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WO2016132814A1 - Resin composition for baked pastes, and baked paste - Google Patents

Resin composition for baked pastes, and baked paste 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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WO
WIPO (PCT)
Prior art keywords
meth
monomer
paste
acrylic polymer
nitrogen
Prior art date
Application number
PCT/JP2016/051834
Other languages
French (fr)
Japanese (ja)
Inventor
広斗 松本
津介 藪中
修一 後藤
Original Assignee
綜研化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 綜研化学株式会社 filed Critical 綜研化学株式会社
Priority to JP2017500566A priority Critical patent/JP6667497B2/en
Priority to CN201680009520.6A priority patent/CN107207820B/en
Publication of WO2016132814A1 publication Critical patent/WO2016132814A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • 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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Abstract

[Problem] The present invention addresses the problem of providing: a resin composition for baked pastes; and a baked paste which achieves a good balance between viscosity increase and pseudoplasticity, and which is adapted to various printing methods. [Solution] A resin for baked pastes, which is characterized by being obtained by blending an acidic group-containing (meth)acrylic polymer (A) and a nitrogen-containing (meth)acrylic polymer (B) so that the molar ratio of the acidic group-containing monomer to the nitrogen-containing monomer is from 5:95 to 85:15. The acidic group-containing (meth)acrylic polymer (A) is a copolymer of a monomer component containing an alkyl (meth)acrylate ester and an acidic group-containing monomer that contains a group selected from among a carboxyl group and a sulfonic acid group, and the acidic group-containing (meth)acrylic polymer (A) has a weight average molecular weight of from 10,000 to 500,000 and a glass transition temperature of 30°C or more. The nitrogen-containing (meth)acrylic polymer (B) is a copolymer of a monomer component containing a nitrogen-containing monomer and an alkyl (meth)acrylate ester, and the nitrogen-containing (meth)acrylic polymer (B) has a weight average molecular weight of from 10,000 to 500,000 and a glass transition temperature of 30°C or more.

Description

焼成ペースト用樹脂組成物および焼成ペーストResin composition for fired paste and fired paste
　本発明は、焼成ペースト用樹脂組成物、および当該焼成ペースト用樹脂組成物を用いた焼成ペーストならびにその用途に関する。 The present invention relates to a fired paste resin composition, a fired paste using the fired paste resin composition, and uses thereof.
　焼成ペーストは、金属粉末、金属酸化物粉末、セラミック粉末、ガラス粉末、蛍光粉末等の無機粉末（フィラー）、バインダー樹脂および溶剤等を含む組成物であって、基材に塗工後、焼成して、バインダー樹脂を熱分解し、無機粉末によるパターンを形成するために用いられるペースト状の組成物である。 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.
　例えば、導電性粉末を含む焼成ペーストである導電ペースト組成物は、回路形成やコンデンサーの製造等に用いられている。また、セラミック粉末を含むセラミックペースト組成物やガラス粉末を含むガラスペースト組成物は、プラズマディスプレイパネル（ＰＤＰ）の誘電体層や積層セラミックコンデンサー（ＭＬＣＣ）の誘電体層、蛍光表示管に用いられている。さらに、スズドープ酸化インジウム（ＩＴＯ）を含むペースト組成物は、ＰＤＰ、液晶ディスプレイパネル（ＬＣＤ）、タッチパネル、太陽電池パネルの駆動部の回路形成等を製造するための透明電極材料等に用いられている。加えて、蛍光体を含むペースト組成物は、無機エレクトロルミネッセンス（ＥＬ）素子、ＰＤＰ、等に用いられ、銀を含むペースト組成物は、太陽電池、発光ダイオード（ＬＥＤ）等に用いられている。 For example, 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. Yes. Furthermore, 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. . In addition, paste compositions containing phosphors are used for inorganic electroluminescence (EL) devices, PDPs, and the like, and paste compositions containing silver are used for solar cells, light emitting diodes (LEDs), and the like.
　この焼成ペーストの基材への塗工には、例えば、スクリーン印刷、ダイコート印刷、ドクターブレード印刷、ロールコート印刷、オフセット印刷、グラビア印刷、フレキソ印刷、インクジェット印刷、ディスペンス印刷等を用いた塗布法あるいはシート状に加工するためのキャスティング法等が用いられている。 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.
　したがって、焼成ペーストに用いられる上記バインダー樹脂には、上記塗工方法による基材への塗工性および無機粉末の分散性が良好であることが求められる。 Therefore, 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.
　さらに、焼成後に炭素成分の残渣があると、たとえばペースト組成物中の導電性の無機粉末によるパターンが形成された電子製品の性能に悪影響を及ぼす等の問題が生じるため、上記バインダー樹脂には、焼成により炭素成分の残渣を残すことなく熱分解される性質（焼成性）が良好であることも望まれる。 Furthermore, if there is a carbon component residue after firing, problems such as adversely affecting the performance of electronic products in which a pattern of conductive inorganic powder in the paste composition is formed, the binder resin, It is also desired that the property (baking property) to be pyrolyzed without leaving a carbon component residue by firing is good.
　たとえば、特許文献１（特開２０１３－５８４０３号公報）には、炭素数１～６のエステル置換基を有するアクリルモノマーと、エステル置換基に水酸基またはポリエチレンオキサイドを有するアクリルモノマーとから得られる（メタ）アクリル樹脂と、導電性粒子と、有機溶剤とを含有する導電ペーストが記載されている。 For example, 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.
　特許文献２（特開２０１３－２２７５１４号公報）には、溶解度パラメータから算出した数値が特定の関係にある不溶性ポリマーと、可溶性ポリマーとを組み合わせた、ペースト用樹脂組成物が記載されている。しかしながら、特許文献１および特許文献２の構成では、焼成ペーストの塗工性等が充分ではなく、さらなる改善が望まれる。 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. However, in the configurations of Patent Document 1 and Patent Document 2, the coating property of the fired paste is not sufficient, and further improvement is desired.
特開２０１３－５８４０３号公報JP 2013-58403 A 特開２０１３－２２７５１４号公報JP 2013-227514 A
　本発明の課題は、ペーストの高粘度化や擬塑性を発現し塗工性に優れ、かつ、焼成性が良好な焼成ペースト用樹脂組成物およびそれを用いた焼成ペーストを提供することにある。 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.
　本発明者は、鋭意検討した結果、以下の構成を有する焼成ペースト用樹脂を用いることにより上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventor has found that the above problems can be solved by using a resin for a baking paste having the following configuration, and has completed the present invention.
　本発明の構成は以下の〔１〕～〔６〕の通りである。 The configuration of the present invention is as follows [1] to [6].
　〔１〕カルボキシル基およびスルホン酸基から選ばれる少なくとも１種の基を含有する酸性基含有モノマーと、（メタ）アクリル酸アルキルエステルとを含むモノマー成分（ａ）の共重合体であり、重量平均分子量１万～５０万、ガラス転移温度３０℃以上である酸性基含有（メタ）アクリル系ポリマー（Ａ）、および、
　窒素含有モノマーと、（メタ）アクリル酸アルキルエステルとを含むモノマー成分（ｂ）の共重合体であり、重量平均分子量１万～５０万、ガラス転移温度３０℃以上である窒素含有（メタ）アクリル系ポリマー（Ｂ）を、
　酸性基含有モノマー：窒素含有モノマーのモル比が、５：９５～８５：１５の比率となるようにブレンドすることを特徴とする焼成ペースト用樹脂組成物。 [1] A copolymer of a monomer component (a) containing an acidic group-containing monomer containing at least one group selected from a carboxyl group and a sulfonic acid group, and a (meth) acrylic acid alkyl ester, and having a weight average An acidic group-containing (meth) acrylic polymer (A) having a molecular weight of 10,000 to 500,000 and a glass transition temperature of 30 ° C. or higher; and
A copolymer of a monomer component (b) containing a nitrogen-containing monomer and a (meth) acrylic acid alkyl ester, and having a weight average molecular weight of 10,000 to 500,000 and a glass transition temperature of 30 ° C. or higher. 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.
　〔２〕前記モノマー成分（ａ）および前記モノマー成分（ｂ）の少なくとも一方が、水酸基含有モノマーを含むことを特徴とする請求項１記載の焼成ペースト用樹脂組成物。 [2] The resin composition for firing paste according to claim 1, wherein at least one of the monomer component (a) and the monomer component (b) contains a hydroxyl group-containing monomer.
　〔３〕前記窒素含有モノマーが、ヘテロ環構造を有することを特徴とする前記〔１〕または〔２〕に記載の焼成ペースト用樹脂組成物。 [3] The resin composition for fired paste according to [1] or [2], wherein the nitrogen-containing monomer has a heterocyclic structure.
　〔４〕前記〔１〕～〔３〕のいずれか１項に記載の焼成ペースト用樹脂組成物と、無機粉末と、溶剤とを含むことを特徴とする焼成ペースト。 [4] 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.
　〔５〕さらに分散剤を含むことを特徴とする前記〔４〕に記載の焼成ペースト。 [5] The fired paste according to [4], further including a dispersant.
　〔６〕前記〔４〕または〔５〕に記載の焼成ペーストを用いて製造された多層セラミックコンデンサー。 [6] A multilayer ceramic capacitor manufactured using the fired paste according to [4] or [5].
