WO2017057393A1 - 炭素繊維用分散剤、炭素繊維分散組成物、および炭素繊維シートの製造方法 - Google Patents
炭素繊維用分散剤、炭素繊維分散組成物、および炭素繊維シートの製造方法 Download PDFInfo
- Publication number
- WO2017057393A1 WO2017057393A1 PCT/JP2016/078515 JP2016078515W WO2017057393A1 WO 2017057393 A1 WO2017057393 A1 WO 2017057393A1 JP 2016078515 W JP2016078515 W JP 2016078515W WO 2017057393 A1 WO2017057393 A1 WO 2017057393A1
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- WO
- WIPO (PCT)
- Prior art keywords
- carbon fiber
- random copolymer
- dispersant
- carbon
- ethylene oxide
- Prior art date
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 191
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 191
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 42
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 163
- 239000006185 dispersion Substances 0.000 title claims description 28
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- 238000005259 measurement Methods 0.000 description 8
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- 125000003118 aryl group Chemical group 0.000 description 7
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Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/08—Dispersing agents for fibres
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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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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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
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/017—Mixtures of compounds
- C09K23/018—Mixtures of two or more different organic oxygen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/16—Amines or polyamines
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/52—Natural or synthetic resins or their salts
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
- D21H13/46—Non-siliceous fibres, e.g. from metal oxides
- D21H13/50—Carbon fibres
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
- D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/52—Epoxy resins
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/57—Polyureas; Polyurethanes
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material
Definitions
- the present invention relates to a carbon fiber dispersant, a carbon fiber dispersion composition containing a carbon fiber dispersant, and a method for producing a carbon fiber sheet from the carbon fiber dispersion composition.
- Carbon fiber has excellent properties such as high mechanical properties, chemical resistance, electrical conductivity, and thermal conductivity. Therefore, carbon fiber is used in the fields of aircraft, automobiles and leisure goods for the purpose of improving mechanical strength. And is widely used in the field of electronic equipment parts for the purpose of imparting thermal conductivity.
- carbon fibers In order to produce the above mechanical and functional composite materials using carbon fibers, it is required that the carbon fibers be uniformly dispersed in the solution, the resin solution, and the resin.
- carbon fiber since carbon fiber generally has a strong cohesive force, it is a material that is difficult to disperse uniformly, and there is a demand for a method and a dispersing agent that enable more uniform dispersion.
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 30 unsubstituted or substituted carbon atoms, an unsubstituted or substituted hydroxyalkyl group, alkyloxy A group, an acyloxy group, a carboxyl group, an acyl group, a primary to tertiary amino group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, or an unsubstituted or substituted heterocyclic group, R 5 and R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 30 unsub
- R 6 or R 7 is a hydroxyl group
- the hydrogen atom may be substituted with an unsubstituted or substituted heterocyclic group
- R 3 , R 5 and R 9 are each independently a hydrogen atom
- a substituted or substituted alkyl group having 1 to 30 carbon atoms, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted pyranosyl group Alternatively, it represents an unsubstituted or substituted furanosyl group, or in the case of a group bonded through an oxygen atom, the group adjacent to the group may be removed to form
- a surfactant having an alkyl ester group, a vinylidene group and an anionic group Patent Document 4
- Patent Document 5 a dispersion for carbon filler
- R 1 is a hydrogen atom or a methyl group
- R 2 is an alkyl group having 16 to 22 carbon atoms
- R 3 is a hydrogen atom or a methyl group
- R 4 is a hydrogen atom or a carbon number of 1 to 22 is an alkyl group
- AO is an oxyalkylene group having 2 to 4 carbon atoms
- n is an integer of 1 to 100.
- a carbon material dispersant Patent Document 6
- a 1 O is an oxyethylene group, a is 3 to 25, A 2 O is an oxypropylene group, b is 1 to 10, and 5 ⁇ a + b ⁇ 30 and 1 ⁇ a / b ⁇ 5 is satisfied, R is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and n is 1 to 4.
- An aqueous dispersant (Patent Document 7) which is a polyether compound having a molecular weight of 1,000 to 5,000, is also known.
- an object of the present invention is to provide a carbon fiber that can uniformly disperse carbon fibers of, for example, 12.5 mm or more, particularly 10.0 mm to 100.0 mm, more preferably 12.5 mm to 50.0 mm, in an aqueous medium.
- a carbon fiber sheet having a very good texture is obtained by papermaking and drying a carbon fiber dispersion composition containing such a carbon fiber dispersant, carbon fiber and water. That is.
- the present invention includes the following preferred embodiments.
- A a random copolymer of phenyl glycidyl ether and ethylene oxide, or a random copolymer of phenyl glycidyl ether and ethylene oxide and propylene oxide;
- B A carbon fiber dispersant using a combination of a polyethylene glycol and / or a polyether-type polyurethane resin based on hexamethylene diisocyanate, which is a bifunctional polyol that is an ethylene oxide / propylene oxide random copolymer.
- carbon capable of uniformly dispersing relatively long carbon fibers for example, 12.5 mm or more, particularly 10.0 mm to 100.0 mm, more preferably 12.5 mm to 50.0 mm, in an aqueous medium.
- a fiber dispersant is provided.
- the dispersant for carbon fiber of the present invention is (A) a random copolymer of phenyl glycidyl ether and ethylene oxide, or a random copolymer of phenyl glycidyl ether and ethylene oxide and propylene oxide; (B) Polyether glycol based on polyethylene glycol and / or a bifunctional polyol which is an ethylene oxide / propylene oxide random copolymer and hexamethylene diisocyanate is used in combination.
- “used in combination” means that the random copolymer (A) and the polyether type polyurethane resin (B) are mixed and used, and the random copolymer (A) and the polyether type polyurethane resin. Either (B) may be used in any order.
- the random copolymer (A) is based on phenyl glycidyl ether (PGE), ethylene oxide (EO) and propylene oxide (PO), and has the following chemical formula: [Wherein, l and n are integers of 1 or more, m is an integer of 0 or more, and the arrangement order of PGE, EO and PO is random. ] It has a structural unit shown by.
