WO2016158175A1 - バインダー樹脂組成物 - Google Patents
バインダー樹脂組成物 Download PDFInfo
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- WO2016158175A1 WO2016158175A1 PCT/JP2016/056412 JP2016056412W WO2016158175A1 WO 2016158175 A1 WO2016158175 A1 WO 2016158175A1 JP 2016056412 W JP2016056412 W JP 2016056412W WO 2016158175 A1 WO2016158175 A1 WO 2016158175A1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63464—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
- C08G64/0208—Aliphatic polycarbonates saturated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
- C08G64/0208—Aliphatic polycarbonates saturated
- C08G64/0216—Aliphatic polycarbonates saturated containing a chain-terminating or -crosslinking agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
- C08G64/0291—Aliphatic polycarbonates unsaturated
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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
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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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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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
- C08L31/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
Definitions
- the present invention relates to a binder resin composition and an inorganic fine particle-dispersed paste composition containing the resin composition.
- a molding binder polyvinyl butyral (PVB), ethyl cellulose (EC), carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), acrylic polymer, and the like are used. It is preferable that the binder component completely disappears during sintering. However, the above-mentioned binder is difficult to decompose, and if heated simply, a binder residue remains in the formed ceramic, which adversely affects the performance of the ceramic.
- An aliphatic polycarbonate resin such as polypropylene carbonate and polyethylene carbonate has been studied as a binder that does not require oxygen during sintering and can undergo endothermic decomposition.
- the decomposition temperature of these resins may be too low depending on the production process (see Patent Document 1). Therefore, as a means for solving the problem, a method of increasing the decomposition temperature by sealing the molecular chain end is known (see Patent Document 2 and Non-Patent Document 1).
- An object of the present invention is to provide a binder resin composition capable of accurately controlling the decomposition temperature and an inorganic fine particle-dispersed paste composition containing the resin composition.
- the inventors of the present invention have arbitrarily selected a resin in which the end of the aliphatic polycarbonate resin is sealed with a sealing agent (terminal sealing agent) and a resin that is not sealed. By mixing at a ratio, it was found that the decomposition start temperature can be controlled almost arbitrarily within the range of the decomposition start temperatures of both resins. As a result of further studies, the present invention has been completed.
- R 1 , R 2 , R 3 and R 4 may be the same or different and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and m is 40 (It is an integer of ⁇ 23000)
- R 5 , R 6 , R 7 and R 8 may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X and Y May be the same or different, and is a group having at least one functional group selected from a carboxy group, an ester group, a carbamate group, a silicate group, an isocyanate group, an ether group, an acetal group, and a halogen atom at the terminal.
- N is an integer from 40 to 23000)
- the binder resin composition of the present invention has an excellent effect that the decomposition temperature can be accurately controlled.
- 2 is a thermal decomposition curve of the resin compositions obtained in Examples 1 to 5 and Reference Examples 1 and 2.
- 5 is a graph showing the relationship between the composition ratio of the resin compositions obtained in Examples 1 to 5 and Reference Examples 1 and 2 and the thermal decomposition start temperature.
- 3 is a graph showing the relationship between the composition ratios of the resin compositions obtained in Examples 1 to 5 and Reference Examples 1 and 2 and the 50 mass% decomposition temperature.
- the binder resin composition of the present invention has the formula (1):
- R 1 , R 2 , R 3 and R 4 may be the same or different and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and m is 40 (It is an integer of ⁇ 23000)
- R 5 , R 6 , R 7 and R 8 may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X and Y May be the same or different, and is a group having at least one functional group selected from a carboxy group, an ester group, a carbamate group, a silicate group, an isocyanate group, an ether group, an acetal group, and a halogen atom at the terminal.
- N is an integer from 40 to 23000
- an end-capped aliphatic polycarbonate resin is an integer from 40 to 23000.
- the binder resin composition of the present invention is as if it is a single resin according to the mixing ratio of each resin. Therefore, the decomposition temperature of the binder resin composition can be accurately controlled.
- the alkyl group has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms.
- a linear or branched, substituted or unsubstituted alkyl group is preferable.
- the alkyl group is substituted with one or more substituents selected from, for example, an alkoxy group, an ester group, a silyl group, a sulfanyl group, a cyano group, a nitro group, a sulfo group, a formyl group, an aryl group, a halogen atom, and the like. It may be.
- the aryl group has 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms.
- the aryl group include a phenyl group, an indenyl group, a naphthyl group, a tetrahydronaphthyl group, and the like.
- the aryl group is, for example, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group, or another aryl group such as a phenyl group or a naphthyl group.
- An alkoxy group, an ester group, a silyl group, a sulfanyl group, a cyano group, a nitro group, a sulfo group, a formyl group, a halogen atom and the like, may be substituted.
- n and m are integers of 40 to 23000, preferably 200 to 5000. n and m may be the same or different, but n and m are preferably closer, and the ratio of n to m (n / m) is preferably 0.5 to 2.0, more preferably 0.7 to 1.3. .
- X and Y are groups other than a hydroxy group at the end, and at least one selected from a carboxy group, an ester group, a carbamate group, a silicate group, an isocyanate group, an ether group, an acetal group, and a halogen atom.
- a group having a terminal functional group is preferable, and a group having at least one functional group selected from a carboxy group, an ester group, a carbamate group, and an isocyanate group at the terminal is preferable from the viewpoint of easy sealing reaction.
