WO2022186260A1 - Particules creuses et leur procédé de production - Google Patents

Particules creuses et leur procédé de production Download PDF

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Publication number
WO2022186260A1
WO2022186260A1 PCT/JP2022/008809 JP2022008809W WO2022186260A1 WO 2022186260 A1 WO2022186260 A1 WO 2022186260A1 JP 2022008809 W JP2022008809 W JP 2022008809W WO 2022186260 A1 WO2022186260 A1 WO 2022186260A1
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hollow particles
cross
water
soluble resin
particles according
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PCT/JP2022/008809
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Japanese (ja)
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宏 坂部
奈緒子 栗生
康佑 中島
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株式会社クレハ
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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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating

Definitions

  • the present invention relates to hollow particles and a method for producing the same.
  • Hollow particles are used as fillers for weight reduction, design imparting materials that give a three-dimensional effect to paper and wallpaper, and functional additives.
  • hollow particles for example, hollow particles obtained by expanding expandable particles in which a foaming agent is enclosed inside a polymer outer shell are known (see, for example, Patent Document 1).
  • hollow particles obtained by spray-drying a composition containing glass as a main component see, for example, Patent Document 2
  • hollow particles obtained by spray-drying a dispersion containing a layered silicate and an inorganic phosphate for example, see Patent Document 3
  • Patent Document 4 hollow silica particles obtained by removing the core particle
  • Hollow particles composed of a resin as in Patent Document 1 have a high hollowness, but it is desired to further improve heat resistance.
  • Hollow particles composed of an inorganic compound such as those disclosed in Patent Documents 2 to 4 have high heat resistance, but have the problem of low hollowness and difficulty in weight reduction. Therefore, hollow particles having both a high hollowness and high heat resistance are desired.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide hollow particles that can be produced by a simple method and have both a high hollowness ratio and high heat resistance, and a method for producing the same.
  • the hollow particles of the present invention contain a crosslinked water-soluble resin and an inorganic filler.
  • the method for producing hollow particles of the present invention includes spray-drying a dispersion containing a water-soluble resin having a crosslinkable group, a cross-linking agent, and an inorganic filler; and a step of cross-linking with the agent.
  • hollow particles that can be produced by a simple method and have both a high hollowness and high heat resistance, and a method for producing the same.
  • the present inventors spray-dry a dispersion liquid in which a water-soluble resin having a crosslinkable group, a crosslinker, and an inorganic filler are dispersed, and perform a crosslink reaction between the water-soluble resin having a crosslinkable group and the crosslinker. It was found that hollow particles having both a high hollowness and heat resistance can be obtained by the method of
  • fine droplets of the dispersion liquid are dispersed, for example, in hot air to evaporate the dispersion medium from the droplets while cross-linking the water-soluble resin having a cross-linkable group and the cross-linking agent.
  • hollow particles containing a crosslinked water-soluble resin and an inorganic filler can be obtained in a short time. Since the hollow particles contain a crosslinked water-soluble resin and an inorganic filler, they have a higher hollowness and higher heat resistance than inorganic hollow particles (not containing resin).
  • this method does not require a core particle elution removal step or a foaming step using a foaming agent as in Patent Document 4, hollow particles can be obtained by a simple method. The present invention will be described in detail below.
  • the hollow particles of the present invention comprise a crosslinked water-soluble resin and an inorganic filler.
  • the crosslinked water-soluble resin is a crosslinked product of a water-soluble resin having a crosslinkable group, and has a crosslinked structure formed by reacting the crosslinkable group of the water-soluble resin with a cross-linking agent. Whether or not it has the crosslinked structure can be confirmed by checking whether the degree of crosslinkage of the water-soluble resin described later is 10% or more.
  • the cross-linking may be ionic cross-linking by ionic bond or chemical cross-linking by covalent bond.
