JP4098387B2

JP4098387B2 - Molding method of solid detergent for toilet

Info

Publication number: JP4098387B2
Application number: JP03274098A
Authority: JP
Inventors: 栄治国友
Original assignee: Kobayashi Pharmaceutical Co Ltd
Current assignee: Kobayashi Pharmaceutical Co Ltd
Priority date: 1998-02-16
Filing date: 1998-02-16
Publication date: 2008-06-11
Anticipated expiration: 2018-02-16
Also published as: JPH11228998A

Description

【０００１】
【発明の属する技術分野】
本発明は、トイレ用固形洗浄剤の成形方法、特に、従来の脆さが改善された保形性の高いトイレ用固形洗浄剤の成形方法に関する。
【０００２】
【従来の技術】
トイレ用固形洗浄剤は、従来、トイレ用洗浄剤組成物を混練機を用いて混練したものを、押出成形機を用いて成形する２段階方式又は混練押出成形機を用いて一度に混練と押出成形を行う１段階方式で製造されていた。
【０００３】
しかし、この場合、混練物の粘りが大きく付着性の高いものや、潤滑性があまりなく固い混練物の場合は、混練機等の成形機内において摩擦が大きくなり成形作業に支障を生じるばかりか金型内で混練物が滞留して閉塞する場合がある。そのため、成形機内の抵抗を小さくすべく金型の絞り込みを小さくする（入口径と出口径の差を小さくする）手段や、混練物に粘りが少なく付着性が小さい組成物を用いる等の改良が行われたが、いずれの場合も、保形性が悪く、成形品が脆くて運送中や使用中に一部が欠けたり、ひび割れが発生したりした。したがって、このような成形品は、押出成形後の後工程においてヒビ割れたり、折れたりする問題があり、また、これを切断して製品にする場合には、切断面にササクレが生じ、製品の外観を損なう問題があった。更に、運送中や使用中に一部欠けたり、水洗時における水への溶解量のバラツキが大きい問題があった。
【０００４】
【発明が解決しようとする課題】
そこで、本発明は、成形品の保形性が高く、運送中や使用中に一部欠けるといった脆さやヒビ割れの問題、前記切断面のササクレ等の問題が発生せず、しかも水洗時における水への溶解量のバラツキが少ないトイレ用固形洗浄剤の成形方法を提供することを目的とする。
【０００５】
【課題を解決するための手段】
かかる目的を達成するため、鋭意研究した結果、少なくとも所定の成分を有するトイレ用固形洗浄剤組成物を、減圧状態で混練して、金型より押出成形すれば、脆さが改善され、保形性が高い成形品が得られることを見出だし、本発明を完成させた。
【０００６】
すなわち、本発明のうち請求項１記載の発明は、界面活性剤としての椰子油混合脂肪酸塩、ポリエチレングリコール、溶解調整剤としてのカルボキシメチルセルロース塩及び香料、その他の配合物からなり、そのうち、混練中の加熱状態において組成物全体の潤滑剤となる性質を示す物質として「ポリエチレングリコールと香料との合計量」が２０〜６０重量％配合されてなるトイレ用洗浄剤組成物を、減圧下、混練手段を用いて混練しつつ押し出す工程を経て、成形することを特徴とするトイレ用固形洗浄剤の成形方法であり、請求項２記載の発明は、固形ビルダ−、界面活性剤としての椰子油混合脂肪酸塩、ポリエチレングリコール、溶解調整剤としてのカルボキシメチルセルロース塩及び香料、その他の配合物からなり、そのうち、混練中の加熱状態において組成物全体の潤滑剤となる性質を示す物質として「ポリエチレングリコールと香料との合計量」が２０〜６０重量％配合されてなるトイレ用洗浄剤組成物を、減圧下、混練手段を用いて混練しつつ押し出す工程を経て、成形することを特徴とするトイレ用固形洗浄剤の成形方法である。
【０００７】
本発明に用いる界面活性剤としては椰子油混合脂肪酸塩とポリエチレングリコールが必要であるが、これら以外の非イオン界面活性剤、アニオン界面活性剤、カチオン界面活性剤、両性イオン界面活性剤、その他の界面活性剤を混合して用いてもよい。
【０００８】
非イオン界面活性剤としては、高級アルコ−ルエチレンオキサイド付加物、アルキルフェノ−ルエチレンオキサイド付加物、脂肪酸エチレンオキサイド付加物、多価アルコ−ル脂肪酸エステルエチレンオキサイド付加物、高級アルキルアミンエチレンオキサイド付加物、脂肪酸アミドエチレンオキサイド付加物、油脂のエチレンオキサイド付加物、ポリプロピレングルコ−ルエチレンオキサイド付加物等のポリエチレングリコ−ル型界面活性剤や、グリセロ−ルの脂肪酸エステル、ペンタエリスリト−ルの脂肪酸エステル、ソルビト−ル及びソルビタンの脂肪酸エステル、ショ糖の脂肪酸エステル、多価アルコ−ルのアルキルエ−テル、アルカノ−ルアミン類の脂肪酸エステル等の多価アルコ−ル型界面活性剤が使用できる。
【０００９】
アニオン界面活性剤としては、セッケン、その他のカルボン酸塩、高級アルコ−ル硫酸エステル塩、高級アルキルエ−テル硫酸エステル塩、硫酸化油、硫酸化脂肪酸エステル、硫酸化オレフィン等の硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、パラフィンスルホン酸塩、イゲボンＴ、エアロゾルＯＴ等のスルホン酸塩、高級アルコ−ルリン酸エステル塩等のリン酸エステル塩が使用できる。
【００１０】
なお、カチオン界面活性剤としては、炭素数８から１８の長鎖アルキルジメチルアミンを塩化メチル、塩化ベンジル等と反応させて得られるテトラアルキルアンモニウム塩、ピリジンに長鎖のハロゲン化アルキルを作用させて合成するピリジニウム塩等の第四級アンモニウム型界面活性剤や長鎖アミン又は複素環アミン（イミダゾ−ル等）の塩の型で用いられるアミン型界面活性剤が例示され、両性界面活性剤としては、親水基としてアミノ酸やベタインを有する界面活性剤が例示される。
【００１１】
