Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B28—WORKING CEMENT, CLAY, OR STONE
  • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
  • B28B1/00—Producing shaped prefabricated articles from the material
  • B28B1/30—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
  • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
  • C04B35/632—Organic additives
  • C04B35/634—Polymers
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/48—Polymers modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • 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 plasticizer for ceramic green sheets.
• Ceramic green sheets used in the manufacture of ceramic capacitors contain plasticizers to impart plasticity. This improves workability during molding and adhesion during the lamination process, and can improve yields in the manufacturing process of ceramic capacitors.
• alkyl phthalates such as dioctyl phthalate (DOP) have been the main plasticizers used (see, for example, Patent Document 1).
• One aspect of the present invention has been made in consideration of the above problems.
• the objective of one aspect of the present invention is to provide a plasticizer (C) for ceramic green sheets that provides ceramic green sheets with excellent plasticity, little bleed-out, and excellent formability.
• the plasticizer (C) for a ceramic green sheet is For an active hydrogen compound containing 1 to 15 carbon atoms and 1 to 6 active hydrogen groups, A plasticizer (C) for a ceramic green sheet, comprising a polyether polyol (C1) having 1 to 65 moles of an alkylene oxide compound having 2 to 12 carbon atoms added thereto, The value ([X] ⁇ [Y]) obtained by multiplying the solubility parameter (SP value) [Y] (cal/cm 3 ) 1/2 of the active hydrogen compound by the number average molecular weight [X] of the polyether polyol (C1) is 10,000 to 25,000.
• SP value solubility parameter
• the ceramic green sheet (G) produced using the ceramic green sheet plasticizer (C) according to one embodiment of the present invention has excellent plasticity, little bleed-out, and excellent moldability.
• a to B indicating a numerical range means “greater than or equal to A and less than or equal to B.”
• a ceramic green sheet refers to an unfired ceramic sheet whose main component is ceramic. By firing the ceramic green sheet, a sheet of sintered ceramic is obtained.
• the SP value is called a solubility parameter and is a parameter used as an index of polarity.
• ⁇ H represents the molar heat of vaporization (cal/mol)
• V represents the molar volume (cm 3 /mol).
• ⁇ H and V are calculated by using the sum of the molar heat of vaporization ( ⁇ ei) of the atomic groups described in "R. F. Fedors, Polym. Eng. Sci., 14(2), 147-154 (1974)" as ⁇ H and the sum of the molar volumes ( ⁇ vi) as V.
• the SP value of the mixture is calculated by taking the weighted average of the SP values of each molecule contained in the mixture based on their weight ratio.
• a plasticizer (C) for ceramic green sheets according to one embodiment of the present invention contains a polyether polyol (C1) in which 1 to 65 moles of an alkylene oxide compound having 2 to 12 carbon atoms are added to an active hydrogen compound containing 1 to 15 carbon atoms and 1 to 6 active hydrogen groups, and the value ([X] x [Y]) obtained by multiplying the solubility parameter (SP value) [Y] (cal/cm 3 ) 1/2 of the active hydrogen compound by the number average molecular weight [X] of the polyether polyol (C1) is 10,000 to 25,000.
• SP value solubility parameter
• Compounds containing active hydrogen groups include compounds containing at least one hydroxyl group (-OH), imino group (-NH-), amino group (-NH 2 ) and/or carboxyl group (-COOH). Such compounds include alcohols, amides, amines, carboxylic acids, hydroxycarboxylic acids and aminocarboxylic acids.
• Alcohols having 1 to 15 carbon atoms include monools (methanol, ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-butanol, 2-methyl-2-propanol, 1-hexanol, 1-octanol, 1-decanol, 1-dodecanol, 1-tetradecanol, 1-pentadecanol, etc.) and polyols (ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-propanediol, 1, 6-hexanediol, 1,2-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, diethylene glycol, glycerin, diglycerin, trimethylolpropane, pentaerythri
• Amides having 1 to 15 carbon atoms include monoamides (formic acid amide, propionic acid amide, stearyl amide, etc.) and polyamides (malonic acid diamide, ethylene bis octyl amide, etc.).
• Amines having 1 to 15 carbon atoms include monoamines (dimethylamine, ethylamine, t-butylamine, hexylamine, aniline, etc.) and polyamines (ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, toluenediamine, etc.).
• Carboxylic acids having 1 to 15 carbon atoms include monocarboxylic acids (formic acid, acetic acid, caproic acid, caprylic acid, lauric acid, myristic acid, benzoic acid, etc.) and polycarboxylic acids (oxalic acid, maleic acid, malonic acid, succinic acid, phthalic acid, isophthalic acid, terephthalic acid, hexanedioic acid, etc.).
