JP2004075797A - Liquid detergent packed in container - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent packed in a container excellent in deterging performances, preservation stability and photostability. <P>SOLUTION: The liquid detergent packed in a container comprises a liquid detergent composition comprising (a) a surfactant, (b) a chelating agent containing in the molecule at least one nitrogen atom and 2-5 COOM groups (wherein M is a hydrogen atom, Na, K, NH<SB>4</SB>or an alkanol amine) and having a calcium stability constant of 4-15 and a molecular weight of at most 1,000, (c) a reducing agent, (d) a perfume and (e) water. The liquid detergent packed in a container is filled in a container which has at least 60 area percent of the part contacted with the liquid detergent composition having an average transmittance of light having a wavelength of 300-350nm of 5-50% and an average transmittance of light having a wavelength of 400-700nm of 50-90%. <P>COPYRIGHT: (C)2004,JPO

Description

【００４１】
〔式中、Ｒ^１は炭素数７〜２０、好ましくは９〜１５のアルキル基又はアルケニル基、Ｒ^２、Ｒ^３はそれぞれ炭素数１〜３のアルキル基もしくは炭素数２〜３のアルケニル基、好ましくは炭素数１のアルキル基又は水素原子である。Ｒ^４は水素原子又は炭素数１〜５のアルキル基もしくは炭素数２〜５のアルケニル基、好ましくは水素原子又はメチル基、ｍは１〜５、好ましくは３の数を示す。〕
【００４２】
【化４】

【００４３】
〔式中、Ｒ^５は炭素数８〜２０、好ましくは１２〜１４のアルキル基又はアルケニル基、Ｒ^６、Ｒ^７はそれぞれ炭素数１〜３のアルキル基もしくは炭素数２〜３のアルケニル基、好ましくは炭素数１のアルキル基、又は水素原子、ｐは０〜１０、好ましくは２〜４の数を示す。〕。
【００４４】
＜（ｂ）成分＞
本発明に係る液体洗浄剤組成物は、（ｂ）成分として、分子内に少なくとも１個の窒素原子と２〜５個のＣＯＯＭ基（Ｍは水素原子、Ｎａ、Ｋ、ＮＨ_４）を有するカルシウム安定度定数が４〜１５である分子量１０００以下のキレート剤を含有する。洗浄性能の点で、カルシウム安定度定数は５〜１４が好ましく、６〜１３がより好ましく、６〜１０が更に好ましく、６〜８が特に好ましい。洗浄性能の点で、分子量は８００以下が好ましく、６００以下がより好ましい。分子量の下限は２００以上が好ましい。
【００４５】
洗浄性能、液物性、色、匂いの安定性の点で、本発明に係る液体洗浄剤組成物は、（ｂ）成分を１〜３０質量％含有することが好ましく、２〜２５質量％がより好ましく、３〜２０質量％が更に好ましく、３．５〜１５質量％がより更に好ましく、４〜１２質量％が特に好ましい。
【００４６】
尚、本発明において、カルシウム安定度定数は次の方法で求められるものをいう。
【００４７】
（カルシウム安定度定数の測定方法）
緩衝液として０．１ｍｏｌ／リットルのＮＨ_４Ｃｌ−ＮＨ_４ＯＨ（ｐＨ１０）溶液を調製する。この緩衝液を用いて全ての試料溶液を調製する。Ｃａ^２＋濃度の測定にはオリオン（株）製のイオンメーター９２０ＡとＣａ^２＋イオン電極を用いる。先ず、塩化カルシウム濃度と電極の電位の関係を求め、検量線を作成する。塩化カルシウムの５．３６×１０^−２ｍｏｌ／リットル溶液、キレート剤試料の５．３６×１０^−４ｍｏｌ／リットル溶液を調製する。キレート剤試料溶液１００ｍｌに塩化カルシウム溶液を１ｍｌ加え、５分間撹拌する。残存しているＣａ^２＋濃度をＣａ^２＋イオン電極を用いて測定する。キレート剤はＣａ^２＋と１：１でキレート錯体を形成すると仮定して下記の式からカルシウム安定度定数（Ｃａ安定度定数）を求める。
【００４８】
【数１】

【００４９】
（ｂ）成分としては、アミノカルボン酸（塩）、ヒドロキシアミノカルボン酸（塩）がより好ましく、アミノカルボン酸（塩）が更に好ましい。
【００５０】
アミノカルボン酸（塩）として、ニトリロ三酢酸（塩）、エチレンジアミンテトラ酢酸（塩）、β−アラニンジ酢酸（塩）、アスパラギン酸ジ酢酸（塩）、メチルグリシンジ酢酸（塩）、イミノジコハク酸（塩）等が挙げられる。
【００５１】
ヒドロキシアミノカルボン酸（塩）として、セリンジ酢酸（塩）、ヒドロキシイミノジコハク酸（塩）、ヒドロキシエチルエチレンジアミントリ酢酸（塩）、ジヒドロキシエチルグリシン（塩）等が挙げられる。
【００５２】
中でも洗浄性能、環境適性の点で下記一般式（Ｉ）で表される化合物が好ましい。
【００５３】
【化５】

