WO2023058521A1 - Composition de liant pour moulage de céramique et composition de suspension - Google Patents

Composition de liant pour moulage de céramique et composition de suspension Download PDF

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WO2023058521A1
WO2023058521A1 PCT/JP2022/036168 JP2022036168W WO2023058521A1 WO 2023058521 A1 WO2023058521 A1 WO 2023058521A1 JP 2022036168 W JP2022036168 W JP 2022036168W WO 2023058521 A1 WO2023058521 A1 WO 2023058521A1
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component
formula
mass
ceramic
group
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PCT/JP2022/036168
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English (en)
Japanese (ja)
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将啓 田中
晴香 小室
敦 長澤
文隆 吉川
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日油株式会社
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Priority to CN202280051817.4A priority Critical patent/CN117693494A/zh
Priority to JP2023552826A priority patent/JPWO2023058521A1/ja
Priority to KR1020247002130A priority patent/KR20240072989A/ko
Publication of WO2023058521A1 publication Critical patent/WO2023058521A1/fr

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    • 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
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63424—Polyacrylates; Polymethacrylates
    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62625—Wet mixtures
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • 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

Definitions

  • the present invention relates to a binder composition used for molding ceramics and a slurry composition containing this binder composition.
  • the MLCC has a structure in which dielectric layers formed using ceramic powder and electrode layers formed using a conductive material are alternately laminated.
  • the dielectric layer is manufactured, for example, by the following method. First, ceramic powder, a solvent, and a binder are mixed to prepare a ceramic slurry, which is uniformly coated on a support with a doctor blade or the like, and then dried to obtain a ceramic green sheet (hereinafter referred to as a "green sheet”). ) can be fired to form the dielectric layer.
  • polyvinyl butyral (hereinafter sometimes referred to as "PVB"), which is excellent in strength and elongation, is commonly used, as described in Patent Document 1, for example.
  • PVB polyvinyl butyral
  • the degreasing performance was poor and residue was generated on the green sheet, and the performance of the MLCC was sometimes deteriorated. Therefore, an acrylic resin is useful as a binder having good degreasing properties, as described in Patent Document 2, for example.
  • PVB or acrylic resin as a binder can add strength to the green sheet, but it has poor elongation and cracks may occur. In such a case, it is effective to use a plasticizer together for the purpose of imparting flexibility to the green sheet.
  • a plasticizer for example, as described in Patent Document 3, an aromatic carboxylic acid ester, a polyalkylene glycol-based plasticizer, a vegetable oil-based compound, or the like can be used.
  • the present invention is intended to solve the above-mentioned problems, and is a binder composition for ceramic molding that is excellent in degreasing of the binder by heat treatment and capable of producing a green sheet or the like that is excellent in strength, elongation and smoothness.
  • Another object of the present invention is to provide a slurry composition containing this binder composition for molding ceramics.
  • the present inventors have made intensive studies in view of the above problems, and found that an acrylic copolymer obtained by polymerizing a specific monomer at a specific ratio and a specific polyalkylene glycol compound at a predetermined ratio. It was found that a binder composition for ceramic molding and a slurry composition that can achieve the above objects can be obtained by combining the above.
  • the present invention is a ceramic molding binder composition containing 15 to 95% by mass of the following component (A) and 5 to 85% by mass of the following component (B).
  • a copolymer formula (1) having a weight average molecular weight of 50,000 to 1,000,000 CH2 CR1 -COO- R2 (In formula (1), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 1 to 8 carbon atoms.)
  • Component (B): a compound represented by the following formula (3) Formula (3) R 5 O—(EO) p —(PO) q —H (In the formula (3), R 5 is an alkyl group having 9 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, p is the average number of added moles of oxyethylene groups, p 3 to 9, and q is oxypropylene. The average number of
  • the present invention in another aspect is a slurry composition containing the binder composition for molding ceramics, ceramic powder, dispersant, and organic dispersion medium.
