WO2022209895A1 - 強化繊維用サイジング剤及びその用途 - Google Patents
強化繊維用サイジング剤及びその用途 Download PDFInfo
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- WO2022209895A1 WO2022209895A1 PCT/JP2022/011863 JP2022011863W WO2022209895A1 WO 2022209895 A1 WO2022209895 A1 WO 2022209895A1 JP 2022011863 W JP2022011863 W JP 2022011863W WO 2022209895 A1 WO2022209895 A1 WO 2022209895A1
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- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
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- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
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- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
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- 238000001746 injection moulding Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
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- 239000004033 plastic Substances 0.000 description 1
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- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 1
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- 229920001451 polypropylene glycol Polymers 0.000 description 1
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- CZMAXQOXGAWNDO-UHFFFAOYSA-N propane-1,1,2-triol Chemical compound CC(O)C(O)O CZMAXQOXGAWNDO-UHFFFAOYSA-N 0.000 description 1
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- 239000010935 stainless steel Substances 0.000 description 1
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- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 1
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 1
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- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/507—Polyesters
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
Definitions
- the present invention relates to a sizing agent for reinforcing fibers and uses thereof. More particularly, it relates to a reinforcing fiber sizing agent used to reinforce a matrix resin, a reinforcing fiber strand and a fiber-reinforced composite material using the same.
- Fiber-reinforced composite materials in which plastic materials (called matrix resins) are reinforced with various synthetic fibers, are widely used for automotive applications, aerospace applications, sports and leisure applications, and general industrial applications.
- Fibers used in these composite materials include various inorganic fibers such as carbon fibers, glass fibers and ceramic fibers, and various organic fibers such as aramid fibers, polyamide fibers and polyethylene fibers.
- These various synthetic fibers are usually manufactured in a filament shape, and then processed into a sheet-like intermediate material called a unidirectional prepreg by a hot-melt method, a drum winding method, or the like, or processed by a filament winding method, or in some cases, a woven fabric. Or it is used as a reinforcing fiber through various high-order processing processes such as being processed into chopped fiber shape.
- Epoxy resins are widely used as matrix resins for reinforcing fiber composite materials.
- unsaturated polyester resins, vinyl ester resins, acrylic resins, etc. are used as matrix resins for radical polymerization.
- the wettability and adhesiveness between the matrix resin and the reinforcing fiber are important. Sizing agents that improve adhesion have been proposed (for example, Patent Documents 1 and 2).
- Patent Document 1 and Patent Document 2 improve the wettability and adhesiveness of reinforcing fibers and epoxy resins and radically polymerized matrix resins, respectively, it is difficult to achieve both.
- the physical properties of the final composite material were unsatisfactory.
- some reinforcing fibers have low elongation and brittle properties.
- These reinforcing fibers to which a conventional sizing agent is applied are subject to mechanical friction during the processing process, which may cause problems such as fluffing, fiber breakage, and insufficient bundling.
- an object of the present invention is to provide a reinforcing fiber sizing agent that improves the wettability of a matrix resin with respect to reinforcing fiber strands, and a reinforcing fiber strand and a fiber-reinforced composite material using the sizing agent.
- the present inventors found that a reinforcing fiber sizing agent containing a specific resin and a specific surfactant in a specific ratio can solve the above problems.
- the sizing agent for reinforcing fibers of the present invention contains an epoxy resin (A), an acetylenic surfactant (B), and a nonionic surfactant (C) other than the acetylenic surfactant (B).
- the weight ratio of the activator (B) to the total of the epoxy resin (A) and the activator (C) ((B)/(A)+(C)) is 0.001 to 0.15.
- the weight ratio ((B)/(C)) of the acetylenic surfactant (B) and the active agent (C) is preferably 0.01 to 0.2. It is preferable that the activator (C) has a molecular weight of 1,000 to 20,000.
- the acetylenic surfactant (B) is selected from acetylene alcohol (B1), acetylene diol (B2), compound (B3) obtained by adding alkylene oxide to acetylene alcohol, and compound (B4) obtained by adding alkylene oxide to acetylene diol. preferably at least one of the
- the acetylene alcohol (B1) is a compound represented by the following general formula (1)
- the acetylene diol (B2) is a compound represented by the following general formula (2)
- an alkylene oxide is added to the acetylene alcohol.
- the compound (B3) is a compound represented by the following general formula (3)
- the compound (B4) obtained by adding an alkylene oxide to the acetylenediol is a compound represented by the following general formula (4).
- R 1 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms.
- R 3 , R 4 , R 5 and R 6 are each independently an alkyl group having 1 to 8 carbon atoms.
- R 1 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms; R 7 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; AO is a carbon represents an oxyalkylene group of numbers 2 to 4. n is a number of 1 to 50.
- R 3 , R 4 , R 5 and R 6 are each independently an alkyl group having 1 to 8 carbon atoms.
- R 7 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- the plurality of R 7 in the formula (4) may be the same or different,
- AO represents an oxyalkylene group having 2 to 4 carbon atoms, m and n are each independently It is a number from 1 to 50.
- a resin component (D) which is at least one selected from the group consisting of polyurethane resins, vinyl ester resins, polyamide resins, polyolefin resins, polyester resins and phenol resins.
- the reinforcing fiber strand of the present invention is a reinforcing fiber strand obtained by attaching the reinforcing fiber sizing agent to a raw material reinforcing fiber strand.
- the fiber-reinforced composite material of the present invention includes a matrix resin and the reinforcing fiber strands.
- the matrix resin is a thermosetting resin.
- the sizing agent for reinforcing fibers of the present invention can uniformly apply the sizing agent to the reinforcing fibers.
- excellent wettability and adhesiveness to the matrix resin can be imparted to the reinforcing fibers.
- a reinforcing fiber composite material having excellent physical properties can be obtained.
- Epoxy resin (A) is an essential component of the reinforcing fiber sizing agent of the present invention.
- An epoxy resin is a compound having two or more reactive epoxy groups in its molecular structure. Typical epoxy resins are glycidyl ether type obtained from epichlorohydrin and an active hydrogen compound, and glycidyl ester type, glycidyl amine type, alicyclic type, and the like. One type of epoxy resin may be used, or two or more types may be used in combination.
- the epoxy equivalent of the epoxy resin is preferably 100-1500 g/eq, more preferably 120-1000 g/eq, and even more preferably 150-800 g/eq.
- the epoxy equivalent is less than 100 g/eq, the reinforcing fiber strands may be cured over time. If the epoxy equivalent exceeds 1500 g/eq, the adhesiveness to the matrix resin may deteriorate.
- the epoxy equivalent is based on JIS-K7236.
- the weight average molecular weight of the epoxy resin is preferably from 100 to 10,000, more preferably from 100 to 8,000, even more preferably from 150 to 7,000. If the weight-average molecular weight is less than 100, heat resistance may be insufficient during the step of drying the reinforcing fiber strands, and volatilization may occur. If the weight average molecular weight exceeds 10,000, the long-term storage stability of the sizing agent may deteriorate.
