JP3547240B2 - Granular detergent in container and method for sprinkling granular detergent in container - Google Patents

Description

【００３９】
上記一般式（１）中、Ｘ_１ はメチル、ＨまたはＣＯＯＸ_３ を、Ｘ_２ はメチル、ＨまたはＯＨを、Ｘ_３ はＨ、アルカリ金属、アルカリ土類金属、ＮＨ_４ またはエタノールアミンを示す。
【００４０】
上記一般式（１）において、アルカリ金属としては、Ｎａ，Ｋ，Ｌｉ等が挙げられ、アルカリ土類金属としては、Ｃａ，Ｍｇ等が挙げられる。
【００４１】
その重合体あるいは共重合体は、例えばアクリル酸、（無水）マレイン酸、メタクリル酸、α−ヒドロキシアクリル酸、クロトン酸、イソクロトン酸、およびその塩等の重合反応、または各モノマーの共重合反応、あるいは他の重合性モノマーとの共重合反応によって合成されるものである。このとき共重合に用いられる他の共重合モノマーの例としては、例えばアコニット酸、イタコン酸、シトラコン酸、フマル酸、ビニルホスホン酸、スルホン化マレイン酸、ジイソブチレン、スチレン、メチルビニルエーテル、エチレン、プロピレン、イソブチレン、ペンテン、ブタジエン、イソプレン、酢酸ビニル（及び共重合後に加水分解した場合はビニルアルコール）、アクリル酸エステル等が挙げられるが、特に限定されるものではない。なお、重合反応は特に限定されることなく、通常公知の方法を用いることができる。
また、特開昭５４‐５２１９６号公報記載のポリグリオキシル酸等のポリアセタールカルボン酸重合体を用いることもできる。
【００４２】
上記の重合体、共重合体としては、重量平均分子量が８００〜１００万のものが用いられ、好ましくは、５０００〜２０万のものが用いられる。重量平均分子量が８００未満であると重合体特有の効果による洗浄性能が得られず、１００万を越えると逆に重合体の影響により再汚染が起こり洗浄性能が妨げられる。
【００４３】
また、共重合させる場合の一般式（１）の繰り返し単位と他の共重合モノマーとの共重合率も特に限定されないが、好ましくは一般式（１）の繰り返し単位／他の共重合モノマー＝１／１００〜９０／１０の範囲の共重合比率である。
【００４４】
また、金属イオン封鎖剤として、下記式（２）で示されるイオン交換容量が２００ＣａＣＯ_３ ｍｇ／ｇ以上のアルミノケイ酸塩を含有してもよい。
ｘ”（Ｍ_２ Ｏ）・Ａｌ_２ Ｏ_３ ・ｙ”（ＳｉＯ_２ ）・ｗ”（Ｈ_２ Ｏ） （２）
（式中、Ｍはナトリウム、カリウム等のアルカリ金属、ｘ”，ｙ”，ｗ”は各成分のモル数を表し、一般的には０．７≦ｘ”≦１．５、０．８≦ｙ”≦６、ｗ”は任意の定数である。）
【００４５】
上記のアルミノケイ酸塩としては、結晶性のものと非晶質のものが例示されるが、結晶性のものとしては、特に次の一般式で示されるものが好ましい。
Ｎａ_２ Ｏ・Ａｌ_２ Ｏ_３ ・ｙＳｉＯ_２ ・ｗＨ_２ Ｏ
（式中、ｙは１．８〜３．０、ｗは１〜６の数を表す。）
結晶性アルミノケイ酸塩（ゼオライト）としては、Ａ型、Ｘ型、Ｐ型ゼオライトに代表される平均一次粒子径０．１〜１０μｍの合成ゼオライトが好適に使用される。ゼオライトは粉末及び／又はゼオライトスラリー又はスラリーを乾燥して得られるゼオライト凝集乾燥粒子として用いてもよい。
【００４６】
上記の結晶性アルミノケイ酸塩は、常法により製造することができる。例えば、特開昭５０‐１２３８１号公報及び特開昭５１‐１２８０５号公報に記載の方法を用いることができる。
【００４７】
一方、上記の結晶性アルミノケイ酸塩と同様の一般式で示される非晶質アルミノケイ酸塩は、常法により製造することができる。例えば、ＳｉＯ_２ とＭ_２ Ｏ（Ｍはアルカリ金属を意味する）のモル比がＳｉＯ_２ ／Ｍ_２ Ｏ＝１．０〜４．０であり、Ｈ_２ ＯとＭ_２ Ｏのモル比がＨ_２ Ｏ／Ｍ_２ Ｏ＝１２〜２００であるケイ酸アルカリ金属塩水溶液を用いて、これにＭ_２ ＯとＡｌ_２ Ｏ_３ のモル比がＭ_２ Ｏ／Ａｌ_２ Ｏ_３ ＝１．０〜２．０であり、Ｈ_２ ＯとＭ_２ Ｏのモル比がＨ_２ Ｏ／Ｍ_２ Ｏ＝６．０〜５００である低アルカリアルミン酸アルカリ金属塩水溶液を通常１５〜６０℃、好ましくは３０〜５０℃の温度のもとで強攪拌下に添加する。
【００４８】
次いで、生成した白色沈澱物スラリーを通常７０〜１００℃、好ましくは９０〜１００℃の温度で、通常１０分以上１０時間以下、好ましくは５時間以下加熱処理し、その後濾過、洗浄、乾燥する事により有利に得る事ができる。このとき添加方法は、低アルカリアルミン酸アルカリ金属塩水溶液にケイ酸アルカリ金属塩水溶液を添加する方法であってもよい。
【００４９】
金属イオン封鎖剤の含有量は、全組成物中、１０〜９０重量％であり、中でも上記の重合体あるいは共重合体は、全組成物中に２〜５０重量％、好ましくは５〜３０重量％配合される。２重量％未満であると充分な洗浄性能の向上が図られず、５０重量％を越えると添加効果は飽和し、いたずらにコストを上げるだけで意味がないものとなる。
【００５０】
本発明の粒状洗剤の組成物としては、上記成分の他、洗浄剤ビルダー、例えば、アミノトリ（メチレンホスホン酸）、１−ヒドロキシエチリデン−１，１−ジホスホン酸、エチレンジアミンテトラ（メチレンホスホン酸）、ジエチレントリアミンペンタ（メチレンホスホン酸）、及びそれらの塩、２−ホスホノブタン−１，２−ジカルボン酸等のホスホノカルボン酸の塩、アスパラギン酸、グルタミン酸等のアミノ酸の塩、ニトリロ三酢酸塩、エチレンジアミン四酢酸塩等のアミノポリ酢酸塩、ポリエチレングリコール、ポリビニルアルコール、ポリビニルピロリドン等の非解離高分子、ジグリコール酸塩、クエン酸塩、オキシカルボン酸塩等の有機酸の塩等のビルダー、カルボキシメチルセルロースといった一般的に洗浄剤に配合することが知られているキレート剤や色あせ防止剤、再汚染防止剤などが挙げられる。
【００５１】
その他に本発明の粒状洗剤の組成物としては、以下の様な成分も含有する事ができる。即ち、プロテアーゼ、リパーゼ、セルラーゼ、アミラーゼ等の酵素、炭素数１〜４程度の低級アルキルベンゼンスルホン酸塩、スルホコハク酸塩、タルク、カルシウムシリケート等のケーキング防止剤、第３ブチルヒドロキシトルエン、ジスチレン化クレゾール等の酸化防止剤、過炭酸ナトリウムなどの漂白剤又はテトラアセチルエチレンジアミン等の漂白活性化剤、蛍光染料、青味付剤、香料等を含むことができるが、これらについては特に限定されず、目的に応じた配合がなされてよい。
【００５２】
洗剤の一回使用量を少なくするためには、結晶性のケイ酸塩を使用することが好ましく少量で優れた洗浄力を得ることができる。
結晶性ケイ酸塩としては、０．２重量％分散液において１０．６以上のｐＨを示し、優れたアルカリ能を示す。また、アルカリ緩衝効果についても特に優れており、炭酸ソーダや炭酸カリウムと比較してもアルカリ緩衝効果が優れるという性質を示すものであり、ＳｉＯ２ ／Ｍ２ Ｏ＝０．９〜２．６（Ｍ：アルカリ金属）のものを使用することによって可能となる。このような結晶性ケイ酸塩のうち特開平５‐１８４９４６号公報および特開昭６０‐７４５９５号公報に記載されているものを使用することができ、具体的な組成としては次の組成を有するものが例示される。
▲１▼ ｘＭ_２ Ｏ・ｙＳｉＯ_２ ・ｚＭｅ_ｍ Ｏ_ｎ ・ｗＨ_２ Ｏ （３）
（式中、Ｍは周期律表のＩａ族元素、ＭｅはＩＩａ、ＩＩｂ、 ＩＩＩａ、ＩＶａもしくはＶＩＩＩ族元素から選ばれる１種または２種以上の組合せを示し、ｙ／ｘ＝０．５〜２．６、ｚ／ｘ＝０．０１〜１．０、ｎ／ｍ＝０．５〜２．０、ｗ＝０〜２０である。）
▲２▼ Ｍ_２ Ｏ・ｘ’ＳｉＯ_２ ・ｙ’Ｈ_２ Ｏ （４）
（式中、Ｍはアルカリ金属を表し、ｘ’＝１．５〜２．６、ｙ’＝０〜２０である。）
【００５３】
まず、上記▲１▼の組成の結晶性アルカリ金属ケイ酸塩について説明する。
一般式（３）において、Ｍは周期律表のＩａ族元素から選ばれ、Ｉａ族元素としてはＮａ、Ｋ等が挙げられる。これらは単独であるいは例えばＮａ_２ ＯとＫ_２ Ｏとが混合してＭ_２ Ｏ成分を構成していてもよい。
Ｍｅは周期律表のＩＩａ，ＩＩｂ，ＩＩＩａ，ＩＶａまたはＶＩＩＩ族元素から選ばれ、例えばＭｇ、Ｃａ、Ｚｎ、Ｙ、Ｔｉ、Ｚｒ、Ｆｅ等が挙げられる。これらは特に限定されるものではないが、資源及び安全上の点から好ましくはＭｇ、Ｃａである。また、これらは単独であるいは２種以上混合していてもよく、例えばＭｇＯ、ＣａＯなどが混合してＭｅ_ｍ Ｏ_ｎ 成分を構成していてもよい。
また、本発明における結晶性アルカリ金属ケイ酸塩においては、水和物であってもよく、この場合の水和量はｗ＝０〜２０の範囲である。
【００５４】