【００５４】
〔式中、Ｒは−（ＣＨ_２）_ｎ−Ａであり、Ａは水素原子、ＯＨ、ＣＯＯＭであり、Ｍは水素原子、Ｎａ、Ｋ、ＮＨ_４、好ましくはＮａであり、ｎは０〜５の数を示す。〕。
【００５５】
これらの有機カルボン酸（塩）は酸の形で配合した後、水酸化カリウム、水酸化ナトリウム、水酸化アンモニウム、炭酸カリウム、炭酸ナトリウム、モノエタノールアミン、ジエタノールアミン等により中和して少なくとも一部を塩としても良い。また、予めカルボキシル基の少なくとも一部を塩とした後に配合しても良い。洗浄性能の点で、特に少なくとも一部のカルボキシル基がカリウム塩又はアンモニウム塩であることが好ましい。
【００５６】
＜（ｃ）成分＞
本発明に係る液体洗浄剤組成物は、（ｃ）成分として還元剤を含有する。色、匂いの安定性の点で組成物中の（ｃ）成分の比率は０．０１〜１０質量％が好ましく、０．０１〜１質量％がより好ましく、０．０５〜０．５質量％が更に好ましい。
【００５７】
還元剤としては、亜硫酸、二亜硫酸、重亜硫酸、チオ硫酸、ホウ酸及びこれらの塩、アルデヒド類、糖類、ギ酸、シュウ酸等が挙げられる。中でも、亜硫酸、二亜硫酸、重亜硫酸、チオ硫酸、ホウ酸及びこれらの塩から選ばれる一種以上が色、匂いの安定性の点で好ましく、亜硫酸（塩）を含有することがより好ましい。
【００５８】
＜（ｄ）成分＞
本発明に係る液体洗浄剤組成物は、（ｄ）成分として香料を含有する。組成物中の（ｄ）成分の比率は、色、匂いの安定性、洗浄性能の点で０．０１〜１０質量％が好ましく、０．０１〜１質量％がより好ましく、０．０５〜０．５質量％が更に好ましい。
【００５９】
香料としては、例えば「香料の化学」（昭和５８年９月１６日発行、著者：赤星亮一、発行者：佐久間裕三、発行所：大日本図書株式会社）記載の調合香料用化合物から得られる。
【００６０】
＜（ｅ）成分＞
本発明に係る液体洗浄剤組成物は、（ｅ）成分として水を含有する。組成物中の（ｅ）成分の比率は、洗浄性能、液物性の点で５０〜９５質量％が好ましく、５５〜９０質量％がより好ましく、６０〜８５質量％が更に好ましく、６５〜８０質量％が特に好ましい。
【００６１】
＜その他の成分＞
本発明に係る液体洗浄剤組成物は、洗浄性能、液物性の点で、アルカリ剤〔以下、（ｆ）成分という〕を含有することが好ましく、組成物中の比率は１〜３０質量％が好ましく、３〜２５質量％がより好ましく、５〜２０質量％が特に好ましく、５〜１５質量％が最も好ましい。
【００６２】
（ｆ）成分としては、例えば炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、炭酸水素カリウム等のアルカリ金属炭酸塩、珪酸ナトリウム、珪酸カリウム等のアルカリ金属珪酸塩、オルトリン酸塩、メタリン酸塩、ピロリン酸塩、ヘキサメタリン酸塩等のポリリン酸塩、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン類、リン酸水素二ナトリウム、リン酸三ナトリウム、ホウ酸塩等が挙げられる。
【００６３】
（ｆ）成分は洗浄性能の点で、（ｆ）成分の０．０２５質量％濃度の水溶液もしくは分散液の最大ｐＨが１０以上（２０℃）であり、且つ該水溶液もしくは分散液１リットルをｐＨ９（２０℃）にするために０．１Ｎの塩酸水溶液を１０ｍｌ以上必要とする化合物であることが好ましい。このような化合物としては、炭酸ナトリウム、炭酸カリウム、珪酸ナトリウム、リン酸三ナトリウム、モノエタノールアミン等が挙げられる。中でも炭酸ナトリウム、炭酸カリウム、珪酸ナトリウムがより好ましく、特に炭酸ナトリウム、炭酸カリウムが好ましい。
【００６４】
本発明に係る液体洗浄剤組成は、低温安定性、液物性の点で、ハイドロトロープ剤〔以下、（ｇ）成分という〕を含有することが好ましく、組成物中の比率は１〜３０質量％が好ましく、２〜１５質量％が更に好ましく、３〜１０質量％が特に好ましい。
【００６５】
（ｇ）成分としては、メタノール、エタノール、プロパノール、グリセリン、エチレングリコール、プロピレングリコール等の炭素数１〜４の低級アルコール、トルエンスルホン酸又はその塩、キシレンスルホン酸又はその塩、下記一般式（ＩＶ）で示される化合物等が挙げられる。
【００６６】
Ｘ−（Ｐｈ）−Ｏ（ＣＨ_２ＣＨ_２Ｏ）_ｐ（ＣＨ_２ＣＨＲＯ）_ｑＹ　（ＩＶ）
〔式中、Ｘは、水素原子、炭素数１〜４のアルキル基もしくは炭素数２〜４のアルケニル基、水酸基、又はハロゲンであり、Ｙは、水素原子、メチル基、又はエチル基であり、Ｐｈは、フェニレン基であり、Ｒは、水素原子、メチル基、又はエチル基であり、ｐは、１〜６、好ましくは１〜３、ｑは、０〜４、好ましくは０〜２であり、ｐ＋ｑは、１〜１０、好ましくは１〜６である。〕。
