JPS62198695A - Production of thermally reactive sugar etherified substance and modifier for synthetic fiber - Google Patents
Production of thermally reactive sugar etherified substance and modifier for synthetic fiberInfo
- Publication number
- JPS62198695A JPS62198695A JP4264586A JP4264586A JPS62198695A JP S62198695 A JPS62198695 A JP S62198695A JP 4264586 A JP4264586 A JP 4264586A JP 4264586 A JP4264586 A JP 4264586A JP S62198695 A JPS62198695 A JP S62198695A
- Authority
- JP
- Japan
- Prior art keywords
- water
- examples
- agent
- group
- synthetic fibers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002994 synthetic fiber Polymers 0.000 title claims abstract description 46
- 239000012209 synthetic fiber Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000003607 modifier Substances 0.000 title claims description 8
- 239000000126 substance Substances 0.000 title abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 48
- 229920001542 oligosaccharide Polymers 0.000 claims abstract description 20
- 150000002482 oligosaccharides Chemical class 0.000 claims abstract description 20
- 150000004676 glycans Chemical class 0.000 claims abstract description 19
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 19
- 239000005017 polysaccharide Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 67
- 238000006266 etherification reaction Methods 0.000 claims description 35
- 239000004744 fabric Substances 0.000 claims description 14
- -1 urethane compound Chemical group 0.000 abstract description 32
- 150000001875 compounds Chemical class 0.000 abstract description 30
- 239000005056 polyisocyanate Substances 0.000 abstract description 13
- 229920001228 polyisocyanate Polymers 0.000 abstract description 13
- 239000002981 blocking agent Substances 0.000 abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 5
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 abstract description 3
- LHORZPMPPHTXFQ-UHFFFAOYSA-N 1-chloroethanesulfonic acid Chemical compound CC(Cl)S(O)(=O)=O LHORZPMPPHTXFQ-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001720 carbohydrates Chemical class 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 abstract description 2
- 125000005843 halogen group Chemical group 0.000 abstract description 2
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 abstract 4
- 150000001450 anions Chemical class 0.000 abstract 2
- 241000047703 Nonion Species 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 238000007363 ring formation reaction Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 35
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000007787 solid Substances 0.000 description 25
- 229920000728 polyester Polymers 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000012948 isocyanate Substances 0.000 description 12
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 11
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 125000000129 anionic group Chemical group 0.000 description 9
- 238000004043 dyeing Methods 0.000 description 9
- 229920005862 polyol Polymers 0.000 description 9
- 125000002091 cationic group Chemical group 0.000 description 8
- 229920002678 cellulose Polymers 0.000 description 8
- 239000001913 cellulose Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000975 dye Substances 0.000 description 8
- 150000003944 halohydrins Chemical class 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 150000003077 polyols Chemical class 0.000 description 8
- 241000238557 Decapoda Species 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
- 239000000985 reactive dye Substances 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical group [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 3
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 3
- 229940008406 diethyl sulfate Drugs 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 229940050176 methyl chloride Drugs 0.000 description 3
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 125000001302 tertiary amino group Chemical group 0.000 description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- VZIQXGLTRZLBEX-UHFFFAOYSA-N 2-chloro-1-propanol Chemical compound CC(Cl)CO VZIQXGLTRZLBEX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000000986 disperse dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- JZQGUNMRCOTWIQ-UHFFFAOYSA-N oxiran-2-ylmethanamine;hydrochloride Chemical compound [Cl-].[NH3+]CC1CO1 JZQGUNMRCOTWIQ-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 1
- AKANXUIAFDKRMU-UHFFFAOYSA-N 1-aminoethanesulfonic acid;sodium Chemical compound [Na].CC(N)S(O)(=O)=O AKANXUIAFDKRMU-UHFFFAOYSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- GECPBKDVIFOEIV-UHFFFAOYSA-N 2,4-diisocyanato-1-methylbenzene 2-ethyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound CC=1C(N=C=O)=CC(N=C=O)=CC1.CC=1C(N=C=O)=CC(N=C=O)=CC1.CC=1C(N=C=O)=CC(N=C=O)=CC1.C(O)C(CC)(CO)CO GECPBKDVIFOEIV-UHFFFAOYSA-N 0.000 description 1
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- RUUHDEGJEGHQKL-UHFFFAOYSA-M 2-hydroxypropyl(trimethyl)azanium;chloride Chemical compound [Cl-].CC(O)C[N+](C)(C)C RUUHDEGJEGHQKL-UHFFFAOYSA-M 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- MBCUNESSWNAVFL-UHFFFAOYSA-N C=C.C=C.C=C.N=C=O.N=C=O Chemical compound C=C.C=C.C=C.N=C=O.N=C=O MBCUNESSWNAVFL-UHFFFAOYSA-N 0.000 description 1
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- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
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- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
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- 238000009940 knitting Methods 0.000 description 1
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- 230000000116 mitigating effect Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- SFKTYEXKZXBQRQ-UHFFFAOYSA-J thorium(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Th+4] SFKTYEXKZXBQRQ-UHFFFAOYSA-J 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】 成繊維、半合成繊維用改質剤に関する。[Detailed description of the invention] This invention relates to a modifier for synthetic fibers and semi-synthetic fibers.
従来より、多゛糖類、オリゴ糖類及びそれらの誘導体と
有機ポリイソシアネート化合物の反応についての提案は
１通常のウレタン化同様非水系、かつ有機溶剤下で行な
われる方法が一般的であった・
ポリエステル系、ポリアミド系、ポリアクリロニトリル
系、ポリオレフィン系、ポリアセテート系などの合成繊
維、半合ｅｔａ維は均質であり、強度、耐久性、耐薬品
性などの物性が優れていることから、近年その生［ｔや
需要量は綿、ウール、絹などの天然ｍＩａを上回るほど
に成長してきたが、吸水、吸湿性の不足や繊維表面の不
活性さや内部構造の緻密さに基づく接着性や染色性不足
など更に改良、改質が望まれる物性面も有している。こ
れらの合成繊維、半合成Ｉａｒａに対する改良、改質技
術としては、各種の目的、用途において種々の試み、提
案がなされているが、いまだ不充分なものが多い。Conventionally, proposals for the reaction of polysaccharides, oligosaccharides, and their derivatives with organic polyisocyanate compounds have generally been carried out in a non-aqueous and organic solvent, similar to ordinary urethanization. , polyamide-based, polyacrylonitrile-based, polyolefin-based, polyacetate-based synthetic fibers, and semi-synthetic eta fibers are homogeneous and have excellent physical properties such as strength, durability, and chemical resistance. The demand for mIa has grown to the extent that it exceeds that of natural mIa such as cotton, wool, and silk. It also has physical properties that require further improvement and modification. Various attempts and proposals have been made to improve and modify these synthetic fibers and semi-synthetic Iara for various purposes and uses, but many are still insufficient.
例えば、ポリエステル系、ポリアミド系！ａ雄に耐久性
のある吸水性を付与させるため、ポリエチレンオキサイ
ド鎖を主体とする重合性化合物を後加工することが提案
されているが、それらのほとんどが分散染料での染色堅
牢度、特に摩擦堅牢度の著しい低下を伴うという欠点を
有しており、またこれらの化合物では実質的に吸湿性を
与えるまでには至らなかった。For example, polyester and polyamide! It has been proposed to post-process polymerizable compounds mainly consisting of polyethylene oxide chains in order to impart durable water absorbency to a-mole, but most of these have been found to be difficult to improve dyeing fastness with disperse dyes, especially abrasion. These compounds have the disadvantage of being accompanied by a significant decrease in fastness, and these compounds have not been able to provide substantial hygroscopicity.
また、合成繊維の中で特にポリエステル繊維は構造が緻
密であり、官能基も少ないことからイオン性染料や反応
性染料で染色することができず、唯一染色可能な分散染
料ですら １３０℃以上という高温下でしか染着しなか
った。この点については、アニオン基含有二塩基酸又は
それらの誘導体などの共重合でカチオン染料可染型ポリ
エステルやポリエチレンオキサイド鎖含有グリコールな
どの共重合により、ボイル染色を可能にならしむる様に
工夫した易染性ポリエステル繊維などが登場してきてい
るが、これらは特殊原料の使用によるコストアップや強
度などの物性面の低下を伴うことや低温染色化しえたと
しても実質的には１００〜１２０℃の高温染色がなされ
ているのが実情である。Furthermore, among synthetic fibers, polyester fiber has a particularly dense structure and has few functional groups, so it cannot be dyed with ionic dyes or reactive dyes, and even the only disperse dye that can be dyed has a temperature exceeding 130℃. Dyeing only occurred at high temperatures. Regarding this point, we have devised a way to make boil dyeing possible by copolymerizing dibasic acids containing anionic groups or their derivatives with cationic dye-dyable polyesters and glycols containing polyethylene oxide chains. Easily dyed polyester fibers have appeared, but these require increased costs and decreased physical properties such as strength due to the use of special raw materials, and even if they can be dyed at low temperatures, they are practically dyed at high temperatures of 100 to 120°C. The reality is that it is dyed.
更には、タイヤコード、ベルトコード又は重布、合成皮
革製造時などの強化材として、ポリエステル系やポリオ
レフィン系等の合成ｍ維を利用する場合にそのｍ雄表面
に官能基がないことや緻密な表面組織になっていること
のため各種樹脂類との接着性が乏しく、しばしば問題に
なっているのが現状である。Furthermore, when synthetic fibers such as polyester or polyolefin fibers are used as reinforcing materials in the production of tire cords, belt cords, heavy fabrics, and synthetic leathers, it is important to note that there are no functional groups on the surface of the fibers, and there are no dense fibers. Due to its surface texture, it has poor adhesion with various resins, which is often a problem.
例えば、タイヤコードではゴムとの接着剤であるレゾル
シンフォルマリンラテックスとの親和性が悪いために、
各種の前処理が検討されているが、充分満足されるに至
っていない。For example, tire cords have a poor affinity with resorcin formalin latex, which is an adhesive for rubber.
Although various pretreatments have been considered, they have not yet been fully satisfied.