本発明に用いるビルダ−としては、水溶性の充填剤であればいずれも使用できるが、具体的には次の水溶性無機充填剤、水溶性有機充填剤が例示できる。なお、これらのビルダ−は、単独で用いてもよいし、２種以上を混合して用いてもよい。水溶性無機充填剤としては、アルカリ金属の塩化物、炭酸塩、炭酸水素塩、硫酸塩、リン酸塩、ホウ酸塩及びケイ酸塩が使用でき、例えば、硫酸ナトリウム、塩化ナトリウム、炭酸ナトリウム、炭酸水素ナトリウム、トリポリリン酸ナトリウム、ピロリン酸ナトリウム、ケイ酸ナトリウム等の比較的水に溶けやすいものから、ホウ砂等の比較的水に難溶性のものまで含まれる。
【００１２】
水溶性有機充填剤としては、炭素数が２〜１０のカルボン酸、炭素数が２〜１０のヒドロキシカルボン酸、ポリカルボン酸及びヒドロキシポリカルボン酸等の有機酸並びにそれらの塩、炭素数が２〜１０のアミノカルボン酸、アミノポリカルボン酸若しくはポリアミノカルボン酸又はそれらの塩等が使用できる。具体例としては、例えば、クエン酸、リンゴ酸、コハク酸、マレイン酸、フマ−ル酸、グルコン酸、アジピン酸等の有機酸及びそれらの塩、エチレンジアミン四酢酸、ニトリロ三酢酸、ヒドロキシエチルイミノ二酢酸、ジヒドロキシエチルグリシン、ヒドロキシエチレンジアミン三酢酸、ジエチレントリアミン五酢酸、トリエチレントリアミン六酢酸等のアミノカルボン酸及びそれらの塩等が使用でき、これらの塩としては、例えばナトリウム塩等が挙げられ、また、ブドウ糖、ショ糖、果糖、乳糖等の糖類、尿素等も使用できる。
【００１３】
本発明において、「混練中の加熱状態」とは、混練中の摩擦熱による加熱のみならず、外部からの加熱手段により加熱する場合をも含む。この場合、加熱状態の温度は２０〜８０℃とするのが好ましく、更に好ましい温度は３０〜６０℃である。また、「混練中の加熱状態において組成物全体の潤滑剤となる性質を示す物質」とは、上記過熱状態において、混練中にシリンダ−内の組成物を閉塞状態にしない程度の潤滑性を示すものであり、例えば、加熱混練中に溶融して流動化し潤滑性を示すものや常温で少し粘性のある液状のものを用いるのが好ましく、このようなものとしては、前記ポリエチレングリコール、香料を、例示することができる。なお、これら以外に、適宜、目的に応じて、着色剤、芳香剤、溶解調節剤、滑沢剤、離型剤等の他の配合剤が配合されていてもよい。
【００１４】
このように形成すると、トイレ用洗浄剤組成物の各構成物は、混練、押し出しの各工程中、減圧状態にあるので、それらの構成物間に介在する空気が脱気され、接触状態が密になり、相互の結合力が強まる結果、成形品の保形性が高く、押出成形後の後工程おけるひび割れ、折れ及び運送中や使用中に一部欠けるといった脆さやひび割れの問題が発生しないトイレ用固形洗浄剤が得られる。この場合、使用中に一部欠けるといった脆さの問題が発生しないので、水洗時における水への溶解量のバラツキも少なくなる。しかも、切断時の切断面にササクレが発生しないので、製品の外観がよくなり、商品価値を高めことができる。
【００１５】
また、本発明において、前記「混練中の加熱状態において組成物全体の潤滑剤となる性質を示す物質」の配合量は、請求項１，２記載の発明の如く、２０〜６０重量％にするのが好ましく、より好ましくは２０〜４０重量％である。２０重量％未満では成形作業性を損ねる場合があり、一方、６０重量％を超えると洗浄剤の洗浄効果に悪影響を与える場合があるからである。
【００１６】
本発明において、前記「減圧下、混練手段を用いて混練しつつ押し出す工程」は、請求項４記載の発明の如く、混練・押出手段を有する第１シリンダ−と押出手段を有する第２シリンダ−とを減圧下のチャンバ−で連通・連結させた状態で、前記トイレ用洗浄剤組成物を第１シリンダ−、チャンバ−、第２シリンダ−の順に移動させて金型に導く工程で構成されていることが好ましい。
【００１７】
ここで、「第１シリンダ−と第２シリンダ−とをチャンバ−で連通・連結させた状態」とは、第１シリンダ−とチャンバ−及び該チャンバ−と第２シリンダ−が、それぞれ、相互に、通気状態で連結されていることを意味する。このように形成すると、第１シリンダ−が減圧状態になり、そこでトイレ用洗浄剤組成物が脱気されながら混練されると共に、減圧下のチャンバ−を通過するので、チャンバ−通過の際、さらに該組成物中の空気の脱気が行われ、その構成物の結合力をより高めることになる。
【００１８】
この場合、第１シリンダ−とチャンバ−との間には、格子状の孔が形成された隔壁を設けることが好ましい。混練物が隔壁を通過する際の抵抗で第１シリンダ−に内圧がかかりよく混練できると共にチャンバ−の減圧状態が維持しやすくなるからである。また、第１シリンダ−の混練物が棒状に分離されてチャンバ−に入るので表面積が大きくなり、混練物中の空気が更に抜けやすくなるからである。なお、この場合、第１シリンダ−を上段に、第２シリンダ−を下段に置き、チャンバ−はその間に位置するようにするのが好ましい。上段の第１シリンダ−の混練物が、棒状となって下段の第２シリンダ−ヘ、すなわちチャンバ−内を上から下に移動することになり、棒状の形状を維持しやすく、脱気と成形作業の容易性が確保できるからである。
【００１９】
本発明において、前記減圧下の減圧の程度は、請求項５記載の発明の如く、５６０〜０．０１ｍｍＨｇにすることが好ましい。更に好ましくは、３８０〜０．０１ｍｍＨｇである。前記組成物の脱気を十分に行い、構成物の結合力を十分高め、成形品の保形性をより十分に確保するためである。
【００２０】
【発明の実施の形態】
以下、本発明の実施の形態を、以下に示すトイレ用洗浄剤組成物を用い、図面に基づいて説明するが、本発明はこの実施の形態に示す方法に限定されるものではない。なお、図１は本発明に用いる成形工程を実施できる成形機の長さ方向の縦断面図であり、図２は図１のＡ−Ａ間における縦断面図である。
【００２１】
本発明にかかるトイレ用固形洗浄剤の成形方法の一つの好ましい形態は、少なくとも、固形ビルダ−として前記水溶性無機充填剤の２０〜５０重量％、前記アニオン界面活性剤としての椰子油脂肪酸塩の１０〜３０重量％、前記ポリエチレングリコール及び液体香料の２０〜３０重量％からなるトイレ用洗浄剤組成物を、図１に示す成形機を用い、投入口５から投入後、混練・押出手段を有する第１シリンダ−１と押出手段を有する第２シリンダ−２とを３８０〜０．０１ｍｍＨｇに減圧したチャンバ−３で連通・連結させた状態で、第１シリンダ−１、続いてチャンバ−３、第２シリンダ−２の順に加熱状態で混練しつつ移動させて金型４に導き、押出成形する方法が採用される。この場合、加熱状態の温度は３０〜６０℃とするのが好ましい。加熱は、混練時の摩擦熱を用いる場合の他、これと外部からの公知の加熱手段とを併用してもよい。公知の加熱手段としては、第１シリンダ−等にジャケット構造で温水や温油を循環させる方法が例示できる。
