JP2016069767A - Water and oil repellent fabric - Google Patents
Water and oil repellent fabric Download PDFInfo
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- JP2016069767A JP2016069767A JP2014201526A JP2014201526A JP2016069767A JP 2016069767 A JP2016069767 A JP 2016069767A JP 2014201526 A JP2014201526 A JP 2014201526A JP 2014201526 A JP2014201526 A JP 2014201526A JP 2016069767 A JP2016069767 A JP 2016069767A
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- 239000004744 fabric Substances 0.000 title claims abstract description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000005871 repellent Substances 0.000 title claims abstract description 62
- 230000002940 repellent Effects 0.000 title claims abstract description 48
- -1 isocyanate compound Chemical class 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000012948 isocyanate Substances 0.000 claims abstract description 26
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 20
- 229940126062 Compound A Drugs 0.000 claims abstract description 12
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000003373 anti-fouling effect Effects 0.000 claims abstract description 8
- 150000002222 fluorine compounds Chemical class 0.000 claims description 50
- 239000007921 spray Substances 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 abstract description 10
- 239000011737 fluorine Substances 0.000 abstract description 10
- 238000005299 abrasion Methods 0.000 abstract description 9
- 239000007787 solid Substances 0.000 description 22
- 239000000835 fiber Substances 0.000 description 18
- 238000009940 knitting Methods 0.000 description 18
- 229920000728 polyester Polymers 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003431 cross linking reagent Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 229920000877 Melamine resin Polymers 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000003984 copper intrauterine device Substances 0.000 description 7
- 238000004043 dyeing Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- 239000004640 Melamine resin Substances 0.000 description 6
- 239000002759 woven fabric Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 3
- 238000007447 staining method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010014 continuous dyeing Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000000986 disperse dye Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000985 reactive dye Substances 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 1
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009990 desizing Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 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
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 238000004394 yellowing prevention Methods 0.000 description 1
Landscapes
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
本発明は、高い撥水撥油性を有し、湿潤摩耗耐久性に優れるとともに、汚れの除去が容易で防汚性に優れる撥水撥油性布帛に関する。 The present invention relates to a water / oil repellent fabric having high water / oil repellency, excellent wet wear durability, easy removal of dirt and excellent antifouling properties.
従来、布帛に高度の撥水撥油性を与える方法としては、フッ素系化合物を含有する撥水撥油加工剤を用いて、繊維表面に撥水撥油剤皮膜を形成する方法が行われている。
しかし、ポリエステル等の化学繊維は親油性であるため、依然として油等の汚れを吸着し易いという問題があった。また、布帛同士の接触時や、布帛と他の物体との摩擦により、撥水撥油剤皮膜が簡単に繊維から脱落して撥水撥油性能、特に撥油性能が大幅に低下するという問題もあった。
Conventionally, as a method of imparting a high degree of water / oil repellency to a fabric, a method of forming a water / oil repellent film on the fiber surface using a water / oil repellent finish containing a fluorine compound has been performed.
However, since chemical fibers such as polyester are oleophilic, there is still a problem that dirt such as oil is still easily adsorbed. In addition, there is a problem that the water / oil repellent film easily drops off from the fiber when the fabrics come into contact with each other or due to friction between the fabric and other objects, and the water / oil repellent performance, particularly the oil repellent performance is greatly reduced. there were.
摩擦による撥水撥油性の低下を防ぐ方法としては、例えば、特許文献１には、フッ素系化合物を含有する撥水撥油加工剤にイソシアネート系架橋剤を添加する方法が記載されている。
また、特許文献２には、イソシアネート系架橋剤に加えて、メラミン系架橋剤、カルボジイミド系架橋剤、オキサゾリン系架橋剤を用いる方法が記載されている。
As a method for preventing a decrease in water and oil repellency due to friction, for example, Patent Document 1 describes a method of adding an isocyanate crosslinking agent to a water and oil repellent finishing agent containing a fluorine compound.
Patent Document 2 describes a method using a melamine-based crosslinking agent, a carbodiimide-based crosslinking agent, and an oxazoline-based crosslinking agent in addition to the isocyanate-based crosslinking agent.
一方で、昨今の撥水撥油性布帛には、従来よりも更に高い撥油性が要求されている。加えて、僅かな汚れが付着したような状況では、汚れが付着した箇所を、ウェットティシュや液体洗剤をしみ込ませた布等で拭き取ることは日常よく行われている。この場合、汚れが除去しにくい場合や、拭き取り忘れがあってシミになった部分がある場合は、より強い力で擦られることとなる。従って、昨今の撥水撥油性布帛には、湿潤摩耗に対する耐久性（湿潤摩耗しても撥水撥油性が低下しないこと）も要求される。
しかしながら、特許文献１及び２に記載の撥水撥油性布帛では、撥水性に優れるものの、撥油性が低下するという問題があった。
また、特許文献１及び２に記載の撥水撥油性布帛では、湿潤摩耗耐久性に優れる撥水撥油性については一切検討されていなかった。
On the other hand, recent water and oil repellent fabrics are required to have higher oil repellency than before. In addition, in a situation where a slight amount of dirt has adhered, it is common practice to wipe off the area where the dirt has adhered with a cloth soaked with wet tissue or liquid detergent. In this case, if the dirt is difficult to remove, or if there is a spot that has been forgotten to be wiped off, it will be rubbed with a stronger force. Accordingly, recent water and oil repellent fabrics are also required to have durability against wet wear (the water and oil repellency does not decrease even when wet worn).
However, the water- and oil-repellent fabrics described in Patent Documents 1 and 2 are excellent in water repellency, but have a problem that the oil repellency is lowered.
In addition, in the water / oil repellent fabrics described in Patent Documents 1 and 2, water / oil repellent properties excellent in wet wear durability have not been studied at all.
本発明は、上記現状に鑑み、高い撥水撥油性を有し、湿潤摩耗耐久性に優れるとともに、汚れの除去が容易で防汚性に優れる撥水撥油性布帛を提供することを目的とする。 In view of the above situation, an object of the present invention is to provide a water / oil repellent fabric having high water / oil repellency, excellent wet wear durability, easy removal of dirt and excellent antifouling properties. .
本発明は、炭素数４のパーフルオロアルキル基を含むフッ素系化合物Ａと、炭素数６のパーフルオロアルキル基を含むフッ素系化合物Ｂと、イソシアネート化合物と、トリアジン化合物とを含有する皮膜を有し、ＡＡＴＣＣ ＴＭ１１８滴下法による撥油性が７級以上である撥水撥油性布帛である。
以下に本発明を詳述する。
The present invention has a film containing a fluorine compound A containing a C4 perfluoroalkyl group, a fluorine compound B containing a C6 perfluoroalkyl group, an isocyanate compound, and a triazine compound. A water- and oil-repellent fabric having an oil repellency of 7 or higher according to the AATCC TM118 dropping method.