【００６７】
中でも炭素数２〜３の低級アルコール、ｐ−トルエンスルホン酸又はその塩がより好ましい。
【００６８】
その他、本発明に係る液体洗浄剤組成物には、（１）重量平均分子量５０００以上のポリエチレングリコール、ナフタレンスルホン酸塩ホルマリン縮合物等の再汚染防止剤及び分散剤０．０１〜１０質量％、（２）ポリビニルピロリドン等の色移り防止剤０．０１〜１０質量％、（３）シリコーン、シリカ等の調泡剤０．００１〜２質量％、（４）着色剤、（５）抗菌防腐剤、（６）アミラーゼ、プロテアーゼ、リパーゼ、セルラーゼ等の酵素、（７）塩化カルシウム、硫酸カルシウム、ホウ酸（ホウ素化合物）等の酵素安定化剤、（８）ポリアクリル酸（塩）、ポリマレイン酸（塩）、カルボキシメチルセルロース、アクリル酸−マレイン酸共重合体若しくはその塩、無水マレイン酸−ジイソブチレン共重合体若しくはその塩、無水マレイン酸−メチルビニルエーテル共重合体若しくはその塩、無水マレイン酸−イソブチレン共重合体若しくはその塩、無水マレイン酸−酢酸ビニル共重合体若しくはその塩、及び特開昭５９−６２６１４号公報の請求項１〜２１（１頁３欄５行〜３頁４欄１４行）記載のポリマー等といった有機多価カルボン酸及び／又はその塩等を配合することができる。
【００６９】
〔容器〕
本発明に用いる容器は、前記液体洗浄剤組成物と接触する部分の６０％（面積比）以上、好ましくは７０％以上、より好ましくは８０％以上、更に好ましくは９０％以上、特に好ましくは１００％が、波長３００〜３５０ｎｍの光の平均透過率が５〜５０％且つ波長４００〜７００ｎｍの光の平均透過率が５０〜９５％である。
【００７０】
容器の材質はガラスでも良いが、取り扱いの容易性の点で、熱可塑性樹脂が好ましい。熱可塑性樹脂としては、ポリプロピレン、ポリエステル、ポリカーボネート、ポリアミド等が挙げられる。中でもポリプロピレンが生産性の点で好ましい。
【００７１】
本発明に係る容器において、波長３００〜３５０ｎｍの光の平均透過率は、色、匂いの安定性の点で１０〜４０％が好ましく、１０〜３０％がより好ましく、１５〜３０％が更に好ましい。
【００７２】
また、本発明に係る容器において、波長４００〜７００ｎｍの光の平均透過率は、内容物の視認性の良さ、外観の美しさの点で６０〜９０％が好ましく、６０〜８０％がより好ましい。
【００７３】
このような状態を得るために、特開平７−４０９５４号公報、段落００１５〜００２１記載の紫外線吸収剤を用いることができる。紫外線吸収剤は、容器が単層樹脂であっても樹脂中に含有させることができる。紫外線吸収剤が内容液に移行し変質することがないように、容器を多層樹脂とし、接液しない樹脂層に紫外線吸収剤を含有させることが好ましい。また、紫外線吸収剤を含有する熱収縮性フィルム（好ましくはポリエステル）を用いることが生産性の点で好ましい。
【００７４】
また、樹脂を着色したり、ボトル表面に印刷層を形成したり、印刷層のある熱収縮性フィルム（好ましくはポリエステル）を樹脂ボトルに装着することにより透過度を調整することができる。更に表面をエンボス処理することによって調整することができる。
【００７５】
【実施例】
参考例
表１に示す液体洗浄剤組成物１〜７を調製した。得られた組成物の粘度は何れも２〜１５ｍＰａ・ｓ（Ｂ型粘度計、２０℃、６０ｒ／ｍｉｎ）、ｐＨ１０〜１１であった。
【００７６】
これらについて以下に示す方法により、洗浄力の評価を行った。その結果を表１に示す。
【００７７】
＜洗浄力の評価＞
（襟あか布の調製）
ＪＩＳ　Ｋ３３６２：１９９８記載の襟あか布を調製する。
【００７８】
（洗浄条件及び評価方法）
２槽式洗濯機（東芝銀河３．６）の洗濯槽にＪＩＳ　Ｋ３３６２：１９９８記載の使用水４０Ｌを入れ、これに１．４ｋｇの綿製の未着用肌着及び０．６ｋｇの綿／ポリエステル混紡の未着用ワイシャツを入れる。更に、ＪＩＳ　Ｋ３３６２：１９９８記載の洗浄力判定用指標洗剤（蛍光増白剤無添加）５３ｇ（無水物換算）投入する。更に上記襟あか布１枚に付き、液体洗浄剤組成物４ｇを塗布した後、５分間静置した襟あか布６枚（３段階の汚れを各２枚）を洗濯槽に入れ、１０分間普通洗浄する。その後１分間脱水し、８分間１５Ｌ／ｍｉｎの水量で流水すすぎする。その後５分間脱水し、室内で自然乾燥させる。
【００７９】
液体洗浄剤組成物を塗布しないで同様の操作を行ったものをブランクとして、目視により一対比較し、以下の判定基準により評価する。
【００８０】
評価基準
◎：３段階の汚れ全てにおいて、ブランクより明らかに汚れが落ちている。
○：３段階の汚れ全てにおいて、ブランクよりやや汚れが落ちている。
×：３段階の汚れ全てにおいて、ブランクとほとんど差がない、又は汚れ落ちに劣る。
【００８１】
【表１】

