Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
  • C08F212/36—Divinylbenzene
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
  • A01N25/10—Macromolecular compounds
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
  • A01N25/28—Microcapsules or nanocapsules
• • 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
• • 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
  • B01J13/20—After-treatment of capsule walls, e.g. hardening
  • B01J13/203—Exchange of core-forming material by diffusion through the capsule wall
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/18—Suspension polymerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
  • C08L2205/18—Spheres
  • C08L2205/20—Hollow spheres

Definitions

• the present invention relates to hollow particles, and more particularly to hollow particles with high porosity and excellent electrical insulation.
• Patent Document 1 discloses a heat-sensitive coloring layer formed by successively laminating an intermediate layer and a heat-sensitive coloring layer containing a leuco dye and a color developer as main components on a support.
• Hollow resin particles for heat-sensitive recording material which are used in the intermediate layer of the recording material, wherein the repeating unit constituting the resin part is an acid group-containing polymerizable monomer unit in a proportion of 10 to 60% by mass, Number ratio of particles containing 5 to 65% by mass of crosslinkable monomer units, having a porosity of 70 to 90%, a number average particle diameter of 0.8 to 3.5 ⁇ m, and a particle diameter of 10 ⁇ m or more is less than 1.0%.
• a hollow particle comprising a shell containing a resin and a hollow portion surrounded by the shell, the resin comprises a shell polymer containing crosslinkable monomer units,
• the hollow particles have a true density of 1.18 g/cm 3 or less,
• a hollow particle is provided in which the value of C calculated from the following formula (1) for the hollow particle is 1.16 or less.
• C A ⁇ (100-B) / 100 formula (1) (In the above formula (1), A represents the value of the true density of the hollow particles (unit: g/cm 3 ), and B represents the content ratio of the monofunctional monomer unit in the shell polymer (unit: mass %).)
• the content of the heteroatom-containing monomer units in the shell polymer is preferably 90% by mass or less.
• the hollow particles of the present invention are preferably those obtained through an in-liquid solvent removal method.
• the hollow particles of the present invention preferably have a porosity of 60% or more.
• the shell polymer preferably further contains a monofunctional monomer unit, and more preferably contains a monofunctional hydrocarbon monomer unit as the monofunctional monomer unit.
• the hollow particles of the present invention are hollow particles comprising a shell containing a resin and a hollow portion surrounded by the shell, wherein the resin comprises a shell polymer containing a crosslinkable monomer unit,
• the hollow particles have a true density of 1.18 g/cm 3 or less and a C value of 1.16 or less calculated from the following formula (1) of the hollow particles.
• the shell of the hollow particles of the present invention contains a resin made of a shell polymer.
• Crosslinkable monomers forming crosslinkable monomer units include crosslinkable hydrocarbon monomers and heteroatom-containing crosslinkable monomers.
• the crosslinkable hydrocarbon monomer is not particularly limited, but includes, for example, divinylbenzene, divinyldiphenyl, divinylnaphthalene, etc. Among them, divinylbenzene is preferred.
• Containing crosslinkable monomers and the like can be mentioned.
• ethylene glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate and pentaerythritol tri(meth)acrylate are preferred, and ethylene glycol di(meth)acrylate and pentaerythritol Tetra(meth)acrylates are more preferred, and ethylene glycol dimethacrylate and pentaerythritol tetraacrylate are even more preferred.
• crosslinkable monomer a crosslinkable hydrocarbon monomer, ethylene glycol di(meth)acrylate and pentaerythritol tetra(meth)acrylate are preferable, and divinylbenzene, ethylene glycol dimethacrylate and pentaerythritol tetra(meth)acrylate are more preferable.
• the crosslinkable monomers can be used alone or in combination of two or more.
• a cross-linking hydrocarbon monomer and a heteroatom-containing cross-linking monomer can be used in combination.
• the heteroatom-containing crosslinkable monomer two or more heteroatom-containing crosslinkable monomers can be used in combination.
• the above heteroatom-containing crosslinkable monomers can be used in combination.
• amide group-containing monomers examples include acrylamide and dimethylacrylamide.
• the monofunctional monomer units can be used either alone or in combination of two or more.
• the content of the crosslinkable monomer units in the shell polymer is not particularly limited, but from the viewpoint of the mechanical strength of the hollow particles, it is preferably 60% by mass or more, more preferably 70% by mass or more. preferably 75% by mass or more, even more preferably 80% by mass or more, even more preferably 85% by mass or more, particularly preferably 90% by mass or more, and 95% by mass % or more is most preferable.