本発明により予めブロック化イソシアネート基を含有す
るエーテル化剤を合成しておき、それを用いて多糖類、
オリゴ糖類、単糖類及びそれらの誘導体に、ブロック化
イソシアネート基を導入せしめることは、このような化
合物の合成技術として新しい！想で合成しえたものであ
り、もちろんこれは有機溶剤下でも可能であるが、それ
以上に最も安全な水系でも、又はエタノール、ＩＰＡｈ
Ｉ？のアルコール溶剤／水系でも反応の実施を可能にし
えたことが最大の特徴であり、工業的規模での製造に際
しては、安全性と低コスト化に大なる効果を有する製法
となる０本発明は、合成繊維、半合成ｍ雑木来の性質を
損なわず、合成ｔａ維、半合成繊維の表面を化学的に改
質して合成繊維の吸湿、場１七吸水性、保水性、染色性
、他物質に対する親和性、更には溶融性等を改質しよう
とするものである。According to the present invention, an etherifying agent containing a blocked isocyanate group is synthesized in advance, and using it, polysaccharides,
Introducing blocked isocyanate groups into oligosaccharides, monosaccharides, and their derivatives is a new synthetic technology for such compounds! Of course, this is possible in an organic solvent, but even more so in an aqueous system, which is the safest, or in ethanol, IPAh, etc.
I? The greatest feature of the present invention is that it enables the reaction to be carried out even in an alcohol solvent/water system, and it is a manufacturing method that is highly effective in terms of safety and cost reduction when manufacturing on an industrial scale. Chemically modifying the surface of synthetic fibers and semi-synthetic fibers without impairing the properties of synthetic fibers and semi-synthetic fibers to improve moisture absorption, water retention, dyeability, and other substances of synthetic fibers The aim is to improve the affinity for, as well as the meltability, etc.
例えば、本発明は従来のポリエチレンオキサイド鎖を主
体とする化合物を用いて合成繊維に吸水性能を与えよう
とする場合に生ずる。For example, the present invention arises when an attempt is made to impart water absorption performance to synthetic fibers using conventional compounds mainly consisting of polyethylene oxide chains.
■吸水性は与えるが、吸湿性、保水性を与えるまでに至
らない、■染色堅牢度の低下が著しく染色堅牢度の良好
な染料を用いたものしか使用できない等の欠点を解決す
るためになされたものである。■ It provides water absorption, but does not provide hygroscopicity or water retention, and ■ Color fastness is significantly reduced, and only dyes with good color fastness can be used. It is something that
更に、本発明改質剤、改質技術は、合成繊維、特にポリ
エステル表面を耐久性のある糖エーテル化物で被覆する
ため、ポリエステル表面にヒドロキシル基を付与するこ
とができ１例えば反応性染料の如く１００℃以下という
比較的低エネルギー下で、染色可能な染料による染色を
可能にし、また例えばレゾルシン−ホルマリンラテック
スとの接触性を容易にする。Furthermore, the modifier and modification technology of the present invention coats the surface of synthetic fibers, especially polyester, with a durable sugar etherified product, so it is possible to add hydroxyl groups to the polyester surface. It enables dyeing with dyes that can be dyed under relatively low energy of 100°C or less, and also facilitates contact with, for example, resorcinol-formalin latex.
更に本発明は合成繊維の持つ摩擦又は熱による溶融性を
改良するためになされたものである。Furthermore, the present invention has been made to improve the meltability of synthetic fibers due to friction or heat.
本発明は、多糖類、オリゴ糖類及びそれらの誘導体とブ
ロック化イソシアネート基含有エーテル化剤とを反応さ
せて得られる水溶性又は水分散性で、かつ熱反応性の糖
エーテル化物の製法であり、かつ前記糖エーテル化物を
合成繊維、半合成繊維の糸に付着させ、又は合成繊維布
帛に付着させ、熱処理を行なうことを特徴とする合成ｍ
１１１、半合成繊維用改質剤に関するものである。The present invention is a method for producing a water-soluble or water-dispersible, heat-reactive sugar etherified product obtained by reacting polysaccharides, oligosaccharides, and their derivatives with a blocked isocyanate group-containing etherification agent, and a synthetic m characterized in that the sugar etherified product is attached to a thread of synthetic fiber or semi-synthetic fiber, or attached to a synthetic fiber cloth, and then heat-treated.
No. 111 relates to modifiers for semi-synthetic fibers.
本発明は、多糖類、オリゴ糖類及びそれらの誘導体とブ
ロック化イソシアネート基含有エーテル化剤とを反応さ
せて成る水溶性又は水分散性で、かつ熱反応性の糖エー
テル化物を新規なエーテル化剤を用いることにより、こ
れまで有機溶剤系のみでしか行ない得なかったものを水
系からも製造しうる方法を与えるものである。The present invention provides a novel etherification agent for converting a water-soluble or water-dispersible and heat-reactive sugar etherification product by reacting polysaccharides, oligosaccharides, and their derivatives with an etherification agent containing blocked isocyanate groups. By using this method, it is possible to produce from an aqueous system what was previously only possible using an organic solvent system.
以下上配糖エーテル化物の製法について説明する。The method for producing the supersugar etherified product will be described below.
前記多糖類、オリゴ糖類及びそれらの誘導体としては１
例えば、スターチ、デキストリン、タマリンドガム、グ
アーガム、セルロース、キトサン、マルトース、トレハ
ロース、ゲンチオビオール、シヨ糖などの多糖類、オリ
ゴ糖類があげられる。The polysaccharides, oligosaccharides and derivatives thereof include 1
Examples include polysaccharides and oligosaccharides such as starch, dextrin, tamarind gum, guar gum, cellulose, chitosan, maltose, trehalose, gentiobiol, and sucrose.
更に上記多糖類、オリゴ糖類の誘導体としては、例えば
、上記多糖類、オリゴ糖類にモノクロル酢酸、モノクロ
ルエタンスルホン酸なとアニオン化剤を通常の方法によ
り置換させた誘導体、又はエチレンオキサイド、プロピ
レンオキサイド、ブチレンオキサイドなどのフルキレン
オキサイドを通常の方法により付加させた誘導体、又は
メチルクロライドを置換させて成る誘導体、又はメチル
クロライドをご換させ、かつ上記アルキレンオキサイド
を付加させた誘導体、又は３−クロロ−２−ヒドロキシ
プロピルトリメチルアンモニウムクロライド、グリシジ
ルアンモニウムクロライドなどカチオン化剤を置換又は
付加させて成る誘導体があげられる。Furthermore, the derivatives of the above polysaccharides and oligosaccharides include, for example, derivatives obtained by substituting the above polysaccharides and oligosaccharides with an anionizing agent such as monochloroacetic acid and monochloroethanesulfonic acid by a conventional method, or ethylene oxide, propylene oxide, A derivative obtained by adding a fullylene oxide such as butylene oxide by a conventional method, a derivative obtained by substituting methyl chloride, a derivative obtained by replacing methyl chloride and adding the above alkylene oxide, or a 3-chloro- Examples include derivatives substituted with or added with a cationizing agent such as 2-hydroxypropyltrimethylammonium chloride and glycidylammonium chloride.
なお、セルロースにモノクロル酢酸を反応すせた具体例
にはカルボキシメチルセルロースがあげられ、またアル
キレンオキサイドを付加させた具体例には、ヒドロキシ
エチルセルロース、ヒドロキシプロピルセルロース、ヒ
ドロキシブチルセルロースがあげられ、更にアルキレン
オキサイド部分が重付加されたものがあげられる。また
、メチルクロライドを置換させた具体例としては、メチ
ルセルロースがあげられ、またメチルクロライドを置換
させ、かつアルキレンオキサイドを付加させた具体例と
しては、メチルヒドロキシエチルセルロース、メチルヒ
ドロキシプロピルセルロースがあげられ、また３−クロ
ロ−２−ヒドロキシプロピルトリメチルアンモニウムク
ロライド、グリシジルアンモニウムクロライド等を置換
又は付加させた具体例としてはカチオン化セルロースが
あげられる。Specific examples of cellulose reacted with monochloroacetic acid include carboxymethyl cellulose, and specific examples of cellulose added with alkylene oxide include hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxybutyl cellulose, and alkylene oxide. Examples include those with multiple parts added. Specific examples of methyl chloride substituted include methyl cellulose; specific examples of methyl chloride substituted and alkylene oxide added include methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, and methyl hydroxypropyl cellulose. Specific examples of substituted or added 3-chloro-2-hydroxypropyltrimethylammonium chloride, glycidyl ammonium chloride, etc. include cationized cellulose.
本発明に使用されるブロック化イソシアネート基含有エ
ーテル化剤は、次のような一般構造式を有し、疎水性前
記エーテル化剤と親水性前記エーテル化剤とがある。The blocked isocyanate group-containing etherification agent used in the present invention has the following general structural formula, and includes the hydrophobic etherification agent and the hydrophilic etherification agent.
（Ｘ−Ｒ−０００ＩＮ）ａ −Ａ −（ＮＨＣＯＢ）ｂ
（ＮＨＣＯＹ）ｃ
Ａ：有機ポリイソシアネートモノマー又は遊離のイソシ
アネート基を有するウレタン化合物残基
Ｂ：熱処理によりイソシアネート基を再生するブロッキ
ング剤残基
Ｘ：ハロゲン基
Ｒ：フルキレンハロヒドリン、エビハロヒドリン開環誘
導体の化合物残基
Ｙ：少なくとも活性水素を １個有し、同一分子内にア
ニオン基又はカチオン基又は非イオン基を有する化合物
残基
ａ、ｂ： １以上の整数
ａ＋ ｂ＋ ｃ＝ ２以上の整数
Ｃ：０以上の整数
上記の内、疎水性のブロック化イソシアネート基含有エ
ーテル化剤は、有機ポリイソシアネート、又は遊離のイ
ソシアネート基を有するウレタン化合物と、熱処理によ
りイソシアネート基を再生するブロッキング剤との反応
により得られる遊離イソシアネート基を有するブロック
化ウレタン化物とアルキレンハロヒドリン又はエピハロ
ヒドリンの開環誘導体を反応することにより得られる。(X-R-000IN)a -A-(NHCOB)b
(NHCOY)c A: Organic polyisocyanate monomer or urethane compound residue having a free isocyanate group B: Blocking agent residue that regenerates isocyanate groups by heat treatment X: Halogen group R: Flukylene halohydrin, ring-opened derivative of shrimp halohydrin Compound residue Y: Compound residue a, b having at least one active hydrogen and an anionic group, a cationic group, or a nonionic group in the same molecule: a + b + c = an integer of 2 or more C : An integer greater than or equal to 0 Among the above, the hydrophobic blocked isocyanate group-containing etherifying agent is obtained by reacting an organic polyisocyanate or a urethane compound having a free isocyanate group with a blocking agent that regenerates the isocyanate group by heat treatment. It is obtained by reacting the resulting blocked urethane compound having free isocyanate groups with a ring-opened derivative of alkylene halohydrin or epihalohydrin.
