JP5671039B2 - 悪臭結合ポリマー及び悪臭中和剤を含むフレッシュニング組成物 - Google Patents
悪臭結合ポリマー及び悪臭中和剤を含むフレッシュニング組成物 Download PDFInfo
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- JP5671039B2 JP5671039B2 JP2012529894A JP2012529894A JP5671039B2 JP 5671039 B2 JP5671039 B2 JP 5671039B2 JP 2012529894 A JP2012529894 A JP 2012529894A JP 2012529894 A JP2012529894 A JP 2012529894A JP 5671039 B2 JP5671039 B2 JP 5671039B2
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- composition
- malodor
- present
- freshening
- fabric
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- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
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- 229920001778 nylon Polymers 0.000 description 1
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- 239000003921 oil Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
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- WTSXICLFTPPDTL-UHFFFAOYSA-N pentane-1,3-diamine Chemical compound CCC(N)CCN WTSXICLFTPPDTL-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
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- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005932 reductive alkylation reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 230000008786 sensory perception of smell Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000002470 solid-phase micro-extraction Methods 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 230000009870 specific binding Effects 0.000 description 1
- 229940063673 spermidine Drugs 0.000 description 1
- 229940063675 spermine Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
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- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
- 241000007181 unidentified human coronavirus Species 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 229940118696 vibrio cholerae Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 238000003260 vortexing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- UZFLPKAIBPNNCA-FPLPWBNLSA-N α-ionone Chemical compound CC(=O)\C=C/C1C(C)=CCCC1(C)C UZFLPKAIBPNNCA-FPLPWBNLSA-N 0.000 description 1
