WO2016088663A1 - 炭素繊維前駆体繊維、炭素繊維及び炭素繊維の製造方法 - Google Patents
炭素繊維前駆体繊維、炭素繊維及び炭素繊維の製造方法 Download PDFInfo
- Publication number
- WO2016088663A1 WO2016088663A1 PCT/JP2015/083342 JP2015083342W WO2016088663A1 WO 2016088663 A1 WO2016088663 A1 WO 2016088663A1 JP 2015083342 W JP2015083342 W JP 2015083342W WO 2016088663 A1 WO2016088663 A1 WO 2016088663A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon fiber
- fiber
- carbon
- general formula
- polymer
- Prior art date
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/28—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds from polyamides
- D01F9/30—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds from polyamides from aromatic polyamides
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
- D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Definitions
- the present invention relates to a carbon fiber precursor fiber, a carbon fiber, and a carbon fiber manufacturing method using a novel heat-resistant aromatic polymer that does not require infusibilization treatment (pretreatment including flameproofing treatment).
- Carbon fiber is widely used from aircraft to building materials, and if it improves productivity and lowers prices, it can be used as an alternative to steel plates in automobile bodies.
- carbon fiber is It is mainly produced using polyacrylonitrile (PAN) fibers and pitch fibers as raw materials (carbon fiber precursor fibers).
- PAN fibers and pitch fibers require a pretreatment called an infusible treatment prior to carbonization, and this treatment is a significant barrier to cost and energy reduction required for production, and productivity improvement.
- PAN fibers and pitch fibers melt in the process of carbonization treatment (high-temperature heat treatment at 1,000 ° C. or higher) and cannot maintain the fiber shape, so that they do not melt by air oxidation treatment called infusibilization treatment.
- Carbon fiber is obtained by changing to fiber and carbonizing it.
- strict temperature condition management for suppressing thermal runaway due to an exothermic reaction is required.
- certain heat-resistant aromatic polymers for example, aramid fiber and phenol resin fiber
- aramid fibers and phenol resin fibers have the property of being carbonized without being melted. can get.
- mechanical strength tensile strength, elastic modulus, etc.
- just maintaining the shape and carbonizing does not develop sufficient mechanical properties (strength, elasticity, etc.) required for carbon fiber products, so it is necessary to develop new materials that give sufficient mechanical properties. It becomes.
- the present inventors have found a graphite film having a heterocyclic polymer obtained by condensing an aromatic tetracarboxylic acid and an aromatic tetraamine (see Patent Document 1).
- a graphite film having a heterocyclic polymer obtained by condensing an aromatic tetracarboxylic acid and an aromatic tetraamine (see Patent Document 1).
- crystallization with too high two-dimensional (layered) orientation occurs, such as a graphite film, fiber cracking may occur due to peeling in a direction parallel to the graphite crystal layer bonded only by intermolecular force. As a result, there is a problem that the fiber becomes extremely weak in strength.
- PBB carbon fiber poly [bis- (benzimidazobenzisoquinolinone)]
- PBB carbon fiber is obtained only by performing high-temperature heat treatment without performing infusibilizing treatment on the precursor fiber, and exhibits excellent mechanical properties.
- PBB is not a widely spread material at present and is an expensive material compared to the existing precursor fiber, the practical use of PBB carbon fiber has a problem in cost. Is the current situation.
- Non-Patent Document 2 a resin formed from a polymer material having a polyoxazine structure as a repeating unit is known (see Non-Patent Document 2). That is, this polymer material is a polymer that can be synthesized using phenols, anilines, and paraformaldehyde, which are widely used as organic compound materials, and can be manufactured at low cost.
- phenols, anilines, and paraformaldehyde which are widely used as organic compound materials, and can be manufactured at low cost.
- such a polymer material is only considered for application to a resin film, and nothing has been studied about preparing this into a fiber and making it into carbon fiber. The carbonization conditions included and the mechanical strength when carbonized were unknown.
- a substance having an oxazine ring can be seen as a kind of phenolic resin because it exhibits ring-opening polymerization by heat treatment and exhibits thermosetting properties. Therefore, it is assumed that an amorphous structure having no orientation is obtained even when carbonized, and as a result, it is assumed that it is difficult to obtain a practical carbon fiber product excellent in mechanical properties.
- monomers having an oxazine structure are practically used as a thermosetting resin, a matrix resin for composite materials, and a sizing agent for carbon fibers. There are no examples of products.
- the present invention provides a carbon fiber precursor fiber, a carbon fiber, and a method for producing the carbon fiber, which can efficiently produce a carbon fiber excellent in mechanical strength at low cost without performing an infusibilization treatment. For the purpose.
- a carbon fiber precursor fiber comprising a polymer having a structural unit represented by the following general formula (1).
- X and Y are each independently —O—, —S—, —OSO—, —NH—, —CO—, —CH 2 —, and —CH (CH 3) 2 - represents any structure that forms a fused ring divalent substituent selected from the group, the one side of the two rings single bond and adjacent to share to the.
- Ar 1 represents an aryl group represented by any one of the following structural formulas (1) to (5)
- Ar 2 represents the following structural formulas (6) and (7).
- An aryl group represented by any one of ⁇ 3> A carbon fiber obtained by carbonizing the carbon fiber precursor fiber according to any one of ⁇ 1> to ⁇ 2>.
- ⁇ 4> The carbon fiber according to ⁇ 3>, wherein the fiber diameter is 1 ⁇ m or more.
- X and Y are each independently —O—, —S—, —OSO—, —NH—, —CO—, —CH 2 —, and —CH (CH 3) 2 - represents any structure that forms a fused ring divalent substituent selected from the group, the one side of the two rings single bond and adjacent to share to the.
- a carbon fiber precursor fiber acquisition step including a polymer having a structural unit represented by the general formula (1) and a polymer having a structural unit represented by the following general formula (2)
- the method for producing carbon fiber according to the above ⁇ 5> which is a step of spinning a carbon compound to obtain a carbon fiber precursor fiber.
- Ar 1 represents an aryl group represented by any one of the following structural formulas (1) to (5)
- Ar 2 represents the following structural formulas (6) and (7).
- the above-mentioned problems in the prior art can be solved, and a carbon fiber precursor fiber that can efficiently produce carbon fibers having excellent mechanical strength at low cost without performing infusibilization treatment.
- the carbon fiber and the method for producing the carbon fiber can be provided.
- the carbon fiber precursor fiber of this invention is a fiber body containing the polymer which has a structural unit represented by following General formula (1).