• the content of the crosslinkable monomer is within the above range, the covalent bond network is densely spread in the shell, and the occurrence of continuous pores in the shell and shell defects is suppressed. It becomes excellent in mechanical strength.
• the volume average particle size (Dv) of the hollow particles is relatively large, the particle size distribution (Dv/Dn) of the hollow particles tends to be small.
• the content is not particularly limited, but is preferably 99.2% by mass or less, more preferably 98% by mass or less, further preferably 95% by mass or less, and 92.5% by mass or less. It is particularly preferable that the content is 90% by mass or less.
• the content of monofunctional monomer units in the shell polymer is not particularly limited from the viewpoint of the mechanical strength of the hollow particles, but is preferably 0 to 40% by mass, more preferably 0 to 30% by mass. is more preferably 0 to 25% by mass, even more preferably 0 to 20% by mass, even more preferably 0 to 15% by mass, and 0 to 10% by mass is particularly preferred, and 0 to 5% by mass is most preferred.
• Dv volume average particle size
• Dv/Dn particle size distribution of the hollow particles tends to be small.
• the content is not particularly limited, but is preferably 0.8% by mass or more, more preferably 2% by mass or more, further preferably 5% by mass or more, and 7.5% by mass or more. It is particularly preferable that the content is 10% by mass or more, and most preferably 10% by mass or more.
• the value of the content ratio of the crosslinkable monomer unit in the shell polymer (unit: mass %) is represented by (100-B) in the formula (1) described later, and the monofunctional monomer in the shell polymer
• the value of the body unit content (unit: % by mass) is represented by B in formula (1) described later.
• the shell polymer may contain heteroatom-containing monomer units.
• the heteroatom-containing monomers forming the heteroatom-containing monomer units include the heteroatom-containing crosslinkable monomers and the heteroatom-containing monofunctional monomers described above.
• the content of the heteroatom-containing monomer unit is 1% by mass or more. 2% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, or 30% by mass or more.
• the hollow particles of the present invention are particles comprising a shell (outer shell) containing the above resin and a hollow portion surrounded by the shell.
• the hollow portion is a hollow space clearly distinguished from the shell of the hollow particle made of resin.
• the hollow particles of the present invention may have one or more hollow portions, but preferably have only one hollow portion in order to maintain a good balance between high porosity and mechanical strength. .
• the proportion of particles having only one hollow portion is preferably 90% by mass or more, more preferably 95% by mass or more.
• the outer shape of the hollow particles can be confirmed, for example, by observing the particles with SEM or TEM. Further, the internal shape of the hollow particles can be confirmed by, for example, SEM observation of the cross section of the particles or TEM observation of the particles.
• the hollow particles of the present invention may contain, as impurities, a small amount of particles with low circularity that are cracked or deformed, but the circularity of 100% by mass of the hollow particles of the present invention is 0.85 or less. is preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, even more preferably 4% by mass or less, and particularly preferably 3% by mass or less.
• the hollow particles of the present invention have a true density of 1.18 g/cm 3 or less, and a C value of 1.16 or less calculated from the formula (1) described later.
• the true density of the hollow particles and the value of C calculated from formula (1) can be adjusted by adjusting the monomer composition of the shell polymer.
• the porosity of the hollow particles is calculated from the apparent density D1 and the true density D0 of the hollow particles.
• the apparent density D1 corresponds to the density of the entire hollow particle when the hollow portion is regarded as part of the hollow particle.
• the porosity is determined by assuming that the densities of the components other than the components constituting the shell are equal to the true density D0 of the hollow particles.
• the apparent density D1 is calculated using the mass including the mass of the components other than the components constituting the shell, and then the apparent density D1 calculated in this way is used. to calculate the porosity of the hollow particles.
• the hollow particles of the present invention include, for example, low dielectric materials used in various fields such as automobiles, electricity, electronics, construction, aviation, space, members such as heat insulating materials, sound insulating materials and light reflecting materials, and food containers. , footwear such as sports shoes and sandals, household appliance parts, bicycle parts, stationery, tools, etc.
• the hollow particles of the present disclosure are excellent in dielectric properties, and thus are suitably used as an additive for realizing low transmission loss in the field of electricity or electronics.
• the hollow particles of the present invention are suitably used as an electronic circuit board material. Specifically, by incorporating the hollow particles of the present invention into an insulating resin layer of an electronic circuit board, the transmission loss of the electronic circuit board is reduced. can be reduced.
