JP5481717B2 - Liquid photobleachable composition for textile products - Google Patents
Liquid photobleachable composition for textile products Download PDFInfo
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- JP5481717B2 JP5481717B2 JP2008318378A JP2008318378A JP5481717B2 JP 5481717 B2 JP5481717 B2 JP 5481717B2 JP 2008318378 A JP2008318378 A JP 2008318378A JP 2008318378 A JP2008318378 A JP 2008318378A JP 5481717 B2 JP5481717 B2 JP 5481717B2
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- 239000000203 mixture Substances 0.000 title claims description 43
- 239000004753 textile Substances 0.000 title claims description 21
- 239000007788 liquid Substances 0.000 title claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 23
- -1 Polyoxyethylene Polymers 0.000 claims description 18
- 238000004061 bleaching Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 150000005215 alkyl ethers Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- 239000007844 bleaching agent Substances 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 239000002689 soil Substances 0.000 claims description 3
- 238000009994 optical bleaching Methods 0.000 claims 1
- 239000007921 spray Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 description 24
- 239000011941 photocatalyst Substances 0.000 description 18
- 239000004744 fabric Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000835 fiber Substances 0.000 description 9
- 241000282320 Panthera leo Species 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 244000269722 Thea sinensis Species 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 150000008442 polyphenolic compounds Chemical class 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 235000006468 Thea sinensis Nutrition 0.000 description 3
- 235000020279 black tea Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 101100422634 Postia placenta (strain ATCC 44394 / Madison 698-R) STS-02 gene Proteins 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000013616 tea Nutrition 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 125000005501 benzalkonium group Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SIYLLGKDQZGJHK-UHFFFAOYSA-N dimethyl-(phenylmethyl)-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethyl]ammonium Chemical class C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 SIYLLGKDQZGJHK-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Description
本発明は、光触媒作用により、ポリフェノール等の色素成分を含むシミを効果的に落とすことができる繊維製品用液体光漂白性組成物に関する。 The present invention relates to a liquid photobleachable composition for textiles that can effectively remove a stain containing a pigment component such as polyphenol by photocatalysis.
光触媒は、光（紫外線）があたるとその表面でＯＨラジカルを発生させ、接触する物質を分解させることができるため、窓ガラスや外壁などに塗布して汚れが付着するのを防止したり、空気清浄機やおむつ等のパーソナルケア製品に使用して悪臭物質を除去したりするのに使用されている。
このような光触媒の性質は繊維製品にも利用されている。光触媒を繊維製品に適用する場合、一般的に、バインダー等で光触媒を繊維製品に固着することが行われている。この場合、一度の加工で効果が継続するという利点がある反面、光触媒による繊維やバインダーの劣化が問題となるため、光触媒を無機粉体に担持させる等、光触媒による分解効果をある程度抑制せざるを得ないことが多い。
一方で、光触媒をスプレー等で繊維に付着させ、臭いやシミを分解させることが検討されている。この場合、洗濯等により光触媒は除去されるため、都度使用の必要性はある反面、光触媒による繊維の劣化はほぼ問題とならないため、光触媒による分解効果を十分に引き出し、活用することができるという利点がある。
特許文献１には、防汚、防臭、防黴効果を有する光触媒含有洗浄剤が開示されている。洗浄剤である故、その液性は中性ないし弱アルカリ性である。特許文献２及び３には、酸化チタン等の金属酸化物粒子を含有する繊維製品用処理剤組成物が開示されている。これらの組成物は消臭効果を有する。特許文献４には、光触媒を汚れ部分に付着させて、汚れ物質を分解、漂白する洗濯仕上げ法が開示されている。
Photocatalysts can generate OH radicals on the surface when exposed to light (ultraviolet rays) and decompose substances that come into contact with them. Used in personal care products such as purifiers and diapers to remove malodorous substances.
Such a property of the photocatalyst is also used for textile products. When a photocatalyst is applied to a fiber product, the photocatalyst is generally fixed to the fiber product with a binder or the like. In this case, there is an advantage that the effect is continued by one processing, but since the deterioration of the fiber and the binder due to the photocatalyst becomes a problem, it is necessary to suppress the decomposition effect by the photocatalyst to some extent, such as supporting the photocatalyst on the inorganic powder. Often not.
On the other hand, it has been studied to attach a photocatalyst to fibers by spraying or the like to decompose odors and spots. In this case, since the photocatalyst is removed by washing or the like, there is a need to use it every time, but degradation of the fiber due to the photocatalyst is hardly a problem, so that the decomposition effect by the photocatalyst can be fully extracted and utilized There is.