前記有機ポリイソシアネートモノマーとしては、トルエ
ンジイソシアネート、ジフェニルメタンジイソシアネー
トなど芳香族イソシアネート、ヘキサメチレンジイソシ
アネート、Ｈ１２ＭＤ１． イソホロンジイソシアネ
ートなどの脂肪族又は脂環式イソシアネート類、本シリ
レンジイソシアネートなどの芳香脂肪族イソシアネート
類、更にはビューレフト化へキサメチレンジイソシアネ
ート、トリメチロールプロパントリトルエンジイソシア
ネートアダクトなどの誘導体があげられる。Examples of the organic polyisocyanate monomer include aromatic isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate, hexamethylene diisocyanate, H12MD1. Examples include aliphatic or cycloaliphatic isocyanates such as isophorone diisocyanate, aromatic aliphatic isocyanates such as the present silylene diisocyanate, and further derivatives such as biurefted hexamethylene diisocyanate and trimethylolpropane tritoluene diisocyanate adduct.
更に、遊離イソシアネート基を有するウレタン化合物と
しては、一般にウレタン製造に用いられる活性水素を２
個以上含有する化合物と有機ポリイソシアネートモノマ
ーとを通常の方法によりイシソアネート基／活性水素基
の比が、イソシアネート基が過剰になるようにして反応
させて得られるイソシアネート基を有するプレポリマー
があげられる。Furthermore, as a urethane compound having a free isocyanate group, active hydrogen, which is generally used for urethane production, is
Examples include prepolymers having isocyanate groups, which are obtained by reacting a compound containing at least 100 isocyanate groups with an organic polyisocyanate monomer in a conventional manner such that the ratio of isocyanate groups to active hydrogen groups is such that the isocyanate groups are in excess.
前記活性水素を２個以上含有する化合物としては、例え
ば、アルキレンオキサイドの付加重合により得られるポ
リエーテルポリオールやポリエステルポリオール、３級
アミノ基含有ポリオールあるいは同一分子内に４級化カ
チオン基を１個以上含有するポリオール、例えば、トリ
エタノールアミンやＮ−メチルジェタノールアミンなど
のフルキレンオキサイドを付加重合した３級アミノ基含
有ポリエーテルの３級アミ７基をジエチル硫酸などで４
級化したポリオールなと、更に特殊な例としては有機シ
リコン系ポリオール、有機弗素系ポリオール等があげら
れるが、これらに限定されるものではない。Examples of the compound containing two or more active hydrogens include polyether polyols and polyester polyols obtained by addition polymerization of alkylene oxide, polyols containing tertiary amino groups, or one or more quaternized cation groups in the same molecule. The 7 tertiary amino groups of a tertiary amino group-containing polyether obtained by addition polymerization of a polyol containing, for example, fullkylene oxide such as triethanolamine or N-methyljetanolamine, are treated with diethyl sulfate or the like.
More specific examples of graded polyols include, but are not limited to, organosilicon polyols and organofluorine polyols.
なお、使用する前記有機ポリイソシアネートモノマーと
しては、本加工剤が、衣料用途を対象とする場合には、
無黄変である必要があり、これらの観点からキシリレン
ジイソシアネートなどの芳香脂肪族イソシアネート、イ
ンホロンジイソシアネートなどの脂環式イソシアネート
、ヘキサメチレンジイソシアネートなどの脂肪族イソシ
アネートなどが好ましい。In addition, as the organic polyisocyanate monomer to be used, when this processing agent is intended for clothing use,
It is necessary to be non-yellowing, and from these viewpoints, aromatic aliphatic isocyanates such as xylylene diisocyanate, alicyclic isocyanates such as inphorone diisocyanate, aliphatic isocyanates such as hexamethylene diisocyanate, etc. are preferable.
前記熱処理により、イソシアネート基を再生するブロッ
キング剤（一般式■、Ｂ ）としては、例えば、水溶性
又は水分散性を有し得ない２級又は３級アルコール類、
活性メチレン化合物、フェノール類、ハロゲン化フェノ
ール類、オキシム類、ラクタム類イミダゾール類、があ
げられ、一方、水溶性又は水分散性を有るものとしては
、重亜硫酸塩があげられる。The blocking agent (general formula ①, B) that regenerates isocyanate groups by the heat treatment includes, for example, secondary or tertiary alcohols that cannot be water-soluble or water-dispersible;
Examples include active methylene compounds, phenols, halogenated phenols, oximes, lactams, and imidazoles, while examples of water-soluble or water-dispersible substances include bisulfites.
前記の水溶性又は水分散性を有し得ないブロッキング剤
と前記有機ポリイソシアネートとの反応による前記遊離
ポリイソシアネート基を有するブロック化ウレタン物の
製造は、その製造に際して有機ポリイソシアネート１分
子中の少なくともイソシアネート基１個をブロックする
ことが好ましく、これらの反応は一般に知られているよ
うに、通常のウレタン化触媒やアルカリ金属のアルコラ
ードのごとき触媒の存在下あるいは無触媒下で、常温以
上、かつ１００℃以下で行なわれる。In the production of the blocked urethane product having free polyisocyanate groups by the reaction of the blocking agent that cannot be water-soluble or water-dispersible with the organic polyisocyanate, at least one molecule of the organic polyisocyanate is It is preferable to block one isocyanate group, and as is generally known, these reactions are carried out at room temperature or higher and at It is carried out at temperatures below ℃.
なお１反応系粘度、均一性、溶解性などの点から、必要
に応じて有機溶剤を使用しても良く、使用する有機溶剤
としては、イソシアネートと不活性である必要があり、
特にジオキサン、メチルエチルケトン、ジチメルホルム
アミド、ジメチルスルホキシド、などの親水性溶剤が好
ましい。Note that from the viewpoint of 1. reaction system viscosity, uniformity, solubility, etc., an organic solvent may be used as necessary, and the organic solvent used must be inert with the isocyanate.
Particularly preferred are hydrophilic solvents such as dioxane, methyl ethyl ketone, dithymelformamide, and dimethyl sulfoxide.
次いで、以上で製造された遊離イソシアネート基を有す
るブロック化ウレタン物とアルキレンハロヒドリン又は
エピハロヒドリン開環誘導体との反応を行軽うか、この
順序は逆でも良い。Next, the blocked urethane product having free isocyanate groups produced above is reacted with an alkylene halohydrin or an epihalohydrin ring-opened derivative, or the order may be reversed.
ブロック化イソシアネート基含有エーテル化剤の製造に
使用されるアルキレンハロヒドリン又はエピハロヒドリ
ン開環誘導体としては、エチレンクロルヒドリン、エチ
レンブロムヒドリンプロピレンクロルヒドリン、プロピ
レンジクロルヒドリン、エピクロルヒドリン、又はエピ
ブロムヒドリンにエチレンオキサイド、プロピレンオキ
サイドを反応させたエピハロヒドリンのアルキレンオキ
サイド付加体等があげられる。The ring-opened alkylene halohydrin or epihalohydrin derivatives used in the production of the blocked isocyanate group-containing etherification agent include ethylene chlorohydrin, ethylene bromohydrin, propylene chlorohydrin, propylene dichlorohydrin, epichlorohydrin, or epibromohydrin. Examples include alkylene oxide adducts of epihalohydrin, which are made by reacting hydrin with ethylene oxide or propylene oxide.
これらの製造に際しては、遊離のイソシアネート基とフ
ルキレンハロヒドリン又はエビハロヒドリンの開環誘導
体の活性水素基の比は、 １．。In the production of these, the ratio of free isocyanate groups to active hydrogen groups of the ring-opened derivative of fullkylene halohydrin or shrimp halohydrin is 1. .
が好ましいが、反応速度の関係上、アルキレンハロヒド
リン又はエビハロヒドリンの開環誘導体の活性水素基を
１．００〜１．２０としても良い。However, in view of the reaction rate, the active hydrogen group of the ring-opened derivative of alkylene halohydrin or shrimp halohydrin may be set to 1.00 to 1.20.
なお、上記ブロッキング剤において、重亜Ｉ＆酸塩を用
いる場合は、後に記すが、有機ポリイソシアネートと前
記アルキレンハロヒトリンスはエビハロヒドリンの開環
誘導体を有機ポリイソシアネートの少なくとも１個のイ
ソシアネート基と反応した後、残余のイソシアネートと
当量か又は １．３倍モルの範囲で重亜硫酸塩と反応さ
せる工程を取る。In the above-mentioned blocking agent, in the case of using I bienite and an acid salt, as will be described later, the organic polyisocyanate and the alkylene halohydrin are prepared by reacting a ring-opened derivative of shrimp halohydrin with at least one isocyanate group of the organic polyisocyanate. After that, a step is taken to react with bisulfite in an equivalent amount or 1.3 times the mole of the remaining isocyanate.
次に親水性のブロック化イソシアネート基含有エーテル
化剤は、有機ポリイソシアネート化合物又は遊はイソシ
アネート基を有するウレタン化物と、
■前記水溶性又は水分散性を有しないブロッキング剤と
、前記アルキレンハロヒドリン又ハエビハロヒドリンの
開環誘導体を反応させた後、残余のイソシアネート基と
前記少なくとも活性水素を１個有し、同一分子内に７ニ
オン性基又はカチオン性基又は非イオン性基を有する化
合物と反応したタイプ
■前記アルキレンハロヒドリン又はエピハロヒドリンの
開環誘導体を反応させた後、残余のイソシアネート基と
前記水溶性又は水分散性を有するブロー、キング剤であ
る重亜硫酸塩を反応したタイプ
■前記水溶性又は水分散性を有しないブロッキング剤と
、前記アルキレンハロヒドリン又はエビハロヒドリンの
開環誘導体を反応させた後、残余のイソシアネート基と
前記水溶性又は水分散性を有するブロッキング剤である
重亜硫酸塩を反応したタイプ
更に
■遊離イソシアネート基を有するウレタン化物の製造時
に使用される２個以上の活性水素を有する化合物として
、エチレンオキサイド重付加体又は２個以上の活性水素
を有し、かつアニオン性基を有する化合物又は２個以上
の活性水素を、かつカチオン基を有する化合物を必須と
して製造される水溶性の遊離イソシアネート基を有する
ウレタン化物に、前記アルキレンハロヒドリン又はエピ
ハロヒドリンの開環誘導体及び前記ブロッキング剤を反
応させたタイプ
とがある。Next, the hydrophilic blocked isocyanate group-containing etherifying agent is an organic polyisocyanate compound or a urethane compound having free isocyanate groups; (1) the blocking agent that is not water-soluble or water-dispersible; and the alkylene halohydrin In addition, after reacting the ring-opened derivative of shrimp halohydrin, it has the remaining isocyanate group and at least one active hydrogen, and has 7 anionic group, cationic group, or nonionic group in the same molecule. A type that reacts with a compound ■ A type that reacts with the ring-opened derivative of the alkylene halohydrin or epihalohydrin, and then reacts the remaining isocyanate group with the water-soluble or water-dispersible blowing and kinging agent bisulfite. (2) The blocking agent that is not water-soluble or water-dispersible is reacted with the ring-opened derivative of alkylene halohydrin or shrimp halohydrin, and then the remaining isocyanate group is the blocking agent that is water-soluble or water-dispersible. Bisulfite-reacted type In addition: (1) As a compound having two or more active hydrogens used in the production of a urethane compound having a free isocyanate group, an ethylene oxide polyadduct or a compound having two or more active hydrogens, and A ring-opened derivative of the alkylene halohydrin or epihalohydrin is added to the urethane compound having a water-soluble free isocyanate group, which is produced by essentially including a compound having an anionic group or two or more active hydrogen atoms and a compound having a cationic group. and a type in which the above-mentioned blocking agent is reacted.
