WO2012017877A1 - 強化繊維用サイジング剤、合成繊維ストランドおよび繊維強化複合材料 - Google Patents
強化繊維用サイジング剤、合成繊維ストランドおよび繊維強化複合材料 Download PDFInfo
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- WO2012017877A1 WO2012017877A1 PCT/JP2011/067029 JP2011067029W WO2012017877A1 WO 2012017877 A1 WO2012017877 A1 WO 2012017877A1 JP 2011067029 W JP2011067029 W JP 2011067029W WO 2012017877 A1 WO2012017877 A1 WO 2012017877A1
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- CWKVFRNCODQPDB-UHFFFAOYSA-N 1-(2-aminoethylamino)propan-2-ol Chemical compound CC(O)CNCCN CWKVFRNCODQPDB-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 1
- HVYJSOSGTDINLW-UHFFFAOYSA-N 2-[dimethyl(octadecyl)azaniumyl]acetate Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CC([O-])=O HVYJSOSGTDINLW-UHFFFAOYSA-N 0.000 description 1
- CDMGNVWZXRKJNS-UHFFFAOYSA-N 2-benzylphenol Chemical class OC1=CC=CC=C1CC1=CC=CC=C1 CDMGNVWZXRKJNS-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- CJKRXEBLWJVYJD-UHFFFAOYSA-N N,N'-diethylethylenediamine Chemical compound CCNCCNCC CJKRXEBLWJVYJD-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- AOMUHOFOVNGZAN-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CCO)CCO AOMUHOFOVNGZAN-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- KFGCQOLKVDHXJP-UHFFFAOYSA-N benzene-1,3-dicarboxylic acid;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.OC(=O)C1=CC=CC(C(O)=O)=C1 KFGCQOLKVDHXJP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 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
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 229940031957 lauric acid diethanolamide Drugs 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 238000001304 sample melting Methods 0.000 description 1
- HWCHICTXVOMIIF-UHFFFAOYSA-M sodium;3-(dodecylamino)propanoate Chemical compound [Na+].CCCCCCCCCCCCNCCC([O-])=O HWCHICTXVOMIIF-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- D06M13/322—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 nitrogen
- D06M13/325—Amines
- D06M13/332—Di- or polyamines
-
- 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
- D06M13/322—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 nitrogen
- D06M13/368—Hydroxyalkylamines; Derivatives thereof, e.g. Kritchevsky bases
-
- 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
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Definitions
- the present invention relates to a sizing agent for reinforcing fibers used for reinforcing a thermoplastic matrix resin, a synthetic fiber strand and a fiber reinforced composite material using the same. More specifically, the present invention relates to a sizing agent for reinforcing fibers capable of imparting excellent adhesion to a thermoplastic matrix resin to a synthetic fiber strand, and a synthetic 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 automobile applications, aerospace applications, sports / leisure applications, general industrial applications, and the like.
- 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 or a drum winding method, processed by a filament winding method, or in some cases a textile Or it is used as a reinforced fiber through various high-order processing steps such as being processed into a chopped fiber shape.
- so-called heat such as polyolefin resin, nylon resin, polycarbonate resin, polyacetal resin, ABS resin, polyphenylene sulfide resin, polyetherimide resin, etc.
- heat such as polyolefin resin, nylon resin, polycarbonate resin, polyacetal resin, ABS resin, polyphenylene sulfide resin, polyetherimide resin, etc.
- a fiber reinforced composite material using a plastic resin is expected.
- polyolefin resins are excellent in moldability, chemical resistance, etc., and are advantageous in terms of cost. Therefore, fiber reinforced composite materials using the polyolefin resin as a matrix resin have a high degree of attention and are widely used as general-purpose materials. Application to applications is expected.
- Reinforcing fibers are often used in the form of chopped fibers generally cut to a length of 1 to 15 mm.
- the focusing property of the chopped fiber is important. If this is inappropriate, the amount of chopped fiber supplied will become unstable. In addition, strand breakage or the like may occur, and physical properties of the obtained composite material may deteriorate.
- many techniques for applying a sizing agent based on a modified polyolefin resin have been proposed for the purpose of imparting appropriate sizing properties to fibers (see Patent Documents 1 and 2), and are widely used industrially. ing.
- the fibers are not integrated like a form called a long fiber pellet or a composite material using a thermosetting resin as a matrix.
- the number of cases in which a thermoplastic resin is impregnated and molded in a directional sheet, tape-like or woven state is increasing. In such a case, it is possible to quickly impregnate the inside of the fiber strand, specifically, between the fiber and the fiber, with the thermoplastic resin melted at the time of molding the composite, thereby shortening the molding process time and the physical properties of the obtained composite material. It is important in terms of improvement.
- thermoplastic resin particularly a polyolefin resin as a matrix resin
- a sizing agent that increases the affinity between the fiber and the matrix resin and can be firmly bonded.
- the object of the present invention is to provide a reinforcing fiber sizing agent that can impart excellent adhesion to reinforcing fibers used to reinforce thermoplastic matrix resins, particularly polyolefin-based resins, It is to provide a synthetic fiber strand and a fiber reinforced composite material using the same.
- the present inventors have found that, in a sizing agent containing a modified polypropylene resin among modified polyolefin resins, the melting endotherm of the non-volatile content of the neutralizing agent component and the sizing agent is improved in adhesiveness. I found that it was particularly influential. Specifically, it includes 1) a neutralized product of a modified polypropylene resin and a specific amine compound having two or more hydroxyl groups in the molecular structure or two or more amino groups in the molecular structure. If the sizing agent has a melting endotherm of not more than a specific value, it has been found that the adhesion to the thermoplastic matrix resin is remarkably excellent, and the present invention has been achieved.
- the modified polyolefin resin other than the modified polypropylene resin is not improved in adhesion regardless of the type of the neutralizing agent
- the neutralizing agent is an alkali metal salt or the above specified one.
- the sizing agent contains a neutralized product of the modified polypropylene resin and the specific amine compound, the non-volatile content of the sizing agent It was found that when the melting endotherm of the glass exceeded a specific value, no improvement in adhesion was observed, and the present invention was reached.
- the sizing agent for reinforcing fibers of the present invention is a sizing agent for reinforcing fibers used to reinforce a thermoplastic matrix resin, and includes a modified polypropylene resin and two or more hydroxyl groups in the molecular structure or in the molecular structure.
- a neutralized product with an amine compound having two or more amino groups is essential, and the melting endotherm when the nonvolatile content of the sizing agent is measured with a differential scanning calorimeter (DSC) is 50 J / g or less.
- DSC differential scanning calorimeter
- the sizing agent for reinforcing fibers of the present invention is prepared by blending the modified polypropylene resin in an amount of 10 to 90% by weight and the amine compound in an amount of 1 to 20% by weight with respect to the entire nonvolatile content of the sizing agent. is there.
- the boiling point of the amine compound is preferably 240 to 340 ° C.
- the amine compound is preferably a compound represented by the following general formula (1) and / or the following general formula (2).
- R 1 N (CH 2 CH 2 OH) 2 (1) (Wherein R 1 is a hydrogen atom, —CH 2 CH 2 OH, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a residue obtained by removing an OH group from a fatty acid having 1 to 18 carbon atoms.)
- the melting endotherm when the modified polypropylene resin is measured with a differential scanning calorimeter (DSC) is preferably 70 J / g or less.
- the acid value of the modified polypropylene resin is preferably 20 to 80 KOHmg / g.
- the sizing agent for reinforcing fibers of the present invention further contains at least one polymer component (A) selected from an aromatic polyester resin and an aromatic polyester urethane resin in an amount of 5 to 80% based on the entire nonvolatile content of the sizing agent. % Content is preferable.
- the thermoplastic matrix resin is preferably a polyolefin resin.
- the sizing agent for reinforcing fibers of the present invention preferably further contains water, and the neutralized product is preferably dispersed or dissolved in water.
- the synthetic fiber strand of the present invention is obtained by adhering the sizing agent for reinforcing fibers to the raw synthetic fiber strand.
- the synthetic fiber of the synthetic fiber strand is composed of carbon fiber, aramid fiber, polyethylene fiber, polyethylene terephthalate fiber, polybutylene terephthalate fiber, polyethylene naphthalate fiber, polyarylate fiber, polyacetal fiber, PBO fiber, polyphenylene sulfide fiber and polyketone fiber. It is preferably at least one selected.
- the fiber-reinforced composite material of the present invention includes a thermoplastic matrix resin and the above synthetic fiber strand.
- the sizing agent for reinforcing fibers of the present invention can give remarkably excellent adhesion to reinforcing fibers used for reinforcing thermoplastic matrix resins, particularly polyolefin resins.
- the synthetic fiber strand obtained by processing with the sizing agent for reinforcing fibers of the present invention has remarkably excellent adhesiveness to the thermoplastic matrix resin.
- a fiber-reinforced composite material having excellent physical properties can be obtained.
- the present invention is a sizing agent for reinforcing fibers used to reinforce a thermoplastic matrix resin, which essentially contains a modified polypropylene resin and a neutralized product with a specific amine compound, and shows a non-volatile content of the sizing agent.
- the melting endotherm when measured with a scanning calorimeter (DSC) is 50 J / g or less. This will be described in detail below.
- the modified polypropylene resin of the present invention is a copolymer substantially composed of propylene and unsaturated carboxylic acids, and can be produced by a known method. A random copolymer obtained by copolymerizing propylene and an unsaturated carboxylic acid may be used, or a graft copolymer obtained by grafting unsaturated carboxylic acids onto polypropylene may be used.