  • the ceramic molding binder composition of the present invention can be slowly thermally decomposed by heat treatment and can suppress the generation of residues.
  • an MLCC using the binder composition of the present invention, it is possible to obtain a green sheet that exhibits high smoothness even when thinned and has excellent strength and elongation. and the demand for multi-layering can be met.
  • a slurry composition containing the ceramic molding binder composition of the present invention is also useful for producing ceramic compacts corresponding to thinning and multilayering, particularly ceramic green sheets.
  • (Meth)acrylic acid represents acrylic acid or methacrylic acid.
  • (meth)acrylates may be used alone or in combination of two or more.
  • (meth)acrylate denotes acrylate and/or methacrylate, where there can be two species, acrylate and methacrylate, with the same ester moiety.
  • binder composition for ceramic molding>
  • binder composition contains the following component (A) and the following component (B).
  • component (A) used in the present invention (hereinafter sometimes referred to as “component (A) of the present invention") is a monomer (a-1) represented by the following formula (1), and the following Polymerizing a monomer mixture containing the monomer (a-2) represented by formula (2) as an essential component and further containing other copolymerizable monomer (a-3) This is the obtained copolymer.
  • component (A) of the present invention may be used alone or in combination of two or more.
  • the monomer (a-1) used for producing the component (A) of the present invention (hereinafter sometimes referred to as "monomer (a-1) of the present invention") has the above formula ( 1), it is an alkyl mono(meth)acrylate having a polymerizable functional group.
  • the monomer (a-1) of the present invention may be used alone or in combination of two or more.
  • R 1 in formula (1) is preferably a methyl group from the viewpoint of ease of polymerization of the monomer (a-1).
  • R 2 in the formula (1) is an alkyl group having 1 to 8 carbon atoms from the viewpoint of enhancing the degreasing property of the ceramic slurry prepared using the component (A). It may be cyclic, or any combination thereof.
  • the number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 4, more preferably 1-2.
  • Examples of the monomer (a-1) of the present invention include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and isobutyl (meth)acrylate. , tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, (meth)acrylic acid -2-ethylhexyl and the like.
  • the content of structural units derived from the monomer (a-1) in component (A) is 70 to 99 mol%, preferably 85 to 99 mol%. When the content of structural units derived from the monomer (a-1) is within this range, the strength of the green sheet can be improved when the green sheet is produced.
  • the content of structural units derived from the monomer (a-1) in component (A) is the total content (moles) of all monomers constituting component (A). It can be calculated by the ratio (mol%) of the content (mol) of the body (a-1).
  • the content of each structural unit derived from monomers (a-2) and (a-3) described below can also be calculated in the same manner.
  • the total content of structural units derived from monomers (a-1), (a-2) and (a-3) is 100 mol %.
  • Monomer (a-2) The monomer (a-2) used for producing the component (A) of the present invention (hereinafter sometimes referred to as "monomer (a-2) of the present invention") has the above formula ( 2), it is an alkyl mono(meth)acrylate having a hydroxy group.
  • the monomer (a-2) of the present invention may be used alone or in combination of two or more.
  • R 3 in formula (2) is preferably a methyl group from the viewpoint of ease of polymerization of the monomer (a-2).
  • R 4 in formula (2) is a hydroxyalkyl group having 1 to 8 carbon atoms and having 1 to 2 hydroxyl groups, and the alkyl group may be linear, branched, cyclic, or a combination thereof. linear chain is preferred.
  • the number of hydroxyl groups in the hydroxyalkyl group is preferably one from the viewpoint of improving the uniformity of the prepared slurry composition and producing a highly smooth ceramic compact. Further, the number of carbon atoms is 1 to 8, preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 2 from the viewpoint of the strength of the green sheet when the green sheet is produced.
  • Examples of the monomer (a-2) of the present invention include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acryl 4-hydroxybutyl acid, 6-hydroxyhexyl (meth)acrylate, glycerin mono(meth)acrylate and the like.