- Examples of the method for producing the aliphatic polycarbonate resin include a method of polymerizing epoxide and carbon dioxide.
- the epoxide used for producing the aliphatic polycarbonate resin represented by the formula (1) or the formula (2) is not particularly limited, for example, ethylene oxide, propylene oxide, 1,2 -Butylene oxide, 2,3-butylene oxide, isobutylene oxide, 1-pentene oxide, 2-pentene oxide, 1-hexene oxide, 1-octene oxide, 1-dodecene oxide, cyclopentene oxide, cyclohexene oxide, styrene oxide, vinyl Cyclohexane oxide, 3-phenylpropylene oxide, 3,3,3-trifluoropropylene oxide, 3-naphthylpropylene oxide, 2-phenoxypropylene oxide, 3-naphthoxypropylene oxide, butadiene monooxide, 3-vinyloxypropylene oxide Sid and 3-trimethylsilyloxypropylene oxide.
- the aliphatic polycarbonate resin represented by the formula (1) and the aliphatic polycarbonate resin represented by the formula (2) may be the same or different, but polyethylene carbonate, polypropylene carbonate, and polybutylene. At least one selected from the group consisting of carbonates is preferred, and polyethylene carbonate and / or polypropylene carbonate is more preferred.
- the polymerization reaction between the epoxide and carbon dioxide is preferably performed in the presence of a metal catalyst.
- metal catalysts examples include zinc-based catalysts, aluminum-based catalysts, chromium-based catalysts, and cobalt-based catalysts.
- a zinc-based catalyst and / or a cobalt-based catalyst is preferable because of high polymerization activity in the polymerization reaction of epoxide and carbon dioxide, and a zinc-based catalyst is more preferable from the viewpoint of obtaining a high molecular weight product.
- Examples of zinc-based catalysts include organic zinc catalysts such as zinc acetate, diethyl zinc, and dibutyl zinc; primary amines, divalent phenols (benzene diols), aromatic dicarboxylic acids, aromatic hydroxy acids, aliphatic dicarboxylic acids, fatty acids And an organic zinc catalyst obtained by reacting a compound such as a group monocarboxylic acid with a zinc compound.
- organic zinc catalysts an organic zinc catalyst obtained by reacting a zinc compound, an aliphatic dicarboxylic acid and an aliphatic monocarboxylic acid is preferable because it has higher polymerization activity, and zinc oxide, glutaric acid and acetic acid are preferred.
- An organozinc catalyst obtained by reacting is more preferable.
- the use amount of the metal catalyst used in the polymerization reaction is preferably 0.001 mol or more, more preferably 0.005 mol or more, from the viewpoint of promoting the progress of the polymerization reaction with respect to 1 mol of epoxide, and an effect commensurate with the use amount. From the viewpoint of obtaining the above, it is preferably 0.2 mol or less, more preferably 0.1 mol or less.
- a reaction solvent may be used as necessary.
- the reaction solvent is not particularly limited, but various organic solvents can be used.
- the organic solvent include aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; methylene chloride, chloroform, carbon tetrachloride, 1, Halogenated hydrocarbons such as 1-dichloroethane, 1,2-dichloroethane, ethyl chloride, trichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, chlorobenzene, bromobenzene Solvents; ether solvents such as dimethoxyethane, tetrahydrofuran, 2-methylte
- the amount of the reaction solvent used is preferably 100 to 10,000 parts by mass with respect to 100 parts by mass of the epoxide from the viewpoint of allowing the reaction to proceed smoothly.
- the method of polymerizing the epoxide and carbon dioxide in the presence of a metal catalyst is not particularly limited.
- an autoclave is charged with an epoxide, a metal catalyst, and, if necessary, a promoter, a reaction solvent, etc., and then mixed.
- carbon dioxide is injected and reacted.
- the amount of carbon dioxide used in the polymerization reaction is preferably 0.5 to 10 moles, more preferably 0.6 to 5 moles, and even more preferably 0.7 to 3 moles per mole of epoxide.
- the working pressure of carbon dioxide used in the polymerization reaction is not particularly limited, but is preferably 0.1 MPa or more, more preferably 0.2 MPa or more, further preferably 0.5 MPa or more, from the viewpoint of smoothly proceeding the reaction. From the viewpoint of obtaining an effect commensurate with the pressure, it is preferably 20 MPa or less, more preferably 10 MPa or less, and even more preferably 5 MPa or less.
- the polymerization reaction temperature in the polymerization reaction is not particularly limited, but from the viewpoint of shortening the reaction time, it is preferably 0 ° C. or higher, more preferably 20 ° C. or higher, and further preferably 30 ° C. or higher. From the viewpoint of improving the rate, it is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 60 ° C. or lower.
- the polymerization reaction time cannot be determined unconditionally because it varies depending on the polymerization reaction conditions, but it is usually preferably about 1 to 40 hours.
- an end-capping agent is continued after the polymerization reaction. And a method of reacting the isolated aliphatic polycarbonate resin represented by the formula (1) with an end-capping agent.