  • the crosslinkable group in the water-soluble resin having a crosslinkable group may be one that forms a crosslinked structure by reacting with a crosslinker.
  • crosslinkable groups include acidic groups (such as carboxyl groups, sulfonic acid groups or salts thereof), preferably carboxyl groups.
  • a resin having a carboxyl group can be a polymer containing structural units derived from a carboxyl group-containing monomer.
  • carboxyl group-containing monomers include carboxyl group-containing ethylenically unsaturated monomers such as (meth)acrylic acid, ⁇ -carboxyethyl acrylate, fumaric acid, itaconic acid, maleic acid, crotonic acid. Among them, (meth)acrylic acid and ⁇ -carboxyethyl acrylate are preferred. Only one type of these may be included, or two or more types may be included.
  • (Meth)acrylic acid means at least one of acrylic acid and methacrylic acid.
  • the polymer may further contain structural units derived from other copolymer components such as alkyl (meth)acrylates having 1 to 20 carbon atoms, vinyl monomers having a sulfonic acid group, and styrenes.
  • the content of structural units derived from carboxyl group-containing monomers in the polymer is preferably 30% by mass or more, more preferably 70% by mass or more, based on the total structural units.
  • a resin having a carboxyl group is preferable, a polymer containing a structural unit derived from acrylic acid is more preferable, and polyacrylic acid is particularly preferable.
  • the weight-average molecular weight of the water-soluble resin having a crosslinkable group may be within a range that allows it to be sprayed as a dispersion.
  • the weight-average molecular weight is within the above range, the heat resistance of the hollow particles can be easily increased without impairing the sprayability.
  • the weight-average molecular weight of the water-soluble resin having a crosslinkable group is more preferably 10,000 to 200,000.
  • the weight average molecular weight can be measured in terms of polystyrene by gel permeation chromatography (GPC). By reducing the concentration of the dispersion liquid, it is also possible to spray even a molecular weight higher than the above range.
  • the content of the water-soluble resin having a crosslinkable group is preferably 40 to 90% by mass with respect to the total solid content constituting the hollow particles.
  • crosslinking agent is not particularly limited as long as it is a compound that reacts with the cross-linking group of the water-soluble resin.
  • a cross-linking agent such as a metal for ion cross-linking may be used, or a compound that reacts with a cross-linkable group may be used.
  • cross-linking agents for ion cross-linking include salts of divalent or higher metal ions.
  • compounds that react with crosslinkable groups include one or more selected from the group consisting of isocyanate compounds, oxazoline compounds, carbodiimide compounds, silane compounds, titanium compounds, and zirconium compounds.
  • Salts of divalent or higher metal ions include alkaline earth metal ions such as Ca ions, Sr ions, Ba ions and Mg ions, divalent metal ions such as Zn ions, and trivalent Fe ions or Al ions. It can be a salt of a polyvalent metal ion such as Salts can be carbonates, sulfates, lactates, hydroxides or chlorides, and the like. Among them, calcium salts such as calcium chloride, calcium sulfate, calcium lactate and calcium hydroxide are preferred.
  • the isocyanate compound is a compound having two or more isocyanate groups in one molecule, examples of which include aromatic polyisocyanates such as tolylene diisocyanate and xylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate; hexamethylene diisocyanate and aliphatic polyisocyanates such as
  • the isocyanate group of the isocyanate compound may be protected with a protecting group (for example, a blocking agent, etc.).
  • Oxazoline compounds are compounds having two or more oxazoline groups in one molecule, examples of which include 2,2'-bis(2-oxazoline), 2,2'-bis(3-methyl-2-oxazoline ), 2,2′-(1,4-phenylene)-bis(2-oxazoline), 2,2′-(1,3-phenylene)-bis(2-oxazoline); ) oxazoline group-containing polymers such as WS-300, WS-500, WS-700, K-2010E, K-2020E, and K-2030E (manufactured by Nippon Shokubai Co., Ltd.).