- the modified polypropylene resin of the present invention may be used alone or in combination of two or more.
- the modified polypropylene resin referred to in the present invention refers to a resin in which acidic groups such as carboxyl groups introduced by copolymerization are not neutralized with a basic compound.
- unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, itaconic anhydride, citraconic anhydride, methacrylic acid And methyl. These may be used alone or in combination of two or more.
- the copolymerization ratio of propylene and unsaturated carboxylic acids is 80 to 99.9 mol% of propylene and 0.1 to 20 mol% of unsaturated carboxylic acid, where the total amount of monomers to be copolymerized is 100 mol%. 90 to 99.7 mol%, unsaturated carboxylic acid is preferably 0.3 to 10 mol%, propylene 95 to 99.4 mol%, and unsaturated carboxylic acid 0.6 to 5 mol%. preferable.
- the mol% of propylene is less than 80 mol%, the compatibility with the matrix resin may be lowered.
- the mol% of propylene exceeds 99.9 mol%, the adhesion between the fiber and the matrix resin may be inhibited.
- the sizing agent when used as an aqueous solution, water dispersibility is lowered, and it may be difficult to uniformly apply the fibers.
- the total amount of monomers to be copolymerized is 100 mol%
- the total ratio of propylene and unsaturated carboxylic acids is 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, 100 mol% is more preferable. When it is less than 90 mol%, adhesion between the reinforcing fiber and the matrix resin is inhibited.
- the modified polypropylene resin of the present invention does not contain olefinic monomers excluding propylene, or even if it contains, when the total amount of monomers to be copolymerized is 100 mol%, the copolymerization ratio of olefinic monomers excluding propylene Is less than 10 mol%.
- the copolymerization ratio is more preferably less than 5 mol%, further preferably less than 2 mol%, and particularly preferably 0 mol%.
- the olefin monomer excluding propylene is 10 mol% or more, the adhesion between the fiber and the matrix resin is inhibited.
- olefin monomers other than propylene examples include ethylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-hexene, Decene, 1 dodecene and the like can be mentioned.
- the modified polypropylene resin of the present invention has a melting endotherm based on crystal melting of an endothermic peak when measured with a differential scanning calorimeter (DSC).
- the melting endotherm based on the crystal melting of the endothermic peak in the present invention is based on JIS-K7121 and K7122, and at the endothermic peak expressed on the DSC curve obtained by the DSC measurement described later, it departs from the baseline before and after the endotherm. It is defined as a value (unit: J / g) calculated by the integral value of the area surrounded by the straight line connecting the point and the point returning to the baseline and the peak curve.
- the melting endotherm when the modified polypropylene resin of the present invention is measured by DSC is preferably 70 J / g or less, more preferably 1 to 68 J / g, further preferably 5 to 65 J / g, and particularly preferably 10 to 60 J / g. . If the heat of fusion exceeds 70 J / g, the sizing agent may not contribute to the adhesion between the fiber and the matrix resin at all due to an increase in the crystal region in the molecular structure.
- the acid value of the modified polypropylene resin of the present invention is preferably 20 to 80 KOH mg / g, more preferably 30 to 70 KOH mg / g, and preferably 40 to 60 KOH mg / g.
- the oxidation is less than 20 KOH mg / g, the water dispersibility may be lowered in the case of an aqueous solution.
- the content of polypropylene as the main structure may decrease, and the compatibility with the matrix resin may decrease.
- the weight average molecular weight of the modified polypropylene resin is preferably 3000 to 150,000, more preferably 8000 to 100,000, and still more preferably 20,000 to 60,000. When the weight average molecular weight is less than 3000, the heat resistance may be inferior. If it exceeds 150,000, water dispersibility may be lowered in the case of an aqueous solution.
- the amine compound of the present invention is an amine compound having two or more hydroxyl groups in the molecular structure or two or more amino groups in the molecular structure, such as a carboxyl group introduced by copolymerization of the modified polypropylene resin of the present invention. Used to neutralize modifying groups.
- a neutralized product obtained by neutralizing the modified polypropylene resin with the amine compound of the present invention the melting endotherm based on crystal melting of the modified polypropylene resin can be lowered, and high adhesive strength can be obtained. .
- the outstanding drying property can be provided, As a result, the drying time in an operation process can be shortened and the operation speed can be increased.
- the drying property of the sizing agent is poor, the sizing agent is thermally deteriorated in the operation process, and the adhesiveness to the matrix resin is deteriorated. .
- amine compounds having two or more hydroxyl groups in the molecular structure include diethanolamine, triethanolamine, triisopropanolamine, t-butyldiethanolamine, n-butyldiethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, fatty acid alkanolamide, etc. Of these amines.
- amine compounds having two or more amino groups in the molecular structure include N-aminoethylethanolamine, N-aminoethylisopropanolamine, dimethylaminopropylamine, diethylethylenediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepenta And amines such as amine and pentaethyleneexamine.
- the boiling point of the amine compound of the present invention is preferably 240 to 340 ° C, more preferably 250 to 330 ° C, and further preferably 260 to 320 ° C.
- the amine compound is not volatilized by heating when the matrix resin and the reinforcing fiber are kneaded, and the melting endotherm based on crystal melting of the modified polypropylene resin can be reduced. it can.
- the crystal region of the sizing agent is reduced and the adhesion between the fiber and the matrix resin is improved.
- the amine compound is preferably a compound represented by the general formula (1) and / or the general formula (2) from the viewpoint of improving the adhesion between the fiber and the matrix resin.
- the amine compound represented by the general formula (1) is more preferable.
- R 1 is a hydrogen atom, —CH 2 CH 2 OH, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a residue obtained by removing an OH group from a fatty acid having 1 to 18 carbon atoms. .
- R 1 is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or a residue obtained by removing an OH group from a fatty acid having 5 to 18 carbon atoms, and an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Or a residue obtained by removing an OH group from a fatty acid having 8 to 15 carbon atoms.
- the aliphatic hydrocarbon group having 1 to 10 carbon atoms may be saturated or unsaturated, and may be linear or branched.
- the number of carbon atoms of the aliphatic hydrocarbon group is preferably from 1 to 10, more preferably from 1 to 8, and even more preferably from 1 to 5, from the viewpoint of improving the adhesion between the fiber and the matrix resin and the stability of the emulsion.
- the fatty acid preferably has 5 to 18 carbon atoms, and more preferably 8 to 15 carbon atoms.
- R 2 is an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
- the aliphatic hydrocarbon group having 1 to 4 carbon atoms may be saturated or unsaturated, and may be linear or branched.
- the number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 3, more preferably 1 to 2, from the viewpoint of improving the adhesion between the fiber and the matrix resin and the stability of the emulsion.
- the sizing agent for reinforcing fibers of the present invention is at least one polymer component selected from an aromatic polyester resin and an aromatic polyester urethane resin from the viewpoint of improving the film forming property of the sizing agent and improving the sizing property of the reinforcing fiber. It is preferable to contain (A).
- the polymer component (A) has an endothermic peak having a glass transition point of 20 ° C. or higher and a melting endotherm based on crystal melting of 3 J / g or higher when measured with a differential scanning calorimeter (DSC). Preferably not.
- the glass transition point as used in the present invention is based on JIS-K7121, and in a portion showing a step-like change in the DSC curve obtained by DSC measurement described later, it is equidistant from the extended straight line of each baseline in the vertical axis direction. It is defined as the point (unit: ° C) where a straight line and the curve of the step-like change part intersect.
- the melting endotherm is the same as that defined for the modified polypropylene resin.
- the glass transition point of the polymer component (A) is 20 ° C. or higher, the mobility of the polymer molecules is suppressed, a tough interface layer is formed between the fiber and the matrix resin, and the adhesive strength is increased.
- the glass transition point of the polymer component is preferably 25 to 200 ° C, more preferably 30 to 150 ° C.
- the polymer component (A) of the present invention does not have an endothermic peak having a melting endotherm based on crystal melting of 3 J / g or more. That is, it is important that the polymer component (A) of the present invention does not have an endothermic peak based on crystal melting or has an endothermic amount based on the endothermic peak of less than 3 J / g.
- the reason is not necessarily clear, but is considered as follows.
- the intermolecular force of a crystalline region in which polymer chains are regularly arranged is weakened, and the properties rapidly change from solid to liquid.
- the property change is confirmed by a clear endothermic peak having an endotherm of 3 J / g or more in DSC measurement.
- this sudden property change sometimes causes the sizing agent components to elute and diffuse into the heated and melted matrix resin during composite molding, which causes the sizing agent to adhere to the fiber and matrix resin. There may be no contribution at all.
- the polymer component (A) in the present invention has a slow property change from solid to liquid during heating compared to the above general crystalline polymer. It is considered that the adhesiveness between the fibers and the matrix resin can be improved because the sizing agent component remains sufficiently on the top.
- the polymer component (A) of the present invention does not have an endothermic peak with a melting endotherm based on crystal melting of 2 J / g or more (even if it does not have an endothermic peak based on crystal melting or not)
- the melting endotherm based on the crystal melting is preferably less than 2 J / g), and the melting endotherm based on the crystal melting does not have an endothermic peak of 1 J / g or more (the endothermic peak based on the crystal melting has or does not have). Is more preferably less than 1 J / g based on the endothermic peak, and more preferably no endothermic peak.
- the temperature range in which the melting endotherm based on crystal melting does not have an endothermic peak of 3 J / g or more may be in the range of 300 ° C. from the temperature at the end of the glass transition.
