JP4017940B2 - Foam-coated laundry pretreatment agent - Google Patents

Description

【００３１】
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。
【００３２】
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。
【００３３】
ヒドロキシカルボン酸（塩）としては、ヒドロキシ酢酸（塩）、酒石酸（塩）、クエン酸（塩）、グルコン酸（塩）、リンゴ酸（塩）、乳酸（塩）、グリコール酸（塩）等が挙げられる。
【００３４】
シクロカルボン酸（塩）としては、ピロメリット酸（塩）、ベンゾポリカルボン酸（塩）、シクロペンタンテトラカルボン酸（塩）等が挙げられる。
【００３５】
エーテルカルボン酸（塩）としては、カルボキシメチルトロネート、カルボキシメチルオキシサクシネート、オキシジサクシネート、酒石酸ジサクシネート等が挙げられる。
【００３６】
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。
【００３７】
＜（ｃ）成分＞
本発明の洗濯前処理剤組成物は、目的とする泡物性を得るために（ｃ）成分として親水性溶剤を含有する。（ｃ）成分の比率は、組成物中、１〜３０質量％が好ましく、２〜２０質量％が更に好ましく、３〜１５質量％が特に好ましい。
【００３８】
（ｃ）成分としては、特に、下記一般式（Ｉ）で示されるグリコール系溶剤若しくは低級アルコールが好ましい。これらの溶剤は、単独で用いても、また２種以上併用して用いても良い。
【００３９】
ＲＯ｛(Ｃ₂Ｈ₄Ｏ)_m(Ｃ₃Ｈ₆Ｏ)_n｝Ｈ （Ｉ）
〔式中、Ｒは炭素数１〜８のアルキル基又はベンゼン環、ｍ及びｎは各々０〜６の数であり、両者が同時に０になることはなく、｛ ｝内はｍ及びｎが０より大きいときに、オキシエチレン基とオキシプロピレン基がランダム状及び／又はブロック状に結合しているポリオキシアルキレン鎖である。〕。
【００４０】
上記一般式（Ｉ）で表されるグリコール系溶剤の具体例としては、エチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテル（ブチルカルビトール）、プロピレングリコールジエチレングリコールモノブチルエーテル、ジプロピレングリコールエチレングリコールモノブチルエーテル、エチレングリコールモノフェニルエーテル、トリエチレングリコールモノフェニルエーテル等を挙げることができる。
【００４１】
また、低級アルコールは炭素数１〜４のものが好ましく、具体例としては、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、イソブタノール、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を挙げることができる。これらの中でも、好ましくはエタノール、プロピレングリコールが好適である。
【００４２】
＜（ｄ）成分＞
本発明の洗濯前処理剤組成物は、目的とする泡物性を得るために（ｄ）成分として重量平均分子量２千〜５万のポリカルボン酸ポリマーを含有する。（ｄ）成分の比率は、洗浄性能、泡物性の点で組成物中０．０５〜１５質量％が好ましく、０．１〜１２質量％が更に好ましく、０．２〜１０質量％が特に好ましく、０．３〜５質量％が最も好ましい。洗浄性能、泡物性の点で重量平均分子量は２千〜２万がより好ましい。この重量平均分子量は、ゲルパーミエーションクロマトグラフィーにより測定されたものである。
【００４３】
（ｄ）成分は、分子内にＣＯＯＭ基（Ｍは水素原子、Ｎａ、Ｋ、ＮＨ₄、アルカノールアミン）を有する高分子化合物である。中でも、洗浄性能の点で、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）記載のポリマー等の有機多価カルボン酸及び／又はその塩が好ましい。特にポリアクリル酸又はその塩が好ましい。
【００４４】
＜（ｅ）成分＞
本発明の洗濯前処理剤組成物は、（ｅ）成分として水を含有する。洗浄性能、塗布性の点で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。
【００４５】
＜その他成分＞
本発明の洗濯前処理剤組成物は、襟汚れ、袖汚れ等の人由来の汚れに対する洗浄性能、泡物性の点で、アルカリ剤〔以下、（ｆ）成分という〕を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。
【００４６】
（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。
【００４７】
（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。
【００４８】
本発明の洗濯前処理剤組成物には、（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）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％、（５）着色剤、（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、ギ酸、ホウ酸（ホウ素化合物）等の酵素安定化剤、（８）香料、（９）抗菌防腐剤、（１０）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等のハイドロトロープ剤等を配合することができる。
【００４９】
〔洗濯前処理方法〕
襟汚れ、袖汚れ、しみ汚れ等の被洗浄部位に、本発明の洗濯前処理剤組成物を泡吐出容器から泡状に塗布した後、通常の洗濯を行うことで、洗濯における洗浄力を増強させることができる。泡状に塗布した後、通常の洗濯を行うまでの間に、従来のように手指等でもむ、たたく、ブラシ等でこする、超音波振動を加える等、被洗浄物に物理的な力を加えても良い。
