WO2016132814A1 - Composition de résine destinée à des pâtes cuites et pâte cuite - Google Patents

Composition de résine destinée à des pâtes cuites et pâte cuite Download PDF

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Publication number
WO2016132814A1
WO2016132814A1 PCT/JP2016/051834 JP2016051834W WO2016132814A1 WO 2016132814 A1 WO2016132814 A1 WO 2016132814A1 JP 2016051834 W JP2016051834 W JP 2016051834W WO 2016132814 A1 WO2016132814 A1 WO 2016132814A1
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meth
monomer
paste
acrylic polymer
nitrogen
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PCT/JP2016/051834
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English (en)
Japanese (ja)
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広斗 松本
津介 藪中
修一 後藤
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綜研化学株式会社
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Priority to JP2017500566A priority Critical patent/JP6667497B2/ja
Priority to CN201680009520.6A priority patent/CN107207820B/zh
Publication of WO2016132814A1 publication Critical patent/WO2016132814A1/fr

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    • 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
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • 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
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • 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 fired paste resin composition, a fired paste using the fired paste resin composition, and uses thereof.
  • Firing paste is a composition containing inorganic powder (filler) such as metal powder, metal oxide powder, ceramic powder, glass powder, fluorescent powder, binder resin, solvent, etc., and is fired after coating on a substrate. And a paste-like composition used to thermally decompose the binder resin to form a pattern of inorganic powder.
  • inorganic powder iller
  • a paste-like composition used to thermally decompose the binder resin to form a pattern of inorganic powder.
  • a conductive paste composition which is a fired paste containing conductive powder, is used for circuit formation, capacitor manufacture, and the like.
  • Ceramic paste compositions containing ceramic powder and glass paste compositions containing glass powder are used for dielectric layers of plasma display panels (PDP), dielectric layers of multilayer ceramic capacitors (MLCC), and fluorescent display tubes.
  • a paste composition containing tin-doped indium oxide (ITO) is used as a transparent electrode material or the like for manufacturing a circuit for a driving part of a PDP, a liquid crystal display panel (LCD), a touch panel, a solar cell panel, or the like.
  • paste compositions containing phosphors are used for inorganic electroluminescence (EL) devices, PDPs, and the like
  • paste compositions containing silver are used for solar cells, light emitting diodes (LEDs), and the like.
  • the baking paste can be applied to the base material by, for example, a screen printing method, a die coating printing method, a doctor blade printing method, a roll coating printing method, an offset printing method, a gravure printing method, a flexographic printing method, an ink jet printing method, a dispensing printing method or the like.
  • a casting method or the like for processing into a sheet shape is used.
  • the binder resin used in the fired paste is required to have good coating properties on the base material and dispersibility of the inorganic powder by the coating method.
  • Patent Document 1 Japanese Patent Laid-Open No. 2013-58403 discloses an acrylic monomer having an ester substituent having 1 to 6 carbon atoms and an acrylic monomer having a hydroxyl group or polyethylene oxide as the ester substituent (Metal). ) A conductive paste containing an acrylic resin, conductive particles, and an organic solvent is described.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2013-227514 describes a resin composition for paste in which an insoluble polymer having a specific value calculated from a solubility parameter and a soluble polymer are combined.
  • the coating property of the fired paste is not sufficient, and further improvement is desired.
  • An object of the present invention is to provide a resin composition for a firing paste that exhibits high viscosity and pseudoplasticity of the paste, is excellent in coating property, and has good firing properties, and a firing paste using the same.
  • the configuration of the present invention is as follows [1] to [6].
  • Based polymer (B) A resin composition for a baked paste, characterized by blending such that the molar ratio of acidic group-containing monomer: nitrogen-containing monomer is 5:95 to 85:15.
  • a fired paste comprising the resin composition for a fired paste according to any one of [1] to [3], an inorganic powder, and a solvent.
  • the resin composition for fired paste of the present invention forms a network by hydrogen bonding between polymers by blending an acidic group-containing polymer and a nitrogen-containing polymer at a predetermined ratio, which is impossible with conventional acrylic resins.
  • a baking paste resin it is possible to provide a baking paste suitable for various printing methods.
  • (meth) acryloyl is used to indicate acryloyl and / or methacryloyl
  • (meth) acrylate is used to indicate acrylate and / or methacrylate
  • (Meth) acryl is used to indicate both or one of acrylic and methacrylic.
