JP2005120538A - Polyurethane coated cloth - Google Patents
Polyurethane coated cloth Download PDFInfo
- Publication number
- JP2005120538A JP2005120538A JP2003359174A JP2003359174A JP2005120538A JP 2005120538 A JP2005120538 A JP 2005120538A JP 2003359174 A JP2003359174 A JP 2003359174A JP 2003359174 A JP2003359174 A JP 2003359174A JP 2005120538 A JP2005120538 A JP 2005120538A
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- JP
- Japan
- Prior art keywords
- polyurethane
- polyurethane resin
- tannin
- fabric
- dyed
- 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.)
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- 239000004744 fabric Substances 0.000 title claims abstract description 72
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 40
- 239000004814 polyurethane Substances 0.000 title claims abstract description 40
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 60
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- 229920001864 tannin Polymers 0.000 claims abstract description 40
- 239000001648 tannin Substances 0.000 claims abstract description 40
- 235000018553 tannin Nutrition 0.000 claims abstract description 40
- 239000000986 disperse dye Substances 0.000 claims abstract description 29
- 239000000835 fiber Substances 0.000 claims description 36
- 239000000975 dye Substances 0.000 claims description 22
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 22
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 19
- 239000001263 FEMA 3042 Substances 0.000 claims description 18
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 18
- 229920002258 tannic acid Polymers 0.000 claims description 18
- 229940033123 tannic acid Drugs 0.000 claims description 18
- 235000015523 tannic acid Nutrition 0.000 claims description 18
- 238000012546 transfer Methods 0.000 claims description 17
- 229920000728 polyester Polymers 0.000 claims description 15
- 238000011109 contamination Methods 0.000 claims description 13
- 238000012360 testing method Methods 0.000 claims description 8
- 238000013508 migration Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 239000004753 textile Substances 0.000 abstract 2
- 239000007788 liquid Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- -1 polyethylene terephthalate Polymers 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000000980 acid dye Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 210000004177 elastic tissue Anatomy 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000011527 polyurethane coating Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000005108 dry cleaning Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002649 leather substitute Substances 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229940026189 antimony potassium tartrate Drugs 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 125000005521 carbonamide group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229920001461 hydrolysable tannin Polymers 0.000 description 1
- 239000003230 hygroscopic agent Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000005080 phosphorescent agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- AFWAHDXCIBPFNW-UHFFFAOYSA-J sodium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [Na+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O AFWAHDXCIBPFNW-UHFFFAOYSA-J 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical group 0.000 description 1
- 150000003457 sulfones Chemical group 0.000 description 1
- LRBQNJMCXXYXIU-YIILYMKVSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)C(OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-YIILYMKVSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Coloring (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
本発明は、分散染料で染色された分散染料可染型繊維布帛にポリウレタン樹脂が付着してなるポリウレタン加工布帛であって、ポリウレタン樹脂の機能を維持しつつ分散染料移行性の少ないポリウレタン加工布帛に関するものである。 The present invention relates to a polyurethane-processed fabric obtained by attaching a polyurethane resin to a disperse dye-dyed fiber fabric dyed with a disperse dye, and relates to a polyurethane-processed fabric having a low disperse dye transfer property while maintaining the function of the polyurethane resin. Is.
従来、布帛に制電性、接着性、防水性、柔軟性などの機能を付加するためにポリウレタン樹脂を布帛に含浸させたりフィルムラミネートすることが広く行われている（例えば非特許文献１参照）。 Conventionally, in order to add functions such as antistatic properties, adhesiveness, waterproofness, and flexibility to fabrics, it has been widely practiced to impregnate the fabric with polyurethane resin or film laminate (for example, see Non-Patent Document 1). .
しかしながら、ポリエステル繊維などの分散染料可染型繊維からなる布帛を分散染料で染色したものにかかるポリウレタン樹脂を付着させると、染料が、繊維と接触しているポリウレタン樹脂内に移行し汚染するという問題があった。かかる染料移行の理由として、分散染料による染着機構が、ナイロン繊維を酸性染料で染めた場合のような化学結合によるものではなく、分散染料の分子が繊維分子内に単に入り込んだだけであることがあげられる。この現象は、分散染料を用いて濃色に染色された繊維と、淡色または白色のポリウレタン樹脂が接触する場合顕著である。 However, when a polyurethane resin is applied to a fabric made of disperse dyeable fiber such as polyester fiber and dyed with disperse dye, the dye migrates into the polyurethane resin in contact with the fiber and becomes contaminated. was there. The reason for this dye transfer is that the disperse dye dyeing mechanism is not due to chemical bonds as in the case of dyeing nylon fibers with acid dyes, but only the disperse dye molecules have entered the fiber molecules. Can be given. This phenomenon is remarkable when a fiber dyed in a dark color using a disperse dye comes into contact with a light or white polyurethane resin.
この対策として、分散染料可染型繊維がポリエステル繊維である場合には、カチオン染料可染性ポリエステル繊維が使用されることもあるが、該繊維は通常繊維強度の点で不十分なため限られた分野でのみ使用されている。 As a countermeasure, when the disperse dyeable fiber is a polyester fiber, a cationic dyeable polyester fiber may be used. However, the fiber is usually limited in terms of fiber strength. Used only in certain fields.
また、特許文献１では、ポリエステル系繊維布帛を分散染料で染色した後、ポリウレタン系樹脂などをコーテイングした後、低温プラズマ処理することが提案されている。しかるに、低温プラズマ処理するために専用の高価な装置を必要とした。 Further, Patent Document 1 proposes that a polyester fiber fabric is dyed with a disperse dye and then coated with a polyurethane resin and then subjected to low-temperature plasma treatment. However, a dedicated and expensive apparatus is required for the low temperature plasma treatment.
