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
  • 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
  • C08K3/02—Elements
  • C08K3/08—Metals
• • 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
  • C08K3/24—Acids; Salts thereof
• • 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
  • C08K5/05—Alcohols; Metal alcoholates
  • C08K5/053—Polyhydroxylic alcohols
• • 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
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
  • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
• • 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
  • C08K5/10—Esters; Ether-esters
  • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
• • 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
  • H01G4/30—Stacked capacitors
• • 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
  • C08K3/02—Elements
  • C08K3/08—Metals
  • C08K2003/0881—Titanium

Definitions

• the present invention relates to a polyvinyl acetal resin composition, a slurry composition in which inorganic fine particles are dispersed, and a multilayer ceramic capacitor.
• 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 the surface of a support such as a polyethylene terephthalate film that has undergone mold release treatment or an SUS plate using a doctor blade, reverse roll coater, etc., and is 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. Next, on the obtained ceramic green sheets, 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.
• a support such as a polyethylene terephthalate film that has undergone mold release treatment or an SUS plate using a doctor blade, reverse roll coater, etc.
• 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.
• the present disclosure (1) has a water content of 5.0% by weight or less, contains a polyvinyl acetal resin, carbon atoms, hydrogen atoms, and oxygen atoms, and the ratio of the number of oxygen atoms to the total number of atoms (number of oxygen atoms/total This is a polyvinyl acetal resin composition containing a compound A having a number of atoms) of 0.18 or more.
• the present disclosure (2) is the polyvinyl acetal resin composition of the present disclosure (1), which contains 2.8 parts by weight or more and 20 parts by weight or less of the compound A based on 100 parts by weight of the polyvinyl acetal resin.
• the solubility parameter value of polyvinyl acetal resin calculated by the Fedors method is S1
• the solubility parameter of compound A is S2
• the absolute value of the difference between S1 and S2 is 9.0 (cal/ cm 3 ) 0.5 or less
• the polyvinyl acetal resin composition of the present disclosure (1) or (2) is a polyvinyl acetal resin composition in any combination with any of the present disclosures (1) to (3), in which the molecular weight of compound A is 90 or more and 450 or less.
• the present disclosure (5) provides that the compound A is at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2).
• R 1 and R 3 represent a carboxyl group or a salt thereof
• R 2 consists of a carbon atom, a hydrogen atom, or an oxygen atom that may be substituted with a single bond, a hydroxyl group, a carboxyl group, or a salt thereof.
• R 4 and R 6 each independently represent a hydrogen atom, a hydroxyl group, an acetyl group, or an acetoxy group
• R 5 is substituted with a hydroxyl group, an acetyl group, an acetoxy group, a carboxyl group, or a salt thereof.
• R 2 is a linear alkylene group having 1 to 6 carbon atoms having at least one of a single bond, a hydroxyl group, a carboxyl group, or a salt thereof, or a hydroxyl group;
• the polyvinyl acetal resin composition of the present disclosure (5) is a branched alkylene group having 3 to 6 carbon atoms and having at least one of a carboxyl group or a salt thereof.
• R 5 is a linear alkylene group having 1 to 6 carbon atoms having at least one of a hydroxyl group, an acetyl group, an acetoxy group, a carboxyl group, or a salt thereof; , a branched alkylene group having 3 to 6 carbon atoms having at least one of an acetyl group, an acetoxy group, a carboxyl group, or a salt thereof, or a glycerin unit having a repeating number of 2 to 11, or (5) of the present disclosure or ( 6) is the polyvinyl acetal resin composition.
• the present disclosure (8) provides the present disclosure (5) to (7), wherein the compound represented by formula (1) is at least one compound selected from the group consisting of tartaric acid, malic acid, citric acid, and salts thereof.
• the compound represented by formula (1) is at least one compound selected from the group consisting of tartaric acid, malic acid, citric acid, and salts thereof.
• ) is a polyvinyl acetal resin composition in any combination with any of the following.
• the present disclosure (9) is a compound represented by formula (2), which is at least one compound selected from the group consisting of pentaerythritol and pentaerythritol tetraacetate.
