JP3637005B2 - Articles for pre-washing treatment - Google Patents

Description

【００１７】
〔式中、Ｒ¹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、Ｒ²、Ｒ³はそれぞれ炭素数１〜３のアルキル基もしくはアルケニル基、好ましくは炭素数１のアルキル基又は水素原子である。Ｒ⁴は水素原子又は炭素数１〜５のアルキル基もしくはアルケニル基、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。〕
【００１８】
【化３】

【００１９】
〔式中、Ｒ⁵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、Ｒ⁶、Ｒ⁷はそれぞれ炭素数１〜３アルキル基もしくはアルケニル基、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。〕。
【００２０】
陰イオン界面活性剤としては、アルコールの硫酸エステル塩、アルコールのエトキシレート化物の硫酸エステル塩、アルキルベンゼンスルホン酸塩、パラフィンスルホン酸塩、α−オレフィンスルホン酸塩、α−スルホ脂肪酸塩、α−スルホ脂肪酸アルキルエステル塩又は脂肪酸塩が挙げられる。特に、アルキル鎖の炭素数が１２〜１４の直鎖アルキルベンゼンスルホン酸塩、炭素数１２〜１８のアルキル硫酸エステル塩が好ましく、対イオンとしては、アルカリ金属類、アルカノールアミン塩が好ましい。
【００２１】
非イオン界面活性剤としては、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルキルフェニルエーテル、ポリオキシアルキレンソルビタン脂肪酸エステル、ポリオキシアルキレングリコール脂肪酸エステル、ポリオキシエチレンポリオキシプロピレンブロックポリマー、脂肪酸アルカノールアミド、アルキルポリグリコシド等が好ましい。特に、アルキルポリグリコシドが好ましい。
【００２２】
陽イオン界面活性剤としては、４級型のモノ長鎖アルキル又はジ長鎖アルキルアンモニウム塩等が挙げられる。
【００２３】
＜（ｂ）成分＞
本発明の洗濯前処理剤組成物は、（ｂ）アルカリ剤を含有する。洗浄性能、成泡性の点で１〜３０質量％含有することが好ましく、３〜２５質量％がより好ましく、５〜２０質量％が更に好ましく、５〜１５質量％が特に好ましい。
【００２４】
（ｂ）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。
【００２５】
（ｂ）成分は洗浄性能の点で、（ｂ）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が好ましい。
【００２６】
＜（ｃ）成分＞
本発明の洗濯前処理剤組成物は、（ｃ）キレート剤を含有する。洗浄性能、成泡性の点で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％が特に好ましく、４〜１２質量％が最も好ましい。
【００２７】
（ｃ）成分は、洗浄性能の点で、分子量は１０００以下が好ましく、８００以下がより好ましく、６００以下が更に好ましい。
【００２８】
洗浄力、環境適性の点で、（ｃ）成分のカルシウム捕捉量は２００〜６００ＣａＣＯ₃ｍｇ／ｇが好ましく、２５０〜５５０ＣａＣＯ₃ｍｇ／ｇがより好ましく、３００〜５００ＣａＣＯ₃ｍｇ／ｇが更に好ましい。また、カルシウム安定度定数は４〜１０が好ましく、５〜９がより好ましく、６〜８が更に好ましく、６．５〜８が特に好ましい。
【００２９】
尚、本発明において、カルシウム安定度定数及びカルシウム捕捉量は次の方法で求められるものをいう。
【００３０】
（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ＮＨ₄Ｃｌ−ＮＨ₄ＯＨ（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。Ｃａ²⁺濃度の測定にはオリオン(株)製のイオンメーター９２０ＡとＣａ²⁺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Ｃａ²⁺濃度をＣａ²⁺イオン電極を用いて測定する。キレート剤はＣａ²⁺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。
【００３１】
【数１】

【００３２】
（カルシウム捕捉量の測定方法）
カルシウム捕捉量（Ｃａ捕捉量）は、特開平３−２７７６９６号公報３頁右下欄６行目から４頁左上欄６行目記載の方法（但し、陰イオン性界面活性剤をキレート剤と読み替える）により求める。
【００３３】
（ｃ）成分としては、分子内にＣＯＯＭ基（ＭはＨ、Ｎａ、Ｋ、ＮＨ₄）を２〜５個、好ましくは３〜５個有する化合物が挙げられる。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。
【００３４】
【化４】