- PGE phenyl glycidyl ether
- EO ethylene oxide
- PO propylene oxide
- L is an integer of 1 or more, and m is an integer of 0 or more.
- n is an integer of 1 or more, preferably 60 or more, and particularly preferably 150 or more.
- the copolymerization ratio EO: PGE is preferably 70:30 to 99.5: 0.5, more preferably 80:20 to 99.5: 0.5, particularly preferably 80:20 to 99: 1.
- the copolymerization ratio of PO is preferably 30 or less, more preferably 20 or less, and particularly preferably 10 or less.
- the copolymerization ratio EO: PGE is a mass ratio of ethylene oxide and phenylglycidyl ether in the random copolymer (A), and the copolymerization ratio of PO is propylene oxide in the random copolymer (A).
- a nuclear magnetic resonance spectrum 1 H-NMR
- the weight average molecular weight Mw of the random copolymer (A) is preferably larger from the viewpoint of dispersibility, for example, preferably 4,000 to 10,000,000, more preferably 4,000 to 1,000,000. Particularly preferred is 10,000 to 200,000.
- the weight average molecular weight Mw can be measured under the following measurement conditions using, for example, gel permeation chromatography (GPC).
- the molecular weight distribution (weight average molecular weight M w / number average molecular weight M n ) of the random copolymer (A) is not particularly limited, but is preferably 5 or less, more preferably 3 or less, and particularly preferably 2 or less.
- the number average molecular weight M n can be measured using gel permeation chromatography (GPC) as in the measurement of the weight average molecular weight M w described above.
- GPC gel permeation chromatography
- the randomness of the random copolymer (A) is not particularly limited.
- the random copolymer (A) can be produced by copolymerizing phenyl glycidyl ether and ethylene oxide, or phenyl glycidyl ether and ethylene oxide and propylene oxide, preferably at the copolymerization ratio described above.
- the copolymerization of phenyl glycidyl ether and ethylene oxide, or the copolymerization of phenyl glycidyl ether and ethylene oxide and propylene oxide can be carried out using a known method such as a solution polymerization method or a solvent slurry polymerization method.
- Copolymerization by adding a predetermined amount of phenylglycidyl ether and ethylene oxide or a predetermined amount of phenylglycidyl ether and ethylene oxide and propylene oxide to a solution obtained by adding a suitable catalyst to a suitable solvent at room temperature under a gas atmosphere Can be performed.
- a suitable catalyst a general catalyst used for producing a random copolymer from glycidyl ether and alkylene oxide can be used.
- an organoaluminum catalyst, an organozinc catalyst, an organotin / phosphorus catalyst can be used.
- Examples thereof include acid ester condensate catalysts, alkali metal hydroxide catalysts such as potassium hydroxide and sodium methoxide, alkali metal alkoxides, and catalyst compositions obtained by combining them.
- alkali metal hydroxide catalysts such as potassium hydroxide and sodium methoxide
- alkali metal alkoxides and catalyst compositions obtained by combining them.
- a suitable solvent a general solvent used for producing a random copolymer from glycidyl ether and alkylene oxide can be used, for example, ethers, aliphatic hydrocarbons, aromatic hydrocarbons.
- Halogenated solvents ketones, and the like, and mixtures of two or more of these solvents.
- the generated random copolymer is easily dried and is not dissolved in a solvent and can be handled as a powder without aggregation, n-butane, isobutane, n-pentane
- cyclopentane industrial hexane, n-hexane, isohexane, cyclohexane, n-heptane, n-octane, and isooctane are preferably used, and they can be handled as a solution because they are dissolved in a solvent.
- the reaction temperature (copolymerization temperature) for carrying out copolymerization is not particularly limited as long as it is a general temperature, and may be, for example, 150 ° C. or less, preferably 50 ° C. or less.
- the reaction solution is filtered or concentrated, and the residue is dried by a general method (for example, using a vacuum dryer) to obtain the random copolymer (A) as a viscous liquid or solid. Can do.
- random copolymer (A) a commercially available phenyl glycidyl ether / ethylene oxide / propylene oxide random copolymer may be used.
- Alcox (registered trademark) CP- manufactured by Meisei Chemical Co., Ltd. may be used.
- the polyether type polyurethane resin (B) is based on a bifunctional polyol which is a polyethylene glycol and / or an ethylene oxide / propylene oxide random copolymer and hexamethylene diisocyanate.
- the polymerization ratio (bifunctional polyol: hexamethylene diisocyanate) is preferably 99.5: 0.5 to 60:40, more preferably 99.5: 0.5 to 80:20, particularly preferably 99: 1 to 95: 5.
- the polymerization ratio (bifunctional polyol: hexamethylene diisocyanate) is a mass ratio of the bifunctional polyol and hexamethylene diisocyanate in the polyether-type polyurethane resin (B), for example, as described above. It can be measured using a nuclear magnetic resonance spectrum ( 1 H-NMR).
- the polymerization ratio in the polyether-type polyurethane resin (B) is within the above range, the water-solubility of the polyether-type polyurethane resin (B) is improved, and the wettability with respect to the carbon fiber is improved, whereby the dispersibility of the carbon fiber is improved.
- the improvement effect is easily exhibited well.
- the polyether type polyurethane resin (B) has a weight average molecular weight Mw of preferably 5,000 to 1,000,000, more preferably 10,000 to 1,000,000, particularly preferably 20,000 to 100,000. 000.
- the weight average molecular weight Mw can be measured, for example, using gel permeation chromatography (GPC) as described above.
- GPC gel permeation chromatography
- the molecular weight distribution (M w / M n ) of the polyether type polyurethane resin (B) is not particularly limited.
- the polyether type polyurethane resin (B) is obtained by polymerizing polyethylene glycol and / or a bifunctional polyol which is an ethylene oxide / propylene oxide random copolymer and hexamethylene diisocyanate, preferably at the polymerization ratio described above. Can be manufactured.
- the weight average molecular weight Mw of polyethylene glycol which is one of the bifunctional polyols for producing the polyether type polyurethane resin (B), is preferably 200 to 300,000, more preferably 400 to 200,000, particularly Preferably it is 400-20,000.
- the weight average molecular weight Mw can be measured, for example, using gel permeation chromatography (GPC) as described above.