Patent Document 1 discloses a photocatalyst-containing cleaning agent having antifouling, deodorizing and antifungal effects. Since it is a cleaning agent, its liquidity is neutral to weakly alkaline. Patent Documents 2 and 3 disclose a treating agent composition for a textile product containing metal oxide particles such as titanium oxide. These compositions have a deodorizing effect. Patent Document 4 discloses a laundry finishing method in which a photocatalyst is attached to a soiled portion to decompose and bleach the soiled material.
本発明は、ポリフェノール系の色素成分を含有するシミを効果的に落とすことができる繊維製品用液体光漂白性組成物を提供することを目的とする。 An object of this invention is to provide the liquid photobleachable composition for textiles which can remove effectively the stain containing the polyphenol-type pigment | dye component.
本発明者らが鋭意検討した結果、光触媒とポリオキシエチレン含有ノニオン性化合物とを含有する酸性ないし弱酸性液体組成物を、ポリフェノール系の色素成分を含有する紅茶等のシミに適用して天日干しすると、シミを効果的に落とすことができることを見出した。すなわち、本発明は、ａ）アナターゼ型酸化チタン、ｂ）ポリオキシエチレン含有ノニオン性化合物、及びｃ）水を含有し、25℃におけるｐＨが１〜５である繊維製品用液体光漂白性組成物を提供する。
本発明はまた、上記組成物を、繊維製品に噴霧することを含む繊維製品の漂白方法を提供する。
As a result of intensive studies by the present inventors, an acidic or weakly acidic liquid composition containing a photocatalyst and a polyoxyethylene-containing nonionic compound is applied to a stain such as black tea containing a polyphenol-based pigment component and sun-dried. Then, it discovered that a spot could be removed effectively. That is, the present invention relates to a liquid photobleachable composition for textiles, which contains a) anatase-type titanium oxide, b) a polyoxyethylene-containing nonionic compound, and c) water and has a pH of 1 to 5 at 25 ° C. I will provide a.
The present invention also provides a method for bleaching a textile product comprising spraying the composition onto the textile product.
本発明によれば、ポリフェノール系の色素成分を含有する紅茶等のシミを効果的に落とすことができる。本発明の組成物は、シミに対して噴霧、塗布又は滴下し、そのまま天日干しするだけで、漂白組成物を塗布し、洗濯した場合と同等以上の漂白力を発揮することができる。 According to the present invention, it is possible to effectively remove spots such as black tea containing a polyphenol-based pigment component. The composition of the present invention can exhibit a bleaching power equal to or higher than that obtained when the bleaching composition is applied and washed simply by spraying, coating or dripping on the stain and drying as it is.
ａ）成分：アナターゼ型酸化チタン
本発明のａ）成分は、光触媒として作用し、ｂ）成分と一緒になって、光触媒の機能に基づく漂白作用を発揮する。
本発明のａ）成分として用いることができるアナターゼ型酸化チタンの形態は特に限定されず、例えば、粉体や水分散ゾルがあげられる。粉体としては、ＳＴ−０１（石原産業株式会社製）、ＡＭＴ−１００（テイカ株式会社製）等が商業的に入手できる。水分散ゾルは、酸性タイプのように、酸性水（塩酸水溶液、硝酸水溶液）に分散させたものであってもよいし、シリカコートタイプ、ポリアクリル酸塩コートタイプのように、その表面が被覆されたチタンのゾルであってもよい。商業的に入手できる水分散ゾルとしては、酸性タイプとして、ＴＫＳ−２０２（硝酸酸性、テイカ株式会社製）、ＳＴＳ−０２（塩酸酸性、石原産業株式会社製）等；シリカコートタイプとして、ＭＰＴ−４２２（石原産業株式会社製）等；ポリアクリル酸塩コートタイプとして、ＳＴＳ−２１（石原産業株式会社製）等があげられる。
ａ）成分としては、光漂白効果の強さの観点から、水分散ゾルが好ましく、酸性タイプの水分散ゾルがより好ましい。
a) Component: Anatase Titanium Oxide The a) component of the present invention acts as a photocatalyst and, together with the b) component, exhibits a bleaching action based on the function of the photocatalyst.
The form of the anatase-type titanium oxide that can be used as the component a) of the present invention is not particularly limited, and examples thereof include powder and water-dispersed sol. As the powder, ST-01 (manufactured by Ishihara Sangyo Co., Ltd.), AMT-100 (manufactured by Teika Co., Ltd.) and the like are commercially available. The water-dispersed sol may be dispersed in acidic water (hydrochloric acid aqueous solution, nitric acid aqueous solution) as in the acidic type, or the surface is coated as in the silica coated type or polyacrylate coated type. It may also be a titanium sol. Commercially available water-dispersed sols include TKS-202 (nitric acid acid, manufactured by Teika Co., Ltd.), STS-02 (hydrochloric acid acid, manufactured by Ishihara Sangyo Co., Ltd.), etc .; 422 (manufactured by Ishihara Sangyo Co., Ltd.), etc .; Examples of the polyacrylate coating type include STS-21 (manufactured by Ishihara Sangyo Co., Ltd.).
