Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D17/00—Pigment pastes, e.g. for mixing in paints
  • C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/28—Compounds of silicon
  • C09C1/30—Silicic acid
  • C09C1/3081—Treatment with organo-silicon compounds
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/113—Silicon oxides; Hydrates thereof
  • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
  • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
  • C01B33/145—Preparation of hydroorganosols, organosols or dispersions in an organic medium
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability

Definitions

• the present disclosure relates to particle dispersions and the like.
• Patent Document 1 describes a particle dispersion using silica particles.
• the particles may aggregate.
• the particle dispersion is required to have excellent dispersibility when subjected to dispersion treatment.
• One aspect of the present disclosure aims to provide a particle dispersion liquid that has excellent dispersibility when subjected to a dispersion treatment.
• the present disclosure relates to the following [1] to [14].
• [1] A particle dispersion containing particles and a liquid medium, wherein the distance between the HSP value of the particles and the HSP value of the liquid medium is 5.50 MPa 0.5 or less.
• [2] The particle dispersion according to [1], wherein the liquid medium contains an organic solvent.
• [3] The particle dispersion according to [1], wherein the liquid medium contains a plurality of organic solvents.
• the particle dispersion according to [3], wherein the liquid medium contains methyl isobutyl ketone and toluene.
• [5] The particle dispersion according to any one of [2] to [4], wherein the content of the organic solvent is 80% by mass or more based on the total mass of the liquid medium.
• [6] The particle dispersion according to any one of [1] to [5], wherein the particles include inorganic particles.
• [8] The particle dispersion according to any one of [1] to [7], wherein the particles contain silica.
• the content of the particles is 30 to 90% by mass based on the total mass of the particle dispersion, [1 ] to [12].
• a numerical range indicated using "-" indicates a range that includes the numerical values written before and after "-" as the minimum and maximum values, respectively.
• the upper limit or lower limit of the numerical range of one step can be arbitrarily combined with the upper limit or lower limit of the numerical range of another step.
• the upper limit or lower limit of the numerical range may be replaced with the values shown in the examples.
• “A or B” may include either A or B, or may include both.
• the materials exemplified herein can be used alone or in combination of two or more, unless otherwise specified.
• the content of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified.
• the particle dispersion according to the present embodiment contains particles and a liquid medium, and the distance between the HSP value of the particles and the HSP value of the liquid medium (hereinafter referred to as "HSP distance of the particles with respect to the liquid medium” in some cases) is 5.50MPa 0.5 or less.
• the particle dispersion according to this embodiment has excellent dispersibility (particle dispersibility) when subjected to a dispersion treatment. According to the findings of the present inventors, it is preferable to compare the dispersibility of the particles when the solid content is the same, and by comparing the particles when the solid content is 3% by mass, it is easy to see the difference in dispersibility and it is possible to disperse the particles appropriately. be able to evaluate gender.
• the particle dispersion according to the present embodiment is obtained by adjusting the solid content to 3% by mass immediately after performing a dispersion treatment (for example, a dispersion treatment by cavitation) on a liquid mixture obtained by mixing the components contained in the particle dispersion. It has excellent dispersibility.
• the coefficient of variation (CV) of the particle size The volume fraction of particles with a particle size of D100 or more in a polydisperse state with Coefficient of Variation) of 20 or more, or the particle size D50 in a monodisperse state with a particle size variation coefficient of less than 20.
• the volume fraction of particles having a particle size that is twice the particle size or more can be obtained, for example, 7.0% or less (preferably 5.0% or less, or less than 5.0%).
• evaluation can be performed without adjusting the solid content.
• the solid content of the particle dispersion may be adjusted by diluting it with a liquid medium having the same composition as the liquid medium of the particle dispersion, and the solid content of the particle dispersion may be adjusted by volatilizing the liquid medium of the particle dispersion. good.
• the particles may aggregate over time.
• excellent dispersion stability (storage stability) can be obtained even when storing the particle dispersion immediately after dispersion treatment.
• the evaluation shown in Examples below when the solid content was adjusted to 3% by mass after the particle dispersion was left to stand for 7 days immediately after dispersion treatment) evaluation
• the volume fraction of particles with a particle size of D100 or more in a polydisperse state with a particle size variation coefficient of 20 or more, or in a monodisperse state with a particle size variation coefficient of less than 20 For example, 20.0% or less (preferably 12.0% or less, or 5.0% or less) as the volume fraction of particles having a particle size of twice the particle size D50 or more in a certain case. Can be done.
• the volume fraction of particles with a particle size of D100 or more in a polydisperse state with a particle size variation coefficient of 20 or more, or in a monodisperse state with a particle size variation coefficient of less than 20 is obtained, for example, 30.0% or less (preferably 15.0% or less, or 10.0% or less) as the volume fraction of particles having a particle size larger than or equal to twice the particle size D50 in a certain case. Can be done.
