JP4177706B2 - Deodorants - Google Patents

Description

（一般式［１］において、Ｒ ¹ は炭素数８〜２２のアルキル基、ヒドロキシアルキル基又はアルケニル基であり、Ｒ ² 及びＲ ³ は、それぞれに、炭素数１〜４のアルキル基若しくはヒドロキシアルキル基又は−Ｒ ⁴ Ｏ ( ＡＯ )n Ｈで表される基であり、Ｒ ⁴ は炭素数１〜４のアルキレン基であり、Ａは炭素数１〜４のアルキレン基であり、ｎは１〜５０である。）
を提供するものである。
【０００５】
【発明の実施の形態】
本発明の消臭剤は、オキソカルボン酸又はその塩と、アミンオキサイド系界面活性剤とを含有する。オキソカルボン酸とは、カルボキシル基−ＣＯＯＨの外に、アルデヒド基−ＣＨＯ又はケトン基＞ＣＯを有するカルボン酸である。
本発明に用いるオキソカルボン酸に特に制限はなく、例えば、グリオキシル酸、ホルミル酢酸、β−ホルミルプロピオン酸、４−ホルミル酪酸、グルクロン酸、アゼライン酸セミアルデヒド、β−ホルミルアクリル酸、ホルミルマロン酸、ホルミルコハク酸、ホルミルフェニル酢酸、フタルアルデヒド酸、ｍ−ホルミル安息香酸、ｐ−ホルミル安息香酸、８−ホルミル−１−ナフトエ酸、２−ホルミルイソフタル酸、ｐ−(３−ホルミルプロピル)安息香酸などのアルデヒド酸、ピルビン酸、プロピオニルギ酸、２−ケト吉草酸、２−ケトイソ吉草酸、２−ケトカプロン酸、トリメチルピルビン酸、２−ケトエナント酸、２−ケトカプリル酸、２−ケトカプリン酸、２−ケトペラルゴン酸、２−ケトウンデカン酸、２−ケトパルミチン酸、メソキサル酸、オキサル酢酸、２−ケトグルタル酸、２−ケトグルコン酸、α−ケトピメリン酸、２−ケトグロン酸、ベンゾイルギ酸、フェニルピルビン酸、ベンジルピルビン酸、２−ナフタレングリオキシル酸などのα−ケトン酸、アセト酢酸、プロピオニル酢酸、ブチリル酢酸、３−ケトエナント酸、３−ケトカプリル酸、３−ケトカプリン酸、３−ケトウンデカン酸、３−ケトラウリン酸、３−ケトトリデカン酸、３−ケトミリスチン酸、３−ケトペンタデカン酸、３−ケトパルミチン酸、３−ケトステアリン酸、３−ケトナノデカン酸、３−ケトベヘン酸、α−アセト酪酸、２−プロピオニルプロピオン酸、３−ケトグルタル酸、シクロヘキサノン−２−カルボン酸、ベンゾイル酢酸、１−インデンアセト酢酸などのβ−ケトン酸、レブリン酸、ホモレブリン酸、４−ケトエナント酸、４−ケトカプリル酸、４−ケトペラルゴン酸、４−ケトカプリン酸、４−ケトラウリン酸、４−ケトミリスチン酸、４−ケトペンタデカン酸、４−ケトパルミチン酸、４−ケトステアリン酸、４−ケトベヘン酸、β−アセト酪酸、ケトエイコセン酸、ヒドロケリドン酸、ホロン酸、β−ベンゾイルプロピオン酸、シクロヘキサノン−３−カルボン酸などのγ−ケトン酸、γ−アセト酪酸、５−ケトエナント酸、５−ケトカプリル酸、５−ケトペラルゴン酸、５−ケトカプリン酸、５−ケトウンデカン酸、５−ケトパルミチン酸、５−ケトアゼライン酸、５−ケトグルコン酸、ケトウロン酸、シクロヘキサノン−４−カルボン酸などのδ−ケトン酸、６−ケトエナント酸、６−ケトカプリル酸、６−ケトステアリン酸、７−ケトカプリル酸、７−ケトペラルゴン酸、７−ケトパルミチン酸、７−ケトステアリン酸、８−ケトペラルゴン酸、８−ケトカプリン酸、８−ケトパルミチン酸、８−ケトステアリン酸、９−ケトカプリン酸、９−ケトウンデカン酸、９−ケトラウリン酸、９−ケトパルミチン酸、９−ケトマルガリン酸、９−ケトステアリン酸、１０−ケトウンデカン酸、１０−ケトラウリン酸、１０−ケトトリデカン酸、１０−ケトパルミチン酸、１０−ケトステアリン酸、１０−ケトナノデカン酸、１０−ケトベヘン酸、１１−ケトペンタデカン酸、１１−ケトパルミチン酸、１１−ケトステアリン酸、１２−ケトトリデカン酸、１２−ケトステアリン酸、１３−ケトミリスチン酸、１４−ケトペンタデカン酸、１４−ケトベヘン酸、２−(シクロヘキシルカルボニル)−１−ナフトエ酸などのその他のケトン酸、グリオキシルカルボン酸などのケトアルデヒド酸などを挙げることができる。これらの中で、炭素数２〜６のオキソカルボン酸を好適に用いることができ、特にグリオキシル酸は、多種類の悪臭物質に対して良好な消臭効果を発揮するので、最も好適に用いることができる。
【０００６】
本発明に用いるオキソカルボン酸の塩に特に制限はなく、例えば、アンモニウム塩、リチウム、ナトリウム、カリウム、ルビジウム、セシウムなどのアルカリ金属塩、マグネシウム、カルシウム、ストロンチウム、バリウムなどのアルカリ土類金属塩、モノエタノールアミン、ジエタノールアミン、トリエタノールアミンなどのアミン塩などを挙げることができる。
本発明の消臭剤においては、オキソカルボン酸及びその塩の含有量の合計が０.００５〜１０質量％であることが好ましく、０.０５〜５質量％であることがより好ましく、０.１〜０.９質量％であることがさらに好ましい。オキソカルボン酸及びその塩の含有量の合計が０.００５質量％未満であると、消臭効果が不十分となるおそれがある。オキソカルボン酸及びその塩の含有量の合計が１０質量％を超えると、含有量の増加に見合う効果が発現しないおそれがある。
【０００７】
本発明に用いるアミンオキサイド系界面活性剤に特に制限はなく、例えば、疎水性基を有する第三級アミンを、過酸化水素、過酸、ペルオキシ硫酸などを用いて酸化して得られるアミンオキサイド系界面活性剤などを挙げることができる。これらの中で、一般式［１］で表される構造を有するアミンオキサイド系界面活性剤を好適に用いることができる。
【化２】

一般式［１］において、Ｒ¹は炭素数８〜２２のアルキル基、ヒドロキシアルキル基又はアルケニル基である。また、Ｒ²及びＲ³は、それぞれに、炭素数１〜４のアルキル基若しくはヒドロキシアルキル基又は−Ｒ⁴Ｏ(ＡＯ)nＨで表される基であり、Ｒ⁴は、炭素数１〜４のアルキレン基であり、Ａは、炭素数１〜４のアルキレン基であり、ｎは、１〜５０である。
このようなアミンオキサイド系界面活性剤としては、例えば、ラウリルジメチルアミンオキサイド、ミリスチルジメチルアミンオキサイド、パルミチルジメチルアミンオキサイド、ステアリルジメチルアミンオキサイド、オレイルジメチルアミンオキサイド、べへニルジメチルアミンオキサイド、ポリオキシエチレン(３モル)ラウリルアミンオキサイドなどを挙げることができる。