- Examples of the end capping agent include carboxylic acids such as formic acid, acetic acid, propionic acid, and benzoic acid; acid anhydrides such as acetic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, and pyromellitic anhydride; acetyl Acid halides such as chloride, propionic acid chloride, benzoic acid chloride, p-toluenesulfonic acid chloride, oxalyl chloride, succinic acid dichloride, adipic acid dichloride, terephthalic acid dichloride; methyl isocyanate, ethyl isocyanate, phenyl isocyanate, benzyl isocyanate, 1 Isocyanate compounds such as 1,6-hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate; organic silicate compounds such as methyl silicate, e
- Examples of the method of reacting the aliphatic polycarbonate resin and the end-capping agent include a method of reacting in an organic solvent and a method of reacting by melt kneading.
- the organic solvent used for the reaction between the aliphatic polycarbonate resin and the end capping agent is not particularly limited as long as it is a solvent that can dissolve the aliphatic polycarbonate resin and does not react with the end capping agent.
- Aromatic hydrocarbon solvents such as xylene; halogenated hydrocarbon solvents such as dichloromethane (methylene chloride), chloroform, 1,2-dichloroethane, chlorobenzene; dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane Ether solvents such as 1,3-dioxolane; ester solvents such as ethyl acetate, n-propyl acetate and isopropyl acetate; ketone solvents such as acetone, methyl ethyl ketone and mayyl isobutyl ketone; N, N-dimethylformamide Amide solvents such as N, N-d
- a catalyst may or may not be used.
- Catalysts used for the reaction with the end-capping agent include amine compounds such as triethylamine, tripropylamine, tributylamine, and 4,4-dimethylaminopyridine; nitrogen-containing heterocyclic compounds such as pyridine and N-methylimidazole; trimethyl Organophosphorus compounds such as phosphine, triethylphosphine, triphenylphosphine; organotin compounds such as dibutyltin and tin octoate.
- the amount of the catalyst used is preferably about 0.01 to 1 mol per 1 mol of the end-capping agent.
- Examples of the apparatus used for carrying out the reaction between the aliphatic polycarbonate resin and the end-capping agent by melt kneading include kneading machines such as rolls, extruders, Banbury mixers, plast mills, and Brabenders.
- the reaction temperature between the aliphatic polycarbonate resin and the end-capping agent is not particularly limited, but when reacting in an organic solvent, the reaction can be performed at a temperature of about 20 to 120 ° C. When the reaction is performed by melt kneading, for example, the reaction can be performed at a temperature of about 80 to 200 ° C.
- the amount of the end-capping agent used can be adjusted according to the amount of the end group when controlling the end-capping amount.
- the amount is preferably 0.3 parts by mass or more, and is preferably 5 parts by mass or less from the viewpoint of preventing performance deterioration as a binder due to excess residual end-capping agent.
- the use amount of the terminal blocking agent is preferably 0.3 to 5 parts by mass, more preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the aliphatic polycarbonate resin.
- the weight average molecular weight of the aliphatic polycarbonate resin represented by the formula (1) or the formula (2) is an aliphatic polycarbonate resin when the binder resin composition is mixed with inorganic fine particles and used as an inorganic fine particle dispersed paste composition. From the viewpoint of stably dispersing inorganic fine particles therein, it is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 100,000 or more, and the handleability is reduced due to the lower solubility of the binder resin composition in the solvent. From the viewpoint of avoidance, it is preferably 2,000,000 or less, more preferably 1,000,000 or less, and further preferably 500,000 or less.
- the molecular weight distribution (mass average molecular weight / number average molecular weight) of the aliphatic polycarbonate resin represented by the formula (1) or formula (2) is preferably 1.0 to 20.0 from the viewpoint of easy control of the binder solution viscosity. More preferably, it is 1.0 to 15.0, and still more preferably 1.0 to 10.0.
- a method for producing the binder resin composition of the present invention a method in which the aliphatic polycarbonate resin represented by the formula (1) and the end-capped aliphatic polycarbonate resin represented by the formula (2) are mixed at an arbitrary ratio, respectively. Is mentioned.
- the blending ratio of the aliphatic polycarbonate resin represented by the formula (1) and the end-capped aliphatic polycarbonate resin represented by the formula (2) is appropriately determined according to the target thermal decomposition temperature.
- the polycarbonate resin is preferably 10/90 to 90/10, more preferably 20/80 to 80/20.
- the binder resin composition of the present invention may contain additives such as a thixotropic agent, a surfactant, a plasticizer, and a storage stabilizer, as necessary.
- Examples of the thixotropic agent include fatty acid amide, silica fine particles, and organic bentonite.
- the surfactant include polyoxyethylene surfactants and fatty acid ester surfactants.
- examples of the plasticizer include polyether polyol and phthalate ester.
- examples of the storage stabilizer include amine compounds, carboxylic acid compounds, phosphorus compounds, sulfur compounds, and triazole compounds.
- the additive content in the binder resin composition of the present invention is 100 binder resin (total of the aliphatic polycarbonate resin represented by the formula (1) and the end-capped aliphatic polycarbonate resin represented by the formula (2)). Preferably it is 30 mass parts or less with respect to a mass part, More preferably, it is 20 mass parts or less.
- a slurry is produced by mixing the binder resin composition of the present invention, an inorganic powder such as a solvent and ceramics, and additives as necessary, and a product having a desired shape is produced by molding and sintering. be able to.
- the present invention further provides an inorganic fine particle-dispersed paste composition containing the binder resin composition of the present invention, inorganic fine particles, and a solvent.
- the inorganic fine particles are not particularly limited, but at least one selected from the group consisting of conductor particles, ceramic powder, glass powder, and inorganic phosphor fine particles is preferable.