• Hydroxycarboxylic acids having 1 to 15 carbon atoms include hydroxyacetic acid, tartaric acid, and malic acid.
• Aminocarboxylic acids having 1 to 15 carbon atoms include glycine, 4-aminobutyric acid, and 6-aminohexanoic acid.
• active hydrogen compounds containing active hydrogen groups are preferably monohydric to hexahydric alcohols having 1 to 15 carbon atoms, more preferably monohydric to hexahydric aliphatic alcohols having 1 to 8 carbon atoms or monohydric to trihydric aromatic alcohols having 6 to 15 carbon atoms, particularly preferably monohydric to hexahydric aliphatic alcohols having 1 to 6 carbon atoms or monohydric to dihydric aromatic alcohols having 6 to 15 carbon atoms, and most preferably methanol, butanol, ethylene glycol, propylene glycol, glycerin, pentaerythritol, sorbitol or bisphenol A.
• the use of these active hydrogen compounds facilitates the synthesis of polyether polyol (C1), increases the stability of the plasticizer (C), and increases the plasticity of the ceramic green sheet (G).
• alkylene oxide compounds having 2 to 12 carbon atoms include ethylene oxide (hereinafter sometimes abbreviated as EO), propylene oxide (hereinafter sometimes abbreviated as PO), 1,2-butylene oxide, 2,3-butylene oxide, 1,4-butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran, styrene oxide, ⁇ -olefin oxide, and epichlorohydrin.
• EO ethylene oxide
• PO propylene oxide
• 1,2-butylene oxide 2,3-butylene oxide
• 1,4-butylene oxide 1,2-butylene oxide
• tetrahydrofuran 2,3-butylene oxide
• 1,4-butylene oxide 1,4-butylene oxide
• tetrahydrofuran 3-methyltetrahydrofuran
• styrene oxide 3-methyltetrahydrofuran
• styrene oxide ⁇ -olefin oxide
• epichlorohydrin epich
• the alkylene oxide compound having 2 to 12 carbon atoms is preferably ethylene oxide or propylene oxide.
• the use of these compounds increases the plasticity of the ceramic green sheet (G) and reduces bleed-out.
• the addition form of the alkylene oxide compound having 2 to 12 carbon atoms may be any of random addition, block addition, and alternating addition, but from the viewpoint of ease of synthesis, random addition and block addition are preferred.
• the number of moles added of the alkylene oxide compound having 2 to 12 carbon atoms is 1 or more, preferably 13 or more, and more preferably 15 or more.
• the number of moles added is 65 or less, preferably 60 or less, and more preferably 40 or less. If the number of moles added is within the above range, the plasticity of the ceramic green sheet (G) is high and bleed-out is reduced.
• the plasticity of the ceramic green sheet (G) is influenced by the number average molecular weight [X] of the polyether polyol (C1) and the solubility parameter (SP value) [Y] (cal/cm 3 ) 1/2 of the active hydrogen compound.
• the mechanism by which the polyether polyol (C1) contained in the ceramic green sheet plasticizer (C) affects the plasticity and bleed-out of the ceramic green sheet (G) is believed to be as follows (however, this mechanism is merely a guess and does not limit the scope of the present invention). That is, when the polyether polyol (C1) penetrates into the binder resin (B) in the ceramic green sheet (G), the intermolecular forces of the binder resin (B) are weakened. This improves the plasticity of the ceramic green sheet (G) and reduces bleed-out.
• the active hydrogen compound can easily penetrate into the binder resin (B), thereby improving the plasticity of the ceramic green sheet (G).
• the value ([X] x [Y]) obtained by multiplying the solubility parameter (SP value) [Y] (cal/cm 3 ) 1/2 of the active hydrogen compound by the number average molecular weight [X] of the polyether polyol (C1) is 10,000 to 25,000, preferably 10,000 to 24,500, and more preferably 10,000 to 24,000.
• SP value solubility parameter
• [X] x [Y] is 10,000 to 25,000, preferably 10,000 to 24,500, and more preferably 10,000 to 24,000.
• the SP value [Y] of the active hydrogen compound is preferably 3.5 (cal/ cm3 ) 1/2 or more, more preferably 8.0 (cal/ cm3 ) 1/2 or more, and even more preferably 9.0 (cal/ cm3 ) 1/2 or more.
• the SP value [Y] is preferably 50.0 (cal/ cm3 ) 1/2 or less, more preferably 30.0 (cal/ cm3 ) 1/2 or less, and even more preferably 26.0 (cal/ cm3 ) 1/2 or less.
• the number average molecular weight [X] of the polyether polyol (C1) is preferably 500 or more, more preferably 950 or more, and even more preferably 970 or more.