本発明においては、アミンオキサイド系界面活性剤の含有量が、０.００５〜１０質量％であることが好ましく、０.０５〜５質量％であることがより好ましい。アミンオキサイド系界面活性剤の含有量が０.００５質量％未満であると、消臭効果が不十分となるおそれがある。アミンオキサイド系界面活性剤の含有量が１０質量％を超えると、含有量の増加に見合う効果が発現しないおそれがある。
本発明の消臭剤は、ｐＨが５〜９であることが好ましく、ｐＨが６〜８であることがより好ましい。ｐＨが５未満であると、酸性悪臭や硫黄系悪臭に対する消臭性が低下するおそれがある。ｐＨが９を超えると、塩基性悪臭に対する消臭性が低下するおそれがある。
【０００８】
本発明の消臭剤には、ｐＨ緩衝剤を含有させることが好ましい。ｐＨ緩衝剤を含有させてｐＨ緩衝能を付与することにより、オキソカルボン酸自体の臭気を抑制するとともに、消臭対象物質が酸性又はアルカリ性であっても、安定した消臭効果を発現することができる。含有させるｐＨ緩衝剤に特に制限はなく、例えば、炭酸、硫酸、シュウ酸、マロン酸、コハク酸、フタル酸などの二塩基酸の酸性塩、ホウ酸、燐酸、クエン酸、トリメリット酸などの三塩基酸の酸性塩などを挙げることができる。これらの中で、燐酸水素二ナトリウム及び燐酸水素二カリウムを特に好適に用いることができる。本発明において、ｐＨ緩衝剤の含有量に特に制限はないが、０.０１〜１５質量％であることが好ましく、０.１〜１０質量％であることがより好ましい。
本発明においては、必要に応じて、消臭剤に他の界面活性剤を含有させることができる。含有させる他の界面活性剤としては、例えば、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、アルキルエーテル硫酸エステル塩、アルキル燐酸エステル塩などのアニオン界面活性剤、アルキルトリメチルアンモニウム塩、アルキルジヒドロキシエチルアンモニウム塩、アルキルアミン塩などのカチオン界面活性剤、ソルビタン脂肪酸エステル、グリセリン脂肪酸モノエステルなどのエステル系ノニオン界面活性剤、ポリオキシアルキレンアルキルエーテル、ポリオキシエチレンポリオキシプロピレングリコールなどのエーテル系ノニオン界面活性剤、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸部分エステルなどのエステル・エーテル系ノニオン界面活性剤、脂肪酸ジエタノールアミド、ポリオキシエチレン脂肪酸アミドなどのアミド系ノニオン界面活性剤などを挙げることができる。本発明においては、さらに必要に応じて、消臭剤に、各種の抗菌剤、防腐剤、香料などを添加することができる。
本発明の消臭剤の形態に特に制限はなく、使用目的、用途などに応じて適宜選択することができる。例えば、水、エタノール、イソプロパノールなどの低級アルコール、これらの混合溶媒などを媒体とした液剤として使用することができ、活性炭、シリカゲル、ゼオライトなどの多孔質担体に含浸、担持させて使用することもでき、あるいは、粉末、錠剤、顆粒剤などに成型して使用することもできる。使用方法に特に制限はなく、例えば、悪臭源に噴霧又は混合する方法、悪臭を感じる空間に噴霧又は備え付ける方法などを挙げることができる。
【０００９】
【実施例】
以下に、実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例によりなんら限定されるものではない。
なお、参考例、実施例及び比較例において、消臭効果は、下記の方法により評価した。
（１）アンモニアに対する消臭効果
１００ｍＬの共栓三角フラスコに、アンモニア濃度２５０ｐｐｍ（質量比）のアンモニア水０.５ｍＬと、消臭剤０.５ｍＬとを入れて密栓し、軽く混合して１分間放置したのち、ガス検知管［(株)ガステック、３Ｌ］を用いて、三角フラスコ内の空気中のアンモニアの濃度を測定する。また、空試験として、消臭剤の代わりに蒸留水を用いて、三角フラスコ内の空気中のアンモニアの濃度を測定する。
（２）イソ吉草酸に対する消臭効果
１００ｍＬの共栓三角フラスコに、濃度１質量％のイソ吉草酸のエタノール溶液０.５ｍＬと、消臭剤０.５ｍＬとを入れて密栓し、軽く混合して１分間放置したのち、ガス検知管［(株)ガステック、８１Ｌ］を用いて、三角フラスコ内の空気中のイソ吉草酸の濃度を測定する。また、空試験として、消臭剤の代わりに蒸留水を用いて、三角フラスコ内の空気中のイソ吉草酸の濃度を測定する。
（３）メチルメルカプタンに対する消臭効果
１００ｍＬの共栓三角フラスコに、濃度６ｐｐｍ（質量比）のメチルメルカプタンのベンゼン溶液０.５ｍＬと、消臭剤０.５ｍＬとを入れて密栓し、軽く混合して１分間放置したのち、ガス検知管［(株)ガステック、７１」を用いて三角フラスコ内の空気中のメチルメルカプタンの濃度を測定する。また、空試験として、消臭剤の代わりに蒸留水を用いて、三角フラスコ内の空気中のメチルメルカプタンの濃度を測定する。
アンモニア、イソ吉草酸及びメチルメルカプタンについて、消臭剤を用いたときの濃度と、空試験の濃度から、次式にしたがって消臭率（％）を算出する。
消臭率(％)＝｛１−(消臭剤を用いたときの濃度)／(空試験の濃度)｝×１００
【００１０】
実施例１
蒸留水９６質量部に、グリオキシル酸０.５質量部、ラウリルジメチルアミンオキサイド０.５質量部及び燐酸水素二カリウム３.０質量部を溶解して消臭剤を調製し、消臭効果の評価を行った。なお、この消臭剤のｐＨは７.０であった。
アンモニアは、消臭剤を用いたときは検出されず、空試験の濃度は７０ｐｐｍ（容量比）であり、消臭率は１００％であった。イソ吉草酸は、消臭剤を用いたときの濃度１.８ｐｐｍ（容量比）、空試験の濃度１８ｐｐｍ（容量比）であり、消臭率９０％であった。メチルメルカプタンは、消臭剤を用いたときの濃度０.５３ｐｐｍ（容量比）、空試験の濃度３.５ｐｐｍ（容量比）であり、消臭率８５％であった。
上記のｐＨ７.０の消臭剤に０.１モル／Ｌの塩酸を添加してｐＨを６.０に調整し、同様に消臭効果の評価を行った。消臭率は、アンモニア１００％、イソ吉草酸８０％、メチルメルカプタン７８％であった。
