JP2004059606A

JP2004059606A - Press-molded solid matter

Info

Publication number: JP2004059606A
Application number: JP2002215843A
Authority: JP
Inventors: Satoru Nagase; 長瀬　悟
Original assignee: Kansai Koso KK
Current assignee: Kansai Koso KK
Priority date: 2002-07-24
Filing date: 2002-07-24
Publication date: 2004-02-26

Abstract

<P>PROBLEM TO BE SOLVED: To provide a press-molded solid matter which is easily handled and is suppressed or prevented from the occurrence of cracks and splittings in its storage, use, and handling or a press-molded solid matter which contains a shaped matter therein and is suppressed or prevented from the occurrence of cracks and splittings in its handling. <P>SOLUTION: The press-molded solid matter is a detergent, a perfuming agent, a deodorant, a bleacher, a sliminess remover, a water quality improver, a sludge improver, a bait to be scattered, a fertilizer, or a solid cosmetic and is prepared by mixing a powdery material with a liquid material containing PEG having an average mol.wt. of 500-3,700 and fluidized with a solvent containing DPG and/or 1,3-butylene glycol and press-molding the resultant water-soluble wet powder under a pressure of 0.5-10 kgf/cm<SP>2</SP>or by burying a shaped matter in the water-soluble wet powder followed by press-molding under a pressure of 0.5-10 kgf/cm<SP>2</SP>. <P>COPYRIGHT: (C)2004,JPO