- the polymer component (A) of the present invention does not have an exothermic peak due to crystallization of the polymer in the same meaning as having no endothermic peak due to crystal melting as described above.
- the polymer component (A) of the present invention can be obtained by controlling the type and ratio of the monomer component in the production of these resins.
- the polymer component of the present invention may be used alone or in combination of two or more.
- the aromatic polyester resin is a copolymer of a polycarboxylic acid or an anhydride thereof and a polyol, and at least one of the polycarboxylic acid or the anhydride and the polyol is a polymer containing an aromatic compound. is there.
- the sizing agent of the present invention when used in a water emulsion, it has a hydrophilic group in the molecular skeleton including the terminal and is self-emulsifying from the viewpoint that it is not necessary to add an emulsifier component such as a surfactant. It is preferable that Examples of the hydrophilic group include polyalkylene oxide groups, sulfonates, carboxyl groups, and neutralized salts thereof.
- the polymer can be produced by a known method.
- polycarboxylic acid examples include aromatic dicarboxylic acids, sulfonate-containing aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and trifunctional or higher functional polycarboxylic acids.
- Aromatic dicarboxylic acids include phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, phthalic anhydride, etc. Can be mentioned.
- sulfonate-containing aromatic dicarboxylic acid examples include sulfoterephthalate and 5-sulfoisophthalate.
- Aliphatic dicarboxylic acids or alicyclic dicarboxylic acids include fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, 1,4-cyclohexanedicarboxylic acid, succinic anhydride, anhydrous And maleic acid.
- tri- or higher functional polycarboxylic acid examples include trimellitic acid, pyromellitic acid, trimellitic anhydride, pyromellitic anhydride, and the like.
- Examples of the polyol include diols and trifunctional or higher polyols.
- Diols include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polybutylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, tetramethylene glycol 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, resorcin, hydroquinone, bisphenol A or an alkylene oxide adduct thereof.
- Examples of the tri- or higher functional polyol include trimethylolpropane, glycerin, pentaerythritol and the like.
- At least one of the polycarboxylic acid or its anhydride (sometimes referred to as the total polycarboxylic acid component) and the polyol may contain an aromatic compound.
- 40 to 99 mol% of the total polycarboxylic acid component is preferably an aromatic dicarboxylic acid, and more preferably 80 to 99 mol%.
- 1 to 10 mol% of the total polycarboxylic acid component is a sulfonate-containing aromatic dicarboxylic acid.
- polycarboxylic acids include phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and diphenyldicarboxylic acid. Acid, diphenoxyethanedicarboxylic acid, phthalic anhydride, sulfoterephthalate, and 5-sulfoisophthalate are preferable.
- the polyol ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, tetramethylene glycol, and neopentyl glycol are preferable. .
- the weight average molecular weight of the copolyester resin is preferably 3,000 to 100,000, and more preferably 10,000 to 30,000.
- the weight average molecular weight is less than 3,000, the heat resistance is inferior, and when it exceeds 100,000, the emulsion stability in an aqueous solution is inferior, which is not preferable.
- the aromatic polyester urethane resin is a polymer obtained by a polyaddition reaction between an aromatic polyester polyol and a polyisocyanate.
- the sizing agent of the present invention when used in a water emulsion, it has a hydrophilic group in the molecular skeleton including the terminal and is self-emulsifying from the viewpoint that it is not necessary to add an emulsifier component such as a surfactant.
- the hydrophilic group include polyalkylene oxide groups, sulfonates, carboxyl groups, and neutralized salts thereof.
- the polymer can be produced by a known method.
- the aromatic polyester polyol is a copolymer of a polycarboxylic acid or an anhydride thereof and a polyol, and at least one of the polycarboxylic acid or an anhydride thereof and the polyol contains an aromatic compound.
- polycarboxylic acid or its anhydride, and a polyol, the compound illustrated in the above-mentioned aromatic polyester resin is mentioned.
- polyisocyanate examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, and the like.
- At least one of the polycarboxylic acid or its anhydride and polyol may contain an aromatic compound.
- polycarboxylic acid or its anhydride Is preferably aromatic dicarboxylic acid, more preferably 80 to 100 mol%.
- Preferred polycarboxylic acid and polyol combinations are the same as those described for the aromatic polyester resin.
- As the polyisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, and 1,5-naphthalene diisocyanate are preferable.
- the weight average molecular weight of the aromatic polyester-based urethane resin is preferably 3,000 to 100,000, more preferably 10,000 to 50,000. If the weight average molecular weight is less than 3,000, the heat resistance is poor, and if it exceeds 10,000, the emulsion stability in the case of an aqueous solution is poor, which is not preferable.
- the sizing agent of the present invention is for reinforcing fibers used to reinforce a thermoplastic matrix resin, and essentially contains a neutralized product of the aforementioned modified polypropylene resin and the aforementioned amine compound.
- a method for producing the neutralized product is not particularly limited, and a known method can be adopted.
- the above-mentioned modified polypropylene resin and each component of the above-mentioned amine compound are put into warm water with stirring and emulsified, dispersed or dissolved, or the respective components are mixed, and the resulting mixture is heated above the softening point. Thereafter, a method of gradually injecting water and applying phase inversion emulsification while applying mechanical shearing force using a homogenizer, a homomixer, a ball mill, or the like can be used.
- the fiber-reinforced sizing agent of the present invention containing the neutralized product is blended in a proportion of 10 to 90% by weight of the modified polypropylene resin and 1 to 20% by weight of the amine compound with respect to the entire nonvolatile content of the sizing agent. What was prepared in this way is preferable.
- the proportion of the modified polypropylene resin is more preferably 30 to 85% by weight, and further preferably 50 to 80% by weight. When the ratio of the modified polypropylene resin is less than 10% by weight, the modified polypropylene resin on the surface of the reinforcing fiber may be insufficient, and the adhesion with the matrix resin may not be improved. When the proportion of the modified polypropylene resin is more than 90% by weight, the fiber convergence may be lowered.
- the proportion of the amine compound is more preferably 3 to 15% by weight, and further preferably 5 to 12% by weight.
- the ratio of the amine compound is less than 1% by weight, the effect of reducing the crystal region of the modified polypropylene resin is small, and the adhesion between the reinforcing fiber and the matrix resin may not be improved.
- the proportion of the amine compound exceeds 20% by weight, the sizing agent may not be dispersed in water.
- the melting endotherm when the nonvolatile content of the sizing agent is measured by DSC is 50 J / g or less, preferably 1 to 48 J / g, more preferably 5 to 45 J / g. 10 to 40 J / g is more preferable.
- the melting endotherm exceeds 50 J / g, there are many crystal regions in the molecular structure of the neutralized product of the modified polypropylene resin and the amine compound, and the sizing agent does not contribute to the adhesion between the fiber and the matrix resin.
- the non-volatile content in the present invention refers to an absolutely dry component when the sizing agent is heat treated at 105 ° C. to remove the solvent and the like and reach a constant weight.
- the melting endotherm is the same as that defined for the modified polypropylene resin.
- the sizing agent of this invention is excellent in the drying property when water
- the volatile content when 2.0 g of a sizing agent having a nonvolatile content concentration of 5.0% by weight is passed through an infrared moisture meter for 10 minutes is preferably 75% by weight or more, more preferably 78% by weight or more, and 80% by weight or more. preferable.
- the polymer component (A) is preferably contained in an amount of 5 to 80% by weight, more preferably 10 to 75% by weight, more preferably 20 to The content is more preferably 70% by weight, and particularly preferably 30 to 60% by weight.
- a strong sizing agent non-volatile component forms a film with excellent adhesion to the matrix resin between the fibers and the matrix resin, and a tough interface layer. Therefore, high adhesiveness can be obtained.
- the sizing agent of the present invention can be used in a state dispersed or dissolved in an organic solvent such as acetone or methyl ethyl ketone, but it is safe for the human body during handling, disaster prevention such as fire, pollution of the natural environment. From the viewpoint of prevention and the like, it is preferable that water is further contained, and the neutralized product and the polymer component (A) are dispersed in water (aqueous dispersion) or dissolved in water (aqueous solution).
- the method for producing the sizing agent of the present invention as an aqueous dispersion or aqueous solution is not particularly limited, and a known method can be employed.
- each component constituting the sizing agent is poured into warm water under stirring and emulsified, dispersed or dissolved, or each component constituting the sizing agent is mixed, and the resulting mixture is heated to a temperature above the softening point.
- a method of phase inversion emulsification by gradually adding water while applying mechanical shearing force using a homogenizer, homomixer, ball mill or the like.
- the water dispersion or the aqueous solution is not limited to water such as an organic solvent within the range that does not impair the advantages of the water dispersion and the aqueous solution for the purpose of improving the operability during production and the stability of the aqueous dispersion over time.
- the solvent can be contained.
- the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; glycols or glycol ethers such as ethylene glycol, propylene glycol, ethylene glycol monoisopropyl ether, and ethylene glycol monobutyl ether; ketones such as acetone and methyl ethyl ketone. It can be illustrated.
- the content is preferably 100% by weight or less, more preferably 50% by weight or less, based on the nonvolatile content of the sizing agent, in order not to impair the advantages of the aqueous dispersion and aqueous solution, although it depends on the type of solvent.
- the concentration of the non-volatile content is not particularly limited, and the stability of the aqueous dispersion and the viscosity easy to handle as a product are determined by the non-volatile composition of the sizing agent. However, it is preferably 10% by weight or more, more preferably 20 to 60% by weight, and particularly preferably 30 to 50% by weight in consideration of the transportation cost of the product.