  • carbodiimide compounds are compounds having two or more carbodiimide groups in one molecule, examples of which include Carbodilite V-02 manufactured by Nisshinbo Chemical Co., Ltd., Carbodilite V-02-L2, Carbodilite V-04, and Carbodilite. E-01 etc. are included.
  • silane compounds are compounds having two or more reactive groups (e.g., two or more alkoxysilyl groups, alkoxysilyl groups and epoxy groups, alkoxysilyl groups and amino groups, etc.) in one molecule, and examples thereof include: include KBM-403 (epoxy group) and KBM-903 (amino group) manufactured by Shin-Etsu Chemical Co., Ltd.;
  • the titanium compound can be an organic titanium compound such as an organic titanium alkoside, a hydrolysis reaction product thereof, an organic titanium chelate, or an organic titanium acylate.
  • organotitanium alkoxides include tetramethyl titanate, tetraethyl titanate, tetra-propyl titanate, tetra-isopropyl titanate, tetra-butyl titanate, tetraisobutyl titanate, tetra-t-butyl titanate, tetraoctyl titanate, tetra(2-ethylhexyl)
  • Organic titanium alkoxides alkoxides having 1 to 6 carbon atoms
  • titanate and tetramethyl titanate are included.
  • hydrolysates of organic titanium alkoxides include titanium butyl dimer, titanium butyl tetramer, and the like.
  • An organotitanium chelate can be a compound having a chelate substituent attached to the titanium atom.
  • Chelate substituents include ⁇ -diketones such as acetylacetone, alkylcarbonylcarboxylic acids and their esters such as acetoacetic acid, alkanolamines such as triethanolamine.
  • organotitanium chelates include organotitanium chelate complexes such as titanium acetylacetonate, titanium octylene glycolate, titanium tetraacetylacetonate, titanium ethylacetoacetate, titanium triethanolaluminate, titanium oxalate, and the like.
  • organotitanium acylates include polyhydroxytitanium stearate and the like. Titanium tetrachloride, titanium lactate, titanium triethanolamine, diisopropoxytitanium bis(triethanolamine) and the like are included.
  • Orgatics TA-10 examples include Orgatics TA-10, Orgatics TC-100, Orgatics TC-300, Orgatics TC-310, Orgatics TC-315 (manufactured by Matsumoto Fine Chemicals Co., Ltd.).
  • the zirconium compound can be an organic zirconium compound such as an organic zirconium alcoside, a hydrolysis reaction product thereof, an organic zirconium chelate, or an organic zirconium acylate.
  • titanium compounds and zirconium compounds are preferable from the viewpoint of easily increasing the degree of cross-linking and the hollowness.
  • Salts of divalent or higher metal ions are preferred from the viewpoint of increasing the yield.
  • One type of cross-linking agent may be used, or two or more types may be used in combination.
  • the content of the cross-linking agent depends on the type of cross-linking agent used, it is preferably 0.1 to 30% by mass relative to the water-soluble resin having a cross-linkable group.
  • the content of the cross-linking agent is 0.1% by mass or more, the water-soluble resin is easily crosslinked sufficiently during spray drying, and the heat resistance of the resulting hollow particles is likely to be increased. Hollowness is less likely to be lost.
  • the content of the cross-linking agent is more preferably 0.5 to 25% by mass relative to the water-soluble resin having a cross-linkable group.
  • inorganic filler The type of inorganic filler is not particularly limited, and may be an inorganic layered compound or inorganic particles.
  • inorganic layered compounds include layered silicates, layered graphite, layered chalcogenides, layered hydrotalcite compounds, layered lithium aluminum composite hydroxides, layered zirconium phosphate compounds, and the like.
  • Chalcogenides are dichalcogenides of group IV (Ti, Zr, Hf), group V (V, Nb, Ta) and/or group VI (Mo, W) elements, and MX 2 (M: the above element, X: Chalcogen (S, Se, Te)).