Description

【０００１】
【発明の属する技術分野】
本発明は、低圧力成形により得られた、保存時、輸送時、取扱時における亀裂及び割れの発生が抑制又は防止された加圧成形固形物に関する。
【０００２】
【従来の技術】
固体化粧料、洗剤、芳香剤等の固形物は、例えば、液状化した原料を所望の型に入れ冷却固化させた後に型抜きする方法、粉末原料を所望大きさに造粒する方法、所望物をカプセルに内包させる方法、粉末原料を打錠成型機により加圧成形する方法、原料を手作業により所望形状に固める方法により製造されている。これらの方法により得られる固形物は、例えば、使用される原料成分が同じ場合であっても、その製造法により得られる固体の硬さや弾力性等が異なり、物理的にそれぞれ区別できる。
ところで、上記各方法により得られる固形物の中でも加圧成形によって得られる従来の固形物は、生産性に優れ、しかも表面硬度が高いため取扱い性にも優れる。
加圧成形により製造される従来の固形物は、通常、打錠成型機を用いて１方向から１００ｋｇｆ／ｃｍ^２以上の圧力により成形される。このように製造された固形物は、硬度が高いが弾力性がなく、衝撃により亀裂及び割れが生じ易いという欠点がある。そこで、商品化に際しては、水溶性高分子による表面コートが施されることが多い。しかし、表面コートが施された固形物であっても、落下による強い衝撃を受けた場合には内部に亀裂が生じ割れ易くなり、また、使用時に表面のコート層が溶解しはじめた直後に割れが生じ、商品価値が著しく低下するという欠点がある。このような問題は、固形物が内部に有形物を包埋している場合、並びに１個の固形物が１０ｇ以上の場合に生じ易い。
前記打錠成型機を用いて高圧力により成形される水等への溶解を目的とした固形物は、高圧力成形によって溶解性が低下するため、通常、発泡成分としての有機酸及び炭酸塩を含むことが多い。しかし、発泡成分を含む場合であっても高圧力により成形されているために、必ずしも溶解性が十分であるとは言い難い。また、従来の固形物では加圧成形時の加圧が１方向からの高圧で行なわれているために、球状、タマゴ形状又は楕円状に成形し難く、更に、高圧成形においては、該高圧によって変形、破壊、癒着等が生じる有形物を包埋できない。
【０００３】
【発明が解決しようとする課題】
そこで、上記課題を解決するために、加圧成形時の圧力を低圧にすることが考えられる。しかし、圧力を低くすると成形自体が困難であり、成形できた場合でも亀裂及び割れの発生が抑制できない。特に、有形物を包埋した場合には保存時における亀裂又は割れが発生するか、若しくは水又は湯に接触させて使用する場合には、水又は湯に接触した直後に割れが生じ均一溶解できないという問題が生じる。
【０００４】
本発明の目的は、取扱いが良好であり、保存時、使用時、取扱い時に亀裂及び割れの発生が抑制又は防止された加圧成形固形物を提供することにある。
本発明の他の目的は、内部に有形物を含み、球状、タマゴ形状又は楕円形状等の形状を有し、取扱いが良好で、保存時、使用時、取扱い時に、亀裂及び割れの発生が抑制又は防止された加圧成形固形物を提供することにある。
【０００５】
【課題を解決するための手段】
本発明者らは、上記課題を解決するために鋭意検討した。まず、打錠成型機を用いて高圧下に成形された従来の固形物と見かけ上同程度の硬度を有する固形物の作製を試みた。しかし、低圧による成形であるために成形不能であったり、成形できたとしても非常に脆いものであった。そこで、原料について種々検討した結果、特定分子量のポリエチレングリコール（ＰＥＧ）を流動化して用いることにより、低圧であっても従来の固形物と見かけ上同程度の硬度を有する固形物が得られることを見出した。ところが、このようにして得られる固形物は、低圧成形されていても、必ずしも亀裂及び割れが十分に抑制できるものではなく、特に、有形物を包埋した場合には保存時において亀裂や割れを抑制することが困難であった。
そこで、更に鋭意検討した結果、特定分子量のＰＥＧを流動化させる溶剤としてジプロピレングリコール（ＤＰＧ）及び／又は１，３−ブチレングリコール（１，３−ＢＧ）を含む溶剤を用いて加圧成形する原料を湿潤粉末とし、特定圧力で加圧成形することによって得られる固形物が、高さ１ｍからコンクリート床に落下させた際にも、亀裂及び割れが生じずに若干凹む程度の弾性力を有し、従来にない固形物が得られることを見出し、本発明を完成させた。
【０００６】
即ち、本発明によれば、粉体原料と、ジプロピレングリコール及び／又は１，３−ブチレングリコールを含む溶剤により流動化させた平均分子量５００〜３７００のポリエチレングリコールを含む液状原料とを混合して得た水溶性湿潤粉末を、圧力０．５〜１０ｋｇｆ／ｃｍ^２で加圧成形して得た、若しくは前記水溶性湿潤粉末に、有形物を包埋し、圧力０．５〜１０ｋｇｆ／ｃｍ^２で加圧成形して得た、洗剤、芳香剤、消臭剤、漂白剤、ぬめり取り剤、水質改善剤、汚泥改良剤、撒き餌又は肥料であることを特徴とする加圧成形固形物が提供される。
また本発明によれば、粉体原料と、ジプロピレングリコール及び／又は１，３−ブチレングリコールを含む溶剤により流動化させた平均分子量５００〜３７００のポリエチレングリコールを含む液状原料とを混合して得た水溶性湿潤粉末であって、有機酸及び炭酸塩からなる発泡成分を含有しない水溶性湿潤粉末を、圧力０．５〜１０ｋｇｆ／ｃｍ^２で加圧成形して得た、若しくは前記水溶性湿潤粉末に、有形物を包埋し、圧力０．５〜１０ｋｇｆ／ｃｍ^２で加圧成形して得た、固体化粧料であることを特徴とする加圧成形固形物が提供される。
【０００７】
【発明の実施の形態】
以下本発明を更に詳細に説明する。
本発明の加圧成形固形物としては、洗剤、芳香剤、消臭剤、漂白剤、ぬめり取り剤、水質改善剤、汚泥改良剤、撒き餌、肥料、固体化粧料が挙げられる。中でも固体化粧料は、発泡成分としての有機酸及び炭酸塩を含有せず、例えば、入浴剤、皮膚洗浄剤、垢すり剤、害虫忌避剤、足浴剤、制汗剤、固形化粧水又は固形乳液等が挙げられる。
本発明の加圧成形固形物は、打錠成形機により高圧力で加圧成形された従来の固形物と見かけ上同等の硬度を有し、高さ１ｍからコンクリート床に落下させた際に亀裂及び割れが生じずに若干凹む程度の弾性力を有する。ここで、従来の固体化粧料と見かけ上同等の硬度とは、硬度計により測定したものではなく、触った感じが従来の錠剤程度のハードな硬さを有し、ほぼ同様な取扱いができることを意味する。
【０００８】
本発明の加圧成形固形物は、加圧によって成形しうる特定の水溶性湿潤粉末（Ａ）、若しくは有機酸及び炭酸塩からなる発泡成分を含まない水溶性湿潤粉末（Ｂ）を、特定の圧力で加圧成形して得られる。ここで、湿潤粉末とは、例えば、粉末原料が特定の溶剤により流動化したＰＥＧ等により湿った状態となった粉末を意味する。また、水溶性湿潤粉末とは、該粉末を構成するほとんどの成分が水溶性であることを意味し、例えば、水不溶性である油溶性芳香成分等を含んでいても良い。