  • the resin composition for a fired paste of the present invention has a weight average molecular weight of 10,000 to 500,000, an acidic group-containing (meth) acrylic polymer (A) having a glass transition temperature of 30 ° C. or higher, a weight average molecular weight of 10,000 to 500,000, It is a blend with a nitrogen-containing (meth) acrylic polymer (B) having a glass transition temperature of 30 ° C. or higher.
  • the acidic group-containing (meth) acrylic polymer (A) includes an acidic group-containing monomer (monomer (a1)) containing a carboxyl group and / or a sulfonic acid group, and a (meth) acrylic acid alkyl ester (monomer (a2)). It is obtained by copolymerizing a monomer component (a) containing
  • Acid group-containing monomer (monomer (a1)) is a polymerizable monomer containing a carboxyl group and / or a sulfone group as an acidic group.
  • Examples of the monomer (a1) which is an acidic group-containing monomer include ⁇ -carboxyethyl (meth) acrylate, 5-carboxypentyl (meth) acrylate, mono (meth) acryloyloxyethyl ester succinate, and ⁇ -carboxypolyester.
  • Examples include carboxyl group-containing (meth) acrylates such as caprolactone mono (meth) acrylate; acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, and the like.
  • Examples of the sulfonic acid group-containing monomer include vinyl sulfonic acid and styrene sulfonic acid, and examples thereof include a (meth) acrylic monomer having a sulfate group in the side chain.
  • the amount of the monomer (a1) used is usually 0.1 to 10% by mass, preferably 0.5 to 5%. % By mass, more preferably 1 to 5% by mass.
  • (Meth) acrylic acid alkyl ester (monomer (a2))
  • Examples of the monomer (a2) which is a (meth) acrylic acid alkyl ester include compounds represented by CH 2 ⁇ CR 1 —COOR 2 .
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is an alkyl group having 1 to 18 carbon atoms.
  • the alkyl group preferably has 1 to 4 carbon atoms.
  • Examples of the monomer (a2) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, and tert-butyl (meth) acrylate.
  • These monomers (a2) are selected such that the Tg of the resulting acidic group-containing (meth) acrylic polymer (A) is 30 ° C. or higher, and may be used alone or in combination of two or more. It may be used.
  • the amount of the monomer (a2) used is usually 30 to 97% by mass, preferably 40 to 95% by mass, and more. Preferably, it is 50 to 90% by mass.
  • the monomer (a2) is contained in the above range, a resin composition for a fired paste having good solubility in various solvents and good fireability can be obtained.
  • the monomer component (a) forming the acidic group-containing (meth) acrylic polymer (A) is a hydroxyl group-containing monomer (monomer (a3)) as a copolymer component from the viewpoint of improving the dispersibility and viscosity characteristics of various fillers. May be included. However, the hydroxyl group-containing (meth) acrylamides described in the monomer (b1) described later are not included in the monomer (a3).
  • Examples of the monomer (a3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl.
  • Examples include hydroxyalkyl (meth) acrylates such as (meth) acrylate.
  • the number of carbon atoms of the hydroxyalkyl group in the hydroxyalkyl (meth) acrylate is usually 2 to 8, preferably 2 to 6.
  • a hydroxyl group-containing monomer having a cyclic alkyl such as hydroxycyclohexyl (meth) acrylate can also be used.
  • the amount used is usually 0.5 to 100% by mass in the monomer component (a). It is 30% by mass, preferably 1 to 25% by mass, more preferably 3 to 15% by mass.
  • the monomer (a3) is contained in the above range, it is possible to obtain a fired paste having good dispersibility of various fillers and having a viscosity suitable for coating.
  • the monomer component (a) that forms the other (meth) acrylic acid ester acidic group-containing (meth) acrylic polymer (A) includes, in addition to the monomers (a1) to (a3), optional copolymerization components such as , Alkoxyalkyl (meth) acrylates, alkoxypolyalkylene glycol mono (meth) acrylates, alicyclic groups or aromatic ring-containing (meth) acrylates and other (meth) acrylic esters.
  • alkoxyalkyl (meth) acrylate examples include methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl ( And (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate.
  • alkoxypolyalkylene glycol mono (meth) acrylate examples include methoxydiethylene glycol mono (meth) acrylate, methoxydipropylene glycol mono (meth) acrylate, ethoxytriethylene glycol mono (meth) acrylate, ethoxydiethylene glycol mono (meth) acrylate, And methoxytriethylene glycol mono (meth) acrylate.
