WO2024018991A1 - Copolymère d'acide lactique-vinyle, composition de liant et pâte à utiliser lors du frittage - Google Patents

Copolymère d'acide lactique-vinyle, composition de liant et pâte à utiliser lors du frittage Download PDF

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Publication number
WO2024018991A1
WO2024018991A1 PCT/JP2023/025920 JP2023025920W WO2024018991A1 WO 2024018991 A1 WO2024018991 A1 WO 2024018991A1 JP 2023025920 W JP2023025920 W JP 2023025920W WO 2024018991 A1 WO2024018991 A1 WO 2024018991A1
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lactic acid
vinyl copolymer
vinyl
mass
viscosity
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PCT/JP2023/025920
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English (en)
Japanese (ja)
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孝徳 高橋
秀二 岡本
豪 宮本
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綜研化学株式会社
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Publication of WO2024018991A1 publication Critical patent/WO2024018991A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/34—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups
    • C08C19/36—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups with carboxy radicals
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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

Definitions

  • the present invention relates to a lactic acid-vinyl copolymer, a binder composition, and a baking paste.
  • Ethyl cellulose (EC) and polyvinyl butyral (PVB) are used as binders in inorganic particle-containing firing pastes used when manufacturing internal electrodes (for example, MLCCs (Multilayer Ceramic Capacitors)).
  • MLCCs Multilayer Ceramic Capacitors
  • Patent Document 1 discloses an invention related to a dry film for internal electrodes of a multilayer ceramic capacitor formed of a composition containing conductive powder and an organic binder resin, in which ethyl cellulose and polyvinyl butyral are used as the binder resin. It is disclosed that it includes. Further, Patent Document 2 discloses a paste composition containing an inorganic substance, a binder resin, and a solvent, wherein the binder resin is a homopolymer of lactic acid and a copolymer of lactic acid and a copolymerizable monomer. Disclosed is a paste composition characterized by comprising at least one (co)polymer selected from the following.
  • the present invention has been made in view of these circumstances, and has excellent firing properties, is soluble in a solvent without any visible insoluble matter, and has an effective rheology when mixed with a solvent.
  • the present invention provides a lactic acid-vinyl copolymer for use in a baking paste, which has characteristics and has less stringiness, a binder composition containing the lactic acid-vinyl copolymer, and a baking paste.
  • a lactic acid-vinyl copolymer containing a lactic acid unit derived from lactic acid and a vinyl monomer unit derived from a vinyl monomer, the lactic acid-vinyl copolymer being used for baking paste.
  • the present inventors conducted extensive studies and found that a lactic acid-vinyl copolymer containing a lactic acid unit derived from lactic acid and a vinyl monomer unit derived from a vinyl monomer has excellent sinterability and is It has been discovered that the binder for baking pastes can be dissolved in a solvent without visible insoluble matter, has effective rheological properties when mixed with a solvent, and has low stringiness, and the present invention has been made based on the present invention. has been completed.
  • the lactic acid-vinyl copolymer according to [1] which has a viscosity of 2.0 Pa ⁇ s or more as measured by the following method.
  • ⁇ Viscosity measurement method 1) Pour 30% by mass of the lactic acid-vinyl copolymer and 70% by mass of butyl carbitol acetate or dihydroterpinyl acetate into a closed container, stir at 2000 rpm with a revolution-revolution mixer until there is no undissolved residue, After defoaming at 2200 rpm until no air bubbles disappear, leave it at 25°C for 1 day to prepare a lactic acid-vinyl copolymer solution 2) Add a Cone Plate with a diameter of 20 mm and a cone angle of 0.975° to the viscosity/viscoelasticity measuring device.
  • ⁇ Method for measuring viscosity A and viscosity B > 1) Pour 30% by mass of the lactic acid-vinyl copolymer and 70% by mass of butyl carbitol acetate or dihydroterpinyl acetate into a closed container, stir at 2000 rpm with a revolution-revolution mixer until there is no undissolved residue, After defoaming at 2200 rpm until no air bubbles disappear, leave it at 25°C for 1 day to prepare a lactic acid-vinyl copolymer solution 2) Add a Cone Plate with a diameter of 20 mm and a cone angle of 0.975° to the viscosity/viscoelasticity measuring device.
  • [5] The lactic acid-vinyl copolymer according to any one of [1] to [4], wherein the micro residual carbon content of the lactic acid-vinyl copolymer is 2.00% by mass or less. Lactic acid-vinyl copolymer.
  • [6] The lactic acid-vinyl copolymer according to any one of [1] to [5], wherein the lactic acid-vinyl copolymer includes a vinyl polymer block, and the lactic acid-vinyl copolymer includes a vinyl polymer block.
  • lactic acid-vinyl copolymer according to any one of [1] to [8], wherein the vinyl monomer is at least one of (meth)acrylic acid and (meth)acrylic ester. lactic acid-vinyl copolymer, including one.
  • a lactic acid-vinyl copolymer containing 5.0% by mass to 99.9% by mass of the lactic acid unit.
  • a binder composition for preparing a baking paste comprising the lactic acid-vinyl copolymer according to any one of [1] to [13] and a solvent.
  • a binder composition for preparing a baking paste according to [14] wherein the ratio A'/B' of viscosity A' and viscosity B' measured by the following method is 3.0 or more.
  • binder composition binder composition.
  • Method for measuring viscosity A' and viscosity B'> A Cone Plate with a diameter of 20 mm and a cone angle of 0.975° was attached to the viscosity/viscoelasticity measuring device with a clearance of 23 ⁇ m, the binder composition was set in the measuring section, and the shear rate was set at a set temperature of 25° C. for 0.01 sec.
  • the material has excellent firing properties, is soluble in a solvent without any visible insoluble matter, has effective rheological properties when mixed with a solvent, and has no stringiness.
  • a small amount of lactic acid-vinyl copolymer for baking paste can be obtained.
  • the lactic acid-vinyl copolymer according to the present invention can be dissolved in a solvent without any visible insoluble matter, and can be used as a binder composition for preparing a baking paste in which the binder is uniformly dispersed.
  • a paste for baking can be obtained.
  • the lactic acid-vinyl copolymer according to the present invention has effective rheological properties when mixed with a solvent, that is, it has an appropriate viscosity and pseudoplasticity, so it can be used for baking with excellent coating properties.
  • a paste can be prepared.
  • the lactic acid-vinyl copolymer of the present invention, the binder composition for preparing a baking paste containing the lactic acid-vinyl copolymer, and the baking paste have excellent sinterability, and the residual carbon after the paste is sintered. None or very few.
  • the lactic acid-vinyl copolymer according to the present invention is mixed with a solvent to form a lactic acid-vinyl copolymer solution, it is possible to obtain a baking paste that has less stringiness and is less prone to problems such as extrusion during printing. be able to.
  • the lactic acid-vinyl copolymer according to the present invention is a lactic acid-vinyl copolymer for baking paste containing lactic acid units derived from lactic acid and vinyl monomer units derived from vinyl monomers.
  • Polylactic acid consisting only of lactic acid units has difficulty achieving solvent solubility, and polymers consisting only of vinyl monomer units have difficulty achieving appropriate viscosity and pseudoplasticity when mixed with a solvent. was difficult.
  • According to the present invention by containing both a lactic acid unit derived from lactic acid and a vinyl monomer unit derived from a vinyl monomer, it has excellent sinterability and can be dissolved in a solvent without visually recognizable insoluble matter. Thus, it is possible to obtain a lactic acid-vinyl copolymer for use in baking pastes that has effective rheological properties and less stringiness when mixed with a solvent.
  • the lactic acid-vinyl copolymer according to the present invention contains lactic acid units derived from lactic acid.
  • the lactic acid unit according to the present invention can contain at least one of an L-lactic acid unit and a D-lactic acid unit, and preferably contains an L-lactic acid unit and a D-lactic acid unit.
  • the lactic acid units can be derived from at least one of meso-lactide, L-lactide, and D-lactide.
  • the lactic acid-vinyl copolymer according to the present invention has a content of L-lactic acid units when the total of L-lactic acid units and D-lactic acid units contained in the lactic acid-vinyl copolymer is 100% by mass. , for example, 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100% by mass, even if it is within the range between any two of the numerical values exemplified here. good.
  • the content of L-lactic acid units can be, for example, 30 to 70% by mass.
  • the content of D-lactic acid units can be, for example, 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100% by mass, and any of the values exemplified here. It may be within a range between the two.
  • the content of D-lactic acid units can be, for example, 30 to 70% by mass.
  • the lactic acid-vinyl copolymer according to the present invention contains a vinyl monomer unit.
  • the vinyl monomer according to one embodiment of the present invention means a monomer containing at least one vinyl group (carbon-carbon unsaturated double bond).
  • the lactic acid-vinyl copolymer according to the present invention may contain one or more types of vinyl monomer units.