さらに、上記のｐＨ７.０の消臭剤に０.１モル／Ｌの水酸化ナトリウム水溶液を添加してｐＨを８.０に調整し、同様に消臭効果の評価を行った。消臭率は、アンモニア９５％、イソ吉草酸９３％、メチルメルカプタン８８％であった。
参考例２
蒸留水９６質量部に、ピルビン酸０.５質量部、ラウリルジメチルアミンオキサイド０.５質量部及び燐酸水素二カリウム３.０質量部を溶解して消臭剤を調製し、消臭効果の評価を行った。この消臭剤のｐＨは、７.２であった。消臭率は、アンモニア９９％、イソ吉草酸８５％、メチルメルカプタン７９％であった。
参考例３
蒸留水９６質量部に、レブリン酸０.５質量部、ミリスチルジメチルアミンオキサイド０.５質量部及び燐酸水素二カリウム３.０質量部を溶解して消臭剤を調製し、消臭効果の評価を行った。この消臭剤のｐＨは、６.８であった。消臭率は、アンモニア９９％、イソ吉草酸８２％、メチルメルカプタン７２％であった。
実施例４
蒸留水９６質量部に、グリオキシル酸０.３質量部、ピルビン酸０.２質量部、ラウリルジメチルアミンオキサイド０.３質量部、ミリスチルジメチルアミンオキサイド０.２質量部及び燐酸水素二カリウム３.０質量部を溶解して消臭剤を調製し、消臭効果の評価を行った。この消臭剤のｐＨは、７.５であった。消臭率は、アンモニア１００％、イソ吉草酸８８％、メチルメルカプタン８１％であった。
参考例５
蒸留水９６質量部に、グリオキシル酸ナトリウム０.５質量部、ラウリルジメチルアミンオキサイド０.５質量部及び燐酸水素二カリウム３.０質量部を溶解して消臭剤を調製し、消臭効果の評価を行った。この消臭剤のｐＨは、６.３であった。消臭率は、アンモニア１００％、イソ吉草酸８９％、メチルメルカプタン８３％であった。
【００１１】
比較例１
蒸留水９６.５質量部に、グリオキシル酸０.５質量部及び燐酸水素二カリウム３.０質量部を溶解して消臭剤を調製し、消臭効果の評価を行った。この消臭剤のｐＨは、６.８であった。消臭率は、アンモニア６５％、イソ吉草酸５２％、メチルメルカプタン３２％であった。
比較例２
蒸留水９６.５質量部に、ラウリルジメチルアミンオキサイド０.５質量部及び燐酸水素二カリウム３.０質量部を溶解して消臭剤を調製し、消臭効果の評価を行った。この消臭剤のｐＨは、７.２であった。消臭率は、アンモニア４５％、イソ吉草酸５２％、メチルメルカプタン５％であった。
比較例３
蒸留水９６質量部に、グリオキシル酸０.５質量部、エーテル系ノニオン界面活性剤［日華化学(株)、ポリオキシエチレン(９モル)ラウリルエーテル］０.５質量部及び燐酸水素二カリウム３.０質量部を溶解して消臭剤を調製し、消臭効果の評価を行った。この消臭剤のｐＨは、７.０であった。消臭率は、アンモニア３８％、イソ吉草酸２５％、メチルメルカプタン０％であった。
比較例４
蒸留水９６質量部に、グリオキシル酸０.５質量部、カチオン界面活性剤［日華化学(株)、ラウリルジメチルベンジルアンモニウムクロライド］０.５質量部及び燐酸水素二カリウム３.０質量部を溶解して消臭剤を調製し、消臭効果の評価を行った。この消臭剤のｐＨは、６.９であった。消臭率は、アンモニア４７％、イソ吉草酸２３％、メチルメルカプタン０％であった。
実施例１及び４、参考例２、３及び５の消臭剤の配合組成と消臭率とｐＨを第１表に、比較例１〜４の消臭剤の配合組成と消臭率とｐＨを第２表に示す。
【００１２】
【表１】

【００１３】
【表２】

【００１４】
第１表に見られるように、グリオキシル酸、ピルビン酸、レブリン酸又はグリオキシル酸ナトリウムと、ラウリルジメチルアミンオキサイド又はミリスチルジメチルアミンオキサイドとを含有する実施例１及び４、参考例２、３及び５の消臭剤は、アンモニアに対する消臭率９５％以上、イソ吉草酸に対する消臭率８０％以上、メチルメルカプタンに対する消臭率７０％以上に達し、塩基性悪臭、酸性悪臭、硫黄系悪臭のすべてに対して優れた消臭効果を発揮している。また、実施例１において、グリオキシル酸とラウリルジメチルアミンオキサイドの含有量が同じであっても、消臭剤のｐＨを８.０にするとｐＨ７.０に比べてアンモニアに対する消臭率は低下するが、イソ吉草酸とメチルメルカプタンに対する消臭率は向上する。したがって、消臭の対象とする悪臭の性質に応じて、消臭剤のｐＨを選択することにより、消臭効果を高め得ることが分かる。
これに対して、グリオキシル酸のみを含有してアミンオキサイド系界面活性剤を含有しない比較例１の消臭剤と、ラウリルジメチルアミンオキサイドのみを含有してオキソカルボン酸を含有しない比較例２の消臭剤は、いずれも消臭効果が小さい。また、グリオキシル酸と界面活性剤とを含有する消臭剤であっても、エーテル系ノニオン界面活性剤を用いた比較例３の消臭剤と、カチオン界面活性剤を用いた比較例４の消臭剤は、アンモニア及びイソ吉草酸に対する消臭効果は実施例１及び４、参考例２、３及び５の消臭剤より劣っており、メチルメルカプタンに対する消臭効果はほとんど見られない。
【００１５】
【発明の効果】
本発明の消臭剤は、消臭剤の有効成分が低濃度であっても、多種多様の悪臭物質に対して、特に通常は消臭されにくいメチルメルカプタンに対しても優れた消臭効果を発揮する。したがって、本発明の消臭剤を用いることにより、生活の場の快適化はもとより、悪臭公害の低減にも寄与することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a deodorant. More specifically, the present invention relates to a deodorant that effectively acts on various malodorous substances such as ammonia, amines, fatty acids, mercaptans, and hydrogen sulfide.
[0002]
[Prior art]