• the use of the particle dispersion according to this embodiment is not particularly limited.
• the particle dispersion according to this embodiment is applicable to laminated plates (copper-clad laminates, etc.), die bonding films, circuit connection members, polishing liquids (CMP polishing liquids, etc.), sealing materials, electrode active materials for batteries, transfer-type transparent It can be applied to the production or use of conductive films, etc.
• the particle dispersion according to the present embodiment can be used in the production of semiconductor members, and can be used as a slurry for obtaining laminates of semiconductor members, insulating films (insulating films of sealing materials, etc.), etc. Can be done.
• the HSP distance of a particle with respect to a liquid medium can be calculated from the following formula based on ⁇ d (dispersion term), ⁇ p (polarization term), and ⁇ h (hydrogen bond term) in the Hansen solubility parameter (HSP).
• ⁇ d1 , ⁇ p1 and ⁇ h1 are the ⁇ d , ⁇ p and ⁇ h of the particles
• ⁇ d2 , ⁇ p2 and ⁇ h2 are the ⁇ d , ⁇ p and ⁇ h of the liquid medium.
• HSP distance ⁇ 4 ⁇ ( ⁇ d1 - ⁇ d2 ) 2 + ( ⁇ p1 - ⁇ p2 ) 2 + ( ⁇ h1 - ⁇ h2 ) 2 ⁇ 0.5
• the ⁇ d , ⁇ p and ⁇ h of commonly used substances for example, the ⁇ d , ⁇ p and ⁇ h of a desired substance can be obtained by referring to the database. can do.
• Parameters of substances that are not registered in the database can be calculated using computer software such as HSPiP (Hansen Solubility Parameter in Practice; written by Prof. Steven Abbott and Dr. Hiroshi Yamamoto). I can.
• ⁇ d1 , ⁇ p1 and ⁇ h1 of particles can be calculated by the following procedure. First, the particles are collected by drying the particle dispersion, etc., and 16 types of evaluation solvents with known parameters ( ⁇ d , ⁇ p and ⁇ h ) are prepared. Next, a dispersibility test of the particles to be evaluated with respect to each evaluation solvent is conducted to determine whether each evaluation solvent is a "solvent with excellent dispersibility" or "a solvent with poor dispersibility.” The dispersibility test can be conducted by the method shown in Examples below.
• ⁇ d1 , ⁇ p1 and ⁇ h1 are the particle material type, particle size, particle size distribution (coefficient of variation of particle size), surface treatment details (type of surface treatment agent, amount of surface treatment agent used, surface treatment method, etc.) It changes depending on the situation. For example, as the particle size increases, ⁇ d1 tends to increase and ⁇ p1 and ⁇ h1 tend to decrease. Furthermore, as the coefficient of variation of particle size increases, ⁇ p1 tends to increase and ⁇ h1 tends to decrease.
• ⁇ d1 , ⁇ p1 , and ⁇ h1 of the surface-treated particles are intended for the entire surface-treated particle in consideration of the influence of the surface treatment. As ⁇ d1 , ⁇ p1 and ⁇ h1 , values at 25° C. can be used.
• ⁇ d2 , ⁇ p2 and ⁇ h2 of the liquid medium can be calculated based on the composition of the liquid medium in the particle dispersion.
• ⁇ d2 , ⁇ p2 and ⁇ h2 of the liquid medium are determined by the parameters of each component ( ⁇ d , ⁇ p or ⁇ h ) and the volume proportion of each component to the entire mixture. It can be calculated as the sum of the products.
• the ⁇ d , ⁇ p and ⁇ h of each component constituting the liquid medium were analyzed using the analysis software HSPiP (Hansen Solubility Parameter in Practice; written by Prof. Steven Abbott and Dr. Yamamoto Hir).
• ⁇ d , ⁇ p and ⁇ h are structural analysis software used as ⁇ d2 , ⁇ p2 and ⁇ h2 .
• SMILES structural analysis software
• the present inventors have found that adjusting the HSP distance of particles with respect to a liquid medium is effective in adjusting the dispersibility of particles.
• the particle dispersion according to this embodiment has excellent dispersibility since the HSP distance of the particles with respect to the liquid medium is 5.50 MPa 0.5 or less. Regarding the reason why such an effect is obtained, it is presumed that when the HSP distance is within the above range, the particles and the liquid medium are thermodynamically easy to mix with each other, so that excellent dispersibility can be obtained.
• the factors that produce the effect are not limited to the content.
• the HSP distance of the particles with respect to the liquid medium is greater than 0, 0.50 or greater, 1.00 or greater, 1.50 or greater, 2.00 or greater, 2.50 or greater, 3.00 or greater, 3.40 or greater, 3.45 3.50 or more, 3.60 or more, 3.70 or more, 3.90 or more, 4.00 or more, 4.10 or more, 4.30 or more, 4.50 or more, 4.70 or more, 4.80 It may be 4.90 or more, 5.00 or more, 5.05 or more, 5.10 or more, 5.15 or more, 5.20 or more, 5.25 or more, or 5.30 or more. From these viewpoints, the HSP distance of the particles with respect to the liquid medium may be greater than 0 and less than or equal to 5.50, 3.00 to 5.50, or 3.00 to 5.40.