本発明の加圧成形固形物において、製造のために用いる前記水溶性湿潤粉末（Ａ）及び（Ｂ）は、粉末原料と、特定溶剤により流動化させた特定分子量のＰＥＧとを含み、必要に応じて用途に応じた他の成分を含有するが、水溶性湿潤粉末（Ｂ）は、上記発泡成分を含まない。
【０００９】
本発明に用いる前記溶剤は、ＤＰＧ及び／又は１，３−ＢＧを含む。好ましくはＤＰＧ及び／又は１，３−ＢＧのみであり、特に好ましくはＤＰＧ単独である。ＤＰＧ及び／又は１，３−ＢＧは、ＰＥＧを原料全体に分散させ、上述の本発明における特徴的な硬度及び弾力性を付与するために必要である。本発明に用いるＰＥＧは、例えば、エタノールにも溶解するが、ＤＰＧ及び／又は１，３−ＢＧを使用せずにエタノールのみを使用した場合、亀裂及び割れが抑制されうる本発明の所望の効果が得られない。特に有形物を包埋した場合には保存時に亀裂又は割れが生じる可能性が高くなる。
【００１０】
本発明に用いる前記ＰＥＧの平均分子量は５００〜３７００である。このような分子量のＰＥＧは、通常ペースト状態からフレーク状態を呈し、例えば、市販品又は市販品を所望分子量となるように混合した混合物が使用できる。ＰＥＧの平均分子量が上記範囲外の場合には、加圧成形性が悪化し、加圧成形固形物に所望の硬度及び弾性力を付与することが困難である。
前記特定溶剤により流動化させた特定分子量のＰＥＧは、例えば、ＤＰＧ及び／又は１，３−ＢＧを含む溶剤に前記ＰＥＧを混合し、６０〜７０℃程度に加温してＰＥＧを溶解させる方法により得られる。この際、ＤＰＧ及び／又は１，３−ＢＧを含む溶剤とＰＥＧとの配合割合は、ＰＥＧが流動化するように適宜選択できるが、本発明の所望の効果をより有効に得るために、質量比で１：０．５〜２０、特に１：０．５〜１０が好ましい。また、有形物を除く加圧成形固形物中の前記ＰＥＧの含有割合は、２〜５０質量％が好ましい。
【００１１】
本発明の製造に用いる粉末原料は、その用途に応じて適宜選択でき、公知の成分から選択することができる。また、水溶性湿潤粉末（Ａ）の場合には、有機酸及び炭酸塩からなる発泡成分を含んでいても良く、該発泡成分は、水分と反応し、炭酸ガスを発生し、加圧成形固形物が水や湯に溶解して用いる場合等において、溶解性を補助する成分である。発泡成分は粉体として使用でき、その粒径は、原料として加圧によって成形しうるものであれば良い。
前記有機酸は、クエン酸、フマル酸、酒石酸、アジピン酸及びコハク酸からなる群より選択される１種又は２種以上が好ましい。特に、本発明の加圧成形固形物における発泡力及び均一溶解性の点でクエン酸の使用が好ましい。
前記炭酸塩としては、例えば、炭酸ナトリウム、炭酸水素ナトリウム、セスキ炭酸ナトリウム、これらのカリウム塩が挙げられる。
発泡成分としての有機酸及び炭酸塩の配合割合は、質量比で通常１：０．２〜３．０であり、特に１：１に近い割合が望ましい。また、有形物を除く水溶性湿潤粉末（Ａ）中において、前記有機酸及び炭酸塩の合計の含有割合は３０〜９０質量％が好ましい。
【００１２】
本発明の加圧成形固形物の比重を１ｇ／ｃｍ^３以上にする必要がある場合には、比重調整剤として、無水硫酸ナトリウムを用いることが好ましい。該無水硫酸ナトリウムは、加圧成形性を悪化させない成分である。従って、無水硫酸ナトリウムを用いる場合の配合割合は、加圧成形固形物の比重を勘案して適宜決定することができるが、通常、１〜５０質量％の範囲から適宜選択することができる。無水硫酸ナトリウムは、粉体として使用でき、その粒径は原料として加圧によって成形しうるものであれば良い。
【００１３】
前記水溶性湿潤粉末には、必要に応じて前記溶剤に溶解したＰＥＧ以外にも、芳香成分等の液状成分を含有させることもできる。
前記水溶性湿潤粉末（Ａ）及び（Ｂ）において、前記粉末原料と前記流動化させたＰＥＧとの配合割合は、好ましくは質量比で１：０．０１〜２０、特に、１：０．１〜１５である。流動化されたＰＥＧの配合割合が粉末原料１に対して０．０１未満では、強度が付与できず成形不可能であり、２０を超える場合にはスラリー状となり成形が困難であるので好ましくない。
【００１４】
本発明の加圧成形固形物には、有形物が包埋されていても良い。有形物は、水不溶性有形物又は水溶性有形物を含む。水不溶性有形物としては、例えば、樹脂製玩具、水不溶性のフィルム、水不溶性のカプセル、水不溶性のゲル状物が挙げられる。水溶性有形物としては、例えば、水溶性のフィルム、水溶性の固形物、水溶性のカプセル、水溶性のゲル状物が挙げられる。具体的な有形物としては、高圧力気体を封入した糖類粒状物、カプセル剤、多糖フィルム、植物乾燥物、スポンジ類、アクセサリー、玩具、錠剤等が挙げられ、所望の加圧成形固形物の種類等に応じて適宜選択できる。
有形物の形状は特に限定されず、玩具等の比較的大きく、また形状が複雑なものであっても良い。有形物の大きさは、加圧成形固形物の大きさ等に応じて適宜選択することが好ましい。有形物の比重も特に限定されない。
有形物を包埋させる方法は特に限定されないが、例えば、上記水溶性湿潤粉末に予め凹部を設け、この凹部に有形物を載置した後に包埋させる方法が挙げられる。
【００１５】
本発明の加圧成形固形物は、上記水溶性湿潤粉末（Ａ）又は（Ｂ）、若しくは有形物を包埋させた水溶性湿潤粉末（Ａ）又は（Ｂ）を、圧力０．５〜１０ｋｇｆ／ｃｍ^２、好ましくは０．５〜５ｋｇｆ／ｃｍ^２特に好ましくは０．８〜５ｋｇｆ／ｃｍ^２で加圧成形する方法により得られる。圧力が０．５ｋｇｆ／ｃｍ^２未満では、成形が困難であるか、加圧成形固形物に所望強度が付与できず、一方、１０ｋｇｆ／ｃｍ^２を超える場合には、所望の溶解性が得られず、また、包埋された有形物が変形、破壊、癒着等して商品価値が低下する。
前記加圧成形は、通常の打錠成形機を改良したもので、１回の加圧により行なうことができるが、前記圧力範囲内であれば加圧を２回以上に分けて行うこともできる。特に、有形物を包埋させる場合には、加圧を２回以上に分け、１回目の圧力を低くし、２回目以降に最終圧力とすることによって、水溶性湿潤粉末を有形物の外形に沿って密に充填できる。また、加圧成形固形物の形状を球状、タマゴ形状又は楕円状等にする場合には、２方向以上からの加圧を行うこともできる。尚、加圧成形固形物の形状は、特に限定されず、上記形状以外に、キューブ状、三角柱、星型柱、円柱状、更には人形の形状をした複雑形状であっても良い。
【００１６】
本発明の加圧成形固形物の総質量は、特に限定されないが、所望の効果が顕著に現れる１０〜３００ｇ、特に、５０〜３００ｇが好ましい。このような総質量の範囲の場合、従来の数ｇ程度の錠剤型固形物より大きいので、亀裂及び割れが生じる可能性が大きくなるが、本発明の加圧成形固形物の場合はこのような問題が有効に抑制又は防止される。
本発明の加圧成形固形物は、上記加圧成形後、乾燥して得ることができるが、必要に応じて、例えば、保存時における空気との接触による表面の劣化及び取扱い性を向上させるために、加圧成形固形物の表面に蒸気等の水分を反応させ、表面のみを中性塩とすることもできる。また加圧成形固形物の保存時、輸送時、使用時における亀裂及び割れの発生を更に有効に防止するために、必要に応じて、公知のシュリンク包装を行うこともできる。