- the epoxy resin is preferably an aromatic epoxy resin having an aromatic ring in its molecular structure.
- the aromatic epoxy resins include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, and pyrocatechol; Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as bisphenol F novolak, bisphenol A novolak, dicyclopentadiene-modified phenol, triphenylmethane, and tetraphenylethane can be used.
- R 8 , R 9 , R 10 and R 11 are each independently a hydrogen atom or a methyl group.
- p is an integer of 0 to 30, preferably 0 to 20, more preferably 0 to 10, from the viewpoint of improving the wettability of the matrix resin.
- the method for producing the epoxy resin described above is not particularly limited, and known methods can be adopted. Moreover, the epoxy resins described above are generally commercially available, and the sizing agent for carbon fibers of the present invention can use these commercially available epoxy resins.
- the carbon fiber sizing agent of the present invention essentially contains an acetylenic surfactant (B).
- B acetylenic surfactant
- the acetylenic surfactant refers to a compound having an acetylene group and a hydrophilic group such as a hydroxyl group in its molecular structure.
- the acetylenic surfactant (B) may be used alone or in combination of two or more.
- Acetylene-based surfactant (B) is selected from acetylene alcohol (B1), acetylene diol (B2), compound (B3) obtained by adding alkylene oxide to acetylene alcohol, and compound (B4) obtained by adding alkylene oxide to acetylene diol. preferably at least one.
- the compound (B3) obtained by adding alkylene oxide to acetylene alcohol and the compound (B4) obtained by adding alkylene oxide to acetylene diol are preferable, and the compound (B4) obtained by adding alkylene oxide to acetylene diol is more preferable.
- Acetylene alcohol (B1) is a compound having an acetylene group and one hydroxyl group in its molecular structure.
- Acetylene alcohol (B1) is preferably a compound represented by the general formula (1).
- Acetylene diol (B2) is a compound having an acetylene group and two hydroxyl groups in its molecular structure.
- Acetylene diol (B2) is preferably a compound represented by the general formula (2).
- the compound (B3) obtained by adding alkylene oxide to acetylene alcohol is a compound obtained by adding alkylene oxide to the hydroxyl group of acetylene alcohol.
- the compound (B3) obtained by adding alkylene oxide to acetylene alcohol is preferably a compound represented by the general formula (3).
- the compound (B4) obtained by adding alkylene oxide to acetylenediol is a compound obtained by adding alkylene oxide to at least one hydroxyl group of acetylenediol.
- the compound (B4) obtained by adding alkylene oxide to acetylenediol is preferably a compound represented by the general formula (4).
- R 1 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms.
- the alkyl group may be linear or may have a branched structure.
- the number of carbon atoms in the alkyl group is preferably 1-7, more preferably 1-6, and still more preferably 1-5.
- R 3 , R 4 , R 5 and R 6 are each independently an alkyl group having 1 to 8 carbon atoms.
- the alkyl group may be linear or may have a branched structure.
- the number of carbon atoms in the alkyl group is preferably 1-7, more preferably 1-6, and still more preferably 1-5.
- R 7 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- the number of carbon atoms in the alkyl group is preferably 1-4, more preferably 1-3, even more preferably 1-2.
- AO represents an oxyalkylene group having 2 to 4 carbon atoms. That is, it represents an oxyethylene group, an oxypropylene group or an oxybutylene group.
- the oxyalkylene group is preferably an oxyethylene group or an oxypropylene group, more preferably an oxyethylene group.
- AO constituting (AO) n or (AO) m may be of one type or two or more types. In the case of two or more types, any of block adducts, alternate adducts and random adducts may be used.
- n is a number from 1 to 50. n is preferably 1 to 45, more preferably 1 to 40, even more preferably 1 to 35.
- m and n are each independently a number from 1 to 50. m and n are each independently preferably 1 to 45, more preferably 1 to 40, even more preferably 1 to 35.
- the HLB of the acetylenic surfactant (B) is preferably 4 to 25, more preferably 5 to 20, and even more preferably 6 to 18, from the viewpoint of emulsifiability.
- HLB in the present invention can be determined experimentally by the atlas method proposed by Griffin et al.
- the acetylenic surfactant (B) is a known compound and can be easily produced by a known method.
- a compound can be obtained by a method called a Reppe reaction, in which acetylene is reacted with a ketone or aldehyde under pressure in the presence of a catalyst such as an alkali or a metal compound.
- the above compound (B3) or compound (B4) is obtained by adding an alkylene oxide (e.g., ethylene oxide and/or propylene oxide) to acetylene alcohol (B1) or acetylene diol (B2), respectively, using a catalyst such as an alkali or a metal compound. It can be obtained by addition polymerization in the presence.
- an alkylene oxide e.g., ethylene oxide and/or propylene oxide
- Nonionic surfactant (C) other than acetylenic surfactant (B) is a non-acetylenic nonionic surfactant other than the acetylenic surfactant (B).
- surfactant (C) examples include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether such as polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene dodecylphenyl Polyoxyalkylene alkylphenyl ether such as ether; polyoxyethylene tristyrylphenyl ether, polyoxyethylene distyrylphenyl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene dibenzylphenyl ether, poly Polyoxyalkylene alkylarylphenyl ether such as oxyethylene benzylphenyl ether; polyoxyethylene monolaurate, polyoxyethylene monooleate, polyoxyethylene monostearate, polyoxyethylene monomyristate, polyoxyethylene dilaurate, polyoxy Polyoxyalkylene fatty acid esters such as ethylene
- the weight average molecular weight of the surfactant (C) is preferably 1,000 to 20,000, more preferably 1,500 to 18,000, more preferably 1,800 to 17,000, and even more preferably 2,000 to 16,000, from the viewpoint of achieving the effects of the present application.
- the oxyethylene-oxypropylene block or random copolymer is preferably a block copolymer from the viewpoint of exhibiting the effects of the present application.
- the average added mole number of oxyethylene groups constituting the oxyethylene-oxypropylene block or random copolymer is preferably 10 to 500, more preferably 30 to 450, and further preferably 50 to 400, from the viewpoint of achieving the effect of the present application. preferable.
- the average number of added moles of oxypropylene groups is preferably 1 to 100, more preferably 5 to 80, and even more preferably 10 to 70, from the viewpoint of achieving the effect of the present application. , 15-60 are particularly preferred.
- Resins (D) other than epoxy resins include at least one selected from the group consisting of polyurethane resins, vinyl ester resins, polyamide resins, polyolefin resins, saturated polyester resins, unsaturated polyester resins and phenol resins.
- the polyurethane resin is not particularly limited as long as it is a reaction product containing a known polyisocyanate and a known polyol as main components.
- the polyisocyanate may be either an aromatic polyisocyanate compound or an aliphatic polyisocyanate compound.
