutes to uniformly dissolve or disperse the catalyst.
  • the catalyst solution or the catalyst dispersion A-1 having a predetermined concentration is prepared.
  • a predetermined amount for example, 1 part by mass
  • 9 parts by mass of ion-exchanged water is added and stirred with a paint shaker for 30 minutes to prepare a catalyst suspension B-1 in which the catalyst solution or the catalyst dispersion is suspended in water in the form of droplets.
  • IPA isopropyl alcohol
  • the catalyst particles of the second embodiment are embodiments in which a part or all of the surface of the resin microcapsules or the catalyst particles of the first embodiment is further covered with inorganic particles.
  • the catalyst particles of the second embodiment are such that the inorganic particles are attached to at least a part of the surface of the resin microcapsules or the catalyst particles of the first embodiment. be.
  • some inorganic particles may be embedded inside the catalyst particles.
  • the inorganic particles are not particularly limited, and examples thereof include metal oxides such as MgO, CaCO 3 , Al 2 O 3 , SiO 2 , and ZrO 2. These inorganic particles can be used alone or in combination of two or more. By covering a part or all of the surface of the catalyst particles with these inorganic particles, the effect of making the particle size of the resin microcapsules uniform can be obtained. Further, as will be described later, in the case where a part or all of the surface of the catalyst particles covered with the inorganic particles is further covered with the resin, the wettability with the resin can be adjusted by the presence of the inorganic particles. can.
  • the average particle size of the inorganic particles is not particularly limited, but is, for example, 1 nm to 100 ⁇ m, preferably 10 nm to 1 ⁇ m, and more preferably 20 to 500 nm.
  • the average particle size of the inorganic particles is within such a range, it is easy to make the particle size of the resin microcapsules uniform, and it is easy to cover the surface of the resin microcapsules or the catalyst particles.
  • the method of covering a part or all of the surface of the catalyst particles with the inorganic particles is not particularly limited, and a known method can be used.
  • Examples of the method of covering with inorganic particles include wet suspension and dry mixing.
  • the coverage of the inorganic particles is not particularly limited, but can be, for example, 10% to 100% of the surface area of the catalyst particles, and 30% to 100%. Is preferable, and 50% to 100% is more preferable.
  • the coverage is within such a range, so that the resin microcapsules are easily stabilized.
  • the coverage of the inorganic particles (adhesion amount of the inorganic particles) can be changed to an arbitrary range in consideration of the use and reactivity of the catalyst particles.
  • the average particle size of the catalyst particles is not particularly limited, but can be 20 nm to 5 mm, preferably 1 ⁇ m to 100 ⁇ m. When the average particle size of the catalyst particles is within such a range, the resin microcapsules are easy to stabilize and the curing rate is easy to control.
  • a predetermined amount (for example, 1 part by mass) of the catalyst solution or the catalyst dispersion A-1 having a predetermined concentration (for example, 1% by mass) is put into a stirring container, and a predetermined amount (for example, 9 parts by weight) of pure water is added.
  • a predetermined amount (for example, 0.1 part by mass) of inorganic particles (for example, MgO particles) having a predetermined particle size (for example, a primary particle size of about 2 ⁇ m) is added, and the mixture is stirred with a paint shaker for 30 minutes to prepare a catalyst dispersion.
  • a catalyst suspension B-2 suspended in water in the form of droplets is obtained. If necessary, a suspension stabilizer may be added.
  • the inorganic particles and the suspension stabilizer may be the same.
  • a predetermined amount (for example, 100 parts by mass) of the catalyst suspension B-2 is put into a stirring vessel, and a predetermined amount (for example, 1 part by mass) of a curable resin for forming an outer shell (for example, dicyclopentadiene) is added.
  • the mixture is stirred with a paint shaker for 30 minutes and allowed to stand at room temperature for 60 minutes to obtain suspended particles containing a catalyst dispersion.
  • the curable resin for forming the outer shell the whole liquid containing the suspended particles is transferred to a separating funnel and washed with water multiple times to obtain suspended particles C-2 dispersed in water.
  • a replacement solution for example, IPA
  • the replacement liquid is removed from the dispersion liquid of the suspended particles with a dropper, a sufficient amount of the replacement liquid is added, and the washing operation of stirring is repeated three times to dehydrate the suspended particles, and the catalyst particles C-2 dispersed in the replacement liquid are used. do.
  • a method of adhering the inorganic particles to the surface of the catalyst particles by utilizing the viscosity of the catalyst liquid, and electrostatic particles being electrostatically attached to the catalyst particles Adhesion method: After mixing the catalyst particles and the inorganic particles, the surface of the catalyst particles (preferably only the surface of the catalyst particles) is melted or softened by hot air or spraying (plasma) to attach the inorganic particles to the catalyst particles.
  • the method etc. can be applied. More specifically, the method for melting or softening the catalyst particles is preferably carried out by heating, which is a temperature condition that is equal to or higher than the melting temperature or softening temperature of the catalyst particles and lower than the melting temperature of the inorganic particles.
  • the catalyst particles of the third embodiment are further resin (B). ) Is covered.
  • the catalyst particles of the third embodiment are the catalyst particles of the first embodiment, the catalyst particles of the second embodiment, or at least a part of the surface of the catalyst particles of the first embodiment.
  • the resin (B) is attached to the resin (B).
  • the resin (B) is not particularly limited as long as it has the property of activating the catalyst by an external stimulus or the like.
  • the property that the catalyst is activated by an external stimulus or the like is, for example, in a catalyst having thermal potential, when the resin microcapsules reach a predetermined temperature, the resin microcapsules melt and the reactant and the catalyst. Is a property that allows contact. In addition to thermal potential, optical potential and the like can be mentioned. Further, the case where the internal catalyst permeates the outside of the microcapsules or the microcapsules swell due to the contained solvent or dispersion liquid activates the catalyst.
  • the resin (B) include natural or synthetic organic polymers (including carbon atoms) produced by addition or condensation polymerization.
  • the polymer is a homopolymer or random and block copolymer produced by free radical, ion, coordination, or condensation polymerization of one or more polymerizable monomers.