• a polyvinyl acetal resin composition of any combination of The present disclosure (10) provides any combination of the present disclosure (1) to (9), in which the Y value expressed by the following formula is 6.3 ⁇ 10 ⁇ 9 or more and 45.0 ⁇ 10 ⁇ 9 or less.
• a combination polyvinyl acetal resin composition ((W A ⁇ M A ⁇ O R ) ⁇ (100-W W )) ⁇ (M PVB ⁇ M A ) ⁇ S 0.4 W A : Content of compound A relative to 100 parts by weight of polyvinyl acetal resin M A : Molecular weight of compound A O R : Ratio of the number of oxygen atoms to the total number of atoms in compound A (number of oxygen atoms/total number of atoms) W W : Moisture content of the polyvinyl acetal resin composition M PVB : Weight average molecular weight of the polyvinyl acetal resin S: When the solubility parameter value of the polyvinyl acetal resin calculated by the Fedors method is S1, and the solubility parameter of compound A is S2.
• the present disclosure (11) is an inorganic fine particle dispersed slurry composition containing the polyvinyl acetal resin composition of any of the present disclosure (1) to (10), an organic solvent, and inorganic fine particles. It is.
• the present disclosure (12) is the inorganic fine particle dispersion slurry composition of the present disclosure (11), which further contains a plasticizer.
• the present disclosure (13) is the inorganic fine particle dispersion slurry composition of the present disclosure (11) or (12), wherein the inorganic fine particles are barium titanate powder or nickel powder.
• the present disclosure (14) is a multilayer ceramic capacitor having a dielectric layer or an electrode layer formed using the inorganic fine particle dispersed slurry composition according to any one of the present disclosure (11) to (13). The present invention will be explained in detail below.
• the polyvinyl acetal resin composition 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 18 mol% or more, and 20% by mole or more, since it can improve the toughness of the resin. More preferably mol % or more, and even more preferably 22 mol % or more. Moreover, since the solvent solubility can be further improved, the content is preferably 50 mol% or less, more preferably 39 mol% or less, and even more preferably 38 mol% or less.
• the amount of hydroxyl groups is preferably 18 to 50 mol%, more preferably 20 to 39 mol%, even more preferably 22 to 38 mol%.
• the amount of hydroxyl groups can be measured, for example, by NMR.
• 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 mol% or more because it can suppress increase in viscosity. It is preferably 0.6 mol% or more, more preferably 1 mol% or more. In addition, since the flexibility of the polyvinyl acetal resin does not increase too much and handling properties can be improved, the content is preferably 20 mol% or less, more preferably 16 mol% or less, and even more preferably 14 mol% or less.
• the amount of acetyl groups is preferably 0.5 to 20 mol%, more preferably 0.6 to 16 mol%, and even more preferably 1 to 14 mol%. The amount of acetyl groups can be measured, for example, by NMR.
• 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 mol% or more, since it can further improve the solubility in a solvent. is preferable, 47 mol% or more is more preferable, and even more preferably 49 mol% or more. Moreover, since the toughness of the resin can be improved, the content is preferably 80 mol% or less, more preferably 78 mol% or less, and even more preferably 76 mol% or less.
• the amount of acetal groups is preferably 45 to 80 mol%, more preferably 47 to 78 mol%, even more preferably 49 to 76 mol%.
• the amount of acetal groups can be measured, for example, by NMR.
• 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) of the above formula.
• 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 lower limit of the carbon number of the alkylene group represented by R 1b and R b2 is preferably 0, the upper limit is preferably 5, the lower limit is more preferably 1, and the upper limit is 3.
• the number of carbon atoms in the alkylene group is more preferably 0 to 5, and even more preferably 1 to 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 when at least one of X 1b and X 2b 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-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 in the alkyl group is preferably 1 to 5, and even 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.
• 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.
• the ethylene oxide group and the propylene oxide group may be arranged in either a block or random arrangement.
• 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, a methyl group, Straight chain alkyl groups such as ethyl, propyl and n-butyl groups are preferred, and hydrogen atoms, methyl and ethyl groups are more preferred.
• the content of the structural unit having the functional group in the polyvinyl acetal resin is preferably 0 mol% or more, more preferably 0.1 mol% or more, even more preferably 0.5 mol% or more, and preferably 5 mol% or less. , more preferably 3 mol% or less.