　本発明の焼成ペースト用樹脂組成物は、酸性基含有ポリマー、および、窒素含有ポリマーを、所定の割合でブレンドすることにより、ポリマー間で水素結合によるネットワークを形成し、従来のアクリル樹脂では不可能であったペーストの高粘度化と擬塑性とを両立させることができ、このような焼成ペースト用樹脂を用いることで、種々印刷方式に適合した焼成ペーストを提供できる。 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. Thus, it is possible to achieve both high viscosity and pseudoplasticity of the paste, and by using such a baking paste resin, it is possible to provide a baking paste suitable for various printing methods.
　以下、本発明について具体的に説明する。 Hereinafter, the present invention will be specifically described.
　本明細書において、「（メタ）アクリロイル」は、アクリロイルおよびメタクリロイルの両方または一方を示すために用いられ、「（メタ）アクリレート」は、アクリレートおよびメタクリレートの両方または一方を示すために用いられ、「（メタ）アクリル」は、アクリルおよびメタクリルの両方または一方を示すために用いられる。 Herein, “(meth) acryloyl” is used to indicate acryloyl and / or methacryloyl, “(meth) acrylate” is used to indicate acrylate and / or methacrylate, and “ “(Meth) acryl” is used to indicate both or one of acrylic and methacrylic.
＜焼成ペースト用樹脂組成物＞
　本発明の焼成ペースト用樹脂組成物は、重量平均分子量１万～５０万、ガラス転移温度３０℃以上の酸性基含有（メタ）アクリル系ポリマー（Ａ）と、重量平均分子量１万～５０万、ガラス転移温度３０℃以上の窒素含有（メタ）アクリル系ポリマー（Ｂ）とのブレンド物である。 <Resin composition for baking paste>
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.
＜酸性基含有（メタ）アクリル系ポリマー（Ａ）＞
　酸性基含有（メタ）アクリル系ポリマー（Ａ）は、カルボキシル基および／またはスルホン酸基を含有する酸性基含有モノマー（モノマー（ａ１））と、（メタ）アクリル酸アルキルエステル（モノマー（ａ２））とを含むモノマー成分（ａ）を共重合して得られたものである。 <Acid group-containing (meth) acrylic polymer (A)>
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
酸性基含有モノマー（モノマー（ａ１））
　本発明に係る酸性基含有モノマー（モノマー（ａ１））は、酸性基としてカルボキシル基および／またはスルホン基を含有する重合性モノマーである。 Acid group-containing monomer (monomer (a1))
The acidic group-containing monomer (monomer (a1)) according to the present invention is a polymerizable monomer containing a carboxyl group and / or a sulfone group as an acidic group.
　酸性基含有モノマーであるモノマー（ａ１）としては、例えば、（メタ）アクリル酸β－カルボキシエチル、（メタ）アクリル酸５－カルボキシペンチル、コハク酸モノ（メタ）アクリロイルオキシエチルエステル、ω－カルボキシポリカプロラクトンモノ（メタ）アクリレート等のカルボキシル基含有（メタ）アクリレート；アクリル酸、メタクリル酸、イタコン酸、クロトン酸、フマル酸、マレイン酸等が挙げられる。また、スルホン酸基含有モノマーとしては、ビニルスルホン酸、スチレンスルホン酸等が挙げられ、側鎖に硫酸基を有する（メタ）アクリル系モノマー等も挙げられる。 Examples of the monomer (a1) which is an acidic group-containing monomer include β-carboxyethyl (meth) acrylate, 5-carboxypentyl (meth) acrylate, mono (meth) acryloyloxyethyl ester succinate, and ω-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.
　酸性基含有（メタ）アクリル系ポリマー（Ａ）を形成するモノマー成分（ａ）１００質量％中、モノマー（ａ１）の使用量は、通常０．１～１０質量％、好ましくは０．５～５質量％、より好ましくは１～５質量％である。前記範囲でモノマー（ａ１）を共重合して得られた酸性基含有（メタ）アクリル系ポリマー（Ａ）を、窒素含有（メタ）アクリル系ポリマー（Ｂ）とブレンドすることにより、ペーストの高粘度化と擬塑性を両立でき、種々印刷方式に適合する粘度を有する焼成ペースト用樹脂組成物が得られる。 In 100% by mass of the monomer component (a) for forming the acidic group-containing (meth) acrylic polymer (A), 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. By blending the acidic group-containing (meth) acrylic polymer (A) obtained by copolymerizing the monomer (a1) within the above range with the nitrogen-containing (meth) acrylic polymer (B), a high viscosity of the paste is obtained. Thus, a resin composition for firing paste having a viscosity compatible with various printing methods can be obtained.
（メタ）アクリル酸アルキルエステル（モノマー（ａ２））
　（メタ）アクリル酸アルキルエステルであるモノマー（ａ２）としては、例えば、ＣＨ2＝ＣＲ1－ＣＯＯＲ2で表される化合物が挙げられる。式中、Ｒ1は水素原子またはメチル基であり、Ｒ2は炭素数１～１８のアルキル基である。上記アルキル基の炭素数は１～４が好ましい。 (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 . In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 is an alkyl group having 1 to 18 carbon atoms. The alkyl group preferably has 1 to 4 carbon atoms.
　モノマー（ａ２）としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｉｓｏ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、へプチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、ｉｓｏ－オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、ｉｓｏ－ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ｉｓｏ－デシル（メタ）アクリレート、ウンデカ（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、ｉｓｏ－ステアリル（メタ）アクリレート等が挙げられる。これらモノマー（ａ２）は、得られる酸性基含有（メタ）アクリル系ポリマー（Ａ）のＴｇが３０℃以上となるように選択され、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 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. Pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, nonyl (meth) acrylate, iso-nonyl (meth) acrylate, decyl (meth) acrylate, iso-decyl (meth) acrylate, undeca (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, iso-steari (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.
　酸性基含有（メタ）アクリル系ポリマー（Ａ）を形成するモノマー成分（ａ）１００質量％中、モノマー（ａ２）の使用量は、通常３０～９７質量％、好ましくは４０～９５質量％、より好ましくは５０～９０質量％である。モノマー（ａ２）が前記範囲で含まれていると、各種溶媒への溶解性や焼成性が良好な焼成ペースト用樹脂組成物を得ることができる。 In 100% by mass of the monomer component (a) forming the acidic group-containing (meth) acrylic polymer (A), 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. When 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.
水酸基含有モノマー（モノマー（ａ３））
　酸性基含有（メタ）アクリル系ポリマー（Ａ）を形成するモノマー成分（ａ）は、各種フィラーの分散性や粘度特性の向上の観点から、共重合成分として、水酸基含有モノマー（モノマー（ａ３））を含むものであってもよい。ただし、後述のモノマー（ｂ１）に記載する水酸基含有（メタ）アクリルアミド類はモノマー（ａ３）には含まれない。 Hydroxyl group-containing monomer (monomer (a3))
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).
　モノマー（ａ３）としては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロシキブチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレートが挙げられる。ヒドロキシアルキル（メタ）アクリレートでのヒドロキシアルキル基の炭素数は、通常２～８、好ましくは２～６である。また、ヒドロキシシクロヘキシル（メタ）アクリレート等の環状アルキルを有する水酸基含有モノマーも使用することが可能である。 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.
　酸性基含有（メタ）アクリル系ポリマー（Ａ）を形成するモノマー成分（ａ）としてモノマー（ａ３）を使用する場合、その使用量は、モノマー成分（ａ）１００質量％中、通常０．５～３０質量％、好ましくは１～２５質量％、より好ましくは３～１５質量％である。モノマー（ａ３）が前記範囲で含まれていると、各種フィラーの分散性が良好で、塗工に適切な粘度を有する焼成ペーストを得ることができる。 When the monomer (a3) is used as the monomer component (a) for forming the acidic group-containing (meth) acrylic polymer (A), 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. When 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.
その他の（メタ）アクリル酸エステル
　酸性基含有（メタ）アクリル系ポリマー（Ａ）を形成するモノマー成分（ａ）は、モノマー（ａ１）～（ａ３）の他に、任意の共重合成分として、例えば、アルコキシアルキル（メタ）アクリレート、アルコキシポリアルキレングリコールモノ（メタ）アクリレート、脂環式基または芳香環含有（メタ）アクリレートなどの、その他の（メタ）アクリル酸エステルを含むことができる。 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.
　アルコキシアルキル（メタ）アクリレートとしては、例えば、メトキシメチル（メタ）アクリレート、２－メトキシエチル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、３－メトキシプロピル（メタ）アクリレート、３－エトキシプロピル（メタ）アクリレート、４－メトキシブチル（メタ）アクリレート、４－エトキシブチル（メタ）アクリレートが挙げられる。 Examples of the alkoxyalkyl (meth) acrylate 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.
　アルコキシポリアルキレングリコールモノ（メタ）アクリレートとしては、例えば、メトキシジエチレングリコールモノ（メタ）アクリレート、メトキシジプロピレングリコールモノ（メタ）アクリレート、エトキシトリエチレングリコールモノ（メタ）アクリレート、エトキシジエチレングリコールモノ（メタ）アクリレート、メトキシトリエチレングリコールモノ（メタ）アクリレートが挙げられる。 Examples of the alkoxypolyalkylene glycol mono (meth) acrylate 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.
　脂環式基または芳香環含有（メタ）アクリレートとしては、例えば、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレートが挙げられる。 Examples of the alicyclic group or aromatic ring-containing (meth) acrylate include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and phenyl (meth) acrylate.