  • the lactic acid-vinyl copolymer according to one embodiment of the present invention includes unsaturated monocarboxylic acids such as (meth)acrylic acid, unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, and esters thereof. , styrene, vinyl acetate, acrylonitrile, acrylamide, and derivatives thereof.
  • the lactic acid-vinyl copolymer preferably contains vinyl monomer units derived from at least one of (meth)acrylic acid and (meth)acrylic ester, and the vinyl monomer unit derived from (meth)acrylic ester.
  • it contains a mer unit, and it is even more preferable that it contains a vinyl monomer unit derived from a methacrylic acid ester.
  • a vinyl monomer unit derived from the above-mentioned vinyl monomer it is easy to obtain a binder that has better sinterability and better solvent solubility.
  • Vinyl monomers are usually used in the lactic acid-vinyl copolymer according to one embodiment of the present invention.
  • the vinyl monomer preferably contains a vinyl monomer containing an alkyl group having 1 to 22 carbon atoms, and more preferably contains a (meth)acrylic acid alkyl ester in which the number of carbon atoms in the alkyl group is within the above range. .
  • the number of carbon atoms in the alkyl group is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, and may be within the range between any two of the numerical values exemplified here.
  • the lactic acid-vinyl copolymer according to one embodiment of the present invention has monomer units derived from a vinyl monomer having an alkyl group having 1 to 7 carbon atoms (a vinyl monomer containing a short-chain alkyl group). It is more preferable to include a monomer unit derived from a vinyl monomer having an alkyl group having 8 to 18 carbon atoms (a vinyl monomer containing a long-chain alkyl group).
  • the carbon number of the short-chain alkyl group-containing vinyl monomer is, for example, 1, 2, 3, 4, 5, 6, or 7, and even if it is within the range between any two of the numerical values exemplified here. good.
  • the carbon number of the long-chain alkyl group-containing vinyl monomer is, for example, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, and any two of the numerical values exemplified here. It may be within the range between.
  • the lactic acid-vinyl copolymer according to one embodiment of the present invention preferably contains a vinyl monomer unit derived from a vinyl monomer containing a functional group.
  • the functional group is preferably at least one selected from the group consisting of a hydroxyl group, a carbonyl group, an epoxy group, an amino group, an isocyanate group, a thiol group, and an alkoxysilyl group; It is preferable that there be.
  • the vinyl monomer containing a functional group is preferably at least one of (meth)acrylic acid and (meth)acrylic ester containing a functional group, such as 2-hydroxyethyl (meth)acrylate, 2- Hydroxyalkyl (meth)acrylates such as hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, 4-hydroxy-butyl (meth)acrylate - Epoxy group-containing vinyl monomers such as glycidyl ether.
  • a functional group such as 2-hydroxyethyl (meth)acrylate, 2- Hydroxyalkyl (meth)acrylates such as hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, 4-hydroxy-butyl (meth)acrylate - Epoxy group-containing
  • the lactic acid-vinyl copolymer according to one embodiment of the present invention contains vinyl monomer units derived from vinyl monomers containing functional groups, the lactic acid monomer units bond (for example, a lactic acid-vinyl copolymer obtained by graft polymerization can also be obtained.
  • the lactic acid-vinyl copolymer according to one embodiment of the present invention may contain vinyl monomer units derived from vinyl monomers that do not contain functional groups (eg, the functional groups described above).
  • the vinyl monomer that does not contain a functional group is preferably at least one of (meth)acrylic acid and (meth)acrylic acid ester that does not contain a functional group, such as methyl (meth)acrylate, ethyl (meth)acrylate, etc.
  • acrylate n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate , n-heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate ) acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, be
  • (meth)acrylic acid aryl esters (meth)acrylic acid aryloxyalkyl esters such as phenoxyethyl (meth)acrylate, (meth)acrylic acid aryloxyalkyl esters such as benzyl (meth)acrylate, and the like.
  • the lactic acid-vinyl copolymer according to one embodiment of the present invention includes vinyl monomer units derived from a vinyl monomer containing a functional group and vinyl monomer units derived from a vinyl monomer not containing a functional group. It is preferable to include. Note that the vinyl monomer containing a functional group may be a short-chain alkyl group-containing vinyl monomer, and the vinyl monomer not containing a functional group may be a long-chain alkyl group-containing vinyl monomer. Good too.
  • the lactic acid-vinyl copolymer contains 0 vinyl monomer units derived from vinyl monomers containing functional groups based on 100% by mass of the total vinyl monomer units contained in the lactic acid-vinyl copolymer.
  • the content of vinyl monomer units derived from vinyl monomers containing functional groups is, for example, 0.5, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60. , 65, and 70% by mass, and may be within a range between any two of the numerical values exemplified here.
  • the solvent solubility of the lactic acid-vinyl copolymer and other physical properties such as rheological properties are improved. It is easy to achieve both.
  • the lactic acid-vinyl copolymer is a polymer mainly composed of lactic acid units and vinyl monomer units, but it may be used as long as it does not impair the effects of the present invention. It may also contain components derived from other monomers depending on the situation. Examples of other monomers include monomers having functional groups, such as monomers having hydroxyl groups, carbonyl groups, epoxy groups, amino groups, isocyanate groups, thiol groups, and alkoxysilyl groups. In addition, other monomers can include a chain transfer agent used for molecular weight adjustment, and examples of chain transfer agents include chain transfer agents described later in "2. Method for producing lactic acid-vinyl copolymer". be able to.
  • a monomer having a functional group capable of reacting with a functional group of a vinyl monomer containing a functional group can be included.
  • diglycidyl ethers such as bisphenol A diglycidyl ether and polyalkylene oxide diglycidyl ether can be mentioned.
  • Other monomer units may be incorporated into the main chain of the vinyl polymer, or may be included as side chains by reacting with vinyl monomers having functional groups.
  • the lactic acid-vinyl copolymer according to the present invention contains monomer units other than lactic acid units and vinyl monomer units, for example, 0, 5, 10, It may be contained in an amount of 15 or 20% by mass, or within a range between any two of the numerical values exemplified here.
  • the lactic acid-vinyl copolymer according to the present invention may also consist of only lactic acid units and vinyl monomer units.
  • the lactic acid-vinyl copolymer according to one embodiment of the present invention has a lactic acid unit content of 5.0 to 99.0% based on 100% by mass of the lactic acid-vinyl copolymer.
  • the content is preferably 9% by mass.
  • the content of lactic acid units is, for example, 5.0, 10.0, 15.0, 20.0, 25.0, 30.0, 35.0, 40.0, 45.0, 50.0, 55 .0, 60.0, 65.0, 70.0, 75.0, 80.0, 85.0, 90.0, 95.0, 99.0, 99.9% by mass, and examples are given here. It may be within the range between any two of the above values.
  • lactic acid monomer units By keeping the content of lactic acid monomer units below the above upper limit, solvent solubility can be easily maintained. Further, by setting the content of lactic acid units to the above lower limit or more, appropriate viscosity and pseudoplasticity can be obtained when mixed with a solvent. According to one embodiment of the present invention, even if the content of lactic acid monomer in the lactic acid-vinyl copolymer is extremely small, if the lactic acid monomer unit is contained, the lactic acid-vinyl copolymer Pseudoplasticity improves when the polymer is mixed with a solvent, and although the mechanism is not necessarily clear, it is assumed as follows.
  • the improvement in pseudoplasticity is thought to be related to the hydrogen bonding between the carboxylic acids of the lactic acid monomer units present at the ends of the lactic acid-vinyl copolymer, and even if the lactic acid monomer units contained in the entire lactic acid-vinyl copolymer Even if the content of mer units is small (for example, even if the polylactic acid block is short), it is presumed that pseudoplasticity can be maintained as long as the amount of lactic acid monomer units present at the terminals can be maintained to a certain extent.
  • the lactic acid-vinyl copolymer according to an embodiment of the present invention may contain 0.1 to 95.0% by mass of vinyl monomer units based on 100% by mass of the lactic acid-vinyl copolymer. preferable.
  • the content of vinyl monomer units is, for example, 0.0, 5.0, 10.0, 15.0, 20.0, 25.0, 30.0, 35.0, 40.0, 45. 0, 50.0, 55.0, 60.0, 65.0, 70.0, 75.0, 80.0, 85.0, 90.0, 95.0% by mass, as exemplified here. It may be within a range between any two values.
  • the lactic acid-vinyl copolymer according to one embodiment of the present invention may include a vinyl polymer block.
  • the vinyl polymer block may be a vinyl polymer block consisting of one type of vinyl monomer unit, or may be a vinyl (co)polymer block consisting of two or more types of vinyl monomer units.
  • the vinyl polymer block includes at least one of a vinyl monomer unit derived from a vinyl monomer that includes a functional group and a vinyl monomer unit that is derived from a vinyl monomer that does not include a functional group.
  • a vinyl monomer unit derived from a vinyl monomer containing a functional group and a vinyl monomer unit derived from a vinyl monomer not containing a functional group, and these monomer units may be randomly polymerized polymer blocks.