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Description
悪臭を減少させる本発明のフレッシュニング組成物は、悪臭結合ポリマーと、少なくとも1つの脂肪族アルデヒドを含む悪臭中和剤と、水性キャリアと、を含み、前記組成物は、布地に汚れ又は染みを付ける材料を本質的に含まない。本発明のフレッシュニング組成物中の界面活性剤(例えば、可溶化剤、湿潤剤)の総量は、フレッシュニング組成物の0重量%〜3重量%、すなわち3重量%以下、あるいは0重量%〜1重量%、すなわち1重量%以下、あるいは0重量%〜0.9重量%、すなわち0.9重量%以下、あるいは0重量%〜0.7、すなわち0.7重量%以下、あるいは0重量%〜0.5重量%、これらの代わりに0.5重量%以下、あるいは0重量%〜0.3重量%、すなわち0.3重量%以下である。濃度の高い組成物ほど、布地が汚れの影響を受けやすくなり得、及び/又は、フレッシュニング組成物の溶液が蒸発すると、許容不能な目に見える染みが布地上に残り得る。
本発明のフレッシュニング組成物は悪臭結合ポリマーを含む。悪臭結合ポリマーは、悪臭構成成分を中和する親和性を有する利用可能な官能基(例えば、アミン)を有するポリマーである。悪臭構成成分を中和する親和性を有する利用可能な官能基を有するモノマーも考えられる。アミン系化合物の場合、アミンがアルデヒドの悪臭に対する親和性を有することになる。このアミンは、アルデヒドの悪臭と反応して、臭気性ではないアミノール、イミン、又はエナミンのような新たな化合物を形成することができる。
いくつかの実施形態では、悪臭結合ポリマーは、分子量が100ダルトン超のアミン系化合物であり、そのアミン基の少なくとも10%は一級アミンである。1つの実施形態では、アミン系化合物は、分子量が150ダルトン超のポリアミンであり、そのアミン基の15%〜80%は一級アミンである。別の実施形態では、悪臭結合ポリマーは、分子量が1000ダルトン超のアミン系化合物であり、そのアミン基の0%〜約10%、あるいは10%未満が一級アミンである。
B−(NH2)n;
式中、Bはキャリア材料であり、nは少なくとも1の値の指数である。好適なBキャリアとしては、無機及び有機双方のキャリア部分が挙げられる。「無機キャリア」とは、炭素系ではないか、又は実質的に炭素系ではない骨格鎖からなるキャリアを意味する。
本発明ではモノアミンを用いてもよい。本発明で用いるのに適したモノアミンの非限定例としては、2−ヒドロキシアミン及び/又は3−ヒドロキシアミンのようにヒドロキシ及び/又はアルコキシ官能基も含む一級アミン、特にそのモノアミンを有益剤と相互作用させたときに、その官能基のないモノアミンと比べて、そのモノアミンの析出を高める官能基も含む一級又は二級アミンが挙げられるが、これらに限定されない。本発明では、一級モノアミンを二級モノアミンと組み合わせて用いてもよい。しかし、このような組み合わせ内の全てのアミン基のうちの少なくとも10%が一級アミン基となるように、十分なレベルの一級アミンを用いなければならない。
代表的なアミノアリール誘導体はアミノ−ベンゼン誘導体であり、4−アミノベンゾエート化合物のアルキルエステル、エチル−4−アミノベンゾエート、フェニルエチル−4−アミノベンゾエート、フェニル−4−アミノベンゾエート、4−アミノ−N’−(3−アミノプロピル)−ベンズアミド、又はこれらの混合物が挙げられる。
本発明の目的において、少なくとも1つの一級アミン基を含む好適なアミノ官能ポリマーの例は、下記のとおりである。
−分子量が300〜2.10E6ダルトンのポリビニルアミン(例えば、BASFから入手可能なLupamineシリーズ1500、4500、5000、9000)
−分子量が600ダルトン以上であり、エトキシル化度が少なくとも0.5であるアルコキシル化ポリビニルアミン
−ポリビニルアミンビニルアルコール(モル比2:1)、ポリビニルアミンビニルホルムアミド(モル比1:2)、及びポリビニルアミンビニルホルムアミド(モル比2:1)
−トリエチレンテトラミン、ジエチレントリアミン、テトラエチレンペンタミン
−ビス−アミノプロピルピペラジン
−分子量が400〜300,000ダルトンの範囲のアミノ置換ポリビニルアルコール
−例えば、Sigmaから入手可能なポリオキシエチレンビス[アミン]
−例えば、Sigmaから入手可能なポリオキシエチレンビス[6−アミノヘキシル]
−直鎖又は分岐鎖N,N’−ビス−(3−アミノプロピル)−1,3−プロパンジアミン(TPTA)
−N,N’−ビス−(3−アミノプロピル)エチレンジアミン
−直鎖又は分岐鎖ビス(アミノアルキル)アルキルジアミン
−1,4−ビス−(3−アミノプロピル)ピペラジン(BNPP)。
