JP3916926B2 - High density granular detergent composition - Google Patents

Description

【０００９】
〔式中、M はアルカリ金属イオン、第４級アンモニウムイオン、又はアルカノールアミン由来のイオンである。m は平均値で10〜200 である。〕
【００１０】
本発明の衣料用洗浄剤組成物に配合される界面活性剤としては、例えば次のものが例示される。
【００１１】
陰イオン性界面活性剤としては
１．平均炭素数10〜16のアルキル基を有する直鎖又は分枝鎖アルキルベンゼンスルホン酸塩。
２．平均炭素数10〜20の直鎖又は分枝鎖のアルキル基又はアルケニル基を有し、１分子内に平均 0.5〜８モルのエチレンオキサイドあるいはプロピレンオキサイドあるいはブチレンオキサイドあるいはエチレンオキサイド／プロピレンオキサイド＝ 0.1／ 9.9〜 9.9／0.1 の比であるいはエチレンオキサイド／ブチレンオキサイド＝ 0.1／ 9.9〜 9.9／0.1 の比で付加したアルキル又はアルケニルエーテル硫酸塩。
３．平均炭素数10乃至20のアルキル基又はアルケニル基を有するアルキル又はアルケニル硫酸塩。
４．平均10〜20の炭素原子を１分子中に有するオレフィンスルホン酸塩。
５．平均10〜20の炭素原子を１分子中に有するアルカンスルホン酸塩。
６．平均炭素数10〜20のアルキル基またはアルケニル基を有し、１分子中に平均0.5 〜８モルのエチレンオキサイドあるいはプロピレンオキサイドあるいはブチレンオキサイドあるいはエチレンオキサイド／プロピレンオキサイド＝ 0.1／9.9 〜 9.9／0.1 の比であるいはエチレンオキサイド／ブチレンオキサイド＝0.1 ／9.9 〜9.9 ／0.1 の比で付加したアルキル又はアルケニルエーテルカルボン酸塩。
７．下記の式で表わされるα−スルホ脂肪酸塩又はエステル。
【００１２】
【化３】