• the hollow particles of the present invention are also suitable for use as a rust inhibitor.
• the hollow particles of the present invention are also useful as an additive that reduces electrical conductivity. It can be used as a paint (paint base, lubricating paint, etc.).
• the hollow particles added to the antirust paint can contain an antirust additive.
• hydrophobic organic solvent a hydrocarbon-based solvent having 5 to 8 carbon atoms is preferable.
• the hydrocarbon-based solvent having 5 to 8 carbon atoms is easily included in the precursor particles during the polymerization step described below, and can be easily removed from the precursor particles during the solvent removal step described below.
• hydrocarbon solvents having 6 to 8 carbon atoms are particularly preferred.
• hydrophobic organic solvents having a dielectric constant of 3 or less at 20° C. examples include heptane (1.9), cyclohexane (2.0), benzene (2.3), and toluene (2.4). (values in parentheses are relative permittivity values).
• known literature for example, "Kagaku Binran Basic Edition” edited by The Chemical Society of Japan, Revised 4th Edition, Maruzen Co., Ltd., September 30, 1993, II-498 to II-503 page
• a method for measuring the dielectric constant at 20°C for example, a dielectric constant test conforming to JISC 2101:23 of 1999 and carried out at a measurement temperature of 20°C can be mentioned.
• Water-soluble polyvalent metal salts include hydrochlorides, sulfates, nitrates, acetates, etc. of polyvalent metals such as magnesium, calcium, aluminum, iron, copper, manganese, nickel, and tin. Among these, water-soluble salts of magnesium and calcium are preferred.
• Alkali metal hydroxides include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. For example, when magnesium hydroxide is used as the dispersion stabilizer, a combination of magnesium chloride and sodium hydroxide is suitable as the two or more precursor compounds.
• the method of mixing two or more precursor compounds in an aqueous medium is not particularly limited.
• a method of dropping an aqueous medium solution of an alkali metal hydroxide into an aqueous medium solution of a polyvalent metal salt is suitable.
• the mixed liquid can be obtained by mixing the above components by stirring or the like. In this case, in addition to each component described above, other materials may be mixed as necessary.
• an oil phase containing a polymerizable monomer, a hydrophobic organic solvent, and a lipophilic material such as a polymerization initiator is added to an aqueous medium, and an aqueous phase containing a dispersion stabilizer used as necessary.
• a mixed liquid is prepared in which the particles are dispersed with a particle size of about several millimeters. Depending on the type of each component, the state of dispersion of these components in the mixture can be observed with the naked eye.
• (B) Suspension step In the suspension step, a polymerizable monomer containing a polymerizable monomer, a hydrophobic organic solvent, and a polymerization initiator is suspended by suspending the mixture obtained in the mixture preparation step described above. It is a step of preparing a suspension in which droplets of the monomer composition are dispersed in an aqueous medium.
• (C) Polymerization step In the polymerization step, the suspension prepared in the above-described suspension step is subjected to a polymerization reaction to have a hollow portion and to include a hydrophobic organic solvent in the hollow portion to obtain a solution that is more pure than water.
• the polymerizable monomer in the droplets is polymerized to form a polymer of the polymerizable monomer.
• Precursor particles are formed having a shell containing a resin and a hollow portion filled with a hydrophobic organic solvent.
• the droplets of the polymerizable monomer composition are subjected to the polymerization reaction while encapsulating the hydrophobic organic solvent, so that the polymerization reaction easily proceeds while maintaining the shape, and the precursor particles It is easy to adjust the size and porosity of the
• the polarity of the hydrophobic organic solvent is low with respect to the shell of the precursor particles, and the hydrophobic organic solvent is difficult to mix with the shell, resulting in phase separation. It tends to occur sufficiently to have only one hollow portion.
• the hollow particles of the present invention have a shell made of the shell polymer described above, have a true density of 1.18 g/cm 3 or less, and have a value of C calculated from the formula (1) of 1.16 or less. Therefore, the hydrophobic organic solvent contained in the precursor particles can be sufficiently removed even when the precursor particles are obtained through the solvent removal method in liquid. Furthermore, the hollow particles of the present invention have a high porosity and excellent electrical insulation even if they are obtained through the in-liquid solvent removal method.
• the bubbling conditions are appropriately adjusted according to the type and amount of the hydrophobic organic solvent so that the hydrophobic organic solvent contained in the precursor particles can be removed, and are not particularly limited.
• the bubbling time is preferably 1 to 48 hours, more preferably 3 to 24 hours.