【００５０】
洗浄性能、経済性の点で、被洗浄部位１００cm²当たり、洗濯前処理剤組成物を泡状に１〜２０ｇ塗布することが好ましく、１．５〜１５ｇがより好ましく、２〜１０ｇが更に好ましい。この場合、泡は、２０℃における嵩密度が５０〜３００ｇ／Ｌ、２０℃における静置した１００ｍＬの泡から７０質量％相当の液層が現れるまでの時間が３０秒〜１０分、２０℃における粘度が１００〜７００ｍＰａ・ｓを満たすことが好ましい。これらの測定方法は前述の通りである。
【００５１】
洗浄性能の点で、泡状に塗布してから１０秒以上経過後に洗濯するのが好ましく、３０秒以上がより好ましく、１分以上が更に好ましく、５分以上が特に好ましい。効果及び簡便性の点で、５時間以下が好ましく、２時間以下がより好ましく、１時間以下が更に好ましく、３０分以下が特に好ましい。
【００５２】
【実施例】
表１に示す洗濯前処理剤組成物を調製した。組成物の２０℃における粘度は何れも１０〜５０ｍＰａ・ｓ、２０℃における粘度Ｐ₂₀と５℃における粘度Ｐ₅の比Ｐ₂₀／Ｐ₅は１／１〜１／２であった。組成物の起泡力は５０〜１５０ｍｍ、泡の安定度は２５〜１５０ｍｍであった。
【００５３】
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、容器入り洗濯前処理剤を得た。得られた実施例の容器入り洗濯前処理剤から吐出される泡は、何れも嵩密度１００〜２００ｇ／Ｌ、静置した１００ｍＬの泡から泡の７０質量％相当の液層が現れるまでの時間は３〜８分であった。また、実施例の容器入り洗濯前処理剤から吐出される泡は、２０℃における粘度が１００〜７００ｍＰａ・ｓの範囲であった。
【００５４】
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。
【００５５】
＜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
（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、容器入り洗濯前処理剤より洗濯前処理剤組成物４ｇを泡状に塗布し、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。
【００５６】
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。
【００５７】
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。
【００５８】
【表１】

【００５９】
・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の直鎖アルキル基を有するアルキルベンゼンスルホン酸ナトリウム
・陰イオン界面活性剤３：ポリオキシエチレンアルキルエーテル硫酸エステル塩（炭素数１２／１４の直鎖アルキル、エチレンオキシド平均付加モル数３、ナトリウム塩）
・陰イオン界面活性剤４：炭素数１４〜１８のα−オレフィンスルホン酸ナトリウム
・非イオン界面活性剤１：パーム核油脂肪酸ジエタノールアミド（アミノーンPK‐02S、花王（株））
・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
・非イオン界面活性剤３：炭素数１２〜１４の２級アルコールにエチレンオキサイドを平均７モル付加させたもの
・キレート剤１：メチルグリシンジ酢酸ナトリウム塩
・キレート剤２：エチレンジアミンテトラ酢酸ナトリウム塩
・キレート剤３：ニトリロ三酢酸ナトリウム塩
・キレート剤４：クエン酸ナトリウム塩
・キレート剤５：リンゴ酸ナトリウム塩
・ポリマー１：ポリアクリル酸ナトリウム（重量平均分子量５０００）
・ポリマー２：クインフロー５４０（日本ゼオン（株）、ポリカルボン酸系ポリマー）
・ポリマー３：特開平１０−６０４７６号公報の実験例１のポリマー
・酵素：エバラーゼ16.0Ｌ−ＥＸ（プロテアーゼ、ノボザイムズ社製）。
【００６０】
なお、実施例１〜７の組成物を、それぞれホモミキサーにて撹拌し、２０℃における嵩密度が３５０〜４００ｇ／Ｌになるように調製した。このときの２０℃における泡の粘度は５０ｍＰａ・ｓより大きかった。この泡を用いて、上記実施例と同様の洗浄力の評価を行ったところ、何れもブランクとほとんど差がなかった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a containerized laundry pretreatment agent and a laundry pretreatment method which are used by being applied to an object to be washed in foam. More specifically, the present invention relates to a container-containing pretreatment agent for washing and a pretreatment method for washing, which are applied in a foamy manner on a portion of an object to be cleaned where the dirt is concentrated, thereby enhancing 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, the collar sleeve and stain stains are dealt with by applying detergent directly to the detergent to partially increase the detergent concentration and washing it manually or mechanically using a brush or the like.