【００１３】
（式中、Y は炭素数１〜３のアルキル基又は対イオン、Z は対イオンである。R は炭素数10〜20のアルキル基又はアルケニル基を表わす。）
【００１４】
ここで陰イオン性界面活性剤の対イオンとしてはナトリウム、カリウム等のアルカリ金属イオン、カルシウム、マグネシウム等のアルカリ土類金属イオン、アンモニウムイオン、炭素数２又は３のアルカノール基を１〜３個有するアルカノールアミン（例えば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、トリイソプロパノールアミンなど）を挙げることができる。
【００１５】
８．炭素数８〜22の脂肪酸塩。
【００１６】
非イオン性界面活性剤としては、
９．平均炭素数10〜20のアルキル基又はアルケニル基を有し、１〜20モルのエチレンオキサイドを付加したポリオキシエチレンアルキル又はアルケニルエーテル。
10．平均炭素数６〜12のアルキル基を有し、１〜20モルのエチレンオキサイドを付加したポリオキシエチレンアルキルフェニルエーテル。
11．平均炭素数10〜20のアルキル基又はアルケニル基を有し、１〜20モルのプロピレンオキサイドを付加したポリオキシプロピレンアルキル又はアルケニルエーテル。
12．平均炭素数10〜20のアルキル基又はアルケニル基を有し１〜20モルのブチレンオキサイドを付加したポリオキシブチレンアルキル又はアルケニルエーテル。
13．平均炭素数10〜20のアルキル基又はアルケニル基を有し、総和で１〜30モルのエチレンオキサイドとプロピレンオキサイドあるいはエチレンオキサイドとブチレンオキサイドを付加した非イオン性活性剤（エチレンオキサイドとプロピレンオキサイド又はブチレンオキサイドとの比は 0.1／9.9 〜 9.9／0.1）。
14．平均炭素数10〜20の高級脂肪酸アルカノールアミド又はそのアルキレンオキサイド付加物。
15．平均炭素数10〜20の脂肪酸とショ糖から成るショ糖脂肪酸エステル。
16．平均炭素数10〜20の脂肪酸とグリセリンから成る脂肪酸グリセリンモノエステル。
17．アルキルアミンオキサイド。
【００１７】
また、その他の界面活性剤として、
18．カルボキシベタイン又はスルホベタイン型界面活性剤などの両性界面活性剤。
19．その他陽イオン性界面活性剤。
も挙げられる。
【００１８】
上記の界面活性剤のうち、本発明では特に１，２，４，５，８，９，10，11，12，13，14が好ましく、主界面活性剤としては１，２，３，８，９を用いることが望ましい。尚、主界面活性剤とは、全界面活性剤中に40重量％以上の割合を占めるものを言う。
本発明において界面活性剤の組成物中の配合量は、総量で20〜50重量％配合される。
【００１９】
本発明の高密度粒状洗浄剤組成物には結晶性アルミノ珪酸塩が配合される。結晶性アルミノ珪酸塩由来の水不溶物の低減には結晶性アルミノ珪酸塩配合量の低減が直接的であるが、本発明の高密度粒状洗浄剤組成物においては、結晶性アルミノ珪酸塩は洗浄性能を低下させない水準の硬水軟化作用を有する量である10〜30重量％が配合される。
【００２０】
結晶性アルミノ珪酸塩としては、具体的には次式で示される結晶性アルミノ珪酸塩が挙げられる。
x'(M₂O)・Al₂O₃・y'(SiO₂)・w'(H₂O)
（式中、M はナトリウム、カリウム等のアルカリ金属原子、x',y',w'は各成分のモル数を表わし、一般的には、0.7 ≦x'≦1.5 、0.8 ≦y'≦６、w'は任意の定数である。）
これらの中で、特に次の一般式で示されるものが好ましい。
Na₂O・Al₂O₃・ｙSiO₂・ｗH₂O
（式中、ｙは1.8 〜3.0 、ｗは１〜６の数を表わす。）
特に、結晶性アルミノ珪酸塩（ゼオライト）としては、Ａ型、Ｘ型ゼオライトに代表される平均一次平均粒子径 0.1〜10μm であり、平均粒子径が15μm 以下の合成ゼオライトが好適に使用される。
【００２１】
本発明の高密度粒状洗浄剤組成物には、上記界面活性剤と結晶性アルミノ珪酸塩に、更に(a) 炭酸カリウム、(b) 分子量1000以上でカルシウムイオンとの安定度定数ｐＫ_Caが４以上の特定のポリマーキレート剤及び(c) 珪酸ナトリウムが配合される。
【００２２】
炭酸カリウム(a) は、組成物中に２〜15重量％配合される。炭酸カリウムは、制限された珪酸ナトリウム配合量によるアルカリ成分による洗浄力を２〜15重量％配合することにより補うのみならず、結晶性アルミノ珪酸塩の水不溶物の衣料への残留を抑制する。
【００２３】
また、本発明の高密度粒状洗浄剤組成物は、分子量1000以上、好ましくは5000以上でカルシウムイオンとの安定度定数ｐＫ_Caが４以上、好ましくは５以上の特定のポリマーキレート剤(b) と、珪酸ナトリウム(c) を、 (b)＋(c) ＝５〜20重量％、且つ (b)／(c) ＝１／20〜２／１（重量比）、好ましくは１／10〜１／１の割合で含有することを特徴とする。 (b)／(c) 重量比が１／20未満では本発明の効果が充分得られず、また、２／１を超えると、例えば炭酸カリウム配合時においてスラリーの粘度が増加し、噴霧乾燥が困難となるため、製造適性が悪化し好ましくない。
【００２４】
一般に洗濯後の衣類に残留する水不溶物は、結晶性アルミノ珪酸塩の凝集物であるが、洗剤中にアルカリ成分として通常配合される珪酸ナトリウム、炭酸ナトリウムが、洗濯水中の硬度成分（カルシウム、マグネシウム）と反応して不溶性の塩を生成し、これが結晶性アルミノ珪酸塩の凝集物のバインダーとなっている。分子量1000以上でカルシウムイオンとの安定度定数ｐＫ_Caが４以上の特定のポリマーキレート剤(b) を配合すると、これら不溶性塩の生成を抑制するため、その結果、結晶性アルミノ珪酸塩由来の水不溶物の発生が減少するものと考えられる。
【００２５】
分子量1000以上でカルシウムイオンとの安定度定数ｐＫ_Caが４以上のポリマーキレート剤(b) としては、一般式（Ｉ）で表される繰り返し単位を有するポリマーが用いられる。
【００２６】
【化４】

【００２７】
〔式中、M はアルカリ金属イオン、第４級アンモニウムイオン、又はアルカノールアミン、例えば炭素数２〜３のモノ、ジ、トリアルカノールアミン由来のイオンである。m は平均値で10〜200 である。〕
【００２８】
上記一般式（Ｉ）で表されるセグメントを有するポリマーは、アセタールカルボキシレートの重合体であって、特開昭54-52196号公報に記載されている。特に、上記特開昭54-52196号公報に記載される如く、グリオキシルアルデヒドのエステルと重合開始剤を重合条件下に混合し、そして得られる重合体をアルカリ性溶液中での迅速な解重合に対して安定化させることにより製造されたものを使用するのが好ましい。又この重合体の塩を形成するために、安定化させた共重合体を鹸化することができる。この際上記グリオキシル酸アルデヒドのエステルと重合し得る共単量体の一種又は以上を共重合させることも出来る。適当な共単量体としては例えばエポキシ化合物、例えばエチレンオキサイド、プロピレンオキサイド、エピハロヒドリンエポキシサクシネートなど、アルデヒド例えばホルムアルデヒド、アセトアルデヒドなど、及び20個以下の炭素原子を含有するアルデヒドなどが挙げられる。１〜４個の炭素原子を有する共単量体、例えばエチレンオキサイド、ホルムアルデヒドまたはアセトアルデヒドが好ましい。
【００２９】
共単量体の混合物を前記アルデヒドエステルと重合させてターポリマーとすることもでき、あるいはより複雑な重合体構造とすることもできる。
【００３０】
かかる重合体或いは共重合体は重合体末端に化学的反応性を有する基を付与してアルカリ性溶液中での迅速な解重合に対して安定化される。特に適当な末端基としてはアルキル基、酸素含有アルキル基及び酸素含有環式アルキル基、例えばオキシアルキル基例えばメトキシ、エトキシなど、カルボン酸類例えば
【００３１】
【化５】