　酸性基含有（メタ）アクリル系ポリマー（Ａ）を形成するモノマー成分（ａ）１００質量％中、上記その他の（メタ）アクリル酸エステルの使用量は、３０質量％以下であることが好ましく、より好ましくは２０質量％以下である。 In 100% by mass of the monomer component (a) forming the acidic group-containing (meth) acrylic polymer (A), the amount of the other (meth) acrylic acid ester used is preferably 30% by mass or less. Preferably it is 20 mass% or less.
　その他の（メタ）アクリル酸エステルは１種単独で用いてもよく、２種以上を用いてもよい。
共重合性モノマー
　また、酸性基含有（メタ）アクリル系ポリマー（Ａ）を形成するモノマー成分は、酸性基含有（メタ）アクリル系ポリマー（Ａ）の物性を損わない範囲で、例えば、スチレン系単量体、酢酸ビニルなどのその他の共重合性モノマーをモノマー成分（ａ）に含むことができる。 Other (meth) acrylic acid esters may be used alone or in combination of two or more.
Copolymerizable monomer 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).
　スチレン系単量体としては、例えば、スチレン；メチルスチレン、ジメチルスチレン、トリメチルスチレン、プロピルスチレン、ブチルスチレン、へキシルスチレン、ヘプチルスチレン、オクチルスチレン等のアルキルスチレン；フロロスチレン、クロロスチレン、ブロモスチレン、ジブロモスチレン、ヨウ化スチレン等のハロゲン化スチレン；ニトロスチレン、アセチルスチレン、メトキシスチレンが挙げられる。 Examples of the styrenic monomer 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.
　酸性基含有（メタ）アクリル系ポリマー（Ａ）を形成するモノマー成分（ａ）１００質量％中、上記その他の共重合性モノマーの使用量は、２０質量％以下であることが好ましく、より好ましくは１０質量％以下である。 In 100% by mass of the monomer component (a) forming the acidic group-containing (meth) acrylic polymer (A), the amount of the other copolymerizable monomer used is preferably 20% by mass or less, more preferably. It is 10 mass% or less.
　その他の共重合性モノマーは１種単独で用いてもよく、２種以上を用いてもよい。
＜酸性基含有（メタ）アクリル系ポリマー（Ａ）の物性＞
　酸性基含有（メタ）アクリル系ポリマー（Ａ）のゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定される重量平均分子量（Ｍｗ）は、ポリスチレン換算値で、１万～５０万、好ましくは２万～３０万であり、さらに好ましくは３万～１５万である。 Other copolymerizable monomers may be used alone or in combination of two or more.
<Physical properties of acidic group-containing (meth) acrylic polymer (A)>
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.
　酸性基含有（メタ）アクリル系ポリマー（Ａ）のＭｗが上記範囲であると、糸曳き性、スクリーン印刷性に優れた焼成ペースト用樹脂組成物を得ることができる。 When the Mw of the acidic group-containing (meth) acrylic polymer (A) is in the above range, a resin composition for a fired paste having excellent stringiness and screen printability can be obtained.
　また、ガラス転移温度（Ｔｇ）は示差走査型熱量計（ＤＳＣ）による測定で求められる。 Further, the glass transition temperature (Tg) is obtained by measurement with a differential scanning calorimeter (DSC).
　測定条件としては試料５ｍｇ、窒素雰囲気下とし、１回目の測定（１ｓｔ ＲＵＮ）で昇温速度２０℃／分で－１００℃から２００℃まで昇温した後、降温速度９９.９℃／分で－１００℃まで冷却し、さらに２回目の測定（２ｎｄ ＲＵＮ）で昇温速度２０℃／分で－１００℃から２００℃まで昇温した。ここでガラス転移温度は２ｎｄ ＲＵＮに おいて－１００℃から２００℃まで昇温したときに測定されるＤＳＣ曲線のベースラインが吸熱方向にシグモイド型に変化する領域において、シグモイド型に変化する領域より低温側のベースラインの延長線と、シグモイドにおける変曲点の接線の交点を指す。 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. After cooling to −100 ° C., the temperature was increased from −100 ° C. to 200 ° C. at a temperature increase rate of 20 ° C./min in the second measurement (2ndｎRUN). Here, 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.
　ＤＳＣよって求められる酸性基含有（メタ）アクリル系ポリマー（Ａ）のＴｇは、通常３０℃以上、好ましくは５０～１５０℃である。このようなＴｇを有する酸性基含有（メタ）アクリル系ポリマー（Ａ）を用いることにより、糸曳き性、焼成性に優れた焼成ペースト用樹脂組成物を得ることができる。酸性基含有（メタ）アクリル系ポリマー（Ａ）のＴｇが３０℃より低い場合、ポリマー重合時不均化停止反応が少なくなるため、解重合性が悪く、焼成ペースト用樹脂組成物の焼成後に炭素残渣が残り、また、印刷表面のべたつきを生じてしまう等の不具合を起こす恐れがある。 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. By using such an acidic group-containing (meth) acrylic polymer (A) having Tg, a resin composition for a fired paste having excellent stringiness and fireability can be obtained. When 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.
＜窒素含有（メタ）アクリル系ポリマー（Ｂ）＞
　窒素含有（メタ）アクリル系ポリマー（Ｂ）は、窒素含有モノマー（モノマー（ｂ１））と、（メタ）アクリル酸アルキルエステル（モノマー（ｂ２））とを含むモノマー成分（ｂ）を共重合して得られたものである。 <Nitrogen-containing (meth) acrylic polymer (B)>
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.
窒素含有モノマー（モノマー（ｂ１））
　モノマー（ｂ１）としては、例えば、（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ－ｉｓｏ-プロピル（メタ）アクリルアミド、Ｎ－ｔｅｒｔ－ブチル（メタ）アクリルアミド等の（メタ）アクリルアミド類；
（メタ）アクリルロイルモルフォリン、（メタ）アクリロイルピロリドン、（メタ）アクリロイルピロリジン等の環状（メタ）アクリルアミド類；
　Ｎ－（ヒドロキシメチル）（メタ）アクリルアミド、Ｎ－（２－ヒドロキシエチル）（メタ）アクリルアミド、Ｎ－（２－ヒドロキシプロピル）（メタ）アクリルアミド、Ｎ－（１－ヒドロキシプロピル）（メタ）アクリルアミド、Ｎ－（３－ヒドロキシプロピル）(メタ)アクリルアミド、Ｎ－（２－ヒドロキシブチル）（メタ）アクリルアミド、Ｎ－（３－ヒドロキシブチル）(メタ)アクリルアミド、Ｎ－（４－ヒドロキシブチル）（メタ）アクリルアミド等の水酸基含有（メタ）アクリルアミド類；
　Ｎ－ビニル－２－ピロリドン、Ｎ－ビニル－２－ピペリドン、Ｎ－ビニル－３－モルホリノン、Ｎ－ビニル－２－カプロラクタム、Ｎ－ビニル－１，３－オキサジン－２－オン、Ｎ－ビニル－３，５－モルホリンジオン、Ｎ－ビニルピリジン、Ｎ－ビニルピリミジン、Ｎ－ビニルピペラジン、Ｎ－ビニルピロール等のＮ－ビニル環状アミド類などが挙げられる。 Nitrogen-containing monomer (monomer (b1))
Examples of the monomer (b1) 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) acrylamide, N- (3-hydroxybutyl) (meth) acrylamide, N- (4-hydroxybutyl) (meth) Hydroxyl-containing (meth) acrylamides such as acrylamide;
N-vinyl-2-pyrrolidone, N-vinyl-2-piperidone, N-vinyl-3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl- And N-vinyl cyclic amides such as 3,5-morpholinedione, N-vinylpyridine, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrrole and the like.
　さらに、上記以外のモノマー（ｂ１）として、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレート、ｔｅｒｔ-ブチルアミノエチル(メタ)アクリレート、Ｎ－メチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ－エチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチルアミノプロピル（メタ）アクリルアミド、２，２，６，６－テトラメチル－４－ピペリジル(メタ)アクリレート、１，２，２，６，６－ペンタメチル－４－ピペリジル(メタ)アクリレート、ウレイド（メタ）アクリレート等も使用することが可能である。 Further, as the monomer (b1) other than the above, 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.