一方、特許文献２では、ポリウレタン弾性繊維にタンニン系化合物を含有させることにより、ポリウレタン弾性繊維が分散染料によって過度に染色されるのを防止し、ドライクリーニング液の汚染を防止することが提案されている。しかしながら、かかる方法は、染色されたポリウレタン弾性繊維内の分散染料がドライクリーニング液を汚染するのを防止することを主目的とするものであり、繊維と接触しているポリウレタン樹脂内への染料の移行を防止することを目的とするものではなかった。 On the other hand, Patent Document 2 proposes that the polyurethane elastic fiber contains a tannin-based compound, thereby preventing the polyurethane elastic fiber from being excessively dyed by the disperse dye and preventing the contamination of the dry cleaning liquid. Yes. However, such a method is mainly intended to prevent the disperse dyes in the dyed polyurethane elastic fibers from contaminating the dry cleaning liquid, and the dyes into the polyurethane resin that is in contact with the fibers. It was not intended to prevent migration.
本発明は、上記の背景に鑑みなされたものであり、その目的は、分散染料で染色された分散染料可染型繊維布帛にポリウレタン樹脂が付着してなるポリウレタン加工布帛であって、ポリウレタン樹脂の機能を維持しつつ分散染料移行性の少ないポリウレタン加工布帛を提供することにある。 The present invention has been made in view of the above background, and an object of the present invention is a polyurethane-processed fabric in which a polyurethane resin adheres to a disperse dye-dyed fiber fabric dyed with a disperse dye, An object of the present invention is to provide a polyurethane-processed fabric having a low disperse dye transfer property while maintaining its function.
本発明者らは、上記目的を達成するため鋭意検討した結果、ポリウレタン樹脂にタンニン系化合物を含有および／または付着させることにより、ポリウレタン樹脂の機能を維持しつつ該ポリウレタン樹脂に接触している繊維からの染料移行を防止できることを知り、さらに鋭意検討を重ねることにより本発明に想到した。 As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that fibers containing and / or adhering a tannin compound to a polyurethane resin are in contact with the polyurethane resin while maintaining the function of the polyurethane resin. The present invention has been conceived by knowing that the dye transfer from the toner can be prevented, and further intensive studies.
かくして、本発明によれば「分散染料で染色された分散染料可染型繊維布帛にポリウレタン樹脂が付着してなるポリウレタン加工布帛であって、前記ポリウレタン樹脂にタンニン系化合物が含有および／または付着してなることを特徴とするポリウレタン加工布帛。」が提供される。 Thus, according to the present invention, “a polyurethane processed fabric obtained by attaching a polyurethane resin to a disperse dye-dyed fiber fabric dyed with a disperse dye, wherein the polyurethane resin contains and / or adheres a tannin-based compound. A polyurethane-processed fabric characterized by comprising:
その際、ポリウレタン樹脂が染色されていないことが好ましい。また、タンニン系化合物が、ポリウレタン樹脂の重量に対して０．０１〜２００重量％付着および／または含有していることが好ましい。前記タンニン系化合物が、合成タンニン、天然タンニン酸及び天然タンニン酸誘導体より選択されるいずれか１種であることが好ましい。ポリウレタン樹脂は制電機能を有していてもよい。また、本発明の布帛を構成する分散染料可染型布帛としては、ポリエステル繊維が好適である。本発明のポリウレタン加工布帛において、染料移行汚染堅牢度試験で３級以上であることが好ましい。また、ポリウレタン樹脂が制電機能を有する場合には、摩擦帯電圧で２５００Ｖ以下であることが好ましい。 At that time, it is preferable that the polyurethane resin is not dyed. Moreover, it is preferable that the tannin type compound adheres and / or contains 0.01 to 200% by weight with respect to the weight of the polyurethane resin. It is preferable that the tannin compound is any one selected from synthetic tannin, natural tannic acid and natural tannic acid derivatives. The polyurethane resin may have an antistatic function. Further, as the disperse dye-dyed fabric constituting the fabric of the present invention, a polyester fiber is suitable. In the polyurethane processed fabric of the present invention, it is preferable that it is grade 3 or higher in the dye migration contamination fastness test. Further, when the polyurethane resin has an antistatic function, the frictional voltage is preferably 2500 V or less.
本発明によれば、分散染料で染色された分散染料可染型繊維布帛にポリウレタン樹脂が付着してなるポリウレタン加工布帛であって、ポリウレタン樹脂の機能を維持しつつ分散染料移行性の少ないポリウレタン加工布帛が得られる。 According to the present invention, a polyurethane-processed fabric obtained by attaching a polyurethane resin to a disperse dye-dyed fiber fabric dyed with a disperse dye, wherein the polyurethane processing has a low disperse dye transfer property while maintaining the function of the polyurethane resin. A fabric is obtained.
以下、本発明の実施の形態について詳細に説明する。
まず、本発明のポリウレタン加工布帛を構成する分散染料可染型繊維とは、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリトリメチレンテレフタレート、第３成分を共重合させたポリエステル、アセテート、ポリアミド、ポリアクリル、ポリビニルアルコール等、分散染料に可染の繊維をいう。
Hereinafter, embodiments of the present invention will be described in detail.
First, the disperse dyeable fiber constituting the polyurethane processed fabric of the present invention is polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyester obtained by copolymerizing a third component, acetate, polyamide, polyacryl, polyvinyl. This refers to fibers that are dyeable to disperse dyes such as alcohol.
これらの繊維を形成するポリマーには、本発明の目的を損なわない範囲内で必要に応じて、微細孔形成剤、カチオン染料可染剤、着色防止剤、熱安定剤、蛍光増白剤、艶消し剤、着色剤、吸湿剤、無機微粒子が１種または２種以上含まれていてもよい。 The polymer forming these fibers may include a fine pore forming agent, a cationic dye dyeing agent, a coloring inhibitor, a heat stabilizer, a fluorescent whitening agent, a glossy agent as necessary within the range not impairing the object of the present invention. One type or two or more types of eraser, colorant, hygroscopic agent, and inorganic fine particles may be contained.
かかる繊維の繊維形態も特に限定されず、長繊維（マルチフィラメント糸条）でもよいし、短繊維でもよい。さらには、撚糸や、空気加工、仮撚捲縮加工がほどこされていてもよい。繊維の断面形状も特に限定されず、丸、三角、扁平、中空など公知の断面形状が採用できる。分散染料可染型繊維の総繊度、単糸繊度、フィラメント数も特に限定されないが、風合いや生産性の点で各々３０〜３００ｄｔｅｘ、０．６〜１０ｄｔｅｘ、１０〜５０本の範囲が好ましい。 The fiber form of such fibers is not particularly limited, and may be long fibers (multifilament yarns) or short fibers. Furthermore, twisted yarn, air processing, and false twist crimping may be applied. The cross-sectional shape of the fiber is not particularly limited, and a known cross-sectional shape such as a circle, a triangle, a flat shape, or a hollow shape can be employed. The total fineness, single yarn fineness, and number of filaments of the disperse dyeable fiber are not particularly limited, but are preferably 30 to 300 dtex, 0.6 to 10 dtex, and 10 to 50 in terms of texture and productivity, respectively.
