Classifications

• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/092—Polycarboxylic acids
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/28—Condensation with aldehydes or ketones
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
  • C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G4/00—Fixed capacitors; Processes of their manufacture
  • H01G4/002—Details
  • H01G4/018—Dielectrics
  • H01G4/06—Solid dielectrics
  • H01G4/08—Inorganic dielectrics
  • H01G4/12—Ceramic dielectrics
  • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G4/00—Fixed capacitors; Processes of their manufacture
  • H01G4/30—Stacked capacitors
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/13—Energy storage using capacitors

Definitions

• the present invention relates to a resin composition for ceramic green sheets.
• multilayer ceramic capacitors are generally manufactured through the following steps. First, a plasticizer, a dispersant, etc. are added to a solution of a binder resin such as polyvinyl butyral resin or poly(meth)acrylic acid ester resin dissolved in an organic solvent, and then ceramic raw material powder is added and mixed using a bead mill, ball mill, etc. A ceramic slurry composition having a constant viscosity after being uniformly mixed by a device and defoamed is obtained.
• a plasticizer, a dispersant, etc. are added to a solution of a binder resin such as polyvinyl butyral resin or poly(meth)acrylic acid ester resin dissolved in an organic solvent, and then ceramic raw material powder is added and mixed using a bead mill, ball mill, etc.
• a ceramic slurry composition having a constant viscosity after being uniformly mixed by a device and defoamed is obtained.
• This slurry composition is cast onto a support such as a release-treated polyethylene terephthalate film or an SUS plate using a doctor blade, reverse roll coater, etc., and heated to remove volatile components such as solvents. After this, the ceramic green sheet is peeled off from the support to obtain a ceramic green sheet.
• a plurality of conductive pastes which will become internal electrodes, are applied by screen printing and are alternately stacked and bonded under heat and pressure to produce a laminate. After that, a process of thermally decomposing and removing the binder resin components contained in the laminate, a so-called degreasing process, is performed, and an external electrode is sintered on the end face of the ceramic sintered body obtained by firing. A capacitor is obtained.
• Patent Document 1 describes a polyvinyl acetal resin suitable as a ceramic binder that has a predetermined degree of polymerization, content of vinyl ester units, and degree of acetalization, and has a portion acetalized by acetaldehyde and acetalized by butyraldehyde.
• a polyvinyl acetal resin is described in which the molar ratio with the converted moiety is within a predetermined range.
• Patent Document 2 describes a polyvinyl acetal resin having a predetermined degree of polymerization, content of vinyl ester units, and degree of acetalization, and having a specific structural unit.
• An object of the present invention is to provide a resin composition for a ceramic green sheet that has excellent solvent solubility, reduces the amount of fine undissolved matter when dissolved in an organic solvent, and is capable of producing a highly reliable ceramic capacitor. purpose.
• the present disclosure (1) provides a resin composition for a ceramic green sheet, which contains a polyvinyl acetal resin and a compound A represented by the following formula (1), and the content of the compound A is 2 ppm or more on a weight basis. It is a thing.
• R 1 and R 3 each independently represent a carboxyl group or a salt thereof
• R 2 is a single bond or at least one selected from the group consisting of a hydroxyl group, a carboxyl group, and a salt thereof. Represents a divalent group optionally substituted with one substituent.
• the present disclosure (2) provides that in formula (1), R 2 is a linear chain having 1 to 6 carbon atoms, which may be substituted with at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, and a salt thereof.
• the resin composition for a ceramic green sheet according to the present disclosure (1) is an alkylene group.
• the present disclosure (4) is for a ceramic green sheet in any combination with any of the present disclosures (1) to (3), where X represented by the following formula (2) is 1.6 or more and 4.5 or less. It is a resin composition.
• the present disclosure (5) provides any of the present disclosures (1) to (4), wherein the compound A is at least one compound selected from the group consisting of tartaric acid, malic acid, citric acid, and salts thereof. This is a combined resin composition for ceramic green sheets.
• the present disclosure (6) provides that the polyvinyl acetal resin has a solution viscosity of 50 mPa ⁇ s or more at 20° C. when dissolved at 10% by weight in an ethanol/toluene mixed solution (weight ratio 1:1).
• the present disclosure (7) provides a resin for ceramic green sheets in any combination with any of the present disclosures (1) to (6), wherein the acetyl group content of the polyvinyl acetal resin is 0.5% by weight or more and 20% by weight or less. It is a composition.
• the present disclosure (8) is a resin composition for ceramic green sheets in any combination with any of the present disclosures (1) to (7), in which the average degree of polymerization of the polyvinyl acetal resin is 500 or more. The present invention will be explained in detail below.
• the present inventors have found that by creating a resin composition in which a predetermined amount of Compound A with a specific structure is added to polyvinyl acetal resin, it has excellent solvent solubility, and when dissolved in an organic solvent, The present inventors have discovered that it is possible to produce a highly reliable ceramic capacitor by reducing the amount of undissolved matter, and have completed the present invention.
• the above resin composition for ceramic green sheets contains polyvinyl acetal resin.
• the above polyvinyl acetal resin usually includes a structural unit having a hydroxyl group represented by the following formula (a-1), a constitutional unit having an acetyl group represented by the following formula (a-2), and a structural unit having the following formula (a-3). It has a structural unit having an acetal group represented by
• R 1a represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
• alkyl group having 1 to 20 carbon atoms examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, Examples include tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, and the like. Among these, methyl, ethyl, and propyl groups are preferred.
• the content of the structural unit having a hydroxyl group represented by the above formula (a-1) in the polyvinyl acetal resin is preferably 11% by weight or more, and 13% by weight or more, since it can improve the toughness of the resin. It is more preferably at least 15% by weight, even more preferably at least 15% by weight. Moreover, since the solvent solubility can be further improved, the content is preferably 40% by weight or less, more preferably 35% by weight or less, and even more preferably 30% by weight or less.
• the amount of hydroxyl groups is preferably 11 to 40% by weight, more preferably 13 to 35% by weight, even more preferably 15 to 30% by weight.
• the amount of hydroxyl groups can be determined, for example, by measuring the content (mol %) of each structural unit by NMR and calculating the weight ratio.