また、一般式においてｙ／ｘが０．５〜２．６であり、好ましくは１．５〜２．２である。ｙ／ｘが０．５未満では耐水溶性が不十分であり、ケーキング性、溶解性、粒状洗剤の粉末物性に著しく悪影響を及ぼす。ｙ／ｘが２．６を越えると、アルカリ能が低くなりアルカリ剤として不十分となり、かつイオン交換能も低くなり、イオン交換体としても不十分である。ｚ／ｘは０．０１〜１．０であり、好ましくは０．０２〜０．９である。ｚ／ｘが０．０１未満では耐水溶性が不十分であり、１．０を越えるとイオン交換能が低くなり、イオン交換体として不十分である。ｘ，ｙ，ｚは前記のｙ／ｘおよびｚ／ｘに示されるような関係であれば、特に限定されるものではない。なお、前記のようにｘＭ_２ Ｏが例えばｘ’Ｎａ_２ Ｏ・ｘ”Ｋ_２ Ｏとなる場合は、ｘはｘ’＋ｘ”となる。このような関係は、ｚＭｅ_ｍ Ｏ_ｎ 成分が２種以上のものからなる場合におけるｚにおいても同様である。また、ｎ／ｍ＝０．５〜２．０は、当該元素に配位する酸素イオン数を示し、実質的には０．５、１．０、１．５、２．０の値から選ばれる。
【００５５】
本発明の粒状洗剤における結晶性アルカリ金属ケイ酸塩は、前記の一般式に示されるようにＭ_２ Ｏ、ＳｉＯ_２ 、Ｍｅ_ｍ Ｏ_ｎ の三成分よりなっている。したがって、本発明の粒状洗剤における結晶性アルカリ金属ケイ酸塩を製造するには、その原料として各成分が必要になるが、本発明の粒状洗剤においては特に限定されることなく、公知の化合物が適宜用いられる。例えば、Ｍ_２ Ｏ成分、Ｍｅ_ｍ Ｏ_ｎ 成分としては、各々の当該元素の単独あるいは複合の酸化物、水酸化物、塩類、当該元素含有鉱物が用いられる。具体的には例えば、Ｍ_２ Ｏ成分の原料としては、ＮａＯＨ、ＫＯＨ、Ｎａ_２ ＣＯ_３ 、Ｋ_２ ＣＯ_３ 、Ｎａ_２ ＳＯ_４ 等が、Ｍｅ_ｍ Ｏ_ｎ 成分の原料としては、ＣａＣＯ_３ 、ＭｇＣＯ_３ 、Ｃａ（ＯＨ）_２ 、Ｍｇ（ＯＨ）_２ 、ＭｇＯ、ＺｒＯ_２ 、ドロマイト等が挙げられる。ＳｉＯ_２ 成分としてはケイ石、カオリン、タルク、溶融シリカ、ケイ酸ソーダ等が用いられる。
【００５６】
本発明の粒状洗剤における結晶性アルカリ金属ケイ酸塩の調製方法は、目的とする結晶性アルカリ金属ケイ酸塩のｘ，ｙ，ｚの値となるように所定の量比で上記の原料成分を混合し、通常３００〜１５００℃、好ましくは５００〜１０００℃、さらに好ましくは６００〜９００℃の範囲で焼成して結晶化させる方法が例示される。この場合、加熱温度が３００℃未満では結晶化が不十分で耐水溶性に劣り、１５００℃を越えると粗大粒子化しイオン交換能が低下する。加熱時間は通常０．１〜２４時間である。このような焼成は通常、電気炉、ガス炉等の加熱炉で行う事ができる。
【００５７】
なお、本発明の粒状洗剤における結晶性アルカリ金属ケイ酸塩は、アルカリ能だけでなくイオン交換能も示し、少なくとも１００ＣａＣＯ_３ ｍｇ／ｇ以上、好ましくは２００〜６００ＣａＣＯ_３ ｍｇ／ｇを有している。
【００５８】
本発明の高密度粒状洗剤の製造方法は特に限定されることなく、従来より公知の方法を用いることができる。例えば、特開昭６１‐６９８９７号公報、特開昭６１‐６９８９９号公報、特開昭６１‐６９９００号公報、特開平５‐２０９２００号公報に記載の方法を使用することができる。
【００５９】
次に、図面を参照して本発明の粒状洗剤を充填する容器の実施形態を説明する。
【００６０】
図１、図２に示す粒状洗剤充填用のボトル状容器１は、高分子ポリマーからブロー成形された弾性変形可能な容器本体２と、この容器本体２の上部に取り付けられる定量用栓体３とを備える。
【００６１】
その容器本体２は、底壁１１と、この底壁１１の周囲から上方に伸びる周壁１２と、図３に示すように、この周壁１２の上端開口１２Ａを囲む頸部１３とを有し、粒状洗剤が全容積に対し体積率で例えば５０〜９０％充填される。
【００６２】
その周壁１２は、相対向する左右側壁部１２ａ、１２ｂ（図２において上下方向を左右方向とする）と、相対向する前後側壁部（図２において左右方向を前後方向とする）１２ｃ、１２ｄと、左右側壁部１２ａ、１２ｂと前側壁部１２ｃとの間の上下方向に沿う連結部１２ｅ、１２ｆと、左右側壁部１２ａ、１２ｂと後側壁部１２ｄとの間の上下方向に沿う連結部１２ｇ、１２ｈとを有し、上記栓体３に設けられた振出口２７の下方の洗剤充填空間を囲む。
【００６３】
その後側壁部１２ｄの上部は前方に向かい傾斜し、これにより、上記開口１２Ａは前方側に偏って配置されている。
【００６４】
図４において、前後側壁部１２ｃ、１２ｄの厚さｔ１、ｔ２と、左右側壁部１２ａ、１２ｂと前側壁部１２ｃとの間の連結部１２ｅ、１２ｆの厚さｔ３、ｔ４とは、左右側壁部１２ａ、１２ｂにおける後述の把持部１５ａ、１５ｂの厚さｔ７、ｔ８よりも薄くされている。
また、左右側壁部１２ａ、１２ｂと前側壁部１２ｃとの間の連結部１２ｅ、１２ｆの厚さｔ３、ｔ４は、前側壁部１２ｃの厚さｔ１よりも薄くされている。
【００６５】
図２に示すように、その左右側壁部１２ａ、１２ｂの間隔Ｗは８０ｍｍ以下とされる。また、図１、図４示すように、左右側壁部１２ａ、１２ｂは周囲部分よりも容器内側に凹んだ部分を有し、この凹んだ部分が把持部１５ａ、１５ｂとされる。その把持部１５ａ、１５ｂの厚さｔ７、ｔ８は、その周壁１２における他の部分の壁厚、すなわち、左右側壁部１２ａ、１２ｂにおける把持部１５ａ、１５ｂの周囲部分の厚さ、前後側壁部１２ｃ、１２ｄの厚さｔ１、ｔ２、及び連結部１２ｅ、１２ｆ、１２ｇ、１２ｈの厚さｔ３、ｔ４、ｔ５、ｔ６よりも厚くされている。
【００６６】
その把持部１５ａ、１５ｂを把持することで、容器本体２内で緊密充填により一時的に固化した粒状洗剤を崩すことができるように、その周壁１２は弾性変形可能とされている。その把持部１５ａ、１５ｂを直径２．１５ｍｍの円形面を介して１．０ｋｇｆの力で加圧した場合、その周壁１２は変形前と比較して洗剤充填空間において容器内側に１．０ｍｍ以上凹む部分を有する。
【００６７】
上記栓体３は、２０ｇ以下の粒状洗剤を計量可能な計量器として機能するもので、図３に示すように、上記頸部１３の外周にねじ合わされる外筒２１と、この外筒２１に一体化される内筒２２と、この内筒２２の下部に上下位置変更可能に嵌め合わされる有底の可動筒２３とを有する。その可動筒２３の内筒２２に対する上下動により、内筒２２の容積を変更することが可能とされている。
【００６８】
その内筒２２は上記開口１２Ａに嵌め合わされ、容器本体２内の粒状洗剤が開口１２Ａから流出するのを防止する。この内筒２２の周壁の上下間に、後ろ向きに開口する流入口２２ａが形成されている。
【００６９】
その内筒２２に仕切り２４が一体化されている。その仕切り２４は、上端が外筒２１の上端に至り、下端が上記流入口２２ａの下方であって内筒２２の下端の上方まで至ることで、栓体３の内部の上方側を、後方側の流入空間２５と前方側の排出空間２６とに仕切っている。その排出空間２６の上端が粒状洗剤の振出口２７とされ、この振出口２７を開閉する蓋２８が外筒２１に一体化されている。その排出空間２６の上方側２６ａが、振出口２７から下方に向かうに従い前方に向かうように、その仕切り２４と外筒２１の形状が設定されている。
【００７０】
上記栓体３によれば、図５に示すように容器本体２を左右方向回りに傾けると、容器本体２内の粒状洗剤Ｓが流入口２２ａから流入空間２５に流入する。その流入量は、計量しようとする量を超えるものとされる。次に、図３に示すように容器本体２の傾きを解除すると、計量しようとする量を超える粒状洗剤Ｓは流入口２２ａから排出され、残りの粒状洗剤Ｓが流入口２２ａより下方の内筒２２内に一定量保持される。次に、容器本体２を再び傾けると、その保持された粒状洗剤Ｓのうち排出空間２６に位置する粒状洗剤Ｓ、即ち所望の設定量の粒状洗剤Ｓが振出口２７から振り出され、同時に、容器本体２内の粒状洗剤Ｓが次の計量のために流入口２２ａから流入空間２５に流入する。また、その排出空間２６の上方側２６ａは振出口２７から下方に向かうに従い前方に向かうので、計量された粒状洗剤Ｓを完全に振り出すには、その排出空間２６の上方側２６ａが上下方向に沿うように、容器本体２の傾き量を充分に大きくする必要がある。これにより、容器本体２内の粒状洗剤Ｓの残量が少なくなった場合でも、容器本体２の傾き量を充分に大きくするので、次の計量のために粒状洗剤Ｓを流入口２２ａから流入空間２５に流入させることができる。
【００７１】
なお、本発明は上記実施形態に限定されない。例えば、計量器としては振り出し量を計量可能なものであれば特に限定されず、実開昭６２‐４５２４８号公報に開示されているように、バルブを開くことで計量された粒状物を振り出すものや、実開昭５８‐６５２８０号公報、実開昭６１‐４３１７６号公報、実開昭６２‐１０８２５６号公報、特開平３‐４５８５９号公報に開示されているように、振出口が容器の上面中央に設けられているものや、実開昭５５‐１６４１６７号公報、実開昭５５‐１７６１２１号公報、実開昭５８‐５３０８６号公報に開示されているように、振出口が容器の側面に形成されているものや、実開昭６０‐３２２８０号公報、実開昭６１‐５７７５号公報に開示されているように、計量部が容器の下部に設けられているものであってもよい。
【００７２】
以下、本発明の実施例を説明する。
【実施例１】
本実施例に使用した洗剤は、以下の方法で調整した。