- aromatic polyisocyanate compounds include tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, xylene diisocyanate, naphthylene-1,5-diisocyanate, mono- or dichlorophenylene-2,4-diisocyanate, diphenylmethane- 4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 3-methyldiphenylmethane-4,4'-diisocyanate, metaphenylene-diisocyanate, paraphenylene-diisocyanate, triphenylmethane triisocyanate, etc.
- polystyrene resin examples include 1,6-hexamethylene-diisocyanate, propyl diisocyanate, and butyl diisocyanate.
- polyisocyanate compound one or a combination of two or more of the polyisocyanate compounds exemplified above may be used.
- Polyols include, for example, polyethylene glycol, polypropylene glycol, polyether polyols such as ethylene oxide and/or propylene oxide adducts of bisphenol A, polyesters which are condensates of polyols and polybasic acids such as succinic acid, adipic acid and phthalic acid.
- Examples include polyols, polyols having a carboxyl group or a sulfonic acid group such as 2,2-dimethylolpropionic acid and 1,4-butanediol-2-sulfonic acid, and polyol compounds exemplified as constituents of polyester resins. .
- vinyl ester resins include epoxy (meth)acrylate obtained by esterifying the above epoxy resin and ⁇ , ⁇ -unsaturated monocarboxylic acid.
- ⁇ , ⁇ -unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, tiglic acid and cinnamic acid, and two or more of these may be used in combination.
- Specific examples of the vinyl ester resin include, for example, a bisphenol-type epoxy resin (meth)acrylate-modified product (a terminal (meth) acrylate-modified resin, etc.).
- the polyamide resin is not particularly limited as long as it is a resin that forms a main chain by repeating amide bonds, and polyamide 6 (by ring-opening polymerization of ⁇ -caprolactam), polyamide 66 (by condensation polymerization of hexamethylenediamine and adipic acid ), and polyamide resins made water-soluble by introducing a hydrophilic group into the main chain.
- Polyolefin resins include, for example, polyethylene, polypropylene, ethylene-propylene copolymers, olefin homo- or copolymers such as poly(methylpentene-1), copolymers of olefins and copolymerizable monomers ( ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, etc.). These polyolefin resins can be used alone or in combination of two or more.
- Polyolefin resins include polypropylene resins having a propylene content of 50% by weight or more (especially 75 to 100% by weight), such as polypropylene, propylene-ethylene copolymers, propylene-butene copolymers, propylene-ethylene-butene copolymers. Polymers and the like are included.
- saturated polyester resins include aliphatic polyester resins and aromatic polyester resins.
- aromatic polyester resins are used, such as polyalkylene arylate resins or saturated aromatic polyester resins.
- aromatic polyester resins include poly C2-4 alkylene terephthalates such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); etc.); 1,4-cyclohexyldimethylene terephthalate (PCT)).
- the aromatic polyester resin may be a copolyester containing alkylene arylate units as a main component (for example, 50% by weight or more), and the copolymer components include C2 such as ethylene glycol, propylene glycol, butanediol, and hexanediol. -6 alkylene glycol, polyoxy C2-4 alkylene glycol, phthalic acid, asymmetric aromatic dicarboxylic acids such as isophthalic acid or their acid anhydrides, and aliphatic dicarboxylic acids such as adipic acid. Additionally, a small amount of polyol and/or polycarboxylic acid may be used to introduce a branched chain structure into the linear polyester.
- a modified polyester resin modified with a modifying compound for example, an aromatic polyester resin having at least one selected from amino groups and oxyalkylene groups
- Modified compounds include polyamines (ethylenediamine, trimethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane and other carbon Aliphatic diamines such as linear or branched alkylenediamines having a number of about 2 to 10; Alicyclic diamines such as isophoronediamine, bis(4-amino-3-methylcyclohexyl)methane, and bis(aminomethyl)cyclohexane ; for example, phenylenediamine, xylylenediamine, aromatic diamines such as diaminodiphenylmethane; etc.
- unsaturated polyester resins include unsaturated polyesters obtained by reacting acid components containing ⁇ , ⁇ -unsaturated dicarboxylic acids with alcohols.
- the ⁇ , ⁇ -unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, and derivatives thereof such as acid anhydrides. Two or more of these may be used in combination.
- acid components other than ⁇ , ⁇ -unsaturated dicarboxylic acids such as saturated dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid and sebacic acid, and acid anhydrides thereof.
- Derivatives may be used in combination with ⁇ , ⁇ -unsaturated dicarboxylic acids.
- alcohols include aliphatic glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol.
- cyclopentanediol cyclohexanediol and other alicyclic diols
- hydrogenated bisphenol A bisphenol A propylene oxide adducts (1 to 100 mol)
- aromatic diols such as xylene glycol, trimethylolpropane, pentaerythritol and other polyhydric diols Alcohols and the like can be mentioned, and two or more of these may be used in combination.
- unsaturated polyester resins include, for example, condensation products of fumaric acid or maleic acid and ethylene oxide (hereinafter abbreviated as EO) adduct of bisphenol A, propylene oxide of fumaric acid or maleic acid and bisphenol A (hereinafter abbreviated as EO) , abbreviated as PO.) adducts, and condensates of fumaric acid or maleic acid and EO and PO adducts of bisphenol A (the addition of EO and PO may be random or block). can.
- EO ethylene oxide
- PO propylene oxide of fumaric acid or maleic acid and bisphenol A
- the weight average molecular weight of the unsaturated polyester resin is preferably 4000-8000.
- phenolic resins include resins obtained by condensation of phenols such as phenol, cresol, xylenol, t-butylphenol, nonylphenol, cashew oil, lignin, resorcin and catechol with aldehydes such as formaldehyde, acetaldehyde and furfural.
- examples include novolak resins and resole resins.
- a novolak resin is obtained by reacting phenol and formaldehyde under the conditions of the same amount or an excess amount of phenol in the presence of an acid catalyst such as oxalic acid.
- a resole resin is obtained by reacting phenol and formaldehyde in the presence of a basic catalyst such as sodium hydroxide, ammonia, or an organic amine under the conditions of the same amount or excess formaldehyde.
- the weight ratio ((B)/(A)+(C)) of the activator (B) to the total of the epoxy resin (A) and the activator (C) is 0. 0.001 to 0.15.
- ((B)/(A)+(C)) is less than 0.001, the wettability of the matrix resin is insufficient, and when it exceeds 0.15, the adhesiveness to the matrix resin is insufficient.
- ((B)/(A)+(C)) is preferably 0.001 to 0.15, more preferably 0.005 to 0.12, and 0.01 ⁇ 0.1 is more preferred.
- the weight ratio ((B)/(C)) of the acetylenic surfactant (B) and the activator (C) is preferably 0.01 to 0.2, more preferably 0.02 to 0.15, even more preferably 0.03 to 0.12.
- the method for producing the sizing agent of the present invention is not particularly limited, and known methods can be adopted.
- Each component constituting the sizing agent is mixed, and after heating the resulting mixture to a softening point or higher, water is gradually added while mechanical shearing force is applied using a homogenizer, homomixer, ball mill, or the like.