  • layered silicates are preferable from the viewpoint of water resistance, durability, and ease of handling.
  • layered silicates include kaolin minerals such as kaolinite and halloysite; talc and pyrophyllite, the smectite family (saponite, herculite, montmorillonite, etc.), vermiculite, the mica family (phlogopite, muscovite, sericite, etc.). included.
  • Other layered silicates include not only naturally occurring natural products, but also synthetic products obtained by artificial synthesis, such as synthetic mica and synthetic smectite.
  • inorganic particles include particles of metal oxides such as silica (silicon dioxide), alumina (aluminum oxide), titanium oxide, and zinc oxide.
  • metal oxides such as silica (silicon dioxide), alumina (aluminum oxide), titanium oxide, and zinc oxide.
  • colloidal silica is particularly preferred from the viewpoint of stably dispersible in an aqueous dispersion medium.
  • Colloidal silica is preferably one that can be stably dispersed in, for example, an aqueous dispersion medium of a resin having a carboxyl group. From such a viewpoint, it is preferable to select colloidal silica that stabilizes the dispersion according to the pH of the dispersion. Also, pH-stable colloidal silica can be preferably used.
  • Colloidal silica is widely commercially available in the form of dispersions containing colloidal silica, ie, colloidal silica dispersions, see W. et al.
  • the average particle size of the inorganic particles is not particularly limited, it is preferably 4 to 500 nm, for example.
  • the average particle size of inorganic particles can be measured by dynamic light scattering, TEM, or the like.
  • the content of the inorganic filler is preferably 1 to 70% by mass with respect to the water-soluble resin having a crosslinkable group.
  • the content of the inorganic filler is 1% by mass or more, the water-soluble resin is easily crosslinked sufficiently during spray drying, so the heat resistance of the resulting hollow particles is likely to increase. rate is unlikely to be compromised.
  • the content of the inorganic filler is more preferably 20 to 60% by mass relative to the water-soluble resin having a crosslinkable group.
  • the degree of cross-linking of the water-soluble resin cross-linked by the reaction of the cross-linkable groups can be determined from the elution ratio of the uncross-linked water-soluble resin when the hollow particles are immersed in water under predetermined conditions. Specifically, 0.03 g of hollow particles containing a crosslinked water-soluble resin are placed in 6 g of pure water, irradiated with ultrasonic waves for 1 minute, and then allowed to stand for 24 hours.
  • the degree of cross-linking represented by the following formula (1) is 10% or more, where A (g) is the amount and B (g) is the mass after drying the collected supernatant liquid at 80°C for 3 hours.
  • degree of cross-linking (%) 100- ⁇ (B/A) x 6/0.03 x 100 ⁇
  • degree of cross-linking 10% or more
  • the water-soluble resin is sufficiently cross-linked, and the obtained hollow particles can have sufficient heat resistance.
  • the degree of cross-linking of the water-soluble resin is more preferably 40 to 90%.
  • the degree of cross-linking indicates the degree of cross-linking when the cross-linkable group is ion-crosslinked or chemically cross-linked. Therefore, even if the degree of cross-linking is 40% or less, heat resistance can be improved by further adding an ionic cross-linking agent that is not ion-cross-linked (that is, unreacted metal ions).
  • the degree of cross-linking of the cross-linked water-soluble resin can be adjusted by the spray outlet temperature described later. By increasing the spray outlet temperature, the degree of cross-linking can be increased, and the heat resistance of the hollow particles can be easily increased.
  • the degree of cross-linking of the cross-linked water-soluble resin can be adjusted by the type and content of the cross-linking agent, the spray outlet temperature, etc.
  • the degree of cross-linking tends to increase when an organic titanium compound is used as the cross-linking agent, the content of the cross-linking agent is increased, or the temperature during spray drying is increased.
  • the average particle diameter of the hollow particles is not particularly limited, it is preferably 1 to 100 ⁇ m, more preferably 2 to 80 ⁇ m.
