WO2024252983A1 - Résine (méth) acrylique, composition de véhicule, composition de bouillie et composant électronique - Google Patents

Résine (méth) acrylique, composition de véhicule, composition de bouillie et composant électronique Download PDF

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WO2024252983A1
WO2024252983A1 PCT/JP2024/019527 JP2024019527W WO2024252983A1 WO 2024252983 A1 WO2024252983 A1 WO 2024252983A1 JP 2024019527 W JP2024019527 W JP 2024019527W WO 2024252983 A1 WO2024252983 A1 WO 2024252983A1
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meth
monomer
acid ester
acrylic acid
weight
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Japanese (ja)
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丈 大塚
健司 山内
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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Priority to JP2024534345A priority Critical patent/JP7685118B2/ja
Priority to CN202480007410.0A priority patent/CN120476158A/zh
Priority to KR1020257017171A priority patent/KR20260018011A/ko
Publication of WO2024252983A1 publication Critical patent/WO2024252983A1/fr
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    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1803—C3-(meth)acrylate, e.g. (iso)propyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters

Definitions

  • the present invention relates to a (meth)acrylic resin.
  • a multilayer ceramic capacitor is known to have a structure that includes a laminate in which dielectric layers and internal electrodes are alternately stacked, and a pair of external electrodes that sandwich the laminate.
  • the external electrodes are formed by applying a conductive paste for the external electrodes to the surface of the laminate and sintering the paste.
  • Patent Document 1 describes the use of acrylic resins, polyvinyl butyral resins, polyvinyl acetal resins, ethyl cellulose resins, and the like, and in particular describes the use of polyvinyl butyral resins or polyvinyl acetal resins to make the sheets thinner.
  • Patent Document 2 describes a methacrylate copolymer obtained by copolymerizing isobutyl methacrylate, 2-ethylhexyl methacrylate, and a methacrylate having a hydroxyl group in a predetermined ratio, and claims that the use of such a binder resin provides good moldability and degreasing properties.
  • JP 2011-84433 A Japanese Patent Application Publication No. 10-167836
  • the binder resin In order to thin the ceramic green sheet, the binder resin needs to have sufficient strength, and in order to increase the strength, it is generally necessary to increase the molecular weight. However, if the molecular weight is increased, the viscosity of the slurry composition in which the inorganic particles and the binder are dispersed becomes too high, which deteriorates the dispersibility of the inorganic particles, resulting in the generation of foreign matter in the ceramic green sheet and causing a decrease in strength. As described in Patent Document 1, the use of polyvinyl butyral resin makes it possible to thin the sheet, but there is a problem that the decomposition temperature is high and degreasing cannot be performed at low temperatures.
  • the present invention aims to provide a (meth)acrylic resin that can achieve both excellent low-temperature decomposition of a slurry composition and high strength of a ceramic green sheet, and can be used to produce a ceramic laminate that can be further thinned. It also aims to provide a vehicle composition, a slurry composition, and an electronic component that contain the (meth)acrylic resin.
  • the present disclosure (1) is a (meth)acrylic resin having a constitutional unit derived from a (meth)acrylic acid ester monomer, the (meth)acrylic acid ester monomer includes a (meth)acrylic acid ester monomer A and a (meth)acrylic acid ester monomer B, and when the number of carbon atoms of an ester substituent possessed by the (meth)acrylic acid ester monomer A is X, the number of carbon atoms of an ester substituent possessed by the (meth)acrylic acid ester monomer B is 4X.
  • the present disclosure (2) is the (meth)acrylic resin of the present disclosure (1), in which the ratio of the content of the constitutional unit derived from the (meth)acrylic acid ester monomer B to the content of the constitutional unit derived from the (meth)acrylic acid ester monomer A (monomer B/monomer A) is 3 or more and 12 or less.
  • the present disclosure (3) is the (meth)acrylic resin of the present disclosure (1) or (2), wherein the (meth)acrylic acid ester monomer is a methacrylic acid ester monomer.
  • the present disclosure (4) is a (meth)acrylic resin in any combination with any of the present disclosures (1) to (3), in which the Ti value of a resin solution dissolved in butyl acetate is 1.5 or more and 2.5 or less.
  • the present disclosure (5) is a (meth)acrylic resin in any combination with any of the present disclosures (1) to (4), in which the (meth)acrylic acid ester monomer includes a (meth)acrylic acid ester monomer having a branched chain ester substituent and a (meth)acrylic acid ester monomer having a linear chain ester substituent, the ester substituents having the same number of carbon atoms.
  • the present disclosure (6) is the (meth)acrylic resin of the present disclosure (5), in which the ratio of the content of constitutional units derived from (meth)acrylic ester monomers having branched-chain ester substituents to the content of constitutional units derived from (meth)acrylic ester monomers having linear ester substituents, in which the ester substituents have the same number of carbon atoms, ((meth)acrylic ester monomers having branched-chain ester substituents/(meth)acrylic ester monomers having linear ester substituents (the ester substituents have the same number of carbon atoms)) is 0.5 or more and 2.0 or less.
  • the present disclosure (7) is a vehicle composition containing the (meth)acrylic resin of any one of the present disclosures (1) to (6) and an organic solvent.
  • the present disclosure (8) is the vehicle composition of the present disclosure (7), further containing water, wherein the content of the water is 10 ppm by weight or more and 12,000 ppm by weight or less.
  • the present disclosure (9) is a slurry composition containing the vehicle composition of the present disclosure (7), inorganic particles, and a dispersant.
  • the present disclosure (10) is a slurry composition containing the vehicle composition of the present disclosure (8), inorganic particles, and a dispersant.
  • the present disclosure (11) is an electronic component formed using the slurry composition of the present disclosure (9).
  • the present disclosure (12) is an electronic component formed using the slurry composition of the present disclosure (10). The present invention will be described in detail below.
  • the present inventors have found that a slurry composition capable of exhibiting excellent low-temperature decomposition properties can be obtained by combining and using multiple (meth)acrylic acid ester monomers that satisfy the relationship that when the number of carbon atoms of the ester substituent of (meth)acrylic acid ester monomer A is X, the number of carbon atoms of the ester substituent of (meth)acrylic acid ester monomer B is 4X.
  • the inventors have found that when such a (meth)acrylic resin is used as a binder for dispersing inorganic particles, a ceramic green sheet with high strength can be obtained, making it possible to further reduce the thickness.