- Examples include a method of phase inversion emulsification, and a method of mixing an emulsified and dispersed liquid in an oil bath in which the sizing agent is applied.
- the sizing agent of the present invention is preferably self-emulsified and/or emulsified and dispersed in water.
- the average particle size is not particularly limited, but is preferably 10 ⁇ m or less, more preferably 0.01 to 1 ⁇ m, more preferably 0.01 to 1 ⁇ m, from the viewpoint of storage stability. 0.01 to 0.5 ⁇ m is more preferred. If the average particle size exceeds 10 ⁇ m, the sizing agent itself may separate in a few days, resulting in poor storage stability and impracticality.
- the average particle size as used in the present invention refers to the average value calculated from the particle size distribution measured by a laser diffraction/scattering particle size distribution analyzer (LA-920, manufactured by Horiba).
- the reinforcing fiber strand of the present invention is obtained by attaching the above reinforcing fiber sizing agent to a raw material synthetic fiber strand, and is a reinforcing fiber for reinforcing a thermosetting resin or a thermoplastic matrix resin.
- the manufacturing method of the reinforcing fiber strand of the present invention is a manufacturing method including a sizing treatment step of attaching the reinforcing fiber sizing agent described above to the raw material synthetic fiber strand and drying the resulting deposit.
- the method of attaching the reinforcing fiber sizing agent to the raw material synthetic fiber strand to obtain the deposit is not particularly limited. Any method may be used as long as it is attached to the raw material synthetic fiber strand. Among these methods, the roller dipping method is preferable because the reinforcing fiber sizing agent can be uniformly attached to the raw material synthetic fiber strand.
- the method for drying the obtained deposit is not particularly limited, and for example, it can be dried by heating with a heating roller, hot air, a hot plate, or the like.
- thermosetting resins such as epoxy resins, vinyl ester resins and phenolic resins and/or polyolefin resins other than the polymer component of the present invention, nylon resins, polycarbonate resins, polyester resins, etc.
- Thermoplastic resins such as polyacetal resins, ABS resins, phenoxy resins, polymethyl methacrylate resins, polyphenylene sulfide resins, polyetherimide resins, and polyetherketone resins may be adhered to the starting synthetic fiber strands.
- the reinforcing fiber strand of the present invention is used as a reinforcing fiber for composite materials in which various thermosetting resins or various thermoplastic resins are used as a matrix resin. It may be in a state where
- the amount of non-volatile matter of the reinforcing fiber sizing agent attached to the raw material synthetic fiber strand can be selected as appropriate, and may be the amount necessary for the synthetic fiber strand to have the desired function. It is preferably 0.1 to 20% by weight.
- the adhesion amount thereof is more preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the raw material synthetic fiber strands. Further, in a strand cut into a predetermined length, it is more preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight.
- the adhesion amount of the sizing agent for reinforcing fibers is small, it is difficult to obtain the effects of the present invention regarding wettability with the matrix resin, and the bundling of synthetic fiber strands may be insufficient, resulting in poor handleability.
- the amount of the sizing agent for reinforcing fibers attached is too large, the synthetic fiber strands become too rigid, and the resin impregnation property may deteriorate during composite molding, which is not preferable.
- Synthetic fibers of the (raw material) synthetic fiber strand to which the sizing agent for reinforcing fibers of the present invention can be applied include various inorganic fibers such as carbon fiber, glass fiber, and ceramic fiber, aramid fiber, polyethylene fiber, polyethylene terephthalate fiber, and polybutylene.
- Various organic fibers such as terephthalate fiber, polyethylene naphthalate fiber, polyarylate fiber, polyacetal fiber, PBO fiber, polyphenylene sulfide fiber and polyketone fiber can be used.
- the fiber-reinforced composite material of the present invention contains a thermosetting matrix resin or a thermoplastic matrix resin and the reinforcing fiber strands described above. Since the reinforcing fiber strands are treated with the reinforcing fiber sizing agent of the present invention, the reinforcing fiber strands and the thermoplastic matrix resin have good affinity, resulting in a fiber-reinforced composite material with excellent adhesiveness.
- the fiber-reinforced composite material of the present invention contains a matrix resin and the reinforcing fiber strands described above.
- the reinforcing fiber strands are treated with the sizing agent of the present invention so that the sizing agent is evenly adhered to the reinforcing fiber strands, which improves the affinity between the reinforcing fiber strands and the matrix resin, resulting in a fiber-reinforced composite material with excellent adhesiveness. Furthermore, thermal decomposition of the sizing agent during high-temperature treatment can be suppressed, and inhibition of adhesion to the matrix resin due to thermal decomposition can be suppressed.
- the matrix resin refers to a matrix resin made of a thermosetting resin or a thermoplastic resin, and may contain one or more types.
- thermosetting resin is not particularly limited, and examples thereof include epoxy resins, phenol resins, unsaturated polyester resins, vinyl ester resins, cyanate ester resins, polyimide resins, and the like.
- the thermoplastic resin is not particularly limited, and may be polyolefin resin, polyamide resin, polycarbonate resin, polyester resin, polyacetal resin, ABS resin, phenoxy resin, polymethyl methacrylate resin, polyphenylene sulfide resin, polyetherimide resin, poly Ether ketone resin and the like are included.
- thermosetting resins are preferred, and epoxy resins and vinyl ester resins are more preferred, because the sizing agent of the present invention is more effective in improving adhesion.
- the matrix resins may be partially or wholly modified for the purpose of further improving adhesion to the reinforcing fiber strands.
- the method for producing the fiber-reinforced composite material is not particularly limited, and known methods such as compound injection molding using chopped fibers, long fiber pellets, etc., press molding using UD sheets, woven sheets, etc., and other filament winding molding can be used.
- the content of the synthetic fiber strands in the fiber-reinforced composite material is also not particularly limited, and may be appropriately selected depending on the type and form of the fibers, the type of the thermoplastic matrix resin, etc. 5 to 70% by weight is preferred, and 20 to 60% by weight is more preferred.
- Epoxy resin 100 parts by weight of epoxy resin jER828 (manufactured by Mitsubishi Chemical Co., Ltd.) and 3 parts by weight of DICY (manufactured by Mitsubishi Chemical Co., Ltd.) A drop of matrix resin was heated at 80° C. for 1 hour and 150° C. for 3 hours. Hardened.
- the wettability of the matrix resin was evaluated using a composite material interface property evaluation device HM410 (manufactured by Toei Sangyo Co., Ltd.).
- a carbon fiber filament is taken out from the carbon fiber strands obtained in Examples and Comparative Examples and set in a sample holder.
- a matrix resin drop was formed on a carbon fiber filament, 20 drops having a drop diameter in the drawing direction of 100 to 120 ⁇ m were selected, the contact angle to the carbon fiber filament was measured, and the average value was obtained.