【００８２】
・両性界面活性剤１：ラウラミドプロピルアミンオキシド（ソフタゾリンＬＡＯ−Ｃ、川研ファインケミカル（株）、純分換算量）
・両性界面活性剤２：ジメチルラウリルアミンオキサイド（アンヒトール２０Ｎ、花王（株）、純分換算）
・両性界面活性剤３：ラウリル（２−ヒドロキシ−３−スルホプロピル）ジメチルベタイン（アンヒトール２０ＨＤ、花王（株）、純分換算）
・非イオン界面活性剤１：デシルグルコシド（マイドール１０、花王（株）、純分換算）
・非イオン界面活性剤２：炭素数１０〜１４の直鎖第１級アルコールにエチレンオキサイドを平均８モル、プロピレンオキサイドを平均２モルランダム付加させたもの
・陰イオン界面活性剤１：ヤシ油脂肪酸ナトリウム
・陰イオン界面活性剤２：炭素数１０〜１４の直鎖アルキルベンゼンスルホン酸ナトリウム
・キレート剤１：メチルグリシン二酢酸三ナトリウム（トリロンＭリキッド、ＢＡＳＦジャパン（株）、純分換算）（Ｃａ安定度定数６．１）
・キレート剤２：アスパラギン酸−Ｎ，Ｎ−二酢酸四ナトリウム（Ｃａ安定度定数６．７）
・キレート剤３：セリン二酢酸三ナトリウム（Ｃａ安定度定数６．５）
・キレート剤４：グルタミン酸二酢酸四ナトリウム（Ｃａ安定度定数５．８）
・キレート剤５：エチルグリシン二酢酸三ナトリウム（Ｃａ安定度定数５．７）
・カルボン酸系ポリマー：特開平１０−６０４７６号公報の４頁段落００２１の合成例１記載の方法で合成したフェノキシポリエチレングリコール、アクリル酸、マレイン酸共重合体（重量平均分子量１００００、固形分５１．２重量％）
・酵素：エバラーゼ１６．０Ｌ−ＥＸ（プロテアーゼ、ノボザイムズ社製）
・色素：カヤシオンオレンジ（組成物中に１０ｐｐｍ（質量比）添加）。
【００８３】
実施例１
表１の液体洗浄剤組成物１〜７と、表２に示す容器１〜５とを、表３に示す組み合わせで用い、容器入り液体洗浄剤を得た。該容器入り液体洗浄剤（サンプル）を、下記の保存条件で保存し、以下の方法により匂い、色、を評価した。結果を表３に示す。
【００８４】
（保存条件）
サンプルを温調可能なガラス容器に入れ、４０℃に温調しながら、日光暴露（１万ｋＪ／ｍ^３）させた。尚、実験は５月に行った。
【００８５】
＜匂い評価＞
保存後のサンプルと、調製直後のサンプルとを比較して、嗅覚判定する。
【００８６】
判定基準
○：匂いの変化が認められない。
【００８７】
△：やや匂いの変化が認められる。
【００８８】
×：明らかに匂いの変化が認められる。
【００８９】
＜色評価＞
保存後のサンプルと、調製直後のサンプルとを比較して、視覚判定する。
【００９０】
判定基準
○：色調変化が認められない。
【００９１】
△：やや色調変化が認められる。
【００９２】
×：明らかに色調変化が認められる。
【００９３】
【表２】