本発明の布帛は、上記の繊維により構成される。その際、布帛の形態は特に限定されず、織物、編物、不織布などいずれでもよい。また、布帛の厚み、目付け、外観、織編組織などに制限はない。 The fabric of this invention is comprised by said fiber. In that case, the form of the fabric is not particularly limited, and any of a woven fabric, a knitted fabric, a nonwoven fabric and the like may be used. Moreover, there is no restriction | limiting in the thickness of fabric, a fabric weight, an external appearance, a woven / knitted structure, etc.
本発明の布帛には、例えば、カヤロン・ポリエスター・スカーレットＧＳ（日本化薬（株）製）など通常の分散染料を用いて公知の方法で染色が施されている。その際、分散染料可染型繊維として、ポリエステル繊維を選定した場合、分散染料のほか、均染剤、ｐＨ調製剤等を含んだ染料水溶液にて１００〜１４０℃で２０〜９０分染色を行う。 The fabric of the present invention is dyed by a known method using an ordinary disperse dye such as Kayalon Polyester Scarlet GS (manufactured by Nippon Kayaku Co., Ltd.). At that time, when a polyester fiber is selected as the disperse dyeable fiber, dyeing is performed at 100 to 140 ° C. for 20 to 90 minutes with a dye aqueous solution containing a disperse dye, a leveling agent, a pH adjusting agent, and the like. .
本発明のポリウレタン加工布帛には、かかる布帛にポリウレタン樹脂が付着している。該ポリウレタン樹脂の種類は特に限定されず、布帛に付加する機能に応じて適宜選定される。 In the polyurethane processed fabric of the present invention, a polyurethane resin is adhered to the fabric. The type of the polyurethane resin is not particularly limited, and is appropriately selected according to the function added to the fabric.
例えば、人工皮革に柔軟性や耐摩耗性等の機能を付与するための人工皮革用ポリウレタン樹脂としては、平均分子量７００〜３０００のポリエステルジオール、ポリエーテルジオール、ポリエステルエーテルジオール、ポリラクトンジオール、ポリカーボネートジオールなどから選ばれた少なくとも１種のポリマージオールと、芳香族ジイソシアネートおよび脂環族ジイソシアネート等を配合した有機イソシアネートと、さらに低分子ジオール、低分子ジアミン、ヒドラジン、ヒドロキシアミンなど活性水素原子を２個有する低分子化合物とを、溶液重合法、溶融重合法、塊状重合法などによって重合して得たポリエステル系ポリウレタン、ポリエーテル系ポリウレタン、ポリエステルポリエーテル系ポリウレタン、ポリラクトン系ポリウレタン、ポリカーボネート系ポリウレタンなどがあげられる。 For example, as a polyurethane resin for artificial leather for imparting functions such as flexibility and wear resistance to artificial leather, polyester diol, polyether diol, polyester ether diol, polylactone diol, polycarbonate diol having an average molecular weight of 700 to 3000 At least one polymer diol selected from the above, an organic isocyanate blended with an aromatic diisocyanate and an alicyclic diisocyanate, and two active hydrogen atoms such as a low molecular diol, a low molecular diamine, hydrazine, and hydroxyamine Polyester polyurethane, polyether polyurethane, polyester polyether polyurethane, polylactone polyurethane obtained by polymerizing low molecular weight compounds with solution polymerization, melt polymerization, bulk polymerization, etc. Emissions, such as polycarbonate-based polyurethane, and the like.
また、制電加工用ポリウレタン樹脂としては、制電性能を有する分子鎖を有し、かつ少なくとも２個のイソシアネート基を有する化合物からなる重合体が例示される。かかる制電性能を有する分子鎖としてはポリアルキレングリコール（例えば、ポリエチレングリコール）単位（基）があげられる。 Examples of the antistatic polyurethane resin include a polymer having a molecular chain having antistatic performance and made of a compound having at least two isocyanate groups. Examples of molecular chains having such antistatic performance include polyalkylene glycol (for example, polyethylene glycol) units (groups).
布帛にウレタン樹脂を付与する方法としては特に限定されるものではない。例えば、布帛の少なくとも片面に、デイップニップ方式、浸漬方式、乾式コーテイング方式、湿式コーテイング方式、ラミネート方式などにより樹脂皮膜を形成する方法があげられる。 The method for applying the urethane resin to the fabric is not particularly limited. For example, there is a method of forming a resin film on at least one surface of the fabric by a dip nip method, a dipping method, a dry coating method, a wet coating method, a laminating method, or the like.
前記のポリウレタン樹脂は染色されていてもよいが、染色されていないことが好ましい。ポリウレタン樹脂が染色されていない場合、本発明の主目的である染料の移行汚染を防止する効果が十分に発現される。例えば、布帛とポリウレタン樹脂とが同色に染色されていると染料の移行汚染が防止されたかどうか判明できない恐れがある。なお、ここでいう「染色」とは、染色加工されているという意味であり、染料汚染は含まれない。 The polyurethane resin may be dyed, but is preferably not dyed. When the polyurethane resin is not dyed, the effect of preventing dye transfer contamination, which is the main object of the present invention, is sufficiently exhibited. For example, if the fabric and the polyurethane resin are dyed in the same color, it may not be possible to determine whether the dye transfer contamination has been prevented. Here, “dyeing” means that it is dyed and does not include dye contamination.
本発明において、タンニン系化合物がポリウレタン樹脂に付着および／または含有している。ここで、タンニン系化合物とは、合成タンニン、天然タンニン酸および天然タンニン酸誘導体の群から選ばれる少なくとも１種である。 In the present invention, the tannin compound is attached to and / or contained in the polyurethane resin. Here, the tannin compound is at least one selected from the group of synthetic tannin, natural tannic acid and natural tannic acid derivatives.