The component a) is preferably a water-dispersed sol, more preferably an acidic type water-dispersed sol, from the viewpoint of the strength of the photobleaching effect.
本発明のａ）成分は、光漂白効果の強さの観点から、Ｘ線測定による１次粒径の上限が１００ｎｍであるのが好ましく、５０ｎｍであるのがより好ましく、２０ｎｍであるのがさらに好ましい。粒径の下限は１ｎｍであるのが好ましい。
本発明の組成物中におけるａ）成分の配合量（質量基準）は、光漂白効果の強さの観点から、下限が、好ましくは０．０１％、より好ましくは０．１％、更に好ましくは０．５％である。上限は、過剰量のａ）成分が繊維製品表面に残存してしまうことに起因する白化を防止する観点から、好ましくは５．０％、より好ましくは２．０％、更に好ましくは１．０％である。
In the component a) of the present invention, from the viewpoint of the strength of the photobleaching effect, the upper limit of the primary particle size by X-ray measurement is preferably 100 nm, more preferably 50 nm, and further 20 nm. preferable. The lower limit of the particle size is preferably 1 nm.
The blending amount (mass basis) of component a) in the composition of the present invention is preferably 0.01%, more preferably 0.1%, and still more preferably from the viewpoint of the strength of the photobleaching effect. 0.5%. The upper limit is preferably 5.0%, more preferably 2.0%, and still more preferably 1.0 from the viewpoint of preventing whitening due to the excessive amount of component a) remaining on the fiber product surface. %.
ｂ）成分
本発明のｂ）成分は、ａ）成分と一緒になって、光触媒の機能に基づく漂白作用を発揮する。
如何なる理論にも拘束されるものではないが、光漂白効果は、基本的には、ポリオキシエチレン（ＰＯＥ）含有ノニオン性化合物中のエチレンオキサイド（ＥＯ）の平均重合モル数Ｎが影響すると考えられ、Ｎがある範囲内においては光漂白効果が高い傾向にあるが、その一方、Ｎが当該範囲内にあっても、ＰＯＥ含有ノニオン性化合物中のＰＯＥの割合が低いと光漂白効果が有意に発揮されないことから、ＮとＰＯＥの割合と光漂白効果との間に相関関係があることを見出した。ＥＯの平均重合モル数Ｎと該ノニオン性化合物中のＰＯＥの質量分率Ｐとの積である「ＮＰ値」が光漂白効果の強さを表す指標となる。アナターゼ型酸化チタンによる漂白効果は、一般的には、紫外線を吸収した際に生じる励起電子により水が分解され、ヒドロキシラジカル等の活性種が発生することによると考えられており、本発明のｂ）成分は、親水性のＰＯＥ鎖を適度な割合で有するので、ａ）成分の近傍で水を保持し、ａ）成分が漂白作用を発揮する時間を長くすることが出来、これにより、漂白効果が向上したと推察される。
b) Component The b) component of the present invention exhibits a bleaching action based on the function of the photocatalyst together with the a) component.
Although not bound by any theory, it is considered that the photobleaching effect is basically influenced by the average polymerization mole number N of ethylene oxide (EO) in the polyoxyethylene (POE) -containing nonionic compound. , N tends to have a high photobleaching effect within a certain range. On the other hand, even if N is within this range, if the proportion of POE in the POE-containing nonionic compound is low, the photobleaching effect is significant. Since it was not exhibited, it was found that there is a correlation between the ratio of N and POE and the photobleaching effect. The “NP value” which is the product of the average polymerization mole number N of EO and the mass fraction P of POE in the nonionic compound is an index representing the strength of the photobleaching effect. The bleaching effect by anatase-type titanium oxide is generally considered to be due to the fact that water is decomposed by excited electrons generated when ultraviolet rays are absorbed to generate active species such as hydroxy radicals. Component) has a moderate proportion of hydrophilic POE chains, so that water can be retained in the vicinity of component a), and the time for component a) to exert a bleaching action can be lengthened. Is estimated to have improved.