【００３５】
〔式中、Ｒは−(ＣＨ₂)_n−Ａであり、ＡはＨ、ＯＨ、ＣＯＯＭであり、ＭはＨ、Ｎａ、Ｋ、ＮＨ₄、好ましくはＮａであり、ｎは０〜５の数を示す。〕。
【００３６】
本発明において、（ｃ）成分、好ましくは一般式（Ｉ）で表される化合物と、（ａ）成分、好ましくは両性界面活性剤の質量比は、（ａ）／（ｃ）＝３／１〜１／５であることが好ましく、より好ましくは２／１〜１／３、更に好ましくは１／１〜１／３、特に好ましくは１／１〜１／２である。
【００３７】
＜（ｄ）成分＞
本発明の衣料用洗濯前処理剤組成物は、（ｄ）水を５０〜９５質量％含有する。洗浄性能、塗布性の点で５５〜９０質量％が好ましく、６０〜８５質量％がより好ましく、６５〜８０質量％が更に好ましい。
【００３８】
＜その他成分＞
本発明の洗濯前処理剤組成物は、低温安定性、成泡性、非詰まり性の点で、ハイドロトロープ剤を１〜３０質量％含有することが好ましく、２〜１５質量％がより好ましく、３〜１０質量％が更に好ましい。
【００３９】
ハイドロトロープ剤としては、エタノール、メタノール、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。
【００４０】
Ｘ−(Ｐｈ)−Ｏ(ＣＨ₂ＣＨ₂Ｏ)_p(ＣＨ₂ＣＨＲＯ)_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。〕。
【００４１】
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。
【００４２】
本発明の洗濯前処理剤組成物には他に、（１）ポリアクリル酸又はその塩、ポリマレイン酸又はその塩、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０．０１〜１０質量％、（２）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％、（３）ポリビニルピロリドン等の色移り防止剤０．０１〜１０質量％、（４）シリコーン、シリカ等の調泡剤０．０１〜２質量％、（５）ブチルヒドロキシトルエン、ジスチレン化クレゾール、亜硫酸ナトリウム及び亜硫酸水素ナトリウム等の酸化防止剤０．０１〜２質量％、（６）着色剤、（７）アミラーゼ、プロテアーゼ、リパーゼ、セルラーゼ等の酵素、（８）塩化カルシウム、硫酸カルシウム、ギ酸、ホウ酸（ホウ素化合物）等の酵素安定化剤、（９）香料、（１０）抗菌防腐剤等を配合することができる。
【００４３】
〔泡吐出容器〕
泡吐出容器としては、トリガー式泡吐出容器、ポンプ機構を備えたキャップの頭部を手指で押圧することにより使用されるポンプ式泡吐出容器、軟質容器の胴部を手指で押圧することにより使用するスクイズフォーマー、エアゾール等が挙げられるが、使用性、経済性、環境適合性等よりトリガー式スプレー容器、スクイズフォーマーがより好ましく、トリガー式スプレー容器が特に好ましい。トリガー式スプレー容器の場合、使用性の点で１回の吐出量は０．５〜１ｇが好ましい。
【００４４】
【実施例】
実施例１〜７、比較例１〜３
表１に示す洗濯前処理剤組成物を調製した。得られた実施例の組成物の２０℃のｐＨは何れも１０〜１１であった。また、実施例の組成物の粘度は何れも２〜１５ｍＰａ・ｓ（Ｂ型粘度計、２０℃、６０ｒ／ｍｉｎ）であった。
【００４５】
調製した組成物を市販のトリガー式泡吐出容器（ファミリーシンクまわりクリーナー２５０ｍＬ、花王（株）製）に充填し、洗濯前処理用物品を得た。得られた実施例の洗濯前処理用物品から吐出される泡は、何れも嵩密度５０〜３００ｇ／Ｌ、静置した１００ｍＬの泡から１０ｍＬの液層が現れるまでの時間が１〜２０分であった。
【００４６】
これらについて以下に示す方法により、洗浄力の評価、泡吐出性の評価を行った。その結果を表１に示す。
【００４７】
＜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。
【００４８】
（洗浄条件及び評価方法）
自動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、洗濯前処理用物品より洗濯前処理剤組成物４ｇを塗布し、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。
【００４９】
洗濯前処理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。
【００５０】
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。
−：容器より吐出しないため評価不能。
【００５１】
＜泡吐出性の評価＞
握力２５〜３０ｋｇの５名に洗濯前処理用物品のトリガーを作動させて洗濯前処理剤組成物を吐出させてもらった。そのときの操作性を以下の基準で評価した。
【００５２】
評価基準
○：泡状に問題なく吐出した。
△：泡と液の混合状態で吐出した。
×：吐出しない。
【００５３】
【表１】