　窒素含有（メタ）アクリル系ポリマー（Ｂ）を形成するモノマー成分（ｂ）１００質量％中、モノマー（ｂ１）の使用量は、通常１～５０質量％、好ましくは３～４０質量％、より好ましくは５～３０質量％である。前記範囲でモノマー（ｂ１）を共重合して得られた窒素含有（メタ）アクリル系ポリマー（Ｂ）を、酸性基含有（メタ）アクリル系ポリマー（Ａ）とブレンドして得られる樹脂組成物を用いることで、ペーストの高粘度化と擬塑性を両立でき、種々印刷方式に適合する粘度を有する焼成用ペーストが得られる。これらモノマー（ｂ１）のうち、糸曳き性、スクリーン印刷性、および、酸性基含有（メタ）アクリル系ポリマー（Ａ）とブレンドした際に、酸性基含有（メタ）アクリル系ポリマー（Ａ）と窒素含有（メタ）アクリル系ポリマー（Ｂ）間で適した水素結合ネットワークを形成できる点で、ヘテロ環構造を有するものが好ましく、特に２，２，６，６－テトラメチル－４－ピペリジル（メタ）アクリレート、１，２，２，６，６－ペンタメチル－４－ピペリジル（メタ）アクリレートを使用することが好ましい。 In 100% by mass of the monomer component (b) forming the nitrogen-containing (meth) acrylic polymer (B), 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. A resin composition obtained by blending a nitrogen-containing (meth) acrylic polymer (B) obtained by copolymerizing the monomer (b1) within the above range with an acidic group-containing (meth) acrylic polymer (A). By using it, it is possible to achieve both high viscosity and pseudoplasticity of the paste and to obtain a baking paste having a viscosity suitable for various printing methods. Of these monomers (b1), when blended with stringiness, screen printability, and acidic group-containing (meth) acrylic polymer (A), acidic group-containing (meth) acrylic polymer (A) and nitrogen Those having a heterocyclic structure are preferred in that a suitable hydrogen bond network can be formed between the containing (meth) acrylic polymer (B), and in particular, 2,2,6,6-tetramethyl-4-piperidyl (meth) Preference is given to using acrylate, 1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate.
（メタ）アクリル酸アルキルエステル（モノマー（ｂ２））
　モノマー（ｂ２）としては、上記モノマー（ａ２）と同様のものが使用できる。
　窒素含有（メタ）アクリル系ポリマー（Ｂ）を形成するモノマー成分（ｂ）１００質量％中、モノマー（ｂ２）の使用量は、通常３０～９７質量％、好ましくは４０～９５質量％、より好ましくは５０～９０質量％である。モノマー（ｂ２）が前記範囲で含まれていると、各種溶媒への溶解性や焼成性の点で優れた焼成ペースト用樹脂組成物を得ることができる。 (Meth) acrylic acid alkyl ester (monomer (b2))
As the monomer (b2), the same monomer (a2) can be used.
In 100% by mass of the monomer component (b) forming the nitrogen-containing (meth) acrylic polymer (B), 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. When 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.
水酸基含有モノマー（モノマー（ｂ３））
　窒素含有（メタ）アクリル系ポリマー（Ｂ）を形成するモノマー成分（ｂ）は、各種フィラーの分散性や粘度特性向上の観点から、共重合成分として、水酸基含有モノマー（モノマー（ｂ３））を含むものであってもよく、モノマー（ｂ３）としては、上記モノマー（ａ３）と同様のものを使用できる。 Hydroxyl group-containing monomer (monomer (b3))
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).
　窒素含有（メタ）アクリル系ポリマー（Ｂ）を形成するモノマー成分（ｂ）１００質量％中、モノマー（ｂ３）の使用量は、０．５～３０質量％、好ましくは１～２５質量％、より好ましくは３～１５質量％である。モノマー（ｂ３）が前記範囲で含まれていると、各種フィラーの分散性が良好で、塗工に適切な粘度を有する焼成ペーストを得ることができる。 In 100% by mass of the monomer component (b) forming the nitrogen-containing (meth) acrylic polymer (B), 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. When 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.
　窒素含有（メタ）アクリル系ポリマー（Ｂ）を形成するモノマー成分（ｂ）は、物性を損なわない範囲で、モノマー（ｂ１）～（ｂ３）の他に、モノマー成分（ａ）に含むことのできるその他の（メタ）アクリル酸エステルおよび共重合性モノマーとして上記したような任意の共重合成分を含むものであってもよい。
＜窒素含有（メタ）アクリル系ポリマー（Ｂ）の物性＞
　窒素含有（メタ）アクリル系ポリマー（Ｂ）のゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定される重量平均分子量（Ｍｗ）は、ポリスチレン換算値で、通常１万～５０万、好ましくは２万～３０万であり、さらに好ましくは３万～１５万である。 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.
　窒素含有（メタ）アクリル系ポリマー（Ｂ）のＭｗが上記範囲であると、糸曳き性、スクリーン印刷性に優れた焼成ペースト用樹脂組成物を得ることができる。 When the Mw of the nitrogen-containing (meth) acrylic polymer (B) is within the above range, a resin composition for a fired paste having excellent stringiness and screen printing properties can be obtained.
　また、窒素含有（メタ）アクリル系ポリマー（Ｂ）のガラス転移温度（Ｔｇ）は、上記酸性基含有（メタ）アクリル系ポリマー（Ａ）と同様、ガラス転移温度（Ｔｇ）は示差走査型熱量計（ＤＳＣ）により測定して求められる。 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).
　ＤＳＣにより求められる窒素含有（メタ）アクリル系ポリマー（Ｂ）のＴｇは、通常３０℃以上、好ましくは５０～１５０℃である。このようなＴｇを有する窒素含有（メタ）アクリル系ポリマー（Ｂ）を用いることにより、糸曳き性、焼成性に優れた焼成ペースト用樹脂組成物を得ることができる。窒素含有（メタ）アクリル系ポリマー（Ｂ）のＴｇが３０℃より低い場合、ポリマー重合時不均化停止反応が少なくなるため、解重合性が悪く、焼成ペースト用樹脂組成物の焼成後に炭素残渣が残り、また、印刷表面のべたつきを生じてしまう等の不具合を起こす恐れがある。 The Tg of the nitrogen-containing (meth) acrylic polymer (B) determined by DSC is usually 30 ° C. or higher, preferably 50 to 150 ° C. By using such a nitrogen-containing (meth) acrylic polymer (B) having Tg, a resin composition for a fired paste having excellent stringiness and fireability can be obtained. When 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.
酸性基含有（メタ）アクリル系ポリマー（Ａ）および窒素含有（メタ）アクリル系ポリマー（Ｂ）の製造方法
　本発明の酸性基含有（メタ）アクリル系ポリマー（Ａ）および窒素含有（メタ）アクリル系ポリマー（Ｂ）の重合方法は、特に制限されるものではないが、通常は溶液重合を用いることが好ましい。溶液重合は、一般に、重合槽内に所定の有機溶媒、各モノマー、重合開始剤を仕込み、窒素等の不活性ガス気流中、適当な重合温度で、撹拌しながら数時間加熱反応させることにより行われる。この場合、有機溶媒、各モノマー、重合開始剤および／または連鎖移動剤の少なくとも一部を逐次添加してもよい。 Method for producing acidic group-containing (meth) acrylic polymer (A) and nitrogen-containing (meth) acrylic polymer (B) Acidic group-containing (meth) acrylic polymer (A) and nitrogen-containing (meth) acrylic of the present invention The polymerization method of the polymer (B) is not particularly limited, but it is usually preferable to use solution polymerization. In general, 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. In this case, at least a part of the organic solvent, each monomer, the polymerization initiator, and / or the chain transfer agent may be sequentially added.
　重合用有機溶媒としては、ベンゼン、トルエン、エチルベンゼン、ｎ－プロピルベンゼン、ｔｅｒｔ－ブチルベンゼン、ｏ－キシレン、ｍ－キシレン、ｐ－キシレン、テトラリン、デカリン、芳香族ナフサ等で例示される芳香族炭化水素；ｎ－ヘキサン、ｎ－ヘプタン、ｎ－オクタン、ｉｓｏ－オクタン、ｎ－デカン、ジペンテン、石油スピリット、石油ナフサ、テレピン油等で例示される脂肪族系または脂環族系炭化水素；酢酸アルキル（ここで、アルキルとしてはメチル、エチル、プロピル、ブチル、ペンチルなどが例示される。以下、同じ。）、安息香酸メチル等で例示されるエステル；エチレングリコールもしくはジエチレングリコールのモノアセテート、ジアセテート、アルキルエーテルアセテート（例えば、ジエチレングリコールモノブチルエーテルアセテート）、モノアルキルエーテル、ジアルキルエーテル等で例示されるエチレングリコールの誘導体；プロピレングリコール、ジプロピレンエチレングリコール、トリプロピレングリコールのいずれかのグリコールのモノアセテート、ジアセテート、アルキルエーテルアセテート、モノアルキルエーテル（例えば、トリプロピレングリコールモノブチルエーテル）、ジアルキルエーテル等で例示されるプロピレングリコール誘導体；アセトン、メチルエチルケトン、メチル－ｉｓｏ－ブチルケトン、イソホロン、シクロヘキサノン、メチルシクロヘキサノン等で例示されるケトン、テキサノール（２，２，４－トリメチルペンタン－１，３－ジオールモノ－ｉｓｏ－ブチレート）などを挙げることができる。これらの有機溶媒はそれぞれ単独で、または、２種以上混合して用いることができる。 As an organic solvent for polymerization, aromatic carbonization exemplified by benzene, toluene, ethylbenzene, n-propylbenzene, tert-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, aromatic naphtha, etc. Hydrogen; aliphatic or alicyclic hydrocarbon exemplified by n-hexane, n-heptane, n-octane, iso-octane, n-decane, dipentene, petroleum spirit, petroleum naphtha, turpentine oil, etc .; alkyl acetate (Herein, examples of alkyl include methyl, ethyl, propyl, butyl, pentyl and the like. The same applies hereinafter.) 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-trimethylpentane-1,3-diol mono-iso-butyrate). These organic solvents can be used alone or in combination of two or more.
　重合用有機溶媒としては沸点が高い溶剤が好ましく、具体的には沸点が５０～３００℃の溶剤がより好ましい。 As the organic solvent for polymerization, 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.