光漂白効果の強さの観点から、ＮＰ値の下限は好ましくは３、より好ましくは５、更に好ましくは１０、特に好ましくは２０である。光漂白効果の強さの観点から、ＮＰ値の上限は好ましくは２００、より好ましくは７５、更に好ましくは６０、特に好ましくは３５である。
ＰＯＥの平均重合モル数Ｎの下限は、光漂白効果の強さの観点から、好ましくは５、より好ましくは１０、更に好ましくは２０である。光漂白効果の強さの観点から、上限は、好ましくは２００、より好ましくは７５、更に好ましくは６０、特に好ましくは３５である。
ＰＯＥの質量分率Ｐの下限は、光漂白効果の強さの観点から、好ましくは０．５、より好ましくは０．８、更に好ましくは０．９である。上限は、好ましくは１である。
本発明の組成物中におけるｂ）成分の配合量（質量基準）は、光漂白効果の強さの観点から、下限が、好ましくは０．１％、より好ましくは０．５％、更に好ましくは１．０％である。上限は、過剰量のｂ）成分により起因して繊維の風合が変化するのを防止する観点から、好ましくは１０％、より好ましくは５％、更に好ましくは２％である。
From the viewpoint of the strength of the photobleaching effect, the lower limit of the NP value is preferably 3, more preferably 5, still more preferably 10, particularly preferably 20. From the viewpoint of the strength of the photobleaching effect, the upper limit of the NP value is preferably 200, more preferably 75, still more preferably 60, and particularly preferably 35.
The lower limit of the average polymerization mole number N of POE is preferably 5, more preferably 10, and still more preferably 20 from the viewpoint of the strength of the photobleaching effect. From the viewpoint of the strength of the photobleaching effect, the upper limit is preferably 200, more preferably 75, still more preferably 60, and particularly preferably 35.
The lower limit of the mass fraction P of POE is preferably 0.5, more preferably 0.8, and still more preferably 0.9 from the viewpoint of the strength of the photobleaching effect. The upper limit is preferably 1.
The blending amount (mass basis) of component b) in the composition of the present invention is preferably 0.1%, more preferably 0.5%, and still more preferably from the viewpoint of the strength of the photobleaching effect. 1.0%. The upper limit is preferably 10%, more preferably 5%, and even more preferably 2% from the viewpoint of preventing the fiber texture from being changed due to an excessive amount of b) component.
本発明のｂ）成分として用いることのできるポリオキシエチレン（ＰＯＥ）含有ノニオン性化合物としては、ポリエチレングリコール、ポリオキシエチレンアルキルエーテル、ポリオキシエチレン付加シリコーン等があげられる。 Examples of the polyoxyethylene (POE) -containing nonionic compound that can be used as the component b) of the present invention include polyethylene glycol, polyoxyethylene alkyl ether, and polyoxyethylene-added silicone.
ｃ）成分
本発明のｃ）成分である水は、ａ）及びｂ）成分を溶解する溶剤として作用する。本発明の組成物を調製するのに使用できる水としては蒸留水、イオン交換水、水道水等が挙げられ、イオン交換水が好ましい。本発明の組成物中におけるｃ）成分の配合量（質量基準）は特に制限されるものではないが、前述のａ）及び／又はｂ）成分の好ましい配合量を達成できる量であることが好ましい。
c) Component Water which is the component c) of the present invention acts as a solvent for dissolving the components a) and b). Examples of water that can be used to prepare the composition of the present invention include distilled water, ion exchange water, and tap water, and ion exchange water is preferred. The blending amount (mass basis) of component c) in the composition of the present invention is not particularly limited, but is preferably an amount that can achieve the preferred blending amount of component a) and / or b) described above. .
本発明の組成物のｐＨは２５℃における値で１〜５である。低いほうが高い漂白効果を発揮するが、安全性を担保する観点からは、下限は、好ましくは１．５、より好ましくは２．０、更に好ましくは２．５である。上限は、光漂白効果の強さの観点から、好ましくは４．５、より好ましくは４．０、更に好ましくは３．５である。
ｐＨの調整は、酸（例えば塩酸）又はアルカリ（例えば水酸化ナトリウム）を適宜使用して行うことができる。本発明の組成物のｐＨは、25℃において、ガラス電極を用いｐＨメータにより測定することができる。
The pH of the composition of this invention is 1-5 in the value in 25 degreeC. A lower value exhibits a higher bleaching effect, but from the viewpoint of ensuring safety, the lower limit is preferably 1.5, more preferably 2.0, and even more preferably 2.5. The upper limit is preferably 4.5, more preferably 4.0, and even more preferably 3.5 from the viewpoint of the strength of the photobleaching effect.
The pH can be adjusted using an acid (for example, hydrochloric acid) or an alkali (for example, sodium hydroxide) as appropriate. The pH of the composition of the present invention can be measured with a pH meter at 25 ° C. using a glass electrode.