- components other than those described above constituting the sizing agent of the present invention include various surfactants, various smoothing agents, antioxidants, flame retardants, antibacterial agents, crystal nucleating agents, antifoaming agents, and the like. be able to. These may be used alone or in combination of two or more.
- the surfactant when the surfactant has a resin component that is water-insoluble or hardly soluble in the sizing agent of the present invention, aqueous surfactant emulsification can be efficiently carried out by using it as an emulsifier. Therefore, the sizing agent can be made into an aqueous dispersion.
- the proportion by weight of the entire nonvolatile content is preferably 5 to 40% by weight, more preferably 10 to 30% by weight, and even more preferably 15 to 25% by weight.
- the surfactant is not particularly limited, and a known one can be appropriately selected from nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. Surfactant may use together 1 type (s) or 2 or more types.
- Nonionic surfactants include, for example, alkylene oxide-added nonionic surfactants (higher alcohols, higher fatty acids, alkylphenols, styrenated phenols, benzylphenols, sorbitans, sorbitan esters, castor oil, hydrogenated castor oil, etc. And alkylene oxides such as oxides and propylene oxides (two or more types can be used together), polyalkylene glycols added with higher fatty acids, and ethylene oxide / propylene oxide copolymers.
- the anionic surfactant include carboxylic acid (salt), sulfate ester salt of higher alcohol / higher alcohol ether, sulfonate salt, phosphate ester salt of higher alcohol / higher alcohol ether, and the like.
- cationic surfactants include quaternary ammonium salt type cationic surfactants (such as lauryltrimethylammonium chloride and oleylmethylethylammonium etosulphate), amine salt type cationic surfactants (polyoxyethylene laurylamine), and the like. Lactate etc.).
- amphoteric surfactants include amino acid type amphoteric surfactants (such as sodium laurylaminopropionate), betaine type amphoteric surfactants (such as stearyl dimethyl betaine, lauryl dihydroxyethyl betaine), and the like.
- the sizing agent for reinforcing fibers of the present invention is used in combination with a modified polyolefin resin other than the modified polypropylene resin (hereinafter referred to as a modified polyolefin resin (B))
- a modified polyolefin resin (B) is not substantially contained because it causes a decrease in fiber adhesion.
- the weight percentage of the modified polyolefin resin (B) in the entire nonvolatile content of the sizing agent is preferably 10% by weight or less, more preferably 5% by weight or less, further preferably 2% by weight or less, and 0% by weight. % Is particularly preferred.
- Modified polyolefin resin (B) (modified polyolefin resin other than the above-mentioned modified polypropylene resin) is a copolymer composed of olefinic monomers and unsaturated carboxylic acids, and does not contain any propylene in the molecular structure. Or when propylene is included, the total copolymerization ratio of propylene and unsaturated fatty acids is less than 90 mol% when the total of monomers to be copolymerized is 100 mol%.
- the modified polyolefin resin (B) is a copolymer composed of an olefin monomer and an unsaturated carboxylic acid, and the olefin monomer excluding propylene when the total amount of monomers to be copolymerized is 100 mol%. It can also be said that the copolymerization ratio is more than 10 mol%. Examples of the olefinic monomers and unsaturated fatty acids other than propylene include those described above for the modified polypropylene resin.
- the modified polyolefin resin (B) includes neutralized products neutralized with the above amine compounds, other amine compounds, and basic compounds such as sodium hydroxide and sodium hydroxide.
- the synthetic fiber strand of the present invention is a reinforcing fiber for reinforcing the thermoplastic matrix resin by adhering the sizing agent for reinforcing fiber to the raw synthetic fiber strand.
- the manufacturing method of the synthetic fiber strand of this invention is a manufacturing method including the sizing process process which makes the sizing agent mentioned above adhere to a raw material synthetic fiber strand, and dries the obtained deposit.
- the method of attaching the sizing agent to the raw synthetic fiber strand to obtain a deposit but the sizing agent is attached to the raw synthetic fiber strand by a kiss roller method, roller dipping method, spray method or other known methods. Any method can be used. Among these methods, the roller dipping method is preferable because the sizing agent can be uniformly attached to the raw synthetic fiber strand.
- the drying method of the obtained deposit For example, it can heat-dry with a heating roller, a hot air, a hot plate, etc.
- thermosetting resin such as an epoxy resin, a vinyl ester resin, and a phenol resin and / or a urethane resin other than the polymer component of the present invention, a polyester resin, a nylon resin, an acrylic resin, etc.
- the thermoplastic resin may be attached to the raw synthetic fiber strand.
- the synthetic fiber strand of the present invention is used as a reinforcing fiber of a composite material using various thermoplastic resins as a matrix resin, and may be used in a continuous fiber state or a state cut to a predetermined length.
- the adhesion amount of the non-volatile component of the sizing agent to the raw synthetic fiber strand can be selected as appropriate, and it may be a necessary amount for the synthetic fiber strand to have a desired function, but the adhesion amount is 0 with respect to the raw synthetic fiber strand. It is preferably 1 to 20% by weight.
- the adhesion amount is more preferably 0.1 to 10% by weight, and further preferably 0.5 to 5% by weight with respect to the raw material synthetic fiber strand.
- the content is more preferably 0.5 to 20% by weight, and further preferably 1 to 10% by weight.
- the adhesion amount of the sizing agent is small, it is difficult to obtain the effects of the present invention relating to the resin impregnation property and adhesion property, and the converging property of the synthetic fiber strand is insufficient, and the handleability may be deteriorated.
- the amount of the sizing agent attached is too large, the synthetic fiber strand becomes too stiff and the handling property becomes worse, and the resin impregnation property becomes worse at the time of molding the composite.
- Synthetic fibers of (raw material) synthetic fiber strand to which the sizing agent of the present invention can be applied include various inorganic fibers such as carbon fibers, glass fibers, ceramic fibers, aramid fibers, polyethylene fibers, polyethylene terephthalate fibers, polybutylene terephthalate fibers, Examples include various organic fibers such as polyethylene naphthalate fiber, polyarylate fiber, polyacetal fiber, PBO fiber, polyphenylene sulfide fiber, and polyketone fiber.
- the fiber-reinforced composite material of the present invention includes a thermoplastic matrix resin and synthetic fiber strands as the aforementioned reinforcing fibers. Since the synthetic fiber strand is treated with the sizing agent of the present invention, the affinity with the synthetic fiber strand and the thermoplastic matrix resin is good, and a fiber-reinforced composite material having excellent adhesion is obtained.
- the matrix resin refers to a base material that holds the reinforcing fibers of the fiber-reinforced composite material
- the thermoplastic matrix resin refers to a matrix resin made of a thermoplastic resin.
- the thermoplastic matrix resin may contain 1 type (s) or 2 or more types.
- thermoplastic matrix resin Polyolefin-type resin, nylon resin, polycarbonate resin, polyester resin, polyacetal resin, ABS resin, phenoxy resin, polymethylmethacrylate resin, polyphenylene sulfide resin, polyetherimide resin, polyether Examples thereof include ketone resins.
- a polyolefin-based resin having a higher effect of improving the adhesion by the sizing agent of the present invention is preferable.
- These thermoplastic matrix resins may be partially or wholly modified for the purpose of further improving the adhesion to the synthetic fiber strand.
- the method for producing the fiber reinforced composite material is not particularly limited, and known methods such as compound injection molding using chopped fibers and long fiber pellets, press molding using UD sheets and woven sheets, and other filament winding molding can be employed.
- the content of the synthetic fiber strand in the fiber reinforced composite material is not particularly limited, and may be appropriately selected according to the type of fiber, the form, the type of thermoplastic matrix resin, etc. 5 to 70% by weight is preferable, and 20 to 60% by weight is more preferable.
- ⁇ Glass transition point> Based on JIS-K7121, a differential scanning calorimeter (DSC) (JADE DSC LAB SYSTEM manufactured by PerkinElmer Instruments Co., Ltd.) was used under the conditions of a sample weight of about 10 mg and a heating rate of 10 ° C./min. Specifically, a sample precisely weighed at 10 ⁇ 1 mg is set in a differential scanning calorimeter, and the temperature is raised to the sample melting temperature Tm + 30 ° C. confirmed by the preliminary measurement. Next, after the temperature is lowered to the glass transition point Tg-50 ° C. confirmed by the preliminary measurement, the temperature is raised to 300 ° C. at a temperature raising rate of 10 ° C./min.
- DSC differential scanning calorimeter
- the point where the straight line equidistant from the extended straight line of each base line in the vertical axis direction and the curve of the step-like change portion intersect is the glass transition point Tg (unit: : ° C).
- the composite material interface property evaluation apparatus HM410 manufactured by Toei Sangyo Co., Ltd. was used, and the adhesion was evaluated by the microdroplet method. Carbon fiber filaments are taken out from the carbon fiber strands produced in the examples and comparative examples, and set in a composite material interface property evaluation apparatus. A drop of the polypropylene resin mixture J-900GP (manufactured by Idemitsu Petrochemical Co., Ltd.) melted on the apparatus was formed on the carbon fiber filament and cooled sufficiently at room temperature to obtain a sample for measurement.
- the measurement sample was set in the apparatus again, the drop was sandwiched between apparatus blades, the carbon fiber filament was run on the apparatus at a speed of 0.06 mm / min, and the maximum pulling load F when the drop was pulled out from the carbon fiber filament was measured. .