The present invention is described in detail below.
本発明者らは、従来技術において、特に撥油性が低下する原因を検討したところ、撥水撥油剤と架橋剤との組み合わせが適切でないことに起因しているとの考えに至った。
そして、撥水撥油剤と架橋剤との組み合わせについて試行錯誤を繰り返したところ、特定炭素数のパーフルオロアルキル基を含む２種のフッ素系化合物を併用することに加え、特定の架橋剤を組み合わせて使用することで、意外にも高い撥油性を有し、湿潤摩耗耐久性に優れるとともに、汚れの除去が容易で防汚性に優れる撥水撥油性布帛が得られることを見出し、本発明を完成させるに至った。
The inventors of the present invention have examined the cause of the decrease in oil repellency, particularly in the prior art, and have come to believe that the combination of the water / oil repellent and the crosslinking agent is not appropriate.
And when trial and error was repeated about the combination of a water / oil repellent and a crosslinking agent, in addition to using together two kinds of fluorine compounds containing a perfluoroalkyl group having a specific carbon number, a specific crosslinking agent was combined. By using it, it was found that a water / oil repellent fabric having surprisingly high oil repellency, excellent wet wear durability, easy removal of dirt and excellent antifouling properties was obtained, and the present invention was completed. I came to let you.
本発明の撥水撥油性布帛は、炭素数４のパーフルオロアルキル基を含むフッ素系化合物Ａと、炭素数６のパーフルオロアルキル基を含むフッ素系化合物Ｂと、イソシアネート化合物と、トリアジン化合物とを含有する皮膜を有するものである。 The water / oil repellent fabric of the present invention comprises a fluorine compound A containing a C4 perfluoroalkyl group, a fluorine compound B containing a C6 perfluoroalkyl group, an isocyanate compound, and a triazine compound. It has a film to contain.
本発明では、２種類のフッ素系化合物を使用する。
上記２種類のフッ素系化合物は、ともにパーフルオロオクタン酸を含有しない。また、上記２種類のフッ素系化合物は、フッ素系化合物中にパーフルオロオクタン酸が残留或いは経時的に生成し難いものである。これにより、環境汚染の防止に貢献することができる。
また、炭素数の異なる２種類のフッ素系化合物を使用することで、撥水性と撥油性とを兼ね備えた皮膜を形成することができる。
In the present invention, two types of fluorine compounds are used.
Both of the two types of fluorine compounds do not contain perfluorooctanoic acid. In addition, the two types of fluorine compounds are those in which perfluorooctanoic acid remains in the fluorine compounds or is difficult to form over time. Thereby, it can contribute to prevention of environmental pollution.
Moreover, the film which has both water repellency and oil repellency can be formed by using two types of fluorine compounds from which carbon number differs.
上記２種類のフッ素系化合物は、炭素数４のパーフルオロアルキル基、炭素数６のパーフルオロアルキル基をそれぞれ含むものであれば、特に限定されないが、上記パーフルオロアルキル基を含有する重合体と重合可能な他の重合性単量体を公知ないしは周知の重合方法によって重合した共重合体を用いることができる。例えば、アクリレート、メタクリレート、スチレン、塩化ビニル等のビニル化合物との共重合体等が挙げられる。
なかでも、アクリル共重合体であることが好ましい。
The two kinds of fluorine-based compounds are not particularly limited as long as each of them contains a perfluoroalkyl group having 4 carbon atoms and a perfluoroalkyl group having 6 carbon atoms, and a polymer containing the perfluoroalkyl group and A copolymer obtained by polymerizing another polymerizable monomer capable of polymerization by a known or well-known polymerization method can be used. For example, a copolymer with a vinyl compound such as acrylate, methacrylate, styrene, or vinyl chloride can be used.
Among these, an acrylic copolymer is preferable.
上記２種類のフッ素系化合物としては、通常、水溶性のエマルションの形態でフッ素系撥水撥油剤として市販されているものを使用することができる。
上記炭素数４のパーフルオロアルキル基を含むフッ素系化合物Ａ、又は、フッ素系化合物Ａとフッ素系化合物Ｂとの混合物を含むエマルションとしては、例えば、スコッチガードＰＭ３６２２、スコッチガードＰＭ４９０、スコッチガードＰＭ９３０（何れも住友スリーエム社製）、パラガードＴＯ−８（大原パラヂウム化学社製）等が挙げられる。
上記炭素数６のパーフルオロアルキル基を含むフッ素系化合物Ｂを含むエマルションとしては、例えば、アサヒガードＡＧ−Ｅ５００Ｄ、アサヒガードＡＧ−Ｅ０９２、アサヒガードＡＧ−Ｅ０８１（何れも旭硝子株式会社製）、パラガードＴＯＳ−８、パラガードＥＣ−１１００（何れも大原パラヂウム化学社製）等が挙げられる。
As the two types of fluorine compounds, those commercially available as fluorine-based water and oil repellents in the form of water-soluble emulsions can be used.
Examples of the emulsion containing fluorine compound A containing a perfluoroalkyl group having 4 carbon atoms or a mixture of fluorine compound A and fluorine compound B include, for example, Scotch guard PM 3622, Scotch guard PM 490, and Scotch guard PM 930 ( All of them are manufactured by Sumitomo 3M Co., Ltd.), Paragard TO-8 (manufactured by Ohara Palladium Chemical Co., Ltd.) and the like.
Examples of the emulsion containing the fluorine compound B containing a C6 perfluoroalkyl group include Asahi Guard AG-E500D, Asahi Guard AG-E092, Asahi Guard AG-E081 (all manufactured by Asahi Glass Co., Ltd.), Paraguard TOS-8, Paragard EC-1100 (both manufactured by Ohara Palladium Chemical Co., Ltd.) and the like can be mentioned.
上記フッ素系化合物Ａ及びフッ素系化合物Ｂの含有比は特に限定されないが、１０：９０〜９０：１０であることが好ましい。フッ素系化合物Ａが１０％未満であると、本発明を満足する撥油性能が得られないことがあり、フッ素系化合物Ｂが１０％を超えると、本発明を満足する撥水性能が得られなくなることがある。 The content ratio of the fluorine compound A and the fluorine compound B is not particularly limited, but is preferably 10:90 to 90:10. When the fluorine compound A is less than 10%, the oil repellency performance that satisfies the present invention may not be obtained, and when the fluorine compound B exceeds 10%, the water repellency performance that satisfies the present invention is obtained. It may disappear.