- the fiber body of the polymer can be carbonized as it is without performing infusibilization treatment, and sufficient mechanical strength can be obtained when it is carbonized by heat treatment. This is because, as shown in the general formula (1), the polymer has a rod-like aromatic polymer structure at the stage before fiberization, and therefore, molecules in the fiber axis direction are caused by the stress that the polymer chain receives during spinning.
- X and Y are each independently —O—, —S—, —OSO—, —NH—, —CO—, —CH 2 —, and —CH (CH 3) 2 - represents any structure that forms a fused ring divalent substituent selected from the group, the one side of the two rings single bond and adjacent to share to the.
- the polymer having the structural unit represented by the general formula (1) can be synthesized by the following method. That is, an aromatic dihydroxy compound represented by the following general formula (3), or an aromatic dihydroxy compound derivative such as an acid chloride, acid anhydride, ester or amide thereof, and the following general formula (4) It can be obtained by reacting the aromatic diamine or its salt with paraformaldehyde as a starting material.
- X and Y are each independently —O—, —S—, —OSO—, —NH—, —CO—, —CH 2 —, and A divalent substituent selected from the group —CH (CH 3 ) 2 —, a single bond, and a structure that forms a condensed ring by sharing one side of two adjacent rings are shown.
- aromatic dihydroxy compound examples include 4,4-dihydroxydiphenyl ether, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis ( 4-hydroxyphenyl) amine, 4′4-dihydroxybenzophenone, 2,2, -bis (4-hydroxyphenyl) propane can be exemplified, and specific compounds of the aromatic diamine include 4,4-diaminodiphenyl ether.
- the aromatic dihydroxy compound or derivative thereof and the aromatic diamine or salt thereof are added to a reaction vessel containing the paraformaldehyde and a solvent, and the mixture is added in chloroform for 3 hours to 48 hours.
- a method of stirring and refluxing for a time to obtain a polymer having the structural unit represented by the general formula (1) can be mentioned.
- the solvent is not particularly limited as long as it dissolves the starting material and does not hinder polymerization. Specific examples include chloroform, methanol, benzene, toluene and the like.
- the carbon fiber precursor may be a fiber body obtained from the polymer itself having the structural unit represented by the general formula (1) as a repeating unit, as long as the effects of the present invention are not impaired. Further, it may be a fiber body obtained by adding an arbitrary substituent to the polymer terminal. Examples of the substituent include an ester group, an amide group, an imide group, a hydroxyl group, and a nitro group.
- the number of repeating units of the structural unit represented by the general formula (1) is about 100 to 100,000.
- the carbon fiber precursor fiber can be produced by spinning a spin compound (polymer) containing a polymer having a structural unit represented by the general formula (1).
- the intrinsic viscosity of the compound to be spun is not particularly limited, but is preferably 0.05 dL ⁇ g ⁇ 1 to 5 dL ⁇ g ⁇ 1 . If the intrinsic viscosity is less than 0.05 dL ⁇ g ⁇ 1 , the fiber may break during spinning, and if it exceeds 5 dL ⁇ g ⁇ 1 , it may not be uniformly dissolved in the solvent used for spinning described later. . Note that 1 dL ⁇ g ⁇ 1 corresponds to 10 ⁇ 4 m 3 ⁇ g ⁇ 1 .
- the carbon fiber precursor may be a fiber body containing another polymer as long as the effects of the present invention are not hindered.
- Such other polymer is not particularly limited as long as it is a polymer that can be carbonized without performing infusibilization treatment.
- polymers, such as imidazole are mentioned, From a viewpoint of raising mechanical strength, among these, the polymer which has a structural unit represented by following General formula (2) is preferable.
- Ar 1 represents an aryl group represented by any one of the following structural formulas (1) to (5)
- Ar 2 represents the following structural formulas (6) and (7).
- the polymer having the structural unit represented by the general formula (2) can be synthesized by the following method. That is, it is obtained by reacting an aromatic tetracarboxylic acid or an aromatic tetracarboxylic acid derivative such as an acid chloride, acid anhydride, ester or amide thereof with an aromatic tetraamine or a salt thereof as a starting material. be able to.
- aromatic tetracarboxylic acid include 1,4,5,8-naphthalenetetracarboxylic acid and 4,4′-binaphthyl-1,1 ′, 8,8′-tetracarboxylic acid.
- the tetraamine examples include 1,2,4,5-benzenetetraamine and 3,3 ′, 4,4′-biphenyltetraamine.
- the aromatic tetracarboxylic acid or a carboxylic acid derivative thereof and the aromatic tetraamine or a salt thereof are added to a reaction vessel containing a solvent, and the reaction is performed at 100 to 250 ° C. for 3 hours to An example is a method of stirring for 48 hours to obtain a polymer having the structural unit represented by the general formula (2) as a repeating unit.
- the solvent is not particularly limited as long as the solvent dissolves the starting material and the polymer to be produced and has a function as a catalyst for promoting polymerization. Specific examples include methanesulfonic acid in which polyphosphoric acid, polyphosphoric acid ester, diphenylcresyl phosphate and the like, diphosphorus pentoxide and the like are dissolved.
- the 1,4,5,8-naphthalenetetracarboxylic acid can be synthesized from pyrene by two steps of oxidation with potassium permanganate and oxidation with a sodium hypochlorite solution.
- the 4,4′-binaphthyl-1,1 ′, 8,8′-tetracarboxylic acid is converted from 4, -chloro-1,8, -naphthalic anhydride to esterification, coupling and hydrolysis. It can be synthesized in 3 steps.
- the 1,2,4,5-benzenetetraamine can be synthesized from m-chlorobenzene by three steps of nitration, amination and reduction of the nitro group, and can be isolated and used as a tetrahydrochloride.
- 3,3 ′, 4,4′-biphenyltetraamine can be synthesized from o (ortho) -nitroaniline by three steps of iodination, cross-coupling, and reduction of amino group. In addition, you may purchase and use a commercial item about these.
- arbitrary substituents may be added to the said polymer terminal.
- substituents include an ester group, an amide group, an imide group, a hydroxyl group, and a nitro group.
- the number of repeating units of the structural unit represented by the general formula (2) is about 100 to 100,000.
- the carbon fiber precursor fiber is composed of a fibrous body containing a polymer having a structural unit represented by the general formula (1) and a polymer having a structural unit represented by the general formula (2).