• the content of the structural unit having the above functional group is preferably 0 to 5 mol%, more preferably 0.1 to 5 mol%, and even more preferably 0.5 to 3 mol%.
• the content of the structural unit having the above-mentioned functional group can be measured by, for example, NMR.
• 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 mol% or more, more preferably 3 mol% or more, preferably 20 mol% or less, and 10 mol%. The following are more preferred.
• the above ethylene content is preferably 1 to 20 mol%, more preferably 3 to 10 mol%.
• the above ethylene content can be measured, for example, by NMR.
• 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 ethylene content/hydroxyl group amount is preferably 0.01 to 1.0.
• the average degree of polymerization of the polyvinyl acetal resin is preferably 300 or more, more preferably 600 or more, even more preferably 1,000 or more, particularly preferably 1,300 or more, since mechanical strength can be improved. Further, from the viewpoint of solvent solubility and viscosity, the molecular weight is preferably 10,000 or less, more preferably 8,000 or less, even more preferably 3,500 or less, and particularly preferably 3,000 or less. The average degree of polymerization is preferably 300 to 10,000, more preferably 600 to 8,000, even more preferably 1,000 to 3,500, and particularly preferably 1,300 to 3,000. 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 weight average molecular weight (Mw) of the polyvinyl acetal resin is preferably 80,000 or more, preferably 2,500,000 or less, more preferably 150,000 or more, more preferably 2,000,000 or less, and 250,000 or more. The above is more preferable, 875,000 or less is even more preferable, 300,000 or more is even more preferable, and 440,000 or less is even more preferable.
• the weight average molecular weight (Mw) is preferably 80,000 to 2,500,000, more preferably 150,000 to 2,000,000, even more preferably 250,000 to 875,000, and even more preferably 300,000 to 440. ,000 is even more preferred.
• weight average molecular weight (Mw) of the polyvinyl acetal resin By setting the weight average molecular weight (Mw) of the polyvinyl acetal resin to be at least the above-mentioned lower limit, mechanical strength can be improved, and by setting it to be below the above-mentioned upper limit, solvent solubility can be improved.
• the weight average molecular weight can be determined by gel permeation chromatography (GPC) using a suitable standard (eg, a polystyrene standard). Examples of the column used to measure the Mw include TSKgel SuperHZM-H (manufactured by Tosoh).
• the content of polyvinyl acetal resin in the polyvinyl acetal resin composition is preferably 80.0% by weight or more, more preferably 85.0% by weight or more, even more preferably 90.0% by weight or more, and 97.2% by weight or less. is preferable, 97.0% by weight or less is more preferable, and even more preferably 96.5% by weight or less.
• the content of the polyvinyl acetal resin is preferably 80.0 to 97.2% by weight, more preferably 85.0 to 97.0% by weight, even more preferably 90.0 to 96.5% 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 resins with alkali, acid, aqueous ammonia, etc. can be used, for example.
• the above-mentioned polyvinyl alcohol resin may be completely saponified, but it is not necessary to be completely saponified as long as there is at least one unit having a double hydroxyl group in the meso or racemo position at least at one location in the main chain. , partially saponified polyvinyl alcohol resin.
• polyvinyl alcohol resin copolymers of vinyl alcohol and monomers that can be copolymerized with vinyl alcohol, such as ethylene-vinyl alcohol copolymer resins and partially saponified ethylene-vinyl alcohol copolymer resins, can also be used.
• examples of the polyvinyl acetate resin include ethylene-vinyl acetate copolymer.
• the degree of saponification of the polyvinyl alcohol resin is preferably 80 mol% or more, more preferably 84 mol% or more, even more preferably 88 mol% or more, preferably 99.5 mol% or less, and more preferably 99.4 mol% or less. It is preferably 99 mol% or less, and more preferably 99 mol% or less.
• the saponification degree is preferably 80 to 99.5 mol%, more preferably 84 to 99.4 mol%, and even 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.
• 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 polyvinyl acetal resin composition contains compound A.