【００２２】
このように形成すれば、第１シリンダ−１で脱気されながら混練され、チャンバ−３内で更に混練物中の空気が除かれながら第２シリンダ−２に移動しここでも脱気されるので、混練物が密になると共に、非イオン界面活性剤等が潤滑剤の役割を果たすので、混練物は成形機内をスム−ズに移動する。その結果、構成物間の結合力が強くなって、脆さ、ひび割れ、ササクレがなく保形性のよい成形物が効率よく得られる。また、成形物の硬度が向上するため、従来の方法を用いると柔らかすぎる成形品が得られる場合の処方にも対応可能となり、処方設計の幅が広がり、生産効率の改善も可能となる。
【００２３】
なお、この場合において、第１シリンダ−１とチャンバ−３との間には、格子状の多数の孔が形成された隔壁（図示せず）を設けると共に、第１シリンダ−１を上段に、第２シリンダ−２を下段に置き、チャンバ−３はその間に位置するようにするのが好ましい。第１シリンダ−１の混練物が複数の棒状に分離されて下段のチャンバ−３、更に下の第２シリンダ−２に入るので、棒状の形状の維持の容易性と、表面積の増大とをもたらし、そのため混練物の脱気と成形作業が容易に行われるからである。
【００２４】
本発明の実施の形態における前記トイレ用洗浄剤組成物については、目的に応じ、前記着色剤等のその他の配合剤を配合してもよいのは勿論である。
【００２５】
【実施例】
以下、実施例を用いて本発明を更に具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
【００２６】
（参考例１）まず、表１の参考例１に示すトイレ用洗浄剤組成物（配合量の単位は重量％である）を調整する。この組成物は、アニオン界面活性剤として椰子油混合脂肪酸塩（第一工業製薬株式会社製）の２０重量％と、非イオン界面活性剤としてポリエチレングリコ−ル６０００（第一工業製薬株式会社製ＰＥＧ６０００Ｐ）の１０重量％と、ビルダ−として無水硫酸塩（四国化成工業株式会社製中性無水芒硝）の５０重量％と、溶解調節剤としてカルボキシメチルセルロ−ス塩（第一工業製薬株式会社製セロゲン）の１０重量％と、着色剤として青色１号（三国住友化学工業株式会社製）の１０重量％とを配合し、調整されたものである。
【００２７】
次に、この組成物を、パドル１ａとフィ−ドスクリュー１ｂが２本のシャフト８に配置された２軸型の混練・押出手段を有する第１シリンダ−１と、真空ポンプ７からの排気パイプが連結され、第１シリンダ−１との間に格子状の多数の孔のある隔壁（図示せず）を設けたチャンバ−３と、スクリュー２ａが配置された第２シリンダ−２と、金型４とがこの順に連結された図１に示す成形機を用い、３８０〜０．０１ｍｍＨｇの減圧下において、混練し、押し出し、成形した。なお、真空ポンプ７による脱気は、原料が原料投入口５から投入され、金型４から成形品６が押し出された状態、すなわち成形機の入口と出口が塞がり成形作業が立ち上がった時点で行えばよい。この場合において、減圧下における混練時の組成物の温度は、約４５℃であった。この成形物６の下記物性を評価し、その結果を表２に示す。
【００２８】
（参考例２，３及び実施例１〜４）表１の参考例２ , ３及び実施例１〜４の如く配合した組成物を、参考例１と同様にして、減圧下に、押出成形した。この場合、混練時の各組成物の温度は、いずれも、約４５℃であった。各成形物の下記物性を評価し、その結果を表２に示す。
【００２９】
（比較例１〜７）表１の比較例１〜７の如く配合した組成物を、減圧にせず、常圧で行った以外は、参考例１と同様にして、成形した。この場合、混練時の各組成物の温度は、いずれも、約４５℃であった。各成形物の下記物性を評価し、その結果を表２に示す。
【００３０】
（物性試験方法）「脆さ」について；次に示す「折れ時の荷重」にて評価した。長さが３０ｍｍ、直径が６ｍｍの円柱形の押出成形物を、レオメ−タ（サン科学社製モデルＣＲ−３００）のサンプル受台（幅１０ｍｍ、深さ４ｍｍの溝を有する）の溝に横方向に跨がるように架け、次に針入弾性用アダプタ−（直径５ｍｍの棒）を溝に架かった部分のサンプルの中央部に当て、続いて前記サンプル受台を一定速度（６０ｍｍ／ｍｉｎ）で押し上げて、サンプルが折れた時の荷重（ｇ）を求めた。
【００３１】
「硬度」について；次に示す「突き刺し時の荷重」にて評価した。長さが２５ｍｍ、直径が３０ｍｍの円柱形の押出成形物を、レオメ−タ（サン科学社製モデルＣＲ−３００）のサンプル受台に円形の断面が上下面になるように取り付けた後、サンプルの上面の中央部に、針入度用アダプタ−（直径３ｍｍの棒であって、先端部は高さ５ｍｍの円錐形となり尖っている）の先端を当て、前記サンプル受台を一定速度（６０ｍｍ／ｍｉｎ）で押し上げて、前記アダプタ−の先端が一定深さ（６ｍｍ）に達するまで突き刺し、その時の荷重を（ｇ）を求めた。
【００３２】
「ササクレ」について；次の「切断試験」を行い、ササクレの程度を目視で評価した。直径が２０ｍｍの棒状の押出成形物をカッタ−ナイフ（コクヨ株式会社製ＨＡ−２Ａ）を用いて、幅方向に切断した時の切り口の状態を目視で観察した。
○：ササクレが認められないか、ほとんど認められない。
×：切り口の下部にササクレが明確に認められる。
【００３３】
「密度（ｇ／ｃｍ³）」について；長さが１００ｍｍ、直径が２０ｍｍの円柱形の押出成形物の体積と重量を測定し、算出した。
【００３４】
「均一溶解性」について；一つのサンプル（例えば、実施例１のサンプル）の試験において、２個のロ−タタンク（ＴＯＴＯ株式会社製Ｓ７２１Ｂ）の手洗い部のそれぞれに、直径３０ｍｍの押出成形物の２５ｇを入れた容器（小林製薬株式会社製貝殻型）を一個づつ合計２個を設置し、１回のフラッシュに対し６０秒で満水になるように水流を調整した後、１時間に１回の割合で１日に２４回フラッシュし、これを７日間、１４８回繰り返した。２個の押出成形物につき各回のたまり水の吸光度（６３０ｎｍ）を分光光度計で測定し、そのバラツキの幅にて一つのサンプルの均一溶解性を評価した。
【００３５】
【表１】

