JP4503368B2 - Bleaching method - Google Patents
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- JP4503368B2 JP4503368B2 JP2004193226A JP2004193226A JP4503368B2 JP 4503368 B2 JP4503368 B2 JP 4503368B2 JP 2004193226 A JP2004193226 A JP 2004193226A JP 2004193226 A JP2004193226 A JP 2004193226A JP 4503368 B2 JP4503368 B2 JP 4503368B2
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- 238000004061 bleaching Methods 0.000 title claims description 61
- 238000000034 method Methods 0.000 title claims description 30
- 239000000203 mixture Substances 0.000 claims description 60
- 125000004181 carboxyalkyl group Chemical group 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 20
- 239000007844 bleaching agent Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000470 constituent Substances 0.000 claims description 13
- 229920002678 cellulose Polymers 0.000 claims description 12
- 239000001913 cellulose Substances 0.000 claims description 11
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 9
- -1 fatty acid salt Chemical class 0.000 description 22
- 230000000694 effects Effects 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 239000000835 fiber Substances 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- 239000005708 Sodium hypochlorite Substances 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 235000010980 cellulose Nutrition 0.000 description 9
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000003093 cationic surfactant Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 6
- 238000012856 packing Methods 0.000 description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 239000003599 detergent Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical group 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical group [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- VJHCJDRQFCCTHL-UHFFFAOYSA-N acetic acid 2,3,4,5,6-pentahydroxyhexanal Chemical compound CC(O)=O.OCC(O)C(O)C(O)C(O)C=O VJHCJDRQFCCTHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000003862 amino acid derivatives Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920003064 carboxyethyl cellulose Polymers 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000011888 snacks Nutrition 0.000 description 1
- DSYVTLPHGJLVKD-UHFFFAOYSA-M sodium 1,5-dimethylcyclohexa-2,4-diene-1-sulfonate Chemical compound [Na+].C1(CC(=CC=C1)C)(C)S(=O)(=O)[O-] DSYVTLPHGJLVKD-UHFFFAOYSA-M 0.000 description 1
- 229940079842 sodium cumenesulfonate Drugs 0.000 description 1
- 229940048842 sodium xylenesulfonate Drugs 0.000 description 1
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- QEKATQBVVAZOAY-UHFFFAOYSA-M sodium;4-propan-2-ylbenzenesulfonate Chemical compound [Na+].CC(C)C1=CC=C(S([O-])(=O)=O)C=C1 QEKATQBVVAZOAY-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
- Detergent Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は、カビ汚れ、特に硬表面におけるカビ汚れなどの強固な汚れに対する漂白技術に関する。具体的には、本発明は、特定の漂白方法、該漂白方法に供される漂白キット及び該漂白方法に供される液体保持性を有するシートに関する。 The present invention relates to a bleaching technique for mold stains, particularly strong stains such as mold stains on hard surfaces. Specifically, the present invention relates to a specific bleaching method, a bleaching kit to be used in the bleaching method, and a sheet having liquid retaining property to be used in the bleaching method.
住居の硬質表面の汚れは、対象とする洗浄面によって異なり多種多様である。一般に、台所のレンジ廻りには変性油とホコリなどが複合化した汚れが付着しやすく、トイレや浴室については、無機質並びに有機質が不溶性の塩を形成しそのまま汚れとなる場合や、それらを基質として細菌やカビが繁殖し汚れとなる場合がある。硬質表面の汚れの中でも、これら細菌やカビに由来する黒ずみ汚れは、界面活性剤や研磨剤を主成分とする洗浄剤では十分に除去することが難しいため、次亜塩素酸塩を配合した塩素系の液体漂白洗浄剤が用いられている。これら液体漂白洗浄剤は、カビ汚れが発生した部分に直接塗布する方法以外に、手動式噴霧装置を用いてカビ汚れに吹きつける方法で主に使用される。特許文献１〜３には塩素系カビ取り剤の遊離アルカリを低減させ、貯蔵安定性及び漂白効果の両者を満足する技術が開示されている。 The dirt on the hard surface of a residence varies depending on the target cleaning surface, and varies. In general, dirt mixed with denatured oil and dust tends to adhere around the kitchen range. For toilets and bathrooms, inorganic and organic substances form insoluble salts and become dirty as they are, or they can be used as substrates. Bacteria and fungi may grow and become dirty. Among the hard surface stains, dark stains derived from these bacteria and molds are difficult to remove sufficiently with detergents mainly composed of surfactants and abrasives, so chlorine containing hypochlorite System liquid bleach detergents are used. These liquid bleaching detergents are mainly used in a method of spraying mold stains using a manual spraying apparatus, in addition to a method of directly applying to a portion where mold stains are generated. Patent Documents 1 to 3 disclose techniques that reduce the free alkali of the chlorinated mold removing agent and satisfy both the storage stability and the bleaching effect.
一方、特許文献４には、洗浄を要する箇所に水溶性紙を接着し、洗浄剤を吸着させて所要時間経過後水溶性紙と洗浄剤を共に水洗する洗浄方法が開示されており、水溶性紙としてカルボキシメチルセルロースを含有する木材パルプが、また洗浄成分として塩素系漂白剤が例示されている。 On the other hand, Patent Document 4 discloses a cleaning method in which water-soluble paper is adhered to a portion that requires cleaning, the cleaning agent is adsorbed, and the water-soluble paper and the cleaning agent are washed with water after the required time has elapsed. A wood pulp containing carboxymethyl cellulose is exemplified as paper, and a chlorine bleach is exemplified as a cleaning component.
また、洗浄成分や漂白成分を含む薬剤をシートに担持させて、漂白対象部位に張り付けて使用する清掃用シートやカビ取りシートが知られている（特許文献５〜６）。
従来の塩素系の漂白洗浄剤はタイルや目地、その他黒ずみ汚れに対して十分な効果を示したが、最近では、タイルや目地以外に、壁と浴槽等のつなぎ目に使用されているシリコーン樹脂系のコーキングや軟質ポリ塩化ビニル樹脂系のパッキンなどの樹脂部にカビが発生する例が増加してきており、タイルや目地に対して十分な効果を発揮していた従来の漂白洗浄剤であっても、これら樹脂部に発生したカビ汚れに対しては漂白・分解除去が必ずしも十分ではなかった。 Conventional chlorine-based bleaching detergents have shown a sufficient effect on tiles, joints and other dark stains. Recently, in addition to tiles and joints, silicone resin-based materials used in joints between walls and bathtubs. Examples of molds occurring in resin parts such as caulking and soft polyvinyl chloride resin-based packing are increasing, and even conventional bleaching detergents that have been sufficiently effective against tiles and joints The mold stains generated in these resin parts were not always sufficiently bleached and decomposed and removed.