- the wettability of the matrix resin was evaluated according to the following criteria in comparison with the contact angle obtained in the same manner using the carbon fiber filament taken out from the carbon fiber strand not treated with the sizing agent.
- ⁇ The contact angle is 1° or more smaller than the contact angle of carbon fiber not treated with a sizing agent.
- ⁇ Almost equivalent to the contact angle of sizing agent untreated carbon fiber (difference in contact angle is less than ⁇ 1 °)
- x The contact angle is 1° or more larger than the contact angle of carbon fiber not treated with a sizing agent.
- Adhesion was evaluated by a microdroplet method using a composite material interface property evaluation device HM410 (manufactured by Toei Sangyo Co., Ltd.).
- a carbon fiber filament is taken out from the carbon fiber strands obtained in Examples and Comparative Examples and set in a sample holder.
- a drop of each matrix resin was formed on a carbon fiber filament to obtain a sample for measurement.
- a measurement sample was set in the device, the drop was sandwiched between device blades, the carbon fiber filament was run on the device at a speed of 0.06 mm/min, and the maximum pull-out load F when the drop was pulled out from the carbon fiber filament was measured.
- the interfacial shear strength ⁇ was calculated from the following formula to evaluate the adhesiveness between the carbon fiber filament and the matrix resin.
- the above epoxy resin was used as the matrix resin.
- the method of curing the epoxy resin is given above.
- Interfacial shear strength ⁇ (unit: MPa) F/ ⁇ dl (F: Maximum pull-out load d: Carbon fiber filament diameter l: Particle diameter in the pull-out direction of the drop)
- ⁇ Scratch resistance> Using a TM-type friction coupling force tester TM-200 (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.), a tension of 50 g was applied through three mirror-finished chrome-plated stainless steel needles arranged in a zigzag pattern. The obtained carbon fiber strand was rubbed 1,000 times (reciprocating motion speed: 300 times/min), and the state of fluff on the carbon fiber strand was visually evaluated according to the following criteria. ⁇ : Absolutely no fluff was observed as before rubbing. Good: A few fluffs were observed, but at a practically acceptable level. ⁇ : A lot of fluffing was observed, and some thread breakage was also confirmed. x: A large number of fluffing and single yarn breakage were observed.
- Carbon fiber was sized with each sizing agent (diluted to 3% with water, target adhesion rate of 1%), and was visually evaluated as to whether or not it could be loosened when 10 pieces of 5 mm length were cut out with a utility knife. Judgment was made according to the following evaluation criteria, and ⁇ and ⁇ were regarded as acceptable. ⁇ : 2 or less can be unraveled ⁇ : 3 to 4 can be unraveled ⁇ : 5 to 7 can be unraveled ⁇ : 8 or more can be unraveled
- C1: POEO Block polyether (PO/EO 20/80) (Mw15500)
- an aromatic polyester resin D1 which is a water emulsion having a non-volatile content of 20% by weight.
- the sizing agents of Examples include epoxy resins (A), acetylenic surfactants (B), and nonionic surfactants other than the acetylenic surfactants (B) ( C), and the weight ratio of the activator (B) to the total of the epoxy resin (A) and the activator (C) ((B)/(A)+(C)) is 0.001 to 0. 0.15, it gives the reinforcing fibers excellent wettability with the matrix resin.