  • 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-(meth)acrylate is at least one selected from the group consisting of hydroxyhexyl, More preferably, at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate, More preferred is 2-hydroxyethyl (meth)acrylate.
  • the content of structural units derived from the monomer (a-2) in component (A) is 1 to 30 mol%, preferably 1 to 15 mol%.
  • the uniformity of the prepared slurry composition can be improved, and a highly smooth ceramic compact can be produced.
  • the monomer (a-3) used for producing the component (A) of the present invention (hereinafter sometimes referred to as "monomer (a-3) of the present invention") is a monomer A monomer other than (a-1) and (a-2), which is copolymerizable with these monomers (a-1) and (a-2).
  • Examples of the monomer (a-3) of the present invention include unsaturated carboxylic acids such as acrylic acid and methacrylic acid; polymerizable aromatic unsaturated compounds such as styrene, p-styrenesulfonic acid and indene; isobutylene and isoprene.
  • olefins such as N-phenylmaleimide; other acrylamides; vinyl acetate; and acrylonitrile. These monomers may be used individually by 1 type, and may use 2 or more types together.
  • the content of structural units derived from the monomer (a-3) in the component (A) is 0 to 29 mol%, preferably 0 to 15 mol%.
  • the content of structural units derived from the monomer (a-3) is within this range, high thermal decomposability and good degreasing properties can be obtained.
  • Method for producing component (A) Known methods such as suspension polymerization, solution polymerization and emulsion polymerization can be selected as the method for producing component (A). Among these polymerization methods, suspension polymerization is preferable because the component (A) having a high molecular weight can be easily obtained.
  • the polymerization initiator for radical polymerization in an organic solvent system or solventless system is not particularly limited. Initiator and the like can be mentioned. These polymerization initiators may be used individually by 1 type, and may use 2 or more types together.
  • a chain transfer agent may be used during polymerization for the purpose of controlling the molecular weight of component (A).
  • chain transfer agents general-purpose compounds such as ⁇ -methylstyrene dimer and 1-thioglycerol can be used.
  • the weight average molecular weight of component (A) of the present invention is 50,000 to 1,000,000, preferably 100,000 to 800,000, more preferably 200,000 to 700,000, and still more preferably 400. ,000 to 650,000, particularly preferably 500,000 to 600,000. If the weight average molecular weight of component (A) is too low, the strength of the green sheet obtained from the binder composition of the present invention may be insufficient. On the other hand, if the weight average molecular weight of component (A) is too high, the slurry composition of the present invention tends to be stringy, which may impair the surface smoothness of the ceramic molded body (especially ceramic green sheet).
  • the weight average molecular weight of the component (A) of the present invention can be determined in terms of polystyrene using gel permeation chromatography (GPC).
  • Component (B) used in the present invention is a compound represented by the following formula (3).
  • the component (B) of the present invention may be used alone or in combination of two or more.
  • R5 is an alkyl group having 9 carbon atoms, and the alkyl group may be either branched or linear.
  • the alkyl group is preferably branched because it has good compatibility with the component (A) and can enhance the extensibility of the produced green sheet.
  • Examples of the alkyl group having 9 carbon atoms include nonyl, isononyl, 3,5,5-trimethyl-1-hexyl and the like, preferably isononyl and 3,5,5-trimethyl-1- It is a hexyl group.
  • p in formula (3) is the average number of added moles of oxyethylene groups, p is not limited to an integer and may be a decimal number. p is a number from 3 to 9, preferably from 5 to 9, more preferably from 7 to 8. If p is too small, the compatibility between the component (A) and the component (B) will be reduced, and the ceramic molded article formed from the slurry composition will be difficult to exhibit flexibility and stretchability may be reduced. On the other hand, if p is too large, thermal decomposition up to around 300° C. in the degreasing treatment will be difficult to progress, and thermal decomposition will rapidly progress in the temperature range from 300° C. to 400° C., resulting in fine voids in the green sheet. smoothness may be lost.