  • the vinyl polymer block preferably has a glass transition temperature of 0 to 100°C.
  • the glass transition temperature is, for example, 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100°C, and even if it is within the range between any two of the numerical values exemplified here. good.
  • the glass transition temperature of the vinyl polymer block is within the above numerical range, it is possible to improve the handling properties of a baking paste using a lactic acid-vinyl copolymer as a binder.
  • the glass transition temperature can be determined theoretically using the Fox equation based on the weight fraction of the monomers blended as raw materials and the glass transition temperature of the homopolymer of the monomers. It can be calculated using the method described in .
  • the vinyl polymer block preferably has a weight average molecular weight of 3,000 to 1,000,000, more preferably 8,000 to 700,000.
  • the weight average molecular weight is, for example, 3,000, 5,000, 8,000, 10,000, 20,000, 30,000, 50,000, 70,000, 100,000, 200,000, 300,000. , 500,000, 700,000, and 1,000,000, and may be within the range between any two of the numerical values exemplified here.
  • the solvent solubility, viscosity, and pseudoplasticity of the lactic acid-vinyl copolymer can be adjusted more appropriately.
  • the lactic acid-vinyl copolymer according to one embodiment of the present invention preferably has lactic acid units bonded to functional groups contained in vinyl monomers.
  • the functional group is preferably at least one functional group selected from the group consisting of a hydroxyl group, a carbonyl group, an epoxy group, an amino group, an isocyanate group, a thiol group, and an alkoxysilyl group.
  • the lactic acid-vinyl copolymer according to one embodiment of the present invention may contain a polylactic acid block.
  • the polylactic acid block may include lactic acid monomer units derived from at least one of meso-lactide, L-lactide, and D-lactide, and the polylactic acid block may include L-lactic acid units and D-lactic acid units. It may contain at least one of the units, and may be a polymer block in which L-lactic acid units and D-lactic acid units are randomly polymerized.
  • the lactic acid-vinyl copolymer according to one embodiment of the present invention may include a polylactic acid block and a vinyl polymer block.
  • the lactic acid-vinyl copolymer according to one embodiment of the present invention is a block copolymer (particularly a diblock copolymer) or a graft copolymer containing a polylactic acid block and a vinyl monomer block. can do.
  • a diblock copolymer it tends to be a lactic acid-vinyl copolymer with appropriate viscosity and pseudoplasticity.
  • graft copolymer it tends to be a lactic acid-vinyl copolymer with appropriate pseudoplasticity.
  • the lactic acid-vinyl copolymer according to one embodiment of the present invention can be a graft copolymer.
  • the graft copolymer can include a backbone chain containing vinyl monomer units and a branch chain containing lactic acid monomer units. Furthermore, the branch chain containing the lactic acid monomer unit can be bonded to a functional group contained in the vinyl monomer contained in the main chain.
  • the lactic acid-vinyl copolymer according to an embodiment of the present invention has a shear rate of It is preferable that the viscosity A of the lactic acid-vinyl copolymer solution at a speed of 1 sec -1 is 2.0 Pa ⁇ s or more.
  • the viscosity A of the lactic acid-vinyl copolymer solution is, for example, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 20.0, 30.0, 40.0, 50.0, 60. 0, 70.0, 80.0, 90.0, 100.0, 200.0, 300.0, 400.0, 500.0, 600.0, 700.0, 800.0, 900.0, 1000.0 Pa ⁇ s, and may be within a range between any two of the numerical values exemplified here.
  • the binder composition can be used to prepare a baking paste with excellent coating properties.
  • the lactic acid-vinyl copolymer according to an embodiment of the present invention exhibits the following properties when the shear rate is increased at a constant rate of change from 0.01 sec -1 to 10,000 sec -1 over 150 seconds at 25°C.
  • the viscosity B of the lactic acid-vinyl copolymer solution at a shear rate of 9,000 sec -1 is preferably 0.05 to 2.0 Pa ⁇ s.
  • the viscosity B of the lactic acid-vinyl copolymer solution is, for example, 0.05, 0.1, 0.2, 0.3, 0.5, 0.8, 1.0, 1.1.0, 1.
  • the binder composition can be used to prepare a baking paste with excellent coating properties.
  • the lactic acid-vinyl copolymer solution according to one embodiment of the present invention has a shear rate of 0.01 sec -1 to 10,000 sec -1 at a constant rate of change over 150 seconds at 25°C.
  • the ratio A/B of viscosity A at a shear rate of 1 sec -1 to viscosity B at a shear rate of 9000 sec -1 is preferably 3.0 or more.
  • A/B is, for example, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0 , 8.5, 9.0, 9.5, 10.0, 20.0, 30.0, 40.0, 50.0, 60.0, 70.0, 80.0, 90.0, 100 .0, 200.0, 300.0, 400.0, 500.0, 600.0, 700.0, 800.0, 900.0, 1,000.0Pa ⁇ s, and the numerical values illustrated here It may be within the range between any two. That is, the lactic acid-vinyl copolymer solution according to one embodiment of the present invention preferably exhibits pseudoplasticity in which the higher the shear rate, the lower the viscosity.
  • the lactic acid-vinyl copolymer solution means a solution containing 30% by mass of the lactic acid-vinyl copolymer and 70% by mass of butyl carbitol acetate or dihydroterpinyl acetate. That is, the lactic acid-vinyl copolymer according to one embodiment of the present invention preferably satisfies at least one of the following requirements. - The viscosity of the lactic acid-vinyl copolymer butyl carbitol acetate solution containing 30% by mass of the lactic acid-vinyl copolymer and 70% by mass of butyl carbitol acetate satisfies the above requirements.
  • the viscosity of the lactic acid-vinyl copolymer dihydroterpinyl acetate solution containing 30% by mass of the lactic acid-vinyl copolymer and 70% by mass of dihydroterpinyl acetate satisfies the above requirements. Further, the viscosities of both the lactic acid-vinyl copolymer butyl carbitol acetate solution and the lactic acid-vinyl copolymer dihydroterpinyl acetate solution may satisfy the above requirements.
  • the viscosity of the lactic acid-vinyl copolymer solution can be controlled by adjusting the types and amounts of lactic acid units and vinyl monomer units contained in the lactic acid-vinyl copolymer, as well as the weight average molecular weight and structure. can.
  • the viscosity of the lactic acid-vinyl copolymer solution at each shear rate at 25°C can be measured using a rotational viscometer, such as a rheometer, and can be measured by the following method. can be measured by the method described in Examples.
  • ⁇ Method for measuring viscosity A and viscosity B > 1) Pour 30% by mass of the lactic acid-vinyl copolymer and 70% by mass of butyl carbitol acetate or dihydroterpinyl acetate into a closed container, stir at 2000 rpm with a revolution-revolution mixer until there is no undissolved residue, After defoaming at 2200 rpm until no air bubbles disappear, leave it at 25°C for 1 day to prepare a lactic acid-vinyl copolymer solution 2) Add a Cone Plate with a diameter of 20 mm and a cone angle of 0.975° to the viscosity/viscoelasticity measuring device.
  • the lactic acid-vinyl copolymer according to one embodiment of the present invention preferably has a weight average molecular weight of 10,000 to 3,000,000.
  • the weight average molecular weight is, for example, 10,000, 50,000, 100,000, 200,000, 300,000, 500,000, 1,000,000, 2,000,000, 3,000,000. , it may be within the range between any two of the numerical values exemplified here. By setting the weight average molecular weight within the above numerical range, it is easy to achieve a balance between solvent solubility, viscosity, and pseudoplasticity of the lactic acid-vinyl copolymer.
  • the weight average molecular weight can be determined by the GPC method, and specifically can be measured under the conditions described in the Examples.
  • the weight average molecular weight can be controlled by adjusting the polymerization conditions.
  • a solvent for example, a lactic acid-vinyl copolymer containing 30% by mass of the lactic acid-vinyl copolymer and 70% by mass of butyl carbitol acetate
  • a solvent for example, a lactic acid-vinyl copolymer containing 30% by mass of the lactic acid-vinyl copolymer and 70% by mass of butyl carbitol acetate
  • a solvent for example, a lactic acid-vinyl copolymer containing 30% by mass of the lactic acid-vinyl copolymer and 70% by mass of butyl carbitol acetate
  • a solvent for example, a lactic acid-vinyl copolymer containing 30% by mass of the lactic acid-vinyl copolymer and 70% by mass of butyl carbitol acetate
  • Solvent solubility can be specifically evaluated under the conditions described in Examples. Solvent solubility can be controlled by adjusting the types and amounts of lactic acid units and vinyl monomer units contained in the lactic acid-vinyl copolymer, as well as the weight average molecular weight and structure.
  • the lactic acid-vinyl copolymer according to one embodiment of the present invention preferably has a micro residual carbon content of 2.00% by mass or less.