- the mass ratio of the following formula is preferably 1/3 to 3. If the mass ratio is less than 1/3, the mechanical strength may not be sufficiently increased, and if it exceeds 3, the mechanical strength may not be changed and the cost may be simply increased.
- the carbon fiber precursor fiber is a polymer having a structural unit represented by the general formula (1), and a polymer having a structural unit represented by the general formula (2) as necessary.
- Etc. can be produced by spinning a spun body compound (polymer).
- spinning method there is no restriction
- the solvent used in the wet spinning method and the dry / wet spinning method is not particularly limited as long as the compound to be spun is soluble, and examples thereof include chloroform, toluene, methanesulfonic acid, and the like.
- solidifies the said spinning body compound as said carbon fiber precursor fiber For example, water, alcohol, dilute sulfuric acid etc. are mentioned.
- the carbon fiber precursor fiber does not lose its shape during the subsequent carbonization treatment even if its fiber diameter is increased.
- limiting in particular as said fiber diameter Although it can select suitably according to the objective, It can be 50 micrometers or more as needed. In addition, as an upper limit of the said fiber diameter, it is about 1,000 micrometers.
- a stretching process may be performed as necessary. As the stretching treatment, the spun yarn may be directly performed in a coagulation bath, or the wound yarn may be washed in water and then stretched in the bath. The stretching ratio is preferably about 1.2 to 10 times.
- the carbon fiber of the present invention is obtained by carbonizing the carbon fiber precursor fiber. Moreover, the manufacturing method of the said carbon fiber includes the carbonization process which heats the said carbon fiber precursor fiber under inert gas, and carbonizes.
- the heating method following preheating for the purpose of ring-opening polymerization of the oxazine ring of the polymer having the structural unit represented by the general formula (1), the ring-opened polymer is carbonized.
- the method of heating is mentioned.
- the preheating is not particularly limited as long as the ring-opening polymerization reaction proceeds, but is preferably performed under a nitrogen atmosphere at a temperature of 200 ° C. to 600 ° C. for the purpose of improving the efficiency of the production process.
- this preheating can also be implemented simultaneously with the said extending
- the main heating can be performed at a high speed.
- the conditions for the main heating are not particularly limited, but the rate of temperature rise can be 5 ° C./min or more. In addition, as an upper limit of the said temperature increase rate, it is about 500 degrees C / min.
- the temperature condition for the main heating at the time of the most heating is preferably 800 ° C. to 2,000 ° C. When heated at such a temperature, it can be carbonized while maintaining the shape of the carbon fiber precursor. At this time, in the carbon fiber precursor fiber including the polymer having the structural unit represented by the general formula (1), it is possible to moderately develop graphite crystals and impart a three-dimensional crosslinked structure. A carbon fiber having sufficient mechanical properties can be produced.
- a graphitization step of graphitizing the carbon fiber by heating at a higher temperature may be included.
- the heating temperature of the graphitization step is not particularly limited, but is preferably 2,000 ° C to 3,200 ° C. With such a heating temperature, the carbon fiber having a high carbonization yield, high density, and sufficient mechanical properties can be produced. In addition, it is preferable to implement the said graphitization process under the said inert gas similarly to the said carbonization process.
- the carbon fiber can be increased in diameter while maintaining the mechanical strength by spinning the carbon fiber precursor fiber into a thick fiber during the spinning.
- carbon fibers such as PAN-based carbon fibers
- fibers having a fiber diameter of about 7 ⁇ m are generally used.
- the carbon fibers have a fiber diameter of 1 ⁇ m to less than 8 ⁇ m, The mechanical strength is maintained even when the fiber diameter is increased to 8 ⁇ m or more, and further to 16 ⁇ m or more.
- the upper limit of the fiber diameter is about 30 ⁇ m.
- the carbon fiber may be a short fiber (span) or a continuous fiber (filament) depending on the spinning mode.
- equimolar amounts of bis (4-hydroxyphenyl) methane also known as bisphenol F, BPF, manufactured by Tokyo Chemical Industry Co., Ltd., vendor code No. B0819
- 4,4-oxydianiline Alias: 4,4-diaminodiphenyl ether, ODA, manufactured by Tokyo Chemical Industry Co., Ltd., distributor code No.O0088
- BNTCA 4,4′-binaphthyl-1,1 ′, 8,8′-tetracarboxylic acid
- DMAc in the synthesis method (2) represents dimethylacetamide.
- the carbon fiber according to Example 1-2 was produced in the same manner as in Example 1-1 except that the carbonization was performed by raising the temperature at 10 ° C. and holding for 10 minutes. In addition, the fiber diameter of the obtained carbon fiber was 9 micrometers. Micrographs of the carbon fibers according to Example 1-2 are shown in FIGS. 1 (a) to 1 (c).
- 1A is a view showing a scanning microscope image obtained by imaging the carbon fiber according to Example 1-2, and FIG.
- FIG. 1B is a fiber length of the carbon fiber shown in FIG. 1A. It is a figure which shows the scanning microscope image expanded in the direction, and FIG.1 (c) is a figure which shows the scanning microscope image which expanded the carbon fiber shown to Fig.1 (a) in the fiber diameter direction.
- the carbon fiber according to Example 2-2 was produced in the same manner as in Example 2-1, except that the carbonization was performed by raising the temperature at 10 ° C. and holding for 10 minutes. In addition, the fiber diameter of the obtained carbon fiber was about 9 ⁇ m.
- the carbon fiber according to Example 3-2 was produced in the same manner as in Example 3-1, except that the carbonization was performed by raising the temperature at 10 ° C. and holding for 10 minutes. In addition, the fiber diameter of the obtained carbon fiber was about 12 micrometers.
- Comparative Example 1-1 The composition of the spinning stock solution was changed, and the spinning stock solution prepared by dissolving only 50 g of PBB in 1 L of methanesulfonic acid was used, and the heating rate from room temperature to 1,300 ° C. was not carried out at 240 ° C. for 30 minutes.
- a carbon fiber according to Comparative Example 1-1 was produced in the same manner as in Example 1-1 except that the carbonization was performed by raising the temperature at 10 ° C./min and holding for 10 minutes. In addition, the fiber diameter of the obtained carbon fiber was about 9 ⁇ m.
- Comparative Example 1-2 The carbonization temperature was changed, and the carbon fiber precursor fiber was carbonized by raising the temperature from room temperature to 1,500 ° C. at a heating rate of 10 ° C./min and holding for 10 minutes under a nitrogen atmosphere, A carbon fiber according to Comparative Example 1-2 was produced in the same manner as Comparative Example 1-1. In addition, the fiber diameter of the obtained carbon fiber was about 9 ⁇ m.
