JP3912838B2 - Washing method - Google Patents
Washing method Download PDFInfo
- Publication number
- JP3912838B2 JP3912838B2 JP07906797A JP7906797A JP3912838B2 JP 3912838 B2 JP3912838 B2 JP 3912838B2 JP 07906797 A JP07906797 A JP 07906797A JP 7906797 A JP7906797 A JP 7906797A JP 3912838 B2 JP3912838 B2 JP 3912838B2
- Authority
- JP
- Japan
- Prior art keywords
- washing
- laundry
- detergent composition
- liquid
- washing liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 238000005406 washing Methods 0.000 title claims description 217
- 238000000034 method Methods 0.000 title claims description 48
- 239000007788 liquid Substances 0.000 claims description 89
- 239000000203 mixture Substances 0.000 claims description 75
- 239000003599 detergent Substances 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000003352 sequestering agent Substances 0.000 claims description 18
- -1 alkylbenzene sulfonate Chemical class 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 150000005215 alkyl ethers Chemical class 0.000 claims description 4
- 150000008051 alkyl sulfates Chemical class 0.000 claims 1
- 239000004744 fabric Substances 0.000 description 29
- 229910001424 calcium ion Inorganic materials 0.000 description 23
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 21
- 239000002738 chelating agent Substances 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 12
- 239000008399 tap water Substances 0.000 description 12
- 235000020679 tap water Nutrition 0.000 description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 11
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
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Images
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- Accessory Of Washing/Drying Machine, Commercial Washing/Drying Machine, Other Washing/Drying Machine (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、洗濯方法に関する。更に詳しくは、予め洗剤組成物を溶解させて得られる洗濯液と被洗濯物とを接触させることを特徴する、洗剤組成物の有する洗浄力を充分発揮させることができる洗濯方法に関する。
【０００２】
【従来の技術】
一般に衣料用に使用される洗剤組成物は、繊維表面の界面張力を低下させ、汚れの洗濯液中への可溶化や分散を促進させる為の界面活性剤と、繊維を膨潤させ、加えて汚れの洗濯液中への分散性を助長するアルカリ剤、水道中のカルシウムイオンやマグネシウムイオン等の硬度成分による影響を無くすための金属イオン封鎖剤、並びにその他添加物より構成されている。
【０００３】
一方、洗剤組成物の形態としては、液体、ぺースト、粉末ないし塊状等のあらゆる形態がこれまで提案されており、それぞれの形態に応じた組成、並びに製造方法が検討され、数多くの出願がなされてきた。
【０００４】
しかしながら、その組成と形態との関係について検討されたものは少なく、溶解性や粉末物性の向上のために特定の成分を分けて配合する以外は、製造方法やそれに費やすコストを考慮した場合、通常、洗剤組成物を構成している洗剤成分は同一媒体中に存在させることが一般的である。例えば、液体洗剤組成物については言うまでもなく、粉末ないし塊状の洗剤組成物については、加熱により劣化する成分（例えば、香料、酵素又は漂白剤）を除いた成分のスラリーを乾燥、冷却、粉砕、造粒、打錠等の処理を行うことにより容易に得ることができる。
【０００５】
このように、一般の洗剤組成物は、金属イオン封鎖剤とアルカリ剤が同一媒体内に存在しているため、かかる洗剤組成物を水に溶解及び／又は分散させた場合、アルカリ剤と水との反応よるアルカリ能の発現よりも、金属イオン封鎖剤と水中のカルシウムイオンやマグネシウムイオンとの反応の方が速度的に遅い。そのために、洗濯液の硬度の低下速度は遅く、一方で洗濯液がアルカリ性を呈する速度は極めて速いことが考えられる。
【０００６】
ところで、人体由来の皮脂汚れはその大半において、脂肪酸を含有している。洗浄中において、洗濯液中のカルシウムイオン、マグネシウムイオンは界面活性剤の界面活性能を低下させる以外に汚れの水中への分散を防げる原因になる。これは、上記汚れ中の脂肪酸とカルシウムイオン、マグネシウムイオンとの反応により、溶解性の低いスカムが形成されることによる。
【０００７】
特に我々は、脂肪酸とカルシウムイオン及びマグネシウムイオンとのスカム形成速度が洗濯液のアルカリ度（ｐＨ）の高い時ほど速くなることに気づいた。これは、汚れ中の脂肪酸とカルシウムイオンやマグネシウムイオンとの反応速度よりも、アルカリ剤によってイオン化した脂肪酸とこれらのイオンとの反応速度の方が大きいことによるものと考えられる。従って、通常の洗濯を行う上で、洗濯液のアルカリ性化が洗濯液の硬度の低下よりも速い状況では、汚れ表面でのスカムの形成が起こりやすく、それにより汚れの洗濯液への遊離・分散が阻害されることが考えられる。しかしながら、充分な洗浄力を得るためには、洗濯液がアルカリ性を呈することは極めて重要な条件である。つまり、従来の一般的な洗濯方法は、洗剤組成物のパフォーマンスを充分に生かしきれているとは必ずしも言えないことに我々は気づいた。
【０００８】
現在市販されている洗濯機の中には洗濯槽に添加する前に洗剤組成物を溶解させるための溶解槽を有するものがある。しかしながら、これらの溶解槽の目的の大半は洗濯槽内での洗剤組成物の溶け残りを無くすことである。洗浄力の向上について言及する商品もいくつか存在するが、これらの技術はいずれも、洗濯槽内での洗剤組成物の溶解時間を短縮することによって洗浄力の向上を計るものであるのに過ぎず、調製された洗濯液の硬度が充分に下がらない状況で洗濯液と被洗濯物とが接触するおそれがある。その上、洗濯槽内に洗剤組成物のほとんどが添加された後でも、洗濯液の硬度を充分考慮していないために、洗濯槽内にカルシウムイオン、マグネシウムイオン等を含有する洗濯用水の添加が無配慮のまま行われ得る。そのため、洗濯槽の洗濯液の硬度は暫く高いままのおそれもある。
【０００９】
【発明が解決しようとする課題】
本発明の目的は、従来の衣料用の洗剤組成物を使用して衣類等の被洗濯物を洗濯する際に、洗剤組成物の持つ洗浄能力を充分に引き出し、より優れた洗浄力を発揮させるための洗濯方法を提供することである。
【００１０】
【課題を解決するための手段】
本発明者らは、鋭意検討の結果、先に洗剤組成物を洗濯用水に溶解及び／又は分散させ、洗濯液の硬度を予め低下させた後、被洗濯物と接触させることによって、洗浄力が従来よりも上昇することを見出し、本発明を完成するに至った。
【００１１】
即ち、本発明の要旨は、