かかるタンニン系化合物は、ポリウレタン樹脂の重量に対して０．０１〜２００重量％（より好ましくは１〜１００重量％）付着および／または含有していることが好ましい。該含有量が０．０１重量％よりも小さいと、布帛中の染料がポリウレタン樹脂に移行するのを十分に防止できず、ポリウレタン樹脂が汚染される恐れがある。逆に、該含有量が２００重量％よりも大きいと、制電性、防水性、接着性などポリウレタン樹脂の機能が損なわれる恐れがある。 Such a tannin compound is preferably attached and / or contained in an amount of 0.01 to 200% by weight (more preferably 1 to 100% by weight) based on the weight of the polyurethane resin. If the content is less than 0.01% by weight, the dye in the fabric cannot be sufficiently prevented from transferring to the polyurethane resin, and the polyurethane resin may be contaminated. Conversely, if the content is greater than 200% by weight, the functions of the polyurethane resin, such as antistatic properties, waterproofness, and adhesiveness, may be impaired.
前記天然タンニン酸は、植物から抽出・精製され得られる多価フェノール化合物である。天然タンニン酸は、その原料、製造方法、精製などにより様々な組成のものが得られるが、どの組成のものを用いてもよい。好ましくは、五倍子、没食子等から得られる、分子内にガロイル基を有するガロタンニンを主成分とする加水分解型タンニンである。 The natural tannic acid is a polyhydric phenol compound obtained by extraction and purification from a plant. Natural tannic acid can be obtained in various compositions depending on the raw material, production method, purification, etc., but any composition may be used. Preferably, it is a hydrolyzable tannin obtained mainly from a gallotanin having a galloyl group in the molecule, obtained from a quintuplet, a gallic and the like.
前記天然タンニン酸誘導体とは、例えば、前述の天然タンニン酸を化学的に縮合し高分子量化した化合物、天然タンニン酸に金属を作用させた金属錯塩等が挙げられる。 Examples of the natural tannic acid derivative include compounds obtained by chemically condensing the above-mentioned natural tannic acid to increase the molecular weight, and metal complex salts obtained by allowing a metal to act on natural tannic acid.
また、前記合成タンニンとは、ポリアミド繊維用の酸性染料の固着剤において、上記天然タンニン酸に対して、一般に合成タンニンと称せられる合成化合物固着剤のことであり、本発明においてはいずれの合成タンニンを使用してもよい。例えば、ナフチルアミン、フェノール、ナフトール等のスルホン化物がホルムアルデヒドで結合されたオリゴマータイプの化合物で、フェノール系化合物、チオフェノール系化合物、ジヒドロキシジフェニールスルホン系化合物、ナフタリン系化合物、スルホンアミド系化合物、カルボジイミド系化合物等があげられ、なかにはさらにカルボンアミド、スルホンアミド、スルホン、ウレイド等の極性基を有するものがある。市販品としては、例えば、ハイフィックスＧＭ（大日本製薬（株）製ナイロン用酸性染料固着剤；ジヒドロキシジフェニールスルホン系化合物）、デイマフィックスＥＳ（明成化学工業（株）製ナイロン酸性染料固着剤；フェノール系スルホン化合物）等がある。 The synthetic tannin is a synthetic compound fixing agent generally referred to as a synthetic tannin with respect to the natural tannic acid in the acidic dye fixing agent for polyamide fibers, and any synthetic tannin is used in the present invention. May be used. For example, oligomer-type compounds in which sulfonated products such as naphthylamine, phenol, naphthol, etc. are bonded with formaldehyde. Examples of such compounds include compounds having polar groups such as carbonamide, sulfonamide, sulfone and ureido. Commercially available products include, for example, HiFix GM (Dainippon Pharmaceutical Co., Ltd. Acid Dye Fixing Agent for Nylon; Dihydroxydiphenyl Sulfone Compound), Deimafix ES (Maysei Chemical Industry Co., Ltd. Nylon Acid Dye Fixing Agent) A phenol-based sulfone compound).
かかるタンニン系化合物のポリウレタン樹脂への付与手段は特に限定されない。例えば、ウレタン樹脂を染色された布帛に付与する際、タンニン系化合物を含むポリウレタン処理液を該布帛に付与してもよいし、好ましくは、ポリウレタン樹脂を染色された布帛に付与したのち、タンニン系化合物を含む処理液を付与してもよい。その際、ポリウレタン樹脂を染色された布帛に付与する前および／または付与した後に通常の還元洗浄剤、熱アルカリ剤の存在下、７０〜８０℃で１０〜２０分間還元洗浄することは好ましいことである。 The means for applying such a tannin compound to the polyurethane resin is not particularly limited. For example, when a urethane resin is applied to a dyed fabric, a polyurethane treatment liquid containing a tannin compound may be applied to the fabric, or preferably, after applying a polyurethane resin to the dyed fabric, A treatment liquid containing a compound may be applied. In that case, it is preferable to reduce and wash at 70 to 80 ° C. for 10 to 20 minutes in the presence of a normal reducing cleaning agent and a thermal alkali agent before and / or after applying the polyurethane resin to the dyed fabric. is there.
ここで、タンニン系化合物を含む処理液を付与する方法では、処理液に対してタンニン系化合物を０．００１〜５重量％含む処理液を用いることが好ましい。０．００１重量％に満たない濃度の場合、処理液を過剰に付与することが必要となり、逆に、５重量％を越える場合、処理液中に均一に溶解または分散することが難しくなる。また、これらのタンニン系化合物を含有する処理液は、前記のようにウレタン樹脂に対して０．０１〜２００重量％となるよう付与することが好ましい。特に仕上げ剤にこれらのタンニン系化合物が不溶または難溶である場合にはホモミキサー等で平均粒径１．０μｍ以下の粒子としておくことが好ましい。 Here, in the method of applying the treatment liquid containing the tannin compound, it is preferable to use a treatment liquid containing 0.001 to 5% by weight of the tannin compound with respect to the treatment liquid. When the concentration is less than 0.001% by weight, it is necessary to apply the treatment liquid excessively. On the other hand, when the concentration exceeds 5% by weight, it becomes difficult to uniformly dissolve or disperse in the treatment liquid. Moreover, it is preferable to provide the process liquid containing these tannin compounds so that it may become 0.01 to 200 weight% with respect to a urethane resin as mentioned above. In particular, when these tannin-based compounds are insoluble or hardly soluble in the finishing agent, it is preferable to prepare particles having an average particle diameter of 1.0 μm or less with a homomixer or the like.
