WO2020152939A1 - 重合体、導電性ペースト組成物、セラミックス用バインダー樹脂、セラミックススラリー組成物および導電ペースト用バインダー樹脂 - Google Patents
重合体、導電性ペースト組成物、セラミックス用バインダー樹脂、セラミックススラリー組成物および導電ペースト用バインダー樹脂 Download PDFInfo
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- WO2020152939A1 WO2020152939A1 PCT/JP2019/043445 JP2019043445W WO2020152939A1 WO 2020152939 A1 WO2020152939 A1 WO 2020152939A1 JP 2019043445 W JP2019043445 W JP 2019043445W WO 2020152939 A1 WO2020152939 A1 WO 2020152939A1
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- monomer
- binder resin
- parts
- conductive paste
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- RKFHXLBWROBFRL-UHFFFAOYSA-N CCC(CCC1OC(NC)=O)CC1O Chemical compound CCC(CCC1OC(NC)=O)CC1O RKFHXLBWROBFRL-UHFFFAOYSA-N 0.000 description 2
- NNKWBMSBCXHDAJ-UHFFFAOYSA-N CCC(COC(NC)=O)O Chemical compound CCC(COC(NC)=O)O NNKWBMSBCXHDAJ-UHFFFAOYSA-N 0.000 description 2
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
- C08F220/346—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links and further oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
Definitions
- the present invention relates to a polymer having excellent thixotropy and thermal decomposability, which is particularly suitable as a binder resin for paste.
- the present invention also relates to a polymer having excellent sheet strength and thermal decomposability, which is particularly suitable as a binder resin for ceramics.
- the present invention also relates to a binder resin for a conductive paste, which has excellent solubility in a low polar solvent, excellent thixotropy and thermal decomposability, and excellent adhesiveness to a sheet.
- the metal paste used for forming internal electrode layers of multilayer electronic components such as multilayer ceramic capacitors and conductive layers of solar cells is mainly composed of metal powder such as nickel or copper, a solvent, and a binder resin. It is printed on the sheet by a method such as printing.
- Patent Document 1 As the binder resin, an ethyl cellulose resin having high thixotropy, no stringing or bleeding during printing, and suitable for printing was used. However, since ethyl cellulose has a low thermal decomposability and carbon content remains during firing, there is a large amount of heating residue, leading to a problem of electrode defects.
- the thixotropic property of the metal paste means a property that the apparent viscosity becomes low in a state where the shear rate is high, and the apparent viscosity becomes high in a state where the shear rate is low and the state where the shear rate is not sheared.
- Ceramic slurries used for sheet formation such as formation of dielectric layers of multilayer electronic components such as monolithic ceramic capacitors are mainly composed of ceramic powders such as metal oxides such as barium titanate and alumina and nitrides such as silicon nitride. It is composed of a solvent and a binder resin, and formed into a sheet by a method such as a doctor blade method.
- the green sheet formed into a sheet is required to have strength and flexibility so as not to have a dimensional change or a breakage when the sheet is handled. Therefore, as shown in Patent Document 2, a polyvinyl butyral resin having excellent strength has been used as the binder resin.
- Conductive pastes used for forming internal electrode layers of multilayer electronic components such as multilayer ceramic capacitors and conductive layers of solar cells mainly consist of metal particles such as nickel and copper, solvent and binder resin, and are screen-printed. It is printed on the sheet by a method such as.
- the binder resin an ethyl cellulose resin having a high thixotropic property and suitable for printing has been used.
- the thixotropic property means a property that the apparent viscosity becomes low in a state where the shear rate is high, and the apparent viscosity becomes high in a state where the shear rate is low and the state where the shear rate is not sheared.
- Patent Document 3 the addition of polyvinyl butyral to ethyl cellulose has been studied to improve the sheet adhesiveness, but there is a problem that thermal decomposability is lowered and sufficient adhesiveness cannot be obtained. there were.
- An object of the present invention is to provide a novel polymer which can provide a paste having excellent thixotropy and thermal decomposability.
- Another object of the present invention is to provide a binder resin for ceramics which has high sheet strength and flexibility and is excellent in thermal decomposability.
- An object of the present invention is to provide a binder resin for a conductive paste, which has excellent solubility in a low-polarity solvent, as well as excellent thixotropy, thermal decomposability, and adhesiveness.
- the present inventor found that the above problems can be solved by a polymer having a specific structure having a hydroxyurethane structure.
- the present invention is as follows. [1] The molar ratio of the monomer (A) represented by the following formula (1) is 10 to 100 mol %, and the molar ratio of the other monomer (B) copolymerizable with the monomer (A) is 0. % To 90 mol %, and a weight average molecular weight of 10,000 to 1,000,000.
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents an alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl group having 1 to 18 carbon atoms
- A represents an alkylene group having 1 to 10 carbon atoms
- X represents 0 or 1
- Y 1 is one or more structures selected from the group consisting of hydroxyurethane structures of the following formulas (2) and (3).
- the ratio of the polymer is 0.5 to 30 parts by weight and the ratio of the organic solvent is 10 to 200 parts by weight when the ratio of the metal particles is 100 parts by weight.
- a ceramic binder resin made of a polymer having a specific structure having a hydroxyurethane structure can solve the above problems.
- the ceramic binder resin of the present invention is as follows. [4] A binder resin for ceramics, comprising the polymer described in [1].
- a ceramics slurry composition comprising the binder resin of [4], an organic solvent and ceramics particles.
- the binder resin for conductive paste of the present invention is as follows. [7] A binder resin for conductive paste, which comprises the polymer of [1], The molar ratio of the monomer (A) represented by the formula (1) is 10 to 90 mol %, and the other monomer (B) is an alkyl (meth)acrylate represented by the following general formula (Z). Ester (C) and the monomer (A) and another monomer (D) copolymerizable with the (meth)acrylic acid alkyl ester (C), and the molar ratio of the (meth)acrylic acid alkyl ester (C).
- R 3 represents a hydrogen atom or a methyl group
- R 4 represents an alkyl group having 1 to 18 carbon atoms.
- a conductive paste composition comprising the binder resin for conductive paste according to [7] or [8], an organic solvent, and metal particles.
- the mass ratio of the binder resin for conductive paste is 0.5 to 30 parts by mass and the mass ratio of the organic solvent is 10 to 200 parts by mass with respect to 100 parts by mass of the metal particles.
- the polymer of the present invention has excellent solubility in paste solvents, excellent thixotropy, no stringing or bleeding during printing, and excellent thermal decomposability.
- the paste using the polymer of the present invention as the binder resin, particularly the metal paste has high printability and can reduce the residual carbon content during firing.
- the binder resin composition for ceramics of the present invention has excellent sheet strength and flexibility, excellent solubility in paste solvents, and excellent thermal decomposability.
- the ceramic green sheet using the binder resin for ceramics of the present invention has excellent sheet strength and flexibility, and can reduce the residual carbon content during firing.
- the polymer of the present invention has excellent solubility in a paste solvent, thixotropy, thermal decomposition, and adhesiveness.
- the conductive paste using the polymer of the present invention as a binder resin has high printability and adhesiveness, and further has a small amount of residual carbon upon firing.
- a conductive paste can be prepared using a low-polarity solvent, and sheet attack can be suppressed.
- R 1 is a hydrogen atom or a methyl group, and a methyl group is particularly preferable from the viewpoint of ease of polymerization.
- R 2 is an alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl group having 1 to 18 carbon atoms.
- alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, iso-butyl group, tert-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, decyl group, dodecyl group, stearyl group and the like can be mentioned.
- the number of carbon atoms of the alkyl group constituting R 2 is preferably 2 to 12, and more preferably 3 to 6.
- the number of carbon atoms of the alkyl group of R 2 is preferably 2 to 12, and more preferably 3 to 6 from the viewpoint of ease of synthesis and sheet strength. Further, by setting the carbon number of the alkyl group of R 2 to be 3 to 6, both flexibility and sheet strength can be achieved.
- hydroxyalkyl group having 1 to 18 carbon atoms examples include hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, 5-hydroxybutyl group, 8 -Hydroxyoctyl group, 12-hydroxydodecyl group and the like can be mentioned.
- the hydroxyalkyl group constituting R 2 preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms. ..
- the number of hydroxyalkyl group carbon atoms in R 2 is preferably 2 to 12, and more preferably 3 to 6 from the viewpoint of ease of synthesis and sheet strength. Further, by setting the hydroxyalkyl group of R 2 to have 3 to 6 carbon atoms, both flexibility and sheet strength can be achieved.
- R 2 is more preferably an alkyl group.
- A is an alkylene group having 1 to 10 carbon atoms, preferably 6 or less carbon atoms, more preferably 4 or less carbon atoms from the viewpoint of thixotropy. From the viewpoint of sheet strength, A preferably has 6 or less carbon atoms, and more preferably 4 or less carbon atoms.
- X is 0 or 1, and 0 is preferable from the viewpoint of thixotropy or sheet strength.
- Y 1 is one or more hydroxyurethane structures selected from the group consisting of the hydroxyurethane structures of formula (2) and formula (3). From the viewpoint of thixotropy, the structure of the formula (2) having sheet strength and heat decomposability is particularly preferable.
- the monomer (A) one type may be used alone, or two or more types may be used in combination.
- the molar ratio of the monomer (A) is 10 mol% or more. If the molar ratio of the monomer (A) is too low, thixotropy and sheet strength may decrease. Therefore, the amount is 10 mol% or more, preferably 15 mol% or more, and more preferably 20 mol% or more.