前記少なくとも活性水素を１個有し、同一分子内にアニ
オン性基を有する化合物としては、例えばアミノエタン
スルホン酸、アミノカルボン酸があげられる。Examples of the compound having at least one active hydrogen and an anionic group in the same molecule include aminoethanesulfonic acid and aminocarboxylic acid.
これらの内、アミノエタンスルホン酸、アミノカルボン
酸は、リチウム塩、ナトリウム塩、カリウム塩、アンモ
ニウム塩、トリエチルアミン塩とした後、水系下でイソ
シアネート基と反応される。なお１反応部度は常温〜５
０℃下で実施される。Among these, aminoethanesulfonic acid and aminocarboxylic acid are converted into lithium salt, sodium salt, potassium salt, ammonium salt, and triethylamine salt, and then reacted with an isocyanate group in an aqueous system. In addition, 1 reaction part temperature is room temperature ~ 5
It is carried out at 0°C.
前記少なくとも活性水素を１個有し、同一分子内にカチ
オン性基を有する化合物としては、例えばジメチルエタ
ノールアミン、ジエチルエタノールアミン等にジエチル
硫酸、塩化メチルなどで四級化した化合物があげられる
。これらとイソシアネート基との反応は、非水系下で必
要であれば、イソシアネートと不活性な前記有機溶剤下
で常温〜９５℃下で実施される。Examples of the compound having at least one active hydrogen and a cationic group in the same molecule include compounds obtained by quaternizing dimethylethanolamine, diethylethanolamine, etc. with diethyl sulfate, methyl chloride, etc. The reaction between these and the isocyanate group is carried out in a non-aqueous system, if necessary, in the presence of the isocyanate and the above-mentioned inert organic solvent at room temperature to 95°C.
前記少なくとも活性水素を１個有し、同一分子内に非イ
オン性基を有する化合物としては１例えばメタノール、
エタノール、ＩＰＡ等のモノアルコールにエチレンオキ
サイドを重付加させた化合物、フェノール、ノニルフェ
ノール等のフェノール類にエチレンオキサイドを重付加
させた化合物があげられる。これらとイソシアネート基
との反応は、非水系下で必要であれば、イソシアネート
と不活性な前記有機溶剤下で常温〜９５℃下で実施され
る。Examples of the compound having at least one active hydrogen and a nonionic group in the same molecule include methanol,
Examples include compounds in which ethylene oxide is polyadded to monoalcohols such as ethanol and IPA, and compounds in which ethylene oxide is polyadded to phenols such as phenol and nonylphenol. The reaction between these and the isocyanate group is carried out in a non-aqueous system, if necessary, in the presence of the isocyanate and the above-mentioned inert organic solvent at room temperature to 95°C.
前記水溶性又は水分散性を有するブロッキング剤である
重亜ＶＬ酸塩とイソシアネート基との反応は、水溶液の
状態でイソシアネート基と反応され、常温〜５０℃下で
実施される。この反応においては、エタノール、ＩＰＡ
、エチルセロソルブ、メチルエチルケトン、ジオキサン
等の親水性溶剤を加え実施することが好ましい。The reaction between the water-soluble or water-dispersible blocking agent, ie, the bienite VL salt, and the isocyanate group is carried out in the form of an aqueous solution at room temperature to 50°C. In this reaction, ethanol, IPA
It is preferable to add a hydrophilic solvent such as , ethyl cellosolve, methyl ethyl ketone, and dioxane.
前記水溶性の遊撃イソシアネート基を有するウレタン化
合物の製造に使用されるエチレンオキサイド重付加体と
しては、例えば、ポリエチレングリコールのごときポリ
エーテルポリオールがあげられる。また、活性水素を２
個以上有し、アニオン性基を有する化合物としては、例
えばジメチロールプロピオン酸があげられる。Examples of the ethylene oxide polyadduct used in the production of the urethane compound having a water-soluble mitigating isocyanate group include polyether polyols such as polyethylene glycol. In addition, active hydrogen is
Examples of compounds having anionic groups include dimethylolpropionic acid.
更に活性水素を２個以上有し、カチオン性基を有する化
合物としては１例えば、Ｎ−メチルジェタノールアミン
、トリエタノールアミンのジエチル硫酸、塩化メチルな
どにより四級化された化合物があげられる。Examples of compounds having two or more active hydrogen atoms and a cationic group include compounds obtained by quaternizing N-methyljetanolamine, triethanolamine with diethyl sulfate, methyl chloride, and the like.
これらとイソシアネート基との反応は、通常のウレタン
化と同様に実施される。The reaction between these and isocyanate groups is carried out in the same manner as usual urethanization.
以上で得られた水溶性の遊離イソシアネート基を有する
ウレタン化合物は１次に前記アルキレンハロヒドリン又
はエビハロヒドリンの開環誘導体及び前記ブロッキング
剤を反応させて、水溶性前記エーテル化剤が製造される
。The water-soluble urethane compound having free isocyanate groups obtained above is first reacted with the ring-opened derivative of alkylene halohydrin or shrimp halohydrin and the blocking agent to produce the water-soluble etherifying agent.
なお、ジメチロールプロピオン酸を使用した場合、エー
テル他剤反応終了後、そのカルボキシル基ノトリエチル
アミン、アンモニア、水酸化すトリウム、水酸化カリウ
ム、水酸化リチウム等で水和を行なう。In addition, when dimethylolpropionic acid is used, hydration is carried out with notriethylamine of the carboxyl group, ammonia, thorium hydroxide, potassium hydroxide, lithium hydroxide, etc. after the reaction with the ether and other agents is completed.
次いで、前記多糖類、オリゴ糖類及びそれらの誘導体と
以上で製造された前記ブロック化インシアネーＨ＆含有
エーテ′ル化剤との反応について説明する。Next, the reaction between the polysaccharide, oligosaccharide and their derivatives and the blocked incyane H&-containing etherifying agent produced above will be explained.
第−殴階として、使用するブロック化イソシアネート基
含有エーテル化剤と当量又はそれ以上の水酸化ナトリウ
ム又は水酸化カリウム等の水酸化アルカリの水溶液又は
トリエチルアミンのような有機アミンを多糖類、オリゴ
糖類及びそれらの誘導体に加え、混合する。なお、使用
する水酸化アルカリ、有機アミンは、使用するブロック
化イソシアネート基含有エーテル化剤に対して１．Ｑ〜
１．３倍モルが好ましい。As a first step, an aqueous solution of an alkali hydroxide such as sodium hydroxide or potassium hydroxide or an organic amine such as triethylamine is added to polysaccharides, oligosaccharides and Add to those derivatives and mix. Note that the alkali hydroxide and organic amine used are 1. Q~
1.3 times the mole is preferable.
更に反応系、粘度、均一性などの点から、あらかじめ多
ａｇ類、オリゴ糖類及びそれらの誘導体を水又は有機溶
剤−水混合溶媒に溶解又は懸濁させておいても良く、使
用する溶媒量は、多糖類、オリゴ糖類及びそれらの誘導
体に対して １〜２０倍量で使用される。Furthermore, from the viewpoint of reaction system, viscosity, uniformity, etc., polyags, oligosaccharides, and their derivatives may be dissolved or suspended in water or an organic solvent-water mixed solvent in advance, and the amount of solvent used may be determined by , polysaccharides, oligosaccharides and their derivatives.
また、使用する有機溶剤としては、ジオキサン、ジメチ
ルスルホキサイド、ジメチルホルムアミド、エタノール
、イソプロピルアルコール、メチルエチルケトン、セロ
ソルブアセテート等の親木性溶剤が好ましい０以上の工
程は。In addition, as the organic solvent used, wood-philic solvents such as dioxane, dimethyl sulfoxide, dimethylformamide, ethanol, isopropyl alcohol, methyl ethyl ketone, and cellosolve acetate are preferable in the 0 or more steps.
室温〜４０℃の範囲で１０〜１２０分を要し行なわれる
。この工程は、必ずしも必要ではないが、これに続くエ
ーテル化反応を促進するためには、この工程を入れる方
が好ましい。The process takes 10 to 120 minutes at a temperature ranging from room temperature to 40°C. Although this step is not absolutely necessary, it is preferable to include this step in order to promote the subsequent etherification reaction.
次いで、ブロックイソシアネート基含有エーテル化剤を
添加し、エーテル化反応を行う０通常、常温〜８０℃の
範囲で行なわれるが、ブロックイソシアネート基含有エ
ーテル化剤の加水分解反応の防止の観点より低温側が好
ましい、また、これらの反応は、水共存下で行なうが、
イソシアネート基は、ブロック化されているため安定で
ある。Next, a blocked isocyanate group-containing etherification agent is added and the etherification reaction is carried out. Usually, the reaction is carried out in the range of room temperature to 80°C, but from the viewpoint of preventing the hydrolysis reaction of the block isocyanate group-containing etherification agent, lower temperatures are preferred. Preferably, these reactions are carried out in the presence of water,
The isocyanate group is stable because it is blocked.