• the number average molecular weight [X] is preferably 3,000 or less, more preferably 2,700 or less, and even more preferably 2,200 or less. If the value of [X] is within the above range, the plasticity of the ceramic green sheet (G) is improved and bleed-out is reduced.
• the number average molecular weight [X] of the polyether polyol (C1) can be measured by gel permeation chromatography (GPC) under the following measurement conditions.
• GPC gel permeation chromatography measurement conditions
• Apparatus HLC-8320GPC (manufactured by Tosoh Corporation)
• Analytical column TSKgel Guardcolumn Super AW, TSKgel Super AW4000, TSKgel Super AW3000 and TSKgel Super AW2500 connected in this order (all columns are manufactured by Tosoh Corporation, and TSKgel is a registered trademark of Tosoh Corporation).
• Sample solution 0.125% by weight N,N-dimethylformamide solution
• Solution injection volume 20 ⁇ L
• Flow rate 0.6mL/min
• ⁇ Measurement temperature 40°C ⁇ Detection device: Refractive index detector
• ceramic green sheet (G) is affected by the HLB [Z] of polyether polyol (C1) contained in ceramic green sheet plasticizer (C) and the number average molecular weight [X] of polyether polyol (C1).
• the mechanism by which the polyether polyol (C1) contained in the ceramic green sheet plasticizer (C) affects the formability of the ceramic green sheet (G) is believed to be as follows (however, this mechanism is merely a guess and does not limit the scope of the present invention). That is, the polyether polyol (C1) that has penetrated into the binder resin (B) in the ceramic green sheet (G) exerts plasticity and increases the dispersibility of the ceramic particles (A) in the ceramic green sheet (G). This improves the formability of the ceramic green sheet (G).
• the molecular weight [X] and HLB [Z] of the polyether polyol (C1) contained in the plasticizer (C) for ceramic green sheets are within a specific appropriate range, the compatibility with the binder resin (B) contained in the plasticizer (C) for ceramic green sheets and the dispersibility of the ceramic particles (A) are improved. As a result, the moldability of the ceramic green sheet (G) is improved, and defects in the ceramic green sheet can be reduced.
• the ratio ([X]/[Z]) of the number average molecular weight [X] of the polyether polyol (C1) to the hydrophilic-hydrophobic balance (HLB) value [Z] of the polyether polyol (C1) is preferably 1100 or less, more preferably 500 or less, and even more preferably 300 or less.
• the value of [X]/[Z] is preferably 24 or more, and more preferably 30 or more. If the value of [X]/[Z] is within the above range, the moldability of the ceramic green sheet (G) is improved.
• the SP value [Y'] of the polyether polyol (C1) is preferably 8.0 to 12.0 (cal/cm 3 ) 1/2 , more preferably 8.5 to 12.0 (cal/cm 3 ) 1/2 , and even more preferably 8.8 to 12.0 (cal/cm 3 ) 1/2 .
• the value of [Y'] is within the above range, the plasticity of the ceramic green sheet (G) is improved and bleed-out is reduced.
• the hydroxyl value of the polyether polyol (C1) is preferably 25 to 350 mgKOH/g. If the hydroxyl value is within the above range, the plasticity of the ceramic green sheet (G) is improved and bleed-out is reduced. In this specification, the hydroxyl value is determined according to JIS K-1557-1 (method of determining hydroxyl value).
• Polyether polyol (C1) can be synthesized by addition reaction of an alkylene oxide compound having 2 to 12 carbon atoms with an active hydrogen compound containing 1 to 15 carbon atoms and 1 to 6 active hydrogen groups.
• the addition reaction is carried out after dehydration treatment of polyether polyol (C1).
• the addition reaction can be carried out without a catalyst or in the presence of a catalyst.
• the reaction temperature of the addition reaction can be 50 to 200°C.
• the addition reaction can be a one-step reaction or a multi-step reaction.
• Catalysts include alkali catalysts and Lewis acid catalysts.
• Alkaline catalysts include hydroxides of alkali metals and alkaline earth metals, specifically lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, etc. Of these, potassium hydroxide and cesium hydroxide are preferred.
• Lewis acid catalysts include tin tetrachloride, antimony pentachloride, iron trichloride, and boron trifluoride.
• the amount of catalyst used is preferably more than 0 and not more than 0.5% by weight, more preferably more than 0 and not more than 0.3% by weight, based on the total weight of the active hydrogen compound containing 1 to 15 carbon atoms and 1 to 6 active hydrogen groups and the alkylene oxide having 2 to 12 carbon atoms, in terms of reaction rate.
• the catalyst may be left in the polyether polyol (C1) as it is, or may be removed by adsorption and filtration using an adsorbent, or by neutralizing with an acid to inactivate the catalyst.