- ⁇ Convergence of carbon fiber chop> The bulk density of the carbon fiber chop after stirring the carbon fiber chop with a mixer at 400 rpm for 3 minutes was determined by dividing the bulk density before the stirring treatment. The larger the value, the worse the convergence. The bulk density was determined as follows. Bulk density of carbon fiber chop: 70 g of carbon fiber chop was put into a 500 mL graduated cylinder, and the weight was calculated by dividing the weight by the volume of the carbon fiber chop after subjecting the graduated cylinder to 60 vertical vibrations for 1 minute. .
- Table 1 shows the boiling point, the number of hydroxyl groups, and the number of amino groups of the neutralizing agents used in the production of PP-1 to PP-21.
- PP-1 to PP-21 water emulsion water emulsion (PP-1 / PE-1) mixed with PP-1 and PE-1, water emulsion (PP-1 / PU-1) mixed with PP-1 and PU-1 -1 / PU-1) was heat-treated at 105 ° C., and the endothermic product obtained by removing the solvent and the like was measured for endothermic melting by DSC measurement.
- the results are shown in Table 2.
- the ratios of PP-1 / PE-1 and PP-1 / PU-1 in Table 2 indicate the weight ratio of the non-volatile content of each emulsion.
- PP-1 was diluted with water to prepare a sizing agent emulsion having a nonvolatile content concentration of 15% by weight. After immersing and impregnating sizing agent-untreated carbon fiber strands (fineness: 800 tex, number of filaments: 12,000), 105 ° C. And sizing agent-treated carbon fiber strand having a theoretical adhesion amount of 5%. About this strand, the matrix resin adhesiveness was evaluated by the above-mentioned method. The results are shown in Table 3.
- Example 1 a sizing agent-treated carbon fiber strand was prepared in the same manner as in Example 1 except that a sizing agent emulsion having a non-volatile content of 15% by weight was prepared so that the sizing agent non-volatile composition shown in Tables 3 to 5 was obtained. Got. The evaluation results of each characteristic value are shown in Tables 3 to 5.
- the sizing agent non-volatile composition shown in Tables 3 to 5 indicates the ratio of non-volatile content of each of the emulsions PP-1 to PP-21, PE-1, and PU-1 to the entire non-volatile content.
- a fiber reinforced composite material in which a thermoplastic matrix resin is reinforced with reinforcing fibers is used in automobile applications, aerospace applications, sports / leisure applications, general industrial applications, and the like.
- the reinforcing fiber include various inorganic fibers such as carbon fiber, glass fiber, and ceramic fiber, and various organic fibers such as aramid fiber, polyamide fiber, and polyethylene fiber.
- the sizing agent of this invention can be used conveniently with respect to the reinforced fiber for reinforcing a thermoplastic matrix resin.
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Abstract
Description
しかし、基本的に濡れ性に乏しいポリオレフィン系樹脂においては、従来技術に記載されたサイジング剤を適用しても、成型時のマトリックス樹脂と繊維との濡れ性および接着性の悪さをさらに助長する結果となり、複合材料としての機械的特性をさらに低いものとする場合があった。
詳細には、1)変性ポリプロピレン樹脂と、分子構造内に2個以上の水酸基または分子構造内に2個以上のアミノ基を有する特定のアミン化合物との中和物を含み、サイジング剤の不揮発分の融解吸熱量が特定数値以下となるサイジング剤であれば、熱可塑性マトリックス樹脂との接着性が格段に優れることを見出し、本発明に到達した。
さらには、2)変性ポリプロピレン樹脂以外の変性ポリオレフィン樹脂では、中和剤の種類を問わず接着性の向上がみられないこと、3)変性ポリプロピレン樹脂では、中和剤がアルカリ金属塩や上記特定のアミン化合物以外のアミン化合物の場合、接着性の向上がみられないこと、4)変性ポリプロピレン樹脂と上記特定のアミン化合物との中和物を含むサイジング剤であっても、サイジング剤の不揮発分の融解吸熱量が特定数値を超えると、接着性の向上が見られないことを見出し、本発明に到達した。
また、前記アミン化合物は、下記一般式(1)および/または下記一般式(2)で示される化合物であることが好ましい。
(式中R1は、水素原子、-CH2CH2OH、炭素数1~10の脂肪族炭化水素基、または炭素数1~18の脂肪酸からOH基を除いた残基である。)
(式中R2は、炭素数1~4の脂肪族炭化水素基である。)
前記熱可塑性マトリックス樹脂は、ポリオレフィン系樹脂であることが好ましい。
本発明の強化繊維用サイジング剤は、さらに水を含有し、前記中和物が水に分散した状態または水に溶解した状態であることが好ましい。
前記合成繊維ストランドの合成繊維は、炭素繊維、アラミド繊維、ポリエチレン繊維、ポリエチレンテレフタレート繊維、ポリブチレンテレフタレート繊維、ポリエチレンナフタレート繊維、ポリアリレート繊維、ポリアセタール繊維、PBO繊維、ポリフェニレンサルフィド繊維およびポリケトン繊維から選ばれる少なくとも1種であることが好ましい。
本発明の強化繊維用サイジング剤で処理して得られる合成繊維ストランドは、熱可塑性マトリックス樹脂に対して、格段に優れた接着性を有する。本発明の合成繊維ストランドを使用することにより、優れた物性を有する繊維強化複合材料が得られる。
本発明の変性ポリプロピレン樹脂とは、プロピレンと不飽和カルボン酸類から実質的に構成される共重合体であり、公知の方法で製造できる。プロピレンと不飽和カルボン酸とを共重合させたランダム共重合体でもよいし、ポリプロピレンに不飽和カルボン酸類をグラフトしたグラフト共重合体でもよい。本発明の変性ポリプロピレン樹脂は、1種または2種以上を使用してもよい。本発明でいう変性ポリプロピレン樹脂は、共重合により導入したカルボキシル基等の酸性基が塩基性化合物で中和されていないものをいう。
不飽和カルボン酸類としては、例えば、アクリル酸、メタクリル酸、クロトン酸、イソクロトン酸、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、シトラコン酸、メサコン酸、無水イタコン酸、無水シトラコン酸、メタクリル酸メチルなどが挙げられる。これらは単独、あるいは2種以上を組み合わせて使用することもできる。
また、共重合するモノマーの合計を100モル%としたとき、プロピレンと不飽和カルボン酸類の合計の比率は、90モル%以上であり、95モル%以上が好ましく、98モル%以上がより好ましく、100モル%がさらに好ましい。90モル%未満の場合、強化繊維とマトリックス樹脂との接着性阻害となる。
また、変性ポリプロピレン樹脂の重量平均分子量としては、3000~150000が好ましく、8000~100000がより好ましく、20000~60000がさらに好ましい。重量平均分子量が3000未満であると、耐熱性に劣ることがある。150000を超えると、水溶液とする場合に水分散性が低下することがある。
本発明のアミン化合物は、分子構造内に2個以上の水酸基または分子構造内に2個以上のアミノ基を有するアミン化合物であり、本発明の変性ポリプロピレン樹脂の共重合により導入したカルボキシル基などの変性基を中和するために用いられる。前述の変性ポリプレピレン樹脂を本発明のアミン化合物で中和した中和物を必須に含有することにより、変性ポリプロピレン樹脂の結晶融解に基づく融解吸熱量を下げることができ、高い接着性強度が得られる。また、優れた乾燥性を付与でき、その結果、操業工程での乾燥時間を短縮でき、操業速度を速めることができる。さらに、乾燥時間を短縮できることによってサイジング剤の熱劣化を抑制でき、マトリックス樹脂との優れた接着性を付与できる。