- GPC gel permeation chromatography
- the molecular weight distribution (M w / M n ) of polyethylene glycol is not particularly limited.
- Such polyethylene glycol is commercially available from Sanyo Chemical Industries, Ltd. under the trade name “PEG Series” or from Meisei Chemical Industries, Ltd. under the trade name “Alcox Series”.
- An ethylene oxide / propylene oxide random copolymer which is one of the bifunctional polyols for producing the polyether type polyurethane resin (B) is based on ethylene oxide (EO) and propylene oxide (PO).
- the copolymerization ratio EO: PO is preferably 90:10 to 10:90.
- the copolymerization ratio EO: PO is the mass ratio of ethylene oxide to propylene oxide in the ethylene oxide / propylene oxide random copolymer.
- the nuclear magnetic resonance spectrum 1 H— NMR.
- the weight average molecular weight Mw of the ethylene oxide / propylene oxide random copolymer is preferably 200 to 150,000, more preferably 400 to 110,000, and particularly preferably 400 to 20,000.
- the weight average molecular weight Mw can be measured, for example, using gel permeation chromatography (GPC) as described above.
- GPC gel permeation chromatography
- the molecular weight distribution (M w / M n ) of the ethylene oxide / propylene oxide random copolymer is not particularly limited.
- the randomness of the ethylene oxide / propylene oxide random copolymer is not particularly limited.
- the ethylene oxide / propylene oxide random copolymer can be produced by copolymerizing ethylene oxide and propylene oxide, preferably at the copolymerization ratio described above.
- the copolymerization of ethylene oxide and propylene oxide can be carried out using a known method described in JP-A-7-243178, JP-A-2011-32398, and the like. This can be carried out by addition polymerization of propylene oxide.
- the diol compound ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, hexylene glycol and the like can be used.
- a suitable catalyst a general catalyst used for producing a random copolymer from ethylene oxide and propylene oxide can be used.
- an alkali metal hydroxide, an alkali metal alcoholate, etc. can be mentioned. Among these, it is preferable to use sodium hydroxide and potassium hydroxide from the viewpoint of easy handling.
- the amount of the catalyst used is usually 0.01 to 1% by mass, preferably 0.05 to 0.5% by mass, more preferably 0.1 to 0.3% by mass relative to the ethylene oxide / propylene oxide random copolymer. % By mass.
- a suitable solvent a general solvent used for producing a random copolymer from ethylene oxide and propylene oxide can be used, and examples thereof include BTXs such as toluene and xylene. From the viewpoint of production cost, it is preferable to synthesize without solvent.
- the reaction temperature (copolymerization temperature) for carrying out the copolymerization is not particularly limited as long as it is a general temperature, and may be, for example, 80 to 200 ° C.
- the unreacted monomer and solvent are removed, and the catalyst is removed by a method such as adsorptive filtration as necessary, whereby an ethylene oxide / propylene oxide random copolymer can be obtained as a liquid or a solid.
- ethylene oxide / propylene oxide random copolymer a commercially available ethylene oxide / propylene oxide random copolymer may be used.
- “New Paul (registered trademark) 75H-90000 manufactured by Sanyo Chemical Industries, Ltd.” may be used.
- polymerization of a bifunctional polyol and hexamethylene diisocyanate to produce a polyether type polyurethane resin (B) is disclosed in JP-A-10-147706, JP-A-2001-354742, and JP-A-7-243178.
- the difunctional polyol can be heated and dehydrated under an inert gas atmosphere, dissolved in a suitable solvent after cooling, and then dissolved in a suitable solvent. It can be carried out by adding a catalyst and polymerizing.
- a suitable catalyst a general catalyst used for producing a polyether type polyurethane resin can be used.
- an amine catalyst triethylamine, dimethylcyclohexylamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, triethylenediamine
- a amine catalyst triethylamine, dimethylcyclohexylamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, triethylenediamine
- tin catalysts dibutyltin dilaurate, trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, etc.
- lead catalysts lead oleate, lead 2-ethylhexanoate, lead naphthenate
- lead octylate lead octylate
- the amount of the catalyst used is usually 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the polyether type polyurethane resin.
- a suitable solvent a general solvent used for producing a polyether type polyurethane resin can be used, and examples thereof include acetone, toluene, xylene, ethyl acetate, methyl ethyl ketone, and methyl isobutyl ketone. Can do. Among these, acetone is preferably used from the viewpoint of easy solvent removal.
- the reaction temperature (polymerization temperature) for carrying out the polymerization is not particularly limited as long as it is a general temperature, and may be, for example, 20 to 150 ° C., preferably 20 to 80 ° C.
- an aqueous solution of the polyether type polyurethane resin (B) can be obtained by removing the solvent by a general method (for example, distilling off) and replacing with water.
- polyether type polyurethane resin (B) a commercially available polyether type polyurethane resin can also be used, and examples thereof include Pulset HA manufactured by Meisei Chemical Industry Co., Ltd.
- a dispersant for carbon fiber of the present invention a random copolymer (A) of phenyl glycidyl ether and ethylene oxide, or a random copolymer (A) of phenyl glycidyl ether and ethylene oxide and propylene oxide, and a specific polyether type A polyurethane resin (B) is used in combination.
- the random copolymer (A) includes a structural unit having an aryl group in the side chain (phenylglycidyl ether portion) and a structural unit having no aryl group in the side chain (ethylene oxide portion and propylene oxide portion).
- a structural unit having an aryl group in the side chain is due to the fact that the aryl group (aromatic ring) has an electron-rich ⁇ -electron system. Due to the ⁇ - ⁇ interaction unique to different aromatic rings, it exerts the effect of interacting with the ⁇ -electron system on the carbon fiber surface in the dispersion medium. Thereby, a random copolymer (A) expresses an intermolecular interaction (adsorption action) non-covalently with carbon fiber.
- random copolymer (A) can adsorb
- the polyether type urethane resin (B) has a strong cohesive force of the urethane resin itself, if it is once blended and inserted between the carbon fibers, it may have an effect of inhibiting the aggregation of the carbon fibers. It is done.