【００３２】
など、アルデヒド、エーテルおよび他の酸素含有アルキル基例えば
【００３３】
【化６】

【００３４】
などが挙げられる。これらの末端基において、M はアルカリ金属、アンモニウム、アルカノールアミン、１〜４個の炭素原子を有するアルキル基であり、またR は水素または１〜８個の炭素原子を有するアルキル基である。重合体末端におけるこれらの化学的に安定な末端基は同一であってもあるいは相異なっていてもよい。
【００３５】
本発明の高密度粒状洗浄剤組成物には、上記の必須成分に加え、他の成分、ニトリロ三酢酸塩、エチレンジアミン四酢酸塩、クエン酸塩等の有機ビルダー類、カルボキシメチルセルロース等の再汚染防止剤、プロテアーゼ、セルラーゼ、アミラーゼ、リパーゼなどの酵素、亜硫酸塩等の還元剤、過炭酸ソーダ、過硼酸ソーダ等の漂白剤、蛍光増白剤、香料等の洗剤常用成分を必要に応じて配合できる。
【００３６】
本発明の高密度粒状洗浄剤組成物は、例えば、特開昭61−69897 号、特開昭61−69891 号、特開昭61−69900 号、欧州特許第513824号明細書記載の方法により製造できる。本発明の組成物は、嵩密度が 0.6〜1.2 ｇ／ml、好ましくは 0.7〜0.9 ｇ／mlであり、嵩密度の測定方法はJIS K 3362記載の方法を用いる。
【００３７】
【発明の効果】
本発明の高密度粒状洗浄剤組成物は、洗剤を製造後、長期保存後に非常に高い硬度の洗濯水中で洗濯を行っても、洗剤配合組成物中の結晶性アルミノ珪酸塩由来の水不溶物が少なく、衣料への付着、残留を激減することができる。
【００３８】
【実施例】
以下、実施例をもって本発明を更に詳述するが、本発明は以下の実施例によって限定されるものではない。
【００３９】
実施例１
1)＜洗剤の製造＞
表１に示す洗剤成分のうち、結晶性アルミノ珪酸塩の10重量％及び少量添加物である酵素などの後で乾式混合した方が望ましい成分を除いた組成で含水分50重量％のスラリーを調製し、それを噴霧乾燥して得られた粉末をハイスピードミキサー（攪拌転動造粒機、深江工業株式会社製）に投入し、先に除いておいた結晶性アルミノ珪酸塩10重量％のうち５重量％を水１重量％で湿らせたものを加えて造粒し、更に結晶性アルミノ珪酸塩３重量％を加えて造粒して得られた粒子に残りの結晶性アルミノ珪酸塩２重量％と酵素等の少量添加物を乾式混合することにより、嵩密度が0.70〜0.80ｇ／cm³の高密度粒状洗剤を得た。
【００４０】
2)＜高密度粒状洗剤の洗濯硬度差の違いによる結晶性アルミノ珪酸塩由来の水不溶物評価＞
洗濯の影響による結晶性アルミノ珪酸塩由来の水不溶物の衣料への残留蓄積性を評価する為に図１ (a)〜(c) に示す洗濯機のモデルをステンレスで作製した。図１(c) の内側の八方に穴の開いた上部開放の筒１は全自動洗濯機の内槽に相当し、外側の筒２は洗濯機の外槽に相当する。
また、このモデルは筒２の下部に開けられた半円の穴におけるゴム栓３の開閉により系内の排水を行うものである。また、筒１の底の中心にスターラピース（７mm×40mm) を置き、回転(500rpm)させることにより水流を起こす。
【００４１】
評価は次の要領で行った。予め、筒２の重量を測定し（ゴム栓なし）、筒２の側面下部の穴にゴム栓３をし、20℃、硬度15°ＤＨの水１リットルを筒１の中心に２リットル／分の流速で注入した。その時、筒２には、筒１の側面に開けられた穴より水が流出し、筒１と筒２の水位が一致する。次にスターラピースを回転(500rpm)させ、水流を起こし、30秒後水流が安定した時点で、上記 1) で製造した洗剤１ｇを筒１の水面に投入し攪拌する。洗剤投入より10分後スターラを停止すると同時に筒２の側面のゴム栓３を引き抜き、洗液を排出した。
上記操作を 100回繰り返した後、筒１を筒２より取り外し、筒２を 105℃で２時間乾燥した後、重量を測定し、結晶性アルミノ珪酸塩由来の水不溶物の残留による重量増加分を求めた。その結果を表１に示す。
尚、上記の試験に使用した洗剤の保存条件は以下の通りである。
・洗剤製造後 20℃，60％ＲＨ室で７日間放置…保存条件１
・洗剤製造後 20℃，60％ＲＨ室で30日間放置…保存条件２
3)筒２の重量増加（ｇ）と実際の洗濯における衣料への水不溶物の付着、残留性の関係を以下に示す。
前述の洗濯機モデルによる試験は以下の条件で洗濯した場合に相当する。
・洗濯機：松下電器ＮＡ−Ｆ４２Ｙ５
・洗濯衣料：黒布〔混紡（ポリエステル／綿＝65／35）〕20枚
・洗剤：40ｇ
・洗濯コース：中水位（水量表示40リットル）
洗濯９分→すすぎ２回→脱水３分→乾燥（20℃、40％RHで24時間放置）
衣料乾燥後、黒布20枚のうち10枚を任意に選択する。その際の黒布への水不溶物付着、残留性と、筒２の重量増加との関係は以下の通りである。