【００３６】
【表２】

【００３７】
表１に示すように、実施例１〜４と比較例４〜７、参考例１〜３と比較例１〜３の組成物の種類と配合割合は、いずれも同じであり、双方の相違は、実施例と参考例が３８０〜０．０１ｍｍＨｇの減圧下において、混練し、押し出し、成形しているのに対し、比較例は減圧にしていない点にある。なお、表１において、前記「混練中の加熱状態において組成物全体の潤滑剤となる性質を示す物質」は、ポリエチレングリコ−ル６０００と香料混合物である。なお、これらの配合がないと、成形機内での摩擦が特に減圧下で大きくなる傾向にあり、閉塞が生じる等成形作業がスム−ズに進まない。
【００３８】
表２示すように、同じ組成の実施例、参考例と比較例を対比すると、実施例、参考例は、折れ強さが比較例の２倍に改善され、密度、硬度も比較例より高く、また比較例の切断表面がササクレが生じるのに対し、実施例、参考例のそれはササクレを生じない。これは、混練・押出成形中、実施例、参考例は減圧下、組成物中の空気が脱気されるので、組成物の密度が高くなり、組成構成物の結合力が高まったことによると考えられる。したがって、運送中や使用中に成形物の一部が欠ける問題や製品外観を損なう問題を生じない。
【００３９】
さらに、これらの成形品を、実際にトイレに使用した場合の、水への均一溶解性を比較すると、表２に示すように、実施例は比較例に比べ、吸光度のバラツキの幅が小さく、着色剤を配合していないため吸光度がゼロの参考例２と比較例２は別として、特に実施例１〜４は比較例の半分以下のバラツキになっている。これは、一回のフラッシュごとに溶ける薬剤の量は、実施例が均一であることを示しており、使用上のメリットは大きい。
【００４０】
【発明の効果】
以上説明したように、請求項１、２記載の発明によれば、混練、押出しの各工程中、減圧状態にあるので、組成構成物の接触状態が密になり、相互の結合力が強まる結果、成形品の保形性が高く、押出成形後の後工程おけるひび割れ、折れ及び運送中や使用中に一部欠けるといった脆さやひび割れの問題が発生せず、切断時のササクレがなく、硬度が高く、水洗時における水への溶解量のバラツキも少ないトイレ用固形洗浄剤が得られる。また、請求項１，２記載の発明によれば、潤滑剤の配合量が好ましいため、成形作業性を損ねることもなく、洗浄剤の洗浄効果にも悪影響を与えることもない。
【００４１】
請求項３記載の発明によれば、第１シリンダ−で減圧下混練されたトイレ用洗浄剤組成物が、減圧下のチャンバ−を通過するので、該組成物中の空気の脱気がより十分に行われ、請求項４記載の発明によれば、減圧の程度が、前記組成物の脱気を十分に行う上で好ましく、請求項１、２の効果の向上をもたらす。
【図面の簡単な説明】
【図１】本発明に用いる一つの成形工程を実施できる成形機の長さ方向の縦断面図である。
【図２】図２は図１のＡ−Ａ間における縦断面図である。
【符号の説明】
１・・・第１シリンダ−
１ａ・・・パドル
１ｂ・・・フィ−ドスクリュ−
２・・・第２シリンダ−
２ａ・・・スクリュ−
３・・・チャンバ−
４・・・金型
５・・・原料投入口
６・・・トイレ用固形洗浄剤成形物
７・・・真空ポンプ
８・・・シャフト[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for forming a toilet solid cleaning agent, and more particularly to a conventional method for forming a toilet solid cleaning agent having improved shape and high shape retention.
[0002]
[Prior art]
Toilet solid detergents are conventionally kneaded and extruded at once using a two-stage method or a kneading extrusion molding machine in which a toilet cleaning composition is kneaded using a kneader. Manufactured in a one-step manner of molding.
[0003]
However, in this case, in the case of a kneaded material with high stickiness and high adhesion, or a hard kneaded material with little lubricity, friction is increased in a molding machine such as a kneader, which not only hinders the molding operation. The kneaded material may stay in the mold and clog. Therefore, there are improvements such as a means for reducing the narrowing of the mold (to reduce the difference between the inlet diameter and the outlet diameter) in order to reduce the resistance in the molding machine, and the use of a composition with less stickiness and low adhesion to the kneaded product. In each case, the shape retention was poor, the molded product was fragile, and part of the molded product was missing or cracked during transportation or use. Therefore, such a molded product has a problem that it is cracked or broken in the post-process after extrusion molding. There was a problem of damaging the appearance. Further, there are problems that a part is missing during transportation or use, or that the amount of dissolution in water during washing is large.
[0004]
[Problems to be solved by the invention]
Therefore, the present invention has a high shape-retaining property, does not cause problems such as brittleness and cracks that are partially lost during transportation and use, and problems such as crusting of the cut surface, and water in washing An object of the present invention is to provide a method for forming a solid detergent for toilets in which the amount of dissolution in the toilet is small.
[0005]
[Means for Solving the Problems]
As a result of diligent research to achieve such an object, if a toilet solid detergent composition having at least a predetermined component is kneaded in a reduced pressure state and extruded from a mold, brittleness is improved and shape retention is improved. The present inventors have found that a molded product having high properties can be obtained and completed the present invention.
[0006]
That is, According to one aspect of the present invention, coconut oil mixed fatty acid salts, polyethylene glycol as a surfactant, carboxymethylcellulose salts, and flavoring as dissolution modifiers, it consists other formulations, Chi thereof cormorants, toilet detergent composition as substance exhibiting the property of the lubricant of the total composition in a heated state in mixed kneaded "the total amount of polyethylene glycol and perfume" is formed by 20 to 60 wt% blended vacuo The method for forming a solid detergent for toilets is characterized by forming through a step of extruding while kneading using a kneading means. The invention according to claim 2 is a solid builder, an insulator as a surfactant. oil mixed fatty acid salts, polyethylene glycol, carboxymethyl cellulose salts and flavors as dissolution modifiers, consists other formulations, Chi thereof cormorants, mixed The toilet detergent composition formed by 20 to 60 wt% blending "the total amount of polyethylene glycol and perfume" as a substance showing the property of the lubricant of the total composition in a heated state in, under vacuum, kneading A method for forming a solid cleaning agent for toilets, wherein the forming is performed through a step of extruding while kneading using means.
[0007]
As the surfactant used in the present invention, coconut oil mixed fatty acid salt and polyethylene glycol are necessary. Other than these , nonionic surfactant, anionic surfactant, cationic surfactant, zwitterionic surfactant, other A surfactant may be mixed and used .