〔任意成分〕
本発明の組成物は、ａ）〜ｃ）成分のみからなるのが好ましいが、本発明の効果を損なわない範囲で、さらに以下の成分を含有することができる。
・界面活性剤：ポリオキシエチレンアルキルエーテル硫酸塩、直鎖アルキルベンゼンスルホン酸塩、α-オレフィンスルホン酸塩等のアニオン界面活性剤。モノアルキルトリメチルアンモニウム塩、ジアルキルジメチルアンモニウム塩、ベンザルコニウム塩、ベンゼトニウム塩等のカチオン界面活性剤。脂肪酸ジエタノールアミド、脂肪酸モノエタノールアミド、アルキルポリグリコシド、アルキルポリグリセリルエーテル、アルキルポリグリセリルエステル、アルキルアミンオキシド等のノニオン界面活性剤。
・溶剤（水を除く）：エタノール、イソプロパノール等の低級アルコール、エチレングリコール、プロピレングリコール、へキシレングリコール等のグリコール系溶剤、グリセリン、ソルビトール等のポリオール系溶剤。
・香料：例えば、特開２００２−１４６３９９号公報に記載されているような、香料成分と、溶剤と、安定化剤とを含有する香料組成物。
・ｐＨ調整剤：酸としては、塩酸、硫酸、硝酸等の無機酸、酢酸、クエン酸等のカルボン酸。アルカリとしては、水酸化ナトリウム等のアルカリ金属塩、トリエタノールアミン等のアルカノールアミン。
[Optional ingredients]
The composition of the present invention preferably comprises only the components a) to c), but may further contain the following components as long as the effects of the present invention are not impaired.
Surfactant: Anionic surfactant such as polyoxyethylene alkyl ether sulfate, linear alkylbenzene sulfonate, α-olefin sulfonate. Cationic surfactants such as monoalkyltrimethylammonium salts, dialkyldimethylammonium salts, benzalkonium salts, and benzethonium salts. Nonionic surfactants such as fatty acid diethanolamides, fatty acid monoethanolamides, alkyl polyglycosides, alkyl polyglyceryl ethers, alkyl polyglyceryl esters, and alkyl amine oxides.
Solvent (excluding water): lower alcohols such as ethanol and isopropanol, glycol solvents such as ethylene glycol, propylene glycol and hexylene glycol, and polyol solvents such as glycerin and sorbitol.
-Fragrance | flavor: For example, the fragrance | flavor composition containing the fragrance | flavor component, the solvent, and the stabilizer which are described in Unexamined-Japanese-Patent No. 2002-146399.
-PH adjuster: Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and carboxylic acids such as acetic acid and citric acid. Examples of the alkali include alkali metal salts such as sodium hydroxide and alkanolamines such as triethanolamine.
本発明の組成物は、ａ）〜ｃ）成分を、必要により任意成分と共に混合することにより製造することができる。
本発明の組成物は、トリガー容器やディスペンサー容器、エアゾール缶などに充填し、繊維製品に付着した汚れ部分に直接噴霧することにより使用することもできる。その他、繊維製品に付着した汚れ部分へ本発明の組成物を塗布又は滴下して使用することもできる。
本発明の組成物は、繊維製品の原料が天然繊維でも合成繊維でも区別なく使用することができる。
本発明の組成物は、光触媒により漂白効果を発揮するものであるので、本発明の組成物を適用した繊維製品を天日干しするのが最も良いが、室内干しでも効果を発揮する。
また、汚れ除去効果を得るために適用後に繊維製品を洗濯する必要があった従来の漂白剤とは異なり、本発明の組成物は、当該組成物を適用（噴霧、塗布又は滴下）した繊維製品を洗濯することなく、天日干しするだけで汚れを除去することができる。したがって、汚れが付着した衣類を洗濯し、干す時に、汚れが除去できていなかったことに気付いた場合でも、本発明の組成物を用いれば、更なる洗濯を行うことなく、そのまま干すだけで汚れを除去することができる。この場合、適用後の洗濯が不要である本発明の組成物は、従来の漂白剤よりも高い汚れ除去効果が得られる。
本発明の組成物は、ポリフェノール等の色素成分を含む汚れ、例えば紅茶やワイン等によるシミを効果的に除去することができる。
The composition of the present invention can be produced by mixing the components a) to c) together with optional components as necessary.
The composition of the present invention can also be used by filling a trigger container, a dispenser container, an aerosol can or the like and directly spraying it on a soiled part adhering to a textile product. In addition, the composition of the present invention can be applied or dripped onto a soiled part adhering to a textile product.
