JP2017115277A - Hydrolyzable paper wiper - Google Patents
Hydrolyzable paper wiper Download PDFInfo
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- JP2017115277A JP2017115277A JP2015254419A JP2015254419A JP2017115277A JP 2017115277 A JP2017115277 A JP 2017115277A JP 2015254419 A JP2015254419 A JP 2015254419A JP 2015254419 A JP2015254419 A JP 2015254419A JP 2017115277 A JP2017115277 A JP 2017115277A
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- fiber
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- 239000000835 fiber Substances 0.000 claims abstract description 44
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 39
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 31
- 238000004140 cleaning Methods 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 13
- 150000007942 carboxylates Chemical group 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052737 gold Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 24
- 229920002201 Oxidized cellulose Polymers 0.000 claims description 21
- 229940107304 oxidized cellulose Drugs 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 19
- 230000003301 hydrolyzing effect Effects 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000003232 water-soluble binding agent Substances 0.000 claims description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 229940105329 carboxymethylcellulose Drugs 0.000 claims description 3
- 230000001954 sterilising effect Effects 0.000 abstract description 15
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 13
- 150000001298 alcohols Chemical class 0.000 abstract description 7
- 229920002678 cellulose Polymers 0.000 abstract description 6
- 239000001913 cellulose Substances 0.000 abstract description 6
- 230000000638 stimulation Effects 0.000 abstract description 5
- 239000012530 fluid Substances 0.000 abstract 1
- 239000000123 paper Substances 0.000 description 51
- 235000019441 ethanol Nutrition 0.000 description 25
- 239000002253 acid Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 12
- 150000002736 metal compounds Chemical class 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 7
- 238000001000 micrograph Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000249 desinfective effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011122 softwood Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000013055 pulp slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical group OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical group CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 239000004067 bulking agent Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- -1 drainage improvers Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000013054 paper strength agent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000011012 sanitization Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Landscapes
- Non-Flushing Toilets (AREA)
- Sanitary Thin Papers (AREA)
- Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
- Paper (AREA)
Abstract
Description
本発明は、トイレ周辺の清掃後にトイレに流せる水解性の紙ワイパーに関する。 The present invention relates to a water-degradable paper wiper that can be poured into a toilet after cleaning around the toilet.
トイレ周辺の清掃後にトイレに流せる水解性ワイパーとして、紙、不織布などにエタノールやイソプロピルアルコール等の洗浄/除菌液を含浸させたものが用いられている（特許文献１，２）。特に、パルプを主体とした抄紙シートは不織布に比べて水解性が高いという特徴がある。 As a water-degradable wiper that can be poured into a toilet after cleaning around the toilet, a paper / nonwoven fabric impregnated with a cleaning / disinfecting liquid such as ethanol or isopropyl alcohol is used (Patent Documents 1 and 2). In particular, a papermaking sheet mainly composed of pulp is characterized by high water decomposability compared to a nonwoven fabric.
しかしながら、パルプシートは不織布と比べて水解性が高い分、湿潤強度が低いため、洗浄/除菌液を予め含侵した後に折り加工を行うと、シート破れが発生し易く生産性が低下する。そこで、折り加工や積層後のシート積層体に洗浄/除菌液を含侵することが望ましいが、四級アンモニウム塩等の除菌成分はパルプ繊維に吸着されやすく含侵ムラが生じやすい。除菌成分の含侵ムラは、使用時の除菌性能のバラつきや、シートの保存安定性低下の原因となる。
そこで、パルプシートに対する含侵ムラが発生しにくいエタノールやイソプロピルアルコール等のアルコール類が除菌成分として使用されるが、アルコール類は特有の刺激臭が有り、アルコール過敏な人に皮膚の赤化等が生じるおそれがある。一方、アルコール類の含有量を少なくすると、除菌性能が低下する。
However, since the pulp sheet has higher wettability than the non-woven fabric, its wet strength is low. Therefore, when folding is performed after impregnating the washing / sterilizing solution in advance, sheet tearing is likely to occur and productivity is reduced. Therefore, it is desirable to impregnate the sheet laminate after folding or lamination with a cleaning / disinfecting solution, but disinfecting components such as quaternary ammonium salts are easily adsorbed to the pulp fibers and easily cause impregnation unevenness. The uneven infiltration of the sterilization component causes variations in the sterilization performance at the time of use and decreases the storage stability of the sheet.
Therefore, alcohols such as ethanol and isopropyl alcohol, which are less likely to cause uneven impregnation of pulp sheets, are used as disinfecting components, but alcohols have a specific irritating odor and cause redness of the skin to people who are sensitive to alcohol. May occur. On the other hand, when the alcohol content is reduced, the sterilization performance is lowered.
従って本発明は、水解性及び除菌性能に優れ、アルコール類による刺激が少ない水解紙ワイパーの提供を目的とする。 Accordingly, an object of the present invention is to provide a hydrolyzed paper wiper that is excellent in water decomposability and sterilization performance and is less irritating by alcohols.
上記課題を解決するため、本発明の水解紙ワイパーは、表面にカルボキシル基又はカルボキシレート基を有する酸化セルロース繊維に対し、Ａｇ、Ａｕ、Ｐｔ、Ｐｄ、Ｎｉ、Ｍｎ、Ｆｅ、Ｔｉ、Ａｌ、Ｚｎ及びＣｕの群から選ばれる１種以上の金属元素のイオンを含有してなる金属イオン含有セルロース繊維と、パルプ繊維と、を繊維全体に対して合計５０質量％を超えて含む水解紙ワイパーであって、炭素数１〜３の１価アルコールの配合率が１０質量％未満である洗浄液を含む。
この水解紙ワイパーによれば、水解紙ワイパーが上記した金属イオン含有セルロース繊維を含むことで、洗浄液中の炭素数１〜３の１価アルコールの配合率が低くても、セルロース繊維中の金属イオンが除菌効果を発揮し、除菌性能の低下を抑制できる。又、洗浄液中の炭素数１〜３の１価アルコールの配合率を低減できるので、アルコール類による刺激が少ない。
In order to solve the above-mentioned problems, the hydrolytic paper wiper of the present invention is made of Ag, Au, Pt, Pd, Ni, Mn, Fe, Ti, Al, Zn with respect to oxidized cellulose fibers having a carboxyl group or a carboxylate group on the surface. And a hydrolytic paper wiper containing a metal ion-containing cellulose fiber containing ions of at least one metal element selected from the group of Cu and pulp fiber in a total amount exceeding 50% by mass with respect to the total fiber. And the washing | cleaning liquid whose compounding rate of a C1-C3 monohydric alcohol is less than 10 mass% is included.