【００７３】
＜調整例１（Ａ洗剤）＞
本実施例で用いている粒状洗剤Ａは以下の方法で調整した。
ポリオキシエチレンアルキルエーテル３重量部、結晶性アルミノ珪酸塩１１重量部、ＬＡＳ‐Ｎａ２３重量部、ＡＳ‐Ｎａ５重量部、石鹸３重量部、非結晶性珪酸塩１０重量部、ポリアクリル酸ナトリウム（平均分子量２００００）５重量部、炭酸ナトリウム１０重量部、炭酸カリウム３重量部、硫酸ナトリウム１．５重量部、ポリエチレングリコール１重量部、蛍光染料０．５重量部を含む含水率５０重量％のスラリーを調整し、それを噴霧乾燥することにより嵩密度０．３ｇ／ｃｍ^３ の粉末を得た。次に、これらの粉末と結晶性アルミノ珪酸塩４重量部、結晶性アルカリ金属珪酸塩２重量部、ポリオキシエチレンアルキルエーテル３重量部をハイスピードミキサー（攪拌転動造粒機、深江工業（株））に投入し、造粒した。更に、結晶性アルミノ珪酸塩５重量％を加えて造粒した後（表面被覆工程）、得られた粒子に結晶性アルミノ珪酸塩２重量部と酵素２重量部を乾式混合することにより、水分を６重量部含む粒状洗剤を得た（嵩密度０．７５ｇ／ｃｍ^３ 、平均粒径４６８μｍ）。
【００７４】
＜調整例２（Ｂ洗剤）＞
本実施例で用いている粒状洗剤Ｂは以下の方法で調整した。
結晶性アルミノ珪酸塩１５重量部、マレイン酸コポリマー５重量部、亜硫酸ナトリウム１重量部、硫酸ナトリウム５重量部、蛍光染料０．５重量部を含む含水率５０重量％のスラリーを調整し、噴霧乾燥することで、嵩密度０．５９ｇ／ｃｍ^３ の粉末を得た。次に、この粉末と非晶質アルミノ珪酸塩１９重量部、炭酸ナトリウム１９重量部をレディゲミキサー（攪拌転動造粒機、松坂技研（株）製）に投入し、攪拌を開始した。ジャケットには４０℃の温水を流した。そこに予めポリオキシエチレンアルキルエーテル２０重量部とパルミチン酸４重量部を７０℃で加熱混合した混合液を投入し、造粒を行った。更に結晶アルミノ珪酸塩７重量部を加えて造粒した後（表面被覆工程）、得られた粒子に結晶性アルミノ珪酸塩２重量部と酵素２重量部を乾式混合することにより、水分を１．７重量部含む粒状洗剤を得た（嵩密度０．８１ｇ／ｃｍ^３ 、平均粒径４２０μｍ）。
【００７５】
本実施例に用いた各成分を以下に詳述する。
・ＬＡＳ‐Ｎａ塩：直鎖アルキル（Ｃ_{１０−１３} ）ベンゼンスルホン酸ナトリウム。
・ＡＳ‐Ｎａ塩：アルキル硫酸ナトリウム（Ｃ_１２アルコール５０％及びＣ_１４アルコール５０％の混合アルコールの硫酸化物）。
・石鹸：牛脂（Ｃ_{１４−１８} ）脂肪酸ナトリウム。
・ノニオン：ポリオキシエチレンアルキルエーテル（ドバノール２３（三菱油化製）にエチレンオキサイドを平均８モル付加させたもの）。
・結晶性アルカリ金属珪酸塩：ＳＫＳ‐６（ヘキスト社製、平均粒径１２０μｍ，１２５μｍ以上４５％をハンマーミルで粉砕したもの（平均粒径５０μｍ））。
・非晶性珪酸塩：１号珪酸ナトリウム（東曹産業（株）製、固形分４４重量％）。
・結晶性アルミノ珪酸塩：４Ａ型ゼオライト、平均粒子径３μｍ（ゼオビルダー（株）製）。
・マレイン酸コポリマー：マレイン酸／アクリル酸＝３０／７０（モル比）、分子量６００００、中和度７０％のナトリウム塩。
・ポリエチレングリコール：平均分子量１００００。
・蛍光染料：チノパールＣＢＳ‐Ｘ（チバガイギ社製）とホワイテックスＳＡ（住友化学（株）製）を１／１の重量比で配合。
・酵素：セルラーゼＫ（特開昭６３‐２６４６９９号公報記載）０．５重量％、ＡＰＩ‐２１（昭和電工（株））重量１．０％、リポラーゼ１００Ｔ（ノボ社）０．５重量％。
【００７６】
本実施例に使用した容器は以下の条件に合うように形成した。
形態：図１に示した実施形態のボトル状容器（容量：約１０００ｍｌ）を使用した。
性状：φ２．１５ｃｍの円柱状圧縮子により、２０ｍｍ／ｍｉｎの圧縮条件で容器把握部の数カ所を加圧して測定したときに（圧縮測定機器として（株）島津製作所製ＡＵＴＯＧＲＡＰＨ ＡＧ‐５００Ｅ使用）、２．１ｍｍ〜３．０ｍｍの容器内側への凹みを生じる様にした。
素材：容器形成の素材にはＨＤＰＥを用いた。
厚さ：周壁に１ｍｍ以下となるような箇所が少なくとも１カ所存在するように、０．７ｍｍ〜３．０ｍｍに形成した。
【００７７】
上記容器に洗剤を８０体積％充填し、緊密充填のためにタッピング式密度填カサ密度測定器（筒井理化学機器株式会社製ＴＶＡ‐１形）を用いて３ｃｍの高さから３０回タッピングを行い、把持部を把持して静かに容器を傾動させて、容器内を観察してブロッキングの有無を判定した。なお、その容器の把持は、容器を変形させる意識を持つことなく行なう。
【００７８】
また、上記実施形態の定量栓体（設計計量値２０ｇ）をボトル状容器に装着し、同様のタッピングを行う。次いで、容器の上下を転倒することにより計量部に洗剤を充填した後、容器の計量部が上になるように再度転倒する。しかる後に、計量部のふたを開け、容器を傾動させながら洗剤の振り出しを行い、計量部が真下になるまでの初回の振り出し量を重量計で測定した。
【００７９】
【実施例２】
容器形成の素材にＰＰを用い、φ２．１５ｃｍの圧縮子により２０ｍｍ／ｍｉｎの圧縮条件で容器把握部の数カ所を測定したときに２．６ｍｍ〜３．０ｍｍの凹みを生じる様にし、周壁を厚さ０．９ｍｍ〜３．２ｍｍに形成した以外は、実施例１と同様の実験を行った。
【００８０】
【実施例３】
容器形成の素材に硬質ＰＶＣを用い、φ２．１５ｃｍの圧縮子により２０ｍｍ／ｍｉｎの圧縮条件で容器把握部の数カ所を測定したときに１．３ｍｍ〜１．８ｍｍの凹みを生じる様にし、周壁を厚さ０．８ｍｍ〜２．６ｍｍに形成した以外は、実施例１と同様の実験を行った。
【００８１】
【実施例４】
容器形成の素材にＰＥＴを用い、φ２．１５ｃｍの圧縮子により２０ｍｍ／ｍｉｎの圧縮条件で容器把握部の数カ所を測定したときに１．９ｍｍ〜２．８ｍｍの凹みを生じる様にし、周壁を厚さ０．６ｍｍ〜１．４ｍｍに形成した以外は、実施例１と同様の実験を行った。
【００８２】
【比較例１】
容器形成の素材に硬質ＰＶＣを用い、φ２．１５ｃｍの圧縮子により２０ｍｍ／ｍｉｎの圧縮条件で容器把握部の数カ所を測定したときに０．５ｍｍ〜０．９ｍｍの凹みを生じる様にし、周壁の厚さが１ｍｍ以下となる場所が存在しないように１．６ｍｍ〜４．０ｍｍに形成した以外は、実施例１と同様の実験を行った。
【００８３】
【比較例２】
容器形成の素材にガラスを用いた。ガラスは加工が難しいことから、図６に示すように、上記実施例１〜４及び比較例１とは異なる形態の容器１″を使用した。その形態は底面が９ｃｍ×９ｃｍ、高さが１３ｃｍの直方体の天面に、外直径４ｃｍ、高さ３ｃｍの開口部を有し、角部がＲ５ｍｍで面取りされたものである。他例と同じく、φ２．１５ｃｍの圧縮子により２０ｍｍ／ｍｉｎの圧縮条件で容器把握部の数カ所を測定したが凹みは生じなかった。容器条件以外は、実施例１と同様の実験を行った。なお、図６において上記実施形態と同一部分は同一符号で示す。
【００８４】
上記実施例１〜４および比較例１、２による実験結果を以下の表１に示す。
【００８５】
【表１】

【００８６】
上記表１より、実施例によれば容器内で高密度粒状洗剤がブロッキングした場合でも、洗剤を振り出すまでに容器を把持して変形させることでブロッキングを解消でき、また、粒状洗剤の計量を正確に行なえることを確認できる。また、周壁の把持部分において直径２．１５ｍｍの円形面を介して１．０ｋｇｆの力で加圧した場合に容器内側に１．０ｍｍ以上凹む部分を有し、容器の材質として高分子ポリマーを用いる場合に周壁の厚さが１ｍｍ以下となる箇所が存在することで、本発明の効果を容易に得られることを確認できる。
【００８７】
【比較例３】
図７に示した中空柄１００を把握部とする容器１′を用い、実施例１〜４と同様の実験を行なった結果、粒状洗剤のブロッキングの問題を解消することはできず、比較例２と同様な定量性を示した。なお、図７において上記実施形態と同様部分は同一符号で示す。
【００８８】
【発明の効果】
本発明によれば、輸送時の振動等により容器内の高密度粒状洗剤がブロッキングした場合でも、洗剤を振り出すまでに容器を把持して変形させることで、使用時に容易に振り出すことができ、計量器を用いて振り出し量の定量を正確に行なうことも可能になる。
【図面の簡単な説明】
【図１】本発明の実施形態の容器の側面図
【図２】本発明の実施形態の容器の平面図
【図３】本発明の実施形態の容器の部分断面図
【図４】図１の実施形態の容器のＩＶ‐ＩＶ線断面図
【図５】本発明の実施形態の容器の計量機能の説明用部分断面図
【図６】比較例２の容器の（１）は平面図、（２）は側面図、（３）は底面図
【図７】本発明の比較例３の容器の側面図
【符号の説明】
１ 容器
３ 栓体（計量器）
１２ 周壁
１２ａ、１２ｂ 左右側壁部
１２ｅ、１２ｆ 連結部
１５ａ、１５ｂ 把持部
２７ 振出口[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a high-density granular detergent filled in a shake-out type container.