  • Examples of the alicyclic group or aromatic ring-containing (meth) acrylate include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and phenyl (meth) acrylate.
  • the amount of the other (meth) acrylic acid ester used is preferably 30% by mass or less. Preferably it is 20 mass% or less.
  • the monomer component forming the acidic group-containing (meth) acrylic polymer (A) is, for example, styrene based on a range that does not impair the physical properties of the acidic group-containing (meth) acrylic polymer (A).
  • Other copolymerizable monomers such as monomers and vinyl acetate can be included in the monomer component (a).
  • styrenic monomer examples include styrene; methyl styrene, dimethyl styrene, trimethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene, and other alkyl styrenes; fluorostyrene, chlorostyrene, bromostyrene, Halogenated styrene such as dibromostyrene and iodinated styrene; nitrostyrene, acetylstyrene, and methoxystyrene.
  • the amount of the other copolymerizable monomer used is preferably 20% by mass or less, more preferably. It is 10 mass% or less.
  • the weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) method of the acidic group-containing (meth) acrylic polymer (A) is from 10,000 to 500,000, preferably from 20,000 to polystyrene. 300,000, more preferably 30,000 to 150,000.
  • the glass transition temperature (Tg) is obtained by measurement with a differential scanning calorimeter (DSC).
  • the measurement conditions were 5 mg of the sample in a nitrogen atmosphere, the temperature was increased from ⁇ 100 ° C. to 200 ° C. at a temperature increase rate of 20 ° C./min in the first measurement (1st RUN), and the temperature decrease rate was 99.9 ° C./min.
  • the temperature was increased from ⁇ 100 ° C. to 200 ° C. at a temperature increase rate of 20 ° C./min in the second measurement (2ndnRUN).
  • the glass transition temperature is 2nd RUN, where the baseline of the DSC curve measured when the temperature is raised from ⁇ 100 ° C. to 200 ° C. changes to the sigmoid type in the endothermic direction. Refers to the intersection of the extension of the baseline on the low temperature side and the tangent of the inflection point in the sigmoid.
  • the Tg of the acidic group-containing (meth) acrylic polymer (A) determined by DSC is usually 30 ° C. or higher, preferably 50 to 150 ° C.
  • a resin composition for a fired paste having excellent stringiness and fireability can be obtained.
  • the Tg of the acidic group-containing (meth) acrylic polymer (A) is lower than 30 ° C., the disproportionation termination reaction during polymer polymerization is reduced, so that the depolymerization is poor, and the carbon after firing the resin composition for firing paste Residues may remain and cause problems such as stickiness of the printing surface.
  • the nitrogen-containing (meth) acrylic polymer (B) is obtained by copolymerizing a monomer component (b) containing a nitrogen-containing monomer (monomer (b1)) and a (meth) acrylic acid alkyl ester (monomer (b2)). It is obtained.
  • Nitrogen-containing monomer (monomer (b1)) examples include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-iso-propyl (meth) acrylamide, N-tert-butyl ( (Meth) acrylamides such as (meth) acrylamide; Cyclic (meth) acrylamides such as (meth) acryloylmorpholine, (meth) acryloylpyrrolidone, (meth) acryloylpyrrolidine; N- (hydroxymethyl) (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N- (1-hydroxypropyl) (meth) acrylamide, N- (3-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meth)
  • N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, tert-butylaminoethyl (meth) acrylate, N-methylaminopropyl ( (Meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-ethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, 2,2,6,6-tetramethyl-4- Piperidyl (meth) acrylate, 1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate, ureido (meth) acrylate, and the like can also be used.
  • the amount of the monomer (b1) used is usually 1 to 50% by mass, preferably 3 to 40% by mass, more preferably Is 5-30% by mass.
  • the same monomer (a2) can be used.
  • the amount of the monomer (b2) used is usually 30 to 97% by mass, preferably 40 to 95% by mass, more preferably Is 50 to 90% by mass.
  • the monomer (b2) is contained within the above range, a resin composition for a fired paste that is excellent in terms of solubility in various solvents and fireability can be obtained.
  • the monomer component (b) forming the nitrogen-containing (meth) acrylic polymer (B) contains a hydroxyl group-containing monomer (monomer (b3)) as a copolymerization component from the viewpoint of improving the dispersibility and viscosity characteristics of various fillers.
  • the monomer (b3) may be the same as the monomer (a3).