  • the micro residual carbon content is, for example, 0.10, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, 0.90, 1.00, 1. 10, 1.20, 1.30, 1.40, 1.50, 1.60, 1.70, 1.80, 1.90, 2.00% by mass, and any of the numerical values exemplified here. It may be within a range between the two.
  • the micro residual carbon content refers to the residual carbon content determined by the micro method. Specifically, a sample was weighed in a test container, placed in a furnace, and heated to 500°C under specified conditions under a nitrogen atmosphere. After that, the test container is further maintained at 500° C. for 15 minutes, left to cool, and then weighed, and the residual carbon content is determined by calculating the percentage of mass decreased relative to the initial mass (% by mass). Specifically, the micro residual carbon content can be determined by the method described in Examples. The micro residual carbon content can be adjusted by controlling the types and amounts of lactic acid units and vinyl monomer units contained in the lactic acid-vinyl copolymer.
  • the lactic acid-vinyl copolymer according to one embodiment of the present invention preferably has a 95% weight loss temperature (TD95) of less than 400°C.
  • TD95 is, for example, 350, 355, 360, 365, 370, 375, 380, 385, 390, 395°C, less than 400°C, even if it is within the range between any two of the numerical values exemplified here. good.
  • TD95 means the temperature at which the weight decreases by 95% when the sample is heated at 10 ° C./min, and can be specifically determined by the method described in the Examples using a thermogravimetric differential thermal analyzer. Can be done. TD95 can be adjusted by controlling the types and amounts of lactic acid units and vinyl monomer units contained in the lactic acid-vinyl copolymer solution.
  • the lactic acid-vinyl copolymer according to an embodiment of the present invention is prepared by sticking a glass rod into a lactic acid-vinyl copolymer solution adjusted to have a viscosity A of 5 Pa ⁇ s in an environment of 25°C and pulling it up 10 cm.
  • the time required for the thread-like solution existing between the solution surface and the glass rod to break is preferably 4 seconds or less.
  • stringiness can be determined by the method described in Examples.
  • the stringiness can be adjusted by controlling the types and amounts of lactic acid units and vinyl monomer units contained in the lactic acid-vinyl copolymer.
  • the acid value of the lactic acid-vinyl copolymer toluene solution is preferably 0.1 mgKOH/g or more and 20.0 mgKOH/g or less.
  • the acid value is, for example, 0.1, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, 12.0, 13.0, 14.0, 15.0, 16.0, 17.0, 18.0, 19.0, 20.0mgKOH/g, and the numerical values exemplified here. It may be within the range between any two.
  • the acid value is thought to be correlated with the amount of carboxylic acid in the lactic acid unit present at the end of the lactic acid-vinyl copolymer.
  • the acid value is correlated with the number of branch chains. It is thought that this is related.
  • the lactic acid-vinyl copolymer toluene solution may contain 25% by mass of the lactic acid-vinyl copolymer and 75% by mass of toluene.
  • the acid value can be measured by dissolving the sample in a solvent and performing potentiometric titration using a 0.1 mol/l potassium hydroxide ethanol solution. Specifically, it can be determined by the method described in the Examples. can. The acid value is determined by adjusting the type and amount of lactic acid units and vinyl monomer units contained in the lactic acid-vinyl copolymer, as well as the polymerization conditions, and controlling the weight average molecular weight and structure of the lactic acid-vinyl copolymer. It can be adjusted by
  • the lactic acid-vinyl copolymer according to the present invention is a lactic acid-vinyl copolymer for baking paste, and can be suitably used as a binder for baking paste.
  • the lactic acid-vinyl copolymer according to the present invention has excellent sinterability due to the presence of lactic acid units and vinyl monomer units, and is soluble in solvents without any visible insoluble matter.
  • a firing paste in which the binder is uniformly dispersed has excellent coating properties, has little stringiness, and has little residual carbon during firing, and is suitable for manufacturing capacitors that have become smaller in recent years. Also, it is possible to form a pattern without causing any defects, and organic substances originating from the binder do not remain in the resulting capacitor, providing the advantage of reducing the risk of defects.
  • a method for producing a lactic acid-vinyl copolymer according to an embodiment of the present invention includes: A vinyl (co)polymerization step in which a raw material containing one or more vinyl monomers is polymerized to obtain a vinyl (co)polymer, and a raw material containing the vinyl (co)polymer and lactic acid. may include a lactic acid-vinyl copolymer polymerization step in which a lactic acid-vinyl copolymer is obtained by polymerizing the lactic acid-vinyl copolymer.
  • Vinyl (co)polymerization process In the vinyl (co)polymerization process, raw materials containing one or more types of vinyl monomers are polymerized to obtain a vinyl (co)polymer. In the vinyl (co)polymerization step, conventionally known polymerization methods such as solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization can be employed, and among these, solution polymerization is preferred. .
  • a raw material containing one or more vinyl monomers and, if necessary, a chain transfer agent, a solvent, etc. are charged into a reaction vessel, and the reaction is carried out under an inert gas atmosphere such as nitrogen gas.
  • a polymerization initiator is added, and the reaction system is maintained at a temperature of usually 50 to 90°C, preferably 60 to 90°C, and the reaction is carried out for 2 to 20 hours. Further, during the polymerization reaction, a polymerization initiator, chain transfer agent, monomer, and solvent may be additionally added as appropriate.
  • the raw material can include a vinyl monomer containing a functional group and a vinyl monomer not containing a functional group, and specific examples of a vinyl monomer containing a functional group and a vinyl monomer not containing a functional group,
  • the blending ratio is as described above.
  • solvents examples include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; water, etc. can be used.
  • aromatic solvents such as toluene and xylene
  • ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone
  • ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate
  • water etc.
  • lactide such as meso-lactide, L-lactide, D-lactide, etc., which will be a raw material for
  • Examples of the polymerization initiator include azo initiators and peroxide polymerization initiators.
  • Examples of azo initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2- cyclopropylpropionitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carboxylic acid), nitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'- Azobis(N,N'-dimethyleneisobutyramidine), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl
  • chain transfer agents include thiol compounds (mercaptans). Specifically, alkyl mercaptans such as n-octyl mercaptan, t- or n-dodecyl mercaptan, hydroxyl group-containing mercaptans such as 2-mercaptoethanol, thioglycerol, and 3-mercaptohexan-1-ol, thioglycolic acid, 2- Mercaptopropionic acid, 3-mercaptopropionic acid, 4-mercaptobutanoic acid, 6-mercaptohexanoic acid, 11-mercaptoundecanoic acid, 3-mercaptopyruvate, 2-mercaptobenzoic acid, 3-mercaptobenzoic acid, 4-mercapto Carboxyl group-containing mercaptans such as benzoic acid and thiomalic acid, alkoxysilanes such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldieth
  • mercaptans Mention may be made of mercaptans.
  • Other examples include polyfunctional thiols such as pentaerythritol tetrakis (3-mercaptopropionate), styrene dimers such as ⁇ -methylstyrene dimer, and naphthoquinone compounds.
  • a chain transfer agent it is preferably 0.01 to 5.00 parts by mass, more preferably 0.02 to 3.00 parts by mass, even more preferably 0.03 parts by mass, per 100 parts by mass of the monomer. Amounts within the range of 2.50 parts by weight can be used.
  • the polymerization initiator, chain transfer agent, and solvent may be used alone or in combination of two or more.
  • the weight average molecular weight of the vinyl (co)polymer can be adjusted by adjusting the type and amount of the polymerization initiator and chain transfer agent, and polymerization conditions such as polymerization temperature and time.
  • Lactic acid-vinyl copolymer polymerization step In the lactic acid-vinyl copolymer polymerization step, raw materials containing a vinyl (co)polymer and lactic acid are further polymerized to obtain a lactic acid-vinyl copolymer.
  • lactic acid-vinyl copolymerization step conventionally known polymerization methods such as solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization can be employed, and among these, solution polymerization is preferred. .
  • lactide is ring-opening polymerized with tin octylate or the like.
  • raw materials containing a vinyl (co)polymer and lactic acid and a solvent as needed are placed in a reaction vessel, a catalyst is added under an inert gas atmosphere such as nitrogen gas, and the reaction vessel is heated.
  • the reaction is carried out at a temperature of 150 to 210°C, preferably 160 to 200°C, for 2 to 20 hours.
  • a catalyst, a monomer, and a solvent may be additionally added as appropriate.
  • the raw material containing lactic acid may contain lactide, which is a cyclic dimer, and may contain at least one of meso-lactide, L-lactide, and D-lactide.
  • a catalyst can be used for polymerization, and examples of the catalyst include tin lactate, tin tartrate, tin dicaprylate, tin dilaurate, tin dipaltimate, tin distearate, tin dioleate, ⁇ -tin naphetoate, and ⁇ .
  • - Organotin compounds such as tin naphetoate and tin octylate; powdered tin; zinc dust, zinc halide, zinc oxide, organozinc compounds; titanium compounds such as tetrapropyl titanate; zirconium compounds such as zirconium isopropoxide ;
  • antimony compounds such as antimony trioxide.