本発明の加圧成形固形物は、長期保存する際に変色及び変臭を抑制又は防止し、商品価値を持続するために、光不透過性であり、且つ袋状の包装材中に包装することもできる。該包装材としては、例えば、アルミ箔等が挙げられる。また本発明の加圧成形固形物を袋状の包装材中に入れ、減圧装置を用いて減圧し、密封することもできる。更に、本発明の加圧成形固形物には、公知の水溶性高分子成分による表面コートが施されていても良い。
【００１７】
【発明の効果】
本発明の加圧成形固形物は、粉末原料と、ＤＰＧ及び／又は１，３−ＢＧを含む溶剤により流動化させた特定分子量のＰＥＧとを含む水溶性湿潤粉末を、特定圧力で加圧成形して得たものであるので、取扱いが良好であり、保存時、使用時、取扱い時に亀裂及び割れの発生が抑制又は防止される。更に、低圧力成形で製造されるため、有形物が包埋された加圧成形固形物であっても有形物の変形、破壊、癒着等がほとんど生じることなく、包埋時に有形物の若干の収縮が生じた場合でも、保存時等に該収縮が回復される力が生じる場合であっても亀裂及び割れを有効に抑制又は防止できる。従って、加圧成形により製造しうる洗剤、芳香剤、消臭剤、漂白剤、ぬめり取り剤、水質改善剤、汚泥改良剤、撒き餌又は肥料、更には、各種固形化粧料に極めて有用である。
【００１８】
【実施例】
以下実施例により本発明を更に詳細に説明するが、本発明はこれらに限定されない。
実施例１
平均分子量５００のＰＥＧ　６．０質量部及び平均分子量３７００のＰＥＧ　６．０質量部を、温度６０℃でジプロピレングリコール６．０質量部に溶解し、平均分子量２１００のＰＥＧ溶液を調製した。次いで、ラウリル硫酸ナトリウム２０．０質量部、ポリオキシエチレンオレイルエーテル５質量部、エデト酸二ナトリウム１質量部及び炭酸ナトリウム５６．０質量部に、前記ＰＥＧ溶液を混合撹拌し、水溶性湿潤粉末の固形洗剤原料を調製した。
得られた固形洗剤原料を円柱形の容器に入れ、中心部に凹部を形成し、該凹部に複数の高圧力気体を封入した糖類粒状物をを導入した後、複数の高圧力気体を封入した糖類粒状物を包埋した。次いで、上方より半球状凹部を有する押圧板を用いて圧力１．０ｋｇｆ／ｃｍ^２で第１回目の加圧を行った後、上下方向から半球状凹部を有する２枚の押圧板を用いて圧力２．０ｋｇｆ／ｃｍ^２で第２回目の加圧を行い、タマゴ型の固形洗剤を調製し乾燥した。得られた固形洗剤について以下に示す各評価を行なった。結果を表１に示す。
【００１９】
＜成形状態＞
加圧成形固形物を１０人のパネルにより触手し、打錠成型機で製造した従来の錠剤と同様に強固な感触が得られ、且つ成形が強固であるものを３点、成形が軟弱であるものを２点、成形不能なものを１点とした。結果は１０人の平均点とした。
＜亀裂及び割れの発生＞
加圧成形固形物を高さ１ｍからコンクリート床に落下させ、亀裂又は割れの発生を観察した。亀裂又は割れが観察されたものは×、観察されなかったものを○とした。
＜有形物の状態＞
加圧成形固形物中に包埋した有形物が、変形、破壊、癒着等が生じないで使用時に有効に機能した場合を○、機能しなかった場合を×とした。
＜長期保存性＞
加圧成形固形物をアルミ箔製の袋に入れ包装した後、常温で６ヶ月間保存した。６ヶ月後袋を開封し製造時の臭い及び色と比較した。ほとんど変化がないものを○、臭い及び色の少なくとも一方に変化が認められたものを×とした。
【００２０】
実施例２
平均分子量５００のＰＥＧ　６．０質量部及び平均分子量３７００のＰＥＧ　６．０質量部を、温度６０℃でジプロピレングリコール６．０質量部に溶解し、平均分子量２１００のＰＥＧ溶液を調製した。次いで、マルトース８１．８質量部、植物エキス０．１質量部、ヒアルロン酸ナトリウム０．０１質量部及び香料０．０９質量部に、前記ＰＥＧ溶液を混合撹拌し、水溶性湿潤粉末の固形化粧水原料を調製した。
得られた固形化粧水原料を実施例１と同様な加圧成形器を用いて加圧成形時の圧力を１ｋｇｆ／ｃｍ^２として楕円状の固形化粧水を製造した。得られた固形化粧水について、実施例１における成形性、亀裂及び割れの発生、並びに長期保存性の各試験を行なった。結果を表１に示す。
【００２１】
実施例３
平均分子量５００のＰＥＧ　６．０質量部及び平均分子量３７００のＰＥＧ　６．０質量部を、温度６０℃でジプロピレングリコール６．０質量部に溶解し、平均分子量２１００のＰＥＧ溶液を調製した。次いで、ポリオキシエチレンオレイルエーテル２質量部及び過炭酸ナトリウム８０．０質量部に、前記ＰＥＧ溶液を混合撹拌し、水溶性湿潤粉末の固形漂白剤原料を調製した。
得られた固形漂白剤原料を用いて実施例１と同様な加圧成形器を用いて加圧成形時の圧力を２ｋｇｆ／ｃｍ^２としてタマゴ型状の固形漂白剤を製造した。得られた固形漂白剤について、実施例２と同様な各試験を行なった。結果を表１に示す。
【００２２】
実施例４
平均分子量５００のＰＥＧ　８．０質量部及び平均分子量３７００のＰＥＧ　８．０質量部を、温度６０℃でジプロピレングリコール８．０質量部に溶解し、平均分子量２１００のＰＥＧ溶液を調製した。次いで、エデト酸四ナトリウム１０質量部、ラウリル硫酸ナトリウム５．０質量部及び炭酸ナトリウム６１．０質量部に、前記ＰＥＧ溶液を混合撹拌し、水溶性湿潤粉末の固形浴槽つけおき洗剤原料を調製した。
得られた固形浴槽つけおき洗剤原料を用い、実施例１の複数の高圧力気体を封入した糖類粒状物の代わりに圧縮スポンジを包埋し、タマゴ型の固形浴槽つけおき洗剤を調製した。得られた固形浴槽つけおき洗剤について実施例１と同様な試験を行なった。結果を表１に示す。
【００２３】
実施例５
平均分子量５００のＰＥＧ　６．０質量部及び平均分子量３７００のＰＥＧ　６．０質量部を、温度６０℃でジプロピレングリコール６．０質量部に溶解し、平均分子量２１００のＰＥＧ溶液を調製した。次いで、ショ糖６０．０質量部、グルタミン酸ナトリウム２０．９質量部、リボフラビン０．１質量部及び香料１．０質量部に、前記ＰＥＧ溶液を混合撹拌し、水溶性湿潤粉末の入浴剤原料を調製した。
得られた入浴剤原料を用い、実施例１の複数の高圧力気体を封入した糖類粒状物の代わりに複数のプルランフィルムを包埋し、タマゴ型の固形入浴剤を調製した。得られた固形入浴剤について実施例１と同様な試験を行なった。結果を表１に示す。
【００２４】
実施例６
平均分子量５００のＰＥＧ　５．０質量部及び平均分子量３７００のＰＥＧ　５．０質量部を、温度６０℃でジプロピレングリコール５．０質量部に溶解し、平均分子量２１００のＰＥＧ溶液を調製した。次いで、乾燥オキアミ８５質量部に、前記ＰＥＧ溶液を混合撹拌し、水溶性湿潤粉末の固形撒き餌原料を調製した。
得られた固形撒き餌原料を用いて実施例１と同様な加圧成形器を用いて加圧成形時の圧力を１ｋｇｆ／ｃｍ^２として楕円状の固形撒き餌を製造した。得られた固形撒き餌について、実施例２と同様な各試験を行なった。結果を表１に示す。
【００２５】
【表１】