Twenty to thirty years ago, deodorization and deodorization were essential processes such as chemical factories, food manufacturing factories, livestock farming, sewage / sewage treatment plants, etc. Responses to the spread of target substances were made.
However, in recent years, due to changes in the social environment, lifestyle, user consciousness, etc., traditionally deodorization and deodorization have not been an essential requirement, for example, living in residences, offices, cars, shared facilities, restaurants, etc. There is also a growing demand for deodorization and deodorization. However, the cause of the bad odor generated from these places of life is not a single cause, and a wide variety of bad odor substances are mixed, and identification is often difficult.
Many commercially available deodorants are generally classified as follows.
(1) Sensory deodorant: Masks the odor with the fragrance of an aromatic substance, improves the quality of the odor, and reduces the degree of discomfort.
{Circle around (2)} Chemical reaction system deodorant: Odorous substances are made non-brominated with oxidation, reduction, neutralization, desulfurization, addition and condensation reactions.
(3) Physical adsorption deodorant: A malodorous substance is physically adsorbed by a porous substance such as activated carbon, silica gel, alumina gel, activated clay, and zeolite.
(4) Chemical adsorption deodorant: Adsorbed with an impregnated activated carbon, an ion exchange resin, an iron oxide-based substance, etc., accompanied by a chemical reaction with a malodorous substance.
(5) Microbial deodorant: Deodorizes with enzymes produced by microorganisms.
However, in (1) sensory deodorants, it is important to consider compatibility with malodorous substances, and it is difficult to deal with every place of life, and the aroma of aromatic substances varies according to the person. By the way. (2) It is extremely difficult to select compounds that react efficiently with a wide variety of malodorous substances even in chemical reaction deodorants. Even if the compounds correspond to relatively many kinds of malodorous substances, strong acids Or it is a strong alkali, and it is hard to say that it is safe with respect to a human body, and stability of a deodorizer itself is also low. (3) Physical adsorption type deodorant and (4) Chemical adsorption type deodorant have a limit in the amount of malodorous substances adsorbed and have a problem of re-diffusion. In addition, there is a drawback that it takes time and cost to replace the adsorbent. (5) Microbial deodorants are not practical because they are not suitable for deodorization in daily life and the onset of deodorizing effects is slow. Thus, no satisfactory one is obtained in any type.