  • examples include styrene polymers, polyolefins, polyethers, polyureas, acrylic polymers, polyurethanes, polyesters, polyamides, polysiloxanes, polyvinyl alcohols, cellulose derivatives, polypeptides, polypeptides, polynucleotides and the like, as well as mixtures thereof. Be done.
  • Preferred are styrene-based polymers, polyolefins, and mixtures thereof. Particularly preferred is polystyrene.
  • Polymers can be produced by bulk, solution, suspension, or emulsion polymerization.
  • the polymer may be a hydrocarbon or may contain functional groups such as halogens, hydroxyl groups, amines, phosphines, phosphine oxides, arsine, sulfur, sulfur oxides, alkoxys, silanes, siloxys and carboxys. Examples thereof include polyurea resin, polystyrene resin, cyclopentadiene resin, nylon, wax and the like. These materials can be used alone or in combination of two or more.
  • the material of the microcapsules and the material of the resin (B) may be the same. , May be different.
  • a known method can be used and is not particularly limited.
  • a coating method for example, a catalyst is blended in a heat-melted resin or a monomer, and the surface of the catalyst is coated with a resin (B) by solidification by cooling, a thermosetting reaction, a photocuring reaction, a urethanization reaction, a ring-opening metathesis polymerization reaction, or the like. ) Can be mentioned.
  • a resin composition in which the resin (B) is dissolved in a solvent (or a resin composition in which the resin (B) is dispersed in a dispersion medium) is prepared, and the resin composition is applied / sprayed on the catalyst surface (
  • the surface of the catalyst can be coated with the resin (B) by adhering the resin composition to the surface of the catalyst by immersing the catalyst in the resin composition) and then drying the resin composition.
  • the coverage of the resin (B) (adhesion amount of the resin (B)) can be changed to an arbitrary range in consideration of the use of the catalyst particles, reactivity and the like.
  • the coverage of the resin (B) is preferably, for example, 50% to 100% with respect to the surface area of the outermost surface layer of the catalyst particles.
  • the resin (B) covering the surface of the catalyst particles may be composed of only one kind or two or more kinds of resins.
  • the present embodiment also includes a structure in which the catalyst particles are covered with a plurality of resin layers, such as having a resin (B1) layer covering the surface of the catalyst particles and a resin (B2) layer covering the resin (B1) layer.
  • the pores of the porous particle formed by melting or softening the surface of the porous particle whose constituent component is resin are maintained while maintaining the internal space of the porous particle.
  • a surface-covered (pore-closed) structure is considered to be a structure in which part or all of the surface of the I-th catalyst particle is covered with resin.
  • the resin constituting the porous particles and the resin covering the surface of the porous particles (resin derived from the porous particles) are made of the same material. Further, in this case, another resin (a resin different from the resin of the porous particles) may be attached to the surface of the catalyst particles.
  • Whether or not the pores of the porous particles are covered with the resin can be determined by observing the cross section of the particles with a TEM or the like. In this case, the coverage of the resin on the porous particles can be determined by the ratio of the pores closed by the resin, based on the number of pores originally possessed by the porous material.
  • the average particle size of the catalyst particles of this embodiment is not particularly limited, but can be 100 nm to 5 mm, preferably 1 ⁇ m to 100 ⁇ m. When the average particle size of the catalyst particles is in such a range, it is easy to control the curing rate.
  • the resin (B) (for example, having a melting point of 50 ° C.) in which the replacement liquid is removed from the dispersion liquid of the catalyst particles C-1, the catalyst particles C-2, or the first catalyst particles with a dropper and preheated to a temperature equal to or higher than the melting point to make a liquid.
  • a sufficient amount for example, an amount in which all the catalyst particles C-1 or C-2 are immersed
  • is added for example, the paraffin wax is heated to 70 ° C. to make it liquid
  • the dispersion liquid of the suspended particles (the catalyst particles) is added. obtain.
  • Suspended particles to which wax is attached are taken out from the dispersion, put into warm water at a predetermined temperature (70 ° C. when paraffin wax is used), and gradually stirred to a temperature at which the resin (B) solidifies. Cool naturally. In this way, the catalyst particles D in which the suspended particles (catalyst particles) are embedded in the resin (B) can be obtained.
  • the catalyst particles of the fourth embodiment are catalyst particles containing the resin particles (A) and the catalyst contained in the resin particles (A), and a part or all of the surface of the catalyst particles is formed.
  • Catalytic particles characterized by being covered with inorganic particles.
  • the catalyst particles of the fourth embodiment are catalyst particles containing the resin particles (A) and the catalyst contained in the resin particles (A), and the catalyst particles of the catalyst particles. These are catalyst particles with inorganic particles attached to the surface. In addition, some inorganic particles may be embedded inside the catalyst particles.
  • the resin particles (A) are not particularly limited as long as they have the property of activating the catalyst by an external stimulus or the like.
  • the property that the catalyst is activated by an external stimulus or the like is, for example, in a catalyst having thermal potential, when the resin particles (A) reach a predetermined temperature, the resin particles (A) are melted and the resin particles (A) are melted. It is a property that enables the reactant and the catalyst to come into contact with each other. In addition to thermal potential, optical potential and the like can be mentioned. Further, the case where the internal catalyst permeates the outside of the resin particles (A) or the resin particles (A) swells due to the contained solvent or dispersion liquid activates the catalyst. ..
  • the resin particles (A) include natural or synthetic organic polymers (including carbon atoms) produced by addition or condensation polymerization.
  • the polymer is a homopolymer or random and block copolymer produced by free radical, ion, coordination, or condensation polymerization of one or more polymerizable monomers.
  • examples include styrene polymers, polyolefins, polyethers, polyureas, acrylic polymers, polyurethanes, polyesters, polyamides, polysiloxanes, polyvinyl alcohols, cellulose derivatives, polypeptides, polypeptides, polynucleotides and the like, as well as mixtures thereof. Be done.
  • polystyrene-based polymers Preferred are styrene-based polymers, polyolefins, and mixtures thereof. Particularly preferred is polystyrene.
  • Polymers can be produced by bulk, solution, suspension, or emulsion polymerization.