• the above compound A contains carbon atoms, hydrogen atoms, and oxygen atoms, and the ratio of the number of oxygen atoms to the total number of atoms (number of oxygen atoms/total number of atoms) is 0.18 or more. Further, the number of oxygen atoms/total number of atoms is preferably 0.19 or more, more preferably 0.30 or more, even more preferably 0.35 or more, preferably 0.90 or less, more preferably 0.70 or less, and 0. 60 or less is more preferable.
• the number of oxygen atoms/total number of atoms is preferably 0.18 to 0.90, more preferably 0.19 to 0.70, even more preferably 0.30 to 0.70, and even more preferably 0.35 to 0.60. more preferred.
• the thermal decomposition property of the polyvinyl acetal resin can be improved.
• the molecular weight of the compound A is preferably 90 or more, more preferably 130 or more, even more preferably 150 or more, and 10 ,000 or less is preferable, 450 or less is more preferable, and even more preferably 400 or less.
• the above molecular weight is preferably from 90 to 10,000, more preferably from 130 to 450, even more preferably from 150 to 400. Note that the above molecular weight is a calculated molecular weight.
• solubility parameter value S1 of the polyvinyl acetal resin and the solubility parameter value S2 of the compound A calculated by the Fedors method may be adjusted as appropriate depending on the intended use.
• the absolute value of the difference between S1 and S2 is preferably 9.0 (cal/cm 3 ) 0.5 or less, and 8.5 (cal/cm 3 ) 0 because it has the advantage of improving thermal decomposition. .5 or less is more preferable, and 5.5 (cal/cm 3 ) 0.5 or less is even more preferable.
• the above compound A has the advantage of improving compatibility with polyvinyl acetal resin, and therefore at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2). Preferably, there is one.
• R 1 and R 3 represent a carboxyl group or a salt thereof
• R 2 consists of a carbon atom, a hydrogen atom, and an oxygen atom that may be substituted with a single bond, a hydroxyl group, a carboxyl group, or a salt thereof
• R 4 and R 6 each independently represent a hydrogen atom, a hydroxyl group, an acetyl group, or an acetoxy group
• R 5 is substituted with a hydroxyl group, an acetyl group, an acetoxy group, a carboxyl group, or a salt thereof.
• R 4 and R 6 may be the same or different, but preferably the same.
• the above R 2 is preferably a single bond or a divalent hydrocarbon group which may be substituted with a hydroxyl group, a carboxyl group, or a salt thereof.
• 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 a linear alkylene group having 1 to 6 carbon atoms having at least one of a single bond, a hydroxyl group, a carboxyl group, or a salt thereof, or at least one of a hydroxyl group, a carboxyl group, or a salt thereof.
• a branched alkylene group having 3 to 6 carbon atoms is preferable, and more specifically, a single bond, a methylene group, a trimethylene group, a hydroxymethylene group, a hydroxyethylene group, a 1,2-dihydroxyethylene group, a 2-hydroxy, -carboxytrimethylene group is preferred, and hydroxyethylene group, 1,2-dihydroxyethylene group, and 2-hydroxy,2-carboxytrimethylene group are more preferred.
• R 5 examples include a divalent hydrocarbon group having at least one of a hydroxyl group, an acetyl group, an acetoxy group, a carboxyl group or a salt thereof, and an acetyl group, a divalent group having a glycerin unit, etc. It will be done. Examples of the above-mentioned hydrocarbon group include those listed as R 2 .
• branched alkylene group having 3 to 5 carbon atoms and a divalent group having a glycerin unit having at least one of a hydroxyl group, an acetyl group, an acetoxy group, a carboxyl group or a salt thereof, and a divalent group having 3 to 5 carbon atoms are preferred. More preferred are branched alkylene groups and glycerin units having a repeating number of 2 to 11.
• R 5 is preferably a 2,2-dihydroxymethyltrimethylene group, a 2,2-diacetoxymethyltrimethylene group, or a glycerin unit having a repeating number of 2 to 11.
• the compound represented by the above formula (1) 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,
• aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, and suberic acid.
• citric acid, malic acid, and tartaric acid are preferred.
• Specific examples of the compound represented by the above formula (2) include pentaerythritol, pentaerythritol tetraacetate, glycerin, and polyglycerin having 2 to 11 glycerin units. Among them, pentaerythritol and pentaerythritol tetraacetate are preferred.