In view of the above circumstances, deodorizers that are effective against a wide variety of malodorous substances have been studied. For example, as a deodorant that exhibits excellent deodorizing effects against a wide variety of odors and has excellent temporal stability, an organic deodorizing ingredient extracted from plants, organic acids such as tartaric acid, glyoxylic acid and glycerin A deodorant obtained by adding a wetting agent such as the above has been proposed (Patent Document 1). However, the operation of extracting the deodorant active ingredient from a natural plant is complicated, and there is a problem that the deodorization effect is not always stable due to the difference in the type of plant. In addition, as a deodorant that exhibits a wide range of deodorizing effects on various causative substances that constitute malodors, glyoxylic acid is an active ingredient, and the pH is 2.4 to 9, and further the interface A deodorant containing an activator and having a pH of 5 to 8 has been proposed (Patent Document 2). However, with this deodorant, in order to increase the deodorizing effect on methyl mercaptan, it is necessary to increase the concentration of glyoxylic acid, and it cannot be said that the deodorizing effect on methyl mercaptan is sufficient. Furthermore, it contains pyruvic acid, glyoxylic acid or their salts and water as a deodorant having a low odor of itself and showing an excellent deodorizing effect on the odors of amines, mercaptans and lower fatty acids, pH A deodorant having a buffering capacity has been proposed (Patent Document 3). However, with this deodorant, especially when trying to obtain a high effect on methyl mercaptan, pyruvic acid, glyoxylic acid or a salt thereof must be blended at a high concentration, and it is used such as generation of white powder and stickiness. The above problem is not enough.
[Patent Document 1]
JP 2000-325453 A (page 2)
[Patent Document 2]
JP 2001-137323 A (page 2, page 4)
[Patent Document 3]
JP 2002-306583 A (2nd page)
[0003]
[Problems to be solved by the invention]
The present invention provides a deodorant that effectively acts on various malodorous substances such as basic malodors such as ammonia and amines, acidic malodors such as fatty acids, and sulfur-based malodors such as mercaptans and hydrogen sulfide. It was made for the purpose.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have combined an amine oxide surfactant with an oxocarboxylic acid or a salt thereof as an active ingredient of a deodorant, in particular, methyl mercaptan. It has been found that the deodorizing effect can be improved, and even if the oxocarboxylic acid or its salt is at a low concentration, it has been found that an excellent deodorizing effect is exhibited, and the present invention has been completed based on this finding. It was.
That is, the present invention
(1) 0.005 to 10% by mass of glyoxylic acid or a salt thereof, 0.05 to 5% by mass of an amine oxide surfactant of the following general formula [1] and pH with respect to 100 parts by mass of the deodorant aqueous solution A deodorant is prepared by dissolving either disodium hydrogen phosphate or dipotassium hydrogen phosphate as an adjusting agent, and an acid or alkali is added as desired to adjust the pH to a predetermined pH of 6-8. Deodorant, characterized by
[Chemical formula 2]

(In General Formula [1], R ¹ is an alkyl group having 8 to 22 carbon atoms, a hydroxyalkyl group or an alkenyl group, and R ² and R ³ are each an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group. Or a group represented by —R ⁴ O ( AO ) nH , R ⁴ is an alkylene group having 1 to 4 carbon atoms, A is an alkylene group having 1 to 4 carbon atoms, and n is 1 to 1 50.)
Is to provide.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The deodorizer of the present invention contains oxocarboxylic acid or a salt thereof and an amine oxide surfactant. The oxocarboxylic acid is a carboxylic acid having an aldehyde group -CHO or a ketone group> CO in addition to the carboxyl group -COOH.
The oxocarboxylic acid used in the present invention is not particularly limited, and examples thereof include glyoxylic acid, formylacetic acid, β-formylpropionic acid, 4-formylbutyric acid, glucuronic acid, azelaic acid semialdehyde, β-formylacrylic acid, formylmalonic acid, Formylsuccinic acid, formylphenylacetic acid, phthalaldehyde acid, m-formylbenzoic acid, p-formylbenzoic acid, 8-formyl-1-naphthoic acid, 2-formylisophthalic acid, p- (3-formylpropyl) benzoic acid, etc. Aldehyde acid, pyruvic acid, propionylformic acid, 2-ketovaleric acid, 2-ketoisovaleric acid, 2-ketocaproic acid, trimethylpyruvic acid, 2-ketoenanthic acid, 2-ketocaprylic acid, 2-ketocapric acid, 2-ketoperargonic acid 2-ketoundecanoic acid, 2-ketopalmitic acid, mesoki Α-ketonic acids such as phosphoric acid, oxalic acid, 2-ketoglutaric acid, 2-ketogluconic acid, α-ketopimelic acid, 2-ketogulonic acid, benzoylformic acid, phenylpyruvic acid, benzylpyruvic acid, 2-naphthaleneglyoxylic acid, aceto Acetic acid, propionyl acetic acid, butyryl acetic acid, 3-ketoenanthic acid, 3-ketocaprylic acid, 3-ketocapric acid, 3-ketoundecanoic acid, 3-ketolauric acid, 3-ketotridecanoic acid, 3-ketomyristic acid, 3-ketopentadecanoic acid 3-ketopalmitic acid, 3-ketostearic acid, 3-ketonanodecanoic acid, 3-ketobehenic acid, α-acetobutyric acid, 2-propionylpropionic acid, 3-ketoglutaric acid, cyclohexanone-2-carboxylic acid, benzoylacetic acid, 