• hydrotalcite-based adsorbents e.g., Kyoward 500, Kyoward 600S (registered trademark), Kyoward 700SL (registered trademark), Kyoward 1000 (registered trademark), Kyoward 1000S, Kyoward 2000, etc. (all manufactured by Kyowa Chemical Industry Co., Ltd.)
• basic activated carbon e.g., Strong Shirasagi A (manufactured by Osaka Gas Chemical Co., Ltd.)
• filter aids such as diatomaceous earth (e.g., Radiolite 600 (registered trademark), Radiolite 800 (registered trademark), Radiolite 900 (registered trademark) (all manufactured by Showa Chemical Industry Co., Ltd.)), etc.
• diatomaceous earth e.g., Radiolite 600 (registered trademark), Radiolite 800 (registered trademark), Radiolite 900 (registered trademark) (all manufactured by Showa Chemical Industry Co., Ltd.)
• the reaction temperature is preferably 50°C or higher, more preferably 70°C or higher, and even more preferably 80°C or higher.
• the reaction temperature is preferably 200°C or lower, and more preferably 180°C or lower.
• the amount of the polyether polyol (C1) contained in the ceramic green sheet plasticizer (C) is preferably 30 to 100% by weight, and more preferably 50 to 100% by weight, based on the weight of the ceramic green sheet plasticizer (C). If the content is within the above range, the plasticity of the ceramic green sheet (G) is improved and bleed-out is reduced.
• the plasticizer (C) for the ceramic green sheet may contain any other components.
• Ceramic green sheet plasticizer (C) includes ceramic additives, plasticizers, dispersants, antistatic agents, etc.
• the content of the ceramic particles (A) based on the total weight of the ceramic green sheet plasticizer (C), the ceramic particles (A) and the binder resin (B) [(A)/ ⁇ (A)+(B)+(C) ⁇ ] is preferably 70-95% by weight, and more preferably 75-95% by weight. If the content is within the above range, the ceramic green sheet (G) can be made thinner.
• the content of the binder resin (B) based on the total weight of the ceramic green sheet plasticizer (C), the ceramic particles (A) and the binder resin (B) [(B)/ ⁇ (A)+(B)+(C) ⁇ ] is preferably 4-25% by weight, and more preferably 4-20% by weight. If the content is within the above range, the ceramic green sheet (G) can be made thinner.
• the content of the polyether polyol (C1) based on the total weight of the ceramic green sheet plasticizer (C), the ceramic particles (A) and the binder resin (B) [(C1)/ ⁇ (A)+(B)+(C) ⁇ ] is preferably 0.12-12% by weight, and more preferably 0.2-12% by weight. If the content is within the above range, the plasticity of the ceramic green sheet (G) is improved and bleed-out is reduced.
• the dielectric paste (F) may contain a solvent as necessary.
• a solvent an organic solvent is preferably used, for example, hydrocarbons such as toluene, xylene, methylcyclohexane, etc.; alcohols such as ethanol, n-propanol, isopropanol, n-butanol, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, etc.; esters such as ethyl acetate, butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, etc.
• hydrocarbons such as toluene, xylene, methylcyclohexane, etc.
• alcohols such as ethanol, n-propano
• the dielectric paste (F) may contain known additives such as leveling agents, defoamers, fluorescent dyes, fluorescent brighteners, ultraviolet absorbers, and preservatives.
• the dielectric paste (F) can be produced by mixing the ceramic green sheet plasticizer (C), ceramic particles (A), binder resin (B), dispersant, solvent, and known additives added as necessary, using various mixers such as a bead mill, ball mill, blender mill, and triple roll mill.
• a ceramic is a solid material composed of inorganic compounds such as oxides, carbides, nitrides or borides.
• the number-average primary particle diameter of the ceramic particles (A) is preferably 10 to 400 ⁇ m from the viewpoint of thinning the ceramic green sheet.
• the number-average primary particle diameter of ceramic particles (A) is measured using an electron microscope. Specifically, ceramic particles (A) are subjected to sputtering treatment if necessary, and then observed with a transmission electron microscope [product name: JEM-2100, manufactured by JEOL Ltd.] at an acceleration voltage of 80 kV and an observation magnification of 50,000 times. Primary particles of 100 particles in the image are randomly selected, and their particle diameters (average of major and minor diameters) are measured. The number average of the 100 particles is calculated to be the number-average primary particle diameter of ceramic particles (A).
• the binder resin (B) is a resin used for forming the ceramic particles (A) into a ceramic green sheet (G).