衣料への付着、残留性は、重量増加が 0.4ｇ以上では明らかに問題となる。
【００４２】
【表１】

【００４３】
注）表中の略号は以下の意味であり、ポリエチレングリコールとポリアクリル酸ナトリウムの分子量をあわせて以下に示す。
・ＬＡＳ−Ｎａ：直鎖アルキル(C₁₀〜C₁₃)ベンゼンスルホン酸ナトリウム
・ＡＳ−Ｎａ：アルキル(C₁₂〜C₁₈)硫酸ナトリウム
・ノニオン：ポリオキシエチレン（エチレンオキサイド平均付加モル数＝１）アルキル(C₁₂〜C₁₄)エーテル
なお、ポリマーキレート剤は、以下の表２に示すものを用いた。
【００４４】
【表２】

【図面の簡単な説明】
【図１】実施例で用いた洗濯機モデルの概略図である。
【符号の説明】
１…筒（内槽）
２…筒（外槽）
３…ゴム栓[0001]
[Industrial application fields]
The present invention relates to a high density granular detergent composition having improved detergent particle solubility.
[0002]
[Prior art]
Conventionally, powder detergents have mainly been low-density products obtained by spray drying. In recent years, there has been an increasing demand for miniaturized high-density detergents for convenience such as transport of detergents, carrying and storage of housewives. Since high density detergents are densified, there are problems that conventional low density detergents do not have. The most important problem is that it has poor solubility compared to low density detergents, and many studies have been made to solve this problem.
[0003]
Japanese Patent Application Laid-Open No. 61-246300 discloses a surfactant containing an olefin sulfonate, 1 to 15% by weight of sodium silicate, and 1.5 to 50% by weight of potassium salt based on the surfactant. Japanese Patent Publication No. 1-10039 discloses a surfactant, a water-soluble and crystalline inorganic salt, an organic divalent metal ion scavenger and an alkaline inorganic salt (sodium carbonate, sodium sulfate). Etc. are preferred) and a high bulk density granular detergent composition is disclosed.
[0004]
These studies have gradually solved the solubility problem, and the recent spread of high-density detergents is remarkable. However, with regard to residual water-insoluble matter derived from crystalline aluminosilicate that is produced when washing is performed using washing water having a relatively high hardness (for example, 6 ° DH or more) such as well water after long-term storage of the detergent. Is not touched and not enough. In addition, JP-B-3-58400 discloses a granular detergent composition comprising a surfactant, zeolite, an alkali metal carbonate as an alkaline salt, and an acrylic polymer. It is a conventional low-density detergent that contains a large amount of sodium sulfate. In addition, it is sufficient for the residue of water-insoluble matter derived from crystalline aluminosilicate in clothing when using a washing liquid with relatively high hardness. I could not say.
[0005]
[Problems to be solved by the invention]
High density detergents increase the amount of surfactant and crystalline aluminosilicate compared to conventional low density detergents and reduce inorganic salts to the minimum necessary. Since the decrease in the content of inorganic salts and the increase in the content of zeolite reduce the solubility, many attempts have been made to improve them. However, when a detergent stored for a long period of time is washed with water having relatively high hardness, a water-insoluble matter derived from crystalline aluminosilicate is generated, and the water-insoluble matter adheres to the laundry garment. Therefore, it cannot be said that conventional high-density detergents are still sufficient to suppress the formation of water-insoluble matter derived from crystalline aluminosilicate, and some improvement has been desired.
[0006]
[Means for Solving the Problems]
As a result of diligent research, the present inventors have found that (a) potassium carbonate, (b) calcium ion having a molecular weight of 1000 or more, and high-density granular detergent containing a specific amount of surfactant and crystalline aluminosilicate. By blending a specific polymer chelating agent having a stability constant pK _Ca of 4 or more and (c) sodium silicate at a specific ratio, water-insoluble matter derived from crystalline aluminosilicate in clothing with a high-density detergent As a result, the present inventors have found that this effect can be exhibited remarkably even when used for washing with high hard water after long-term storage.
[0007]
That is, the present invention relates to a high-density granular detergent containing 20 to 50% by weight of a surfactant and 10 to 30% by weight of a crystalline aluminosilicate,
(a) 2-15% by weight of potassium carbonate,
(b) a polymer chelating agent having a repeating unit represented by the following general formula (I) and having a molecular weight of 1000 or more and a stability constant pK _Ca of 4 or more with calcium ions;
(c) Sodium silicate, (b) + (c) = 5-20% by weight, and (b) / (c) = 1 / 20-2 / 1 (weight ratio)
The high-density granular detergent composition characterized by containing in the ratio is provided. Here, “high density” means a bulk density of 0.5 g / cm ³ or more.
[0008]
[Chemical 2]