  • the inventors have found that by using such a (meth)acrylic resin, a ceramic laminate with excellent properties can be manufactured, and have completed the present invention.
  • the (meth)acrylic resin has a structural unit derived from a (meth)acrylic acid ester monomer.
  • the (meth)acrylic acid ester monomer includes a (meth)acrylic acid ester monomer A and a (meth)acrylic acid ester monomer B.
  • the number of carbon atoms of the ester substituent of the (meth)acrylic acid ester monomer A is X
  • the number of carbon atoms of the ester substituent of the (meth)acrylic acid ester monomer B is 4X.
  • the (meth)acrylic resin having the above-mentioned structure six-membered ring carbon is less likely to be formed during the decomposition process during sintering, so that the residue during sintering can be reduced, and furthermore, the (meth)acrylic resin can be made excellent in low-temperature decomposition property.
  • the part of the (meth)acrylic resin derived from the (meth)acrylic acid ester monomer A has a short molecular chain of the ester substituent, and van der Waals forces act strongly
  • the part of the (meth)acrylic resin derived from the (meth)acrylic acid ester monomer B has a long molecular chain of the ester substituent, and van der Waals forces act weakly, and by mixing these two parts, a molded product with good tensile performance can be obtained.
  • the (meth)acrylic resin has structural units derived from the (meth)acrylic acid ester monomer.
  • the (meth)acrylic acid ester monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, and n-octyl (meth)acrylate.
  • alkyl (meth)acrylate examples include alkyl (meth)acrylates having a straight chain alkyl group or a branched chain alkyl group, such as n-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, isolauryl (meth)acrylate, n-tetradecyl (meth)acrylate, n-stearyl (meth)acrylate, and isostearyl (meth)acrylate.
  • alkyl (meth)acrylates having a straight chain alkyl group or a branched chain alkyl group such as n-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth
  • Examples of the (meth)acrylic acid ester monomer include (meth)acrylates having a polyoxyalkylene structure, such as polytetramethylene glycol monomethacrylate, poly(ethylene glycol.polytetramethylene glycol) monomethacrylate, poly(propylene glycol.tetramethylene glycol) monomethacrylate, propylene glycol.polybutylene glycol monomethacrylate, methoxypolytetramethylene glycol monomethacrylate, methoxypoly(ethylene glycol.polytetramethylene glycol) monomethacrylate, methoxypoly(propylene glycol.tetramethylene glycol) monomethacrylate, and methoxypropylene glycol.polybutylene glycol monomethacrylate.
  • polytetramethylene glycol monomethacrylate poly(ethylene glycol.polytetramethylene glycol) monomethacrylate
  • examples of the (meth)acrylic acid ester monomer include (meth)acrylates having a polar group, such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, (meth)acrylic acid, glycidyl (meth)acrylate, and glycerol mono(meth)acrylate.
  • the (meth)acrylic acid ester monomer is preferably an alkyl (meth)acrylate, and more preferably methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-lauryl (meth)acrylate.
  • the (meth)acrylic acid ester monomer is preferable because it can reduce residues during sintering and can further improve low-temperature decomposition properties.
  • the above-mentioned (meth)acrylic acid ester monomer is preferably a (meth)acrylic acid ester monomer having a linear ester substituent (hereinafter also referred to as a "linear monomer”) or a (meth)acrylic acid ester monomer having a branched chain ester substituent (hereinafter also referred to as a "branched monomer”), and from the viewpoint of improving the strength of the obtained ceramic green sheet, it is preferable to include a (meth)acrylic acid ester monomer having a linear ester substituent and a (meth)acrylic acid ester monomer having a branched chain ester substituent.
  • the ratio of the content of the constituent units derived from the (meth)acrylic acid ester monomer having a branched chain ester substituent to the content of the constituent units derived from the (meth)acrylic acid ester monomer having a straight chain ester substituent in the (meth)acrylic resin (branched monomer/straight chain monomer) is preferably 0.5 or more, and preferably 2.0 or less, more preferably 0.6 or more, and more preferably 1.6 or less, from the viewpoint of improving the strength of the obtained ceramic green sheet.
  • the number of carbon atoms in the ester substituent of the (meth)acrylic acid ester monomer is preferably 1 to 18, more preferably 1 to 14, and even more preferably 1 to 12.
  • the (meth)acrylic acid ester monomer preferably includes a (meth)acrylic acid ester monomer having an ester substituent with 1 to 4 carbon atoms.
  • a (meth)acrylic acid ester monomer having an ester substituent with 1 to 4 carbon atoms methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and isobutyl (meth)acrylate are preferred, and methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate are more preferred.
  • the (meth)acrylic acid ester monomer having an ester substituent with 1 to 4 carbon atoms a (meth)acrylic acid ester monomer having an ester substituent with 1 to 3 carbon atoms is more preferable, and a (meth)acrylic acid ester monomer having an ester substituent with 1 to 2 carbon atoms is even more preferable.
  • the content of structural units derived from (meth)acrylic acid ester monomers in which the ester substituent has 1 to 4 carbon atoms in the (meth)acrylic resin is preferably 20% by weight or more, preferably 100% by weight or less, and more preferably 30% by weight or more.
  • a (meth)acrylic acid ester monomer having an ester substituent with 1 to 4 carbon atoms a (meth)acrylic acid ester monomer having a straight-chain ester substituent with 1 to 4 carbon atoms (hereinafter also referred to as a "C1-4 straight-chain monomer”) and a (meth)acrylic acid ester monomer having a branched-chain ester substituent with 3 to 4 carbon atoms (hereinafter also referred to as a "C3-4 branched monomer”) may be used in combination.
  • the ratio of the content of constitutional units derived from (meth)acrylic acid ester monomers having a branched chain ester substituent having 3 to 4 carbon atoms to the content of constitutional units derived from (meth)acrylic acid ester monomers having a linear ester substituent having 1 to 4 carbon atoms in the (meth)acrylic resin is preferably 0 or more, preferably 12 or less, and more preferably 3 or less.
  • the content of constituent units derived from (meth)acrylic acid ester monomers having an ester substituent with 1 to 3 carbon atoms in the (meth)acrylic resin is preferably 0% by weight or more, more preferably 3% by weight or more, and even more preferably 5% by weight or more, and is preferably 70% by weight or less, and more preferably 50% by weight or less.