• the content of the compound A in the polyvinyl acetal resin composition is preferably 2.8 parts by weight or more based on 100 parts by weight of the polyvinyl acetal resin, since it has the advantage of improving thermal decomposition properties. It is more preferably 0 parts by weight or more, and even more preferably 3.5 parts by weight or more. From the viewpoint of improving the solvent solubility of the polyvinyl acetal resin composition, the amount is preferably 20.0 parts by weight or less, more preferably 15.0 parts by weight or less, and even more preferably 10.0 parts by weight or less.
• the content of the compound A is preferably 2.8 to 20.0 parts by weight, more preferably 3.0 to 15.0 parts by weight, and more preferably 3.5 to 10.0 parts by weight, based on 100 parts by weight of the polyvinyl acetal resin. More preferably 0 parts by weight.
• the water content of the polyvinyl acetal resin composition is 5.0% by weight or less. When the water content is 5.0% by weight or less, the handleability and solvent solubility of the polyvinyl acetal resin composition can be improved.
• the water content is preferably 0.01% by weight or more, more preferably 0.02% by weight or more, preferably 3.0% by weight or less, and more preferably 2.0% by weight or less.
• the water content is preferably 0.01 to 5.0% by weight, more preferably 0.02 to 3.0% by weight, and even more preferably 0.02 to 2.0% by weight.
• the above-mentioned water content means the content of water in the polyvinyl acetal resin composition, and can be measured by an infrared moisture meter or NMR. Further, the moisture content can be adjusted by the drying temperature and drying time after acetalization, and the drying temperature and drying time after mixing the polyvinyl acetal resin and compound A.
• the polyvinyl acetal resin composition preferably has a Y value expressed by the following formula of 6.3 ⁇ 10 ⁇ 9 or more and 45.0 ⁇ 10 ⁇ 9 or less.
• Y ((W A ⁇ M A ⁇ O R ) ⁇ (100-W W )) ⁇ (M PVB ⁇ M A ) ⁇ S 0.4 W A : Content of compound A relative to 100 parts by weight of polyvinyl acetal resin
• M A Molecular weight of compound A O R : Ratio of the number of oxygen atoms to the total number of atoms in compound A (number of oxygen atoms/total number of atoms)
• W W Moisture content M of the polyvinyl acetal resin composition
• PVB Weight average molecular weight of the polyvinyl acetal resin S: When the solubility parameter value of the polyvinyl acetal resin calculated by the Fedors method is S1, and the solubility parameter of compound A is S2.
• the above Y value is more preferably 9.0 ⁇ 10 ⁇ 9 or more, and more preferably 15.0 ⁇ 10 ⁇ 9 or less.
• the above Y value is preferably 6.3 ⁇ 10 ⁇ 9 to 45.0 ⁇ 10 ⁇ 9 , more preferably 9.0 ⁇ 10 ⁇ 9 to 15.0 ⁇ 10 ⁇ 9 .
• the polyvinyl acetal resin composition may contain components such as a dispersant, an antioxidant, a plasticizer, and a surfactant, as long as they do not impede the effects described above.
• the above-mentioned compound A and other additives added as necessary are added to a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with an aldehyde.
• a method of adjusting the moisture content by adding, mixing, and drying can be mentioned.
• Another method is to acetalize polyvinyl alcohol with an aldehyde in the presence of Compound A and dry it to adjust the water content.
• the above compound A and other additives added as necessary are added and mixed to a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with an aldehyde, and the water content is adjusted by drying. A method of doing so is preferred.
• the above polyvinyl acetal resin composition can be suitably used in applications where ordinary polyvinyl acetal resin is used, such as ceramic molded bodies, metal pastes, heat-developable photosensitive materials, paints, inks, reflective sheets, etc.
• a coating solution for manufacturing can be obtained.
• adhesive compositions such as adhesives for display films, interlayer adhesives for ceramic laminates, liquid glues, solid glues, and the like.
• An inorganic fine particle-dispersed slurry composition can be prepared by mixing the polyvinyl acetal resin composition, 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, sulfides, etc. 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 content of the inorganic fine particles 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 By setting the boiling point to 240° C. or higher, it becomes easier to evaporate in the drying process, and it is possible to prevent it from remaining in the molded product. Further, by setting the temperature to be less than 390°C, generation of residual carbon can be prevented. 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 3.0% by weight. It is preferably at most 2.5% by weight, more preferably at most 2.5% by weight.
