WO2024071033A1 - Sol de solvant organique de particules de silice creuses contenant une amine, et sa méthode de production - Google Patents

Sol de solvant organique de particules de silice creuses contenant une amine, et sa méthode de production Download PDF

Info

Publication number
WO2024071033A1
WO2024071033A1 PCT/JP2023/034712 JP2023034712W WO2024071033A1 WO 2024071033 A1 WO2024071033 A1 WO 2024071033A1 JP 2023034712 W JP2023034712 W JP 2023034712W WO 2024071033 A1 WO2024071033 A1 WO 2024071033A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
hollow silica
sol
silica particles
amine
Prior art date
Application number
PCT/JP2023/034712
Other languages
English (en)
Japanese (ja)
Inventor
透 西村
修平 山田
将大 飛田
Original Assignee
日産化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日産化学株式会社 filed Critical 日産化学株式会社
Publication of WO2024071033A1 publication Critical patent/WO2024071033A1/fr

Links

Classifications

    • 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
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • 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
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only

Definitions

  • the present invention relates to a sol containing an amine and having hollow silica particles dispersed in an organic solvent, a method for producing the sol, and a film-forming composition containing the sol.
  • Hollow silica particles have a silica outer shell and a space inside the shell, and due to their characteristics, they have properties such as a low refractive index, low thermal conductivity (thermal insulation), and electrical insulation.
  • Hollow silica particles consist of a core which corresponds to the hollow portion and a shell which forms the outside of the core.
  • An aqueous dispersion of hollow silica particles can be obtained by forming a silica layer on the outside of the core in an aqueous medium and then removing the core.
  • a composition for forming a transparent coating film containing hollow silica particles having a surface charge amount of 5 to 20 ⁇ eq/g-SiO 2 and a binder component has been disclosed (see Patent Document 1).
  • hollow silica particles whose surfaces are coated with a silane compound and whose thermal weight loss at 200° C. to 500° C. is 1% by mass or more have been disclosed (see Patent Document 2).
  • the present invention provides an organic solvent sol of hollow silica particles that contain an amine in the sol and have a space inside the outer shell, a method for producing the sol, and a coating-forming composition that contains the sol.
  • the present invention provides an organic solvent sol of hollow silica particles containing an amine in the sol and having a space inside an outer shell;
  • the sol according to the first aspect in which the amine is at least one amine selected from the group consisting of primary amines, secondary amines, and tertiary amines having 1 to 10 carbon atoms;
  • the sol according to the first or second aspect wherein the amine is a water-soluble amine having a water solubility of 80 g/L or more.
  • the sol according to any one of the first to third aspects in which the content of the amine is 0.001 to 10 mass% relative to the SiO2 of the hollow silica particles;
  • the sol according to any one of the first to fourth aspects in which the hollow silica particles have an average particle size of 20 to 150 nm as measured by a dynamic light scattering method.
  • the sol according to any one of the first to fifth aspects in which the hollow silica particles have a surface charge amount calculated per gram of SiO2 of 5 to 250 ⁇ eq/g;
  • the sol according to any one of the first to sixth aspects in which the organic solvent is an alcohol, a ketone, an ether, or an ester having 1 to 10 carbon atoms;
  • the hollow silica particles may further be represented by formula (1), formula (2), or formula (3): (In formula (1), R 1 represents an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and is bonded to a silicon atom via a Si-C bond; R 2 represents an alkoxy group, an acyloxy group, or a
  • the sol according to any one of the first to seventh aspects which is coated with at least one silane compound selected from the group consisting of silane compounds represented by the following formula:
  • a coating-forming composition comprising the sol according to any one of the first to eighth aspects and an organic resin;
  • a film obtained from the film-forming composition according to the ninth aspect the film having a visible light transmittance of 80% or more.
  • the present invention relates to the following steps (A) to (C): Step (A): preparing a hollow silica aqueous sol; Step (B): adding at least one amine selected from the group consisting of primary amines, secondary amines, and tertiary amines having a water solubility of 80 g/L or more and having 1 to 10 carbon atoms to the hollow silica aqueous sol of step (A) in an amount of 0.001 to 10% by mass based on the SiO2 of the hollow silica particles; A process (C) for replacing the aqueous medium of the aqueous sol of hollow silica particles obtained in the process (B) with an alcohol, a ketone, an ether, or an ester having 1 to 10 carbon atoms; As a twelfth aspect, a method for producing a sol according to the eleventh aspect, the method including, after completion of the step (C), a step (D) of further adding at least one si
  • the present invention relates to an organic solvent sol of hollow silica particles containing amines in the sol and having a space inside the outer shell. It is known that hollow silica particles dispersed in an organic solvent have a charge on the surface.
  • the organic solvent sol of hollow silica particles itself, or the amount of surface charge of the hollow silica particles when the organic solvent sol of hollow silica particles is mixed with an organic resin binder, can greatly affect the stability and dispersibility. For example, when hollow silica particles are dispersed in a highly polar solvent or resin binder, stable dispersibility can be obtained if the amount of surface charge of the hollow silica particles is within a specific range.
  • the reason for the need to obtain stable dispersibility is that when a coating is formed, it is advantageous for the hollow silica particles to be uniformly present in the cured coating and not localized in order to exert their function. This is because the hollow silica particles are delocalized in the cured coating, so that the entire film has the same effect. When the effect is an optical anti-reflection function, it is preferable in that the entire film maintains uniform performance.
  • the surface charge amount of hollow silica particles in a dispersion medium is due to the silanol groups on the surface of the silica particles, but it has been found that the surface charge amount can be adjusted to any specific range by adding an amine.
  • the present invention relates to an organic solvent sol of hollow silica particles containing an amine in the sol and having spaces inside the outer shell, a method for producing the organic solvent sol, and a coating-forming composition using the organic solvent sol.
  • the present invention is an organic solvent sol of hollow silica particles that contain an amine in the sol and have a space inside the outer shell (hereinafter, also referred to as hollow silica organic solvent sol).
  • Hollow silica particles have a silica shell and a space inside the shell. Hollow silica particles are obtained by forming a shell mainly composed of silica on the surface of the part corresponding to the core, which is called the template in a dispersion medium, and removing the part corresponding to the core.
  • the aqueous hollow silica sol (hollow silica aqueous sol) obtained in this way can be solvent-substituted with an alcohol solvent, which is an organic solvent, after adding an amine.
  • the above-mentioned alcohol solvent is preferably an alcohol having 1 to 5 carbon atoms that may have an ether bond, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.
  • the hollow silica particles can be coated with a silane compound, and the solvent can then be further solvent-substituted with another organic solvent.
  • organic solvents examples include alcohols, ketones, ethers, and esters having 1 to 10 carbon atoms.
  • the alcohol having 1 to 10 carbon atoms is an aliphatic alcohol, and examples of such alcohol include primary alcohols, secondary alcohols, and tertiary alcohols. Furthermore, it is also possible to use polyhydric alcohols, such as dihydric alcohols and trihydric alcohols.
  • Examples of the monohydric primary alcohol include methanol, ethanol, 1-propanol, 1-butanol, and 1-hexanol.
  • Examples of the monohydric secondary alcohol include 2-propanol, 2-butanol, cyclohexanol, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.
  • An example of the monohydric tertiary alcohol is tert-butyl alcohol.
  • Examples of the dihydric alcohol include methanediol, ethylene glycol, and propylene glycol.
  • An example of the trihydric alcohol is glycerin.
  • an aliphatic ketone can be preferably used as the ketone having 1 to 10 carbon atoms.
  • examples include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, methyl cyclopentanone, etc.
  • an aliphatic ether can be preferably used as the ether having 1 to 10 carbon atoms.
  • examples include dimethyl ether, ethyl methyl ether, diethyl ether, tetrahydrofuran, 1,4-dioxane, etc.
  • an aliphatic ester can be preferably used as the ester having 1 to 10 carbon atoms.
  • Examples include methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl acrylate, ethyl acrylate, propyl acrylate, dimethyl maleate, diethyl maleate, dipropyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, etc.
  • the hollow silica particles can have an average particle size measured by dynamic light scattering (DLS) in the range of 20 to 150 nm, or 30 to 150 nm, or 40 to 150 nm, or 50 to 150 nm, or 60 to 150 nm, or 60 to 120 nm.
  • the concentration of SiO2 particles can be 1 to 50 mass% or 5 to 40 mass%, typically 10 to 30 mass%.
  • the sol has an alkaline pH, for example, 7.5 to 12 or 7.5 to 11, but can typically be used in the range of 7.5 to 10.