- the polyether-type polyurethane resin (B) is preferably 20 to 500 parts by mass, more preferably the polyether-type polyurethane resin (B) 25 to 400 parts by mass with respect to 100 parts by mass of the random copolymer (A). Parts, particularly preferably 50 to 250 parts by weight of the polyether type polyurethane resin (B), more preferably 70 to 200 parts by weight of the polyether type polyurethane resin (B), still more preferably 80 to 80 parts by weight of the polyether type polyurethane resin (B). It also relates to a dispersant for carbon fiber using 150 parts by mass. When the amount of the polyether-type polyurethane resin (B) with respect to the random copolymer (A) is within the above range, the effect of improving the dispersibility of the carbon fibers is easily exhibited well.
- the present invention further relates to a carbon fiber dispersion composition comprising the carbon fiber dispersant of the present invention, carbon fiber and water.
- the carbon fiber is not particularly limited, and any known carbon fiber can be used. Examples thereof include polyacrylonitrile-based (PAN-based) carbon fiber, rayon-based carbon fiber, and pitch-based carbon fiber. Carbon fibers may be used alone or in admixture of two or more. From the viewpoint of inexpensive cost and good mechanical properties, it is preferable to use PAN-based carbon fiber. Such carbon fibers are available as commercial products.
- PAN-based polyacrylonitrile-based
- Carbon fibers may be used alone or in admixture of two or more. From the viewpoint of inexpensive cost and good mechanical properties, it is preferable to use PAN-based carbon fiber. Such carbon fibers are available as commercial products.
- the diameter of the carbon fiber is preferably 3 to 15 ⁇ m, more preferably 5 to 10 ⁇ m.
- carbon fiber reinforced plastic CFRP
- CFRP carbon fiber reinforced plastic
- a recycled carbon fiber nonwoven fabric may be used as the carbon fiber.
- These carbon fibers may also be used alone or in admixture of two or more. Since the regenerated carbon fiber is relatively inexpensive, it is preferable from the viewpoint of cost.
- the method for regenerating carbon fiber is not particularly limited, and examples thereof include a method of removing a resin portion from CFRP by combustion, a method of removing by dissolving or decomposing with a solvent, and the like. In the regeneration of carbon fibers, it is difficult to obtain staples having a uniform fiber length, and very short fibers are mixed. In the present invention, such extremely short fibers may be mixed in the regenerated carbon fiber to such an extent that the effects of the present invention are not impaired.
- the length of carbon fiber is usually 5 to 100 mm.
- the carbon fiber may be cut into, for example, 12.5 mm or more, particularly 10.0 mm to 100.0 mm, and further 12.5 mm to 50.0 mm.
- the carbon fiber may or may not be subjected to a general treatment for modifying the surface state of the carbon fiber.
- a general treatment for modifying the surface state of the carbon fiber examples include application of an oil composition, introduction of a hydrophilic functional group by oxidation treatment, and removal of an irregular surface fragile layer by applying a high voltage.
- the dispersant of the present invention is a dispersant suitable for the carbon fiber itself, the presence of components other than the carbon fiber may inhibit the effect of improving the dispersibility of the carbon fiber. No carbon fiber is preferred.
- the carbon fiber dispersion composition of the present invention can be produced, for example, by introducing a carbon fiber dispersant, carbon fiber and water into a general mixer and stirring (disaggregating).
- the order of adding the carbon fiber dispersant, carbon fiber, and water is not particularly limited.
- the carbon fiber dispersant may be added as a mixture of the random copolymer (A) and the polyether type polyurethane resin (B), or the random copolymer (A) and the polyether type polyurethane resin (B). May be input separately in any order.
- Examples of the mixer include various disintegrators (pulpers), various beaters such as a Niagara beater, various refiners such as a single disc refiner and a double disc refiner, and various mixers.
- the dispersion medium water water such as distilled water and purified water can be used in addition to normal tap water.
- the dispersion medium is an aromatic hydrocarbon solvent, hydrocarbon solvent, halogenated hydrocarbon solvent, ether solvent, ketone solvent, ester solvent, glycol ether solvent, acetate ester solvent, dialkyl ether solvent. You may contain a solvent, an alcohol solvent, a glycol solvent, a nitrile solvent, a carbonate solvent, etc.
- the solvent may be used alone or in combination of two or more.
- the carbon fiber content in the carbon fiber dispersion composition is preferably 0.01 to 1.0% by mass, and more preferably 0.03 to 0.5% by mass.
- the carbon fibers are easily dispersed efficiently.
- the present invention further preferably comprises 2 to 30 parts by mass of a carbon fiber dispersant, more preferably 2.5 to 20 parts by mass, and particularly preferably a carbon fiber dispersion with respect to 100 parts by mass of carbon fiber.
- the present invention also relates to a carbon fiber dispersion composition containing 3 to 10 parts by mass of the agent.
- the present invention further relates to a method for producing a carbon fiber sheet, comprising the steps of papermaking and drying the carbon fiber dispersion composition.
- a carbon fiber sheet can be produced by a so-called wet papermaking method in which the dispersion medium is removed from the carbon fiber dispersion composition to form a sheet.
- the carbon fiber dispersion composition Prior to the papermaking step, the carbon fiber dispersion composition may be appropriately diluted with a dispersion medium as necessary.
- a paper machine used in the wet papermaking method for example, a known paper machine such as an inclined wire type paper machine, a circular net paper machine, a long net paper machine, or a short net paper machine can be used.
- the strength (wetted paper) as a handleable sheet may be insufficient only by physical entanglement between the fibers.
- a binder may be added to bind the fibers.
- a binder in the step of forming the carbon fiber sheet by a wet papermaking method, a solution containing the binder or an emulsion containing the binder is added internally, or after the carbon fiber sheet is formed, the binder is added to the carbon fiber sheet. It is preferable to provide a step of applying or impregnating and drying by heating.
- a binder those generally used in the production of nonwoven fabrics can be used. Examples thereof include acrylic resin, styrene-acrylic resin, epoxy resin, phenol resin, urethane resin, polyamide (nylon).
- Resins polyester resins, modified polyester resins (core-sheath structure), polypropylene resins, polyethylene resins, resins that melt with hot water such as polyvinyl alcohol, and the like can be mentioned. Further, other fibers other than carbon fibers may be mixed.