• acetyl group amount The content of the structural unit having an acetyl group represented by the above formula (a-2) in the polyvinyl acetal resin (hereinafter referred to as "acetyl group amount") is 0.5% by weight or more because it can suppress increase in viscosity. It is preferably 0.7% by weight or more, more preferably 0.8% by weight or more, even more preferably 1% by weight or more. In addition, since the flexibility of the polyvinyl acetal resin does not increase too much and handling properties can be improved, the amount is preferably 30% by weight or less, more preferably 26% by weight or less, even more preferably 22% by weight or less, and 20% by weight or less. Even more preferred.
• the amount of acetyl groups is preferably 0.5 to 30% by weight, more preferably 0.7 to 26% by weight, even more preferably 0.8 to 22% by weight, and even more preferably 1 to 20% by weight.
• the amount of acetyl groups can be determined, for example, by measuring the content (mol %) of each structural unit by NMR and calculating the weight ratio.
• the content of the structural unit having an acetal group represented by the above formula (a-3) in the polyvinyl acetal resin (hereinafter referred to as "acetal group amount") is 45% by weight or more, since it can further improve the solubility in solvents. is preferable, 47% by weight or more is more preferable, and even more preferably 49% by weight or more. Moreover, since the toughness of the resin can be improved, the content is preferably 86% by weight or less, more preferably 85% by weight or less, and even more preferably 83% by weight or less.
• the amount of acetal groups is preferably 45 to 86% by weight, more preferably 47 to 85% by weight, and even more preferably 49 to 83% by weight.
• the amount of acetal groups can be determined, for example, by measuring the content (mol %) of each structural unit by NMR and calculating the weight ratio.
• the calculation method of the acetal group amount since the acetal group of polyvinyl acetal resin is obtained by acetalizing two hydroxyl groups of polyvinyl alcohol, the structural unit having an acetal group is calculated as two structural units having a hydroxyl group. A method of converting and counting can be adopted.
• the polyvinyl acetal resin may have other structural units in addition to the structural units (a-1), (a-2), and (a-3).
• Other structural units may include, for example, structural units having functional groups such as carboxyl groups, sulfonic acid groups, alkylene oxide groups, and amide groups, or ethylene units.
• the structural units having a carboxyl group include the structural unit represented by the following formula (b-1), the structural unit represented by the following formula (b-2), and the structural unit represented by the following formula (b-3). Examples include units.
• R 1b and R 2b each independently represent an alkylene group having 0 to 10 carbon atoms
• X 1b and X 2b each independently represent a hydrogen atom, a metal atom, or a methyl group. represents.
• the preferable lower limit of the number of carbon atoms in the alkylene group represented by R 1b and R 2b is 0, the preferable upper limit is 5, the more preferable lower limit is 1, and the more preferable upper limit is 3.
• the above R 1b and R 2b may be the same or different, but preferably different. Moreover, it is preferable that at least one of them is a single bond.
• alkylene group having 0 to 10 carbon atoms examples include a single bond, a linear alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a decamethylene group.
• branched alkylene groups such as methylmethylene group, methylethylene group, 1-methylpentylene group, and 1,4-dimethylbutylene group
• cyclic alkylene groups such as cyclopropylene group, cyclobutylene group, and cyclohexylene group.
• single bonds linear alkylene groups such as methylene groups, ethylene groups, n-propylene groups, and n-butylene groups are preferred, and single bonds, methylene groups, and ethylene groups are more preferred.
• X 1b and X 2b are a metal atom
• the metal atom include a sodium atom, a lithium atom, a potassium atom, and the like. Among these, a sodium atom is preferred.
• the structural unit represented by the above formula (b-1) is preferably derived from an ⁇ -dicarboxy monomer.
• ⁇ -dicarboxy monomers include dicarboxylic acids having radically polymerizable unsaturated double bonds such as methylene malonic acid, itaconic acid, 2-methylene glutaric acid, 2-methylene adipic acid, and 2-methylene sebacic acid; Examples include metal salts or methyl esters thereof. Among these, itaconic acid, its metal salt, or its methyl ester are preferably used.
• the ⁇ -dicarboxy monomer refers to a monomer having two carboxyl groups at the ⁇ -position carbon.
• R 3b , R 4b and R 5b each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 6b is an alkylene group having 0 to 10 carbon atoms.
• X 3b represents a hydrogen atom, a metal atom, or a methyl group.
• the preferable lower limit of the number of carbon atoms in the alkyl group represented by R 3b , R 4b and R 5b is 1, the preferable upper limit is 5, and the more preferable upper limit is 3.
• the number of carbon atoms is preferably 1 to 5, more preferably 1 to 3.
• R 3b , R 4b , and R 5b may be the same or different, but the same is more preferable. Moreover, it is preferable that R 3b , R 4b and R 5b are hydrogen atoms.
• alkyl group having 1 to 10 carbon atoms examples include methyl group, ethyl group, propyl group, n-butyl group, n-pentyl group, n-heptyl group, n-octyl group, n-nonyl group, n- Straight chain alkyl groups such as decyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, 2,2-dimethylpropyl group, 1,1,3,3-tetramethylbutyl group, Branched alkyl groups such as a 2-ethylhexyl group, cycloalkyl groups such as a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.
• linear alkyl groups such as methyl
• R 6b in the above formula (b-2) examples include those similar to those exemplified for R 1b and R 2b in the above formula (b-1), and among them, a single bond, a methylene group, an ethylene group, A linear alkylene group such as a trimethylene group or a tetramethylene group is preferable, a single bond, a methylene group or an ethylene group is more preferable, and a single bond is even more preferable.
• X 3b is a metal atom
• examples of the metal atom include a sodium atom, a lithium atom, a potassium atom, and the like. Among these, a sodium atom is preferred.
• the structural unit represented by the above formula (b-2) is preferably derived from a monocarboxy monomer.
• the monocarboxy monomer include monocarboxylic acids having radically polymerizable unsaturated double bonds such as acrylic acid, crotonic acid, methacrylic acid, and oleic acid, metal salts thereof, and methyl esters thereof.
• crotonic acid, its metal salt, or its methyl ester are preferably used.
• R 7b and R 9b each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
• R 8b and R 10b represent an alkylene group having 0 to 10 carbon atoms
• X 4b and X 5b represent a hydrogen atom, a metal atom, or a methyl group.
• the lower limit of the number of carbon atoms in the alkyl group represented by R 7b and R 9b is preferably 1, the upper limit is preferably 5, and the upper limit is more preferably 3.
• the number of carbon atoms is preferably 1 to 5, more preferably 1 to 3.