1 -Β-ketonic acid such as indeneacetoacetic acid, levulinic acid , Homolevulinic acid, 4-ketoenanthic acid, 4-ketocaprylic acid, 4-ketopelargonic acid, 4-ketocapric acid, 4-ketolauric acid, 4-ketomyristic acid, 4-ketopentadecanoic acid, 4-ketopalmitic acid, 4-keto Γ-ketonic acid such as stearic acid, 4-ketobehenic acid, β-acetobutyric acid, ketoeicosenoic acid, hydrochelidonic acid, holonic acid, β-benzoylpropionic acid, cyclohexanone-3-carboxylic acid, γ-acetobutyric acid, 5-ketoenanthic acid 5-ketocaprylic acid, 5-ketoperargonic acid, 5-ketocapric acid, 5-ketoundecanoic acid, 5-ketopalmitic acid, 5-ketoazelineic acid, 5-ketogluconic acid, ketouronic acid, cyclohexanone-4-carboxylic acid, etc. δ-ketonic acid, 6-ketoenanthic acid, 6-ketocaprylic acid, 6-ketos Thealic acid, 7-ketocaprylic acid, 7-ketoperargonic acid, 7-ketopalmitic acid, 7-ketostearic acid, 8-ketopelargonic acid, 8-ketocapric acid, 8-ketopalmitic acid, 8-ketospartic acid, 9-ketocaprin Acid, 9-ketoundecanoic acid, 9-ketolauric acid, 9-ketopalmitic acid, 9-ketomargaric acid, 9-ketostearic acid, 10-ketoundecanoic acid, 10-ketolauric acid, 10-ketotridecanoic acid, 10-ketopalmitin Acid, 10-ketostearic acid, 10-ketonanodecanoic acid, 10-ketobehenic acid, 11-ketopentadecanoic acid, 11-ketopalmitic acid, 11-ketostearic acid, 12-ketotridecanoic acid, 12-ketostearic acid, 13-keto Myristic acid, 14-ketopentadecanoic acid, 14-ketobehenic acid, - (cyclohexylcarbonyl) -1 other ketones acids such as naphthoic acid, and keto aldehyde acids such as glyoxylic acid can be exemplified. Among these, oxocarboxylic acids having 2 to 6 carbon atoms can be preferably used, and glyoxylic acid is particularly suitable because it exhibits a good deodorizing effect on a variety of malodorous substances. Can do.
[0006]
The salt of oxocarboxylic acid used in the present invention is not particularly limited, and examples thereof include ammonium salts, alkali metal salts such as lithium, sodium, potassium, rubidium and cesium, alkaline earth metal salts such as magnesium, calcium, strontium and barium, Examples thereof include amine salts such as monoethanolamine, diethanolamine, and triethanolamine.
In the deodorizer of the present invention, the total content of oxocarboxylic acids and salts thereof is preferably 0.005 to 10% by mass, more preferably 0.05 to 5% by mass, and More preferably, it is 1-0.9 mass%. If the total content of oxocarboxylic acid and its salt is less than 0.005% by mass, the deodorizing effect may be insufficient. If the total content of oxocarboxylic acids and salts thereof exceeds 10% by mass, the effects commensurate with the increase in content may not be exhibited.
[0007]
There are no particular limitations on the amine oxide surfactant used in the present invention. For example, an amine oxide surfactant obtained by oxidizing a tertiary amine having a hydrophobic group with hydrogen peroxide, peracid, peroxysulfuric acid, or the like. Surfactant etc. can be mentioned. Among these, amine oxide surfactants having a structure represented by the general formula [1] can be suitably used.
[Chemical formula 2]

In General Formula [1], R ¹ is an alkyl group having 8 to 22 carbon atoms, a hydroxyalkyl group, or an alkenyl group. R ² and R ³ are each an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group or a group represented by —R ⁴ O (AO) nH, and R ⁴ is a group having 1 to 4 carbon atoms. A is an alkylene group having 1 to 4 carbon atoms, and n is 1 to 50.
Examples of such amine oxide surfactants include lauryl dimethylamine oxide, myristyl dimethylamine oxide, palmityl dimethylamine oxide, stearyl dimethylamine oxide, oleyl dimethylamine oxide, behenyl dimethylamine oxide, and polyoxyethylene. (3 mol) laurylamine oxide and the like can be mentioned.
In the present invention, the content of the amine oxide surfactant is preferably 0.005 to 10% by mass, and more preferably 0.05 to 5% by mass. If the content of the amine oxide surfactant is less than 0.005% by mass, the deodorizing effect may be insufficient. When the content of the amine oxide surfactant exceeds 10% by mass, an effect commensurate with the increase in content may not be exhibited.
The deodorizer of the present invention preferably has a pH of 5 to 9, more preferably 6 to 8. There exists a possibility that the deodorizing property with respect to an acidic malodor and sulfur type malodor may fall that pH is less than 5. When pH exceeds 9, there exists a possibility that the deodorizing property with respect to a basic malodor may fall.
[0008]
The deodorizer of the present invention preferably contains a pH buffer. By adding a pH buffering agent and imparting pH buffering ability, the odor of the oxocarboxylic acid itself can be suppressed, and a stable deodorizing effect can be exhibited even if the substance to be deodorized is acidic or alkaline. it can. There is no particular limitation on the pH buffering agent to be contained, for example, acid salts of dibasic acids such as carbonic acid, sulfuric acid, oxalic acid, malonic acid, succinic acid, phthalic acid, boric acid, phosphoric acid, citric acid, trimellitic acid, etc. The acid salt of a tribasic acid etc. can be mentioned. Among these, disodium hydrogen phosphate and dipotassium hydrogen phosphate can be particularly preferably used. In the present invention, the content of the pH buffering agent is not particularly limited, but is preferably 0.01 to 15% by mass, and more preferably 0.1 to 10% by mass.