なお、ブロックイソシアネート基含有エーテル化剤の使
用においては、非水溶性多糖類、オリゴａ！ｉ類及びそ
れらの誘導体との反応には、前記水溶性のブロックイソ
シアネート基含有エーテル化剤を使用することとし、ま
た親水性多糖類、オリゴ糖類及びそれらの誘導体との反
応においては、前記水溶性の前記エーテル化剤及び疎水
性の前記エーテル化剤いずれも使用できる。ただし、多
糖類、オリゴ糖類の誘導体の内、アニオン性、カチオン
性の誘導体に前記水溶性エーテル化剤を用いる場合、非
イオン性のエーテル化剤を用いるか、同一のイオン性を
有する前記水溶性のエーテル化剤を用いることを原則と
する。In addition, when using the blocked isocyanate group-containing etherification agent, water-insoluble polysaccharides, oligo a! The water-soluble blocked isocyanate group-containing etherifying agent is used in the reaction with Group i and their derivatives, and the water-soluble etherifying agent is used in the reaction with hydrophilic polysaccharides, oligosaccharides, and their derivatives. Both the above-mentioned etherification agent and the above-mentioned hydrophobic etherification agent can be used. However, when using the water-soluble etherification agent for anionic or cationic derivatives among polysaccharide and oligosaccharide derivatives, use a nonionic etherification agent or use the water-soluble etherification agent with the same ionicity. In principle, use the following etherification agent.
ただし、前記水溶性のエーテル剤使用において、アニオ
ン性又はカチオン性のいずれかを過剰にすれば、混合系
も製造できる。However, when using the water-soluble ether agent, if either the anionic or cationic agent is used in excess, a mixed system can also be produced.
以上の反応工程により、多糖類、オリゴ糖類及びそれら
の誘導体にブロックイソシアネート基を導入した水溶性
又は水分散性で、かつ熱反応性の糖エーテル化物が製造
される。最後に上記反応終了後、過剰の塩基性化合物を
例えばリン酸、１ｉ！酸、硝酸、塩酸、又は酢酸、ギ酸
などの無機酸、有機酸で中和を行う。Through the above reaction steps, a water-soluble or water-dispersible, heat-reactive sugar etherified product in which blocked isocyanate groups are introduced into polysaccharides, oligosaccharides, and derivatives thereof is produced. Finally, after the above reaction is completed, remove the excess basic compound, for example, with phosphoric acid, 1i! Neutralize with acid, nitric acid, hydrochloric acid, or inorganic or organic acids such as acetic acid or formic acid.
以上のように合成した本発明に用いる糖エーテル化物は
、更に水稀釈され、水系で貯蔵されるが、イソシアネー
ト基がブロック化されているため安定である。The sugar etherified product synthesized as described above and used in the present invention is further diluted with water and stored in an aqueous system, but it is stable because the isocyanate groups are blocked.
本発明は、更に上記方法で合成した水溶性又は水分散性
、かつ熱反応性の糖エーテル化物を合成ｍ維、半合成繊
維の糸に付着させ、又は合成繊維、半合成繊維の布帛に
付着させ、しかる後に熱処理を行うことにより繊維上で
架橋し、合成繊維、半合成繊維の表面を化学的に改質し
て合成繊維の吸水、吸湿性、保水性、染色性、他基材と
の親和性、更には熱溶融性の改良等を与えるという目的
を達成するものである。The present invention further provides a method for attaching a water-soluble or water-dispersible, heat-reactive sugar etherified product synthesized by the above method to synthetic fibers or semi-synthetic fibers, or to a synthetic fiber or semi-synthetic fiber fabric. The surface of synthetic fibers and semi-synthetic fibers is chemically modified by cross-linking on the fibers by heat treatment, and improves the water absorption, hygroscopicity, water retention, dyeability, and compatibility with other substrates of synthetic fibers. This achieves the purpose of providing improved affinity and further improved thermal meltability.
なお、本発明の糖エーテル化物は１合成繊維、半合成繊
維に対して０．１％ｏｗｊ以上の付着量で実施される。The sugar etherified product of the present invention is applied in an amount of 0.1% owj or more per synthetic fiber or semi-synthetic fiber.
更に熱処理は１００〜２４０℃の範囲で実施される。Furthermore, heat treatment is carried out in the range of 100 to 240°C.
また、上記合成繊維、半合成繊維への付与は、本発明糖
エーテル化物の水溶液の浸漬法、コーティング法などが
適応される。In addition, the above-mentioned synthetic fibers and semi-synthetic fibers can be coated with a dipping method, a coating method, etc. with an aqueous solution of the sugar etherified product of the present invention.
次に本発明による改質性が得られる理由について説明す
る。Next, the reason why the modification property according to the present invention can be obtained will be explained.
耐久性については、熱反応性の糖エーテル化物が熱処理
によりイソシアネート基が再生され、架橋することによ
るものと考えられる。The durability is thought to be due to the isocyanate groups of the heat-reactive sugar etherified product being regenerated and crosslinked by heat treatment.
吸水、吸湿、保水性については、多Ｓ類、オリゴ糖類、
及びそれらの誘導体によるものと考えられる。更に染色
堅牢度に優れる利点は、合成繊維、半合成繊維の染色に
用いられる染料と上記糖類との一卵性の不良によるもの
と考えられる。Regarding water absorption, moisture absorption, and water retention, polyS, oligosaccharides,
It is thought that this is due to the following: and their derivatives. Furthermore, the advantage of excellent color fastness is thought to be due to poor compatibility between the dyes used for dyeing synthetic fibers and semi-synthetic fibers and the above-mentioned saccharides.
染色性及び他基材、他物質との親和性改質については、
前記熱反応性の糖エーテル化物が合成繊維、半合成繊維
表面を被覆するため、即ち、合成繊維表面に官能基（上
記糖類のヒドロキシル基）を付与するためと考えられる
。それにより、アニオン染料、反応性染料等での染色性
が可能になり、かつ他基材との親和性及び他物質の反応
性が向上又は可使となる。Regarding dyeability and affinity modification with other base materials and other substances,
This is thought to be because the heat-reactive sugar etherified product coats the surface of the synthetic fiber or semi-synthetic fiber, that is, it imparts a functional group (hydroxyl group of the sugar) to the surface of the synthetic fiber. This makes it possible to dye with anionic dyes, reactive dyes, etc., and improves affinity with other substrates and reactivity with other substances, or makes it usable.
合成繊維の熱溶融性の改良については、熱溶融性を有し
得ない前記熱反応性の糖エーテル化物が合成繊維の表面
を被覆するためになされるものと考えられる。It is thought that the heat-melting property of synthetic fibers is improved because the heat-reactive sugar etherified product, which cannot have heat-melting properties, coats the surface of the synthetic fibers.
更に、本発明糖エーテル化物が付与された合成繊維、半
合成繊維の表面は、綿ライクな触感、風合を与える。Furthermore, the surface of the synthetic fiber or semi-synthetic fiber to which the sugar etherified product of the present invention has been applied gives a cotton-like touch and feel.
なお１本発明を実施するにあたり、種々の添加剤（柔軟
剤、帯電防止剤、浸透剤等）を併用しても良いことは当
然のことである。Note that it is a matter of course that various additives (softeners, antistatic agents, penetrants, etc.) may be used in combination in carrying out the present invention.
またブロック化イソシアネート基の硬化を促進するため
に、ソジウムメチラート、トリエチルアミン又は一般の
ウレタン化触媒を併用することが好ましい。Further, in order to accelerate the curing of the blocked isocyanate group, it is preferable to use sodium methylate, triethylamine or a general urethanization catalyst in combination.
以下本発明の方法を実施例に基づき説明するが、本発明
はその要旨を超えない限り以下の実施例に限定されるも
のではない。The method of the present invention will be explained below based on Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.
（ブロック化イソシアネート基含有エーテル化剤の合成
）
Ｄ１
ヘキサメチレンジイソシアネー） １００部（重量部
、以下同様）に４５℃下でメチルエチルケトオキシム５
２．０部を６０分間を要し、徐々に滴下し、その後同温
にて反応を６０分間行ない。(Synthesis of blocked isocyanate group-containing etherification agent) D1 Hexamethylene diisocyanate) 100 parts (parts by weight, hereinafter the same) were mixed with 5 methyl ethyl ketoxime at 45°C.
2.0 parts were gradually added dropwise over 60 minutes, and the reaction was then carried out at the same temperature for 60 minutes.
イソシアネート１２４．０％（ヘキサメチレンジイソシ
アネート量に対して）を含有するブロック化ウレタン物
を得た。A blocked urethane product containing 124.0% of isocyanate (based on the amount of hexamethylene diisocyanate) was obtained.
次にエチレンクロルヒドリ７４８．３部をメチルエチル
ケトン８０部に溶解した溶液を温度７５℃下で６０分間
を要し１滴下し、その後同温にて反応を９０分間行ない
、イソシアネート基が消失したことを確認した６以上操
作により固型分７１．４８％、結合ｃ１分１Ｇ、１ｌｉ
３％（固型分に対して）のブロック化イソシアネートＸ
含有エーテル化剤を得た。Next, one drop of a solution of 748.3 parts of ethylene chlorohydride dissolved in 80 parts of methyl ethyl ketone was added over 60 minutes at a temperature of 75°C, and the reaction was then carried out for 90 minutes at the same temperature to confirm that the isocyanate group had disappeared. Solid content 71.48%, bond c 1 min 1 G, 1 li by confirmed 6 or more operations
3% (based on solids) blocked isocyanate X
A containing etherification agent was obtained.
ｂ２
プロピレンオキサイド重付加体（分子量４００）のポリ
エーテルポリオール１００部にヘキサメチレンジイソシ
アネー） ８４．５部を添加し、９０℃にて９０分間反
応を行い、イソシアネート基１１．３５％（ポリエーテ
ルポリオールとへキサメチレンジイソシアネート総量に
対して）を含有するウレタンプレポリマーを得た０次に
前記ウレタンプレポリマーにフェノール２３．４部をメ
チルエチルケトン５０部に溶解した溶液を添加し、後に
トリエチルアミン０．２部を添加して系内温度６５℃に
て９部分間反応を行ない、イソシアネート基５．５６％
（前記ウレタンズレポリマー量に対して）を含有するブ
ロック化ウレタン物を得た０次にプロピレンクロルヒド
リン２４．２部を添加し、系内 温度７５℃にて２００
分反応を行ない、イソシアネート基が消失したことを確
認した０以上操作により固型分８２．２％、結合ｃ１分
３．９２％（固型分に対して）のブロック化イソシアネ
ート基含有エーテル化剤を得た。b2 84.5 parts of hexamethylene diisocyanate (hexamethylene diisocyanate) was added to 100 parts of polyether polyol of propylene oxide polyadduct (molecular weight 400), and the reaction was carried out at 90°C for 90 minutes, resulting in 11.35% of isocyanate groups (polyether Next, a solution of 23.4 parts of phenol dissolved in 50 parts of methyl ethyl ketone was added to the urethane prepolymer, and then 0.2 parts of triethylamine was added to the urethane prepolymer containing (based on the total amount of polyol and hexamethylene diisocyanate) was added and a 9-part reaction was carried out at a system internal temperature of 65°C, resulting in 5.56% of isocyanate groups.