  • the polymer may be a hydrocarbon or may contain functional groups such as halogens, hydroxyl groups, amines, phosphines, phosphine oxides, arsine, sulfur, sulfur oxides, alkoxys, silanes, siloxys and carboxys. Examples thereof include polyurea resin, polystyrene resin, cyclopentadiene resin, nylon, wax and the like. These materials can be used alone or in combination of two or more.
  • the catalyst is the same as the catalyst described in the first embodiment.
  • the inorganic particles are the same as the inorganic particles described in the second embodiment.
  • a known method can be used as the method for encapsulating the catalyst in the resin particles (A), and the method is not particularly limited.
  • Examples of the method of encapsulating the catalyst include a method of utilizing mechanical dispersion and a method of utilizing the difference in melting point.
  • the method for coating the inorganic particles is the same as the method described in the second embodiment.
  • the content ratio of the catalyst and the resin particles (A) is not particularly limited, but for example, the catalyst: resin particles (A) can be set to 1:10 to 10: 1. 3, 10 to 5:10 are preferable.
  • the content ratio of the catalyst and the resin particles (A) is within such a range, the curing is completed immediately after the curing reaction is started.
  • the average particle size of the catalyst particles of this embodiment is not particularly limited, but may be 10 nm to 5 mm, preferably 1 ⁇ m to 100 ⁇ m. When the average particle size of the catalyst particles is in such a range, it is easy to control the curing reaction.
  • the resin component constituting the resin particles (A) may be expressed as the resin (A).
  • a predetermined amount (for example, 10 parts by weight) of the catalyst is weighed, and a predetermined amount (for example, 50 parts by mass) of the resin (A) having an average particle diameter of 1 ⁇ m obtained by pulverizing and classifying the resin (A) (for example, paraffin wax) is used. ) Weigh and mix these dry.
  • This mixture is heated to a predetermined temperature (a temperature at which the resin (A) becomes liquid, for example, about 70 ° C. when paraffin wax is used), heated for 30 minutes, and the resin (A) is wound around the catalyst.
  • a resin particle embedding catalyst to which particles are attached is obtained.
  • the resin particle embedding catalyst is crushed to obtain catalyst particles E having a predetermined average particle diameter (for example, 30 ⁇ m).
  • the obtained catalyst particles E are put into a stirring container in a predetermined amount (for example, 1 part by mass), and inorganic particles (for example, silica particles) having a predetermined average particle diameter (for example, 0.5 ⁇ m) are added in a predetermined amount (for example, 100 parts).
  • mass part the mixture is stirred with a paint shaker for 10 minutes, heated at a predetermined temperature (a temperature at which the resin (A) becomes liquid, for example, about 70 ° C. in the case of paraffin wax) for 30 minutes, and the surface of the catalyst particles E is heated. It is possible to obtain the catalyst particles F embedded in the resin particles to which the inorganic particles are attached.
  • the catalyst particle of the fifth embodiment is an embodiment in which a part or the whole of the surface of the catalyst particle of the fourth embodiment is further covered with the resin (B). According to another expression, the catalyst particles of the fifth embodiment are embodiments in which the resin (B) is attached to the surface of the catalyst particles of the fourth embodiment.
  • the resin (B) is the same as the resin (B) described in the third embodiment.
  • the average particle size of the catalyst particles of this embodiment is not particularly limited, but can be 100 nm to 5 mm, preferably 1 ⁇ m to 100 ⁇ m. When the average particle size of the catalyst particles is in such a range, it is easy to control the curing reaction.
  • the material of the resin (A) contained in the catalyst particles of the fourth embodiment and the material of the resin (B) of the present embodiment may be the same or different.
  • the catalyst particles F according to the fourth embodiment are placed in a container filled with an air flow (for example, a dry air flow or a nitrogen flow), and the temperature at which the resin (B) becomes liquid (for example, the melting point as the resin (B)) is set.
  • an air flow for example, a dry air flow or a nitrogen flow
  • the temperature at which the resin (B) becomes liquid for example, the melting point as the resin (B)
  • the resin (B) liquefied by heating to 100 ° C.) is sprayed, and the catalyst particles F and the resin (B) are mixed in an air stream and cooled. In this way, the catalyst particles G in which the resin (B) is adhered around the inorganic particle resin particle embedding catalyst particles F can be obtained.
  • the catalyst particles in this embodiment are catalyst particles having resin microcapsules, the resin microcapsules contain a catalyst, and a part or all of the surface of the resin microcapsules is covered with inorganic particles. It is a catalyst particle characterized by being present.
  • the resin microcapsules are the same as the resin microcapsules described in the first embodiment.
  • the catalyst is the same as the catalyst described in the first embodiment.
  • the inorganic particles are the same as the inorganic particles described in the first embodiment.
  • the method for producing resin microcapsules is the same as the method for producing catalyst particles described in the first embodiment, except that it does not contain a solvent or a dispersion liquid.
  • the average particle size of the catalyst particles of this embodiment is not particularly limited, but may be 10 nm to 5 mm, preferably 1 ⁇ m to 100 ⁇ m. When the average particle size of the catalyst particles is in such a range, it is easy to control the curing rate.
  • the suspended particles C-2 dispersed in the dispersion medium (for example, IPA) obtained in the second embodiment are freeze-dried, and the suspension particles are vaporized by vaporizing the dispersion medium and the solvent contained in the suspended particles. It is possible to obtain the catalyst particles H in which the catalyst in a solid state is contained therein.
  • the dispersion medium for example, IPA
  • the catalyst particles of the seventh embodiment is an embodiment in which a part or all of the surface of the catalyst particles of the sixth embodiment is further covered with the resin (B).
  • the average particle size of the catalyst particles of this embodiment is not particularly limited, but can be 100 nm to 5 mm, preferably 1 ⁇ m to 100 ⁇ m. When the average particle size of the catalyst particles is in such a range, it is easy to control the curing rate.
  • Paraffin having a melting point of 90 ° C. as the temperature at which the resin (B) becomes liquid Paraffin having a melting point of 90 ° C.