[0002]
[Prior art]
The former granular detergent has a bulk density of 0.2 to 0.4 g / cm. ³ Because of its low density, the usual amount of use in Japan domestic conditions is 30 g of washing liquid, 40 g in weight and 100-200 cm in volume. ³ Met. Therefore, when the granular detergent for 60 to 100 uses is put in a paper box, the product is 2.5 to 4.5 kg in weight and 6000 to 20,000 cm in volume. ³ It was heavy and bulky. This not only increases the transportation cost from the factory, but also is inconvenient for the consumer in terms of carrying and placing.
[0003]
To solve the above problem, for example, the high-density granular detergents disclosed in JP-A-48-61511, JP-A-53-36508 and JP-A-58-132093 have a bulk density of 0. 5g / cm ³ And the volume thereof is reduced, so that it has been noted as a solution to the above problem.
[0004]
Further, in order to improve the solubility and dispersibility of the high-density granular detergent, the applicant of the present application discloses, for example, JP-A-62-167399, JP-A-5-271700, and JP-A-61-69897. As disclosed in JP-A-61-69899, JP-A-61-69900, JP-A-4-339988, and JP-A-5-209200, many techniques have been found, This has contributed to the practical use of detergents.
[0005]
A single use of the high-density granular detergent is 25 g in weight and about 35 cm in volume per 30 liters of washing liquid. ³ Therefore, when the granular detergent used for 50 to 60 times of use is filled in the container, the product is lighter and smaller than the conventional product, which is excellent in the benefit.
[0006]
Conventionally, as a container for filling the high-density granular detergent, the shape is the same as that of a conventional paper box, but it is more excellent in moisture resistance and strength than a paper box, and a carton-shaped one whose upper end opening is opened and closed by a top lid is used. I have. In addition, due to a decrease in the volume used at one time due to high density, weighing with a spoon is performed.
[0007]
Further, due to a decrease in the volume used at one time due to the densification, a high-density granular detergent in a container adopting a new measuring method has been proposed. For example, Japanese Patent Application Laid-Open No. 53-43710 proposes a method in which a high-density granular detergent filled in a transparent resin container is measured with a cap attached to the container. In addition, the applicant of the present application has proposed a high-density granular detergent in a container having a built-in measuring device capable of measuring the amount of spouting in Japanese Patent Application Laid-Open No. 61-57699.
[0008]
[Problems to be solved by the invention]
Due to the heavy weight of the high-density granular detergent, when it is actually filled into a container, the particles are closely packed close to each other due to vibrations during transportation and temporarily solidified (hereinafter referred to as "blocking"). ) Occurs.
[0009]
The blocking tends to occur when the particle size of the detergent is small or when the particle size distribution is wide. In addition, the decrease in the amount of inorganic substances such as sodium sulfate, which is one of the technologies for increasing the density, has resulted in an increase in the surfactant concentration in the particles, which is the main cause of the viscoelasticity of the particles themselves. , As one of the causes of blocking.
[0010]
With conventional high-density granular detergent in a container filled in a carton-shaped container and weighed by a spoon, even if such blocking occurs, the blocking is eliminated by breaking down the granular detergent solidified by the spoon at the time of weighing. There is no particular problem because it can be done.
[0011]
However, when a high-density granular detergent is filled in a spout-type container, if blocking occurs, the detergent is clogged in the spout. In particular, in a vertical bottle-shaped container having a relatively small outlet as described in Japanese Patent Application Laid-Open No. 61-57699, it is easy to cause a problem in the ejection, and furthermore, when a measuring instrument is built in the container. Causes blocking to reduce weighing accuracy.
[0012]
An object of the present invention is to provide a granular detergent in a container and a method of sprinkling the granular detergent in a container, which can solve the above problems.
[0013]
[Means for Solving the Problems]
The granular detergent in a container according to the present invention contains 10 to 50% by weight of a surfactant and has a bulk density of 0.6 g / cm. ³ As described above, the container is filled in a container having an average particle diameter of 250 to 1000 μm and having a vibrating port and a peripheral wall surrounding a detergent filling space below the vibrating port, and is tightly closed in the container by gripping the peripheral wall. The peripheral wall is characterized by being deformable so that the granular detergent temporarily solidified by filling can be broken.
[0014]
The present invention is based on the following findings.
The blocking of the granular detergent in the container is promoted to such an extent that the container is easily elastically deformed. This is considered to be because the granular detergent is not only compressed downward by its own weight, but also compressed from the lateral direction by the elasticity of the container itself, and is more tightly packed. For this reason, it has been considered that a swing-type container that is filled with a high-density granular detergent is preferably one that does not easily deform.
However, a comparison of the ease with which the high-density granular detergent was spun out of the container revealed that a container that was easily deformed could be easily spun out from a container that hardly deformed.
Further, the container in which the high-density granular detergent can be easily sprinkled is provided with a separate handle or a hollow handle as described in JP-A-53-43710 and JP-A-61-57699. Instead of holding the container, the peripheral wall surrounding the detergent filling space below the outlet was gripped.
On the other hand, blocking of high-density granular detergent is a phenomenon that, unlike caking, in which the viscosity of particles increases due to moisture absorption and solidifies, the detergent particles are temporarily solidified by tight packing based on the inherent viscoelasticity of the detergent particles. is there. Therefore, the granular detergent solidified by the blocking can recover the powder physical properties by breaking down.
From the above, by deformation of the container by gripping the peripheral wall, when it is possible to break down the granular detergent temporarily solidified by tight filling in the container, it has been found that it is possible to solve the problem caused by blocking in the spout type container, The present invention has been achieved.
[0015]
The deformation of the container due to the gripping of the peripheral wall may occur between immediately after the gripping and immediately before the detergent is sprinkled. In addition, the gripping part of the peripheral wall is not particularly limited, and may be any part that can be easily gripped when the outlet is set upward, but is usually located between the bottom surface and the top surface of the container.
[0016]
The reason why the surfactant concentration of the granular detergent of the present invention is 10 to 50% by weight is that if it exceeds 50% by weight, it is difficult to eliminate blocking, and if it is less than 10% by weight, a small amount is sufficient. This is because the cleaning power cannot be obtained. The surfactant concentration is preferably 20 to 40% by weight in order to enable good detergent spouting and obtain sufficient detergency with a small amount of use.
[0017]
As the surfactant, it is preferable to incorporate a polyoxyethylene alkyl ether type nonionic surfactant in an amount of 5% by weight or more from the viewpoint of improving the cleaning effect. Although the blocking is promoted by the addition of the polyoxyethylene alkyl ether, according to the present invention, there is no problem because the blocking can be eliminated.
[0018]
The average particle size of the granular detergent of the present invention is set to 250 to 1000 μm, because if it is less than 250 μm, it is difficult to eliminate blocking, and if the solubility at the time of washing is taken into consideration, it is preferably 1000 μm or less. . In order to make it possible to satisfactorily dispense the detergent and to improve the solubility, it is preferable that the average particle size is 300 to 900 μm. The particle size distribution of the detergent particles is preferably sharp in order to eliminate blocking, and in particular, particles having a particle size of 125 μm or less are preferably 8% by weight or less, and particles having a particle size of 1000 μm or more are preferably 10% by weight or less.
[0019]
The bulk density of the granular detergent of the present invention is 0.6 g / cm. ³ 0.7-1.2 g / cm ³ It is preferred that 0.6g / cm ³ In the following, the capacity for one operation increases, and the usability deteriorates.
[0020]
Examples of the material of the container include a high-molecular polymer and paper.
Examples of the high-molecular polymer include polyvinyl chloride (PVC), polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), and polystyrene (PS). Care must be taken because there is a possibility of damage due to impact such as dropping. In the present invention, it is preferable to use a material having excellent impact resistance, such as high-density polyethylene (HDPE) or polypropylene, in case the container is accidentally dropped at the time of shaking. In addition, a preferable transition temperature or elasticity may be obtained by using a method of lowering the transition temperature by adding a plasticizer.