- the molar ratio of the monomer (A) is 100 mol% or less.
- the polymer of the present invention becomes a homopolymer, and when the molar ratio of the monomer (A) is less than 100 mol %, the polymer of the present invention. Is a copolymer.
- the molar ratio of the monomer (A) is 50 mol% or less, the thermal decomposability of the polymer is further improved, but from this viewpoint, it is more preferably 40 mol% or less.
- the molar ratio of the monomer (A) among the monomers constituting the polymer is 10 mol% or more. If the molar ratio of the monomer (A) is too low, thixotropy may be deteriorated, so the content is set to 10 mol% or more, preferably 15 mol% or more, and more preferably 20 mol% or more. Further, in the case of the conductive binder resin, the molar ratio of the monomer (A) among the monomers constituting the polymer is 90 mol% or less. When the molar ratio of the monomer (A) is 50 mol% or less, the thermal decomposability of the polymer is further improved, but from this viewpoint, it is more preferably 40 mol% or less.
- the monomer (A) a compound in which the hydroxy urethane structure of Y 1 of the formula (1) is mixed with an isomer of the monomer (A) represented by the formula (4) or the formula (5) may be used. ..
- the monomer (B) is a vinyl-based monomer copolymerizable with the monomer (A), and examples thereof include (meth)acrylic acid ester compounds, aromatic alkenyl compounds, vinyl cyanide compounds, and acrylamide compounds.
- Examples of the (meth)acrylic acid ester compound include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, n- Hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate and the like can be mentioned.
- aromatic alkenyl compounds examples include styrene, ⁇ -methylstyrene, p-methylstyrene, p-methoxystyrene and the like.
- vinyl cyanide compounds examples include acrylonitrile and methacrylonitrile.
- acrylamide compounds include acrylamide and methacrylamide.
- the monomer (B) one type may be used alone, or two or more types may be used in combination.
- the (meth)acrylic acid ester compound is preferable, and the (meth)acrylic acid alkyl ester compound is particularly preferable, from the viewpoint of solvent solubility and thermal decomposability or sheet strength.
- the alkyl group preferably has 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 8 carbon atoms, and particularly preferably 1 to 4 carbon atoms.
- Methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate and iso-butyl (meth)acrylate are preferable, and methyl methacrylate and iso-butyl methacrylate are particularly preferable.
- the molar ratio is preferably 1/1 to 1/20, more preferably 1/2 to 1/10.
- the total amount of the monomer (A) and the monomer (B) is 100 mol %. Therefore, the molar ratio of the monomer (B) is 0 to 90 mol %, but from the viewpoint of thermal decomposability, it is preferably 40 to 90 mol %, and more preferably 50 to 90 mol %.
- the weight average molecular weight of the polymer of the present invention can be determined in terms of polystyrene using gel permeation chromatography (GPC), and is 10,000 to 1,000,000, preferably 10,000 to 800, 000, more preferably 30,000 to 300,000. If the weight average molecular weight of the polymer is too low, the strength and viscosity of the polymer will be insufficient, and if the weight average molecular weight is too high, solvent solubility and printability may decrease.
- GPC gel permeation chromatography
- the weight average molecular weight of the polymer constituting the binder resin for ceramics of the present invention can be determined in terms of polystyrene using gel permeation chromatography (GPC), and is 10,000 to 1,000,000. It is preferably 30,000 to 800,000, more preferably 50,000 to 500,000. If the weight average molecular weight of the polymer is too low, the sheet strength will be insufficient, and if the weight average molecular weight is too high, the slurry may thicken and the coating property may be deteriorated.
- GPC gel permeation chromatography
- the monomer (A) of the present invention is a monomer having a hydroxyurethane bond.
- the monomer (A) can be obtained, for example, by an addition reaction of a compound having both a (meth)acryloyl group and a 5-membered ring carbonate group with an amine compound.
- the compound having both a (meth)acryloyl group and a 5-membered ring carbonate group used in the present invention is represented by the general formulas (6) and (7).
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents an alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl group having 1 to 19 carbon atoms
- A is An alkylene group having 1 to 10 carbon atoms is shown, and X is 0 or 1.
- the amine compound is preferably a primary amine compound or a secondary amine compound, more preferably a primary amine compound.
- the reaction between the 5-membered cyclic carbonate compound and the amine compound can be carried out by a known method by mixing the two and raising the temperature if desired. Moreover, you may add a well-known polymerization inhibitor as needed. It is desirable to carry out this reaction at a temperature of 0 to 100°C, preferably 5 to 50°C. Further, the above reaction may use a solvent, and can be carried out, for example, in the presence of acetone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, xylene, tetrahydrofuran or the like.
- the polymer in the invention can be obtained by radical polymerization of a monomer mixture containing at least the monomer (A).
- the polymerization can be performed by a known method.
- solution polymerization, suspension polymerization, emulsion polymerization and the like can be mentioned, but solution polymerization and suspension polymerization are preferable from the viewpoint of easily adjusting the weight average molecular weight of the copolymer within the above range.
- a well-known thing can be used for a polymerization initiator.
- organic peroxide such as di(4-t-butylcyclohexyl)peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,2′-azobis
- azo-based polymerization initiators such as isobutyronitrile.
- These polymerization initiators may be used alone or in combination of two or more.
- the amount of the polymerization initiator used can be appropriately set according to the combination of monomers used, reaction conditions, and the like.
- the whole amount may be charged all at once, a part thereof may be charged all at once and the rest may be added dropwise, or the whole amount may be added dropwise. Further, it is preferable to add a polymerization initiator together with the above-mentioned monomer, because the reaction can be easily controlled, and it is preferable to add a polymerization initiator after the addition of the monomer because the residual monomer can be reduced.
- a solvent in which a monomer and a polymerization initiator are dissolved can be used. Specifically, methanol, ethanol, 1-propanol, acetone, methyl ethyl ketone, propylene glycol monomethyl ether, etc. Can be mentioned.
- the concentration of the monomer (total amount) in the polymerization solvent is preferably 10 to 60% by mass, particularly preferably 20 to 50% by mass. If the concentration of the monomer mixture is too low, the monomer is likely to remain, and the molecular weight of the resulting copolymer may decrease. If the concentration of the monomer is too high, it may be difficult to control heat generation.
- the whole amount may be charged all at once, a part thereof may be charged all at once and the rest may be added dropwise, or the entire amount may be added dropwise. From the viewpoint of easy control of heat generation, it is preferable to charge a part of them all at once and drop the rest, or drop the entire amount.
- the polymerization temperature depends on the type of polymerization solvent, and is, for example, 50°C to 110°C.
- the polymerization time depends on the kind of the polymerization initiator and the polymerization temperature. For example, when di(4-t-butylcyclohexyl)peroxydicarbonate is used as the polymerization initiator, when the polymerization temperature is 70° C. About 6 hours is suitable.
- a copolymer relating to the resin composition of the present invention can be obtained.
- the obtained copolymer may be used as it is or may be isolated by subjecting the reaction solution after the polymerization reaction to filtration and purification.
- Metal paste The polymer of the present invention is particularly suitable as a binder resin for metal paste.
- the metal paste contains a metal powder and a solvent in addition to the polymer of the present invention.
- Examples of such metal powder include platinum, gold, silver, copper, nickel, tin, palladium, aluminum and alloys of these metals. Among these, silver, copper, nickel and aluminum are preferable, and nickel is more preferable.
- the median particle diameter (D 50 ) of the metal powder is preferably 0.05 ⁇ m to 50.0 ⁇ m. Among these, 0.06 ⁇ m to 10.0 ⁇ m is more preferable, 0.07 ⁇ m to 1.00 ⁇ m is still more preferable, and 0.10 ⁇ m to 0.30 ⁇ m is particularly preferable.
- the particle size can be determined by a dynamic light scattering method or a laser diffraction type particle size distribution measuring device.
- hydrocarbon solvents such as toluene and xylene
- ester solvents such as ethyl acetate and butyl acetate
- alcohol solvents such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, 1-butanol and diacetone alcohol
- Glycol ether solvents such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, glycol ether acetate solvents such as propylene glycol monomethyl ether acetate, terpineol, dihydroterpineol , Terpineol-based solvents such as dihydroterpineol acetate, and ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.
- glycol ether acetate solvents and terpineol solvents are preferable, terpineol solvents are more preferable, terpineol or dihydroterpineol are further preferable, and dihydroterpineol is particularly preferable. These may be used alone or in combination of two or more.
- the content of the binder resin in the metal paste is preferably 0.5 to 30 parts by weight, more preferably 1 to 15 parts by weight, and further preferably 1 to 10 parts by weight, based on 100 parts by weight of the metal powder. Preferred is 1 to 5 parts by weight, and particularly preferred. Further, the content of the solvent in the metal paste is preferably 10 to 200 parts by weight, more preferably 50 to 150 parts by weight, and further preferably 75 to 125 parts by weight, based on 100 parts by weight of the metal powder. .. In addition to these, other components such as a surfactant and an antioxidant can be blended if necessary.
- any known means can be used for stirring without particular limitation, and for example, a PD mixer or a planetary kneader can be preferably used, and a planetary kneader is particularly preferably used.
- a kneader, a bead mill, or a triple roll can be preferably used, and a triple roll is particularly preferably used.
- the metal paste is printed on the sheet by a method such as screen printing
- the polymer of the present invention is particularly suitable as a binder resin for ceramics slurry.