好適なアミン系化合物としてはポリアミノ酸が挙げられる。ポリアミノ酸は、アミノ酸又は化学修飾アミノ酸からなる。アミノ酸は、システイン、ヒスチジン、イソロイシン、チロシン、トリプトファン、ロイシン、リシン、グルタミン酸、グルタミン、グリシン、アラニン、アスパラギン酸、アルギニン、アスパラギン、フェニルアラニン、プロリン、セリン、ヒスチジン、スレオニン、メチオニン、バリン、及びこれらの混合物から選択してもよい。アミノ酸誘導体は、チロシンエチラート、グリシンメチラート、トリプトファンエチラート、若しくはこれらの混合物、アミノ酸ホモポリマー、ヒドロキシアミン、ポリアミノ酸、又はこれらの混合物であってもよい。
更なる有用なアミン系化合物は、ポリプロピレンイミンデントリマー、市販されているDendritech製のStarburst(登録商標)というポリアミドアミン(PAMAM)デンドリマー(ジェネレーションG0〜G10)、ジアミノブタンポリアミンDAB(PA)xデンドリマー(x=2n×4であり、nは一般に0〜4である)であるDSM製のAstromols(登録商標)というデンドリマー(ジェネレーション1〜5)である。
1つの実施形態では、悪臭結合ポリマーはPEIである。pHが約4〜約8、あるいは5超〜約8、あるいは7のアミン系ポリマーがアミン系の臭いを中和できることが驚くべきことに発見された。PEIは下記の一般式を有する。
−(CH2−CH2−NH)n−(n=10〜105)
本発明のフレッシュニング組成物では、1種以上の悪臭中和剤を用いてもよい。悪臭中和剤としては、臭気化合物の蒸気圧を下げるか、悪臭化合物を可溶化するか、臭いを物理的に捕捉する(例えば、凝集又は封入する)か、臭いを物理的に結合するか、又は臭いを物理的にはじいて、無生物表面に結合させないようにする構成成分を挙げてもよい。例えば、脂肪族アルデヒドは、魚及びタバコの臭いのようなアミン臭と反応する。悪臭結合ポリマーと組み合わせて用いると、フレッシュニング組成物は、より広範な悪臭を中和でき、ひいては、空気中又は無生物表面上の悪臭を更に減少させる物質を発生させる。
1つの実施形態では、本発明のフレッシュニング組成物は、布地に優しく、黄ばむことのない脂肪族アルデヒドを1種以上有する香料混合物を含む。複数の二重結合及びベンゼン環を含むタイプのアルデヒドを用いる製品とは異なり、直鎖の脂肪族骨格鎖を主に含む特定のタイプのアルデヒドは、布地を変色させない。下記の表には、布地の黄ばみを回避するアルデヒドの選択肢が示されている。
本発明のフレッシュニング組成物の臭気中和性を向上させる悪臭中和剤として、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、及び/又はグリセリンなど、水と比べて沸点が比較的高い低分子量ポリオールを用いてもよい。このようなポリオール、例えば、ジプロピレングリコールはまた、本発明の組成物中の一部の香料成分の可溶化を促進するのにも有用である。
いくつかの実施形態では、本発明のフレッシュニング組成物は、可溶化された水溶性の非錯化シクロデキストリンを含んでもよい。本明細書で使用される用語「シクロデキストリン」は、6〜12個のグルコース単位を含有する非置換型シクロデキストリン、特に、α−シクロデキストリン、β−シクロデキストリン、γ−シクロデキストリン、及び/又はこれらの誘導体及び/又はこれらの混合物のような既知のシクロデキストリンのいずれかを含む。α−シクロデキストリンは6個のグルコース単位からなり、β−シクロデキストリンは7個のグルコース単位からなり、γ−シクロデキストリンは、ドーナツ状の環に配置された8個のグルコース単位からなる。これらのグルコース単位の特異結合及びコンホメーションによって、特定の体積の中空の内側を有する剛性の円錐形分子構造をシクロデキストリンにもたらす。内部空洞の「内張り」は、水素原子とグリコシド結合の酸素原子によって形成されているので、この表面はかなりの疎水性を有する。この空洞の独自の形と物理的・化学的特性によって、シクロデキストリン分子は、その空洞に収まることのできる有機分子又は有機分子の一部を吸収する(その空洞に収まることのできる有機分子又は有機分子の一部と包接錯体を形成する)ことができるようになる。多くの香料分子は、上記の空洞に収まることができる。
本発明のフレッシュニング組成物は、二塩基酸、カルボン酸、又はマレイン酸のようなジカルボン酸であってもよい緩衝剤を含む。この酸は立体的に安定していてもよく、所望のpHを保つ目的のみで、本発明の組成物で用いてもよい。本発明のフレッシュニング組成物のpHは約3〜約8、あるいは約4〜約7、あるいは約5〜約8、あるいは約6〜約8、あるいは約6〜約7、あるいは約7、あるいは約6.5であってもよい。
透明な溶液が形成されるように、本発明のフレッシュニング組成物は、本組成物に加えることができるが、本組成物に容易には溶解できないいずれかの過剰な疎水性有機物質、詳細にはいずれかの香料物質、及び任意成分(例えば、害虫忌避剤、酸化防止剤等)を可溶化する可溶化補助剤を含んでもよい。好適な可溶化補助剤は、非起泡性又は低起泡性界面活性剤のような界面活性剤である。好適な界面活性剤は、非イオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤、双極性界面活性剤、及びこれらの混合物である。