Further, in order to reduce the influence of the light on the detergent components, titanium dioxide may be kneaded with the material of the container to improve the light-shielding properties of the container. For example, ultraviolet rays such as benzotriazole, benzophenone and cyanoacrylate may be used. A material obtained by kneading an absorbent into a material may be used. It is also conceivable to color the high-density granular detergent itself with a dye that does not transfer color to the fiber.
[0021]
When a high-molecular polymer is used as the material of the container, the peripheral wall surrounding the detergent-filled space preferably has a portion having a wall thickness of 1 mm or less, preferably 0.8 mm or less. The portion having a wall thickness of 1 mm or less does not necessarily need to be present in the grip portion. For example, when a peripheral wall is formed by a plurality of walls, the wall thickness of the connecting portion of the wall may be 1 mm or less. By having such a portion having a wall thickness of 1 mm or less, it is possible to easily obtain a container that is deformed by gripping so that the granular detergent temporarily solidified by close packing in the container can be broken. . The wall thickness is preferably 0.4 mm or more from the viewpoint of strength.
[0022]
The deformation of the peripheral wall due to the gripping is elastic, and it is preferable that the shape before the gripping can be restored by releasing the gripping. It is difficult to maintain a constant gripping force for gripping the peripheral wall from immediately after gripping until the detergent is sprinkled, and the weight acting on the gripped part changes based on the weight of the detergent by tilting the container for sprinkling. I do. Therefore, the amount of elastic deformation of the container changes between immediately after the holding and the time when the detergent is spouted, and the blocking of the granular detergent can be effectively eliminated as compared with the case where the amount of container deformation does not change elastically.
[0023]
The form of the container in the present invention is not particularly limited as long as it has a swing outlet and a peripheral wall surrounding the detergent filling space below the shake outlet, but even in the case of a container using the same material, the form is different. In such a case, there is a possibility that the film may not be easily deformed at the time of grasping, or may be easily damaged even if deformed. Therefore, in order to obtain a suitable container, selection of a material and a form is important.
Therefore, the peripheral wall has opposing side walls and a connecting portion between the side walls along the vertical direction, and at least one of the connecting portions has a wall thickness smaller than that of each side wall, The peripheral wall is preferably deformable so that the gripping of the wall can disintegrate the granular detergent temporarily solidified by tight packing in the container. As a result, a portion deformed by the grip of the peripheral wall is generated over a wide area in contact with the granular detergent.
Each of the opposing side walls has a recessed portion on the inner side of the container than the surrounding part, and the distance between the opposing side walls is preferably 80 mm or less, which is preferable for gripping.
Preferably, the peripheral wall has a portion that is recessed inward of the container from the surrounding portion, and the wall thickness of the recessed portion is preferably greater than the wall thickness of other portions of the peripheral wall. As a result, a portion that deforms when the concave portion is gripped occurs over a wide area in contact with the granular detergent.
Further, the height of the container is preferably longer than the maximum diameter of the bottom surface.
[0024]
When the gripping portion of the peripheral wall is pressed with a force of 1.0 kgf via a circular surface having a diameter of 2.15 mm, the peripheral wall preferably has a portion that is recessed by 1.0 mm or more inside the container as compared with before the deformation. . As a method of measuring the amount of dent, a container not filled with detergent is fixed on a flat surface, assuming grasping by a human palm, and a force of 1.0 kgf is applied vertically through a circular surface having a diameter of 2.15 mm. Measure the amount of depression when pressed. Thereby, by grasping the peripheral wall, the peripheral wall can be deformed without being conscious of deforming the peripheral wall, and the granular detergent temporarily solidified by tight filling in the container can be reliably broken to eliminate blocking. It is sufficient that at least one concave portion is provided. The dent amount is more preferably 1.5 to 5.0 mm. This is because if the dent amount exceeds 5.0 mm, the strength of the container decreases.
The amount of depression of the container can be quantified using, for example, a compression measurement device as described in the examples.
[0025]
The total volume of the container is 1500cm ³ It is preferred that: 1500cm in volume ³ If it exceeds the limit, it will be difficult for those with weakness to hold with one hand, and because of the shape of the container, it will not be possible to hold with sufficient force to deform the container, and it will not be possible to obtain the blocking eliminating effect. is there. More preferred volume is 200-1200cm ³ It is.
[0026]
It is preferable that the container has a built-in measuring device capable of measuring the amount of shakeout. According to the present invention, the blocking of the granular detergent can be eliminated, and the measuring accuracy of the granular detergent by the measuring device can be improved.
In this case, it is preferable that the weighed amount is 20 g or less. The volume of the product can be reduced as the amount of the weighed-out portion is smaller. More preferably, the weighed amount is 5 to 20 g in weight and 5 to 35 cm in volume. ³ It is. The reason for determining the lower limit of the weighed amount to be weighed is that the weighing error at the time of weighing becomes large.
[0027]
It is preferable that the surface of the granular detergent is coated with a water-insoluble inorganic powder. This is because the coating not only can relatively suppress the blocking property of the detergent but also can prevent caking of the granular detergent due to moisture absorption. Examples of the inorganic substance include talc, a viscous substance, an aluminosilicate (crystalline or amorphous) such as calcium carbonate, silica and zeolite, and an aluminosilicate such as zeolite is particularly preferable.
[0028]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, an embodiment of the granular detergent in a container of the present invention will be described.
[0029]
First, conventionally known components can be blended as the components blended in the high-density granular detergent in the present invention.
[0030]
That is, as the surfactant, those generally used in detergents can be used without particular limitation. Specifically, it is at least one selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants exemplified below. For example, the same type may be selected only from a plurality of nonionic surfactants, or various types from anionic surfactants and nonionic surfactants. May be selected.
[0031]
Examples of the nonionic surfactant include the following, including the above. That is, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, polyethylene glycol fatty acid alkyl ester, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene castor oil, Examples thereof include polyoxyethylene alkylamine, glycerin fatty acid ester, higher fatty acid alkanolamide, alkylglucoside, alkylglucose amide, and alkylamine oxide.
[0032]
Among them, in particular, as a nonionic surfactant, an ethylene oxide adduct of a linear or branched primary or secondary alcohol having 10 to 18 carbon atoms and having an average addition mole number of 5 to 15 polyoxyethylene alkyl It is desirable to use ethers. It is more preferable to use an ethylene oxide adduct of a linear or branched primary or secondary alcohol having 12 to 14 carbon atoms, and to use a polyoxyethylene alkyl ether having an average addition mole number of 6 to 10 .
[0033]
When 5% or more of a polyoxyethylene alkyl ether type surfactant is blended into the high-density granular detergent, particularly when 5 to 30% is blended, it is effective from the viewpoint of cleaning performance. Polyoxyethylene alkyl ethers tend to increase the inter-particle adhesion of high-density granular detergents.
[0034]
Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid salt or ester salt, alkyl or alkenyl ether carboxylate, Amino acid type surfactants, N-acyl amino acid type surfactants and the like are exemplified, and preferred are alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate and the like.
[0035]
Examples of the cationic surfactant include quaternary ammonium salts such as an alkyltrimethylamine salt. Examples of the amphoteric surfactant include carboxy-type and sulfobetaine-type amphoteric surfactants.
[0036]
The content of the surfactant is 10 to 50% by weight in the whole composition, and it is more preferable to use washing water having a hardness of 2 to 6 ° DH.
The content of such a surfactant is an amount sufficient to make the surfactant concentration in the washing liquid 0.07 g / L or more at a standard usage amount (0.40 to 1.00 g / L). It is.
[0037]
As a sequestering agent, the ability to capture Ca ions is 200 CaCO ₃ Those containing 10% by weight or more of a carboxylate polymer of not less than mg / g in the sequestering agent are preferred.
Specific examples of such a polymer include a polymer or a copolymer having a repeating unit represented by the following general formula (1).
[0038]
Embedded image

[0039]
In the general formula (1), X ₁ Is methyl, H or COOX ₃ To X ₂ Represents methyl, H or OH, X ₃ Is H, alkali metal, alkaline earth metal, NH ₄ Or ethanolamine.
[0040]
In the general formula (1), examples of the alkali metal include Na, K, and Li, and examples of the alkaline earth metal include Ca and Mg.
[0041]
The polymer or copolymer is, for example, a polymerization reaction of acrylic acid, (anhydride) maleic acid, methacrylic acid, α-hydroxyacrylic acid, crotonic acid, isocrotonic acid, and salts thereof, or a copolymerization reaction of each monomer, Alternatively, it is synthesized by a copolymerization reaction with another polymerizable monomer. At this time, examples of other copolymer monomers used for copolymerization include, for example, aconitic acid, itaconic acid, citraconic acid, fumaric acid, vinylphosphonic acid, sulfonated maleic acid, diisobutylene, styrene, methyl vinyl ether, ethylene, and propylene. , Isobutylene, pentene, butadiene, isoprene, vinyl acetate (and vinyl alcohol when hydrolyzed after copolymerization), acrylate, and the like, but are not particularly limited thereto. The polymerization reaction is not particularly limited, and a generally known method can be used.
Further, a polyacetal carboxylic acid polymer such as polyglyoxylic acid described in JP-A-54-52196 can also be used.
[0042]
As the above-mentioned polymer and copolymer, those having a weight average molecular weight of 800 to 1,000,000 are used, and those having a weight average molecular weight of 5000 to 200,000 are preferably used. If the weight-average molecular weight is less than 800, cleaning performance due to the effect peculiar to the polymer cannot be obtained. If the weight average molecular weight exceeds 1,000,000, re-contamination occurs due to the effect of the polymer, and cleaning performance is hindered.
[0043]
In addition, when copolymerized, the copolymerization ratio of the repeating unit of the general formula (1) with another copolymerized monomer is not particularly limited, but preferably, the repeating unit of the general formula (1) / the other copolymerized monomer = 1. / 100 to 90/10.