- the ceramics slurry contains ceramics powder and a solvent in addition to the polymer of the present invention.
- Ceramic powders examples include metal oxides such as alumina and barium titanate, and nitrides such as silicon nitride and aluminum nitride.
- the central particle diameter (D50) of the ceramic powder that is, the volume cumulative particle diameter D50 measured by a laser diffraction/scattering particle size distribution measuring device is preferably 0.05 ⁇ m to 50.0 ⁇ m.
- the solvent include hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, alcohol solvents such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, 1-butanol, diacetone alcohol, and ethylene glycol.
- Glycol ether solvents such as monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, glycol ether acetate solvents such as propylene glycol monomethyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl
- Examples thereof include ketone solvents such as ketones, and these can be used alone or as a mixture of two or more kinds.
- the content of the binder resin in the ceramic slurry is preferably 0.5 to 30 parts by weight when the weight of the ceramic powder is 100 parts by weight. Further, the content of the solvent in the ceramic slurry is preferably 10 to 200 parts by weight when the weight of the ceramic powder is 100 parts by weight. In addition to these, other components such as a surfactant and an antioxidant can be blended if necessary.
- the mixture is stirred and dispersed to obtain a ceramic slurry.
- Any known means can be used for stirring without particular limitation, and for example, a ball mill, a bead mill, a planetary kneader or the like can be used, and a ball mill is particularly preferably used.
- Ceramics slurry is molded on a carrier film by a method such as doctor blade method
- the resin of the present invention has a molar ratio of the monomer (A) represented by the formula (1) of 10 mol% to 90 mol %, and the other monomer (B) is represented by the following general formula ( Z) a (meth)acrylic acid alkyl ester (C) and the monomer (A), and another monomer (D) copolymerizable with the (meth)acrylic acid alkyl ester (C), )
- the molar ratio of the alkyl acrylate (C) is 10 to 90 mol %
- the molar ratio of the other monomer (D) is 0 to 30 mol %.
- the (meth)acrylic acid alkyl ester (C) of the present invention is represented by the following general formula (Z).
- R 3 is a hydrogen atom or a methyl group.
- R 4 is an alkyl group having 1 to 18 carbon atoms. Examples of the alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, iso-butyl group, tert-butyl group, n-hexyl group, n-octyl group, Examples thereof include a 2-ethylhexyl group, a decyl group, a dodecyl group, and a stearyl group. From the viewpoint of polymerizability and the glass transition point of the polymer, R 4 preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms.
- the (meth)acrylic acid alkyl ester (C) one type may be used alone, or two or more types may be used in combination. From the viewpoint of thermal decomposability, it is preferable to use a (meth)acrylic acid alkyl ester in which R 4 is a branched alkyl group and a (meth)acrylic acid alkyl ester in which R 4 is a linear alkyl group in combination.
- Examples of the branched alkyl group constituting R 4 include an isopropyl group, an iso-butyl group, a tert-butyl group, and a 2-ethylhexyl group, and examples of a linear alkyl group for R 4 include a methyl group and an ethyl group. , N-propyl group, n-butyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-stearyl group and the like.
- the ratio of the (meth)acrylic acid alkyl ester having a branched alkyl group of R 4 in the (meth)acrylic acid alkyl ester (C) is preferably 40 to 95 mol %, more preferably 50 to 90 mol %.
- R 3 is a hydrogen atom (b1) and R 3 is a combination of a monomer of methyl groups (b2).
- the ratio [(b1)/ ⁇ (b1)+(b2) ⁇ of (b1) to the total amount of (b1) and (b2) is preferably 1 to 50 mol %, more preferably 5 to 30 mol %. preferable.
- the molar ratio of the (meth)acrylic acid alkyl ester (C) is 10 mol% or more. If the molar ratio of the (meth)acrylic acid alkyl ester (C) is too low, the strength and thermal decomposability of the binder resin may decrease, so it is set to 10 mol% or more, preferably 30 mol% or more, 50 mol% or more is particularly preferable.
- the molar ratio of the (meth)acrylic acid alkyl ester (C) is 90 mol% or less. If the molar ratio of the (meth)acrylic acid alkyl ester (C) is too high, thixotropy may be deteriorated. Therefore, it is 90 mol% or less, preferably 85 mol% and particularly preferably 80 mol% or less.
- Examples of the (meth)acrylic acid ester compound (C) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate. , N-hexyl(meth)acrylate, n-octyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, decyl(meth)acrylate, dodecyl(meth)acrylate, stearyl(meth)acrylate and the like.
- the polymer of the present invention may consist of the monomer (A) and the (meth)acrylic acid alkyl ester (C), or may further contain another monomer (D) capable of being polymerized therewith in an amount of 30 mol% or less. Good.
- the ratio of the other monomer is 30 mol% or less, more preferably 15 mol% or less, and may be 0 mol%.
- acrylamide dimethylacrylamide, diethylacrylamide, acrylonitrile, etc. can be mentioned.
- the weight average molecular weight of the binder resin for conductive paste of the present invention can be determined in terms of polystyrene by gel permeation chromatography (GPC), and is 10,000 to 1,000,000, preferably 10,000. It is ⁇ 800,000, and more preferably 30,000 to 300,000. If the weight average molecular weight of the polymer is too low, the strength and viscosity of the polymer will be insufficient, and if the weight average molecular weight is too high, solvent solubility and printability may decrease.
- GPC gel permeation chromatography
- the polymer in the present invention can be obtained by radical polymerization of a monomer mixture containing at least the monomer (A) and the monomer (C).
- the polymerization can be performed by a known method.
- solution polymerization, suspension polymerization, emulsion polymerization and the like can be mentioned, but solution polymerization and suspension polymerization are preferable from the viewpoint of easily adjusting the weight average molecular weight of the copolymer within the above range.
- polymerization initiator known ones can be used.
- organic peroxide such as di(4-t-butylcyclohexyl)peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,2′-azobis
- azo-based polymerization initiators such as isobutyronitrile.
- the amount of the polymerization initiator used can be appropriately set according to the combination of monomers used, reaction conditions, and the like.
- the polymerization initiator for example, the whole amount may be charged all at once, a part thereof may be charged all at once and the rest may be added dropwise, or the whole amount may be added dropwise.
- a solvent in which a monomer and a polymerization initiator are dissolved can be used, and specifically, methanol, ethanol, 1-propanol, acetone, methyl ethyl ketone, propylene glycol monomethyl ether, etc. Can be mentioned.
- the concentration of the monomer (total amount) in the polymerization solvent is preferably 10 to 60% by mass, and particularly preferably 20 to 50% by mass. If the concentration of the monomer mixture is too low, the monomer is likely to remain, and the molecular weight of the resulting copolymer may decrease. If the concentration of the monomer is too high, it may be difficult to control heat generation.
- the whole amount may be charged all at once, a part thereof may be charged all at once and the rest may be added dropwise, or the entire amount may be added dropwise. From the viewpoint of easy control of heat generation, it is preferable to charge a part of them all at once and drop the rest, or drop the entire amount.
- the polymerization temperature depends on the type of polymerization solvent, and is, for example, 50°C to 110°C.
- the polymerization time depends on the kind of the polymerization initiator and the polymerization temperature. For example, when di(4-t-butylcyclohexyl)peroxydicarbonate is used as the polymerization initiator, when the polymerization temperature is 70° C. About 6 hours is suitable.
- a copolymer relating to the resin composition of the present invention can be obtained.
- the obtained copolymer may be used as it is or may be isolated by subjecting the reaction solution after the polymerization reaction to filtration and purification.
- the polymer of the present invention is particularly suitable as a binder resin for conductive paste.
- the conductive paste contains a metal powder and a solvent in addition to the polymer of the present invention.
- Examples of such metal powder include platinum, gold, silver, copper, nickel, tin, palladium, aluminum and alloys of these metals. Among these, silver, copper, nickel and aluminum are preferable, and nickel is more preferable.
- the median particle diameter (D 50 ) of the metal powder is preferably 0.05 ⁇ m to 50.0 ⁇ m. Among these, 0.06 ⁇ m to 10.0 ⁇ m is more preferable, 0.07 ⁇ m to 1.00 ⁇ m is still more preferable, and 0.10 ⁇ m to 0.30 ⁇ m is particularly preferable.
- the particle size can be determined by a dynamic light scattering method or a laser diffraction type particle size distribution measuring device.
- hydrocarbon solvents such as toluene and xylene
- ester solvents such as ethyl acetate and butyl acetate
- alcohol solvents such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, 1-butanol and diacetone alcohol
- Glycol ether solvents such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, glycol ether acetate solvents such as propylene glycol monomethyl ether acetate, terpineol, dihydroterpineol , Terpineol-based solvents such as dihydroterpineol acetate, and ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.
- glycol ether acetate-based solvents and terpineol-based solvents are preferable, terpineol-based solvents are more preferable, terpineol or dihydroterpineol are more preferable, and dihydroterpineol is particularly preferable. These may be used alone or in combination of two or more.
- the solvent is preferably a low polar solvent.
- the low-polarity solvent in the present invention means one having an SP value [(cal/cm 3 ) 0.5 ] at 25° C. of 9.0 or less.
- the SP value at 25° C. [(cal/cm 3 ) 0.5 ] is preferably in the range of 7.5 to 9.0.
- the SP value can be obtained from Fedor's estimation method (SP value basics/applications and calculation method published by Information Technology Corporation, 2005).