- Fiber-reinforced composite materials in which matrix resin is reinforced with reinforcing fibers, are used for automotive applications, aerospace applications, sports and leisure applications, and general industrial applications.
- reinforcing fibers include various inorganic fibers such as carbon fibers, glass fibers and ceramic fibers, and various organic fibers such as aramid fibers, polyamide fibers and polyethylene fibers.
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Abstract
Description
強化繊維複合材料の機械強度を向上させるためには、マトリックス樹脂と強化繊維の濡れ性や接着性が重要となり、上記のエポキシ樹脂、ラジカル重合系のマトリックス樹脂に対して、強化繊維の濡れ性や接着性が向上するサイジング剤(例えば、特許文献1、2等)が提案されている。
よって、繊維強化複合材料の分野において、強化繊維とマトリックス樹脂との濡れ性を高めて、強固に接着させることができ、強化繊維ストランドの毛羽抑制、集束性向上を可能とし、さらには長期保管安定性に優れたサイジング剤の開発が望まれている。
すなわち、本発明の強化繊維用サイジング剤は、エポキシ樹脂(A)、アセチレン系界面活性剤(B)及び前記アセチレン系界面活性剤(B)以外の非イオン性界面活性剤(C)を含有し、
前記エポキシ樹脂(A)及び前記活性剤(C)の合計に対する前記活性剤(B)の重量割合((B)/(A)+(C))が0.001~0.15である。
前記活性剤(C)の分子量が1000~20000であると好ましい。
前記アセチレン系界面活性剤(B)が、アセチレンアルコール(B1)、アセチレンジオール(B2)、アセチレンアルコールにアルキレンオキサイドを付加した化合物(B3)及びアセチレンジオールにアルキレンオキサイドを付加した化合物(B4)から選ばれた少なくとも1種であると好ましい。
本発明の繊維強化複合材料は、マトリックス樹脂と、上記強化繊維ストランドとを含む。
前記マトリックス樹脂が熱硬化性樹脂であると好ましい。
〔エポキシ樹脂(A)〕
エポキシ樹脂(A)は、本発明の強化繊維用サイジング剤の必須成分である。エポキシ樹脂とは、分子構造内に反応性のエポキシ基を2個以上有する化合物である。エポキシ樹脂としては、エピクロルヒドリンと活性水素化合物から得られるグリシジルエーテル型が代表的であり、その他にグリシジルエステル型、グリシジルアミン型、脂環型等が挙げられる。エポキシ樹脂は、1種でもよく、2種以上を併用してもよい。
上記の芳香族エポキシ樹脂としては、ハイドロキノン、レゾルシン、ピロカテコールなどの単核多価フェノール化合物のポリグリシジルエーテル化合物;ジヒドロキシナフタレン、ビフェノール、ビスフェノールF、ビスフェノールA、フェノールノボラック、オルソクレゾールノボラック、レゾルシンノボラック、ビスフェノールFノボラック、ビスフェノールAノボラック、ジシクロペンタジエン変性フェノール、トリフェニルメタン、テトラフェニルエタンなどの多核多価フェノール化合物のポリグリシジルエーテル化合物などが挙げられる。
pは0~30の整数であり、マトリックス樹脂の濡れ性が向上する観点から、0~20が好ましく、0~10がさらに好ましい。
本発明の炭素繊維用サイジング剤は、アセチレン系界面活性剤(B)を必須に含有する。エポキシ樹脂(A)及びアセチレン系界面活性剤(B)を併用することにより、表面張力を下げ、またマトリックス樹脂との親和性が高まることでマトリックス樹脂の濡れ性を向上させることができると推測する。
アセチレン系界面活性剤(B)を使用せずに、他の界面活性剤のみを用いた場合、エポキシ樹脂(A)を用いた場合であっても、表面張力を下げる効果はあるが、マトリックス樹脂の濡れ性は十分ではないと推測する。
なお、アセチレン系界面活性剤とは、分子構造中にアセチレン基と水酸基等の親水基を有する化合物をいう。アセチレン系界面活性剤(B)は一種単独でもよく、二種以上を組み合わせて用いてもよい。
アセチレンアルコール(B1)は、上記一般式(1)で表される化合物であることが好ましい。
アセチレンジオール(B2)は、上記一般式(2)で表される化合物であることが好ましい。
アセチレンアルコールにアルキレンオキサイドを付加した化合物(B3)とは、上記一般式(3)で表される化合物であることが好ましい。
アセチレンジオールにアルキレンオキサイドを付加した化合物(B4)は、上記一般式(4)で表される化合物であることが好ましい。
式(2)及び(4)中、R3、R4、R5及びR6は、それぞれ独立して炭素数1~8のアルキル基である。当該アルキル基は直鎖でもよく、分岐構造を有していてもよい。当該アルキル基の炭素数は、好ましくは1~7、より好ましくは1~6、さらに好ましくは1~5である。
式(3)及び式(4)中、AOは炭素数2~4のオキシアルキレン基を示す。つまり、オキシエチレン基、オキシプロピレン基又はオキシブチレン基を示す。オキシアルキレン基としては、オキシエチレン基、オキシプロピレン基が好ましく、オキシエチレン基がさらに好ましい。(AO)n又は(AO)mを構成するAOは、1種でもよく、2種以上であってもよい。2種以上の場合、ブロック付加体、交互付加体、ランダム付加体のいずれであってもよい。
式(4)中、m、nはそれぞれ独立して1~50の数である。m、nは、それぞれ独立して、1~45が好ましく、1~40がより好ましく、1~35がさらに好ましい。
また、上記の化合物(B3)又は化合物(B4)は、それぞれ、アセチレンアルコール(B1)又はアセチレンジオール(B2)にアルキレンオキサイド(例えばエチレンオキサイド及び/又はプロピレンオキサイド)をアルカリや金属化合物などの触媒の存在下で付加重合させることにより得ることができる。
アセチレン系界面活性剤(B)以外の非イオン性界面活性剤(C)は、アセチレン系界面活性剤(B)を除く非アセチレン系非イオン性界面活性剤である。
オキシエチレン-オキシプロピレンブロックまたはランダム共重合体を構成するオキシエチレン基の平均付加モル数としては、本願効果を奏する観点から、10~500が好ましく、30~450がより好ましく、50~400が更に好ましい。
エポキシ樹脂以外の樹脂(D)としては、ポリウレタン樹脂、ビニルエステル樹脂、ポリアミド樹脂、ポリオレフィン樹脂、飽和ポリエステル樹脂、不飽和ポリエステル樹脂およびフェノール樹脂からなる群から選ばれる少なくとも1種が挙げられる。
ポリイソシアネートとしては、芳香族ポリイソシアネート化合物でも脂肪族ポリイソシアネート化合物でもよい。
芳香族ポリイソシアネート化合物としては、たとえば、トリレン-2,4-ジイソシアネート、トリレン-2,6-ジイソシアネート、キシレンジイソシアネート、ナフチレン-1,5-ジイソシアネート、モノまたはジクロロフェニレン-2,4-ジイソシアネート、ジフェニルメタン-4,4’-ジイソシアネート、3,3’-ジメチルジフェニルメタン-4,4’-ジイソシアネート、3-メチルジフェニルメタン-4,4’-ジイソシアネート、メタフェニレン-ジイソシアネート、パラフェニレン-ジイソシアネート、トリフェニルメタントリイソシアネート等を挙げることができる。
また、脂肪族ポリイソシアネート化合物としては、たとえば、1,6-ヘキサメチレン-ジイソシアネート、プロピルジイソシアネート、ブチルジイソシアネート等を挙げることができる。ポリイソシアネート化合物として、上記で例示したポリイソシアネート化合物を1種または2種以上を組み合わせて用いてもよい。