[0009]
[Wherein M is an ion derived from an alkali metal ion, a quaternary ammonium ion, or an alkanolamine. m is an average value of 10 to 200. ]
[0010]
Examples of the surfactant to be blended in the garment cleaning composition of the present invention include the following.
[0011]
As an anionic surfactant, 1. A linear or branched alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16.
2. It has a straight chain or branched chain alkyl group or alkenyl group having an average carbon number of 10 to 20, and an average of 0.5 to 8 moles of ethylene oxide, propylene oxide, butylene oxide or ethylene oxide / propylene oxide in one molecule = 0.1 / Alkyl or alkenyl ether sulfate added at a ratio of 9.9 to 9.9 / 0.1 or at a ratio of ethylene oxide / butylene oxide = 0.1 / 9.9 to 9.9 / 0.1.
3. An alkyl or alkenyl sulfate having an average alkyl group or alkenyl group having 10 to 20 carbon atoms.
4). An olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule.
5. Alkane sulfonates with an average of 10-20 carbon atoms in one molecule.
6). An alkyl group or alkenyl group having an average carbon number of 10 to 20, and an average of 0.5 to 8 moles of ethylene oxide, propylene oxide, butylene oxide, or ethylene oxide / propylene oxide in one molecule = ratio of 0.1 / 9.9 to 9.9 / 0.1 Or an alkyl or alkenyl ether carboxylate added in a ratio of ethylene oxide / butylene oxide = 0.1 / 9.9 to 9.9 / 0.1.
7). Α-sulfo fatty acid salt or ester represented by the following formula.
[0012]
[Chemical 3]