  • an air flow for example, a dry air flow or a nitrogen flow.
  • the resin (B) heated to 100 ° C.) is sprayed, and the catalyst particles H and the resin (B) are mixed in an air flow and cooled. In this way, the catalyst particles G in which the resin (B) is adhered around the catalyst particles H can be obtained.
  • the eighth embodiment is a catalyst particle containing the resin particle (A) and the catalyst contained in the resin particle (A), and a part or all of the surface of the catalyst particle is a resin ( It is a catalyst particle characterized by being covered with B).
  • the resin (A) and the resin (B) may be the same or different.
  • This embodiment is the same as the fifth embodiment except that it does not contain inorganic particles.
  • the average particle size of the catalyst particles of this embodiment is not particularly limited, but can be 100 nm to 5 mm, preferably 1 ⁇ m to 100 ⁇ m. When the average particle size of the catalyst particles is in such a range, it is easy to control the curing rate.
  • the catalyst particles E of the fourth embodiment are placed in a container filled with an air flow (for example, a dry air flow or a nitrogen flow), and the temperature at which the resin (A) becomes liquid (paraffin having a melting point of 90 ° C. as the resin (A)) is placed.
  • an air flow for example, a dry air flow or a nitrogen flow
  • the temperature at which the resin (A) becomes liquid paraffin having a melting point of 90 ° C. as the resin (A)
  • wax the resin (A) heated to 100 ° C.) is sprayed, and the catalyst particles E and the resin (A) are mixed in an air flow and cooled. In this way, the catalyst particles H in which the resin (A) is adhered around the catalyst particles E can be obtained.
  • the catalyst particles have a resin microcapsule as an outer shell, and the resin microcapsule contains a catalyst, and a part or all of the surface of the resin microcapsule is covered with the resin (B). It is a catalyst particle characterized by.
  • This embodiment is the same as the seventh embodiment except that it does not contain inorganic particles.
  • the average particle size of the catalyst particles of this embodiment is not particularly limited, but can be 100 nm to 5 mm, preferably 1 ⁇ m to 100 ⁇ m. When the average particle size of the catalyst particles is within such a range, the effect that the curing rate can be easily controlled can be obtained.
  • the catalyst particles C-1 dispersed in the dispersion medium (for example, IPA) obtained in the first embodiment are freeze-dried, and the dispersion solvent and the solvent contained in the suspended particles are vaporized in the catalyst particles.
  • the catalyst particles I contain a solid-state catalyst.
  • the catalyst particles I When the catalyst particles I are placed in a container filled with an air flow (for example, a dry air flow or a nitrogen flow) and a paraffin wax having a melting point of 90 ° C. is used as the temperature at which the resin (B) becomes liquid (for example, the resin (B)).
  • the resin (B) liquefied by heating to 100 ° C.) is sprayed.
  • the catalyst particles I and the resin (B) are mixed in an air flow and cooled. In this way, the catalyst particles J in which the resin (B) is adhered around the catalyst particles I can be obtained.
  • the present invention includes all the catalyst particles obtained by combining these in the first to ninth aspects of the first embodiment and the second embodiment described above. Further, the present invention also includes the catalyst particles described in the second embodiment, in which the fine particles are attached to the catalyst particles and / or the resin is attached to the catalyst particles a plurality of times to form a multilayer.
  • the catalyst particles having a multilayer structure having a layer made of resin, a layer made of inorganic particles, and the like have been described.
  • the catalyst particles are one layer or a plurality of layers made of a mixture of resin and inorganic particles. You may have. In that case, the mixing ratio of the resin and the inorganic particles can be adjusted as appropriate. Further, such catalyst particles can be produced by mixing inorganic particles with the resin when the resin is attached to the surface of the catalyst particles.
  • the "form in which a part of the surface of the catalyst particles is covered with the inorganic particles" means that (1) a part of the surface of the catalyst particles is covered with the inorganic particles, and the other areas are the catalyst.
  • It has a form in which the surface of the particles is exposed, (2) a region made of inorganic particles covering a part of the surface of the catalyst particles, and a region made of a resin covering another part of the surface of the catalyst particles.
  • a form may be used, such as (3) a form in which a part or all of the surface of the catalyst particles is covered with a layer composed of a mixture of the resin and the inorganic particles. The same applies to "a form in which a part of the surface of the catalyst particles is covered with resin".
  • the exudation rate of the catalyst liquid from the catalyst particles can be reduced by increasing the coating area, the thickness of the layers, the number of layers, and the like.
  • the catalyst particles of the present invention can be used for resin molding of stirrers, motors, pumps and the like. Further, the catalyst particles of the present invention require a vigorous stirring state and can be used as a catalyst in a manufacturing process in which the potential cannot be maintained by the conventional catalyst particles having microcapsules or the like.
  • the catalyst particles of the present invention can be particularly suitably used in the molding process of the reaction injection molding method (RIM method), which is a molding method in which the curing reaction and the shaping are simultaneously performed in the mold.
  • RIM method reaction injection molding method
  • Example 1 ⁇ Method for producing catalyst particles without using porous particles >>> ⁇ Example 1 >> The catalyst particles of Example 1 were prepared as follows. ⁇ How to prepare a catalyst solution> Weigh 1 part by mass of Umicore M42 (Fujifilm Wako Pure Chemical Industries, Ltd.) as a catalyst in a glass vial, add 99 parts by mass of cyclohexane as a solvent, and stir with a paint shaker for 10 minutes to uniformly dissolve the catalyst. 1% by mass of the catalyst solution A was obtained.
  • Umicore M42 Flujifilm Wako Pure Chemical Industries, Ltd.
  • ⁇ Method for preparing catalyst suspension> Weigh 1 part by mass of the obtained catalyst solution A in a glass vial, add 9 parts by mass of ion-exchanged water and 0.1 part by mass of MgO particles having a primary particle diameter of about 2 ⁇ m as inorganic particles, and use a paint shaker. The mixture was stirred for 10 minutes to obtain a catalyst suspension B in which the catalyst solution was suspended in water in the form of droplets.