ポリオールとしては、たとえば、ポリエチレングリコール、ポリプロピレングリコール、ビスフェノールAのエチレンオキシドおよび/またはプロピレンオキシド付加物等のポリエーテルポリオール、ポリオールとコハク酸、アジピン酸、フタル酸等の多塩基酸の縮合物であるポリエステルポリオール、2,2-ジメチロールプロピオン酸、1,4-ブタンジオール-2-スルホン酸等のカルボキシル基やスルホン酸基を有するポリオール、ポリエステル樹脂の構成成分として例示したポリオール化合物等を挙げることができる。
芳香族ポリエステル樹脂としては、例えば、ポリエチレンテレフタレート(PET)、ポリブチレンテレフタレート(PBT)等のポリC2-4アルキレンテレフタレート;このポリアルキレンテレフタレートに対応するポリC2-4アルキレンナフタレート(例えば、ポリエチレンナフタレートなど);1,4-シクロへキシルジメチレンテレフタレート(PCT))等を挙げることができる。芳香族ポリエステル樹脂は、アルキレンアリレート単位を主成分(例えば、50重量%以上)として含むコポリエステルであってもよく、共重合成分には、エチレングリコール、プロピレングリコール、ブタンジオール、ヘキサンジオールなどのC2-6アルキレングリコール、ポリオキシC2-4アルキレングリコール、フタル酸、イソフタル酸などの非対称芳香族ジカルボン酸又はその酸無水物、アジピン酸などの脂肪族ジカルボン酸等を挙げることができる。さらに、少量のポリオール及び/又はポリカルボン酸を用い、線状ポリエステルに分岐鎖構造を導入してもよい。さらに、変性化合物で変性した変性ポリエステル系樹脂(例えば、アミノ基及びオキシアルキレン基から選択された少なくとも一種を有する芳香族ポリエステル樹脂)を用いてもよい。変性化合物としては、ポリアミン類(エチレンジアミン、トリメチレンジアミン、プロピレンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、トリメチルヘキサメチレンジアミン、1,7-ジアミノヘプタン、1,8-ジアミノオクタンなどの炭素数2~10程度の直鎖又は分岐鎖状アルキレンジアミン等の脂肪族ジアミン類;イソホロンジアミン、ビス(4-アミノ-3-メチルシクロヘキシル)メタン、ビス(アミノメチル)シクロヘキサン等の脂環族ジアミン類;例えば、フェニレンジアミン、キシリレンジアミン、ジアミノジフェニルメタン等の芳香族ジアミン類;等)、ポリオール類(例えば、(ポリ)オキシエチレングリコール、(ポリ)オキシトリメチレングリコール、(ポリ)オキシプロピレングリコール、(ポリ)オキシテトラメチレングリコール等の(ポリ)オキシC2-4アルキレングリコール類等)等を挙げることができる。変性は、例えば、ポリエステル樹脂と変性化合物とを加熱混合し、アミド化、エステル化又はエステル交換反応を利用して行うことができる。
不飽和ポリエステル樹脂の具体例としては、例えば、フマル酸又はマレイン酸とビスフェノールAのエチレンオキサイド(以下、EOと略す)付加物との縮合物、フマル酸又はマレイン酸とビスフェノールAのプロピレンオキサイド(以下、POと略す。)付加物との縮合物、フマル酸又はマレイン酸とビスフェノールAのEO及びPO付加物(EO及びPOの付加は、ランダムでもブロックでもよい)との縮合物等を挙げることができる。
本発明の強化繊維用サイジング剤は、前記エポキシ樹脂(A)及び前記活性剤(C)の合計に対する前記活性剤(B)の重量割合((B)/(A)+(C))が0.001~0.15である。((B)/(A)+(C))が0.001未満では、マトリックス樹脂の濡れ性が不足し、0.15を超えるとマトリックス樹脂との接着性が不足する。
マトリックス樹脂の濡れ性を向上させる観点から、((B)/(A)+(C))は、0.001~0.15が好ましく、0.005~0.12がより好ましく、0.01~0.1がさらに好ましい。
本発明の強化繊維ストランドは、原料合成繊維ストランドに対して、上記の強化繊維用サイジング剤を付着させたものであり、熱硬化性樹脂又は熱可塑性マトリックス樹脂を補強するための強化繊維である。
強化繊維用サイジング剤を原料合成繊維ストランドに付着させて付着物を得る方法については、特に限定はないが、強化繊維用サイジング剤をキスローラー法、ローラー浸漬法、スプレー法その他公知の方法で、原料合成繊維ストランドに付着させる方法であればよい。これらの方法のうちでも、ローラー浸漬法が、強化繊維用サイジング剤を原料合成繊維ストランドに均一付着できるので好ましい。
得られた付着物の乾燥方法については、特に限定はなく、例えば、加熱ローラー、熱風、熱板等で加熱乾燥することができる。
本発明の繊維強化複合材料は、熱硬化性マトリックス樹脂又は熱可塑性マトリックス樹脂と前述の強化繊維ストランドを含むものである。強化繊維ストランドは本発明の強化繊維用サイジング剤により処理されているので、強化繊維ストランドおよび熱可塑性マトリックス樹脂との親和性が良好となり、接着性に優れた繊維強化複合材料となる。
本発明の繊維強化複合材料は、マトリックス樹脂と前述の強化繊維ストランドを含むものである。強化繊維ストランドは本発明のサイジング剤により処理されて、サイジング剤が均一に付着しており、強化繊維ストランド及びマトリックス樹脂との親和性が良好となり、接着性に優れた繊維強化複合材料となる。さらに、高温処理時のサイジング剤の熱分解を抑制でき、熱分解に起因したマトリックス樹脂との接着阻害を抑制できる。ここで、マトリックス樹脂とは、熱硬化性樹脂又は熱可塑性樹脂からなるマトリックス樹脂をいい、1種又は2種以上含んでいてもよい。熱硬化性樹脂としては、特に制限はなく、エポキシ樹脂、フェノール樹脂、不飽和ポリエステル樹脂、ビニルエステル樹脂、シアネートエステル樹脂、ポリイミド樹脂等が挙げられる。熱可塑性樹脂としては、特に制限はなく、ポリオレフィン系樹脂、ポリアミド系樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリアセタール樹脂、ABS樹脂、フェノキシ樹脂、ポリメチルメタクリレート樹脂、ポリフェニレンサルフィド樹脂、ポリエーテルイミド樹脂、ポリエーテルケトン樹脂等が挙げられる。これらの中でも本発明のサイジング剤による接着性向上効果がより高い点から熱硬化性樹脂が好ましく、エポキシ樹脂、ビニルエステル樹脂がさらに好ましい。
繊維強化複合材料の製造方法としては、特に限定はなく、チョップドファイバー、長繊維ペレットなどによるコンパウンド射出成型、UDシート、織物シートなどによるプレス成型、その他フィラメントワインディング成型など公知の方法を採用できる。
繊維強化複合材料中の合成繊維ストランドの含有量についても特に限定はなく、繊維の種類、形態、熱可塑性マトリックス樹脂の種類などにより適宜選択すればよいが、得られる繊維強化複合材料に対して、5~70重量%が好ましく、20~60重量%がより好ましい。
浸透性の評価を次のフェルト沈降試験にて実施した。
2cm×2cmに切断したニッケ社製オリフェルトS20(No.103)を有効成分1%に希釈した各エマルション100mLに浮かべ、沈降するまでの時間(秒数)を計測し、浸透性の評価を行った。温度:23℃。沈降するまでの時間が短い程浸透性に優れることを意味する。
指標は次の通りで、◎及び○を合格とした。
非常に良好(◎):90秒以下
良好 (○):90秒超180秒以下
やや不良 (△):180秒超300秒以下
不良 (×):300秒超
サイジング剤組成物を付与した繊維約10gをソックスレー抽出器に入れ、メチルエチルケトンで2時間抽出し、抽出前後の繊維の重量差から算出した。
マトリックス樹脂は、エポキシ樹脂を用いた。
エポキシ樹脂:エポキシ樹脂jER828(三菱ケミカル株式会社製)100重量部、DICY(三菱ケミカル株式会社製)3重量部に調整されたマトリックス樹脂のドロップを80℃×1時間、150℃×3時間加熱し硬化させた。