特許文献１〜３は遊離アルカリ剤の含有量を低減化させることにより、漂白効果を向上させた技術であるが、上記コーキングやパッキンに発生したカビ汚れに対しては、更なる効果の向上が望まれる。また、特許文献４の方法では、カルボキシメチルセルロースは紙に水溶性を付与する目的で用いられており、漂白効果を向上させる点については何ら示唆されておらず、しかも、具体的に示される塩素系漂白剤を含浸させた水溶性紙をコーキングやパッキンに発生したカビに湿布しても、未だ満足できる効果を得ることができない。 Patent Documents 1 to 3 are techniques that improve the bleaching effect by reducing the content of the free alkali agent, but the effect is further improved against mold stains generated in the above caulking and packing. desired. Further, in the method of Patent Document 4, carboxymethyl cellulose is used for the purpose of imparting water solubility to paper, and there is no suggestion of improving the bleaching effect, and the chlorine type specifically shown. Even if a water-soluble paper impregnated with a bleaching agent is laid on a mold generated in caulking or packing, a satisfactory effect cannot still be obtained.
一方、特許文献５は水溶性シートと支持シートを含む構造とする必要があり、また、粉末成分を担持させるために、漂白効果の発現に時間がかかることがある。加えて、かびとり成分を均一にシートに担持させるため製造が難しく、また、かびとり成分が空気中の水分を吸収して分解するのを抑制するための封止手段（シール部）が必要であった。特許文献６は、シートの製造過程で塩素系の漂白成分を水に溶解させるため、製造効率が低下し、また、実質的にシートに漂白成分が固体状態で担持されるため、漂白効果の発現には時間がかかる。更に、特許文献５同様、かびとり成分の均一な担持が難しく、また、封止手段（シール部）を必要とするものであった。 On the other hand, Patent Document 5 needs to have a structure including a water-soluble sheet and a support sheet. In addition, since the powder component is supported, it sometimes takes time to develop the bleaching effect. In addition, it is difficult to manufacture because the mold mold component is uniformly supported on the sheet, and a sealing means (seal part) is required to prevent the mold mold component from absorbing and decomposing moisture in the air. there were. In Patent Document 6, since the chlorine-based bleaching component is dissolved in water during the production process of the sheet, the production efficiency is lowered, and since the bleaching component is substantially supported on the sheet in a solid state, the bleaching effect is exhibited. Takes time. Furthermore, as in Patent Document 5, it is difficult to uniformly carry the mold component, and a sealing means (seal part) is required.
本発明の課題は、塩素ガスの発生が極めて少なく、しかもコーキングやパッキンに発生したカビ汚れに対して高い漂白効果を有する漂白手段を提供することである。 An object of the present invention is to provide a bleaching means that generates very little chlorine gas and has a high bleaching effect on mold stains generated in caulking and packing.
本発明は、下記（Ａ）の構成材料中に存在するカルボキシアルキル基の全モル数が、下記（Ｂ）中のアルカリ金属水酸化物のモル数に対して０．５〜３倍になる比率で、下記（Ａ）に下記（Ｂ）を含浸させた漂白用部材を、漂白対象物に接触させる漂白方法に関する。
（Ａ）カルボキシアルキルセルロースを構成材料中５０〜１００質量％含有する、液体保持性を有するシート。
（Ｂ）次亜ハロゲン酸塩１〜５質量％、アルカリ金属水酸化物０．２〜１質量％、及び水を含有する液体漂白剤組成物。
In the present invention, the ratio in which the total number of moles of carboxyalkyl groups present in the constituent material (A) below is 0.5 to 3 times the number of moles of alkali metal hydroxide in (B) below. Then, the present invention relates to a bleaching method in which a bleaching member obtained by impregnating the following (A) with the following (B) is brought into contact with an object to be bleached.
(A) The sheet | seat which has 50 to 100 mass% of carboxyalkyl cellulose in a constituent material, and has liquid retainability.
(B) A liquid bleach composition containing 1 to 5% by weight of hypohalite, 0.2 to 1% by weight of alkali metal hydroxide, and water.
また本発明は、（Ａ）カルボキシアルキルセルロース〔以下、（ａ）成分という〕を構成材料中５０〜１００質量％含有する、液体保持性を有するシート〔以下、シート（Ａ）という〕、並びに（Ｂ）次亜ハロゲン酸塩〔以下、（ｂ）成分という〕１〜５質量％、アルカリ金属水酸化物〔以下、（ｃ）成分という〕０．２〜１質量％、及び水を含有する液体漂白剤組成物〔以下、組成物（Ｂ）という〕を構成要素とする、上記本発明の漂白方法に供される漂白キットに関する。 Moreover, this invention contains (A) carboxyalkyl cellulose [henceforth (component) (a)] 50-100 mass% in a constituent material, and the sheet | seat [henceforth a sheet (A)] which has liquid retainability, and ( B) Hypohalite [hereinafter referred to as component (b)] 1 to 5% by mass, alkali metal hydroxide (hereinafter referred to as component (c)) 0.2 to 1% by mass, and a liquid containing water The present invention relates to a bleaching kit used in the bleaching method of the present invention, comprising a bleaching agent composition (hereinafter referred to as composition (B)) as a constituent element.
また、本発明は、カルボキシアルキルセルロースを構成材料中５０〜１００質量％含有する、上記本発明の漂白方法に供される液体保持性を有するシートに関する。 Moreover, this invention relates to the sheet | seat which has the liquid retainability used for the bleaching method of the said invention which contains 50-100 mass% of carboxyalkyl cellulose in a constituent material.
本発明によれば、漂白対象物に深く入りこんだカビ汚れに対して、簡便で、且つ高い漂白効果が得られる漂白手段が提供される。本発明の漂白方法や漂白キットでは、漂白を行う際の刺激臭の発生も抑制されることが期待される。 ADVANTAGE OF THE INVENTION According to this invention, the bleaching means which is easy and can obtain the high bleaching effect with respect to the mold stain which penetrated deeply into the bleaching object is provided. In the bleaching method and bleaching kit of the present invention, it is expected that the generation of an irritating odor during bleaching is also suppressed.