• R 7b and R 9b may be the same or different, but the same is more preferable.
• R 7b and R 9b in the above formula (b-3) include those similar to those exemplified for R 3b , R 4b and R 5b in the above formula (b-2), and among them, hydrogen Atoms are preferred.
• R 8b and R 10b in the above formula (b-3) include those similar to those exemplified for R 1b and R 2b in the above formula (b-1), including single bonds, methylene
• a linear alkylene group such as a group, an ethylene group, a trimethylene group, or a tetramethylene group is preferable, a single bond, a methylene group, or an ethylene group is more preferable, and a single bond is even more preferable.
• X 4b and X 5b are metal atoms
• examples of the metal atoms include sodium atom, lithium atom, potassium atom, and the like. Among these, a sodium atom is preferred.
• Examples of the above-mentioned structural unit having a sulfonic acid group include a structural unit represented by the following formula (c).
• R 1c represents an alkylene group having 0 to 10 carbon atoms
• X 1c represents a hydrogen atom, a metal atom, or a methyl group.
• R 1c in the above formula (c) examples include those similar to those exemplified for R 1b and R 2b in the above formula (b-1), and among them, a single bond, a methylene group, an ethylene group, Linear alkylene groups such as trimethylene group and tetramethylene group are preferred, single bonds, methylene groups and ethylene groups are more preferred, and single bonds and methylene groups are even more preferred.
• X 1c is a metal atom
• examples of the metal atom include a sodium atom, a lithium atom, a potassium atom, and the like. Among these, a sodium atom is preferred.
• Examples of the above-mentioned structural unit having an alkylene oxide group include a structural unit represented by the following formula (d).
• R d1 represents a group having an alkylene oxide group having 2 to 6 carbon atoms.
• alkylene oxide group having 2 to 6 carbon atoms examples include ethylene oxide group, propylene oxide group, butylene oxide group, pentylene oxide group, and hexylene oxide group.
• Examples of the structural unit having an alkylene oxide group represented by the above formula (d) include those having multiple ethylene oxide groups such as polyethylene glycol, those having a single ethylene oxide group, and those having different alkylene oxide groups. etc.
• the above structural unit having an alkylene oxide group is a structural unit having an ethylene oxide group represented by the following formula (e-1), or an ethylene oxide group and a propylene oxide group represented by the following formula (e-2). It is preferable that it is a structural unit having the following.
• R e1 and R e2 represent a linking group or a single bond having at least one selected from the group consisting of C and O, and n 1 represents an integer.
• the above R e1 is a linking group or a single bond having at least one selected from the group consisting of C and O.
• the above R e1 is preferably an alkylene group having 1 to 10 carbon atoms, a carbonyl group, or an oxygen atom.
• Examples of the above R e1 include a methylene group, an ethylene group, a carbonyl group, an ether group, an allyl ether group, and an amide group.
• the above R e2 is a linking group or a single bond having at least one selected from the group consisting of C and O.
• the above R e2 is preferably an alkylene group having 1 to 10 carbon atoms, a carbonyl group, or an oxygen atom.
• R e2 examples include a methylene group, an ethylene group, a propylene group, a carbonyl group, and an ether group.
• the integer n 1 which is the number of repeats of alkylene oxide, is not particularly limited, but is preferably from 2 to 70, more preferably from 5 to 50.
• R e3 , R e4 and R e5 represent a linking group or a single bond having at least one selected from the group consisting of C and O, and n 2 and n 3 represent integers. represent.
• R e3 , R e4 and R e5 include those exemplified as R e1 and R e2 in formula (e-1) above.
• the integers n 2 and n 3 which are the repeating numbers of alkylene oxide, are not particularly limited, but it is preferable that n 2 is from 1 to 40, more preferably from 20 to 30.
• n 3 is preferably from 1 to 40, more preferably from 20 to 30.
• Examples of the structural unit having an amide group include a structural unit represented by the following formula (f).
• R 1f represents an alkyl group having 1 to 10 carbon atoms.
• R 1f in the above formula (f) examples include those similar to those exemplified for R 3b , R 4b and R 5b in the above formula (b-2), and among them, a hydrogen atom, Linear alkyl groups such as methyl, ethyl, propyl and n-butyl are preferred, and hydrogen, methyl and ethyl are more preferred.
• the content of the structural unit having the functional group in the polyvinyl acetal resin is preferably 0% by weight or more, more preferably 0.1% by weight or more, even more preferably 0.5% by weight or more, and preferably 5% by weight or less. , more preferably 3% by weight or less.
• the content of the structural unit having the functional group is preferably 0 to 5% by weight, more preferably 0.1 to 3% by weight, and even more preferably 0.5 to 3% by weight.
• the content of the structural units having the above-mentioned functional groups can be determined, for example, by measuring the content (mol %) of each structural unit by NMR and calculating the weight ratio.
• Examples of the above ethylene unit include a structural unit represented by the following formula (g).
• the content of the ethylene units (hereinafter also referred to as "ethylene content”) is preferably 1% by weight or more, more preferably 3% by weight or more, preferably 20% by weight or less, and 10% by weight. The following are more preferred.
• the above ethylene content is preferably 1 to 20% by weight, more preferably 3 to 10% by weight.
• the ethylene content can be determined, for example, by measuring the content (mol %) of each structural unit by NMR and calculating the weight ratio.
• the ethylene content of the polyvinyl acetal resin means the apparent ethylene content of the entire polyvinyl acetal resin. That is, for example, when a polyvinyl acetal resin contains multiple resins having different ethylene contents, the ethylene content of the polyvinyl acetal resin is obtained by multiplying the ethylene content of each resin by the content ratio of that resin. It is determined by summing each value.
• the ratio of the ethylene content to the hydroxyl group amount is preferably 0.01 or more, and preferably 1.0 or less. The above ratio is preferably 0.01 to 1.0.
• the average degree of polymerization of the polyvinyl acetal resin is preferably 200 or more, more preferably 300 or more, since mechanical strength can be improved. Further, from the viewpoint of solvent solubility and viscosity, the molecular weight is preferably 500 or more, more preferably 10,000 or less, and even more preferably 5,500 or less. The average degree of polymerization is preferably from 200 to 10,000, more preferably from 300 to 5,500, even more preferably from 500 to 5,500. Note that the above average degree of polymerization is the same as the average degree of polymerization of the raw material polyvinyl alcohol resin. The average degree of polymerization of the raw material polyvinyl alcohol resin can be measured in accordance with JIS K 6726.