【００９４】
【表３】

【００９５】
（注１）○数字のものは比較品である。
（注２）液体洗浄剤組成物と接触する容器の部分のうち、波長３００〜３５０ｎｍの光の平均透過率が５〜５０％且つ波長４００〜７００ｎｍの光の平均透過率が５０〜９５％の部分の比率[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a container-based liquid detergent. More preferably, the present invention relates to a liquid detergent in a container, which is applied to a portion of the object to be washed where dirt is concentrated, and enhances the detergency in subsequent washing.
[0002]
[Prior art]
Liquid detergent compositions are provided in various forms due to advantages such as high functionality due to being a liquid, high flexibility in individual packaging, high flexibility in use, and the like. In the liquid detergent composition, the commercial power is not determined only by the basic performance of the cleaning power, and factors such as the appearance (transparency, color) and smell of the composition strongly influence the determination of the commercial power. The more intense the use, the stronger the influence, for example, in the case of application at hand than in the case of using a washing machine.
[0003]
For this reason, studies have been made to make not only the detergency but also the appearance and odor attractive. However, undesired changes such as discoloration and coloring, deterioration of odor and unpleasant odor often occur due to long-term storage, heat, light and the like. Not all of the causes of such changes have been elucidated, especially for fragrances in which fragrance components are combined in a complex manner, and for substances that carry over in trace amounts in the blending ingredients, etc. It is difficult to exclude from.
[0004]
As one of methods for preventing such undesired changes, it is known to use a container having a light-shielding property or a container that absorbs light of a specific wavelength (for example, Patent Documents 1, 2, 3, 4). However, even if they can reduce the effects of light, they cannot escape from the effects other than light such as long-term storage and heat.
[0005]
On the other hand, as a composition, stabilization by combining an antioxidant, an ultraviolet absorber, a specific nitrogen-containing compound and a sulfite or a soap, or a specific carboxylic acid is known (for example, Patent Documents 5 and 6). , 7, 8, 9, 10). However, these techniques were not enough. Further, it is known that an alternative component is blended without blending a component considered as a specific coloring component (for example, see Patent Documents 11 and 12). However, these are effects of a specific coloring component, and do not take into account that fragrance and other coloring substances are changed by light.
[0006]
Further, a liquid detergent article in which a specific fragrance and an antioxidant are stored in a bag having a specific total light transmittance is known (for example, see Patent Document 13). However, the total light transmittance is too low to appeal the contents, and the commercial power is not improved.
[0007]
Preferred forms of the surfactant-containing liquid composition include products for pre-laundering treatment. This is a product that is intended to be applied directly to a partial stain and then washed normally. It has excellent detergency against collars and cuffs that frequently perform partial washing, dirt and sock dirt, and has excellent usability when applying and using, such as easy adjustment of liquid volume during application and ease of application. There is a need for the development of liquid detergent compositions. In particular, since it is used by hand when used for application, there is a higher demand for color and odor than when used for washing water. In addition, products for pre-washing treatment are desired to be compact, exhibit transparency and freshness, due to the method of use.
[0008]
Conventionally, as a detergent for application, an article filled in a container having an ejection port and a spread surface (for example, see Patent Documents 1 and 4) and an article having a brush-like ejection port (for example, Patent Document 2) , 3, 4) are known. However, these cannot be said to have sufficient stability and cleaning performance of the content liquid by light.
[0009]
[Patent Document 1]
JP-A-8-53165
[Patent Document 2]
JP-A-7-40954
[Patent Document 3]
JP-A-8-301363
[Patent Document 4]
JP-A-11-12371
[Patent Document 5]
Japanese Unexamined Patent Publication No. Hei 7-500862
[Patent Document 6]
JP-A-7-197777
[Patent Document 7]
JP-A-10-237499
[Patent Document 8]
JP-A-11-106800
[Patent Document 9]
JP-A-2000-8099
[Patent Document 10]
Japanese Patent No. 3076629
[Patent Document 11]
JP-A-10-121093
[Patent Document 12]
JP-A-11-256187
[Patent Document 13]
JP 2001-98300 A
[Patent Document 14]
JP-A-11-269500
[Patent Document 15]
JP-A-10-52321
[Patent Document 16]
JP-A-10-52392
[Patent Document 17]
JP 2001-181592 A
[Problems to be solved by the invention]
An object of the present invention is to provide a liquid detergent in a container having excellent cleaning performance, storage stability, and light stability. Liquid washing in a container suitable for pre-washing treatment, in which excellent washing performance is obtained by washing after applying it to the object to be washed, and excellent in resistance to odor deterioration due to storage and light, and resistance to coloring due to storage and light. To provide an agent.
[0027]
[Means for Solving the Problems]
The present invention relates to (a) a surfactant (hereinafter, referred to as a component (a)), (b) at least one nitrogen atom and 2 to 5 COOM groups (M is a hydrogen atom, Na, K, NH ₄₎ calcium stability constant of 1000 or less molecular weight chelating agent is 4 to 15 having a [hereinafter, (b) as component], (c) a reducing agent [hereinafter, referred to as component (c)], (d) perfume A liquid detergent in a container filled with a liquid detergent composition containing [hereinafter, referred to as (d) component] and (e) water [hereinafter, referred to as (e) component], wherein the liquid detergent composition The average transmittance of light having a wavelength of 300 to 350 nm is 5 to 50% and the average transmittance of light having a wavelength of 400 to 700 nm is 50 to 95% for 60% (area ratio) or more of the portion of the container that comes into contact with an object. A liquid cleaning agent in a container.
[0028]
BEST MODE FOR CARRYING OUT THE INVENTION
The liquid detergent in a container of the present invention is obtained by filling the following liquid detergent composition into the following container.
[0029]
(Liquid detergent composition)
The liquid detergent composition according to the present invention comprises (a) a surfactant, (b) at least one nitrogen atom and 2 to 5 COOM groups (M is a hydrogen atom, Na, K, and NH ₄ ) in the molecule. Alkanolamine), a chelating agent having a calcium stability constant of 4 to 15 and a molecular weight of 1000 or less, (c) a reducing agent, (d) a fragrance, and (e) water.
[0030]
In the liquid detergent composition according to the present invention, the pH at 20 ° C. according to the method described in JIS K 3362: 1998 is preferably 7.5 to 12, and more preferably 8 to 11 in terms of detergency and safety. , 8.5 to 11, more preferably 9 to 11, and most preferably 10 to 11.
[0031]
The liquid detergent composition according to the present invention preferably has a viscosity at 20 ° C. of 1 to 50 mPa · s (B-type viscometer, 60 r / min) from the viewpoint of easy discharge from the container, and in particular, spraying or When discharging in the form of foam, 1 to 30 mPa · s is more preferable, 1 to 20 mPa · s is more preferable, and 2 to 15 mPa · s is particularly preferable.
[0032]
<(A) component>
The liquid detergent composition according to the present invention contains a surfactant as the component (a). The ratio of the component (a) in the composition is preferably 0.05 to 10% by mass, more preferably 0.1 to 9% by mass, and still more preferably 0.5 to 8% by mass in terms of cleaning performance and liquid properties. , 1 to 7% by mass is particularly preferred.
[0033]
Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like.
[0034]
Examples of the anionic surfactant include a sulfate salt of an alcohol, a sulfate salt of an ethoxylated alcohol, an alkylbenzene sulfonate, a paraffin sulfonate, an α-olefin sulfonate, an α-sulfo fatty acid salt, and an α-sulfo fatty acid salt. Examples thereof include fatty acid alkyl ester salts and fatty acid salts. In particular, a straight-chain alkylbenzene sulfonate having an alkyl chain having 12 to 14 carbon atoms and an alkyl sulfate ester salt having an alkyl chain having 12 to 18 carbon atoms are preferable. As counter ions, alkali metals and alkanolamine salts are preferable. .
[0035]
Examples of the nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycol fatty acid ester, polyoxyethylene polyoxypropylene block polymer, fatty acid alkanolamide, and alkyl polyalkylene. Glycosides and the like are preferred. In particular, alkyl polyglycosides are preferred.
[0036]
Examples of the cationic surfactant include quaternary mono-long-chain alkyl and di-long-chain alkylammonium salts.
[0037]
Examples of the amphoteric surfactant include alkyl betaine, imidazolinium betaine, amine oxide, alkyl alanine and the like.
[0038]
Above all, it is preferable to contain an amphoteric surfactant from the viewpoint of cleaning performance, more preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more of the surfactant. Is particularly preferred.
[0039]
As the amphoteric surfactant, an amphoteric surfactant selected from a compound represented by the following general formula (II) and a compound represented by the following general formula (III) is preferable in terms of cleaning performance, and these are surfactants. The content is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, and particularly, the compound represented by the general formula (II) is 50% by mass or more in the surfactant, and further preferably 60% by mass. %, Particularly preferably 70% by mass or more.
[0040]
Embedded image

[0041]
[Wherein, R ¹ is an alkyl group or alkenyl group having 7 to 20, preferably 9 to 15 carbon atoms, R ² and R ³ are an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, respectively. It is preferably an alkyl group having 1 carbon atom or a hydrogen atom. R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably a hydrogen atom or a methyl group, and m represents a number of 1 to 5, preferably 3. ]
[0042]
Embedded image