  • the above pH is the pH when the organic solvent sol and the same mass of pure water are mixed at a ratio of 1:1. It is possible to measure the pH when an organic solvent that can be mixed with water is used as the organic solvent, but when the solvent is subsequently replaced with a hydrophobic organic solvent, it is preferable to measure the pH in advance at the stage of the methanol solvent sol.
  • the pH can be measured using a solution in which pure water and the sol are mixed in a mass ratio of 1: 1.
  • the pH can be measured using a solution in which pure water, methanol, and methyl ethyl ketone sol are mixed in a mass ratio of 1: 1: 1.
  • Hollow silica organic solvent sol can be obtained by replacing the aqueous medium of the aqueous sol with an alcohol solvent having 1 to 5 carbon atoms, and if desired, further replacing the solvent with an organic solvent, and moisture may remain in the solvent during this process.
  • the sol may contain, for example, 0.1 to 3.0% by mass of residual moisture.
  • the sol may contain 0.01 to 0.5% by mass of residual moisture.
  • the viscosity of hollow silica organic solvent sol can be set in the range of 1.0 to 10.0 mPa ⁇ s.
  • An amine can be added to the hollow silica organic solvent sol of the present invention.
  • the amine used in the present invention may be a water-soluble amine having a water solubility of 80 g/L or more, or 100 g/L or more.
  • the raw material hollow silica aqueous sol and the hollow silica organic solvent sol obtained by solvent replacement may contain amine, or amine and ammonia.
  • the amine may be added and contained in the range of 0.001 to 10 mass%, or 0.01 to 10 mass%, or 0.1 to 10 mass% relative to the SiO 2 of the hollow silica particles.
  • the base component which is the amine or the amine and ammonia, may be expressed as the total nitrogen amount in the hollow silica particle organic solvent sol, and may be contained in the range of, for example, 10 to 100,000 ppm, or 100 to 10,000 ppm, or 100 to 3,000 ppm, or 100 to 2,000 ppm, typically 200 to 2,000 ppm.
  • the above amines include aliphatic amines and aromatic amines, with aliphatic amines being preferred. At least one amine selected from the group consisting of primary amines, secondary amines, and tertiary amines having 1 to 10 carbon atoms can be used as the amine.
  • the amines are water-soluble and at least one amine selected from the group consisting of primary amines, secondary amines, and tertiary amines having 1 to 10 carbon atoms.
  • primary amines include monomethylamine, monoethylamine, monopropylamine, monoisopropylamine, monobutylamine, monoisobutylamine, monosec-butylamine, mono-tert-butylamine, monomethanolamine, monoethanolamine, monopropanolamine, monoisopropanolamine, monobutanolamine, monoisobutanolamine, monosec-butanolamine, mono-tert-butanolamine, etc.
  • Secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, N-methylethylamine, N-ethylisobutylamine, dimethanolamine, diethanolamine, dipropanolamine, diisopropanolamine, N-methanolethylamine, N-methylethanolamine, N-ethanolisobutylamine, and N-ethylisobutanolamine.
  • Tertiary amines include trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, trisec-butylamine, tritert-butylamine, trimethanolamine, triethanolamine, tripropanolamine, triisopropanolamine, tributanolamine, triisobutanolamine, trisec-butanolamine, tritert-butanolamine, etc.
  • amines having a water solubility of 80 g/L or more, or 100 g/L or more can be preferably used.
  • primary amines and secondary amines are preferred, and secondary amines are preferably used due to their low volatility and high solubility, such as diisopropylamine and diethanolamine.
  • the surface charge amount of the hollow silica particles converted to 1 g of SiO 2 can be set to 5 ⁇ eq/g or more, or 25 ⁇ eq/g or more. Typically, it can be set in the range of 5 to 250 ⁇ eq/g, or 25 to 250 ⁇ eq/g, or 25 to 100 ⁇ eq/g, or 25 to 80 ⁇ eq/g, or 25 to 50 ⁇ eq/g.
  • the surface charge amount of the hollow silica particles can be adjusted to any desired value by adjusting the type and amount of the amine added.
  • the surfaces of the hollow silica particles can be coated with a silane compound.
  • a silane compound a hydrolysate of at least one silane compound selected from the group consisting of silane compounds represented by formulas (1) to (3) can be used.
  • R 1 represents an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having a polyether group, an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and is bonded to a silicon atom via a Si-C bond
  • R 2 represents an alkoxy group, an acyloxy group, or a halogen group
  • a represents an integer of 1 to 3
  • R3 and R5 each represent an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and are bonded to a silicon atom via a Si-C bond
  • R4 and R6 each represent an alkoxy group, an acyloxy group, or a halogen group
  • Y represents an alkylene group, an NH group, or an oxygen atom
  • the alkyl group may be an alkyl group having 1 to 18 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, a cyclopentyl group,
  • Alkylene groups include those derived from the alkyl groups mentioned above.
  • the above aryl group includes aryl groups having 6 to 30 carbon atoms, such as, but not limited to, a phenyl group, a naphthyl group, an anthracene group, and a pyrene group.
  • the alkenyl group may be an alkenyl group having 2 to 10 carbon atoms, such as an ethenyl group, a 1-propenyl group, a 2-propenyl group, a 1-methyl-1-ethenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 2-methyl-1-propenyl group, a 2-methyl-2-propenyl group, a 1-ethylethenyl group, a 1-methyl-1-propenyl group, a 1-methyl-2-propenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-n-propylethenyl group, a 1-methyl-1-butenyl group, a 1-methyl-2-butenyl group, a 1-methyl-3-butenyl group, a 2-ethyl-2-propenyl group, a
  • alkoxy groups include alkoxy groups having 1 to 10 carbon atoms, such as, but not limited to, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentyloxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, and n-hexyloxy.
  • the above acyloxy group includes acyloxy groups having 2 to 10 carbon atoms, such as, but not limited to, methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, i-propylcarbonyloxy group, n-butylcarbonyloxy group, i-butylcarbonyloxy group, s-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, 1-methyl-n-butylcarbonyloxy group, 2-methyl-n-butylcarbonyloxy group, 3-methyl-n-butylcarbonyloxy group, 1,1-dimethyl-n-propylcarbonyloxy group, 1,2-dimethyl-n-propylcarbonyloxy group, 2,2-dimethyl-n-propylcarbonyloxy group, 1-ethyl-n-propylcarbonyloxy group, n-hexylcarbony
  • halogen groups include fluorine, chlorine, bromine, iodine, etc.
  • An example of an organic group having a polyether group is a polyetherpropyl group having an alkoxy group, such as (CH 3 O) 3 SiC 3 H 6 (OC 2 H 4 ) n OCH 3.
  • n can be in the range of 1 to 100 or 1 to 10.
  • organic groups having an epoxy group examples include the 2-(3,4-epoxycyclohexyl)ethyl group and the 3-glycidoxypropyl group.
  • the above (meth)acryloyl group refers to both acryloyl and methacryloyl groups.
  • organic groups having a (meth)acryloyl group include a 3-methacryloxypropyl group and a 3-acryloxypropyl group.
  • An example of an organic group having a mercapto group is the 3-mercaptopropyl group.
  • organic groups having an amino group examples include a 2-aminoethyl group, a 3-aminopropyl group, an N-2-(aminoethyl)-3-aminopropyl group, an N-(1,3-dimethyl-butylidene)aminopropyl group, an N-phenyl-3-aminopropyl group, and an N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl group.
  • An example of an organic group having a ureido group is the 3-ureidopropyl group.
  • An example of an organic group having a cyano group is the 3-cyanopropyl group.
  • the silane compounds represented by the above formulas (2) and (3) are preferably compounds capable of forming trimethylsilyl groups on the surface of silica particles. Examples of such compounds include the following.
  • R 12 represents an alkoxy group, for example, a methoxy group or an ethoxy group.
  • a silane compound manufactured by Shin-Etsu Chemical Co., Ltd. can be used.
  • the hydroxyl groups on the surface of the silica particles for example the silanol groups in the case of silica particles, react with the above-mentioned silane compound, and the surface of the silica particles can be coated with the above-mentioned silane compound through siloxane bonds.
  • the reaction can be carried out at temperatures ranging from 20°C to the boiling point of the dispersion medium, for example, at temperatures ranging from 20°C to 100°C.
  • the reaction can be carried out for about 0.1 to 6 hours.
  • the surfaces of the hollow silica particles can be coated by adding a silane compound to the silica sol in an amount corresponding to a coating amount of 0.1 silicon atoms/nm 2 to 6.0 silicon atoms/nm 2 on the silica particle surfaces.
  • Water is necessary for the hydrolysis of the silane compound, and if the sol is an aqueous solvent, the aqueous solvent is used.
  • the aqueous medium is replaced with an organic solvent, the water remaining in the solvent can also be used.
  • water present in the organic solvent at 0.01 to 1% by mass can be used.
  • the hydrolysis can be performed with or without a catalyst.
  • the reaction is carried out without a catalyst, the surface of the silica particles is on the acidic side.
  • examples of the hydrolysis catalyst include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.
  • Examples of the metal chelate compounds as the hydrolysis catalyst include triethoxy mono(acetylacetonato)titanium and triethoxy mono(acetylacetonato)zirconium.
  • Examples of the organic acids as the hydrolysis catalyst include acetic acid and oxalic acid.
  • Examples of the inorganic acids as the hydrolysis catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.
  • Examples of the organic bases as the hydrolysis catalyst include pyridine, pyrrole, piperazine, and quaternary ammonium salts.
  • Examples of the inorganic bases as the hydrolysis catalyst include ammonia, sodium hydroxide, and potassium hydroxide.