[0044]
Further, as a sequestering agent, an ion exchange capacity represented by the following formula (2) is 200 CaCO 2 ₃ mg / g or more of aluminosilicate may be contained.
x "(M ₂ O) · Al ₂ O ₃ ・ Y ”(SiO ₂ ) ・ W ″ (H ₂ O) (2)
(Where M is an alkali metal such as sodium and potassium, x ″, y ″, and w ″ represent the number of moles of each component, and are generally 0.7 ≦ x ″ ≦ 1.5, 0.8 ≦ y ″ ≦ 6, w ″ is an arbitrary constant.)
[0045]
Examples of the above aluminosilicate include crystalline ones and amorphous ones. As the crystalline ones, those represented by the following general formula are particularly preferable.
Na ₂ O ・ Al ₂ O ₃ ・ YSiO ₂ ・ WH ₂ O
(In the formula, y represents a number of 1.8 to 3.0, and w represents a number of 1 to 6.)
As the crystalline aluminosilicate (zeolite), a synthetic zeolite having an average primary particle diameter of 0.1 to 10 μm typified by A-type, X-type, and P-type zeolites is suitably used. The zeolite may be used as zeolite agglomerated dry particles obtained by drying the powder and / or the zeolite slurry or the slurry.
[0046]
The above-mentioned crystalline aluminosilicate can be produced by a conventional method. For example, the methods described in JP-A-50-12381 and JP-A-51-12805 can be used.
[0047]
On the other hand, an amorphous aluminosilicate represented by the same general formula as the above crystalline aluminosilicate can be produced by a conventional method. For example, SiO ₂ And M ₂ The molar ratio of O (M means an alkali metal) is SiO ₂ / M ₂ O = 1.0-4.0, H ₂ O and M ₂ O molar ratio is H ₂ O / M ₂ Using an aqueous solution of an alkali metal silicate having O = 12 to 200, ₂ O and Al ₂ O ₃ Is M ₂ O / Al ₂ O ₃ = 1.0 to 2.0, and H ₂ O and M ₂ O molar ratio is H ₂ O / M ₂ An aqueous solution of a low alkali alkali aluminate having an O of 6.0 to 500 is added under a strong stirring at a temperature of usually 15 to 60 ° C, preferably 30 to 50 ° C.
[0048]
Next, the resulting white precipitate slurry is subjected to heat treatment at a temperature of usually 70 to 100 ° C., preferably 90 to 100 ° C., for usually 10 minutes to 10 hours, preferably 5 hours or less, followed by filtration, washing and drying. Can be obtained more advantageously. At this time, the adding method may be a method of adding an aqueous solution of an alkali metal silicate to an aqueous solution of a low alkali alkali metal aluminate.
[0049]
The content of the sequestering agent is 10 to 90% by weight in the whole composition, and among them, the above-mentioned polymer or copolymer is 2 to 50% by weight in the whole composition, preferably 5 to 30% by weight. %. If the amount is less than 2% by weight, the washing performance cannot be sufficiently improved, and if the amount exceeds 50% by weight, the effect of addition is saturated, and the cost is increased unnecessarily, and it becomes meaningless.
[0050]
As the composition of the granular detergent of the present invention, in addition to the above components, detergent builders, for example, aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriamine Penta (methylenephosphonic acid) and salts thereof, salts of phosphonocarboxylic acids such as 2-phosphonobutane-1,2-dicarboxylic acid, salts of amino acids such as aspartic acid and glutamic acid, nitrilotriacetic acid salts, ethylenediaminetetraacetic acid salts Non-dissociating polymers such as aminopolyacetate, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, etc .; builders such as organic acid salts such as diglycolate, citrate, oxycarboxylate; and carboxymethylcellulose. Incorporating in detergent It is known chelating agents and fading preventing agents, such as anti-redeposition agents.
[0051]
In addition, the composition of the granular detergent of the present invention may contain the following components. That is, enzymes such as protease, lipase, cellulase and amylase, anti-caking agents such as lower alkylbenzene sulfonate having about 1 to 4 carbon atoms, sulfosuccinate, talc and calcium silicate, tertiary butylhydroxytoluene, distyrenated cresol and the like Antioxidants, bleaching agents such as sodium percarbonate or bleaching activators such as tetraacetylethylenediamine, fluorescent dyes, bluing agents, fragrances, and the like, but these are not particularly limited and Appropriate formulations may be made.
[0052]
In order to reduce the amount of detergent used at one time, it is preferable to use a crystalline silicate, and an excellent detergency can be obtained with a small amount.
The crystalline silicate exhibits a pH of 10.6 or more in a 0.2% by weight dispersion and exhibits excellent alkalinity. In addition, it has a particularly excellent alkali buffering effect, and exhibits a property that the alkali buffering effect is superior to that of sodium carbonate or potassium carbonate, and SiO 2 / M 2 O = 0.9 to 2.6 (M: This is made possible by using an alkali metal). Among such crystalline silicates, those described in JP-A-5-184946 and JP-A-60-74595 can be used, and the specific composition has the following composition. Are exemplified.
▲ 1 ▼ xM ₂ O ・ ySiO ₂ ・ ZMe _m O _n ・ WH ₂ O (3)
(Wherein, M represents an element of Group Ia of the periodic table, Me represents one or a combination of two or more elements selected from Group IIa, IIb, IIIa, IVa or VIII, and y / x = 0.5 to 2). 0.6, z / x = 0.01-1.0, n / m = 0.5-2.0, w = 0-20.)
▲ 2 ▼ M ₂ Ox'SiO ₂ ・ Y'H ₂ O (4)
(In the formula, M represents an alkali metal, and x ′ = 1.5 to 2.6 and y ′ = 0 to 20.)
[0053]
First, the crystalline alkali metal silicate having the composition (1) will be described.
In the general formula (3), M is selected from Group Ia elements of the periodic table, and examples of Group Ia elements include Na and K. These can be used alone or, for example, in Na ₂ O and K ₂ O mixed with M ₂ An O component may be included.
Me is selected from Group IIa, IIb, IIIa, IVa or Group VIII elements of the periodic table, and includes, for example, Mg, Ca, Zn, Y, Ti, Zr, Fe and the like. These are not particularly limited, but are preferably Mg and Ca from the viewpoint of resources and safety. These may be used alone or in combination of two or more. For example, MgO, CaO, _m O _n Components may be included.
In addition, the crystalline alkali metal silicate of the present invention may be a hydrate, and the hydration amount in this case is in the range of w = 0 to 20.
[0054]
In the general formula, y / x is 0.5 to 2.6, and preferably 1.5 to 2.2. When y / x is less than 0.5, the water resistance is insufficient and the caking property, the solubility, and the physical properties of the granular detergent powder are significantly adversely affected. If y / x exceeds 2.6, the alkalinity becomes low and becomes insufficient as an alkali agent, and the ion exchange ability also becomes low, making it insufficient as an ion exchanger. z / x is 0.01 to 1.0, preferably 0.02 to 0.9. When z / x is less than 0.01, water resistance is insufficient, and when z / x exceeds 1.0, the ion exchange capacity is lowered and the ion exchanger is insufficient. x, y, and z are not particularly limited as long as they have the relationship shown in the above y / x and z / x. Note that as described above, xM ₂ O is, for example, x'Na ₂ O x x K ₂ In the case of O, x is x '+ x ". Such a relationship is expressed by zMe _m O _n The same applies to z when the component is composed of two or more components. Further, n / m = 0.5 to 2.0 indicates the number of oxygen ions coordinated to the element, and is substantially selected from the values of 0.5, 1.0, 1.5, and 2.0. It is.
[0055]
The crystalline alkali metal silicate in the granular detergent of the present invention has a value of M as shown in the above general formula. ₂ O, SiO ₂ , Me _m O _n It consists of three components. Therefore, in order to produce a crystalline alkali metal silicate in the granular detergent of the present invention, each component is required as a raw material, but the granular detergent of the present invention is not particularly limited, and a known compound may be used. Used as appropriate. For example, M ₂ O component, Me _m O _n As the components, oxides, hydroxides, salts, and minerals containing the element are used alone or in combination. Specifically, for example, M ₂ NaOH, KOH, Na ₂ CO ₃ , K ₂ CO ₃ , Na ₂ SO ₄ Etc. are Me _m O _n The raw material of the component is CaCO ₃ , MgCO ₃ , Ca (OH) ₂ , Mg (OH) ₂ , MgO, ZrO ₂ And dolomite. SiO ₂ As the components, silica stone, kaolin, talc, fused silica, sodium silicate and the like are used.
[0056]
The method for preparing the crystalline alkali metal silicate in the granular detergent according to the present invention comprises the step of mixing the above-mentioned raw material components in a predetermined quantitative ratio so that the desired x, y, z values of the crystalline alkali metal silicate are obtained. For example, a method of mixing and baking at a temperature of usually 300 to 1500 ° C., preferably 500 to 1000 ° C., more preferably 600 to 900 ° C. for crystallization is exemplified. In this case, if the heating temperature is lower than 300 ° C., crystallization is insufficient and the water resistance is poor. If the heating temperature is higher than 1500 ° C., coarse particles are formed and the ion exchange ability is reduced. The heating time is usually 0.1 to 24 hours. Such firing can be usually performed in a heating furnace such as an electric furnace or a gas furnace.
[0057]
Note that the crystalline alkali metal silicate in the granular detergent of the present invention exhibits not only an alkali ability but also an ion exchange ability, and has at least 100 CaCO 2. ₃ mg / g or more, preferably 200 to 600 CaCO ₃ mg / g.
[0058]
The method for producing the high-density granular detergent of the present invention is not particularly limited, and a conventionally known method can be used. For example, the methods described in JP-A-61-69897, JP-A-61-69899, JP-A-61-69900, and JP-A-5-209200 can be used.
[0059]
Next, an embodiment of a container for filling the granular detergent of the present invention will be described with reference to the drawings.
[0060]
A bottle-shaped container 1 for filling a granular detergent shown in FIGS. 1 and 2 comprises an elastically deformable container body 2 blow-molded from a high-molecular polymer, and a fixed-quantity plug 3 attached to an upper portion of the container body 2. Is provided.