  • the amount of the catalyst added can be 0.001 to 1 part by mass, and can be 0.005 to 0.5 part by mass, based on a total of 100 parts by mass of the raw material, such as lactide.
  • a polylactic acid block is formed.
  • the vinyl (co)polymer used as a raw material has a functional group
  • the functional group has a polylactic acid block. It is thought that the structure is a combination of the two.
  • the type and amount of catalyst added, and polymerization conditions such as polymerization temperature and time, the weight average molecular weight and structure of polylactic acid block and lactic acid-vinyl copolymer, and the physical properties of lactic acid-vinyl copolymer can be adjusted. can do.
  • Binder Composition A binder composition according to one embodiment of the present invention contains the above-described lactic acid-vinyl copolymer and a solvent, and can be used to prepare a paste for baking.
  • the binder composition according to one embodiment of the present invention contains a lactic acid-vinyl copolymer as a binder, and may contain a binder other than the lactic acid-vinyl copolymer.
  • binders that the binder composition according to an embodiment of the present invention may include in addition to the lactic acid-vinyl copolymer include ethyl cellulose and polyvinyl butyral.
  • the binder composition according to an embodiment of the present invention preferably contains 50% by mass or more, and preferably 80% by mass or more of the lactic acid-vinyl copolymer, when the binder contained in the binder composition is 100% by mass. is preferable, and it is more preferable that the content is 90% by mass or more.
  • the content of the lactic acid-vinyl copolymer when the binder is 100% by mass is, for example, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100% by mass, where It may be within the range between any two of the illustrated numerical values.
  • the binder composition according to one embodiment of the present invention may contain only a lactic acid-vinyl copolymer as a binder.
  • the solvent that can be contained in the binder composition according to one embodiment of the present invention is not particularly limited, and any known solvent can be used.
  • the solvent preferably has excellent compatibility with the lactic acid-vinyl copolymer according to the present invention, and for example, a lactic acid-vinyl copolymer containing 30% by mass of the lactic acid-vinyl copolymer according to the present invention and 70% by mass of the solvent.
  • the boiling point of the solvent is preferably 150 to 300°C, more preferably 200 to 290°C, even more preferably 220 to 280°C.
  • the solvent include alcohol solvents and ester solvents.
  • alcoholic solvents include cycloalkanols such as cyclohexanol, terpineol (including ⁇ , ⁇ , and ⁇ isomers, or any mixture thereof), terpene alcohols (monoterpene alcohols, etc.) such as dihydroterpineol, dihydro Examples include terpineol, myrtenol, sobrerol, menthol, carveol, perillyl alcohol, pinocarveol, sobrerol, verbenol, dipropylene glycol, butyl carbitol, and the like.
  • ester solvents examples include butyl carbitol acetate (BCA), dihydroterpinyl acetate (DHTA), butyl glycol acetate (BMGAC), diethylene glycol alkyl ether acetate (here, alkyl is ethyl, propyl, n- (Examples include butyl.
  • Acetates such as ethylene glycol alkyl ether acetate, ethylene glycol diacetate, propylene glycol alkyl ether acetate, 2,2,4-trimethylpentane-1,3-diol mono-iso- butyrate, 2,2,4-trimethylpentane-1,3-diol mono-iso-butyrate ether, dipropylene glycol monomethyl ether, diethylene glycol alkyl ether, ethylene glycol alkyl ether, dipropylene glycol alkyl ether, and the like.
  • the solvent contains at least one of the ester solvents. Moreover, it is more preferable that the solvent contains at least one of butyl carbitol acetate (BCA), butyl glycol acetate (BMGAC), dihydroterpinyl acetate (DHTA), terpineol, and dihydroterpineol, and butyl carbitol acetate ( Even more preferably, it contains at least one of BCA) and dihydroterpinyl acetate (DHTA).
  • BCA butyl carbitol acetate
  • BMGAC butyl glycol acetate
  • DHTA dihydroterpinyl acetate
  • DHTA dihydroterpinyl acetate
  • DHTA dihydroterpinyl acetate
  • the binder composition according to one embodiment of the present invention can contain 1 to 40% by mass of the binder when the binder composition is 100% by mass.
  • the binder content when the binder composition is 100% by mass is, for example, 1, 5, 10, 15, 20, 25, 30, 35, 40% by mass, and any 2 of the values exemplified here. It may be within the range between two.
  • the binder composition according to one embodiment of the present invention may also contain other additives as necessary within a range that does not impair the effects of the present invention.
  • Other additives include dispersants, surfactants, antioxidants, flame retardants, plasticizers, lubricants, mold release agents, and the like.
  • the binder composition according to one embodiment of the present invention has a shear rate of 1 sec when the shear rate is increased at a constant rate of change from 0.01 sec -1 to 10,000 sec -1 over 150 seconds at 25°C.
  • the viscosity A' at -1 is preferably 2.0 Pa ⁇ s or more.
  • the viscosity A' of the binder composition is, for example, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5.
  • the binder composition can be used to prepare a baking paste with excellent coating properties.
  • the binder composition according to an embodiment of the present invention has a shear rate of 9 when the shear rate is increased at a constant rate of change from 0.01 sec -1 to 10,000 sec -1 over 150 seconds at 25°C.
  • the viscosity B' at ,000 sec -1 is preferably 0.05 to 2.0 Pa ⁇ s.
  • the viscosity B' is, for example, 0.05, 0.1, 0.2, 0.3, 0.5, 0.8, 1.0, 1.1.0, 1.2, 1.3, 1 .4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0 Pa ⁇ s, and may be within the range between any two of the numerical values exemplified here. .
  • the binder composition can be used to prepare a baking paste with excellent coating properties.
  • the binder composition according to one embodiment of the present invention has a shear rate of 1 sec when the shear rate is increased at a constant rate of change from 0.01 sec -1 to 10,000 sec -1 over 150 seconds at 25°C.
  • the ratio A'/B' of viscosity A' at -1 and viscosity B' at shear rate 9,000 sec -1 is preferably 3.0 or more.
  • A'/B' is, for example, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7 .0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 20.0, 30.0, 40.0, 50.0, 60.0, 70.0 , 80.0, 90.0, 100.0, 200.0, 300.0, 400.0, 500.0, 600.0, 700.0, 800.0, 900.0, 1000.0Pa ⁇ s and may be within the range between any two of the numerical values exemplified here. That is, the binder composition according to one embodiment of the present invention preferably exhibits pseudoplasticity in which the viscosity decreases as the shear rate increases.
  • the viscosity of the binder composition can be controlled by adjusting the type, amount, and weight average molecular weight of each monomer unit in the lactic acid-vinyl copolymer, as well as the type and amount of the binder and solvent. .
  • the viscosity of the binder composition at each shear rate at 25° C. can be measured using a rotational viscometer, such as a rheometer, by the method described below, and specifically by the method described in the Examples. be able to.
  • ⁇ Method for measuring viscosity A' and viscosity B'> A Cone Plate with a diameter of 20 mm and a cone angle of 0.975° was attached to the viscosity/viscoelasticity measuring device with a clearance of 23 ⁇ m, the binder composition was set in the measuring section, and the shear rate was set at a set temperature of 25° C. for 0.01 sec. When increasing from -1 to 10,000 sec -1 at a constant rate of change over 150 seconds, measure the viscosity A' at a shear rate of 1 sec -1 and the viscosity B' at a shear rate of 9,000 sec -1 .
  • a viscosity/viscoelasticity measuring device “Discovery HR30” manufactured by TA Instruments can be used as the elasticity measuring device.
  • the binder composition according to one embodiment of the present invention has no visually recognizable insoluble matter of the binder.
  • the binder composition according to one embodiment of the present invention preferably has a micro residual carbon content of 2.00% by mass or less.
  • the micro residual carbon content is, for example, 0.10, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, 0.90, 1.00, 1. 10, 1.20, 1.30, 1.40, 1.50, 1.60, 1.70, 1.80, 1.90, 2.00% by mass, and any of the numerical values exemplified here. It may be within a range between the two.
  • the micro residual carbon content can be determined by the method described in Examples.
  • the binder composition according to one embodiment of the present invention preferably has a 95% weight loss temperature (TD95) of less than 400°C.
  • TD95 is, for example, 350, 355, 360, 365, 370, 375, 380, 385, 390, 395°C, less than 400°C, even if it is within the range between any two of the numerical values exemplified here. good.
  • TD95 can be determined by the method described in Examples using a thermogravimetric differential thermal analyzer.
  • the binder composition according to one embodiment of the present invention is obtained by inserting a glass rod into a lactic acid-vinyl copolymer solution adjusted to have a viscosity A of 5 Pa ⁇ s in an environment of 25° C. and pulling it up by 10 cm. It is preferable that the time required for the thread-like solution existing between the solution surface and the glass rod to break is 4 seconds or less. Specifically, stringiness can be determined by the method described in Examples.