  • the amount of the monomer (b3) used is 0.5 to 30% by mass, preferably 1 to 25% by mass. Preferably, the content is 3 to 15% by mass.
  • the monomer (b3) is contained in the above range, it is possible to obtain a fired paste having good dispersibility of various fillers and having a viscosity suitable for coating.
  • the monomer component (b) forming the nitrogen-containing (meth) acrylic polymer (B) can be contained in the monomer component (a) in addition to the monomers (b1) to (b3) as long as the physical properties are not impaired.
  • the other (meth) acrylic acid ester and the copolymerizable monomer may contain any copolymerization component as described above.
  • ⁇ Physical properties of nitrogen-containing (meth) acrylic polymer (B)> The weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) method of the nitrogen-containing (meth) acrylic polymer (B) is usually from 10,000 to 500,000, preferably from 20,000 to polystyrene in terms of polystyrene. 300,000, more preferably 30,000 to 150,000.
  • the glass transition temperature (Tg) of the nitrogen-containing (meth) acrylic polymer (B) is the same as that of the acidic group-containing (meth) acrylic polymer (A), but the glass transition temperature (Tg) is a differential scanning calorimeter. (DSC).
  • the Tg of the nitrogen-containing (meth) acrylic polymer (B) determined by DSC is usually 30 ° C. or higher, preferably 50 to 150 ° C.
  • a resin composition for a fired paste having excellent stringiness and fireability can be obtained.
  • the Tg of the nitrogen-containing (meth) acrylic polymer (B) is lower than 30 ° C., the disproportionation stop reaction during polymer polymerization is reduced, so that the depolymerization is poor and the carbon residue after firing the resin composition for firing paste May remain and may cause problems such as stickiness of the printing surface.
  • the polymerization method of the polymer (B) is not particularly limited, but it is usually preferable to use solution polymerization.
  • solution polymerization is carried out by charging a predetermined organic solvent, each monomer, and a polymerization initiator in a polymerization tank and heating them for several hours with stirring at an appropriate polymerization temperature in an inert gas stream such as nitrogen. Is called.
  • at least a part of the organic solvent, each monomer, the polymerization initiator, and / or the chain transfer agent may be sequentially added.
  • aromatic carbonization exemplified by benzene, toluene, ethylbenzene, n-propylbenzene, tert-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, aromatic naphtha, etc.
  • alkyl acetate examples of alkyl include methyl, ethyl, propyl, butyl, pentyl and the like.
  • Esters exemplified by methyl benzoate and the like ethylene glycol or diethylene glycol monoacetate, diacetate, alkyl Ether acetate (eg diethyleneglycol) Monobutyl ether acetate), derivatives of ethylene glycol exemplified by monoalkyl ether, dialkyl ether, etc .; monoacetate, diacetate, alkyl ether acetate, monoalkyl of any one of propylene glycol, dipropylene ethylene glycol, tripropylene glycol Propylene glycol derivatives exemplified by ethers (for example, tripropylene glycol monobutyl ether) and dialkyl ethers; ketones exemplified by acetone, methyl ethyl ketone, methyl-iso-butyl ketone, isophorone, cyclohexanone, methylcyclohexanone, texanol (2,2 , 4-
  • a solvent having a high boiling point is preferable, and specifically, a solvent having a boiling point of 50 to 300 ° C. is more preferable.
  • Polymerization initiators include benzoyl peroxide, lauroyl peroxide, caproyl peroxide, di-tert-butyl peroxide, di-iso-propyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, tert-butyl.
  • Organic peroxides exemplified by peroxybivalate and the like; 2,2′-azobis-iso-butyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobis-4-methoxy
  • An azo compound exemplified by -2,4-dimethylvaleronitrile and the like can be used alone or in combination.
  • the amount of the polymerization initiator used is that of the monomer component (a) that forms the acidic group-containing (meth) acrylic polymer (A) or the monomer component (b) that forms the nitrogen-containing (meth) acrylic polymer (B). Generally, it is 0.01 to 5 parts by mass per 100 parts by mass in total, and is preferably in the range of 0.02 to 2 parts by mass.
  • chain transfer agent examples include n-dodecyl mercaptan, 2-mercaptoethanol, thioglycerol, ⁇ -mercaptopropionic acid, and ⁇ -methylstyrene dimer.
  • chain transfer agent By using a chain transfer agent, the weight average molecular weights of the acidic group-containing (meth) acrylic polymer (A) and nitrogen-containing (meth) acrylic polymer (B) to be produced can be controlled.