  • the organic acid may be at least one organic acid selected from the group consisting of divalent aliphatic carboxylic acids, aliphatic oxycarboxylic acids, amino acids, and chelating agents.
  • Divalent aliphatic carboxylic acids include oxalic acid, malonic acid, and succinic acid.
  • Aliphatic oxycarboxylic acids include glycolic acid, lactic acid, malic acid, tartaric acid, and citric acid.
  • Amino acids include glycine, alanine, valine, leucine, serine, and threonine.
  • Chelating agents include ethylenediaminetetraacetic acid, L-aspartic acid-N,N-diacetic acid, and diethylenetriaminepentaacetic acid.
  • Organic acid salts include alkali metal salts, ammonium salts, and amine salts of the above organic acids.
  • Alkali metals include sodium and potassium.
  • a film-forming composition that contains the hollow silica organic solvent sol and an organic resin.
  • a film-forming composition is obtained by selecting and mixing a thermosetting or photocurable resin as the organic resin.
  • a cured product can be obtained by adding a curing agent such as an amine-based curing agent, an acid anhydride-based curing agent, a radical generator-based curing agent (thermal radical generator, photoradical generator), or an acid generator-based curing agent (thermal acid generator, photoacid generator).
  • a curing agent such as an amine-based curing agent, an acid anhydride-based curing agent, a radical generator-based curing agent (thermal radical generator, photoradical generator), or an acid generator-based curing agent (thermal acid generator, photoacid generator).
  • the film-forming composition of the present invention contains an organic resin and a curing agent, and the film-forming composition can be applied to or filled into a substrate and then heated, irradiated with light, or a combination thereof to form a cured product.
  • organic resins include resins having functional groups such as epoxy groups or (meth)acryloyl groups, and isocyanate-based resins.
  • photocurable polyfunctional acrylates can be preferably used.
  • polyfunctional acrylate examples include polyfunctional acrylates having difunctional, trifunctional, tetrafunctional or higher functional groups in the molecule, such as neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. These polyfunctional acrylates may also be described below.
  • the film-forming composition of the present invention may contain a surfactant (leveling agent).
  • the surfactant (leveling agent) may be an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or a silicone surfactant.
  • the surfactant (leveling agent) may be added in an amount of 0.01 to 5 phr or 0.01 to 1 phr relative to the organic resin.
  • Anionic surfactants that can be used in the present invention include sodium and potassium salts of fatty acids, alkylbenzene sulfonates, higher alcohol sulfates, polyoxyethylene alkyl ether sulfates, ⁇ -sulfofatty acid esters, ⁇ -olefin sulfonates, monoalkyl phosphates, and alkanesulfonates.
  • alkylbenzenesulfonates include sodium salts, potassium salts and lithium salts, such as sodium C10-C16 alkylbenzenesulfonate, C10-C16 alkylbenzenesulfonic acid, and sodium alkylnaphthalenesulfonate.
  • higher alcohol sulfate ester salts include sodium dodecyl sulfate (sodium lauryl sulfate) with 12 carbon atoms, triethanolamine lauryl sulfate, and triethanolammonium lauryl sulfate.
  • polyoxyethylene alkyl ether sulfates examples include sodium polyoxyethylene styrenated phenyl ether sulfate, ammonium polyoxyethylene styrenated phenyl ether sulfate, sodium polyoxyethylene decyl ether sulfate, ammonium polyoxyethylene decyl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene tridecyl ether sulfate, and sodium polyoxyethylene oleyl cetyl ether sulfate.
  • ⁇ -olefin sulfonates examples include sodium ⁇ -olefin sulfonate.
  • alkane sulfonates examples include sodium 2-ethylhexyl sulfate.
  • Cationic surfactants that can be used in the present invention include, for example, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, and amine salt agents.
  • Alkyltrimethylammonium salts are quaternary ammonium salts that have chloride or bromide ions as counterions. Examples include dodecyltrimethylammonium chloride, cetyltrimethylammonium chloride, coconut alkyltrimethylammonium chloride, and alkyl (C16-18) trimethylammonium chloride.
  • Dialkyldimethylammonium salts have two lipophilic main chains and two methyl groups. Examples include bis(hydrogenated tallow)dimethylammonium chloride, such as didecyldimethylammonium chloride, dicoconucleic acid alkyldimethylammonium chloride, dihydrogenated tallow alkyldimethylammonium chloride, and dialkyl(C14-18)dimethylammonium chloride.
  • bis(hydrogenated tallow)dimethylammonium chloride such as didecyldimethylammonium chloride, dicoconucleic acid alkyldimethylammonium chloride, dihydrogenated tallow alkyldimethylammonium chloride, and dialkyl(C14-18)dimethylammonium chloride.
  • Alkyl dimethyl benzyl ammonium salts are quaternary ammonium salts that have one lipophilic main chain, two methyl groups, and one benzyl group, and examples of these include benzauconium chloride, such as alkyl (C8-18) dimethyl benzyl ammonium chloride.
  • Amine salt agents include those in which the hydrogen atom of ammonia is replaced with one or more hydrocarbon groups, such as N-methylbishydroxyethylamine fatty acid ester hydrochloride.
  • amphoteric surfactants used in the present invention include N-alkyl- ⁇ -alanine type alkylamino fatty acid salts, alkylcarboxybetaine type alkylbetaines, and N,N-dimethyldodecylamine oxide type alkylamine oxides. Examples of these include lauryl betaine, stearyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, and lauryl dimethylamine oxide.
  • the nonionic surfactant used in the present invention is selected from polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, alkyl glucosides, polyoxyethylene fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and fatty acid alkanolamides.
  • examples of polyoxyethylene alkyl ethers include polyoxyethylene dodecyl ether (polyoxyethylene lauryl ether), polyoxyalkylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyalkylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene behenyl ether, polyoxyethylene-2-ethylhexyl ether, and polyoxyethylene isodecyl ether.
  • polyoxyethylene dodecyl ether polyoxyethylene lauryl ether
  • polyoxyalkylene lauryl ether polyoxyethylene tridecyl ether
  • polyoxyalkylene tridecyl ether polyoxyethylene myristyl ether
  • polyoxyethylene cetyl ether polyoxyethylene oleyl ether
  • polyoxyethylene stearyl ether polyoxyethylene behenyl ether
  • polyoxyethylene alkylphenol ethers examples include polyoxyethylene styrenated phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene distyrenated phenyl ether, and polyoxyethylene tribenzyl phenyl ether.
  • alkyl glucosides examples include decyl glucoside and lauryl glucoside.
  • polyoxyethylene fatty acid esters examples include polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, polyethylene glycol distearate, polyethylene glycol dioleate, and polypropylene glycol dioleate.
  • Sorbitan fatty acid esters include sorbitan monocaprylate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan monosesquioleate, and ethylene oxide adducts thereof.
  • polyoxyethylene sorbitan fatty acid esters examples include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan triisostearate.
  • Fatty acid alkanolamides include coconut oil fatty acid diethanolamide, beef tallow fatty acid diethanolamide, lauric acid diethanolamide, and oleic acid diethanolamide.
  • polyoxyalkyl ethers or polyoxyalkyl glycols such as polyoxyethylene polyoxypropylene glycol, polyoxyethylene fatty acid esters, polyoxyethylene hydrogenated castor oil ether, sorbitan fatty acid ester alkyl ethers, alkyl polyglucosides, sorbitan monooleate, and sucrose fatty acid esters.
  • the silicone surfactant used in the present invention is a compound having a repeating unit containing a siloxane bond in the main chain.
  • Silicone surfactants having a weight average molecular weight in the range of 500 to 50,000 can be used. These may be modified silicone surfactants, and examples of such surfactants include those having an organic group introduced into the side chain and/or end of a polysiloxane. Examples of organic groups include amino groups, epoxy groups, alicyclic epoxy groups, carbinol groups, mercapto groups, carboxyl groups, aliphatic ester groups, aliphatic amide groups, and polyether groups.
  • silicone surfactants include the following product names: Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), Silwet l-77, L-7280, L-7001, L-7002, L-7200.
  • the product name L-7001 (manufactured by Dowsil Corporation) can be suitably used as a polyether modified silicone.
  • a film-forming composition containing the above organic solvent sol and an organic resin is obtained.
  • the film-forming composition can be obtained by removing the organic solvent from the organic solvent sol to form a film-forming composition containing hollow silica particles and an organic resin.
  • the heat curing agent can be contained in the range of 0.01 to 50 phr, or 0.01 to 10 phr, relative to the resin containing a functional group such as an epoxy group or a (meth)acryloyl group.
  • the heat curing agent can be contained in a ratio of 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents, relative to the functional group such as an epoxy group or a (meth)acryloyl group.
  • the equivalent of the heat curing agent relative to the curable resin is indicated by the equivalent ratio of the heat curing agent to the functional group of the cured resin.
  • heat curing agent examples include phenol resins, amine-based curing agents, polyamide resins, imidazoles, polymercaptans, acid anhydrides, heat radical generators, heat acid generators, etc.
  • radical generator-based curing agents, acid anhydride-based curing agents, and amine-based curing agents are preferred.
  • thermosetting agents Even if these thermosetting agents are solid, they can be used by dissolving them in a solvent. However, evaporation of the solvent causes a decrease in density of the cured product, and the formation of pores, resulting in a decrease in strength and a decrease in water resistance. Therefore, it is preferable that the curing agent itself is liquid at room temperature and normal pressure.