- the carbon fiber sheet thus obtained can be adjusted to an appropriate thickness by drying using a cylinder dryer, an air dryer or the like, and then subjecting the carbon fiber sheet to a hot pressing process such as a heat calender roll process.
- the basis weight of the carbon fiber sheet is preferably 10 to 1,000 g / m 2 , and more preferably 20 to 700 g / m 2 .
- the basis weight is within the above range, it is easy to avoid a decrease in operability in a paper machine such as cutting of a carbon fiber sheet, and the carbon fiber sheet can be dried within an appropriate time, thus avoiding a decrease in productivity. It is preferable because it is easy.
- the paper making speed of the carbon fiber sheet is preferably 10 m / min or more.
- the upper limit of the take-up speed is usually 100 m / min or less.
- the drying temperature of the carbon fiber sheet with a cylinder dryer or the like is usually 100 to 200 ° C., preferably 100 to 150 ° C.
- the carbon fiber sheet produced by the method for producing a carbon fiber sheet of the present invention has a very uniform texture. This represents that the carbon fiber was dispersed extremely uniformly in the aqueous medium by the carbon fiber dispersant of the present invention.
- Weight average molecular weight M w , number average molecular weight M n and molecular weight distribution M w / M n > The weight average molecular weight M w , number average molecular weight M n and molecular weight distribution M w / M n were measured using gel permeation chromatography (GPC) as described above.
- the carbon fiber sheet has a very uniform texture and no unevenness (fiber binding) 8 (good), the sheet has a very uneven texture, and the entire sheet has unevenness (fiber binding) 1 (Defect) ⁇ The texture is extremely uniform> 8, 7, 6, 5, 4, 3, 2, 1 ⁇ Evaluation was performed in 8 stages: the texture was extremely uneven>.
- Example 1 A carbon fiber not subjected to surface treatment (manufactured by Toho Tenax Co., Ltd .: trade name “HT C110”, fiber diameter 9 ⁇ m) was cut into a fiber length of 13 mm to obtain a chopped fiber.
- the mixture in the mixer was stirred for 2 minutes to obtain a slurry-like carbon fiber dispersion composition.
- the obtained carbon fiber dispersion composition was diluted with water (water volume: 5000 mL), and paper was made using a TAPPI square sheet machine (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) so as to have a basis weight of 20 g / m 2 .
- the carbon fiber dispersion composition after papermaking was dried and the texture of the obtained carbon fiber sheet was evaluated.
- Example 2 the carbon fiber sheet was prepared in the same manner as in Example 1 except that the addition amount of the random copolymer (A) was 0.05 g and the addition amount of the polyether type polyurethane resin (B) was 0.05 g. Prepared and evaluated the texture of the carbon fiber sheet.
- Example 3 the carbon fiber sheet was prepared in the same manner as in Example 1 except that the addition amount of the random copolymer (A) was 0.08 g and the addition amount of the polyether type polyurethane resin (B) was 0.02 g. Prepared and evaluated the texture of the carbon fiber sheet.
- a carbon fiber sheet was prepared in the same manner as in Example 1 except that 1,000 g / mol and a molecular weight distribution of about 2.0) were used, and the texture of the carbon fiber sheet was evaluated.
- Example 5 a carbon fiber sheet was prepared in the same manner as in Example 4 except that the addition amount of the random copolymer (A) was 0.05 g and the addition amount of the polyether type polyurethane resin (B) was 0.05 g. Prepared and evaluated the texture of the carbon fiber sheet.
- Example 6 a carbon fiber sheet was prepared in the same manner as in Example 4 except that the addition amount of the random copolymer (A) was 0.02 g and the addition amount of the polyether type polyurethane resin (B) was 0.08 g. Prepared and evaluated the texture of the carbon fiber sheet.
- Example 7 a carbon fiber sheet was prepared in the same manner as in Example 2 except that carbon fiber having a fiber length cut to 25 mm was used, and the texture of the carbon fiber sheet was evaluated.
- Example 8 a carbon fiber sheet was prepared in the same manner as in Example 5 except that carbon fiber having a fiber length cut to 25 mm was used, and the texture of the carbon fiber sheet was evaluated.
- Example 1 a carbon fiber sheet was prepared in the same manner as in Example 1 except that 0.1 g of the random copolymer (A) alone was used, and the texture of the carbon fiber sheet was evaluated.
- Example 2 a carbon fiber sheet was prepared in the same manner as in Example 1 except that only 0.1 g of the polyether type polyurethane resin (B) was used, and the texture of the carbon fiber sheet was evaluated.
- Example 4 a carbon fiber sheet was prepared in the same manner as in Example 4 except that only 0.1 g of the random copolymer (A) was used, and the texture of the carbon fiber sheet was evaluated.
- Example 4 In Example 1, instead of the random copolymer (A) and the polyether type polyurethane resin (B), manufactured by Kao Corporation: trade name “Emulgen 120” (polyoxyethylene lauryl ether, HLB15.3, cloud point 98 ° C. A carbon fiber sheet was prepared in the same manner as in Example 1 except that 0.1 g of a viscosity of 32.3 mPa ⁇ s (50 ° C.) was used, and the texture of the carbon fiber sheet was evaluated.
- Emulgen 120 polyoxyethylene lauryl ether, HLB15.3, cloud point 98 ° C.
- Example 5 In Example 1, instead of the random copolymer (A) and the polyether type polyurethane resin (B), manufactured by Kao Corporation: trade name “Emanon 3199V” (polyethylene glycol monostearate, HLB 19.4, melting point 56.5) A carbon fiber sheet was prepared in the same manner as in Example 1 except that 0.1 g of ⁇ 61.5 ° C. and a viscosity of 1,950 mPa ⁇ s (70 ° C.) was used, and the texture of the carbon fiber sheet was evaluated.
- Emanon 3199V polyethylene glycol monostearate, HLB 19.4, melting point 56.5
- Example 6 In Example 1, in place of the random copolymer (A) and the polyether type polyurethane resin (B), except that 0.1 g of trade name “Alcox SR” (polyethylene oxide) manufactured by Meisei Chemical Industry Co., Ltd. was used. Produced a carbon fiber sheet in the same manner as in Example 1, and evaluated the texture of the carbon fiber sheet.