- dihydroterpineol, dihydroterpineol acetate and diethylene glycol monobutyl ether acetate are preferred, and dihydroterpineol acetate and diethylene glycol monobutyl ether acetate are particularly preferred.
- the content of the binder resin in the conductive paste is preferably 0.5 to 30 parts by weight, more preferably 1 to 15 parts by weight, and further preferably 1 to 10 parts by weight, based on 100 parts by weight of the metal powder. Preferred is 1 to 5 parts by weight, and particularly preferred. Further, the content of the solvent in the conductive paste is preferably 10 to 200 parts by weight, more preferably 50 to 150 parts by weight, and further preferably 75 to 125 parts by weight, based on 100 parts by weight of the metal powder. .. In addition to these, other components such as a surfactant and an antioxidant can be blended if necessary.
- the mixture is stirred and dispersed to obtain a conductive paste.
- Any known means can be used for stirring without particular limitation, and for example, a PD mixer or a planetary kneader can be preferably used, and a planetary kneader is particularly preferably used.
- known means can be used without particular limitation, and for example, a kneader, a bead mill, or a triple roll can be preferably used, and a triple roll is particularly preferably used.
- Conductive paste is printed on the sheet by a method such as screen printing.
- the monomer A1 was obtained as an isomer mixture in which Y 1 of the formula (1) had the structures of the formulas (2) and (3), and was used for polymerization as a monomer solution as it was after adjusting the monomer concentration to 50 wt %.
- the temperature inside the reaction vessel was raised to 75°C, and the monomer solution and the polymerization initiator solution were simultaneously added dropwise over 3 hours. Then, the mixture was reacted at 75° C. for 3 hours to obtain a solution of copolymer A in dihydroterpineol.
- Copolymer B A copolymer B was obtained in the same manner as in Polymerization Example 1 except that the amount of isobutyl methacrylate used was changed to 112.3 g and the amount of 50% solution of the monomer A1 used was changed to 175.5 g.
- Copolymer C The amount of isobutyl methacrylate used was changed to 70.8 g, the amount of 50% solution of monomer A1 was changed to 258.3 g, and the amount of 2,2′-azobis(2,4-dimethylvaleronitrile) was changed to 0.9 g. Copolymer C was obtained in the same manner as in Polymerization Example 1 except for the above.
- Copolymer E A copolymer E was obtained in the same manner as in Polymerization Example 1, except that the amount of isobutyl methacrylate used was 100.4 g, the solution of the monomer A1 was changed to the solution of the monomer A3, and 199.3 g was used.
- Copolymer F A copolymer F was obtained in the same manner as in Polymerization Example 1 except that the amount of isobutyl methacrylate used was 102.2 g, the solution of the monomer A1 was changed to the solution of the monomer A4, and 195.6 g was used.
- copolymer H was prepared in the same manner as in Polymerization Example 1 except that the amount of isobutyl methacrylate used was changed to 84.2 g, the amount of the solution of the monomer A1 used was changed to 184.2 g, and 23.7 g of methyl methacrylate was used. Obtained.
- Copolymer L was obtained in the same manner as in Polymerization Example 1 except that the amount of isobutyl methacrylate used was changed to 182.5 g and the amount of the solution of the monomer A1 used was changed to 35.0 g.
- Copolymer M A copolymer M was obtained in the same manner as in Polymerization Example 1 except that 143.7 g of isobutyl methacrylate was used and 56.3 g of 2-hydroxyethyl methacrylate was used instead of the monomer A1.
- the obtained Ni paste was screen-printed, the obtained printed material was confirmed with an optical microscope, and it was visually confirmed whether there was any bleeding or a trace of stringing. When no bleeding or stringing was observed, it was marked with " ⁇ " (good), and when bleeding or stringing was found, it was marked with "x" (poor).
- Comparative Example 1 the proportion of the monomer A1 was less than 10 mol %, but the heating residue was small, but the thixotropy value was low and the printability was low.
- Comparative Example 2 the copolymer containing no monomer of the present invention was used, but the heating residue was small, but the thixotropy value was low and the printability was low.
- the monomer A1 was obtained as an isomer mixture in which Y 1 of the formula (1) had the structures of the formula (2) and the formula (3), and the monomer concentration was adjusted to 50 wt %, and then used as a monomer solution for polymerization as it was.
- Synthesis Example 5 Monomer A5
- 50 wt% of monomer A5 (mixture of isomers) was prepared in the same manner as in Synthesis Example 1 except that glycidyl methacrylate was changed to 3,4-epoxycyclohexylmethyl methacrylate (manufactured by Daicel, trade name: Cyclomer M-100). A solution was obtained.
- Isobutyl methacrylate product name: Acryester IB (manufactured by Mitsubishi Chemical Co., Ltd.)) 137.1 g, methyl methacrylate (product name: acrylic ester M (manufactured by Mitsubishi Gas Chemical Co., Ltd.)) 12.9 g, 50% of monomer A1 Solution 100.0 g of mixed monomer solution, and toluene 50 g and 2,2'-azobis(2,4-dimethylvaleronitrile) (product name: V-65 (manufactured by Wako Pure Chemical Industries, Ltd.)) 0.3 g Polymerization initiator solutions were prepared by mixing the above.
- the temperature inside the reaction vessel was raised to 75°C, and the monomer solution and the polymerization initiator solution were simultaneously added dropwise over 3 hours. Then, the mixture was reacted at 75° C. for 3 hours to obtain a toluene solution of copolymer A.
- Copolymer D The amount of isobutyl methacrylate used was 98.2 g, the amount of methyl methacrylate used was 11.5 g, and the solution of the monomer A1 was changed to a solution of the monomer A2, and 180.5 g was used to prepare 2,2′-azobis(2,4-dimethyl). Copolymer D was obtained in the same manner as in Polymerization Example 1 except that the amount of valeronitrile) used was changed to 0.1 g.
- Polymerization Example 8 Copolymer H
- the amount of isobutyl methacrylate used was 68.7 g
- the amount of methyl methacrylate used was 12.1 g
- the amount used of the solution of monomer A1 was changed to 188.0 g
- 25.2 g of styrene was used.
- the copolymer I was obtained by the method of.
- copolymer K was obtained in the same manner as in Polymerization Example 1 except that the amount of isobutyl methacrylate used was 182.5 g and the amount of the solution of the monomer A1 used was 35.0 g.
- Copolymer L was obtained in the same manner as in Polymerization Example 1 except that 143.7 g of isobutyl methacrylate was used and 56.3 g of 2-hydroxyethyl methacrylate was used instead of the monomer A1.
- the ceramic slurry was applied by a doctor blade method onto a PET film which is a carrier sheet so as to have a thickness of 20 ⁇ m, and then dried at 90° C. for 10 minutes to produce a green sheet.
- the strength of the produced green sheet was measured with a tensile tester at a pulling speed of 10 mm/min, and an average value measured 5 times was used.
- Comparative Example 1 the ratio of the monomer 1 was less than 10 mol% and the heating residue was small, but the sheet strength and flexibility were low.
- Comparative Example 2 the copolymer containing no monomer of the present invention was used, but the heating residue was small, but the sheet strength and flexibility were low.
- the monomer A1 was obtained as an isomer mixture in which Y 1 of the formula (1) had the structures of the formulas (2) and (3), and was used for polymerization as a monomer solution as it was after adjusting the monomer concentration to 50 wt %.
- the temperature inside the reaction vessel was raised to 75°C, and the monomer solution and the polymerization initiator solution were simultaneously added dropwise over 3 hours. Then, after reacting at 75° C. for 3 hours, the solid content was adjusted to 25% to obtain a dihydroterpineol solution of copolymer 1.
- Copolymer 2 was obtained in the same manner as in Polymerization Example 1 except that the monomer solution was changed to 186.5 g of isobutyl methacrylate, 21.0 g of butyl acrylate, and 85.0 g of a 50% solution of monomer A1.
- Copolymer 3 (Polymerization Example 3: Copolymer 3) The monomer solution was changed to 120.8 g of isobutyl methacrylate, 18.3 g of butyl acrylate, 222.2 g of a 50% solution of monomer A2, and the amount of 2,2'-azobis(2,4-dimethylvaleronitrile) used was changed to 1.0 g. Copolymer 3 was obtained in the same manner as in Polymerization Example 1 except for the above.
- Copolymer 4 (Polymerization Example 4: Copolymer 4)
- the monomer solution was changed to 108.3 g of isobutyl methacrylate, 16.3 g of butyl acrylate, and 251.0 g of a 50% solution of monomer A3, and the amount of 2,2′-azobis(2,4-dimethylvaleronitrile) used was changed to 0.2 g.
- Copolymer 4 was obtained in the same manner as in Polymerization Example 1 except for the above.
- Copolymer 5 was obtained in the same manner as in Polymerization Example 1, except that the monomer solution was changed to 110.3 g of isobutyl methacrylate, 16.5 g of butyl acrylate, and 246.0 g of a 50% solution of the monomer A4.
- Copolymer 6 was obtained in the same manner as in Polymerization Example 1 except that the monomer solution was changed to 111.0 g of isobutyl methacrylate, 16.8 g of butyl acrylate, and 244.5 g of a 50% solution of monomer A5.
- Polymerization Example 7 Copolymer 7
- a copolymer 7 was obtained by the method.