　重合開始剤としては、ベンゾイルパーオキシド、ラウロイルパーオキシド、カプロイルパーオキシド、ジ－ｔｅｒｔ－ブチルパーオキシド、ジ－ｉｓｏ－プロピルパーオキシジーボネート、ジ－２－エチルヘキシルパーオキシジカーボネート、ｔｅｒｔ－ブチルパーオキシビバレート等で例示される有機過酸化物；２，２'－アゾビス－ｉｓｏ－ブチロニトリル、２，２'－アゾビス－２，４－ジメチルバレロニトリル、２，２'－アゾビス－４－メトキシ－２，４－ジメチルバレロニトリル等で例示されるアゾ化合物などをそれぞれ単独又は組み合わせて使用することができる。 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.
　重合開始剤の使用量は、酸性基含有（メタ）アクリル系ポリマー（Ａ）を形成するモノマー成分（ａ）、または窒素含有（メタ）アクリル系ポリマー（Ｂ）を形成するモノマー成分（ｂ）の合計１００質量部当り、一般には、０．０１～５質量部であり、０．０２～２質量部の範囲内とすることが好ましい。 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.
　連鎖移動剤としては、例えば、ｎ－ドデシルメルカプタン、２－メルカプトエタノール、チオグリセロール、β－メルカプトプロピオン酸、α－メチルスチレンダイマーが挙げられる。連鎖移動剤を用いることにより、製造される酸性基含有（メタ）アクリル系ポリマー（Ａ）および窒素含有（メタ）アクリル系ポリマー（Ｂ）の重量平均分子量を制御することができる。これらの連鎖移動剤は１種単独で用いてもよく、２種以上を用いてもよい。 Examples of the chain transfer agent include n-dodecyl mercaptan, 2-mercaptoethanol, thioglycerol, β-mercaptopropionic acid, and α-methylstyrene dimer. 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. These chain transfer agents may be used individually by 1 type, and may use 2 or more types.
　連鎖移動剤は、酸性基含有（メタ）アクリル系ポリマー（Ａ）を形成するモノマー成分（ａ）、または窒素含有（メタ）アクリル系ポリマー（Ｂ）を形成するモノマー成分（ｂ）１００質量部に対して、通常１質量部以下、好ましくは０．０１～０．５質量部の範囲内の量で使用することができる。 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). On the other hand, 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.
　重合温度としては、４０～１８０℃が好ましい。重合温度が上記範囲であると、充分な反応速度が得られるとともに、温度が高すぎることによる解重合が生じることもない。 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.
　上記重合温度で反応させる時間は４～１６時間が好ましい。反応時間が上記範囲であると、反応を完全に進行させることができる。 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.
　ポリマーの重量平均分子量を、本発明の範囲とするためには、重合開始剤を重合の初期に添加することに加えて、重合がある程度進行してから、さらに重合開始剤を添加することも好ましい。その場合、重合開始剤の使用量は、すべての添加量の合計で上記範囲内にあることが好ましい。 In order to make the weight average molecular weight of the polymer within the range of the present invention, 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.
　上記反応を行なった後、反応混合物は室温まで冷却する。そして、ヘキサン等の非極性溶媒を用いて、ポリマーを析出させる。析出したポリマーは濾別して、乾燥させる。
＜焼成ペースト用樹脂組成物＞
　本発明に係る焼成ペースト用樹脂組成物は、酸性基含有（メタ）アクリル系ポリマー（Ａ）と、窒素含有（メタ）アクリル系ポリマー（Ｂ）とのブレンド物である。 After performing the above reaction, the reaction mixture is cooled to room temperature. Then, the polymer is deposited using a nonpolar solvent such as hexane. The precipitated polymer is filtered off and dried.
<Resin composition for baking paste>
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).
　酸性基含有（メタ）アクリル系ポリマー（Ａ）および窒素含有（メタ）アクリル系ポリマー（Ｂ）のブレンド比としては、酸性基含有モノマーであるモノマー（ａ１）と窒素含有モノマーであるモノマー（ｂ１）のモル比（モノマー（ａ１）とモノマー（ｂ１）の合計を１００モル％とした場合のモル％比）が、モノマー（ａ１）：モノマー（ｂ１）＝５：９５～８５：１５の範囲であることが好ましく、１０：９０～８０：２０の範囲であることがより好ましく、４０：６０～８０：２０の範囲であることがさらに好ましい。 As a blend ratio of the acidic group-containing (meth) acrylic polymer (A) and the 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 The molar ratio of the monomer (a1) and the monomer (b1) is 100% by mole. The monomer (a1): monomer (b1) = 5: 95 to 85:15. Preferably, it is in the range of 10:90 to 80:20, more preferably in the range of 40:60 to 80:20.
　酸性基含有（メタ）アクリル系ポリマー（Ａ）および窒素含有（メタ）アクリル系ポリマー（Ｂ）のブレンド比を、前記範囲とした焼成ペースト用樹脂組成物を用いることで、糸曳き現象を起こさず、ペーストの高粘度化と擬塑性を両立した塗工性に優れる焼成ペーストを提供できる。 By using the resin composition for fired paste with the blend ratio of the acidic group-containing (meth) acrylic polymer (A) and the nitrogen-containing (meth) acrylic polymer (B) within the above range, no stringing phenomenon occurs. Thus, it is possible to provide a fired paste having excellent coating properties that achieves both high viscosity and pseudoplasticity of the paste.
　なお、一般に、ポリマー鎖内およびポリマー鎖間の相互作用が強すぎると、糸曳き現象が確認され、相互作用が弱いほど糸曳き減少は抑制されると考えられる。 In general, if the interaction in the polymer chain and between the polymer chains is too strong, the stringing phenomenon is confirmed, and it is considered that the decrease in stringing is suppressed as the interaction is weak.
　一方で、相互作用が弱すぎると、焼成ペースト用樹脂の粘度が下がりすぎてしまい、焼成ペースト用樹脂を含む組成物を基材に塗布した際に塗膜を形成することが難しくなる等の問題が生じてしまうが、塗工時には組成物の粘度が下がった方が望ましい。なぜなら、たとえばスクリーン印刷により焼成ペースト用樹脂組成物を基板に塗布する場合は、焼成ペースト用樹脂組成物を目の細かなメッシュ上にスキージで擦って塗布するため、焼成ペースト用樹脂組成物がメッシュをきれいに通り抜ける必要があるためである。 On the other hand, if the interaction is too weak, 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. However, 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.
　したがって、焼成ペースト用樹脂には、適度な粘度を有しつつ、塗工時には擦りや攪拌等の応力を与えることにより適度な流動性（擬塑性）を有するといいう二律背反の特性が求められる。 Therefore, 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.
　本発明に係る焼成ペースト用樹脂では、酸性基と窒素含有基との間の相互作用により、水素結合ネットワークが形成されているものと考えられる。そして、このネットワークは、焼成ペースト用樹脂に適度な粘度を生じさせる一方で、共有結合よりも弱いため、塗工時には擦りや攪拌等の応力により容易に切断される。 In the fired paste resin according to the present invention, it is considered that 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.
　その結果、酸性基含有（メタ）アクリル系ポリマー（Ａ）および窒素含有（メタ）アクリル系ポリマー（Ｂ）をブレンドした焼成ペースト用樹脂は、適度な粘度を有しながら、擦りや攪拌等により応力を与えると流動性が生じ、良好な塗工性を発揮するという良好なチキソトロピック性を発揮しているものと考えられる。 As a result, 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.
＜焼成ペースト＞
　本発明の焼成ペーストは、上記酸性基含有（メタ）アクリル系ポリマー（Ａ）および窒素含有（メタ）アクリル系ポリマー（Ｂ）のブレンド物からなる焼成ペースト用樹脂組成物、溶剤（Ｃ）および無機粉末（Ｄ）を含み、さらに、必要に応じて分散剤（Ｅ）を含む。 <Baking paste>
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.
焼成ペースト用
　本発明の焼成ペーストは、焼成ペースト１００質量％中、焼成ペースト用樹脂組成物（酸性基含有（メタ）アクリル系ポリマー（Ａ）および窒素含有（メタ）アクリル系ポリマー（Ｂ）のブレンド物）を、１～２０質量％含むことが好ましく、４～１０質量％含むことがより好ましい。 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.
　焼成ペースト用樹脂組成物（酸性基含有（メタ）アクリル系ポリマー（Ａ）および窒素含有（メタ）アクリル系ポリマー（Ｂ）のブレンド物）の含有割合が前記範囲にあると、溶剤（Ｃ）との相溶性が良好であるとともに、得られる焼成ペーストに適度な粘性を付与することができ、焼成ペーストの無機粉末（Ｄ）の分散性および焼成ペーストの基板への結着性も良好である。 When the content ratio of the resin composition for baking paste (a blended product of acidic group-containing (meth) acrylic polymer (A) and nitrogen-containing (meth) acrylic polymer (B)) is in the above range, 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.
溶剤（Ｃ）
　溶剤（Ｃ）としては、焼成後に残渣が残らず、酸性基含有（メタ）アクリル系ポリマー（Ａ）および窒素含有（メタ）アクリル系ポリマー（Ｂ）を溶解することができる溶剤であれば制限なく用いることができる。 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.