  • q in formula (3) is the average number of added moles of oxypropylene groups, q is not limited to an integer and may be a decimal number. q is a number from 2 to 4, preferably from 2.5 to 3.5. If q is too small, the compatibility of the component (B) with the organic dispersion medium contained in the slurry composition is reduced, and the slurry composition becomes non-uniform, which may reduce the smoothness of the ceramic compact. . If q is too large, the compatibility between the component (A) and the component (B) is reduced, and the flexibility of the ceramic molded body formed from the slurry composition may be difficult to exhibit, resulting in reduced elongation.
  • the ratio of p and q (that is, p/q) in formula (3) is 1.0 to 3.0, preferably 1.6 to 3.0, more preferably 2.4 to 3.0. is. If p/q is too small, the compatibility between the component (A) and the component (B) will be reduced, making it difficult for the ceramic molded body formed from the slurry composition to exhibit its flexibility and elongation. be. On the other hand, if p/q is too large, the compatibility of the component (B) with the organic dispersion medium contained in the slurry composition is reduced, and the slurry composition becomes non-uniform, resulting in reduced smoothness of the ceramic compact. I have something to do. In addition, since the number of oxyethylene groups is relatively too large, the thermal decomposition is difficult to proceed, and the degreasing property may be lowered.
  • the component (B) of the present invention can be produced, for example, by adding ethylene oxide corresponding to EO to the starting material alcohol, and then adding propylene oxide corresponding to PO. Addition of alkylene oxides is well known to those skilled in the art, and those skilled in the art can produce component (B) by appropriately setting the addition conditions.
  • the content of component (A) in the ceramic molding binder composition of the present invention is 15 to 95% by mass, preferably 40 to 95% by mass, more preferably 70 to 95% by mass.
  • the content of component (B) in the ceramic molding binder composition of the present invention is 5 to 85% by mass, preferably 5 to 60% by mass, more preferably 5 to 30% by mass.
  • the total content of component (A) and component (B) is 100% by mass. If the content of component (B) is too high, the strength of the ceramic molded body (particularly the green sheet) formed from the slurry composition of the present invention may be insufficient, and the smoothness of the molded body may be impaired. be. If the content of component (B) is too low, the extensibility of the ceramic molded body (especially green sheet) formed from the slurry composition of the present invention may be impaired.
  • the slurry composition of the present invention contains the ceramic molding binder composition, ceramic powder, dispersant, and organic dispersion medium.
  • Each of the ceramic powder, dispersant, and organic dispersion medium may be used alone or in combination of two or more.
  • the ceramic powder used in the present invention may be either oxide ceramic powder or non-oxide ceramic powder.
  • oxide ceramic powder include alumina, titania, zirconia, barium titanate, and lead zirconate titanate.
  • non-oxide ceramic powders include silicon carbide and silicon nitride.
  • the average diameter of the ceramic powder is preferably 0.05 to 50.0 ⁇ m, more preferably 0.10 to 10.0 ⁇ m, still more preferably 0.20 to 5.00 ⁇ m, particularly preferably 0.20 to 1.00 ⁇ m. is.
  • the average diameter of the ceramic powder is the particle diameter at which the volume cumulative detection frequency is 50% in the volume-based particle size distribution measured using a laser diffraction scattering particle size distribution analyzer, that is, the median diameter. means d50.
  • the dispersant used in the present invention is not particularly limited, and any of cationic dispersants, anionic dispersants, nonionic dispersants, and amphoteric dispersants can be used. good too.
  • Examples of cationic dispersants include polyamine-based dispersants.
  • Examples of the anionic dispersant include carboxylic acid-based dispersants, phosphate-based dispersants, sulfate-based dispersants, and sulfonate-based dispersants.
  • nonionic dispersants include polyethylene glycol-based dispersants.
  • polymeric dispersants include polymeric polycarboxylic acid-based dispersants.
  • Organic dispersion medium As the organic dispersion medium used in the present invention, a highly volatile organic dispersion medium is preferable from the viewpoint of the sheet formability of the slurry composition.