タンニン系化合物をポリウレタン処理液に含有させる場合、これらのタンニン系化合物をポリウレタン処理液中で溶解または微分散した状態で混合する。また、ポリウレタン処理液に溶剤が使用されている場合は、これらのタンニン系化合物をこの溶剤に溶解もしくは微分散させた後、この溶液をウレタン樹脂溶液に添加、混合することが好ましい。特にこのポリウレタン処理液に不溶または難溶である場合には、これらの添加タンニン系化合物を平均粒子径１．０μｍ以下の粒子状に微分散しておくことが好ましい。 When the tannin compound is contained in the polyurethane treatment liquid, these tannin compounds are mixed in a state of being dissolved or finely dispersed in the polyurethane treatment liquid. Further, when a solvent is used in the polyurethane treatment liquid, it is preferable to dissolve or finely disperse these tannin compounds in this solvent and then add and mix this solution to the urethane resin solution. In particular, when it is insoluble or hardly soluble in this polyurethane treatment liquid, it is preferable to finely disperse these added tannin compounds into particles having an average particle diameter of 1.0 μm or less.
タンニン系化合物として天然タンニン酸が含まれる場合、天然タンニン酸と、多価金属塩とを同時に存在させ、この多価金属塩が天然タンニン酸に対して１〜２００重量％存在させることが好ましい。この多価金属塩に含まれる多価金属としては、マグネシウム、カルシウム、亜鉛、バリウム、アルミニウム、スズ、鉛、アンチモン、銅、ニッケル、コバルト、ビスマスから選ばれる１種類以上の金属であることが好ましい。これらの多価金属塩としては、例えば、酢酸マグネシウム、酢酸カルシウム、酒石酸アンチモンナトリウム、酒石酸アンチモンカリウム等があげられる。天然タンニン酸では、単独でも十分目的とする効果が発揮されるが、これらの多価金属塩が存在することにより錯体を形成し強固な皮膜となるため、より性能が向上すると考えられる。ここで、この多価金属塩の添加量が天然タンニン酸に対して１％に満たない場合、十分な錯体を形成することができす、多価金属塩を添加する性能向上効果が得られない。逆に、２００％を越えても効果は向上せず経済的でない。 When natural tannic acid is included as the tannin-based compound, it is preferable that natural tannic acid and a polyvalent metal salt are simultaneously present, and the polyvalent metal salt is present in an amount of 1 to 200% by weight based on the natural tannic acid. The polyvalent metal contained in the polyvalent metal salt is preferably one or more metals selected from magnesium, calcium, zinc, barium, aluminum, tin, lead, antimony, copper, nickel, cobalt, and bismuth. . Examples of these polyvalent metal salts include magnesium acetate, calcium acetate, sodium antimony tartrate, potassium antimony tartrate, and the like. Natural tannic acid can provide the intended effect even when used alone, but the presence of these polyvalent metal salts forms a complex and a strong film, which is considered to improve performance. Here, when the addition amount of the polyvalent metal salt is less than 1% with respect to natural tannic acid, a sufficient complex can be formed, and the performance improvement effect of adding the polyvalent metal salt cannot be obtained. . Conversely, if it exceeds 200%, the effect is not improved and it is not economical.
ポリウレタン樹脂中に、この多価金属塩を天然タンニン酸と共存させる方法は、どの段階で行ってもよい。また、多価金属塩を仕上げ剤に含有させる場合には、仕上げ剤に対して多価金属塩を０．０１〜２０重量％含む仕上げ剤を使用することが好ましい。 The method of allowing the polyvalent metal salt to coexist with natural tannic acid in the polyurethane resin may be carried out at any stage. Moreover, when making a finishing agent contain a polyvalent metal salt, it is preferable to use the finishing agent which contains 0.01-20 weight% of polyvalent metal salts with respect to a finishing agent.
本発明では、ポリウレタン樹脂にタンニン系化合物が存在している状態で、４０〜１７０℃の条件下で０．５〜６０分乾熱処理されることが好ましい。また、天然タンニン酸がタンニン系化合物として含まれる場合には、同時に多価金属塩がポリウレタン樹脂内に含まれた状態で乾熱処理することもできる。乾熱処理することにより、タンニン系化合物がウレタンポリマーに結びつきやすくなり効果が向上する。ここで、乾熱処理温度が４０℃に満たない温度では、熱処理する前後での効果の向上が少なく、逆に、１７０℃を越えても効果は向上しないだけでなく、ポリウレタン樹脂の熱劣化が起こるため好ましくない。なお、かかる乾熱処理は通常の方法でよい。 In the present invention, dry heat treatment is preferably performed for 0.5 to 60 minutes under conditions of 40 to 170 ° C. in a state where a tannin compound is present in the polyurethane resin. Moreover, when natural tannic acid is contained as a tannin-based compound, dry heat treatment can also be performed in a state in which a polyvalent metal salt is simultaneously contained in the polyurethane resin. By performing the dry heat treatment, the tannin-based compound is easily bonded to the urethane polymer, and the effect is improved. Here, when the temperature of the dry heat treatment is less than 40 ° C., the improvement in the effect before and after the heat treatment is small. Conversely, when the temperature exceeds 170 ° C., the effect is not improved and the polyurethane resin is thermally deteriorated. Therefore, it is not preferable. In addition, this dry heat processing may be a normal method.