- Examples of the conductive particles include metal particles made of copper, iron, nickel, palladium, platinum, gold, silver, aluminum, tungsten, alloys thereof, and the like.
- the ceramic powder examples include powders of alumina, zirconia, titanium oxide, barium titanate, alumina nitride, silicon nitride, boron nitride, silicon carbide, and the like.
- nano ITO titanium oxide used for transparent electrode material, nano titanium oxide used for a dye-sensitized solar cell, etc. can be used suitably.
- the glass powder examples include various silicon oxides such as CaO—Al 2 O 3 —SiO 2 , MgO—Al 2 O 3 —SiO 2 , LiO 2 —Al 2 O 3 —SiO 2 , and bismuth oxide glass. And glass powders such as silicate glass, lead glass, zinc glass, and boron glass.
- glass powder PbO—B 2 O 3 —SiO 2 mixture, BaO—ZnO—B 2 O 3 —SiO 2 mixture, ZnO—Bi 2 O 3 —B 2 O 3 —SiO 2 mixture, Bi 2 O 3 —B 2 O 3 —BaO—CuO mixture, Bi 2 O 3 —ZnO—B 2 O 3 —Al 2 O 3 —SrO mixture, ZnO—Bi 2 O 3 —B 2 O 3 mixture, Bi 2 O 3 —SiO 2 mixture, P 2 O 5 —Na 2 O—CaO—BaO—Al 2 O 3 —B 2 O 3 mixture, P 2 O 5 —SnO mixture, P 2 O 5 —SnO—B 2 O 3 mixture, P 2 O 5 —SnO—SiO 2 mixture, CuO—P 2 O 5 —RO mixture, SiO 2 —B 2 O 3 —ZnO—Na 2 O—Li 2 O—Na
- Examples of the inorganic phosphor fine particles include BaMgAl 10 O 17 : Eu, Zn 2 SiO 4 : Mn, (Y, Gd) BO 3 : Eu, and the like.
- the content of the binder resin composition in the inorganic fine particle-dispersed paste composition is such that the dispersibility of the inorganic fine particles is reduced with respect to 100 parts by mass of the inorganic fine particles. Is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and still more preferably 0.1 part by mass or more, when the inorganic fine particle dispersed paste composition is sintered. From the viewpoint of reducing a decomposition product generated by excessive decomposition of the group polycarbonate resin and obtaining a dense sintered body, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less. It is.
- the solvent is not particularly limited.
- N-methyl-2-pyrrolidone, terpineol, terpineol acetate, ethyl carbitol acetate, butyl carbitol acetate, texanol, and propylene carbonate are used from the viewpoint of moderately high boiling point and easy volatilization during sintering. preferable.
- These organic solvents may be used alone or in combination of two or more.
- the content of the solvent in the inorganic fine particle-dispersed paste composition is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and still more preferably 0.1 part by mass with respect to 100 parts by mass of the inorganic fine particle, from the viewpoint of dispersibility of the inorganic fine particle. From the viewpoint of adjusting the viscosity of the inorganic fine particle dispersed paste composition, it is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 50 parts by mass or less.
- the inorganic fine particle dispersed paste composition of the present invention may contain an additive as necessary.
- Additives include adhesion promoters, surfactants, plasticizers, storage stabilizers, antifoaming agents, and the like.
- adhesion promoter examples include amine-based silane coupling agents and glycidyl-based silane coupling agents.
- surfactant include polyoxyethylene surfactants and fatty acid ester surfactants.
- plasticizer examples include polyether polyol and phthalate ester.
- storage stabilizer examples include amine compounds, carboxylic acid compounds, phosphorus compounds, sulfur compounds, and triazole compounds.
- antifoaming agents include hydrophobic silica, polyalkylene derivatives, polyether derivatives and the like.
- the content of the additive in the inorganic fine particle dispersed paste composition is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, with respect to 100 parts by mass of the inorganic fine particles.
- the method for producing the inorganic fine particle-dispersed paste composition of the present invention is not particularly limited, but the aliphatic polycarbonate resin, solvent, inorganic fine particles, and additives as necessary are mixed and stirred using a conventionally known stirring method. And the like.
- Examples of the known stirring method include a kneading method using an apparatus such as a ball mill, a Brabender mill, and a three roll mill, and a kneading method using a mortar.
- Mass average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of aliphatic polycarbonate resin were determined.
- Catalyst production example 1 [Production of organozinc catalyst]
- a 1 L four-necked flask equipped with a stirrer, nitrogen gas inlet tube, thermometer, Dean-Stark tube, and reflux condenser zinc oxide 77.3 g (0.95 mol), glutaric acid 123 g (1 mol), acetic acid 1.14 g ( 0.02 mol) and 760 g of toluene were charged.
- the temperature was raised to 55 ° C., and the reaction was performed by stirring at the same temperature for 4 hours.
- Resin production example 1 Production of succinic anhydride-capped polypropylene carbonate
- a slurry liquid containing an organozinc catalyst obtained in Catalyst Production Example 1 (an organozinc catalyst was added) 135 mmol
- 577.2 g of dimethyl carbonate and 78.3 g (1.35 mol) of propylene oxide.
- carbon dioxide was added with stirring, and carbon dioxide was charged until the reaction system became 1 MPa.