[0043]
[Wherein, R ⁵ is an alkyl group or alkenyl group having 8 to 20, preferably 12 to 14 carbon atoms, R ⁶ and R ⁷ are an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, Preferably, it is an alkyl group having 1 carbon atom or a hydrogen atom, and p is a number of 0 to 10, preferably 2 to 4. ].
[0044]
<(B) component>
The liquid detergent composition according to the present invention comprises, as a component (b), calcium having at least one nitrogen atom and 2 to 5 COOM groups (M is a hydrogen atom, Na, K, and NH ₄ ) in the molecule. It contains a chelating agent having a stability constant of 4 to 15 and a molecular weight of 1000 or less. From the viewpoint of washing performance, the calcium stability constant is preferably from 5 to 14, more preferably from 6 to 13, still more preferably from 6 to 10, and particularly preferably from 6 to 8. From the viewpoint of cleaning performance, the molecular weight is preferably 800 or less, more preferably 600 or less. The lower limit of the molecular weight is preferably 200 or more.
[0045]
The liquid detergent composition according to the present invention preferably contains the component (b) in an amount of 1 to 30% by mass, more preferably 2 to 25% by mass in terms of washing performance, liquid physical properties, color, and odor stability. It is more preferably 3 to 20% by mass, still more preferably 3.5 to 15% by mass, particularly preferably 4 to 12% by mass.
[0046]
In the present invention, the calcium stability constant is determined by the following method.
[0047]
(Method of measuring calcium stability constant)
A 0.1 mol / liter NH ₄ Cl—NH ₄ OH (pH 10) solution is prepared as a buffer. All sample solutions are prepared using this buffer. For the measurement of the Ca ²⁺ concentration, an ion meter 920A manufactured by Orion Co., Ltd. and a Ca ²⁺ ion electrode are used. First, the relationship between the calcium chloride concentration and the potential of the electrode is determined, and a calibration curve is created. 5.36 × ¹⁰ -2 mol / l solution of calcium chloride, a 5.36 × ¹⁰ -4 mol / l solution of a chelating agent sample are prepared. 1 ml of calcium chloride solution is added to 100 ml of the chelating agent sample solution, and the mixture is stirred for 5 minutes. The remaining Ca ²⁺ concentration is measured using a Ca ²⁺ ion electrode. The calcium stability constant (Ca stability constant) is determined from the following equation, assuming that the chelating agent forms a chelate complex with Ca ²⁺ at 1: 1.
[0048]
(Equation 1)

[0049]
As the component (b), aminocarboxylic acids (salts) and hydroxyaminocarboxylic acids (salts) are more preferred, and aminocarboxylic acids (salts) are even more preferred.
[0050]
As aminocarboxylic acids (salts), nitrilotriacetic acid (salt), ethylenediaminetetraacetic acid (salt), β-alanine diacetate (salt), aspartic acid diacetate (salt), methylglycine diacetic acid (salt), iminodisuccinic acid (salt) ) And the like.
[0051]
Examples of the hydroxyaminocarboxylic acid (salt) include serine diacetate (salt), hydroxyiminodisuccinic acid (salt), hydroxyethylethylenediaminetriacetic acid (salt), dihydroxyethylglycine (salt), and the like.
[0052]
Among them, a compound represented by the following general formula (I) is preferable in terms of cleaning performance and environmental suitability.
[0053]
Embedded image