- Polymerization Example 8 Copolymer 8 Except that the monomer solution was changed to 76.0 g of isobutyl methacrylate, 53.0 g of 2-ethylhexyl methacrylate (light ester EH Kyoeisha Chemical Co., Ltd.), 17.0 g of butyl acrylate, and 208.0 g of a 50% solution of monomer A1. Copolymer 8 was obtained in the same manner as in Polymerization Example 1.
- Copolymer 10 (Polymerization Example 10: Copolymer 10) Copolymer 10 was prepared in the same manner as in Polymerization Example 1, except that the monomer solution was changed to 105.3 g of isobutyl methacrylate, 14.8 g of butyl acrylate, 14.8 g of dimethylacrylamide, and 230.5 g of a 50% solution of monomer A1. Obtained.
- Copolymer 11 was obtained in the same manner as in Polymerization Example 1 except that the monomer solution was changed to 71.3 g of isobutyl methacrylate, 16.0 g of butyl acrylate, and 325.0 g of a 50% solution of monomer A1.
- Copolymer 11 was obtained in the same manner as in Polymerization Example 1 except that the monomer solution was changed to 32.0 g of isobutyl methacrylate, 14.5 g of butyl acrylate, and 407.5 g of a 50% solution of monomer A1.
- Copolymer 11 was obtained in the same manner as in Polymerization Example 1 except that the amount of isobutyl methacrylate used in the monomer solution was changed to 241.0 g and the amount of the 50% solution of monomer A1 used was changed to 18.0 g.
- copolymer 12 was obtained in the same manner as in Polymerization Example 1 except that the amounts of isobutyl methacrylate used were changed to 179.5 g and 2-hydroxyethyl methacrylate 70.5 g.
- the weight average molecular weights of the copolymers 1 to 12 were determined using gel permeation chromatography (GPC) under the following conditions.
- Device Tosoh Corp., HLC-8220 Column: shodex, LF-804 Standard substance: polystyrene Eluent: THF (tetrahydrofuran) Flow rate: 1.0 ml/min Column temperature: 40°C Detector: RI (differential refractive index detector)
- the copolymer solution was diluted with acetone to prepare a diluted solution having a copolymer concentration of 20%.
- a reprecipitation operation was performed in which this diluted solution was dropped into 20 times the amount of hexane. The supernatant was removed, and the precipitate was vacuum dried at 80°C to obtain a copolymer.
- 19 g of dihydroterpineol acetate was added to 1 g of the obtained copolymer, and the mixture was stirred at room temperature for 1 hour. The appearance after stirring was visually evaluated.
- the sample in which no insoluble matter was observed was rated as “ ⁇ ” (good) and the sample in which insoluble matter was observed was rated as “x” (poor).
- Ni powder made by JFE Mineral: NFP201S
- oleoyl sarcosine made by NOF: ESREAM 221P
- NOF: ESREAM 221P oleoyl sarcosine
- dihydroterpineol 81 parts by weight of dihydroterpineol
- the obtained Ni paste was printed on a green sheet prepared by screen printing, dried at 90° C. for 10 minutes, and a green sheet was further stacked thereon, and pressure-bonded under the conditions of 50° C., 100 kg/cm 2 and 5 seconds. It was The pressure-bonded sheet was separated by a tensile tester, and the force required for peeling was measured.
- Comparative Example 1 As shown in Table 12, in Comparative Example 1, the amount of the monomer A exceeds 90 mol %, but the solubility is low. In Comparative Example 2, the amount of the monomer A is less than 10 mol% and the amount of the monomer B is more than 90 mol%, but the thixotropy and the adhesiveness are low. In Comparative Example 3, the monomer A was not contained, but the solubility, thixotropy and adhesiveness were low. In Comparative Example 4, ethyl cellulose was used, but the heating residue was large and the adhesiveness was low.
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Abstract
Description
また、本発明は、シート強度および熱分解性に優れた、セラミックス用バインダー樹脂として特に好適な重合体に関するものである。
また、本発明は、低極性溶剤への溶解性に優れ、さらにチキソトロピー性および熱分解性に優れ、またさらにシートへの接着性にも優れた、導電ペースト用のバインダー樹脂に関するものである。
[1] 下記式(1)で示されるモノマー(A)のモル比が10モル%~100モル%であり、前記モノマー(A)と共重合可能な他のモノマー(B)のモル比が0~90モル%であり、重量平均分子量が10,000~1,000,000であることを特徴とする、重合体。
(式(1)中、
R1は、水素原子またはメチル基を示し、
R2は、炭素数1~18のアルキル基または炭素数1~18のヒドロキシアルキル基を示し、
Aは、炭素数1以上、10以下のアルキレン基を示し、
Xは0または1を示し、
Y1は、下記式(2)および下記式(3)のヒドロキシウレタン構造からなる群より選ばれた一種以上の構造である。)
[4] [1]の記載の重合体からなることを特徴とする、セラミックス用バインダー樹脂。
[7] [1]の重合体からなる導電ペースト用バインダー樹脂であって、
前記式(1)で示されるモノマー(A)のモル比が10モル%~90モル%であり、前記他のモノマー(B)が、下記一般式(Z)で示される(メタ)アクリル酸アルキルエステル(C)および前記モノマー(A)および前記(メタ)アクリル酸アルキルエステル(C)と共重合可能な他のモノマー(D)であり、前記(メタ)アクリル酸アルキルエステル(C)のモル比が10~90モル%であり、前記他のモノマー(D)のモル比が0~30モル%であることを特徴とする、導電ペースト用バインダー樹脂。
(式(Z)中、
R3は水素原子またはメチル基を示し、
R4は炭素数1~18のアルキル基を示す。)
セラミックス用バインダー樹脂の場合には、合成のしやすさとシート強度の観点から、R2のアルキル基の炭素数は2~12が好ましく、3~6がより好ましい。またR2のアルキル基の炭素数を3~6とすることで柔軟性とシート強度を両立することができる。
セラミックス用バインダー樹脂の場合には、合成のしやすさとシート強度の観点から、R2のヒドロキシアルキル基炭素数は2~12が好ましく、3~6がより好ましい。またR2のヒドロキシアルキル基の炭素数を3~6とすることで柔軟性とシート強度を両立することができる。