  • the content of structural units derived from (meth)acrylic acid ester monomers having an ester substituent with 1 to 2 carbon atoms in the (meth)acrylic resin is preferably 0% by weight or more, more preferably 3% by weight or more, and even more preferably 5% by weight or more, and is preferably 70% by weight or less, and more preferably 50% by weight or less.
  • the (meth)acrylic acid ester monomer preferably contains a (meth)acrylic acid ester monomer having an ester substituent with 4 to 16 carbon atoms.
  • Examples of the (meth)acrylic acid ester monomer having an ester substituent having 4 to 16 carbon atoms include n-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isode
  • n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-lauryl (meth)acrylate are preferred, and n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate are more preferred.
  • (meth)acrylic acid ester monomer having an ester substituent with 4 to 16 carbon atoms a (meth)acrylic acid ester monomer having an ester substituent with 4 to 12 carbon atoms is more preferable, and a (meth)acrylic acid ester monomer having an ester substituent with 4 to 8 carbon atoms is even more preferable.
  • the content of structural units derived from (meth)acrylic acid ester monomers in which the ester substituent has 4 to 16 carbon atoms in the (meth)acrylic resin is preferably 30% by weight or more, and preferably 100% by weight or less, more preferably 50% by weight or more, more preferably 97% by weight or less, and even more preferably 95% by weight or less.
  • a (meth)acrylic acid ester monomer having an ester substituent with 4 to 16 carbon atoms a (meth)acrylic acid ester monomer having a straight-chain ester substituent with 4 to 16 carbon atoms (hereinafter also referred to as a "C4-16 straight-chain monomer”) and a (meth)acrylic acid ester monomer having a branched-chain ester substituent with 4 to 16 carbon atoms (hereinafter also referred to as a "C4-16 branched monomer”) may be used in combination.
  • the ratio of the content of constitutional units derived from (meth)acrylic acid ester monomers having a branched chain ester substituent having 4 to 16 carbon atoms to the content of constitutional units derived from (meth)acrylic acid ester monomers having a linear ester substituent having 4 to 16 carbon atoms in the (meth)acrylic resin is preferably 0 or more and 3.5 or less, more preferably 0.2 or more, and more preferably 2.5 or less.
  • the content of constituent units derived from (meth)acrylic acid ester monomers having an ester substituent with 4 to 12 carbon atoms in the (meth)acrylic resin is preferably 30% by weight or more, and preferably 100% by weight or less, more preferably 50% by weight or more, more preferably 97% by weight or less, and even more preferably 95% by weight or less.
  • the content of structural units derived from (meth)acrylic acid ester monomers having an ester substituent with 4 to 8 carbon atoms in the (meth)acrylic resin is preferably 25% by weight or more, preferably 95% by weight or less, and more preferably 50% by weight or more.
  • the (meth)acrylic acid ester monomer may include a (meth)acrylic acid ester monomer having an ester substituent with 17 or more carbon atoms, but preferably does not include a (meth)acrylic acid ester monomer having an ester substituent with 17 or more carbon atoms.
  • the (meth)acrylic acid ester monomer may contain a (meth)acrylic acid ester monomer having an ester substituent with 13 or more carbon atoms, but more preferably does not contain a (meth)acrylic acid ester monomer having an ester substituent with 13 or more carbon atoms.
  • the (meth)acrylic acid ester monomer is preferably an alkyl (meth)acrylate.
  • the (meth)acrylic acid ester monomer may contain a (meth)acrylic acid ester monomer other than an alkyl (meth)acrylate (hereinafter also referred to as "other monomers"), but it is more preferable that the (meth)acrylic acid ester monomer does not contain other monomers.
  • the (meth)acrylic acid ester monomer has a linear monomer and a branched monomer in which the number of carbon atoms in the ester substituents is the same.
  • the ratio of the content of structural units derived from branched monomers to the content of structural units derived from linear monomers having the same number of carbon atoms in the ester substituents in the (meth)acrylic resin is preferably 0.5 or more, and preferably 2.0 or less, more preferably 0.6 or more, and more preferably 1.7 or less, from the viewpoint of improving the strength of the resulting ceramic green sheet.
  • the (meth)acrylic acid ester monomer includes a (meth)acrylic acid ester monomer A (hereinafter also referred to as “monomer A”) and a (meth)acrylic acid ester monomer B (hereinafter also referred to as "monomer B").
  • the number of carbon atoms of the ester substituent of the monomer A is X
  • the number of carbon atoms of the ester substituent of the monomer B is 4X.
  • the monomer A a (meth)acrylic acid ester monomer having an ester substituent with 1 to 4 carbon atoms is preferable, a (meth)acrylic acid ester monomer having an ester substituent with 1 to 3 carbon atoms is more preferable, and a (meth)acrylic acid ester monomer having an ester substituent with 1 to 2 carbon atoms is even more preferable.
  • the monomer A may be a straight-chain monomer or a branched monomer, and is preferably a straight-chain monomer.
  • the content of the structural unit derived from the monomer A in the (meth)acrylic resin is preferably 2% by weight or more and preferably 70% by weight or less, more preferably 3% by weight or more and more preferably 65% by weight or less.
  • the content of the structural units derived from the above-mentioned monomer A means the total amount of the (meth)acrylic acid ester monomers corresponding to the above-mentioned monomer A.
  • the monomer B may be a straight-chain monomer, a branched monomer, or a monomer containing a straight-chain monomer and a branched monomer, so long as the number of carbon atoms of the ester substituent of the monomer A is 4X, where X is the number of carbon atoms of the ester substituent of the monomer B.
  • the content of the structural units derived from the monomer B in the (meth)acrylic resin is preferably 20% by weight or more and preferably 85% by weight or less, more preferably 25% by weight or more and more preferably 80% by weight or less.
  • the content of the structural units derived from the above-mentioned monomer B means the total amount of the (meth)acrylic acid ester monomers corresponding to the above-mentioned monomer B.
  • the ratio of the content of the structural units derived from the branched monomer to the content of the structural units derived from the linear monomer in the structural units derived from the monomer B is preferably 0.5 or more, preferably 2.0 or less, more preferably 0.6 or more, and more preferably 1.7 or less.
  • the ratio of the content of the constituent units derived from the monomer B to the content of the constituent units derived from the monomer A in the (meth)acrylic resin is preferably 3 or more and is preferably 12 or less, more preferably 4 or more and more preferably 7 or less.