上記フッ素系化合物の総付着量としては、皮膜を形成する布帛（原料たる繊維布帛）１００質量部に対して０．１〜２．０質量部であることが好ましい。上記総付着量が０．１質量部未満であると、撥水撥油性能が不充分となることがあり、２．０質量部を超えると、撥水撥油性布帛の風合いが硬くなるとともに、摩耗性が悪化して摩耗撥水撥油性能が不充分となることがある。
さらに、上記フッ素系化合物は、分子中に親水性基を含有しないものであることが好ましい。親水性基を含有すると、高度な撥水撥油性が得られない場合がある。なお、上記にフッ素系化合物Ａ、又は、フッ素系化合物Ａとフッ素系化合物Ｂとの混合物を含むエマルション、並びに、フッ素系化合物Ｂを含むエマルションとして列挙した製品は、分子中に親水性基を含有しないものである。
上記親水性基としては、ポリエチレングリコール基、ポリプロピレングリコール基等のポリエーテル基が挙げられる。また、同様の理由から、後述するフッ素系化合物等を含む処理液には、親水性成分を含有する化合物を配合しないことが好ましい。
The total adhesion amount of the fluorine-based compound is preferably 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the fabric forming the film (fiber fabric as a raw material). When the total adhesion amount is less than 0.1 parts by mass, the water / oil repellency may be insufficient, and when it exceeds 2.0 parts by mass, the texture of the water / oil repellent fabric becomes hard, Abrasion may deteriorate and wear / water / oil repellency may be insufficient.
Furthermore, it is preferable that the said fluorine-type compound is a thing which does not contain a hydrophilic group in a molecule | numerator. If a hydrophilic group is contained, high water / oil repellency may not be obtained. In addition, the above-mentioned emulsions containing the fluorine compound A or a mixture of the fluorine compound A and the fluorine compound B and the emulsion containing the fluorine compound B contain a hydrophilic group in the molecule. It is something that does not.
Examples of the hydrophilic group include polyether groups such as a polyethylene glycol group and a polypropylene glycol group. For the same reason, it is preferable not to add a compound containing a hydrophilic component to the treatment liquid containing a fluorine-based compound or the like described later.
上記イソシアネート化合物としては、例えば、ジイソシアネート化合物、トリイソシアネート化合物、ポリイソシアネート化合物が好ましく、例えば、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ヘキサメチレントリイソシアネート、リジンエステルトリイソシアネート、イソホロンジイソシアネート、水添キシリレンジイソシアネート、トルエンジイソシアネート、キシレ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等が挙げられる。
なかでも、上記イソシアネート化合物としては、１分子中にイソシアネート基を３個以上有する多官能イソシアネート化合物であることが好ましい。上記多官能イソシアネート化合物を使用することで、架橋が進み、皮膜の耐久性が向上し、かつ繊維との密着性も上がる。かかる多官能イソシアネート化合物としては、トリイソシアネート化合物、例えば、ヘキサメチレンジイソシアネートのトリスビュレット変性体等が挙げられ、このような化合物を使用することで後述のトリアジン化合物との架橋が進みやすく好ましい。
As the isocyanate compound, for example, a diisocyanate compound, a triisocyanate compound, and a polyisocyanate compound are preferable. For example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene triisocyanate, lysine ester triisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate. , Toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate and the like.
Among these, the isocyanate compound is preferably a polyfunctional isocyanate compound having 3 or more isocyanate groups in one molecule. By using the said polyfunctional isocyanate compound, bridge | crosslinking advances, the durability of a film | membrane improves and adhesiveness with a fiber also goes up. Examples of such polyfunctional isocyanate compounds include triisocyanate compounds, for example, tris burette modified products of hexamethylene diisocyanate, and the use of such compounds is preferable because crosslinking with a triazine compound described later easily proceeds.
上記イソシアネート化合物の付着量としては、フッ素系化合物（合計、固形分）１００質量部に対して０．０１〜１．０質量部の範囲であることが好ましい。上記付着量が０．０１質量部未満であると、本発明で目的とする湿潤摩耗耐久性が得られにくく、また、付着量が１．０質量部を超えても湿潤摩耗耐久性が飽和に達するだけでなく、布帛の風合いが硬くなるために好ましくない。 The amount of the isocyanate compound adhered is preferably in the range of 0.01 to 1.0 part by mass with respect to 100 parts by mass of the fluorine-based compound (total, solid content). If the adhesion amount is less than 0.01 parts by mass, it is difficult to obtain the intended wet wear durability in the present invention, and even if the adhesion amount exceeds 1.0 parts by mass, the wet wear durability is saturated. This is not preferable because the texture of the fabric becomes hard.
上記トリアジン化合物としては下記（１）に示す一般式で示される化合物が使用できる。
上記一般式（１）で示される化合物の中では、特にトリメチロールメラミン、ヘキサメチロールメラミン等が好ましく用いられる。
As the triazine compound, a compound represented by the following general formula (1) can be used.
Among the compounds represented by the general formula (1), trimethylol melamine, hexamethylol melamine and the like are particularly preferably used.
上記トリアジン化合物の付着量は、フッ素系化合物（合計、固形分）１００質量部に対して０．０１〜１．０質量部の範囲であることが好ましい。上記付着量が０．０１質量部未満であると、湿潤摩耗耐久性が得られにくくなることがあり、上記付着量が１．０質量部を超えても湿潤摩耗耐久性が飽和に達するだけでなく、布帛の風合いが硬くなるために好ましくない。 The adhesion amount of the triazine compound is preferably in the range of 0.01 to 1.0 part by mass with respect to 100 parts by mass of the fluorine compound (total, solid content). If the adhesion amount is less than 0.01 parts by mass, it may be difficult to obtain wet wear durability. Even if the adhesion amount exceeds 1.0 parts by mass, the wet wear durability only reaches saturation. And the texture of the fabric becomes hard.