• the polyvinyl acetal resin preferably has a solution viscosity of 50 mPa ⁇ s or more at 20°C when dissolved at a concentration of 10% by weight in an ethanol/toluene mixed solution (weight ratio 1:1), and preferably 70 mPa ⁇ s or more. More preferably, it is 100 mPa ⁇ s or more, more preferably 20,000 mPa ⁇ s or less, more preferably 18,000 mPa ⁇ s or less, and 16,000 mPa ⁇ s or less More preferably.
• the viscosity is preferably 50 to 20,000 mPa ⁇ s, more preferably 70 to 18,000 mPa ⁇ s, and even more preferably 100 to 16,000 mPa ⁇ s. By setting it as the said range, uniform solvent solubility can be ensured and mechanical strength can be improved.
• the above viscosity can be measured, for example, using a B-type viscometer at a solution temperature of 20°C.
• the shape of the polyvinyl acetal resin is not particularly limited, it is preferably particulate. Further, when the polyvinyl acetal resin is in the form of particles, the solubility in organic solvents can be further increased, so the porosity is preferably 20% or more, more preferably 25% or more, and 30% or more. It is more preferably at least 80%, more preferably at most 70%, even more preferably at most 60%. The porosity is preferably 20 to 80%, more preferably 25 to 70%, even more preferably 30 to 60%.
• the above-mentioned porosity means the volume of voids with a pore radius of 0.0038 to 7.5 ⁇ m occupying the volume of the resin particles.
• the porosity can be measured by mercury porosimetry using, for example, a porosimeter (Thermo Pascal 14B, manufactured by Thermo Fisher Scientific).
• the above-mentioned porosity can be adjusted by adjusting the concentration of polyvinyl alcohol resin and stirring conditions in the acetalization step, or by adjusting the temperature in the neutralization step of the obtained resin particles. For example, during the acetalization reaction, the lower the polyvinyl alcohol concentration relative to the amount of pure water, the higher the porosity of the resulting resin particles.
• the specific surface area is preferably 10 m 2 /g or more, more preferably 12 m 2 /g or more, since the solubility in organic solvents can be further increased. It is more preferably 15 m 2 /g or more, preferably 30 m 2 /g or less, more preferably 25 m 2 /g or less, and even more preferably 20 m 2 /g or less.
• the specific surface area is preferably 10 to 30 m 2 /g, more preferably 12 to 25 m 2 /g, and even more preferably 15 to 20 m 2 /g.
• the specific surface area refers to the surface area per unit weight, and can be measured by mercury porosimetry using a porosimeter (Thermo Pascal 14B, manufactured by Thermo Fisher Scientific), for example.
• the D50 particle size is preferably 30 ⁇ m or more, more preferably 50 ⁇ m or more, and 100 ⁇ m or more, since the solubility in organic solvents can be further increased. is more preferable, preferably 800 ⁇ m or less, more preferably 600 ⁇ m or less, even more preferably 500 ⁇ m or less.
• the D50 particle size is preferably 30 to 800 ⁇ m, more preferably 50 to 600 ⁇ m, and even more preferably 100 to 500 ⁇ m.
• the D90 particle size is preferably 30 ⁇ m or more, more preferably 50 ⁇ m or more, even more preferably 100 ⁇ m or more, preferably 1000 ⁇ m or less, more preferably 900 ⁇ m or less, and 800 ⁇ m or less. It is more preferable that it is the following.
• the D90 particle diameter is preferably 30 to 1000 ⁇ m, more preferably 50 to 900 ⁇ m, and even more preferably 100 to 800 ⁇ m.
• the D10 particle size is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, even more preferably 30 ⁇ m or more, preferably 400 ⁇ m or less, more preferably 300 ⁇ m or less, and 200 ⁇ m or less. It is more preferable that it is the following.
• the D10 particle diameter is preferably 10 to 400 ⁇ m, more preferably 20 to 300 ⁇ m, and even more preferably 30 to 200 ⁇ m.
• the above “D90 particle diameter (D90)” is the particle diameter at the point where the cumulative frequency of distribution from the small particle side reaches 90% in particle size distribution measurement, and the “D50 particle diameter (D50)” is Similarly, it is the particle diameter at the point where the cumulative frequency of the distribution reaches 50%, and "D10 particle diameter (D10)” is the particle diameter at the point where the cumulative frequency of the distribution reaches 10%.
• the above D90, D50, and D10 can be measured using, for example, a laser diffraction particle size distribution measuring device (Mastersizer 3000, manufactured by Malvern Panalytical).
• Examples of methods for controlling the particle size include a method of adjusting the concentration and stirring conditions of the polyvinyl alcohol resin in the acetalization step, and a method of adjusting the temperature and concentration in the neutralization step of the obtained resin particles. Furthermore, for example, the higher the polyvinyl alcohol concentration relative to the amount of pure water during the acetalization reaction, the greater the D50 of the resulting resin particles.
• the particle size distribution ⁇ of the particles is preferably 0.01 or more, more preferably 0.50 or more, preferably 4.00 or less, and more preferably 3.00 or less.
• the particle size distribution ⁇ is preferably 0.01 to 4.00, more preferably 0.50 to 3.00. Note that the particle size distribution ⁇ is calculated from [(D90-D10)/D50].
• the content of polyvinyl acetal resin in the resin composition for ceramic green sheets is preferably 94% by weight or more, more preferably 95% by weight or more, even more preferably 96% by weight or more, preferably 99.99% by weight or less, and 99% by weight or more.
• the content is more preferably .5% by weight or less, and even more preferably 99% by weight or less.
• the above content is preferably 94 to 99.99% by weight, more preferably 95 to 99.5% by weight, and even more preferably 96 to 99% by weight.
• the above polyvinyl acetal resin can usually be produced by acetalizing polyvinyl alcohol resin.
• polyvinyl alcohol resin conventionally known polyvinyl alcohol resins such as resins produced by saponifying polyvinyl acetate-based resins with alkali, acid, ammonia water, etc. can be used, for example.
• the above-mentioned polyvinyl alcohol resin may be completely saponified, but it must be completely saponified if there is at least one unit having two hydroxyl groups in the meso and racemo positions at least at one location in the main chain.
• partially saponified polyvinyl alcohol resin may be used.