  • the above-mentioned ratio (monomer B/monomer A) is calculated by summing up the product of the ratio (monomer B/monomer A) in the monomers having the same X and the total content of the monomers having the same X, and dividing the product by the sum of the total content of monomers A and B for each monomer having the same X.
  • the content of the constituent units derived from the (meth)acrylic acid ester monomer different from the constituent units derived from the monomer A and the constituent units derived from the monomer B may be 0% by weight, is preferably 1% by weight or more, is preferably 80% by weight or less, is more preferably 5% by weight or more, and is more preferably 70% by weight or less.
  • the content of the structural unit derived from the acrylic monomer in the (meth)acrylic resin is preferably 5% by weight or less, more preferably 1% by weight or less, since the lower content has the advantage of improving low-temperature decomposition.
  • the lower limit is not particularly limited, but is, for example, 0% by weight or more.
  • the content of the structural unit derived from the acrylic monomer is preferably 0 to 5% by weight, more preferably 0 to 1% by weight, and even more preferably 0% by weight.
  • the acrylic monomer means acrylic acid and acrylic esters.
  • the weight average molecular weight (Mw) of the (meth)acrylic resin is preferably 30,000 or more, and preferably 5,000,000 or less.
  • the weight average molecular weight (Mw) is more preferably 200,000 or more, more preferably 4,500,000 or less, even more preferably 300,000 or more, still more preferably 4,000,000 or less, and particularly preferably 1,000,000 or more.
  • the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the (meth)acrylic resin is at least 1, and is preferably at most 5.0, more preferably at most 4.0, and even more preferably at most 3.5. When it is within the above range, fine undissolved matter is less likely to be generated in the vehicle composition, the strength of the ceramic green sheet can be further increased, and the generation of voids in the ceramic laminate after firing can be prevented.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are average molecular weights calculated based on polystyrene standards, and can be obtained by GPC measurement using, for example, column LF-804 (manufactured by Showa Denko KK).
  • the average particle size of the resin particles is, from the viewpoint of solubility, preferably 0.1 ⁇ m or more and preferably 1.0 ⁇ m or less, more preferably 0.2 ⁇ m or more, more preferably 0.9 ⁇ m or less, even more preferably 0.3 ⁇ m or more, and even more preferably 0.8 ⁇ m or less.
  • the average particle size can be determined, for example, by measuring the volume average particle size using a laser diffraction/scattering type particle size distribution measuring device.
  • the CV value of the particle size of the (meth)acrylic resin particles is preferably 15% or less, more preferably 12% or less, even more preferably 10% or less, and even more preferably 8% or less.
  • the solubility of the (meth)acrylic resin can be further improved.
  • the improved solubility leads to increased productivity, and the reduced amount of undissolved resin leads to improved tensile properties.
  • the lower limit is not particularly limited, and is, for example, 0%.
  • the CV value can be calculated from the average particle size and standard deviation of 100 particles by observing the (meth)acrylic resin particles using a scanning electron microscope. The CV value tends to be smaller when a persulfate such as ammonium persulfate or potassium persulfate is used.
  • the (meth)acrylic resin preferably has a Ti value of 1.5 or more and 2.5 or less in a resin solution obtained by dissolving the (meth)acrylic resin in butyl acetate.
  • the Ti value is more preferably 1.6 or more and more preferably 2.2 or less.
  • the Ti value can be determined by calculating the ratio (viscosity (2 rpm)/viscosity (20 rpm)) of the viscosity (2 rpm) measured at 25° C. and 2 rpm using a BH type viscometer to the viscosity (20 rpm) measured at 25° C. and 20 rpm.
  • the resin solution for example, a butyl acetate solution containing 15% by weight of a (meth)acrylic resin can be used.
  • the Ti value can be adjusted to a preferred range by adjusting the ratio of the content of the structural unit derived from the monomer A to the content of the structural unit derived from the monomer B.
  • the (meth)acrylic resin preferably has a glass transition temperature (Tg) of 30° C. or higher and preferably 85° C. or lower, more preferably 32° C. or higher and more preferably 80° C. or lower, even more preferably 42° C. or higher and still more preferably 75° C. or lower.
  • Tg glass transition temperature
  • the glass transition temperature (Tg) can be measured, for example, by using a differential scanning calorimeter (DSC).
  • the (meth)acrylic resin preferably has a 90% by weight decomposition temperature of 280°C or less when heated from 30°C at 5°C/min, more preferably 270°C or less, and even more preferably 260°C or less. There is no particular lower limit, and it is 30°C or more, and the lower the better.
  • the 90% by weight decomposition temperature is preferably 30 to 280°C, more preferably 30 to 270°C, and even more preferably 30 to 260°C.
  • Examples of a method for producing the (meth)acrylic resin include a method in which an organic solvent or the like is added to a raw material monomer mixture containing a (meth)acrylic acid ester monomer or the like to prepare a monomer mixture, and a polymerization initiator and a chain transfer agent are further added to the obtained monomer mixture to copolymerize the raw material monomers.
  • the polymerization method is not particularly limited, and examples thereof include emulsion polymerization, suspension polymerization, bulk polymerization, interfacial polymerization, solution polymerization, etc. Among these, emulsion polymerization is preferred.
  • organic solvents examples include toluene, ethyl acetate, butyl acetate, pentyl acetate, hexyl acetate, ethyl butyrate, butyl butyrate, pentyl butyrate, hexyl butyrate, isopropanol, methyl isobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisobutyl ether, trimethylpentanediol monoisobutyrate, butyl carbitol, butyl carbitol acetate, terpineol, terpineol acetate, dihydroterpineol, dihydro
  • butyl acetate, terpineol, terpineol acetate, dihydroterpineol, dihydroterpineol acetate, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisobutyl ether, butyl carbitol, butyl carbitol acetate, and texanol are preferred.
  • butyl acetate, terpineol, terpineol acetate, dihydroterpineol, and dihydroterpineol acetate are more preferred.
  • These organic solvents may be used alone or in combination of two or more.
  • polymerization initiator examples include t-butyl peroxypivalate, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroxyperoxide, t-butyl hydroxyperoxide, cyclohexanone peroxide, and disuccinic acid peroxide.
  • water-soluble azo compounds such as 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamidine] tetrahydrate, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], and 4,4'-azobis-4-cyanovaleric acid; oxoacids such as potassium persulfate (potassium perox).