  • a highly volatile organic dispersion medium is an organic solvent that is liquid at 20° C. and has a boiling point of 150° C. or lower, preferably 100° C. or lower. Examples thereof include methanol, ethanol, toluene, acetone, and methyl ethyl ketone.
  • One of these organic dispersion media may be used alone, or two or more of them may be used in combination, but it is preferable to use two or more of a plurality of organic dispersion media in combination.
  • a polar dispersion medium such as ethanol or methyl ethyl ketone and a nonpolar dispersion medium such as toluene in combination. 9:1 to 1:9 is preferred, 4:1 to 1:4 is more preferred, and 2:1 to 1:2 is even more preferred.
  • the content of the ceramic molding binder composition in the slurry composition of the present invention is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, more preferably 5 to 20 parts by mass, based on 100 parts by mass of the ceramic powder. Parts by mass are more preferred.
  • the content of the dispersant in the slurry composition of the present invention is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, more preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the ceramic powder. 2 parts by mass is more preferred.
  • the content of the organic dispersion in the slurry composition of the present invention is preferably 10 to 500 parts by mass, more preferably 20 to 200 parts by mass, and even more preferably 25 to 100 parts by mass with respect to 100 parts by mass of the ceramic powder. .
  • the slurry composition of the present invention contains, in addition to the above binder composition, ceramic powder, dispersant, and organic dispersion medium, other components different from these within the range that does not impair the effects of the present invention.
  • Other components include, for example, antifoaming agents and the like.
  • a ceramic compact such as a green sheet can be produced using the slurry composition of the present invention.
  • Such a method is not particularly limited, and a known method can be adopted.
  • Known methods include, for example, a press molding method and a sheet molding method.
  • a process for manufacturing a green sheet as a ceramic compact by a sheet molding method will be briefly described.
  • a slurry composition is applied onto a support and the slurry composition is dried to produce a green sheet.
  • the support used in the sheet molding method is not particularly limited, and known supports can be used. Materials for the support include, for example, polyethylene terephthalate, polycarbonate, stainless steel (SUS), and glass. Examples of the coating method include known coating methods such as a doctor blade method.
  • a method for drying the applied slurry composition is not particularly limited, and drying can be performed by a known method using a dryer.
  • the dryer includes, for example, a drying oven, a hot dryer and the like.
  • the atmosphere during drying may be an air atmosphere or an inert gas atmosphere such as nitrogen gas.
  • the pressure during drying may be normal pressure or reduced pressure.
  • the drying temperature and time vary depending on the components of the slurry composition, but the temperature is, for example, 30 to 150° C., and the drying time is, for example, 5 to 60 minutes. Moreover, it is preferable to apply the slurry composition so that the film thickness of the green sheet obtained after drying is 0.5 to 20.0 ⁇ m.
  • a green sheet is peeled off from the support, and a conductive paste that will be an internal electrode is applied to the surface by screen printing or the like.
  • a plurality of these sheets are alternately stacked and heat-pressed to obtain a laminate, which is cut into chips. forming a laminated laminate.
  • a degreasing treatment is performed to remove the organic components contained in the chipped laminate, and a fired ceramic product is obtained by firing.
  • An MLCC is manufactured by sintering an external electrode on the end face of the fired ceramic product.
  • the degreasing method is not particularly limited, and a known method can be used.
  • the binder composition that is, component (A) and component (B) are produced. can be removed.
  • MMA methyl methacrylate
  • IBMA isobutyl methacrylate
  • HEMA 2-hydroxyethyl methacrylate
  • St styrene
  • INA isononanol
  • PVB polyvinyl butyral (“S-Lec (registered trademark) BM-2” manufactured by Sekisui Chemical Co., Ltd.)
  • Components (A-1) to (A-5) which are copolymers obtained in Synthesis Examples 1 to 5, types of monomers used in the synthesis of these copolymers, and these monomers Table 1 shows the content of constituent units derived from these copolymers and the weight average molecular weights of these copolymers.