• polyvinyl alcohol resin a copolymer of vinyl alcohol and a monomer copolymerizable with vinyl alcohol, such as an ethylene-vinyl alcohol copolymer resin or a partially saponified ethylene-vinyl alcohol copolymer resin, may also be used. I can do it.
• polyvinyl acetate resin examples include ethylene-vinyl acetate copolymer.
• the degree of saponification of the polyvinyl alcohol resin is preferably 80 mol% or more, more preferably 88 mol% or more, preferably 99.4 mol% or less, and more preferably 99 mol% or less.
• the saponification degree is preferably 80 to 99.4 mol%, more preferably 88 to 99 mol%.
• the acetalization can be carried out using a known method, and is preferably carried out in an aqueous solvent, in a mixed solvent of water and an organic solvent with which water is compatible, or in an organic solvent.
• an organic solvent that is compatible with water for example, an alcohol-based organic solvent can be used.
• the organic solvent include alcohol-based organic solvents, aromatic organic solvents, aliphatic ester-based solvents, ketone-based solvents, lower paraffinic solvents, ether-based solvents, amide-based solvents, amine-based solvents, and the like.
• the alcoholic organic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol.
• Examples of the aromatic organic solvent include xylene, toluene, ethylbenzene, methyl benzoate, and the like.
• Examples of the aliphatic ester solvent include methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl acetoacetate, and ethyl acetoacetate.
• Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, benzophenone, and acetophenone.
• Examples of the lower paraffinic solvent include hexane, pentane, octane, cyclohexane, decane, and the like.
• Examples of the ether solvent include diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, and the like.
• Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, acetanilide, and the like.
• amine solvent examples include ammonia, trimethylamine, triethylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, aniline, N-methylaniline, N,N-dimethylaniline, and pyridine. These solvents can be used alone, or two or more solvents can be used as a mixture. Among these, ethanol, n-propanol, isopropanol, and tetrahydrofuran are particularly preferred from the viewpoint of solubility in the resin and ease of purification.
• the acetalization is preferably performed in the presence of an acid catalyst.
• the above acid catalysts are not particularly limited, and include mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid, carboxylic acids such as formic acid, acetic acid, and propionic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, and paratoluenesulfonic acid. Examples include sulfonic acids such as acids.
• These acid catalysts may be used alone or in combination of two or more kinds of compounds. Among these, hydrochloric acid, nitric acid, and sulfuric acid are preferred, and nitric acid is particularly preferred.
• the acetalization is preferably performed in the presence of the compound A.
• the compound A specifically, the compounds mentioned below can be used.
• a uniform acetalization reaction can be carried out.
• the amount of the compound A added is preferably 0.8 parts by weight or more, more preferably 1.2 parts by weight or more, even more preferably 1.6 parts by weight or more, and 100 parts by weight or less based on 100 parts by weight of the polyvinyl alcohol resin. is preferable, 50 parts by weight or less is more preferable, and even more preferably 30 parts by weight or less.
• the amount added is preferably 0.8 to 100 parts by weight, more preferably 1.2 to 50 parts by weight, and even more preferably 1.6 to 30 parts by weight.
• aldehyde used in the acetalization examples include aldehydes having a chain aliphatic group, a cyclic aliphatic group, or an aromatic group having 1 to 10 carbon atoms. As these aldehydes, conventionally known aldehydes can be used.
• the aldehyde used in the acetalization reaction is not particularly limited, and examples thereof include aliphatic aldehydes, aromatic aldehydes, and the like.
• Examples of the aliphatic aldehyde include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde, 2-ethylhexylaldehyde, n-heptylaldehyde, n- Examples include octylaldehyde, n-nonylaldehyde, n-decylaldehyde, amylaldehyde and the like.
• aromatic aldehyde examples include benzaldehyde, cinnamaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, ⁇ -phenylpropionaldehyde, and the like. These aldehydes may be used alone or in combination of two or more.
• aldehydes examples include formaldehyde, acetaldehyde, butyraldehyde, and 2-ethylhexylaldehyde, which have excellent acetalization reactivity and can provide a sufficient internal plasticizing effect to the resulting resin, resulting in good flexibility.
• Preferred is n-nonylaldehyde.
• formaldehyde, acetaldehyde, and butyraldehyde are more preferred because they yield an adhesive composition particularly excellent in impact resistance and adhesion to metals.
• the amount of the aldehyde added can be appropriately set depending on the amount of acetal groups in the target polyvinyl acetal resin.
• the above resin composition for ceramic green sheets contains a compound A represented by the following formula (1).
• a compound A represented by the following formula (1) By containing the above compound A, it is possible to reduce the amount of fine undissolved substances when dissolved in an organic solvent.
• R 1 and R 3 each independently represent a carboxyl group or a salt thereof
• R 2 is a single bond or at least one selected from the group consisting of a hydroxyl group, a carboxyl group, and a salt thereof.
• R 1 and R 3 may be the same or different, but preferably the same.
• R 2 is preferably a divalent group having at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, and a salt thereof.
• divalent group examples include divalent hydrocarbon groups.
• the above hydrocarbon group includes a linear alkylene group having 1 to 6 carbon atoms, a branched alkylene group having 3 to 6 carbon atoms, a linear alkenylene group having 2 to 6 carbon atoms, and a branched alkenylene group having 3 to 6 carbon atoms. , a cycloalkylene group having 3 to 6 carbon atoms, a cycloalkenylene group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 carbon atoms, and the like.
• linear alkylene groups having 1 to 4 carbon atoms and branched alkylene groups having 3 to 4 carbon atoms are preferred, and linear alkylene groups having 1 to 3 carbon atoms are more preferred.
• linear alkylene group having 1 to 6 carbon atoms examples include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, and the like.
• Examples of the branched alkylene group having 3 to 6 carbon atoms include 1-methylethylene group, 2-methyltrimethylene group, 2-methyltetramethylene group, and 2-methylpentamethylene group.
• linear alkenylene group having 2 to 6 carbon atoms examples include vinylene group, propenylene group, butenylene group, and hexenylene group.
• Examples of branched alkenylene groups having 3 to 6 carbon atoms include isopropenylene group, 1-ethylethenylene group, 2-methylpropenylene group, 2,2-dimethylbutenylene group, 3-methyl-2-butenylene group, 3- Examples include ethyl-2-butenylene group.