The composition of the present invention can be used regardless of whether the raw material of the textile product is natural fiber or synthetic fiber.
Since the composition of the present invention exhibits a bleaching effect by a photocatalyst, it is best to dry the fiber product to which the composition of the present invention is applied in the sun, but it can also be effective in indoor drying.
Moreover, unlike the conventional bleaching agent which needed to wash the textile after application in order to obtain the soil removal effect, the composition of the present invention is a textile produced by applying (spraying, applying or dripping) the composition. Without washing, dirt can be removed simply by drying in the sun. Therefore, even if it is noticed that the dirt has not been removed when washing and drying the soiled clothes, the composition of the present invention can be used to wash the clothes without further washing. Can be removed. In this case, the composition of the present invention that does not require washing after application can provide a higher soil removal effect than conventional bleaching agents.
The composition of the present invention can effectively remove stains containing a pigment component such as polyphenol, such as stains caused by tea or wine.
実施例及び比較例の組成物を調製するのに用いた成分は以下のとおりである。
ａ）成分
a-1 アナターゼ型酸化チタン：粉末、一次粒径７ｎｍ、石原産業株式会社製、ＳＴ−０１
a-2 アナターゼ型酸化チタン：水分散ゾル、一次粒径７ｎｍ、塩酸酸性、石原産業株式会社製、ＳＴＳ−０２
a'-1 ルチル型酸化チタン：粉末、一次粒径短軸５〜１５ｎｍ、長軸３０〜９０ｎｍ、石原産業株式会社製、ＴＴＯ−Ｖ−３
The components used to prepare the compositions of the examples and comparative examples are as follows.
a) Component
a-1 Anatase type titanium oxide: powder, primary particle size 7 nm, manufactured by Ishihara Sangyo Co., Ltd., ST-01
a-2 Anatase type titanium oxide: water-dispersed sol, primary particle size 7 nm, hydrochloric acid acid, manufactured by Ishihara Sangyo Co., Ltd., STS-02
a'-1 Rutile-type titanium oxide: powder, primary particle size minor axis 5-15 nm, major axis 30-90 nm, manufactured by Ishihara Sangyo Co., Ltd., TTO-V-3
ｂ）成分
b-1 ポリエチレングリコール：ＰＥＧ＃３００、Ｎ：６、Ｐ：１、ＮＰ：６、ライオン株式会社製
b-2 ポリエチレングリコール：ＰＥＧ＃１０００、Ｎ：２２、Ｐ：１、ＮＰ：２２、ライオン株式会社製
b-3 ポリエチレングリコール：ＰＥＧ＃４０００、Ｎ：９０、Ｐ：１、ＮＰ：９０、ライオン株式会社製
b-4 ポリエチレングリコール：ＰＥＧ６０００Ｐ、Ｎ：２００、Ｐ：１、ＮＰ：２００、ライオン株式会社製
b-5 ポリオキシエチレンアルキルエーテル：アルキル基の炭素数１２、Ｎ：５、Ｐ：０．５８、ＮＰ：３、日本エマルジョン株式会社製、ＥＭＡＬＥＸ７０５
b-6 ポリオキシエチレンアルキルエーテル：アルキル基の炭素数１２、Ｎ：２０、Ｐ：０．８４、ＮＰ：１７、ライオン株式会社製、ＥＭＡＬＥＸ７２０
b-7 ポリオキシエチレンアルキルエーテル：アルキル基の炭素数１３、Ｎ：６０、Ｐ：０．９４、ＮＰ：５６、ライオン株式会社製、ＴＤ６００−７５
b-8 ポリエーテル変性シリコーン（下記式１）、Ｎ：６０、Ｐ：０．５８、ＮＰ：３５、合成品
b) Component
b-1 Polyethylene glycol: PEG # 300, N: 6, P: 1, NP: 6, manufactured by Lion Corporation
b-2 Polyethylene glycol: PEG # 1000, N: 22, P: 1, NP: 22, manufactured by Lion Corporation
b-3 Polyethylene glycol: PEG # 4000, N: 90, P: 1, NP: 90, manufactured by Lion Corporation
b-4 Polyethylene glycol: PEG6000P, N: 200, P: 1, NP: 200, manufactured by Lion Corporation
b-5 Polyoxyethylene alkyl ether: alkyl group having 12 carbon atoms, N: 5, P: 0.58, NP: 3, manufactured by Nippon Emulsion Co., Ltd., EMALEX 705
b-6 Polyoxyethylene alkyl ether: alkyl group having 12 carbon atoms, N: 20, P: 0.84, NP: 17, Lion Corporation, EMALEX 720