In the present invention, if necessary, the deodorizer can contain other surfactant. Examples of other surfactants to be contained include anionic surfactants such as alkylbenzene sulfonate, alkyl sulfate ester salt, alkyl ether sulfate ester salt, and alkyl phosphate ester salt, alkyl trimethyl ammonium salt, alkyl dihydroxyethyl ammonium salt, Cationic surfactants such as alkylamine salts, ester nonionic surfactants such as sorbitan fatty acid ester and glycerin fatty acid monoester, ether nonionic surfactants such as polyoxyalkylene alkyl ether and polyoxyethylene polyoxypropylene glycol, poly Ester / ether type nonionic surfactants such as oxyethylene fatty acid ester and polyoxyethylene sorbitan fatty acid partial ester, fatty acid diethanolamide, polyoxy An amide-based nonionic surfactants such as polyoxyethylene fatty acid amide can be mentioned. In the present invention, various antibacterial agents, preservatives, fragrances and the like can be added to the deodorant as necessary.
There is no restriction | limiting in particular in the form of the deodorizer of this invention, According to a use purpose, a use, etc., it can select suitably. For example, it can be used as a liquid agent using water, lower alcohols such as ethanol and isopropanol, and mixed solvents thereof as a medium, and can also be used by being impregnated and supported on a porous carrier such as activated carbon, silica gel and zeolite. Alternatively, it can be molded into a powder, tablet, granule or the like. There is no restriction | limiting in particular in a usage method, For example, the method of spraying or mixing to a malodor source, the method of spraying or providing in the space which feels malodor, etc. can be mentioned.
[0009]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In the reference examples, examples and comparative examples, the deodorizing effect was evaluated by the following method.
(1) Deodorizing effect on ammonia A 100 mL stoppered Erlenmeyer flask was charged with 0.5 mL of ammonia water with an ammonia concentration of 250 ppm (mass ratio) and 0.5 mL of deodorant, and lightly mixed for 1 minute. After leaving, the concentration of ammonia in the air in the Erlenmeyer flask is measured using a gas detector tube [Gastech, 3L]. As a blank test, the concentration of ammonia in the air in the Erlenmeyer flask is measured using distilled water instead of the deodorant.
(2) Deodorizing effect on isovaleric acid In a 100 mL stoppered Erlenmeyer flask, put 0.5 mL of ethanol solution of isovaleric acid with a concentration of 1% by mass and 0.5 mL of deodorant and seal it lightly. 1 minute, and then the concentration of isovaleric acid in the air in the Erlenmeyer flask is measured using a gas detector tube [Gastech, 81L]. As a blank test, the concentration of isovaleric acid in the air in the Erlenmeyer flask is measured using distilled water instead of the deodorant.
(3) Deodorizing effect on methyl mercaptan In a 100 mL stoppered Erlenmeyer flask, put 0.5 mL of a methyl mercaptan benzene solution with a concentration of 6 ppm (mass ratio) and 0.5 mL of a deodorizing agent, tightly stopper, and mix gently. 1 minute, and then the concentration of methyl mercaptan in the air in the Erlenmeyer flask is measured using a gas detector tube [Gastech, 71]. Further, as a blank test, the concentration of methyl mercaptan in the air in the Erlenmeyer flask is measured using distilled water instead of the deodorant.
For ammonia, isovaleric acid and methyl mercaptan, the deodorization rate (%) is calculated according to the following formula from the concentration when a deodorant is used and the concentration of the blank test.
Deodorization rate (%) = {1− (concentration when using deodorant) / (concentration in blank test)} × 100
[0010]
Example 1
Deodorant was prepared by dissolving 0.5 parts by mass of glyoxylic acid, 0.5 parts by mass of lauryldimethylamine oxide and 3.0 parts by mass of dipotassium hydrogen phosphate in 96 parts by mass of distilled water, and evaluating the deodorizing effect. Went. The deodorant had a pH of 7.0.
Ammonia was not detected when a deodorant was used, the concentration in the blank test was 70 ppm (volume ratio), and the deodorization rate was 100%. Isovaleric acid had a concentration of 1.8 ppm (volume ratio) when a deodorant was used, a concentration of 18 ppm (volume ratio) in a blank test, and a deodorization rate of 90%. Methyl mercaptan had a concentration of 0.53 ppm (volume ratio) and a blank test concentration of 3.5 ppm (volume ratio) when a deodorant was used, and a deodorization rate of 85%.
0.1 mol / L hydrochloric acid was added to the pH 7.0 deodorant to adjust the pH to 6.0, and the deodorizing effect was similarly evaluated. The deodorization rate was 100% ammonia, 80% isovaleric acid, and 78% methyl mercaptan.
Further, a 0.1 mol / L sodium hydroxide aqueous solution was added to the pH 7.0 deodorant to adjust the pH to 8.0, and the deodorizing effect was similarly evaluated. The deodorization rate was 95% ammonia, 93% isovaleric acid, and 88% methyl mercaptan.
Reference example 2
Deodorant was prepared by dissolving 0.5 parts by mass of pyruvic acid, 0.5 parts by mass of lauryldimethylamine oxide and 3.0 parts by mass of dipotassium hydrogen phosphate in 96 parts by mass of distilled water, and evaluating the deodorizing effect. Went. The pH of this deodorant was 7.2. The deodorization rate was 99% ammonia, 85% isovaleric acid, and 79% methyl mercaptan.
Reference example 3
Deodorant was prepared by dissolving 0.5 parts by mass of levulinic acid, 0.5 parts by mass of myristyldimethylamine oxide and 3.0 parts by mass of dipotassium hydrogen phosphate in 96 parts by mass of distilled water, and evaluating the deodorizing effect. Went. The pH of this deodorant was 6.8. The deodorization rate was 99% ammonia, 82% isovaleric acid, and 72% methyl mercaptan.
Example 4
To 96 parts by weight of distilled water, 0.3 part by weight of glyoxylic acid, 0.2 part by weight of pyruvic acid, 0.3 part by weight of lauryl dimethylamine oxide, 0.2 part by weight of myristyl dimethylamine oxide and 3.0 parts by weight of dipotassium hydrogen phosphate Deodorizing agents were prepared by dissolving parts by mass, and the deodorizing effect was evaluated. The pH of this deodorant was 7.5. The deodorization rate was 100% ammonia, 88% isovaleric acid, and 81% methyl mercaptan.