- Alcox SR polyethylene oxide
- Example 7 a carbon fiber sheet was prepared in the same manner as in Example 2, except that Meisei Chemical Co., Ltd. product name “Alcox SR” (polyethylene oxide) was used instead of the random copolymer (A). The texture of the carbon fiber sheet was evaluated.
- Alcox SR polyethylene oxide
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Abstract
Description
で示される炭素繊維用分散剤(特許文献2)、および
下記一般式(1):
で示される炭素繊維用分散剤(特許文献3)が知られている。
からなり、(a1)と(a2)の質量比(a1)/(a2)が90/10~10/90であり、重量平均分子量が3,000~500,000である共重合体(A)からなる炭素材料用分散剤(特許文献6)、および下記式(1):
で示され、分子量が1000~5000であるポリエーテル系化合物である水系分散剤(特許文献7)等も知られている。
〔1〕(A)フェニルグリシジルエーテルおよびエチレンオキサイドのランダム共重合体、またはフェニルグリシジルエーテルおよびエチレンオキサイドおよびプロピレンオキサイドのランダム共重合体と、
(B)ポリエチレングリコールおよび/またはエチレンオキサイド・プロピレンオキサイドランダム共重合体である二官能性ポリオールとヘキサメチレンジイソシアネートとに基づくポリエーテル型ポリウレタン樹脂と
を組み合わせて用いる炭素繊維用分散剤。
〔2〕前記ランダム共重合体(A)100質量部に対して前記ポリエーテル型ポリウレタン樹脂(B)20~500質量部を用いる、上記〔1〕に記載の炭素繊維用分散剤。
〔3〕上記〔1〕または〔2〕に記載の炭素繊維用分散剤、炭素繊維および水を含む、炭素繊維分散組成物。
〔4〕前記炭素繊維100質量部に対して前記炭素繊維用分散剤2~30質量部を含む、上記〔3〕に記載の炭素繊維分散組成物。
〔5〕上記〔3〕または〔4〕に記載の炭素繊維分散組成物を抄紙および乾燥する工程を含む、炭素繊維シートの製造方法。
本発明の炭素繊維用分散剤は、
(A)フェニルグリシジルエーテルおよびエチレンオキサイドのランダム共重合体、またはフェニルグリシジルエーテルおよびエチレンオキサイドおよびプロピレンオキサイドのランダム共重合体と、
(B)ポリエチレングリコールおよび/またはエチレンオキサイド・プロピレンオキサイドランダム共重合体である二官能性ポリオールとヘキサメチレンジイソシアネートとに基づくポリエーテル型ポリウレタン樹脂と
を組み合わせて用いる。
ランダム共重合体(A)は、フェニルグリシジルエーテル(PGE)、エチレンオキサイド(EO)およびプロピレンオキサイド(PO)に基づき、下記化学式:
で示される構造単位を有する。
ここで、共重合比EO:PGEとは、ランダム共重合体(A)におけるエチレンオキサイドとフェニルグリシジルエーテルの質量比であり、POの共重合比とは、ランダム共重合体(A)におけるプロピレンオキサイドの質量比であり、例えば核磁気共鳴スペクトル(1H-NMR)を用いて下記測定条件下で測定することができる。
<測定条件>
機器:製品名「JNM-AL400」(日本電子株式会社製)
観測核:1H
観測範囲:7992.01Hz
データポイント数:32768
パルス幅:5.80μsec
待ち時間:50.00μsec
積算回数:512
測定温度:25℃
測定溶媒:重水素化クロホルム
試料濃度:0.01g/mL
ランダム共重合体(A)における共重合比が上記範囲内であると、炭素繊維の分散性向上効果が良好に発揮されやすい。
重量平均分子量Mwは、例えば、ゲルパーミエーションクロマトグラフィー(GPC)を用いて下記測定条件下で測定することができる。
<測定条件>
装置:製品名「LC-10AD」(株式会社島津製作所製)
検出器:示差屈折率検出器(RID)
カラム:製品名「SHODEX KF-804」(昭和電工株式会社製)
測定温度:30℃
溶離液:THF
流速:1.0mL/min
サンプル濃度:0.2質量%(THF)
サンプル注入量:100μL
換算標準:ポリエチレンオキサイド
ランダム共重合体(A)の重量平均分子量が上記範囲内であると、炭素繊維の分散性向上効果が良好に発揮されやすい。
ランダム共重合体(A)は、フェニルグリシジルエーテルおよびエチレンオキサイド、またはフェニルグリシジルエーテルおよびエチレンオキサイドおよびプロピレンオキサイドを、好ましくは先に記載した共重合比で、共重合させることにより製造することができる。フェニルグリシジルエーテルおよびエチレンオキサイドの共重合、またはフェニルグリシジルエーテルおよびエチレンオキサイドおよびプロピレンオキサイドの共重合は、溶液重合法または溶媒スラリー重合法等の公知の方法を用いて行うことができ、例えば、不活性ガス雰囲気下、室温で適当な触媒を適当な溶媒に加えて得た溶液に、所定量のフェニルグリシジルエーテルおよびエチレンオキサイド、または所定量のフェニルグリシジルエーテルおよびエチレンオキサイドおよびプロピレンオキサイドを添加して共重合させることにより行うことができる。適当な触媒としては、グリシジルエーテルとアルキレンオキサイドとからランダム共重合体を生成するために用いられる一般的な触媒を用いることができ、例えば、有機アルミニウム系触媒、有機亜鉛系触媒、有機スズ・リン酸エステル縮合物触媒、水酸化カリウムやナトリウムメトキシド等のアルカリ金属水酸化物触媒、アルカリ金属のアルコキシド、およびそれらを組み合わせた触媒組成物を挙げることができる。