b-7 Polyoxyethylene alkyl ether: carbon number of alkyl group 13, N: 60, P: 0.94, NP: 56, manufactured by Lion Corporation, TD600-75
b-8 Polyether-modified silicone (Formula 1 below), N: 60, P: 0.58, NP: 35, synthetic product
（式中、ｘ＝２０、ｙ＝３、ｍ＝２０、ｎ＝０、Ｒ＝Ｈ）
(Where, x = 20, y = 3, m = 20, n = 0, R = H)
＜b-8合成方法＞
撹拌装置、凝縮機、温度計及び窒素挿入口を備えた１Ｌの４つ口フラスコに、下記式２のオルガノハイドロジェンポリシロキサンを１００ｇ、イソプロピルアルコールを１００ｇ、ポリオキシエチレン（２０）アリルエーテルを１６０ｇ、塩化白金酸のClを中和したものを０．２ｇ投入して、これらを窒素雰囲気下、９０℃で３時間反応させた。反応終了後、溶媒を減圧留去することにより（ｂ−８）を得た。
<B-8 synthesis method>
In a 1 L four-necked flask equipped with a stirrer, condenser, thermometer and nitrogen inlet, 100 g of organohydrogenpolysiloxane of the following formula 2, 100 g of isopropyl alcohol, 160 g of polyoxyethylene (20) allyl ether Then, 0.2 g of chloroplatinic acid neutralized with Cl was added, and these were reacted at 90 ° C. for 3 hours in a nitrogen atmosphere. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain (b-8).
（式中、ｘ＝２０、ｙ＝３）
(Where x = 20, y = 3)
上に示したａ）〜ｃ）成分を混合することにより、表１記載の実施例及び比較例の組成物を調製した。表１中、各組成物におけるａ）及びｂ）成分の配合量は質量基準の値である。ｃ）成分のイオン交換水に関する表示「Ｂ」はバランスを意味する。
組成物のｐＨは２５℃における値である。なお、組成物のｐＨは、１規定塩酸又は１規定水酸化ナトリウムにより調整した。
Compositions of Examples and Comparative Examples described in Table 1 were prepared by mixing the components a) to c) shown above. In Table 1, the blending amounts of components a) and b) in each composition are values based on mass. c) The indication “B” regarding the ion-exchanged water of the component means balance.
The pH of the composition is a value at 25 ° C. The pH of the composition was adjusted with 1N hydrochloric acid or 1N sodium hydroxide.
＜シミ漂白性評価方法＞
（評価布作成方法）
市販の紅茶ティーバッグ（リプトン ブリクス ティーバッグ）１個を２００ｍＬの熱湯（水道水、３°ＤＨ、９５℃）に投入し、５分間放置した。次いで、この紅茶抽出液を、５ｃｍ×５ｃｍの綿メリヤス布（白色、無蛍光、０．０２ｇ／ｃｍ2）の中心に０．１ｇ滴下し、風乾したものを評価布として用いた。
<Stain bleaching evaluation method>
(Evaluation cloth creation method)
One commercially available tea tea bag (Lipton Brix tea bag) was put into 200 mL of hot water (tap water, 3 ° DH, 95 ° C.) and left for 5 minutes. Next, 0.1 g of this black tea extract was dropped on the center of a 5 cm × 5 cm cotton knitted fabric (white, non-fluorescent, 0.02 g / cm 2 ) and air-dried to use as an evaluation fabric.
（光漂白力評価）
小型電気洗濯機（Ｎ−ＢＫ２、松下電器産業（株）製）を用いて、水道水（１５℃、３°ＤＨ）４Ｌ中に市販衣料用粉末洗剤（トップ、ライオン（株）製）を６６７ｐｐｍの濃度になるよう投入し、１分間撹拌後、上記評価布を投入し、１０分間洗浄した。次いで、評価布を２００％ｏ．ｗ．ｆ．の含水量になるまで脱水後、水道水（１５℃、３°ＤＨ）４Ｌで３分間すすぐ工程を２回繰り返した。最後に評価布を２００％ｏ．ｗ．ｆ．の含水量になるまで脱水した。
市販ディスペンサー（スタイルガード・スーツ用、７０ｍＬ、ライオン（株）製の内容物を抜いた後、容器をイオン交換水で数回すすぎ、乾燥させたもの）を用いて、上記脱水した評価布のシミ全体に表１記載の組成物が適用されるよう、約２ｃｍの距離から１プッシュ（約０．１５ｇ）噴霧した。
(Photobleaching power evaluation)
Using a small electric washing machine (N-BK2, manufactured by Matsushita Electric Industrial Co., Ltd.), 667 ppm of a commercial powder detergent for clothing (Top, manufactured by Lion Corporation) in 4 L of tap water (15 ° C., 3 ° DH) Then, after stirring for 1 minute, the evaluation cloth was added and washed for 10 minutes. The evaluation fabric was then 200% o. w. f. After dehydration until the water content became, the rinsing process with 4 L of tap water (15 ° C., 3 ° DH) for 3 minutes was repeated twice. Finally, the evaluation fabric is 200% o. w. f. It was dehydrated until the water content became.