　溶剤（Ｃ）としては、例えば、ターピネオール、ジヒドロターピネオール、ジヒドロターピニルアセテート、ブチルカルビトールアセテート、ジプロピレングリコール、ジプロピレングリコールモノメチルエーテル、ブチルカルビトール、ジエチレングリコールアルキルエーテルアセテート（ここで、アルキルとしては、エチル、プロピル、ｎ－ブチルなどが例示される。以下同じ。）、エチレングリコールアルキルエーテルアセテート、エチレングリコールジアセテート、ジエチレングリコールアルキルエーテル、エチレングリコールアルキルエーテル、ジプロピレングリコールアルキルエーテル、プロピレングリコールアルキルエーテルアセテート、２，２，４－トリメチルペンタン－１，３－ジオールモノ－ｉｓｏ－ブチレート、２，２，４－トリメチルペンタン－１，３－ジオールジ－ｉｓｏ－ブチレート等の有機溶剤が挙げられる。これらの溶剤はそれぞれ単独で、または、２種以上混合して用いることができる。 As the 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. The same shall apply hereinafter), 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.
　これらの溶剤の内、沸点、レベリング性の観点から、より好ましい溶剤は、ターピネオール、ジヒドロターピネオール、ジヒドロターピニルアセテート、ブチルカルビトールアセテートである。 Among these solvents, terpineol, dihydroterpineol, dihydroterpinyl acetate, and butyl carbitol acetate are more preferable from the viewpoint of boiling point and leveling property.
　また、溶剤（Ｃ）の沸点は１５０～３００℃であることが好ましく、２００～２９０℃であることがより好ましく、２２０～２８０℃であることがさらに好ましい。沸点が上記範囲にあると、焼成ペーストをスクリーン印刷した後のペーストの乾燥速度が速すぎて版の目詰まりとなることもない一方で、乾燥速度が遅すぎて作業性が低下することもない。 Further, 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. When the boiling point is in the above range, 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. .
　本発明の焼成ペーストは、焼成ペースト１００質量％中に、溶剤（Ｃ）を２０～７０質量％含むことが好ましく、３０～６０質量％含むことがより好ましい。 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.
　溶剤（Ｃ）の割合が上記範囲にあると、焼成ペースト用樹脂組成物との相溶性が良好であるとともに、得られる焼成ペーストが所望の粘度を発現することができる。
無機粉末（Ｄ）
　無機粉末（Ｄ）としては、例えば、金属粉末、金属酸化物粉末、ガラス粉末、顔料粉末、蛍光体粉末、セラミック粉末、およびこれらに感光性を付与した粉末等が挙げられる。これらの無機粉末は用途に応じて選択されるが、それぞれ単独で、または、２種以上混合して用いることができる。 When the ratio of the solvent (C) is in the above range, 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 of the inorganic powder (D) 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.
　金属粉末および金属酸化物粉末は、導電性粉末として用いられることが好ましく、ガラス粉末およびセラミック粉末は、誘電体粉末として用いられることが好ましい。 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.
　金属粉末としては、例えば、ニッケル、パラジウム、白金、金、銀、銅、鉄、アルミニウム、タングステンやこれらの合金等からなる粉末等が挙げられる。金属酸化物粉末としては、例えば、スズドープ酸化インジウム（ＩＴＯ）、アンチモンドープ酸化スズ（ＡＴＯ）、フッ素ドープ酸化スズ（ＦＴＯ）等が挙げられる。ガラス粉末としては、例えば、酸化ビスマスガラス、ケイ酸塩ガラス、鉛ガラス、亜鉛ガラス、ボロンガラスや各種ケイ素酸化物のガラス粉末等が挙げられる。セラミック粉末としては、例えば、アルミナ、ジルコニア、酸化チタン、チタン酸バリウム、窒化アルミナ、窒化ケイ素、窒化ホウ素等が挙げられる。 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.
　本発明の焼成ペーストは、焼成ペースト１００質量％中に、無機粉末（Ｄ）を２０～７０質量％含むことが好ましく、３５～６０質量％含むことがより好ましい。 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.
　無機粉末（Ｄ）の割合が上記範囲にあると、本発明の焼成ペーストから得られる焼成体の導電性等の各性能が良好であるとともに、焼成ペースト中での分散性も良好である。 When the ratio of the inorganic powder (D) is in the above range, 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.
分散剤（Ｅ）
　分散剤（Ｅ）としては、例えば、カチオン系分散剤、アニオン系分散剤、ノニオン系分散剤、両性界面活性剤、高分子系分散剤が挙げられる。これらの分散剤はそれぞれ単独で、または、２種以上混合して用いることができる。 Dispersant (E)
Examples of the dispersant (E) 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.
　カチオン系分散剤としては、ポリアミン系の分散剤等が挙げられる。アニオン系分散剤としては、カルボン酸系、リン酸エステル系、硫酸エステル系、スルホン酸エステル系の分散剤等が挙げられる。ノニオン系分散剤としては、ポリエチレングリコール系分散剤等が挙げられる。両性界面活性剤としては、カルボン酸と第４級アンモニウム塩とを有する界面活性剤等が挙げられる。高分子系分散剤としては、ポリビニルピロリドン、ポリビニルアルコール等が挙げられる。 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.
　本発明の焼成ペーストは、分散剤（Ｅ）を使用する場合には、焼成ペースト１００質量％中に、分散剤（Ｅ）を０．０１～５質量％含むことが好ましく、０．１～３質量％含むことがより好ましい。 When the dispersant (E) is used, 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%.
　分散剤（Ｅ）の割合が上記範囲にあると、無機粉末（Ｄ）の焼成ペースト中での分散性がより良好となる。
添加剤
　本発明の焼成ペーストは、上述した成分のほかに、本発明の目的を損なわない範囲で従来知られている可塑剤、湿潤剤、消泡剤等を含有してもよい。 When the proportion of the dispersant (E) is in the above range, the dispersibility of the inorganic powder (D) in the fired paste becomes better.
Additives 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.
焼成ペーストの製造方法
　本発明の焼成ペーストは、後述のとおり粘性を有するため、上述した各成分の混合物を、ミキサー、ロール等を単独または適宜組み合わせて１段階または数段階に分けて混練することによって製造されることが好ましい。また、必要に応じて、３０～１５０℃で加熱してもよい。 Manufacturing method of baked paste Since 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. Preferably it is manufactured. Further, it may be heated at 30 to 150 ° C. as necessary.
焼成ペーストの粘度
　本発明の焼成ペーストの２５℃における粘度は、好ましくは２０～２００Ｐａ・ｓ、より好ましくは５０～２００Ｐａ・ｓ、さらに好ましくは１００～２００Ｐａ・ｓである。焼成ペーストの粘度が前記範囲にあると、塗工性に優れるとともに塗膜形成性も優れる。粘度の測定方法は、後述の実施例に記載の方法による。上記粘度は、焼成ペーストを組成物が均一な状態になるまで混練してから測定した値である。 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. When the viscosity of the fired paste is in the above range, the coating property is excellent as well as the coating property. 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.
焼成ペーストの使用方法
　上記焼成ペーストは、通常、基材に塗布したのち（以下「塗布工程」ともいう。）、乾燥させ（以下「乾燥工程」ともいう。）、積層物を焼成して（以下「焼成工程」ともいう。）使用される。 Method of Using Firing Paste 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”.
　塗布工程における基材としては、金属、セラミックス、グリーンシート、プラスチック、半導体等の部材が挙げられる。 Examples of the base material in the coating process include members such as metals, ceramics, green sheets, plastics, and semiconductors.
　塗布工程における塗布方法としては、スクリーン印刷、ダイコート印刷、ドクターブレード印刷、ロールコート印刷、オフセット印刷、グラビア印刷、フレキソ印刷、インクジェット印刷、ディスペンス印刷等を用いた塗布法、シート状に加工するためのキャスティング法が挙げられ、スクリーン印刷が好ましい。 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.
　乾燥工程は、溶剤（Ｃ）の乾燥を行う。 In the drying step, the solvent (C) is dried.
　焼成工程は、焼成ペースト用樹脂（酸性基含有（メタ）アクリル系ポリマー（Ａ）および窒素含有（メタ）アクリル系ポリマー（Ｂ））を熱分解させるため、窒素ガス等の不活性ガス気流下、通常５００～１，０００℃で、１～５時間行われる。 In the firing step, 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.
焼成ペーストの用途
　本発明の焼成ペーストの具体的な用途としては、ＭＬＣＣの製造に用いられる内部電極用ペースト、端子電極用ペースト、低温同時焼成セラミックス（ＬＴＣＣ）の製造に用いられる内部電極用ペースト、タッチパネルスクリーン用ペースト、ＰＤＰ製造に用いられる誘電体ペースト、隔壁材ペースト、蛍光体ペーストやＦＥＤの封止やＩＣパッケージの封止に用いられる封止用ガラスペースト、グリーンシート用ペースト等が挙げられ、例えば、ＭＬＣＣのグリーンシートの製造のために使用することが好ましい。ここで、グリーンシートとは、焼成ペーストを基材に塗布して得られた薄板状の未焼成体を意味する。 Uses of Firing Paste Specific uses of 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. For example, it is preferably used for the production of MLCC green sheets. Here, the green sheet means a thin plate-like unfired body obtained by applying a fired paste to a substrate.