これらの中でも、触媒活性の強さおよび重合度の調整や取扱いの容易さの観点から、有機アルミニウム系触媒と、アルカリ金属のアルコキシドまたはアルカリ金属水酸化物とを含む触媒組成物を使用することが好ましい。適当な溶媒としては、グリシジルエーテルとアルキレンオキサイドとからランダム共重合体を生成するために用いられる一般的な溶媒を使用することができ、例えば、エーテル類、脂肪族炭化水素類、芳香族炭化水素類、ハロゲン系溶媒、ケトン類等、およびこれら溶媒の2つ以上の混合物を挙げることができる。これらの中でも、生成されるランダム共重合体が乾燥されやすく、溶媒中に溶解しないために粉体のまま凝集を伴わずに取り扱うことができるという観点から、n-ブタン、イソブタン、n-ペンタン、シクロペンタン、工業用ヘキサン、n-ヘキサン、イソヘキサン、シクロヘキサン、n-ヘプタン、n-オクタン、イソオクタンを使用することが好ましく、また、溶媒中に溶解するため溶液のまま取り扱うことができるという観点から、トルエン、キシレンを使用することが好ましい。共重合を実施する際の反応温度(共重合温度)は、一般的な温度であれば特に限定されず、例えば150℃以下、好ましくは50℃以下であってよい。共重合反応後、反応液を濾過または濃縮し、残渣を一般的な方法で(例えば真空乾燥機を用いて)乾燥させることにより、ランダム共重合体(A)を粘稠液体または固体として得ることができる。
ポリエーテル型ポリウレタン樹脂(B)は、ポリエチレングリコールおよび/またはエチレンオキサイド・プロピレンオキサイドランダム共重合体である二官能性ポリオールとヘキサメチレンジイソシアネートとに基づく。
ポリエーテル型ポリウレタン樹脂(B)は、ポリエチレングリコールおよび/またはエチレンオキサイド・プロピレンオキサイドランダム共重合体である二官能性ポリオールとヘキサメチレンジイソシアネートとを、好ましくは先に記載した重合比で、重合させることにより製造することができる。
ポリエーテル型ポリウレタン樹脂(B)を製造するための二官能性ポリオールの1つであるポリエチレングリコールの重量平均分子量Mwは、好ましくは200~300,000、より好ましくは400~200,000、特に好ましくは400~20,000である。重量平均分子量Mwは、例えば、先に記載したようにゲルパーミエーションクロマトグラフィー(GPC)を用いて測定することができる。ポリエチレングリコールの重量平均分子量が上記範囲内であると、ポリエーテル型ポリウレタン樹脂(B)の水溶性が向上し、炭素繊維に対する濡れ性が向上し、これにより炭素繊維の分散性向上効果が良好に発揮されやすい。
ポリエーテル型ポリウレタン樹脂(B)を製造するための二官能性ポリオールの1つであるエチレンオキサイド・プロピレンオキサイドランダム共重合体は、エチレンオキサイド(EO)およびプロピレンオキサイド(PO)に基づく。
本発明の炭素繊維用分散剤として、フェニルグリシジルエーテルおよびエチレンオキサイドのランダム共重合体(A)、またはフェニルグリシジルエーテルおよびエチレンオキサイドおよびプロピレンオキサイドのランダム共重合体(A)と、特定のポリエーテル型ポリウレタン樹脂(B)とが組み合わせて用いられる。ランダム共重合体(A)は、側鎖にアリール基を有する構造単位(フェニルグリシジルエーテル部分)と側鎖にアリール基を有さない構造単位(エチレンオキサイド部分およびプロピレンオキサイド部分)を含む。これにより、炭素繊維のように親油性で表面エネルギーの低い物質にも優れた分散性を発揮することができる。具体的には、側鎖にアリール基を有する構造単位(フェニルグリシジルエーテル部分)は、アリール基(芳香族環)が電子豊富なπ電子系を有することに起因して、疎水性相互作用とは異なる芳香族環特有のπ-π相互作用により、分散媒中で炭素繊維表面のπ電子系と相互作用する効果を発揮する。これにより、ランダム共重合体(A)は、炭素繊維と非共有結合的に分子間相互作用(吸着作用)を発現する。そして、ランダム共重合体(A)は、側鎖に芳香族環を複数有することにより、炭素繊維表面に多点吸着できるため、一旦吸着すると炭素繊維表面から離れにくい。一方、ポリエーテル型ウレタン樹脂(B)はウレタン樹脂自体の凝集力が強いため、炭素繊維間に一度配合され挿入されてしまうと、炭素繊維同士の凝集を阻害する効果があるのではないかと考えられる。
本発明は更に、本発明の炭素繊維用分散剤、炭素繊維および水を含む炭素繊維分散組成物にも関する。
炭素繊維は特に限定されず、既知の炭素繊維のいずれのものでも使用することができる。その例として、ポリアクリロニトリル系(PAN系)炭素繊維、レーヨン系炭素繊維、ピッチ系炭素繊維等を挙げることができる。炭素繊維は、それぞれ単独でまたは2種以上を混合して使用してよい。安価なコストと良好な機械的特性の観点から、PAN系炭素繊維を使用することが好ましい。そのような炭素繊維は、市販品として入手可能である。
本発明は更に、炭素繊維分散組成物を抄紙および乾燥する工程を含む、炭素繊維シートの製造方法にも関する。
実施例および比較例における各種測定方法および評価方法は、次の通りである。
共重合比は、先に記載したように核磁気共鳴スペクトル(1H-NMR)を用いて測定した。
重量平均分子量Mw、数平均分子量Mnおよび分子量分布Mw/Mnは、先に記載したようにゲルパーミエーションクロマトグラフィー(GPC)を用いて測定した。
炭素繊維シートの地合いが極めて均一で、全くムラ(繊維の結束)がないものを8(良)、シートの地合いが極めて不均一で、シート全体にムラ(繊維の結束)が存在するものを1(不良)として、地合いの均一性を、
<地合いが極めて均一である> 8、7、6、5、4、3、2、1 <地合いが極めて不均一である>の8段階で評価した。
表面処理が施されていない炭素繊維(株式会社東邦テナックス製:商品名「HT C110」、繊維直径9μm)を繊維長13mmにカットし、チョップドファイバを得た。