一方、本発明のアミン化合物以外のアミン化合物を中和剤に用いた場合、マトリックス樹脂と補強繊維を混練する際の加熱によりアミン化合物が揮散してしまい、変性ポリプロピレン樹脂とアミン化合物との相乗効果がなくなり、より高い接着性強度が得られなくなる。また、水酸化ナトリウム、水酸化カリウム等のアルカリ金属塩を中和剤に用いた場合、サイジング剤の乾燥性が悪く、操業工程でサイジング剤が熱劣化し、マトリックス樹脂との接着性が悪くなる。
分子構造内に2個以上のアミノ基を有するアミン化合物としては、N-アミノエチルエタノールアミン、N-アミノエチルイソプロパノールアミン、ジメチルアミノプロピルアミン、ジエチルエチレンジアミン、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンエキサミンなどのアミン類が挙げられる。
炭素数1~10の脂肪族炭化水素基は、飽和であっても不飽和であってもよく、直鎖であっても分岐を有していてもよい。脂肪族炭化水素基の炭素数は、繊維とマトリックス樹脂との接着性が向上する点及び乳化安定性の点から、1~10が好ましく、1~8がより好ましく、1~5がさらに好ましい。炭素数1~18の脂肪酸からOH基を除いた残基において、脂肪酸の炭素数は5~18が好ましく、8~15がさらに好ましい。
本発明の強化繊維用サイジング剤は、サイジング剤の被膜形成性向上、強化繊維の集束性向上の点から、さらに芳香族系ポリエステル樹脂および芳香族ポリエステル系ウレタン樹脂から選ばれる少なくとも1種のポリマー成分(A)を含有することが好ましい。
本発明でいうガラス転移点とは、JIS-K7121に準拠し、後述するDSC測定により得られるDSC曲線の階段状変化を示す部分において、各ベースラインの延長した直線から縦軸方向に等距離にある直線と、階段状変化部分の曲線とが交わる点(単位:℃)として定義される。また、融解吸熱量は、変性ポリプロピレン樹脂で定義したものと同じである。
それに対し本発明におけるポリマー成分(A)は、上記の一般的な結晶性ポリマーに比較して、加温時の固体状から液状への性状変化が緩慢な為、コンポジット成型の際にも繊維表面上にサイジング剤成分が十分に残存している為、繊維とマトリックス樹脂との接着性を向上できると考えられる。
結晶融解に基づく融解吸熱量が3J/g以上の吸熱ピークを有しない温度範囲としては、ガラス転移終了時の温度から300℃の範囲であればよい。
芳香族系ポリエステル樹脂とは、ポリカルボン酸またはその無水物と、ポリオールとの共重合体で、前記ポリカルボン酸またはその無水物、およびポリオールの中の少なくとも1種が芳香族化合物を含むポリマーである。なお、本発明のサイジング剤を水エマルジョンで使用する場合に、界面活性剤などの乳化剤成分を添加する必要がなくなるとの観点から、末端を含む分子骨格中に親水基を有し、自己乳化性であることが好ましい。上記親水基としては、例えばポリアルキレンオキサイド基、スルホン酸塩、カルボキシル基、これらの中和塩などが挙げられる。本ポリマーは公知の方法で製造できる。
芳香族ジカルボン酸としては、フタル酸、テレフタル酸、イソフタル酸、オルトフタル酸、1,5-ナフタレンジカルボン酸、2,6-ナフタレンジカルボン酸、ジフェニルジカルボン酸、ジフェノキシエタンジカルボン酸、無水フタル酸などが挙げられる。
スルホン酸塩含有芳香族ジカルボン酸としては、スルホテレフタル酸塩、5-スルホイソフタル酸塩などが挙げられる。
脂肪族ジカルボン酸または脂環式ジカルボン酸としては、フマル酸、マレイン酸、イタコン酸、コハク酸、アジピン酸、アゼライン酸、セバシン酸、ダイマー酸、1,4-シクロヘキサンジカルボン酸、無水コハク酸、無水マレイン酸などが挙げられる。
3官能以上のポリカルボン酸としては、トリメリット酸、ピロメリット酸、無水トリメリット酸、無水ピロメリット酸などが挙げられる。
ジオールとしては、エチレングリコール、ジエチレングリコール、ポリエチレングリコール、プロピレングリコール、ポリプロピレングリコール、ポリブチレングリコール、1,3-プロパンジオール、1,4-ブタンジオール、1,6-ヘキサンジオール、ネオペンチルグリコール、テトラメチレングリコール、1,4-シクロヘキサンジオール、1,4-シクロヘキサンジメタノール、レゾルシン、ハイドロキノン、ビスフェノールAまたはそのアルキレンオキサイド付加物などが挙げられる。
3官能以上のポリオールとしては、トリメチロールプロパン、グリセリン、ペンタエリスリトールなどが挙げられる。
芳香族ポリエステル系ウレタン樹脂とは、芳香族ポリエステルポリオールとポリイソシアネートとの重付加反応等により得られるポリマーである。なお、本発明のサイジング剤を水エマルジョンで使用する場合に、界面活性剤などの乳化剤成分を添加する必要がなくなるとの観点から、末端を含む分子骨格中に親水基を有し、自己乳化性であることが好ましい。上記親水基としては、例えばポリアルキレンオキサイド基、スルホン酸塩、カルボキシル基、これらの中和塩などが挙げられる。本ポリマーは公知の方法で製造できる。
本発明のサイジング剤は、熱可塑性マトリックス樹脂を補強するために用いられる強化繊維用であり、前述の変性ポリプロピレン樹脂と前述のアミン化合物との中和物を必須に含有するものである。中和物を製造する方法としては、特に限定なく、公知の方法を採用できる。例えば、前述の変性ポリプロピレン樹脂と前述のアミン化合物の各成分を攪拌下の温水中に投入して乳化分散または溶解する方法や、各成分を混合し、得られた混合物を軟化点以上に加温後、ホモジナイザー、ホモミキサー、ボールミル等を用いて機械せん断力を加えつつ、水を徐々に投入して転相乳化する方法等が挙げられる。
前記変性ポリプロピレン樹脂の割合は、30~85重量%がより好ましく、50~80重量%がさらに好ましい。変性ポリプロピレン樹脂の割合が10重量%未満の場合、強化繊維表面上の変性ポリプロピレン樹脂が不足し、マトリクス樹脂との接着性が向上しないことがある。変性ポリプロピレン樹脂の割合が90重量%超の場合、繊維の集束性が低下することがある。
前記アミン化合物の割合は3~15重量%がより好ましく、5~12重量%がさらに好ましい。アミン化合物の割合が1重量%未満の場合、変性ポリプロピレン樹脂の結晶領域を減少させる効果が少なく強化繊維とマトリックス樹脂との接着性が向上しないことがある。アミン化合物の割合が20重量%超の場合は、サイジング剤を水分散できなくなることがある
不揮発分濃度が5.0重量%のサイジング剤2.0gを赤外線水分計で10分経過した時の揮発分は、75重量%以上が好ましく、78重量%以上がより好ましく、80重量%以上が好ましい。
有機溶剤としては、メチルアルコール、エチルアルコール、イソプロピルアルコール等のアルコール類;エチレングリコール、プロピレングリコール、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル等のグリコールまたはグリコールエーテル類;アセトン、メチルエチルケトン等のケトン類が例示できる。その含有量としては、溶媒の種類にもよるが、水分散体や水溶液の利点を損なわないために、サイジング剤の不揮発分に対して100重量%以下が好ましく、50重量%以下がさらに好ましい。
本発明のサイジング剤を構成する上記で説明した以外の成分としては、たとえば、各種界面活性剤や、各種平滑剤、酸化防止剤、難燃剤、抗菌剤、結晶核剤、消泡剤等を挙げることができる。これらは1種または2種以上を併用してもよい。
界面活性剤としては、特に限定されず、非イオン系界面活性剤、アニオン系界面活性剤、カチオン系界面活性剤および両性界面活性剤から、公知のものを適宜選択して使用することができる。界面活性剤は、1種または2種以上を併用してもよい。
アニオン系界面活性剤としては、たとえば、カルボン酸(塩)、高級アルコール・高級アルコールエーテルの硫酸エステル塩、スルホン酸塩、高級アルコール・高級アルコールエーテルの燐酸エステル塩等を挙げることができる。
両性界面活性剤としては、たとえば、アミノ酸型両性界面活性剤(ラウリルアミノプロピオン酸ナトリウム等)、ベタイン型両性界面活性剤(ステアリルジメチルベタイン、ラウリルジヒドロキシエチルベタイン等)等を挙げることができる。
変性ポリオレフィン樹脂(B)(上記変性ポリプロピレン樹脂以外の変性ポリオレフィン樹脂)とは、オレフィン系モノマーと不飽和カルボン酸類とから構成される共重合体であって、分子構造中にプロピレンを全く含まないものであるか、プロピレンを含む場合は、共重合するモノマーの合計を100モル%としたとき、プロピレンと不飽和脂肪酸類の合計の共重合比率が90モル%未満のものをいう。また、変性ポリオレフィン樹脂(B)は、オレフィン系モノマーと不飽和カルボン酸類とから構成される共重合体であって、共重合するモノマーの合計を100モル%としたとき、プロピレンを除くオレフィン系モノマーの共重合比率が10モル%超のものということもできる。プロピレンを除くオレフィン系モノマー、不飽和脂肪酸類は、変性ポリプロピレン樹脂で前述したものが挙げられる。変性ポリオレフィン樹脂(B)には、上記のアミン化合物やその他のアミン化合物、水酸化ナトリウム、水酸化ナトリウム等の塩基性化合物で中和された中和物も含む。
本発明の合成繊維ストランドは、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。
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、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、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。
サイジング剤の付着量が少ないと、樹脂含浸性、接着性に関する本発明の効果が得られにくく、また、合成繊維ストランドの集束性が不足し、取扱い性が悪くなることがある。また、サイジング剤の付着量が多過ぎると、合成繊維ストランドが剛直になり過ぎて、かえって取扱い性が悪くなったり、コンポジット成型の際に樹脂含浸性が悪くなったりすることがあり好ましくない。
本発明の繊維強化複合材料は、熱可塑性マトリックス樹脂と前述の強化繊維としての合成繊維ストランドを含むものである。合成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いるので、合成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。
ここで、マトリックス樹脂とは繊維強化複合材料の強化繊維を保持する母材をいい、熱可塑性マトリックス樹脂とは、熱可塑性樹脂からなるマトリックス樹脂をいう。熱可塑性マトリックス樹脂は、1種または2種以上含んでいてもよい。熱可塑性マトリックス樹脂としては特に制限はなく、ポリオレフィン系樹脂、ナイロン樹脂、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ポリオレフィン系樹脂が好ましい。これら熱可塑性マトリックス樹脂は、合成繊維ストランドとの接着性をさらに向上させるなどの目的で、その一部または全部が変性したものであっても差し支えない。