[0003]
As a cleaning agent for partial washing, for example, an article having a discharge port in a sponge shape or a brush shape is known. However, many people feel resistance to using these because the soil and the container are in direct contact. Further, since the liquid is directly applied, the amount used tends to be difficult to catch visually, and the amount used tends to be excessive.
[0004]
Many cleaning agents are known that are applied in the form of foam. However, nothing has been known that has a sufficient cleaning effect when used for collar sleeves and stains.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to enable easy and safe application to an object to be cleaned, and to perform washing after applying the object to the object to be cleaned before washing in a container for foam application. It is providing the processing agent and the pre-washing method.
[0006]
[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) a chelating agent having a molecular weight of 1000 or less (hereinafter referred to as component (b)) 1 to 30% by mass. (C) a hydrophilic solvent (hereinafter referred to as component (c)), (d) a polycarboxylic acid polymer having a weight average molecular weight of 2,000 to 50,000 (hereinafter referred to as component (d)), and (e) water (hereinafter referred to as component). , (E) component)], and before washing into a foam-coated container in which a foam pre-treatment composition filled with 10% by weight or more of (a) an anionic surfactant is filled in a foam discharge container It is a treatment agent, and the foaming power at 20 ° C. described in JIS K 3362: 1998 of the pre-washing treatment composition is 50 to 300 mm, and the foam stability at 20 ° C. described in JIS K 3362: 1998 is 25 to 250 mm. The viscosity at 20 ° C. is 1 to 50 mPa S, the ratio P ₂₀ / P ₅ of the viscosity P _{20 at} 20 ° C. to the viscosity P _{5 at} 5 ° C. is 1/1 to 1/5, and the foam discharged from the foam discharge container has a bulk density at 20 ° C. 50 to 300 g / L, the time until a liquid layer corresponding to 70% by mass appears from 100 mL foam left at 20 ° C. for 30 seconds to 10 minutes, and the viscosity of the foam at 20 ° C. satisfies 100 to 700 mPa · s. , It relates to a pretreatment agent for washing in a container.
[0007]
The present invention also relates to a laundry pretreatment method in which 1 to 20 g of a laundry pretreatment composition is applied in a foam form from the foam-coated container-type laundry pretreatment agent of the present invention, and 10 seconds or more elapses.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The pre-washing agent in a container of the present invention has a foamy 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). Used by applying to. 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 10 seconds or more, more preferably 30 seconds or more, further preferably 1 minute or more, and particularly 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.
[0009]
By applying it in the form of foam, it is safe without sucking or entering the eyes, and is excellent in economic efficiency without being overused due to the visual effect of the pre-washing composition at the time of application. Moreover, the surfactant concentration on the surface is increased by making it foamy, so that the washing pretreatment composition can easily penetrate into the soil and the cleaning power is improved.