〔１〕 洗濯用水に、金属イオン封鎖剤及びアルカリ剤を含有する洗剤組成物を溶解及び／又は分散させ、洗濯液の硬度が１．５°ＤＨ以下、かつ、ｐＨが８．０以上になるまで熟成させて洗濯液を調製した後、該洗濯液と被洗濯物とを接触させ、硬度１．５°ＤＨ以下、かつ、ｐＨが８．０以上の該洗濯液により洗浄することを特徴とする洗濯方法、並びに
〔２〕 洗濯用水に溶解及び／または分散させる洗剤組成物が、更にアルキルベンゼンスルホン酸塩、アルキル硫酸エステル塩及びポリオキシエチレンアルキルエーテルから選ばれる界面活性剤を含有することを特徴とする前記〔１〕記載の洗濯方法、に関するものである。
【００１２】
【発明の実施の形態】
１．本発明の洗濯方法
本発明の洗濯方法は、洗濯用水に、洗剤組成物を溶解及び／又は分散させて洗濯液を調製した後、該洗濯液と被洗濯物とを接触させることを特徴とする。
【００１３】
本発明において用いられる洗濯用水としては、通常洗濯に用いられるものであれば特に限定されるものではない。例えば、水道水が一般的であるが、地域によっては地下水や河川の水を使用している場合もある。
【００１４】
洗濯液は、洗濯用水に洗剤組成物を溶解及び／又は分散させることにより調製される。金属イオン封鎖剤として用いられるゼオライト等の、水に不溶性の成分は、洗濯液に分散した状態で存在する。
洗剤組成物を洗濯用水に溶解及び／又は分散させるために、通常何らかの物理的な操作を行う。例えば、洗濯用水と洗剤組成物を攪拌羽根等で攪拌したり、またはループ状の管をつくり、ポンプにて管内を循環させることにより溶解及び／又は分散させる等の、洗濯用水と洗剤組成物とを強制的に混合させる態様が考えられるが、単に勢いよく、洗剤組成物に洗濯用水を添加する等の方法でも構わない。いずれに場合も、洗剤組成物を充分に洗濯液に溶解及び／又は分散させることが好ましく、そうすることによって硬度の低下速度も速くなる。
【００１５】
一般に硬度低下剤として洗剤組成物に含まれている金属イオン封鎖剤の主成分であるゼオライトは水に不溶性であるため、かかる成分を洗濯用水に添加してから洗濯液の硬度が充分に低下し終えるまでに時間を要する。従って本発明では、洗濯用水に洗剤組成物を溶解及び／又は分散させた後、熟成させて洗浄液を調製することが好ましい。熟成操作としては、例えば洗濯用水に洗剤組成物を溶解及び／又は分散させた後、このものを放置したり、攪拌したり、温度を上げる等の、金属イオン封鎖剤の能力を発揮させて洗濯液の硬度を低下させる操作が挙げられる。かかる熟成操作に要する時間（熟成時間）は特に限定されるものではないが、１０秒間以上が好ましく、３０秒間以上がより好ましく、１分間以上が特に好ましい。
【００１６】
上記のようにして調製される洗濯液の硬度は低い方が好ましい。具体的には、調製された洗濯液の硬度が１．５°ＤＨ以下が好ましく、０．８°ＤＨ以下がより好ましく、０．５°ＤＨ以下が特に好ましい。
【００１７】
洗濯液の硬度の測定法としては、洗剤組成物に配合されている金属イオン封鎖剤がイオン交換体である時は、孔サイズ０．２μｍのメンブランフィルター（アドバンテック社：ニトロセルロース製）を用いて洗濯液をろ過し、ろ液中に含有される硬度成分量をＩＣＰ法（イオンプラズマカップリング法）もしくはＥＤＴＡ滴定法を用いて容易に測定することができる。
また、洗剤組成物に配合されている金属イオン封鎖剤がキレート剤の場合は、キレート指示薬法を採用することで良好な結果を得ることができる。キレート指示薬法は、被験洗濯液に相当するｐＨ及びイオン強度下で検量線を作成する必要性があるが、キレート剤等の金属イオン封鎖剤に捕捉されえなかった遊離の硬度成分量を、洗濯液そのものから定量することができる。具体的には、例えば 4th WORLD SURFACTANTS CONGRESS 要旨集第２巻 p.159に記載されている Chrome Violet（東京化成工業（株）より入手可能）による方法を用いることができる。
【００１８】
さらに多くの洗剤組成物がそうであるように、洗剤組成物に、イオン交換体とキレート剤が金属イオン封鎖剤として併用されてる場合には、上記のメンブランフィルターを用いる方法とキレート指示薬法を組み合わせることで目的を達成することができる。即ち、被験洗濯液を速やかに孔サイズ０．２μｍのメンブランフィルターを用いて洗濯液中のイオン交換体をろ過し、得られたろ液に Chrome Violet液を添加後、着色液の可視吸収波長を測定することで、キレート剤に捕捉されていない遊離の硬度成分量を定量するものである。
【００１９】
次いで、調製された洗濯液と、衣類等の被洗濯物とを接触させて洗濯を行う。このときの洗濯方法としては、洗濯液と被洗濯物との接触が行われる場である洗濯槽に予め洗剤組成物を充分に溶解及び／又は分散させた後、被洗濯物を洗濯槽に投入する方法の他に、別途、別の槽で調製しておいた洗濯液を被洗濯物の入った洗濯槽に添加する方法等が挙げられる。具体的には、前者としては洗濯槽上部に被洗濯物を乗せるための網を設けてその上に被洗濯物を乗せておき、洗濯槽に洗濯液が調製されてから網を反転させたり割ること等により、被洗濯物を洗濯槽に投入する方法等が挙げられ、後者としては、洗濯液を調製したり貯蔵するための予備溶解槽を別途備えた洗濯装置を用いて、予備溶解槽から被洗濯物が投入された洗濯槽に適宜洗濯液を供給する方法等が挙げられる。
【００２０】
また、本発明の洗濯方法においては、洗濯中に被洗浄物、洗濯液等を追加しても良い。具体的には、被洗濯物と接触後の洗濯液の硬度が２．０°ＤＨ以下であることが好ましく、１．５°ＤＨ以下であることがより好ましく、０．８°ＤＨ以下であることが特に好ましい。
【００２１】
本発明に用いられる調製された洗濯液は、洗浄性の観点からアルカリ性を呈することが好ましい。具体的には、該洗濯液のｐＨが８．０以上が好ましく、ｐＨが９〜１２の範囲がより好ましい。ここで、洗濯液のｐＨは通常のガラス電極ｐＨ計等により２５℃で測定される。
【００２２】
２．本発明における洗濯装置
本発明における洗濯装置としては、本発明の洗濯方法を行い得るものであれば特に限定されないが、例えば以下に示す態様が示される。
（Ａ）本発明の洗濯方法を行うための洗濯装置であって、
１）洗濯液と被洗濯物とを接触させるための接触機構、及び
２）洗濯液を調製し、該洗濯液を溜めると共に被洗濯物を収容し洗濯手段を有する洗濯槽、
を具備してなる洗濯装置。
（Ｂ）本発明の洗濯方法を行うための洗濯装置であって、
１）洗濯液を溜めると共に被洗濯物を収容し洗濯手段を有する洗濯槽、及び
２）洗濯液を調製し、該洗濯液を貯蔵する予備溶解槽、
を具備してなる洗濯装置。
【００２３】
（Ａ）の態様の洗濯装置
本態様の洗濯装置は、洗濯液を溜めると共に被洗濯物を収容し洗濯手段を有する洗濯槽で洗濯液を調製する。即ち、洗濯液と被洗濯物との接触が行われる場である洗濯槽に予め洗剤組成物を充分に溶解及び／又は分散させた後、被洗濯物を洗濯槽に投入する方法に好適に適用される。洗濯装置のタイプとしては、いわゆるパルセータ方式の洗濯装置が好ましいものとして挙げられる。
【００２４】
また、洗濯液と被洗濯物とを接触させるための接触機構としては、洗濯槽にて洗剤組成物が充分に溶解及び／又は分散した後に被洗濯物を洗濯槽に投入する手段が例示される。より具体的には、洗濯槽上部に設けられた、被洗濯物を乗せるための網であって、洗濯槽にて洗剤組成物が充分に溶解及び／又は分散した後に例えば反転したり割れること等により被洗濯物を洗濯槽に投入することができる網等が挙げられる。かかる接触機構を設けることにより、洗剤組成物が充分に溶解及び／又は分散する前に洗濯液と被洗濯物との接触が行われることが防がれる。
かかる接触機構には、洗濯槽内の洗濯液が所望の程度に溶解及び／又は分散した段階で被洗濯物を洗濯槽内に投入するための投入制御手段を設けても良い。かかる投入制御手段としては、例えば、所定の熟成時間の経過後に接触手段を操作して、被洗濯物を洗濯槽内に投入するタイマー等を備えたもの等が挙げられる。
【００２５】
（Ｂ）の態様の洗濯装置
本態様の洗濯装置は、洗濯液を溜めると共に被洗濯物を収容し洗濯手段を有する洗濯槽と、洗濯液を調製し、該洗濯液を貯蔵する機構（予備溶解槽）とが別個に存在してなる装置である。本態様においては、予備溶解槽から被洗濯物が投入された洗濯槽に適宜洗濯液が供給される。また、洗濯槽には最初に洗濯液を供給する必要はなく、例えば、洗濯槽に、まず被洗濯物を投入し、次いで予備溶解槽からで洗濯液を供給しても良い。洗濯装置のタイプとしては、いわゆるドラム方式の洗濯装置が好ましいものとして挙げられる。これは、ドラム方式の洗濯装置の場合、洗濯する時の洗濯液は比較的少量であるため、予備溶解槽を備え付けやすいからである。
【００２６】
また、本態様においては、予備溶解槽にて洗濯液の調製が行われる場合、被洗濯物と接触する洗濯液を洗剤組成物が充分に溶解及び／又は分散したものとすることができる。そのため、（Ａ）の態様の洗濯装置のような、洗濯液と被洗濯物とを接触させるための接触機構を設けなくても良い。