[0008]
Nonionic surfactants include higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, higher alkylamine ethylene oxide additions. , Fatty acid amide ethylene oxide adduct, oil and fat ethylene oxide adduct, polypropylene glycol ethylene oxide adduct and other polyethylene glycol type surfactants, glyceryl fatty acid ester, pentaerythritol fatty acid Polyhydric alcohol surfactants such as esters, sorbitol and fatty acid esters of sorbitan, fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, fatty acid esters of alkanolamines and the like can be used.
[0009]
Anionic surfactants include soap, other carboxylates, higher alcohol sulfates, higher alkyl ether sulfates, sulfate oils, sulfated fatty acid esters, sulfate esters such as sulfated olefins, and alkylbenzenes. Phosphonate salts such as sulfonates, alkylnaphthalene sulfonates, paraffin sulfonates, Igebon T, aerosol OT, and higher alcohol phosphates can be used.
[0010]
As the cationic surfactant, a tetraalkylammonium salt obtained by reacting a long-chain alkyldimethylamine having 8 to 18 carbon atoms with methyl chloride, benzyl chloride or the like, or a long-chain alkyl halide is allowed to act on pyridine. Examples of amphoteric surfactants include quaternary ammonium type surfactants such as pyridinium salts to be synthesized and amine type surfactants used in the form of salts of long chain amines or heterocyclic amines (imidazole, etc.). Examples of the surfactant include amino acids and betaines as hydrophilic groups.
[0011]
As the builder used in the present invention, any water-soluble filler can be used, and specific examples thereof include the following water-soluble inorganic fillers and water-soluble organic fillers. In addition, these builders may be used independently and may be used in mixture of 2 or more types. As the water-soluble inorganic filler, alkali metal chlorides, carbonates, hydrogen carbonates, sulfates, phosphates, borates and silicates can be used, for example, sodium sulfate, sodium chloride, sodium carbonate, Examples include those that are relatively soluble in water such as sodium hydrogen carbonate, sodium tripolyphosphate, sodium pyrophosphate, and sodium silicate, and those that are relatively insoluble in water such as borax.
[0012]
Examples of the water-soluble organic filler include carboxylic acids having 2 to 10 carbon atoms, hydroxycarboxylic acids having 2 to 10 carbon atoms, polycarboxylic acids, hydroxycarboxylic acid, and other organic acids and salts thereof, and 2 carbon atoms. -10 aminocarboxylic acids, aminopolycarboxylic acids or polyaminocarboxylic acids or their salts can be used. Specific examples include, for example, organic acids such as citric acid, malic acid, succinic acid, maleic acid, fumaric acid, gluconic acid, adipic acid, and salts thereof, ethylenediaminetetraacetic acid, nitrilotriacetic acid, hydroxyethyliminodioxy Aminocarboxylic acids such as acetic acid, dihydroxyethyl glycine, hydroxyethylenediamine triacetic acid, diethylenetriaminepentaacetic acid, triethylenetriaminehexaacetic acid, and salts thereof can be used, and examples of these salts include sodium salts. Sugars such as glucose, sucrose, fructose and lactose, urea and the like can also be used.
[0013]
In the present invention, the “heating state during kneading” includes not only heating by frictional heat during kneading but also heating by an external heating means. In this case, the temperature in the heated state is preferably 20 to 80 ° C., and more preferably 30 to 60 ° C. The “substance exhibiting the property of becoming a lubricant for the entire composition in the heated state during kneading” refers to lubricity to such an extent that the composition in the cylinder is not closed during kneading in the overheated state. are those, for example, it is preferable to use those of the liquid with a slightly viscous ones or room temperature showing the lubricity was melted and fluidized in the heating and kneading, as such, the polyethylene glycol, perfume and Can be exemplified. In addition to these, other compounding agents such as a colorant, a fragrance, a dissolution regulator, a lubricant, and a release agent may be appropriately blended depending on the purpose.
[0014]
When formed in this manner, each component of the toilet cleaner composition is in a reduced pressure state during the kneading and extruding steps, so the air intervening between these components is degassed and the contact state is tight. As a result, the shape of the molded product is high, and as a result, the toilet does not suffer from the problems of brittleness and cracking, such as cracking, bending, and partial chipping during transportation and use after extrusion. A solid cleaning agent is obtained. In this case, since the problem of brittleness that is partially lost during use does not occur, there is less variation in the amount of water dissolved during washing. Moreover, since no crust is generated on the cut surface during cutting, the appearance of the product is improved and the commercial value can be increased.
[0015]
In the present invention, the amount of the “substance exhibiting the property of becoming a lubricant of the entire composition in the heated state during kneading” is 20 to 60% by weight as in the inventions of