  • a baking paste according to one embodiment of the present invention contains the above binder composition and inorganic particles.
  • the inorganic particles known powders can be used depending on the purpose. Examples of inorganic particles include gold, silver, copper, nickel, palladium, ITO, alumina, zirconia, titanium oxide, barium titanate, aluminum nitride, silicon nitride, boron nitride, various glass powders, inorganic phosphors, and graphite powder. , solder powder, etc., and these can be used alone or in combination of two or more. For example, silver, copper, nickel, etc.
  • the firing paste according to one embodiment of the present invention can be used to prepare a firing paste used when printing a wiring pattern by screen printing, etc., and it is preferable to use nickel.
  • the firing paste according to one embodiment of the present invention can be used for multilayer ceramic capacitors (MLCCs), for example, for internal electrodes of MLCCs.
  • MLCCs multilayer ceramic capacitors
  • the firing paste according to one embodiment of the present invention can be used for internal electrodes and contains nickel as inorganic particles.
  • the composition of the firing paste is appropriately adjusted so that the firing paste has good applicability and the sintered body obtained by sintering the firing paste has various good properties.
  • the firing paste is molded into the desired shape by a known method such as screen printing, dispensing, or doctor blading. A molded body can be obtained.
  • the obtained molded body is heated and dried at an appropriate temperature as necessary, and then fired to remove the binder in the firing paste, sinter the inorganic powder, and form a sintered body. can be obtained.
  • the baking paste containing the lactic acid-vinyl copolymer according to the present invention has excellent coating properties, can be molded, for example, by the method described above, and has less stringiness, causing problems such as extrusion during printing. It is possible to obtain electrodes and conductor wiring with less residual carbon derived from the lactic acid-vinyl copolymer after firing and with less risk of defects.
  • a vinyl copolymer was prepared according to the following procedure.
  • ⁇ Manufacture example A-1> In a 1 liter flask equipped with a stirring device, a gas inlet tube, a thermometer and a reflux condenser, 50 parts by mass of isobutyl methacrylate (iBMA) and 50 parts by mass of 2-hydroxyethyl methacrylate (HEMA) were added as monomers.
  • iBMA isobutyl methacrylate
  • HEMA 2-hydroxyethyl methacrylate
  • a total of 200 parts by mass of a monomer and solvent mixture consisting of 100 parts by mass of methyl ethyl ketone (MEK) was charged as a solvent, and the mixture was stirred while flowing nitrogen gas into the flask from the gas introduction tube at a flow rate of 0.3 liters/min for 30 minutes.
  • MEK methyl ethyl ketone
  • the mixture in the flask was heated to 75°C.
  • V-601 dimethyl-2,2'-azobis(2-methylpropionate)
  • the temperature of the contents in the flask was maintained at 75° C. by adding .5 parts by mass and heating and cooling as appropriate.
  • Vinyl copolymer 1 was prepared by drying the obtained vinyl copolymer solution at 105° C. for 8 hours. The weight average molecular weight of the obtained vinyl copolymer 1 was 516,000.
  • iBMA isobutyl methacrylate
  • HEMA 2-hydroxyethyl methacrylate
  • EtAc ethyl acetate
  • TGL thioglycerol
  • Vinyl copolymer 3 was prepared in the same manner as in Example 1. The weight average molecular weight of the obtained vinyl copolymer 3 was 287,000.
  • Vinyl copolymer 4 was prepared in the same manner as in Example 1. The weight average molecular weight of the obtained vinyl copolymer 4 was 140,000.
  • ⁇ Manufacture example A-5> The monomer and solvent mixture was 90 parts by mass of isobutyl methacrylate (iBMA), 10 parts by mass of 2-hydroxyethyl methacrylate (HEMA), and 100 parts by mass of ethyl acetate (EtAc), and thioglycerol (TGL) was used as a chain transfer agent.
  • iBMA isobutyl methacrylate
  • HEMA 2-hydroxyethyl methacrylate
  • EtAc ethyl acetate
  • TGL thioglycerol
  • Vinyl copolymer 5 was prepared in the same manner as in Production Example A-1, except that the amount was 0.2 parts by mass, for a total of 200.2 parts by mass.
  • the weight average molecular weight of the obtained vinyl copolymer 5 was 63,000.
  • iBMA isobutyl methacrylate
  • HEMA 2-hydroxyethyl methacrylate
  • PVA polyvinyl alcohol
  • the mixture in the flask was heated to 75°C.
  • the mixture in the flask was heated and cooled to maintain the temperature at 75°C, and the reaction was continued for an additional 3 hours.
  • the mixture was cooled to room temperature to obtain a vinyl copolymer emulsion.
  • the obtained vinyl copolymer emulsion was cooled to room temperature, filtered, and then dried at 105° C. for 8 hours to prepare vinyl copolymer 6.
  • the weight average molecular weight of the obtained vinyl copolymer 6 was 440,000.
  • iBMA isobutyl methacrylate
  • HEMA 2-hydroxyethyl methacrylate
  • mLA meso-lactide
  • a vinyl copolymer 8/meso-lactide mixture reacted in the same manner as A-1 was prepared.
  • the weight average molecular weight of the obtained vinyl copolymer 8 was 193,000.
  • ⁇ Manufacture example A-10> The monomer and solvent mixture was made into 70 parts by mass of stearyl methacrylate (SMA), 30 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 80 parts by mass of ethyl acetate (EtAc), and 20 parts by mass of toluene (To), and further subjected to chain transfer.
  • Vinyl copolymer 10 was prepared in the same manner as in Production Example A-1, except that 0.1 part by mass of thioglycerol (TGL) was used as the agent for a total of 200.1 parts by mass.
  • TGL thioglycerol
  • the weight average molecular weight of the obtained vinyl copolymer 10 was 95,000.
  • ⁇ Manufacture example A-11> A total of 200 parts by mass of the monomer and solvent mixture, 90 parts by mass of stearyl methacrylate (SMA), 10 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 80 parts by mass of ethyl acetate (EtAc), and 20 parts by mass of toluene (To). Vinyl copolymer 11 was prepared in the same manner as in Production Example A-1 except that. The weight average molecular weight of the obtained vinyl copolymer 11 was 320,000.
  • ⁇ Manufacture example A-12> The monomer and solvent mixture was made into 96 parts by mass of stearyl methacrylate (SMA), 4 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 80 parts by mass of ethyl acetate (EtAc), and 20 parts by mass of toluene (To), and further subjected to chain transfer.
  • Vinyl copolymer 12 was prepared in the same manner as in Production Example A-1, except that 0.1 part by mass of thioglycerol (TGL) was used as the agent for a total of 194.1 parts by mass.
  • TGL thioglycerol
  • the weight average molecular weight of the obtained vinyl copolymer 12 was 74,000.
  • ⁇ Manufacture example A-13> The monomer and solvent mixture was mixed with 9096 parts by mass of stearyl methacrylate (SMA), 4 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 80 parts by mass of ethyl acetate (EtAc), and 20 parts by mass of toluene (To), for a total of 194 parts by mass.
  • Vinyl copolymer 13 was prepared in the same manner as in Production Example A-1 except that. The weight average molecular weight of the obtained vinyl copolymer 13 was 217,000.
  • iBMA isobutyl methacrylate
  • HEMA 2-hydroxyethyl methacrylate
  • mLA meso-lactide
  • a vinyl copolymer 13/meso-lactide mixture reacted in the same manner as A-1 was prepared.
  • the weight average molecular weight of the obtained vinyl copolymer 14 was 142,000.
  • a lactic acid-vinyl copolymer was prepared in the following procedure.
  • mLA meso-lactide
  • vinyl copolymer 1 was placed in a 1-liter flask equipped with a stirring device, a gas inlet tube, a thermometer, and a reflux condenser. A total of 100 parts by mass of was charged, and the contents of the flask were heated to 180° C. while flowing nitrogen gas into the flask from the gas introduction tube at a flow rate of 0.3 liters/min, and then stirred to perform nitrogen substitution.
  • tin octylate was added as a catalyst, and heating and cooling were performed to maintain the content in the flask at 180°C for an additional 3 Allowed time to react.
  • the mixture was cooled to room temperature to obtain lactic acid-vinyl copolymer 1.
  • the weight average molecular weight of the obtained lactic acid-vinyl copolymer 1 was 1,871,000.
  • Lactic acid-vinyl copolymer 2 was prepared in the same manner as in Production Example B-1, except that the monomer/polymer mixture was changed to 100 parts by mass, consisting of 50 parts by mass of mLA and 50 parts by mass of vinyl copolymer 2. Prepared. The weight average molecular weight of the obtained lactic acid-vinyl copolymer 2 was 136,000.