【００５４】
・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のアルキル基を有する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、ＢＡＳＦジャパン（株）、純分換算）（Ｃａ捕捉量４３０ＣａＣＯ₃ｍｇ／ｇ、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捕捉量３２８ＣａＣＯ₃ｍｇ／ｇ、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捕捉量３４７ＣａＣＯ₃ｍｇ／ｇ、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捕捉量３０５ＣａＣＯ₃ｍｇ／ｇ、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捕捉量４１９ＣａＣＯ₃ｍｇ／ｇ、Ｃａ安定度定数５．７）
・カルボン酸系ポリマー：特開平１０−６０４７６号公報の頁１１６行〜１３行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質量％）
・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）[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an article for pre-washing treatment that is used by being applied to an object to be cleaned in a foam form. More particularly, the present invention relates to an article for pre-washing treatment that is applied in a foamy manner on a portion of an object to be cleaned where the dirt is concentrated to enhance the cleaning power in subsequent washing.
[0002]
[Prior art]
In the case of severely soiled parts such as collared sleeves and spilled foods, normal washing may not remove the dirt sufficiently or leave it as a stain. In general, collar sleeves and stains are dealt with by partially increasing the detergent concentration by directly applying detergent.
[0003]
For example, JP-A-60-101199 and JP-A-10-298599 disclose coating detergents for washing after being applied to an object to be cleaned. However, in the contents disclosed by these, the detergency is insufficient, and in particular, the detergency is not sufficient for human-derived stains such as collar sleeve stains. Moreover, foaming property was not enough.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide an article for pre-washing treatment that can be applied to an object to be cleaned easily and safely, and can be washed after being applied to the object to be cleaned, so that excellent cleaning performance can be obtained. There is.
[0005]
[Means for Solving the Problems]
The present invention comprises (a) a surfactant (hereinafter referred to as component (a)) 0.05 to 10% by mass, (b) an alkali agent (hereinafter referred to as component (b)), (c) a chelating agent [hereinafter referred to as component (a). The present invention relates to an article for pretreatment for washing in which a foam discharge container is filled with a washing pretreatment composition containing (c) component] and (d) water (hereinafter referred to as component (d)).
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The article for pre-washing treatment according to the present invention has a foamed content on a portion of the object to be cleaned such as collar stains, sleeve stains and stains (especially collar stains and sleeve stains which are human-derived stains). Apply and use. Effective washing can be performed by applying in a foam and washing after a certain period of time. In terms of cleaning performance, washing is preferably performed after 30 seconds or more, more preferably 1 minute or more, and even more preferably 5 minutes or more. In terms of effects and convenience, 5 hours or less is preferable, 2 hours or less is more preferable, 1 hour or less is further preferable, and 30 minutes or less is particularly preferable.
[0007]
By applying in the form of foam, it is safe without sucking or entering the eyes, and has excellent retention of the pre-washing treatment composition at the time of application. Foaming increases the surfactant concentration on the surface, facilitates penetration of the laundry pretreatment composition into dirt, and improves cleaning power.
[0008]
In particular, the article of the present invention is preferably capable of discharging foam having a bulk density of 50 to 300 g / L, more preferably 80 to 250 g / L, and still more preferably 100 to 200 g / L. Further, it is more preferable that 100 mL of foam is allowed to stand, and the time until a 10 mL liquid layer appears due to spontaneous bubble breakage can be discharged for 1 to 20 minutes, further 3 to 15 minutes, particularly 5 to 10 minutes.
[0009]
The bulk density of the foam was determined at 20 ° C. using a 100 mL graduated cylinder (inner diameter 27 mm, manufactured by Asahi Techno Glass Co., Ltd.), and the mass of 100 mL was determined. Moreover, this was left still and the time until a 10 mL liquid layer appeared by natural bubble breaking was calculated | required.
[0010]
For the purpose of filling the pre-washing agent composition into the foam discharge container, the pre-washing agent composition may be filled into a standing pouch, a refill bottle, or the like.
[0011]
[Laundry pretreatment composition]
The laundry pretreatment agent composition of the present invention preferably has a pH at 20 ° C. of 7.5 to 12 and more preferably 8 to 11 by the method described in JIS K 3362: 1998 in terms of detergency and safety. 8.5-11 are more preferred, 9-11 are particularly preferred, and 10-11 are most preferred.
[0012]
The pretreatment washing composition of 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 at the time of application, and 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.
[0013]
<(A) component>
The laundry pretreatment composition of the present invention contains 0.05 to 10% by mass of (a) a surfactant. In terms of cleaning performance and foamability, 0.1 to 9% by mass is preferable, 0.5 to 8% by mass is more preferable, and 1 to 7% by mass is particularly preferable.
[0014]
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Among them, it is preferable to contain an amphoteric surfactant in terms of washing performance and foamability, more preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass in the surfactant. It is particularly preferable to contain at least%.
[0015]
Examples of amphoteric surfactants include alkyl betaines, imidazolinium betaines, amine oxides, and alkylalanines. In terms of cleaning performance, the compound represented by the following general formula (II) or (III) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more in the surfactant. The compound represented by the general formula (II) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more in the surfactant.
[0016]
[Chemical formula 2]