• the particles may be dispersed in a liquid medium.
• the particles make up the solid content of the particle dispersion.
• the particles may be inorganic or organic particles.
• the constituent materials of the inorganic particles include oxides such as silica, ceria, alumina, titania, zirconia, magnesia, yttria, zinc oxide, and iron oxide; nitrides such as silicon nitride, titanium nitride, and boron nitride; cerium hydroxide, etc. hydroxide; metal materials such as copper, nickel, gold, silver, tin, zinc, nickel, platinum, bismuth, indium, antimony; silicon carbide; calcium carbonate; aluminum sulfate; barium sulfate; potassium titanate; barium titanate ; Examples include calcium titanate.
• oxides such as silica, ceria, alumina, titania, zirconia, magnesia, yttria, zinc oxide, and iron oxide
• nitrides such as silicon nitride, titanium nitride, and boron nitride
• Inorganic particles may be produced by a melting method, a sol-gel method, a liquid phase method, or the like.
• resin materials can be used, and examples thereof include acrylic resin, styrene resin, urea resin, phenol resin, epoxy resin, benzoguanamine resin, and the like.
• the constituent materials of the particles can be used alone or in combination of two or more.
• the particles may include inorganic particles or nonmetallic materials from the viewpoint of easily obtaining excellent dispersibility, and are selected from the group consisting of silica, ceria, alumina, titania, boron nitride, and calcium titanate. It may contain at least one kind and may contain silica.
• the surface treatment agent examples include silane compounds (for example, silane coupling agents), titanium compounds (for example, titanium coupling agents), aluminate compounds (for example, aluminate coupling agents), and the like.
• the surface treatment agent may have an alkoxy group, an alkoxysilyl group, a phenyl group, a vinyl group, an epoxy group, an acryloyl group, a methacryloyl group, an amino group, a ureido group, a mercapto group, an isocyanate group, and the like.
• the surface treatment agent may contain a silane compound, and may contain a silane compound having an alkoxysilyl group, from the viewpoint of easily obtaining excellent dispersibility.
• the silane compound may include a silane compound having an alkoxy group bonded to a silicon atom as a silane compound having an alkoxysilyl group.
• the number of alkoxy groups bonded to silicon atoms may be 1 to 4, 1 to 3, 2 to 3, or 3 to 4 from the viewpoint of easily obtaining excellent dispersibility.
• the silane compound may include a silane compound having a nitrogen-containing organic group from the viewpoint of easily obtaining excellent dispersibility.
• the nitrogen-containing organic group include an alkylamino group, an alkylaminoalkyl group, an arylamino group, an arylaminoalkyl group, a heteroarylamino group, and a heteroarylaminoalkyl group.
• the nitrogen-containing organic group may include an arylaminoalkyl group, a phenylaminoalkyl group, or a phenylaminopropyl group.
• silane compounds include N-phenyl-3-aminopropyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, epoxytrimethoxysilane, methacryltrimethoxysilane, aminotrimethoxysilane, ureidotrimethoxysilane, and mercaptopropyltrimethoxysilane.
• the silane compound may include N-phenyl-3-aminopropyltrimethoxysilane from the viewpoint of easily obtaining excellent dispersibility.
• the content of the surface treatment agent may be in the following range with respect to 100 parts by mass of particles (not including the content of the surface treatment agent).
• the content of the surface treatment agent is 0.01 parts by mass or more, 0.05 parts by mass or more, 0.1 parts by mass or more, 0.3 parts by mass or more, 0.5 parts by mass from the viewpoint of easily obtaining excellent dispersibility. parts or more, 0.8 parts by mass or more, or 1.0 parts by mass or more. From the viewpoint of easily obtaining excellent dispersibility, the content of the surface treatment agent is 10 parts by mass or less, 8.0 parts by mass or less, 5.0 parts by mass or less, 3.0 parts by mass or less, 2.0 parts by mass or less. , 1.5 parts by mass or less, or 1.0 parts by mass or less.
• the particle diameter D50 at 50% accumulation in the volume-based cumulative particle size distribution of particles may be in the following range from the viewpoint of adjusting dispersibility.
• Particle size D50 is 0.1 ⁇ m or more, more than 0.1 ⁇ m, 0.3 ⁇ m or more, 0.5 ⁇ m or more, 0.8 ⁇ m or more, 1.0 ⁇ m or more, 1.2 ⁇ m or more, 1.5 ⁇ m or more, 1.8 ⁇ m or more, It may be 2.0 ⁇ m or more, 2.2 ⁇ m or more, or 2.5 ⁇ m or more.