室温でミキサー(東芝社製:商品名「MX-C20G」)に、上記炭素繊維1.0g、ランダム共重合体(A)(明成化学工業株式会社製:商品名「アルコックスCP-B1」、共重合比EO:PO:PGE=98:1:1、重量平均分子量約100,000g/mol、分子量分布約2.0)0.02g、ポリエーテル型ポリウレタン樹脂(B)(明成化学工業株式会社製:商品名「パルセットHA」、重合比〔二官能性ポリオール:ヘキサメチレンジイソシアネート〕=97.1:2.9)0.08gおよび蒸留水500mLを添加し、スライダックを用いて電圧を30Vに制御しながら、ミキサー内の混合物を2分間撹拌し、スラリー状の炭素繊維分散組成物を得た。
得られた炭素繊維分散組成物を水で希釈し(水量5000mL)、TAPPI式角形シートマシン(株式会社安田精機製作所製)を用いて、坪量20g/m2となるように抄紙した。
抄紙後の炭素繊維分散組成物を乾燥し、得られた炭素繊維シートの地合いを評価した。
実施例1において、ランダム共重合体(A)の添加量を0.05g、ポリエーテル型ポリウレタン樹脂(B)の添加量を0.05gとした以外は実施例1と同様にして炭素繊維シートを作成し、炭素繊維シートの地合いを評価した。
実施例1において、ランダム共重合体(A)の添加量を0.08g、ポリエーテル型ポリウレタン樹脂(B)の添加量を0.02gとした以外は実施例1と同様にして炭素繊維シートを作成し、炭素繊維シートの地合いを評価した。
実施例1において、ランダム共重合体(A)として明成化学工業株式会社製の商品名「アルコックスCP-B2」(共重合比EO:PO:PGE=97:1:2、重量平均分子量約100,000g/mol、分子量分布約2.0)を使用した以外は実施例1と同様にして炭素繊維シートを作成し、炭素繊維シートの地合いを評価した。
実施例4において、ランダム共重合体(A)の添加量を0.05g、ポリエーテル型ポリウレタン樹脂(B)の添加量を0.05gとした以外は実施例4と同様にして炭素繊維シートを作成し、炭素繊維シートの地合いを評価した。
実施例4において、ランダム共重合体(A)の添加量を0.02g、ポリエーテル型ポリウレタン樹脂(B)の添加量を0.08gとした以外は実施例4と同様にして炭素繊維シートを作成し、炭素繊維シートの地合いを評価した。
実施例2において、炭素繊維として繊維長を25mmにカットしたものを用いた以外は実施例2と同様にして炭素繊維シートを作成し、炭素繊維シートの地合いを評価した。
実施例5において、炭素繊維として繊維長を25mmにカットしたものを用いた以外は実施例5と同様にして炭素繊維シートを作成し、炭素繊維シートの地合いを評価した。
実施例1において、ランダム共重合体(A)のみを0.1g用いた以外は実施例1と同様にして炭素繊維シートを作成し、炭素繊維シートの地合いを評価した。
実施例1において、ポリエーテル型ポリウレタン樹脂(B)のみを0.1g用いた以外は実施例1と同様にして炭素繊維シートを作成し、炭素繊維シートの地合いを評価した。
実施例4において、ランダム共重合体(A)のみを0.1g用いた以外は実施例4と同様にして炭素繊維シートを作成し、炭素繊維シートの地合いを評価した。
実施例1において、ランダム共重合体(A)およびポリエーテル型ポリウレタン樹脂(B)に換えて花王株式会社製:商品名「エマルゲン120」(ポリオキシエチレンラウリルエーテル、HLB15.3、曇点98℃、粘度32.3mPa・s(50℃))を0.1g用いた以外は実施例1と同様にして炭素繊維シートを作成し、炭素繊維シートの地合いを評価した。
実施例1において、ランダム共重合体(A)およびポリエーテル型ポリウレタン樹脂(B)に換えて花王株式会社製:商品名「エマノーン3199V」(ポリエチレングリコールモノステアレート、HLB19.4、融点56.5~61.5℃、粘度1,950mPa・s(70℃))を0.1g用いた以外は実施例1と同様にして炭素繊維シートを作成し、炭素繊維シートの地合いを評価した。
実施例1において、ランダム共重合体(A)およびポリエーテル型ポリウレタン樹脂(B)に換えて、明成化学工業株式会社製:商品名「アルコックスSR」(ポリエチレンオキサイド)を0.1g用いた以外は実施例1と同様にして炭素繊維シートを作成し、炭素繊維シートの地合いを評価した。
実施例2において、ランダム共重合体(A)に換えて明成化学工業株式会社製:商品名「アルコックスSR」(ポリエチレンオキサイド)を用いた以外は実施例2と同様にして炭素繊維シートを作成し、炭素繊維シートの地合いを評価した。
Claims (5)
- (A)フェニルグリシジルエーテルおよびエチレンオキサイドのランダム共重合体、またはフェニルグリシジルエーテルおよびエチレンオキサイドおよびプロピレンオキサイドのランダム共重合体と、
(B)ポリエチレングリコールおよび/またはエチレンオキサイド・プロピレンオキサイドランダム共重合体である二官能性ポリオールとヘキサメチレンジイソシアネートとに基づくポリエーテル型ポリウレタン樹脂と
を組み合わせて用いる炭素繊維用分散剤。 - 前記ランダム共重合体(A)100質量部に対して前記ポリエーテル型ポリウレタン樹脂(B)20~500質量部を用いる、請求項1に記載の炭素繊維用分散剤。
- 請求項1または2に記載の炭素繊維用分散剤、炭素繊維および水を含む、炭素繊維分散組成物。
- 前記炭素繊維100質量部に対して前記炭素繊維用分散剤2~30質量部を含む、請求項3に記載の炭素繊維分散組成物。
- 請求項3または4に記載の炭素繊維分散組成物を抄紙および乾燥する工程を含む、炭素繊維シートの製造方法。
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JP2019150773A (ja) * | 2018-03-03 | 2019-09-12 | 明成化学工業株式会社 | 炭素繊維用分散剤組成物、炭素繊維用分散剤キット、炭素繊維分散組成物、及び炭素繊維シートの製造方法 |
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US20180313037A1 (en) | 2018-11-01 |
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