• the content of the plasticizer is preferably 0.1 to 3.0% by weight, more preferably 0.2 to 2.5% by weight. By keeping it within the above range, it is possible to reduce the firing residue of the plasticizer.
• the fine particle dispersed slurry composition may contain other resins than the polyvinyl acetal resin composition, such as polyvinyl acetal resin, acrylic resin, and ethyl cellulose, as long as the above effects are not impaired.
• the content of the polyvinyl acetal resin composition is 50% by weight or more based on the total binder resin.
• 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 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 method for producing the above-mentioned inorganic fine particle dispersed slurry composition is not particularly limited, and conventionally known stirring methods may be used. Examples include a method of stirring the organic solvent, plasticizer, and other components in 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 having a dielectric layer or an electrode layer formed using the above inorganic fine particle dispersed slurry composition is also one of the aspects of the present invention.
• a polyvinyl acetal resin composition that is particularly excellent in thermal decomposition properties and can exhibit high solvent solubility. Furthermore, an inorganic fine particle dispersed slurry composition and a multilayer ceramic capacitor can be provided.
• Example 1 Preparation of polyvinyl acetal hydrous resin PVB1 3000 g of pure water was added to 300 g of polyvinyl alcohol resin (average degree of polymerization 3,300, degree of saponification 99 mol%), and the mixture was stirred at 90° C. for 2 hours to dissolve. This solution was cooled to 40° C., and 200 g of hydrochloric acid with a concentration of 35% by weight and 160 g of n-butyraldehyde were added thereto to carry out an acetalization reaction to precipitate a reaction product. Thereafter, the reaction was completed by holding at 40° C.
• polyvinyl acetal hydrous resin PVB1 The moisture content of the polyvinyl acetal hydrous resin PVB1 was measured with an infrared moisture meter and was found to be 60% by weight.
• citric acid was added in an amount of 3.2 parts by weight per 100 parts by weight of the polyvinyl acetal resin component, mixed, and dried at 40°C for 48 hours to form a polyvinyl acetal resin. A composition was obtained.
• the amount of acetal groups, the amount of acetyl groups, and the amount of hydroxyl groups were determined.
• the content was as shown in Table 1.
• the moisture content was measured using an infrared moisture meter (MX-50, manufactured by A&D Co., Ltd.). The moisture content was measured at a temperature of 125°C until the moisture content changed to 0.05%/min.
• the citric acid content was measured by ion chromatography and was as shown in Table 1.
• an ion chromatography system ICS900 manufactured by Thermo Fisher Scientific, column: Ionpac AS22 (4 ⁇ x 250 mm), detector: electrical conductivity meter
• Example 2 A polyvinyl acetal resin composition was obtained in the same manner as in Example 1 except that tartaric acid was used instead of citric acid.
• Example 3 A polyvinyl acetal resin composition was obtained in the same manner as in Example 1 except that malic acid was used instead of citric acid.
• Example 1 A polyvinyl acetal resin composition was obtained in the same manner as in Example 1 except that citric acid was not added.
• Example 2 A polyvinyl acetal resin composition was obtained in the same manner as in Example 1, except that tartaric acid was used instead of citric acid and the water content was adjusted to 6.5% by weight by drying at 40° C. for 26 hours.
• Example 4 Preparation of polyvinyl acetal hydrous resin PVB2
• a polyvinyl acetal hydrous resin PVB2 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.
• a polyvinyl acetal resin composition was obtained in the same manner as in Example 1 except that the polyvinyl acetal hydrous resin PVB2 was used.
• Example 5 A polyvinyl acetal resin composition was obtained in the same manner as in Example 4 except that tartaric acid was used instead of citric acid.
• Example 6 A polyvinyl acetal resin composition was obtained in the same manner as in Example 4 except that malic acid was used instead of citric acid.
• Example 7 A polyvinyl acetal resin composition was obtained in the same manner as in Example 4, except that pentaerythritol was used in place of citric acid.