本発明のフレッシュニング組成物は、空気中又は無生物表面上の微生物を減少させる化合物を有効量含んでもよい。抗菌性化合物は、ヒトの皮膚又はペットと接触した室内表面(カウチ、枕、ペットの寝具、及びカーペット等)の上に典型的に存在するグラム陰性及びグラム陽性バクテリア及び菌類に有効である。このような微生物種としては、肺炎杆菌、黄色ブドウ球菌、黒色アスペルギルス、肺炎杆菌、化膿レンサ球菌、豚コレラ菌、大腸菌、毛瘡白癬菌、及び緑膿菌が挙げられる。いくつかの実施形態では、抗菌性化合物は、H1−N1、ライノウイルス、RSウイルス、1型ポリオウイルス、ロタウイルス、A型インフルエンザ、1型及び2型単純ヘルペス、A型肝炎、及びヒトコロナウイルスのようなウイルスにも有効である。
本発明のフレッシュニング組成物は防腐剤を含んでもよい。防腐剤は本発明中に、特定の期間にわたり腐敗を防ぐか、又は、不注意にも加わってしまった微生物の増殖を防ぐのに十分であるが、フレッシュニング組成物の臭気中和性能に寄与するのに十分ではない量で含まれる。換言すれば、防腐剤は、微生物によって生じる臭いを消す目的でフレッシュニング組成物を堆積させる表面上の微生物を殺す抗菌性化合物として用いられているのではない。むしろ、フレッシュニング組成物の貯蔵寿命を長くする目的で、防腐剤を用いて、フレッシュニング組成物の腐敗を防ぐ。
ポリエステル及びナイロンのような疎水性表面上に、フレッシュニング組成物が容易かつより均一に展着できるようにする低い表面張力をもたらす湿潤剤を、本発明のフレッシュニング組成物は含んでもよい。本発明の水溶液は、このような湿潤剤がないと、十分には展着しないことが分かっている。本組成物によって処理した物質をユーザーがすぐに使える状態にできるように、組成物を展着させることによって、組成物がより早く乾くようにする。更に、湿潤剤を含む組成物は、疎水性の油汚れに、より浸透して、悪臭中和性を向上させることができる。湿潤剤を含む組成物は、「衣服着用中」の静電気制御性を向上させることもできる。濃縮組成物では、湿潤剤は、濃縮水性組成物中の抗菌性活性物質及び香料のような多くの活性物質の分散を促す。
本発明のフレッシュニング組成物は水性キャリアを含んでもよい。用いる水性キャリアは、蒸留したもの、脱イオン化したもの、又は水道水であってもよい。水は、本発明の組成物が水溶液になる量で存在してもよい。いくつかの実施形態では、水は、前記フレッシュニング組成物の約85重量%〜99.5重量%、あるいは約90重量%〜約99.5重量%、あるいは約92重量%〜約99.5重量%、あるいは約95重量%の量で存在してもよい。低分子量一価アルコール、例えば、エタノール、メタノール、及びイソプロパノール、又はポリオール(エチレングリコール、及びプロピレングリコールなど)を少量含む水も有用であり得る。しかし、エタノール及び/又はイソプロパノールのような揮発性の低分子量一価アルコールは制限すべきである。これらの揮発性有機化合物は、引火性の問題と環境汚染の問題の双方の一因になるからである。少量の低分子量一価アルコールを香料として、及び一部の防腐剤の安定化剤として本発明の組成物に加えたために、少量の低分子量一価アルコールが本発明の組成物に存在する場合、一価アルコールのレベルは、フレッシュニング組成物の約6重量%未満、あるいは約3重量%未満、あるいは約1重量%未満であってもよい。
アジュバントを既知の目的で、本発明のフレッシュニング組成物に任意で加えることができる。このようなアジュバントとしては、水溶性金属塩、帯電防止剤、害虫及び蛾忌避剤、着色剤、酸化防止剤、及びこれらの混合物が挙げられるが、これらに限定されない。
本発明のフレッシュニング組成物は、当該技術分野において既知のいずれかの好適な方法で作製することができる。全ての成分を単に混合することができる。特定の実施形態では、成分の濃縮混合物を作製し、フレッシュニング組成物を空気中又は無生物表面上に散布する前に、その濃縮混合物を水性キャリアに加えることによって希釈するのが望ましい場合がある。別の実施形態では、脱イオン水及びエタノール、並びに低分子量ポリオールを含む1つの容器中に、悪臭結合ポリマーを分散させてもよい。続いて、完全に分散され、視覚上溶解するまで、この容器に緩衝剤を加える。別の容器で、均質になるまで可溶化剤と香料を混合する。続いて、可溶化剤と香料の溶液を第1の混合容器に加え、均質になるまで混合する。
本発明のフレッシュニング組成物は、散布することによって、例えば、スプレーディスペンサーのような分配手段の中に本発明の水溶液を入れ、有効量を空気中、又は所望の表面若しくは物品上にスプレーすることによって、使うことができる。有効量とは、本明細書における定義では、ヒトの臭覚によって認識できないうえに、物品又は表面に液体が染みこんだり、又は液体の水溜りができたりして、乾いたときに、容易には認識可能な目に見える堆積物ができることのないレベルで、悪臭を中和するのに十分な量を意味する。散布は、スプレー器具、ローラー、パッド等を用いて行うことができる。