また、Aは、シート強度の観点からは炭素数6以下が好ましく、炭素数4以下がより好ましい。
モノマー(A)は、1種類を単独で用いてもよく、2種類以上を併用してもよい。
また、導電性バインダー樹脂の場合には、重合体を構成するモノマーのうち、モノマー(A)のモル比は、90モル%以下とする。モノマー(A)のモル比を50モル%以下とすることにより、重合体の熱分解性が更に向上するが、この観点からは、40モル%以下とすることが更に好ましい。
モノマー(B)は、モノマー(A)と共重合可能なビニル系モノマーであり、例えば、(メタ)アクリル酸エステル化合物や芳香族アルケニル化合物、シアン化ビニル化合物、アクリルアミド化合物などを挙げることができる。
本発明の重合体の重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)を用いてポリスチレン換算で求めることができ、10,000~1,000,000であり、好ましくは10,000~800,000、より好ましくは30,000~300,000である。重合体の重量平均分子量が低すぎると、ポリマーの強度や粘度が不足し、重量平均分子量が高すぎると、溶媒溶解性や印刷適性の低下が生じるおそれがある。
本発明のモノマー(A)は、ヒドロキシウレタン結合を有するモノマーである。
上記モノマー(A)は例えば、(メタ)アクリロイル基と5員環カーボネート基の両方を有する化合物とアミン化合物との付加反応により得ることができる。
次に、本発明の重合体を製造する方法について説明する。
本発明における重合体は、モノマー(A)を少なくとも含有するモノマー混合物をラジカル重合させることにより得ることができる。重合は公知の方法で行うことができる。例えば、溶液重合、懸濁重合、乳化重合などが挙げられるが、共重合体の重量平均分子量を上記範囲内に調整しやすいという面で、溶液重合や懸濁重合が好ましい。
重合開始剤の使用量は、用いるモノマーの組み合わせや、反応条件などに応じて適宜設定することができる。
本発明の重合体は、金属ペーストのバインダー樹脂として特に好適である。金属ペーストは、本発明の重合体の他、金属粉体および溶媒を含有する。
本発明の重合体は、セラミックススラリーのバインダー樹脂として特に好適である。セラミックススラリーは、本発明の重合体の他、セラミックス粉体および溶媒を含有する。
本発明の(メタ)アクリル酸アルキルエステル(C)は下記一般式(Z)で示される。
R4は、炭素数1~18のアルキル基である。炭素数1~18のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、iso-ブチル基、tert-ブチル基、n-ヘキシル基、n-オクチル基、2-エチルヘキシル基、デシル基、ドデシル基、ステアリル基などが挙げられ、重合性とポリマーのガラス転移点の観点から、R4の炭素数は1~12が好ましく、1~8がより好ましい。
(メタ)アクリル酸アルキルエステル(C)におけるR4が分岐アルキル基の(メタ)アクリル酸アルキルエステルの比としては、40~95モル%であることが好ましく、50~90モル%がより好ましい。
次に、本発明の導電ペースト用バインダー樹脂を構成する重合体を製造する方法について説明する。
本発明における重合体は、モノマー(A)およびモノマー(C)を少なくとも含有するモノマー混合物をラジカル重合させることにより得ることができる。重合は公知の方法で行うことができる。例えば、溶液重合、懸濁重合、乳化重合などが挙げられるが、共重合体の重量平均分子量を上記範囲内に調整しやすいという面で、溶液重合や懸濁重合が好ましい。
なお、重合開始剤を投入するに際しては、例えば、全量を一括仕込みしてもよいし、一部を一括仕込みして残りを滴下してもよく、あるいは全量を滴下してもよい。また、前記モノマーとともに重合開始剤を滴下すると、反応の制御が容易となるので好ましく、さらにモノマー滴下後も重合開始剤を添加すると、残存モノマーを低減できるので好ましい。
重合溶媒に対するモノマー(合計量)の濃度は、10~60質量%が好ましく、特に好ましくは20~50質量%である。モノマー混合物の濃度が低すぎると、モノマーが残存しやすく、得られる共重合体の分子量が低下するおそれがあり、モノマーの濃度が高すぎると、発熱を制御し難くなるおそれがある。
本発明の重合体は、導電ペーストのバインダー樹脂として特に好適である。導電ペーストは、本発明の重合体の他、金属粉体および溶媒を含有する。
以下、実施例及び比較例を挙げて本発明をさらに具体的に説明する。
下記の表1に、モノマー(A)の構造と略号を示す。
撹拌機、温度計、冷却器、滴下ロート及び気体導入管を取り付けた反応装置にグリシジルメタクリレート(日油株式会社製、商品名:ブレンマーG)100部と、触媒として臭化リチウム(和光純薬製)5部と、N-メチル-2-ピロリドン100部とを入れ、撹拌しながら二酸化炭素を連続して吹き込み、100℃にて12時間反応した。ガスクロマトグラフィー(島津製作所製、商品名:GC-2014、カラム DB-1)により、原料であるグリシジルメタクリレートのピークの消失にて反応の進行を確認した。反応終了後、トルエン200部と水200部を入れ、混合した後、静置することで水層を分離した。水層を除去した後、水100部にて3回洗浄した。洗浄した有機層を減圧濃縮することで、5員環カーボネート化合物を合成した。
アミン化合物をブチルアミンから3-アミノー1-プロパノールへ変更した以外は、合成例1と同様の手法で、モノマーA2(異性体混合)の50wt%溶液を得た。
アミン化合物をブチルアミンからノニルアミンへ変更した以外は、合成例1と同様の手法で、モノマーA3(異性体混合)の50wt%溶液を得た。
グリシジルメタクリレートを4-ヒドロキシブチルアクリレートグリシジルエーテル(日本化成株式会社製、商品名:4HBAGE)へ変更した以外は、合成例1と同様の手法で、モノマーA4(異性体混合)の50wt%溶液を得た。
グリシジルメタクリレートを3,4-エポキシシクロヘキシルメチルメタアクリレート(株式会社ダイセル製、商品名:サイクロマーM-100)へ変更した以外は、合成例1と同様の手法で、モノマーA5(異性体混合)の50wt%溶液を得た。
撹拌機、温度計、冷却器、滴下ロート及び窒素導入管を取り付けた1Lセパラブルフラスコに、ジヒドロターピネオール350gを仕込み、フラスコ内を窒素置換して、窒素雰囲気下にした。イソブチルメタクリレート(製品名:アクリエステルIB(三菱レイヨン(株)製))151.3gとモノマーA1の50%溶液 97.4gを混合したモノマー溶液、及びジヒドロターピネオール50gと2,2‘-アゾビス(2,4-ジメチルバレロニトリル)(製品名:V-65(和光純薬工業(株)製))0.4gを混合した重合開始剤溶液をそれぞれ調製した。
イソブチルメタクリレートの使用量を112.3g、モノマーA1の50%溶液の使用量を175.5gに変更したこと以外は重合例1と同様の手法で共重合体Bを得た。
イソブチルメタクリレートの使用量を70.8g、モノマーA1の50%溶液の使用量を258.3gに、2,2‘-アゾビス(2,4-ジメチルバレロニトリル)の使用量を0.9gに変更したこと以外は、重合例1と同様の手法で共重合体Cを得た。
イソブチルメタクリレートの使用量を111.9g、モノマーA1の溶液をモノマーA2の溶液に変え、176.2g使用し、2,2‘-アゾビス(2,4-ジメチルバレロニトリル)の使用量を0.2gに変更したこと以外は、重合例1と同様の手法で共重合体Dを得た。
イソブチルメタクリレートの使用量を100.4g、モノマーA1の溶液をモノマーA3の溶液に変え、199.3g使用したこと以外は、重合例1と同様の手法で共重合体Eを得た。
イソブチルメタクリレートの使用量を102.2g、モノマーA1の溶液をモノマーA4の溶液に変え、195.6g使用したこと以外は、重合例1と同様の手法で共重合体Fを得た。
イソブチルメタクリレートの使用量を102.9g、モノマーA1の溶液をモノマーA5の溶液に変え、194.3g使用したこと以外は、重合例1と同様の手法で共重合体Gを得た。
イソブチルメタクリレートの使用量を84.2g、モノマーA1の溶液の使用量を184.2gに変更し、メチルメタクリレートを23.7g使用したこと以外は、重合例1と同様の手法で共重合体Hを得た。
イソブチルメタクリレートの使用量を83.8g、モノマーA1の溶液の使用量を183.3gに変更し、スチレンを24.5g使用したこと以外は、重合例1と同様の手法で共重合体Iを得た。
イソブチルメタクリレートの使用量を101.3g、モノマーA1の溶液の使用量を184.8gに変更し、アクリロニトリルを6.3g使用したこと以外は、重合例1と同様の手法で共重合体Jを得た。
イソブチルメタクリレートの使用量を100.2g、モノマーA1の溶液の使用量を182.8gに変更し、アクリルアミドを8.4g使用したこと以外は、重合例1と同様の手法で共重合体Kを得た。
イソブチルメタクリレートの使用量を182.5g、モノマーA1の溶液の使用量を35.0gに変更したこと以外は、重合例1と同様の手法で共重合体Lを得た。
イソブチルメタクリレートの使用量を143.7g、モノマーA1の代わりに2-ヒドロキシエチルメタクリレートを56.3g使用したこと以外は、重合例1と同様の手法で共重合体Mを得た。
ゲルパーミエーションクロマトグラフィー(GPC)を用いて以下の条件により、共重合体A~Mの重量平均分子量を求めた。
装置:東ソー(株)社製、HLC-8220
カラム:shodex社製、LF-804
標準物質:ポリスチレン
溶離液:THF(テトラヒドロフラン)
流量:1.0ml/min
カラム温度:40℃
検出器:RI(示差屈折率検出器)
20wt%の共重合体溶液(溶媒 ジヒドロターピネオール)を調製し、レオメーターにて1s-1から1,000s-1の範囲で粘度のせん断速度依存性を測定した。1s-1と1,000s-1のときの粘度の比を、TI値として算出した。
共重合体5mgをアルミパンにいれ、TG/DTAにて、空気雰囲気下、昇温速度10℃/分で500℃まで昇温し、サンプルの残存量を測定した。
Ni粉(JFEミネラル製:NFP201S)100重量部に対して、オレオイルザルコシン(日油製:エスリーム221P)を1重量部、バインダー樹脂を3重量部、ジヒドロターピネオールを90重量部加える。これらの混合物を遊星式混練機を使用し攪拌後、3本ロールにて混練しNiペーストを得た。
撹拌機、温度計、冷却器、滴下ロート及び気体導入管を取り付けた反応装置にグリシジルメタクリレート(日油株式会社製、商品名:ブレンマーG)100部と、触媒として臭化リチウム(和光純薬製)5部と、N-メチル-2-ピロリドン100部とを入れ、撹拌しながら二酸化炭素を連続して吹き込み、100℃にて12時間反応した。ガスクロマトグラフィー(島津製作所製、商品名:GC-2014、カラム DB-1)により原料であるグリシジルメタクリレートのピークの消失にて反応の進行を確認した。反応終了後、トルエン200部と水200部を入れ、混合した後、静置することで水層を分離した。水層を除去した後、水100部にて3回洗浄した。洗浄した有機層を減圧濃縮することで、5員環カーボネート化合物を合成した。