[0054]
Wherein R is-(CH ₂ ) _n -A, A is a hydrogen atom, OH, COOM, M is a hydrogen atom, Na, K, NH ₄ , preferably Na, and n is 0 to The number 5 is shown. ].
[0055]
These organic carboxylic acids (salts) are compounded in the form of an acid, and then neutralized with potassium hydroxide, sodium hydroxide, ammonium hydroxide, potassium carbonate, sodium carbonate, monoethanolamine, diethanolamine, etc., and at least a part thereof is neutralized. Good as salt. Further, it may be blended after at least part of the carboxyl group is converted into a salt in advance. From the viewpoint of washing performance, it is particularly preferable that at least a part of the carboxyl group is a potassium salt or an ammonium salt.
[0056]
<(C) component>
The liquid detergent composition according to the present invention contains a reducing agent as the component (c). From the viewpoint of color and odor stability, the proportion of the component (c) in the composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 1% by mass, and 0.05 to 0.5% by mass. Is more preferred.
[0057]
Examples of the reducing agent include sulfurous acid, disulfurous acid, bisulfurous acid, thiosulfuric acid, boric acid and salts thereof, aldehydes, saccharides, formic acid, oxalic acid and the like. Among them, one or more selected from sulfurous acid, disulfurous acid, bisulfurous acid, thiosulfuric acid, boric acid, and salts thereof are preferable in terms of color and odor stability, and more preferably contain sulfurous acid (salt).
[0058]
<(D) component>
The liquid detergent composition according to the present invention contains a fragrance as the component (d). The proportion of the component (d) in the composition is preferably from 0.01 to 10% by mass, more preferably from 0.01 to 1% by mass, and preferably from 0.05 to 0%, from the viewpoints of color, odor stability and cleaning performance. 0.5 mass% is more preferred.
[0059]
The fragrance is obtained, for example, from a compound for compounded fragrance described in "Chemicals of Perfume" (published on September 16, 1983, author: Ryoichi Akahoshi, publisher: Yuzo Sakuma, publishing office: Dainippon Tosho Co., Ltd.).
[0060]
<(E) component>
The liquid detergent composition according to the present invention contains water as the component (e). The proportion of the component (e) in the composition is preferably from 50 to 95% by mass, more preferably from 55 to 90% by mass, still more preferably from 60 to 85% by mass, and more preferably from 65 to 80% by mass in terms of cleaning performance and liquid physical properties. % Is particularly preferred.
[0061]
<Other ingredients>
The liquid detergent composition according to the present invention preferably contains an alkaline agent (hereinafter, referred to as component (f)) in terms of cleaning performance and liquid physical properties, and the ratio in the composition is preferably 1 to 30% by mass. Preferably, it is 3 to 25% by mass, more preferably 5 to 20% by mass, and most preferably 5 to 15% by mass.
[0062]
As the component (f), for example, alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate and potassium hydrogen carbonate, alkali metal silicates such as sodium silicate and potassium silicate, orthophosphate, metaphosphate, pyrophosphate Salts, polyphosphates such as hexametaphosphate, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, disodium hydrogen phosphate, trisodium phosphate, borate and the like can be mentioned.
[0063]
The component (f) has a maximum pH of 10 or more (20 ° C.) of the aqueous solution or dispersion having a concentration of 0.025% by mass of the component (f) in terms of washing performance, and 1 liter of the aqueous solution or dispersion has a pH of 9 It is preferable that the compound requires 10 ml or more of 0.1N hydrochloric acid aqueous solution in order to attain (20 ° C.). Such compounds include sodium carbonate, potassium carbonate, sodium silicate, trisodium phosphate, monoethanolamine and the like. Among them, sodium carbonate, potassium carbonate and sodium silicate are more preferable, and sodium carbonate and potassium carbonate are particularly preferable.
[0064]
The liquid detergent composition according to the present invention preferably contains a hydrotrope agent (hereinafter, referred to as a component (g)) in terms of low-temperature stability and liquid physical properties, and the ratio in the composition is 1 to 30% by mass. Is preferably, more preferably 2 to 15% by mass, and particularly preferably 3 to 10% by mass.
[0065]
As the component (g), lower alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol, glycerin, ethylene glycol and propylene glycol, toluenesulfonic acid or a salt thereof, xylenesulfonic acid or a salt thereof, and a compound represented by the following general formula (IV) And the like.
[0066]
_{X- (Ph) -O (CH 2} CH 2 O) p (CH 2 CHRO) q Y (IV)
[In the formula, X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, a hydroxyl group, or a halogen, Y is a hydrogen atom, a methyl group, or an ethyl group, Ph is a phenylene group, R is a hydrogen atom, a methyl group, or an ethyl group, p is 1 to 6, preferably 1 to 3, q is 0 to 4, preferably 0 to 2. , P + q is 1 to 10, preferably 1 to 6. ].
[0067]
Among them, a lower alcohol having 2 to 3 carbon atoms, p-toluenesulfonic acid or a salt thereof is more preferable.
[0068]
In addition, the liquid detergent composition according to the present invention comprises (1) a polyethylene glycol having a weight average molecular weight of 5,000 or more, a re-staining inhibitor such as a naphthalene sulfonate formalin condensate and a dispersant 0.01 to 10% by mass, (2) 0.01 to 10% by mass of a color transfer inhibitor such as polyvinylpyrrolidone, (3) 0.001 to 2% by mass of a foam control agent such as silicone and silica, (4) a colorant, and (5) an antibacterial preservative. (6) enzymes such as amylase, protease, lipase, and cellulase; (7) enzyme stabilizers such as calcium chloride, calcium sulfate and boric acid (boron compound); (8) polyacrylic acid (salt); polymaleic acid ( Salt), carboxymethylcellulose, acrylic acid-maleic acid copolymer or salt thereof, maleic anhydride-diisobutylene copolymer or salt thereof, maleic anhydride Acid-methyl vinyl ether copolymer or salt thereof, maleic anhydride-isobutylene copolymer or salt thereof, maleic anhydride-vinyl acetate copolymer or salt thereof, and claims 1 to 3 of JP-A-59-62614. Organic polycarboxylic acids and / or salts thereof such as polymers described in No. 21 (page 1, column 3, line 5 to page 3, column 4, line 14) can be blended.
[0069]
〔container〕
The container used in the present invention is at least 60% (area ratio), preferably at least 70%, more preferably at least 80%, further preferably at least 90%, particularly preferably at least 100%, of the portion in contact with the liquid detergent composition. %, The average transmittance of light having a wavelength of 300 to 350 nm is 5 to 50%, and the average transmittance of light having a wavelength of 400 to 700 nm is 50 to 95%.
[0070]
The container may be made of glass, but is preferably made of a thermoplastic resin in terms of ease of handling. Examples of the thermoplastic resin include polypropylene, polyester, polycarbonate, and polyamide. Among them, polypropylene is preferable in terms of productivity.
[0071]
In the container according to the present invention, the average transmittance of light having a wavelength of 300 to 350 nm is preferably from 10 to 40%, more preferably from 10 to 30%, and still more preferably from 15 to 30%, in terms of color and odor stability. .
[0072]
In the container according to the present invention, the average transmittance of light having a wavelength of 400 to 700 nm is preferably from 60 to 90%, more preferably from 60 to 80%, in terms of good visibility of contents and beauty of appearance. .
[0073]
In order to obtain such a state, an ultraviolet absorber described in JP-A-7-40954, paragraphs 0015 to 0021 can be used. The ultraviolet absorber can be contained in the resin even if the container is a single-layer resin. It is preferable that the container is made of a multilayer resin and the resin layer not in contact with the liquid contains the ultraviolet absorbent so that the ultraviolet absorbent does not migrate into the content liquid and deteriorate. It is preferable to use a heat-shrinkable film (preferably polyester) containing an ultraviolet absorber from the viewpoint of productivity.
[0074]
The transmittance can be adjusted by coloring the resin, forming a print layer on the bottle surface, or attaching a heat-shrinkable film (preferably polyester) having a print layer to the resin bottle. It can be further adjusted by embossing the surface.
[0075]
【Example】
Reference Example Liquid cleaning compositions 1 to 7 shown in Table 1 were prepared. The viscosity of each of the obtained compositions was 2 to 15 mPa · s (B-type viscometer, 20 ° C., 60 r / min) and pH 10 to 11.
[0076]
These were evaluated for detergency by the method described below. Table 1 shows the results.
[0077]
<Evaluation of detergency>
(Preparation of collar cloth)
A collar fabric described in JIS K3362: 1998 is prepared.
[0078]
(Cleaning conditions and evaluation method)
Into a washing tub of a two-tank washing machine (Toshiba Ginga 3.6), put 40 L of used water described in JIS K3362: 1998, and put 1.4 kg of unweared underwear made of cotton and 0.6 kg of cotton / polyester blend. Put an unworn shirt. Further, 53 g (in terms of anhydride) of an index detergent (without adding a fluorescent whitening agent) described in JIS K3362: 1998 for determining detergency is added. Further, 4 g of the liquid detergent composition is applied to one of the above-mentioned collar cloths, and then 6 pieces of the collar cloth (two pieces of three-step dirt) which are allowed to stand for 5 minutes are put into a washing tub for 10 minutes. Wash. Then, dehydrate for 1 minute, and rinse with running water at a flow rate of 15 L / min for 8 minutes. After that, it is dehydrated for 5 minutes and naturally dried indoors.
[0079]
A blank subjected to the same operation without applying the liquid detergent composition is used as a blank, and a pair is visually compared, and evaluated according to the following criteria.
[0080]
Evaluation criteria A: In all three levels of dirt, dirt is clearly removed from the blank.
：: At all three levels of dirt, dirt is slightly removed from the blank.
X: In all three levels of stains, there is almost no difference from the blank, or the stain removal is poor.
[0081]
[Table 1]