[0017]
[Wherein R ¹ is an alkyl or alkenyl group having 7 to 20 carbon atoms, preferably 9 to 15 carbon atoms, and R ² and R ³ are each an alkyl or alkenyl group having 1 to 3 carbon atoms, preferably 1 carbon atom. An alkyl group or a hydrogen atom; R ⁴ represents a hydrogen atom or an alkyl or alkenyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or a methyl group, and m represents a number of 1 to 5, preferably 3. ]
[0018]
[Chemical 3]

[0019]
[Wherein R ⁵ is an alkyl group or alkenyl group having 8 to 20 carbon atoms, preferably 12 to 14 carbon atoms, and R ⁶ and R ⁷ are each an alkyl group or alkenyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 carbon atom. A group or a hydrogen atom, p represents a number of 0 to 10, preferably 2 to 4; ].
[0020]
Anionic surfactants include alcohol sulfates, alcohol ethoxylate sulfates, alkylbenzene sulfonates, paraffin sulfonates, α-olefin sulfonates, α-sulfo fatty acid salts, α-sulfo salts. Examples include fatty acid alkyl ester salts or fatty acid salts. In particular, linear alkylbenzene sulfonates having 12 to 14 carbon atoms in the alkyl chain and alkyl sulfate esters having 12 to 18 carbon atoms are preferred, and alkali metals and alkanolamine salts are preferred as the counter ion.
[0021]
Nonionic surfactants 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, alkyl polyalkylene. Glycosides are preferred. In particular, alkyl polyglycosides are preferred.
[0022]
Examples of the cationic surfactant include quaternary mono long chain alkyl or di long chain alkyl ammonium salts.
[0023]
<(B) component>
The laundry pretreatment agent composition of the present invention contains (b) an alkaline agent. It is preferable to contain 1-30 mass% from the point of washing | cleaning performance and foamability, 3-25 mass% is more preferable, 5-20 mass% is still more preferable, 5-15 mass% is especially preferable.
[0024]
Examples of the component (b) include 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 and pyrophosphate. Examples thereof include salts, polyphosphates such as hexametaphosphate, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, disodium hydrogen phosphate, trisodium phosphate, and borate.
[0025]
The component (b) has a cleaning performance, and the maximum pH of the aqueous solution or dispersion of 0.025% by mass of the component (b) is 10 or more (20 ° C.), and 1 liter of the aqueous solution or dispersion is pH 9 It is preferable that the compound requires 10 ml or more of a 0.1N hydrochloric acid aqueous solution in order to achieve (20 ° C.). Examples of such compounds include sodium carbonate, potassium carbonate, sodium silicate, trisodium phosphate, monoethanolamine and the like. Of these, sodium carbonate, potassium carbonate, and sodium silicate are more preferable, and sodium carbonate is particularly preferable.
[0026]
<(C) component>
The laundry pretreatment agent composition of the present invention contains (c) a chelating agent. It is preferable to contain 1-30 mass% at the point of washing | cleaning performance and foamability, 2-25 mass% is more preferable, 3-20 mass% is still more preferable, 3.5-15 mass% is especially preferable, 4 ˜12% by weight is most preferred.
[0027]
Component (c) has a molecular weight of preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less in terms of cleaning performance.
[0028]
Detergency, in terms of environmental suitability, (c) calcium trapping amount of the component is preferably _{200~600CaCO 3 mg / g, 250~550CaCO 3} mg / g , and still more preferably 300~500CaCO ₃ mg / g. Moreover, 4-10 are preferable, as for a calcium stability constant, 5-9 are more preferable, 6-8 are still more preferable, and 6.5-8 are especially preferable.
[0029]
In the present invention, the calcium stability constant and the calcium capture amount are those obtained by the following method.
[0030]
(Measurement method of calcium stability constant)
_{0.1mol / NH 4 Cl-NH 4} OH (pH10) liters to prepare a solution as a buffer. All sample solutions are prepared using this buffer. For measuring the Ca ²⁺ concentration, an ion meter 920A manufactured by Orion Co., Ltd. and a Ca ²⁺ ion electrode are used. First, a relationship between the calcium chloride concentration and the electrode potential is obtained, 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. Add 1 ml of calcium chloride solution to 100 ml of chelating agent sample solution and stir for 5 minutes. The remaining Ca ²⁺ concentration is measured using a Ca ²⁺ ion electrode. Assuming that the chelating agent forms a chelate complex with Ca ²⁺ at 1: 1, the calcium stability constant (Ca stability constant) is obtained from the following formula.
[0031]
[Expression 1]