- Resin production example 2 [Production of end-capped polypropylene carbonate] After completion of the reaction, the autoclave was cooled and depressurized, and then the reaction solution was filtered and dried under reduced pressure without adding succinic anhydride, and in the same manner as in Resin Production Example 1, 123 g of polypropylene carbonate resin (B) Got.
- the obtained polypropylene carbonate had a weight average molecular weight of 315,000 and a molecular weight distribution (Mw / Mn) of 9.74.
- Resin production example 3 [Production of isocyanate-capped polypropylene carbonate] Charge 40 g of polypropylene carbonate resin (B) and 0.4 g of 4,4'-diphenylmethane diisocyanate into a kneader (Toyo Seiki Seisakusho, Labo Plast Mill 4C150), melt for 5 minutes at a kneading temperature of 160 ° C and a rotation speed of 40 r / min. Kneading was performed to obtain a polypropylene carbonate resin (C) whose ends were sealed with isocyanate groups. The obtained polypropylene carbonate had a mass average molecular weight of 323,000 and a molecular weight distribution (Mw / Mn) of 8.82.
- Mw / Mn molecular weight distribution
- Resin production example 4 [Production of succinic anhydride-capped polyethylene carbonate] 40 g of polyethylene carbonate resin (D) (Empowermaterials, trade name QPAC25, Mw: 198,000, Mw / Mn: 3.48) and 0.3 g of succinic anhydride were charged into a kneader (Toyo Seiki Seisakusho, Lab Plast Mill 4C150). Then, melt kneading was performed for 5 minutes at a kneading temperature of 100 ° C. and a rotation speed of 40 r / min to obtain a polyethylene carbonate resin (E) whose ends were sealed with carboxy groups with succinic anhydride. The obtained polyethylene carbonate had a mass average molecular weight of 197,000 and a molecular weight distribution (Mw / Mn) of 3.49.
- Resin production example 5 [Production of end-capped polybutylene carbonate] After replacing the interior of a 1 L autoclave system equipped with a stirrer, a gas introduction pipe, and a thermometer with a nitrogen atmosphere in advance, 117.3 g of a slurry liquid containing an organozinc catalyst obtained in Catalyst Production Example 1 (an organozinc catalyst was added) 135 mmol), 577.2 g of dimethyl carbonate, and 97.3 g (1.35 mol) of 1,2-butylene oxide. Next, carbon dioxide was added with stirring, and carbon dioxide was charged until the reaction system became 1 MPa.
- polybutylene carbonate resin F
- the obtained polybutylene carbonate had a mass average molecular weight of 273,000 and a molecular weight distribution (Mw / Mn) of 12.2.
- Resin production example 6 [Production of acetic anhydride-capped polybutylene carbonate] 11.6 g (100 mmol) of the polybutylene carbonate resin (F) obtained in Resin Production Example 5 was dissolved in 120 g of dichloromethane, 0.51 g (5.0 mmol) of acetic anhydride, 0.3 g (3.25 mmol) of triethylamine and 4,4-dimethylamino were dissolved. 0.2g (1.63mmol) of pyridine was added and stirred at 25 ° C for 24 hours.
- the resulting polybutylene carbonate resin had a weight average molecular weight of 290,000 and a molecular weight distribution (Mw / Mn) of 10.4.
- Example 1 In a 50 mL glass vial, 0.2 g of the polypropylene carbonate resin (A) obtained in Resin Production Example 1 and 0.8 g of the polypropylene carbonate resin (B) obtained in Resin Production Example 2 are weighed and dissolved in 10 g of acetone. A solution was prepared. This solution was dried to obtain 1.0 g of a binder resin composition.
- the obtained binder resin composition had a thermal decomposition starting temperature of 215.5 ° C. and a 50 mass% decomposition temperature of 217.2 ° C.
- Examples 2-5 A binder resin composition (1.0 g) was obtained in the same manner as in Example 1 except that the polypropylene carbonate resin (A) and the polypropylene carbonate resin (B) were used in the ratios shown in Table 1.
- Reference examples 1 and 2 A uniform solution was prepared by dissolving 1.0 g of polypropylene carbonate resin (A) or polypropylene carbonate resin (B) in 10 g of acetone. This solution was dried to obtain 1.0 g of a binder resin composition.
- the thermal decomposition temperature (Td) and 50% by mass decomposition temperature (Td50) of the binder resin composition obtained in each example and reference example were measured by the following methods. The results are shown in Table 1.
- Thermal decomposition temperature (Td) and 50 mass% decomposition temperature (Td50) of the binder resin composition Using TG / DTA7220 manufactured by SII NanoTechnology, the change in thermogravimetry is measured while raising the temperature from room temperature to 500 ° C at a rate of 10 ° C / min in a nitrogen atmosphere.
- the thermal decomposition start temperature (Td) is the intersection of a line parallel to the horizontal axis passing through the mass before the start of test heating and a tangent drawn so that the gradient between the bending points in the decomposition curve is maximized.
- the 50 mass% decomposition temperature (Td50) reads the temperature when the thermal mass of the sample becomes half (50%) of the mass before starting the test heating.
- the thermal decomposition curves of the resin compositions obtained in Examples 1 to 5 and Reference Examples 1 and 2 are shown in FIG.
- a graph showing the relationship between the composition ratio of the resin compositions obtained in Examples 1 to 5 and Reference Examples 1 and 2 and the thermal decomposition start temperature (Td) is shown in FIG.
- a graph showing the relationship of the mass% decomposition temperature (Td50) is shown in FIG.