• Particle size D50 is 20 ⁇ m or less, 15 ⁇ m or less, 10 ⁇ m or less, 9.0 ⁇ m or less, 8.0 ⁇ m or less, 7.0 ⁇ m or less, 6.0 ⁇ m or less, 5.0 ⁇ m or less, 4.0 ⁇ m or less, 3.0 ⁇ m or less, 2 .8 ⁇ m or less, 2.5 ⁇ m or less, 2.2 ⁇ m or less, 2.0 ⁇ m or less, 1.8 ⁇ m or less, 1.5 ⁇ m or less, 1.2 ⁇ m or less, 1.0 ⁇ m or less, 0.8 ⁇ m or less, or 0.5 ⁇ m or less It may be. From these viewpoints, the particle size D50 may be 0.1 to 20 ⁇ m, 0.5 to 20 ⁇ m, or 0.5 to 3.0 ⁇ m.
• the particle diameter D95 at 95% accumulation in the volume-based cumulative particle size distribution of the particles is within the following range from the viewpoint of adjusting dispersibility and from the viewpoint of making it easy to obtain a varnish suitable for producing the insulating film of the laminate. It's fine.
• Particle size D95 is 0.3 ⁇ m or more, 0.5 ⁇ m or more, 1.0 ⁇ m or more, 1.5 ⁇ m or more, 2.0 ⁇ m or more, 2.5 ⁇ m or more, 3.0 ⁇ m or more, 3.5 ⁇ m or more, 4.0 ⁇ m or more, Alternatively, it may be 4.5 ⁇ m or more.
• Particle size D95 is 30 ⁇ m or less, 25 ⁇ m or less, 20 ⁇ m or less, 15 ⁇ m or less, 10 ⁇ m or less, 9.0 ⁇ m or less, 8.0 ⁇ m or less, 7.0 ⁇ m or less, 6.0 ⁇ m or less, 5.0 ⁇ m or less, 4.5 ⁇ m or less, It may be 4.0 ⁇ m or less, 3.5 ⁇ m or less, 3.0 ⁇ m or less, 2.5 ⁇ m or less, 2.0 ⁇ m or less, 1.5 ⁇ m or less, 1.0 ⁇ m or less, or 0.6 ⁇ m or less. From these viewpoints, the particle size D95 may be 0.3 to 30 ⁇ m, 0.5 to 30 ⁇ m, or 0.5 to 5.0 ⁇ m.
• the cumulative particle size distribution for obtaining the particle size D50 and the particle size D95 can be measured by a laser diffraction/scattering method.
• the specific gravity (unit: g/cm 3 ) of the particles may be within the following range from the viewpoint of adjusting dispersibility.
• the specific gravity of the particles may be 0.1 or more, 0.5 or more, 1.0 or more, 1.5 or more, or 2.0 or more.
• the specific gravity of the particles may be 8.0 or less, 7.0 or less, 6.0 or less, 5.0 or less, 4.0 or less, 3.0 or less, or 2.5 or less. From these viewpoints, the specific gravity of the particles may be from 0.1 to 8.0, from 1.0 to 8.0, or from 1.0 to 5.0.
• the ⁇ p1 (unit: MPa 0.5 ) of the particles may be in the following range from the viewpoint of adjusting dispersibility.
• ⁇ p1 of the particles is 1.0 or more, 1.5 or more, 2.0 or more, 2.5 or more, 3.0 or more, 3.5 or more, 4.0 or more, 4.5 or more, 5.0 or more , 5.5 or more, 6.0 or more, 6.5 or more, 7.0 or more, or 7.5 or more.
• the content of the inorganic particles is determined by the total mass of the particles (particles included in the particle dispersion) from the viewpoint of easily obtaining excellent dispersibility. 50% by mass or more, more than 50% by mass, 70% by mass or more, 80% by mass or more, 90% by mass
• the content may be 92% by mass or more, 95% by mass or more, 97% by mass or more, 98% by mass or more, 99% by mass or more, or substantially 100% by mass.
• the content A1 may be in the following range based on the total mass of the particle dispersion from the viewpoint of adjusting dispersibility.
• Content A1 is 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more.
• Content A1 is 99% by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, It may be 55% by mass or less, 50% by mass or less, or 45% by mass or less. From these viewpoints, the content A1 may be 0.1 to 99% by mass, 20 to 95% by mass, or 30 to 90% by mass.
• liquid medium examples include organic solvents, water, resin materials (for example, resin materials that are liquid at 25° C.), and the like.
• Organic solvent is a general term for organic compounds that have the property of dissolving other substances, and is widely used in painting, cleaning, printing, etc.
• the organic solvent may be liquid at 25°C.
• only one of an organic solvent, water, and a resin material may be used, or at least two of an organic solvent, water, and a resin material may be used in combination.
• Each of the organic solvent and the resin material can be used alone or in combination of two or more.