＜シート（Ａ）＞
シート（Ａ）は、（ａ）成分であるカルボキシアルキルセルロース、好ましくはアルキル基の炭素数が１〜３のカルボキシアルキル基を有するカルボキシアルキルセルロース、より好ましくはカルボキシメチルセルロース、カルボキシエチルセルロースを、シートの構成材料中５０〜１００質量％、好ましくは６０〜１００質量％、特に好ましくは６０〜９０質量％含有する。カルボキシアルキルセルロースの、カルボキシアルキル基の置換度は、好ましくは０．２〜２．０、より好ましくは０．２〜１．５、特に好ましくは０．２〜１．０である。この置換度は、カルボキシアルキルセルロースの構成単位であるグルコース１分子あたりの水酸基の水素原子がカルボキシアルキル基で置換されている個数の平均値であり、理論上の最大値は３である。
<Sheet (A)>
The sheet (A) is a carboxyalkyl cellulose as the component (a), preferably a carboxyalkyl cellulose having a carboxyalkyl group having 1 to 3 carbon atoms in an alkyl group, more preferably carboxymethylcellulose or carboxyethylcellulose. 50-100 mass% in a material, Preferably it is 60-100 mass%, Most preferably, it contains 60-90 mass%. The degree of substitution of the carboxyalkyl group of the carboxyalkyl cellulose is preferably 0.2 to 2.0, more preferably 0.2 to 1.5, and particularly preferably 0.2 to 1.0. This degree of substitution is an average value of the number of hydroxyl groups substituted by carboxyalkyl groups per glucose molecule as a constituent unit of carboxyalkyl cellulose, and the theoretical maximum value is 3.
本発明の（Ａ）のシート材は、フィルム、紙、不織布の形態を採用することができ、本発明では漂白後、剥離できるものでも良いが、水により洗い流せるなどの使い勝手の点から、紙又は不織布の形態が好ましい。 The sheet material (A) of the present invention can adopt the form of a film, paper, or non-woven fabric. In the present invention, the sheet material may be peelable and can be peeled off, but from the viewpoint of ease of use such as washing with water, The form of a nonwoven fabric is preferable.
紙又は不織布の場合には、シートの坪量は、好ましくは２０〜１２０ｇ／ｍ2、より好ましくは２０〜８０ｇ／ｍ2、特に好ましくは２０〜６０ｇ／ｍ2が湿布時のシートの付着性の点から好適である。このような坪量に調整するためには（ａ）成分と共に本発明の効果を損なわない程度に水溶性又は水分散性の繊維（以下（ａ’）成分という）を併用することが好適である。（ａ’）成分としては、木材パルプ繊維、非木材系植物繊維、レーヨン繊維、ポリエステル繊維、アクリル繊維、生分解性を有するポリ乳酸からなる繊維、ポリビニールアルコール繊維、ポリオレフィン系繊維等を挙げることができ、特に洗い流す目的の紙の形態においては、木材パルプ繊維、非木材系植物繊維、再生セルロース繊維（レーヨン）、生分解を有するポリ乳酸繊維を用いることが好ましい。（ａ’）成分の含有量は、シート（Ａ）の構成材料中、好ましくは０〜５０質量％、より好ましくは０〜４０質量％、特に好ましくは１０〜４０質量％である。 In the case of paper or non-woven fabric, the sheet has a basis weight of preferably 20 to 120 g / m 2 , more preferably 20 to 80 g / m 2 , and particularly preferably 20 to 60 g / m 2 . From the point of view, it is preferable. In order to adjust to such a basis weight, it is preferable to use a water-soluble or water-dispersible fiber (hereinafter referred to as the component (a ′)) together with the component (a) so as not to impair the effects of the present invention. . Examples of the component (a ′) include wood pulp fibers, non-wood plant fibers, rayon fibers, polyester fibers, acrylic fibers, fibers made of biodegradable polylactic acid, polyvinyl alcohol fibers, polyolefin fibers, and the like. In particular, in the form of paper to be washed away, it is preferable to use wood pulp fibers, non-wood plant fibers, regenerated cellulose fibers (rayon), and biodegradable polylactic acid fibers. The content of the component (a ′) is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, and particularly preferably 10 to 40% by mass in the constituent material of the sheet (A).
シート（Ａ）の製法は特に限定されず、例えば紙の形態を採用する場合には、従来から知られている湿式法、又は乾式法を用いれば良い。例えば、（ａ）成分単体分散液もしくは、（ａ）成分と（ａ’）成分の混合物の分散液を、抄紙、乾燥することによって得られる。不織布の場合にはスパンレース、サーマルボンド不織布などを用いることが可能である。 The method for producing the sheet (A) is not particularly limited. For example, when a paper form is adopted, a conventionally known wet method or dry method may be used. For example, it can be obtained by paper-making and drying a component single component dispersion (a) or a mixture of component (a) and component (a ′). In the case of a nonwoven fabric, a spunlace, a thermal bond nonwoven fabric, etc. can be used.
シート（Ａ）は、液体保持性を有するが、シート（Ａ）の質量に対して１〜２０倍、更に５〜１５倍の下記組成物（Ｂ）を保持できることが好ましい。そして、組成物（Ｂ）は、シート（Ａ）が保持できる組成物（Ｂ）の量に対して７０〜１００質量％、更に８０〜１００質量％、特には１００質量％（すなわち飽和量で）保持させて用いることが、後述する理由から好ましい。 The sheet (A) has liquid retainability, but preferably can hold the following composition (B) 1 to 20 times, and further 5 to 15 times the mass of the sheet (A). And a composition (B) is 70-100 mass% with respect to the quantity of the composition (B) which a sheet | seat (A) can hold | maintain, 80-100 mass% especially 100 mass% (namely, in saturated amount). It is preferable to hold and use it for the reason described later.