[0013]
(In the formula, Y represents an alkyl group having 1 to 3 carbon atoms or a counter ion, Z represents a counter ion, and R represents an alkyl group or alkenyl group having 10 to 20 carbon atoms.)
[0014]
Here, the counter ion of the anionic surfactant has 1 to 3 alkali metal ions such as sodium and potassium, alkaline earth metal ions such as calcium and magnesium, ammonium ions, and alkanol groups having 2 or 3 carbon atoms. Alkanolamines (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.) can be mentioned.
[0015]
8). Fatty acid salt having 8 to 22 carbon atoms.
[0016]
Non-ionic surfactants include
9. A polyoxyethylene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and having 1 to 20 moles of ethylene oxide added thereto.
Ten. Polyoxyethylene alkylphenyl ether having an alkyl group having an average carbon number of 6 to 12 and having 1 to 20 moles of ethylene oxide added thereto.
11． A polyoxypropylene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and having 1 to 20 moles of propylene oxide added thereto.
12． A polyoxybutylene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and having 1 to 20 moles of butylene oxide added thereto.
13. Nonionic activator (ethylene oxide and propylene oxide or butylene having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and having a total of 1 to 30 moles of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide added The ratio with oxide is 0.1 / 9.9 to 9.9 / 0.1).
14. A higher fatty acid alkanolamide having an average carbon number of 10 to 20 or an alkylene oxide adduct thereof.
15． Sucrose fatty acid ester consisting of fatty acids with an average carbon number of 10-20 and sucrose.
16． Fatty acid glycerin monoester consisting of fatty acid having an average carbon number of 10 to 20 and glycerin.
17． Alkylamine oxide.
[0017]
In addition, as other surfactants,
18． Amphoteric surfactants such as carboxybetaine or sulfobetaine type surfactants.
19. Other cationic surfactants.
Also mentioned.
[0018]
Among the above surfactants, 1,2,4,5,8,9,10,11,12,13,14 are particularly preferred in the present invention, and 1,2,3,8, It is desirable to use 9. The main surfactant refers to a surfactant that occupies a proportion of 40% by weight or more in the total surfactant.
In the present invention, the total amount of the surfactant in the composition is 20 to 50% by weight.
[0019]
Crystalline aluminosilicate is blended in the high-density granular detergent composition of the present invention. In order to reduce water-insoluble matter derived from crystalline aluminosilicate, the amount of crystalline aluminosilicate is directly reduced. However, in the high-density granular detergent composition of the present invention, crystalline aluminosilicate is washed. 10 to 30% by weight, which is an amount having a water softening effect at a level that does not deteriorate the performance, is blended.
[0020]
Specific examples of the crystalline aluminosilicate include a crystalline aluminosilicate represented by the following formula.
x '(M ₂ O) ・ Al ₂ O ₃・ y' (SiO ₂ ) ・ w '(H ₂ O)
(In the formula, M is an alkali metal atom such as sodium or potassium, x ′, y ′, w ′ represents the number of moles of each component, generally 0.7 ≦ x ′ ≦ 1.5, 0.8 ≦ y ′ ≦ 6. , W 'is an arbitrary constant.)
Of these, those represented by the following general formula are particularly preferred.
Na ₂ O ・ Al ₂ O ₃・ ySiO ₂・ wH ₂ O
(In the formula, y represents 1.8 to 3.0, and w represents a number of 1 to 6.)
In particular, as the crystalline aluminosilicate (zeolite), a synthetic zeolite having an average primary average particle diameter of 0.1 to 10 μm represented by A-type and X-type zeolite and an average particle diameter of 15 μm or less is preferably used.
[0021]
The high-density granular detergent composition of the present invention has a stability constant pK _Ca of 4 (a) potassium carbonate, (b) a molecular weight of 1000 or more and calcium ions in addition to the surfactant and the crystalline aluminosilicate. The above specific polymer chelating agent and (c) sodium silicate are blended.
[0022]
Potassium carbonate (a) is blended in the composition in an amount of 2 to 15% by weight. Potassium carbonate not only compensates by adding 2 to 15% by weight of the detergency due to the alkali component due to the limited amount of sodium silicate, but also suppresses the residue of crystalline aluminosilicate water insoluble matter in clothing.
[0023]
The high-density granular detergent composition of the present invention comprises a specific polymer chelating agent (b) having a molecular weight of 1000 or more, preferably 5000 or more and a stability constant pK _Ca with calcium ions of 4 or more, preferably 5 or more. Sodium silicate (c), (b) + (c) = 5 to 20% by weight, and (b) / (c) = 1/20 to 2/1 (weight ratio), preferably 1/10 to 1 / 1 in a ratio. When the weight ratio (b) / (c) is less than 1/20, the effect of the present invention cannot be sufficiently obtained. When the weight ratio exceeds 2/1, for example, the viscosity of the slurry increases when blended with potassium carbonate, and spray drying is not possible. Since it becomes difficult, manufacturing aptitude deteriorates and it is not preferable.
[0024]
In general, water-insoluble matter remaining in clothes after washing is an agglomerate of crystalline aluminosilicate, but sodium silicate and sodium carbonate, which are usually blended as alkaline components in detergents, are hardened in washing water (calcium, Reacts with (magnesium) to form an insoluble salt, which is a binder for crystalline aluminosilicate aggregates. When a specific polymer chelating agent (b) having a molecular weight of 1000 or more and a stability constant pK _Ca with calcium ions of 4 or more is blended, the formation of these insoluble salts is suppressed. As a result, water derived from crystalline aluminosilicate is obtained. It is thought that the generation of insoluble materials is reduced.
[0025]
As the polymer chelating agent (b) having a molecular weight of 1000 or more and a stability constant pK _Ca with calcium ions of 4 or more, a polymer having a repeating unit represented by the general formula (I) is used.
[0026]
[Formula 4]