• organic solvents examples include ketone compounds such as methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), acetone, cyclohexanone, acetophenone, and benzophenone; aromatic hydrocarbon compounds such as benzene, toluene, and xylene; pentane, hexane, heptane, Aliphatic hydrocarbon compounds such as octane, nonane, decane; alicyclic hydrocarbon compounds such as cyclohexane, methylcyclohexane, decahydronaphthalene; chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene Chlorinated hydrocarbon compounds such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol,
• the liquid medium may contain an organic solvent, may contain methyl isobutyl ketone, may contain a plurality of organic solvents, and may contain methyl isobutyl ketone and toluene, from the viewpoint of easily obtaining excellent dispersibility.
• the liquid medium may contain a hydrophobic organic solvent, or may contain a plurality of hydrophobic organic solvents.
• a hydrophobic organic solvent a solvent having a solubility in water of 1 g/100 mL or less at 25° C. may be used.
• the ⁇ d2 (unit: MPa 0.5 ) of the liquid medium may be within the following range from the viewpoint of adjusting dispersibility.
• the ⁇ d2 of the liquid medium is 10.0 or more, 11.0 or more, 12.0 or more, 13.0 or more, 14.0 or more, 15.0 or more, 16.0 or more, or 16.5 or more. It's fine.
• ⁇ d2 of the liquid medium is 25.0 or less, 22.0 or less, 20.0 or less, 19.5 or less, 19.0 or less, 18.5 or less, 18.0 or less, 17.5 or less, 17.0 Below, it may be 16.5 or less, 16.0 or less, or 15.5 or less. From these points of view, the ⁇ d2 of the liquid medium may be from 10.0 to 25.0, from 12.0 to 20.0, or from 15.0 to 17.0.
• ⁇ p2 (unit: MPa 0.5 ) of the liquid medium may be in the following range from the viewpoint of adjusting dispersibility.
• ⁇ p2 of the liquid medium is 1.0 or more, 1.5 or more, 2.0 or more, 2.5 or more, 3.0 or more, 3.5 or more, 4.0 or more, 4.5 or more, 5.0 It may be 5.5 or more, or 6.0 or more.
• ⁇ p2 of the liquid medium is 15.0 or less, 12.0 or less, 10.0 or less, 9.5 or less, 9.0 or less, 8.5 or less, 8.0 or less, 7.5 or less, 7.0 Below, it may be 6.5 or less, 6.0 or less, 5.5 or less, 5.0 or less, 4.5 or less, or 4.0 or less. From these points of view, the ⁇ p2 of the liquid medium may be from 1.0 to 15.0, from 2.0 to 10.0, or from 3.5 to 6.5.
• the ⁇ h2 (unit: MPa 0.5 ) of the liquid medium may be in the following range from the viewpoint of adjusting dispersibility.
• the ⁇ h2 of the liquid medium may be greater than or equal to 1.0, greater than or equal to 1.5, greater than or equal to 2.0, greater than or equal to 2.5, greater than or equal to 3.0, greater than or equal to 3.5, or greater than or equal to 4.0.
• ⁇ h2 of the liquid medium is 15.0 or less, 12.0 or less, 10.0 or less, 9.5 or less, 9.0 or less, 8.5 or less, 8.0 or less, 7.5 or less, 7.0 Below, it may be 6.5 or less, 6.0 or less, 5.5 or less, 5.0 or less, 4.5 or less, 4.0 or less, or 3.5 or less. From these points of view, the ⁇ h2 of the liquid medium may be from 1.0 to 15.0, from 2.0 to 8.0, or from 3.0 to 4.5.
• the content of the organic solvent is 20% by mass or more, 30% by mass or more, 50% by mass or more based on the total mass of the liquid medium (total amount of the liquid medium contained in the particle dispersion). mass% or more, more than 50 mass%, 70 mass% or more, 80 mass% or more, 90 mass% or more, 92 mass% or more, 95 mass% or more, 97 mass% or more, 98 mass% or more, 99 mass% or more, or , may be substantially 100% by weight.
• the content of the liquid medium is 100 parts by mass of the particles (if the particles are surface-treated: including the content of the surface treatment agent) or 100 parts by mass of the particles (if the particles are surface-treated: including the content of the surface treatment agent). (excluding the content of surface treatment agent) may be within the following range.
• the content of the liquid medium is 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, 45 parts by mass or more, 50 parts by mass.
• the amount may be 60 parts by mass or more, 80 parts by mass or more, 100 parts by mass or more, or 120 parts by mass or more.
• the content of the liquid medium is 200 parts by mass or less, 150 parts by mass or less, 120 parts by mass or less, 100 parts by mass or less, less than 100 parts by mass, 80 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 45 parts by mass.
• the amount may be 40 parts by mass or less, or 35 parts by mass or less. From these points of view, the content of the liquid medium may be 10 to 200 parts by weight, 20 to 100 parts by weight, or 30 to 60 parts by weight.