[0010]
In the pre-washing agent for a container of the present invention, the bulk density at 20 ° C. of the foam discharged from the foam discharge container is 50 to 300 g / L. 60 to 250 g / L is preferable, 70 to 200 g / L is more preferable, and 100 to 200 g / L is particularly preferable in terms of cleaning performance and usability. Moreover, as for the foam discharged from the said foam discharge container, it is 30 seconds-10 minutes until the liquid layer equivalent to 70 mass% appears from the 100 mL foam left still at 20 degreeC. From the viewpoint of cleaning performance and usability, 1 to 10 minutes is more preferable, 2 to 9 minutes is further preferable, and 3 to 8 minutes is particularly preferable. Moreover, the viscosity of the foam discharged from the said foam discharge container is 100-700 mPa * s. 200 to 600 mPa · s is more preferable in terms of cleaning performance and usability, 200 to 500 mPa · s is more preferable, and 300 to 500 mPa · s is particularly preferable.
[0011]
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 the liquid layer equivalent to 70 mass% of said foam appeared was calculated | required.
[0012]
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.
[0013]
[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, 0.3 to 2 g is preferable, and 0.5 to 1.5 g is more preferable for a single discharge amount at 20 ° C. in terms of usability.
[0014]
[Laundry pretreatment composition]
The washing pretreatment composition of the present invention has a foaming power at 20 ° C. of 50 to 300 mm according to the method described in JIS K 3362: 1998, and the foam stability at 20 ° C. according to the method described in JIS K 3362: 1998. 25-250 mm. The foaming power is preferably 50 to 250 mm, more preferably 100 to 200 mm, and particularly preferably 150 to 200 mm in terms of detergency and usability. In terms of detergency and usability, the stability of the foam is preferably 50 to 250 mm, more preferably 100 to 200 mm, and particularly preferably 150 to 200 mm.
[0015]
The laundry pretreatment composition of the present invention has a viscosity at 20 ° C. of 1 to 50 mPa · s (B-type viscometer, 60 r / min, rotor 1, after 1 minute), and a viscosity P _{20 at} 20 ° C. and 5 ° C. The ratio P ₂₀ / P ₅ of the viscosity P ₅ at 1/1 is 1/1 to 1/5. The viscosity at 20 ° C. is preferably 1 to 30 mPa · s, more preferably 1 to 20 mPa · s, and particularly preferably 2 to 15 mPa · s from the viewpoint of easy discharge from the container at the time of application. The ratio P ₂₀ / P ₅ of the viscosity P ₂₀ at 20 ° C. and the viscosity P _{5 at} 5 ° C. is preferably 1/1 to 1/4 in terms of easy discharge from the container at the time of application, and 1/1 to 1 / 3 is more preferable, and 1/1 to 1/2 is particularly preferable.
[0016]
The laundry pretreatment composition of the present invention preferably has a pH of 7 to 12 at 20 ° C. according to the method described in JIS K 3362: 1998 in terms of detergency and safety. For human-derived stains such as collar stains and sleeve stains, pH 8 to 11 is preferred, 8.5 to 11 is more preferred, 9 to 11 is still more preferred, and 10 to 11 is particularly preferred. In this case, it is preferable to contain an alkali agent. On the other hand, pH 7-9 is preferable, 7-8 is more preferable, 7.2-8 is still more preferable, and 7.2-7.8 is especially preferable for the stains derived from food and drink.
[0017]
According to the present invention, (a) 0.05 to 10% by mass of a surfactant, (b) 1 to 30% by mass of a chelating agent having a molecular weight of 1000 or less, (c) a hydrophilic solvent, and (d) a weight average molecular weight of 2,000. A laundry pretreatment composition containing 50,000 to 50,000 polycarboxylic acid polymer and (e) water, wherein 10% by mass or more in (a) is an anionic surfactant, and described in JISK 3362: 1998 The foaming power at 20 ° C. is 50 to 300 mm, the stability of the foam at 20 ° C. described in JIS K 3362: 1998 is 25 to 250 mm, the viscosity at 20 ° C. is 1 to 50 mPa · s, and the viscosity P ₂₀ and 5 at 20 ° C. A laundry pretreatment composition having a ratio P ₂₀ / P ₅ of viscosity P ₅ at ° C. of 1/1 to 1/5 is provided. The composition is suitable for foam application.
[0018]
<(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.