• the amount of gas bubbling per minute is preferably 0.1 to 10 times, more preferably 0.5 to 2 times, the volume of the precursor composition to be subjected to solvent removal in liquid. A volumetric amount is more preferred.
• the temperature during bubbling is more preferably a temperature equal to or higher than the temperature obtained by subtracting 30°C from the boiling point of the hydrophobic organic solvent, in order to reduce the residual amount of the hydrophobic organic solvent in the hollow particles. It is more preferable that the temperature is equal to or higher than the temperature.
• the aqueous medium is removed from the hollow particle slurry, and the solid content containing the hollow particles can be recovered.
• the solid-liquid separation method is not particularly limited, and known methods can be used.
• a solid-liquid separation method it is preferable to employ a centrifugal separation method or a filtration method.
• the solid-liquid separation conditions are not particularly limited as long as the conditions are such that the aqueous medium can be removed from the hollow particle slurry.
• the drying method By the drying method, the aqueous medium is removed from the hollow particle slurry or the solid content obtained after the solid-liquid separation step, and the solid content containing the hollow particles can be recovered.
• the drying method is not particularly limited as long as it is a method capable of removing the aqueous medium. Drying methods include, for example, a vacuum drying method, a heat drying method, a flash drying method, and a combination thereof.
• the above production method preferably includes a washing step before or after the recovery step.
• a dispersion stabilizer before the recovery step, an acid or alkali is added for washing to remove the dispersion stabilizer remaining in the hollow particle slurry containing the hollow particles and the aqueous medium. It is preferable to include a washing step that is carried out.
• the dispersion stabilizer used is an acid-soluble dispersion stabilizer, it is preferable to wash by adding an acid to the precursor composition containing the precursor particles.
• an alkali-soluble dispersion stabilizer it is preferable to add an alkali to the precursor composition containing the precursor particles for washing.
• thermoplastic resin a known one can be used and is not particularly limited, but examples include polyolefins such as polypropylene and polyethylene; polyamides such as PA6, PA66 and PA12; polyimides, polyamideimides, polyetherimides and polyethers.
• resins such as epoxy resins, thermosetting modified polyphenylene ether resins, thermosetting polyimide resins, silicon resins, benzoxazine resins, Insulating resins such as melamine-based resins, urea-based resins, allyl-based resins, phenol-based resins, unsaturated polyester-based resins, polyurethane-based resins, and aniline-based resins are preferably used.
• Resins, modified polyphenylene ether-based resins, silicon-based resins, benzoxazine-based resins, melamine-based resins, and the like are preferably used. These insulating resins can be used alone or in combination of two or more.
• the content of the resin is not particularly limited, it is preferably 50 to 95% by mass or less based on 100% by mass of the total solid content of the resin composition.
• the content of the resin is at least the above lower limit, the moldability of the resin molded article is excellent, and the mechanical strength of the obtained resin molded article is excellent.
• the content of the resin is equal to or less than the above upper limit, the hollow particles of the present invention can be sufficiently contained, so that the effects of the hollow particles of the present invention, such as low dielectric loss tangent, can be fully exhibited. can be done.
• liquid resin composition As a method for applying the liquid resin composition, known methods can be used, such as dip coating, roll coating, curtain coating, die coating, slit coating, gravure coating, and the like.
• Example 1 (1) Mixed Solution Preparation Step First, the following materials were mixed to prepare an oil phase. Divinylbenzene (crosslinkable hydrocarbon monomer) 37.5 parts Ethylvinylbenzene (monofunctional hydrocarbon monomer) 1.6 parts t-butyl peroxydiethyl acetate (oil-soluble polymerization initiator) 0.89 parts Hydrophobic solvent: heptane 60.8 parts Next, in a stirring tank, An aqueous solution obtained by dissolving 15.67 parts of magnesium chloride (water-soluble polyvalent metal salt) in 225 parts of ion-exchanged water, and an aqueous solution obtained by dissolving 10.97 parts of sodium hydroxide (alkali metal hydroxide) in 55 parts of ion-exchanged water.
• Divinylbenzene crosslinkable hydrocarbon monomer
• Ethylvinylbenzene monofunctional hydrocarbon monomer
• t-butyl peroxydiethyl acetate oil-soluble polymerization initi

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• 2022
  • 2022-12-26 KR KR1020247020593A patent/KR20240122780A/ko active Pending
  • 2022-12-26 US US18/723,982 patent/US20250075018A1/en active Pending
  • 2022-12-26 CN CN202280083263.6A patent/CN118434774A/zh active Pending
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