　本発明の焼成ペーストを用いて、例えば、以下の方法を用いてＭＬＣＣを製造することができる。セラミック原料に、エタノール、およびポリビニルブチラール系バインダーを加えて混合、分散し、セラミックスラリーを作製する。次いで、このセラミックスラリーをシート状に成形し、セラミックグリーンシートを得る。そして、このセラミックグリーンシートに、内部電極形成用の本発明の焼成ペースト（無機粉末（Ｄ）としてニッケル粉末を使用）を印刷して、内部電極パターン（導電性ペースト層）を形成し、乾燥させる。 Using the fired paste of the present invention, for example, 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. .
　次いで、内部電極パターンが形成されたセラミックグリーンシートを、内部電極パターンが交互に逆の端部側に引き出されるように複数枚積層し、未焼成の積層体を得る。 Next, a plurality of ceramic green sheets on which the internal electrode patterns are formed are stacked so that the internal electrode patterns are alternately drawn out to the opposite end side to obtain an unfired stacked body.
　上記未焼成の積層体を、Ｎ2等の不活性ガス雰囲気中で焼成してセラミック積層体（積層セラミック素子）を得る。焼成後得られたセラミック積層体の両端面にＣｕペーストを塗布し、Ｎ2等の不活性ガス雰囲気中で焼成し、内部電極と電気的に接続された端子電極を形成することにより、ＭＬＣＣが得られる。 The unfired laminate is fired in an inert gas atmosphere such as N 2 to obtain a ceramic laminate (multilayer ceramic element). By 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.
　以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.
　実施例における各値の測定条件は以下の通りである。
＜重量平均分子量（Ｍｗ）＞
重量平均分子量は、ゲルパーミエーションクロマトグラフィー法（ＧＰＣ法）による分析を行い、ポリスチレン換算により算出した。
・測定装置：ＨＬＣ－８３２０ＧＰＣ（東ソー社製）
・ＧＰＣカラム構成：以下の４連カラム（すべて東ソー社製）
（１）ＴＳＫｇｅｌ　ＨｘＬ－Ｈ（ガードカラム）
（２）ＴＳＫｇｅｌ　ＧＭＨｘＬ
（３）ＴＳＫｇｅｌ　ＧＭＨｘＬ
（４）ＴＳＫｇｅｌ　Ｇ２５００ＨｘＬ
・流速：１．０ｍＬ／ｍｉｎ
・カラム温度：４０℃
・サンプル濃度：１．５（ｗ／ｖ）　（テトラヒドロフランで希釈）
・移動相溶媒：テトラヒドロフラン The measurement conditions for each value in the examples are as follows.
<Weight average molecular weight (Mw)>
The weight average molecular weight was analyzed by gel permeation chromatography (GPC method) and calculated by polystyrene conversion.
・ Measurement device: HLC-8320GPC (manufactured by Tosoh Corporation)
-GPC column configuration: The following four columns (all manufactured by Tosoh Corporation)
(1) TSKgel HxL-H (guard column)
(2) TSKgel GMHxL
(3) TSKgel GMHxL
(4) TSKgel G2500HxL
・ Flow rate: 1.0 mL / min
-Column temperature: 40 ° C
Sample concentration: 1.5 (w / v) (diluted with tetrahydrofuran)
・ Mobile phase solvent: Tetrahydrofuran
［製造例１］
　攪拌装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、酢酸エチル１００質量部、およびｉｓｏ－ブチルメタクリレート８８質量部、メタクリル酸２質量部、２－ヒドロキシプロピルメタクリレート１０質量部を仕込み、フラスコ内に窒素ガスを導入しながら３０分攪拌して窒素置換を行った後、フラスコの内容物を８０℃まで昇温した。次いで、フラスコ内の内容物を８０℃に維持しながら、２，２'－アゾビス－ｉｓｏ－ブチロニトリル（ＡＩＢＮ）０．３質量部を１時間おきに計５回添加した。８０℃で、最初のＡＩＢＮ投入より８時間反応させた後、室温まで冷却した。得られたポリマー溶液を、ｎ－ヘキサン２０００質量部中へ３０分かけて滴下を行い、ポリマー析出物を生成させた。ポリマー析出物については、２００メッシュ金網で濾別し、１０５℃で８時間乾燥することで、酸性基含有（メタ）アクリル系ポリマー（Ａ１）（ポリマー（Ａ１））を調製した。得られたポリマー（Ａ１）の重量平均分子量（Ｍｗ）は８万であり、ガラス転移温度（Ｔｇ）は４８℃であった。 [Production Example 1]
In a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 100 parts by mass of ethyl acetate, 88 parts by mass of iso-butyl methacrylate, 2 parts by mass of methacrylic acid, and 10 parts by mass of 2-hydroxypropyl methacrylate After charging and performing nitrogen substitution by introducing nitrogen gas into the flask for 30 minutes, the temperature in the flask was raised to 80 ° C. Next, while maintaining the contents in the flask at 80 ° C., 0.3 part by mass of 2,2′-azobis-iso-butyronitrile (AIBN) was added every 5 hours for a total of 5 times. 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.
［製造例２～９］
　重合反応に用いたモノマー成分を表1および表２に示すように変更したこと以外は製造例１と同様に行い、ポリマー（Ａ２）～（Ａ４）、および、ポリマー（Ｂ１）～（Ｂ５）を調製した。結果を表１、表２に示す。 [Production Examples 2 to 9]
The same procedure as in Production Example 1 was conducted except that the monomer components used in the polymerization reaction were changed as shown in Tables 1 and 2, and the polymers (A2) to (A4) and the polymers (B1) to (B5) were changed. Prepared. The results are shown in Tables 1 and 2.
　なお、ポリマー（Ａ４）、ポリマー（Ｂ５）については、添加するＡＩＢＮを０．３質量部から２質量部に変更して調製した。 In addition, about the polymer (A4) and the polymer (B5), AIBN to add was changed from 0.3 mass part to 2 mass parts, and was prepared.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
 ［実施例１］
　ポリマー（Ａ１）を２．７質量部、ポリマー（Ｂ１）を７．３質量部（モノマー（ａ１）：モノマー（ｂ１）のモル％比＝９．０：９１．０）を混合して得られる焼成ペースト用樹脂組成物１０質量％と、溶剤としてのジヒドロターピニルアセテート（沸点：２２０℃）９０質量部を混合し、ポリマーが溶剤に溶解した後、無機粉末としてのＮｉフィラー（平均粒径２００ｎｍ）を１００質量部配合し、自転・公転ミキサー（商品名「あわとり練太郎」、シンキー社製）で混練した。その後、さらに３本ロールで混練して、焼成ペーストを得た。焼成ペーストの各物性の測定結果を表３に示す。
Figure JPOXMLDOC01-appb-T000002
 [Example 1]
It is obtained by mixing 2.7 parts by mass of the polymer (A1) and 7.3 parts by mass of the polymer (B1) (monomer (a1): monomer (b1) molar ratio = 9.0: 91.0). After mixing the resin composition for baking paste 10% by mass and 90 parts by mass of dihydroterpinyl acetate (boiling point: 220 ° C.) as a solvent, the polymer is dissolved in the solvent, and then Ni filler (average particle diameter) as inorganic powder (200 nm) was blended in an amount of 100 parts by mass, and kneaded with a rotation / revolution mixer (trade name “Awatori Nertaro”, manufactured by Shinky Corporation). Thereafter, the mixture was further kneaded with three rolls to obtain a fired paste. Table 3 shows the measurement results of the physical properties of the fired paste.
［実施例２～５、比較例１～４］
　実施例１において、各ポリマーの配合種、および配合比を表３に記載のとおり変更した以外は、実施例１と同様にして焼成ペーストを製造し、各物性を評価した。測定結果を表３、表４に示す。 [Examples 2 to 5, Comparative Examples 1 to 4]
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.
《評価》
＜粘度＞
　実施例・比較例で得られた焼成ペーストを、Ｅ型粘度計によって２５℃にて粘度の測定を行ない、以下の基準で評価した。 <Evaluation>
<Viscosity>
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.
　粘度が１００Ｐａ・ｓ以上、２００Ｐａ・ｓ以下の場合：Ａ
　粘度が５０Ｐａ・ｓ以上、１００Ｐａ・ｓ未満である場合：Ｂ
　粘度が２０Ｐａ・ｓ以上、５０Ｐａ・ｓ未満である場合：Ｃ
　粘度が２０Ｐａ・ｓ未満である場合：Ｄ When the viscosity is 100 Pa · s or more and 200 Pa · s or less: A
When the viscosity is 50 Pa · s or more and less than 100 Pa · s: B
When the viscosity is 20 Pa · s or more and less than 50 Pa · s: C
When the viscosity is less than 20 Pa · s: D
＜印刷性＞
　実施例・比較例で得られた焼成ペーストをガラス板に６４０メッシュ、ギャップ０．１ｍｍ、速度３０ｃｍ／秒でスクリーン塗工、乾燥したものの表面粗さ（Ｒａ）を表面粗さ計で測定し、該表面粗さ（μｍ）の値を指標として以下の基準にしたがって印刷性を評価した。 <Printability>
The surface roughness (Ra) of the baked paste obtained in Examples / Comparative Examples was measured on a glass plate by screen coating at 640 mesh, gap 0.1 mm, speed 30 cm / sec, and dried with a surface roughness meter. Using the surface roughness (μm) value as an index, printability was evaluated according to the following criteria.