According to this hydrolyzed paper wiper, when the hydrolyzed paper wiper contains the above-described metal ion-containing cellulose fibers, the metal ions in the cellulose fibers can be obtained even if the mixing ratio of the monohydric alcohol having 1 to 3 carbon atoms in the cleaning liquid is low. Exerts a sterilization effect and can suppress a decrease in sterilization performance. Moreover, since the compounding rate of C1-C3 monohydric alcohol in a washing | cleaning liquid can be reduced, there is little irritation | stimulation by alcohol.
さらにカルボキシメチルセルロース、カルボキシメチルセルロースナトリウム塩、及びポリビニルアルコールの群から選ばれる一種以上からなる水溶性バインダーを含むことが好ましい。
さらに、水溶性Ｃａ塩、水溶性Ｍｇ塩、水溶性Ｚｎ塩、及びホウ酸の群から選ばれる１種類以上のバインダー不溶化剤を含有することが好ましい。
ＭＤ方向の引張強度が２６０Ｎ／ｍ以上、ＣＤ方向の引張強度が１００Ｎ／ｍ以上、かつ、ＪＩＳ-Ｐ４５０１に基づく１枚当たりのほぐれ易さが１００秒以下であることが好ましい。
Furthermore, it is preferable that the water-soluble binder which consists of 1 or more types chosen from the group of carboxymethylcellulose, carboxymethylcellulose sodium salt, and polyvinyl alcohol is included.
Furthermore, it is preferable to contain at least one binder insolubilizing agent selected from the group consisting of water-soluble Ca salt, water-soluble Mg salt, water-soluble Zn salt, and boric acid.
It is preferable that the tensile strength in the MD direction is 260 N / m or more, the tensile strength in the CD direction is 100 N / m or more, and the ease of loosening per sheet based on JIS-P4501 is 100 seconds or less.
この発明によれば、水解性及び除菌性能に優れ、アルコール類による刺激が少ない水解紙ワイパーが得られる。 According to the present invention, a hydrolyzed paper wiper that is excellent in water decomposability and sterilization performance and less stimulated by alcohols can be obtained.
本発明の実施形態に係る水解紙ワイパーは、表面にカルボキシル基又はカルボキシレート基を有する酸化セルロース繊維に対し、Ａｇ、Ａｕ、Ｐｔ、Ｐｄ、Ｍｎ、Ｆｅ、Ｔｉ、Ａｌ、Ｚｎ及びＣｕの群から選ばれる１種以上の金属元素のイオンを含有してなる金属イオン含有セルロース繊維と、パルプ繊維と、を繊維全体に対して合計５０質量％を超えて含み、炭素数１〜３の１価アルコールの配合率が１０質量％未満である洗浄液を含む。 The hydrolyzed paper wiper according to the embodiment of the present invention is obtained from the group of Ag, Au, Pt, Pd, Mn, Fe, Ti, Al, Zn and Cu with respect to the oxidized cellulose fiber having a carboxyl group or a carboxylate group on the surface. A monohydric alcohol having 1 to 3 carbon atoms, including a metal ion-containing cellulose fiber containing ions of one or more metal elements selected, and a pulp fiber in total exceeding 50 mass% with respect to the entire fiber. A cleaning solution having a blending ratio of less than 10% by mass.
この金属イオン含有セルロース繊維は、セルロース繊維表面にカルボキシル基又はカルボキシレート基を導入した酸化セルロース繊維に対し、金属化合物水溶液を接触させることによって得ることができる。また、本発明の実施形態に係る水解紙ワイパーの製造方法としては、酸化セルロース繊維を含む原料を抄造したシートに上記金属化合物水溶液を接触させる方法の他、予め酸化セルロース繊維に金属イオンを含有させ、この金属イオン含有セルロース繊維を含む原料を抄造する方法を例示することできる。 This metal ion-containing cellulose fiber can be obtained by bringing a metal compound aqueous solution into contact with an oxidized cellulose fiber having a carboxyl group or a carboxylate group introduced on the surface of the cellulose fiber. In addition, as a method for producing a hydrolyzed paper wiper according to an embodiment of the present invention, in addition to a method in which the metal compound aqueous solution is brought into contact with a sheet made from a raw material containing oxidized cellulose fibers, metal ions are added to the oxidized cellulose fibers in advance. A method of making a raw material containing the metal ion-containing cellulose fiber can be exemplified.
上記酸化セルロース繊維は、Ｎ−オキシル化合物を触媒に用いて木材パルプなどのセルロース繊維を酸化することにより製造できる。この酸化反応により、セルロース表面のグルコピラノース環のＣ６位の一級水酸基が選択的に酸化され、表面にカルボキシル基またはカルボキシレート基を有する酸化セルロース繊維が得られる。原料のセルロースは天然セルロースが好ましい。上記酸化反応は、水中で行うことが好ましい。反応におけるセルロース繊維の濃度は特に限定されないが、５質量％以下が好ましい。Ｎ−オキシル化合物の量は、反応系に対し０．１〜４ｍｍｏｌ／Ｌ程度であればよい。反応には公知の共酸化剤を用いてもよい。共酸化剤の例には、ジ亜ハロゲン酸またはその塩が含まれる。共酸化剤の量は、Ｎ−オキシル化合物１ｍｏｌに対して１〜４０ｍｏｌが好ましい。
反応温度は４〜４０℃が好ましく、室温がより好ましい。反応系のｐＨは８〜１１が好ましい。酸化の度合いは、反応時間、Ｎ−オキシル化合物の量等により適宜調整できる。
このようにして得た酸化セルロース繊維は、表面に酸基が存在し、内部にはほとんど酸基は存在しない。これはセルロース繊維が結晶性であるため、酸化剤が繊維の内部にまで拡散しにくいためと考えられる。
The oxidized cellulose fiber can be produced by oxidizing cellulose fiber such as wood pulp using an N-oxyl compound as a catalyst. By this oxidation reaction, the primary hydroxyl group at the C6 position of the glucopyranose ring on the cellulose surface is selectively oxidized, and an oxidized cellulose fiber having a carboxyl group or a carboxylate group on the surface is obtained. The raw material cellulose is preferably natural cellulose. The oxidation reaction is preferably performed in water. Although the density | concentration of the cellulose fiber in reaction is not specifically limited, 5 mass% or less is preferable. The amount of the N-oxyl compound may be about 0.1 to 4 mmol / L with respect to the reaction system. A known cooxidant may be used for the reaction. Examples of the co-oxidant include dihalous acid or a salt thereof. The amount of the co-oxidant is preferably 1 to 40 mol with respect to 1 mol of the N-oxyl compound.