• the content of the liquid medium may be in the following range based on the total mass of the particle dispersion from the viewpoint of adjusting dispersibility.
• the content of the liquid medium is 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass.
• the content may be 45% by mass or more, or 50% by mass or more.
• the content of the liquid medium is 99.9% by mass or less, 99.5% by mass or less, 99% by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less , 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, or 25% by mass % or less. From these points of view, the content of the liquid medium may be 1 to 99.9% by weight, 5 to 80% by weight, or 10 to 70% by weight.
• Total amount of particles and liquid medium (if particles are surface treated: including content of surface treatment agent), Total amount of particles and liquid medium (if particles are surface treated: content of surface treatment agent) ), the total amount of inorganic particles and liquid medium (including the content of surface treatment agent if inorganic particles are surface treated), or the total amount of inorganic particles and liquid medium (if inorganic particles are If treated, the content of surface treatment agent is not included) is 50% by mass or more, more than 50% by mass, 70% by mass based on the total mass of the particle dispersion, from the viewpoint of adjusting dispersibility.
• the content may be 80% by mass or more, 90% by mass or more, 92% by mass or more, 95% by mass or more, 97% by mass or more, 98% by mass or more, 99% by mass or more, or substantially 100% by mass.
• the particle dispersion according to this embodiment may contain components other than the particles and the liquid medium.
• a component for example, a component that dissolves in a liquid medium can be used.
• Components other than the particles and the liquid medium include resin materials that are not liquid at 25°C.
• the viscosity V1 (unit: mPa ⁇ s) of the particle dispersion at 25° C. and a shear rate of 1 min ⁇ 1 may be in the following range. From the viewpoint of suppressing particle sedimentation and easily obtaining excellent dispersibility, the viscosity V1 is 100 or more, 150 or more, 200 or more, 250 or more, 300 or more, 350 or more, 400 or more, 450 or more, 500 or more, 550 or more, It may be 600 or more, 650 or more, 700 or more, or 750 or more.
• the viscosity V1 is 5000 or less, 4000 or less, 3000 or less, 2000 or less, 1500 or less, 1000 or less, 950 or less, 900 or less, 850 or less, 800 or less, It may be 750 or less, 700 or less, 650 or less, 600 or less, 550 or less, 500 or less, 450 or less, 400 or less, 350 or less, 300 or less, or 250 or less. From these viewpoints, the viscosity V1 may be 100-5000, 150-2000, or 200-800.
• the viscosity V10 (unit: mPa ⁇ s) of the particle dispersion at 25° C. and a shear rate of 10 min ⁇ 1 may be in the following range. From the viewpoint of suppressing particle sedimentation and easily obtaining excellent dispersibility, the viscosity V10 is 10 or more, 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, 100 or more, It may be 110 or more, 120 or more, or 130 or more.
• the viscosity V10 is 1000 or less, 900 or less, 800 or less, 700 or less, 600 or less, 500 or less, 400 or less, 300 or less, 250 or less, 200 or less, It may be 150 or less, 140 or less, 130 or less, 120 or less, 110 or less, 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, or 30 or less. From these viewpoints, the viscosity V10 may be 10-1000, 15-500, or 20-150.
• Silica particles A manufactured by Admatex Co., Ltd., product name "SO-32R”, particles produced by melting method, specific gravity 2.2 g/cm 3
• Silica particles B1 manufactured by Nippon Shokubai Co., Ltd., product name “KE-S50”, particles produced by sol-gel method, specific gravity 2.2 g/cm 3
• Silica particles B2 manufactured by Nippon Shokubai Co., Ltd., product name "KE-S150”, particles produced by sol-gel method, specific gravity 2.2 g/cm 3 Silica particles B3: manufactured by Nippon Shokubai Co., Ltd., product name "KE-S250”, particles produced by sol-gel method, specific gravity 2.2 g/cm 3
• Silane coupling agent N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-573"
• MIBK Methyl isobutyl ketone
• the beaker containing this mixed solution was placed in a water bath at 60°C, and wet treatment was performed for 1 hour at a rotation speed of 150 min -1 using a 3-1 motor with 2 stirring blades (made of Teflon) to solidify it.
• a mixed solution having a quantity of 70% by mass was obtained.
• dispersion treatment by cavitation (nanomizer treatment conditions : Pass through the nozzle three times; Filmix processing conditions: 40 m/s, 1 minute) to prepare a particle dispersion (silica slurry) with a solid content of 70% by mass.
• Examples 2, 3, 7 A particle dispersion (silica slurry) having a solid content of 70% by mass was prepared in the same manner as in Example 1, except that the volume ratio of MIBK and toluene in the liquid medium was changed to the ratio shown in Table 1.
• this mixed solution was stirred (processing conditions: 2000 min -1 for 1 minute) using a product named "Awatori Rentaro ARE-310" manufactured by THINKY Co., Ltd. to eliminate aggregates of silica particles. did.