　Ｒａが０．２０以下である場合：Ａ
　Ｒａが０．２０を超えかつ０．３０以下である場合：Ｂ
　Ｒａが０．３０を超えかつ０．４０以下である場合：Ｃ
　Ｒａが０．４０より大きい場合：Ｄ 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
＜糸曳き性＞
　Ｅ型粘度計により２５℃で測定した粘度が１０Ｐａ・ｓとなるように実施例・比較例に記載の配合比で配合したポリマー（Ａ）およびポリマー（Ｂ）のブレンド物（焼成ペースト用樹脂組成物）を、ジヒドロターピニルアセテート溶剤に溶解した溶液に、ガラス棒を突き刺し引き上げた際に、溶液表面とガラス棒間に糸状で存在する溶液が切れるのに要する時間について測定を行い、以下の基準で評価した。 <Strongness>
Blend of polymer (A) and polymer (B) blended at blending ratios described in Examples and Comparative Examples so that the viscosity measured at 25 ° C. with an E-type viscometer is 10 Pa · s (resin composition for baked paste) When a glass rod is stabbed into a solution dissolved in a dihydroterpinyl acetate solvent, 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.
　３秒以下で溶液が切れる場合：Ａ
　３秒を超えて溶液が切れる場合：Ｂ
＜焼成性＞
　実施例・比較例記載の配合比で配合したポリマー（Ａ）およびポリマー（Ｂ）のブレンド物（焼成ペースト用樹脂組成物）を窒素雰囲気中７００℃で１時間の焼成（ＴＧ－ＤＴＡ）を行った場合の残炭の有無を以下の基準にしたがって目視にて確認して、共重合体の焼成性を以下の基準で評価した。 If the solution runs out in 3 seconds or less: A
If the solution runs out after 3 seconds: B
<Baking properties>
The blend of polymer (A) and polymer (B) (resin composition for fired paste) blended at the blending ratio described in the examples and comparative examples was fired at 700 ° C. for 1 hour (TG-DTA) in a nitrogen atmosphere. The presence or absence of residual charcoal was confirmed visually according to the following criteria, and the firing properties of the copolymer were evaluated according to the following criteria.
　残炭がない場合：Ａ
　残炭が有る場合：Ｂ When there is no remaining coal: A
When there is residual coal: B
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
 　実施例１～６の焼成ペーストは、適度な粘性を有し、印刷性が良好で、焼成性も良好であることがわかる。
Figure JPOXMLDOC01-appb-T000004
 It can be seen that the fired pastes of Examples 1 to 6 have appropriate viscosity, good printability, and good fireability.
　比較例１のように、ポリマー（Ａ）およびポリマー（Ｂ）のＴｇが３０℃より低い場合、解重合性が悪いため焼成性が悪く、また、印刷表面もべたつきを生じてしまう。 As in Comparative Example 1, when the Tg of the polymer (A) and the polymer (B) is lower than 30 ° C., the depolymerization is poor and the firing property is poor, and the printing surface is also sticky.
　比較例２のように、Ｍｗが５０万よりも小さいポリマー（Ａ）とポリマー（Ｂ）とをブレンドしたものでは粘性が低く、印刷性がよくない。 As in Comparative Example 2, a blend of a polymer (A) and a polymer (B) having an Mw smaller than 500,000 has low viscosity and poor printability.
　比較例３および４のように、ポリマー（Ａ）およびポリマー（Ｂ）のブレンドにおける、モノマー（ａ１）とモノマー（ｂ１）のブレンド比が本発明の範囲を外れたものや、比較例５および６のように、ポリマー（Ａ）またはポリマー（Ｂ）を単独で用いたものは、適度な粘度のものを調製することが困難である。 As in Comparative Examples 3 and 4, 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.
　したがって、本発明の焼成ペースト用樹脂は、ポリマー（Ａ）およびポリマー（Ｂ）を、所定の割合でブレンドすることにより、高粘度化と擬塑性とを両立させ、種々印刷方式に適合した焼成ペースト用樹脂組成物を提供できることがわかる。 Therefore, 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.
　本発明の焼成ペースト用樹脂組成物は、焼成ペーストのバインダー樹脂成分として好適に用いることができる。また本発明の焼成ペーストは、回路形成やコンデンサーの製造等に用いられる導電ペースト、セラミック粉末を含むセラミックペースト、ガラス粉末を含むガラスペーストなどとして、無機粉末によりパターンを形成する用途に好適に用いることができる。 The resin composition for fired paste of the present invention can be suitably used as a binder resin component of the fired paste. Also, 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.

Claims (6)

  1. 　カルボキシル基およびスルホン酸基から選ばれる少なくとも１種の基を含有する酸性基含有モノマーと、（メタ）アクリル酸アルキルエステルとを含むモノマー成分（ａ）の共重合体であり、重量平均分子量１万～５０万、ガラス転移温度３０℃以上である酸性基含有（メタ）アクリル系ポリマー（Ａ）、および、
    　窒素含有モノマーと、（メタ）アクリル酸アルキルエステルとを含むモノマー成分（ｂ）の共重合体であり、重量平均分子量１万～５０万、ガラス転移温度３０℃以上である窒素含有（メタ）アクリル系ポリマー（Ｂ）を、
    　酸性基含有モノマー：窒素含有モノマーのモル比が、５：９５～８５：１５の比率となるようにブレンドすることを特徴とする焼成ペースト用樹脂組成物。     It is a copolymer of a monomer component (a) containing an acidic group-containing monomer containing at least one group selected from a carboxyl group and a sulfonic acid group, and a (meth) acrylic acid alkyl ester, and has a weight average molecular weight of 10,000. Up to 500,000, an acidic group-containing (meth) acrylic polymer (A) having a glass transition temperature of 30 ° C. or higher, and
    A copolymer of a monomer component (b) containing a nitrogen-containing monomer and a (meth) acrylic acid alkyl ester, and having a weight average molecular weight of 10,000 to 500,000 and a glass transition temperature of 30 ° C. or higher. 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.
  2. 　前記モノマー成分（ａ）および前記モノマー成分（ｂ）の少なくとも一方が、水酸基含有モノマーを含むことを特徴とする請求項１に記載の焼成ペースト用樹脂組成物。 The resin composition for a fired paste according to claim 1, wherein at least one of the monomer component (a) and the monomer component (b) contains a hydroxyl group-containing monomer.
  3. 　前記窒素含有モノマーが、ヘテロ環構造を有することを特徴とする請求項１または２に記載の焼成ペースト用樹脂組成物。 The resin composition for fired paste according to claim 1 or 2, wherein the nitrogen-containing monomer has a heterocyclic structure.
  4. 　請求項１～３のいずれか１項に記載の焼成ペースト用樹脂組成物と、無機粉末と、溶剤とを含むことを特徴とする焼成ペースト。 A fired paste comprising the resin composition for a fired paste according to any one of claims 1 to 3, an inorganic powder, and a solvent.
  5. 　さらに分散剤を含むことを特徴とする請求項４に記載の焼成ペースト。 The baking paste according to claim 4, further comprising a dispersant.
  6. 　請求項４または５に記載の焼成ペーストを用いて製造された多層セラミックコンデンサー。 A multilayer ceramic capacitor produced using the fired paste according to claim 4 or 5.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112062895A (en) * 2020-08-06 2020-12-11 无锡亚星新材料科技有限公司 Resin for sintering slurry and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06346048A (en) * 1993-06-08 1994-12-20 Mitsubishi Rayon Co Ltd Fluorescent material paste composition
JPH07238239A (en) * 1994-03-01 1995-09-12 Mitsubishi Rayon Co Ltd Fluorescent paste composition
JPH09111134A (en) * 1995-07-24 1997-04-28 Sanyo Chem Ind Ltd Thermally reversible thickening composition
JP2001089671A (en) * 1999-09-22 2001-04-03 Nippon Synthetic Chem Ind Co Ltd:The Baking resin composition, baking photosensitive resin composition, and process for forming ceramic pattern
JP2005274865A (en) * 2004-03-24 2005-10-06 Taiyo Ink Mfg Ltd Photosensitive paste composition for calcination and calcined pattern using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06346048A (en) * 1993-06-08 1994-12-20 Mitsubishi Rayon Co Ltd Fluorescent material paste composition
JPH07238239A (en) * 1994-03-01 1995-09-12 Mitsubishi Rayon Co Ltd Fluorescent paste composition
JPH09111134A (en) * 1995-07-24 1997-04-28 Sanyo Chem Ind Ltd Thermally reversible thickening composition
JP2001089671A (en) * 1999-09-22 2001-04-03 Nippon Synthetic Chem Ind Co Ltd:The Baking resin composition, baking photosensitive resin composition, and process for forming ceramic pattern
JP2005274865A (en) * 2004-03-24 2005-10-06 Taiyo Ink Mfg Ltd Photosensitive paste composition for calcination and calcined pattern using the same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019009124A1 (en) 2017-07-07 2019-01-10 タツタ電線株式会社 Electroconductive resin composition and method for manufacturing shielded package using same
JPWO2021064826A1 (en) * 2019-09-30 2021-04-08
WO2021064826A1 (en) * 2019-09-30 2021-04-08 昭和電工マテリアルズ株式会社 Copper paste for joining, method for manufacturing joined body, and joined body
JP7392728B2 (en) 2019-09-30 2023-12-06 株式会社レゾナック Copper paste for bonding, method for manufacturing bonded body, and bonded body

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