本発明のポリウレタン加工布帛において、染色された布帛にポリウレタン樹脂が皮膜状に付着しており、かつ該ウレタン樹脂には前記のタンニン系化合物が付着および／または含有している。該タンニン系化合物はウレタンポリマーとしっかりと結合しているため、布帛の染料がウレタン樹脂にほとんど移行することがない。同時に、制電性、防水性、接着性などのポリウレタン樹脂の機能が損なわれることがない。その際、染料移行汚染堅牢度試験で３級以上（より好ましくは４級以上）であることが好ましい。また、ポリウレタン樹脂が制電機能を有する場合には、摩擦帯電圧で２５００Ｖ以下（より好ましくは５０〜１５００Ｖ）であることが好ましい。さらに、タンニン系化合物は通常低着色であるため外観が損なわれることもない。 In the polyurethane processed fabric of the present invention, the polyurethane resin adheres to the dyed fabric in the form of a film, and the urethane resin contains and / or contains the tannin compound. Since the tannin compound is firmly bonded to the urethane polymer, the fabric dye hardly transfers to the urethane resin. At the same time, the functions of the polyurethane resin such as antistatic properties, waterproofness, and adhesiveness are not impaired. In that case, it is preferable that it is the 3rd grade or more (more preferably the 4th grade or more) in the dye transfer contamination fastness test. Moreover, when a polyurethane resin has an antistatic function, it is preferable that it is 2500V or less (more preferably 50-1500V) in a frictional band voltage. Furthermore, since the tannin compound is usually low in color, the appearance is not impaired.
本発明のポリウレタン加工布帛には、必要に応じて通常のアルカリ減量加工が施されてもよい。さらには、常法の吸水加工、撥水加工、起毛加工、紫外線遮蔽あるいは、抗菌剤、消臭剤、防虫剤、蓄光剤、再帰反射剤、マイナスイオン発生剤等の機能を付与する各種加工を付加適用してもよい。 The polyurethane processed fabric of the present invention may be subjected to normal alkali weight reduction processing as necessary. In addition, conventional water-absorbing processing, water-repellent processing, brushed processing, UV shielding or various processing that provides functions such as antibacterial agents, deodorants, insect repellents, phosphorescent agents, retroreflective agents, negative ion generators, etc. Additional applications may be applied.
以下、実施例をあげて本発明を詳細に説明するが、本発明はこれらによって何ら限定されるものではない。なお、実施例中の各物性は下記の方法により測定したものである。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited at all by these. In addition, each physical property in an Example is measured with the following method.
次に本発明の実施例及び比較例を詳述するが、本発明はこれらによって限定されるものではない。
（１）染料移行汚染堅牢性
試験片（５ｃｍ×５ｃｍ）と、該試験片と同一の白布に同一のポリウレタン加工及びタンニン系化合物処理を施した添付片（５ｃｍ×５ｃｍ）とが接触するようにアルミ板２枚の間に挟み込んだ後、そのアルミ板の上に４４．１Ｎ（４．５ｋｇｆ）の荷重をかけ、恒温加熱処理機で１２０℃×８０分の熱処理を行い、試験片から添付白布への染料移行状態を汚染用グレースケールで１〜５級に等級判定を行った。等級が高いほど、堅牢度が良好である。
なお、試験片がポリウレタンコーテイング布帛である場合は、添付片は、試験片と同一生地の白布に同一のポリウレタンコーテイング及びタンニン系化合物処理を施したものを使用し、かつコーテイング面同士を接触させた。
（２）摩擦堅牢度試験
ＪＩＳ Ｌ−０８４９に準じて乾摩擦堅牢度と湿摩擦堅牢度を測定した。堅牢度の判定はグレースケールで１〜５級に等級判定を行った。等級が高いほど、堅牢度が良好である。
（３）ピックアップ率
下記式により求めた。
ピックアップ率（％）＝（（液重量）／（液付与前の布帛重量））×１００
（４）摩擦耐電圧
ＪＩＳ Ｌ １０９４−１９９７により摩擦耐電圧（Ｖ）をｎ数３で測定した。
（５）防水性
＜防水性＞ＪＩＳ Ｌ １０９２−Ｂの高水圧法でｎ数３で測定し、６ｋＰａ以上のものを良好、４ｋＰａ以上６ｋＰａ未満のものを普通、４ｋＰａ未満のものを不良とした。
（６）風合い（硬さ）
試験者３名により官能評価し、「良好」（ソフト性に優れる）、「普通」、「不良」（硬い）の３段階で評価した。
Next, although the Example and comparative example of this invention are explained in full detail, this invention is not limited by these.
(1) Dye transfer contamination fastness The test piece (5 cm × 5 cm) and the attached piece (5 cm × 5 cm) of the same white cloth as the test piece subjected to the same polyurethane processing and tannin compound treatment are in contact with each other. After being sandwiched between two aluminum plates, a load of 44.1 N (4.5 kgf) was applied on the aluminum plate, and heat treatment was performed at 120 ° C. for 80 minutes with a constant temperature heat treatment machine. The state of dye transfer to was graded 1-5 with a gray scale for contamination. The higher the grade, the better the fastness.
In addition, when the test piece is a polyurethane coating fabric, the attached piece is a white cloth of the same fabric as the test piece, and the same polyurethane coating and tannin compound treatment are used, and the coating surfaces are brought into contact with each other. .
(2) Friction fastness test A dry friction fastness and a wet friction fastness were measured according to JIS L-0849. The determination of fastness was graded from 1 to 5 on a gray scale. The higher the grade, the better the fastness.
(3) Pickup rate It calculated | required by the following formula.
Pickup rate (%) = ((liquid weight) / (cloth weight before liquid application)) × 100
(4) Friction withstand voltage Friction withstand voltage (V) was measured by n number 3 according to JIS L 1094-1997.
(5) Waterproofness <Waterproofness> Measured by n number of 3 using the high water pressure method of JIS L 1092-B, those with 6 kPa or more are good, those with 4 kPa or more and less than 6 kPa are normal, and those with less than 4 kPa are bad .
(6) Texture (hardness)
Sensory evaluation was performed by three testers, and was evaluated in three stages: “good” (excellent softness), “normal”, and “bad” (hard).