After obtaining the blocked urethane product containing (relative to the amount of urethane shear polymer), 24.2 parts of propylene chlorohydrin was added, and the system was heated to 200°C at a temperature of 75°C.
A blocked isocyanate group-containing etherification agent with a solid content of 82.2% and a bond c1 of 3.92% (based on the solid content) after conducting a minute reaction and confirming that the isocyanate group has disappeared. I got it.
１’＆）３
トリメチロールプロ３７１０部にヘキサメチレンジイソ
シアネート３７．６部を添加して、系内温度８０℃にて
６０分間反応を行い、Ｔｔ離イソシアネート基１９．５
％（トリメチロールプロパン、ヘキサメチレンジイソシ
アネート総量に対して）を含有するウレタンプレポリマ
ーを得た０次いでメチルエチルケトオキシム６．４部、
エチレンクロルヒドリン５．９部を添加し、系内温度８
５℃にて １２０分間反応を行ない、遊離イソシアネー
ト基６．３％（トリメチロールプロパン、ヘキサメチレ
ンジイソシアネートｌａｍに対して）を有するブロック
化ウレタン物を得た。1'&) 3 37.6 parts of hexamethylene diisocyanate was added to 3710 parts of trimethylolpro, and the reaction was carried out at a system temperature of 80°C for 60 minutes, resulting in a Tt release of 19.5 parts of isocyanate groups.
% (relative to the total amount of trimethylolpropane, hexamethylene diisocyanate) to obtain a urethane prepolymer containing 0 then 6.4 parts of methyl ethyl ketoxime,
5.9 parts of ethylene chlorohydrin was added, and the system temperature was 8.
The reaction was carried out at 5° C. for 120 minutes to obtain a blocked urethane having 6.3% of free isocyanate groups (based on trimethylolpropane, hexamethylene diisocyanate lam).
次にメチルエチルケトン １００部を添加して、系内温
度４０℃にて３０％濃度のアミノエタンスルホン酸ソー
ダー３４．９部を添゛加し、同温にて８０分間攪拌を行
なった。Next, 100 parts of methyl ethyl ketone was added, and at a system internal temperature of 40°C, 34.9 parts of 30% sodium aminoethanesulfonic acid was added, followed by stirring at the same temperature for 80 minutes.
以上操作により固型分３Ｅ１．１２％、結合ｃ１分３゜
８３％（固型分に対して）の親水性のブロック化イソシ
アネート基含有エーテル化剤を得た。By the above operations, a hydrophilic blocked isocyanate group-containing etherifying agent was obtained with a solid content of 3E of 1.12% and a bond c1 of 3.83% (based on the solid content).
ｏ４
トリエチレンジイソシアネート１００部に４０℃下でメ
チルエチルケトオキシム５０．０部を８０分間を要し、
徐々に滴下し、その後同温にて反応を６０分間行ない、
イソシアネート基２３．５％（トルエチレンジイソシア
ネート量に対して）を含有するブロック化ウレタン物を
得た０次にエチレンクロルヒドリンａｓ、０部＆メチル
エチルケトン８０部に溶解した溶液を反応系７０℃下で
、８０分間を要し１滴下し、その後同温にて反応を８０
分間行ない、イソシアネート基が消失したことを確認し
た。o4 50.0 parts of methyl ethyl ketoxime was added to 100 parts of triethylene diisocyanate at 40°C over a period of 80 minutes,
It was gradually added dropwise, and then the reaction was carried out at the same temperature for 60 minutes.
A blocked urethane product containing 23.5% of isocyanate groups (based on the amount of toluethylene diisocyanate) was obtained, and a solution dissolved in 0 parts of ethylene chlorohydrin as and 80 parts of methyl ethyl ketone was added to the reaction system at 70°C. It took 80 minutes to add one drop, and then the reaction was continued at the same temperature for 80 minutes.
It was confirmed that the isocyanate group had disappeared.
以上操作により固型分７１．０％、結合ａｔ分１０゜１
７％（固型分に対して）のブロック化イソシアネート基
含有エーテル化剤を得た。As a result of the above operations, the solid content was 71.0%, and the bound at content was 10°1.
An etherification agent containing 7% (based on solids) of blocked isocyanate groups was obtained.
合成例１
セルロースのグリコース単位１個当たりプロピレンオキ
サイドを６モル付加させたセルロース誘導体 １００部
をメチルエチルケトン３２０部、水８０部を加え、完全
に溶解した。Synthesis Example 1 320 parts of methyl ethyl ketone and 80 parts of water were added to 100 parts of a cellulose derivative to which 6 moles of propylene oxide were added per glycose unit of cellulose, and the mixture was completely dissolved.
次に３５％濃度の水酸化ナトリウム水溶液４．１１部を
添加して３５℃下で３０分間攪拌を行なった０次に前記
ブロック化イソシアネート基含有エーテル化剤Ｎｏｌを
１５．３４部添加し、系内温度７０℃下で、 ４２０
分間反応を行い、ブロック化イソシアネート基含有エー
テル化剤崩１中の結合ｃｌが全て水溶性Ｃ！となったこ
とを確認し、エーテル化反応を終了した。最後に過剰量
の水酸化ナトリウムを酢酸にて中和し、その後水稀釈し
て固型分１２％の半透明粘稠な熱反応性の糖エーテル化
物を得た。Next, 4.11 parts of a 35% sodium hydroxide aqueous solution was added and stirred at 35°C for 30 minutes.Next, 15.34 parts of the blocked isocyanate group-containing etherification agent Nol was added to the system. At an internal temperature of 70℃, 420
The reaction was carried out for a minute, and all of the bonds in the blocked isocyanate group-containing etherification agent solution 1 were water-soluble C! It was confirmed that the etherification reaction was completed. Finally, excess sodium hydroxide was neutralized with acetic acid, and then diluted with water to obtain a translucent, viscous, heat-reactive sugar etherified product with a solid content of 12%.
合成例２
カルボキシメチルセルロース １００部（鐙ｍ１ｌＦ１
．５０、カルボキシル基ナトリウム塩）に水５００部を
加え、完全に溶解した。Synthesis Example 2 100 parts of carboxymethyl cellulose (stirrup m1lF1
．． 50, carboxyl group sodium salt) was added to 500 parts of water and completely dissolved.
次に３５％濃度の水酸化ナトリウム水溶液４．８３部を
添加して３５℃下で３０分間攪拌を行なった０次に前記
ブロック化イソシアネート基含有エーテル化剤Ｎｏ２を
４４．１部添加し、系内温度５０℃下で、７２０分間反
応を行い、ブロック化イソシアネート基含有エーテル化
剤ＮｏＺ中の結合ｃｌが全て水溶性ｃｌとなったことを
確認し、エーテル化反応を終了した。最後に過剰量の水
酸化ナトリウムを酢酸にて中和し、水稀釈して固型分１
０％の半透明粘稠な熱反応性の糖エーテル化物を得た。Next, 4.83 parts of a 35% sodium hydroxide aqueous solution was added and stirred at 35°C for 30 minutes.Next, 44.1 parts of the blocked isocyanate group-containing etherifying agent No. 2 was added, and the system The reaction was carried out for 720 minutes at an internal temperature of 50° C., and it was confirmed that all of the bonded Cl in the blocked isocyanate group-containing etherification agent NoZ had become water-soluble Cl, and the etherification reaction was completed. Finally, excess sodium hydroxide was neutralized with acetic acid, diluted with water, and the solid content was 1
A 0% translucent viscous heat-reactive sugar etherified product was obtained.
合成例３
デンプン １００部にジメチルホルムアミド２００部、
水１００部を加え、次に３５％濃度の水酸化ナトリウム
水溶液４．９３部を添加し３５℃下で３０分間攪拌した
０次に前記ブロック化イソシアネート基含有エーテル化
剤Ｎｏ３を １０３．４部添加し、系内温度４５℃下で
、７００分間反応を行い、ブロック化イソシアネート基
含有エーテル化剤ＮｏＳ中の結合ｃｌが全て水溶性ｃｌ
となったことを確認し、エーテル化を終了した。最後に
過剰量の水酸化ナトリウムをリン酸にて中和し、水稀釈
して固型分１０％の白濁分散状の熱反応性の糖エーテル
化物を得た。Synthesis Example 3 100 parts of starch, 200 parts of dimethylformamide,
Add 100 parts of water, then add 4.93 parts of a 35% sodium hydroxide aqueous solution and stir at 35°C for 30 minutes. Next, add 103.4 parts of the blocked isocyanate group-containing etherification agent No. 3. Then, the reaction was carried out for 700 minutes at an internal system temperature of 45°C, and all of the bonds in the blocked isocyanate group-containing etherification agent NoS were converted to water-soluble Cl.
After confirming that this was the case, the etherification was completed. Finally, excess sodium hydroxide was neutralized with phosphoric acid and diluted with water to obtain a heat-reactive sugar etherified product in the form of a cloudy white dispersion with a solid content of 10%.
合成例４
合成例１と同様のセルロース誘導体１００部をメチルエ
チルケトン３２０部、水８０部を加え完全に溶解した。Synthesis Example 4 100 parts of the same cellulose derivative as in Synthesis Example 1 was completely dissolved in 320 parts of methyl ethyl ketone and 80 parts of water.
次に３５％濃度の水酸化ナトリウム水溶液４．０部を添
加して３５℃下で３０分間攪拌を行なった０次に前記ブ
ロック化イソシアネート基含有エーテル化剤Ｎｏ４を
１５．４０部添加し、系内温度６５℃下で、５００分間
反応を行い、ブロック化イソシアネート基含有エーテル
化剤ＮｏＡ中の結合ｃｌが全て水溶性ｃ１となったこと
を確認し、エーテル化を終了した。最後に過剰量の水酸
化ナトリウムを酢酸にて中和し、その抜水稀釈して固型
分１０％の不透明粘稠な熱反応性の糖エーテル化物を得
た。Next, 4.0 parts of a 35% sodium hydroxide aqueous solution was added and stirred for 30 minutes at 35°C. Next, the blocked isocyanate group-containing etherifying agent No. 4 was added.