アミン化合物をブチルアミンから3-アミノ-1-プロパノールへ変更した以外は合成例1と同様の手法でモノマーA2(異性体混合)の50wt%溶液を得た。
アミン化合物をブチルアミンからノニルアミンへ変更した以外は合成例1と同様の手法でモノマーA3(異性体混合)の50wt%溶液を得た。
グリシジルメタクリレートを4-ヒドロキシブチルアクリレートグリシジルエーテル(日本化成株式会社製、商品名:4HBAGE)へ変更した以外は合成例1と同様の手法でモノマーA4(異性体混合)の50wt%溶液を得た。
グリシジルメタクリレートを3,4-エポキシシクロヘキシルメチルメタアクリレート(株式会社ダイセル製、商品名:サイクロマーM-100)へ変更した以外は合成例1と同様の手法でモノマーA5(異性体混合)の50wt%溶液を得た。
撹拌機、温度計、冷却器、滴下ロート及び窒素導入管を取り付けた1Lセパラブルフラスコに、トルエン350gを仕込み、フラスコ内を窒素置換して、窒素雰囲気下にした。イソブチルメタクリレート(製品名:アクリエステルIB(三菱ケミカル(株)製))137.1g、メチルメタクリレート(製品名:アクリルエステルM(三菱ガス化学(株)製))12.9g、モノマーA1の50%溶液 100.0gを混合したモノマー溶液、及びトルエン50gと2,2‘-アゾビス(2,4-ジメチルバレロニトリル)(製品名:V-65(和光純薬工業(株)製))0.3gを混合した重合開始剤溶液をそれぞれ調製した。
イソブチルメタクリレートの使用量を98.6g、メチルメタクリレートの使用量を11.6g、モノマーA1の50%溶液の使用量を179.7gに変更したこと以外は重合例1と同様の手法で共重合体Bを得た。
イソブチルメタクリレートの使用量を57.9g、メチルメタクリレートの使用量を10.2g、モノマーA1の50%溶液の使用量を263.9gに、2,2‘-アゾビス(2,4-ジメチルバレロニトリル)の使用量を0.7gに変更したこと以外は重合例1と同様の手法で共重合体Cを得た。
イソブチルメタクリレートの使用量を98.2g、メチルメタクリレートの使用量を11.5g、モノマーA1の溶液をモノマーA2の溶液に変え、180.5g使用し、2,2‘-アゾビス(2,4-ジメチルバレロニトリル)の使用量を0.1gに変更したこと以外は重合例1と同様の手法で共重合体Dを得た。
イソブチルメタクリレートの使用量を87.9g、メチルメタクリレートの使用量を10.2g、モノマーA1の溶液をモノマーA3の溶液に変え、203.6g使用したこと以外は重合例1と同様の手法で共重合体Eを得た。
イソブチルメタクリレートの使用量を89.6g、メチルメタクリレートの使用量を10.5g、モノマーA1の溶液をモノマーA4の溶液に変え、199.9g使用したこと以外は重合例1と同様の手法で共重合体Fを得た。
イソブチルメタクリレートの使用量を90.1g、メチルメタクリレートの使用量を10.6g、モノマーA1の溶液をモノマーA5の溶液に変え、198.6g使用したこと以外は重合例1と同様の手法で共重合体Gを得た。
イソブチルメタクリレートの使用量を68.7g、メチルメタクリレートの使用量を12.1g、モノマーA1の溶液の使用量を188.0gに変更し、スチレンを25.2g使用したこと以外は重合例1と同様の手法で共重合体Iを得た。
イソブチルメタクリレートの使用量を86.6g、メチルメタクリレートの使用量を12.2g、モノマーA1の溶液の使用量を189.5gに変更し、アクリロニトリルを6.5g使用したこと以外は重合例1と同様の手法で共重合体Jを得た。
イソブチルメタクリレートの使用量を85.7g、メチルメタクリレートの使用量を12.1g、モノマーA1の溶液の使用量を187.4gに変更し、アクリルアミドを8.6g使用したこと以外は重合例1と同様の手法で共重合体Kを得た。
イソブチルメタクリレートの使用量を182.5g、モノマーA1の溶液の使用量を35.0gに変更したこと以外は重合例1と同様の手法で共重合体Kを得た。
イソブチルメタクリレートの使用量を143.7g、モノマーA1の代わりに2-ヒドロキシエチルメタクリレートを56.3g使用したこと以外は重合例1と同様の手法で共重合体Lを得た。
ゲルパーミエーションクロマトグラフィー(GPC)を用いて以下の条件により、共重合体A~Lの重量平均分子量を求めた。
装置:東ソー(株)社製、HLC-8220
カラム:shodex社製、LF-804
標準物質:ポリスチレン
溶離液:THF(テトラヒドロフラン)
流量:1.0mL/min
カラム温度:40℃
検出器:RI(示差屈折率検出器)
チタン酸バリウム粉末(堺化学製:BT-03)100重量部に対し、高分子ポリカルボン酸系分散剤(日油製:マリアリムAKM-0531)を0.8重量部、トルエン18重量部、エタノール18重量部、粒径1mmのジルコニアボール100重量部をボールミルに入れ、8時間混合後、バインダー樹脂を8重量部、トルエン10重量部、エタノール10重量部を加えさらに12時間混合したのち、ジルコニアボールをろ別し、セラミックスラリーを調製した。そして、セラミックスラリーをドクターブレード法によってキャリアシートであるPETフィルム上に厚さ20μmのシート状に塗布後、90℃、10分間乾燥させ、グリーンシートを作製した。作製したグリーンシートを引張試験機にて、引張り速度10mm/minで強度を測定し、5回測定した平均値を使用した。
膜厚10μmの樹脂シートを作成し、直径2mmの棒を軸に180°折り曲げ、元に戻す操作を20回繰り返し、シートの表面状態を目視で確認した。3回行った平均で評価した。
◎: 20回後もクラックは確認できなかった。
○: 10回後はクラックが確認できなかったが、20回後にはクラックが確認された。
×: 1回でクラックが確認された。
共重合体5mgをアルミパンにいれ、TG/DTAにて、空気雰囲気下、昇温速度10℃/分で500℃まで昇温し、サンプルの残存量を測定した。
比較例2では、本発明のモノマーを含有しない共重合体を用いたが、加熱残分は少なくなったが、シート強度、柔軟性が低くなった。
撹拌機、温度計、冷却器、滴下ロート及び気体導入管を取り付けた反応装置にグリシジルメタクリレート(日油株式会社製、商品名:ブレンマーG)100部と、触媒として臭化リチウム(和光純薬製)5部と、N-メチル-2-ピロリドン100部とを入れ、撹拌しながら二酸化炭素を連続して吹き込み、100℃にて12時間反応した。ガスクロマトグラフィー(島津製作所製、商品名:GC-2014、カラム DB-1)により、原料であるグリシジルメタクリレートのピークの消失にて反応の進行を確認した。反応終了後、トルエン200部と水200部を入れ、混合した後、静置することで水層を分離した。水層を除去した後、水100部にて3回洗浄した。洗浄した有機層を減圧濃縮することで、5員環カーボネート化合物を合成した。
アミン化合物をブチルアミンから3-アミノー1-プロパノールへ変更した以外は、合成例1と同様の手法で、モノマーA2(異性体混合)の50wt%溶液を得た。
アミン化合物をブチルアミンからノニルアミンへ変更した以外は、合成例1と同様の手法で、モノマーA3(異性体混合)の50wt%溶液を得た。
グリシジルメタクリレートを4-ヒドロキシブチルアクリレートグリシジルエーテル(日本化成株式会社製、商品名:4HBAGE)へ変更した以外は、合成例1と同様の手法で、モノマーA4(異性体混合)の50wt%溶液を得た。
グリシジルメタクリレートを3,4-エポキシシクロヘキシルメチルメタアクリレート(株式会社ダイセル製、商品名:サイクロマーM-100)へ変更した以外は、合成例1と同様の手法で、モノマーA5(異性体混合)の50wt%溶液を得た。
撹拌機、温度計、冷却器、滴下ロート及び窒素導入管を取り付けた2Lセパラブルフラスコに、ジヒドロターピネオール350gを仕込み、フラスコ内を窒素置換して、窒素雰囲気下にした。イソブチルメタクリレート(製品名:アクリエステルIB 三菱ケミカル(株)製)121.3gと、ブチルアクリレート(日本触媒(株)製)18.3g、モノマーA1の50%溶液 221.0gを混合したモノマー溶液、及びジヒドロターピネオール50gと2,2‘-アゾビス(2,4-ジメチルバレロニトリル)(製品名:V-65 和光純薬工業(株)製)0.5gを混合した重合開始剤溶液をそれぞれ調製した。
モノマー溶液をイソブチルメタクリレート186.5g、ブチルアクリレート21.0g、モノマーA1の50%溶液85.0gに変更したこと以外は重合例1と同様の手法で共重合体2を得た。
モノマー溶液をイソブチルメタクリレート120.8g、ブチルアクリレート18.3g、モノマーA2の50%溶液222.2gに、2,2‘-アゾビス(2,4-ジメチルバレロニトリル)の使用量を1.0gに変更したこと以外は、重合例1と同様の手法で共重合体3を得た。
モノマー溶液をイソブチルメタクリレート108.3g、ブチルアクリレート16.3g、モノマーA3の50%溶液251.0gに、2,2‘-アゾビス(2,4-ジメチルバレロニトリル)の使用量を0.2gに変更したこと以外は、重合例1と同様の手法で共重合体4を得た。
モノマー溶液をイソブチルメタクリレート110.3g、ブチルアクリレート16.5g、モノマーA4の50%溶液246.0gに変更したこと以外は、重合例1と同様の手法で共重合体5を得た。
モノマー溶液をイソブチルメタクリレート111.0g、ブチルアクリレート16.8g、モノマーA5の50%溶液244.5gに変更したこと以外は、重合例1と同様の手法で共重合体6を得た。
モノマー溶液をイソブチルメタクリレート85.0g、メチルメタクリレート((株)クラレ製)30.0g、ブチルアクリレート19.3g、モノマーA1の50%溶液232.0gに変更したこと以外は、重合例1と同様の手法で共重合体7を得た。
モノマー溶液をイソブチルメタクリレート76.0g、2-エチルヘキシルメタクリレート(ライトエステルEH 共栄社化学(株)製)53.0g、ブチルアクリレート17.0g、モノマーA1の50%溶液208.0gに変更したこと以外は、重合例1と同様の手法で共重合体8を得た。
モノマー溶液をイソブチルメタクリレート105.3g、エチルアクリレート(日本触媒(株)製)29.8g、モノマーA1の50%溶液232.0gに変更したこと以外は、重合例1と同様の手法で共重合体9を得た。
モノマー溶液をイソブチルメタクリレート105.3g、ブチルアクリレート14.8g、ジメチルアクリルアミド14.8g、モノマーA1の50%溶液230.5gに変更したこと以外は、重合例1と同様の手法で共重合体10を得た。
モノマー溶液をイソブチルメタクリレート71.3g、ブチルアクリレート16.0g、モノマーA1の50%溶液325.0gに変更したこと以外は、重合例1と同様の手法で共重合体11を得た。