claims

1 and 2. Preferably, it is 20 to 40% by weight. This is because if it is less than 20 % by weight, molding workability may be impaired, while if it exceeds 60% by weight, the cleaning effect of the cleaning agent may be adversely affected.
[0016]
In the present invention, the “step of extruding while kneading using a kneading means under reduced pressure” includes the first cylinder having kneading and extruding means and the second cylinder having extruding means as described in claim 4. Are connected in a chamber under reduced pressure, and the toilet cleaning composition is moved in the order of the first cylinder, the chamber, and the second cylinder, and led to the mold. Preferably it is.
[0017]
Here, “the state in which the first cylinder and the second cylinder are connected and connected by the chamber” means that the first cylinder and the chamber, and the chamber and the second cylinder are mutually connected. , Means connected in a vented state. When formed in this way, the first cylinder is in a reduced pressure state, and the toilet cleaner composition is kneaded while being degassed and passes through the chamber under reduced pressure. The air in the composition is degassed and the binding force of the component is further increased.
[0018]
In this case, it is preferable to provide a partition wall having a lattice-like hole between the first cylinder and the chamber. This is because the internal pressure is applied to the first cylinder due to the resistance when the kneaded material passes through the partition wall and the kneaded material can be well kneaded and the reduced pressure state of the chamber can be easily maintained. Further, since the kneaded material of the first cylinder is separated into a rod shape and enters the chamber, the surface area is increased, and the air in the kneaded material is more easily released. In this case, it is preferable to place the first cylinder on the upper stage and the second cylinder on the lower stage so that the chamber is positioned between them. The kneaded material of the upper first cylinder becomes a rod shape and moves from the top to the bottom of the second cylinder, that is, the chamber, so that the rod shape can be easily maintained, deaeration and molding. This is because the ease of work can be secured.
[0019]
In the present invention, the degree of decompression under reduced pressure is preferably 560 to 0.01 mmHg, as in the fifth aspect of the present invention. More preferably, it is 380-0.01 mmHg. This is because the composition is sufficiently degassed to sufficiently increase the binding force of the constituents and to ensure the sufficient shape retention of the molded product.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, although the embodiment of the present invention will be described based on the drawings using the toilet cleaner composition shown below, the present invention is not limited to the method shown in this embodiment. 1 is a longitudinal sectional view in the length direction of a molding machine capable of performing the molding process used in the present invention, and FIG. 2 is a longitudinal sectional view taken along a line AA in FIG.
[0021]
One preferable embodiment of the method for forming a solid detergent for toilets according to the present invention is at least 20 to 50% by weight of the water-soluble inorganic filler as a solid builder , and coconut oil fatty acid salt as the anionic surfactant. 10 to 30 wt%, the polyethylene glycol及beauty liquid body lavatory cleanser composition comprising 2 0-30 wt% of the perfume, using a molding machine shown in FIG. 1, after turning the inlet 5, kneaded and extruded In a state where the first cylinder-1 having the means and the second cylinder-2 having the pushing means are communicated and coupled with each other in the chamber-3 decompressed to 380 to 0.01 mmHg, the first cylinder-1 and then the chamber- 3. A method is adopted in which the second cylinder-2 is moved in the order of kneading in the heated state while being kneaded and guided to the mold 4 and extruded. In this case, it is preferable that the temperature of a heating state shall be 30-60 degreeC. In addition to the case of using frictional heat at the time of kneading, the heating may be used in combination with a known heating means from the outside. As a known heating means, a method of circulating hot water or hot oil in the first cylinder or the like with a jacket structure can be exemplified.
[0022]
If it forms in this way, it will be kneaded while being deaerated in the first cylinder-1 and will move to the second cylinder-2 while the air in the kneaded material is further removed in the chamber-3 so that it will also be deaerated here. Since the kneaded material becomes dense and the nonionic surfactant or the like functions as a lubricant, the kneaded material moves smoothly in the molding machine. As a result, the bonding force between the constituents becomes strong, and a molded article having good shape retention without brittleness, cracking, and crusting can be obtained efficiently. Further, since the hardness of the molded product is improved, it is possible to cope with a prescription when a molded product that is too soft is obtained by using a conventional method, the range of the prescription design is widened, and the production efficiency can be improved.
[0023]
In this case, a partition wall (not shown) in which a large number of lattice-shaped holes are formed is provided between the first cylinder-1 and the chamber-3, and the first cylinder-1 is in the upper stage. Preferably, the second cylinder-2 is placed on the lower stage, and the chamber-3 is positioned between them. Since the kneaded material of the first cylinder-1 is separated into a plurality of rods and enters the lower chamber-3 and further the second cylinder-2 below, the rod-like shape is easily maintained and the surface area is increased. For this reason, the degassing and forming operations of the kneaded product are easily performed.