  • chain transfer agents may be used individually by 1 type, and may use 2 or more types.
  • the chain transfer agent is added to 100 parts by mass of the monomer component (a) that forms the acidic group-containing (meth) acrylic polymer (A) or the monomer component (b) that forms the nitrogen-containing (meth) acrylic polymer (B).
  • it can be used usually in an amount of 1 part by mass or less, preferably in the range of 0.01 to 0.5 part by mass.
  • the polymerization temperature is preferably 40 to 180 ° C. When the polymerization temperature is in the above range, a sufficient reaction rate can be obtained, and depolymerization due to the temperature being too high does not occur.
  • the reaction time at the above polymerization temperature is preferably 4 to 16 hours. When the reaction time is within the above range, the reaction can be allowed to proceed completely.
  • the polymerization initiator in addition to adding the polymerization initiator at the beginning of the polymerization, it is also preferable to add the polymerization initiator after the polymerization has progressed to some extent. . In that case, it is preferable that the usage-amount of a polymerization initiator exists in the said range in the sum total of all the addition amounts.
  • the resin composition for baking paste according to the present invention is a blend of an acidic group-containing (meth) acrylic polymer (A) and a nitrogen-containing (meth) acrylic polymer (B).
  • the monomer (a1) which is an acidic group-containing monomer and the monomer (b1) which is a nitrogen-containing monomer is 100% by mole.
  • the monomer (a1): monomer (b1) 5: 95 to 85:15.
  • it is in the range of 10:90 to 80:20, more preferably in the range of 40:60 to 80:20.
  • the viscosity of the resin for the baking paste is too low, and it becomes difficult to form a coating film when a composition containing the resin for the baking paste is applied to the substrate.
  • it is desirable that the viscosity of the composition is lowered during coating. This is because, for example, when the resin composition for firing paste is applied to the substrate by screen printing, the resin composition for firing paste is applied by rubbing with a squeegee on a fine mesh. This is because it is necessary to pass through the street cleanly.
  • the resin for firing paste is required to have a trade-off property that it has an appropriate viscosity and has an appropriate fluidity (pseudoplasticity) by applying a stress such as rubbing or stirring during coating.
  • a hydrogen bond network is formed by the interaction between the acidic group and the nitrogen-containing group. And while this network produces moderate viscosity in the resin for baking paste, it is weaker than a covalent bond, so it is easily cut by stress such as rubbing or stirring during coating.
  • the fired paste resin blended with the acidic group-containing (meth) acrylic polymer (A) and the nitrogen-containing (meth) acrylic polymer (B) has an appropriate viscosity and is stressed by rubbing or stirring. Is considered to exhibit good thixotropic properties such as fluidity and good coating properties.
  • the fired paste of the present invention comprises a resin composition for a fired paste, a solvent (C) and an inorganic material comprising a blend of the acidic group-containing (meth) acrylic polymer (A) and the nitrogen-containing (meth) acrylic polymer (B).
  • a powder (D) is included, and a dispersant (E) is further included as necessary.
  • the fired paste of the present invention for fired paste is a resin composition for fired paste (blend of acidic group-containing (meth) acrylic polymer (A) and nitrogen-containing (meth) acrylic polymer (B)) in 100% by weight of fired paste. 1) to 20% by mass, and more preferably 4 to 10% by mass.
  • solvent (C) and Are compatible with each other can impart an appropriate viscosity to the resulting fired paste, and the dispersibility of the inorganic powder (D) of the fired paste and the binding property of the fired paste to the substrate are also good.
  • Solvent (C) The solvent (C) is not limited as long as no residue remains after firing and can dissolve the acidic group-containing (meth) acrylic polymer (A) and the nitrogen-containing (meth) acrylic polymer (B). Can be used.
  • solvent (C) for example, terpineol, dihydroterpineol, dihydroterpinyl acetate, butyl carbitol acetate, dipropylene glycol, dipropylene glycol monomethyl ether, butyl carbitol, diethylene glycol alkyl ether acetate (here, as alkyl , Ethyl, propyl, n-butyl, etc.
  • ethylene glycol alkyl ether acetate ethylene glycol diacetate, diethylene glycol alkyl ether, ethylene glycol alkyl ether, dipropylene glycol alkyl ether, propylene glycol alkyl ether acetate 2,2,4-trimethylpentane-1,3-diol mono-iso-butyrate, 2, Organic solvents such as 2,4-trimethyl-1,3-diol di -iso- butyrate and the like. These solvents can be used alone or in combination of two or more.