また、洗濯槽における被洗濯物と洗濯液との接触の際の洗濯液が、洗剤組成物が充分に溶解及び／又は分散したものであれば、予備溶解槽における洗濯液は必ずしも洗剤組成物が充分に溶解及び／又は分散したものである必要はない。
また、ドラム方式の洗濯装置の場合、衣料の浴比が低いために本発明の洗濯方法の効果が顕著に現れやすい。従って本発明の洗濯方法は、ドラム方式の洗濯装置を用いた場合が特に好ましい。
【００２７】
本発明において用いられる洗剤組成物としては、通常知られている衣料用の洗剤組成物を使用することができる。具体的には、例えば界面活性剤、金属イオン封鎖剤、アルカリ剤及びその他の洗浄成分から構成されるものが挙げられる。
【００２８】
上記の成分としては、具体的には、アルキルベンゼンスルホン酸塩、アルキル硫酸エステル塩及びポリオキシエチレンアルキルエーテル等の界面活性剤；ゼオライトである結晶性アルミノ珪酸塩、及び特開平7-89712 号公報、特開昭60-227895 公報に記載の結晶性珪酸塩、エチレンジアミン四酢酸（ＥＤＴＡ）及びクエン酸塩等の金属イオン封鎖剤；ポリアクリル酸、アクリル酸とマレイン酸のコポリマー及びカルボキシメチルセルロース等のカルボン酸系ポリマー；ソーダ灰等のアルカリ金属炭酸塩及びＪＩＳ１、２もしくは３号珪酸ナトリウム等のアルカリ金属珪酸塩等のアルカリ剤；硫酸ナトリウム等の増量剤；ポリエチレングリコール（ＰＥＧ）、ポリビニルピロリドン（ＰＶＰ）及びポリビニルアルコール（ＰＶＡ）等の分散剤もしくは色移り防止剤；過炭酸ナトリウム等の漂白剤；テトラアセチルエチレンジアミン（ＴＡＥＤ）や、特開平6-316700号公報に記載の漂白活性化剤；プロテアーゼ、セルラーゼ、アミラーゼ及びリパーゼ等の酵素；ホウ素化合物及び亜硫酸ナトリウム等の酵素安定剤；ビフェニル型、スチルベン型の蛍光染料；シリコーン／シリカ系等の消泡剤；酸化防止剤；青味付剤並びに香料等の従来から公知の成分を挙げることができる。より詳細には特開平8-218093号公報に記載されているものを参考にすることができる。
【００２９】
なお、金属イオン封鎖剤の洗濯用水への添加量は、洗濯用水の硬度を０．５°ＤＨ以下にするのに充分な量であることが特に好ましい。
洗濯用水の硬度を所望の値にするのに必要な金属イオン封鎖剤の量は、用いる洗濯用水の硬度と用いる金属イオン封鎖剤のカルシウムイオン捕捉能（ＣＥＣ）等から求めることができる。なお、用いる洗濯用水のＤＨ硬度はイオンカップリングプラズマ法（ＩＣＰ法）で測定される。
【００３０】
金属イオン封鎖剤のイオン捕捉能の測定方法は、用いる金属イオン封鎖剤がイオン交換体であるかキレート剤であるかによって異なってくる。各物質についてその測定方法を述べると、次のようになる。
【００３１】
イオン交換体の場合
イオン交換体０．１ｇを精秤し、塩化カルシウム水溶液（濃度はＣａＣＯ3 として５００ｐｐｍ）１００ｍＬ中に加え、２５℃で６０分間攪拌した後、孔サイズ０．２μｍのメンブランフィルター（アドバンテック社、ニトロセルロース製）を用いてろ過を行い、そのろ液１０ｍＬ中に含まれるカルシウムイオンの量をEDTA滴定により測定する。その値より、測定の対象のイオン交換体のカルシウムイオン交換容量（カチオン交換容量）を求める。
たとえば本発明では、結晶性アルカリ金属ケイ酸塩、アルミノケイ酸塩（ゼオライト他）などの無機物質をイオン交換体として測定している。
【００３２】
キレート剤の場合
カルシウムイオン電極を用いて、Ｃａイオン捕捉能を下記のようにして測定する。なお、溶液は全て以下の緩衝液を用いて調製する。
緩衝液；０．１Ｍ−ＮＨ4 Ｃｌ−ＮＨ4 ＯＨ ｂｕｆｆｅｒ（ｐＨ１０．０）
（ｉ）検量線の作成
標準カルシウムイオン溶液を作成し、図１の如きカルシウムイオン濃度の対数と電位の関係を示す検量線を作成する。
【００３３】
（ii）カルシウムイオンの捕捉能の測定
約０．１ｇのキレート剤を秤量し、１００ｍＬメスフラスコに入れて上記の緩衝液でメスアップする。このようにして調製されたキレート剤含有緩衝液に、カルシウムイオン濃度が２００００ｐｐｍ（ＣａＣＯ3 換算）に相当するＣａＣｌ2 水溶液（ｐＨ１０．０）をビュレットから滴下する。滴下はＣａＣｌ2 水溶液を０．１〜０．２ｍＬずつ加えて行い、その時の電位を読み取る。また、キレート剤を含有しない緩衝液にも同様にＣａＣｌ2 水溶液滴下を行う。この溶液をブランク溶液と称する。図１の検量線よりカルシウムイオン濃度を求め、ＣａＣｌ2 水溶液の滴下量とカルシウムイオン濃度の関係をグラフに示す（図２）。図２中、線Ｐはブランク溶液（キレート剤を使用しない緩衝液を用いた場合）のデータを示し、線Ｑはキレート剤含有緩衝液を用いた場合のデータを示す。線Ｑの延長線と、横軸との交点をＡとし、Ａにおけるブランク溶液のカルシウムイオン濃度から、キレート剤のカルシウムイオン捕捉能を求める。
たとえば本発明では、クエン酸塩などのポリカルボン酸塩並びにアクリル酸−マレイン酸コポリマー等のカルボキシレート重合体を、キレート剤として測定している。
【００３４】
【実施例】
以下、実施例等により本発明をさらに詳しく説明するが、本発明はこれらの実施例等によりなんら限定されるものではない。
【００３５】
製造例１
以下の方法で表１の配合例１の洗剤組成物を製造した。
表１に記載の各成分が配合された含水率５０重量％の水性スラリーを調製した。ただし、ゼオライトはその使用量の１８／２３倍の量をスラリーに配合し、酵素、香料、及び結晶性シリケートはスラリーには配合しなかった。得られたスラリーを噴霧乾燥して噴霧乾燥粒子を得、次いでこの粒子をスクリュー押し出し造粒機により造粒して洗剤組成物を得た。洗剤組成物をロータリーキルンに入れ、酵素、結晶シリケート及び残りのゼオライトをブレンドし、同時に香料をスプレーして最終洗剤組成物を得た。
【００３６】
製造例２
以下の方法で表１の配合例２の洗剤組成物を製造した。
ＡＥ、吸油担体、ソーダ灰、酵素、香料、及び結晶性シリケート以外の成分を配合して含水率５０重量％の水性スラリーを調製した。得られたスラリーを噴霧乾燥し、噴霧乾燥粒子を得た。得られた噴霧乾燥粒子、ソーダ灰、吸油担体及び結晶性シリケート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。なお、ここでの吸油担体の配合量は、その使用量の８／１３倍の量であった。そこにＡＥをスプレーして造粒を行った。次いでその使用量の３．５／１３倍の量の吸油担体を投入し、表面改質を行った。得られた造粒粒子をロータリーキルンに入れ、残りの吸油担体、酵素をブレンドし、同時に香料をスプレーし最終洗剤組成物を得た。
【００３７】
得られた最終洗剤組成物の粉末物性を下記に示した方法で測定した。その結果を表１に併せて示す。
（Ａ）嵩密度はＪＩＳ：Ｋ−３３６２の方法に従って測定した。
（Ｂ）流動性はＡＳＴＭ：Ｂ２１３−４８に従って測定した。
（Ｃ）平均粒径はＪＩＳ：Ｋ−３３６２の方法に従って測定した。
【００３８】
【表１】
以下に、表１中の各成分について詳述する。
ＬＡＳは、直鎖アルキルベンゼンスルホン酸ナトリウムで炭素数１２〜１３のものを用いた。
α−ＳＦＥは、α−オレフィンスルホン酸ナトリウムのことであり、炭素数１６〜１８のものを用いた。
ＡＥは、ポリオキシエチレンアルキルエーテルで炭素数１２〜１６、平均エチレンオキサイド付加モル数が７．０のものを用いた。
石鹸は、牛脂脂肪酸ナトリウムを用いた。
ゼオライトは、４Ａ型ゼオライト、平均粒子径３μｍ（東ソー（株）製）を用いた。Ｃａイオン捕捉能（ＣＥＣ）は２８０ＣａＣＯ3 ｍｇ／ｇであった。
【００４０】
吸油担体は下記合成例１により得られた非晶質アルミノケイ酸塩を用いた。
合成例１
イオン交換水に炭酸ソーダを溶解させ、６重量％濃度の水溶液を用意した。この水溶液１３２ｇとアルミン酸ソーダ水溶液（濃度50重量％）３８．２８ｇを容量１０００ｍＬの邪魔板付き反応槽に入れてこれらを混合した。得られた混合溶液に、強攪拌下、２倍の水で希釈した３号水ガラス水溶液２０１．４ｇを、４０℃にて、２０分間かけて滴下しつつ反応させた。この際、ＣＯ2 ガスを吹き込むことによって反応系のｐＨをほぼ１０．５にコントロールし、反応速度を最適化した。続いて反応系を５０℃まで加熱し、同温度で３０分間攪拌した。
【００４１】
その後、反応系にＣＯ2 ガスを吹き込み、過剰アルカリを中和した（ｐＨ＝９．０）。得られた中和スラリーを、ろ紙（東洋濾紙（株）製Ｎｏ．５Ｃ）を用いて、減圧下にろ過した。ろ過ケーキを１０００倍の水で洗浄し、次いでろ過乾燥（１０５℃、３００ｔｏｒｒ、１０時間）し、さらに解砕を行い、非晶質アルミノ珪酸塩粉体（平均粒径１０μｍ）を得た。なおアルミン酸ソーダ水溶液は、１０００ｍＬの４つ口フラスコにＡｌ（ＯＨ）3 ２４３ｇと４８重量％ＮａＯＨ水溶液２９８．７ｇを入れて混合し、攪拌下１１０℃で３０分間加熱して溶解させることにより調製した。
【００４２】