[0019]
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. In particular, the composition of the present invention contains 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more of the anionic surfactant in the component (a) in terms of foam formation.
[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]
Examples of amphoteric surfactants include alkyl betaines, imidazolinium betaines, amine oxides, and alkylalanines.
[0024]
<(B) component>
The laundry pretreatment composition of the present invention contains (b) 1 to 30% by mass of a chelating agent having a molecular weight of 1000 or less. It is preferable to contain 2-25 mass% from the point of washing | cleaning performance and foamability, 3-20 mass% is more preferable, 3.5-15 mass% is still more preferable, and 4-12 mass% is especially preferable. The lower limit of the molecular weight is preferably 200 or more.
[0025]
As component (b), organic carboxylic acid (salt) such as aminocarboxylic acid (salt), hydroxyaminocarboxylic acid (salt), hydroxycarboxylic acid (salt), cyclocarboxylic acid (salt), ether carboxylic acid (salt), etc. And inorganic phosphates such as tripolyphosphate and pyrophosphate.
[0026]
When the pH at 20 ° C. of the laundry pretreatment agent composition is 7 to 9, particularly as component (b), (b1) calcium stability constant is 5 to 15, preferably 6 to 14, more preferably 8 to 13 And (b2) a hydroxycarboxylic acid (salt) having a calcium stability constant of 1-4, preferably 2-4, more preferably 3-4, and (b1) / (b2) The cleaning ratio is 1/10 to 10/1, preferably 1/5 to 5/1, more preferably 1/3 to 3/1, and still more preferably 1/2 to 2/1. This is preferable. In the component (b), the total amount of (b1) and (b2) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 99% by mass or more.
[0027]
When the laundry pretreatment composition has a pH of 9 to 11 at 20 ° C., the component (b) preferably contains 80% by mass or more of the aminocarboxylic acid (salt) of (b1), and 90% by mass. The above is more preferable, and 99 mass% or more is still more preferable.
[0028]
In the present invention, the calcium stability constant is determined by the following method.
[0029]
(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.
[0030]
[Expression 1]

[0031]
As aminocarboxylic acid (salt), nitrilotriacetic acid (salt), ethylenediaminetetraacetic acid (salt), β-alanine diacetate (salt), aspartate diacetate (salt), methylglycine diacetate (salt), iminodisuccinic acid (salt) ) And the like.
[0032]
Examples of the hydroxyaminocarboxylic acid (salt) include serine diacetic acid (salt), hydroxyiminodisuccinic acid (salt), hydroxyethylethylenediaminetriacetic acid (salt), dihydroxyethylglycine (salt), and the like.
[0033]
As hydroxycarboxylic acid (salt), hydroxyacetic acid (salt), tartaric acid (salt), citric acid (salt), gluconic acid (salt), malic acid (salt), lactic acid (salt), glycolic acid (salt), etc. Can be mentioned.
[0034]
Examples of the cyclocarboxylic acid (salt) include pyromellitic acid (salt), benzopolycarboxylic acid (salt), and cyclopentanetetracarboxylic acid (salt).
[0035]
Examples of the ether carboxylic acid (salt) include carboxymethyltronate, carboxymethyloxysuccinate, oxydisuccinate, and tartaric acid disuccinate.
[0036]
These organic carboxylic acids (salts) are blended in the form of an acid and then neutralized with potassium hydroxide, sodium hydroxide, ammonium hydroxide, potassium carbonate, sodium carbonate, monoethanolamine, diethanolamine or the like to at least partially Also good as salt. Moreover, you may mix | blend, after making at least one part of a carboxyl group into a salt previously. In terms of cleaning performance, it is particularly preferable that at least a part of the carboxyl groups is a potassium salt or an ammonium salt.
[0037]
<(C) component>
The laundry pretreatment agent composition of the present invention contains a hydrophilic solvent as the component (c) in order to obtain desired foam physical properties. (C) As for the ratio of a component, 1-30 mass% is preferable in a composition, 2-20 mass% is still more preferable, and 3-15 mass% is especially preferable.
[0038]
As the component (c), a glycol solvent or a lower alcohol represented by the following general formula (I) is particularly preferable. These solvents may be used alone or in combination of two or more.