モノマー溶液をイソブチルメタクリレート32.0g、ブチルアクリレート14.5g、モノマーA1の50%溶液407.5gに変更したこと以外は、重合例1と同様の手法で共重合体11を得た。
モノマー溶液をモノマーA1の50%溶液500.0gに変更したこと以外は、重合例1と同様の手法で共重合体13を得た。
モノマー溶液をイソブチルメタクリレートの使用量を241.0g、モノマーA1の50%溶液の使用量を18.0gに変更したこと以外は、重合例1と同様の手法で共重合体11を得た。
イソブチルメタクリレートの使用量を179.5g、2-ヒドロキシエチルメタクリレート70.5gに変更したこと以外は、重合例1と同様の手法で共重合体12を得た。
ゲルパーミエーションクロマトグラフィー(GPC)を用いて以下の条件により、共重合体1~12の重量平均分子量を求めた。
装置:東ソー(株)社製、HLC-8220
カラム:shodex社製、LF-804
標準物質:ポリスチレン
溶離液:THF(テトラヒドロフラン)
流量:1.0ml/min
カラム温度:40℃
検出器:RI(示差屈折率検出器)
共重合体溶液をアセトンで希釈し、共重合体濃度20%の希釈溶液を調製した。この希釈溶液を20倍量のヘキサンへ滴下する再沈殿操作をした。上澄みを除去し、沈殿物を80℃で真空乾燥し、共重合体を得た。得られた共重合体1gを19gのジヒドロターピネオールアセテート加え、室温下で1時間撹拌した。撹拌後の外観を目視で評価した。不溶物がみられないものを「○」(良好)、不溶物がみられたものを「×」(不良)とした。
20wt%の共重合体溶液(溶媒 ジヒドロターピネオール)を調製し、レオメーターにて1s-1から1,000s-1の範囲で粘度のせん断速度依存性を測定した。1s-1と1,000s-1のときの粘度の比を、TI値として算出した。
共重合体5mgをアルミパンにいれ、TG/DTAにて、空気雰囲気下、昇温速度10℃/分で500℃まで昇温し、サンプルの残存量を測定した。
チタン酸バリウム粉末(堺化学製:BT-03)100重量部に対し、高分子ポリカルボン酸系分散剤(日油製:マリアリムAKM-0531)を0.8重量部、トルエン18重量部、エタノール18重量部、粒径1mmのジルコニアボール100重量部をボールミルに入れ、8時間混合後、ポリビニルブチラール(積水化学工業製:エスレックBM-2)8重量部、トルエン10重量部、エタノール重量部を加えさらに12時間混合したのち、ジルコニアボールをろ別し、セラミックスラリーを調製した。そして、セラミックスラリーをドクターブレード法によってキャリアシートであるPETフィルム上に厚さ5μmのシート状に塗布後、90℃、10分間乾燥させ、グリーンシートを作製した。
比較例2では、モノマーAの量が10モル%未満であり、モノマーBの量が90mol%を超えているが、チキソトロピー性および接着性が低い。
比較例3では、モノマーAが含有されていないが、溶解性、チキソトロピー性、接着性が低かった。
比較例4では、エチルセルロースを用いているが、加熱残分が多く、接着性が低かった。
Claims (10)
- 請求項1記載の重合体、有機溶媒および金属粒子を含有することを特徴とする、導電性ペースト組成物。
- 前記金属粒子の比率を100重量部としたとき、前記重合体の比率が0.5~30重量部であり、前記有機溶媒の比率が10~200重量部であることを特徴とする、請求項2記載の導電性ペースト組成物。
- 請求項1記載の記載の重合体からなることを特徴とする、セラミックス用バインダー樹脂。
- 請求項4記載のバインダー樹脂、有機溶媒およびセラミックス粒子を含有することを特徴とする、セラミックススラリー組成物。
- 前記セラミックス粒子100重量部に対して、前記バインダー樹脂を0.5~30重量部および前記有機溶媒を10~200重量部含有することを特徴とする、請求項5記載のセラミックススラリー組成物。
- 請求項1記載の重合体からなる導電ペースト用バインダー樹脂であって、
前記式(1)で示されるモノマー(A)のモル比が10モル%~90モル%であり、前記他のモノマー(B)が、下記一般式(Z)で示される(メタ)アクリル酸アルキルエステル(C)および前記モノマー(A)および前記(メタ)アクリル酸アルキルエステル(C)と共重合可能な他のモノマー(D)であり、前記(メタ)アクリル酸アルキルエステル(C)のモル比が10~90モル%であり、前記他のモノマー(D)のモル比が0~30モル%であることを特徴とする、導電ペースト用バインダー樹脂。
(式(Z)中、
R3は水素原子またはメチル基を示し、
R4は炭素数1~18のアルキル基を示す。) - 前記他のモノマー(D)が、アクリロニトリルおよびアルキルアクリルアミドからなる群より選ばれた一種以上のモノマーであることを特徴とする、請求項7記載の導電ペースト用バインダー樹脂。
- 請求項7または8記載の導電ペースト用バインダー樹脂、有機溶媒および金属粒子を含有することを特徴とする、導電ペースト組成物。
- 前記金属粒子100質量部に対し、前記導電ペースト用バインダー樹脂の質量比が0.5~30質量部であり、前記有機溶媒の質量比が10~200質量部であることを特徴とする、請求項9記載の導電ペースト組成物。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0495269A2 (en) * | 1991-01-14 | 1992-07-22 | Dainippon Ink And Chemicals, Inc. | Thermosetting reactive resin mixture, moulded article and coating made therefrom |
WO2018008580A1 (ja) * | 2016-07-06 | 2018-01-11 | セメダイン株式会社 | 硬化性組成物、及び製品 |
JP2018080319A (ja) * | 2016-11-04 | 2018-05-24 | 日油株式会社 | 重合体およびそれを含んでなるペースト組成物 |
JP2018197321A (ja) * | 2017-05-25 | 2018-12-13 | 日油株式会社 | 導電ペースト用バインダー樹脂および導電ペースト組成物 |
JP2018197323A (ja) * | 2017-05-25 | 2018-12-13 | 日油株式会社 | セラミックス用バインダー樹脂およびセラミックス組成物 |
JP2019196446A (ja) * | 2018-05-10 | 2019-11-14 | 日油株式会社 | 重合体およびペースト組成物 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4487596B2 (ja) | 2004-02-27 | 2010-06-23 | Tdk株式会社 | 積層セラミック電子部品用の積層体ユニットの製造方法 |
JP4870919B2 (ja) | 2004-09-27 | 2012-02-08 | 積水化学工業株式会社 | セラミックグリーンシート用スラリー組成物、セラミックグリーンシート及び積層セラミックコンデンサ |
JP2012181988A (ja) | 2011-03-01 | 2012-09-20 | Yasuhara Chemical Co Ltd | 導電性ペースト |
JP6613551B2 (ja) | 2014-07-31 | 2019-12-04 | 住友金属鉱山株式会社 | 積層セラミックコンデンサ内部電極用ペースト、及び積層セラミックコンデンサ |
CN108929403B (zh) * | 2017-05-25 | 2022-05-27 | 日油株式会社 | 粘结剂树脂、导电膏组合物、陶瓷用粘结剂树脂及陶瓷组合物 |
-
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0495269A2 (en) * | 1991-01-14 | 1992-07-22 | Dainippon Ink And Chemicals, Inc. | Thermosetting reactive resin mixture, moulded article and coating made therefrom |
WO2018008580A1 (ja) * | 2016-07-06 | 2018-01-11 | セメダイン株式会社 | 硬化性組成物、及び製品 |
JP2018080319A (ja) * | 2016-11-04 | 2018-05-24 | 日油株式会社 | 重合体およびそれを含んでなるペースト組成物 |
JP2018197321A (ja) * | 2017-05-25 | 2018-12-13 | 日油株式会社 | 導電ペースト用バインダー樹脂および導電ペースト組成物 |
JP2018197323A (ja) * | 2017-05-25 | 2018-12-13 | 日油株式会社 | セラミックス用バインダー樹脂およびセラミックス組成物 |
JP2019196446A (ja) * | 2018-05-10 | 2019-11-14 | 日油株式会社 | 重合体およびペースト組成物 |
Non-Patent Citations (2)
Title |
---|
ENDO, TAKESHI ET AL.: "Design of new networked polymers based on synthesis of five-membered cyclic carbonate from C02 and epoxide", JOURNAL OF NETWORK POLYMER, JAPAN, vol. 32, no. 2, 2011, pages 101 - 109, XP055727879 * |
OCHIAI BUNGO, HATANO YUGO, ENDO TAKESHI: "Radical Polymerisation of methacrylates bearing hydroxyurethane moieties and functionalization of resulting polymers", JOURNAL OF NETWORK POLYMER, JAPAN, vol. 30, no. 2, 2009, pages 58 - 68, XP055727878, Retrieved from the Internet <URL:https://www.jstage.jst.go.jp/article/networkpolymer/30/2/30_58/_pdf/-char/ja> * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2023054428A1 (ja) * | 2021-09-30 | 2023-04-06 | 日油株式会社 | 撥水剤用重合体、撥水剤組成物および撥水剤処理物 |
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