  • the amount of the polymerization initiator added is preferably 0.03 parts by weight or more, and preferably 4.0 parts by weight or less, more preferably 0.05 parts by weight or more, and more preferably 3.6 parts by weight or less, relative to 100 parts by weight of the raw material monomer.
  • the amount of the polymerization initiator added is preferably 0.03 to 4.0 parts by weight, and more preferably 0.05 to 3.6 parts by weight, relative to 100 parts by weight of the raw material monomer.
  • chain transfer agent examples include 3-mercapto-1,2-propanediol, 3-mercapto-1-propanol, 3-mercapto-2-butanol, 8-mercapto-1-octanol, 2-mercaptobenzimidazole, mercaptosuccinic acid, and mercaptoacetic acid.
  • the amount of the chain transfer agent added is preferably 0.01 parts by weight or more, more preferably 0.02 parts by weight or more, and preferably 10.0 parts by weight or less, more preferably 5.0 parts by weight or less, per 100 parts by weight of the raw material monomer.
  • the amount of the chain transfer agent added is preferably 0.01 to 10.0 parts by weight, more preferably 0.02 to 5.0 parts by weight, per 100 parts by weight of the raw material monomer.
  • the temperature during polymerization is preferably 50°C or higher, and preferably 90°C or lower, more preferably 60°C or higher, and more preferably 80°C or lower.
  • a vehicle composition can be prepared using the above (meth)acrylic resin and a solvent containing an organic solvent.
  • the present invention also includes a vehicle composition containing the above-mentioned (meth)acrylic resin and a solvent containing an organic solvent.
  • the content of the (meth)acrylic resin in the vehicle composition is preferably 5% by weight or more, more preferably 10% by weight or more, and is preferably 50% by weight or less, more preferably 40% by weight or less.
  • the vehicle composition contains a solvent including an organic solvent.
  • organic solvent include alcohols such as aliphatic alcohols, glycols, terpene alcohols, and aromatic alcohols, aromatic hydrocarbons, esters, ketones, and N-methylpyrrolidone.
  • aliphatic alcohols examples include ethanol, propanol, isopropanol, heptanol, octanol, decanol, tridecanol, lauryl alcohol, tetradecyl alcohol, cetyl alcohol, 2-ethyl-1-hexanol, octadecyl alcohol, hexadecenol, oleyl alcohol, texanol, 2-butyl-2-ethyl-1,3-propanediol, and neopentyl glycol.
  • glycols examples include ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisobutyl ether, butyl carbitol, ethylene glycol monoethyl ether acetate, trimethylpentanediol monoisobutyrate, butyl carbitol acetate, Texanol, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, and ethylene glycol ethyl ether.
  • terpene alcohols examples include terpineol, dihydroterpineol, terpineol acetate, and dihydroterpineol acetate.
  • the aromatic alcohols include benzyl alcohol.
  • the aromatic hydrocarbons include toluene and the like.
  • esters include methyl acetate, ethyl acetate, butyl acetate, hexyl acetate, dodecyl acetate, isoamyl acetate, butyl butyrate, butyl lactate, dioctyl phthalate, and dioctyl adipate.
  • ketones examples include methyl isobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and isophorone.
  • esters are preferred, with methyl acetate, ethyl acetate, butyl acetate, hexyl acetate and dodecyl acetate being more preferred, ethyl acetate, butyl acetate and hexyl acetate being even more preferred, and butyl acetate being even more preferred.
  • the content of the organic solvent in the vehicle composition is not particularly limited, but is preferably 50% by weight or more, and preferably 95% by weight or less, more preferably 55% by weight or more, and more preferably 88.8% by weight or less.
  • the solvent preferably further contains water.
  • the content of the water in the vehicle composition is preferably 10 ppm by weight or more and 12,000 ppm by weight or less. By including water in the above range, compatibility with the dispersant improves and low-temperature decomposition properties are further improved.
  • the water content in the vehicle composition is more preferably 300 ppm by weight or more, more preferably 1000 ppm by weight or less, even more preferably 400 ppm by weight or more, and even more preferably 700 ppm by weight or less.
  • the content of the solvent in the vehicle composition is not particularly limited, but is preferably 50% by weight or more, and preferably 95% by weight or less, more preferably 60% by weight or more, and more preferably 90% by weight or less.
  • the vehicle composition can be produced, for example, by adding an organic solvent, water, etc. to the (meth)acrylic resin obtained by the above method and stirring and mixing.
  • a slurry composition can be prepared using the vehicle composition, inorganic particles and dispersant.
  • a slurry composition containing the above vehicle composition, inorganic particles, and a dispersant also constitutes one aspect of the present invention.
  • the content of the (meth)acrylic resin in the slurry composition is preferably 3% by weight or more, and preferably 10% by weight or less, more preferably 5% by weight or more, and more preferably 8% by weight or less.
  • the content of the organic solvent in the slurry composition is preferably 25% by weight or more, and preferably 70% by weight or less, more preferably 30% by weight or more, and more preferably 60% by weight or less.
  • the water content in the above slurry composition is preferably 5 ppm by weight or more, preferably 15,000 ppm by weight or less, more preferably 10 ppm by weight or more, more preferably 12,000 ppm by weight or less, even more preferably 50 ppm by weight or more, even more preferably 10,000 ppm by weight or less, and even more preferably 7,500 ppm by weight or less.
  • the content of the solvent in the slurry composition is preferably 25% by weight or more, and preferably 70% by weight or less, more preferably 30% by weight or more, and more preferably 60% by weight or less.
  • the slurry composition contains inorganic particles.
  • the inorganic particles are not particularly limited, and examples thereof include glass powder, ceramic powder, phosphor particles, silicon oxide particles, metal particles, and the like.
  • the glass powder is not particularly limited, and examples thereof include glass powders such as bismuth oxide glass, silicate glass, lead glass, zinc glass, and boron glass, as well as glass powders of various silicon oxides such as CaO-Al 2 O 3 -SiO 2 , MgO-Al 2 O 3 -SiO 2 , and LiO 2 -Al 2 O 3 -SiO 2 .