［実施例１］
経糸として、総繊度５６ｄｔｅｘ／２０ｆｉｌの通常のポリエチレンテレフタレート繊維、緯糸として、総繊度８４ｄｔｅｘ／３６ｆｉｌの通常のポリエチレンテレフタレート繊維を用い、経糸密度９７本／２．５４ｃｍ、緯糸密度７７本／２．５４ｃｍのタフタ織物を得た。かかるタフタ織物に常法の精錬、リラックス処理を施したのち、分散染料カヤロン・ポリエスター・スカーレットＧＳ（日本化薬（株）製）３．５％ｏｗｆの濃度で、１３０℃の温度で６０分間染色した後、常法により還元洗浄、水洗、乾燥後、１６０℃でセットして基布とした。
[Example 1]
A normal polyethylene terephthalate fiber having a total fineness of 56 dtex / 20 fil is used as the warp, and a normal polyethylene terephthalate fiber having a total fineness of 84 dtex / 36 fil is used as the weft. A taffeta fabric was obtained. After refining and relaxing the conventional taffeta fabric, the disperse dye Kayalon Polyester Scarlet GS (manufactured by Nippon Kayaku Co., Ltd.) at a concentration of 3.5% owf at a temperature of 130 ° C. for 60 minutes After dyeing, it was subjected to reduction washing, water washing and drying by a conventional method, and then set at 160 ° C. to obtain a base fabric.
次いで、下記の処方からなる制電加工用ポリウレタン処理液をピックアップ率５０％となるようにパデイングし、次いで１３０℃で３分間乾熱処理を施した後、１７０℃で１分間ヒートセットを行うことにより、ポリウレタン樹脂が付与された布帛を得た。 Next, by padding the antistatic processing polyurethane treatment liquid having the following formulation so that the pick-up rate is 50%, and then subjecting to a dry heat treatment at 130 ° C. for 3 minutes, and then heat setting at 170 ° C. for 1 minute. A fabric to which a polyurethane resin was applied was obtained.
［制電加工用ポリウレタン処理液の組成］
・水 ８９リットル
・ポリウレタン系制電剤 １０リットル
（エバファノールＡＳ−２１ 日華化学工業（株）社製、有効成分約３３％）
・反応触媒 １リットル
（ＮＫカタリストＳＬ 日華化学工業（株）社製）
次いで、下記の処方からなる８０℃の還元洗浄処理液で５分間還元洗浄を実施後、６０℃で５分の湯洗、１分の水洗を行った。
[Composition of polyurethane treatment liquid for anti-static processing]
-89 liters of water-10 liters of polyurethane antistatic agent (Evaphanol AS-21, manufactured by Nikka Chemical Co., Ltd., active ingredient about 33%)
・ Reaction catalyst 1 liter (NK Catalyst SL, manufactured by Nikka Chemical Co., Ltd.)
Subsequently, after carrying out reduction washing for 5 minutes with the 80 degreeC reduction washing process liquid which consists of the following prescription, 60 minutes water washing for 5 minutes and water washing for 1 minute were performed.
［還元洗浄処理液の組成］
・水 ９６．５重量部
・ハイドロサルファイト ２重量部
・水酸化ナトリウム １重量部
・エステル系非イオン活性剤 ０．５重量部
（トライポールＴＫ 第一工業製薬（株）製）
[Composition of reducing cleaning solution]
-96.5 parts by weight of water-2 parts by weight of hydrosulfite-1 part by weight of sodium hydroxide-0.5 parts by weight of ester-based nonionic active agent (Tripole TK, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
続いて、下記の処方からなる８０℃のタンニン系化合物処理液を、天然タンニン酸と酒石酸アンチモンカリウムとの合計が生地重量に対して１重量％となるよう５分間処理した後、８０℃で５分間の湯洗、１分間の水洗を行い、さらに、１６０℃、１分間熱風乾燥した。 Subsequently, an 80 ° C. tannin compound treatment solution having the following formulation was treated for 5 minutes so that the total of natural tannic acid and potassium antimony tartrate was 1% by weight with respect to the weight of the dough, and then at 80 ° C. for 5 minutes. Washed with hot water for 1 minute, washed with water for 1 minute, and further dried with hot air at 160 ° C. for 1 minute.
［タンニン系化合物処理液の組成］
・天然タンニン酸 １．５重量部
・酒石酸アンチモンカリウム ０．５重量部
・ＰＨ４．５に調製された軟水 １９９８重量部
[Composition of tannin compound treatment solution]
-Natural tannic acid 1.5 parts by weight-Antimony potassium tartrate 0.5 parts by weight-Soft water prepared to PH 4.5 1998 parts by weight
得られたポリウレタン加工布帛において、天然タンニン酸のポリウレタン樹脂に対する重量比は１０重量％であった。また、染料移行汚染堅牢性４−５級、乾摩擦堅牢度４−５級、湿摩擦堅牢度４級、摩擦耐電圧５００Ｖ、風合い「良好」とポリウレタン樹脂の機能（制電性）を維持しつつ分散染料移行性の少ない優れたものであった。 In the obtained polyurethane processed fabric, the weight ratio of natural tannic acid to the polyurethane resin was 10% by weight. Also, dye transfer contamination fastness 4-5, dry friction fastness 4-5, wet friction fastness 4th, friction withstand voltage 500V, texture "good" and the function of polyurethane resin (antistatic) are maintained. However, it was excellent with little disperse dye transferability.
［実施例２］
実施例１において、制電加工用ポリウレタン処理液をパデイングするかわりに、防水用ポリエステル系ポリウレタン樹脂（クリスボン８００６Ｖ、大日本インキ（株）製）のジメチルホルムアミド溶液を通常のナイフコーターで基布に、塗布量１２０ｇ／ｍ２コーテイングし、乾式法で凝固させポリウレタンコーテイング布帛を得て、実施例１と同様にタンニン系化合物処理および乾燥を行った。
[Example 2]
In Example 1, instead of padding the antistatic polyurethane treatment liquid, a dimethylformamide solution of a polyester polyurethane resin for waterproofing (Chrisbon 8006V, manufactured by Dainippon Ink Co., Ltd.) was applied to the base fabric with a normal knife coater. A coating amount of 120 g / m 2 was applied, solidified by a dry method to obtain a polyurethane coating fabric, and the tannin compound treatment and drying were performed in the same manner as in Example 1.