[0024]
For the toilet detergent composition according to the embodiment of the present invention, depending on purpose, it is of course may be blended with other compounding agents such as the coloring agent.
[0025]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely using an Example, this invention is not limited to these Examples.
[0026]
Reference Example 1 First, a toilet cleaning composition (unit of blending amount is% by weight) shown in Reference Example 1 of Table 1 is prepared. This composition contains 20% by weight of coconut oil mixed fatty acid salt (Daiichi Kogyo Seiyaku Co., Ltd.) as an anionic surfactant, and polyethylene glycol 6000 (Daiichi Kogyo Seiyaku Co., Ltd. PEG6000P) as a nonionic surfactant. ), 10% by weight of anhydrous sulfate as a builder (neutral anhydrous sodium sulfate manufactured by Shikoku Kasei Kogyo Co., Ltd.), and carboxymethyl cellulose salt as a dissolution regulator (cellogen produced by Daiichi Kogyo Seiyaku Co., Ltd.). ) And 10% by weight of Blue No. 1 (manufactured by Mikuni Sumitomo Chemical Co., Ltd.) as a colorant.
[0027]
Next, this composition is mixed with a first cylinder-1 having a biaxial kneading and extruding means in which a paddle 1a and a feed screw 1b are disposed on two shafts 8, and an exhaust pipe from a vacuum pump 7. , A chamber-3 having a plurality of lattice-shaped partition walls (not shown) between the first cylinder-1, a second cylinder-2 in which a screw 2a is disposed, and a mold 1 was connected in this order, and kneaded, extruded and molded under a reduced pressure of 380 to 0.01 mmHg. The degassing by the vacuum pump 7 is performed when the raw material is charged from the raw material charging port 5 and the molded product 6 is pushed out from the mold 4, that is, when the inlet and outlet of the molding machine are closed and the molding operation is started. Just do it. In this case, the temperature of the composition at the time of kneading under reduced pressure was about 45 ° C. The following physical properties of this molded product 6 were evaluated, and the results are shown in Table 2.
[0028]
( Reference Examples 2 and 3 and Examples 1 to 4 ) The compositions formulated as Reference Examples 2 and 3 and Tables 1 to 4 in Table 1 were extruded under reduced pressure in the same manner as in Reference Example 1 . . In this case, the temperature of each composition at the time of kneading was about 45 ° C. The following physical properties of each molded product were evaluated, and the results are shown in Table 2.
[0029]
(Comparative Examples 1 to 7) The compositions blended as in Comparative Examples 1 to 7 in Table 1 were molded in the same manner as Reference Example 1 except that the compositions were carried out at normal pressure without reducing the pressure. In this case, the temperature of each composition at the time of kneading was about 45 ° C. The following physical properties of each molded product were evaluated, and the results are shown in Table 2.
[0030]
(Physical property test method) About "brittleness"; it evaluated by the following "load at the time of bending". A cylindrical extruded product having a length of 30 mm and a diameter of 6 mm is placed in the groove of a sample holder (having a groove having a width of 10 mm and a depth of 4 mm) of a rheometer (model CR-300 manufactured by Sun Science Co., Ltd.). Next, the needle-insertion elastic adapter (5 mm diameter rod) is applied to the center of the sample in the part of the groove, and then the sample holder is moved at a constant speed (60 mm / min). ) To obtain the load (g) when the sample was broken.
[0031]
About "hardness"; it evaluated by the "load at the time of stab" shown below. A cylindrical extrudate having a length of 25 mm and a diameter of 30 mm was attached to a sample holder of a rheometer (model CR-300 manufactured by Sun Science Co., Ltd.) so that the circular cross-section is the top and bottom surfaces, and then the sample The tip of a penetration adapter (a rod with a diameter of 3 mm, the tip of which has a conical shape with a height of 5 mm is pointed) is applied to the center of the upper surface of the plate, and the sample holder is placed at a constant speed (60 mm / Min) until the tip of the adapter reaches a certain depth (6 mm), and the load at that time was determined as (g).
[0032]
About “Sasakure”: The following “cutting test” was performed, and the degree of the sausage was visually evaluated. Using a cutter-knife (HA-2A manufactured by KOKUYO Co., Ltd.), a rod-like extruded product having a diameter of 20 mm was visually observed for the state of the cut end.
○: Sasakure is not recognized or hardly recognized.
X: Sasakure is clearly recognized at the bottom of the cut.
[0033]
“Density (g / cm ³ )”: The volume and weight of a cylindrical extruded product having a length of 100 mm and a diameter of 20 mm were measured and calculated.
[0034]
Regarding “uniform solubility”; in the test of one sample (for example, the sample of Example 1), each of the hand-washed portions of two rotor tanks (S721B manufactured by TOTO Corporation) Install a total of 2 containers of 25g each (shell type made by Kobayashi Pharmaceutical Co., Ltd.), adjust the water flow so that it fills up in 60 seconds for one flash, and once a hour Flushed 24 times a day at a rate, this was repeated 148 times for 7 days. Absorbance (630 nm) of accumulated water was measured for each of the two extruded products with a spectrophotometer, and the uniform solubility of one sample was evaluated based on the variation width.
[0035]
[Table 1]