• binder resin (B) examples include silicone resin, epoxy resin, butyral resin, acetal resin, acrylic resin, polybutadiene resin, cellulose resin, (meth)acrylic resin, styrene resin, phenolic resin, polyurethane resin, polyamide resin, polyimide resin, polyamideimide resin, and alkyd resin. From the viewpoint of thinning the ceramic green sheet, butyral resin is preferred, and polyvinyl butyral is even more preferred.
• a dispersant may be used to suppress sedimentation of the ceramic particles (A) in the dielectric paste (F) and to obtain a dielectric paste (F) with a viscosity suitable for forming the ceramic green sheet (G).
• nonionic surfactants nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants or polymeric emulsifying dispersants can be used.
• nonionic surfactants examples include polyoxyethylene alkylphenyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol fatty acid partial esters, polyoxyethylene sorbitan acid fatty partial esters, polyoxyethylene alkyl ether carboxylates, fatty acid alkanolamides, and alkyl dialkylamine oxides.
• cationic surfactants for example, alkylamine salts, dialkylamine salts, or quaternary ammonium salts can be used.
• anionic surfactants examples include ether carboxylates, dialkyl sulfosuccinates, alkanesulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, polyoxyethylene alkylsulfophenyl ether salts, alkyl phosphate salts, polyoxyethylene alkyl ether phosphate salts, sulfate salts of fatty acid alkyl esters, alkyl sulfate salts, polyoxyethylene alkyl ether sulfate salts, fatty acid monoglyceride sulfate salts, and acylated amino acid salts.
• betaine-type amphoteric surfactants or amino acid-type amphoteric surfactants can be used as amphoteric surfactants.
• polymeric emulsifying and dispersing agents examples include polyvinyl alcohol, starch, starch derivatives, cellulose derivatives, and sodium polyacrylate.
• the cellulose derivatives include carboxymethyl cellulose, methyl cellulose, and hydroxyethyl cellulose.
• the ceramic green sheet (G) can be produced by applying a dielectric paste (F) containing a plasticizer for ceramic green sheets (C), ceramic particles (A) and a binder resin (B) to a support and drying it as necessary.
• a dielectric paste (F) containing a plasticizer for ceramic green sheets (C), ceramic particles (A) and a binder resin (B) to a support and drying it as necessary.
• the dielectric paste (F) is applied onto a support such as polyethylene terephthalate (PET) that has been subjected to a release treatment.
• a drying process is performed to remove volatile components from the slurry composition on the support, forming a film, thereby obtaining a ceramic green sheet (G).
• Methods for applying the dielectric paste (F) to the support include known application methods such as using a roll coater, a die coater, and a curtain coater.
• the method for producing a ceramic capacitor uses the ceramic green sheet (G).
• the ceramic capacitor can be obtained, for example, by heat-treating the ceramic green sheet (G).
• the ceramic capacitor can be obtained by applying a dielectric paste (F) to a support, removing volatile components to form a film, obtaining a ceramic green sheet (G), laminating and pressing the ceramic green sheet (G), and then performing a heat treatment (sintering, degreasing (thermal decomposition of a binder, etc.), etc.).
• a plasticizer (C) for a ceramic green sheet comprising a polyether polyol (C1) in which 1 to 65 moles of an alkylene oxide compound having 2 to 12 carbon atoms are added to an active hydrogen compound having 1 to 15 carbon atoms and 1 to 6 active hydrogen groups, wherein the value ([X] x [Y]) obtained by multiplying the solubility parameter (SP value) [Y] (cal/cm 3 ) 1/2 of the active hydrogen compound by the number average molecular weight [X] of the polyether polyol (C1) is 10,000 to 25,000.
• SP value solubility parameter
• the plasticizer (C) for ceramic green sheets according to ⁇ 1> or ⁇ 2>, wherein a ratio ([X]/[Z]) of the number average molecular weight [X] of the polyether polyol (C1) to a hydrophilic-lipophilic balance (HLB) value [Z] of the polyether polyol (C1) is 1,100 or less.
• ⁇ 5> The dielectric paste (F) according to ⁇ 4>, wherein the ceramic particles (A) are barium titanate.
• ⁇ 6> A ceramic green sheet (G) containing ceramic particles (A), a binder resin (B), and a plasticizer for ceramic green sheets (C) according to any one of ⁇ 1> to ⁇ 3>.
• ⁇ 7> A method for producing a ceramic capacitor using the ceramic green sheet (G) according to ⁇ 6>.
• Example 1 Production of plasticizer for ceramic green sheet (C-1) 1. 84.9 parts (1 mol part) of refined glycerin (manufactured by Miyoshi Oil Co., Ltd.) and 2.5 parts of flake caustic potash (manufactured by Toagosei Co., Ltd.) were mixed in a stainless steel autoclave equipped with a stirrer and temperature control device, and dehydration was carried out at 140°C for 1 hour under reduced pressure (1.3 kPa). 2. The temperature in the reaction vessel was raised to 180° C., and then 466.9 parts (11.5 parts by mole) of ethylene oxide (EO) was added dropwise over a period of 3 hours. 3.