The reaction temperature is preferably 4 to 40 ° C., more preferably room temperature. The pH of the reaction system is preferably 8-11. The degree of oxidation can be appropriately adjusted depending on the reaction time, the amount of the N-oxyl compound, and the like.
The oxidized cellulose fiber thus obtained has acid groups on the surface and almost no acid groups inside. This is presumably because the cellulose fiber is crystalline, so that the oxidant hardly diffuses into the fiber.
カルボキシル基とは−ＣＯＯＨで表される基をいい、カルボキシレート基とは−ＣＯＯ−で表される基をいう。酸化セルロース繊維を製造する際のカルボキシレート基のカウンターイオンは特に限定されない。そして、後述する金属のイオンが上記カウンターイオンと置き換わってカルボキシレート基とイオン結合する。また、カルボキシル基は金属イオンとして銅イオンと配位すると思われる。カルボキシル基またはカルボキシレート基を合わせて「酸基」ともいう。
酸基の含有量は、特開２００８−００１７２８号公報の段落００２１に開示されている方法によって測定できる。すなわち、精秤した乾燥セルロース試料を用いて０．５〜１質量％のスラリー６０ｍＬを調製し、０．１ｍｏｌ／Ｌの塩酸水溶液によってｐＨを約２．５とする。その後、０．０５ｍｏｌ／Ｌの水酸化ナトリウム水溶液を滴下して電気伝導度測定を行う。測定はｐＨが約１１になるまで続ける。電気伝導度の変化が緩やかな弱酸の中和段階を示すまでに消費された水酸化ナトリウム量（Ｖ）から、下式を用いて酸基量Ｘ１を求める。
Ｘ１（ｍｍｏｌ／ｇ）＝Ｖ（ｍＬ）×０．０５／セルロースの質量（ｇ）
The carboxyl group refers to a group represented by —COOH, and the carboxylate group refers to a group represented by —COO—. The counter ion of the carboxylate group in producing the oxidized cellulose fiber is not particularly limited. Then, metal ions to be described later are ion-bonded to the carboxylate group replacing the counter ions. In addition, the carboxyl group seems to coordinate with the copper ion as a metal ion. The carboxyl group or carboxylate group is also referred to as an “acid group”.
The content of acid groups can be measured by the method disclosed in paragraph 0021 of JP2008-001728A. That is, using a precisely weighed dry cellulose sample, 60 mL of a 0.5 to 1 mass% slurry is prepared, and the pH is adjusted to about 2.5 with a 0.1 mol / L hydrochloric acid aqueous solution. Then, 0.05 mol / L sodium hydroxide aqueous solution is dripped and electrical conductivity measurement is performed. The measurement is continued until the pH is about 11. From the amount (V) of sodium hydroxide consumed until the neutralization step of the weak acid, where the change in electrical conductivity shows a gradual change, the acid group amount X1 is determined using the following equation.
X1 (mmol / g) = V (mL) × 0.05 / mass of cellulose (g)
上記セルロース繊維の酸基の量は、０．２〜２．２ｍｍｏｌ／ｇが好ましい。酸基の量が０．２ｍｍｏｌ／ｇ未満であると、セルロース繊維表面に存在する金属イオンの量が十分でなく、消臭機能に劣る場合がある。酸基の量が２．２ｍｍｏｌ／ｇを超えると、水解紙ワイパーの抄紙の際のろ水性が悪化し、脱水負荷が大きくなる場合がある。 The amount of acid groups of the cellulose fiber is preferably 0.2 to 2.2 mmol / g. When the amount of acid groups is less than 0.2 mmol / g, the amount of metal ions present on the surface of the cellulose fiber is not sufficient, and the deodorizing function may be inferior. When the amount of acid groups exceeds 2.2 mmol / g, the drainage during paper making of the hydrolytic paper wiper may deteriorate and the dehydration load may increase.
次に、上記酸化セルロース繊維に対し、上記金属の化合物を含む水溶液を接触させ、金属化合物に由来する金属イオンが、カルボキシレート基とイオン結合を形成する。なお、カルボキシル基は電離してカルボキシレート基を経て金属イオンとイオン結合するか、上述のように金属イオンと配位すると思われる。
金属化合物水溶液とは、金属塩の水溶液である。金属塩の例には、錯体（錯イオン）、ハロゲン化物、硝酸塩、硫酸塩、および酢酸塩が含まれる。金属塩は水溶性であることが好ましい。
金属化合物の接触方法に関しては、予め調製したセルロース繊維の分散液と金属化合物水溶液を混合してもよく、セルロース繊維を含む分散液を基材の上に塗布して膜とし、当該膜に金属化合物水溶液を添加して含浸させてもよい。このとき、膜は基板上に固定されたままであってもよいし、基板から剥離された状態であってもよい。
金属化合物水溶液の濃度は特に限定されないが、セルロース繊維１００質量部に対して１０〜８０質量部が好ましく、３０〜６０質量部がより好ましい。
金属化合物を接触させる時間は適宜調整してよい。接触させる際の温度は特に限定されないが２０〜４０℃が好ましい。また、接触させる際の液のｐＨは特に限定されないが、ｐＨが低いと、カルボキシル基に金属イオンが結合しにくくなるため、７〜１３が好ましく、ｐＨ８〜１２が特に好ましい。
Next, an aqueous solution containing the metal compound is brought into contact with the oxidized cellulose fiber, and metal ions derived from the metal compound form an ionic bond with the carboxylate group. The carboxyl group is ionized and ionically bonds with the metal ion via the carboxylate group, or is coordinated with the metal ion as described above.
The metal compound aqueous solution is an aqueous solution of a metal salt. Examples of metal salts include complexes (complex ions), halides, nitrates, sulfates, and acetates. The metal salt is preferably water-soluble.
With regard to the method of contacting the metal compound, a cellulose fiber dispersion prepared in advance and a metal compound aqueous solution may be mixed, and a dispersion containing cellulose fibers is applied onto a substrate to form a film, and the metal compound is applied to the film. An aqueous solution may be added and impregnated. At this time, the film may remain fixed on the substrate or may be peeled from the substrate.
Although the density | concentration of metal compound aqueous solution is not specifically limited, 10-80 mass parts is preferable with respect to 100 mass parts of cellulose fibers, and 30-60 mass parts is more preferable.
You may adjust suitably the time which a metal compound is made to contact. Although the temperature at the time of making it contact is not specifically limited, 20-40 degreeC is preferable. In addition, the pH of the liquid at the time of contacting is not particularly limited. However, when the pH is low, it becomes difficult for metal ions to bind to the carboxyl group, and thus 7 to 13 is preferable, and pH 8 to 12 is particularly preferable.