[0061]
The container body 2 includes a bottom wall 11, a peripheral wall 12 extending upward from the periphery of the bottom wall 11, and a neck 13 surrounding an upper end opening 12A of the peripheral wall 12, as shown in FIG. The detergent is filled at a volume ratio of, for example, 50 to 90% with respect to the total volume.
[0062]
The peripheral wall 12 includes left and right side wall portions 12a and 12b facing each other (vertical direction is defined as a horizontal direction in FIG. 2), and front and rear side wall portions 12c and 12d are defined as left and right directions (a longitudinal direction is defined as a longitudinal direction in FIG. 2). A connecting portion 12e, 12f along the vertical direction between the left and right side wall portions 12a, 12b and the front side wall portion 12c, a connecting portion 12g along the vertical direction between the left and right side wall portions 12a, 12b and the rear side wall portion 12d, 12h, and surrounds the detergent filling space below the outlet 27 provided in the stopper 3.
[0063]
Thereafter, the upper portion of the side wall portion 12d is inclined forward, whereby the opening 12A is arranged to be biased forward.
[0064]
In FIG. 4, the thicknesses t1 and t2 of the front and rear side wall portions 12c and 12d and the thicknesses t3 and t4 of the connection portions 12e and 12f between the left and right side wall portions 12a and 12b and the front side wall portion 12c are the left and right side wall portions. The thicknesses t7 and t8 of grip portions 15a and 15b described later in 12a and 12b are thinner.
The thicknesses t3 and t4 of the connecting portions 12e and 12f between the left and right side wall portions 12a and 12b and the front side wall portion 12c are smaller than the thickness t1 of the front side wall portion 12c.
[0065]
As shown in FIG. 2, the interval W between the left and right side wall portions 12a and 12b is set to 80 mm or less. Also, as shown in FIGS. 1 and 4, the left and right side wall portions 12a and 12b have portions that are recessed inward of the container from surrounding portions, and the recessed portions serve as grip portions 15a and 15b. The thicknesses t7 and t8 of the grip portions 15a and 15b are determined by the wall thickness of the other portion of the peripheral wall 12, that is, the thickness of the left and right side wall portions 12a and 12b around the grip portions 15a and 15b and the front and rear side wall portions 12c. , 12d, and the connecting portions 12e, 12f, 12g, 12h are thicker than the thicknesses t3, t4, t5, t6.
[0066]
By gripping the gripping portions 15a and 15b, the peripheral wall 12 is elastically deformable so that the granular detergent temporarily solidified by tight filling in the container body 2 can be broken. When the grip portions 15a and 15b are pressed with a force of 1.0 kgf through a circular surface having a diameter of 2.15 mm, the peripheral wall 12 is recessed by 1.0 mm or more inside the container in the detergent-filled space as compared with before the deformation. With parts.
[0067]
The stopper 3 functions as a measuring device capable of measuring a granular detergent of 20 g or less. As shown in FIG. 3, the outer cylinder 21 is screwed to the outer periphery of the neck portion 13. It has an inner cylinder 22 that is integrated, and a movable cylinder 23 with a bottom that is fitted to the lower part of the inner cylinder 22 so that the vertical position can be changed. The volume of the inner cylinder 22 can be changed by the vertical movement of the movable cylinder 23 with respect to the inner cylinder 22.
[0068]
The inner cylinder 22 is fitted into the opening 12A to prevent the granular detergent in the container body 2 from flowing out from the opening 12A. An inflow port 22 a that opens rearward is formed between the upper and lower sides of the peripheral wall of the inner cylinder 22.
[0069]
A partition 24 is integrated with the inner cylinder 22. The partition 24 has an upper end reaching the upper end of the outer cylinder 21 and a lower end extending below the inflow port 22a and above the lower end of the inner cylinder 22. And a discharge space 26 on the front side. The upper end of the discharge space 26 serves as an outlet 27 for the granular detergent, and a lid 28 for opening and closing the outlet 27 is integrated with the outer cylinder 21. The shape of the partition 24 and the outer cylinder 21 is set so that the upper side 26a of the discharge space 26 is directed forward as going downward from the outlet 27.
[0070]
According to the stopper 3, when the container body 2 is tilted left and right as shown in FIG. 5, the granular detergent S in the container body 2 flows into the inflow space 25 from the inflow port 22a. The inflow is greater than the amount to be measured. Next, when the inclination of the container main body 2 is released as shown in FIG. 3, the granular detergent S exceeding the amount to be measured is discharged from the inlet 22a, and the remaining granular detergent S is discharged from the inner cylinder below the inlet 22a. A fixed amount is held in the storage 22. Next, when the container body 2 is tilted again, the granular detergent S located in the discharge space 26 among the retained granular detergents S, that is, a desired set amount of the granular detergent S is spouted from the outlet 27, and at the same time, The granular detergent S in the container body 2 flows into the inflow space 25 from the inflow port 22a for the next measurement. Also, since the upper side 26a of the discharge space 26 goes forward as it goes downward from the outlet 27, the upper side 26a of the discharge space 26 needs to be vertically moved to completely shake out the measured granular detergent S. Therefore, it is necessary to make the amount of inclination of the container body 2 sufficiently large. Thereby, even when the residual amount of the granular detergent S in the container main body 2 becomes small, the amount of inclination of the container main body 2 is made sufficiently large, so that the granular detergent S is supplied from the inlet 22a to the inflow space for the next measurement. 25.
[0071]
Note that the present invention is not limited to the above embodiment. For example, the weighing device is not particularly limited as long as the weighed amount can be weighed, and as disclosed in Japanese Utility Model Application Laid-Open No. 62-45248, the weighed granular material is shaken by opening a valve. As disclosed in JP-A-58-65280, JP-A-61-43176, JP-A-62-108256, and JP-A-3-45859, As disclosed in Japanese Unexamined Utility Model Publication Nos. 55-164167, 55-176121, and 58-53086, the swing outlet is provided on the side of the container. Or a device in which a measuring section is provided at the lower portion of the container as disclosed in Japanese Utility Model Laid-Open No. 60-32280 and Japanese Utility Model Laid-Open No. 61-5775. .
[0072]
Hereinafter, examples of the present invention will be described.
Embodiment 1
The detergent used in this example was prepared by the following method.
[0073]
<Adjustment example 1 (A detergent)>
The granular detergent A used in this example was prepared by the following method.
3 parts by weight of polyoxyethylene alkyl ether, 11 parts by weight of crystalline aluminosilicate, 23 parts by weight of LAS-Na, 5 parts by weight of AS-Na, 3 parts by weight of soap, 10 parts by weight of amorphous silicate, sodium polyacrylate (average (Molecular weight 20,000) 5 parts by weight of sodium carbonate, 10 parts by weight of potassium carbonate, 3 parts by weight of sodium carbonate, 1.5 parts by weight of sodium sulfate, 1 part by weight of polyethylene glycol, and 0.5 part by weight of a fluorescent dye are used. Adjusted and spray dried to obtain a bulk density of 0.3 g / cm. ³ Was obtained. Next, these powders, 4 parts by weight of a crystalline aluminosilicate, 2 parts by weight of a crystalline alkali metal silicate, and 3 parts by weight of a polyoxyethylene alkyl ether were mixed with a high-speed mixer (stirring-rolling granulator, Fukae Kogyo Co., Ltd.). )) And granulated. Further, after 5% by weight of a crystalline aluminosilicate is added and granulated (surface coating step), 2 parts by weight of the crystalline aluminosilicate and 2 parts by weight of the enzyme are dry-mixed with the obtained particles to remove water. A granular detergent containing 6 parts by weight (bulk density 0.75 g / cm) was obtained. ³ , Average particle size 468 μm).
[0074]
<Adjustment example 2 (B detergent)>
The granular detergent B used in this example was prepared by the following method.
A slurry having a water content of 50% by weight containing 15 parts by weight of a crystalline aluminosilicate, 5 parts by weight of a maleic acid copolymer, 1 part by weight of sodium sulfite, 5 parts by weight of sodium sulfate, and 0.5 part by weight of a fluorescent dye is prepared and spray-dried. By doing, the bulk density is 0.59 g / cm ³ Was obtained. Next, this powder, 19 parts by weight of an amorphous aluminosilicate and 19 parts by weight of sodium carbonate were charged into a Loedige mixer (stirring-rolling granulator, manufactured by Matsuzaka Giken Co., Ltd.), and stirring was started. Warm water of 40 ° C. was flowed through the jacket. A mixed solution prepared by heating and mixing 20 parts by weight of polyoxyethylene alkyl ether and 4 parts by weight of palmitic acid at 70 ° C. was added thereto and granulated. Further, after adding 7 parts by weight of crystalline aluminosilicate and granulating (surface coating step), 2 parts by weight of crystalline aluminosilicate and 2 parts by weight of the enzyme are dry-mixed to the obtained particles, so that the water content is 1. A granular detergent containing 7 parts by weight was obtained (bulk density: 0.81 g / cm). ³ , Average particle size 420 μm).
[0075]
Each component used in this example is described in detail below.
LAS-Na salt: linear alkyl (C _10-13 ) Sodium benzenesulfonate.
・ AS-Na salt: sodium alkyl sulfate (C ₁₂ 50% alcohol and C ₁₄ Sulfoxide of mixed alcohol with 50% alcohol).
・ Soap: Tallow (C _14-18 ) Fatty acid sodium.
Nonionic: polyoxyethylene alkyl ether (average of 8 moles of ethylene oxide added to Dovanol 23 (manufactured by Mitsubishi Yuka)).
Crystalline alkali metal silicate: SKS-6 (manufactured by Hoechst, average particle size 120 μm, 125 μm or more and 45% pulverized with a hammer mill (average particle size 50 μm)).
Amorphous silicate: No. 1 sodium silicate (manufactured by Tosoh Sangyo Co., Ltd., solid content: 44% by weight).
Crystalline aluminosilicate: 4A type zeolite, average particle size 3 μm (manufactured by Zeobuilder Co., Ltd.).