[0032]
(Measurement method of calcium capture amount)
The calcium trapping amount (Ca trapping amount) is a method described in JP-A-3-277696, page 3, lower right column, line 6 to page 4, upper left column, line 6 (however, an anionic surfactant is read as a chelating agent). )
[0033]
Examples of the component (c) include compounds having 2 to 5, preferably 3 to 5, COOM groups (M is H, Na, K, NH ₄ ) in the molecule. Among these, the compounds represented by the following general formula (I) are preferable from the viewpoint of cleaning performance and environmental suitability.
[0034]
[Formula 4]

[0035]
[Wherein, R is — (CH ₂ ) _n —A, A is H, OH, COOM, M is H, Na, K, NH ₄ , preferably Na, and n is 0-5. Indicates a number. ].
[0036]
In the present invention, the mass ratio of the component (c), preferably the compound represented by the general formula (I), and the component (a), preferably the amphoteric surfactant, is (a) / (c) = 3/1. Is preferably 1/5, more preferably 2/1 to 1/3, still more preferably 1/1 to 1/3, and particularly preferably 1/1 to 1/2.
[0037]
<(D) component>
The laundry pretreatment composition for clothing of the present invention contains (d) 50 to 95% by mass of water. 55-90 mass% is preferable at the point of washing | cleaning performance and applicability | paintability, 60-85 mass% is more preferable, 65-80 mass% is still more preferable.
[0038]
<Other ingredients>
The laundry pretreatment composition of the present invention preferably contains 1 to 30% by mass of a hydrotrope agent, more preferably 2 to 15% by mass, in terms of low-temperature stability, foaming properties, and non-clogging properties. 3-10 mass% is still more preferable.
[0039]
Examples of the hydrotrope include lower alcohols having 1 to 4 carbon atoms such as ethanol, methanol, propanol, glycerin, ethylene glycol and propylene glycol, toluenesulfonic acid or a salt thereof, xylenesulfonic acid or a salt thereof, and the following general formula (IV) And the like.
[0040]
_{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 or alkenyl group having 1 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; Yes, R is a hydrogen atom, a methyl group, or an ethyl group, p is 1-6, preferably 1-3, q is 0-4, preferably 0-2, and p + q is 1- 10, preferably 1-6. ].
[0041]
Of these, lower alcohols having 2 to 3 carbon atoms, p-toluenesulfonic acid or salts thereof are more preferable.
[0042]
In addition to the laundry pretreatment composition of the present invention, (1) polyacrylic acid or a salt thereof, polymaleic acid or a salt thereof, carboxymethylcellulose, an acrylic acid-maleic acid copolymer or a salt thereof, maleic anhydride-di Isobutylene copolymer or salt thereof, maleic anhydride-methyl vinyl ether copolymer or salt thereof, maleic anhydride-isobutylene copolymer or salt thereof, maleic anhydride-vinyl acetate copolymer or salt thereof, and No. 59-62614, organic polycarboxylic acid and / or salt thereof, such as a polymer described in claims 1 to 21 (page 1, column 3, line 5 to page 3, column 4, line 14), 2) Anti-staining agent and dispersant such as polyethylene glycol having an average molecular weight of 5000 or more, naphthalene sulfonate formalin condensate, etc. 1 to 10% by mass, (3) 0.01 to 10% by mass of a color transfer inhibitor such as polyvinylpyrrolidone, (4) 0.01 to 2% by mass of a foaming agent such as silicone and silica, and (5) butylhydroxytoluene 0.01 to 2% by mass of an antioxidant such as distyrenated cresol, sodium sulfite and sodium bisulfite, (6) a coloring agent, (7) an enzyme such as amylase, protease, lipase and cellulase, (8) calcium chloride, Enzyme stabilizers such as calcium sulfate, formic acid, boric acid (boron compound), (9) perfume, (10) antibacterial preservative, and the like can be blended.