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a pressure-formed solid obtained by low-pressure molding, in which generation of cracks and cracks during storage, transportation, and handling is suppressed or prevented.
[0002]
[Prior art]
Solids such as solid cosmetics, detergents, and fragrances are, for example, a method in which a liquefied raw material is put into a desired mold, cooled and solidified, then die-cut, a method of granulating a powder raw material to a desired size, a desired material, Are manufactured by a method of encapsulating the raw material in a capsule, a method of pressing a powder raw material with a tableting machine, and a method of manually solidifying the raw material into a desired shape. The solids obtained by these methods differ, for example, in the hardness and elasticity of the solids obtained by the production method, even when the raw material components used are the same, and can be physically distinguished from each other.
By the way, among solids obtained by the above methods, conventional solids obtained by pressure molding are excellent in productivity and also excellent in handleability due to high surface hardness.
Conventional solids produced by pressure molding are usually molded using a tableting machine at a pressure of 100 kgf / cm ² or more from one direction. The solids produced in this way have a drawback that they have high hardness but lack elasticity and are liable to cracks and cracks due to impact. Therefore, in commercialization, a surface coat with a water-soluble polymer is often applied. However, even if the solid material is coated with a surface, if it is subjected to a strong impact due to dropping, it will crack easily and break easily, and it will break immediately after the surface coating layer begins to dissolve during use. And the commercial value is significantly reduced. Such a problem is likely to occur when a solid material embeds a tangible material therein and when one solid material weighs 10 g or more.
Solids for the purpose of dissolving in water or the like molded by high pressure using the tableting molding machine, since the solubility is reduced by high pressure molding, usually organic acids and carbonates as foaming components. Often contains. However, even if it contains a foaming component, it is hard to say that its solubility is always sufficient because it is molded under high pressure. In addition, in the conventional solid, since the pressure during pressure molding is performed at a high pressure from one direction, it is difficult to mold into a spherical, egg-shaped or elliptical shape. Inability to embed tangible objects that cause deformation, destruction, adhesion, etc.
[0003]
[Problems to be solved by the invention]
Then, in order to solve the above-mentioned problem, it is conceivable to reduce the pressure during pressure molding. However, when the pressure is reduced, the molding itself is difficult, and even when the molding can be performed, generation of cracks and cracks cannot be suppressed. In particular, when tangible objects are embedded, cracks or cracks occur during storage, or when used in contact with water or hot water, cracks occur immediately after contact with water or hot water and uniform dissolution cannot be achieved. The problem arises.
[0004]
SUMMARY OF THE INVENTION An object of the present invention is to provide a pressure-formed solid which has good handling, and in which the occurrence of cracks and cracks is suppressed or prevented during storage, use and handling.
Another object of the present invention is to include a tangible material inside, have a shape such as a spherical shape, an egg shape or an elliptical shape, and handle well, and suppress generation of cracks and cracks during storage, use, and handling. Or to provide a pressed solid that is prevented.
[0005]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems. First, an attempt was made to produce a solid having apparently the same hardness as a conventional solid formed under high pressure using a tableting machine. However, molding was not possible due to molding under low pressure, and even if molding was possible, it was very brittle. Therefore, as a result of various investigations on the raw materials, it was found that a solid having apparently the same hardness as a conventional solid can be obtained even at a low pressure by using a fluidized polyethylene glycol (PEG) having a specific molecular weight. I found it. However, even if the solid obtained in this manner is formed under low pressure, cracks and cracks cannot always be sufficiently suppressed.Especially, when a tangible object is embedded, cracks and cracks occur during storage. It was difficult to control.
Therefore, as a result of further intensive studies, pressure molding is performed using a solvent containing dipropylene glycol (DPG) and / or 1,3-butylene glycol (1,3-BG) as a solvent for fluidizing PEG having a specific molecular weight. The solid material obtained by forming the raw material into a wet powder and pressing it at a specific pressure has an elastic force that is slightly depressed without cracking or cracking even when dropped on a concrete floor from a height of 1 m. Then, they found that an unprecedented solid was obtained, and completed the present invention.
[0006]
That is, according to the present invention, a powder raw material is mixed with a liquid raw material containing polyethylene glycol having an average molecular weight of 500 to 3700 fluidized with a solvent containing dipropylene glycol and / or 1,3-butylene glycol. The obtained water-soluble wet powder was obtained by pressure molding at a pressure of 0.5 to ¹⁰ kgf / cm ² , or a tangible material was embedded in the water-soluble wet powder, and the pressure was 0.5 to 10 kgf / cm ^2. A press-formed solid characterized by being a detergent, a fragrance, a deodorant, a bleaching agent, a slimming agent, a water quality improving agent, a sludge improving agent, a sowing bait or a fertilizer obtained by press-molding with Is done.
Further, according to the present invention, a powder raw material is mixed with a liquid raw material containing polyethylene glycol having an average molecular weight of 500 to 3700 fluidized with a solvent containing dipropylene glycol and / or 1,3-butylene glycol. Water-soluble wet powder obtained by subjecting a water-soluble wet powder, which does not contain a foaming component comprising an organic acid and a carbonate, to pressure molding at a pressure of 0.5 to ¹⁰ kgf / cm ² , or A pressure-formed solid, which is a solid cosmetic, obtained by embedding a tangible material in a powder and pressing under a pressure of 0.5 to ¹⁰ kgf / cm ² is provided.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in more detail.
Examples of the press-molded solid of the present invention include detergents, fragrances, deodorants, bleaching agents, slicking agents, water quality improvers, sludge improvers, bait, fertilizers, and solid cosmetics. Above all, solid cosmetics do not contain organic acids and carbonates as foaming components, and include, for example, bath salts, skin cleansers, desiccants, pest repellents, foot baths, antiperspirants, solid lotions or solid emulsions And the like.
The press-molded solid of the present invention has apparently the same hardness as a conventional solid press-molded at a high pressure by a tablet press, and cracks when dropped on a concrete floor from a height of 1 m. And it has an elastic force that is slightly depressed without cracking. Here, the apparent hardness equivalent to that of the conventional solid cosmetic is not measured by a hardness meter, but the touch feel has a hardness as high as that of a conventional tablet, and it can be handled in substantially the same manner. means.
[0008]
The press-molded solid of the present invention is prepared by converting a specific water-soluble wet powder (A) which can be formed by pressurization or a water-soluble wet powder (B) containing no foaming component comprising an organic acid and a carbonate into a specific water-soluble wet powder (B). It is obtained by pressure molding under pressure. Here, the term “wet powder” refers to, for example, a powder in which a powder raw material is in a wet state by PEG or the like fluidized by a specific solvent. Further, the water-soluble wet powder means that almost all components constituting the powder are water-soluble, and may contain, for example, an oil-soluble aromatic component which is insoluble in water.
In the press-molded solid of the present invention, the water-soluble wet powders (A) and (B) used for the production contain a powder raw material and PEG having a specific molecular weight fluidized with a specific solvent. The water-soluble wet powder (B) does not contain the above-mentioned foaming component, though it contains other components depending on the application.