本発明の撥水撥油性布帛において、上記皮膜を形成する布帛としては、特に限定されないがポリエステル繊維を主に使用するポリエステル布帛が好ましい。
上記ポリエステル布帛としては、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等で代表されるポリエステル糸を５０質量％以上、好ましくは８０質量％以上含有する織物、編物、不織布等が好ましい。
上記ポリエステル布帛は、ポリエステル糸のみで形成された布帛が最も好ましいが、ポリエステル糸と他の糸とで形成されたものであってもよい。
上記ポリエステル糸と共に布帛を形成する他の糸としては、任意の糸が使用でき、例えば、ナイロン６、ナイロン６，６等のポリアミド糸、ポリアクリルニトリル、ポリビニルアルコールの他、ジアセテート、トリアセテート等の半合成繊維糸、あるいは木綿やウールなどの天然繊維との混合繊維等があげられる。本発明では、これらの糸を単独で又は混繊、混紡、交織編して使用する。
In the water / oil repellent fabric of the present invention, the fabric for forming the film is not particularly limited, but a polyester fabric mainly using polyester fibers is preferable.
The polyester fabric is preferably a woven fabric, a knitted fabric or a nonwoven fabric containing 50% by mass or more, preferably 80% by mass or more of a polyester yarn represented by polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate or the like.
The polyester fabric is most preferably a fabric formed only of polyester yarns, but may be formed of polyester yarns and other yarns.
As the other yarn forming the fabric together with the polyester yarn, any yarn can be used, for example, polyamide yarn such as nylon 6, nylon 6, 6, etc., polyacrylonitrile, polyvinyl alcohol, diacetate, triacetate, etc. Examples thereof include semi-synthetic fiber yarns and mixed fibers with natural fibers such as cotton and wool. In the present invention, these yarns are used singly or after being mixed, blended, or knitted.
上記皮膜を形成する布帛に用いられる織物組織および編物組織としては、特に限定されないが、織物組織としては、平織、綾織、朱子織等の三原組織、変化組織、たて二重織、よこ二重織等の片二重組織、たてビロードなどが例示され、よこ編組織としては、平編、ゴム編、両面編、パール編、タック編、浮き編、片畔編、レース編、添え毛編等が例示され、たて編組織としては、シングルデンビー編、シングルアトラス編、ダブルコード編、ハーフ編、ハーフベース編、サテン編、ハーフトリコット編、裏毛編、ジャガード編等などが例示されるがこれらに限定されない。層数も単層でもよいし、２層以上の多層でもよい。なお、これらの織物や編物は常法により製造することができる。 The woven fabric and knitted fabric used in the fabric forming the film are not particularly limited, but the woven fabric may be a three-layered structure such as plain weave, twill weave, satin weave, changed structure, warp double weave, weft double Examples of single knitted fabrics such as weaving, warp velvet, etc., include horizontal knitting, rubber knitting, double-sided knitting, pearl knitting, tuck knitting, floating knitting, one-sided knitting, lace knitting, and splicing Examples of the warp knitting structure include single denby knitting, single atlas knitting, double cord knitting, half knitting, half base knitting, satin knitting, half tricot knitting, back hair knitting, jacquard knitting, etc. However, it is not limited to these. The number of layers may be a single layer or a multilayer of two or more layers. In addition, these woven fabrics and knitted fabrics can be manufactured by a conventional method.
本発明の撥水撥油性布帛は、ＡＡＴＣＣ ＴＭ１１８滴下法による撥油性が７級以上である。これにより、本発明を満足する撥油性能に優れる撥水撥油性布帛となる。好ましくは７．５級以上である。なお、ＡＡＴＣＣ ＴＭ１１８滴下法による撥油性の上限は８級である。 The water / oil repellent fabric of the present invention has an oil repellency of 7 or higher according to the AATCC TM118 dropping method. As a result, a water / oil repellent fabric excellent in oil repellency satisfying the present invention is obtained. Preferably it is 7.5 grade or more. The upper limit of oil repellency by the AATCC TM118 dropping method is 8th grade.
また、本発明の撥水撥油性布帛は、湿潤摩耗耐久性試験後におけるＡＡＴＣＣ ＴＭ１１８滴下法による撥油性が６級以上である。これにより、本発明を満足する撥油性能を有し、湿潤摩耗耐久性に優れる撥水撥油性布帛とすることができる。
なお、上記湿潤摩耗耐久性試験とは、試料の中心付近に２０℃の水７０μｌを３ヵ所に分散して滴下した後、引張荷重、押圧荷重共に２２．３Ｎにて５００回（１００回×５回）の摩耗処理を行うことをいう。
Further, the water / oil repellent fabric of the present invention has an oil repellency of 6 grade or higher by the AATCC TM118 dropping method after the wet abrasion durability test. Thereby, it can be set as the water and oil repellency cloth which has the oil repellency performance which satisfies this invention, and is excellent in wet abrasion durability.
In the wet abrasion durability test, 70 μl of water at 20 ° C. was dispersed in three locations in the vicinity of the center of the sample and dropped, and then 500 times (100 times × 5) at 22.3 N for both tensile load and pressure load. Times) wear treatment.
本発明の撥水撥油性布帛は、ＪＩＳ Ｌ１０９２（スプレー法）による撥水性が４級以上であり、かつ、ＪＩＳ Ｌ１９１９ Ｂ法による防汚性が汚れにくさ、付いた汚れの落ちやすさ共に４級以上である。これにより、本発明を満足する撥水性能を有し、汚れの除去が容易で防汚性に優れる撥水撥油性布帛とすることができる。 The water- and oil-repellent fabric of the present invention has a water repellency according to JIS L1092 (spray method) of grade 4 or higher, and the antifouling property according to JIS L1919 B method is less likely to get dirty, and the attached dirt is easy to remove. It is more than a grade. Thereby, it can be set as the water-repellent | oil-repellent fabric which has the water-repellent performance which satisfies this invention, is easy to remove stain | pollution | contamination, and is excellent in antifouling property.
本発明の撥水撥油性布帛を構成する皮膜は、ポリエステル布帛の少なくとも片面に形成されていることが好ましい。 The film constituting the water / oil repellent fabric of the present invention is preferably formed on at least one surface of the polyester fabric.
本発明の撥水撥油性布帛を製造する方法としては、例えば、炭素数４のパーフルオロアルキル基を含むフッ素系化合物Ａと、炭素数６のパーフルオロアルキル基を含むフッ素系化合物Ｂと、イソシアネート化合物と、トリアジン化合物とを含有する処理液を布帛に付与した後、熱処理を行う方法が好ましい。
なお、上記製造方法に先立ち、布帛を染色してもよい。染色する場合には、例えば、糊抜き精練、漂白、プレセット、アルカリ減量、シルケット加工等の処理をおこなった後、染色すればよい。
Examples of the method for producing the water / oil repellent fabric of the present invention include a fluorine compound A containing a C 4 perfluoroalkyl group, a fluorine compound B containing a C 6 perfluoroalkyl group, and an isocyanate. A method in which a heat treatment is performed after applying a treatment liquid containing the compound and the triazine compound to the fabric is preferred.