- each carbon fiber according to Examples 1-1 to 3-2 are slightly lower or substantially the same density as the carbon fibers according to Comparative Examples 1-1 and 1-2.
- the density of each carbon fiber according to Examples 1-1 to 3-2 is substantially the same as compared with the density of the commercially available PAN-based carbon fiber being about 1.76 to 1.81. Therefore, each carbon fiber according to Examples 1-1 to 3-2 can be manufactured with a density equivalent to that of a practical product.
- each carbon fiber according to Examples 1-1 to 3-2 can be increased in diameter such as 9 ⁇ m and 16 ⁇ m in diameter compared with the commercially available carbon fiber having a diameter of 5 to 7 ⁇ m.
- the strength and elasticity of the carbon fiber depend on the crystallinity and orientation of the graphite crystal constituting the carbon fiber.
- the surface spacing c / 2 and lamination thickness L c of the hexagonal carbon layer in the carbon net plane As a parameter indicative of the crystallinity of graphite crystal was measured, the surface spacing c / 2 and lamination thickness L c of the hexagonal carbon layer in the carbon net plane.
- the conceptual view of a stacked thickness L c of the lattice distance c / 2 and hexagonal carbon carbon net plane in the graphite crystal is shown in FIG. 2 (a).
- symbol 1a, 1b, 1c in Fig.2 (a) shows a carbon network surface.
- Table 2 below shows the spacing c / 2 of the carbon network surface of the pitch-based carbon fiber, the lamination thickness L c of the carbon network surface, and the orientation degree (f) of the graphite crystal.
- “*” indicates a numerical value disclosed in Reference Document 1.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- Inorganic Fibers (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Artificial Filaments (AREA)
Abstract
Description
ポリアクリロニトリル(PAN)繊維及びピッチ繊維を原料(炭素繊維前駆体繊維)として製造されるのが主流となっている。
しかしながら、これらの炭素繊維前駆体繊維は、炭素化に先立って不融化処理と呼ばれる前処理が必要であり、この処理が製造に要するコスト及びエネルギーの低減、並びに生産性向上に対する大きな障壁となっている。
即ち、PAN繊維及びピッチ繊維は、炭素化処理(1,000℃以上の高温熱処理)の過程で溶融し、繊維形状を保てないことから、不融化処理と呼ばれる空気酸化処理によって溶融しない耐炎化繊維に変化させ、これを炭素化することで炭素繊維を得ている。この不融化処理では、酸化反応を均一に制御する必要があることに加え、発熱反応による熱暴走を抑えるための厳密な温度条件管理を必要とする。
しかしながら、アラミド繊維やフェノール樹脂繊維は、繊維形状を維持したまま炭素化するが、機械的強度(引張強度、弾性率等)が弱いという問題がある。
即ち、形状を維持して炭素化するのみでは、炭素繊維製品に求められる十分な機械特性(強度、弾性など)が発現しないことから、更に、十分な機械特性を付与する新材料の開発が必要となる。
しかしながら、黒鉛フィルムのような、二次元(層状)配向性の高すぎる結晶化が起こってしまうと、分子間力のみで結合する黒鉛結晶層に平行な方向での剥離によって、繊維の割れなどが起こり、繊維としては、強度面で極めて弱くなる問題がある。
しかしながら、PBBは、現在のところ、広範に普及した材料ではなく、既存の前駆体繊維と比較して高価な材料であることから、PBB炭素繊維の実用化は、コスト面での問題を有するのが現状である。
しかしながら、このような高分子材料は、樹脂フィルムへの適用が検討されるのみであり、これを繊維状に調製して炭素繊維化することについては、何ら検討されておらず、不融化処理を含めた炭素化条件や炭素化させたときの機械的強度が不明であった。また、オキサジン環を有する物質は、熱処理により開環重合して熱硬化性を発現するため、一種のフェノール樹脂として見ることができる。よって、炭素化しても配向性のないアモルファス構造となることが想定され、その結果、機械的特性に優れた実用的な炭素繊維製品が得難いと想定されていた。実際、オキサジン構造を有するモノマーは、熱硬化性樹脂として、複合材料のマトリックス樹脂や、炭素繊維のサイジング剤として実用に供されているが、オキサジン構造を有する高分子材料を炭素化させて炭素繊維製品とした例は見当たらない状況である。
<1> 下記一般式(1)で表される構成単位を有する重合体を含むことを特徴とする炭素繊維前駆体繊維。
<2> 更に、下記一般式(2)で表される構成単位を有する重合体を含む前記<1>に記載の炭素繊維前駆体繊維。
<4> 繊維直径が1μm以上である前記<3>に記載の炭素繊維。