  • the crude product was taken out from the autoclave and neutralized with hydrochloric acid so that the pH measured according to JIS K1557-5 was 6-7.
  • the crude product after neutralization was subjected to vacuum treatment at 100° C. for 1 hour in order to remove the water derived from hydrochloric acid from the crude product, and finally the salt was removed by filtration to obtain 1913 g of component (B). -1) was obtained.
  • Components (B-1) to (B-4) obtained in Synthesis Example 6 to Synthesis Example 9, Comparative Synthesis Examples 1 to 2, Component (B'-1), Component (B'-2) , and their starting materials, R 5 , p, q and p/q in formula (3) above are listed in Table 2.
  • Components (B-1) to (B-4) correspond to the component (B) of the present invention, but the components (B'-1) and (B'-2) in the formula (3) Since p or q is out of the specified range and p/q is also out of the specified range, it does not correspond to the component (B) of the present invention.
  • Examples 1 to 10 and Comparative Examples 1 to 5 [Preparation of Binder Composition for Ceramic Molding] Using the component (A) and the component (B) produced above, respectively, in the combinations and mixing ratios shown in Tables 3 and 4 below, a total of 10 parts by mass of the component (A) and the component (B), 10 parts by mass of toluene 10 parts by mass of ethanol and 10 parts by mass of ethanol to obtain a binder composition for molding ceramics.
  • PVB was used as component (A') instead of component (A).
  • ⁇ W/ ⁇ T was calculated from the following formula, and the degreasing speed was evaluated according to the following criteria.
  • ⁇ W/ ⁇ T (90-50)/( T90 - T50 ) (Evaluation criteria for degreasing rate) ⁇ : ⁇ W / ⁇ T is less than 1.00 ⁇ : ⁇ W / ⁇ T is 1.00 or more and less than 1.20 ⁇ : ⁇ W / ⁇ T is 1.20 or more
  • Green sheet strength A strip-shaped piece with a length of 60 mm and a width of 20 mm is cut out from the produced green sheet, and a tensile test is performed at a speed of 10 mm / min with an autograph (manufactured by Shimadzu Corporation: EZ-SX) to measure the tensile strength. Then, the green sheet strength was evaluated according to the following criteria. (Evaluation criteria for green sheet strength) ⁇ : Tensile strength is 4.50 N/mm 2 or more ⁇ : Tensile strength is 4.00 N/mm 2 or more and less than 4.50 N/mm 2 ⁇ : Tensile strength is less than 4.00 N/mm 2
  • Green sheet smoothness The surface roughness of the produced green sheet was measured using a surface roughness meter, the arithmetic mean roughness ( ⁇ m) was calculated, and the green sheet smoothness was evaluated according to the following criteria. (Evaluation criteria for green sheet smoothness) ⁇ : Arithmetic mean roughness less than 0.050 ⁇ m ⁇ : Arithmetic mean roughness 0.050 ⁇ m or more and less than 0.060 ⁇ m ⁇ : Arithmetic mean roughness 0.060 ⁇ m or more
  • Evaluation results of the ceramic slurries of Examples 1 to 10 and Comparative Examples 1 to 5 (that is, each parameter for calculating the degreasing rate and the degreasing rate, the residual rate and the degreasing property, the tensile strength and the green sheet strength, Elongation at break and resulting green sheet elongation, arithmetic mean roughness and resulting green sheet smoothness) are shown in Tables 3 and 4.
  • a green sheet obtained from the slurry composition of the present invention can be used, for example, for manufacturing a single-layer ceramic substrate for mounting chip resistors or light-emitting elements.