Prior to the above production method, the fabric may be dyed. In the case of dyeing, for example, after processing such as desizing, bleaching, presetting, alkali weight loss, mercerizing, etc., dyeing may be performed.
上記染色の際に用いられる染料については、用途にて求められる染色堅牢度および染色濃度に応じ、適宜選択することができる。一般的に、ポリエステル繊維に対しては、分散染料が好適に用いられる。また、セルロース系繊維に対しては、直接染料、反応染料あるいはスレン染料が好適に用いられる。したがって、例えば、上記布帛がポリエステル布帛にセルロース系繊維が含まれているものである場合は、分散染料を使用して染色した後、直接染料、反応染料又はスレン染料を用いて染色するとよい。
また、染色方法としては、特に限定されないが、連続染色法やバッチ染色法等が挙げられる。
About the dye used in the case of the said dyeing | staining, it can select suitably according to the dye fastness and dyeing density calculated | required by the use. In general, disperse dyes are preferably used for polyester fibers. For cellulosic fibers, direct dyes, reactive dyes or selenium dyes are preferably used. Therefore, for example, when the above-mentioned fabric is a polyester fabric containing cellulosic fibers, it may be dyed using a disperse dye and then directly using a dye, reactive dye or selenium dye.
Moreover, it does not specifically limit as a dyeing | staining method, A continuous dyeing | staining method, a batch dyeing | staining method, etc. are mentioned.
また、上記フッ素系化合物等を含む処理液は、水溶液や水分散液等の水系処理液であってもよく、ターペンやイソプロピルアルコール、トルエン、メチルエチルケトン、エタノール等を溶媒に用いた溶剤系処理液であってもよい。ただし、環境面、耐久性、黄変防止等の観点から水系処理液が好ましい。
また、処理液中には、適宜添加剤を配合してもよい。この場合、例えば、皮膜に制電性を付与するための帯電防止剤、風合い調整のための柔軟剤、紫外線遮蔽加工のための紫外線吸収剤、処理液安定性の向上のための界面活性剤、抗菌性付与のための抗菌剤、架橋用の触媒等の併用も可能である。
更に、上記処理液には、トリアジン化合物の架橋を促進する目的で触媒を添加することが好ましい。上記触媒としては、例えば、有機アミン塩や金属塩等が挙げられる。
Further, the treatment liquid containing the fluorine compound or the like may be an aqueous treatment liquid such as an aqueous solution or an aqueous dispersion, and is a solvent-based treatment liquid using terpene, isopropyl alcohol, toluene, methyl ethyl ketone, ethanol or the like as a solvent. There may be. However, an aqueous treatment liquid is preferable from the viewpoints of environment, durability, yellowing prevention and the like.
Moreover, you may mix | blend an additive suitably in a process liquid. In this case, for example, an antistatic agent for imparting antistatic properties to the film, a softening agent for adjusting the texture, an ultraviolet absorber for ultraviolet shielding processing, a surfactant for improving the treatment liquid stability, An antibacterial agent for imparting antibacterial properties, a catalyst for crosslinking and the like can also be used in combination.
Furthermore, it is preferable to add a catalyst to the treatment liquid for the purpose of promoting the crosslinking of the triazine compound. Examples of the catalyst include organic amine salts and metal salts.
上記処理液の付与方法としては、特に限定されるものではなく、パッドドライ法、パッド・スチーム法、パッド・ドライ・スチーム法、グラビアコーティング法、スプレー法などの種々の方法を用いることができる。通常のパッドドライ法などを用いた場合、含浸に際してパディング時の絞り率は、特に限定されるものではなく、例えば、４０〜１２０％の範囲の絞り率であればよい。 The method for applying the treatment liquid is not particularly limited, and various methods such as a pad dry method, a pad / steam method, a pad / dry / steam method, a gravure coating method, and a spray method can be used. When a normal pad dry method or the like is used, the squeezing rate during padding during impregnation is not particularly limited, and may be a squeezing rate in the range of 40 to 120%, for example.
上記処理液を布帛に付与した後、乾燥処理を行う。乾燥処理はホットシリンダーを用いるか、またはスチーマー、ノンタッチ型乾燥機、ネットドライヤー、ピンテンター等の公知の熱処理装置を用いて行うことができる。
上記乾燥処理条件は特に限定されるものではなく、例えば、８０〜１５０℃の温度で、ピンテンターなどの通常の熱処理機を用いて１〜１０分間行えばよい。
After the treatment liquid is applied to the fabric, a drying process is performed. The drying treatment can be performed using a hot cylinder or a known heat treatment apparatus such as a steamer, a non-touch dryer, a net dryer, or a pin tenter.
The drying treatment conditions are not particularly limited, and may be performed, for example, at a temperature of 80 to 150 ° C. for 1 to 10 minutes using a normal heat treatment machine such as a pin tenter.
更に、上記乾燥処理後、１５０〜２００℃の範囲で熱処理を追加することが好ましい。熱処理温度が１５０℃未満であると、イソシアネート系化合物及びトリアジン化合物による架橋が充分に行われず、撥水撥油性の耐久性が得られないことがある。一方、熱処理温度が２００℃を超えると、黄変する場合があるので好ましくない。熱処理時間は、特に限定されるものではないが、例えば、３０〜３００秒間であればよい。 Furthermore, it is preferable to add a heat treatment in the range of 150 to 200 ° C. after the drying treatment. When the heat treatment temperature is less than 150 ° C., crosslinking with an isocyanate compound and a triazine compound is not sufficiently performed, and water / oil repellency durability may not be obtained. On the other hand, when the heat treatment temperature exceeds 200 ° C., yellowing may occur, which is not preferable. The heat treatment time is not particularly limited, but may be, for example, 30 to 300 seconds.
本発明の撥水撥油性布帛は衣料用途、産業資材用途に幅広く使用できる。例えば、衣料用途では、スポーツ衣料、ユニフォーム衣料、ワーキング用途等、産業資材用途では、椅子張り、カーシート、カサ地等に使用できる。 The water / oil repellent fabric of the present invention can be widely used for apparel and industrial materials. For example, for apparel use, it can be used for sports apparel, uniform apparel, working use, etc., and for industrial material use, it can be used for chair upholstery, car seats, rust areas and the like.