  • SnO-B 2 O 3 -P 2 O 5 -Al 2 O 3 mixture there are also used SnO-B 2 O 3 -P 2 O 5 -Al 2 O 3 mixture, PbO-B 2 O 3 -SiO 2 mixture, BaO-ZnO-B 2 O 3 -SiO 2 mixture, ZnO-Bi 2 O 3 -B 2 O 3 -SiO 2 mixture, Bi 2 O 3 -B 2 O 3 -BaO-CuO mixture, Bi 2 O 3 -ZnO-B 2 O 3 -Al 2 O 3 -SrO mixture, ZnO-Bi 2 O 3 -B 2 O 3 mixture, Bi 2 O 3 -SiO 2 mixture, P 2 O 5 -Na 2 O-CaO-BaO-Al 2 O 3 -B 2 O 3 mixture, P 2 O 5 -SnO mixture, P 2 O 5 -SnO-B 2 O 3 mixture, P 2 O 5 -SnO-S
  • a glass powder of a PbO-B 2 O 3 -SiO 2 mixture, or a lead-free glass powder such as a lead-free BaO-ZnO-B 2 O 3 -SiO 2 mixture or a lead-free ZnO-Bi 2 O 3 -B 2 O 3 -SiO 2 mixture is preferred.
  • the ceramic powder is not particularly limited, and examples thereof include alumina, ferrite, zirconia, zircon, barium zirconate, calcium zirconate, titanium oxide, barium titanate, strontium titanate, calcium titanate, magnesium titanate, zinc titanate, lanthanum titanate, neodymium titanate, lead zirconate, alumina nitride, silicon nitride, boron nitride, boron carbide, barium stannate, calcium stannate, magnesium silicate, mullite, steatite, cordierite, and forsterite.
  • ITO, FTO, niobium oxide, vanadium oxide, tungsten oxide, lanthanum strontium manganite, lanthanum strontium cobalt ferrite, yttrium stabilized zirconia, gadolinium doped ceria, nickel oxide, lanthanum chromite, and the like can also be used.
  • the phosphor particles are not particularly limited, and for example, the phosphor material may be a blue phosphor material, a red phosphor material, a green phosphor material, etc., which are conventionally known as phosphor materials for displays.
  • the blue phosphor material may be MgAl10O17 :Eu- based , Y2SiO5 :Ce-based, CaWO4 :Pb-based, BaMgAl14O23 : Eu - based , BaMgAl16O27 :Eu - based, BaMg2Al14O23 : Eu - based, BaMg2Al14O27 :Eu - based , or ZnS:(Ag,Cd)-based.
  • red phosphor materials examples include Y2O3 : Eu-based, Y2SiO5 : Eu-based, Y3Al5O12 :Eu-based, Zn3 ( PO4 ) 2 :Mn-based, YBO3 :Eu-based, (Y,Gd) BO3 :Eu-based, GdBO3 :Eu-based, ScBO3 :Eu-based, and LuBO3 :Eu-based materials.
  • the green phosphor material for example, Zn2SiO4 :Mn-based, BaAl12O19 :Mn-based , SrAl13O19 :Mn-based, CaAl12O19 :Mn-based, YBO3 :Tb-based, BaMgAl14O23 : Mn - based , LuBO3 :Tb-based, GdBO3 :Tb-based, ScBO3 : Tb -based , and Sr6Si3O3Cl4 :Eu - based materials are used.
  • ZnO:Zn-based, ZnS:(Cu,Al)-based, ZnS:Ag-based, Y2O2S :Eu-based, ZnS:Zn-based, (Y,Cd) BO3 :Eu - based, and BaMgAl12O23 : Eu-based can also be used.
  • the metal particles are not particularly limited, and examples thereof include powders of iron, copper, nickel, palladium, platinum, gold, silver, aluminum, tungsten, and alloys thereof.
  • metals such as copper and iron, which have good adsorption properties with carboxyl groups, amino groups, amide groups, etc. and are easily oxidized, can also be preferably used. These metal particles may be used alone or in combination of two or more kinds.
  • various carbon blacks, carbon nanotubes, etc. may be used in addition to metal complexes.
  • the inorganic particles preferably contain lithium or titanium.
  • the average particle size of the inorganic particles is preferably 0.01 ⁇ m or more, and preferably 5 ⁇ m or less, more preferably 0.05 ⁇ m or more, more preferably 3 ⁇ m or less, even more preferably 0.1 ⁇ m or more, and even more preferably 1 ⁇ m or less.
  • the average particle size of the inorganic particles is preferably 0.01 to 5 ⁇ m, more preferably 0.05 to 3 ⁇ m, and even more preferably 0.1 to 1 ⁇ m.
  • the average particle size can be determined, for example, by measuring the volume average particle size using a laser diffraction/scattering type particle size distribution measuring device.
  • the content of the inorganic particles in the slurry composition is preferably 20% by weight or more and 90% by weight or less, and within this range, the composition has sufficient viscosity, excellent coatability, and excellent dispersibility of the inorganic particles.
  • the content of the inorganic particles is more preferably 25% by weight or more, more preferably 70% by weight or less, even more preferably 30% by weight or more, even more preferably 60% by weight or less, even more preferably 40% by weight or more, and even more preferably 55% by weight or less.
  • the slurry composition contains a dispersant.
  • Suitable examples of the dispersant include fatty acids, aliphatic amines, alkanolamides, and phosphoric esters. Silane coupling agents may also be used.
  • the fatty acid is not particularly limited, and examples thereof include saturated fatty acids such as behenic acid, stearic acid, palmitic acid, myristic acid, lauric acid, capric acid, caprylic acid, coconut fatty acid, etc., and unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, sorbic acid, beef tallow fatty acid, and hardened castor fatty acid, etc.
  • lauric acid, stearic acid, oleic acid, etc. are preferred.
  • the aliphatic amine is not particularly limited, and examples thereof include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, alkyl(coconut)amine, alkyl(hardened beef tallow)amine, alkyl(beef tallow)amine, and alkyl(soybean)amine.
  • the alkanolamide is not particularly limited, and examples thereof include coconut fatty acid diethanolamide, beef tallow fatty acid diethanolamide, lauric acid diethanolamide, and oleic acid diethanolamide.
  • the phosphate ester is not particularly limited, and examples thereof include polyoxyethylene alkyl ether phosphate ester and polyoxyethylene alkyl allyl ether phosphate ester.
  • the content of the dispersant in the slurry composition is preferably 0.1% by weight or more, and preferably 1.5% by weight or less, more preferably 0.15% by weight or more, and more preferably 1.0% by weight or less.
  • the above-mentioned slurry composition may further contain additives such as a plasticizer and a surfactant.