• dispersion treatment by cavitation (nanomizer treatment conditions : Pass through the nozzle three times; Filmix processing conditions: 40 m/s, 1 minute) to prepare a particle dispersion (silica slurry) with a solid content of 70% by mass.
• Example 5 A particle dispersion (silica slurry) having a solid content of 70% by mass was prepared in the same manner as in Example 4, except that the amount of the silane coupling agent used was changed to 0.5 parts by mass.
• Examples 6, 10 and Comparative Example 5 100 parts by mass of silica particles B3, 0.5 parts by mass of silane coupling agent, 3.5 x 10 -2 parts by mass of pure water, and 33.3 parts by mass of liquid medium (mixing ratio of MIBK and toluene: (see Table 1) in a beaker to obtain a mixed solution.
• the beaker containing this mixed solution was placed in a water bath at 60°C, and wet treatment was performed for 1 hour at a rotation speed of 150 min -1 using a 3-1 motor with 2 stirring blades (made of Teflon) to solidify it.
• a mixed liquid having a quantity of 75% by mass was obtained.
• dispersion treatment by cavitation (nanomizer treatment conditions : Pass through the nozzle three times; Filmix processing conditions: 40 m/s, 1 minute) to prepare a particle dispersion (silica slurry) with a solid content of 75% by mass.
• Example 8 and Comparative Examples 1 to 3 100 parts by mass of silica particles B1, 0.5 parts by mass of silane coupling agent, 3.5 x 10 -2 parts by mass of pure water, and 122 parts by mass of liquid medium (mixing ratio of MIBK and toluene: Table 1
• a mixed solution was obtained by mixing (see) in a beaker.
• the beaker containing this mixed solution was placed in a water bath at 60°C, and wet treatment was performed for 1 hour at a rotation speed of 150 min -1 using a 3-1 motor with 2 stirring blades (made of Teflon) to solidify it.
• a mixed solution having a quantity of 45% by mass was obtained.
• dispersion treatment by cavitation (nanomizer treatment conditions : Pass through the nozzle three times; Filmix processing conditions: 40 m/s, 1 minute) to prepare a particle dispersion (silica slurry) with a solid content of 45% by mass.
• Examples 9, 11, 14 and Comparative Example 4 100 parts by mass of silica particles B2, 0.5 parts by mass of silane coupling agent, 3.5 x 10 -2 parts by mass of pure water, and 42.8 parts by mass of liquid medium (mixing ratio of MIBK and toluene: (See Table 1) were mixed in a beaker to obtain a mixed solution. Next, the beaker containing this mixed solution was placed in a water bath at 60°C, and wet treatment was performed for 1 hour at a rotation speed of 150 min -1 using a 3-1 motor with 2 stirring blades (made of Teflon) to solidify it. A mixed solution having a quantity of 70% by mass was obtained.
• dispersion treatment by cavitation (nanomizer treatment conditions : passed through the nozzle three times, processed three times; Filmix processing conditions: 40 m/s, 1 minute) to prepare a particle dispersion (silica slurry) with a solid content of 70% by mass.
• Example 12 A particle dispersion (silica slurry) having a solid content of 70% by mass was prepared in the same manner as in Example 4 except that only MIBK was used as the liquid medium.
• Example 13 A particle dispersion (silica slurry) having a solid content of 70% by mass was prepared in the same manner as in Example 5 except that only MIBK was used as the liquid medium.
• Powdered particles were recovered by drying the above particle dispersion (silica slurry) at 130° C. for 1 hour. Based on real image observation using a scanning electron microscope (SEM), the particle size D50 (hereinafter referred to as "particle size A”) and particle size D100 of the particles were obtained.
• the 16 organic solvents include MIBK (methyl isobutyl ketone), toluene, methanol, cyclohexanol, acetone, acetonitrile, formamide, benzyl benzoate, dimethyl sulfoxide, ethyl acetate, ethanol, acetic anhydride, ⁇ -butyrolactone, and MEK (methyl ethyl ketone). ), 1-butanol, and cyclohexane were used.
• the above test liquid was subjected to a dispersion treatment for 5 minutes using an ultrasonic dispersion device (manufactured by AS ONE Co., Ltd., trade name "VS-D100”).
• the particle size distribution (cumulative particle size distribution, volume distribution) of the particles in the test liquid was measured using a particle size distribution meter (manufactured by Shimadzu Corporation, trade name "SALD-7500").
• SALD-7500 particle size distribution meter
• particle size B particle size D50
• the coefficient of variation (CV) of the particle size was obtained for each of the 16 types of organic solvents described above.
• the above-mentioned 16 types of organic solvents were judged to be either "a solvent with poor dispersibility" or "a solvent with excellent dispersibility” based on the following criteria.
• a particle size twice the particle size A mentioned above (assuming the particle size when two particles come into contact) is adopted as the threshold value, and if the particle size B mentioned above is equal to or larger than the threshold value, An organic solvent in a certain case was determined to be a "solvent with poor dispersibility", and an organic solvent in which the above-mentioned particle size B was less than the threshold value was determined to be a "solvent with excellent dispersibility".