＜組成物（Ｂ）＞
（ｂ）成分である次亜ハロゲン酸塩としては、具体的には次亜塩素酸ナトリウム、次亜塩素酸カリウム等が挙げられ、これらの中でも、次亜塩素酸ナトリウムがより好ましい。次亜塩素酸ナトリウムには、製造上次亜塩素酸ナトリウムと当モルの塩化ナトリウムが混在するが、塩化ナトリウムが多量に存在する次亜塩素酸ナトリウムは貯蔵安定性を損なう場合があるため、予め塩化ナトリウムを低減化したものを用いることが好ましい。具体的には塩化ナトリウムを次亜塩素酸ナトリウムに対して１０〜６０モル％、好ましくは１０〜４０モル％のものが好適である。このような塩化ナトリウムを低減化した次亜塩素酸ナトリウムは、中食次亜塩素酸ナトリウム、低食次亜塩素酸ナトリウムとして市販されている。組成物（Ｂ）中の（ｂ）成分の含有量は、漂白効果の観点から、１〜５質量％、好ましくは１．５〜３質量％、さらに好ましくは２．０〜３質量％である。
<Composition (B)>
Specific examples of the hypohalite as the component (b) include sodium hypochlorite and potassium hypochlorite. Among these, sodium hypochlorite is more preferable. Sodium hypochlorite contains sodium hypochlorite and equimolar sodium chloride in production, but sodium hypochlorite containing a large amount of sodium chloride may impair storage stability. It is preferable to use a material in which sodium chloride is reduced. Specifically, sodium chloride is 10 to 60 mol%, preferably 10 to 40 mol%, based on sodium hypochlorite. Such sodium hypochlorite in which sodium chloride has been reduced is commercially available as sodium snack hypochlorite and sodium hypochlorite low. The content of the component (b) in the composition (B) is 1 to 5% by mass, preferably 1.5 to 3% by mass, more preferably 2.0 to 3% by mass, from the viewpoint of the bleaching effect. .
（ｃ）成分のアルカリ金属水酸化物としては、水酸化ナトリウム、水酸化カリウム等が挙げられ、この中でも水酸化ナトリウムが好ましい。組成物（Ｂ）中の（ｃ）成分の含有量は、漂白効果と貯蔵安定性の観点から、０．２〜１質量％、好ましくは０．２〜０．８質量％、特に好ましくは０．３〜０．６質量％である。 (C) As an alkali metal hydroxide of a component, sodium hydroxide, potassium hydroxide, etc. are mentioned, Among these, sodium hydroxide is preferable. The content of the component (c) in the composition (B) is 0.2 to 1% by mass, preferably 0.2 to 0.8% by mass, particularly preferably 0, from the viewpoints of the bleaching effect and storage stability. .3 to 0.6% by mass.
組成物（Ｂ）には、目的とする性能を損なわない範囲で、通常の漂白剤や洗浄剤に配合されている成分、例えば界面活性剤、ハイドロトロープ剤、各種着色料、無機塩、アミノホスホン酸−Ｎ−オキサイド等のキレート剤、香料などの成分を配合することができる。 In the composition (B), components blended in ordinary bleaching agents and cleaning agents, such as surfactants, hydrotropes, various colorants, inorganic salts, aminophosphones, as long as the target performance is not impaired. Components such as chelating agents such as acid-N-oxide and fragrances can be blended.
界面活性剤〔以下、（ｄ）成分という〕としては、炭素数６〜２２、好ましくは６〜１８、特に好ましくは８〜１２のアルキル基を有する脂肪酸塩、アルカンスルホン酸塩、アルキル硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、アルキルスルホコハク酸塩、アルキルジフェニルエーテルジスルホン酸塩、アルキルリン酸塩、ポリオキシエチレンアルキルエーテル硫酸エステル塩、ポリオキシエチレンアルキルアリール硫酸エステル塩、ポリオキシエチレンアルキルフェニルエーテルスルホン酸塩から選ばれる陰イオン界面活性剤（アミノ酸誘導体等の含窒素系陰イオン界面活性剤は除く）、炭素数６〜１８、好ましくは８〜１６、特に好ましくは１０〜１４のアルキル基を１つ又は２つ有するアミンオキサイド、スルホベタインなどの両性界面活性剤、炭素数６〜１８、好ましくは６〜１４、特に好ましくは８〜１０のアルキル基を１つ又は２つ有する第４級アンモニウム型カチオン界面活性剤の１種以上を挙げることができる。これら界面活性剤のなかでも、起泡力の点で炭素数８〜１２の脂肪酸塩、炭素数８〜１６のアルカンスルホン酸塩、炭素数８〜１２のアルキル硫酸エステル塩、アルキル基の炭素数が８〜１２でありオキシエチレン基の平均付加モル数が２〜５のポリオキシエチレンアルキルエーテル硫酸エステル塩、炭素数８〜１６のアルキルジメチルアミンオキサイドが好ましく、樹脂部のカビ汚れへの浸透性に対しては、炭素数８〜１２のアルキル基を１つ又は２つと残りが炭素数１〜３のアルキル基もしくはヒドロキシアルキル基又はベンジル基である第４級アンモニウム型カチオン界面活性剤を併用することが好ましい。 As the surfactant [hereinafter referred to as component (d)], a fatty acid salt, alkane sulfonate, alkyl sulfate ester salt having an alkyl group having 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms, particularly preferably 8 to 12 carbon atoms. , Alkylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfosuccinate, alkyl diphenyl ether disulfonate, alkyl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylaryl sulfate, polyoxyethylene alkyl Anionic surfactant selected from phenyl ether sulfonates (excluding nitrogen-containing anionic surfactants such as amino acid derivatives), alkyl having 6 to 18, preferably 8 to 16, particularly preferably 10 to 14 carbon atoms Amines having one or two groups 1 of a quaternary ammonium type cationic surfactant having one or two alkyl groups having 6 to 18 carbon atoms, preferably 6 to 14 carbon atoms, particularly preferably 8 to 10 carbon atoms, such as amphoteric surfactants such as oxide and sulfobetaine. More than species can be mentioned. Among these surfactants, fatty acid salts having 8 to 12 carbon atoms, alkane sulfonates having 8 to 16 carbon atoms, alkyl sulfate esters having 8 to 12 carbon atoms, and carbon numbers of alkyl groups in terms of foaming power. Is preferably a polyoxyethylene alkyl ether sulfate ester salt having an average addition mole number of oxyethylene groups of 2 to 5 and an alkyl dimethylamine oxide of 8 to 16 carbon atoms, and the resin part has a permeability to mold stains. Is used in combination with one or two alkyl groups having 8 to 12 carbon atoms and the remaining quaternary ammonium type cationic surfactant having an alkyl group, hydroxyalkyl group or benzyl group having 1 to 3 carbon atoms. It is preferable.