表1は、本発明によるフレッシュニング組成物の非限定例を示している。
表2は、本発明によるフレッシュニング組成物の非限定例を示している。
Claims (11)
- 悪臭を減少させるフレッシュニング組成物であって、
前記組成物の0.01重量%〜0.07重量%の、分子量が1,000〜2,000,000ダルトンであるホモポリマーポリエチレンイミンを含む、悪臭結合ポリマーと、
少なくとも1つの脂肪族アルデヒドを含む悪臭中和剤と、
水性キャリアと、
前記組成物の総重量に対して0重量%〜3重量%の量で存在する界面活性剤と
を含み、
アニオン性界面活性剤を含まず、
布地に汚れ又は染みを付けるいずれの材料も本質的に含まない組成物。 - 前記悪臭結合ポリマーが、分子量が少なくとも150ダルトンであると共に15%〜80%の一級アミノ基を有するポリアミンである、請求項1に記載の組成物。
- 前記悪臭結合ポリマーの分子量が25000ダルトンである、請求項1に記載の組成物。
- 前記少なくとも1つの脂肪族アルデヒドが、前記組成物の総重量に対して0.001重量%〜5重量%で存在する、請求項1に記載の組成物。
- 前記少なくとも1つの脂肪族アルデヒドが、ブルゲオナール、シトラール、シトロネリルオキシアセトアルデヒド、サイマール、デシルアルデヒド、ヘリオナール、ヘキシルシンナミックアルデヒド、ラウリンアルデヒド、リグストラール、リラール、メロナール、メチルジヒドロジャスモネート、メチルノニルアセトアルデヒド、メチルフェニルカルビニルアセテート、ノニルアルデヒド、2,6−ノナジエン−1−アル、オクチルアルデヒド、オキサン、P.T.ブシナール、ポリサントール、ルバフラン、トリパル、及びこれらの混合物からなる群から選択される、請求項4に記載の組成物。
- 前記組成物が、カルボン酸、ジカルボン酸、N−(2−アセトアミド)−2−アミノエタンスルホン酸、及びこれらの混合物からなる群から選択される緩衝剤を更に含む、請求項1に記載の組成物。
- さらにマレイン酸を含む、請求項1に記載の組成物。
- pHが3〜8である、請求項1に記載の組成物。
- 前記水性キャリアが90%〜99.5%の量で存在する、請求項1に記載の組成物。
- 悪臭を減少させる水性フレッシュニング組成物であって、
分子量が1,000〜2,000,000であるホモポリマーポリエチレンイミンと、
少なくとも1つの脂肪族アルデヒドと、
グリコールと、
pHを3〜8にするジカルボン酸と、
90%〜99.5%の水性キャリアと、を含み、アニオン性界面活性剤を含まず、布地に汚れ又は染みを付けるいずれの材料も本質的に含まず、
界面活性剤の全量が前記組成物の0重量%〜3重量%である組成物。 - 悪臭を減少させる方法であって、
a.請求項1のフレッシュニング組成物を提供する工程と、
b.無生物表面上又は空気中に前記フレッシュニング組成物の有効量を散布する工程と、を含む方法。
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US20160130745A1 (en) | 2016-05-12 |
AU2010295597B2 (en) | 2013-10-24 |
EP2478149A2 (en) | 2012-07-25 |
MX2012003293A (es) | 2012-04-30 |
WO2011034997A2 (en) | 2011-03-24 |
MY158556A (en) | 2016-10-14 |
BR112012006159A2 (pt) | 2016-06-28 |
WO2011034997A4 (en) | 2011-08-25 |
CA2774661C (en) | 2014-11-04 |
AU2010295597A1 (en) | 2012-04-05 |
KR101487220B1 (ko) | 2015-01-28 |
CL2012000683A1 (es) | 2012-07-13 |
CA2774661A1 (en) | 2011-03-24 |
KR20120050488A (ko) | 2012-05-18 |
US9260817B2 (en) | 2016-02-16 |
WO2011034997A3 (en) | 2011-07-07 |
EP2478149B1 (en) | 2019-10-23 |
JP2013504698A (ja) | 2013-02-07 |
US20110070181A1 (en) | 2011-03-24 |
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