15.40 parts were added and the reaction was carried out for 500 minutes at a system internal temperature of 65°C. It was confirmed that all the bonds Cl in the blocked isocyanate group-containing etherification agent NoA had become water-soluble Cl, and the etherification was completed. finished. Finally, excess sodium hydroxide was neutralized with acetic acid, and water was removed and diluted to obtain an opaque and viscous heat-reactive sugar etherified product with a solid content of 10%.
実施例１〜３
合成例１〜３で得られた熱反応性の糖エーテル化物にそ
れぞれ触媒（エラストロンキャタリスト−３２第−工業
製薬−製）を固型分に対して１０％併用し、更に固型分
２％になるように水で稀釈し、処理浴を調整した。得ら
れた処理浴にポリエステルジャージ染色布を浸漬し、マ
ングルで均一に絞り（絞り率 １００％）、ベーキング
機にて１００℃にて３分間前乾燥した後、 １４０℃に
て １分間熱処理し吸水性を測定した。Examples 1 to 3 A catalyst (manufactured by Elastron Catalyst-32 Dai-Kogyo Seiyaku) was added to the heat-reactive sugar etherified products obtained in Synthesis Examples 1 to 3 at 10% based on the solid content, The mixture was further diluted with water to a solid content of 2% to prepare a treatment bath. A polyester jersey dyed cloth was immersed in the resulting treatment bath, squeezed uniformly with a mangle (squeezing ratio 100%), pre-dried in a baking machine at 100℃ for 3 minutes, and then heat-treated at 140℃ for 1 minute to absorb water. The sex was measured.
更に洗濯による吸水性の耐久性についても測定し、その
結果を第１表に示す。Furthermore, the durability of water absorption after washing was also measured, and the results are shown in Table 1.
合成例１〜３で得られた糖エーテル化物を用いたものが
それぞれ実施例１〜３に相当する。Those using the sugar etherified products obtained in Synthesis Examples 1 to 3 correspond to Examples 1 to 3, respectively.
（吸水性） ＪＩＳ １０７９Ｂ （バイシック法）により評価。(Water absorption) Evaluated according to JIS 1079B (bisic method).
（吸水性の耐久性）
中性洗剤２ｇ／ｌを含む洗濯浴を用い、浴比１：３０で
家庭用洗濯機を用いて４０℃で８０分間洗濯後、４０℃
にて６０分間すすぎ、脱水。(Durability of water absorption) After washing at 40°C for 80 minutes using a household washing machine at a bath ratio of 1:30 using a washing bath containing 2 g/l of neutral detergent,
Rinse for 60 minutes and dehydrate.
乾燥し、上述の吸水性を評価。Dry and evaluate water absorption as described above.
比較例１
式：
％式％
で表わされる改質剤（樹脂分 １００％）を用いて処理
浴の樹脂分濃度が２％となるように下記組成を有する処
理浴を７Ａ整した。Comparative Example 1 A treatment bath having the following composition was adjusted to 7A using a modifier (resin content: 100%) represented by the formula: % so that the resin concentration of the treatment bath was 2%.
（処理浴組成）
前記改質剤 ２．０部
過硫酸アンモニウム ０．１部水
９７．３部上記の処理浴
に、実施例１で使用したのと同じのポリエステルジャー
ジ染色布を浸漬して絞り（絞り率！００％）、関係湿度
１００％、温度１００℃にて５分間処理したのち １４
０℃にて１分間ベーキングし、実施例１と同様にして評
価した。それらの結果を第１表に示す。(Treatment bath composition) Modifier 2.0 parts Ammonium persulfate 0.1 part Water
97.3 parts The same polyester jersey dyed cloth used in Example 1 was immersed in the above treatment bath, squeezed (squeezing rate: 00%), and treated for 5 minutes at a relative humidity of 100% and a temperature of 100°C. After that 14
It was baked at 0° C. for 1 minute and evaluated in the same manner as in Example 1. The results are shown in Table 1.
第１表
なお、加工布の触感、風合は、実施例Ｎｏ１〜３いずれ
も綿ライクな触感、風合を与えた。Table 1 Note that the texture and texture of the processed cloths in all of Examples Nos. 1 to 3 were cotton-like.
実施例４〜６
実施例１〜３と同様の操作により、固型分５％になるよ
うに水で稀釈し、実施例１〜３と同様の操作により、ポ
リエステルジャージに付着させ、熱処理を行ない、保水
性を測定した。結果を第２表に示す。Examples 4 to 6 Diluted with water to a solid content of 5% by the same operation as Examples 1 to 3, attached to polyester jersey and heat-treated by the same operation as Examples 1 to 3. , water retention was measured. The results are shown in Table 2.
なお、合成例１〜３で得られた糖エーテル化物を用いた
ものが、それぞれ実施例４〜６に相当する。In addition, those using the sugar etherified products obtained in Synthesis Examples 1 to 3 correspond to Examples 4 to 6, respectively.
処理されたポリエステルジャージ縦横２０×２０ａｌＩ
を常温水中に １時間浸漬後、家庭用法ＷＩ機にて２分
間脱水を行い、重量を測定し以下式より保水性とした。Treated polyester jersey length and width 20 x 20 alI
After soaking in water at room temperature for 1 hour, it was dehydrated for 2 minutes using a household method WI machine, the weight was measured, and the water retention was calculated using the following formula.
浸漬繭重量
〔保水性の耐久性〕
実施例１〜３と同様の操作により、洗濯操作を行った後
、上記保水性測定を行った。Weight of Soaked Cocoons [Durability of Water Retention] After washing the cocoons in the same manner as in Examples 1 to 3, the water retention was measured.
比較例２
比較例１と同様の操作により、固型分５％になるように
水で稀釈し、比較例１と同様の操作により、ポリエステ
ルジャージに付着させ、加熱処理を行ない、実施例４〜
６に示す保水性及び耐久性の評価をした。結果を第２表
に示す。Comparative Example 2 By the same operation as Comparative Example 1, diluted with water to have a solid content of 5%, applied to a polyester jersey by the same operation as Comparative Example 1, and heat-treated.
The water retention and durability were evaluated as shown in 6. The results are shown in Table 2.
第２表
実施例７〜９
実施例１〜３で得られた樹脂加工後のポリエステルジャ
ージ染色布の摩擦堅牢度の評価をＪＩＳ ０８４９法に
より行った。結果を第３表に示す、（実施例７〜９はそ
れぞれ実施例１〜に相当）
比較例３
比較例１で得られた樹脂加工後のポリエステルジャージ
染色布の摩擦堅牢度を実施例７〜９と同様に測定し、そ
の結果を第３表に示す。Table 2 Examples 7 to 9 The abrasion fastness of the resin-treated dyed polyester jersey fabrics obtained in Examples 1 to 3 was evaluated by JIS 0849 method. The results are shown in Table 3. (Examples 7 to 9 correspond to Examples 1 to 9 respectively) Comparative Example 3 The abrasion fastness of the dyed polyester jersey fabric obtained in Comparative Example 1 after resin processing was measured in Examples 7 to 9. Measurements were made in the same manner as in 9, and the results are shown in Table 3.
第３表
実施例１０〜１２
合成例１〜３で得られた熱反応性の糖エーテル化物を、
それぞれ直径１０ａｌのテフロンコーティングシャレー
に固型分が３．０ｇとなるように触媒（エラストロンキ
ャタリスト−３２） ０゜３８ｇともに入れ、−夜風
乾後、６０℃にて３時好、 １４０℃にて１０分間熱処
理し、硬化皮膜を得た。Table 3 Examples 10 to 12 The heat-reactive sugar etherified products obtained in Synthesis Examples 1 to 3 were
Add 0.38g of catalyst (Elastron Catalyst-32) to a Teflon-coated chalet with a diameter of 10al so that the solid content is 3.0g. A cured film was obtained by heat treatment for 10 minutes.
その後、得られた硬化皮膜の２５℃、湿度９０％におけ
る吸湿性を測定した。結果を第４表に示す。Thereafter, the hygroscopicity of the obtained cured film at 25° C. and 90% humidity was measured. The results are shown in Table 4.
２５℃、湿度９０％における皮膜の経時重量変化を測定
し、吸湿性として評価した。The change in weight of the film over time at 25° C. and 90% humidity was measured and evaluated as hygroscopicity.
比較例４
比較例１で使用した改質剤３．０ｇ 、過硫酸アンモニ
ウム０．１５ｇ及び水１０ｇを用いて実施例１Ｏ〜１２
と同様にて硬化皮膜を作成し、吸湿性を測定した。結果
を第４表に示す。Comparative Example 4 Examples 1O to 12 were prepared using 3.0 g of the modifier used in Comparative Example 1, 0.15 g of ammonium persulfate, and 10 g of water.
A cured film was prepared in the same manner as above, and its hygroscopicity was measured. The results are shown in Table 4.
第４表
実施例１３〜１５
実施例４〜６で調整した処理液をポリエステルフィラメ
ント糸（７５デニール／３６フイラメント）にｋｉｓｓ
ローラーを用いて、固型分３．０％付着させた後、ベー
キング機にて １００℃、３分間前乾燥し後、 １４０
℃にて １分間熱処理を行った後、処理されたポリエス
テルフィラメント糸を筒編機にてニットに仕上げ、その
ニット布の吸水性及び洗濯による耐久性を実施例１〜３
と同様に測定した。Table 4 Examples 13 to 15 Kiss the treatment solution prepared in Examples 4 to 6 to polyester filament yarn (75 denier/36 filament).
After applying a solid content of 3.0% using a roller, pre-drying in a baking machine at 100℃ for 3 minutes,
After heat treatment at ℃ for 1 minute, the treated polyester filament yarn was knitted using a tube knitting machine, and the water absorption and washing durability of the knitted fabric were evaluated in Examples 1 to 3.
It was measured in the same way.
結果を第５表に示す、（実施例１３〜１５が実施例４〜
６の処理液にそれぞれ相当する）。The results are shown in Table 5 (Examples 13 to 15 are compared to Examples 4 to 15).
6).
なお、洗濯には加工されたニット布を供した。Note that a processed knit cloth was used for washing.