得られたポリウレタン加工布帛において、天然タンニン酸のポリウレタン樹脂に対する重量比は５重量％であった。また、染料移行汚染堅牢性４−５級、乾摩擦堅牢度４−５級、湿摩擦堅牢度４級、防水性「良好」、風合い「良好」とポリウレタン樹脂の機能（防水性）を維持しつつ分散染料移行性の少ない良好なものであった。 In the obtained polyurethane processed fabric, the weight ratio of natural tannic acid to the polyurethane resin was 5% by weight. Also, dye transfer contamination fastness 4-5, dry friction fastness 4-5, wet friction fastness 4th grade, waterproof "good", texture "good" and polyurethane resin function (waterproof) However, it was good with little disperse dye transferability.
［比較例１］
実施例１において、タンニン系化合物処理を行わないこと以外は実施例１と同様にした。得られたポリウレタン加工布帛において、染料移行汚染堅牢性１級、乾摩擦堅牢度１−２級、湿摩擦堅牢度１級、摩擦耐電圧５００Ｖ、風合い「良好」であり、分散染料移行性のある不十分なものであった。
[Comparative Example 1]
In Example 1, it carried out similarly to Example 1 except not performing a tannin type compound process. In the obtained polyurethane processed fabric, dye transfer contamination fastness 1st grade, dry friction fastness 1st grade 1-2, wet friction fastness 1st grade, friction withstand voltage 500V, texture "good", disperse dye transferability It was insufficient.
［比較例２］
実施例２において、タンニン系化合物処理を行わないこと以外は実施例２と同様にした。得られたポリウレタン加工布帛において、染料移行汚染堅牢性２級、乾摩擦堅牢度２−３級、湿摩擦堅牢度２級、防水性「良好」、風合い「良好」であり、分散染料移行性のある不十分なものであった。
[Comparative Example 2]
In Example 2, it carried out similarly to Example 2 except not performing a tannin-type compound process. In the obtained polyurethane-treated fabric, dye transfer contamination fastness level 2, dry friction fastness level 2-3, wet friction fastness level 2, waterproof property “good”, texture “good”, disperse dye transfer property There was an inadequate thing.
本発明のポリウレタン加工布帛は、ポリウレタン樹脂の機能を維持しつつ、分散染料移行性が少ないため、一般衣料、スポーツ衣料、傘などの産業用に好適であり、その工業的価値は極めて大である。 The polyurethane processed fabric of the present invention is suitable for industrial use such as general clothing, sports clothing, umbrellas and the like because of its low disperse dye transferability while maintaining the function of the polyurethane resin, and its industrial value is extremely large. .
Claims (8)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007002214A (en) * | 2005-06-20 | 2007-01-11 | Everest Textile Co Ltd | Waterproof coating composition and method for producing the same |
| WO2008016060A1 (en) * | 2006-07-31 | 2008-02-07 | Daikin Co., Ltd. | Flameproofing agent for polyester and flameproofing treatment using the same |
| WO2018101016A1 (en) * | 2016-11-30 | 2018-06-07 | 株式会社クラレ | Dyed leather-form sheet and fiber structure |
| CN110392753A (en) * | 2017-05-31 | 2019-10-29 | 株式会社可乐丽 | Leather-shaped sheets and fiber construct |
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| JP2000265367A (en) * | 1999-03-19 | 2000-09-26 | Ajinomoto Co Inc | Synthetic microfiber for electrostatic flocking and fabric using the same |
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| JP2001081670A (en) * | 1999-09-10 | 2001-03-27 | Nicca Chemical Co Ltd | Wet fastness improver for polyamide fiber and method for improving wet fastness of polyamide fiber |
| JP2001140167A (en) * | 1999-11-02 | 2001-05-22 | Asahi Kasei Corp | Antifouling polyurethane elastic fiber and method for producing the same |
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| JPS58149375A (en) * | 1982-02-26 | 1983-09-05 | 旭化成株式会社 | Production of anti-bacterial and anti- fungal processed fiber product |
| JPS61252383A (en) * | 1985-04-30 | 1986-11-10 | セ−レン株式会社 | Production of polyester coated cloth |
| JPH03152271A (en) * | 1989-11-10 | 1991-06-28 | Seiren Co Ltd | Fiber structure containing elastic yarn having excellent durability and production thereof |
| JPH0578569A (en) * | 1991-09-24 | 1993-03-30 | Asahi Chem Ind Co Ltd | Polyurethane composition |
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| JP2000265367A (en) * | 1999-03-19 | 2000-09-26 | Ajinomoto Co Inc | Synthetic microfiber for electrostatic flocking and fabric using the same |
| JP2001020179A (en) * | 1999-07-12 | 2001-01-23 | Toray Ind Inc | Fibrous material |
| JP2001081670A (en) * | 1999-09-10 | 2001-03-27 | Nicca Chemical Co Ltd | Wet fastness improver for polyamide fiber and method for improving wet fastness of polyamide fiber |
| JP2001140167A (en) * | 1999-11-02 | 2001-05-22 | Asahi Kasei Corp | Antifouling polyurethane elastic fiber and method for producing the same |
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| JP2007002214A (en) * | 2005-06-20 | 2007-01-11 | Everest Textile Co Ltd | Waterproof coating composition and method for producing the same |
| WO2008016060A1 (en) * | 2006-07-31 | 2008-02-07 | Daikin Co., Ltd. | Flameproofing agent for polyester and flameproofing treatment using the same |
| JP5297805B2 (en) * | 2006-07-31 | 2013-09-25 | 株式会社ダイキン | Flame retardant treatment for polyester and flame retardant treatment method using the same |
| WO2018101016A1 (en) * | 2016-11-30 | 2018-06-07 | 株式会社クラレ | Dyed leather-form sheet and fiber structure |
| CN109937274A (en) * | 2016-11-30 | 2019-06-25 | 株式会社可乐丽 | Through hyperchromatic leather-like sheet and fiber construct |
| CN109937274B (en) * | 2016-11-30 | 2022-05-24 | 株式会社可乐丽 | Dyed leather-like sheet and fiber structure |
| US11339531B2 (en) | 2016-11-30 | 2022-05-24 | Kuraray Co., Ltd. | Dyed leather-like sheet and fiber structure |
| CN110392753A (en) * | 2017-05-31 | 2019-10-29 | 株式会社可乐丽 | Leather-shaped sheets and fiber construct |
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