得られた非晶質アルミノ珪酸塩の組成は、原子吸光分析及びプラズマ発光分析の結果、Ａｌ2 Ｏ3 ＝２９．６重量％、ＳｉＯ2 ＝５２．４重量％、Ｎａ2 Ｏ＝１８．０重量％であった（１．０Ｎａ2 Ｏ・Ａｌ2 Ｏ3 ・３．１０ＳｉＯ2 ）。また、ＣＥＣは１８５ＣａＣＯ3 ｍｇ／ｇ、吸油能は２８５ｍＬ／１００ｇ、０．１μｍ未満の細孔径を持つ細孔容積の比率は９．４％、０．１〜２．０μｍの細孔径を持つ細孔容積の比率は７６．３％、含有水分量は１１．２重量％であった。
【００４３】
非晶質ケイ酸塩は１号ケイ酸ナトリウム（東ソー（株）製）を用いた。
結晶性シリケートは粉末ＳＫＳ−６（ヘキストトクヤマ（株）製）をハンマーミルで粉砕し、平均粒径５０μｍとしたものを用いた。なお、ＣＥＣは２２４ＣａＣＯ3 ｍｇ／ｇであった。
アクリル酸−マレイン酸共重合体はナトリウム塩（７０モル％中和物）として配合され、モノマー比はアクリル酸／マレイン酸＝３／７（モル比）である。なお、ＣＥＣは３８０ＣａＣＯ3 ｍｇ／ｇであった。
蛍光染料はチノパールＣＢＳ−Ｘ（チバガイギー社製）とホワイテックスＳＡ（住友化学（株）製）を１：１の重量比で配合したものである。
酵素はセルラーゼＫ（特開昭６３−２６４６９９号公報に記載のもの）、ＡＰＩ−２１Ｈ（昭和電工（株）製）、及びリポラーゼ１００Ｔ（ノボ社製）を７：４：１の重量比で配合したものである。
なお、洗濯用水及び洗濯液の硬度は、上記に記載の方法で測定した。
【００４４】
実施例１
パルセータ型全自動洗濯機（ＮＡ−Ｆ７０ＶＰ１型、松下電器産業（株）製）に、先ず４９リットルの水道水（３°ＤＨ、２０℃）を洗濯槽に貯水し、製造例１により得られた洗剤組成物３２．７ｇを投入し、１分間標準水流モードで攪拌し、洗剤組成物を溶解及び／又は分散させた洗濯液を調製した（この時、洗濯液の硬度は０．８°ＤＨ、ｐＨは１０．６であった。）。
ここに、調製例１に示した人工汚染布（５ｃｍ×５ｃｍ角）５枚を木綿金巾２００３布（３０ｃｍ×４５ｃｍ角）の台布に固定した汚染布２組と、未着用木綿メリアス肌着（グンゼ（株）製）１．０９ｋｇ、ポリエステル／綿＝５０／５０混紡生地（ＣＨＯＹＡ（株）製）０．５４ｋｇを洗濯槽に入れ、浴比約３０に調整し、６分間洗濯を行った。続いて上記の水道水を用いて貯め濯ぎを２回行った後、６分間脱水した。洗濯後の人工汚染布の反射率を測定して洗浄率を算出した。本実施例における人工汚染布の洗浄率は６５．３％であった。
【００４５】
比較例１
実施例１と同じ洗濯機に、まず最初に実施例１で用いたものと同じ被洗濯物を投入した。即ち、汚染布２組、未着用木綿メリアス肌着１．０９ｋｇ、及び混紡生地０．５４ｋｇを洗濯槽に投入した。次いで、４９リットルの水道水（３°ＤＨ、２０℃）を洗濯槽に注水し、製造例１で得られた洗剤組成物を３２．７ｇ投入した（浴比約３０）。次いで、実施例１と同様の、６分間洗濯−すすぎ２回−脱水の洗濯操作を実施した。洗濯後の人工汚染布の洗浄率は５６．１％であった。
【００４６】
実施例１及び比較例１より、予め洗濯用水に洗剤組成物を溶解及び／又は分散させた洗濯液を調製した後に、該洗濯液と被洗濯物とを接触させる洗濯方法の方が洗浄率が高いことが分かった。
【００４７】
実施例２
ドラム式洗濯機（ＥＳ−Ｅ６１型、シャープ（株）製）に、先ず２０リットルの水道水（３°ＤＨ、２０℃）をその洗濯槽に貯水し、洗濯槽に製造例２で得られた洗剤組成物１５ｇを投入した。具体的には、０．５リットルの水道水（３°ＤＨ、２０℃）に分散させた洗剤組成物をディスペンサー（洗剤投入口）から洗濯槽へ注入した後、０．５リットルの水道水で予備溶解槽を洗浄しつつ洗濯槽に供給した。次いで、１分間標準水流モードで攪拌し、洗剤組成物を溶解及び／又は分散させた洗濯液を調製した（洗濯液の硬度は０．７°ＤＨ、ｐＨは１０．９であった。）。
【００４８】
ここに、実施例１で用いたものと同じ被洗濯物を投入した。即ち、汚染布２組、未着用木綿メリアス肌着２．０ｋｇ、及び混紡生地１．０ｋｇを洗濯槽に投入した（浴比は約７であった。）。次いで２０分間の洗濯、１０分間の脱水の後、２１リットルの水道水（３°ＤＨ、２０℃）により５分間の貯め濯ぎ工程及びそれに続く１０分間の脱水工程からなるすすぎ工程を３回行った。洗濯後の人工汚染布の洗浄率は６５．３％であった。
【００４９】
比較例２
実施例２と同じ洗濯機に、まず最初に実施例２で用いたものと同じ被洗濯物を投入した。次いで、２１リットルの水道水（３°ＤＨ、２０℃）を洗濯槽に注水し、製造例２で得られた洗剤組成物を１５ｇを実施例２と同様の方法で投入した（浴比約７）。実施例２と同様の洗濯工程、脱水工程、すすぎ工程を行い被洗濯物を洗濯した。洗濯後の人工汚染布の洗浄率は５７．１％であった。
【００５０】
実施例２及び比較例２より、予め洗濯用水に洗剤組成物を溶解及び／又は分散させた洗濯液を調製した後に、該洗濯液と被洗濯物とを接触させる洗濯方法の方が洗浄率が高いことが分かった。
【００５１】
実施例３
洗濯液の調製のための攪拌時間（熟成時間）を１０秒間、３０秒間とした以外、実施例１と同様の操作を行って被洗濯物を洗濯した。熟成時間が１０秒間の場合は、調製された洗濯液の硬度は１．３°ＤＨ、ｐＨ１０．７で、洗濯後の人工汚染布の洗浄率は６０．１％であった。また、熟成時間が３０秒間の場合は、調製された洗濯液の硬度は１．０°ＤＨ、ｐＨ１０．８で、洗濯後の人工汚染布の洗浄率は６３．６％であった。いずれの場合も、予め水に洗剤組成物を溶解及び／又は分散させていない態様で洗濯した場合（比較例１）の、人工汚染布の洗浄率である５６．１％よりも高かった。
【００５２】
実施例４
実施例２とほぼ同様の操作で洗濯を行った。事前に貯水した水量を１０．５リットル、洗濯液の調製のための攪拌時間（熟成時間）を１分間とした。続いて被洗濯物を洗濯槽に入れ、３リットル／分の速度で１０．５リットルの水道水を注水した後に洗濯を実施した。洗濯後の人工汚染布の洗浄率は６１．３％であった。この場合も、予め洗濯用水に洗剤組成物を溶解及び／又は分散させていない態様で洗濯した場合（比較例２）の洗浄率である５７．１％よりも高い洗浄率であった。
【００５３】
なお、前記の洗浄率は次の人工汚染布を用いて、下記の方法で算出したものである
調製例１
下記組成の人工汚染液を布に付着して人工汚染布を調製した。人工汚染液の布への付着は、特願平６−６３２７３号に示されているグラビアロールコーターを用いたグラビア式汚染機を使用した。人工汚染液を布にグラビア印刷させ人工汚染布を作製する工程は、グラビアロールのセル容量５８ｃｍ3 ／ｃｍ2 、塗布速度１．０ｍ／ｍｉｎ、乾燥温度１００℃、乾燥時間１分で行った。布は木綿金巾２００３布（谷頭商店製）を使用した。
【００５４】
〔人工汚染液の組成〕
ラウリン酸 ０．４４重量％
ミリスチン酸 ３．０９重量％
ペンタデカン酸 ２．３１重量％
パルミチン酸 ６．１８重量％
ヘプタデカン酸 ０．４４重量％
ステアリン酸 １．５７重量％
オレイン酸 ７．７５重量％
トリオレイン １３．０６重量％
パルミチン酸ｎ−ヘキサデシル ２．１８重量％
スクアレン ６．５３重量％
卵白レシチン液晶物 １．９４重量％
鹿沼赤土 ８．１１重量％
カーボンブラック ０．０１重量％
水道水 バランス
【００５５】
（洗浄率の算出）
原布及び洗浄前後の５５０ｍμにおける反射率を自記色彩計（島津製作所製）にて測定し、次式によって洗浄率Ｄ（％）を算出した。
Ｄ＝（Ｌ2 −Ｌ1 ）／（Ｌ0 −Ｌ1 ）×１００（％）
Ｌ0 ：原布の反射率
Ｌ1 ：洗浄前汚染布の反射率
Ｌ2 ：洗浄後汚染布の反射率
【００５６】
【発明の効果】
本発明の洗濯方法により、洗剤組成物の持つ洗浄能力を充分に引き出すことができ、それにより、より優れた洗浄力を発揮させることができる。
【図面の簡単な説明】
【図１】図１は、カルシウムイオン濃度の対数と電位の関係を示す検量線を表した図である。
【図２】図２は、ＣａＣｌ2 水溶液の滴下量とカルシウムイオン濃度の関係を示す図である。Ａは線Ｑの延長線と横軸との交点であり、線Ｐはブランクの溶液（キレート剤を使用していない緩衝液を用いた場合）のデータであり、線Ｑはキレート剤含有緩衝液を用いた場合のデータである。[0001]
BACKGROUND OF THE INVENTION
The present invention is a washing methodTo the lawRelated. In more detail, the washing method that can sufficiently exert the cleaning power of the detergent composition, wherein the laundry liquid obtained by dissolving the detergent composition in advance is brought into contact with the laundry.To the lawRelated.