第５表
実施例１６〜１８
合成例１〜３で得られた熱反応性の糖エーテル化物に、
それぞれ触媒（エラストロンキャタリスト−３２）を固
型分に対して１０％併用して、更に固型分１０％になる
よう水で稀釈し、処理浴を調整した。Table 5 Examples 16 to 18 The heat-reactive sugar etherified products obtained in Synthesis Examples 1 to 3,
A treatment bath was prepared by using a catalyst (Elastron Catalyst-32) in a proportion of 10% based on the solid content and further diluting with water to make the solid content 10%.
得られた処理浴にポリエステルジャージ白布を浸漬マン
グルで絞り（絞り率 １００％）、ベーキング機にて
１００℃にて３分間乾燥し。Squeeze a white polyester jersey cloth into the resulting treatment bath using a soaking mangle (squeezing rate: 100%) and use a baking machine.
Dry at 100°C for 3 minutes.
後に１４０℃にて １分間熱処理し１反応性染料による
染色テストを行った。Afterwards, it was heat treated at 140°C for 1 minute and a dyeing test using a 1-reactive dye was performed.
更に上記操作により反応性染料にて染色したポリエステ
ルジャージを実施例１〜３に示す洗濯条件にて洗濯を行
った。それらの結果を第６表に示す。Furthermore, the polyester jersey dyed with the reactive dye by the above procedure was washed under the washing conditions shown in Examples 1 to 3. The results are shown in Table 6.
なお１合成例１〜３で得られた糖エーテル化物を用いた
ものがそれぞれ実施例１６〜１８に相当する。In addition, those using the sugar etherified products obtained in Synthesis Examples 1 to 3 correspond to Examples 16 to 18, respectively.
反応染料による染色条件
浴 比 １ ； ５０
無水芒硝 ３０ｇ／ｌ
染料 旧ｋｃａｃｉｏｎ Ｂｙ目１ｉａｎｔ Ｒｅｄ
Ｂ４％ｏｗｆ （三菱化成社製）
ソーダ灰 ｌＯ％ｏｗｆ
染色熱条件
無水芒硝
染 料 →３５℃→ （２０分）→８５℃ （８０分）
→湯洗加工布
ソーダ灰
第６表
（注）染色状態 最良＠← ４×不良
（全く染色されていない）
以上の如く加工布は 反応性染料で染色され、かつ洗濯
による耐久性を有するものであった。Dyeing conditions with reactive dyes Bath ratio: 1; 50 Anhydrous sodium sulfate 30g/l Dye: Old kcacion By 1iant Red
B4%owf (manufactured by Mitsubishi Kasei Corporation) Soda ash lO%owf Dyeing heat conditions Anhydrous mirabilite dye →35℃→ (20 minutes)→85℃ (80 minutes)
→Hot water washed fabric Soda ash Table 6 (Note) Dyeing condition Best @ ← 4 x Poor (not dyed at all) As mentioned above, processed fabric is dyed with reactive dye and has durability through washing. there were.
実施例１９〜２２
合成例１〜４で得られた糖エーテル化物に、それぞれ触
媒（エラストロンキャタリスト−３２）を固型分に対し
て１０％併用し、この液にナイロンコードを浸清し、固
型分付着量的２．０％とした後、１２０℃、 ３分間乾
燥した６次にこの乾燥コードをＲＦＬ （レゾルシン−
ホルマリン−ラテックス）に浸漬し、ＲＦＬ固型分付着
量約３．０％となるように調整の後、２００℃、２分間
熱処理した。ついで、この処理コードを天然ゴムに埋込
み、１５０℃３０分間加熱した後、剥離強度並びに引抜
強度及び曲げ硬さを測定した。また、比較のためＲＦＬ
（付着量的５％）のみで処理した時の剥離。Examples 19 to 22 A catalyst (Elastron Catalyst-32) was used at 10% based on the solid content of each sugar etherified product obtained in Synthesis Examples 1 to 4, and a nylon cord was immersed in this liquid. After reducing the solid content to 2.0%, the dried cord was dried at 120°C for 3 minutes.
After adjusting the RFL solid content to about 3.0%, the sample was heat-treated at 200° C. for 2 minutes. Next, this treated cord was embedded in natural rubber and heated at 150° C. for 30 minutes, after which peel strength, pull-out strength, and bending hardness were measured. Also, for comparison, RFL
Peeling when treated with only (5% adhesion amount).
引抜強度、曲げ硬さを測定し、これをブランク（１００
）とした時の指数により第７表に結果を示す。The pull-out strength and bending hardness were measured, and this was measured as a blank (100
) The results are shown in Table 7 based on the index.
なお、実施例１９〜２２は、合成例１〜４の化合物に相
当する。In addition, Examples 19-22 correspond to the compounds of Synthesis Examples 1-4.
第７表
第７表より、ブランクに対して明らかに強固な接看が得
られることがわかる。Table 7 From Table 7, it can be seen that a clearly strong contact with the blank can be obtained.
実施例２３〜２５
合成例１〜３で得られた糖エーテル化物に、それぞれ触
媒（エラストロンキャタリスト−３２）を固型分に対し
て１０％併用し、更に固型分１０％になるように水で稀
釈し、処理浴を調整した。Examples 23 to 25 A catalyst (Elastron Catalyst-32) was added to the sugar etherified products obtained in Synthesis Examples 1 to 3 at 10% based on the solid content, and the solid content was further increased to 10%. diluted with water to prepare a treatment bath.
得られた処理浴にポリエステルジャージを浸漬しマング
ルで絞り（絞り率１１０％）、ベーキング機にて １２
０℃にて２分間乾燥し、その後１５０℃にて２分間熱処
理を行った。A polyester jersey was immersed in the obtained treatment bath, squeezed with a mangle (squeezing ratio 110%), and then baked in a baking machine.
It was dried at 0°C for 2 minutes, and then heat-treated at 150°C for 2 minutes.
該加工布を回転数１５０Ｏｒｐｍ 、ローラー表面速度
７ｍ／ｓｉｎのスピードで回転する木製ロール（桜の水
使用）に接触圧１．０ｋｇで加工布を接触させ、溶融し
、穴があくまでの摩擦溶融時間を測定した。結果を第８
表に示す。The processed fabric was brought into contact with a wooden roll (using cherry water) rotating at a rotation speed of 150 rpm and a roller surface speed of 7 m/sin at a contact pressure of 1.0 kg, and the frictional melting time until holes were formed was determined. It was measured. 8th result
Shown in the table.
なお、実施例２３〜２５は１合成例１〜３の化合物にそ
れぞれに相当する。In addition, Examples 23 to 25 correspond to the compounds of 1 Synthesis Examples 1 to 3, respectively.
第８表
実施例２６〜２８
実施例１〜３で得られた処理浴にナイロンタフタを浸清
し、マングルで均一に絞り（絞り率８０％）、実施例１
〜３同様熱処理を行ない、吸水性及び洗濯による吸水性
の耐久性を測定した。結果を第９表に示す。Table 8 Examples 26 to 28 Nylon taffeta was soaked in the treatment bath obtained in Examples 1 to 3 and squeezed uniformly with a mangle (squeezing ratio 80%), Example 1
A heat treatment was performed in the same manner as in ~3, and the water absorbency and durability of water absorbency upon washing were measured. The results are shown in Table 9.
なお、実施例２６〜２８が合成例１〜３の糖エーテル化
物を使用したものに相当する。Note that Examples 26 to 28 correspond to those using the sugar etherified products of Synthesis Examples 1 to 3.
Claims (2)
ク化イソシアネート基含有エーテル化剤とを反応させて
成る熱反応性の糖エーテル化物の製法。(1) A method for producing a heat-reactive sugar etherified product by reacting polysaccharides, oligosaccharides, and their derivatives with a blocked isocyanate group-containing etherification agent.
ク化イソシアネート基含有エーテル化剤とを反応させて
成る水溶性又は水分散性 で、かつ熱反応性の糖エーテル化物を合成繊維、半合成
繊維の糸に付着させ、又は合成繊維、半合成繊維布帛に
付着させ、熱処理を行なうことを特徴とする合成繊維用
改質剤。(2) Synthetic fibers and semi-synthetic fibers made of water-soluble or water-dispersible and heat-reactive sugar etherified products obtained by reacting polysaccharides, oligosaccharides, and their derivatives with blocked isocyanate group-containing etherification agents. 1. A modifier for synthetic fibers, which is applied to yarns of synthetic fibers or synthetic fibers or semi-synthetic fiber fabrics, and subjected to heat treatment.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61042645A JPH0762314B2 (en) | 1986-02-26 | 1986-02-26 | Method of modifying synthetic fibers |
| US07/015,196 US4931524A (en) | 1986-02-17 | 1987-02-17 | Surface-treatment of synthetic or semi-synthetic fiber textile materials |
| DE3705025A DE3705025C2 (en) | 1986-02-17 | 1987-02-17 | Agents and methods for surface treatment of synthetic or semi-synthetic textile fiber materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61042645A JPH0762314B2 (en) | 1986-02-26 | 1986-02-26 | Method of modifying synthetic fibers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62198695A true JPS62198695A (en) | 1987-09-02 |
| JPH0762314B2 JPH0762314B2 (en) | 1995-07-05 |
Family
ID=12641749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61042645A Expired - Fee Related JPH0762314B2 (en) | 1986-02-17 | 1986-02-26 | Method of modifying synthetic fibers |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0762314B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0793634A (en) * | 1993-06-30 | 1995-04-07 | Nakamura Yoshio | Paper money discriminating device |
| JP2002524618A (en) * | 1998-09-15 | 2002-08-06 | ロディア・シミ | Cellulose microfibrils having a modified surface, their production method and their use |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5040884A (en) * | 1973-08-15 | 1975-04-14 | ||
| JPS58180683A (en) * | 1982-04-12 | 1983-10-22 | 三和澱粉工業株式会社 | Size agent for sizing cheese |
-
1986
- 1986-02-26 JP JP61042645A patent/JPH0762314B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5040884A (en) * | 1973-08-15 | 1975-04-14 | ||
| JPS58180683A (en) * | 1982-04-12 | 1983-10-22 | 三和澱粉工業株式会社 | Size agent for sizing cheese |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0793634A (en) * | 1993-06-30 | 1995-04-07 | Nakamura Yoshio | Paper money discriminating device |
| JP2002524618A (en) * | 1998-09-15 | 2002-08-06 | ロディア・シミ | Cellulose microfibrils having a modified surface, their production method and their use |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0762314B2 (en) | 1995-07-05 |
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