  • phenolic resins examples include phenol novolac resin and cresol novolac resin.
  • amine-based hardeners examples include piperidine, N,N-dimethylpiperazine, triethylenediamine, 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di(1-methyl-2-aminocyclohexyl)methane, menthenediamine, isophoronediamine, diaminodicyclohexylmethane, 1,3-diaminomethylcyclohexane, xylylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, 3,3'-diethyl-4,4'-diaminodiphenylmethane, diethyltoluened
  • liquids such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di(1-methyl-2-aminocyclohexyl)methane, menthenediamine, isophoronediamine, diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and diethyltoluenediamine can be preferably used.
  • Polyamide resins include those produced by condensation of dimer acid and polyamine, such as polyamidoamines that have primary and secondary amines in the molecule.
  • Imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, and epoxy imidazole adduct.
  • the polymercaptan is preferably liquid, for example, one in which a mercaptan group is present at the end of a polypropylene glycol chain or one in which a mercaptan group is present at the end of a polyethylene glycol chain.
  • an anhydride of a compound having multiple carboxyl groups in one molecule is preferred.
  • these acid anhydride hardeners include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, methyl butenyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, succinic anhydride, methylcyclohexene dicarboxylic anhydride, and chlorendic anhydride,
  • thermal acid generator examples include sulfonium salts and phosphonium salts, with sulfonium salts being preferred.
  • sulfonium salts examples include sulfonium salts and phosphonium salts, with sulfonium salts being preferred.
  • R represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, and an alkyl group having 1 to 12 carbon atoms is particularly preferred.
  • liquid at room temperature and pressure methyltetrahydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride (methylnadic anhydride, methylhimic anhydride), hydrogenated methylnadic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, methylhexahydrophthalic anhydride, and a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride.
  • These liquid acid anhydrides have a viscosity of about 10 mPas to 1,000 mPas when measured at 25°C.
  • thermal radical generators examples include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methylpropionate)dimethyl, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, and benzoyl peroxide. These can be obtained from Tokyo Chemical Industry Co., Ltd.
  • a curing aid When obtaining the cured product, a curing aid may be used in combination as appropriate.
  • the curing aid include organic phosphorus compounds such as triphenylphosphine and tributylphosphine, quaternary phosphonium salts such as ethyltriphenylphosphonium bromide and methyltriphenylphosphonium diethyl phosphate, and quaternary ammonium salts such as 1,8-diazabicyclo(5,4,0)undecane-7-ene, salts of 1,8-diazabicyclo(5,4,0)undecane-7-ene and octylic acid, zinc octylate, and tetrabutylammonium bromide.
  • These curing aids can be included in a ratio of 0.001 to 0.1 parts by mass per part by mass of the curing agent.
  • the composition is obtained as a thermosetting varnish by mixing a resin, a curing agent, and optionally a curing aid.
  • the mixing can be carried out in a reaction vessel using a stirring blade or kneader.
  • Mixing is done by a hot mixing method at a temperature of 60°C to 100°C for 0.5 to 1 hour.
  • the obtained curable film-forming composition is a thermosetting coating composition, and has an appropriate viscosity for use, for example, as a liquid sealant.
  • the liquid thermosetting film-forming composition can be prepared to any viscosity and can be used as a transparent sealant for LEDs and the like by casting, potting, dispenser, printing, or other methods, allowing partial sealing at any desired location.
  • the liquid thermosetting composition is directly mounted on an LED or the like while still in liquid form using the method described above, and then dried and cured to obtain a cured product.
  • thermosetting film-forming composition (thermosetting coating composition) is applied to a substrate and heated at a temperature of 80 to 200°C to obtain a cured product.
  • the film-forming composition when the film-forming composition is a photocurable resin composition, it can contain 0.01 to 50 phr or 0.01 to 10 phr of photocuring agent (photoradical generator, photoacid generator) relative to the resin containing functional groups such as epoxy groups or (meth)acryloyl groups.
  • photocuring agent photoradical generator, photoacid generator
  • it can contain 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents of photocuring agent (photoradical generator, photoacid generator) relative to functional groups such as epoxy groups or (meth)acryloyl groups.
  • the equivalent of photocuring agent relative to the curable resin is indicated by the equivalent ratio of photocuring agent to functional groups of the resin.
  • the photoradical generator is not particularly limited as long as it generates radicals directly or indirectly when irradiated with light.
  • photoradical polymerization initiators examples include imidazole compounds, diazo compounds, bisimidazole compounds, N-arylglycine compounds, organic azide compounds, titanocene compounds, aluminate compounds, organic peroxides, N-alkoxypyridinium salt compounds, and thioxanthone compounds.
  • azide compounds examples include p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzalacetophenone, 4,4'-diazidochalcone, 4,4'-diazidodiphenyl sulfide, and 2,6-bis(4'-azidobenzal)-4-methylcyclohexanone.
  • Examples of the diazo compound include 1-diazo-2,5-diethoxy-4-p-tolylmercaptobenzene borofluoride, 1-diazo-4-N,N-dimethylaminobenzene chloride, and 1-diazo-4-N,N-diethylaminobenzene borofluoride.
  • Examples of the bisimidazole compound include 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetrakis(3,4,5-trimethoxyphenyl)-1,2'-bisimidazole, and 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-bisimidazole.
  • titanocene compounds include dicyclopentadienyl-titanium-dichloride, dicyclopentadienyl-titanium-bisphenyl, dicyclopentadienyl-titanium-bis(2,3,4,5,6-pentafluorophenyl), dicyclopentadienyl-titanium-bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl-titanium-bis(2,4,6-trifluorophenyl), dicyclopentadienyl-titanium-bis(2,6-difluorophenyl), and dicyclopentadienyl.
  • photoradical generators include 1,3-di(tert-butyldioxycarbonyl)benzophenone, 3,3',4,4'-tetrakis(tert-butyldioxycarbonyl)benzophenone, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone.
  • photoradical polymerization agents are available, for example, under the trade name Irgacure TPO (component is 2,4,6-trimethylbenzoyldiphenylphosphine oxide) (c1-1-1) manufactured by BASF, under the trade name Omnirad 819 (component is bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) (c1-1-2) manufactured by IGM RESINS, and under the trade name Irgacure 184 (component is 1-hydroxycyclohexyl phenyl ketone) (c1-1-3) manufactured by IGM RESINS.
  • Irgacure TPO component is 2,4,6-trimethylbenzoyldiphenylphosphine oxide
  • Omnirad 819 component is bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) (c1-1-2) manufactured by IGM RESINS
  • Irgacure 184 component is 1-hydroxycyclohexyl phenyl
  • the photoacid generator is not particularly limited as long as it generates acid directly or indirectly when irradiated with light.
  • photoacid generators include triazine compounds, acetophenone derivative compounds, disulfone compounds, diazomethane compounds, sulfonic acid derivative compounds, onium salts such as iodonium salts, sulfonium salts, phosphonium salts, and selenium salts, metallocene complexes, and iron arene complexes.
  • the onium salts used as the photoacid generators include iodonium salts such as diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis(p-tert-butylphenyl)iodonium hexafluorophosphate, bis(p-tert-butylphenyl)iodonium mesylate, bis(p-tert-butylphenyl)iodonium tosylate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis(p
  • sulfonium salts include triphenylsulfonium chloride, triphenylsulfonium bromide, tri(p-methoxyphenyl)sulfonium tetrafluoroborate, tri(p-methoxyphenyl)sulfonium hexafluorophosphonate, tri(p-ethoxyphenyl)sulfonium tetrafluoroborate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, and triphenylsulfonium hexafluorophosphate; as well as sulfonium salts such as (4-phenylthiophenyl)diphenylsulfonium hexafluoroantimonate, (4-phenylthiophenyl)diphenylsulfonium hexafluorophosphate, bis[4-(diphenylsulfonio
  • Phosphonium salts include triphenylphosphonium chloride, triphenylphosphonium bromide, tri(p-methoxyphenyl)phosphonium tetrafluoroborate, tri(p-methoxyphenyl)phosphonium hexafluorophosphonate, tri(p-ethoxyphenyl)phosphonium tetrafluoroborate, 4-chlorobenzenediazonium hexafluorophosphate, and benzyltriphenylphosphonium hexafluoroantimonate.
  • Selenium salts such as triphenylselenium hexafluorophosphate, and metallocene complexes such as ( ⁇ 5 or ⁇ 6-isopropylbenzene)( ⁇ 5-cyclopentadienyl)iron(II) hexafluorophosphate are examples.
  • the following compounds can also be used as the photoacid generator.
  • sulfonium salt compounds and iodonium salt compounds are preferred.
  • the anion species thereof include CF3SO3- , C4F9SO3- , C8F17SO3- , camphorsulfonate anion, tosylate anion, BF4- , PF6- , AsF6- , and SbF6- .
  • anion species such as hexafluorophosphate ion and hexafluoroantimonate ion, which show strong acidity , are preferred.
  • the film-forming composition of the present invention may contain conventional additives as necessary.
  • additives include pigments, colorants, thickeners, sensitizers, defoamers, coatability improvers, lubricants, stabilizers (antioxidants, heat stabilizers, light resistance stabilizers, etc.), plasticizers, dissolution promoters, fillers, antistatic agents, etc. These additives may be used alone or in combination of two or more kinds.