<5> 下記一般式(1)で表される構成単位を有する重合体を含む被紡糸体化合物を紡糸して炭素繊維前駆体繊維を取得する炭素繊維前駆体繊維取得工程と、前記炭素繊維前駆体繊維を不活性ガス下で加熱して炭素化する炭素化工程と、を含むことを特徴とする炭素繊維の製造方法。
<6> 炭素繊維前駆体繊維取得工程が、一般式(1)で表される構成単位を有する重合体と、下記一般式(2)で表される構成単位を有する重合体とを含む被紡糸体化合物を紡糸して炭素繊維前駆体繊維を取得する工程である前記<5>に記載の炭素繊維の製造方法。
本発明の炭素繊維前駆体繊維は、下記一般式(1)で表される構成単位を有する重合体を含む繊維体である。
前記重合体の繊維体は、不融化処理を行わずにそのまま炭素化させることができ、また、加熱処理により炭素化したときに十分な機械的強度が得られる。これは、前記重合体が、前記一般式(1)に示すように繊維化前の段階で棒状の芳香族ポリマー構造を有することから、紡糸時に高分子鎖が受ける応力によって繊維軸方向に分子が並びやすい特性を有し、前記紡糸時に一旦このような特性が付与されることで、前記炭素化の際、繊維軸配向性を保持したまま黒鉛結晶が発達可能とされるとともに、オキサジン環(O,N原子を有する複素環)特有の開環重合による高分子鎖間の架橋構造により、炭素繊維の高強度化に必要とされる適度な非晶構造を炭素繊維の組織構造に導入することが可能であるためと考えられる。
即ち、下記一般式(3)で表される芳香族系ジヒドロキシ化合物、或いは、その酸塩化物、酸無水物、エステル又はアミド等の芳香族系ジヒドロキシ化合物誘導体と、下記一般式(4)で表される芳香族系ジアミン又はその塩と、パラホルムアルデヒドとを出発物質として反応させて得ることができる。
また、前記一般式(3)、(4)中のX及びYが前記隣接する2つの環の一辺を共有して縮合環を形成する構造である場合の例としては、前記隣接する2つの環がナフタレン環を形成する構造が挙げられる。なお、この場合のX及びYの構造は、前記一般式(1)のX及びYの構造として、前記一般式(1)で表される構造単位中に導入される。
重合方法としては、前記芳香族系ジヒドロキシ化合物又はその誘導体と、前記芳香族系ジアミン又はその塩とを、前記パラホルムアルデヒドと溶媒とを収めた反応容器内に添加し、クロロホルム中、3時間~48時間撹拌、還流させて、前記一般式(1)で表される構成単位を有する重合体を得る方法が挙げられる。
前記溶媒としては、前記出発物質材料を溶解し、重合を妨げない物であれば特に制限されない。具体的には、クロロホルム、メタノール、ベンゼン、トルエン等を挙げることができる。
なお、これら重合体合成の原料となる化合物としては、公知の方法で合成して用いてもよく、市販品を購入して用いてもよい。
前記置換基としては、例えば、エステル基、アミド基、イミド基、水酸基、ニトロ基等が挙げられる。
なお、前記一般式(1)で表される構成単位の繰り返し単位数としては、100~100,000程度である。
前記被紡糸体化合物の固有粘度としては、特に制限はないが、0.05dL・g-1~5dL・g-1が好ましい。
前記固有粘度が0.05dL・g-1未満であると、紡糸中に繊維が破断することがあり、5dL・g-1を超えると、後記する紡糸に用いる溶媒に均一に溶解しないことがある。なお、1dL・g-1は、10-4m3・g-1に相当する。
このような他の重合体としては、不融化処理を行わずに炭素化することができる重合体であれば、特に制限はなく、例えば、芳香族系のポリアミド、ポリイミド、ポリオキサジアゾール、ポリイミダゾールなどの重合体が挙げられるが、機械的強度を高める観点から、これらの中でも、下記一般式(2)で表される構成単位を有する重合体が好ましい。
即ち、芳香族系テトラカルボン酸、或いは、その酸塩化物、酸無水物、エステル又はアミド等の芳香族系テトラカルボン酸誘導体と、芳香族系テトラアミン又はその塩とを出発物質として反応させて得ることができる。
前記芳香族系テトラカルボン酸としては、1,4,5,8-ナフタレンテトラカルボン酸と4,4’-ビナフチル-1,1’,8,8’-テトラカルボン酸を例示でき、前記芳香族系テトラアミンとしては、1,2,4,5-ベンゼンテトラアミンと3,3’,4,4’-ビフェニルテトラアミンを例示できる。
重合方法としては、前記芳香族系テトラカルボン酸又はそのカルボン酸誘導体と、前記芳香族系テトラアミン又はその塩とを、溶媒を収めた反応容器内に添加し、100℃~250℃で3時間~48時間撹拌させて、前記一般式(2)で表される構成単位を繰り返し単位として有する重合体を得る方法を挙げることができる。
前記溶媒としては、前記出発物質材料及び生成する重合体を溶解し、重合を促進する触媒としての作用を有する物であれば特に制限されない。具体的には、ポリリン酸、ポリリン酸エステル、リン酸ジフェニルクレシル等や五酸化二リン等を溶解したメタンスルホン酸等を挙げることができる。
なお、これらについては市販品を購入して用いてもよい。
前記置換基としては、例えば、エステル基、アミド基、イミド基、水酸基、ニトロ基等が挙げられる。
なお、前記一般式(2)で表される構成単位の繰り返し単位数としては、100~100,000程度である。
前記質量比が1/3未満であると、十分に機械的強度を高めることができないことがあり、また、3を超えても、機械的強度が変わらず、単にコスト高となることがある。
前記湿式紡糸法及び前記乾湿式紡糸法で用いられる溶媒としては、前記被紡糸体化合物が可溶な溶媒であれば特に制限はなく、例えば、クロロホルム、トルエン、メタンスルホン酸等が挙げられる。
また、溶媒を溶出させ、前記被紡糸体化合物を前記炭素繊維前駆体繊維として凝固させる凝固液としても、特に制限はなく、例えば、水、アルコール、或いは希硫酸等が挙げられる。
なお、前記炭素前駆体繊維の調製に際し、必要に応じて延伸処理を行なってもよい。前記延伸処理としては、紡出糸を直接凝固浴中で行なってもよいし、巻取糸を水洗した後に浴中にて延伸してもよい。また、延伸倍率としては、1.2倍~10倍程度が好ましい。
本発明の炭素繊維は、前記炭素繊維前駆体繊維を炭素化して得られる。また、前記炭素繊維の製造方法は、前記炭素繊維前駆体繊維を不活性ガス下で加熱して炭素化する炭素化工程を含む。
前記加熱の方法としては、前記一般式(1)で表される構成単位を有する重合体の前記オキサジン環の開環重合を目的としたプレ加熱に続き、その開環重合体を炭素化する本加熱を行う方法が挙げられる。
前記プレ加熱としては、前記開環重合反応が進む限り、特に制限はないが、製造工程の高効率化を目的として、窒素雰囲気下、200℃~600℃の温度条件で実施することが好ましい。なお、このプレ加熱は、前記延伸処理を実施する場合、前記延伸処理と同時に実施することもできる。
また、前記炭素繊維の製造方法では、前記本加熱を高速で行うことができる。
したがって、前記本加熱の条件としては、特に制限はないが、昇温速度を5℃/min以上とすることができる。なお、前記昇温速度の上限としては、500℃/min程度である。また、最加熱時の前記本加熱の温度条件としては、800℃~2,000℃が好ましい。このような温度で加熱すると、前記炭素繊維前駆体の形状を維持しながら、炭素化することができる。