本発明によれば、環境への負荷が懸念されているパーフルオロオクタン酸を使用したり、発生させたりすることなく、高い撥水撥油性を有し、特に優れた撥油性を有する布帛を提供することができる。
また、本発明の撥水撥油性布帛を構成する皮膜は、湿潤摩耗に対する高い耐久性を有することから、例えば、布帛同士の接触や、布帛と他の物体との摩擦等を行われた場合でも、優れた撥水撥油性を維持することができる。
更に、本発明の撥水撥油性布帛は、汚れを容易に除去できるという特性に加えて、汚れ自体が付着しにくいという優れた特性を有するため、椅子張り、カーシート等の洗濯を行いにくい用途にも好適に使用することができる。
According to the present invention, there is provided a fabric having high water and oil repellency, and particularly excellent oil repellency, without using or generating perfluorooctanoic acid, which is concerned about the burden on the environment. can do.
In addition, since the film constituting the water / oil repellent fabric of the present invention has high durability against wet wear, for example, even when contact between fabrics or friction between the fabric and other objects is performed. , Excellent water and oil repellency can be maintained.
Furthermore, the water- and oil-repellent fabric of the present invention has an excellent characteristic that the dirt itself is difficult to adhere in addition to the characteristic that the dirt can be easily removed. Also, it can be suitably used.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（実施例１）
経糸としてポリエステルマルチフィラメント加工糸（１６７ｄｔｅｘ／４８ｆ）を用い、緯糸としてポリエステルマルチフィラメント加工糸（３３４ｄｔｅｘ／９６ｆ）を用いて、綾織物（経糸密度：１２８本／２．５４ｃｍ、緯糸密度：５８本／２．５４ｃｍ、目付：２００ｇ／ｃｍ２）を製織した。
次いで、該綾織物に対して、通常の方法で精練、プレセットをおこなった後、下記に示す処方１に示される水溶液を調液し、該綾織物を含浸した後、マングルで絞り（絞り率：６０％）、１２０℃で１２０秒間乾燥した。その後、テンター（市金工業社製）にて１７０℃×２分の条件で熱処理を行うことで、撥水撥油性布帛を得た。
なお、得られた撥水撥油性布帛では、フッ素系化合物の総付着量が、原料たる繊維布帛１００質量部に対し１．０質量部であり、イソシアネート化合物及びトリアジン化合物の付着量が、フッ素系化合物（固形分）１００質量部に対し、それぞれ０．３質量部、０．１質量部であった。
Example 1
Polyester multifilament processed yarn (167 dtex / 48f) is used as the warp, and polyester multifilament processed yarn (334 dtex / 96f) is used as the weft. 2.54 cm, basis weight: 200 g / cm 2 ) was woven.
Next, after scouring and presetting the twill fabric by a normal method, the aqueous solution shown in Formula 1 shown below was prepared, impregnated with the twill fabric, and then squeezed with a mangle (squeezing rate) : 60%) and dried at 120 ° C. for 120 seconds. Then, the water- and oil-repellent fabric was obtained by performing heat processing on 170 degreeC * 2 minute conditions with a tenter (made by Ichikin Kogyo Co., Ltd.).
In the obtained water / oil repellent fabric, the total adhesion amount of the fluorine compound is 1.0 part by mass with respect to 100 parts by mass of the fiber fabric as the raw material, and the adhesion amount of the isocyanate compound and the triazine compound is fluorine type. It was 0.3 mass part and 0.1 mass part with respect to 100 mass parts of compounds (solid content), respectively.
＜処方１＞
パラガードＴＯＳ−８（大原パラヂウム化学社製、炭素数６のパーフルオロアルキル基を含むフッ素系化合物：固形分１８〜２２％）４０ｇ／Ｌ
パラガードＴＯ−８（大原パラヂウム化学社製、炭素数４のパーフルオロアルキル基を含むフッ素系化合物と炭素数６のパーフルオロアルキル基を含むフッ素系化合物との混合物：固形分１７〜２１％）２０ｇ／Ｌ
ベッカミンＭ−３（ＤＩＣ社製、メラミン樹脂化合物：固形分８０％）５ｇ／Ｌ
キャタリストＡＣＸ（ＤＩＣ社製、有機アミン塩、メラミン樹脂用触媒）２ｇ／Ｌ
メイカネートＷＥＢ（明成化学工業社製、１分子中にイソシアネート基を３個以上有する多官能イソシアネート化合物：固形分３３％）５ｇ／Ｌ
<Prescription 1>
Paragard TOS-8 (Ohara Palladium Chemical Co., Ltd., fluorine compound containing a C6 perfluoroalkyl group: solid content 18-22%) 40 g / L
20 g of Paragard TO-8 (Ohara Palladium Chemical Co., Ltd., a mixture of a fluorine compound containing a perfluoroalkyl group having 4 carbon atoms and a fluorine compound containing a perfluoroalkyl group having 6 carbon atoms: solid content 17 to 21%) / L
Becamine M-3 (manufactured by DIC, melamine resin compound: solid content 80%) 5 g / L
Catalyst ACX (manufactured by DIC, organic amine salt, catalyst for melamine resin) 2g / L
Meikanate WEB (manufactured by Meisei Chemical Industry Co., Ltd., polyfunctional isocyanate compound having 3 or more isocyanate groups in one molecule: solid content 33%) 5 g / L
（実施例２）
下記処方２に示す水溶液を用いた以外は実施例１と同様にして、撥水撥油性布帛を得た。
得られた撥水撥油性布帛では、フッ素系化合物の総付着量が、原料たる繊維布帛１００質量部に対し１．０質量部であり、イソシアネート化合物及びトリアジン化合物の付着量が、フッ素系化合物（固形分）１００質量部に対し、それぞれ０．３質量部、０．１質量部であった。
(Example 2)
A water / oil repellent fabric was obtained in the same manner as in Example 1 except that the aqueous solution shown in Formula 2 below was used.
In the obtained water / oil repellent fabric, the total adhesion amount of the fluorine compound is 1.0 part by mass with respect to 100 parts by mass of the fiber fabric as the raw material, and the adhesion amount of the isocyanate compound and the triazine compound is the fluorine compound ( It was 0.3 mass part and 0.1 mass part with respect to 100 mass parts of solid content, respectively.