[0009]
The solvent used in the present invention contains DPG and / or 1,3-BG. Preferably, only DPG and / or 1,3-BG are used, and particularly preferably, DPG is used alone. DPG and / or 1,3-BG are necessary for dispersing PEG throughout the raw material and imparting the above-mentioned characteristic hardness and elasticity in the present invention. The PEG used in the present invention dissolves in, for example, ethanol, but when only ethanol is used without using DPG and / or 1,3-BG, the desired effect of the present invention in which cracking and cracking can be suppressed is achieved. Can not be obtained. In particular, when a tangible object is embedded, the possibility of cracking or cracking during storage increases.
[0010]
The average molecular weight of the PEG used in the present invention is 500-3700. PEG having such a molecular weight usually exhibits a flake state from a paste state, and for example, a commercially available product or a mixture of commercially available products so as to have a desired molecular weight can be used. When the average molecular weight of PEG is out of the above range, the press-moldability is deteriorated, and it is difficult to impart desired hardness and elasticity to the press-molded solid.
The PEG having a specific molecular weight fluidized by the specific solvent is, for example, a method in which the PEG is mixed with a solvent containing DPG and / or 1,3-BG, and heated to about 60 to 70 ° C. to dissolve the PEG. Is obtained by At this time, the mixing ratio of the solvent containing DPG and / or 1,3-BG and PEG can be appropriately selected so that the PEG is fluidized, but in order to more effectively obtain the desired effect of the present invention, A ratio of 1: 0.5 to 20, especially 1: 0.5 to 10, is preferred. Further, the content ratio of the PEG in the pressure-formed solid except for the tangible material is preferably 2 to 50% by mass.
[0011]
The powdery raw material used in the production of the present invention can be appropriately selected according to its use, and can be selected from known components. Further, in the case of the water-soluble wet powder (A), it may contain a foaming component composed of an organic acid and a carbonate, and the foaming component reacts with moisture to generate carbon dioxide gas, and is pressurized solid. It is a component that assists solubility when the substance is used by dissolving in water or hot water. The foaming component can be used as a powder, and its particle size may be any as long as it can be molded by pressure as a raw material.
The organic acid is preferably one or more selected from the group consisting of citric acid, fumaric acid, tartaric acid, adipic acid and succinic acid. In particular, the use of citric acid is preferred in view of the foaming power and uniform solubility in the pressure-formed solid of the present invention.
Examples of the carbonate include sodium carbonate, sodium hydrogencarbonate, sodium sesquicarbonate, and potassium salts thereof.
The compounding ratio of the organic acid and the carbonate as the foaming component is usually 1: 0.2 to 3.0 by mass ratio, and a ratio close to 1: 1 is particularly desirable. Further, in the water-soluble wet powder (A) excluding tangible substances, the total content of the organic acid and the carbonate is preferably 30 to 90% by mass.
[0012]
When it is necessary to make the specific gravity of the pressure-formed solid of the present invention 1 g / cm ³ or more, it is preferable to use anhydrous sodium sulfate as a specific gravity adjuster. The anhydrous sodium sulfate is a component that does not deteriorate the pressure moldability. Therefore, the mixing ratio in the case of using anhydrous sodium sulfate can be appropriately determined in consideration of the specific gravity of the press-molded solid, but can be appropriately selected usually from the range of 1 to 50% by mass. Anhydrous sodium sulfate can be used as a powder, and its particle size may be any as long as it can be molded by pressure as a raw material.
[0013]
If necessary, the water-soluble wet powder may contain a liquid component such as an aromatic component in addition to PEG dissolved in the solvent.
In the water-soluble wet powders (A) and (B), the mixing ratio of the powdered raw material and the fluidized PEG is preferably 1: 0.01 to 20, more preferably 1: 0.1 in mass ratio. ~ 15. If the blending ratio of the fluidized PEG is less than 0.01 with respect to 1 of the powder raw material, the strength cannot be imparted, and molding cannot be performed. If it exceeds 20, it is not preferable because it becomes a slurry and molding is difficult.
[0014]
A tangible object may be embedded in the pressure-formed solid of the present invention. The tangible includes a water-insoluble tangible or a water-soluble tangible. Examples of the water-insoluble tangible material include a resin toy, a water-insoluble film, a water-insoluble capsule, and a water-insoluble gel. Examples of the water-soluble tangible material include a water-soluble film, a water-soluble solid, a water-soluble capsule, and a water-soluble gel. Specific tangible materials include saccharide granules, capsules, polysaccharide films, dried plants, sponges, accessories, toys, tablets, etc., in which high-pressure gas is sealed. It can be appropriately selected according to the conditions.
The shape of the tangible object is not particularly limited, and may be a relatively large toy or the like and a complicated shape. It is preferable that the size of the tangible material is appropriately selected according to the size of the pressure-formed solid. The specific gravity of the tangible object is not particularly limited.
The method for embedding the tangible material is not particularly limited. For example, there is a method in which a concave portion is provided in advance in the water-soluble wet powder, the tangible material is placed in the concave portion, and then embedded.
[0015]
The press-molded solid of the present invention is obtained by subjecting the water-soluble wet powder (A) or (B) or the water-soluble wet powder (A) or (B) having a tangible material embedded to a pressure of 0.5 to 10 kgf. / Cm ² , preferably 0.5 to 5 kgf / cm ^2, particularly preferably 0.8 to 5 kgf / cm ² . If the pressure is less than 0.5 kgf / cm ² , molding is difficult or the desired strength cannot be imparted to the pressure-molded solid, while if it exceeds 10 kgf / cm ² , the desired solubility is obtained. In addition, the embedded tangible object is deformed, destroyed, adhered, etc., and the commercial value is reduced.
The pressure molding is a modification of a conventional tablet molding machine, and can be performed by one press. However, the pressure can be divided into two or more times within the pressure range. . In particular, when embedding a tangible object, the pressurization is divided into two or more times, the first pressure is lowered, and the final pressure is applied from the second time onward, so that the water-soluble wet powder becomes the outer shape of the tangible object. Can be densely packed along. When the shape of the pressure-formed solid is spherical, egg-shaped, elliptical, or the like, pressure can be applied from two or more directions. In addition, the shape of the pressure-formed solid is not particularly limited, and may be a cube, a triangular prism, a star-shaped column, a columnar shape, or a complicated shape in the shape of a doll, in addition to the above-mentioned shapes.
[0016]
The total mass of the pressure-formed solid of the present invention is not particularly limited, but is preferably from 10 to 300 g, particularly preferably from 50 to 300 g, in which desired effects are remarkably exhibited. In the case of such a total mass range, since it is larger than a conventional tablet-type solid substance of about several g, the possibility of cracking and cracking increases. The problem is effectively suppressed or prevented.
The press-molded solid of the present invention can be obtained by drying after the above-mentioned press-molding, but if necessary, for example, in order to improve surface deterioration and handleability due to contact with air during storage. Alternatively, moisture such as steam may be caused to react on the surface of the pressure-formed solid, so that only the surface can be made into a neutral salt. In order to further effectively prevent the occurrence of cracks and cracks during storage, transportation, and use of the press-formed solid, known shrink packaging can be performed as necessary.