  • terpineol, dihydroterpineol, dihydroterpinyl acetate, and butyl carbitol acetate are more preferable from the viewpoint of boiling point and leveling property.
  • the boiling point of the solvent (C) is preferably 150 to 300 ° C., more preferably 200 to 290 ° C., and further preferably 220 to 280 ° C.
  • the drying speed of the paste after screen printing the fired paste does not clog the plate while the drying speed is too slow and the workability does not deteriorate. .
  • the fired paste of the present invention preferably contains 20 to 70% by weight, more preferably 30 to 60% by weight of the solvent (C) in 100% by weight of the fired paste.
  • the compatibility with the resin composition for a baking paste is good, and the obtained baking paste can exhibit a desired viscosity.
  • inorganic powder (D) examples include metal powders, metal oxide powders, glass powders, pigment powders, phosphor powders, ceramic powders, and powders imparting photosensitivity thereto. These inorganic powders are selected according to the use, but can be used alone or in combination of two or more.
  • the metal powder and metal oxide powder are preferably used as conductive powder, and the glass powder and ceramic powder are preferably used as dielectric powder.
  • Examples of the metal powder include powder made of nickel, palladium, platinum, gold, silver, copper, iron, aluminum, tungsten, alloys thereof, and the like.
  • Examples of the metal oxide powder include tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), and fluorine-doped tin oxide (FTO).
  • Examples of the glass powder include bismuth oxide glass, silicate glass, lead glass, zinc glass, boron glass, and glass powders of various silicon oxides.
  • Examples of the ceramic powder include alumina, zirconia, titanium oxide, barium titanate, alumina nitride, silicon nitride, and boron nitride.
  • the fired paste of the present invention preferably contains 20 to 70% by weight, more preferably 35 to 60% by weight of the inorganic powder (D) in 100% by weight of the fired paste.
  • each performance such as conductivity of the fired product obtained from the fired paste of the present invention is good, and the dispersibility in the fired paste is also good.
  • Dispersant (E) examples include a cationic dispersant, an anionic dispersant, a nonionic dispersant, an amphoteric surfactant, and a polymer dispersant. These dispersants can be used alone or in admixture of two or more.
  • Examples of cationic dispersants include polyamine dispersants.
  • Examples of the anionic dispersant include carboxylic acid, phosphate ester, sulfate ester, and sulfonate ester dispersants.
  • Examples of nonionic dispersants include polyethylene glycol dispersants.
  • Examples of the amphoteric surfactant include a surfactant having a carboxylic acid and a quaternary ammonium salt.
  • Examples of the polymer dispersant include polyvinyl pyrrolidone and polyvinyl alcohol.
  • the fired paste of the present invention preferably contains 0.01 to 5% by weight of the dispersant (E) in 100% by weight of the fired paste. It is more preferable to contain the mass%.
  • the fired paste of the present invention may contain, in addition to the above-described components, conventionally known plasticizers, wetting agents, antifoaming agents and the like as long as the object of the present invention is not impaired.
  • the baked paste of the present invention has viscosity as will be described later
  • the mixture of the above-described components is kneaded in one step or several steps by using a mixer, a roll or the like alone or in appropriate combination.
  • a mixer, a roll or the like alone or in appropriate combination.
  • it is manufactured. Further, it may be heated at 30 to 150 ° C. as necessary.
  • Viscosity of Firing Paste The viscosity of the calcining paste of the present invention at 25 ° C. is preferably 20 to 200 Pa ⁇ s, more preferably 50 to 200 Pa ⁇ s, still more preferably 100 to 200 Pa ⁇ s.
  • the measuring method of a viscosity is based on the method as described in the below-mentioned Example. The viscosity is a value measured after kneading the fired paste until the composition becomes uniform.
  • the above firing paste is usually applied to a substrate (hereinafter also referred to as “coating step”), dried (hereinafter also referred to as “drying step”), and the laminate is fired (hereinafter referred to as “drying step”). Also referred to as “firing step”.
  • Examples of the base material in the coating process include members such as metals, ceramics, green sheets, plastics, and semiconductors.
  • Application methods in the application process include screen printing, die coating printing, doctor blade printing, roll coating printing, offset printing, gravure printing, flexographic printing, ink jet printing, dispensing printing, etc. There is a casting method, and screen printing is preferred.