  • Examples of methods for applying the film-forming composition of the present invention include flow coating, spin coating, spray coating, screen printing, casting, bar coating, curtain coating, roll coating, gravure coating, dipping, and slitting.
  • the photo-coating composition (film-forming composition) can be applied onto a substrate and cured by exposure to light. It can also be heated before or after exposure to light.
  • the thickness of the coating can be selected from the range of about 0.01 ⁇ m to 10 mm depending on the application of the cured product.
  • it when used as a photoresist, it can be about 0.05 to 10 ⁇ m (particularly 0.1 to 5 ⁇ m), when used as a printed wiring board, it can be about 5 ⁇ m to 5 mm (particularly 100 ⁇ m to 1 mm), and when used as an optical thin film, it can be about 0.1 to 100 ⁇ m (particularly 0.3 to 50 ⁇ m).
  • the coating's visible light transmittance can be made 80% or more, or 90% or more, typically 90 to 96%.
  • the light to which the film-forming composition is irradiated or exposed may be, for example, gamma rays, X-rays, ultraviolet rays, visible light, etc., and is usually visible light or ultraviolet rays, particularly ultraviolet rays.
  • the wavelength of the light is, for example, about 150 to 800 nm, preferably about 150 to 600 nm, more preferably about 200 to 400 nm, particularly about 300 to 400 nm.
  • the amount of light to be irradiated varies depending on the thickness of the coating film, but can be, for example, about 2 to 20,000 mJ/cm 2 , preferably about 5 to 5,000 mJ/cm 2.
  • the light source can be selected according to the type of light to be exposed.
  • a low-pressure mercury lamp a high-pressure mercury lamp, an extra-high-pressure mercury lamp, a deuterium lamp, a halogen lamp, a laser beam (helium-cadmium laser, excimer laser, etc.), etc. can be used.
  • Such light irradiation causes the curing reaction of the composition to proceed.
  • Heating of the coating of the film-forming composition containing a thermal acid generator, or heating of the coating of the film-forming composition containing a photoacid generator, which is performed as necessary before or after light irradiation, is performed, for example, at about 60 to 250°C, preferably 100 to 200°C.
  • the heating time can be selected from the range of 3 seconds or more (for example, about 3 seconds to 5 hours), for example, 5 seconds to 2 hours, preferably about 20 seconds to 30 minutes, and can usually be selected from the range of about 1 minute to 3 hours (for example, about 5 minutes to 2.5 hours).
  • the coating film formed on the substrate may be subjected to pattern exposure.
  • This pattern exposure may be performed by scanning with laser light, or by irradiating light through a photomask.
  • the non-irradiated areas (unexposed areas) generated by such pattern exposure may be developed (or dissolved) with a developer to form a pattern or image.
  • the developer may be an aqueous alkaline solution or an organic solvent.
  • alkaline aqueous solution include aqueous solutions of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate; aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine.
  • alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate
  • quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline
  • amines such as ethanolamine, propylamine, and ethylenediamine.
  • the alkaline developer is generally an aqueous solution having a concentration of 10% by mass or less, and preferably has a concentration of 0.1 to 3.0% by mass, etc.
  • the developer may further contain alcohols or surfactants, and the amount of each of these added is preferably 0.05 to 10 parts by mass relative to 100 parts by mass of the developer.
  • an aqueous solution of 0.1 to 2.38% by weight of tetramethylammonium hydroxide can be used.
  • a general organic solvent can be used, such as acetone, acetonitrile, toluene, dimethylformamide, methanol, ethanol, isopropanol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, ethyl lactate, cyclohexanone, etc., and one or a mixture of two or more of these can be used.
  • propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate, etc. can be preferably used.
  • an adhesion promoter can be added for the purpose of improving the adhesion between the cured film and the substrate after development.
  • adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane, alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane, silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole, vinyltrichlorosilane, 3-chloropropyltrimethoxysilane, and the like.
  • adhesion promoter examples include silanes such as silane, 3-aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-(N-piperidinyl)propyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine; and ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds.
  • silanes such as silane, 3-aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyl
  • the adhesion promoters may be used alone or in combination of two or more.
  • the amount of these adhesion promoters added is usually 18% by mass or less, preferably 0.0008 to 9% by mass, and more preferably 0.04 to 9% by mass, based on the solid content.
  • the solid content refers to the components remaining after removing the solvent from the composition.
  • the composition of the present invention may contain a sensitizer.
  • sensitizers that can be used include anthracene, phenothiazene, perylene, thioxanthone, and benzophenone thioxanthone.
  • sensitizing dyes include thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, and pyrylium salt dyes.
  • Anthracene sensitizers are particularly preferred, and when used in combination with a cationic curing catalyst (radiation-sensitive cationic polymerization initiator), they dramatically improve sensitivity and also have a radical polymerization initiation function.
  • a cationic curing catalyst radiation-sensitive cationic polymerization initiator
  • the catalyst species can be simplified.
  • Specific examples of anthracene compounds that are effective include dibutoxyanthracene and dipropoxyanthraquinone.
  • the amount of sensitizer added is 0.01 to 20% by mass, preferably 0.01 to 10% by mass, based on the solid content.
  • the composition of the present invention can be photocured or thermally cured using a photoradical generator, a thermal radical generator, a photoacid generator, or a thermal acid generator.
  • a photoacid generator or a thermal acid generator for example, commonly used epoxy curing agents (e.g., amines or acid anhydrides) are not used, or even if they are used, the content of these agents is extremely small, which improves the storage stability of the composition.
  • the composition has been found to have photocationic polymerization properties.
  • the composition of the present invention has a higher curing speed than conventional liquid epoxy compounds (e.g., alicyclic epoxy compounds having an epoxycyclohexyl ring). Because of the fast curing speed, it is possible to reduce the amount of acid generator added and to use weak acid generators. Since metals can corrode due to acid active species remaining after UV irradiation, reducing the amount of acid generator used is important in preventing metal corrosion. Because the composition of the present invention has a fast curing speed, thick film curing is possible.
  • thermosetting and photocuring materials using the film-forming composition of the present invention have characteristics such as fast curing, transparency, and small shrinkage on curing, and can be used for coating and bonding electronic parts, optical parts (anti-reflection coating), and precision mechanical parts.
  • they can be used for bonding mobile phone and camera lenses, optical elements such as light-emitting diodes (LEDs) and semiconductor lasers (LDs), liquid crystal panels, biochips, camera lenses and prisms, magnetic parts of hard disks of personal computers, pickups of CD and DVD players (parts that capture optical information reflected from the disk), speaker cones and coils, motor magnets, circuit boards, electronic parts, and parts inside the engine of automobiles.
  • optical elements such as light-emitting diodes (LEDs) and semiconductor lasers (LDs), liquid crystal panels, biochips, camera lenses and prisms, magnetic parts of hard disks of personal computers, pickups of CD and DVD players (parts that capture optical information reflected from the disk), speaker cones and coils, motor magnets, circuit boards, electronic parts, and parts inside the engine of automobiles.
  • LEDs light-emitting diodes
  • LDs semiconductor lasers
  • liquid crystal panels liquid crystal panels
  • biochips biochips
  • camera lenses and prisms magnetic parts of hard disk
  • composition of the present invention can be used as a hard coat material for surface protection of automobile bodies, lamps, electrical appliances, building materials, plastics, etc., and can be applied to, for example, automobile and motorcycle bodies, headlight lenses and mirrors, plastic lenses for glasses, mobile phones, game consoles, optical films, ID cards, etc.
  • composition of the present invention can be used as an ink material for printing on metals such as aluminum, plastics, etc., and can be used as printing ink for cards such as credit cards and membership cards, switches for electrical appliances and office equipment, keyboards, and ink for inkjet printers for CDs, DVDs, etc.
  • composition of the present invention can be used in combination with 3D CAD to harden resins to create complex three-dimensional objects, in photolithography applications such as in the production of industrial product models, and in optical fiber coatings, adhesives, optical waveguides, thick-film resists, etc.
  • the film-forming composition of the present invention can also be suitably used as an insulating resin for electronic materials such as anti-reflective films, semiconductor sealing materials, adhesives for electronic materials, printed wiring board materials, interlayer insulating film materials, and sealing materials for power modules, as well as an insulating resin for high-voltage equipment such as generator coils, transformer coils, and gas-insulated switchgear.