複合材料界面特性評価装置HM410(東栄産業株式会社製)を使用しマトリックス樹脂の濡れ性を評価した。実施例及び比較例で得られた炭素繊維ストランドより、炭素繊維フィラメントを取り出し、試料ホルダーにセッティングする。マトリックス樹脂のドロップを炭素繊維フィラメント上に形成させ、引き抜き方向のドロップ径が100~120μmの範囲にあるドロップを20個選定し、炭素繊維フィラメントに対する接触角を測定、その平均値を得た。サイジング剤未処理炭素繊維ストランドより取り出した炭素繊維フィラメントを用いて同様にして得た接触角と比較して、下記基準に従いマトリックス樹脂濡れ性を評価した。
○:サイジング剤未処理炭素繊維の接触角に比較して1°以上接触角が小さい。
△:サイジング剤未処理炭素繊維の接触角とほぼ同等(接触角の差が±1°未満)
×:サイジング剤未処理炭素繊維の接触角に比較して1°以上接触角が大きい。
複合材料界面特性評価装置HM410(東栄産業株式会社製)を使用し、マイクロドロップレット法により接着性を評価した。
実施例及び比較例で得られた炭素繊維ストランドより、炭素繊維フィラメントを取り出し、試料ホルダーにセッティングする。各マトリックス樹脂のドロップを炭素繊維フィラメント上に形成させ、測定用の試料を得た。測定試料を装置にセッティングし、ドロップを装置ブレードで挟み、炭素繊維フィラメントを装置上で0.06mm/分の速度で走行させ、炭素繊維フィラメントからドロップを引き抜く際の最大引き抜き荷重Fを測定した。
次式により界面剪断強度τを算出し、炭素繊維フィラメントとマトリックス樹脂との接着性を評価した。マトリックス樹脂としては上記のエポキシ樹脂を用いた。エポキシ樹脂の硬化方法は上記に示す。
界面剪断強度τ(単位:MPa)=F/πdl
(F:最大引き抜き荷重 d:炭素繊維フィラメント直径 l:ドロップの引き抜き方向の粒子径)
TM式摩擦抱合力試験機TM-200(大栄科学精器製作所(株)製)を用い、ジグザグに配置した鏡面クロムメッキステンレス針3本を介して50gの張力で、実施例及び比較例で得られた炭素繊維ストランドを1000回擦過させ(往復運動速度300回/分)、炭素繊維ストランドの毛羽たちの状態を下記基準で目視判定した。
◎:擦過前と同じく毛羽発生が全く見られなかった。
○:数本の毛羽は見られたものの、実用上全く問題ないレベルであった。
△:毛羽立ちが多くみられ、糸切れも若干確認できた。
×:毛羽立ち及び単糸の糸切れが非常に多く確認できた。
炭素繊維に各サイジング剤(水で3%に希釈、目標付着率1%)をサイジングしたものを、カッターナイフで5mmの長さで10本切りだした際にほぐれるかどうか目視で評価した。以下の評価基準で判断し、◎及び○を合格とした。
◎:2本以下ほぐれる
○:3~4本ほぐれる
△:5本~7本ほぐれる
×:8本以上ほぐれる
A1:jER1001(三菱ケミカル株式会社製)
A2:jER828(三菱ケミカル株式会社製)
A3:jER807(三菱ケミカル株式会社製)
A4:jER157S65(三菱ケミカル株式会社製)
B1:2,4,7,9-テトラメチル-5-デシン-4,7-ジオールのエチレンオキサイド20モル付加物
B2:2,4,7,9-テトラメチル-5-デシン-4,7-ジオールのエチレンオキサイド5モル付加物
B3:3,6-ジメチル-4-オクチン-3,6-ジオール
B4:2,4,7,9-テトラメチル-5-デシン-4,7-ジオール
C1:POEOブロックポリエーテル(PO/EO=20/80)(Mw15500)
C2:POEOブロックポリエーテル(PO/EO=50/50)(Mw4500)
D1:芳香族系ポリエステル樹脂
D2:芳香族系ポリウレタン樹脂
(合成例D-1)
反応器中に窒素ガスを封入下、ジメチルイソフタレート950部、ジエチレングリコール1000部、酢酸亜鉛0.5部および三酸化アンチモン0.5部を仕込み、140~220℃で3時間エステル交換反応を行った。次に、5-ナトリウムスルホイソフタル酸30部を添加し、220~260℃で1時間エステル化反応を行った後、240~270℃で減圧下2時間重縮合反応を行った。
続いて得られた芳香族系ポリエステル樹脂200部とエチレングリコールモノブチルエーテル100部を乳化器に仕込み、150~170℃で撹拌し、均一化した。続いて撹拌下で水700を徐々に加え、不揮発分20重量%の水エマルジョンである芳香族系ポリエステル樹脂D1を得た。
温度計、撹拌装置、還流冷却管を備えた4ツ口フラスコに、芳香族ポリエステルポリオール(数平均分子量1800、水酸基価60mgKOH/g)を163.9部加え、減圧下120-130℃で脱水を行い、次いで50℃まで冷却して、43.2部のポリエチレングリコール(重量平均分子量400)、12.7部のトリメチロールプロパンおよび150部のメチルエチルケトンを加え、十分撹拌混合した後65.8部のヘキサメチレンジイソシアネートを加え、75℃に加温し、2時間反応させて末端イソシアネート基を有するプレポリマー溶液を得た。反応終了後、40℃まで冷却し、ジメチロールプロピオン酸14.5部を加え、75℃で2時間反応させた。反応終了後、40℃まで冷却し、ジメチルエタノールアミン11.5部を加えて中和反応後、水1200部を加え水エマルジョンとした。得られた水エマルジョンを65℃で減圧処理してメチルエチルケトンを留去し、水分調整を行い、不揮発分20重量%の水エマルジョンである芳香族ポリウレタン樹脂D2を得た。
一方、表3に示すように、比較例1~5では、エポキシ樹脂(A)がない場合(比較例1)、アセチレン系界面活性剤(B)がない場合(比較例2)、非イオン性界面活性剤(C)がない場合(比較例3)、((B)/(A)+(C))が0.001未満である場合(比較例4)、((B)/(A)+(C))が0.15を超える場合(比較例5)では、強化繊維に優れたマトリックス樹脂との濡れ性が不足する。
Claims (9)
- エポキシ樹脂(A)、アセチレン系界面活性剤(B)及び前記アセチレン系界面活性剤(B)以外の非イオン性界面活性剤(C)を含有し、
前記エポキシ樹脂(A)及び前記活性剤(C)の合計に対する前記活性剤(B)の重量割合((B)/(A)+(C))が0.001~0.15である、強化繊維用サイジング剤。 - 前記アセチレン系界面活性剤(B)及び前記活性剤(C)の重量比((B)/(C))が0.01~0.2である、請求項1に記載の強化繊維用サイジング剤。
- 前記活性剤(C)の重量平均分子量が1000~20000である、請求項1又は2に記載の強化繊維用サイジング剤。
- 前記アセチレン系界面活性剤(B)が、アセチレンアルコール(B1)、アセチレンジオール(B2)、アセチレンアルコールにアルキレンオキサイドを付加した化合物(B3)及びアセチレンジオールにアルキレンオキサイドを付加した化合物(B4)から選ばれる少なくとも1種である、請求項1~3のいずれかに記載の強化繊維用サイジング剤。
- 前記アセチレンアルコール(B1)が下記一般式(1)で表される化合物であり、前記アセチレンジオール(B2)が下記一般式(2)で表される化合物であり、前記アセチレンアルコールにアルキレンオキサイドを付加した化合物(B3)が下記一般式(3)で表される化合物であり、前記アセチレンジオールにアルキレンオキサイドを付加した化合物(B4)が下記一般式(4)で表される化合物である、請求項4に記載の強化繊維用サイジング剤。
- ポリウレタン樹脂、ビニルエステル樹脂、ポリアミド樹脂、ポリオレフィン樹脂、ポリエステル樹脂およびフェノール樹脂から選ばれる少なくとも1種である樹脂成分(D)をさらに含有する、請求項1~5のいずれかに記載の強化繊維用サイジング剤。
- 原料強化繊維ストランドに対して、請求項1~6のいずれかに記載の強化繊維用サイジング剤を付着させた、強化繊維ストランド。
- マトリックス樹脂と、請求項7に記載の強化繊維ストランドとを含む、繊維強化複合材料。
- 前記マトリックス樹脂が熱硬化性樹脂である、請求項8に記載の繊維強化複合材料。
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