• EO ethylene oxide
• Example 2 Production of plasticizer for ceramic green sheet (C-2) 1. 71.7 parts (1 part by mole) of normal butanol (manufactured by Mitsubishi Chemical Corporation) and 2.5 parts of flake caustic potassium (manufactured by Toagosei Co., Ltd.) were mixed in a stainless steel autoclave equipped with a stirrer and a temperature control function. 2. The temperature in the reaction vessel was raised to 120° C., and then a mixture of 464.8 parts (10.9 parts by mole) of ethylene oxide (EO) and 461.0 parts (8.2 parts by mole) of propylene oxide (PO) was added dropwise over 8 hours. 3. After the mixture of EO and PO was dropped, the mixture was aged in the reaction vessel at a temperature of 120° C.
• EO ethylene oxide
• PO propylene oxide
• Example 3 Production of plasticizer for ceramic green sheet (C-3) 1. 91.5 parts (1 mol part) of refined glycerin (manufactured by Miyoshi Oil Co., Ltd.) and 2.5 parts of flake caustic potash (manufactured by Toagosei Co., Ltd.) were mixed in a stainless steel autoclave equipped with a stirrer and temperature control device, and dehydration was carried out at 140°C for 1 hour under reduced pressure (1.3 kPa). 2. After the temperature in the reaction vessel was cooled to 105° C., 906.0 parts (15.7 parts by mole) of propylene oxide (PO) was added dropwise over 12 hours. 3.
• PC propylene oxide
• Example 4 Production of plasticizer for ceramic green sheet (C-4) 1. 39.1 parts (1 part by mole) of normal butanol (manufactured by Mitsubishi Chemical Corporation) and 2.5 parts of flake caustic potassium (manufactured by Toagosei Co., Ltd.) were mixed in a stainless steel autoclave equipped with a stirrer and a temperature control function. 2. The temperature in the reaction vessel was raised to 120° C., and then a mixture of 431.9 parts (18.6 parts by mole) of ethylene oxide (EO) and 526.6 parts (17.2 parts by mole) of propylene oxide (PO) was added dropwise over 16 hours. 3. After the mixture of EO and PO was dropped, the mixture was aged in the reaction vessel at a temperature of 120° C.
• EO ethylene oxide
• PO propylene oxide
• Example 6 Production of plasticizer for ceramic green sheet (C-6) 1. 133.6 parts (1 mol part) of 1-octanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 2.5 parts of flake caustic potassium (manufactured by Toagosei Co., Ltd.) were mixed in a stainless steel autoclave equipped with a stirrer and a temperature control function. 2. The temperature in the reaction vessel was raised to 105° C., and then 863.9 parts (14.5 parts by mole) of propylene oxide (PO) was added dropwise over 14 hours. 3. After the PO was dropped, the mixture was aged in the reaction vessel at a temperature of 130° C. for 4 hours to obtain a crude polyether polyol (H-6). 4.
• 1-octanol manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
• flake caustic potassium manufactured by Toagosei Co., Ltd.
• Example 7 Production of plasticizer for ceramic green sheet (C-7)> 1. 186.4 parts (1 mol part) of Sorbitol S (manufactured by Bussan Food Science Co., Ltd.) and 2.5 parts of flake caustic potash (manufactured by Toagosei Co., Ltd.) were mixed in a stainless steel autoclave equipped with a stirrer and a temperature control function, and dehydration was carried out at 130° C. for 1 hour under reduced pressure (1.3 kPa). 2. The temperature in the reaction vessel was kept at 130° C., and 811.1 parts (18.0 parts by mole) of ethylene oxide (EO) was added dropwise over 10 hours. 3.
• Sorbitol S manufactured by Bussan Food Science Co., Ltd.
• flake caustic potash manufactured by Toagosei Co., Ltd.
• ⁇ Example 8 Production of plasticizer for ceramic green sheet (C-8)> 1. 57.0 parts (0.14 parts by mole) of an ethylene oxide (EO) 2.2 mole adduct of bisphenol A (Newpol BPE-20 (registered trademark), manufactured by Sanyo Chemical Industries, Ltd.) was placed in a stainless steel autoclave equipped with a stirrer and a temperature control function and dissolved at 150°C. 2. 255.1 parts (0.86 parts by mole) of bisphenol A (Idemitsu Kosan Co., Ltd.) and 0.5 parts of flake caustic potassium (Toagosei Co., Ltd.) were mixed and dehydrated under reduced pressure (1.3 kPa) at 150° C. for 2 hours. 3.