酸化セルロース繊維が金属イオンを含有（配位）していることは、走査型電子顕微鏡像、及び強酸による抽出液のＩＣＰ発光分析で確認できる。つまり、金属イオンは走査型電子顕微鏡像では存在を確認できず、一方でＩＣＰ発光分析では金属を含有していることを確認できる。これに対し、例えば上記金属がイオンから還元されて金属粒子として存在している場合は、走査型電子顕微鏡像または透過型電子顕微鏡像でも金属粒子を確認することができるので、金属粒子の有無を判定できる。また、走査型電子顕微鏡像と元素マッピングによっても金属イオンの有無を判定できる。つまり、走査型電子顕微鏡像では金属イオンを確認できないが、元素マッピングをすることで金属イオンが存在することを確認できる。
金属イオンとして、Ａｇ及びＣｕの群から選ばれる１種以上のイオンを用いることにより、抗菌機能が付与される。一方、セルロース繊維の酸基のすべてに金属粒子が結合しなくても良く、残存した酸基も臭い成分であるアンモニア等を中和することができ、消臭機能が発揮される。
The fact that the oxidized cellulose fiber contains (coordinates) metal ions can be confirmed by a scanning electron microscopic image and ICP emission analysis of the extract with a strong acid. That is, the presence of metal ions cannot be confirmed in the scanning electron microscope image, while it can be confirmed that the metal ions are contained in the ICP emission analysis. On the other hand, for example, when the metal is reduced as a metal particle and is present as a metal particle, the metal particle can be confirmed by a scanning electron microscope image or a transmission electron microscope image. Can be judged. The presence or absence of metal ions can also be determined by scanning electron microscope images and element mapping. That is, metal ions cannot be confirmed in a scanning electron microscope image, but the presence of metal ions can be confirmed by elemental mapping.
By using one or more ions selected from the group consisting of Ag and Cu as metal ions, an antibacterial function is imparted. On the other hand, metal particles do not have to be bonded to all of the acid groups of the cellulose fiber, and the remaining acid groups can neutralize odorous components such as ammonia and exhibit a deodorizing function.
パルプ繊維としては、例えば針葉樹パルプ（NBKP）又は広葉樹パルプ(LBKP)などのバージンパルプや、古紙から再生した古紙パルプを用いることができる。これらパルプは衛生用紙の要求品質に合わせて、適宜所定の種類及び配合割合で適宜配合される。
湿潤シートの剛性が高く、手持ち感を向上し、拭き掃除を行いやすくする観点から、パルプ繊維としては針葉樹パルプ（NBKP）のみとすることが好ましい。
As the pulp fiber, for example, virgin pulp such as softwood pulp (NBKP) or hardwood pulp (LBKP), or used paper pulp regenerated from used paper can be used. These pulps are appropriately blended in predetermined types and blending ratios according to the required quality of sanitary paper.
From the viewpoint of high wet sheet rigidity, improved hand feeling, and ease of wiping and cleaning, it is preferable to use only softwood pulp (NBKP) as the pulp fiber.
本発明の実施形態に係る水解紙ワイパーは、金属イオン含有セルロース繊維とパルプ繊維とを繊維全体に対して合計５０質量％を超えて含み、さらに、必要に応じて他の繊維を含む抄紙原料を抄紙して製造することができる。なお、繊維全体に対する金属イオン含有セルロース繊維とパルプ繊維の合計割合は、水解紙ワイパーを水洗して水溶性成分（バインダー等）を溶解除去した後の組成物の乾燥重量と、金属イオン含有セルロース繊維とパルプ繊維の合計の乾燥重量とから求める。 The hydrolyzed paper wiper according to the embodiment of the present invention includes a papermaking raw material containing metal ions-containing cellulose fibers and pulp fibers in a total amount exceeding 50% by mass, and further containing other fibers as necessary. It can be manufactured by papermaking. The total ratio of the metal ion-containing cellulose fibers and pulp fibers to the total fibers is the dry weight of the composition after the water-disintegrating wiper is washed to remove water-soluble components (such as binder) and the metal ion-containing cellulose fibers. And the total dry weight of the pulp fiber.
抄紙原料は、要求品質及び操業の安定のために様々な薬品を添加（内添）してもよく、これら薬品としては、柔軟剤、嵩高剤、染料、分散剤、湿潤紙力増強剤、乾燥紙力剤、濾水向上剤、ピッチコントロール剤、歩留向上剤などが挙げられる。
特に、カルボキシメチルセルロース（ＣＭＣ）、カルボキシメチルセルロースナトリウム塩（ＣＭＣ−Ｎａ）、及びポリビニルアルコールの群から選ばれる一種以上からなる水溶性バインダーからなる水溶性バインダーを含むと、後述のように錯体を形成して湿潤強度を向上させることができる。
Various chemicals may be added (internally added) to the papermaking raw material for the required quality and stable operation. These chemicals include softeners, bulking agents, dyes, dispersants, wet paper strength enhancers, and drying agents. Examples thereof include paper strength agents, drainage improvers, pitch control agents, yield improvers, and the like.
In particular, when a water-soluble binder composed of one or more water-soluble binders selected from the group of carboxymethyl cellulose (CMC), carboxymethyl cellulose sodium salt (CMC-Na), and polyvinyl alcohol is included, a complex is formed as described later. The wet strength can be improved.
洗浄液は、水解紙ワイパーに含浸されている。水解紙ワイパーが上記した金属イオン含有セルロース繊維を含むことで、洗浄液中の炭素数１〜３の１価アルコールの配合率が低くても、セルロース繊維中の金属イオンが除菌効果を発揮し、除菌性能の低下を抑制できる。又、洗浄液中の炭素数１〜３の１価アルコールの配合率を低減できるので、アルコール類による刺激が少ない。
洗浄液中の炭素数１〜３の１価アルコールの配合率が、洗浄液全体に対して１０質量％以上であると、アルコール類による刺激が生じる。
なお、洗浄液は、水解紙ワイパーの乾燥重量に対して130〜180質量％含まれているとよい。
洗浄液の割合は、水解紙ワイパーのそのままの重量と、水解紙ワイパーの乾燥重量との差分を洗浄液の重量とみなして求める。
The cleaning liquid is impregnated in the hydrolytic paper wiper. By including the metal ion-containing cellulose fiber as described above, even if the mixing ratio of the monohydric alcohol having 1 to 3 carbon atoms in the cleaning liquid is low, the metal ion in the cellulose fiber exhibits a sterilizing effect, A decrease in sterilization performance can be suppressed. Moreover, since the compounding rate of C1-C3 monohydric alcohol in a washing | cleaning liquid can be reduced, there is little irritation | stimulation by alcohol.