この際、前記一般式(1)で表される構成単位を有する重合体を含む前記炭素繊維前駆体繊維においては、黒鉛結晶の発達と三次元的架橋構造の付与をそれぞれ適度に行うことができ、十分な機械的特性を有する炭素繊維を製造することができる。
なお、前記黒鉛化工程は、前記炭素化工程と同様に前記不活性ガス下で実施することが好ましい。
また、前記炭素繊維としては、前記紡糸の態様に応じて、短繊維(スパン)とすることも、連続繊維(フィラメント)とすることもできる。
<ポリオキサジン/PBB=1/1炭素繊維前駆体繊維の合成>
下記合成方法(1)に従って、等モル量のビス(4-ヒドロキシフェニル)メタン(別名;ビスフェノールF、BPF、東京化成工業社製、販売元コードNo.B0819)及び4,4-オキシジアニリン(別名;4,4-ジアミノジフェニルエーテル、ODA、東京化成工業社製、販売元コードNo.O0088)と、4.3倍等モル量のパラホルムアルデヒド(東京化成工業社製販売元コードNo.P0018)とをクロロフォルム(和光純薬工業社製、販売元コードNo.038-02606)中で5時間還流し、縮重合させることによって、ポリ(N,N’-オキシジフェニレン-4,4’-メチレンジベンゾオキサジン)(以下、「ポリBPF/ODAオキサジン」と略す)を合成した。なお、このポリBPF/ODAオキサジンの固有粘度は、0.056dL・g-1であった。
ポリオキサジン/PBB=1/1炭素繊維前駆体繊維を、窒素雰囲気下にて、240℃で30分間熱処理した後、そのまま1,300℃まで昇温速度10℃/分で昇温し10分間保持することで炭素化し、実施例1-1に係る炭素繊維を製造した。なお、この炭素化処理は、ポリオキサジン/PBB=1/1炭素繊維前駆体繊維に2ミリニュートンの張力を掛けた状態で行った。また、得られた炭素繊維の繊維直径は、およそ9μmであった。
炭素化温度を変更し、ポリオキサジン/PBB=1/1炭素繊維前駆体繊維を、窒素雰囲気下にて、240℃で30分間熱処理した後、そのまま1,500℃まで昇温速度10℃/分で昇温し10分間保持することで炭素化したこと以外は、実施例1-1と同様にして、実施例1-2に係る炭素繊維を製造した。なお、得られた炭素繊維の繊維直径は、9μmであった。この実施例1-2に係る炭素繊維の顕微鏡写真を図1(a)~(c)に示す。なお、図1(a)は、実施例1-2に係る炭素繊維を撮像した走査型顕微鏡像を示す図であり、図1(b)は、図1(a)に示す炭素繊維の繊維長方向における拡大した走査型顕微鏡像を示す図であり、図1(c)は、図1(a)に示す炭素繊維を繊維径方向における拡大した走査型顕微鏡像を示す図である。
PBBの添加量を変更し、ポリBPF/ODAオキサジン25gと、PBB75gとをメタンスルホン酸1Lに溶解させて調製した紡糸原液を用いて湿式紡糸を行った(以下、この紡糸繊維を「ポリオキサジン/PBB=1/3炭素繊維前駆体繊維」と略す)こと以外は、実施例1-1と同様にして、実施例2-1に係る炭素繊維を製造した。なお、得られた炭素繊維の繊維直径は、およそ9μmであった。
炭素化温度を変更し、ポリオキサジン/PBB=1/3炭素繊維前駆体繊維を、窒素雰囲気下にて、240℃で30分間熱処理した後、そのまま1,500℃まで昇温速度10℃/分で昇温し10分間保持することで炭素化したこと以外は、実施例2-1と同様にして、実施例2-2に係る炭素繊維を製造した。なお、得られた炭素繊維の繊維直径は、およそ9μmであった。
湿式紡糸装置のノズル孔の直径を変更し、繊維直径が20μmのポリオキサジン/PBB=1/3炭素繊維前駆体繊維を得たこと以外は、実施例2-1と同様にして、実施例3-1に係る炭素繊維を製造した。なお、得られた炭素繊維の繊維直径は、およそ16μmであった。
炭素化温度を変更し、ポリオキサジン/PBB=1/3炭素繊維前駆体繊維を、窒素雰囲気下にて、240℃で30分間熱処理した後、そのまま1,500℃まで昇温速度10℃/分で昇温し10分間保持することで炭素化したこと以外は、実施例3-1と同様にして、実施例3-2に係る炭素繊維を製造した。なお、得られた炭素繊維の繊維直径は、およそ12μmであった。
紡糸原液の組成を変更し、PBB50gのみをメタンスルホン酸1Lに溶解させて調製した紡糸原液を用いたこと、240℃で30分間の熱処理を実施せず、室温から1,300℃まで昇温速度10℃/分で昇温し10分間保持することで炭素化したこと以外は、実施例1-1と同様にして、比較例1-1に係る炭素繊維を製造した。なお、得られた炭素繊維の繊維直径は、およそ9μmであった。
炭素化温度を変更し、炭素繊維前駆体繊維を、窒素雰囲気下にて室温から1,500℃まで昇温速度10℃/分で昇温し10分間保持することで炭素化したこと以外は、比較例1-1と同様にして、比較例1-2に係る炭素繊維を製造した。なお、得られた炭素繊維の繊維直径は、およそ9μmであった。
<密度>
浮沈法から算出した各炭素繊維の密度を下記表1に示す。
また、実施例1-1~3-2に係る各炭素繊維は、市販の炭素繊維の直径が5~7μmであるのに比べ、直径9μm、16μmといった太径化が実現できている。
炭素繊維の強度及び弾性は、炭素繊維を構成する黒鉛結晶の結晶性及び配向性に依存する。
ここでは、先ず、黒鉛結晶の結晶性を指標するパラメータとして、炭素網面の面間隔c/2及び炭素網面の積層厚Lcを測定した。黒鉛結晶における炭素網面の面間隔c/2及び炭素網面の積層厚Lcを示す概念図を図2(a)に示す。なお、図2(a)中の符号1a、1b、1cは、炭素網面を示す。
炭素網面の面間隔c/2及び炭素網面の積層厚Lcの測定は、Niフィルターで単色化されたCuKα線をX線源とするX線回析装置により、広角X線回折プロファイルを測定することにより行った。即ち、図2(b)に示す赤道方向の光学系について、赤道方向プロファイルの2θ=26°付近に観察される面指数(002)のピークから、炭素網面の面間隔c/2及び炭素網面の積層厚Lcを求めた。なお、図2(b)は、広角X線回折プロファイルを測定する際の光学系を示す概略図であり、検出器を繊維軸に対して垂直と平行な方向を赤道方向と子午線方向としている。また、X線回折装置を用いて2θ=26°付近に前記検出器を固定して子午線方向、赤道方向、子午線方向の順で繊維を回転させることによってX線強度分布をプロファイルすることを方位角測定とする。
次に、前述の方位角測定から得られる黒鉛結晶の配向度fを実用的な強度及び弾性率を有する炭素繊維の指標とする。なお、この配向度fは、実用配向度と呼ばれるもので、炭素材料の場合、2θ=26°付近に観測される黒鉛結晶の002面反射のいわゆるデバイ環に沿って測定された強度分布の半価幅(H°)からf=(1-H°/180)×100によって計算される。f=100であれば、図2(a)に示す、炭素結晶網面が繊維軸方向に全て並んだことを意味して、f=0であれば,炭素結晶網面が繊維軸方向に対して無秩序に配列していることを示す。
参考文献1;A.Takaku, et al., J. Mater. Sci., 25, 4873 (1990).