[0027]
[Wherein M is an alkali metal ion, a quaternary ammonium ion, or an alkanolamine such as an ion derived from mono-, di- or trialkanolamine having 2 to 3 carbon atoms. m is an average value of 10 to 200. ]
[0028]
The polymer having the segment represented by the general formula (I) is a polymer of acetal carboxylate and is described in JP-A No. 54-52196. In particular, as described in JP-A-54-52196, an ester of glyoxylaldehyde and a polymerization initiator are mixed under polymerization conditions, and the resulting polymer is subjected to rapid depolymerization in an alkaline solution. It is preferable to use a product produced by stabilizing the product. Alternatively, the stabilized copolymer can be saponified to form a salt of this polymer. At this time, one or more comonomer that can be polymerized with the ester of glyoxylic aldehyde can be copolymerized. Suitable comonomers include, for example, epoxy compounds such as ethylene oxide, propylene oxide, epihalohydrin epoxy succinate, aldehydes such as formaldehyde, acetaldehyde, and aldehydes containing up to 20 carbon atoms. Preference is given to comonomers having 1 to 4 carbon atoms, such as ethylene oxide, formaldehyde or acetaldehyde.
[0029]
A mixture of comonomers can be polymerized with the aldehyde ester to form a terpolymer, or a more complex polymer structure.
[0030]
Such polymers or copolymers are stabilized against rapid depolymerization in an alkaline solution by imparting chemically reactive groups to the polymer ends. Particularly suitable end groups include alkyl groups, oxygen-containing alkyl groups and oxygen-containing cyclic alkyl groups such as oxyalkyl groups such as methoxy and ethoxy, carboxylic acids such as
[Chemical formula 5]

[0032]
Aldehydes, ethers and other oxygen-containing alkyl groups such as
[Chemical 6]

[0034]
Etc. In these terminal groups, M is an alkali metal, ammonium, alkanolamine, an alkyl group having 1 to 4 carbon atoms, and R is hydrogen or an alkyl group having 1 to 8 carbon atoms. These chemically stable end groups at the polymer ends may be the same or different.
[0035]
In addition to the above essential components, the high-density granular detergent composition of the present invention includes other components, organic builders such as nitrilotriacetate, ethylenediaminetetraacetate, and citrate, and prevention of recontamination such as carboxymethylcellulose. Additives, protease, cellulase, amylase, lipase and other enzymes, reducing agents such as sulfites, bleaching agents such as sodium percarbonate and sodium perborate, detergent whitening agents such as fluorescent whitening agents and fragrances can be added as needed. .
[0036]
The high-density granular detergent composition of the present invention is produced, for example, by the method described in JP-A-61-69897, JP-A-61-69891, JP-A-61-69900, and European Patent No. 513824. it can. The composition of the present invention has a bulk density of 0.6 to 1.2 g / ml, preferably 0.7 to 0.9 g / ml. The bulk density is measured by the method described in JIS K 3362.
[0037]
【The invention's effect】
The high-density granular detergent composition of the present invention is a water-insoluble material derived from crystalline aluminosilicate in a detergent blending composition even after washing for a long time after washing, There are few, and adhesion to clothes and a residue can be reduced sharply.
[0038]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
[0039]
Example 1
1) <Manufacture of detergent>
A slurry with a moisture content of 50% by weight is prepared with the composition excluding the components that are desirable to dry-mix after 10% by weight of crystalline aluminosilicate and enzyme, which is a small amount of additives, among the detergent components shown in Table 1. Then, the powder obtained by spray drying was put into a high speed mixer (stirring tumbling granulator, manufactured by Fukae Kogyo Co., Ltd.), and 10% by weight of the crystalline aluminosilicate previously removed 5% by weight wetted with 1% by weight of water and granulated, and then 3% by weight of crystalline aluminosilicate and granulated to obtain the remaining 2% of crystalline aluminosilicate. % And a small amount of additives such as enzymes were dry-mixed to obtain a high-density granular detergent having a bulk density of 0.70 to 0.80 g / cm ³ .
[0040]
2) <Evaluation of water-insoluble matter derived from crystalline aluminosilicate by difference in washing hardness of high-density granular detergent>
In order to evaluate the residual accumulation of water-insoluble matter derived from crystalline aluminosilicate in clothing due to the influence of washing, the washing machine model shown in FIGS. 1 (a) to (c) was made of stainless steel. In FIG. 1 (c), the upper open cylinder 1 with holes on the inner eight sides corresponds to the inner tub of the fully automatic washing machine, and the outer cylinder 2 corresponds to the outer tub of the washing machine.
This model also drains the system by opening and closing the rubber stopper 3 in a semicircular hole opened in the lower part of the cylinder 2. In addition, a stirrer piece (7 mm x 40 mm) is placed at the center of the bottom of the cylinder 1 and rotated (500 rpm) to generate water flow.
[0041]
Evaluation was performed as follows. Measure the weight of the cylinder 2 in advance (without rubber stopper), place the rubber stopper 3 in the hole at the bottom of the side of the cylinder 2, and add 1 liter of water with 20 ° C and 15 ° DH hardness to the center of the cylinder 1 at 2 liters / minute. The flow rate was. At that time, water flows into the cylinder 2 from a hole formed in the side surface of the cylinder 1 so that the water levels of the cylinder 1 and the cylinder 2 coincide. Next, the stirrer piece is rotated (500 rpm) to generate a water flow, and after 30 seconds, when the water flow is stabilized, 1 g of the detergent produced in 1) above is added to the water surface of the cylinder 1 and stirred. After 10 minutes from the introduction of the detergent, the stirrer was stopped, and at the same time, the rubber stopper 3 on the side of the cylinder 2 was pulled out, and the washing liquid was discharged.
After repeating the above operation 100 times, remove the tube 1 from the tube 2, dry the tube 2 at 105 ° C for 2 hours, measure the weight, and increase the weight due to residual water insoluble matter derived from crystalline aluminosilicate. Asked. The results are shown in Table 1.
In addition, the preservation | save conditions of the detergent used for said test are as follows.
・ After detergent production, leave for 7 days in a room at 20 ℃ and 60% RH ... Storage conditions 1
・ After detergent manufacture, leave it in a room at 20 ℃, 60% RH for 30 days… Storage condition 2
3) The relationship between the weight increase (g) of the cylinder 2 and the adhesion and persistence of water-insoluble matter to the clothing in actual washing is shown below.
The test using the above-described washing machine model corresponds to a case where washing is performed under the following conditions.
・ Washing machine: Matsushita Electric NA-F42Y5
・ Laundry: Black cloth [Blend (Polyester / Cotton = 65/35)] ・ Detergent: 40g
・ Laundry course: Middle water level (40 liters of water)
Washing 9 minutes → Rinse twice → Dehydration 3 minutes → Drying (Leave for 24 hours at 20 ℃, 40% RH)
After drying the clothes, select 10 out of 20 black cloths. In this case, the relationship between the adhesion and persistence of water insoluble matter to the black cloth and the increase in the weight of the cylinder 2 is as follows.