  • the average particle diameter of the hollow particles can be obtained by measuring the particle diameters (particle outer diameters) of arbitrary 100 hollow particles with a microscope and calculating the average value thereof. In addition, it can also measure using a general particle size measuring machine.
  • the average particle size of the hollow particles can be adjusted by the spray drying conditions (for example, spray outlet temperature, dispersion liquid supply speed, pressure, etc.).
  • the heat-resistant hollow particles have a weight loss at 300° C. of preferably 17% by mass or less, more preferably 13% by mass or less, and even more preferably 10% or less.
  • the heat weight loss of the hollow particles can be measured by a thermogravimetric analyzer (TGA) as the weight loss (% by mass) at 300° C. when the temperature is raised at 10° C./min.
  • the weight loss amount of the hollow particles at 300°C can be adjusted by, for example, the content of the inorganic filler. For example, when the content of the inorganic filler is large, the weight loss of the hollow particles upon heating at 300° C. is low, that is, the heat resistance is likely to be improved.
  • the hollowness of the hollow particles is preferably 10 to 99%, more preferably 40 to 99%, even more preferably 60 to 90%. When the hollowness of the hollow particles is within the above range, it can sufficiently contribute to weight reduction.
  • the hollowness can be measured by the following method. 1) First, for each of 100 arbitrary hollow particles, the average particle diameter (particle outer diameter) and partition wall thickness are measured. The partition wall thickness is measured from the cut surface of the hollow particles. 2) Next, for each hollow particle, the particle volume B is calculated from the particle diameter (particle outer diameter). Further, the inner diameter of the particle is obtained by subtracting the partition wall thickness from the particle diameter (outer diameter of the particle), and the hollow volume A is calculated from the inner diameter of the particle. 3) Then, the obtained particle volume B and hollow volume A are applied to the following formula (2) to calculate the hollow ratio.
  • Formula (2): Hollow ratio (%) A/B x 100
  • the hollowness can be adjusted by, for example, the type of cross-linking agent and the spray outlet temperature.
  • the hollowness can be increased by using a titanium compound as a cross-linking agent or by raising the spray outlet temperature.
  • the hollow particles of the present invention are prepared by spray-drying a dispersion liquid in which a water-soluble resin having a crosslinkable group, a crosslinker and an inorganic filler are dispersed, followed by It can be produced through a step of cross-linking with.
  • the dispersion medium used for the dispersion liquid is preferably an aqueous dispersion medium.
  • the aqueous dispersion medium may be water or a water-soluble organic solvent such as alcohol.
  • the pH of the dispersion can be appropriately set according to the type of water-soluble resin having a crosslinkable group, inorganic filler, or the like.
  • polyacrylic acid when used as the water-soluble resin having a crosslinkable group, it is preferably adjusted to be acidic.
  • the solid content concentration of the dispersion is not particularly limited as long as it can be sprayed, and can be, for example, 1 to 40% by mass. When the solid content concentration is 1% by mass or more, particles having a sufficient size are easily generated, and when it is 40% by mass or less, clogging during spraying is less likely to occur. From the same point of view, the solid content concentration of the dispersion is more preferably 3 to 30% by mass, more preferably 12 to 20% by mass. When the molecular weight is high and the solution viscosity is high, the sprayability can be improved by lowering the solid content concentration.
  • Spray drying is a technique in which fine droplets are sprayed in an atmosphere (preferably in hot air) in which the dispersion medium (contained in the droplets) evaporates, and the dispersion medium is instantly evaporated to obtain hollow particles. be. Then, the dispersion medium in the sprayed droplets is evaporated, and the water-soluble resin having a crosslinkable group and the crosslinker are crosslinked under heating by hot air or the like.
  • the spray outlet temperature is preferably a temperature at which the dispersion medium evaporates and the water-soluble resin having a crosslinkable group and the crosslinker undergo a crosslink reaction.