また、実施例1-2、2-2、3-2に係る各炭素繊維の炭素網面の面間隔c/2、及び配向度fの各値は、PAN系炭素繊維及びピッチ系炭素繊維のそれに匹敵する高い値を示している。
c/2 炭素網面の面間隔
Lc 炭素網面の積層厚
Claims (6)
- 請求項1から2のいずれかに記載の炭素繊維前駆体繊維を炭素化して得られることを特徴とする炭素繊維。
- 繊維直径が1μm以上である請求項3に記載の炭素繊維。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP15865501.9A EP3228736B1 (en) | 2014-12-03 | 2015-11-27 | Carbon-fiber precursor fiber and method for producing carbon fiber |
US15/532,388 US20170327973A1 (en) | 2014-12-03 | 2015-11-27 | Carbon-Fiber Precursor Fiber, Carbon Fiber, and Method for Producing Carbon Fiber |
KR1020177017753A KR101933598B1 (ko) | 2014-12-03 | 2015-11-27 | 탄소섬유 전구체 섬유, 탄소섬유 및 탄소섬유의 제조방법 |
CN201580065630.XA CN107002300B (zh) | 2014-12-03 | 2015-11-27 | 碳纤维前体纤维、碳纤维及碳纤维的制造方法 |
JP2016562415A JP6590283B2 (ja) | 2014-12-03 | 2015-11-27 | 炭素繊維前駆体繊維、炭素繊維及び炭素繊維の製造方法 |
US16/996,454 US20200378036A1 (en) | 2014-12-03 | 2020-08-18 | Carbon-Fiber Precursor Fiber, Carbon Fiber, and Method for Producing Carbon Fiber |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014244732 | 2014-12-03 | ||
JP2014-244732 | 2014-12-03 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/532,388 A-371-Of-International US20170327973A1 (en) | 2014-12-03 | 2015-11-27 | Carbon-Fiber Precursor Fiber, Carbon Fiber, and Method for Producing Carbon Fiber |
US16/996,454 Continuation US20200378036A1 (en) | 2014-12-03 | 2020-08-18 | Carbon-Fiber Precursor Fiber, Carbon Fiber, and Method for Producing Carbon Fiber |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016088663A1 true WO2016088663A1 (ja) | 2016-06-09 |
Family
ID=56091608
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/083342 WO2016088663A1 (ja) | 2014-12-03 | 2015-11-27 | 炭素繊維前駆体繊維、炭素繊維及び炭素繊維の製造方法 |
Country Status (6)
Country | Link |
---|---|
US (2) | US20170327973A1 (ja) |
EP (1) | EP3228736B1 (ja) |
JP (1) | JP6590283B2 (ja) |
KR (1) | KR101933598B1 (ja) |
CN (1) | CN107002300B (ja) |
WO (1) | WO2016088663A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3057802A1 (fr) * | 2016-10-26 | 2018-04-27 | Compagnie Generale Des Etablissements Michelin | Renfort metallique ou metallise dont la surface est revetue d'une polybenzoxazine |
US11306229B2 (en) | 2016-10-26 | 2022-04-19 | Compagnie Generale Des Etablissements Michelin | Polybenzoxazine that can be used for coating metal and for the bonding of same to rubber |
US11624002B2 (en) | 2017-06-14 | 2023-04-11 | Compagnie Generale Des Etablissements Michelin | Sulfurized polybenzoxazine that can be used for coating metal and for the bonding of same to rubber |
US11701922B2 (en) | 2017-06-14 | 2023-07-18 | Compagnie Generale Des Etablissements Michelin | Metal or metal-plated reinforcement with sulfur polybenzoxazine-coated surface |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112481817A (zh) * | 2020-11-27 | 2021-03-12 | 中宝(西安)科技集团有限公司 | 一种碳纤维隔热材料及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06505693A (ja) * | 1991-03-12 | 1994-06-30 | エデイソン・ポリマー・イノベイシヨン・コーポレイシヨン | ベンズオキサジンによるコンポジットの緻密化 |
JP2003064180A (ja) * | 2001-06-11 | 2003-03-05 | Nippon Steel Chem Co Ltd | ジヒドロベンゾキサジン環構造を有する硬化性樹脂及び耐熱性硬化樹脂 |
WO2007129640A1 (ja) * | 2006-05-01 | 2007-11-15 | Sekisui Chemical Co., Ltd. | 樹脂焼成物及びこれを搭載した電子機器 |
JP2012505287A (ja) * | 2008-10-09 | 2012-03-01 | アイユーシーエフ エイチワイユー (インダストリー ユニヴァーシティー コオペレイション ファウンデイション ハンヤン ユニヴァーシティー) | 高分子およびその製造方法 |
WO2014084164A1 (ja) * | 2012-11-27 | 2014-06-05 | 独立行政法人産業技術総合研究所 | 炭素繊維前駆体繊維、炭素繊維及び炭素繊維の製造方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1293900A (en) * | 1969-05-17 | 1972-10-25 | Kureha Chemical Ind Co Ltd | Process for production of carbon fibers |
JPS4954629A (ja) * | 1972-09-21 | 1974-05-28 | ||
JP2006144201A (ja) * | 2004-11-24 | 2006-06-08 | Seiko Epson Corp | 炭素複合体、炭素複合体の製造方法および樹脂成形体 |
KR101871909B1 (ko) * | 2014-05-08 | 2018-06-27 | 내셔날 인스티튜트 오브 어드밴스드 인더스트리얼 사이언스 앤드 테크놀로지 | 폴리벤즈이미다졸 탄소섬유 및 그 제조방법 |
-
2015
- 2015-11-27 EP EP15865501.9A patent/EP3228736B1/en active Active
- 2015-11-27 KR KR1020177017753A patent/KR101933598B1/ko active IP Right Grant
- 2015-11-27 CN CN201580065630.XA patent/CN107002300B/zh active Active
- 2015-11-27 US US15/532,388 patent/US20170327973A1/en not_active Abandoned
- 2015-11-27 JP JP2016562415A patent/JP6590283B2/ja active Active
- 2015-11-27 WO PCT/JP2015/083342 patent/WO2016088663A1/ja active Application Filing
-
2020
- 2020-08-18 US US16/996,454 patent/US20200378036A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06505693A (ja) * | 1991-03-12 | 1994-06-30 | エデイソン・ポリマー・イノベイシヨン・コーポレイシヨン | ベンズオキサジンによるコンポジットの緻密化 |