When the blending ratio of the monohydric alcohol having 1 to 3 carbon atoms in the cleaning liquid is 10% by mass or more with respect to the entire cleaning liquid, stimulation with alcohol occurs.
In addition, it is good for the washing | cleaning liquid to be contained 130-180 mass% with respect to the dry weight of a hydrolytic paper wiper.
The ratio of the cleaning liquid is determined by regarding the difference between the weight of the water-disintegrating paper wiper as it is and the dry weight of the water-dissolving paper wiper as the weight of the cleaning liquid.
洗浄液がさらに、水溶性Ｃａ塩、水溶性Ｍｇ塩、水溶性Ｚｎ塩、及びホウ酸の群から選ばれる１種類以上のバインダー不溶化剤を含有することが好ましい。
水溶性Ｃａ塩、水溶性Ｍｇ塩、水溶性Ｚｎ塩は、洗浄液をシートに含浸させた際、上述のＣＭＣ又はＣＭＣ−Ｎａと錯体を生成し、不溶化する。ホウ酸は上述のポリビニルアルコールと錯体を生成し、不溶化する。これら不溶化された錯体は不溶性のバインダーとなって使用中の水解紙ワイパーを高強度化し、湿潤強度を向上させる。使用後、水解紙ワイパーが水中に投棄されると、錯体が多量の水と接触し、電離して水溶化する。
It is preferable that the cleaning liquid further contains one or more binder insolubilizers selected from the group consisting of water-soluble Ca salts, water-soluble Mg salts, water-soluble Zn salts, and boric acid.
The water-soluble Ca salt, water-soluble Mg salt, and water-soluble Zn salt form a complex with the above-mentioned CMC or CMC-Na and become insoluble when the sheet is impregnated with the cleaning liquid. Boric acid forms a complex with the above-mentioned polyvinyl alcohol and insolubilizes it. These insolubilized complexes serve as insoluble binders to increase the strength of hydrolytic paper wipers in use and improve the wet strength. After use, when the hydrolytic paper wiper is thrown into the water, the complex comes into contact with a large amount of water and is ionized to become water-soluble.
水溶性Ｃａ塩、水溶性Ｍｇ塩、水溶性Ｚｎ塩としては、それぞれ塩化カルシウム、塩化マグネシウム、硫酸亜鉛を例示できる。
水溶性バインダー及びバインダー不溶化剤の配合量は、上述の錯体を形成できる量であればよいが、例えば繊維全体に対して1.0〜10.0質量％含まれているとよい。水溶性バインダー及びバインダー不溶化剤は、化学的手法により定量可能である。
Examples of the water-soluble Ca salt, water-soluble Mg salt, and water-soluble Zn salt include calcium chloride, magnesium chloride, and zinc sulfate, respectively.
The blending amount of the water-soluble binder and the binder insolubilizing agent may be an amount that can form the above-mentioned complex, and for example, it may be contained in an amount of 1.0 to 10.0% by mass with respect to the entire fiber. The water-soluble binder and the binder insolubilizer can be quantified by a chemical method.
水解紙ワイパーのＪＩＳ Ｐ ８１２４に従う坪量を例えば６０〜１２０ｇ/ｍ2とすることができる。又、水解紙ワイパーの強度として、乾燥時のＭＤ方向の引張り強さＤＭＤが２６０Ｎ／ｍ以上、乾燥時のＣＤ方向の引張り強さＤＣＤが１００Ｎ／ｍ以上であることが好ましい。なお、ＭＤ方向（流れ方向）は抄紙方向である。ＤＭＤはより好ましくは２２０〜５００Ｎ／ｍ、ＤＣＤはより好ましくは１１０〜２００Ｎ／ｍである。
ＤＭＤ及びＤＣＤは、ＪＩＳ Ｐ８１１３に従って、同ＪＩＳ「５ 装置」に準拠の引張試験機を用い、調湿をせずに試験片幅30mm、つかみ長さ100mm、引張速度毎分100mmの条件で測定する。
The basis weight according to JIS P 8124 of the hydrolytic paper wiper can be set to 60 to 120 g / m 2 , for example. Further, as the strength of the hydrolyzed paper wiper, the tensile strength DMD in the MD direction during drying is preferably 260 N / m or more, and the tensile strength DCD in the CD direction during drying is preferably 100 N / m or more. The MD direction (flow direction) is the paper making direction. DMD is more preferably 220 to 500 N / m, and DCD is more preferably 110 to 200 N / m.
DMD and DCD are measured in accordance with JIS P8113, using a tensile tester compliant with JIS “5 Apparatus”, under the conditions of a test piece width of 30 mm, a grip length of 100 mm, and a tensile speed of 100 mm per minute without humidity control. .
水解紙ワイパーのＪＩＳ-Ｐ４５０１に基づく１枚当たりのほぐれ易さが１００秒以下であることが好ましい。ほぐれ易さが１００秒を超えると水解性が低下し、トイレ周辺の清掃用ワイパー等としてふさわしくない場合がある。
ほぐれ易さが８０秒以下であることがより好ましい。なお、ほぐれ易さの下限は０秒である。
It is preferable that the ease of loosening per sheet based on JIS-P4501 of the hydrolyzed paper wiper is 100 seconds or less. If the ease of unraveling exceeds 100 seconds, the water disintegration property decreases, which may not be suitable as a cleaning wiper around the toilet.
It is more preferable that the ease of loosening is 80 seconds or less. The lower limit of the ease of loosening is 0 seconds.
本発明の実施形態に係る水解紙ワイパーは、公知の抄紙法により製造することができる。まず、金属イオン含有セルロース繊維と、パルプと（さらに必要に応じて他の繊維や薬剤）を適宜混合してなる抄紙原料を原料タンクから供給し、さらに白水により希釈して紙料を調製する。この紙料を脱気スクリーニング除塵後、ファンポンプでストックインレットに送る。ストックインレットは、抄紙機のワイヤー全幅に、均一でフロック（小さな塊）がなく、流れ縞を生じないように繊維をよく分散させた紙料を、適正な濃度、速度、角度でワイヤー上に供給する。ストックインレットとしては、高所に大気開放で設置されるヘッドボックス、加圧式、ハイドローリック式などがあるがいずれを採用しても良い。そして、ストックインレットからワイヤー及びフェルトの間に紙料をジェット吐出し、フェルト上にシート（ウェブ、湿紙）を形成する。 The hydrolytic paper wiper according to the embodiment of the present invention can be produced by a known papermaking method. First, a papermaking raw material obtained by appropriately mixing metal ion-containing cellulose fibers and pulp (and other fibers and chemicals if necessary) is supplied from a raw material tank, and further diluted with white water to prepare a paper stock. This debris is degassed for screening and sent to the stock inlet with a fan pump. The stock inlet supplies paper with a proper concentration, speed, and angle over the entire wire width of the paper machine, with a uniform, floc-free (small lump), and well-dispersed fiber so as not to cause flow streaks. To do. As the stock inlet, there are a head box, a pressurization type, a hydraulic type, etc. which are installed in a high place with the atmosphere open, and any of them may be adopted. Then, a stock is jetted from the stock inlet between the wire and the felt to form a sheet (web, wet paper) on the felt.