[0002]
[Prior art]
In general, a detergent composition used for apparel is used to reduce the interfacial tension on the surface of the fiber and to promote the solubilization and dispersion of the soil in the washing liquid, and to swell the fiber and add soil. Is composed of an alkali agent that promotes dispersibility in the washing liquid, a sequestering agent for eliminating the influence of hardness components such as calcium ions and magnesium ions in tap water, and other additives.
[0003]
On the other hand, all forms of detergent compositions such as liquids, pastes, powders or lumps have been proposed so far, and compositions and production methods according to the respective forms have been studied and numerous applications have been filed. I came.
[0004]
However, there have been few studies on the relationship between the composition and form, and when considering the manufacturing method and the cost spent on it, except for mixing specific components separately to improve solubility and powder properties, The detergent components constituting the detergent composition are generally present in the same medium. For example, it goes without saying about liquid detergent compositions, and for powder or bulk detergent compositions, a slurry of ingredients excluding ingredients that deteriorate due to heating (for example, fragrances, enzymes or bleaching agents) is dried, cooled, ground, or made. It can be easily obtained by processing such as granulation and tableting.
[0005]
Thus, since a general detergent composition has a sequestering agent and an alkali agent in the same medium, when such a detergent composition is dissolved and / or dispersed in water, the alkali agent and water The reaction of the sequestering agent with calcium ions or magnesium ions in water is slower than the expression of alkalinity due to the reaction of. For this reason, it is considered that the rate of decrease in the hardness of the washing liquid is slow, while the speed at which the washing liquid exhibits alkalinity is extremely fast.
[0006]
By the way, most of the sebum dirt derived from the human body contains fatty acids. During washing, calcium ions and magnesium ions in the washing liquid cause the dirt to be prevented from dispersing in the water in addition to reducing the surface activity of the surfactant. This is because scum having low solubility is formed by the reaction of the fatty acid in the soil with calcium ions and magnesium ions.
[0007]
In particular, we have found that the rate of scum formation between fatty acids and calcium ions and magnesium ions increases as the washing solution has a higher alkalinity (pH). This is considered to be because the reaction rate between the fatty acid ionized by the alkaline agent and these ions is larger than the reaction rate between the fatty acid in the soil and calcium ions or magnesium ions. Therefore, in normal washing, when the alkalinity of the washing liquid is faster than the decrease in the hardness of the washing liquid, scum is likely to form on the dirt surface, thereby freeing and dispersing the dirt in the washing liquid. Is thought to be inhibited. However, in order to obtain a sufficient detergency, it is an extremely important condition that the washing liquid exhibits alkalinity. That is, we have noticed that conventional general washing methods cannot always fully utilize the performance of the detergent composition.
[0008]
Some washing machines currently available on the market have a dissolution tank for dissolving the detergent composition before being added to the laundry tub. However, most of the purpose of these dissolution tanks is to eliminate the undissolved residue of the detergent composition in the laundry tub. There are several products that mention increased cleaning power, but all of these techniques are only designed to improve cleaning power by reducing the dissolution time of the detergent composition in the washing tub. Therefore, there is a possibility that the washing liquid and the laundry are in contact with each other in a situation where the hardness of the prepared washing liquid is not sufficiently lowered. In addition, even after most of the detergent composition is added to the washing tub, since the hardness of the washing liquid is not sufficiently taken into account, the washing tub containing calcium ions, magnesium ions, etc. is added to the washing tub. It can be done without consideration. For this reason, the hardness of the washing liquid in the washing tub may remain high for a while.
[0009]
[Problems to be solved by the invention]
The object of the present invention is to sufficiently draw out the cleaning ability of the detergent composition and exert a more excellent detergency when washing clothes such as clothes using a conventional detergent composition for clothing. How to washThe lawIs to provide.
[0010]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have first dissolved and / or dispersed the detergent composition in washing water, reduced the hardness of the washing liquid in advance, and then brought the cleaning power into contact with the laundry. As a result, the present invention has been completed.
[0011]
That is, the gist of the present invention is as follows.
[1] In washing waterContains sequestering agent and alkaline agentThe detergent composition is dissolved and / or dispersed, and the hardness of the washing liquid is 1.5 ° DH or less.And pH is 8.0 or moreAfter aging to prepare a washing liquid, the washing liquid is brought into contact with the laundry.Wash with the washing liquid having a hardness of 1.5 ° DH or less and a pH of 8.0 or more.A washing method characterized by
[2]The detergent composition to be dissolved and / or dispersed in washing water further comprises a surfactant selected from alkylbenzene sulfonate, alkyl sulfate ester salt and polyoxyethylene alkyl ether.The washing method according to [1] aboveToIt is related.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
1. Washing method of the present invention
The washing method of the present invention is characterized in that a washing composition is prepared by dissolving and / or dispersing a detergent composition in washing water, and then the washing solution is brought into contact with the laundry.
[0013]
The washing water used in the present invention is not particularly limited as long as it is usually used for washing. For example, tap water is common, but in some areas, groundwater or river water is used.
[0014]
The washing liquid is prepared by dissolving and / or dispersing the detergent composition in washing water. Water-insoluble components such as zeolite used as a sequestering agent are present in a state dispersed in the washing liquid.
Some physical manipulation is usually performed to dissolve and / or disperse the detergent composition in the wash water. For example, the washing water and the detergent composition may be dissolved and / or dispersed by stirring the washing water and the detergent composition with a stirring blade or the like, or creating a looped tube and circulating the tube with a pump. However, it may be simply vigorous and a method such as adding washing water to the detergent composition may be used. In any case, it is preferable to sufficiently dissolve and / or disperse the detergent composition in the washing liquid, so that the rate of decrease in hardness is increased.
[0015]
In general, zeolite, which is a main component of sequestering agents contained in detergent compositions as a hardness reducing agent, is insoluble in water, so the hardness of the washing liquid is sufficiently reduced after such components are added to the washing water. It takes time to finish. Therefore, in the present invention, it is preferable to prepare a cleaning liquid by dissolving and / or dispersing the detergent composition in washing water and then aging. As the aging operation, for example, after the detergent composition is dissolved and / or dispersed in washing water, it is allowed to stand, stir, raise the temperature, etc. An operation for reducing the hardness of the liquid is mentioned. The time required for the aging operation (aging time) is not particularly limited, but is preferably 10 seconds or more, more preferably 30 seconds or more, and particularly preferably 1 minute or more.