JP2003064180A (ja) * | 2001-06-11 | 2003-03-05 | Nippon Steel Chem Co Ltd | ジヒドロベンゾキサジン環構造を有する硬化性樹脂及び耐熱性硬化樹脂 |
WO2007129640A1 (ja) * | 2006-05-01 | 2007-11-15 | Sekisui Chemical Co., Ltd. | 樹脂焼成物及びこれを搭載した電子機器 |
JP2012505287A (ja) * | 2008-10-09 | 2012-03-01 | アイユーシーエフ エイチワイユー (インダストリー ユニヴァーシティー コオペレイション ファウンデイション ハンヤン ユニヴァーシティー) | 高分子およびその製造方法 |
WO2014084164A1 (ja) * | 2012-11-27 | 2014-06-05 | 独立行政法人産業技術総合研究所 | 炭素繊維前駆体繊維、炭素繊維及び炭素繊維の製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3228736A4 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3057802A1 (fr) * | 2016-10-26 | 2018-04-27 | Compagnie Generale Des Etablissements Michelin | Renfort metallique ou metallise dont la surface est revetue d'une polybenzoxazine |
WO2018078228A1 (fr) * | 2016-10-26 | 2018-05-03 | Compagnie Generale Des Etablissements Michelin | Renfort métallique ou métallisé dont la surface est revêtue d'une polybenzoxazine |
CN109890628A (zh) * | 2016-10-26 | 2019-06-14 | 米其林集团总公司 | 具有经聚苯并噁嗪涂布的表面的金属的或金属化的增强件 |
CN109890628B (zh) * | 2016-10-26 | 2020-11-20 | 米其林集团总公司 | 具有经聚苯并噁嗪涂布的表面的金属的或金属化的增强件 |
US11306229B2 (en) | 2016-10-26 | 2022-04-19 | Compagnie Generale Des Etablissements Michelin | Polybenzoxazine that can be used for coating metal and for the bonding of same to rubber |
US11370935B2 (en) | 2016-10-26 | 2022-06-28 | Compagnie Generale Des Etablissements Michelin | Metal or metallized reinforcement with polybenzoxazine-coated surface |
US11624002B2 (en) | 2017-06-14 | 2023-04-11 | Compagnie Generale Des Etablissements Michelin | Sulfurized polybenzoxazine that can be used for coating metal and for the bonding of same to rubber |
US11701922B2 (en) | 2017-06-14 | 2023-07-18 | Compagnie Generale Des Etablissements Michelin | Metal or metal-plated reinforcement with sulfur polybenzoxazine-coated surface |
Also Published As
Publication number | Publication date |
---|---|
US20200378036A1 (en) | 2020-12-03 |
KR20170088968A (ko) | 2017-08-02 |
EP3228736A4 (en) | 2018-06-27 |
EP3228736B1 (en) | 2022-01-26 |
JP6590283B2 (ja) | 2019-10-16 |
JPWO2016088663A1 (ja) | 2017-09-14 |
US20170327973A1 (en) | 2017-11-16 |
KR101933598B1 (ko) | 2018-12-28 |
EP3228736A1 (en) | 2017-10-11 |
CN107002300A (zh) | 2017-08-01 |
CN107002300B (zh) | 2019-09-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6590283B2 (ja) | 炭素繊維前駆体繊維、炭素繊維及び炭素繊維の製造方法 | |
Dong et al. | Synthesis of organ-soluble copolyimides by one-step polymerization and fabrication of high performance fibers | |
US9011739B2 (en) | Methods of continuously manufacturing polymide fibers | |
Zhang et al. | Structure evolutions involved in the carbonization of polyimide fibers with different chemical constitution | |
Cao et al. | Structural relationship between random copolyimides and their carbon fibers | |
CN114737318B (zh) | 一种聚酰亚胺基高导热石墨纳米纤维膜的制备方法 | |
JP6128610B2 (ja) | 炭素繊維前駆体繊維、炭素繊維及び炭素繊維の製造方法 | |
Xiao et al. | The influence of chemical constitution on the structure and properties of polyimide fibre and their graphite fibre | |
JP6449495B2 (ja) | ポリベンズイミダゾール炭素繊維 | |
Yan et al. | High conductivity electrospun carbon/graphene composite nanofiber yarns | |
JPS5953717A (ja) | 高強度,高モジュラスピッチ系炭素繊維の製造方法 | |
KR102266753B1 (ko) | 유연성을 갖는 폴리이미드계 탄소섬유 및 그 제조방법 | |
Sun et al. | Fabrication of Ultrahigh‐Strength Polybenzimidazole Fibers via a Novel and Green Integrated Liquid Crystal Spinning Process | |
CN110592727A (zh) | 一种高导热中间相沥青基石墨纤维长丝制备方法 | |
KR101470261B1 (ko) | 피치계 탄소섬유 및 이의 제조방법 | |
CN114959949B (zh) | 一种稠环芳烃基碳纤维及其制备方法 | |
US20230167588A1 (en) | Method of preparing carbon composite fiber and carbon composite fiber | |
KR20220094616A (ko) | 폴리이미드계 탄소섬유와 흑연섬유 및 그 제조방법 | |
JPH01207420A (ja) | 炭素繊維の製造方法 | |
Li | carbon fiber precursors based on polyethylene graft pitch copolymer | |
JPS626919A (ja) | 高強度、高モジユラスピツチ系炭素繊維 | |
JPH0314625A (ja) | 炭素繊維用ピッチ及びそれを用いた炭素繊維の製造方法 | |
CN114479070A (zh) | 一种聚酰胺酸和其聚酰亚胺纤维及其制备方法 | |
JP2017166104A (ja) | 炭素繊維前駆体用ポリマー溶液、および、炭素繊維前駆体繊維の製造方法ならびに炭素繊維の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15865501 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016562415 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15532388 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2015865501 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20177017753 Country of ref document: KR Kind code of ref document: A |