- the determination coefficient R 2 shown in Table 1 is obtained by subtracting the ratio of the residual variance and the total variance from 1 when the linear approximation of the graphs of FIGS. 1 and 2 is performed by the least square method. The closer to 1, the better the agreement with the approximate curve.
- Examples 6-8 A binder resin composition 1.0 g was obtained in the same manner as in Example 1 except that the polypropylene carbonate resin (B) and the polypropylene carbonate resin (C) were used in the ratios shown in Table 2.
- Reference example 3 A uniform solution was prepared by dissolving 1.0 g of polypropylene carbonate resin (C) in 10 g of acetone. This solution was dried to obtain 1.0 g of a binder resin composition.
- Examples 9-11 A binder resin composition 1.0 g was obtained in the same manner as in Example 1 except that the polyethylene carbonate resin (D) and the polyethylene carbonate resin (E) were used in the ratios shown in Table 3.
- Reference examples 4 and 5 A uniform solution was prepared by dissolving 1.0 g of polyethylene carbonate resin (D) or polyethylene carbonate resin (E) in 10 g of acetone. This solution was dried to obtain 1.0 g of a binder resin composition.
- Examples 12-14 1.0 g of a binder resin composition was obtained in the same manner as in Example 1 except that the polybutylene carbonate resin (F) and the polybutylene carbonate resin (G) were used in the ratios shown in Table 4.
- Reference Examples 6 and 7 A uniform solution was prepared by dissolving 1.0 g of polybutylene carbonate resin (F) or polybutylene carbonate resin (G) in 10 g of acetone. This solution was dried to obtain 1.0 g of a binder resin composition.
- the binder resin composition of the present invention has a determination coefficient in which the relationship between the mixing ratio of the two resins and the thermal decomposition temperature is close to 1, and by adjusting the mixing ratio, It turns out that it can adjust arbitrarily within the range of the decomposition temperature of each resin.
- Example 15 Production Example of Inorganic Fine Particle Dispersed Paste 0.12 g of the binder resin composition obtained in Example 1 is weighed into a 10 mL glass vial and dissolved in 0.88 g of N-methyl-2-pyrrolidone to prepare a uniform solution. Weigh 4.0 g of silver particles in a mortar and knead for 20 minutes until smooth, while adding the prepared solution, to obtain 5.0 g of silver particle dispersed paste.
- Example 16 In a 10 mL glass vial, 0.12 g of the binder resin composition obtained in Example 1 is weighed and dissolved in 0.88 g of N-methyl-2-pyrrolidone to prepare a uniform solution. The total amount of this solution and 4.0 g of alumina particles are mixed and kneaded using a rotating and rotating mixer to form a paste, and further kneaded using a three-roll mill to obtain 5.0 g of alumina dispersed paste.
- the binder resin composition of the present invention includes general molded products, optical materials such as films, fibers, optical fibers and optical disks, ceramic materials, thermally decomposable materials such as lost foam casting, medical materials such as pharmaceutical capsules, biodegradable resins, and the like. It can be used as an additive, a main component of a biodegradable resin, and the like.