  • a plasticizer include di(butoxyethyl) adipate, dibutoxyethoxyethyl adipate, triethylene glycol dibutyl, triethylene glycol bis(2-ethylhexanoate), triethylene glycol dihexanoate, triethyl acetyl citrate, tributyl acetyl citrate, diethyl acetyl citrate, dibutyl acetyl citrate, dibutyl sebacate, triacetin, diethyl acetyloxymalonate, and diethyl ethoxymalonate.
  • the surfactant is not particularly limited, and examples thereof include cationic surfactants, anionic surfactants, and nonionic surfactants.
  • the nonionic surfactant is not particularly limited, but is preferably a nonionic surfactant having an HLB value of 10 or more and 20 or less.
  • the HLB value is used as an index representing the hydrophilicity and lipophilicity of a surfactant, and several calculation methods have been proposed.
  • the saponification value is S
  • the acid value of the fatty acid constituting the surfactant is A
  • the HLB value is defined as 20 (1-S/A).
  • a nonionic surfactant having a polyethylene oxide in which an alkylene ether is added to an aliphatic chain is suitable, and specifically, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, etc. are preferably used.
  • the nonionic surfactant has good thermal decomposition properties, but if added in a large amount, the thermal decomposition properties of the inorganic particle dispersion slurry composition may decrease, so the preferred upper limit of the content is 5% by weight.
  • the viscosity of the slurry composition is not particularly limited, but the viscosity measured at 25° C. using a B-type viscometer is preferably 200 mPa ⁇ s or more, more preferably 500 mPa ⁇ s or more, and is preferably 100,000 mPa ⁇ s or less, more preferably 50,000 mPa ⁇ s or less.
  • the viscosity is preferably 200 to 100,000 mPa ⁇ s, more preferably 500 to 50,000 mPa ⁇ s.
  • the method for preparing the slurry composition is not particularly limited, and examples thereof include conventionally known stirring methods, specifically, for example, a method in which the vehicle composition, the inorganic particles, the dispersant, and other components such as additional solvents and plasticizers added as necessary are stirred with a three-roll mill or the like.
  • the order of addition of the components of the slurry composition can be set appropriately.
  • An electronic part obtained by using the above-mentioned slurry composition also constitutes one aspect of the present invention.
  • the electronic components include die attachment paste (ACP), die attachment film (ACF), via electrodes for TSV/TGV, touch panels, various circuits for RFID and sensor substrates, various die bonding agents, sealing agents for MEMS devices, solar cells, multilayer ceramic capacitors, LTCC, silicon capacitors, electrode materials for all-solid-state batteries, etc.
  • the material can also be used for antibacterial materials, electromagnetic wave shields, catalysts, fluorescent materials, etc.
  • the slurry composition is applied onto a support film which has been subjected to a release treatment on one side, the organic solvent is dried, and the film is molded to produce an inorganic particle dispersion molded product.
  • the shape of the inorganic particle dispersion molded product is not particularly limited, but may be, for example, a sheet.
  • Examples of a method for producing the above-mentioned inorganic particle dispersion molding include a method in which the above-mentioned slurry composition is applied to a support film by a coating method such as a roll coater, die coater, squeeze coater, or curtain coater to form a uniform coating film.
  • a coating method such as a roll coater, die coater, squeeze coater, or curtain coater to form a uniform coating film.
  • the support film used in producing the inorganic particle dispersion molding is preferably a resin film that is heat-resistant, solvent-resistant, and flexible.
  • the flexibility of the support film allows the inorganic particle dispersion slurry composition to be applied to the surface of the support film by a roll coater, blade coater, or the like, and the resulting inorganic particle dispersion sheet-forming film can be stored and supplied in a rolled-up state.
  • the resin that forms the support film examples include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, fluorine-containing resins such as polyfluoroethylene, nylon, cellulose, and the like.
  • the thickness of the support film is preferably, for example, 10 to 100 ⁇ m.
  • the surface of the support film is preferably subjected to a release treatment, which allows the support film to be easily peeled off in the transfer step.
  • the above slurry composition can be applied and dried to produce a molded product in which inorganic particles are dispersed. Furthermore, by using the above-mentioned slurry composition and inorganic particle dispersion molding for an external electrode conductive paste, a multilayer ceramic capacitor, which is an electronic component, can be produced.
  • the method for manufacturing the multilayer ceramic capacitor includes a manufacturing method including a step of printing and drying a conductive paste on the inorganic particle dispersion molding to produce a dielectric sheet, and a step of laminating the dielectric sheets.
  • the conductive paste contains a conductive powder.
  • the material of the conductive powder is not particularly limited as long as it is a material having conductivity, and examples thereof include nickel, palladium, platinum, gold, silver, copper, molybdenum, tin, and alloys thereof. These conductive powders may be used alone or in combination of two or more kinds.
  • the method for printing the conductive paste is not particularly limited, and examples include screen printing, die coat printing, offset printing, gravure printing, inkjet printing, etc.
  • dielectric sheets printed with the conductive paste are stacked to produce a raw ceramic laminate, which is then fired in a reducing atmosphere at a temperature of 300 to 1500°C, resulting in a large number of component elements.
  • a conductive paste for external electrodes containing the above-mentioned (meth)acrylic resin is applied to both end surfaces of each of these component elements by immersion, and then this is dried at 100 to 200°C and then fired at 300 to 800°C in a reducing atmosphere to form external electrodes on both ends of the component elements.
  • the present invention provides a (meth)acrylic resin that can achieve both excellent low-temperature decomposition of the slurry composition and high strength of the ceramic green sheet, and can be used to produce a ceramic laminate that can be further thinned. It also provides a vehicle composition, a slurry composition, and an electronic component that contain the (meth)acrylic resin.
  • Examples 1 to 19, Comparative Examples 1 to 9 Preparation of (meth)acrylic resin particles
  • a 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath, and a nitrogen gas inlet was prepared, and 100 parts by weight of monomers in total were charged into the 2 L separable flask so as to obtain the composition shown in Table 1. Furthermore, 900 parts by weight of water was mixed to obtain a monomer mixture.