[0039]
_{RO {(C 2 H 4 O} ) m (C 3 H 6 O) n} H (I)
[In the formula, R is an alkyl group having 1 to 8 carbon atoms or a benzene ring, m and n are each 0 to 6 and both are not 0 at the same time, and m and n are 0 in {}. When it is larger, it is a polyoxyalkylene chain in which oxyethylene groups and oxypropylene groups are bonded in a random and / or block form. ].
[0040]
Specific examples of the glycol solvent represented by the general formula (I) include ethylene glycol monobutyl ether, diethylene glycol monobutyl ether (butyl carbitol), propylene glycol diethylene glycol monobutyl ether, dipropylene glycol ethylene glycol monobutyl ether, ethylene glycol mono Examples include phenyl ether and triethylene glycol monophenyl ether.
[0041]
Further, the lower alcohol preferably has 1 to 4 carbon atoms, and specific examples include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, glycerin, ethylene glycol, propylene glycol and the like. Of these, ethanol and propylene glycol are preferable.
[0042]
<(D) component>
The laundry pretreatment agent composition of the present invention contains a polycarboxylic acid polymer having a weight average molecular weight of 2,000 to 50,000 as component (d) in order to obtain the desired foam physical properties. The ratio of the component (d) is preferably 0.05 to 15% by mass, more preferably 0.1 to 12% by mass, and particularly preferably 0.2 to 10% by mass in the composition in terms of cleaning performance and foam physical properties. 0.3 to 5 mass% is most preferable. The weight average molecular weight is more preferably 2,000 to 20,000 in terms of washing performance and foam physical properties. This weight average molecular weight is measured by gel permeation chromatography.
[0043]
The component (d) is a polymer compound having a COOM group (M is a hydrogen atom, Na, K, NH ₄ , alkanolamine) in the molecule. Among them, in terms of cleaning performance, polyacrylic acid or a salt thereof, polymaleic acid or a salt thereof, carboxymethyl cellulose, an acrylic acid-maleic acid copolymer or a salt thereof, a maleic anhydride-diisobutylene copolymer or a salt thereof, anhydrous Maleic acid-methyl vinyl ether copolymer or salt thereof, maleic anhydride-isobutylene copolymer or salt thereof, maleic anhydride-vinyl acetate copolymer or salt thereof, and claim 1 of JP-A-59-62614 Organic polycarboxylic acids such as polymers described in -21 (page 1, column 3, line 5 to page 3, column 4, line 14) and / or salts thereof are preferred. Particularly preferred is polyacrylic acid or a salt thereof.
[0044]
<(E) component>
The laundry pretreatment agent composition of the present invention contains water as the component (e). 50-95 mass% is preferable at the point of washing | cleaning performance and applicability | paintability, 55-90 mass% is more preferable, 60-85 mass% is still more preferable, 65-80 mass% is especially preferable.
[0045]
<Other ingredients>
The laundry pretreatment composition of the present invention contains 1 to 30% by mass of an alkali agent (hereinafter referred to as component (f)) in terms of washing performance against foam stains such as collar stains and sleeve stains and foam physical properties. Preferably 3 to 25% by mass, more preferably 5 to 20% by mass, and particularly preferably 5 to 15% by mass.
[0046]
Examples of the component (f) 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, pyrophosphate Examples thereof include salts, polyphosphates such as hexametaphosphate, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, disodium hydrogen phosphate, trisodium phosphate, and borate.
[0047]
Component (f) has a cleaning performance, and the maximum pH of the aqueous solution or dispersion having a concentration of 0.025% by mass of component (f) is 10 or more (20 ° C.), and 1 liter of the aqueous solution or dispersion is pH 9 (20 It is preferable that the compound requires 10 ml or more of a 0.1N aqueous hydrochloric acid solution in order to obtain a temperature of 0.1 ° 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 and potassium carbonate are particularly preferable.