ワイヤー及びフェルトの間に形成されたウェブは、プレッシャーロールでヤンキードライヤーに密着転送される。次に、ウェブはヤンキードライヤー及びヤンキードライヤーフードにより乾燥され、さらにクレーピングドクターによりクレーピング処理されながらヤンキードライヤーから剥がされ、リールドラムを介してリールに巻き取られる。ヤンキードライヤーは、ウェブを乾燥させるための鋳鉄又は鋳鋼製のドラムであり、外径は一般には2.4〜6ｍである。
ここで、クレーピングは、紙を縦方向（マシン走行方向）に機械的に圧縮してクレープと称される波状の皺を形成する方法であり、紙に嵩（バルク感）、柔らかさ、吸水性、表面の滑らかさ、美観（クレープの形状）などを付与する。そして、ヤンキードライヤーとリールの速度差（リールの速度≦ヤンキードライヤーの速度）により、クレーピングドクターでクレープが形成される。クレープの特性は、上記速度差にもよるが、ヤンキードライヤー上の原紙の坪量が７〜４０ｇ/ｍ2であれば、リール上での坪量は概略９〜５０ｇ/ｍ2となり、ヤンキードライヤー上の坪量より大きくなる。
ヤンキードライヤーとリールの速度差に基づくクレープ率は次式により定義される。
クレープ率（％）＝100×（ヤンキードライヤー速度（ｍ/分）−リール速度（ｍ/分））÷リール速度（ｍ/分）
クレープの品質やクレーピングの操業性は、クレープ率によってほぼ決まり、本発明において、クレープ率は１０〜５０％の範囲が好適である。
The web formed between the wire and the felt is closely transferred to the Yankee dryer by a pressure roll. Next, the web is dried by a Yankee dryer and a Yankee dryer hood, peeled off from the Yankee dryer while being creped by a creping doctor, and wound on a reel via a reel drum. The Yankee dryer is a drum made of cast iron or cast steel for drying the web, and the outer diameter is generally 2.4 to 6 m.
Here, creping is a method in which paper is mechanically compressed in the longitudinal direction (machine traveling direction) to form wavy folds called crepes. The paper is bulky, soft, and absorbs water. , Imparts surface smoothness, aesthetics (crepe shape), etc. Then, a crepe is formed by the creping doctor due to the speed difference between the Yankee dryer and the reel (reel speed ≦ yankee dryer speed). Although the crepe characteristics depend on the speed difference, if the basis weight of the base paper on the Yankee dryer is 7 to 40 g / m 2 , the basis weight on the reel is approximately 9 to 50 g / m 2 . It becomes larger than the above basis weight.
The crepe rate based on the speed difference between the Yankee dryer and the reel is defined by the following equation.
Crepe rate (%) = 100 x (Yankee dryer speed (m / min)-reel speed (m / min)) ÷ reel speed (m / min)
The quality of the crepe and the operability of the creping are substantially determined by the crepe rate, and in the present invention, the crepe rate is preferably in the range of 10 to 50%.
さらに、クレープを付与されたシートを適宜２枚以上に重ねてエンボス加工を施した後に、所定のシート形状に裁断し、パッケージ寸法に折り畳み、折り畳んだ状態で洗浄液を含侵させ、包装して水解紙ワイパー製品を製造することができる。
なお、水解紙ワイパーは、２〜４枚重ねとすると好ましい。
このように、シートの折り畳み加工後に洗浄液を含侵させることで、含浸後に折り畳み加工を行う場合に比べ、シート破れが発生し難く生産性の低下を抑制できる。
In addition, two or more sheets with crepe applied are appropriately overlaid and embossed, then cut into a predetermined sheet shape, folded into package dimensions, impregnated with cleaning liquid in the folded state, packaged, and hydrolyzed. Paper wiper products can be manufactured.
In addition, it is preferable when 2-4 sheets of water-dissipating paper wipers are stacked.
Thus, impregnating the cleaning liquid after folding the sheet makes it difficult to break the sheet and suppresses a decrease in productivity as compared with the case where the folding process is performed after the impregnation.
本発明は上記した実施形態に限定されず、本発明の思想と範囲に含まれる様々な変形及び均等物に及ぶことはいうまでもない。 It goes without saying that the present invention is not limited to the above-described embodiments, and extends to various modifications and equivalents included in the spirit and scope of the present invention.
以下、実施例を挙げて、本発明を具体的に説明するが、本発明は勿論これらの例に限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these examples of course.
＜金属イオン含有セルロース繊維の製造＞
乾燥重量で５．００ｇの未乾燥の針葉樹漂白クラフトパルプ、３９ｍｇの２，２，６，６−テトラメチルピペリジン−１−オキシル（ＴＥＭＰＯ）及び５１４ｍｇの臭化ナトリウムを水５００ｍｌに分散させた後、１５質量％次亜塩素酸ナトリウム水溶液を、１ｇのパルプ（絶乾）に対して次亜塩素酸ナトリウムの量が５．５ｍｍｏｌとなるように加えて反応を開始した。反応中は３ＭのＮａＯＨ水溶液を滴下してｐＨを１０．０に保った。ｐＨに変化が見られなくなった時点で反応終了と見なし、反応物をガラスフィルターにてろ過した後、十分な量の水による水洗、ろ過を２回繰り返し、固形分量１５質量％の水を含浸させたＴＥＭＰＯ酸化セルロース繊維を得た。
このＴＥＭＰＯ酸化セルロース繊維はその表面にカルボキシル基またはカルボキシレート基を有する。金属イオンを含有する前のＴＥＭＰＯ酸化セルロース繊維の酸基量（酸化セルロース繊維１ｇ当たり）を表１に示す。
<Production of metal ion-containing cellulose fibers>
After dispersing 5.00 g dry softwood bleached kraft pulp, 39 mg 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and 514 mg sodium bromide in 500 ml water, The reaction was started by adding 15 mass% sodium hypochlorite aqueous solution so that the amount of sodium hypochlorite was 5.5 mmol with respect to 1 g of pulp (absolutely dry). During the reaction, a 3M NaOH aqueous solution was added dropwise to maintain the pH at 10.0. When the pH no longer changes, the reaction is considered to be complete, the reaction product is filtered through a glass filter, washed with a sufficient amount of water and filtered twice to impregnate water with a solid content of 15% by mass. TEMPO oxidized cellulose fibers were obtained.