  • electronic materials such as anti-reflective films, semiconductor sealing materials, adhesives for electronic materials, printed wiring board materials, interlayer insulating film materials, and sealing materials for power modules
  • an insulating resin for high-voltage equipment such as generator coils, transformer coils, and gas-insulated switchgear.
  • the organic solvent sol of hollow silica particles of the present invention can be produced by a method including the following steps (A) to (C).
  • the hollow silica particles used in step (A) have a silica shell and a space inside the shell.
  • Hollow silica is obtained by forming a shell mainly made of silica on the surface of the part that corresponds to the core, known as the template, in an aqueous dispersion medium, and then removing the part that corresponds to the core.
  • the template can be made from organic matter (e.g., hydrophilic organic resin particles such as polyethylene glycol, polystyrene, polyester, etc.) or inorganic matter (e.g., hydrophilic inorganic compound particles such as calcium carbonate, sodium aluminate, etc.).
  • step (B) an amine is added to the hollow silica aqueous sol of step (A).
  • the amine has a water solubility of 80 g/L or more, or 100 g/L or more, and at least one amine selected from primary to tertiary amines having a total carbon atom number of 1 to 10 can be added in a ratio of 0.001 to 10 mass % based on the SiO 2 of the hollow silica.
  • the amines mentioned above can be used as these amines.
  • the step (C) is a step of subjecting the aqueous medium of the aqueous sol of hollow silica obtained in the step (B) to solvent replacement with an alcohol, ketone, ether or ester having 1 to 10 carbon atoms.
  • the aqueous medium of the aqueous sol of hollow silica can be replaced with an organic solvent, and the aqueous medium of the aqueous sol can be replaced with a hydrophilic organic solvent and then with a hydrophobic organic solvent.
  • step (C) is a step of solvent-substitution of the aqueous medium of the aqueous sol with an alcohol having 1 to 10 carbon atoms, and then further solvent-substitution of the alcohol solvent with a ketone, ether, or ester having 1 to 10 carbon atoms.
  • a step (D) can be added in which at least one silane compound selected from the group consisting of silane compounds represented by the above formulas (1), (2), and (3) is added and heated.
  • step (C) after the aqueous medium of the aqueous sol in step (C) is solvent-substituted with an alcohol having 1 to 10 carbon atoms, at least one silane compound selected from the group consisting of silane compounds represented by formulas (1), (2), and (3) is added and heated in step (D), and then the alcohol solvent in step (C) can be solvent-substituted with a ketone, ether, or ester having 1 to 10 carbon atoms.
  • the heating temperature after adding the silane compound is 40°C or higher, and preferably below the reflux temperature of the solvent used.
  • the heating time can be in the range of 0.1 to 10 hours.
  • the surface charge of hollow silica particles can be adjusted as desired using the above-mentioned method for producing hollow silica organic solvent sol.
  • a titration value was measured until the flow potential of the measurement sample reached zero using an N/1000 DADMAC solution (manufactured by Voith Turbo) as a standard cation titrant.
  • the titration value obtained was divided by the mass of silica contained in the measurement sample to obtain the surface charge ( ⁇ eq/g) converted per 1 g of SiO 2 of the hollow silica particles.
  • Example 1 (Preparation of hollow silica methanol sol (1)) 100.22 g of a commercially available hollow silica aqueous sol (Ningbo Dilato Co., Ltd., HKT-D20-225-1, SiO2 concentration is 20.7 mass%, pH 9.0, dynamic light scattering particle size 88 nm, specific surface area by BET method 107 m2 /g, average primary particle size by TEM 82 nm, specific surface area ratio 3.2) was charged into a 500 mL eggplant flask, and 0.04 g of diisopropylamine was added while stirring with a magnetic stirrer, and mixed for 2 hours. Then, 38.09 g of methanol was added while stirring, and mixed for 2 hours.
  • a commercially available hollow silica aqueous sol Naingbo Dilato Co., Ltd., HKT-D20-225-1, SiO2 concentration is 20.7 mass%, pH 9.0, dynamic light scattering particle size 88 nm,
  • the obtained hollow silica methanol sol had a SiO2 concentration of 15.5 mass%, a moisture content of 1.7%, a viscosity of 1.8 mPa sec, a pH of 8.2, a particle size measured by a dynamic light scattering method of 99 nm, a total nitrogen content of 438 ppm, and a surface charge amount calculated per 1 g of SiO2 of the hollow silica particles of 26 ⁇ eq/g.
  • the total light transmittance of the obtained mixture film was measured using a spectroscopic haze meter (Nippon Denshoku Kogyo Co., Ltd., SH7000), and the result was 91.6%.
  • the total light transmittance of the glass substrate was 91.0%, which was a high value compared to the total light transmittance of a film prepared under the same conditions using only UV curable resin, which was 90.7%, and was a highly transparent mixture film.
  • Example 2 (Preparation of hollow silica methanol sol (2)) 100.01 g of a commercially available hollow silica aqueous sol (Ningbo Dilat Co., Ltd., HKT-D20-225-1, SiO2 concentration 20.7%, pH 9.0, dynamic light scattering particle size 88 nm, BET specific surface area 107 m2 /g, TEM average primary particle size 82 nm, specific surface area ratio 3.2) was charged into a 500 mL recovery flask, and hollow silica methanol sol (2) was obtained by the same procedure as in Example 1, except that the amount of diisopropylamine added was changed to 0.10 g and the amount of methanol was changed to 37.98 g.
  • a commercially available hollow silica aqueous sol Naingbo Dilat Co., Ltd., HKT-D20-225-1, SiO2 concentration 20.7%, pH 9.0, dynamic light scattering particle size 88 nm, BET specific surface area
  • the obtained hollow silica methanol sol (2) had a SiO2 concentration of 15.1 mass%, a moisture content of 0.9%, a viscosity of 1.6 mPa sec, a pH of 8.7, a particle size measured by a dynamic light scattering method of 108 nm, a total nitrogen content of 409 ppm, and a surface charge amount calculated per 1 g of SiO2 of the hollow silica particles of 25 ⁇ eq/g.
  • the obtained hollow silica propylene glycol monomethyl ether sol (1) had a SiO2 concentration of 13.4 mass%, a moisture content of 0.2%, a viscosity of 3.5 mPa ⁇ sec, a pH of 8.1, a particle size measured by dynamic light scattering of 103 nm, and a total nitrogen content of 330 ppm.
  • a film formed from hollow silica propylene glycol monomethyl ether sol (1) / UV curable resin mixed varnish and varnish containing hollow silica propylene glycol monomethyl ether sol (1) was prepared by the same operation as in Example 1, except that 1.86 g of hollow silica propylene glycol monomethyl ether sol (1) (SiO2 concentration 13.4 mass%) obtained in Example 2 was used. The total light transmittance of the obtained blended film was 92.2%, and it was a blended film with high transparency.
  • Example 3 (Preparation of hollow silica methanol sol (3)) 100.15 g of a commercially available hollow silica aqueous sol (Ningbo Dilat Co., Ltd., HKT-D20-225-1, SiO2 concentration 20.7%, pH 9.0, dynamic light scattering particle size 88 nm, BET specific surface area 107 m2 /g, TEM average primary particle size 82 nm, specific surface area ratio 3.2) was charged into a 500 mL recovery flask, and the same procedure as in Example 1 was repeated except that the amount of diisopropylamine added was changed to 0.21 g and the amount of methanol was changed to 38.02 g, to obtain hollow silica methanol sol (3).
  • a commercially available hollow silica aqueous sol Naingbo Dilat Co., Ltd., HKT-D20-225-1, SiO2 concentration 20.7%, pH 9.0, dynamic light scattering particle size 88 nm, BET specific
  • the obtained hollow silica methanol sol (3) had a SiO2 concentration of 15.5 mass%, a moisture content of 1.6%, a viscosity of 1.8 mPa sec, a pH of 8.6, a particle size measured by a dynamic light scattering method of 101 nm, a total nitrogen content of 410 ppm, and a surface charge amount calculated per 1 g of SiO2 of the hollow silica particles of 25 ⁇ eq/g.
  • the bath temperature was 75°C and the pressure was gradually reduced from 500 Torr to 400 Torr, and 150 mL of methyl ethyl ketone was fed to distill off the methanol, thereby obtaining a hollow silica methyl ethyl ketone sol (1).
  • the obtained hollow silica methyl ethyl ketone sol (1) had a SiO2 concentration of 15.5 mass%, a moisture content of 0.1%, a viscosity of 3.1 mPa ⁇ sec, a pH of 7.8, a particle size measured by a dynamic light scattering method of 106 nm, and a total nitrogen content of 360 ppm.
  • the solid content concentration was 10 mass%, and the amount of hollow silica ( SiO2 ) was 100 phr.
  • About 2 mL of the obtained hollow silica methyl ethyl ketone sol (1) / UV curable resin mixed varnish was dropped onto a glass substrate, and a spin coater (Mikasa Co., Ltd., Opticoat MS-B100) was used to uniformly spread the mixture on the glass substrate under the conditions of 200 rpm x 5 sec, 3 sec increase to 1000 rpm, and 1000 rpm x 30 sec. Thereafter, the mixture was baked on a hot plate at 100 ° C.
  • the total light transmittance of the obtained mixture film was measured using a spectroscopic haze meter (Nippon Denshoku Kogyo Co., Ltd., SH7000), and was 92.8%.
  • the total light transmittance of the glass substrate was 91.0%, which was higher than the total light transmittance of 90.7% of a film prepared under the same conditions using only a UV-curable resin, making this a highly transparent blend film.
  • Example 4 (Preparation of hollow silica methanol sol (4)) 100.05 g of a commercially available hollow silica aqueous sol (Ningbo Dilat Co., Ltd., HKT-D20-225-1, SiO2 concentration 20.7%, pH 9.0, dynamic light scattering particle size 88 nm, BET specific surface area 107 m2 /g, TEM average primary particle size 82 nm, specific surface area ratio 3.2) was charged into a 500 mL recovery flask, and hollow silica methanol sol (4) was obtained by the same procedure as in Example 1, except that the amount of diisopropylamine added was changed to 0.50 g and the amount of methanol was changed to 38.06 g.