＜処方２＞
パラガードＴＯＳ−８（大原パラヂウム化学社製、フッ素系撥水撥油剤：固形分１８〜２２％）４０ｇ／Ｌ
パラガードＴＯ−８（大原パラヂウム化学社製、フッ素撥水撥油剤：固形分１７〜２１％）２０ｇ／Ｌ
ベッカミンＭ−３（ＤＩＣ社製、メラミン樹脂化合物：固形分８０％）５ｇ／Ｌ
キャタリストＡＣＸ（ＤＩＣ社製、有機アミン塩、メラミン樹脂用触媒）２ｇ／Ｌ
メイカネートＷＥＢ（明成化学工業社製、イソシアネート化合物：固形分３３％）５ｇ／Ｌ
ナイスポールＦＥ−１８（日華化学社製、帯電防止剤、ポリエステル系樹脂：固形分３０％）５ｇ／Ｌ
<Prescription 2>
Paragard TOS-8 (Ohara Palladium Chemical Co., Ltd., fluorine-based water and oil repellent: solid content 18 to 22%) 40 g / L
Paragard TO-8 (Ohara Palladium Chemical Co., Ltd., fluorine water and oil repellent: solid content 17 to 21%) 20 g / L
Becamine M-3 (manufactured by DIC, melamine resin compound: solid content 80%) 5 g / L
Catalyst ACX (manufactured by DIC, organic amine salt, catalyst for melamine resin) 2g / L
Meikanate WEB (manufactured by Meisei Chemical Industry Co., Ltd., isocyanate compound: solid content 33%) 5 g / L
Nice pole FE-18 (manufactured by Nikka Chemical Co., Ltd., antistatic agent, polyester resin: solid content 30%) 5 g / L
（実施例３）
経糸、緯糸ともにポリエステル／綿混紡（５０：５０）の３３番手双糸を使用し、経糸密度６４本／インチ、緯糸密度５６本／インチの平組織の織物を得た。得られた織物を一般的な精練漂白、乾燥、セット工程を経て分散／スレン染色法で連続染色処理しネイビー色の織物を得た。その後、実施例１の処方１と同じ条件で加工を施すことにより、撥水撥油性布帛を得た。
得られた撥水撥油性布帛では、フッ素系化合物の総付着量が、原料たる繊維布帛１００質量部に対し０．７質量部であり、イソシアネート化合物及びトリアジン化合物の付着量が、フッ素系化合物（固形分）１００質量部に対し、それぞれ０．２４質量部、０．０１質量部であった。
(Example 3)
Polyester / cotton blend (50:50) 33rd double yarn was used for both warp and weft to obtain a plain fabric with a warp density of 64 / inch and a weft density of 56 / inch. The obtained woven fabric was subjected to a general scouring bleaching, drying, and setting process, followed by a continuous dyeing process using a dispersion / slen dyeing method to obtain a navy colored woven fabric. Then, the water- and oil-repellent fabric was obtained by processing on the same conditions as the prescription 1 of Example 1.
In the obtained water / oil repellent fabric, the total adhesion amount of the fluorine compound is 0.7 parts by mass with respect to 100 parts by mass of the fiber fabric as the raw material, and the adhesion amounts of the isocyanate compound and the triazine compound are the fluorine compound ( It was 0.24 mass part and 0.01 mass part with respect to 100 mass parts of solid content, respectively.
（比較例１）
下記処方３に示す水溶液を用いた以外は実施例２と同様にして、撥水撥油性布帛を得た。
得られた撥水撥油性布帛では、フッ素系化合物の総付着量が、原料たる繊維布帛１００質量部に対し１．１質量部であり、イソシアネート化合物及びトリアジン化合物の付着量が、フッ素系化合物（固形分）１００質量部に対し、それぞれ０．３質量部、０．１質量部であった。
(Comparative Example 1)
A water / oil repellent fabric was obtained in the same manner as in Example 2 except that the aqueous solution shown in Formula 3 below was used.
In the obtained water- and oil-repellent fabric, the total adhesion amount of the fluorine compound is 1.1 parts by mass with respect to 100 parts by mass of the fiber fabric as a raw material, and the adhesion amounts of the isocyanate compound and the triazine compound are fluorine compounds ( It was 0.3 mass part and 0.1 mass part with respect to 100 mass parts of solid content, respectively.
＜処方３＞
パラガードＥＣ−１１００（大原パラヂウム社製、炭素数６のパーフルオロアルキル基を含むフッ素系化合物：固形分２０％）７０ｇ／Ｌ
ベッカミンＭ−３（ＤＩＣ社製、メラミン樹脂化合物：固形分８０％）５ｇ／Ｌ
キャタリストＡＣＸ（ＤＩＣ社製、有機アミン塩、メラミン樹脂用触媒）２ｇ／Ｌ
メイカネートＷＥＢ（明成化学工業社製、イソシアネート化合物：固形分３３％）５ｇ／Ｌ
ナイスポールＦＥ−１８（日華化学社製、ポリエステル系樹脂：固形分３０％）５ｇ／Ｌ
<Prescription 3>
Paragard EC-1100 (Ohara Palladium Co., Ltd., fluorine compound containing a C6 perfluoroalkyl group: solid content 20%) 70 g / L
Becamine M-3 (manufactured by DIC, melamine resin compound: solid content 80%) 5 g / L
Catalyst ACX (manufactured by DIC, organic amine salt, catalyst for melamine resin) 2g / L
Meikanate WEB (manufactured by Meisei Chemical Industry Co., Ltd., isocyanate compound: solid content 33%) 5 g / L
Nice pole FE-18 (manufactured by Nikka Chemical Co., Ltd., polyester resin: solid content 30%) 5 g / L
（比較例２）
上記処方３に示す水溶液を用いた以外は実施例３と同様にして、撥水撥油性布帛を得た。
得られた撥水撥油性布帛では、フッ素系化合物の総付着量が、原料たる繊維布帛１００質量部に対し０．８質量部であり、イソシアネート化合物及びトリアジン化合物の付着量が、フッ素系化合物（固形分）１００質量部に対し、それぞれ０．２４質量部、０．０１質量部であった。
(Comparative Example 2)
A water / oil repellent fabric was obtained in the same manner as in Example 3 except that the aqueous solution shown in Formula 3 was used.
In the obtained water- and oil-repellent fabric, the total adhesion amount of the fluorine compound is 0.8 parts by mass with respect to 100 parts by mass of the fiber fabric as a raw material, and the adhesion amounts of the isocyanate compound and the triazine compound are fluorine compounds ( It was 0.24 mass part and 0.01 mass part with respect to 100 mass parts of solid content, respectively.