[0036]
[Table 2]

[0037]
As shown in Table 1, the types and proportions of the compositions of Examples 1 to 4 and Comparative Examples 4 to 7, Reference Examples 1 to 3 and Comparative Examples 1 to 3 are the same, and the difference between the two is The examples and reference examples are kneaded, extruded and molded under a reduced pressure of 380 to 0.01 mmHg, whereas the comparative examples are not reduced in pressure. In Table 1, the “substance exhibiting the property of becoming a lubricant of the entire composition in the heated state during kneading” is polyethylene glycol 6000 and a fragrance mixture. Without these blends, the friction in the molding machine tends to increase particularly under reduced pressure, and the molding operation does not proceed smoothly, such as the occurrence of clogging.
[0038]
As shown in Table 2, when Examples , Reference Examples and Comparative Examples having the same composition are compared, the Examples and Reference Examples are improved in folding strength twice as much as the Comparative Examples, and the density and hardness are also higher than those of the Comparative Examples. In addition, the cut surface of the comparative example has a crust, whereas that of the examples and reference examples does not generate a crust. This is because, in the kneading and extrusion molding, the air in the composition is degassed under reduced pressure in the examples and reference examples , so that the density of the composition is increased and the binding force of the composition component is increased. Conceivable. Therefore, there is no problem that a part of the molded product is missing during transportation or use, or a problem that damages the appearance of the product.
[0039]
Furthermore, when these molded products are actually used for toilets, and compared with the uniform solubility in water, as shown in Table 2, the examples have a smaller variation in absorbance than the comparative examples. Apart from Reference Example 2 and Comparative Example 2 where the absorbance is zero because no colorant is blended, Examples 1 to 4 have a variation that is less than half that of the Comparative Example. This shows that the amount of the drug dissolved in each flash is uniform in the examples, and the merit in use is great.
[0040]
【The invention's effect】
As described above, according to the first and second aspects of the present invention, the pressure is reduced during each of the kneading and extruding steps, so that the contact state of the composition becomes dense and the mutual bonding strength is increased. The molded product has high shape-retaining properties, and there are no problems such as cracks, breaks in the post-extrusion process after extrusion molding, and brittleness and cracks that are partially lost during transportation and use, and there is no crusting at the time of cutting and the hardness is high. A toilet solid detergent that is high and has little variation in the amount of water dissolved during washing can be obtained. In addition, according to the first and second aspects of the present invention, since the blending amount of the lubricant is preferable, the molding workability is not impaired and the cleaning effect of the cleaning agent is not adversely affected.
[0041]
According to the invention described in claim 3, since the toilet cleaning composition kneaded under reduced pressure in the first cylinder passes through the chamber under reduced pressure, the air in the composition is more sufficiently degassed. According to the invention described in claim 4, the degree of decompression is preferable for sufficiently degassing the composition , and the effects of

claims

1 and 2 are improved.
[Brief description of the drawings]
FIG. 1 is a longitudinal sectional view in the length direction of a molding machine capable of carrying out one molding process used in the present invention.
FIG. 2 is a longitudinal sectional view taken along a line AA in FIG.
[Explanation of symbols]
1 ... 1st cylinder
1a ... Paddle 1b ... Feed screw
2 ... Second cylinder
2a ... Screw
3 ... Chamber
4 ... Mold 5 ... Raw material inlet 6 ... Solid detergent molding for toilet 7 ... Vacuum pump 8 ... Shaft

Claims

Coconut oil mixed fatty acid salt as a surfactant, polyethylene glycol, carboxymethyl cellulose salts and flavors as dissolution modifiers, consists other formulations, Chi thereof cormorants, and the lubricant of the total composition in a heated state during mixing kneading Through a step of extruding a toilet cleaner composition containing 20 to 60% by weight of “total amount of polyethylene glycol and fragrance” as a substance exhibiting the following properties while being kneaded using a kneading means under reduced pressure, A method for forming a solid cleaning agent for toilets, comprising molding.

Solid Builder -, coconut oil mixed fatty acid salt as a surfactant, polyethylene glycol, carboxymethyl cellulose salts and flavors as dissolution modifiers, consists other formulations, Chi its earthenware pots, the whole composition in a heated state during mixing kneading A toilet cleaner composition containing 20 to 60% by weight of “total amount of polyethylene glycol and fragrance” as a substance exhibiting the properties of a lubricant is extruded while being kneaded using a kneading means under reduced pressure. A method for forming a solid cleaning agent for toilets, which is formed through a process.

The step of extruding while kneading using the kneading means under the reduced pressure is such that the first cylinder having the kneading / extrusion means and the second cylinder having the extrusion means are communicated and connected in a chamber under reduced pressure. the toilet cleaner composition for the first cylinder -, chamber - a second cylinder - for toilet according to claim 1 or 2, characterized in that it is composed of steps leading to a mold is moved sequentially Molding method of solid detergent.

The method for forming a solid cleaning agent for toilets according to claim 1, 2 or 3, wherein the reduced pressure under reduced pressure is 560 to 0.01 mmHg.