• Example 8 A polyvinyl acetal resin composition was obtained in the same manner as in Example 4, except that pentaerythritol tetraacetate was used in place of citric acid.
• Example 9 A polyvinyl acetal resin composition was obtained in the same manner as in Example 4, except that 16 parts by weight of pentaerythritol tetraacetate was used in place of citric acid.
• Example 10 Example 4 except that polyglycerin having an average repeating number n of glycerin units of 6 was used instead of citric acid, and the moisture content was adjusted to 1.0% by weight by drying at 40°C for 46 hours. A polyvinyl acetal resin composition was obtained in the same manner.
• Example 11 A polyvinyl acetal resin composition was obtained in the same manner as in Example 4 except that oxalic acid was used in place of citric acid.
• Example 12 A polyvinyl acetal resin composition was obtained in the same manner as in Example 4 except that tartronic acid was used in place of citric acid.
• Example 13 A polyvinyl acetal resin composition was obtained in the same manner as in Example 4 except that malonic acid was used in place of citric acid.
• Example 14 A polyvinyl acetal resin composition was obtained in the same manner as in Example 4 except that glutaric acid was used in place of citric acid.
• Example 15 A polyvinyl acetal resin composition was obtained in the same manner as in Example 10 except that 2.5 parts by weight of polyglycerin was used.
• Example 16 A polyvinyl acetal resin composition was obtained in the same manner as in Example 5 except that 25.0 parts by weight of tartaric acid was used.
• Example 3 A polyvinyl acetal resin composition was obtained in the same manner as in Example 4 except that citric acid was not added.
• Example 4 A polyvinyl acetal resin composition was obtained in the same manner as in Example 4, except that 1.6 parts by weight of triethylene glycol di(2-ethylhexanoate) was used in place of citric acid.
• the reaction part was cooled to room temperature to obtain a resin composition containing polyvinyl acetal resin PVB5.
• the citric acid content in the obtained polyvinyl acetal resin composition was measured by ion chromatography, the citric acid content was 14 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin.
• Example 6 A polyvinyl acetal resin composition was obtained in the same manner as in Example 4, except that tartaric acid was used instead of citric acid and the water content was adjusted to 20.0% by weight by drying at 40° C. for 10 hours.
• Example 7 A polyvinyl acetal resin composition was obtained in the same manner as in Example 4, except that formamide was used instead of citric acid and the water content was adjusted to 1.2% by weight by drying at 40° C. for 42 hours.
• Example 17 (Preparation of polyvinyl acetal hydrous resin PVB3) Polyvinyl acetal hydrous resin PVB3 was obtained in the same manner as in Example 1 except that polyvinyl alcohol resin (average degree of polymerization 800, degree of saponification 98.5 mol%) was used.
• a polyvinyl acetal resin composition was obtained in the same manner as in Example 1 except that the polyvinyl acetal hydrous resin PVB3 was used.
• Example 18 A polyvinyl acetal resin composition was obtained in the same manner as in Example 17 except that tartaric acid was used instead of citric acid.
• Example 19 A polyvinyl acetal resin composition was obtained in the same manner as in Example 17 except that malic acid was used in place of citric acid.
• Example 20 To polyvinyl acetal hydrous resin PVB3, 3.2 parts by weight of citric acid was added to 100 parts by weight of polyvinyl acetal resin, and the water content was adjusted to 4.0% by weight by drying at 40°C for 30 hours. A polyvinyl acetal resin composition was obtained.
• Example 21 (Preparation of polyvinyl acetal hydrous resin PVB4)
• Polyvinyl acetal resin PVB4 was prepared in the same manner as in Example 1, except that polyvinyl alcohol resin (average degree of polymerization 850, degree of saponification 94.8 mol%) was used, and 300 g of hydrochloric acid with a concentration of 35% by weight and 180 g of n-butyraldehyde were used. I got it.
• Example 22 (Preparation of carboxylic acid-modified polyvinyl alcohol resin) 30 parts by weight of a vinyl acetate copolymer obtained by copolymerizing vinyl acetate and crotonic acid at a molar ratio of 99.88:0.12 in the presence of a radical polymerization initiator in a conventional manner is dissolved in 60 parts by weight of methanol. I let it happen. Next, 0.4 parts by weight of a 45% by weight aqueous sodium hydroxide solution was added and stirred for 1 hour, then neutralized with concentrated acetic acid, and the precipitated product was washed with methanol.