  • the solvent (C) is dried.
  • the resin for firing paste (the acidic group-containing (meth) acrylic polymer (A) and the nitrogen-containing (meth) acrylic polymer (B)) is thermally decomposed, under an inert gas stream such as nitrogen gas, Usually, it is carried out at 500 to 1,000 ° C. for 1 to 5 hours.
  • the calcining paste of the present invention include internal electrode pastes used for the production of MLCCs, terminal electrode pastes, internal electrode pastes used for the production of low temperature co-fired ceramics (LTCC), Touch panel screen paste, dielectric paste used for PDP manufacture, partition material paste, phosphor paste, sealing glass paste used for FED sealing and IC package sealing, green sheet paste, etc.
  • LTCC low temperature co-fired ceramics
  • the green sheet means a thin plate-like unfired body obtained by applying a fired paste to a substrate.
  • MLCC can be produced using the following method. Ethanol and a polyvinyl butyral binder are added to a ceramic raw material and mixed and dispersed to prepare a ceramic slurry. Next, this ceramic slurry is formed into a sheet to obtain a ceramic green sheet. Then, the fired paste of the present invention for forming internal electrodes (using nickel powder as the inorganic powder (D)) is printed on this ceramic green sheet to form an internal electrode pattern (conductive paste layer) and dried. .
  • the unfired laminate is fired in an inert gas atmosphere such as N 2 to obtain a ceramic laminate (multilayer ceramic element).
  • a ceramic laminate multilayer ceramic element
  • the Cu paste was applied to both end surfaces of the fired resulting ceramic laminate was baked in an inert gas atmosphere such as N 2, to form the internal electrodes and electrically connected to the terminal electrodes, MLCC is can get.
  • the reaction was carried out at 80 ° C. for 8 hours from the first AIBN addition, and then cooled to room temperature.
  • the obtained polymer solution was dropped into 2000 parts by mass of n-hexane over 30 minutes to produce a polymer precipitate.
  • the polymer precipitate was filtered off with a 200 mesh wire net and dried at 105 ° C. for 8 hours to prepare an acidic group-containing (meth) acrylic polymer (A1) (polymer (A1)).
  • the weight average molecular weight (Mw) of the obtained polymer (A1) was 80,000, and the glass transition temperature (Tg) was 48 ° C.
  • AIBN to add was changed from 0.3 mass part to 2 mass parts, and was prepared.
  • Example 2 to 5 Comparative Examples 1 to 4
  • Example 3 In Example 1, except that the blending type and blending ratio of each polymer were changed as shown in Table 3, a fired paste was produced in the same manner as in Example 1, and each physical property was evaluated. Tables 3 and 4 show the measurement results.
  • Viscosity of the fired pastes obtained in Examples and Comparative Examples was measured at 25 ° C. with an E-type viscometer and evaluated according to the following criteria.
  • Ra When Ra is 0.20 or less: A When Ra exceeds 0.20 and is 0.30 or less: B When Ra is more than 0.30 and 0.40 or less: C When Ra is greater than 0.40: D
  • the time required for the solution existing in the form of a thread to break between the solution surface and the glass rod is measured. Evaluated by criteria.
  • fired pastes of Examples 1 to 6 have appropriate viscosity, good printability, and good fireability.
  • a blend of a polymer (A) and a polymer (B) having an Mw smaller than 500,000 has low viscosity and poor printability.
  • the blend ratio of the monomer (a1) and the monomer (b1) in the blend of the polymer (A) and the polymer (B) is out of the scope of the present invention, or Comparative Examples 5 and 6 As described above, it is difficult to prepare a polymer (A) or a polymer (B) alone having an appropriate viscosity.
  • the resin for firing paste of the present invention is a firing paste that is compatible with various printing methods by achieving both high viscosity and pseudoplasticity by blending polymer (A) and polymer (B) at a predetermined ratio. It can be seen that the resin composition can be provided.
  • the resin composition for fired paste of the present invention can be suitably used as a binder resin component of the fired paste.