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Abstract
Description
しかし、焼結の際の高温条件下において酸素が存在すると、無機成分が変質してしまい、焼結体の性能が低下する場合があり、焼結後に、還元雰囲気下でさらに焼結する工程が必要となることが多い。従って、焼結の際に酸素を供給せずに消失することができるバインダーが望まれている。
さらに、前述のバインダーは、発熱分解するため、焼結炉内の温度を制御しながら、一度に大量に焼結することが困難である。
〔1〕 式(1):
で表される脂肪族ポリカーボネート樹脂と、式(2):
で表される末端封止脂肪族ポリカーボネート樹脂を含む、バインダー樹脂組成物、並びに
〔2〕 前記〔1〕記載のバインダー樹脂組成物、無機微粒子、及び溶媒を含有する、無機微粒子分散ペースト組成物
に関する。
で表される脂肪族ポリカーボネート樹脂と、式(2):
で表される末端封止脂肪族ポリカーボネート樹脂を含む。通常、2種類の樹脂を混合し熱分解させると、それぞれの樹脂が独立して熱分解をするが、本発明のバインダー樹脂組成物は、それぞれの樹脂の混合比率に応じ、あたかも単一の樹脂の熱分解のごとく分解するため、バインダー樹脂組成物の分解温度を精度良く制御することができる。
ゲルパーミエーションクロマトグラフィー(日本ウォーターズ製、Waters 2695 セパレーションモジュール)を用いて、30mmol/LのN,N-ジメチルホルミアミド臭化リチウム溶液中40℃にて測定し、標準ポリスチレンを基準にして、質量平均分子量(Mw)及び数平均分子量(Mn)を算出し、分子量分布(Mw/Mn)を求めた。
攪拌機、窒素ガス導入管、温度計、ディーンスターク管、及び還流冷却管を備えた1L容の四つ口フラスコに、酸化亜鉛77.3g(0.95mol)、グルタル酸123g(1mol)、酢酸1.14g(0.02mol)及びトルエン760gを仕込んだ。次に、反応系内に50mL/minの流量で窒素を流しながら、55℃まで昇温し、同温度で4時間攪拌して反応させた。その後、110℃まで昇温し、さらに同温度で2時間攪拌して共沸脱水させ、水分を除去した後、室温まで冷却して、有機亜鉛触媒を含むスラリー液を得た。
攪拌機、ガス導入管、及び温度計を備えた1L容のオートクレーブの系内をあらかじめ窒素雰囲気に置換した後、触媒製造例1により得られた有機亜鉛触媒を含むスラリー液117.3g(有機亜鉛触媒を135mmol含む)、炭酸ジメチル577.2g、及びプロピレンオキシド78.3g(1.35mol)を仕込んだ。次に、攪拌下、二酸化炭素を加え、反応系内が1MPaとなるまで二酸化炭素を充填した。その後、60℃に昇温し、反応により消費される二酸化炭素を補給しながら8時間重合反応を行った。二酸化炭素の消費量は、1.17molであった。反応終了後、オートクレーブを冷却して脱圧したところに、無水コハク酸0.7g(全てのモノマーが反応したと仮定した場合の樹脂100質量部に対して0.5質量部)を添加し、40℃で1時間攪拌した。反応溶液をろ過した後、減圧乾燥して、無水コハク酸により末端がカルボキシ基で封止されたポリプロピレンカーボネート樹脂(A)120gを得た。得られたポリプロピレンカーボネートの質量平均分子量(Mw)は236,000、分子量分布(Mw/Mn)は10.0であった。
反応終了後、オートクレーブを冷却して脱圧した後、無水コハク酸を添加せず、反応溶液をろ過し、減圧乾燥した以外は、樹脂製造例1と同様にして、ポリプロピレンカーボネート樹脂(B)123gを得た。得られたポリプロピレンカーボネートの質量平均分子量は315,000、分子量分布(Mw/Mn)は9.74であった
ポリプロピレンカーボネート樹脂(B)40gと4,4’-ジフェニルメタンジイソシアネート0.4gを混練機(東洋精機製作所製、ラボプラストミル4C150)に投入し、混練温度160℃、回転数40r/minで5分間、溶融混練を行い、末端がイソシアネート基で封止されたポリプロピレンカーボネート樹脂(C)を得た。得られたポリプロピレンカーボネートの質量平均分子量は323,000、分子量分布(Mw/Mn)は8.82であった。
ポリエチレンカーボネート樹脂(D)(Empowermaterials社製、商品名QPAC25、Mw:198,000、Mw/Mn:3.48)40gとコハク酸無水物0.3gを混練機(東洋精機製作所製、ラボプラストミル4C150)に投入し、混練温度100℃、回転数40r/minで5分間、溶融混練を行い、無水コハク酸により末端がカルボキシ基で封止されたポリエチレンカーボネート樹脂(E)を得た。得られたポリエチレンカーボネートの質量平均分子量は197,000、分子量分布(Mw/Mn)は3.49であった。
攪拌機、ガス導入管、及び温度計を備えた1L容のオートクレーブの系内をあらかじめ窒素雰囲気に置換した後、触媒製造例1により得られた有機亜鉛触媒を含むスラリー液117.3g(有機亜鉛触媒を135mmol含む)、炭酸ジメチル577.2g、及び1,2-ブチレンオキシド97.3g(1.35mol)を仕込んだ。次に、攪拌下、二酸化炭素を加え、反応系内が1MPaとなるまで二酸化炭素を充填した。その後、60℃に昇温し、反応により消費される二酸化炭素を補給しながら8時間重合反応を行った。二酸化炭素の消費量は、1.02molであった。反応終了後、オートクレーブを冷却して脱圧し、ろ過した後、減圧乾燥してポリブチレンカーボネート樹脂(F)118gを得た。得られたポリブチレンカーボネートの質量平均分子量は273,000、分子量分布(Mw/Mn)は12.2であった。
樹脂製造例5で得られたポリブチレンカーボネート樹脂(F)11.6g(100mmol)をジクロロメタン120gに溶解させ、無水酢酸0.51g(5.0mmol)、トリエチルアミン0.3g(3.25mmol)及び4,4-ジメチルアミノピリジン0.2g(1.63mmol)を加え、25℃で24時間攪拌した。揮発分を除去し、残留物をメタノール200mLに注ぎ、析出した白色ポリマーを乾燥することで、無水酢酸により末端がエステル基で封止されたポリブチレンカーボネート樹脂(G)を得た。得られたポリブチレンカーボネートの質量平均分子量は290,000、分子量分布(Mw/Mn)は10.4であった。
50mL容ガラスバイアルに樹脂製造例1で得られたポリプロピレンカーボネート樹脂(A)0.2gと樹脂製造例2で得られたポリプロピレンカーボネート樹脂(B)0.8gを計りとり、アセトン10gに溶解させ、均一な溶液を調製した。この溶液を乾燥させ、バインダー樹脂組成物1.0gを得た。得られたバインダー樹脂組成物の熱分解開始温度は215.5℃、50質量%分解温度は217.2℃であった。