• Examples of the cycloalkylene group having 3 to 6 carbon atoms include a cyclopentylene group and a cyclohexylene group.
• Examples of the cycloalkenylene group having 3 to 6 carbon atoms include a cyclopentenylene group, a 2,4-cyclopentadienylene group, and a cyclohexenylene group.
• aromatic hydrocarbon group having 6 carbon atoms examples include 1,2-phenylene and the like.
• R 2 is preferably a hydroxyethylene group, a 1,2-dihydroxyethylene group, a 2-hydroxy,2-carboxytrimethylene group, a hydroxymethylene group, a trimethylene group, or a methylene group; More preferred are 1,2-dihydroxyethylene group and 2-hydroxy,2-carboxytrimethylene group.
• the molecular weight of the compound A is preferably 90 or more, more preferably 130 or more, even more preferably 150 or more, preferably 10,000 or less, more preferably 1,000 or less, and even more preferably 500 or less.
• the above molecular weight is preferably 90 to 10,000, more preferably 130 to 1,000, even more preferably 150 to 500.
• the above compound A includes aliphatic hydroxy acids such as citric acid, malic acid, tartaric acid, tartronic acid, isocitric acid, and mevalonic acid, oxalic acid, malonic acid, fumaric acid, succinic acid, glutaric acid, and adipine acid.
• aliphatic dicarboxylic acids such as suberic acid, and the like.
• citric acid, malic acid, tartaric acid, tartronic acid, glutaric acid, and malonic acid are preferred, and citric acid, malic acid, and tartaric acid are more preferred.
• the content of the compound A in the resin composition for ceramic green sheets is 2 ppm or more on a weight basis since it can improve solubility in organic solvents. Further, the content of compound A is preferably 5 ppm or more, more preferably 10 ppm or more, preferably 29,000 ppm or less, more preferably 28,000 ppm or less, and even more preferably 26,000 ppm or less on a weight basis. The above content is preferably 2 to 29,000 ppm, more preferably 5 to 28,000 ppm, and even more preferably 10 to 26,000 ppm. The content of the compound A can be measured by, for example, ion chromatography.
• the content of the compound A in the resin composition for ceramic green sheets is preferably 2 ppm or more, more preferably 5 ppm or more, still more preferably 10 ppm or more, and 29,000 ppm or less, based on 100 parts by weight of the polyvinyl acetal resin. It is preferably 28,000 ppm or less, more preferably 26,000 ppm or less.
• the above content is preferably 2 to 29,000 ppm, more preferably 5 to 28,000 ppm, and even more preferably 10 to 26,000 ppm.
• X represented by the following formula (2) is preferably 1.6 or more, and preferably 4.5 or less. By setting it as the said range, uniform solvent solubility can be ensured and mechanical strength can be improved.
• the above X is more preferably 1.7 or more, and more preferably 4.4 or less.
• the above X is preferably 1.6 to 4.5, more preferably 1.7 to 4.4.
• the resin composition for ceramic green sheets may contain components such as an antioxidant, an ultraviolet absorber, a surfactant, and an antifoaming agent, as long as they do not impede the effects of the present invention.
• polyvinyl alcohol resin is acetalized with an aldehyde in the presence of the compound A, thereby forming a resin composition for ceramic green sheets containing polyvinyl acetal resin and compound A. It can be made into a resin composition.
• the above compound A and other additives added as necessary may be added and mixed to a polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol resin with an aldehyde to form a ceramic green sheet. It can be made into a resin composition.
• An inorganic fine particle-dispersed slurry composition can be prepared by mixing the above resin composition for ceramic green sheets, an organic solvent, and inorganic fine particles.
• the organic solvent is not particularly limited as long as it can dissolve the polyvinyl acetal resin, and examples thereof include ketones such as acetone, methyl ethyl ketone, dipropyl ketone, and diisobutyl ketone.
• ketones such as acetone, methyl ethyl ketone, dipropyl ketone, and diisobutyl ketone.
• Other examples include alcohols such as methanol, ethanol, isopropanol and butanol, and aromatic hydrocarbons such as toluene and xylene.
• esters such as 2-ethylhexyl acetate and 2-ethylhexyl butyrate.
• Further examples include methyl cellosolve, ethyl cellosolve, butyl cellosolve, terpineol, dihydroterpineol, butyl cellosolve acetate, butyl carbitol acetate, terpineol acetate, dihydroterpineol acetate, and the like.
• Particularly preferred are alcohols, ketones, aromatic hydrocarbons, and mixed solvents thereof from the viewpoint of coating properties and drying properties.
• a mixed solvent of ethanol and toluene and a mixed solvent of methyl ethyl ketone and toluene are more preferable.
• the content of the above-mentioned organic solvent in the above-mentioned inorganic fine particle dispersed slurry composition is set depending on the type of polyvinyl acetal resin used, etc., and is not particularly limited, but if it is too small, kneading It is difficult to achieve the required solubility. Furthermore, if the amount is too large, the viscosity of the slurry composition may become too low, resulting in poor handling properties when producing ceramic green sheets. Therefore, the content of the organic solvent is preferably 20% by weight or more and 80% by weight or less.
• the inorganic fine particle dispersed slurry composition contains inorganic fine particles.
• the inorganic fine particles are not particularly limited, and examples thereof include ceramic powder, glass powder, metal fine particles, and the like.
• the ceramic powder is not particularly limited, and includes powders of metal or nonmetal oxides, carbides, nitrides, borides, or sulfides used in the production of ceramics. Specific examples include Li, K, Mg, B, Al, Si, Cu, Ca, Sr, Ba, Zn, Cd, Ga, In, Y, lanthanide, actinide, Ti, Zr, Hf, Bi, V, Nb. , Ta, W, Mn, Fe, Co, Ni, etc., oxides, carbides, nitrides, borides, sulfides, and the like. These ceramic powders may be used alone or as a mixture of two or more types.
• barium titanate aluminum nitride (AlN), silicon nitride (Si3N4), silicon carbide (SiC), alumina (Al2O3), copper oxide (CuO), and spinel compounds, 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 titanate, alumina nitride, silicon nitride, boron nitride, carbide Examples include boron, barium stannate, calcium stannate, magnesium silicate, mullite, steatite, cordierite, forsterite, and the like.