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。
JIS-K7121に準拠し、示差走査熱量計(DSC)(パーキンエルマー・インスツルメント社製JADE DSC LAB SYSTEM)により、試料重量約10mg、昇温速度10℃/分の条件下で測定した。具体的には、10±1mgで精秤した試料を示差走査熱量計にセットし、予備測定にて確認した試料溶融温度Tm+30℃まで昇温する。次に、予備測定にて確認したガラス転移点Tg-50℃まで降温した後、昇温速度10℃/分で300℃まで昇温する。得られたDSC曲線の階段状変化を示す部分において、各ベースラインの延長した直線から縦軸方向に等距離にある直線と、階段状変化部分の曲線とが交わる点をガラス転移点Tg(単位:℃)とした。
JIS-K7121、K7122に準拠し、上記ガラス転移点測定により得られるDSC曲線上に発現する吸熱ピークにおいて、吸熱前後でベースラインから離れる点とベースラインに戻る点とを結んだ直線と、ピーク曲線により囲まれた面積の積分値により計算される値(単位:J/g)を融解吸熱量とした。
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。
実施例および比較例で製造し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、複合材料界面特性評価装置にセッティングする。装置上で溶融したポリプロピレン樹脂混合物J-900GP(出光石油化学社製)のドロップを炭素繊維フィラメント上に形成させ、室温で十分に冷却し、測定用の試料を得た。再度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ポリプロピレン樹脂との接着性を評価した。
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)
赤外線水分計FD-230型(ケット科学研究所製)を使用して、不揮発分濃度5.0重量%のサイジング剤2.0gを赤外線ランプ照射化下110℃で10分経過した時の揮発分(重量%)を評価した。
アルミトレイ上にサイジング剤不揮発分が純分1.0g残るように、105℃×3時間絶乾し、下記のように目視で判定した。
被膜生成・・・◎
被膜生成したが脆い・・・○
被膜が生成せず脆い・・・△
炭素繊維チョップをミキサーで400rpm、3分間攪拌した後の炭素繊維チョップの嵩密度を、攪拌処理前の嵩密度で除して求めた。数値が大きいほど集束性は悪い。なお、嵩密度は以下のようにして求めた。
炭素繊維チョップの嵩密度:500mLメスシリンダーに70gの炭素繊維チョップを投入し、メスシリンダーに1分間60回の上下振動を与えた後の炭素繊維チョップの体積でその重さを除して求めた。
〔製造例A1〕
ポリプロピレン樹脂をオートクレーブで攪拌しながら加熱溶解させ、無水マレイン酸を添加し、ポリプロピレンに無水マレイン酸をグラフト共重合させ、プロピレン97.8モル%、無水マレイン酸2.2モル%、融解吸熱量58.0J/g、酸価54KOHmg/g、重量平均分子量30000の変性ポリプロピレン樹脂(1)を得た。
ポリプロピレン樹脂をオートクレーブで攪拌しながら加熱溶解させ、無水マレイン酸を添加し、ポリプロピレンに無水マレイン酸をグラフト共重合させ、プロピレン98.3モル%、無水マレイン酸1.7モル%、融解吸熱量62.8J/g、酸価43KOHmg/g、重量平均分子量35000の変性ポリプロピレン樹脂(2)を得た。
ポリプロピレン樹脂をオートクレーブで攪拌しながら加熱溶解させ、無水マレイン酸を添加し、ポリプロピレンに無水マレイン酸をグラフト共重合させ、プロピレン97.0モル%、無水マレイン酸3.0モル%、融解吸熱量51.4J/g、酸価58KOHmg/g、重量平均分子量28000の変性ポリプロピレン樹脂(3)を得た。
プロピレン-エチレン共重合体(プロピレン成分95モル%、エチレン成分5モル%)樹脂をオートクレーブで攪拌しながら加熱溶解させ、無水マレイン酸を添加し、プロピレン-エチレン共重合体樹脂に無水マレイン酸をグラフト共重合させ、プロピレン-エチレン共重合体98.0モル%、無水マレイン酸2.0モル%、融解吸熱量67.8J/g、酸価50KOHmg/g、重量平均分子量31000の変性ポリプロピレン樹脂(4)を得た。
ポリプロピレン樹脂をオートクレーブで攪拌しながら加熱溶解させ、無水マレイン酸を添加し、ポリプロピレンに無水マレイン酸をグラフト共重合させ、プロピレン99.0モル%、無水マレイン酸1.0モル%、融解吸熱量82.2J/g、酸価26KOHmg/g、重量平均分子量40000の変性ポリプロピレン樹脂(5)を得た。
プロピレン-エチレン共重合体(プロピレン成分85モル%、エチレン成分15モル%)樹脂をオートクレーブで攪拌しながら加熱溶解させ、無水マレイン酸を添加し、プロピレン-エチレン共重合体樹脂に無水マレイン酸をグラフト共重合させ、プロピレン-エチレン共重合体98.2モル%、無水マレイン酸1.8モル%、融解吸熱量71.0J/g、酸価45KOHmg/g、重量平均分子量58000の変性ポリオレフィン樹脂(6)を得た。
〔製造例A7〕
プロピレン-エチレン-ブテン-アクリル酸共重合体(プロピレン成分68モル%、エチレン成分8モル%、ブテン成分22モル%、アクリル酸成分2モル%)樹脂をオートクレーブで攪拌しながら加熱溶解させ、無水マレイン酸を添加し、プロピレン-エチレン-ブテン-アクリル酸共重合体樹脂に無水マレイン酸をグラフト共重合させ、プロピレン-エチレン-ブテン-アクリル酸共重合体95.7モル%、無水マレイン酸4.3モル%、融解吸熱量8.8J/g、酸価50KOHmg/g、重量平均分子量70000の変性ポリオレフィン樹脂(7)を得た。
〔製造例B1〕
撹拌装置を備えたオートクレーブ中に、変性ポリプロピレン樹脂(1)222部、ポリオキシエチレン8モル付加オレイルエーテル52部、およびジエタノールアミン26部を仕込み、窒素ガス還流、撹拌下で170~180℃まで昇温した。ついで撹拌下水700部を徐々に投入、170~180℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-1を得た。
撹拌装置を備えたオートクレーブ中に、変性ポリプロピレン樹脂(1)222部、ポリオキシエチレン8モル付加オレイルエーテル52部、およびt-ブチルジエタノールアミン26部を仕込み、窒素ガス還流、撹拌下で170~180℃まで昇温した。ついで撹拌下水700部を徐々に投入、170~180℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-2を得た。
撹拌装置を備えたオートクレーブ中に、変性ポリプロピレン樹脂(1)222部、ポリオキシエチレン8モル付加オレイルエーテル52部、およびn-ブチルジエタノールアミン26部を仕込み、窒素ガス還流、撹拌下で170~180℃まで昇温した。ついで撹拌下水700部を徐々に投入、170~180℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-3を得た。
撹拌装置を備えたオートクレーブ中に、変性ポリプロピレン樹脂(1)222部、ポリオキシエチレン8モル付加オレイルエーテル52部、およびN-メチルジエタノールアミン26部を仕込み、窒素ガス還流、撹拌下で170~180℃まで昇温した。ついで撹拌下水700部を徐々に投入、170~180℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-4を得た。
撹拌装置を備えたオートクレーブ中に、変性ポリプロピレン樹脂(1)222部、ポリオキシエチレン8モル付加オレイルエーテル52部、およびN-エチルジエタノールアミン26部を仕込み、窒素ガス還流、撹拌下で170~180℃まで昇温した。ついで撹拌下水700部を徐々に投入、170~180℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-5を得た。
撹拌装置を備えたオートクレーブ中に、変性ポリプロピレン樹脂(1)224部、ポリオキシエチレン8モル付加オレイルエーテル52部、およびN-アミノエチルエタノールアミン24部を仕込み、窒素ガス還流、撹拌下で170~180℃まで昇温した。ついで撹拌下水700部を徐々に投入、170~180℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-6を得た。
撹拌装置を備えたオートクレーブ中に、変性ポリプロピレン樹脂(1)217部、ポリオキシエチレン8モル付加オレイルエーテル50部、およびトリエタノールアミン33部を仕込み、窒素ガス還流、撹拌下で170~180℃まで昇温した。ついで撹拌下水700部を徐々に投入、170~180℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-7を得た。
撹拌装置を備えたオートクレーブ中に、変性ポリプロピレン樹脂(1)208部、ポリオキシエチレン8モル付加オレイルエーテル49部、およびラウリン酸ジエタノールアミド43部を仕込み、窒素ガス還流、撹拌下で170~180℃まで昇温した。ついで撹拌下水700部を徐々に投入、170~180℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-8を得た。
撹拌装置を備えたオートクレーブ中に、変性ポリプロピレン樹脂(2)224部、ポリオキシエチレン8モル付加オレイルエーテル53部、およびジエタノールアミン23部を仕込み、窒素ガス還流、撹拌下で170~180℃まで昇温した。ついで撹拌下水700部を徐々に投入、170~180℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-9を得た。
撹拌装置を備えたオートクレーブ中に、変性ポリプロピレン樹脂(3)221部、ポリオキシエチレン8モル付加オレイルエーテル51部、およびジエタノールアミン28部を仕込み、窒素ガス還流、撹拌下で170~180℃まで昇温した。ついで撹拌下水700部を徐々に投入、170~180℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-10を得た。
撹拌装置を備えたオートクレーブ中に、変性ポリプロピレン樹脂(4)222部、ポリオキシエチレン8モル付加オレイルエーテル52部、およびジエタノールアミン26部を仕込み、窒素ガス還流、撹拌下で170~180℃まで昇温した。ついで撹拌下水700部を徐々に投入、170~180℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-11を得た。
撹拌装置を備えたオートクレーブ中に、変性ポリプロピレン樹脂(1)225部、ポリオキシエチレン8モル付加オレイルエーテル57部、およびアンモニア18部を仕込み、窒素ガス還流、撹拌下で170~180℃まで昇温した。ついで撹拌下水700部を徐々に投入、170~180℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-12を得た。