  • ⁇ Method of preparing suspended particles Weigh 100 parts by mass of the obtained catalyst suspension B in a glass vial, add 1 part by mass of dicyclopentadiene, which is a curable resin for forming an outer shell, stir with a paint shaker for 10 minutes, and keep the mixture at room temperature for 60 minutes. After allowing to stand for a minute, suspended particles containing a catalyst dispersion were obtained. In order to remove the curable resin for forming the outer shell, the whole liquid containing the suspended particles was transferred to a separating funnel and washed with water multiple times to obtain suspended particles dispersed in water.
  • dicyclopentadiene which is a curable resin for forming an outer shell
  • IPA isopropyl alcohol
  • the volume average particle size of the catalyst particles was measured by a wet method using a laser diffraction type particle size distribution measuring device (manufactured by Shimadzu Corporation: SALD-2300) using a laser diffraction method.
  • the thickness of the outer shell of the catalyst particles was cut using a microtome, and the cross section thereof was measured using a scanning microscope. The measurement was taken as the average value of the thickness of the outer shell measured for 10 catalyst particles.
  • Example 2 is the same as Example 1 except that the amount of dicyclopentadiene in the method for producing suspended particles of Example 1 is 50 parts by mass in Example 2 and 75 parts by mass in Example 3. And 3 catalyst particles were obtained.
  • the average particle size of the catalyst particles of Examples 2 and 3 was 0.8 mm.
  • the thickness of the outer shell of the catalyst particles of Example 2 was 46 ⁇ m, and the thickness of the outer shell of the catalyst particles of Example 3 was 78 ⁇ m.
  • Comparative Example 1 Among the production methods of Example 1, the catalyst solution of Comparative Example 1 was prepared by performing only the method for producing the catalyst solution.
  • Comparative Example 2 Among the production methods of Example 1, the catalyst particles obtained by subjecting the catalyst solution preparation method and the catalyst suspension preparation method to freezing and drying were used as the catalyst particles of Comparative Example 2. The average particle size of the catalyst particles of Comparative Example 2 was 0.9 mm. The catalyst particles are not measured because they do not have an outer shell.
  • FIG. 1 shows a casting container for evaluation.
  • This molded container is provided with a slit of 20 cm to a slit of 1 cm, and is filled with a curable resin liquid (reaction liquid) containing catalyst particles of each Example and each Comparative Example at a rate of 2 L / min.
  • the curability was evaluated.
  • the evaluation of curability was visually confirmed from the following viewpoints. (1) Is it possible to fill the inside of the molded container (20 cm slit ⁇ 1 cm slit) evenly with the reaction solution?
  • the meso hole means a hole having a diameter of 2 nm to 50 nm
  • the macro hole means a hole having a diameter of 50 nm or more.
  • ⁇ Method for producing catalyst particles C Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of silica porous particles having an average particle diameter of 35 um, a BET specific surface area of 310 m 2 / g, a total pore capacity of 1.7 ml / g, and mesopores, and paint. The mixture was stirred with a shaker for 10 minutes to obtain catalyst particles C containing a catalyst solution.
  • the catalyst particles are catalyst particles containing the porous particles and the catalyst liquid held in the pores of the porous particles.
  • Example 5 The catalyst particles of Example 5 were prepared as follows.
  • ⁇ Method for producing catalyst particles C> Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of silica porous particles having an average particle diameter of 35 um, a BET specific surface area of 310 m 2 / g, a total pore capacity of 1.7 ml / g, and mesopores, and average. Five parts of crushed wax particles having a particle diameter of 2 um and a melting point of 61 ° C. were added and stirred with a paint shaker for 10 minutes to obtain a catalyst solution and catalyst particles C containing wax particles.
  • the surface of the catalyst particles C of Example 5 was exposed to hot air generated by electric heating or plasma heating to melt or soften and deform a part of the particle surface to cover a part or the entire surface of the catalyst particles.
  • the catalyst particles are catalyst particles containing the porous particles and the catalyst liquid held in the pores of the porous particles, and at least a part of the surface thereof is covered with a resin.
  • Example 6 The catalyst particles of Example 6 were prepared as follows.
  • ⁇ Method for producing catalyst particles C Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of silica porous particles having an average particle diameter of 35 um, a BET specific surface area of 310 m 2 / g, a total pore capacity of 1.7 ml / g, and mesopores, and paint. The mixture was stirred with a shaker for 10 minutes to obtain catalyst particles C containing a catalyst solution.
  • Example 7 The catalyst particles of Example 7 were prepared as follows.
  • ⁇ Method for producing catalyst particles C> Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of silica porous particles having an average particle diameter of 35 um, a BET specific surface area of 310 m 2 / g, a total pore capacity of 1.7 ml / g, and mesopores, and average. Three parts of MgO particles having a particle diameter of 0.1 um were added and stirred with a paint shaker for 10 minutes to obtain a catalyst solution and catalyst particles C containing MgO particles.
  • the catalyst particles include the porous particles and the catalyst liquid held in the pores of the porous particles, and at least a part of the surface is covered with the inorganic particles (that is, the inorganic particles adhere to the surface). It is a catalyst particle.
  • Example 8 The catalyst particles of Example 8 were prepared as follows.
  • ⁇ Method for producing catalyst particles C> Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of silica porous particles with an average particle size of 35 um, a BET specific surface area of 310 m 2 / g, a total pore capacity of 1.7 ml / g, and mesopores, and average. Add 3 parts of MgO particles with a particle size of 0.1 um, add 5 parts of crushed wax particles with an average particle size of 2 um and a melting point of 61 ° C., and stir with a paint shaker for 10 minutes. I got C.
  • the surface of the catalyst particles C of Example 8 was exposed to hot air generated by electric heating or plasma heating to melt or soften and deform a part of the particle surface to cover a part or the entire surface of the catalyst particles.
  • the catalyst particles include porous particles and a catalyst liquid held in the pores of the porous particles, and at least a part of the surface thereof is covered with inorganic particles and a resin (resin derived from the porous particles). These are catalyst particles that are present (that is, inorganic particles and resin are attached to the surface).
  • Example 9 The catalyst particles of Example 9 were prepared as follows.