  • the fired paste of the present invention is suitably used for applications in which patterns are formed with inorganic powders, such as conductive pastes used in circuit formation and capacitor manufacturing, ceramic pastes containing ceramic powders, glass pastes containing glass powders, etc. Can do.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
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  • Wood Science & Technology (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

La présente invention concerne une composition de résine destinée à des pâtes cuites ; et une pâte cuite qui permet d'obtenir un bon équilibre entre l'augmentation de viscosité et la pseudo-plasticité, et qui est adaptée à divers procédés d'impression. L'invention concerne une résine destinées à des pâtes cuites, qui est caractérisée en ce qu'elle est obtenue par le mélange d'un polymère (méth)acrylique contenant un groupe acide (A) et d'un polymère (méth)acrylique contenant de l'azote (B) de sorte que le rapport molaire du monomère contenant un groupe acide au monomère contenant de l'azote est compris entre 5:95 et 85:15. Le polymère (méth)acrylique contenant un groupe acide (A) est un copolymère d'un constituant monomère contenant un ester de (méth)acrylate d'alkyle et d'un monomère contenant un groupe acide qui contient un groupe choisi parmi un groupe carboxyle et un groupe acide sulfonique, et le polymère (méth)acrylique contenant un groupe acide (A) possède une masse moléculaire moyenne en poids allant de 10 000 à 500 000 et une température de transition vitreuse supérieure ou égale à 30 °C. Le polymère (méth)acrylique contenant de l'azote (B) est un copolymère d'un constituant monomère contenant un monomère contenant de l'azote et un ester de (méth)acrylate d'alkyle, et le polymère (méth)acrylique contenant de l'azote (B) possède une masse moléculaire moyenne en poids allant de 10 000 à 500 000 et une température de transition vitreuse supérieure ou égale à 30 °C.
PCT/JP2016/051834 2015-02-19 2016-01-22 Composition de résine destinée à des pâtes cuites et pâte cuite WO2016132814A1 (fr)

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CN201680009520.6A CN107207820B (zh) 2015-02-19 2016-01-22 烧成糊料用树脂组合物和烧成糊料

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WO2019009124A1 (fr) 2017-07-07 2019-01-10 タツタ電線株式会社 Composition de résine électroconductrice et procédé de fabrication d'un emballage blindé l'utilisant
WO2021064826A1 (fr) * 2019-09-30 2021-04-08 昭和電工マテリアルズ株式会社 Pâte de cuivre d'assemblage, procédé de fabrication de corps assemblé et corps assemblé

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CN112062895A (zh) * 2020-08-06 2020-12-11 无锡亚星新材料科技有限公司 一种烧结浆液用树脂及其制备方法

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JPH06346048A (ja) * 1993-06-08 1994-12-20 Mitsubishi Rayon Co Ltd 蛍光体ペースト組成物
JPH07238239A (ja) * 1994-03-01 1995-09-12 Mitsubishi Rayon Co Ltd 蛍光体ペースト組成物
JPH09111134A (ja) * 1995-07-24 1997-04-28 Sanyo Chem Ind Ltd 熱可逆的増粘性バインダー組成物
JP2001089671A (ja) * 1999-09-22 2001-04-03 Nippon Synthetic Chem Ind Co Ltd:The 焼成用樹脂組成物、焼成用感光性樹脂組成物及びセラミックパターン形成方法
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JPH06346048A (ja) * 1993-06-08 1994-12-20 Mitsubishi Rayon Co Ltd 蛍光体ペースト組成物
JPH07238239A (ja) * 1994-03-01 1995-09-12 Mitsubishi Rayon Co Ltd 蛍光体ペースト組成物
JPH09111134A (ja) * 1995-07-24 1997-04-28 Sanyo Chem Ind Ltd 熱可逆的増粘性バインダー組成物
JP2001089671A (ja) * 1999-09-22 2001-04-03 Nippon Synthetic Chem Ind Co Ltd:The 焼成用樹脂組成物、焼成用感光性樹脂組成物及びセラミックパターン形成方法
JP2005274865A (ja) * 2004-03-24 2005-10-06 Taiyo Ink Mfg Ltd 焼成用感光性ペースト組成物及びそれを用いた焼成物パターン

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019009124A1 (fr) 2017-07-07 2019-01-10 タツタ電線株式会社 Composition de résine électroconductrice et procédé de fabrication d'un emballage blindé l'utilisant
WO2021064826A1 (fr) * 2019-09-30 2021-04-08 昭和電工マテリアルズ株式会社 Pâte de cuivre d'assemblage, procédé de fabrication de corps assemblé et corps assemblé
JPWO2021064826A1 (fr) * 2019-09-30 2021-04-08
JP7392728B2 (ja) 2019-09-30 2023-12-06 株式会社レゾナック 接合用銅ペースト、接合体の製造方法及び接合体

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