[0016]
It is preferable that the washing liquid prepared as described above has a low hardness. Specifically, the hardness of the prepared washing liquid is preferably 1.5 ° DH or less, more preferably 0.8 ° DH or less, and particularly preferably 0.5 ° DH or less.
[0017]
As a method for measuring the hardness of the washing liquid, when the sequestering agent contained in the detergent composition is an ion exchanger, a membrane filter (Advantech: manufactured by Nitrocellulose) having a pore size of 0.2 μm is used. The washing liquid is filtered, and the amount of hardness component contained in the filtrate can be easily measured using an ICP method (ion plasma coupling method) or an EDTA titration method.
Moreover, when the sequestering agent mix | blended with the detergent composition is a chelating agent, a favorable result can be obtained by employ | adopting a chelate indicator method. In the chelate indicator method, it is necessary to prepare a calibration curve under the pH and ionic strength corresponding to the test laundry solution, but the amount of free hardness component that could not be captured by the sequestering agent such as a chelating agent is It can be quantified from the liquid itself. Specifically, for example, a method using Chrome Violet (available from Tokyo Chemical Industry Co., Ltd.) described in 4th WORLD SURFACTANTS CONGRESS Abstract Vol. 2 p.159 can be used.
[0018]
As is the case with many detergent compositions, when the ion exchanger and chelating agent are used in combination as a sequestering agent in the detergent composition, the above-described method using the membrane filter is combined with the chelating indicator method. The purpose can be achieved. That is, quickly filter the ion exchanger in the washing liquid using a membrane filter with a pore size of 0.2 μm, and add the Chrome Violet liquid to the obtained filtrate, and then measure the visible absorption wavelength of the colored liquid. By doing so, the amount of the free hardness component not captured by the chelating agent is quantified.
[0019]
Next, washing is performed by bringing the prepared washing liquid into contact with a laundry such as clothing. As a washing method at this time, after the detergent composition is sufficiently dissolved and / or dispersed in a washing tub where the washing liquid and the laundry are contacted, the laundry is put into the washing tub. In addition to the method of performing, there may be mentioned a method of separately adding a washing liquid prepared in a separate tank to the laundry tank containing the laundry. Specifically, as the former, a net for placing the item to be washed is provided on the upper part of the washing tub, and the item to be washed is placed thereon, and the washing liquid is prepared in the washing tub and then the net is inverted or broken. For example, there is a method of putting the laundry into the washing tub, etc., as the latter, using a washing apparatus separately equipped with a pre-dissolution tank for preparing and storing the washing liquid, For example, a method of appropriately supplying a washing liquid to the washing tub in which the laundry is put can be mentioned.
[0020]
Further, in the washing method of the present invention, an object to be washed during washing, WashingRinseLiquid, etc.May be added. Specifically, the hardness of the washing liquid after contact with the laundry is preferably 2.0 ° DH or less, more preferably 1.5 ° DH or less, and 0.8 ° DH or less. It is particularly preferred.
[0021]
The prepared washing liquid used in the present invention preferably exhibits alkalinity from the viewpoint of detergency. Specifically, the pH of the washing liquid is preferably 8.0 or more, and more preferably in the range of 9 to 12. Here, the pH of the washing liquid is measured at 25 ° C. with a normal glass electrode pH meter or the like.
[0022]
2. The present inventionInWashing machine
The present inventionInThe washing device is not particularly limited as long as it can perform the washing method of the present invention. For example, the following modes are shown.
(A) A washing apparatus for performing the washing method of the present invention,
1) a contact mechanism for bringing the washing liquid into contact with the laundry, and
2) A washing tub which prepares a washing liquid, stores the washing liquid and accommodates a laundry and has a washing means,
A washing apparatus comprising:
(B) A washing apparatus for performing the washing method of the present invention,
1) A washing tub for storing the washing liquid and containing the laundry to be washed and having washing means, and
2) A pre-dissolution tank for preparing the washing liquid and storing the washing liquid;
A washing apparatus comprising:
[0023]
Washing apparatus of aspect (A)
The washing apparatus of this aspect stores the washing liquid and prepares the washing liquid in a washing tub that accommodates a laundry and has a washing means. That is, the present invention is suitably applied to a method in which a laundry composition is sufficiently dissolved and / or dispersed in a washing tub where contact is made between the washing liquid and the laundry, and then the laundry is put into the laundry tub. Is done. As a type of the washing apparatus, a so-called pulsator type washing apparatus is preferable.
[0024]
The contact mechanism for bringing the washing liquid into contact with the laundry is exemplified by means for putting the laundry into the laundry tub after the detergent composition is sufficiently dissolved and / or dispersed in the laundry tub. . More specifically, it is a net provided on the upper part of the laundry tub for placing the laundry, and after the detergent composition is sufficiently dissolved and / or dispersed in the laundry tub, for example, it is inverted or cracked, etc. The net | network etc. which can put a to-be-washed object into a washing tub by are mentioned. By providing such a contact mechanism, contact between the washing liquid and the laundry is prevented before the detergent composition is sufficiently dissolved and / or dispersed.
Such a contact mechanism may be provided with a loading control means for loading the laundry into the washing tub when the washing liquid in the washing tub is dissolved and / or dispersed to a desired degree. Examples of such input control means include those equipped with a timer or the like for operating the contact means after a predetermined aging time has elapsed and putting the laundry into the washing tub.
[0025]
Washing apparatus of aspect (B)
The washing apparatus of this aspect has a washing tub for storing the washing liquid and storing the laundry to have washing means, and a mechanism for preparing the washing liquid and storing the washing liquid (preliminary dissolution tank). It is a device. In this embodiment, the washing liquid is appropriately supplied from the preliminary dissolution tank to the washing tub into which the laundry is put. In addition, it is not necessary to supply the washing liquid to the washing tub first. For example, the laundry may be first supplied into the washing tub and then supplied from the preliminary dissolution tub. As a type of the washing apparatus, a so-called drum-type washing apparatus is preferable. This is because in the case of a drum-type washing apparatus, since a relatively small amount of washing liquid is used for washing, a preliminary dissolution tank is easily provided.
[0026]
Moreover, in this aspect, when the laundry liquid is prepared in the preliminary dissolution tank, the laundry liquid in contact with the laundry can be sufficiently dissolved and / or dispersed in the detergent composition. Therefore, it is not necessary to provide a contact mechanism for bringing the washing liquid into contact with the laundry, such as the washing apparatus of the aspect (A).
In addition, if the washing liquid in the contact between the laundry and the washing liquid in the washing tub is a solution in which the detergent composition is sufficiently dissolved and / or dispersed, the washing liquid in the preliminary dissolving tub is not necessarily the detergent composition. It need not be sufficiently dissolved and / or dispersed.
Further, in the case of a drum-type washing apparatus, the effect of the washing method of the present invention is likely to appear remarkably because the bath ratio of the clothes is low. Therefore, it is particularly preferable that the washing method of the present invention uses a drum-type washing apparatus.
[0027]
As the detergent composition used in the present invention, a generally known detergent composition for clothing can be used. Specifically, what is comprised from surfactant, a sequestering agent, an alkaline agent, and another washing | cleaning component is mentioned, for example.
[0028]
Specific examples of the components include surfactants such as alkylbenzene sulfonates, alkyl sulfate esters and polyoxyethylene alkyl ethers; crystalline aluminosilicates that are zeolites, and JP-A-7-89712. Sequestering agents such as crystalline silicates, ethylenediaminetetraacetic acid (EDTA) and citrate described in JP-A-60-227895; polyacrylic acid, copolymers of acrylic acid and maleic acid, and carboxylic acids such as carboxymethylcellulose -Based polymers; alkali metal carbonates such as soda ash and alkali agents such as alkali metal silicates such as JIS 1, 2 or 3 sodium silicate; bulking agents such as sodium sulfate; polyethylene glycol (PEG), polyvinylpyrrolidone (PVP) and Dispersing agents such as polyvinyl alcohol (PVA) or Transfer inhibitor; bleaching agent such as sodium percarbonate; tetraacetylethylenediamine (TAED) and bleaching activator described in JP-A-6-316700; enzymes such as protease, cellulase, amylase and lipase; boron compounds and sulfurous acid Conventionally known components such as enzyme stabilizers such as sodium; biphenyl type and stilbene type fluorescent dyes; antifoaming agents such as silicone / silica type; antioxidants; bluing agents and fragrances can be mentioned. For more details, reference can be made to what is described in JP-A-8-218093.
[0029]
The amount of sequestering agent added to the washing water is particularly preferably an amount sufficient to make the hardness of the washing water 0.5 ° DH or less.