• EO ethylene oxide
• Newpol BPE-20 registered trademark
• Example 9 Production of plasticizer for ceramic green sheet (C-9)> 1. 135.7 parts (1 part by mole) of toluenediamine (TDA-80 (registered trademark), manufactured by Tosoh Corporation) was placed in a stainless steel autoclave equipped with a stirrer and a temperature control function. 2. The temperature in the reaction vessel was raised to 150° C., and then 122.3 parts (2.5 parts by mole) of ethylene oxide (EO) was added dropwise over a period of 2 hours. 3. After the EO was added dropwise, the mixture was aged in the reaction vessel at 150° C. for 2 hours. 4.
• TDA-80 registered trademark
• EO ethylene oxide
• Example 10 Production of plasticizer for ceramic green sheet (C-10) 1. 56.2 parts (1 part by mole) of 1,4-butanediol (manufactured by Mitsubishi Chemical Corporation), 580.9 parts (12.9 parts by mole) of THF (manufactured by Mitsubishi Chemical Corporation), and 6.1 parts (0.1 parts by mole) of 47% boron trifluoride tetrahydrofuran (manufactured by Stella Chemifa Corporation) were mixed in a stainless steel autoclave equipped with a stirrer and a temperature control function. 2. The temperature in the reaction vessel was raised to 50° C., and then 356.8 parts (13.0 parts by mole) of ethylene oxide (EO) was added dropwise over a period of 5 hours. 3.
• EO ethylene oxide
• the crude polyether polyol (H-10) was filtered using a suction funnel packed with 20 parts of Kyoward 700SL (Kyowa Chemical Industry Co., Ltd.) in a layered form. 7. Dehydration was carried out at 140° C. for 1 hour under reduced pressure (1.3 kPa) to obtain a plasticizer for ceramic green sheets (C-10).
• Comparative Example 1 Production of Plasticizer for Ceramic Green Sheet (C'-1) 1. 77.7 parts (1 part by mole) of methanol (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 0.8 parts of 24% by weight liquid sodium methylate (manufactured by Nippon Soda Co., Ltd.) were mixed in a stainless steel autoclave equipped with a stirrer and a temperature control function. 2. The temperature in the reaction vessel was raised to 105° C., and then 921.5 parts (8.6 parts by mole) of ethylene oxide (EO) was added dropwise over a period of 6 hours. 3. After the EO was dropped, the mixture was aged in the reaction vessel at a temperature of 145° C.
• EO ethylene oxide
• Comparative Example 2 Production of Plasticizer for Ceramic Green Sheet (C'-2) 1. 35.3 parts (1 mol part) of refined glycerin (manufactured by Miyoshi Oil Co., Ltd.) and 2.5 parts of flake caustic potash (manufactured by Toagosei Co., Ltd.) were mixed in a stainless steel autoclave equipped with a stirrer and temperature control device, and dehydration was carried out at 140°C for 1 hour under reduced pressure (1.3 kPa). 2.
• the temperature in the reaction vessel was kept at 140° C., and a mixture of 481.3 parts (28.5 parts by mole) of ethylene oxide (EO) and 480.9 parts (21.6 parts by mole) of propylene oxide (PO) was added dropwise over a period of 23 hours. 3. After the mixture of EO and PO was added dropwise, the mixture was aged in the reaction vessel at a temperature of 140° C. for 3 hours to obtain a crude polyether polyol (H′-2). 4. After the temperature in the reaction vessel was cooled to 90° C., 20 parts of Kyoward 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) and 20 parts of water were mixed and stirred for 1 hour. 5.
• Kyoward 600S manufactured by Kyowa Chemical Industry Co., Ltd.
• the crude polyether polyol (H'-2) was filtered using a suction funnel packed with 20 parts of Kyoward 700SL (Kyowa Chemical Industry Co., Ltd.) in a layered form. 6. Dehydration was carried out at 140° C. for 1 hour under reduced pressure (1.3 kPa) to obtain a plasticizer for ceramic green sheets (C'-2).
• Comparative Example 3 Production of Plasticizer for Ceramic Green Sheet (C'-3) 1. 18.5 parts (1 mol part) of refined glycerin (manufactured by Miyoshi Oil Co., Ltd.) and 2.5 parts of flake caustic potassium (manufactured by Toagosei Co., Ltd.) were mixed in a stainless steel autoclave equipped with a stirrer and temperature control device, and dehydration was carried out at 140°C for 1 hour under reduced pressure (1.3 kPa). 2. After the temperature in the reaction vessel was cooled to 105° C., 979.0 parts (84.0 parts by mole) of PO was added dropwise over 60 hours. 3. After the PO was dropped, the mixture was aged in the reaction vessel at a temperature of 130° C.