• polyvinyl acetal hydrous resin PVB5 To the obtained polyvinyl acetal hydrous resin PVB5, tartaric acid was added in an amount of 3.2 parts by weight per 100 parts by weight of the polyvinyl acetal resin component, mixed, and then dried at 40°C for 28 hours to obtain a water content of 5.
• a polyvinyl acetal resin composition was obtained by adjusting the content to .0% by weight.
• Example 23 2900 g of pure water was added to 193 g of modified polyvinyl alcohol resin (average degree of polymerization 1,700, residual acetyl group amount 12 mol %, ethylene content 10 mol %), and the mixture was stirred at 90° C. for 2 hours to dissolve. This solution was cooled to 20° C., and 40 g of hydrochloric acid with a concentration of 35% by weight and 125 g of n-butyraldehyde were added thereto to carry out an acetalization reaction to precipitate a reaction product. Thereafter, the reaction was completed by holding at 30° C.
• polyvinyl acetal hydrous resin PVB6 The moisture content of the polyvinyl acetal hydrous resin PVB6 was measured with an infrared moisture meter and was found to be 60% by weight.
• polyvinyl acetal hydrous resin PVB6 tartaric acid was added in an amount of 3.2 parts by weight per 100 parts by weight of the polyvinyl acetal resin component, mixed, and then dried at 40°C for 46 hours to obtain a water content of 1.
• a polyvinyl acetal resin composition was obtained by adjusting the content to .0% by weight.
• Example 24 2900 g of pure water was added to 193 g of modified polyvinyl alcohol resin (average degree of polymerization 800, residual acetyl group amount 7 mol %, ethylene content 5 mol %), and the mixture was stirred at 90° C. for 2 hours to dissolve. This solution was cooled to 20° C., and 20 g of hydrochloric acid with a concentration of 35% by weight and 110 g of n-butyraldehyde were added thereto to carry out an acetalization reaction to precipitate a reaction product. Thereafter, the reaction was completed by holding at 30° C.
• polyvinyl acetal hydrous resin PVB7 The moisture content of the polyvinyl acetal hydrous resin PVB7 was measured with an infrared moisture meter and was found to be 60% by weight.
• Weight average molecular weight (Mw) The obtained polyvinyl acetal resin was dissolved in tetrahydrofuran at a concentration of 0.05% by weight, and measured using a GPC device HLC-8220 (manufactured by Tosoh Corporation). Based on the measurement results, a sample was prepared using a monodisperse polystyrene standard sample. The weight average molecular weight Mw was calculated using the molecular weight calibration curve obtained. Note that a column TSKgel SuperHZM-H (manufactured by Tosoh Corporation) was used as the column.
• Examples 1 to 3 and Comparative Example 2 are WB (1) (Comparative Example 1), Examples 4 to 16 and Comparative Examples 4 to 7 are WB (2) (Comparative Example 3), and Example 17.
• ⁇ 20 is WB (3) (Comparative Example 8)
• Example 21 is WB (4) (Comparative Example 9)
• Example 22 is WB (5) (Comparative Example 10)
• Example 23 is WB (6) ( Comparative Example 11)
• Example 24 used WB(7) (Comparative Example 12) for calculation.
• a mixed solvent A having a weight ratio of ethanol and toluene of 1:9 and a mixed solvent B having a weight ratio of ethanol and toluene of 5:5 were prepared.
• a polyvinyl acetal resin composition and a mixed solvent A, B, or C were mixed in a sealed glass container so that the polyvinyl acetal resin content was 9% by weight to prepare 30 g of a solution.
• the solution was mixed for 5 hours using a hot stirrer so that the temperature reached 60°C, and the state of the solution immediately after mixing was visually confirmed and evaluated based on the following criteria.
• C There is undissolved material or the solution is cloudy.
• a polyvinyl acetal resin composition that is particularly excellent in thermal decomposition properties and can exhibit high solvent solubility. Furthermore, an inorganic fine particle dispersed slurry composition and a multilayer ceramic capacitor can be provided.

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