Reference Example 5
A deodorizer is prepared by dissolving 0.5 parts by mass of sodium glyoxylate, 0.5 parts by mass of lauryldimethylamine oxide and 3.0 parts by mass of dipotassium hydrogen phosphate in 96 parts by mass of distilled water. Evaluation was performed. The deodorant had a pH of 6.3. The deodorization rate was 100% ammonia, 89% isovaleric acid, and 83% methyl mercaptan.
[0011]
Comparative Example 1
A deodorant was prepared by dissolving 0.5 part by mass of glyoxylic acid and 3.0 parts by mass of dipotassium hydrogen phosphate in 96.5 parts by mass of distilled water, and the deodorizing effect was evaluated. The pH of this deodorant was 6.8. The deodorization rate was 65% ammonia, 52% isovaleric acid, and 32% methyl mercaptan.
Comparative Example 2
A deodorant was prepared by dissolving 0.5 parts by mass of lauryldimethylamine oxide and 3.0 parts by mass of dipotassium hydrogen phosphate in 96.5 parts by mass of distilled water, and the deodorizing effect was evaluated. The pH of this deodorant was 7.2. The deodorization rate was 45% ammonia, 52% isovaleric acid, and 5% methyl mercaptan.
Comparative Example 3
To 96 parts by weight of distilled water, 0.5 part by weight of glyoxylic acid, 0.5 part by weight of an ether-based nonionic surfactant [Nikka Chemical Co., Ltd., polyoxyethylene (9 mol) lauryl ether] and dipotassium hydrogen phosphate 3 Deodorant was prepared by dissolving 0.0 part by mass, and the deodorizing effect was evaluated. The deodorant had a pH of 7.0. The deodorization rate was 38% ammonia, 25% isovaleric acid, and 0% methyl mercaptan.
Comparative Example 4
In 96 parts by mass of distilled water, 0.5 part by mass of glyoxylic acid, 0.5 part by mass of a cationic surfactant [Nikka Chemical Co., Ltd., lauryldimethylbenzylammonium chloride] and 3.0 parts by mass of dipotassium hydrogen phosphate are dissolved. Then, a deodorant was prepared and the deodorizing effect was evaluated. The deodorant had a pH of 6.9. The deodorization rate was 47% ammonia, 23% isovaleric acid, and 0% methyl mercaptan.
Table 1 shows the composition, deodorization rate, and pH of the deodorizers of Examples 1 and 4 and Reference Examples 2, 3, and 5. Table 1 lists the composition, deodorization rate, and pH of the deodorizers of Comparative Examples 1-4. Is shown in Table 2.
[0012]
[Table 1]

[0013]
[Table 2]

[0014]
As can be seen in Table 1, Examples 1 and 4 and Reference Examples 2, 3 and 5 containing glyoxylic acid, pyruvic acid, levulinic acid or sodium glyoxylate and lauryl dimethylamine oxide or myristyl dimethylamine oxide. Deodorant has a deodorization rate of 95% or more for ammonia, a deodorization rate of 80% or more for isovaleric acid, and a deodorization rate of 70% or more for methyl mercaptan. It has an excellent deodorizing effect. In Example 1, even if the contents of glyoxylic acid and lauryl dimethylamine oxide are the same, when the pH of the deodorant is 8.0, the deodorization rate with respect to ammonia is lower than that of pH 7.0. The deodorization rate for isovaleric acid and methyl mercaptan is improved. Therefore, it can be seen that the deodorizing effect can be enhanced by selecting the pH of the deodorant according to the malodorous property to be deodorized.
On the other hand, the deodorant of Comparative Example 1 containing only glyoxylic acid and not containing an amine oxide-based surfactant, and the deodorizing agent of Comparative Example 2 containing only lauryldimethylamine oxide and containing no oxocarboxylic acid. All odorants have a small deodorizing effect. Moreover, even if it is a deodorizer containing glyoxylic acid and surfactant, the deodorizer of the comparative example 3 using an ether type nonionic surfactant and the deodorizer of the comparative example 4 using a cationic surfactant are used. The deodorizing effect of the odorant on ammonia and isovaleric acid is inferior to that of Examples 1 and 4 and Reference Examples 2, 3 and 5, and almost no deodorizing effect on methyl mercaptan is observed.
[0015]
【The invention's effect】
The deodorant of the present invention has an excellent deodorizing effect against a wide variety of malodorous substances, especially methyl mercaptan, which is usually difficult to deodorize, even if the active ingredient of the deodorant is at a low concentration. Demonstrate. Therefore, by using the deodorant of the present invention, it is possible not only to make the place of life comfortable, but also to reduce the bad odor pollution.

Claims (1)

As 100 to 10 parts by mass of deodorant aqueous solution, 0.005 to 10% by mass of glyoxylic acid or a salt thereof, 0.05 to 5% by mass of an amine oxide surfactant of the following general formula [1], and a pH adjuster A deodorant is prepared by dissolving either disodium hydrogen phosphate or dipotassium hydrogen phosphate, and the pH is adjusted to a predetermined pH of 6 to 8 by adding an acid or alkali as required. Deodorant.

(In General Formula [1], R ¹ is an alkyl group having 8 to 22 carbon atoms, a hydroxyalkyl group or an alkenyl group, and R ² and R ³ are each an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group. Or a group represented by —R ⁴ O ( AO ) nH , R ⁴ is an alkylene group having 1 to 4 carbon atoms, A is an alkylene group having 1 to 4 carbon atoms, and n is 1 to 1 50.)