（比較例３）
実施例１の処方１において、「メイカネートＷＥＢ」を添加しない水溶液を用いた以外は、実施例１と同様の方法により、撥水撥油性布帛を得た。
得られた撥水撥油性布帛では、フッ素系化合物の総付着量が、原料たる繊維布帛１００質量部に対し１．０質量部であり、イソシアネート化合物及びトリアジン化合物の付着量が、フッ素系化合物（固形分）１００質量部に対し、それぞれ０質量部、０．１質量部であった。
(Comparative Example 3)
A water and oil repellent fabric was obtained in the same manner as in Example 1 except that an aqueous solution to which “Meikanate WEB” was not added was used in Formulation 1 of Example 1.
In the obtained water / oil repellent fabric, the total adhesion amount of the fluorine compound is 1.0 part by mass with respect to 100 parts by mass of the fiber fabric as the raw material, and the adhesion amount of the isocyanate compound and the triazine compound is the fluorine compound ( It was 0 mass part and 0.1 mass part with respect to 100 mass parts of solid content, respectively.
（比較例４）
実施例１の処方１において、「ベッカミンＭ−３」及び「キャタリストＡＣＸ」を添加しない水溶液を用いた以外は、実施例１と同様の方法により、撥水撥油性布帛を得た。
得られた撥水撥油性布帛では、フッ素系化合物の総付着量が、原料たる繊維布帛１００質量部に対し１．０質量部であり、イソシアネート化合物及びトリアジン化合物の付着量が、フッ素系化合物（固形分）１００質量部に対し、それぞれ０．３質量部、０質量部であった。
(Comparative Example 4)
A water- and oil-repellent fabric was obtained in the same manner as in Example 1 except that an aqueous solution to which “Becamine M-3” and “Catalyst ACX” were not added was used in Formulation 1 of Example 1.
In the obtained water / oil repellent fabric, the total adhesion amount of the fluorine compound is 1.0 part by mass with respect to 100 parts by mass of the fiber fabric as the raw material, and the adhesion amount of the isocyanate compound and the triazine compound is the fluorine compound ( It was 0.3 mass part and 0 mass part with respect to 100 mass parts of solid content, respectively.
＜評価＞
実施例及び比較例で得られた撥水撥油性布帛について以下の評価を行った。
<Evaluation>
The water and oil repellent fabrics obtained in the examples and comparative examples were evaluated as follows.
（１）撥水性
ＪＩＳ Ｌ １０９２、スプレー法にて撥水性を評価した。
(1) Water repellency JIS L 1092, water repellency was evaluated by the spray method.
（２）撥油性
ＡＡＴＣＣ ＴＭ１１８、滴下法にて撥油性を評価した。
(2) Oil repellency AATCC TM118, oil repellency was evaluated by the dropping method.
（３）湿潤摩耗耐久性
シーファ型摩耗試験機の試料ホルダーに試料を取り付け、摩擦子ホルダーにはろ紙で裏打ちした試料を取り付けた。試料の中心付近に２０℃の水７０μｌを３ヵ所に分散して滴下し、引張荷重、押圧荷重共に２２．３Ｎにて５００回（１００回×５回）の摩耗処理を行った後、風乾させた後の撥水性を（１）、撥油性を（２）記載の方法にて評価した。
(3) Wet Abrasion Durability A sample was attached to a sample holder of a Sifa type abrasion tester, and a sample lined with filter paper was attached to a friction element holder. 70 μl of water at 20 ° C. is dispersed and dropped in the vicinity of the center of the sample, and after 500 times (100 times × 5 times) wear treatment at 22.3 N for both tensile load and pressure load, it is air-dried. Thereafter, the water repellency was evaluated by the method described in (1) and the oil repellency was evaluated by the method described in (2).
（４）汚れにくさ
ＪＩＳ Ｌ １９１９ ８．２Ｂ法（スプレー法）の汚れにくさ試験にて評価した。
(4) Resistance to dirt The evaluation was made in the dirt resistance test of the JIS L 1919 8.2B method (spray method).
（５）付いた汚れの落ちやすさ
ＪＩＳ Ｌ １９１９ ８．２Ｂ法（スプレー法）の付いた汚れの落ちやすさ試験にて評価した。
(5) Ease of removal of dirt attached It was evaluated by a dirt removal test with the JIS L 1919 8.2B method (spray method).
表１から明らかなように、実施例１〜３で得られた撥水撥油性布帛は、比較例で得られた撥水撥油性布帛と、初期撥水性は差が無いが、湿潤摩耗耐久性については比較例で得られた撥水撥油性布帛よりも撥水性、撥油性で優れる結果となった。
また、汚れにくさ、付いた汚れの落ちやすさについても、比較例で得られた撥水撥油性布帛より優れているものであった。
これらの結果から、炭素数４のパーフルオロアルキル基を含むフッ素系化合物Ａは、主に撥油性に優れ、炭素数６のパーフルオロアルキル基を含むフッ素系化合物Ｂは主に撥水性に優れていることが分かる。
As is apparent from Table 1, the water / oil repellent fabrics obtained in Examples 1 to 3 have no difference in initial water repellency from the water / oil repellent fabrics obtained in Comparative Examples, but wet abrasion durability. With respect to, the water and oil repellency fabrics obtained in Comparative Examples were superior in water repellency and oil repellency.
In addition, it was also superior to the water / oil repellent fabric obtained in the comparative example in terms of resistance to soiling and ease of removal of the soiled material.
From these results, the fluorine compound A containing a C4 perfluoroalkyl group is mainly excellent in oil repellency, and the fluorine compound B containing a C6 perfluoroalkyl group is mainly excellent in water repellency. I understand that.
本発明によれば、高い撥水撥油性を有し、湿潤摩耗耐久性に優れるとともに、汚れの除去が容易で防汚性に優れる撥水撥油性布帛を提供できる。 According to the present invention, it is possible to provide a water / oil repellent fabric having high water / oil repellency, excellent wet abrasion durability, easy removal of dirt and excellent antifouling properties.
Claims (4)
ＡＡＴＣＣ ＴＭ１１８滴下法による撥油性が７級以上である
ことを特徴とする撥水撥油性布帛。 A film containing a fluorine compound A containing a C4 perfluoroalkyl group, a fluorine compound B containing a C6 perfluoroalkyl group, an isocyanate compound, and a triazine compound;
A water- and oil-repellent fabric characterized in that the oil-repellent property by the AATCC TM118 dropping method is 7 or higher.
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| KR20210110501A (en) * | 2020-02-29 | 2021-09-08 | 주식회사 윈텍스 | Antifouling fabric and producing method thereof |
| KR102359633B1 (en) * | 2020-02-29 | 2022-02-08 | 주식회사 윈텍스 | Antifouling fabric and producing method thereof |
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