[0043]
[Foam discharge container]
As foam discharge container, trigger type foam discharge container, pump type foam discharge container used by pressing the head of cap equipped with pump mechanism with fingers, used by pressing the barrel of soft container with fingers Squeeze foamers, aerosols, and the like, trigger type spray containers and squeeze foamers are more preferred, and trigger type spray containers are particularly preferred from the viewpoints of usability, economy and environmental compatibility. In the case of a trigger type spray container, the discharge amount per time is preferably 0.5 to 1 g from the viewpoint of usability.
[0044]
【Example】
Examples 1-7, Comparative Examples 1-3
The laundry pretreatment agent composition shown in Table 1 was prepared. The pH of 20 degreeC of the composition of the obtained Example was all 10-11. The viscosities of the compositions of the examples were 2 to 15 mPa · s (B-type viscometer, 20 ° C., 60 r / min).
[0045]
The prepared composition was filled in a commercially available trigger-type foam discharge container (Family sink cleaner 250 mL, manufactured by Kao Corporation) to obtain a pretreatment article for washing. The foam discharged from the laundry pretreatment article of the obtained example has a bulk density of 50 to 300 g / L, and it takes 1 to 20 minutes until a 10 mL liquid layer appears from a 100 mL foam which has been left standing. there were.
[0046]
About these, evaluation of cleaning power and foam dischargeability were performed by the method shown below. The results are shown in Table 1.
[0047]
<Evaluation of cleaning power>
(Preparation of collar fabric)
A collar lining cloth described in JIS K3362: 1998 is prepared.
[0048]
(Cleaning conditions and evaluation method)
40 L of used water described in JIS K3362: 1998 is placed in a washing tub of an automatic two-tank washing machine (Toshiba Galaxy 3.6), and 1.4 kg of cotton unweared underwear and 0.6 kg of cotton / polyester blend Put on an un-wearing shirt. Furthermore, 53 g (in terms of anhydride) of an indicator detergent for determination of detergency described in JIS K3362: 1998 (no addition of fluorescent brightener) is added. Furthermore, 4 pieces of collar covering cloth (two pieces of three stages of stains), which is applied to the above-mentioned one piece of collar covering cloth, is coated with 4 g of the pre-washing treatment composition from the pre-washing article and allowed to stand for 5 minutes. Wash for 10 minutes. Then dehydrate for 1 minute and rinse with running water at a rate of 15 L / min for 8 minutes. Then dehydrate for 5 minutes and let it air dry indoors.
[0049]
A pair obtained by performing the same operation without applying the laundry pretreatment agent composition as a blank is visually compared, and evaluated according to the following criteria.
[0050]
Evaluation Criteria A: In all three levels of dirt, dirt is clearly removed from the blank.
○: Slightly less dirt than blanks in all three stages of dirt.
X: In all three stages of dirt, there is almost no difference from the blank, or the dirt is poorly removed.
-: Since it does not discharge from a container, evaluation is impossible.
[0051]
<Evaluation of foam ejection properties>
Five persons having a grip strength of 25 to 30 kg actuated the trigger for the laundry pretreatment article and discharged the laundry pretreatment composition. The operability at that time was evaluated according to the following criteria.
[0052]
Evaluation criteria (circle): It discharged without a problem in foamy form.
Δ: Discharged in a mixed state of bubbles and liquid.
X: Not discharged.
[0053]
[Table 1]