The amount of the sequestering agent necessary to bring the washing water hardness to a desired value can be determined from the hardness of the washing water used and the calcium ion scavenging ability (CEC) of the sequestering agent used. In addition, DH hardness of the washing water to be used is measured by an ion coupling plasma method (ICP method).
[0030]
The method for measuring the ion trapping ability of the sequestering agent varies depending on whether the sequestering agent used is an ion exchanger or a chelating agent. The measurement method for each substance is described as follows.
[0031]
For ion exchanger
Weigh accurately 0.1 g of ion exchanger, and add calcium chloride aqueous solution (concentration is CaCOThreeAs 500 ppm), and after stirring at 25 ° C. for 60 minutes, filtration is performed using a membrane filter (Advantech, manufactured by Nitrocellulose) having a pore size of 0.2 μm, and calcium ions contained in 10 mL of the filtrate. Is measured by EDTA titration. From the value, the calcium ion exchange capacity (cation exchange capacity) of the ion exchanger to be measured is obtained.
For example, in the present invention, an inorganic substance such as crystalline alkali metal silicate, aluminosilicate (zeolite, etc.) is measured as an ion exchanger.
[0032]
For chelating agents
Using a calcium ion electrode, the Ca ion capturing ability is measured as follows. All solutions are prepared using the following buffers.
Buffer; 0.1M NHFourCl-NHFourOH buffer (pH 10.0)
(I) Creating a calibration curve
A standard calcium ion solution is prepared, and a calibration curve showing the relationship between the logarithm of the calcium ion concentration and the potential as shown in FIG. 1 is prepared.
[0033]
(Ii) Measurement of calcium ion scavenging ability
About 0.1 g of chelating agent is weighed, placed in a 100 mL volumetric flask and made up with the above buffer. In the thus prepared chelating agent-containing buffer, the calcium ion concentration was 20000 ppm (CaCOThree Equivalent to CaCl2 An aqueous solution (pH 10.0) is dropped from the burette. Dropping is CaCl2 It is performed by adding 0.1 to 0.2 mL of an aqueous solution, and the potential at that time is read. Similarly, a buffer solution containing no chelating agent is similarly CaCl.2 An aqueous solution is dropped. This solution is referred to as a blank solution. Obtain the calcium ion concentration from the calibration curve in FIG.2 The relationship between the dripping amount of the aqueous solution and the calcium ion concentration is shown in a graph (FIG. 2). In FIG. 2, a line P shows data of a blank solution (when a buffer solution not using a chelating agent is used), and a line Q shows data when a chelating agent-containing buffer solution is used. The intersection of the extended line Q and the horizontal axis is A, and the calcium ion trapping ability of the chelating agent is determined from the calcium ion concentration of the blank solution in A.
For example, in the present invention, polycarboxylates such as citrate and carboxylate polymers such as acrylic acid-maleic acid copolymers are measured as chelating agents.
[0034]
【Example】
EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further in detail, this invention is not limited at all by these Examples.
[0035]
Production Example 1
The detergent composition of Formulation Example 1 in Table 1 was produced by the following method.
An aqueous slurry having a water content of 50% by weight, in which the respective components shown in Table 1 were blended, was prepared. However, zeolite was blended in the slurry in an amount 18/23 times the amount used, and enzymes, fragrances, and crystalline silicate were not blended in the slurry. The obtained slurry was spray-dried to obtain spray-dried particles, which were then granulated by a screw extrusion granulator to obtain a detergent composition. The detergent composition was placed in a rotary kiln and the enzyme, crystalline silicate and remaining zeolite were blended, and at the same time the fragrance was sprayed to obtain the final detergent composition.
[0036]
Production Example 2
The detergent composition of Formulation Example 2 in Table 1 was produced by the following method.
Components other than AE, oil-absorbing carrier, soda ash, enzyme, fragrance, and crystalline silicate were blended to prepare an aqueous slurry having a water content of 50% by weight. The obtained slurry was spray-dried to obtain spray-dried particles. The obtained spray-dried particles, soda ash, oil-absorbing carrier and crystalline silicate were put into a Redige mixer (stirring tumbling granulator, manufactured by Matsuzaka Giken Co., Ltd.) and stirring was started. In addition, the compounding quantity of the oil absorption carrier here was the quantity of 8/13 times the usage-amount. AE was sprayed there and granulated. Subsequently, the oil-absorbing carrier in an amount 3.5 / 13 times the amount used was added to perform surface modification. The obtained granulated particles were put into a rotary kiln, the remaining oil-absorbing carrier and enzyme were blended, and at the same time, a fragrance was sprayed to obtain a final detergent composition.
[0037]
The powder physical property of the obtained final detergent composition was measured by the method shown below. The results are also shown in Table 1.
(A) The bulk density was measured according to the method of JIS: K-3362.
(B) Fluidity was measured according to ASTM: B213-48.
(C) The average particle diameter was measured according to the method of JIS: K-3362.
[0038]
[Table 1]
Below, each component in Table 1 is explained in full detail.
As LAS, linear alkylbenzene sulfonate sodium having 12 to 13 carbon atoms was used.
α-SFE is sodium α-olefin sulfonate, and one having 16 to 18 carbon atoms was used.
As AE, polyoxyethylene alkyl ether having 12 to 16 carbon atoms and an average ethylene oxide addition mole number of 7.0 was used.
As the soap, beef tallow fatty acid sodium was used.
As the zeolite, 4A-type zeolite and an average particle size of 3 μm (manufactured by Tosoh Corporation) were used. Ca ion capture capacity (CEC) is 280CaCOThreemg / g.
[0040]
As the oil absorbing carrier, amorphous aluminosilicate obtained in Synthesis Example 1 below was used.
Synthesis example 1
Sodium carbonate was dissolved in ion-exchanged water to prepare a 6 wt% aqueous solution. 132 g of this aqueous solution and 38.28 g of sodium aluminate aqueous solution (concentration: 50% by weight) were placed in a reaction vessel equipped with a baffle plate having a capacity of 1000 mL and mixed. To the obtained mixed solution, 201.4 g of No. 3 water glass aqueous solution diluted with double water was reacted under strong stirring at 40 ° C. over 20 minutes while being dropped. At this time, CO2The pH of the reaction system was controlled to approximately 10.5 by blowing gas to optimize the reaction rate. Subsequently, the reaction system was heated to 50 ° C. and stirred at the same temperature for 30 minutes.
[0041]
After that, the reaction system2Gas was blown to neutralize excess alkali (pH = 9.0). The obtained neutralized slurry was filtered under reduced pressure using filter paper (No. 5C manufactured by Toyo Filter Paper Co., Ltd.). The filter cake was washed with 1000 times water, then filtered and dried (105 ° C., 300 torr, 10 hours), and further pulverized to obtain amorphous aluminosilicate powder (average particle size 10 μm). The sodium aluminate aqueous solution was added to a 1000 mL four-necked flask with Al (OH).Three243 g and 488.7% by weight NaOH aqueous solution 298.7 g were mixed and prepared by heating at 110 ° C. with stirring for 30 minutes for dissolution.
[0042]
The composition of the obtained amorphous aluminosilicate was found to be Al as a result of atomic absorption analysis and plasma emission analysis.2OThree= 29.6 wt%, SiO2= 52.4 wt%, Na2O = 18.0 wt% (1.0 Na2O ・ Al2OThree・ 3.10SiO2). CEC is 185CaCOThreemg / g, oil absorption capacity of 285 mL / 100 g, ratio of pore volume with pore diameter of less than 0.1 μm is 9.4%, ratio of pore volume with pore diameter of 0.1 to 2.0 μm is 76 The content of water was 11.2% by weight.
[0043]
As the amorphous silicate, No. 1 sodium silicate (manufactured by Tosoh Corporation) was used.
As the crystalline silicate, powder SKS-6 (manufactured by Hoechst Tokuyama Co., Ltd.) was pulverized with a hammer mill to have an average particle size of 50 μm. CEC is 224CaCOThreemg / g.
The acrylic acid-maleic acid copolymer is blended as a sodium salt (70 mol% neutralized product), and the monomer ratio is acrylic acid / maleic acid = 3/7 (molar ratio). CEC is 380CaCOThreemg / g.
The fluorescent dye is a mixture of Chino Pearl CBS-X (manufactured by Ciba Geigy) and Whitetex SA (manufactured by Sumitomo Chemical Co., Ltd.) at a weight ratio of 1: 1.
The enzyme contains cellulase K (described in JP-A-63-264699), API-21H (manufactured by Showa Denko KK), and lipolase 100T (manufactured by Novo) in a weight ratio of 7: 4: 1. It is a thing.
The hardness of the washing water and the washing liquid was measured by the method described above.