なお、陰イオン界面活性剤の塩としてはナトリウム塩、カリウム塩、マグネシウム塩が好ましく、第４級アンモニウム型カチオン界面活性剤の対イオンとしては塩素イオン、硫酸イオンが好適である。 The salt of the anionic surfactant is preferably a sodium salt, potassium salt or magnesium salt, and the counter ion of the quaternary ammonium type cationic surfactant is preferably a chloride ion or a sulfate ion.
本発明では、アミンオキサイド、脂肪酸及び第４級アンモニウム型カチオン界面活性剤が特に好ましく、アミンオキサイド、脂肪酸及び第４級アンモニウム型カチオン界面活性剤を全て配合することが最も好ましい。これら３者を使用する場合には、脂肪酸／第４級アンモニウム型カチオン界面活性剤の質量比は、好ましくは０．５〜６、特に好ましくは０．６〜４が起泡性と漂白効果の点から好適である。 In the present invention, amine oxides, fatty acids and quaternary ammonium type cationic surfactants are particularly preferable, and it is most preferable to add all of amine oxides, fatty acids and quaternary ammonium type cationic surfactants. When these three are used, the mass ratio of the fatty acid / quaternary ammonium type cationic surfactant is preferably 0.5 to 6, particularly preferably 0.6 to 4 for foamability and bleaching effect. From the point of view, it is preferable.
本発明の組成物（Ｂ）中の（ｄ）成分の含有量は、０．０１〜３．５質量％、更に０．０５〜２．０質量％、特に０．０５〜１．０質量％であることが、貯蔵安定性の点から望ましい。 Content of (d) component in the composition (B) of this invention is 0.01-3.5 mass%, Furthermore, 0.05-2.0 mass%, Especially 0.05-1.0 mass% It is desirable from the viewpoint of storage stability.
本発明の組成物（Ｂ）は、さらに（ｅ）成分として、１〜３個、好ましくは１個の炭素数１〜３のアルキル基で置換されたベンゼンスルホン酸アルカリ金属塩を含有することにより、高温下における保存安定性を向上させることができる。また同時にスプレイヤーにて噴霧する時における起泡力を更に向上でき、使用時の硬質表面への付着性を改善することができる。（ｅ）成分のうち、アルカリ金属塩としては、ナトリウム塩が好ましい。（ｅ）成分としては、クメンスルホン酸ナトリウム、キシレンスルホン酸ナトリウム、トルエンスルホン酸ナトリウムなどが挙げられる。中でも、ｍ−キシレンスルホン酸ナトリウムが好ましい。 The composition (B) of the present invention further contains, as component (e), an alkali metal benzene sulfonate substituted with 1 to 3, preferably 1 to 3 alkyl groups. In addition, the storage stability at high temperatures can be improved. At the same time, the foaming power when spraying with a sprayer can be further improved, and adhesion to a hard surface during use can be improved. Among the components (e), the alkali metal salt is preferably a sodium salt. Examples of the component (e) include sodium cumene sulfonate, sodium xylene sulfonate, and sodium toluene sulfonate. Among these, sodium m-xylene sulfonate is preferable.
本発明の組成物（Ｂ）中の（ｅ）成分の含有量は０．１〜３．０質量％、更に０．１〜２．０質量％が好ましい。この範囲において高温下での次亜塩素酸ナトリウムの保存安定性を高めるとともに、噴霧時の起泡力を更に向上させることができる。 The content of the component (e) in the composition (B) of the present invention is preferably 0.1 to 3.0% by mass, more preferably 0.1 to 2.0% by mass. In this range, the storage stability of sodium hypochlorite at high temperatures can be enhanced, and the foaming power during spraying can be further improved.
本発明の組成物（Ｂ）には、その他の任意成分として、香料成分を配合することができる。次亜塩素酸塩系に配合可能な香料成分の例としては、特開昭５０−７４５８１号公報及び特開昭６２−２０５２００号公報を参考にすることができ、単体香料及びそれらを組合せた配合香料であってもよい。香料は通常、組成物（Ｂ）中に０．００１〜０．５質量％含有されるが、安定性を損なう恐れがあるので、配合成分と配合量の決定には注意を要する。 A fragrance | flavor component can be mix | blended with the composition (B) of this invention as another arbitrary component. As examples of perfume ingredients that can be blended into hypochlorite systems, reference can be made to JP-A-50-74581 and JP-A-62-205200. Perfume may be used. Although a fragrance | flavor is contained 0.001-0.5 mass% normally in a composition (B), since there exists a possibility of impairing stability, a caution is required for the determination of a mixing | blending component and a compounding quantity.
本発明の組成物（Ｂ）の残部は水であり、貯蔵安定性の上で、微量に存在する金属イオンなどを除去したイオン交換水や蒸留水が好ましい。水の含有量は貯蔵安定性の点から、組成物（Ｂ）中８０〜９８質量％、更に９０〜９８質量％が好ましい。また、組成物（Ｂ）の２０℃におけるｐＨを１２．５〜１３．５に調整することが、貯蔵安定性及び漂白効果の点から好ましい。 The balance of the composition (B) of the present invention is water, and ion-exchanged water or distilled water from which metal ions and the like that are present in a trace amount are removed is preferable in terms of storage stability. The content of water is preferably 80 to 98% by mass, more preferably 90 to 98% by mass in the composition (B) from the viewpoint of storage stability. Moreover, it is preferable from the point of storage stability and the bleaching effect to adjust pH at 20 degreeC of a composition (B) to 12.5-13.5.
また、本発明の組成物（Ｂ）は、シート（Ａ）やカビ汚れ等への浸透性の点から粘度が低い方が良好であり、オストワルド粘度計を用いたときの２０℃における動粘度が１〜１０ｍｍ2／ｓ、特に１〜６ｍｍ2／ｓであることが良好である。 In addition, the composition (B) of the present invention has a lower viscosity from the viewpoint of permeability to the sheet (A), mold stains, etc., and has a kinematic viscosity at 20 ° C. when using an Ostwald viscometer. 1 to 10 mm 2 / s, it is good to be particularly 1 to 6 mm 2 / s.