Maleic acid copolymer: maleic acid / acrylic acid = 30/70 (molar ratio), molecular weight 60000, sodium salt having a neutralization degree of 70%.
-Polyethylene glycol: average molecular weight 10,000.
-Fluorescent dye: Tinopearl CBS-X (manufactured by Ciba-Geigy) and Whitetex SA (manufactured by Sumitomo Chemical Co., Ltd.) in a weight ratio of 1/1.
Enzyme: 0.5% by weight of Cellulase K (described in JP-A-63-264699), 1.0% by weight of API-21 (Showa Denko KK), 0.5% by weight of Lipolase 100T (Novo Corporation).
[0076]
The container used in this example was formed so as to meet the following conditions.
Form: The bottle-shaped container (capacity: about 1000 ml) of the embodiment shown in FIG. 1 was used.
Properties: When measured at a pressure of 20 mm / min by compressing several parts of the container grasping part with a cylindrical compressor of φ2.15 cm (using AUTOGRAPH AG-500E manufactured by Shimadzu Corporation) as a compression measuring device. An indentation of 2.1 mm to 3.0 mm was made inside the container.
Material: HDPE was used as the material for forming the container.
Thickness: The thickness was set to 0.7 mm to 3.0 mm so that at least one portion having a thickness of 1 mm or less existed on the peripheral wall.
[0077]
The container is filled with 80% by volume of a detergent, and a tapping-type density filling bulk density meter (TVA-1 manufactured by Tsutsui Chemical Co., Ltd.) is used for 30 times tapping from a height of 3 cm for tight packing. The container was grasped and the container was gently tilted, and the inside of the container was observed to determine the presence or absence of blocking. The holding of the container is performed without being conscious of deforming the container.
[0078]
In addition, the same amount tapping body (design weighing value 20 g) of the above embodiment is attached to a bottle-shaped container, and the same tapping is performed. Next, the measuring part is filled with the detergent by inverting the container up and down, and then the container is again inverted so that the measuring part of the container is upward. Thereafter, the lid of the measuring section was opened, the detergent was spun out while the container was tilted, and the first spouting amount until the measuring section was right below was measured with a weighing scale.
[0079]
Embodiment 2
When PP is used as the material for forming the container, a 2.6 mm to 3.0 mm dent is formed when several places of the container gripping portion are measured under a compression condition of 20 mm / min with a φ2.15 cm compressor, and the peripheral wall is thickened. The same experiment as in Example 1 was performed except that the thickness was set to 0.9 mm to 3.2 mm.
[0080]
Embodiment 3
When using a rigid PVC as a material for forming the container and measuring several places of the container gripping portion under a compression condition of 20 mm / min with a compressor of φ2.15 cm under a compression condition of 20 mm / min, a dent of 1.3 mm to 1.8 mm is generated. The same experiment as in Example 1 was performed except that the thickness was formed to 0.8 mm to 2.6 mm.
[0081]
Embodiment 4
Using PET as a material for forming the container, when measuring several places of the container grasping part under a compression condition of 20 mm / min with a compressor of φ2.15 cm, a 1.9 mm to 2.8 mm dent is formed, and the peripheral wall is thickened. The same experiment as in Example 1 was performed except that the thickness was set to 0.6 mm to 1.4 mm.
[0082]
[Comparative Example 1]
When using a rigid PVC as a material for forming the container and measuring several places of the container grasping part under a compression condition of 20 mm / min with a compressor of φ2.15 cm to form a dent of 0.5 mm to 0.9 mm, a peripheral wall is formed. The same experiment as in Example 1 was performed except that the thickness was set to 1.6 mm to 4.0 mm so that there was no place where the thickness was 1 mm or less.
[0083]
[Comparative Example 2]
Glass was used as the material for forming the container. Since the glass is difficult to process, as shown in Fig. 6, a container 1 "having a shape different from those of Examples 1 to 4 and Comparative Example 1 was used. The bottom had a size of 9 cm x 9 cm and a height of 13 cm. The top of the rectangular parallelepiped has an opening with an outer diameter of 4 cm and a height of 3 cm, and the corners are chamfered with R5 mm. Under the conditions, several places of the container grasping part were measured, but no dent was formed, except for the container conditions, and the same experiment as in Example 1 was performed.
[0084]
Table 1 below shows the experimental results of Examples 1 to 4 and Comparative Examples 1 and 2.
[0085]
[Table 1]

[0086]
From the above Table 1, according to the embodiment, even when the high-density granular detergent is blocked in the container, the blocking can be eliminated by grasping and deforming the container before the detergent is sprinkled, and the measurement of the granular detergent can be performed. We can confirm that we can do it correctly. Further, when a pressure of 1.0 kgf is applied through a circular surface having a diameter of 2.15 mm at the gripping portion of the peripheral wall, the container has a portion which is recessed by 1.0 mm or more inside the container, and a high-molecular polymer is used as a material of the container. In this case, it can be confirmed that the effect of the present invention can be easily obtained by the presence of a portion where the thickness of the peripheral wall is 1 mm or less.
[0087]
[Comparative Example 3]
As a result of performing the same experiment as in Examples 1 to 4 using the container 1 ′ having the hollow handle 100 shown in FIG. 7 as a grasping part, the problem of blocking of the granular detergent could not be solved. Showed the same quantitative property as In FIG. 7, the same parts as those in the above embodiment are denoted by the same reference numerals.
[0088]
【The invention's effect】
According to the present invention, even when the high-density granular detergent in the container is blocked due to vibration during transportation or the like, the container can be grasped and deformed before the detergent is spouted, so that the detergent can be easily sprinkled at the time of use. In addition, it is possible to accurately determine the amount of dispensing using a measuring instrument.
[Brief description of the drawings]
FIG. 1 is a side view of a container according to an embodiment of the present invention.
FIG. 2 is a plan view of the container according to the embodiment of the present invention.
FIG. 3 is a partial cross-sectional view of the container according to the embodiment of the present invention.
FIG. 4 is a sectional view taken along line IV-IV of the container of the embodiment of FIG. 1;
FIG. 5 is a partial cross-sectional view for explaining a weighing function of the container according to the embodiment of the present invention.
FIG. 6 is a plan view, (2) is a side view, and (3) is a bottom view of the container of Comparative Example 2.
FIG. 7 is a side view of the container of Comparative Example 3 of the present invention.
[Explanation of symbols]
1 container
3 stopper (measuring device)
12 Perimeter wall
12a, 12b Left and right side walls
12e, 12f connecting part
15a, 15b gripper
27 Outlet

Claims (13)

A granular detergent containing 10 to 50% by weight of a surfactant, a bulk density of 0.6 g / cm ³ or more, and an average particle size of 250 to 1000 μm,
Filled in a container having an outlet and a peripheral wall surrounding the detergent filling space below the outlet,
The peripheral wall has opposing side walls and a connecting portion between the side walls along the up-down direction, and at least one of the connecting portions has a smaller wall thickness than each side wall portion. The peripheral wall is deformable so that the granular detergent temporarily solidified by close filling in the container can be broken down by gripping the wall portion,
When the gripping portion of the peripheral wall is pressed with a force of 1.0 kgf via a circular surface having a diameter of 2.15 mm, the peripheral wall has a portion that is recessed by 1.0 mm or more inside the container as compared with before the deformation. Granular detergent in a container. 2. The granular detergent in a container according to claim 1, wherein the material of the container is a high-molecular polymer, and there are locations where the thickness of the peripheral wall is 1 mm or less. The granular detergent in a container according to claim 1 or 2, wherein the deformation of the peripheral wall by gripping is elastic. The granular detergent in a container according to any one of claims 1 to 3, wherein each of the opposed side walls has a portion that is recessed inward of the container from a peripheral portion . 5. The peripheral wall according to claim 1, wherein the peripheral wall has a recessed portion inside the container than the peripheral portion, and the wall thickness of the recessed portion is greater than the wall thickness of other portions of the peripheral wall. The granular detergent contained in any one of the containers. The granular detergent in a container according to any one of claims 1 to 5, wherein a distance between the opposed side walls is 80 mm or less . The total volume of the container is 1500 cm ³ The granular detergent in a container according to any one of claims 1 to 6, which is: The granular detergent in a container according to any one of claims 1 to 7, wherein the container has a built-in weighing device capable of measuring a swing amount . 9. The granular detergent in a container according to claim 8, wherein the measured amount of the dispensed is 20 g or less . The granular detergent according to any one of claims 1 to 9, wherein 5% by weight or more of polyoxyethylene alkyl ether is blended as the surfactant . The granular detergent according to any one of claims 1 to 10, wherein the surface of the granular detergent is coated with a water-insoluble inorganic powder . When the grip portion of the peripheral wall is pressed with a force of 1.0 kgf via a circular surface having a diameter of 2.15 mm, the peripheral wall has a portion which is recessed by 1.5 mm to 5 mm inside the container as compared with before deformation. 12. The granular detergent in a container according to any one of 1 to 11 . Contains 10 to 50% by weight of a surfactant and has a bulk density of 0.6 g / cm. ³ As described above, when the granular detergent having an average particle diameter of 250 to 1000 μm is shaken out from the outlet of the container,
As the container, a peripheral wall surrounding the detergent filling space below the outlet has opposing side walls and a connecting portion between the side walls along the vertical direction, and at least one of the connecting portions is provided. The peripheral wall is deformable, so that the wall thickness is thinner than each side wall portion, and the granular detergent temporarily solidified by tight filling in the container can be broken by gripping the side wall portions of the peripheral wall, When the gripping portion of the peripheral wall is pressed with a force of 1.0 kgf through a circular surface having a diameter of 2.15 mm, the peripheral wall having a portion recessed by 1.0 mm or more inside the container as compared with before the deformation is used. ,
The container is deformed by gripping the peripheral wall surrounding the detergent filling space below the outlet,
Breaking down the granular detergent in the container temporarily solidified by close packing due to its deformation,
A method for sprinkling granular detergent in a container, comprising sprinkling the granular detergent from the outlet.

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