• Example 11 Preparation of dielectric paste (F-1)> The following materials were mixed in a bead mill for 1 hour to prepare a dielectric paste (F-1).
• Binder resin (B): Polyvinyl butyral (S-LEC BM-1 (registered trademark), manufactured by Sekisui Chemical Co., Ltd.) 6.76 parts Plasticizer for ceramic green sheet (C): Plasticizer for ceramic green sheet (C-1) ([X] x [Y] 23,020) 0.53 parts
• Dispersant Ether carboxylic acid surfactant (Viewlite LCA-25NH (registered trademark), manufactured by Sanyo Chemical Industries, Ltd.) 0.68 parts
• Solvent: Toluene: Ethanol 1: 1 (weight ratio) solution 47 parts
• the content of each component in the dielectric paste (F-1) based on the total weight of the ceramic green sheet plasticizer (C), ceramic particles (A) and binder resin (B) is as follows: ceramic resin (A): 86.0% by weight, binder resin (B): 12.9% by weight, ceramic green sheet plasticizer (C): 1.0%.
• Dielectric Pastes (F-2) to (F-17) and (F'-1) to (F'-4) Dielectric pastes (F-2) to (F-17) and (F'-1) to (F'-4) were prepared in the same manner as in Example 11, except that the ceramic particles (A), binder resin (B), plasticizer for ceramic green sheet (C) and dispersant shown in Table 2 were used.
• the content of each component based on the total weight of the plasticizer for ceramic green sheet (C), the ceramic particles (A) and the binder resin (B) is as follows: ceramic resin (A): 86% by weight, binder resin (B): 12.9% by weight, plasticizer for ceramic green sheet (C): 1.0%.
• the content of each component based on the total weight of the plasticizer for ceramic green sheet (C), the ceramic particles (A) and the binder resin (B) is as follows: ceramic resin (A): 95.0% by weight, binder resin (B): 4.0% by weight, plasticizer for ceramic green sheet (C): 1.0%.
• the content of each component based on the total weight of the plasticizer for ceramic green sheet (C), the ceramic particles (A) and the binder resin (B) is as follows: ceramic resin (A): 69.7% by weight, binder resin (B): 25.3% by weight, plasticizer for ceramic green sheet (C): 5.0%.
• the content of each component based on the total weight of the plasticizer for ceramic green sheet (C), the ceramic particles (A) and the binder resin (B) is as follows: ceramic resin (A): 86.5% by weight, binder resin (B): 13.1% by weight, plasticizer for ceramic green sheet (C): 0.4% by weight.
• the content of each component based on the total weight of the plasticizer for ceramic green sheet (C), the ceramic particles (A) and the binder resin (B) is as follows: ceramic resin (A): 70.1% by weight, binder resin (B): 18.0% by weight, plasticizer for ceramic green sheet (C): 12.0%.
• Plasticity was judged as follows: tensile elongation of 130% or more was ++, 129-120% was +, 119-110% was -, and less than 110% was -.
• Example 45 Preparation of dielectric paste sheet (E-1)> 9 g of the dielectric paste (F-1) was placed in a petri dish having a diameter of 9.7 cm, and dried for 30 minutes at 30° C., 30 minutes at 40° C., and 30 minutes at 60° C. After that, it was further dried under reduced pressure for 30 minutes at 60° C. to obtain a sheet (E-1) of the dielectric paste on the petri dish.
• Example 46 to 61 and Comparative Examples 12 to 15 Preparation of Dielectric Paste Sheets (E-2) to (E-17) and (E'-1) to (E'-4)> Except for changing the dielectric paste (F-1) to dielectric pastes (F-2) to (F-17), respectively, in the same manner as in Example 45, dielectric paste sheets (E-2) to (E-17) and (E'-1) to (E'-4) were prepared on a petri dish.
• the bleed-out was evaluated as follows: if the value calculated by the following formula (3) was less than 20%, it was evaluated as ++; if it was 29 to 20%, it was evaluated as +; if it was 30% or more, it was evaluated as -: 100 x (So-S)/ ⁇ Do x (Co/100) ⁇ (unit: %)... (3) So: Weight (g) of the dielectric paste sheet (E) before heating S: Weight (g) of the dielectric paste sheet (E) after heating Do: Weight (g) of dielectric paste (F) added to the petri dish Co: weight part of plasticizer (C1) for ceramic green sheet in dielectric paste (F)
• the ceramic green sheet (G) containing the ceramic green sheet plasticizer (C) according to one embodiment of the present invention has high plasticity, reduced bleed-out, and excellent formability, and is therefore useful for ceramic capacitor applications.

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