This TEMPO oxidized cellulose fiber has a carboxyl group or a carboxylate group on its surface. Table 1 shows the acid group amount (per gram of oxidized cellulose fiber) of the TEMPO oxidized cellulose fiber before containing metal ions.
次に、得られたＴＥＭＰＯ酸化セルロース繊維（この時点では金属イオンを含有していない）を解繊（叩解）し、得られた叩解後のＴＥＭＰＯ酸化セルロース繊維に対し、表１に示すｐＨと濃度（ＴＥＭＰＯ酸化セルロース繊維１ｇ当たり）の金属塩水溶液を加えて撹拌した。これにより、ＴＥＭＰＯ酸化セルロース繊維に金属イオンを担持させた。
なお、図１に、実施例に用いた金属イオン含有セルロース繊維の透過型電子顕微鏡像を示す。
Next, the obtained TEMPO oxidized cellulose fibers (which do not contain metal ions at this time) are defibrated (beaten), and the pH and concentration shown in Table 1 are obtained with respect to the obtained TEMPO oxidized cellulose fibers. An aqueous metal salt solution (per gram of TEMPO-oxidized cellulose fiber) was added and stirred. As a result, metal ions were supported on the TEMPO oxidized cellulose fiber.
In addition, in FIG. 1, the transmission electron microscope image of the metal ion containing cellulose fiber used for the Example is shown.
＜水解紙ワイパーの抄紙＞
次に、金属イオン含有セルロース繊維と、パルプ（ＮＢＫＰ及びＬＢＫＰ）とを、表２に示す配合比で配合してパルプスラリーを調製し、さらに表２の水溶性バインダーを、繊維全体に対して５質量％配合したものを抄紙して各実施例の水解紙ワイパーを製造した。
比較例１〜３として、金属イオン含有セルロース繊維を配合せず、パルプのみのパルプスラリーを調製したこと以外は、各実施例と同様に水解紙ワイパーを製造した。
そして、１価アルコールとしてエチルアルコールを用い、さらにプロピレングリコールを洗浄液全体の２質量％添加し、さらに表２に示すバインダー不溶化剤を含む洗浄液を、乾燥状態の水解紙ワイパーに対して１５０質量％含浸させた。なお、バインダー不溶化剤を、洗浄液全体に対して4.0質量％配合した。
<Paper making of hydrolyzed paper wiper>
Next, a metal ion-containing cellulose fiber and pulp (NBKP and LBKP) are blended at a blending ratio shown in Table 2 to prepare a pulp slurry, and the water-soluble binder of Table 2 is further added to the entire fiber by 5 Paper containing the blended by mass% was used to produce hydrolytic paper wipers of each example.
As Comparative Examples 1 to 3, a hydrolyzed paper wiper was produced in the same manner as in each Example, except that a metal-containing cellulose fiber was not blended and a pulp slurry containing only pulp was prepared.
Then, ethyl alcohol is used as the monohydric alcohol, and further 2% by mass of propylene glycol is added to the entire cleaning liquid. Further, the cleaning liquid containing the binder insolubilizer shown in Table 2 is impregnated with 150% by mass of the dry hydrolyzed paper wiper. I let you. In addition, 4.0 mass% of binder insolubilizer was mix | blended with respect to the whole washing | cleaning liquid.
なお、各実施例の水解紙ワイパーを走査型電子顕微鏡で観察したところ、紙の繊維のみが確認された。また、各実施例の水解紙ワイパーにつき、強酸で溶解した後の抽出液のＩＣＰ（（高周波誘導結合プラズマ）発光分析を行い、いずれも金属が含有されていることが確認された。以上のことより、各実施例の水解紙ワイパーは酸化セルロース繊維に金属イオンを含有していることがわかる。 In addition, when the hydrolytic paper wiper of each Example was observed with the scanning electron microscope, only the fiber of paper was confirmed. In addition, ICP ((high frequency inductively coupled plasma) emission analysis of the extract after dissolving with strong acid was performed on the hydrolyzed paper wipers of each example, and it was confirmed that all contained metal. It turns out that the hydrolytic paper wiper of each Example contains a metal ion in the oxidized cellulose fiber.
得られた水解紙ワイパーにつき、以下の評価を行った。
＜坪量＞
得られた水解紙ワイパーの坪量を、ＪＩＳ Ｐ ８１２４に従って測定したところ、90gsmであった。
＜強度＞
得られた水解紙ワイパーのＤＭＤ及びＤＣＤを、ＪＩＳ Ｐ８１１３に従い、上記した条件の通り測定した。
The following evaluation was performed about the obtained hydrolytic paper wiper.
<Basis weight>
The basis weight of the obtained hydrolyzed paper wiper was measured according to JIS P 8124 and found to be 90 gsm.
<Strength>
DMD and DCD of the obtained hydrolytic paper wiper were measured according to JIS P8113 as described above.
＜水解性＞
ＪＩＳ Ｐ４５０１に従い、同ＪＩＳ「4.2 試験条件」に従って調湿した１枚の水解紙ワイパー試料のほぐれやすさを測定した。
＜除菌性能＞
一般社団法人日本衛生材料工業連合会「除菌性能試験」の方法に従って評価した。数値（除菌活性値）が2.0以上であれば問題ない。
＜臭気＞
モニター２０人につき、水解紙ワイパーの臭気の官能評価をした。評価が○であれば、実用上問題はない。
○：刺激臭を感じる人が０〜１人
△：刺激臭を感じる人が２〜５人
×：刺激臭を感じる人が６人以上
<Water decomposability>
According to JIS P4501, the ease of loosening of one hydrolyzed paper wiper sample conditioned according to JIS “4.2 Test Conditions” was measured.
<Sterilization performance>
Evaluation was carried out according to the method of “Sanitization Performance Test” by the Japan Sanitary Materials Industry Association. There is no problem if the numerical value (bactericidal activity value) is 2.0 or more.
<Odor>
Sensory evaluation of the odor of hydrolytic paper wipers was performed for 20 monitors. If the evaluation is ○, there is no practical problem.
○: 0 to 1 people who feel an irritating △: 2 to 5 people who feel an irritating odor ×: 6 or more people who feel an irritating odor
得られた結果を表１、表２に示す。 The obtained results are shown in Tables 1 and 2.