  • MMA methyl methacrylate (carbon number of ester substituent: 1) EMA: ethyl methacrylate (number of carbon atoms in ester substituent: 2) nPMA: n-propyl methacrylate (carbon number of ester substituent: 3) nBMA: n-butyl methacrylate (carbon number of ester substituent: 4) iBMA: isobutyl methacrylate (carbon number of ester substituent: 4) OMA: n-octyl methacrylate (carbon number of ester substituent: 8) 2EHMA: 2-ethylhexyl methacrylate (number of carbon atoms in ester substituent: 8) LMA: n-lauryl methacrylate (carbon number of ester substituent: 12) MA: methyl acrylate (number of carbon atoms in ester substituent: 1) BA: butyl acrylate (carbon number of ester substituent: 4)
  • the resulting monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the atmosphere in the separable flask was replaced with nitrogen gas and the water bath was heated with stirring until it reached 80° C. Thereafter, a chain transfer agent and a polymerization initiator were added in the amounts shown in Table 1 to initiate polymerization. After 7 hours from the start of polymerization, the polymerization was terminated by cooling to room temperature. The resin solution obtained was then dried in an oven at 100° C. to remove water, thereby obtaining (meth)acrylic resin particles.
  • the chain transfer agent and polymerization initiator used were as follows: ⁇ Chain Transfer Agent> CT-1: 3-mercapto-1,2-propanediol ⁇ polymerization initiator> KPS: Potassium persulfate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • the dispersants and inorganic particles used were as follows: ⁇ Dispersant> Nopcosperse 092 (manufactured by Sanyo Chemical Industries, Ltd.) ⁇ Inorganic particles> Barium titanate (BT-02, Sakai Chemical Industry Co., Ltd., average particle size 0.2 ⁇ m)
  • Weight average molecular weight (Mw) The weight average molecular weight (Mw) of the obtained (meth)acrylic resin particles was measured in terms of polystyrene by gel permeation chromatography using an LF-804 (manufactured by SHOKO Corporation) as a column.
  • TGDTA Low temperature decomposition
  • Screen printing machine (MT-320TV, manufactured by Microtec) Screen plate (Tokyo Process Services, ST500, emulsion 2 ⁇ m, 2012 patterns, screen frame 320 mm x 320 mm)
  • Printed glass substrate (soda glass, 150 mm x 150 mm, thickness 1.5 mm) A small surface roughness indicates excellent dispersibility of inorganic particles.
  • the volume of the particles was calculated assuming that the particles were true spheres with a particle size of 0.75 ⁇ m, and the proportion of particles with a particle size of 0.5 to 1.0 ⁇ m (10 -8 volume%) was calculated based on the obtained measurement results. Fewer particles means fewer voids in the ceramic laminate, which is therefore superior.
  • a (meth)acrylic resin capable of producing a ceramic laminate that can be further thinned by achieving both excellent low-temperature decomposition of a slurry composition and high strength of a ceramic green sheet, and further providing a vehicle composition, a slurry composition, and an electronic component that contain the (meth)acrylic resin.

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une résine (méth) acrylique avec laquelle il est possible d'obtenir à la fois une aptitude à la décomposition à basse température supérieure d'une composition de bouillie et une résistance élevée d'une feuille crue de céramique, et avec laquelle un corps stratifié en céramique plus mince peut être produit. La présente invention concerne également une composition de véhicule comprenant la résine (méth) acrylique, ainsi qu'une composition de bouillie et un composant électronique. La présente invention concerne une résine (méth) acrylique ayant des motifs structuraux dérivés de monomères d'ester d'acide (méth) acrylique, les monomères d'ester d'acide (méth) acrylique comprenant un monomère ester d'acide (méth) acrylique A et un monomère ester d'acide (méth) acrylique B, et lorsque le nombre de carbones du substituant ester du monomère ester d'acide (méth) acrylique A est traité en tant que X, le nombre de carbones du substituant ester du monomère ester d'acide (méth) acrylique B est 4X.
PCT/JP2024/019527 2023-06-09 2024-05-28 Résine (méth) acrylique, composition de véhicule, composition de bouillie et composant électronique Pending WO2024252983A1 (fr)

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JP2024534345A JP7685118B2 (ja) 2023-06-09 2024-05-28 （メタ）アクリル樹脂、ビヒクル組成物、スラリー組成物及び電子部品
CN202480007410.0A CN120476158A (zh) 2023-06-09 2024-05-28 （甲基）丙烯酸树脂、载体组合物、浆料组合物和电子部件
KR1020257017171A KR20260018011A (ko) 2023-06-09 2024-05-28 (메트)아크릴 수지, 비이클 조성물, 슬러리 조성물 및 전자 부품

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009031663A1 (fr) * 2007-09-07 2009-03-12 Sekisui Chemical Co., Ltd. Résine liante, composition de véhicule et composition de pâte ayant des microparticules inorganiques dispersées dans celle-ci
JP2021155708A (ja) * 2020-03-25 2021-10-07 積水化学工業株式会社 （メタ）アクリル樹脂組成物、無機微粒子分散用ビヒクル組成物、無機微粒子分散スラリー組成物、及び、無機微粒子分散シート
WO2024048303A1 (fr) * 2022-08-30 2024-03-07 積水化学工業株式会社 Particules de résine (méth)acrylique, composition de véhicule, composition de bouillie, et procédé de fabrication de composants électroniques

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10167836A (ja) 1996-12-17 1998-06-23 Mitsubishi Chem Corp セラミック成形用バインダー樹脂
JP2011084433A (ja) 2009-10-15 2011-04-28 Tdk Corp セラミックスラリー、グリーンシートおよび電子部品の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009031663A1 (fr) * 2007-09-07 2009-03-12 Sekisui Chemical Co., Ltd. Résine liante, composition de véhicule et composition de pâte ayant des microparticules inorganiques dispersées dans celle-ci
JP2021155708A (ja) * 2020-03-25 2021-10-07 積水化学工業株式会社 （メタ）アクリル樹脂組成物、無機微粒子分散用ビヒクル組成物、無機微粒子分散スラリー組成物、及び、無機微粒子分散シート
WO2024048303A1 (fr) * 2022-08-30 2024-03-07 積水化学工業株式会社 Particules de résine (méth)acrylique, composition de véhicule, composition de bouillie, et procédé de fabrication de composants électroniques

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CN120476158A (zh) 2025-08-12
JP7685118B2 (ja) 2025-05-28
JP2025118858A (ja) 2025-08-13
TW202506764A (zh) 2025-02-16
JP2025013863A (ja) 2025-01-28
KR20260018011A (ko) 2026-02-06
JP7683110B2 (ja) 2025-05-26
JPWO2024252983A1 (fr) 2024-12-12

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