＜漂白方法＞
本発明の漂白方法は、シート（Ａ）に含浸させた組成物（Ｂ）中の（ｃ）成分のモル数（Ｍ1）に対して、シート（Ａ）の構成材料中に存在するカルボキシアルキル基の全モル数（Ｍ2）が０．５〜３倍（すなわち、Ｍ2／Ｍ1＝０．５〜３である。）になる比率で、下記（Ａ）に下記（Ｂ）を含浸させた漂白用部材を、漂白対象物に接触させる。
<Bleaching method>
The bleaching method of the present invention is based on the number of moles (M 1 ) of the component (c) in the composition (B) impregnated in the sheet (A). The following (A) is impregnated with the following (B) in such a ratio that the total number of moles (M 2 ) of the group is 0.5 to 3 times (that is, M 2 / M 1 = 0.5 to 3). The bleaching member thus brought into contact with the object to be bleached.
漂白用部材の接触方法としては、例えばシート（Ａ）を貼り付けた後、組成物（Ｂ）を滴下、もしくはトリガー等の噴霧器（スプレーヤー）を用いてスプレーする方法や、漂白対象物に組成物（Ｂ）を好ましくは泡状でスプレーしておき、スプレーされた部分にシート（Ａ）を接触させる方法等が挙げられるが、これらに限定されない。また、漂白対象物への密着性の向上や充分な量の組成物（Ｂ）を供給するために、シート（Ａ）が保持できる組成物（Ｂ）の量に対して飽和量の組成物（Ｂ）を担持させて用いることが好ましい。ここで飽和量とは、シート（Ａ）が保持し得る組成物（Ｂ）の最大含浸量のことをいい、シート（Ａ）の構成材料、構造や、組成物（Ｂ）の組成などにより変動し得る値である。 As a method for contacting the bleaching member, for example, after the sheet (A) is pasted, the composition (B) is dropped or sprayed using a sprayer (sprayer) such as a trigger. A method of spraying the product (B) preferably in the form of a foam and bringing the sheet (A) into contact with the sprayed portion is exemplified, but it is not limited thereto. Further, in order to improve adhesion to the object to be bleached and to supply a sufficient amount of the composition (B), a composition having a saturation amount relative to the amount of the composition (B) that the sheet (A) can hold ( It is preferred to use B) supported. Here, the saturation amount means the maximum impregnation amount of the composition (B) that the sheet (A) can hold, and varies depending on the constituent material and structure of the sheet (A), the composition of the composition (B), and the like. This is a possible value.
本発明の漂白方法において、カルボキシアルキル基のモル数と、組成物（Ｂ）中のアルカリ金属水酸化物のモル数の比率は、シート（Ａ）に組成物（Ｂ）を飽和するまで含浸させた状態を基準に算出されるものと定義される。すなわち、対象となるシート（Ａ）について、組成物（Ｂ）の飽和含浸量を求め、下記の式により組成物（Ｂ）中のアルカリ金属水酸化物のモル数Ｍ1とシート（Ａ）の構成材料中に存在するカルボキシアルキル基の全モル数Ｍ2とを求め、Ｍ2／Ｍ1により当該モル数の比率を算出する。 In the bleaching method of the present invention, the ratio of the number of moles of carboxyalkyl groups to the number of moles of alkali metal hydroxide in the composition (B) is impregnated in the sheet (A) until the composition (B) is saturated. It is defined as being calculated on the basis of the state. That is, with respect to the target sheet (A), the saturated impregnation amount of the composition (B) is determined, and the number of moles M 1 of alkali metal hydroxide in the composition (B) and the sheet (A) are determined by the following formula. The total number of moles M 2 of the carboxyalkyl groups present in the constituent materials is determined, and the ratio of the number of moles is calculated from M 2 / M 1 .
なお、シート（Ａ）中のカルボキシアルキル基のモル数Ｍ2を実験的に算出する方法としては、シート（Ａ）を、既知の規定度の一定量の水酸化ナトリウム水溶液で溶解した後、過剰の水酸化ナトリウムを規定度が既知の硫酸等の酸で逆滴定する方法を挙げることができる。本発明では、このようにして算出した値をモル数Ｍ2として採用してもよい。 In addition, as a method for experimentally calculating the number of moles M 2 of the carboxyalkyl group in the sheet (A), the sheet (A) is dissolved in an aqueous solution of sodium hydroxide having a known normality, and then excess. The sodium hydroxide can be back titrated with an acid such as sulfuric acid having a known normality. In the present invention, it may be employed a value calculated in this manner as moles M 2.
カルボキシアルキル基置換率の異なるカルボキシアルキルセルロースを用いたり、カルボキシアルキルセルロース以外の水分散性繊維との混合比率を変える、また、貯蔵安定性に支障のない範囲で水性漂白剤組成物中のアルカリ金属水酸化物の濃度を調整することで、所望のモル比を達成することができる。 Alkali metals in aqueous bleaching compositions using carboxyalkyl celluloses with different substitution rates of carboxyalkyl groups, changing the mixing ratio with water-dispersible fibers other than carboxyalkyl cellulose, and within the range that does not hinder storage stability A desired molar ratio can be achieved by adjusting the hydroxide concentration.
カルボキシアルキル基のモル数（Ｍ2）が、（ｃ）成分のモル数（Ｍ1）に対して０．５〜３倍、すなわちＭ2／Ｍ1＝０．５〜３になる比率で使用することで安全で高い漂白効果が得られる。好ましくは０．５〜２．３倍、さらに好ましくは１．０〜２．０倍である。このモル比は、シート（Ａ）に含まれるカルボキシアルキル基の量と組成物（Ｂ）中の（ｃ）成分の濃度により適宜調整される。本発明では、シートが（ｃ）成分に対して所定モル比のカルボキシアルキル基を有することで、組成物（Ｂ）のｐＨが速やかに低下する。その結果、シート（Ａ）に組成物（Ｂ）を含浸させた漂白用部材では、漂白活性種が効率的に発生し、例えば市販の塩素系カビ取り剤をティッシュペーパー等に含浸させて漂白対象物に接触させる方法よりも高い漂白効果が得られる。 Used in such a ratio that the number of moles (M 2 ) of the carboxyalkyl group is 0.5 to 3 times the number of moles (M 1 ) of component (c), that is, M 2 / M 1 = 0.5 to 3 By doing so, a safe and high bleaching effect can be obtained. Preferably it is 0.5 to 2.3 times, more preferably 1.0 to 2.0 times. This molar ratio is appropriately adjusted depending on the amount of the carboxyalkyl group contained in the sheet (A) and the concentration of the component (c) in the composition (B). In this invention, pH of a composition (B) falls rapidly because a sheet | seat has a carboxyalkyl group of predetermined molar ratio with respect to (c) component. As a result, the bleaching member in which the sheet (A) is impregnated with the composition (B) efficiently generates bleaching active species. For example, a tissue paper or the like is impregnated into a tissue paper to be bleached. A higher bleaching effect can be obtained than the method of contacting the product.