  • ⁇ Method for producing catalyst particles C> Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of acrylic porous particles with an average particle size of 10 um, a BET specific surface area of 90 m 2 / g, a total pore capacity of 1.5 ml / g, and mesopores, and paint. The mixture was stirred with a shaker for 10 minutes to obtain catalyst particles C containing a catalyst solution.
  • the catalyst particles are catalyst particles containing the porous particles and the catalyst liquid held in the pores of the porous particles.
  • Example 10 The catalyst particles of Example 10 were prepared as follows.
  • ⁇ Method for producing catalyst particles C> Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of acrylic porous particles with an average particle size of 10 um, a BET specific surface area of 90 m 2 / g, a total pore capacity of 1.5 ml / g, and mesopores, and paint. The mixture was stirred with a shaker for 10 minutes to obtain catalyst particles C containing a catalyst solution.
  • the surface of the catalyst particles C of Example 10 was exposed to hot air generated by electric heating or plasma heating to melt or soften and deform a part of the particle surface to cover a part or the entire surface of the catalyst particles.
  • the catalyst particles include the porous particles and the catalyst liquid held in the pores of the porous particles, and the catalyst particles whose surface is at least partially covered with a resin (resin derived from the porous particles). Is.
  • Example 11 The catalyst particles of Example 11 were prepared as follows.
  • ⁇ Method for producing catalyst particles C> Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of acrylic porous particles with an average particle size of 10 um, a BET specific surface area of 90 m 2 / g, a total pore capacity of 1.5 ml / g, and mesopores, and average. Three parts of MgO particles having a particle diameter of 0.1 um were added and stirred with a paint shaker for 10 minutes to obtain a catalyst solution and catalyst particles C containing MgO particles.
  • the surface of the catalyst particles C of Example 11 was exposed to hot air generated by electric heating or plasma heating to melt or soften and deform a part of the particle surface to cover a part or the entire surface of the catalyst particles.
  • the catalyst particles include porous particles and a catalyst liquid held in the pores of the porous particles, and at least a part of the surface thereof is covered with inorganic particles and a resin (resin derived from the porous particles). These are catalyst particles (that is, inorganic particles and resin adhered to the surface).
  • Example 12 The catalyst particles of Example 12 were prepared as follows.
  • ⁇ Method for producing catalyst particles C> Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of acrylic porous particles with an average particle size of 10 um, a BET specific surface area of 90 m 2 / g, a total pore capacity of 1.5 ml / g, and mesopores, and average. Add 3 parts of MgO particles with a particle size of 0.1 um, add 5 parts of crushed wax particles with an average particle size of 2 um and a melting point of 61 ° C., and stir with a paint shaker for 10 minutes. I got C.
  • the surface of the catalyst particles C of Example 12 was exposed to hot air generated by electric heating or plasma heating to melt or soften and deform a part of the particle surface to cover a part or the entire surface of the catalyst particles.
  • the catalyst particles include the porous particles and the catalyst liquid held in the pores of the porous particles, and at least a part of the surface thereof is covered with the resin and the inorganic particles (that is, the resin and the inorganic particles). Are the catalyst particles (attached to the surface).
  • Example 13 The catalyst particles of Example 13 were prepared as follows.
  • ⁇ Method for producing catalyst particles C Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of carbon porous particles with an average particle diameter of 5 um, a BET specific surface area of 300 m 2 / g, a total pore capacity of 0.4 ml / g, and macropores, and paint. The mixture was stirred with a shaker for 10 minutes to obtain catalyst particles C containing a catalyst solution.
  • the catalyst particles are catalyst particles containing the porous particles and the catalyst liquid held in the pores of the porous particles.
  • Example 14 The catalyst particles of Example 14 were prepared as follows.
  • ⁇ Method for producing catalyst particles C> Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of carbon porous particles with an average particle diameter of 5 um, a BET specific surface area of 300 m 2 / g, a total pore capacity of 0.4 ml / g, and macropores, and paint. The mixture was stirred with a shaker for 10 minutes to obtain catalyst particles C containing a catalyst solution.
  • Example 15 The catalyst particles of Example 15 were prepared as follows. ⁇ How to prepare a catalyst solution> Weigh 1 part by mass of Umicore M42 (Fujifilm Wako Pure Chemical Industries, Ltd.) as a catalyst in a glass vial, add 99 parts by mass of cyclohexane as a solvent, and stir with a paint shaker for 10 minutes to uniformly dissolve the catalyst. 1% by mass of the catalyst solution A was obtained.
  • Umicore M42 Flujifilm Wako Pure Chemical Industries, Ltd.
  • ⁇ Method for producing catalyst particles C> Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of carbon porous particles with an average particle size of 5 um, a BET specific surface area of 300 m 2 / g, a total pore capacity of 0.4 ml / g, and macropores, and average. Three parts of MgO particles having a particle diameter of 0.1 um were added and stirred with a paint shaker for 10 minutes to obtain a catalyst solution and catalyst particles C containing MgO particles.
  • the catalyst particles include the porous particles and the catalyst liquid held in the pores of the porous particles, and at least a part of the surface is covered with the inorganic particles (that is, the inorganic particles adhere to the surface). It is a catalyst particle.
  • Example 16 The catalyst particles of Example 16 were prepared as follows.
  • ⁇ Method for producing catalyst particles C> Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of carbon porous particles with an average particle size of 5 um, a BET specific surface area of 300 m 2 / g, a total pore capacity of 0.4 ml / g, and macropores, and average. Add 3 parts of MgO particles with a particle size of 0.1 um, add 5 parts of crushed wax particles with an average particle size of 2 um and a melting point of 61 ° C., and stir with a paint shaker for 10 minutes. I got C.
  • the surface of the catalyst particles C of Example 16 was exposed to hot air generated by electric heating or plasma heating to melt or soften and deform a part of the particle surface to cover a part or the entire surface of the catalyst particles.
  • the catalyst particles include the porous particles and the catalyst liquid held in the pores of the porous particles, and at least a part of the surface thereof is covered with the resin and the inorganic particles (that is, the resin and the inorganic particles). Are the catalyst particles (attached to the surface).