  • a commercially available hollow silica aqueous sol Naingbo Dilat Co., Ltd., HKT-D20-225-1, SiO2 concentration 20.7%, pH 9.0, dynamic light scattering particle size 88 nm, BET specific surface
  • the obtained hollow silica methanol sol (4) had a SiO2 concentration of 15.5 mass%, a moisture content of 1.2%, a viscosity of 1.7 mPa sec, a pH of 8.9, a particle size measured by a dynamic light scattering method of 99 nm, a total nitrogen content of 458 ppm, and a surface charge amount calculated per 1 g of SiO2 of the hollow silica particles of 30 ⁇ eq/g.
  • the obtained hollow silica methyl ethyl ketone sol (2) had a SiO2 concentration of 15.6 mass%, a moisture content of 0.2%, a viscosity of 3.3 mPa ⁇ sec, a pH of 8.3, a particle size measured by dynamic light scattering of 102 nm, and a total nitrogen content of 387 ppm.
  • Example 5 (Preparation of hollow silica methanol sol (5)) 100.15 g of a commercially available hollow silica aqueous sol (Ningbo Dilato Co., Ltd., HKT-D20-225-1, SiO2 concentration 20.7% by mass, pH 9.0, dynamic light scattering particle size 88 nm, BET specific surface area 107 m2 /g, TEM average primary particle size 82 nm, specific surface area ratio 3.2) was charged into a 500 mL recovery flask, and the same procedure as in Example 1 was repeated except that the amount of diisopropylamine added was changed to 1.00 g and the amount of methanol was changed to 38.07 g, to obtain hollow silica methanol sol (5).
  • a commercially available hollow silica aqueous sol Naingbo Dilato Co., Ltd., HKT-D20-225-1, SiO2 concentration 20.7% by mass, pH 9.0, dynamic light scattering particle size 88
  • the obtained hollow silica methanol sol (5) had a SiO2 concentration of 15.5 mass%, a moisture content of 0.8%, a viscosity of 1.6 mPa sec, a pH of 8.5, a particle size measured by a dynamic light scattering method of 98 nm, a total nitrogen content of 414 ppm, and a surface charge amount calculated per 1 g of SiO2 of the hollow silica particles of 27 ⁇ eq/g.
  • the obtained hollow silica methyl ethyl ketone sol (3) had a SiO2 concentration of 15.5 mass%, a moisture content of 0.0%, a viscosity of 2.7 mPa ⁇ sec, a pH of 7.9, a particle size measured by a dynamic light scattering method of 103 nm, and a total nitrogen content of 359 ppm.
  • Example 6 (Preparation of hollow silica methanol sol (6))
  • Commercially available hollow silica aqueous sol (Ningbo Dilat Co., Ltd., HKT-D20-225-1, SiO2 concentration 20.7%, pH 9.0, dynamic light scattering particle size 88 nm, specific surface area 107 m2 /g by BET method, average primary particle size 82 nm by TEM, specific surface area ratio 3.2) 100.06 g was charged into a 500 mL eggplant flask, and 1.41 g of 28% ammonia water was added while stirring the sol with a magnetic stirrer sol, and mixed for 2 hours.
  • the obtained hollow silica methanol sol (6) had a SiO2 concentration of 15.7 mass%, a moisture content of 1.1%, a viscosity of 1.7 mPa sec, a pH of 9.0, a particle size measured by a dynamic light scattering method of 99 nm, a total nitrogen content of 553 ppm, and a surface charge amount calculated per 1 g of SiO2 of the hollow silica particles of 30 ⁇ eq/g.
  • the obtained hollow silica methyl ethyl ketone sol (4) had a SiO2 concentration of 15.6 mass%, a moisture content of 0.3%, a viscosity of 4.2 mPa ⁇ sec, a pH of 8.5, a particle size measured by a dynamic light scattering method of 103 nm, and a total nitrogen content of 436 ppm.
  • Example 7 (Preparation of hollow silica methanol sol (7)) 105.47 g of a commercially available hollow silica aqueous sol (Ningbo Dilat Co., Ltd., HKT-D20-225-1, SiO2 concentration 20.7% by mass, pH 9.0, dynamic light scattering particle size 88 nm, BET specific surface area 107 m2 /g, TEM average primary particle size 82 nm, specific surface area ratio 3.2) was charged into a 500 mL eggplant flask, and hollow silica methanol sol (7) was obtained by the same procedure as in Example 1, except that the amount of 28% ammonia water added was changed to 3.77 g, the amount of diisopropylamine to 0.05 g, and the amount of methanol to 40.07 g.
  • a commercially available hollow silica aqueous sol Naingbo Dilat Co., Ltd., HKT-D20-225-1, SiO2 concentration 20.7% by mass,
  • the obtained hollow silica methanol sol (7) had a SiO2 concentration of 15.5 mass%, a moisture content of 1.1%, a viscosity of 1.4 mPa sec, a pH of 9.3, a particle size measured by a dynamic light scattering method of 101 nm, a total nitrogen content of 1346 ppm, and a surface charge amount calculated per 1 g of SiO2 of the hollow silica particles of 36 ⁇ eq/g.
  • the obtained hollow silica methyl ethyl ketone sol (5) had a SiO2 concentration of 15.5 mass%, a moisture content of 0.1%, a viscosity of 2.8 mPa ⁇ sec, a pH of 8.4, a particle size measured by dynamic light scattering of 102 nm, and a total nitrogen content of 1043 ppm.
  • Example 8 (Preparation of hollow silica methanol sol (8))
  • Commercially available hollow silica aqueous sol (Ningbo Dilato, HKT-A20-40D, SiO2 concentration 20.0%, pH 9.3, dynamic light scattering particle size 55 nm, specific surface area 116 m2 /g by BET method, average primary particle size 43 nm by TEM, specific surface area ratio 1.8) 551.10 g was charged into a 2000 mL eggplant flask, and 0.55 g of diethanolamine was added while stirring with a magnetic stirrer, and mixed for 2 h. Then, 139.76 g of methanol was added while stirring, and mixed for 2 h.
  • the obtained hollow silica methanol sol (8) had a SiO2 concentration of 23.5%, a moisture content of 0.6%, a viscosity of 2.8 mPa sec, a pH of 9.0, a particle size measured by a dynamic light scattering method of 63 nm, a total nitrogen content of 641 ppm, and a surface charge amount calculated per 1 g of SiO2 of the hollow silica particles of 34 ⁇ eq/g.
  • the obtained hollow silica methyl ethyl ketone sol (6) had a SiO2 concentration of 22.4%, a moisture content of 0.4%, a pH of 9.3, and a particle size measured by a dynamic light scattering method of 66 nm.
  • (hollow silica methanol sol) indicates a sol in which hollow silica particles are dispersed in methanol.
  • MeOH in the (dispersion medium) column indicates methanol.
  • (pH) indicates the pH when hollow silica methanol sol and the same mass of pure water are mixed at 1:1.
  • (Amine amount) indicates the addition ratio (mass%) of hollow silica particles to SiO 2 , and was contained in the hollow silica methanol sol according to the addition ratio.
  • (DLS) indicates the average particle size (nm) of hollow silica particles by dynamic light scattering method.
  • Total nitrogen amount indicates the total nitrogen amount (ppm) in the hollow silica particle sol of the base component consisting of amine or amine and ammonia.
  • (Surface charge amount) indicates the surface charge amount ( ⁇ eq/g) converted per 1 g of SiO 2 of the hollow silica particles. Note that gelation indicates that the hollow silica sol has gelled and the physical property value cannot be measured.
  • (hollow silica organic solvent sol) indicates a sol in which hollow silica particles are dispersed in an organic solvent.
  • PGME indicates propylene glycol monomethyl ether
  • MEK indicates methyl ethyl ketone.
  • pH indicates the pH value measured in a solution in which pure water and the sol were mixed at a mass ratio of 1:1 for the propylene glycol monomethyl ether sol, and the pH value measured in a solution in which pure water, methanol, and methyl ethyl ketone sol were mixed at a mass ratio of 1:1:1 for the methyl ethyl ketone sol.
  • N indicates that the surface of the silica particles was not treated with a silane coupling agent
  • MPS indicates that the surface of the silica particles was treated with 3-methacryloxypropyltrimethoxysilane.
  • DLS indicates the average particle size (nm) of the hollow silica particles measured by dynamic light scattering.
  • Total nitrogen content indicates the total nitrogen content (ppm) of the base component consisting of amine or amine and ammonia in the hollow silica particle sol.
  • (film containing hollow silica methanol sol) indicates a film formed by coating a substrate with a resin composition in which a sol of hollow silica particles dispersed in methanol is blended with a UV-curable resin and then photocuring the film.
  • the (UV-curable resin) column indicates the polyfunctional acrylate used, with DPHA indicating KAYARAD DPHA (polyfunctional acrylate: component dipentaerythritol hexaacrylate), manufactured by Nippon Kayaku Co., Ltd.
  • (blended amount) indicates the blended amount (phr) of hollow silica particles relative to the UV-curable resin.
  • Total light transmittance indicates the total light transmittance (%) of the resulting coating.
  • (film containing hollow silica organic solvent sol) shows a film formed by coating a substrate with a resin composition in which a sol of hollow silica particles dispersed in an organic solvent is blended with a UV-curable resin, and then photocuring the film.
  • the (UV-curable resin) column shows the polyfunctional acrylate used, with DPHA being Nippon Kayaku Co., Ltd.'s product name KAYARAD DPHA (polyfunctional acrylate: component dipentaerythritol hexaacrylate).
  • (Amount blended) shows the amount (phr) of hollow silica particles blended with the UV-curable resin.
  • Total light transmittance shows the total light transmittance (%) of the resulting coating.
  • the blended film prepared by blending the obtained hollow silica methanol sol with resin had excellent dispersion uniformity of the hollow silica particles in the resin, and therefore had high transparency (total light transmittance). Furthermore, it was confirmed that the solvent replacement with other organic solvents such as propylene glycol monomethyl ether and methyl ethyl ketone is possible by using the obtained hollow silica methanol sol as a raw material.
  • the present invention provides hollow silica particles that have a specific surface charge and are highly dispersible in resins, and provides an organic solvent sol of hollow silica particles that contain an amine in the sol and have a space inside the outer shell, a method for producing the same, and a coating-forming composition.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Silicon Compounds (AREA)