The press-formed solid of the present invention is light-impermeable and packaged in a bag-shaped packaging material in order to suppress or prevent discoloration and odor during long-term storage and maintain commercial value. You can also. Examples of the packaging material include aluminum foil. Alternatively, the pressure-formed solid of the present invention can be placed in a bag-shaped packaging material, decompressed using a decompression device, and sealed. Further, the pressure-formed solid of the present invention may be provided with a surface coat with a known water-soluble polymer component.
[0017]
【The invention's effect】
The pressure-formed solid of the present invention is obtained by pressing a water-soluble wet powder containing a powder raw material and PEG having a specific molecular weight fluidized with a solvent containing DPG and / or 1,3-BG at a specific pressure. Therefore, the handling is good, and the generation of cracks and cracks during storage, use, and handling is suppressed or prevented. Furthermore, since it is manufactured by low-pressure molding, deformation, destruction, adhesion, etc. of the tangible object hardly occurs even if the tangible object is an embedded pressure-formed solid, Cracks and cracks can be effectively suppressed or prevented even when shrinkage occurs or even when a force for restoring the shrinkage occurs during storage or the like. Therefore, they are extremely useful for detergents, fragrances, deodorants, bleaching agents, slime removers, water quality improvers, sludge improvers, spray baits or fertilizers, and various solid cosmetics that can be produced by pressure molding.
[0018]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
Example 1
6.0 parts by mass of PEG having an average molecular weight of 500 and 6.0 parts by mass of PEG having an average molecular weight of 3700 were dissolved in 6.0 parts by mass of dipropylene glycol at a temperature of 60 ° C. to prepare a PEG solution having an average molecular weight of 2100. Then, the PEG solution was mixed and stirred with 20.0 parts by mass of sodium lauryl sulfate, 5 parts by mass of polyoxyethylene oleyl ether, 1 part by mass of disodium edetate and 56.0 parts by mass of sodium carbonate. A solid detergent raw material was prepared.
The obtained solid detergent raw material was placed in a cylindrical container, a concave portion was formed in the center, and a plurality of high-pressure gases were filled after introducing a saccharide particulate material filled with a plurality of high-pressure gases into the concave portion. The saccharide granules were embedded. Next, after performing the first pressurization at a pressure of 1.0 kgf / cm ² using a pressing plate having a hemispherical concave portion from above, pressure is applied from above and below using two pressing plates having a hemispherical concave portion. A second pressurization was performed at 2.0 kgf / cm ² to prepare an egg-shaped solid detergent and dried. Each evaluation shown below was performed about the obtained solid detergent. Table 1 shows the results.
[0019]
<Molded state>
The pressed solid is touched by a panel of 10 people, giving a strong feel similar to that of a conventional tablet manufactured by a tableting machine, and 3 points where the molding is strong, and the molding is soft. Two points were determined for the sample and one point was determined for the unmoldable one. The result was the average score of 10 people.
<Cracks and cracks>
The pressure-formed solid was dropped from a height of 1 m onto a concrete floor, and the occurrence of cracks or cracks was observed. A sample in which a crack or a crack was observed was evaluated as x, and a sample in which no crack or crack was observed was evaluated as ○.
<State of tangible objects>
The case where the tangible material embedded in the press-molded solid material effectively functioned during use without causing deformation, destruction, adhesion, etc. was evaluated as ○, and the case where it did not function was evaluated as ×.
<Long-term storage>
The press-formed solid was placed in an aluminum foil bag, packaged, and stored at room temperature for 6 months. After 6 months, the bags were opened and compared with the odor and color at the time of manufacture. A sample with little change was rated as "O", and a sample with a change in at least one of odor and color was rated as "x".
[0020]
Example 2
6.0 parts by mass of PEG having an average molecular weight of 500 and 6.0 parts by mass of PEG having an average molecular weight of 3700 were dissolved in 6.0 parts by mass of dipropylene glycol at a temperature of 60 ° C. to prepare a PEG solution having an average molecular weight of 2100. Next, 81.8 parts by mass of maltose, 0.1 parts by mass of plant extract, 0.01 parts by mass of sodium hyaluronate and 0.09 parts by mass of flavor are mixed and stirred with the PEG solution to obtain a solid lotion of a water-soluble wet powder. Raw materials were prepared.
An elliptical solid lotion was manufactured from the obtained solid lotion raw material by using the same press-molding apparatus as in Example 1 at a pressure of 1 kgf / cm ² . With respect to the obtained solid lotion, each test of the moldability, generation of cracks and cracks, and long-term storage stability in Example 1 was performed. Table 1 shows the results.
[0021]
Example 3
6.0 parts by mass of PEG having an average molecular weight of 500 and 6.0 parts by mass of PEG having an average molecular weight of 3700 were dissolved in 6.0 parts by mass of dipropylene glycol at a temperature of 60 ° C. to prepare a PEG solution having an average molecular weight of 2100. Next, the PEG solution was mixed and stirred with 2 parts by mass of polyoxyethylene oleyl ether and 80.0 parts by mass of sodium percarbonate to prepare a solid bleach raw material as a water-soluble wet powder.
An egg-shaped solid bleaching agent was produced using the obtained solid bleaching agent raw material and the same pressure molding machine as in Example 1 at a pressure of 2 kgf / cm ² during pressure molding. The same tests as in Example 2 were performed on the obtained solid bleaching agent. Table 1 shows the results.
[0022]
Example 4
8.0 parts by mass of PEG having an average molecular weight of 500 and 8.0 parts by mass of PEG having an average molecular weight of 3700 were dissolved in 8.0 parts by mass of dipropylene glycol at a temperature of 60 ° C. to prepare a PEG solution having an average molecular weight of 2100. Next, the PEG solution was mixed and stirred with 10 parts by mass of tetrasodium edetate, 5.0 parts by mass of sodium lauryl sulfate, and 61.0 parts by mass of sodium carbonate to prepare a water-soluble wet powder in a solid bath tub to prepare a detergent material. .
Using the obtained solid bathtub detergent raw material, a compressed sponge was embedded in place of the saccharide granules containing a plurality of high-pressure gases of Example 1 to prepare an egg type solid bathtub detergent. The same test as in Example 1 was carried out on the obtained solid bathtub detergent. Table 1 shows the results.
[0023]
Example 5
6.0 parts by mass of PEG having an average molecular weight of 500 and 6.0 parts by mass of PEG having an average molecular weight of 3700 were dissolved in 6.0 parts by mass of dipropylene glycol at a temperature of 60 ° C. to prepare a PEG solution having an average molecular weight of 2100. Next, the PEG solution was mixed and stirred with 60.0 parts by mass of sucrose, 20.9 parts by mass of sodium glutamate, 0.1 parts by mass of riboflavin, and 1.0 parts by mass of fragrance, and the bathing agent raw material of the water-soluble wet powder was mixed. Prepared.
Using the obtained bath additive raw materials, a plurality of pullulan films were embedded in place of the saccharide granules in which a plurality of high-pressure gases of Example 1 were sealed, to prepare an egg-shaped solid bath agent. The same test as in Example 1 was performed on the obtained solid bath agent. Table 1 shows the results.
[0024]
Example 6
5.0 parts by mass of PEG having an average molecular weight of 500 and 5.0 parts by mass of PEG having an average molecular weight of 3700 were dissolved in 5.0 parts by mass of dipropylene glycol at a temperature of 60 ° C. to prepare a PEG solution having an average molecular weight of 2100. Next, the PEG solution was mixed and stirred with 85 parts by mass of dry krill to prepare a water-soluble wet powder solid feed material.
An elliptical solid bait was manufactured using the obtained solid bait raw material and a pressure at the time of press forming of 1 kgf / cm ² using the same press-forming machine as in Example 1. Each test similar to that of Example 2 was performed on the obtained solid soaked bait. Table 1 shows the results.
[0025]
[Table 1]