  • Lactic acid-vinyl copolymer 3 was prepared in the same manner as in Production Example B-1, except that the monomer/polymer mixture was changed to 100 parts by mass, consisting of 83 parts by mass of mLA and 17 parts by mass of vinyl copolymer 3. Prepared. The weight average molecular weight of the obtained lactic acid-vinyl copolymer was 1,448,000.
  • Lactic acid-vinyl copolymer 4 was prepared in the same manner as in Production Example B-1, except that the monomer/polymer mixture was changed to 100 parts by mass, consisting of 50 parts by mass of mLA and 50 parts by mass of vinyl copolymer 4. Prepared. The weight average molecular weight of the obtained lactic acid-vinyl copolymer 4 was 374,000.
  • Lactic acid-vinyl copolymer 5 was prepared in the same manner as in Production Example B-1, except that the monomer/polymer mixture was changed to 100 parts by mass, consisting of 90 parts by mass of MLA and 10 parts by mass of vinyl copolymer 4. Prepared. The weight average molecular weight of the obtained lactic acid-vinyl copolymer 5 was 694,000.
  • lactic acid-vinyl copolymer was prepared in the same manner as in Production Example B-1, except that the monomer/polymer mixture was changed to 100 parts by mass, consisting of 97.5 parts by mass of mLA and 2.5 parts by mass of vinyl copolymer 4. Polymer 6 was prepared. The weight average molecular weight of the obtained lactic acid-vinyl copolymer 6 was 1,055,000.
  • Lactic acid-vinyl copolymer 7 was prepared in the same manner as in Production Example B-1, except that the monomer/polymer mixture was changed to 100 parts by mass, consisting of 90 parts by mass of MLA and 10 parts by mass of vinyl copolymer 5. Prepared. The weight average molecular weight of the obtained lactic acid-vinyl copolymer 7 was 899,000.
  • Lactic acid-vinyl copolymer 8 was prepared in the same manner as in Production Example B-1, except that the monomer/polymer mixture was changed to 100 parts by mass, consisting of 70 parts by mass of mLA and 30 parts by mass of vinyl copolymer 6. Prepared. The weight average molecular weight of the obtained lactic acid-vinyl copolymer 8 was 1,292,000.
  • Lactic acid-vinyl copolymer 9 was prepared in the same manner as in Production Example B-1, except that the monomer/polymer mixture was changed to 100 parts by mass, consisting of 60 parts by mass of mLA and 40 parts by mass of vinyl copolymer 7. Prepared. The weight average molecular weight of the obtained lactic acid-vinyl copolymer 9 was 1,244,000.
  • lactic acid-vinyl Copolymer 10 was prepared.
  • the weight average molecular weight of the obtained lactic acid-vinyl copolymer 10 was 533,000.
  • Lactic acid-vinyl copolymer 11 was prepared in the same manner as in Production Example B-1, except that the monomer/polymer mixture was changed to 100 parts by mass, consisting of 90 parts by mass of MLA and 10 parts by mass of vinyl copolymer 9. Prepared. The weight average molecular weight of the obtained lactic acid-vinyl copolymer 11 was 1,122,000.
  • Lactic acid-vinyl copolymer 12 was prepared in the same manner as in Production Example B-1, except that the monomer/polymer mixture was changed to 103 parts by mass, consisting of 90 parts by mass of MLA and 13 parts by mass of vinyl copolymer 10. Prepared. The weight average molecular weight of the obtained lactic acid-vinyl copolymer 12 was 531,000.
  • Lactic acid-vinyl copolymer 13 was prepared in the same manner as in Production Example B-1, except that the monomer/polymer mixture was changed to 100 parts by mass, consisting of 50 parts by mass of mLA and 50 parts by mass of vinyl copolymer 11. Prepared. The weight average molecular weight of the obtained lactic acid-vinyl copolymer 13 was 92,000.
  • Lactic acid-vinyl copolymer 14 was prepared in the same manner as in Production Example B-1, except that the monomer/polymer mixture was changed to 100 parts by mass, consisting of 50 parts by mass of mLA and 50 parts by mass of vinyl copolymer 9. Prepared. The weight average molecular weight of the obtained lactic acid-vinyl copolymer 14 was 193,000.
  • Lactic acid-vinyl copolymer 15 was prepared in the same manner as in Production Example B-1, except that the monomer/polymer mixture was changed to 100 parts by mass, consisting of 50 parts by mass of mLA and 50 parts by mass of vinyl copolymer 12. Prepared. The weight average molecular weight of the obtained lactic acid-vinyl copolymer 15 was 116,000.
  • Lactic acid-vinyl copolymer 16 was prepared in the same manner as in Production Example B-1, except that the monomer/polymer mixture was changed to 100 parts by mass, consisting of 50 parts by mass of mLA and 50 parts by mass of vinyl copolymer 13. Prepared. The weight average molecular weight of the obtained lactic acid-vinyl copolymer 16 was 578,000.
  • ⁇ Manufacture example B-17> The procedure was the same as in Production Example B-1, except that the monomer/polymer mixture was 100 parts by mass, consisting of 33.3 parts by mass of mLA and 66.7 parts by mass of vinyl copolymer 14/meso-lactide mixture. Lactic acid-vinyl copolymer 17 was prepared. The weight average molecular weight of the obtained lactic acid-vinyl copolymer 17 was 146,000.
  • a binder composition was prepared according to the following procedure.
  • Example 1 Pour 30 parts of lactic acid-vinyl copolymer 1 and 70 parts of BCA as a solvent into a closed container, stir at 2000 rpm until there is no undissolved residue, and stir at 2200 rpm until there are no bubbles left. After degassing until no more bubbles were removed, the mixture was allowed to stand at 25° C. for one day to obtain Binder Composition 1.
  • Table 3 shows the measurement results of each physical property of Binder Composition 1 and Lactic Acid-Vinyl Copolymer 1.
  • Binder composition 2 was obtained in the same manner as in Example 1, except that lactic acid-vinyl copolymer 2 was used in place of lactic acid-vinyl copolymer 1, and DHTA was used in place of BCA.
  • Table 3 shows the measurement results of each physical property of Binder Composition 2 and Lactic Acid-Vinyl Copolymer 2.
  • Binder composition 3 was obtained in the same manner as in Example 1, except that lactic acid-vinyl copolymer 3 was used in place of lactic acid-vinyl copolymer 1.
  • Table 3 shows the measurement results of each physical property of Binder Composition 3 and Lactic Acid-Vinyl Copolymer 3.
  • Binder composition 4 was obtained in the same manner as in Example 2, except that lactic acid-vinyl copolymer 4 was used in place of lactic acid-vinyl copolymer 2.
  • Table 3 shows the measurement results of each physical property of Binder Composition 4 and Lactic Acid-Vinyl Copolymer 4.
  • Binder composition 5 was obtained in the same manner as in Example 1, except that lactic acid-vinyl copolymer 5 was used in place of lactic acid-vinyl copolymer 1.
  • the measurement results of each physical property of Binder Composition 5 and Lactic Acid-Vinyl Copolymer 5 are shown in Table 3.
  • Binder composition 6 was obtained in the same manner as in Example 1, except that lactic acid-vinyl copolymer 6 was used in place of lactic acid-vinyl copolymer 1.
  • Table 3 shows the measurement results of each physical property of Binder Composition 6 and Lactic Acid-Vinyl Copolymer 6.
  • Binder composition 7 was obtained in the same manner as in Example 1, except that lactic acid-vinyl copolymer 7 was used in place of lactic acid-vinyl copolymer 1.
  • the measurement results of each physical property of Binder Composition 7 and Lactic Acid-Vinyl Copolymer 7 are shown in Table 3.
  • Binder composition 8 was obtained in the same manner as in Example 1, except that lactic acid-vinyl copolymer 8 was used in place of lactic acid-vinyl copolymer 1.
  • Table 3 shows the measurement results of each physical property of Binder Composition 8 and Lactic Acid-Vinyl Copolymer 8.
  • Binder composition 9 was obtained in the same manner as in Example 2, except that lactic acid-vinyl copolymer 9 was used in place of lactic acid-vinyl copolymer 2.
  • Table 3 shows the measurement results of each physical property of Binder Composition 9 and Lactic Acid-Vinyl Copolymer 9.
  • Binder composition 10 was obtained in the same manner as in Example 2, except that lactic acid-vinyl copolymer 10 was used in place of lactic acid-vinyl copolymer 2.
  • Table 3 shows the measurement results of each physical property of binder composition 10 and lactic acid-vinyl copolymer 10.
  • Binder composition 11 was obtained in the same manner as in Example 1, except that lactic acid-vinyl copolymer 11 was used in place of lactic acid-vinyl copolymer 1.
  • Table 3 shows the measurement results of each physical property of binder composition 11 and lactic acid-vinyl copolymer 11.
  • Binder composition 12 was obtained in the same manner as in Example 1, except that lactic acid-vinyl copolymer 12 was used in place of lactic acid-vinyl copolymer 1.
  • Table 3 shows the measurement results of each physical property of Binder Composition 12 and Lactic Acid-Vinyl Copolymer 12.