[0054]
・ Amphoteric surfactant 1: Lauramidopropylamine oxide (Softazolin LAO-C, Kawaken Fine Chemicals Co., Ltd.)
-Amphoteric surfactant 2: dimethyl lauryl amine oxide (Amphithol 20N, Kao Corporation, pure conversion)
Amphoteric surfactant 3: lauryl (2-hydroxy-3-sulfopropyl) dimethylbetaine (Amphitol 20HD, Kao Corporation, pure conversion)
Nonionic surfactant 1: Decylglucoside (Mydol 10, Kao Corporation, pure conversion)
・ Nonionic surfactant 2: An average of 8 moles of ethylene oxide and an average of 2 moles of propylene oxide added to a linear primary alcohol having 10 to 14 carbon atoms. ・ Anionic surfactant 1: coconut oil fatty acid Sodium / anionic surfactant 2: Sodium alkylbenzenesulfonate having an alkyl group having 10 to 14 carbon atoms Chelating agent 1: Trisodium methylglycine diacetate (Trilon M, BASF Japan Ltd., pure component conversion) (Ca trapping amount 430CaCO ₃ mg / g, Ca stability constant 6.1)
Chelating agent 2: aspartic acid-N, N-tetrasodium diacetate (Ca trapping amount 328CaCO ₃ mg / g, Ca stability constant 6.7)
Chelating agent 3: serine diacetate trisodium (Ca trapping amount 347 CaCO ₃ mg / g, Ca stability constant 6.5)
Chelating agent 4: tetrasodium glutamic acid diacetate (Ca trapping amount 305 CaCO ₃ mg / g, Ca stability constant 5.8)
Chelating agent 5: trisodium ethylglycine diacetate (Ca trapping amount 419 CaCO ₃ mg / g, Ca stability constant 5.7)
Carboxylic acid polymer: Phenoxypolyethylene glycol, acrylic acid, maleic acid copolymer (weight average molecular weight 10,000, solid content 51.2 mass) synthesized by the method described in pages 116 to 13 of JP-A-10-60476 %)
Enzyme: Everase 16.0L-EX (protease, manufactured by Novozymes)
-Dye: coconut orange (added 10ppm (mass ratio) in the composition)

Claims (4)

(A) Surfactant 0.05 to 10% by mass, (b) Alkaline agent, (c) Calcium capture amount 200 to 600 CaCO ₃ mg / g and calcium stability constant 4 to 10 and having a molecular weight of 1000 or less, the following general A chelating agent selected from the compound represented by formula (I) and (d) water is contained, and 50% by mass or more in (a) is selected from alkylbetaine, imidazolinium betaine, amine oxide, and alkylalanine. An article for pretreatment for washing in which a foam pre-treatment container is filled with a pretreatment composition for washing which is a surfactant .

[Wherein, R is - (CH _{2) n} -A, A is H, OH, a COOM, M is H, Na, K, an NH _4, n is a number of 0 to 5. ] (B) is sodium carbonate, potassium carbonate, sodium silicate, trisodium phosphate, laundry pre-treating articles of claim 1 Symbol placement is a compound selected from monoethanolamine. The article for pre-washing treatment according to claim 1 or 2, wherein a mass ratio of (a) to (c) is (a) / (c) = 3/1 to 1/5 . The article for pre-washing treatment according to any one of claims 1 to 3, comprising 1 to 30% by mass of (c) .