本発明では、シート（Ａ）に組成物（Ｂ）を含浸してから１０分後の含浸液のｐＨが２０℃において９〜１２となることが、漂白効果の速やかな発現という観点から好ましく、ｐＨは１０〜１２が最も好ましい。本発明においては、組成物（Ｂ）のｐＨを低減して漂白対象物に接触させることが重要であり、そのためには、シート（Ａ）に組成物（Ｂ）が含浸されやすく、更には含浸した組成物（Ｂ）中の（ｃ）成分が十分に消費されることが好ましい。そのため、シート（Ａ）に組成物（Ｂ）を含浸させた漂白用部材が保持する液体成分の経時的なｐＨが上記の範囲となることが漂白効果の点で好ましい。 In the present invention, the pH of the impregnating solution 10 minutes after impregnating the sheet (A) with the composition (B) is preferably 9 to 12 at 20 ° C. from the viewpoint of rapid expression of the bleaching effect, The pH is most preferably 10-12. In the present invention, it is important to reduce the pH of the composition (B) and bring it into contact with the object to be bleached. For this purpose, the sheet (A) is easily impregnated with the composition (B), and further impregnation. It is preferable that the component (c) in the composition (B) is sufficiently consumed. Therefore, it is preferable from the viewpoint of the bleaching effect that the pH of the liquid component held by the bleaching member in which the sheet (A) is impregnated with the composition (B) is in the above range.
本発明によれば、このような本発明の漂白方法に好適に使用されるシート（Ａ）と組成物（Ｂ）とを構成要素とする漂白キットが提供される。該漂白キットにおいては、組成物（Ｂ）の２０℃におけるｐＨが１２．５〜１３．２であることが好ましく、このようなｐＨを有する組成物（Ｂ）をシート（Ａ）に含浸させてから１０分経過後に、シート（Ａ）がｐＨ９〜１２の液体成分を保持することが好ましい。 According to the present invention, there is provided a bleaching kit comprising the sheet (A) and the composition (B) suitably used in the bleaching method of the present invention. In the bleaching kit, the pH of the composition (B) at 20 ° C is preferably 12.5 to 13.2, and the sheet (A) is impregnated with the composition (B) having such a pH. 10 minutes later, the sheet (A) preferably retains the liquid component having a pH of 9 to 12.
このように、本発明はシート（Ａ）と組成物（Ｂ）とをセットで使用することが重要であり、上記シート（Ａ）と類似組成のシートを、市販の塩素系カビとり剤と併用するだけでは得られない、安全性を考慮した高い漂白性能を得ることができる。 Thus, in the present invention, it is important to use the sheet (A) and the composition (B) as a set, and the sheet (A) and a sheet having a similar composition are used in combination with a commercially available chlorine mold remover. It is possible to obtain a high bleaching performance in consideration of safety, which cannot be obtained only by doing.
実施例１〜５及び比較例１〜５
＜シート＞
表１にシート例を示す。これらのシートの作成方法を以下に示す。まず、繊維状カルボキシメチルセルロース（ニチリン化学製ＨＣ−Ｍ）およびパルプ（Mackenzie製ＮＢＫＰ）を合計で３質量％程度の濃度で離解機にてパルプが分散するまで撹拌混合する。これに更に水を加え０．０１５質量％程度のスラリーとし、角型手抄き抄紙機にて手抄きシートを作成する。これを１２０℃の熱風乾燥機にて乾燥させ、シートサンプルを作成した。
Examples 1-5 and Comparative Examples 1-5
<Sheet>
Table 1 shows an example sheet. A method for creating these sheets will be described below. First, fibrous carboxymethyl cellulose (HC-M manufactured by Nichirin Chemical Co., Ltd.) and pulp (NBKP manufactured by Mackenzie) are stirred and mixed at a concentration of about 3% by mass until the pulp is dispersed in a disintegrator. Water is further added to make a slurry of about 0.015% by mass, and a handmade sheet is prepared with a square handmade paper machine. This was dried with a 120 ° C. hot air dryer to prepare a sheet sample.
＜漂白剤組成物＞
表２に液体漂白剤組成物を示す。なお、表中の質量％は組成物中の各成分の濃度である。何れの組成物もｐＨ（２０℃）は１２．５〜１３．５、動粘度（２０℃）は１〜１０ｍｍ2／ｓの範囲であった。
<Bleach composition>
Table 2 shows the liquid bleach composition. In addition, the mass% in a table | surface is the density | concentration of each component in a composition. Each composition had a pH (20 ° C.) of 12.5 to 13.5 and a kinematic viscosity (20 ° C.) of 1 to 10 mm 2 / s.
＜評価＞
表１のシート及び表２の液体漂白剤組成物を表３の組み合わせで用いて、漂白性能（樹脂部に発生したカビ汚れの漂白除去効果の評価）を下記の方法で評価した。結果を表３に示す。
<Evaluation>
Using the sheet of Table 1 and the liquid bleach composition of Table 2 in combination of Table 3, the bleaching performance (evaluation of the effect of removing bleaching of mold stains generated in the resin part) was evaluated by the following method. The results are shown in Table 3.
（１）漂白性能
一般家庭の浴室ドアに使用している軟質ポリ塩化ビニル樹脂パッキンに実使用条件にてカビを発生させ、その試験片を採取し約１ｃｍ程度に切断し評価サンプルとした。測色色差計（日本電色工業（株）製、ＮＤ−３００Ａ）を用いて評価サンプルの明度（Ｌ値）を測定した。Ｌ値の差が±２以内の試験片のみを用いて評価を行った。
(1) Bleaching performance Mold was generated on the soft polyvinyl chloride resin packing used for bathroom doors of general households under actual use conditions, and the test piece was collected and cut to about 1 cm to obtain an evaluation sample. The lightness (L value) of the evaluation sample was measured using a colorimetric color difference meter (ND-300A, manufactured by Nippon Denshoku Industries Co., Ltd.). Evaluation was performed using only test pieces having a difference in L value within ± 2.