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition de liant pour moulage céramique comprenant de 15 à 95 % en masse de composant (A) et de 5 à 85 % en masse de composant (B). Composant (A) : un copolymère dans lequel la teneur en pourcentage d'une unité structurale dérivée de la formule (1) est de 70 à 99 % en moles, la teneur en pourcentage d'une unité structurale dérivée de la formule (2) est de 1 à 30 % en moles, la teneur en pourcentage d'autres unités structurales est de 0 à 29 % en moles, et qui a un poids moléculaire moyen en poids de 50 000 à 1 000 000. Formule (1) : CH2=CR1-COO-R2 (R1 représente un atome d'hydrogène ou un groupe méthyle et R2 représente un groupe alkyle ayant de 1 à 8 atomes de carbone).　Formule (2) : CH2=CR3-COO-R4 (R3 représente un atome d'hydrogène ou un groupe méthyle, et R4 représente un groupe hydroxyl alkyle ayant 1 à 2 groupes hydroxyle et ayant 1 à 8 atomes de carbone). Composant (B) : un composé représenté par la formule (3). Formule (3) : R5O-(EO)p-(PO)q-H (R5 représente un groupe alkyle ayant 9 atomes de carbone, EO représente un groupe oxyéthylène, PO représente un groupe oxypropylène, p représente le nombre molaire d'addition moyen d'EO et vaut de 3 à 9, q représente le nombre molaire d'addition moyen de PO et vaut 2 à 4, et p/q = 1,0 à 3,0 est satisfait).
PCT/JP2022/036168 2021-10-07 2022-09-28 Composition de liant pour moulage de céramique et composition de suspension WO2023058521A1 (fr)

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KR1020247002130A KR20240072989A (ko) 2021-10-07 2022-09-28 세라믹 성형용 바인더 조성물 및 슬러리 조성물

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JPH0733533A (ja) * 1993-06-28 1995-02-03 Lion Corp セラミックグリーンシート用添加剤
JPH10167836A (ja) * 1996-12-17 1998-06-23 Mitsubishi Chem Corp セラミック成形用バインダー樹脂
WO2011148521A1 (fr) * 2010-05-26 2011-12-01 第一工業製薬株式会社 Composition se présentant sous la forme d'une dispersion
JP2013071986A (ja) * 2011-09-27 2013-04-22 Goo Chemical Co Ltd 焼成用バインダー組成物
JP2015231924A (ja) * 2014-06-10 2015-12-24 日油株式会社 積層セラミックコンデンサ製造用のスラリー組成物およびセラミックグリーンシート
WO2020179856A1 (fr) * 2019-03-06 2020-09-10 日油株式会社 Auxiliaire de stratification de feuilles de céramique crue et composition de feuille de céramique crue

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Publication number Priority date Publication date Assignee Title
JP4870919B2 (ja) 2004-09-27 2012-02-08 積水化学工業株式会社 セラミックグリーンシート用スラリー組成物、セラミックグリーンシート及び積層セラミックコンデンサ
JP6376818B2 (ja) 2014-04-14 2018-08-22 日本カーバイド工業株式会社 セラミック成形用バインダー組成物及びこれを用いたセラミックグリーンシート
JP2019182925A (ja) 2018-04-03 2019-10-24 住友ベークライト株式会社 樹脂組成物、及び樹脂シート

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0733533A (ja) * 1993-06-28 1995-02-03 Lion Corp セラミックグリーンシート用添加剤
JPH10167836A (ja) * 1996-12-17 1998-06-23 Mitsubishi Chem Corp セラミック成形用バインダー樹脂
WO2011148521A1 (fr) * 2010-05-26 2011-12-01 第一工業製薬株式会社 Composition se présentant sous la forme d'une dispersion
JP2013071986A (ja) * 2011-09-27 2013-04-22 Goo Chemical Co Ltd 焼成用バインダー組成物
JP2015231924A (ja) * 2014-06-10 2015-12-24 日油株式会社 積層セラミックコンデンサ製造用のスラリー組成物およびセラミックグリーンシート
WO2020179856A1 (fr) * 2019-03-06 2020-09-10 日油株式会社 Auxiliaire de stratification de feuilles de céramique crue et composition de feuille de céramique crue

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