  • Example 17 The catalyst particles of Example 17 were prepared as follows.
  • ⁇ Method for producing catalyst particles C Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of carbon porous particles having an average particle diameter of 5 um, a BET specific surface area of 750 m 2 / g, a total pore capacity of 1.8 ml / g, and mesopores, and paint. The mixture was stirred with a shaker for 10 minutes to obtain catalyst particles C containing a catalyst solution.
  • the catalyst particles are catalyst particles containing the porous particles and the catalyst liquid held in the pores of the porous particles.
  • Example 18 The catalyst particles of Example 18 were prepared as follows.
  • ⁇ Method for producing catalyst particles C Weigh 10 parts of the catalyst solution A into a glass vial, and add 10 parts of carbon porous particles having an average particle diameter of 5 um, a BET specific surface area of 1,200 m 2 / g, a total pore capacity of 2.2 ml / g, and mesopores. , Stirred with a paint shaker for 10 minutes to obtain catalyst particles C containing a catalyst solution.
  • the catalyst particles are catalyst particles containing the porous particles and the catalyst liquid held in the pores of the porous particles.
  • Comparative Example 4 The catalyst particles of Comparative Example 4 were prepared as follows.
  • ⁇ Method for producing catalyst particles C> Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of silica particles with an average particle diameter of 1 um and a BET specific surface area of 5 m 2 / g, and stir with a paint shaker for 10 minutes to obtain the catalyst particles C containing the catalyst solution. Obtained.
  • Comparative Example 5 The catalyst particles of Comparative Example 5 were prepared as follows.
  • Example 4-18 The production conditions and evaluation results for Example 4-18, Comparative Example 1, and Comparative Example 4-5 are summarized in Tables 2 and 3.
  • Example 19 The catalyst particles of Example 19 were prepared as follows.
  • ⁇ Method for producing catalyst dispersion> Use a platinum catalyst with an average particle size of 5 nm, weigh 1 part by mass in a glass vial, add 99 parts by mass of 1,3,5-trimethylbenzene as a dispersion medium, and use a paint shaker. The mixture was stirred for 10 minutes to obtain 1% by mass of catalyst dispersion A in which the catalyst was uniformly dispersed.
  • ⁇ Method for producing catalyst particles C Weigh 10 parts of the catalyst dispersion A into a glass vial, add 10 parts of silica porous particles having an average particle diameter of 35 um, a BET specific surface area of 310 m 2 / g, a total pore capacity of 1.7 ml / g, and mesopores. Add 3 parts of MgO particles with an average particle size of 0.1 um, add 5 parts of crushed wax particles with an average particle size of 2 um and a melting point of 61 ° C., and stir with a paint shaker for 10 minutes to contain the catalyst dispersion, MgO particles and wax particles. Catalyst particles C were obtained.
  • the surface of the catalyst particles C of Example 19 was exposed to hot air generated by electric heating or plasma heating to melt or soften and deform a part of the particle surface to cover a part or the entire surface of the catalyst particles.
  • the catalyst particles include the porous particles and the catalyst liquid held in the pores of the porous particles, and at least a part of the surface thereof is covered with the resin and the inorganic particles (that is, the resin and the inorganic particles). Are the catalyst particles (attached to the surface).
  • Comparative Example 6 The catalyst dispersion of Comparative Example 6 was prepared as follows.
  • ⁇ Method for producing catalyst dispersion> Use a platinum catalyst with an average particle size of 5 nm, weigh 1 part by mass in a glass vial, add 99 parts by mass of 1,3,5-trimethylbenzene as a dispersion medium, and use a paint shaker. The mixture was stirred for 10 minutes to obtain 1% by mass of catalyst dispersion A in which the catalyst was uniformly dispersed.
  • Example 19 and Comparative Example 6 The reactivity of Example 19 and Comparative Example 6 was confirmed by the following method.
  • the reaction solutions of Example 19 and Comparative Example 6 were heated to 50 ° C. and filled in the casting container for evaluation shown in FIG. 1 at a rate of 2 L / min. Then, it was heated from the lower surface with a surface heater so as to reach 130 ° C., and the curability was evaluated. The evaluation of curability was visually confirmed from the following viewpoints. (1) Is it possible to fill the inside of the molded container (20 cm slit ⁇ 1 cm slit) evenly with the reaction solution?
  • Example 19 For Example 19 and Comparative Example 6, the manufacturing conditions and evaluation results are summarized in Table 4.
  • Example 20 The catalyst particles of Example 20 were prepared as follows.
  • ⁇ Method for producing resin particles A> Weigh 10 parts of the catalyst solution A in a glass vial, weigh 10 parts of paraffin wax with a melting point of 61 ° C, and stir with a paint shaker for 1 minute while warming to 70 ° C to solidify the wax. It was cooled sufficiently. Then, it was left at 50 ° C. for 12 hours in a nitrogen atmosphere to sufficiently vaporize cyclohexane as a solvent, and then pulverized so that the average particle size was 20 um to obtain resin particles A containing a catalyst in the wax.
  • the surface of the resin particles A of Example 20 was exposed to hot air generated by electric heating or plasma heating to melt or soften and deform a part of the particle surface to cover a part or the entire surface of the catalyst particles.
  • the catalyst particles are catalyst particles including resin particles and a catalyst contained in the resin particles.
  • Example 20 the manufacturing conditions and evaluation results are summarized in Table 5.
  • Example 21 The catalyst particles of Example 21 were prepared as follows.
  • ⁇ Method for producing catalyst particles C> Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of acrylic porous particles with an average particle size of 10 um, a BET specific surface area of 90 m 2 / g, a total pore capacity of 1.5 ml / g, and mesopores, and average. Three parts of CaCO 3 particles having a particle diameter of 0.1 um were added and stirred with a paint shaker for 10 minutes to obtain a catalyst solution and catalyst particles C containing CaCO 3 particles.
  • the surface of the catalyst particles C of Example 21 was exposed to hot air generated by electric heating or plasma heating to melt or soften and deform a part of the particle surface to cover a part or the entire surface of the catalyst particles.