• the criteria for agglomeration in a polydisperse state since the particle size distribution is wide, it is desirable to establish a standard that can easily target aggregated particles, so the above-mentioned particle size D100 is adopted as the threshold value, and the above-mentioned particle size was determined to be a "solvent with poor dispersibility", and an organic solvent in which the above-mentioned particle size B was less than the threshold value was determined to be a "solvent with excellent dispersibility".
• ⁇ HSP value of liquid medium > The ⁇ d , ⁇ p and ⁇ h of MIBK and toluene used as liquid media were analyzed using the analysis software HSPiP (Hansen Solubility Parameter in Practice; written by Prof. Steven Abbott and Dr. Yamamoto). The numerical values from the database of Hiroshi) were used. ⁇ d2 , ⁇ p2 and ⁇ h2 of the liquid medium, which is a mixture of MIBK and toluene, were calculated using the sum of the products of the parameters of each solvent ( ⁇ d , ⁇ p or ⁇ h ) and the volume proportion of each solvent. .
• Table 1 shows ⁇ d2 , ⁇ p2 and ⁇ h2 of the liquid medium in Examples and Comparative Examples. Since the amount of the above-mentioned pure water mixed with the silane coupling agent was small, the influence of the pure water was not considered.
• HSP distance ⁇ 4 ⁇ ( ⁇ d1 - ⁇ d2 ) 2 + ( ⁇ p1 - ⁇ p2 ) 2 + ( ⁇ h1 - ⁇ h2 ) 2 ⁇ 0.5
• the above particle size distribution was measured by the following procedure.
• the particle size distribution of standard particles (MBP1-10) with a defined particle size distribution was measured in advance to confirm that the measurement contents were appropriate.
• Approximately 0.5 mL of the above test liquid (solid content: 3% by mass) was dropped onto a glass substrate for measurement, and then covered with a slide glass to prevent air bubbles from entering to obtain a test specimen.
• the coefficient of variation is 55 (polydisperse), and in the particle dispersion obtained using silica particles B1, the coefficient of variation is 12 (monodisperse),
• the particle dispersion obtained using silica particles B2 had a coefficient of variation of 17 (monodisperse), and the particle dispersion obtained using silica particles B3 had a coefficient of variation of 18 (monodisperse).
• a particle size twice the particle size D50 (assuming the particle size when two particles come into contact) is adopted as the threshold value, and the volume fraction of particles with a particle size larger than the threshold value is calculated. was calculated.
• the criteria for agglomeration in a polydisperse state since the particle size distribution is wide, it is desirable to establish a standard that can easily target agglomerated particles, so the particle size D100 is adopted as a threshold value, and the particle size The volume fraction of particles was calculated. In the particle dispersion obtained using silica particles A, the particle size D100 was 5 ⁇ m. Table 2 shows the volume fraction of particles having a particle size equal to or larger than the threshold value. As shown in Table 2, the volume fraction (immediately after preparation) was 7.0% or less in each Example.
• the above particle dispersion was allowed to stand for 7 days, then manually shaken and stirred 20 times for 10 seconds, and further diluted with the liquid medium of each example to obtain a solid content of 3 mass. % test solution was obtained.
• the particle size distribution (cumulative particle size distribution, volume distribution) of the particles was measured using the same procedure as the evaluation method described above. Table 2 shows the volume fraction of particles having a particle size equal to or larger than the threshold value as described above.
• Example 1 The above-mentioned particle dispersions immediately after preparation of Examples 1 to 5 were allowed to stand for 30 days, then manually shaken and stirred for 10 seconds 20 times, and further diluted with the liquid medium of each Example to determine the solid content. A 3% by mass test solution was obtained. Next, the particle size distribution (cumulative particle size distribution, volume distribution) of the particles was measured using the same procedure as the evaluation method described above. Table 2 shows the volume fraction of particles having a particle size equal to or larger than the threshold value as described above.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)
• Colloid Chemistry (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=89382970

Family Applications (1)

Country Status (7)

Citations (9)

Family Cites Families (2)

• 2023
  • 2023-06-23 KR KR1020257001440A patent/KR20250033226A/ko active Pending
  • 2023-06-23 US US18/878,601 patent/US20250382468A1/en active Pending
  • 2023-06-23 JP JP2024530777A patent/JPWO2024004866A1/ja active Pending
  • 2023-06-23 EP EP23831308.4A patent/EP4527901A4/en active Pending
  • 2023-06-23 CN CN202380044766.7A patent/CN119317676A/zh active Pending
  • 2023-06-23 WO PCT/JP2023/023365 patent/WO2024004866A1/ja not_active Ceased
  • 2023-06-27 TW TW112123773A patent/TW202411395A/zh unknown

Patent Citations (9)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events