Abstract

Le problème décrit par la présente invention est de fournir : un sol de solvant organique de particules de silice creuses, le sol contenant une amine, les particules de silice creuses ayant une charge de surface spécifique, présentant une dispersibilité élevée dans une résine, et ayant un espace à l'intérieur d'une enveloppe externe ; sa méthode de production ; et une composition filmogène. La solution selon l'invention porte sur un sol de solvant organique de particules de silice creuses, le sol contenant une amine et les particules de silice creuses ayant un espace à l'intérieur d'une enveloppe externe. L'amine est au moins un type d'amine choisi parmi une amine primaire, une amine secondaire et une amine tertiaire ayant un total de 1 à 10 atomes de carbone. La solubilité dans l'eau de l'amine est supérieure ou égale à 80 g/L. La teneur en amine est de 0,001 à 10 % en masse par rapport à SiO2 dans les particules de silice creuses. Le diamètre de particule moyen des particules de silice creuses, tel que mesuré à l'aide d'une méthode de diffusion de lumière dynamique, est de 20 à 150 nm. La quantité de charge de surface est de 5 à 250 μeq/g, telle que calculée pour 1 g de SiO2 dans les particules de silice creuses. Le solvant organique est un alcool, une cétone, un éther ou un ester ayant de 1 à 10 atomes de carbone. L'invention concerne également une composition filmogène qui contient le sol de solvant organique de particules de silice creuses et une résine organique.
PCT/JP2023/034712 2022-09-30 2023-09-25 Sol de solvant organique de particules de silice creuses contenant une amine, et sa méthode de production WO2024071033A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-158163 2022-09-30
JP2022158163 2022-09-30

Publications (1)

Publication Number Publication Date
WO2024071033A1 true WO2024071033A1 (fr) 2024-04-04

Family

ID=90477864

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/034712 WO2024071033A1 (fr) 2022-09-30 2023-09-25 Sol de solvant organique de particules de silice creuses contenant une amine, et sa méthode de production

Country Status (2)

Country Link
TW (1) TW202428515A (fr)
WO (1) WO2024071033A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010503693A (ja) * 2006-09-15 2010-02-04 スリーエム イノベイティブ プロパティズ カンパニー ナノ粒子の表面修飾のための方法
WO2014199904A1 (fr) * 2013-06-10 2014-12-18 日産化学工業株式会社 Composition de résine contenant de la silice et son procédé de production, et article moulé produit à partir de la composition de résine contenant de la silice
WO2016181997A1 (fr) * 2015-05-11 2016-11-17 日産化学工業株式会社 Dispersion de silice colloïdale modifiée par un aminosilane et son procédé de fabrication
WO2018186468A1 (fr) * 2017-04-06 2018-10-11 株式会社日本触媒 Particules de silice
JP2020059624A (ja) * 2018-10-10 2020-04-16 株式会社日本触媒 表面処理シリカ粒子、これを含む分散体及び樹脂組成物、並びに樹脂組成物の硬化物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010503693A (ja) * 2006-09-15 2010-02-04 スリーエム イノベイティブ プロパティズ カンパニー ナノ粒子の表面修飾のための方法
WO2014199904A1 (fr) * 2013-06-10 2014-12-18 日産化学工業株式会社 Composition de résine contenant de la silice et son procédé de production, et article moulé produit à partir de la composition de résine contenant de la silice
WO2016181997A1 (fr) * 2015-05-11 2016-11-17 日産化学工業株式会社 Dispersion de silice colloïdale modifiée par un aminosilane et son procédé de fabrication
WO2018186468A1 (fr) * 2017-04-06 2018-10-11 株式会社日本触媒 Particules de silice
JP2020059624A (ja) * 2018-10-10 2020-04-16 株式会社日本触媒 表面処理シリカ粒子、これを含む分散体及び樹脂組成物、並びに樹脂組成物の硬化物

Also Published As

Publication number Publication date
TW202428515A (zh) 2024-07-16

Similar Documents

Publication Publication Date Title
KR20100099240A (ko) 블록화 이소시아네이트기를 갖는 실리콘 함유 레지스트 하층막 형성 조성물
US11961636B2 (en) Silica-containing insulating composition
WO2019124514A1 (fr) Composition pour former un film de revêtement contenant du silicium photodurcissable
WO2022260154A1 (fr) Composition pour former un film de sous-couche de réserve contenant du silicium
JP7564503B2 (ja) シリコン含有レジスト下層膜の製造方法
WO2024071033A1 (fr) Sol de solvant organique de particules de silice creuses contenant une amine, et sa méthode de production
WO2020196563A1 (fr) Composition filmogène
WO2024096130A1 (fr) Particules creuses de silice contenant des atomes d'aluminium et leur méthode de production
WO2022230940A1 (fr) Composition pour former un film de sous-couche de réserve contenant du silicium
JP5585757B2 (ja) 半導体基板の平坦化方法
WO2022114132A1 (fr) Composition de formation de film de sous-couche de photorésine contenant du silicium
WO2022114134A1 (fr) Composition pour formation de film de sous-couche de réserve
WO2024209991A1 (fr) Solution de dispersion de solvant organique contenant des particules d'oxyde stannique conductrices, et son procédé de production
TW202432466A (zh) 含鋁原子之中空二氧化矽粒子及其製造方法
KR20240149444A (ko) 도전성 산화 제 2 주석 입자를 포함하는 유기 용매 분산 졸 및 그 제조 방법
CN118488926A (zh) 含有铝原子的中空二氧化硅粒子及其制造方法
JP7365010B2 (ja) 揮発性アルデヒドの発生を低減した金属酸化物粒子含有組成物
WO2024150761A1 (fr) Sol de silice à base d'eau contenant des particules de silice contenant un groupe mercapto
WO2024080286A1 (fr) Nanofeuilles, composition de formation de couche de revêtement les utilisant, et article moulé
JP7495015B2 (ja) 添加剤含有シリコン含有レジスト下層膜形成組成物
CN118055985A (zh) 减少了挥发性醛的产生的含有金属氧化物粒子的组合物
TW202432465A (zh) 奈米片，及使用其之被覆層形成組成物以及成形品
CN117881628A (zh) 含有环氧基的有机硅溶胶、环氧树脂组合物及其制造方法
WO2024176909A1 (fr) Sol contenant des particules de silice auxquelles est lié un composé silicium à teneur en groupe époxy, et procédé de fabrication de celui-ci
KR20230165801A (ko) 실리콘함유 레지스트 하층막 형성용 조성물

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23872256

Country of ref document: EP

Kind code of ref document: A1