  • Binder composition 13 was obtained in the same manner as in Example 2, except that lactic acid-vinyl copolymer 13 was used in place of lactic acid-vinyl copolymer 2.
  • Table 3 shows the measurement results of each physical property of Binder Composition 13 and Lactic Acid-Vinyl Copolymer 13.
  • Binder composition 14 was obtained in the same manner as in Example 2, except that lactic acid-vinyl copolymer 14 was used in place of lactic acid-vinyl copolymer 2.
  • Table 3 shows the measurement results of each physical property of Binder Composition 14 and Lactic Acid-Vinyl Copolymer 14.
  • Binder composition 15 was obtained in the same manner as in Example 2, except that lactic acid-vinyl copolymer 15 was used in place of lactic acid-vinyl copolymer 2.
  • the measurement results of each physical property of Binder Composition 15 and Lactic Acid-Vinyl Copolymer 15 are shown in Table 3.
  • Binder composition 16 was obtained in the same manner as in Example 2, except that lactic acid-vinyl copolymer 16 was used in place of lactic acid-vinyl copolymer 2.
  • Table 3 shows the measurement results of each physical property of Binder Composition 16 and Lactic Acid-Vinyl Copolymer 16.
  • Binder composition 17 was obtained in the same manner as in Example 2, except that lactic acid-vinyl copolymer 17 was used in place of lactic acid-vinyl copolymer 2.
  • Table 3 shows the measurement results of each physical property of Binder Composition 17 and Lactic Acid-Vinyl Copolymer 17.
  • Binder composition 18 was obtained in the same manner as in Example 2, except that polyiBMA (PiBMA) was used in place of lactic acid-vinyl copolymer 2.
  • Table 3 shows the measurement results of each physical property of binder composition 18 and polyiBMA.
  • Binder composition 19 was obtained in the same manner as in Example 1, except that polylactic acid was used in place of lactic acid-vinyl copolymer 1. Table 3 shows the measurement results of each physical property of Binder Composition 19 and polylactic acid.
  • Tg Glass transition temperature (K) of vinyl copolymer
  • Tg i Glass transition temperature (K) of homopolymer of N types of vinyl monomers
  • Measuring device HLC-8120GPC (manufactured by Tosoh Corporation) GPC column configuration: The following 5 columns (all manufactured by Tosoh Corporation) (1)TSK-GEL G7000HXL (2) TSK-GEL GMHXL (3) TSK-GEL GMHXL (4)TSK-GEL G2500HXL Dilute with tetrahydrofuran so that sample concentration: 1.5 mg/cm3
  • Mobile phase solvent tetrahydrofuran Flow rate: 1 ml/min Column temperature: 40°C
  • ⁇ Solvent solubility> The solubility of each binder in DHTA (dihydroterpinyl acetate) and BCA (butyl carbitol acetate) was evaluated. 70 parts by mass of an organic solvent and 30 parts by mass of a binder were placed in a closed container, and the mixture was stirred for 20 minutes at 2000 rpm using a rotary-revolution mixer "Awatori Rentaro" manufactured by THINKY, and defoamed for 5 minutes at 2200 rpm. Thereafter, 10 g of the sample taken out from the sealed container was placed on a glass plate and spread to an area of about 5 cm 2 , and the solubility of the binder in the solvent was visually evaluated using the following evaluation criteria. ⁇ : The sample placed on the glass plate was uniformly dissolved in the organic solvent, and no undissolved substances were observed. ⁇ : Many insoluble substances were observed on the sample placed on the glass plate.
  • micro residual carbon content was measured using a micro residual carbon content tester (ACR-M3) manufactured by Tanaka Scientific Instruments Manufacturing Co., Ltd. Specifically, approximately 2.0000 g (mass M2) of the binder was weighed into a precisely weighed test container (glass diameter 20.8 mm x height 80 mm, capacity 10 mL, mass M1), and placed in the coking furnace of the test device. . Thereafter, nitrogen was flowed into the coking furnace for 10 minutes at a flow rate of 600 ml per minute to replace the inside of the furnace with a nitrogen atmosphere. Next, while flowing nitrogen at a flow rate of 150 ml/min, the temperature of the coking furnace was raised from room temperature to 500° C.
  • ACR-M3 micro residual carbon content tester
  • TD95 95% weight loss temperature
  • A (B ⁇ f ⁇ 5.611)/S
  • ⁇ Viscosities A, B and viscosity ratio at each shear rate> The viscosity of the lactic acid-vinyl copolymer solution (binder composition) of the present invention was measured using a viscosity/viscoelasticity measuring device "Discovery HR30" manufactured by TA Instruments. Specifically, with the measurement temperature set at 25° C., 0.1 g of the binder composition was set on a measuring section attached to a cone plate with a diameter of 20 mm and a cone angle of 0.975° with a clearance of 23 ⁇ m, and the shear rate was set at 0.
  • the viscosity A at a shear rate of 1 sec-1 and the viscosity B at a shear rate of 9,000 sec- 1 were measured when increasing from .01 sec -1 to 10,000 sec -1 at a constant rate of change over 150 seconds.
  • the viscosity ratio A/B was determined.
  • "increase the shear rate from 0.01 sec -1 to 10,000 sec -1 at a constant rate of change over 150 seconds” means to increase the shear rate so that the shear rate increases by 10 times every 25 seconds. For example, the shear rate 25 seconds after the start of measurement is 0.1 sec -1 , and the shear rate 50 seconds after the start of measurement is 1 sec -1 .

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Abstract

La présente invention concerne : un copolymère d'acide lactique-vinyle pour une pâte destinée à être utilisée lors du frittage, qui présente d'excellentes propriétés de frittage, qui peut être dissous dans un solvant sans produire d'objets insolubles visuellement observables, et qui, lorsqu'il est mélangé à un solvant, présente des propriétés rhéologiques efficaces et moins de stringence ; et une composition de liant et une pâte destinées à être utilisées lors du frittage, qui contiennent le copolymère d'acide lactique-vinyle. Selon la présente invention, l'invention concerne un copolymère d'acide lactique-vinyle pour une pâte destinée à être utilisée lors du frittage, et qui comprend un motif acide lactique dérivé de l'acide lactique et un motif monomère vinylique dérivé d'un monomère vinylique.
PCT/JP2023/025920 2022-07-20 2023-07-13 Copolymère d'acide lactique-vinyle, composition de liant et pâte à utiliser lors du frittage WO2024018991A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09142938A (ja) * 1995-11-17 1997-06-03 Japan Synthetic Rubber Co Ltd ペースト組成物
US5952405A (en) * 1997-08-26 1999-09-14 National Starch And Chemical Investment Holding Corporation Lactide graft copolymers and hot melt adhesives prepared from same
JP2002097215A (ja) * 2000-09-26 2002-04-02 Soken Chem & Eng Co Ltd ペースト状導電性樹脂組成物及びその焼結体の形成方法
JP2004137593A (ja) * 2002-10-17 2004-05-13 Kenji Shinohara 多孔質体セラミックス水電極板
JP2006294559A (ja) * 2005-04-14 2006-10-26 Aisin Chem Co Ltd 撥水ペースト及び燃料電池ガス拡散層並びにその製造方法
JP2007186562A (ja) * 2006-01-12 2007-07-26 Three M Innovative Properties Co ポリ乳酸含有樹脂組成物、ポリ乳酸含有樹脂フィルム及び樹脂繊維
US20160096941A1 (en) * 2014-10-06 2016-04-07 The Regents Of The University Of Michigan Nanofibrous spongy microspheres
JP2019516541A (ja) * 2016-04-01 2019-06-20 ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ 排気ガス浄化用フィルター

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09142938A (ja) * 1995-11-17 1997-06-03 Japan Synthetic Rubber Co Ltd ペースト組成物
US5952405A (en) * 1997-08-26 1999-09-14 National Starch And Chemical Investment Holding Corporation Lactide graft copolymers and hot melt adhesives prepared from same
JP2002097215A (ja) * 2000-09-26 2002-04-02 Soken Chem & Eng Co Ltd ペースト状導電性樹脂組成物及びその焼結体の形成方法
JP2004137593A (ja) * 2002-10-17 2004-05-13 Kenji Shinohara 多孔質体セラミックス水電極板
JP2006294559A (ja) * 2005-04-14 2006-10-26 Aisin Chem Co Ltd 撥水ペースト及び燃料電池ガス拡散層並びにその製造方法
JP2007186562A (ja) * 2006-01-12 2007-07-26 Three M Innovative Properties Co ポリ乳酸含有樹脂組成物、ポリ乳酸含有樹脂フィルム及び樹脂繊維
US20160096941A1 (en) * 2014-10-06 2016-04-07 The Regents Of The University Of Michigan Nanofibrous spongy microspheres
JP2019516541A (ja) * 2016-04-01 2019-06-20 ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ 排気ガス浄化用フィルター

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