Using a commercially available dispenser (for style guard suit, 70 mL, after removing the contents of Lion Co., Ltd., rinsing the container several times with ion-exchanged water and drying it) One push (about 0.15 g) was sprayed from a distance of about 2 cm so that the composition of Table 1 was applied throughout.
組成物を噴霧した評価布を、晴れた屋外（気温：１５℃前後、湿度：７０％前後、風速：２ｍ前後、紫外線強度３ｍＷ／ｃｍ2前後（ＵＶメーター（ＵＶ−３４０、株式会社カスタム製）にて、波長２９０〜３９０ｎｍの紫外線強度を測定））にて、直射日光が当たる場所で水平に固定し、３時間放置した。
最後に、下記の各評価布のＺ値を、測色色差計（ＳＥ２０００、日本電色社製）を用いて測定し、下記式より各サンプルの漂白率（％）を算出した。
Ａ：サンプルを噴霧後、天日干しした評価布のＺ値
Ｂ：洗浄・脱水後にサンプルを噴霧せず天日干した評価布のＺ値
Ｃ：洗浄・脱水後にサンプルを噴霧せず室内干しで乾燥した評価布のＺ値
Ｄ：原布（綿メリヤス）のＺ値
漂白率（％）＝（Ａ−Ｂ）／（Ｄ−Ｃ）×１００
The evaluation cloth sprayed with the composition was sunny outdoors (temperature: around 15 ° C., humidity: around 70%, wind speed: around 2 m, ultraviolet intensity around 3 mW / cm 2 (UV meter (UV-340, custom made)) The UV intensity at a wavelength of 290 to 390 nm was measured and fixed horizontally in a place exposed to direct sunlight, and left for 3 hours.
Finally, the Z value of each evaluation cloth described below was measured using a colorimetric color difference meter (SE2000, manufactured by Nippon Denshoku), and the bleaching rate (%) of each sample was calculated from the following formula.
A: Z value of the evaluation cloth that was sun-dried after spraying the sample B: Z value of the evaluation cloth that was sun-dried without spraying the sample after washing and dehydration C: Dried indoors without spraying the sample after washing and dehydration Z value of evaluation fabric D: Z value of raw fabric (cotton knitted fabric)
Bleaching rate (%) = (A−B) / (D−C) × 100
各サンプルの漂白力は、上記算出により得られた漂白率から、以下の基準に従って評価し、その結果を表１に記載した。
◎：４０％以上
○：３０％以上４０％未満
△：２０％以上３０％未満
×：２０％未満
The bleaching power of each sample was evaluated according to the following criteria from the bleaching rate obtained by the above calculation, and the results are shown in Table 1.
◎: 40% or more ○: 30% or more and less than 40% △: 20% or more and less than 30% ×: less than 20%
Claims (5)
ｂ）ポリオキシエチレン含有ノニオン性化合物であって、該ポリオキシエチレン含有ノニオン性化合物中のエチレンオキサイドの平均付加モル数Ｎと、該ポリオキシエチレン含有ノニオン性化合物中のポリオキシエチレン鎖の質量分率Ｐとの積（ＮＰ値）が、３〜２００の範囲内にある化合物、及び
ｃ）水
を含有し、25℃におけるｐＨが１〜５である繊維製品光漂白用液体組成物であって、
該繊維製品光漂白用液体組成物を繊維製品に適用後、該繊維製品を洗濯することなく天日干し又は室内干しするという漂白方法において使用される、
繊維製品光漂白用液体組成物。 a) anatase-type titanium oxide,
b) Polyoxyethylene-containing nonionic compound, the average addition mole number N of ethylene oxide in the polyoxyethylene-containing nonionic compound, and the mass fraction of the polyoxyethylene chain in the polyoxyethylene-containing nonionic compound the product of the rate P (NP value), compounds within the scope of 3-200, and c) contain water, met textile products optical bleaching liquid composition is 1 to 5 pH at 25 ° C. And
Used in a bleaching method in which the textile product photo-bleaching liquid composition is applied to a textile product and then the textile product is sun-dried or indoor-dried without washing.
Liquid composition for photobleaching textile products .
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