  • the spray outlet temperature is preferably, for example, 50 to 200 ° C., although it depends on the type of the cross-linking agent and the dispersion medium, so that the cross-linking reaction can be further facilitated.
  • the temperature is more preferably 80 to 200°C, more preferably 100 to 190°C, and most preferably 120 to 190°C. That is, if the water is simply evaporated with a spray dryer, the spray outlet temperature is usually adjusted to around 50°C.
  • the spray outlet temperature is within the above range, the cross-linking reaction of the water-soluble resin having a cross-linkable group can be sufficiently caused, so that the hollowness and heat resistance of the resulting hollow particles can be sufficiently improved.
  • spray outlet temperature refers to the temperature of the hot air measured at the outlet of the spray dryer. Under normal conditions such that the sample is sufficiently dried, the temperature of the dried powder will also be close to the spray outlet temperature. Therefore, the spray outlet temperature affects the degree of progress of the cross-linking reaction.
  • the spray outlet temperature can be adjusted by adjusting the spray inlet temperature, hot air flow rate, sample supply speed, and the like.
  • Spray inlet temperature refers to the temperature of the hot air introduced into the spray dryer, and is set to adjust the spray outlet temperature.
  • spray-drying conditions such as the supply rate and pressure of the dispersion liquid
  • the supply rate of the dispersion during spray drying can be about 100 to 1000 g/h.
  • Spray drying can be performed using a known spray dryer.
  • the spray dryer is configured to receive hot air (compressed gas) heated by a heater, for example, and to spray the dispersion liquid from an atomizer (sprayer).
  • the type of atomizer is not particularly limited, and may be any of a pressurized nozzle, a two-fluid nozzle, and a rotary atomizer. Among them, a two-fluid nozzle is preferable from the viewpoint of easy adjustment of the average particle size.
  • the hollow particles of the present invention can be used in various applications.
  • various applications such as paints for automobiles, for the purpose of reducing the weight of plastics, paints, and various materials and adding various functions (e.g., design, slip, heat insulation, cushioning, sound insulation, etc.) It can be preferably used as a filler, wallpaper, etc.
  • Dispersion material water-soluble resin
  • Silica particles (Ludox AM manufactured by WR Grace, colloidal silica, average particle size 12 nm, solid content concentration 30.2% by mass)
  • Titanium compound ORGATIX TC-400 (manufactured by Matsumoto Fine Chemical Co., Ltd., Ti(O-(iC 3 H 7 ) 2 (C 6 H 14 O 3 N) 2 , 79% by mass (Ti amount 8.2% by mass))
  • Ca(OH) 2 calcium hydroxide manufactured by Chichibu Lime Industry Co., Ltd.
  • Example 1 Preparation of hollow particles [Example 1] (Preparation of Dispersion 1) 21.8 g of an aqueous polyacrylic acid solution (45% by mass, Aqualic HL-415 manufactured by Nippon Shokubai Co., Ltd.) was diluted with 21.4 g of water. Also, 16.1 g of colloidal silica aqueous solution (30.2% by mass of Ludox AM manufactured by Grace) was diluted with 39.7 g of water. Then, the diluted colloidal silica aqueous solution was added to the diluted polyacrylic acid aqueous solution with stirring. To this, 9.9 g of calcium hydroxide manufactured by Chichibu Lime Industry Co., Ltd. was gradually added and mixed until completely dissolved to prepare a dispersion liquid 1.
  • an aqueous polyacrylic acid solution 45% by mass, Aqualic HL-415 manufactured by Nippon Shokubai Co., Ltd.
  • 16.1 g of colloidal silica aqueous solution (30.2% by mass of Ludox
  • Hollow particles were prepared by spray-drying the dispersion liquid 1 prepared above with a spray dryer.