Claims

A water-soluble wet powder (A) obtained by mixing a powder material and a liquid material containing polyethylene glycol having an average molecular weight of 500 to 3700 fluidized with a solvent containing dipropylene glycol and / or 1,3-butylene glycol. ) Is a detergent, a fragrance, a deodorant, a bleach, a stripper, a water quality improver, a sludge improver, a sow bait or a fertilizer obtained by press-molding at a pressure of 0.5 to 10 kgf / cm ^2. A pressure-formed solid, characterized in that:

A water-soluble wet powder (A) obtained by mixing a powder material and a liquid material containing polyethylene glycol having an average molecular weight of 500 to 3700 fluidized with a solvent containing dipropylene glycol and / or 1,3-butylene glycol. ), A tangible material is embedded therein, and the resulting product is molded by pressing at a pressure of 0.5 to 10 kgf / cm ² , which is a detergent, an aromatic, a deodorant, a bleach, a slimming agent, a water quality improver, and a sludge improver Pressurized solid, characterized in that it is an agent, a sow bait or a fertilizer.

A water-soluble wet powder obtained by mixing a powder raw material and a liquid raw material containing polyethylene glycol having an average molecular weight of 500 to 3700 fluidized with a solvent containing dipropylene glycol and / or 1,3-butylene glycol. A water-soluble wet powder (B) containing no foaming component comprising an organic acid and a carbonate, which is obtained by press-molding at a pressure of 0.5 to ¹⁰ kgf / cm ² , which is a solid cosmetic. Press molded solids.

A water-soluble wet powder obtained by mixing a powder raw material and a liquid raw material containing polyethylene glycol having an average molecular weight of 500 to 3700 fluidized with a solvent containing dipropylene glycol and / or 1,3-butylene glycol. A solid cosmetic obtained by embedding a tangible material in a water-soluble wet powder (B) containing no foaming component composed of an organic acid and a carbonate and press-forming at a pressure of 0.5 to 10 kgf / cm ^2. Pressure-formed solid, characterized in that it is a material.

The pressure molding according to claim 2 or 3, wherein the solid cosmetic is a bath agent, a skin cleanser, a sizing agent, a pest repellent, a foot bath, an antiperspirant, a solid lotion or a solid emulsion. Solids.

The water-soluble wet powder (A) contains a foaming component comprising one or more organic acids and carbonates selected from the group consisting of citric acid, fumaric acid, tartaric acid, adipic acid and succinic acid. Or a pressure-formed solid according to 2.

Pressing pressure, pressing solids according to any one of the range 1-6 claims a 0.5~5kgf / cm ^2.

3. The tangible material is one or more selected from the group consisting of saccharide granules encapsulating a high-pressure gas, capsules, polysaccharide films, dried plants, sponges, accessories, toys, and tablets. Or a press-formed solid according to item 4.

The pressure-molded solid according to any one of claims 1 to 8, wherein the shape is a sphere, an egg, an ellipse, or a column.

The compounding ratio of a solvent containing dipropylene glycol and / or 1,3-butylene glycol and polyethylene glycol having an average molecular weight of 500 to 3700 is 1: 0.5 to 20 by mass ratio, any one of claims 1 to 9. Item.