• the above-mentioned glass powder is not particularly limited, and includes, for example, glass powder such as bismuth oxide glass, silicate glass, lead glass, zinc glass, boron glass, CaO-Al 2 O 3 -SiO 2 system, MgO-Al 2 O Examples include glass powders of various silicon oxides such as 3- SiO 2 series, LiO 2 -Al 2 O 3 -SiO 2 series, and the like.
• R is an element selected from the group consisting of Zn, Ba, Ca, Mg, Sr, Sn, Ni, Fe, and Mn.
• the metal fine particles are not particularly limited, and include, for example, powders made of copper, nickel, palladium, iron, platinum, gold, silver, aluminum, tungsten, alloys thereof, and the like. In addition to metal complexes, various carbon blacks, carbon nanotubes, etc. may also be used. 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 content of the inorganic fine particles in the inorganic fine particle dispersed slurry composition is not particularly limited, but is preferably 10% by weight or more, more preferably 15% by weight or more, and preferably 90% by weight or less. It is preferably 85% by weight or less, and more preferably 85% by weight or less. By setting it as the said range, it can have sufficient viscosity and excellent coating property, and can also have excellent dispersibility of inorganic fine particles.
• the above content is preferably 10 to 90% by weight, more preferably 15 to 85% by weight.
• the inorganic fine particle dispersed slurry composition contains a plasticizer.
• the plasticizer include monomethyl adipate, di(butoxyethyl) adipate, dibutoxyethoxyethyl adipate, triethylene glycol bis(2-ethylhexanoate), triethylene glycol dihexanoate, Examples include triethyl acetyl citrate, tributyl cetyl citrate, dibutyl sebacate, butylated benzyl phthalate, diisononyl adipate, diisodecyl phthalate, tripropionine, pentaerythritol tetraacetate, di-2-ethylhexyl phthalate, triacetin, and the like.
• triethylene glycol bis(2-ethylhexanoate), butylated benzyl phthalate, diisononyl adipate, diisodecyl phthalate, tripropionine, pentaerythritol tetraacetate, di-2-ethylhexyl phthalate, and the like are preferred.
• the boiling point of the plasticizer is preferably 240°C or higher, and preferably lower than 390°C.
• the boiling point is preferably 240°C or more and less than 390°C. Note that the above boiling point refers to the boiling point at normal pressure.
• the content of the plasticizer in the inorganic fine particle dispersed slurry composition is not particularly limited, but is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and 3% by weight or less.
• the content is preferably 2.5% by weight or less, and more preferably 2.5% by weight or less. By keeping it within the above range, it is possible to reduce the firing residue of the plasticizer.
• the above content is preferably 0.1 to 3% by weight, more preferably 0.2 to 2.5% by weight.
• the viscosity of the inorganic fine particle dispersed slurry composition is not particularly limited, but it is preferable that the viscosity is 0.1 Pa ⁇ s or more when measured at 20°C using a B-type viscometer with the probe rotation speed set at 5 rpm. , 100 Pa ⁇ s or less.
• the above viscosity is preferably 0.1 to 100 Pa ⁇ s.
• the method for producing the above-mentioned inorganic fine particle dispersed slurry composition is not particularly limited, and examples include conventionally known stirring methods.
• the above-mentioned resin composition for ceramic green sheets, the above-mentioned inorganic fine particles, Examples include a method of stirring the organic solvent, plasticizer, and other components to be added using a bead mill or the like.
• An inorganic fine particle dispersed sheet can be produced by coating the above-mentioned inorganic fine particle dispersed slurry composition on a support film that has been subjected to a release treatment on one side, drying the organic solvent, and forming it into a sheet.
• the thickness of the inorganic fine particle dispersed sheet is preferably 0.5 ⁇ m or more, and preferably 3 ⁇ m or less.
• the support film used when manufacturing the inorganic fine particle dispersed sheet is preferably a resin film that has heat resistance and solvent resistance as well as flexibility. Due to the flexibility of the support film, the inorganic fine particle dispersed slurry composition can be applied to the surface of the support film using a roll coater, blade coater, etc., and the resulting inorganic fine particle dispersed sheet forming film is wound into a roll shape. It can be stored and supplied in this state.
• the resin forming the support film examples include fluorine-containing resins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, nylon, and cellulose.
• the thickness of the support film is, for example, preferably 20 ⁇ m or more, and preferably 100 ⁇ m or less.
• the surface of the support film is subjected to a release treatment, so that the peeling operation of the support film can be easily performed in the transfer process.
• a multilayer ceramic capacitor can be manufactured by using the above inorganic fine particle dispersed slurry composition and inorganic fine particle dispersed sheet for a dielectric green sheet and an electrode paste.
• the method for manufacturing a multilayer ceramic capacitor preferably includes a step of printing and drying a conductive paste on the inorganic fine particle dispersed sheet to produce a dielectric sheet, and a step of laminating the dielectric sheets.
• the conductive paste contains conductive powder.
• the material of the conductive powder is not particularly limited as long as it is conductive, and examples thereof include nickel, palladium, platinum, gold, silver, copper, and alloys thereof. These conductive powders may be used alone or in combination of two or more.
• binder resin and organic solvent used in the conductive paste those similar to those used in the inorganic fine particle dispersed slurry composition can be used.
• the method for printing the conductive paste is not particularly limited, and examples thereof include screen printing, die coat printing, offset printing, gravure printing, inkjet printing, and the like.
• a multilayer ceramic capacitor is obtained by stacking dielectric sheets printed with the conductive paste, degreasing and firing, and then installing external electrodes.
• the present invention it is possible to provide a resin composition for a ceramic green sheet that has excellent solvent solubility, reduces the amount of fine undissolved matter when dissolved in an organic solvent, and can produce a highly reliable ceramic capacitor. .
• Example 2 2,300 g of pure water was added to 200 g of polyvinyl alcohol resin (average degree of polymerization 3,300, degree of saponification 99 mol%, purity 96.5%), and the mixture was stirred at 90° C. for 2 hours to dissolve.
• This solution was cooled to 40° C., and 181 g of hydrochloric acid with a concentration of 35% by weight, 3.1 g of malic acid, and 116 g of n-butyraldehyde were added thereto to carry out an acetalization reaction, and a reaction product was precipitated. Thereafter, the reaction was completed by holding at 40° C.
• Example 2 A resin composition for ceramic green sheets was obtained in the same manner as in Example 1 except that tartaric acid was used instead of malic acid.