[0048]
The pretreatment composition for laundry of the present invention includes (1) an anti-contamination agent and a dispersant of 0.01 to 10% by mass, such as (1) polyethylene glycol having a weight average molecular weight of 5000 or more, naphthalene sulfonate formalin condensate, (2 ) 0.01 to 10% by mass of a color transfer inhibitor such as polyvinylpyrrolidone, (3) 0.001 to 2% by mass of a foaming agent such as silicone and silica, (4) butylhydroxytoluene, distyrenated cresol, sodium sulfite and 0.01-2% by mass of an antioxidant such as sodium bisulfite, (5) a coloring agent, (6) an enzyme such as amylase, protease, lipase, cellulase, (7) calcium chloride, calcium sulfate, formic acid, boric acid ( Enzyme stabilizers such as boron compounds), (8) perfumes, (9) antibacterial preservatives, (10) toluenesulfonic acid or salts thereof, xylene sulfate Hydrotrope such as phosphate, or a salt thereof can be formulated.
[0049]
[Washing pretreatment method]
The washing pretreatment composition of the present invention is applied in foam form from the foam discharge container to the parts to be cleaned such as collar stains, sleeve stains, stain stains, etc., and then the usual washing is performed to enhance the washing power in washing. Can be made. After applying in a foam state, until physical washing is performed, physical force is applied to the object to be cleaned, such as wiping with fingers etc., striking, rubbing with a brush, applying ultrasonic vibration, etc. May be added.
[0050]
From the viewpoint of cleaning performance and economy, it is preferable to apply 1 to 20 g of the pretreatment composition for washing in a foamed manner per 100 cm ^{2 of the} site to be cleaned, more preferably 1.5 to 15 g, and even more preferably 2 to 10 g. . In this case, the foam has a bulk density of 50 to 300 g / L at 20 ° C., and the time until a liquid layer corresponding to 70% by mass appears from 100 mL of foam left at 20 ° C. for 30 seconds to 10 minutes, at 20 ° C. It is preferable that the viscosity satisfies 100 to 700 mPa · s. These measurement methods are as described above.
[0051]
From the viewpoint of cleaning performance, washing is preferably performed after 10 seconds or more have been applied after foaming, more preferably 30 seconds or more, still more preferably 1 minute or more, and particularly 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.
[0052]
【Example】
The laundry pretreatment agent composition shown in Table 1 was prepared. The viscosities at 20 ° C. of the compositions were all 10 to 50 mPa · s, and the ratio P ₂₀ / P ₅ of the viscosity P _{20 at} 20 ° C. and the viscosity P _{5 at} 5 ° C. was 1/1 to 1/2. The foaming power of the composition was 50 to 150 mm, and the foam stability was 25 to 150 mm.
[0053]
The prepared composition was filled into a commercially available trigger-type foam discharge container (Family sink around cleaner 250 mL, manufactured by Kao Corporation) to obtain a pretreatment agent for washing in a container. The foam discharged from the containerized laundry pretreatment agent of each of the obtained examples has a bulk density of 100 to 200 g / L, and the time until a liquid layer corresponding to 70% by mass of the foam appears from 100 mL of foam left standing. Was 3-8 minutes. Moreover, the foam discharged from the container-containing laundry pretreatment agent of the example had a viscosity at 20 ° C. in the range of 100 to 700 mPa · s.
[0054]
About these, the cleaning power was evaluated by the method shown below. The results are shown in Table 1.
[0055]
<Evaluation of cleaning power>
(Preparation of collar fabric)
A collar fabric described in JIS K3362: 1998 is prepared (cleaning conditions and evaluation method).
40 L of used water described in JIS K3362: 1998 is placed in a washing tub of a two-tank washing machine (Toshiba Galaxy 3.6), and 1.4 kg of cotton underwear and 0.6 kg of cotton / polyester blend are used. Put an unweared shirt on. Furthermore, 53 g (in terms of anhydride) of an indicator detergent for determining detergency described in JIS K3362: 1998 (no addition of fluorescent brightener) is added. Furthermore, 6 sheets of collar covering cloth (2 sheets of each of the three stages) were applied to one sheet of the above described collar covering cloth, and 4 g of the washing pretreatment composition was applied in a foam form from the container-containing washing pretreatment agent and allowed to stand for 5 minutes. ) In a washing tub and wash normally 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.
[0056]
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.
[0057]
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.