[0082]
-Amphoteric surfactant 1: lauramide propylamine oxide (softazoline LAO-C, Kawaken Fine Chemical Co., Ltd., equivalent to pure content)
-Amphoteric surfactant 2: dimethyl laurylamine oxide (Amphitol 20N, Kao Corporation, converted to pure content)
-Amphoteric surfactant 3: Lauryl (2-hydroxy-3-sulfopropyl) dimethyl betaine (Amphitol 20HD, Kao Corporation, pure content conversion)
・ Nonionic surfactant 1: Decyl glucoside (Mydol 10, Kao Corporation, converted to pure content)
-Nonionic surfactant 2: A linear primary alcohol having 10 to 14 carbon atoms to which 8 mol of ethylene oxide and 2 mol of propylene oxide have been added randomly.-Anionic surfactant 1: Coconut fatty acid Sodium / anionic surfactant 2: straight-chain sodium alkylbenzene sulfonate having 10 to 14 carbon atoms / chelating agent 1: trisodium methylglycine diacetate (Trilon M Liquid, BASF Japan K.K., converted to pure content) (Ca stable) Degree constant 6.1)
Chelating agent 2: aspartic acid-N, N-tetraacetic acid tetrasodium salt (Ca stability constant 6.7)
Chelating agent 3: trisodium serine diacetate (Ca stability constant 6.5)
Chelating agent 4: tetrasodium glutamate diacetate (Ca stability constant 5.8)
-Chelating agent 5: trisodium ethylglycine diacetate (Ca stability constant 5.7)
Carboxylic acid-based polymer: a phenoxypolyethylene glycol, acrylic acid, and maleic acid copolymer (weight average molecular weight 10,000, solid content 51.000) synthesized by the method described in Synthesis Example 1 on page 4, paragraph 0021 of JP-A-10-60476. 2% by weight)
-Enzyme: Evalase 16.0L-EX (Protease, Novozymes)
-Dye: Kayashion orange (10 ppm (mass ratio) added to the composition).
[0083]
Example 1
Using the liquid detergent compositions 1 to 7 in Table 1 and the containers 1 to 5 shown in Table 2 in combinations shown in Table 3, liquid detergents in containers were obtained. The liquid detergent (sample) in the container was stored under the following storage conditions, and odor and color were evaluated by the following methods. Table 3 shows the results.
[0084]
(Storage conditions)
The sample was placed in a temperature-controllable glass container and exposed to sunlight (10,000 kJ / m ³ ) while controlling the temperature at 40 ° C. The experiment was conducted in May.
[0085]
<Smell evaluation>
The sample after storage and the sample immediately after preparation are compared to determine olfaction.
[0086]
Judgment standard: No change in odor was observed.
[0087]
Δ: Slight change in odor is observed.
[0088]
×: A change in odor is clearly observed.
[0089]
<Color evaluation>
The sample after storage and the sample immediately after preparation are compared and visually judged.
[0090]
Judgment standard: No change in color tone was observed.
[0091]
Δ: A slight change in color tone is observed.
[0092]
×: A change in color tone is clearly observed.
[0093]
[Table 2]

[0094]
[Table 3]

[0095]
(Note 1) The ones with numbers are comparative products.
(Note 2) Among the portions of the container that come into contact with the liquid detergent composition, the average transmittance of light having a wavelength of 300 to 350 nm is 5 to 50% and the average transmittance of light having a wavelength of 400 to 700 nm is 50 to 95%. Part ratio

Claims (6)

(A) a surfactant, (b) a calcium stability constant having at least one nitrogen atom and 2 to 5 COOM groups (M is a hydrogen atom, Na, K, and NH ₄ ) in a molecule of 4 to 15; A liquid detergent composition containing a chelating agent having a molecular weight of 1000 or less, (c) a reducing agent, (d) a fragrance, and (e) water. The average transmittance of light having a wavelength of 300 to 350 nm is 5 to 50% and the average transmittance of light having a wavelength of 400 to 700 nm is 50 to 95% for 60% (area ratio) or more of the portion of the container in contact with the composition. Liquid cleaning agent in a container. The liquid detergent in a container according to claim 1, wherein the pH of the liquid detergent composition measured at 20C is 7.5 to 12. The liquid detergent in a container according to claim 1, wherein (b) is a compound represented by the following general formula (I).

[Wherein, R is-(CH ₂ ) _n -A, A is a hydrogen atom, OH, COOM, M is a hydrogen atom, Na, K, NH ₄ , and n is a number of 0-5. Show. ] The liquid detergent in a container according to any one of claims 1 to 3, wherein (c) is at least one selected from sulfurous acid, disulfurous acid, bisulfurous acid, thiosulfuric acid, boric acid, and salts thereof. The liquid detergent in a container according to any one of claims 1 to 4, wherein 50% by mass or more of the component (a) is a compound represented by the following general formula (II).

[Wherein, R ¹ is an alkyl group or alkenyl group having 7 to 20 carbon atoms, and R ² and R ³ are an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or a hydrogen atom, respectively. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and m represents a number of 1 to 5. ] The liquid detergent in a container according to any one of claims 1 to 5, wherein the container is made of polypropylene.