シャーレ上に上記カビパッキン試験片を置き、３ｃｍ×３ｃｍに切断したシートサンプルを上に乗せ、漂白剤組成物を０．７ｍｌ滴下後、シャーレを傾け、余剰の漂白剤組成物をシートより除去し飽和含浸状態として１０分間放置した。その後水洗、風乾し、目視にて観察し下記の基準に従って評価した。
○：全く黒いくすみがない。
○△：殆ど黒いくすみがなくなっている。
△：やや黒いくすみが残っている。
×：黒いくすみがはっきり残っている。
Place the above mold packing test piece on a petri dish, put the sheet sample cut to 3 cm x 3 cm on top, drop 0.7 ml of the bleach composition, tilt the petri dish, and remove the excess bleach composition from the sheet The saturated impregnation state was left for 10 minutes. Thereafter, it was washed with water, air-dried, visually observed and evaluated according to the following criteria.
○: No black dullness.
○ △: Almost no black dullness.
Δ: Slight black dullness remains.
X: Black dullness remains clearly.
（２）塩素ガス発生の評価
２００ｍｌトールビーカーの底部に、３ｃｍ×３ｃｍに裁断したシートを置き、漂白剤組成物を０．７ｍｌ滴下し、プラスチックフィルムにて密封し５分後に北川式ガス検知管塩素ガス０．１−１０．０ｐｐｍ（光明理化学工業株式会社）を用いて測定した。検知管の読み値により下記の基準に従って評価した。なお、シートを入れず、漂白剤組成物のみを０．７ｍｌ滴下して測定を行った場合は検出限界以下であった。
○：検知管の読み値が５ｐｐｍ未満
△：検知管の読み値が５ｐｐｍ以上１０ｐｐｍ未満
×：検知管の読み値が１０ｐｐｍ以上
(2) Evaluation of chlorine gas generation A sheet cut to 3 cm × 3 cm is placed on the bottom of a 200 ml tall beaker, 0.7 ml of the bleach composition is dropped, sealed with a plastic film, and after 5 minutes the Kitagawa gas detector tube It measured using chlorine gas 0.1-10.0ppm (Komei Rikagaku Co., Ltd.). Evaluation was made according to the following criteria based on the reading of the detector tube. In addition, when the measurement was performed by dropping 0.7 ml of only the bleaching composition without putting a sheet, it was below the detection limit.
○: The reading value of the detection tube is less than 5 ppm. Δ: The reading value of the detection tube is 5 ppm or more and less than 10 ppm. X: The reading value of the detection tube is 10 ppm or more.
（３）ｐＨの経時変化
シャーレ上に３ｃｍ×３ｃｍに裁断したシートを置き、漂白剤組成物を０．７ｍｌ滴下し１０分間室温（２０℃）にて放置する。その後シートに含浸した液を絞り、株式会社堀場製作所製フラット型複合電極６２６１−１０ＣにてｐＨ（周囲温度は２０℃）を測定した。
(3) Change with time of pH A sheet cut to 3 cm × 3 cm is placed on a petri dish, 0.7 ml of the bleach composition is dropped and left at room temperature (20 ° C.) for 10 minutes. Thereafter, the liquid impregnated into the sheet was squeezed, and the pH (ambient temperature was 20 ° C.) was measured with a flat composite electrode 6261-10C manufactured by Horiba, Ltd.
（注）
・カルボキシメチルセルロース：ＨＣ−Ｍ、ニチリン化学工業（株）製カルボキシメチルセルロース（置換度０．４５）
・ＮＢＫＰ：パルプ（Mackenzie）
(note)
Carboxymethyl cellulose: HC-M, Nichirin Chemical Industry Co., Ltd. carboxymethyl cellulose (substitution degree 0.45)
・ NBKP: Pulp (Mackenzie)
表３中、ＣＭ基／ＮａＯＨモル比は、３ｃｍ×３ｃｍのシート中の全カルボキシメチル基（ＣＭ基）のモル数と、該シートに飽和になるまで含浸させた漂白剤組成物中の水酸化ナトリウム（ＮａＯＨ）のモル数の比である。 In Table 3, the CM group / NaOH molar ratio is the number of moles of all carboxymethyl groups (CM groups) in a 3 cm × 3 cm sheet and the hydroxylation in the bleach composition impregnated until the sheet is saturated. It is the ratio of the number of moles of sodium (NaOH).
Claims (4)
（Ａ）カルボキシアルキルセルロースを構成材料中５０〜１００質量％含有する、液体保持性を有するシート。
（Ｂ）次亜ハロゲン酸塩１〜５質量％、アルカリ金属水酸化物０．２〜１質量％、及び水を含有する液体漂白剤組成物。 The total number of carboxyalkyl groups present in the constituent material (A) below is 0.5 to 3 times the number of moles of alkali metal hydroxide in (B) below ( A bleaching method in which a bleaching member impregnated with (B) below in A) is brought into contact with an object to be bleached.
(A) The sheet | seat which has 50 to 100 mass% of carboxyalkyl cellulose in a constituent material, and has liquid retainability.
(B) A liquid bleach composition containing 1 to 5% by weight of hypohalite, 0.2 to 1% by weight of alkali metal hydroxide, and water.
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| JP2004193226A JP4503368B2 (en) | 2004-06-30 | 2004-06-30 | Bleaching method |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02164328A (en) * | 1988-12-16 | 1990-06-25 | Asahi Pen:Kk | Washing method and material used therein |
| JPH02229295A (en) * | 1989-02-28 | 1990-09-12 | Kao Corp | Hydrolyzing paper |
| JPH06192991A (en) * | 1992-10-29 | 1994-07-12 | Nichirin Kagaku Kogyo Kk | Production of water-dispersible sheet |
| JP2002212594A (en) * | 2001-01-12 | 2002-07-31 | Kao Corp | Liquid bleaching detergent composition |
-
2004
- 2004-06-30 JP JP2004193226A patent/JP4503368B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02164328A (en) * | 1988-12-16 | 1990-06-25 | Asahi Pen:Kk | Washing method and material used therein |
| JPH02229295A (en) * | 1989-02-28 | 1990-09-12 | Kao Corp | Hydrolyzing paper |
| JPH06192991A (en) * | 1992-10-29 | 1994-07-12 | Nichirin Kagaku Kogyo Kk | Production of water-dispersible sheet |
| JP2002212594A (en) * | 2001-01-12 | 2002-07-31 | Kao Corp | Liquid bleaching detergent composition |
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