[0058]
[Table 1]

[0059]
Anionic surfactant 1: Sodium coconut oil fatty acid Anionic surfactant 2: Sodium alkylbenzene sulfonate having a linear alkyl group having 10 to 14 carbon atoms Anionic surfactant 3: Polyoxyethylene alkyl ether sulfate Ester salt (straight chain alkyl having 12/14 carbon atoms, ethylene oxide average addition mole number 3, sodium salt)
Anionic surfactant 4: α-olefin sulfonic acid sodium salt having 14 to 18 carbon atoms Nonionic surfactant 1: Palm kernel oil fatty acid diethanolamide (Aminone PK-02S, Kao Corporation)
・ Nonionic surfactant 2: Random addition of an average of 8 moles of ethylene oxide and an average of 2 moles of propylene oxide to a linear primary alcohol having 10 to 14 carbon atoms ・ Nonionic surfactant 3: 12 carbon atoms 7 to 14 secondary alcohols with an average of 7 moles of ethylene oxide added. Chelating agent 1: methyl glycine diacetate sodium salt Chelating agent 2: ethylenediaminetetraacetic acid sodium salt Chelating agent 3: nitrilotriacetic acid sodium salt chelate Agent 4: Sodium citrate salt / chelating agent 5: Sodium malate salt / Polymer 1: Sodium polyacrylate (weight average molecular weight 5000)
Polymer 2: Quinnflow 540 (Nippon Zeon Corporation, polycarboxylic acid polymer)
-Polymer 3: Polymer of Experimental Example 1 of JP-A-10-60476-Enzyme: Everase 16.0L-EX (protease, manufactured by Novozymes)
[0060]
In addition, the composition of Examples 1-7 was each stirred with the homomixer, and it prepared so that the bulk density in 20 degreeC might be 350-400 g / L. At this time, the viscosity of the foam at 20 ° C. was larger than 50 mPa · s. When this foam was used to evaluate the same detergency as in the above examples, there was almost no difference from the blank.

Claims (4)

(A) surfactant 0.05 to 10% by mass, (b) 1 to 30% by mass of a chelating agent having a molecular weight of 1000 or less, (c) a hydrophilic solvent, and (d) a polycarboxylic acid having a weight average molecular weight of 2,000 to 50,000. Foam in which a foam discharge container is filled with a laundry pretreatment composition containing an acid polymer, (e) water, and (f) an alkaline agent, wherein 10% by mass or more of (a) is an anionic surfactant It is a coating type pre-washing treatment agent in a container, and the foaming power at 20 ° C. described in JIS K 3362: 1998 of the washing pre-treatment agent composition is 50 to 300 mm, and the foam at 20 ° C. described in JIS K 3362: 1998 Stability of 25 to 250 mm, viscosity at 20 ° C. of 1 to 50 mPa · s, ratio of viscosity P _{20 at} 20 ° C. to viscosity P _{5 at} 5 ° C. P ₂₀ / P ₅ is 1/1 to 1/5, 20 ° C. PH is 8 to 11, and the foam discharge The foam discharged from the vessel has a bulk density at 20 ° C. of 50 to 300 g / L, and the time until a liquid layer corresponding to 70% by mass appears from 100 mL of foam left at 20 ° C. for 30 seconds to 10 minutes, 20 A pretreatment agent for washing in a container having a foam viscosity at 100 ° C. of 100 to 700 mPa · s. (B) contains (b1) an aminocarboxylic acid (salt) having a calcium stability constant of 5 to 15 and (b2) a hydroxycarboxylic acid (salt) having a calcium stability constant of 1 to 4, and (b1) / (b2) containers laundry pretreatment agent foam coating type according to claim 1 Symbol placement mass ratio is 1 / 10-10 / 1. The foam-coated containerized laundry pretreatment agent according to claim 2 , wherein at least a part of the carboxyl groups in (b) is a potassium salt or an ammonium salt. Washing for which 10 seconds or more are applied by applying 1 to 20 g of the pre-washing composition in a foam form from the foam-coating-type pre-washing treatment agent in a container according to any one of claims 1 to 3 per 100 cm ² to be cleaned. Pre-processing method.