  • a spray dryer (Nippon Buchi Co., Ltd.) was used with a two-fluid nozzle, and sprayed at a pressure of 0.23 bar, a spray inlet temperature of 220°C, and an aqueous solution feed rate of about 350 L/h to a spray outlet temperature of 155°C.
  • Examples 2 to 10, Comparative Example 1 and Reference Example 1 Hollow particles were produced in the same manner as in Example 1, except that at least one of the composition of the dispersion and the spray outlet temperature was changed as shown in Table 1 or 2. The spray outlet temperature was adjusted by varying the spray inlet temperature.
  • Example 2 Spray drying was carried out in the same manner as in Example 1, except that the composition of the dispersion and the spray outlet temperature were changed as shown in Table 1. I didn't get it.
  • Example 3 Spray drying was carried out in the same manner as in Example 1, except that the composition of the dispersion was changed as shown in Table 1, but particles were not obtained.
  • the particle diameter (particle outer diameter) of arbitrary 100 hollow particles was measured with a microscope, and the average value thereof was taken as the "average particle diameter”.
  • the hollowness was measured by the following method. 1) First, for each of 100 arbitrary hollow particles, the average particle diameter (particle outer diameter) and partition wall thickness were measured. The partition wall thickness was measured from the cut surface of the hollow particles. 2) Next, for each hollow particle, the particle volume B was calculated from the particle diameter (particle outer diameter). Further, the inner diameter of the particles was obtained by subtracting the partition wall thickness from the particle diameter (outer diameter of the particles), and the hollow volume A was calculated from the inner diameter of the particles. 3) Then, the obtained particle volume B and hollow volume A were applied to the following formula (2) to calculate the hollow ratio.
  • Formula (2): Hollow ratio (%) A/B x 100
  • thermogravimetric analyzer TGA
  • the hollow particles of Examples 1 to 10 have a certain or more hollow ratio, and the heat weight loss at 300 ° C. is as small as 17 mass% or less, and good heat resistance. is found to have
  • Comparative Example 1 obtained using Dispersion 8 that does not contain a specific cross-linking agent have a low hollowness. No particles were obtained in Comparative Example 2 using Dispersion 9 containing at least inorganic particles and Comparative Example 3 using Dispersion 10 containing neither inorganic particles nor a cross-linking agent. Moreover, it can be seen that the particles of Comparative Example 4, which contain neither a cross-linking agent nor inorganic particles, are hardly cross-linked and are dissolved in water.
  • the present invention can provide hollow particles that can be produced by a simple method and have both a high hollowness and high heat resistance. Such hollow particles are suitable for a wide range of applications such as fillers for weight reduction and design imparting materials.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Health & Medical Sciences (AREA)
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Abstract

La présente invention concerne des particules creuses qui peuvent être produites selon un procédé facile et qui présentent à la fois une concavité élevée et une résistance élevée à la chaleur. Les particules creuses de la présente invention comprennent une résine soluble dans l'eau réticulée et une charge inorganique.
PCT/JP2022/008809 2021-03-03 2022-03-02 Particules creuses et leur procédé de production WO2022186260A1 (fr)

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JP2006057019A (ja) * 2004-08-20 2006-03-02 Nippon Synthetic Chem Ind Co Ltd:The 水性アクリル共重合エマルジョン、再分散性アクリル共重合エマルジョン粉末、およびそれらの製造方法
CN101601986A (zh) * 2009-07-09 2009-12-16 南京大学 一种壳聚糖-二氧化硅复合空心微球的制法及应用
US20140243457A1 (en) * 2011-10-05 2014-08-28 Wacker Chemie Ag Dry building material formulations containing polymer powders
JP2018035031A (ja) * 2016-08-31 2018-03-08 国立大学法人 名古屋工業大学 ナノシリカ中空粒子の製造方法
JP2021152127A (ja) * 2020-03-25 2021-09-30 アイカ工業株式会社 アクリル−アミノ樹脂複合中空粒子の製造方法

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