• Example 3 A resin composition for a ceramic green sheet was obtained in the same manner as in Example 1 except that 30.9 g of citric acid was used in place of malic acid.
• Example 4 A resin composition for ceramic green sheets was obtained in the same manner as in Example 1 except that the amount of n-butyraldehyde added was 110 g.
• Example 5 A resin composition for ceramic green sheets was obtained in the same manner as in Example 1 except that tartronic acid was used instead of malic acid.
• Example 6 A resin composition for ceramic green sheets was obtained in the same manner as in Example 1 except that glutaric acid was used instead of malic acid.
• Example 7 A resin composition for a ceramic green sheet was obtained in the same manner as in Example 1 except that 6.2 g of malonic acid was used in place of malic acid.
• Example 8 2,300 g of pure water was added to 200 g of polyvinyl alcohol resin (average degree of polymerization 3,300, degree of saponification 99 mol%, purity 96.5%), and the mixture was stirred at 90° C. for 2 hours to dissolve. This solution was cooled to 40° C., and 181 g of hydrochloric acid with a concentration of 35% by weight, 3.1 g of malic acid, and 116 g of n-butyraldehyde were added thereto to carry out an acetalization reaction, and a reaction product was precipitated. Thereafter, the reaction was completed by holding at 40° C.
• Example 9 2,300 g of pure water was added to 200 g of polyvinyl alcohol resin (average degree of polymerization 3,300, degree of saponification 82 mol%, purity 96.5%), and the mixture was stirred at 90° C. for 2 hours to dissolve. This solution was cooled to 40° C., and 181 g of hydrochloric acid with a concentration of 35% by weight, 3.1 g of malic acid, and 127 g of n-butyraldehyde were added thereto to carry out an acetalization reaction, and a reaction product was precipitated. Thereafter, the reaction was completed by holding at 40° C.
• Example 3 A resin composition for ceramic green sheets was obtained in the same manner as in Example 1, except that 3.1 g of pentaerythritol was used in place of malic acid.
• Example 10 A resin composition for a ceramic green sheet was obtained in the same manner as in Example 1 except that polyvinyl alcohol resin (average degree of polymerization 1,700, degree of saponification 99 mol%) was used.
• Example 11 A resin composition for ceramic green sheets was obtained in the same manner as in Example 10, except that 6.2 g of tartaric acid was used instead of malic acid.
• Example 12 A resin composition for ceramic green sheets was obtained in the same manner as in Example 10, except that the amount of malic acid added was 12.4 g.
• Example 5 A resin composition for a ceramic green sheet was obtained in the same manner as in Example 10 except that malic acid was not added.
• Example 13 2,300 g of pure water was added to 200 g of polyvinyl alcohol resin (average degree of polymerization 700, degree of saponification 98.5 mol%), and the mixture was stirred at 90° C. for 2 hours to dissolve. This solution was cooled to 40° C., and 181 g of hydrochloric acid with a concentration of 35% by weight, 3.1 g of tartaric acid, and 116 g of n-butyraldehyde were added thereto to carry out an acetalization reaction, and a reaction product was precipitated. Thereafter, the reaction was completed by holding at 40° C.
• Example 14 A resin composition for ceramic green sheets was prepared in the same manner as in Example 1, except that polyvinyl alcohol resin (average degree of polymerization 700, degree of saponification 98.5 mol%) was used, and 6.2 g of tartaric acid was used instead of malic acid. Obtained.
• Example 15 A resin composition for ceramic green sheets was obtained in the same manner as in Example 14, except that the amount of tartaric acid added was 12.4 g.
• Example 7 A resin composition for ceramic green sheets was obtained in the same manner as in Example 14 except that polyvinyl alcohol resin (average degree of polymerization 700, degree of saponification 99 mol%) was used and tartaric acid was not added.
• Porosity The porosity of the obtained polyvinyl acetal resin was measured by mercury intrusion method using a porosimeter (Thermo Pascal 14B). Note that the porosity refers to the volume of voids with a pore radius of 0.0038 to 7.5 ⁇ m occupying the volume of the resin particles.
• Dissolution time Pour 192 g of a mixed solvent of ethanol and toluene (weight ratio 1:1) as an organic solvent into a 500 mL beaker, maintain the temperature at 25°C, and stir at a rotation speed of 200 rpm using two stirring blades. Meanwhile, 48.0 g (resin composition concentration: 6% by weight) of the polyvinyl acetal resin compositions (average degree of polymerization of the resin: 3300) obtained in Examples 1 to 9 and Comparative Examples 1 to 4 was added, and the polyvinyl acetal The resin composition was dissolved. Visual observation was performed to measure the dissolution time from the time when the obtained polyvinyl acetal resin composition was added until the undissolved resin disappeared.
• the polyvinyl acetal resin compositions obtained in Examples 10 to 12 and Comparative Examples 5 and 6 had a concentration of 10% by weight
• the polyvinyl acetal resin compositions obtained in Examples 13 to 15 and Comparative Example 7 Regarding the polyvinyl acetal resin composition (average degree of polymerization of the resin: 700)
• the dissolution time was measured at a concentration of 20% by weight.
• Dissolution time reduction rate (%) [(Reference dissolution time - Dissolution time of each example)/Reference dissolution time] x 100
• a resin composition solution was prepared by dissolving the resin composition in the following manner.
• a resin solution was prepared by adding 2 parts by weight of DOP to 98 parts by weight of the obtained resin composition solution and stirring and dissolving.
• the obtained resin composition for ceramic green sheets was added to a mixed solvent of ethanol and toluene (weight ratio 1:1) so that the resin composition concentration was 15% by weight.
• a resin composition solution was prepared by dissolving the resin composition in the following manner.
• a resin solution was prepared by adding 2 parts by weight of DOP to 98 parts by weight of the obtained resin composition solution and stirring and dissolving.
• Preparation of ceramic green sheet A resin solution was added to the obtained inorganic dispersion and stirred in a bead mill for 90 minutes to obtain a composition for a ceramic green sheet.
• the obtained composition for a ceramic green sheet was applied onto a PET film that had been subjected to a release treatment using a coater so that the thickness after drying would be 20 ⁇ m, and then heated and dried to produce a ceramic green sheet.
• the present invention it is possible to provide a resin composition for a ceramic green sheet that has excellent solvent solubility, reduces the amount of fine undissolved matter when dissolved in an organic solvent, and can produce a highly reliable ceramic capacitor. .

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