  • the catalyst particles include the porous particles and the catalyst liquid held in the pores of the porous particles, and at least a part of the surface thereof is covered with the inorganic particles and the resin (that is, the inorganic particles and the resin). Are the catalyst particles (attached to the surface).
  • Example 22 The catalyst particles of Example 22 were prepared as follows.
  • ⁇ Method for producing catalyst particles C> Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of acrylic porous particles with an average particle size of 10 um, a BET specific surface area of 90 m 2 / g, a total pore capacity of 1.5 ml / g, and mesopores, and average. Three parts of Al 2 O 3 particles having a particle diameter of 0.1 um were added and stirred with a paint shaker for 10 minutes to obtain a catalyst solution and catalyst particles C containing Al 2 O 3 particles.
  • the surface of the catalyst particles C of Example 22 was exposed to hot air generated by electric heating or plasma heating to melt or soften and deform a part of the particle surface to cover a part or the entire surface of the catalyst particles.
  • the catalyst particles include the porous particles and the catalyst liquid held in the pores of the porous particles, and at least a part of the surface thereof is covered with the inorganic particles and the resin (that is, the inorganic particles and the resin). Are the catalyst particles (attached to the surface).
  • Example 23 >> The catalyst particles of Example 23 were prepared as follows.
  • ⁇ Method for producing catalyst particles C> Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of acrylic porous particles with an average particle size of 10 um, a BET specific surface area of 90 m 2 / g, a total pore capacity of 1.5 ml / g, and mesopores, and paint. The mixture was stirred with a shaker for 10 minutes to obtain catalyst particles C containing a catalyst solution.
  • the surface of the catalyst particles C of Example 23 was exposed to hot air generated by electric heating or plasma heating to melt or soften and deform a part of the particle surface to cover a part or the entire surface of the catalyst particles.
  • the catalyst particles include the porous particles and the catalyst liquid held in the pores of the porous particles, and at least a part of the surface thereof is covered with a resin (resin derived from the porous particles) (that is,). , The resin is attached to the surface) catalyst particles.
  • a polyvinyl alcohol resin (PVA, manufactured by Mitsubishi Chemical Corporation, Gosenex, LW-100) was dissolved in methanol so as to be 1% by weight to obtain a resin B solution.
  • the catalyst particles include the porous particles and the catalyst liquid held in the pores of the porous particles, and at least a part of the surface thereof is covered with the first resin and the second resin (that is,). These are catalyst particles (with two or more types of resin adhering to the surface).
  • Example 24 The catalyst particles of Example 24 were prepared as follows.
  • ⁇ Method for producing catalyst particles C> Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of acrylic porous particles with an average particle size of 10 um, a BET specific surface area of 90 m 2 / g, a total pore capacity of 1.5 ml / g, and mesopores, and average. Add 3 parts of MgO particles with a particle size of 0.1 um, add 5 parts of crushed wax particles with an average particle size of 2 um and a melting point of 61 ° C., and stir with a paint shaker for 10 minutes. I got C.
  • the surface of the catalyst particles C of Example 24 was exposed to hot air generated by electric heating or plasma heating to melt or soften and deform a part of the particle surface to cover a part or the entire surface of the catalyst particles.
  • the catalyst particles include the porous particles and the catalyst liquid held in the pores of the porous particles, and at least a part of the surface is covered with the resin (that is, the resin adheres to the surface). It is a catalyst particle.
  • a polyvinyl alcohol resin (PVA, manufactured by Mitsubishi Chemical Corporation, Gosenex, LW-100) was dissolved in methanol so as to be 1% by weight to obtain a resin B solution.
  • the catalyst particles include the porous particles and the catalyst liquid held in the pores of the porous particles, and at least a part of the surface thereof is covered with the first resin and the second resin (the first resin and the second resin). That is, it is a catalyst particle (with two or more kinds of resins adhering to the surface).
  • Example 25 The catalyst particles of Example 25 were prepared as follows.
  • ⁇ Method for producing catalyst particles C> Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of acrylic porous particles with an average particle size of 10 um, a BET specific surface area of 90 m 2 / g, a total pore capacity of 1.5 ml / g, and mesopores, and average. Five parts of crushed polyvinyl chloride (referred to as PVC) particles having a particle size of 1.8 um and a melting point of 85 ° C. were added and stirred with a paint shaker for 10 minutes to obtain a catalyst solution and catalyst particles C containing PVC particles.
  • PVC crushed polyvinyl chloride
  • the surface of the catalyst particles C of Example 25 was exposed to hot air generated by electric heating or plasma heating to melt or soften and deform a part of the particle surface to cover a part or the entire surface of the catalyst particles.
  • the catalyst particles include the porous particles and the catalyst liquid held in the pores of the porous particles, and at least a part of the surface is covered with the resin (that is, the resin adheres to the surface). It is a catalyst particle.
  • Example 26 The catalyst particles of Example 26 were prepared as follows.
  • ⁇ Method for producing catalyst particles C> Weigh 10 parts of the catalyst solution A into a glass vial, add 10 parts of acrylic porous particles with an average particle size of 10 um, a BET specific surface area of 90 m 2 / g, a total pore capacity of 1.5 ml / g, and mesopores, and average. Add 3 parts of MgO particles with a particle size of 0.1 um, add 5 parts of crushed polyvinyl chloride (PVC) particles with an average particle size of 1.8 um and a melting point of 85 ° C., and stir with a paint shaker for 10 minutes to prepare a catalyst solution. Catalyst particles C containing MgO particles and PVC particles were obtained.
  • PVC polyvinyl chloride
  • the surface of the catalyst particles C of Example 26 was exposed to hot air generated by electric heating or plasma heating to melt or soften and deform a part of the particle surface to cover a part or the entire surface of the catalyst particles.
  • the catalyst particles include the porous particles and the catalyst liquid held in the pores of the porous particles, and at least a part of the surface thereof is covered with the resin and the inorganic particles (that is, the resin and the inorganic particles). It is a catalyst particle (the particles are attached to the surface).
  • Table 6 summarizes the manufacturing conditions and evaluation results for Examples 21 to 26.
  • the coverage of the resin and the coverage of the inorganic particles were 50% or more.

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