[0044]
Example 1
First, 49 liters of tap water (3 ° DH, 20 ° C.) was stored in a washing tub in a pulsator type fully automatic washing machine (NA-F70VP1 type, manufactured by Matsushita Electric Industrial Co., Ltd.). 32.7 g of the detergent composition was added and stirred in the standard water flow mode for 1 minute to prepare a laundry liquid in which the detergent composition was dissolved and / or dispersed (at this time, the hardness of the laundry liquid was 0.8 ° DH, The pH was 10.6.)
Here, two sets of contaminated cloths obtained by fixing five artificially contaminated cloths (5 cm × 5 cm square) shown in Preparation Example 1 to a base cloth of a cotton gold width 2003 cloth (30 cm × 45 cm square), and unweared cotton melias underwear (Gunze ( Co., Ltd.) 1.09 kg, polyester / cotton = 50/50 blended fabric (CHOYA Co., Ltd.) 0.54 kg was placed in a washing tub, adjusted to a bath ratio of about 30, and washed for 6 minutes. Subsequently, the above-mentioned tap water was used to store and rinse twice, and then dehydrated for 6 minutes. The washing rate was calculated by measuring the reflectance of the artificially contaminated cloth after washing. The washing rate of the artificially contaminated cloth in this example was 65.3%.
[0045]
Comparative Example 1
First, the same laundry as that used in Example 1 was put into the same washing machine as in Example 1. That is, 2 sets of contaminated cloth, 1.09 kg of unweared cotton Melias underwear, and 0.54 kg of blended fabric were put into a washing tub. Next, 49 liters of tap water (3 ° DH, 20 ° C.) was poured into the washing tub, and 32.7 g of the detergent composition obtained in Production Example 1 was added (bath ratio of about 30). Subsequently, the washing operation of washing for 6 minutes-rinsing twice-dehydration similar to Example 1 was performed. The washing rate of the artificially contaminated cloth after washing was 56.1%.
[0046]
From Example 1 and Comparative Example 1, after preparing a washing liquid in which a detergent composition is dissolved and / or dispersed in washing water in advance, the washing method in which the washing liquid is brought into contact with the laundry has a higher washing rate. I found it expensive.
[0047]
Example 2
First, 20 liters of tap water (3 ° DH, 20 ° C.) was stored in the washing tub in a drum type washing machine (ES-E61 type, manufactured by Sharp Corporation), and the washing tub was obtained in Production Example 2. 15 g of the detergent composition was added. Specifically, a detergent composition dispersed in 0.5 liters of tap water (3 ° DH, 20 ° C.) is poured into a washing tub from a dispenser (detergent inlet), and then 0.5 liters of tap water. The preliminary dissolution tank was supplied to the washing tank while being washed. Next, the mixture was stirred for 1 minute in the standard water flow mode to prepare a laundry liquid in which the detergent composition was dissolved and / or dispersed (the hardness of the laundry liquid was 0.7 ° DH and the pH was 10.9).
[0048]
Here, the same laundry as that used in Example 1 was charged. That is, 2 sets of contaminated cloth, 2.0 kg of unweared cotton Melias underwear, and 1.0 kg of blended fabric were put into the washing tub (the bath ratio was about 7). Then, after 20 minutes of washing, 10 minutes of dehydration, a rinsing process consisting of 21 liters of tap water (3 ° DH, 20 ° C.), a 5-minute storage rinse step followed by a 10-minute dehydration step was performed three times. . The washing rate of the artificially contaminated cloth after washing was 65.3%.
[0049]
Comparative Example 2
First, the same laundry as that used in Example 2 was put into the same washing machine as in Example 2. Next, 21 liters of tap water (3 ° DH, 20 ° C.) was poured into the washing tub, and 15 g of the detergent composition obtained in Production Example 2 was added in the same manner as in Example 2 (bath ratio of about 7). ). The same laundry process, dehydration process and rinsing process as in Example 2 were performed to wash the laundry. The washing rate of the artificially contaminated cloth after washing was 57.1%.
[0050]
From Example 2 and Comparative Example 2, after preparing a washing liquid in which a detergent composition is dissolved and / or dispersed in washing water in advance, the washing method in which the washing liquid is brought into contact with the laundry has a higher washing rate. I found it expensive.
[0051]
Example 3
The laundry was washed in the same manner as in Example 1 except that the stirring time (aging time) for preparing the washing liquid was 10 seconds and 30 seconds. When the aging time was 10 seconds, the hardness of the prepared washing liquid was 1.3 ° DH and pH 10.7, and the washing rate of the artificially soiled cloth after washing was 60.1%. When the aging time was 30 seconds, the hardness of the prepared washing liquid was 1.0 ° DH and pH 10.8, and the washing rate of the artificially contaminated cloth after washing was 63.6%. In any case, the washing rate of the artificially contaminated cloth was higher than 56.1% when the laundry was washed in a state where the detergent composition was not previously dissolved and / or dispersed in water (Comparative Example 1).
[0052]
Example 4
Washing was carried out in substantially the same manner as in Example 2. The amount of water stored in advance was 10.5 liters, and the stirring time (aging time) for preparing the washing liquid was 1 minute. Subsequently, the laundry was put into a washing tub and 10.5 liters of tap water was poured at a rate of 3 liters / minute, and then washing was performed. The washing rate of the artificially contaminated cloth after washing was 61.3%. Also in this case, the washing rate was higher than 57.1%, which is the washing rate when the laundry was washed in a state where the detergent composition was not previously dissolved and / or dispersed in the washing water (Comparative Example 2).
[0053]
In addition, the said washing | cleaning rate was computed with the following method using the following artificial contamination cloth.
Preparation Example 1
An artificially contaminated cloth having the following composition was attached to the cloth to prepare an artificially contaminated cloth. For the attachment of the artificial contamination liquid to the cloth, a gravure type contamination machine using a gravure roll coater disclosed in Japanese Patent Application No. 6-63273 was used. The process of producing an artificially contaminated cloth by gravure printing an artificially contaminated liquid on the cloth is a gravure roll cell capacity of 58 cm.Three/ Cm2The coating speed was 1.0 m / min, the drying temperature was 100 ° C., and the drying time was 1 minute. As the cloth, a cotton gold cloth 2003 cloth (manufactured by Tanigami Shoten) was used.
[0054]
[Composition of artificial contamination liquid]
Lauric acid 0.44% by weight
Myristic acid 3.09% by weight
Pentadecanoic acid 2.31% by weight
Palmitic acid 6.18% by weight
Heptadecanoic acid 0.44% by weight
Stearic acid 1.57% by weight
Oleic acid 7.75% by weight
Trio Rain 13.06% by weight
N-hexadecyl palmitate 2.18% by weight
6.5% by weight of squalene
Egg white lecithin liquid crystal 1.94% by weight
Kanuma red soil 8.11% by weight
Carbon black 0.01% by weight
Tap water balance
[0055]
(Calculation of cleaning rate)
The reflectance at 550 mμ before and after washing was measured with a self-recording color meter (manufactured by Shimadzu Corporation), and the washing rate D (%) was calculated by the following formula.
D = (L2-L1) / (L0-L1) X 100 (%)
L0: Reflectivity of raw cloth
L1: Reflection rate of cloth before cleaning
L2： Reflectance of contaminated cloth after washing
[0056]
【The invention's effect】
By the washing method of the present invention, it is possible to sufficiently bring out the cleaning ability of the detergent composition, and thereby it is possible to exert more excellent cleaning power..
[Brief description of the drawings]
FIG. 1 is a diagram showing a calibration curve showing the relationship between logarithm of calcium ion concentration and potential.
FIG. 2 shows CaCl2 It is a figure which shows the relationship between the dripping amount of aqueous solution, and a calcium ion concentration. A is the intersection of the extension line of the line Q and the horizontal axis, the line P is data of a blank solution (when using a buffer solution that does not use a chelating agent), and the line Q is a buffer solution containing a chelating agent. It is data when using.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07906797A JP3912838B2 (en) | 1997-03-12 | 1997-03-12 | Washing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07906797A JP3912838B2 (en) | 1997-03-12 | 1997-03-12 | Washing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10251962A JPH10251962A (en) | 1998-09-22 |
| JP3912838B2 true JP3912838B2 (en) | 2007-05-09 |
Family
ID=13679549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07906797A Expired - Fee Related JP3912838B2 (en) | 1997-03-12 | 1997-03-12 | Washing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3912838B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6995124B1 (en) | 1998-10-24 | 2006-02-07 | The Procter & Gamble Company | Methods for laundering delicate garments in a washing machine |
| US6966696B1 (en) | 1998-10-24 | 2005-11-22 | The Procter & Gamble Company | Methods for laundering delicate garments in a washing machine |
| US7185380B2 (en) | 1998-10-24 | 2007-03-06 | The Procter & Gamble Company | Methods for laundering delicate garments in a washing machine comprising a woven acrylic coated polyester garment container |
-
1997
- 1997-03-12 JP JP07906797A patent/JP3912838B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10251962A (en) | 1998-09-22 |
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