Adhesion and persistence to clothing is clearly a problem when the weight increase is 0.4g or more.
[0042]
[Table 1]

[0043]
Note) Abbreviations in the table have the following meanings, and the molecular weights of polyethylene glycol and sodium polyacrylate are shown below.
- LAS-Na: a linear alkyl (C ₁₀ -C ₁₃₎ sodium benzenesulfonate-AS-Na: alkyl (C ₁₂ -C ₁₈₎ Sodium sulfate Nonionic polyoxyethylene (ethylene oxide average addition molar number = 1) Alkyl (C ₁₂ -C ₁₄ ) ether The polymer chelating agent shown in Table 2 below was used.
[0044]
[Table 2]

[Brief description of the drawings]
FIG. 1 is a schematic view of a washing machine model used in an example.
[Explanation of symbols]
1 ... Cylinder (inner tank)
2 ... Cylinder (outer tank)
3 ... Rubber stopper

Claims (5)

In a high-density granular detergent containing 20-50% by weight of surfactant and 10-30% by weight of crystalline aluminosilicate,
(a) 2-15% by weight of potassium carbonate,
(b) a polymer chelating agent having a repeating unit represented by the following general formula (I) and having a molecular weight of 1000 or more and a stability constant pK _Ca of 4 or more with calcium ions;
(c) Sodium silicate, (b) + (c) = 5-20% by weight, and (b) / (c) = 1 / 20-2 / 1 (weight ratio)
A high-density granular detergent composition, characterized in that the content of inorganic salts excluding crystalline aluminosilicate is 28.8 % by weight or less .

[Wherein M is an ion derived from an alkali metal ion, a quaternary ammonium ion, or an alkanolamine. m is an average value of 10 to 200. ]   2. The high-density granular detergent composition according to claim 1, wherein the molecular weight of the polymer chelating agent is 5000 or more. (b) The high-density granular detergent composition according to claim 1 or 2, wherein the polymer chelating agent has a stability constant pK _Ca with calcium ions of 5 or more. The high-density granular detergent composition according to claim 1, wherein the inorganic salt excluding the crystalline aluminosilicate contains sodium silicate, sodium carbonate, potassium carbonate and sodium sulfate. In the method for producing a high-density granular detergent containing 20 to 50% by weight of surfactant and 10 to 30% by weight of crystalline aluminosilicate,
Surfactant, part of crystalline aluminosilicate, and
(a) 2-15% by weight of potassium carbonate,
(b) a polymer chelating agent having a repeating unit represented by the following general formula (I) and having a molecular weight of 1000 or more and a stability constant pK _Ca of 4 or more with calcium ions;
(c) Sodium silicate, (b) + (c) = 5-20% by weight, and (b) / (c) = 1 / 20-2 / 1 (weight ratio)
In this ratio, the remainder of the crystalline aluminosilicate is added to the powder obtained by spray-drying the slurry obtained by mixing so that the content of the inorganic salt excluding the crystalline aluminosilicate is 28.8 % by weight or less. The manufacturing method of the high-density granular cleaning composition characterized by mixing.

[Wherein M is an ion derived from an alkali metal ion, a quaternary ammonium ion, or an alkanolamine. m is an average value of 10 to 200. ]

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