表２から明らかなように、各実施例の場合、水解性及び除菌性能に優れ、アルコール類による刺激が少ないものとなった。
一方、洗浄液中の１価アルコールの配合率を１０質量％未満とすると共に、金属イオン含有セルロース繊維を含まない比較例１の場合、除菌性能が劣った。
洗浄液中の１価アルコールの配合率が１０質量％以上であると共に、金属イオン含有セルロース繊維を含まない比較例２，３の場合、アルコール類による刺激臭が目立った。又、洗浄液中の１価アルコールの配合率が比較例２より少ない比較例３の場合、除菌性能も劣った。
As is clear from Table 2, in each of the examples, the water decomposability and the sterilization performance were excellent, and the stimulation by alcohols was small.
On the other hand, the mixing ratio of the monohydric alcohol in the cleaning liquid was less than 10% by mass, and in the case of Comparative Example 1 that did not include the metal ion-containing cellulose fiber, the sterilization performance was inferior.
In the case of Comparative Examples 2 and 3 in which the mixing ratio of the monohydric alcohol in the cleaning liquid was 10% by mass or more and no metal ion-containing cellulose fiber was contained, the irritating odor due to the alcohols was conspicuous. Further, in the case of Comparative Example 3 in which the mixing ratio of monohydric alcohol in the cleaning liquid was smaller than that of Comparative Example 2, the sterilization performance was also inferior.
Claims (4)
炭素数１〜３の１価アルコールの配合率が１０質量％未満である洗浄液を含む水解紙ワイパー。 Ion of one or more metal elements selected from the group of Ag, Au, Pt, Pd, Ni, Mn, Fe, Ti, Al, Zn and Cu with respect to oxidized cellulose fibers having a carboxyl group or a carboxylate group on the surface A hydrolytic paper wiper comprising a metal ion-containing cellulose fiber containing a pulp fiber and a total of more than 50% by mass with respect to the whole fiber,
A hydrolyzed paper wiper comprising a cleaning liquid in which the mixing ratio of a monohydric alcohol having 1 to 3 carbon atoms is less than 10% by mass.
かつ、ＪＩＳ-Ｐ４５０１に基づく１枚当たりのほぐれ易さが１００秒以下である請求項１〜３のいずれか一項に記載の水解紙ワイパー。 The tensile strength in the MD direction is 260 N / m or more, the tensile strength in the CD direction is 100 N / m or more,
The water-disintegrating paper wiper according to any one of claims 1 to 3, wherein the ease of loosening per sheet based on JIS-P4501 is 100 seconds or less.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019104798A (en) * | 2017-12-11 | 2019-06-27 | シーバイエス株式会社 | Water-disintegrable cleaning material |
| JP6932284B1 (en) * | 2021-06-15 | 2021-09-08 | 常裕パルプ工業株式会社 | Cleaning tool for toilet bowl |
| JP2022191121A (en) * | 2021-06-15 | 2022-12-27 | 常裕パルプ工業株式会社 | Toilet bowl cleaning tool |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02149237A (en) * | 1988-11-30 | 1990-06-07 | Kao Corp | Water soluble cleaning article |
| JPH1193055A (en) * | 1997-09-12 | 1999-04-06 | Oji Paper Co Ltd | Water-disintegrable nonwoven fabric and its production |
| JP2000254031A (en) * | 1999-03-11 | 2000-09-19 | Meisei Sansho Kk | Hydrolytic wet sheet |
| US6187141B1 (en) * | 1997-09-24 | 2001-02-13 | Uni-Charm Corporation | Water-disintegratable fibrous sheet having layered structure and wiping sheet comprising the same |
| JP2004188091A (en) * | 2002-12-13 | 2004-07-08 | Daio Paper Corp | Wiping sheet |
| JP2007075523A (en) * | 2005-09-16 | 2007-03-29 | Daio Paper Corp | Hydrolyzable sanitary paper |
| JP2010162342A (en) * | 2008-12-16 | 2010-07-29 | Nippon Paper Crecia Co Ltd | Alcohol-containing wet tissue |
| JP2015045113A (en) * | 2013-08-29 | 2015-03-12 | 日本製紙株式会社 | Sanitary tissue paper |
| JP2016513761A (en) * | 2013-03-15 | 2016-05-16 | ゲーペー ツェルローゼ ゲーエムベーハー | Low viscosity kraft fiber with enhanced carboxyl content and methods for making and using the same |
-
2015
- 2015-12-25 JP JP2015254419A patent/JP6596331B2/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02149237A (en) * | 1988-11-30 | 1990-06-07 | Kao Corp | Water soluble cleaning article |
| JPH1193055A (en) * | 1997-09-12 | 1999-04-06 | Oji Paper Co Ltd | Water-disintegrable nonwoven fabric and its production |
| US6187141B1 (en) * | 1997-09-24 | 2001-02-13 | Uni-Charm Corporation | Water-disintegratable fibrous sheet having layered structure and wiping sheet comprising the same |
| JP2000254031A (en) * | 1999-03-11 | 2000-09-19 | Meisei Sansho Kk | Hydrolytic wet sheet |
| JP2004188091A (en) * | 2002-12-13 | 2004-07-08 | Daio Paper Corp | Wiping sheet |
| JP2007075523A (en) * | 2005-09-16 | 2007-03-29 | Daio Paper Corp | Hydrolyzable sanitary paper |
| JP2010162342A (en) * | 2008-12-16 | 2010-07-29 | Nippon Paper Crecia Co Ltd | Alcohol-containing wet tissue |
| JP2016513761A (en) * | 2013-03-15 | 2016-05-16 | ゲーペー ツェルローゼ ゲーエムベーハー | Low viscosity kraft fiber with enhanced carboxyl content and methods for making and using the same |
| JP2015045113A (en) * | 2013-08-29 | 2015-03-12 | 日本製紙株式会社 | Sanitary tissue paper |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019104798A (en) * | 2017-12-11 | 2019-06-27 | シーバイエス株式会社 | Water-disintegrable cleaning material |
| JP6932284B1 (en) * | 2021-06-15 | 2021-09-08 | 常裕パルプ工業株式会社 | Cleaning tool for toilet bowl |
| WO2022264446A1 (en) * | 2021-06-15 | 2022-12-22 | 常裕パルプ工業株式会社 | Toilet cleaning tool |
| JP2022191121A (en) * | 2021-06-15 | 2022-12-27 | 常裕パルプ工業株式会社 | Toilet bowl cleaning tool |
| JP2022190726A (en) * | 2021-06-15 | 2022-12-27 | 常裕パルプ工業株式会社 | Toilet bowl cleaning tool |
| JP7270003B2 (en) | 2021-06-15 | 2023-05-09 | 常裕パルプ工業株式会社 | Toilet cleaning tool |
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