ポリプロピレンカーボネート樹脂(A)とポリプロピレンカーボネート樹脂(B)とを、表1に記載の比率で使用した以外は、実施例1と同様にして、バインダー樹脂組成物1.0gを得た。
ポリプロピレンカーボネート樹脂(A)又はポリプロピレンカーボネート樹脂(B)1.0gをアセトン10gに溶解させ、均一な溶液を調製した。この溶液を乾燥させ、バインダー樹脂組成物1.0gを得た。
エスアイアイ・ナノテクノロジー社製TG/DTA7220を用い、窒素雰囲気下、10℃/minの昇温速度で室温から500℃まで昇温しながら、熱重量の変化を測定する。熱分解開始温度(Td)は、試験加熱開始前の質量を通る横軸に平行な線と、分解曲線における屈曲点間の勾配が最大となるように引いた接線との交点とする。50質量%分解温度(Td50)は、サンプルの熱質量が試験加熱開始前の質量の半分(50%)になったときの温度を読み取る。
ポリプロピレンカーボネート樹脂(B)とポリプロピレンカーボネート樹脂(C)とを、表2に記載の比率で使用した以外は、実施例1と同様にして、バインダー樹脂組成物1.0gを得た。
ポリプロピレンカーボネート樹脂(C)1.0gをアセトン10gに溶解させ、均一な溶液を調製した。この溶液を乾燥させ、バインダー樹脂組成物1.0gを得た。
ポリエチレンカーボネート樹脂(D)とポリエチレンカーボネート樹脂(E)とを、表3に記載の比率で使用した以外は、実施例1と同様にして、バインダー樹脂組成物1.0gを得た。
ポリエチレンカーボネート樹脂(D)又はポリエチレンカーボネート樹脂(E)1.0gをアセトン10gに溶解させ、均一な溶液を調製した。この溶液を乾燥させ、バインダー樹脂組成物1.0gを得た。
ポリブチレンカーボネート樹脂(F)とポリブチレンカーボネート樹脂(G)とを、表4に記載の比率で使用した以外は、実施例1と同様にして、バインダー樹脂組成物1.0gを得た。
ポリブチレンカーボネート樹脂(F)又はポリブチレンカーボネート樹脂(G)1.0gをアセトン10gに溶解させ、均一な溶液を調製した。この溶液を乾燥させ、バインダー樹脂組成物1.0gを得た。
無機微粒子分散ペーストの製造例
10mL容のガラスバイアルに実施例1で得られたバインダー樹脂組成物0.12gを量りとり、N-メチル-2-ピロリドン0.88gに溶解させ、均一な溶液を調製する。乳鉢に銀粒子4.0gを量りとり、調整した溶液を加えながら、滑らかになるまで20分間混錬し、銀粒子分散ペースト5.0gを得る。
10mL容のガラスバイアルに実施例1で得られたバインダー樹脂組成物0.12gを量りとり、N-メチル-2-ピロリドン0.88gに溶解させ、均一な溶液を調製する。この溶液全量と、アルミナ粒子4.0gを混合し、自転公転ミキサーを用いて混錬してペースト化した後、さらに3本ロールミルを用いて混錬し、アルミナ分散ペースト5.0gを得る。
Claims (4)
- 式(1):
で表される脂肪族ポリカーボネート樹脂と、式(2):
で表される末端封止脂肪族ポリカーボネート樹脂を含む、バインダー樹脂組成物。 - 式(2)において、X及びYが、カルボキシ基、エステル基、カルバメート基及びイソシアネート基から選ばれる少なくとも1種の官能基を末端に有する基である、請求項1記載のバインダー樹脂組成物。
- 式(1)で表される脂肪族ポリカーボネート樹脂及び/又は式(2)で表される脂肪族ポリカーボネート樹脂が、ポリエチレンカーボネート、ポリプロピレンカーボネート及びポリブチレンカーボネートからなる群より選ばれる少なくとも1種である、請求項1又は2記載のバインダー樹脂組成物。
- 請求項1~3いずれか記載のバインダー樹脂組成物、無機微粒子、及び溶媒を含有する、無機微粒子分散ペースト組成物。
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EP16772059.8A EP3279265B1 (en) | 2015-03-30 | 2016-03-02 | Binder resin composition |
JP2017509430A JP6745792B2 (ja) | 2015-03-30 | 2016-03-02 | バインダー樹脂組成物 |
US15/557,579 US10457607B2 (en) | 2015-03-30 | 2016-03-02 | Binder resin composition |
SG11201707442VA SG11201707442VA (en) | 2015-03-30 | 2016-03-02 | Binder resin composition |
KR1020177030852A KR20170133402A (ko) | 2015-03-30 | 2016-03-02 | 바인더 수지 조성물 |
CN201680019906.5A CN107406669B (zh) | 2015-03-30 | 2016-03-02 | 粘接剂树脂组合物 |
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JPH06334282A (ja) | 1993-05-24 | 1994-12-02 | Matsushita Electric Ind Co Ltd | セラミック多層基板用グリーンシート |
US8222347B2 (en) | 2007-07-25 | 2012-07-17 | Sabic Innovative Plastics Ip B.V. | Polyester-polycarbonate compositions |
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Also Published As
Publication number | Publication date |
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TW201700604A (zh) | 2017-01-01 |
EP3279265A4 (en) | 2018-09-05 |
CN107406669B (zh) | 2019-07-19 |
TWI683853B (zh) | 2020-02-01 |
US20180057415A1 (en) | 2018-03-01 |
KR20170133402A (ko) | 2017-12-05 |
PH12017501777A1 (en) | 2018-03-19 |
JPWO2016158175A1 (ja) | 2018-01-25 |
SG11201707442VA (en) | 2017-10-30 |
JP6745792B2 (ja) | 2020-08-26 |
CN107406669A (zh) | 2017-11-28 |
EP3279265A1 (en) | 2018-02-07 |
EP3279265B1 (en) | 2019-06-12 |
US10457607B2 (en) | 2019-10-29 |
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