撹拌装置を備えたオートクレーブ中に、変性ポリプロピレン樹脂(1)222部、ポリオキシエチレン8モル付加オレイルエーテル58部、およびトリエチルアミン20部を仕込み、窒素ガス還流、撹拌下で170~180℃まで昇温した。ついで撹拌下水700部を徐々に投入、170~180℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-13を得た。
撹拌装置を備えたオートクレーブ中に、変性ポリプロピレン樹脂(1)221部、ポリオキシエチレン8モル付加オレイルエーテル51部、およびジメチルエタノールアミン28部を仕込み、窒素ガス還流、撹拌下で170~180℃まで昇温した。ついで撹拌下水700部を徐々に投入、170~180℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-14を得た。
撹拌装置を備えたオートクレーブ中に、変性ポリプロピレン樹脂(1)224部、ポリオキシエチレン8モル付加オレイルエーテル52部、およびモノエタノールアミン24部を仕込み、窒素ガス還流、撹拌下で170~180℃まで昇温した。ついで撹拌下水700部を徐々に投入、170~180℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-15を得た。
撹拌装置を備えたオートクレーブ中に、変性ポリプロピレン樹脂(1)228部、ポリオキシエチレン8モル付加オレイルエーテル57部、および水酸化カリウム15部を仕込み、窒素ガス還流、撹拌下で170~180℃まで昇温した。ついで撹拌下水700部を徐々に投入、170~180℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-16を得た。
撹拌装置を備えたオートクレーブ中に、変性ポリプロピレン樹脂(1)228部、ポリオキシエチレン8モル付加オレイルエーテル57部、および水酸化ナトリウム15部を仕込み、窒素ガス還流、撹拌下で170~180℃まで昇温した。ついで撹拌下水700部を徐々に投入、170~180℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-17を得た。
撹拌装置を備えたオートクレーブ中に、変性ポリプロピレン樹脂(5)226部、ポリオキシエチレン8モル付加オレイルエーテル53部、およびジエタノールアミン21部を仕込み、窒素ガス還流、撹拌下で170~180℃まで昇温した。ついで撹拌下水700部を徐々に投入、170~180℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-18を得た。
撹拌装置を備えたオートクレーブ中に、変性ポリオレフィン樹脂(6)226部、ポリオキシエチレン8モル付加オレイルエーテル53部、およびジエタノールアミン21部を仕込み、窒素ガス還流、撹拌下で180~190℃まで昇温した。ついで撹拌下水700部を徐々に投入、180~190℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-19を得た。
撹拌装置を備えたオートクレーブ中に、変性ポリオレフィン樹脂(7)226部、ポリオキシエチレン8モル付加オレイルエーテル53部、およびジエタノールアミン21部を仕込み、窒素ガス還流、撹拌下で170~180℃まで昇温した。ついで撹拌下水700部を徐々に投入、170~180℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-20を得た。
撹拌装置を備えたオートクレーブ中に、変性ポリオレフィン樹脂(6)191部、変性ポリオレフィン樹脂(7)34部、ポリオキシエチレン8モル付加オレイルエーテル53部、およびジエタノールアミン22部を仕込み、窒素ガス還流、撹拌下で180~190℃まで昇温した。ついで撹拌下水700部を徐々に投入、180~190℃で2時間撹拌し、内容物を均一溶解した。その後常温まで冷却し、水分調整を行い、不揮発分30重量%の水エマルジョンであるPP-21を得た。
〔製造例C1〕
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。得られた芳香族系ポリエステル樹脂のNMRによる組成分析結果は以下の通りであった。
イソフタル酸 49モル%
ジエチレングリコール 50モル%
5-ナトリウムスルホイソフタル酸 1モル%
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PE-1を得た。
反応器中に窒素ガスを封入下、テレフタル酸498部、イソフタル酸332部、エチレングリコール248部、ジエチレングリコール106部、テトラメチレングリコール45部およびジブチル錫オキサイド0.2部を仕込み、190~240℃で10時間エステル化反応を行い、芳香族ポリエステルポリオールを得た。次に、得られた芳香族ポリエステルポリオール1000部を120℃で減圧により脱水し、80℃まで冷却後、メチルエチルケトン680部を仕込み撹拌溶解した。引き続きイソホロンジイソシアネート218部および鎖伸張化剤として2,2-ジメチロールプロピオン酸67部を仕込み、70℃で12時間ウレタン化反応を行った。反応終了後、40℃まで冷却し、13.6%アンモニア水97部を加えて中和反応後、水2950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30重量%の水エマルジョンである芳香族ポリエステル系ウレタン樹脂PU-1を得た。
PP-1を水で希釈して、不揮発分濃度15重量%のサイジング剤エマルジョンを調製し、サイジング剤未処理炭素繊維ストランド(繊度800tex、フィラメント数12000本)を浸漬・含浸させた後、105℃で15分間熱風乾燥させて、理論付着量が5%であるサイジング剤処理炭素繊維ストランドを得た。本ストランドについて、前述の方法によりマトリックス樹脂接着性を評価した。その結果を表3に示した。
実施例1において、表3~5に示すサイジング剤不揮発分組成になるように、不揮発分濃度15重量%のサイジング剤エマルジョンを調製した以外は実施例1と同様にして、サイジング剤処理炭素繊維ストランドを得た。各特性値の評価結果を表3~5に示した。なお、表3~5に示すサイジング剤不揮発分組成は、不揮発分全体に占める各エマルジョンPP-1~PP-21、PE-1、PU-1の不揮発分の割合を示す。
Claims (12)
- 熱可塑性マトリックス樹脂を補強するために用いられる強化繊維用サイジング剤であって、
変性ポリプロピレン樹脂と、分子構造内に2個以上の水酸基または分子構造内に2個以上のアミノ基を有するアミン化合物との中和物を必須に含み、
サイジング剤の不揮発分を示差走査熱量計(DSC)で測定したときの融解吸熱量が50J/g以下である、強化繊維用サイジング剤。 - サイジング剤の不揮発分全体に対して、前記変性ポリプロピレン樹脂を10~90重量%、前記アミン化合物を1~20重量%の割合で配合して調製したものである、請求項1に記載の強化繊維用サイジング剤。
- 前記アミン化合物の沸点が240~340℃である、請求項1または2に記載の強化繊維用サイジング剤。
- 前記アミン化合物が、下記一般式(1)および/または下記一般式(2)で示される化合物である、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。
R1N(CH2CH2OH)2 (1)
(式中R1は、水素原子、-CH2CH2OH、炭素数1~10の脂肪族炭化水素基、または炭素数1~18の脂肪酸からOH基を除いた残基である。)
NH2R2NH(CH2CH2OH) (2)
(式中R2は、炭素数1~4の脂肪族炭化水素基である。) - 前記変性ポリプロピレン樹脂を示差走査熱量計(DSC)で測定したときの融解吸熱量が70J/g以下である、請求項1~4のいずれかに記載の強化繊維用サイジング剤。
- 前記変性ポリプロピレン樹脂の酸価が20~80KOHmg/gである、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。
- さらに芳香族系ポリエステル樹脂および芳香族ポリエステル系ウレタン樹脂から選ばれる少なくとも1種のポリマー成分(A)を、サイジング剤の不揮発分全体に対して5~80重量%含有する、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。
- 前記熱可塑性マトリックス樹脂が、ポリオレフィン系樹脂である、請求項1~7のいずれかに記載の強化繊維用サイジング剤。
- さらに水を含有し、前記中和物が水に分散した状態または水に溶解した状態である、請求項1~8のいずれかに記載の強化繊維用サイジング剤。
- 原料合成繊維ストランドに対して、請求項1~9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、合成繊維ストランド。
- 前記合成繊維が、炭素繊維、アラミド繊維、ポリエチレン繊維、ポリエチレンテレフタレート繊維、ポリブチレンテレフタレート繊維、ポリエチレンナフタレート繊維、ポリアリレート繊維、ポリアセタール繊維、PBO繊維、ポリフェニレンサルフィド繊維およびポリケトン繊維から選ばれる少なくとも1種である、請求項10に記載の合成繊維ストランド。
- 熱可塑性マトリックス樹脂と請求項10または11に記載の合成繊維ストランドを含む、繊維強化複合材料。
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JP2015180785A (ja) * | 2014-03-05 | 2015-10-15 | 三菱レイヨン株式会社 | 樹脂強化用炭素繊維束、並びに、樹脂強化用炭素繊維束、炭素繊維強化熱可塑性樹脂組成物及び成形体の製造方法 |
WO2016114352A1 (ja) * | 2015-01-16 | 2016-07-21 | 三井化学株式会社 | 強化繊維束及びそれを用いた炭素繊維強化熱可塑性樹脂成形体、並びに強化繊維束の製造方法 |
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DE112013001737B4 (de) | 2012-03-29 | 2023-05-11 | Matsumoto Yushi-Seiyaku Co., Ltd. | Schlichtemittel für Verstärkungsfasern, Kunstfaserstrang und faserverstärktes Verbundmaterial |
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JP4989790B2 (ja) | 2012-08-01 |
KR101838909B1 (ko) | 2018-03-16 |
JPWO2012017877A1 (ja) | 2013-10-03 |
CN103052748B (zh) | 2015-01-21 |
US20130123407A1 (en) | 2013-05-16 |
KR20130099922A (ko) | 2013-09-06 |
DE112011102624T5 (de) | 2013-05-08 |
CN103052748A (zh) | 2013-04-17 |
US9068054B2 (en) | 2015-06-30 |
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