JP5852313B2 - Raw dry odor control agent - Google Patents
Raw dry odor control agent Download PDFInfo
- Publication number
- JP5852313B2 JP5852313B2 JP2011048164A JP2011048164A JP5852313B2 JP 5852313 B2 JP5852313 B2 JP 5852313B2 JP 2011048164 A JP2011048164 A JP 2011048164A JP 2011048164 A JP2011048164 A JP 2011048164A JP 5852313 B2 JP5852313 B2 JP 5852313B2
- Authority
- JP
- Japan
- Prior art keywords
- odor
- methyl
- hexenoic acid
- dry odor
- raw dry
- 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.)
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Landscapes
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明は、生乾き臭抑制剤に関する。 The present invention relates to a raw dry odor inhibitor.
近年、消費者の生活環境への関心の高まりから、身の回りの不快な臭気（本明細書において、「異臭」ともいう）を除去することが以前にも増して望まれている。タオル、寝具等のサニタリー用品、衣料等の繊維製品に付着する臭気は、タバコなどの外的要因の他に、繊維製品の使用を繰り返すことにより生じる、人体由来の内的要因が挙げられる。 In recent years, it has been increasingly desired to remove unpleasant odors (also referred to as “unpleasant odor” in the present specification) around us due to the growing interest of consumers in the living environment. The odor adhering to textile products such as sanitary goods such as towels and bedding and clothing includes internal factors derived from the human body caused by repeated use of textile products in addition to external factors such as tobacco.
下着、タオル及びハンカチを初めとするヒトの皮膚と直接接触するような繊維製品、又は皮脂を含んだ汗や角質などを吸収又は付着する可能性のある繊維製品は、洗濯後、被洗物を洗濯槽内等の湿気の多い場所にしばらく放置した場合、室内干しの場合、雨や汗で濡れた場合、又は乾燥が不十分の場合に、特有の臭いを生ずることがある。この臭いは一般に生乾き臭と呼ばれるものであり、十分な乾燥を行うことで大部分を除去することができる。しかしながら、十分な乾燥を行い、生乾き臭が感じられなくなった繊維製品であっても、汗や雨などで繊維製品が湿気を帯びると雑巾臭様の生乾き臭が生じることがある。繊維製品がこの生乾き臭を一度発生するようになると、洗濯後の十分な乾燥により一時的には生乾き臭を除去できるが、使用時に雑巾臭様の生乾き臭が再発し易くなる。このような再発し易い生乾き臭は、室内干しの場合のみならず、低温乾燥機能を備えた洗濯機又は乾燥機を用いた場合や、室外干し乾燥の場合でさえも湿気を帯びると生じる場合がある。
再発性の生乾き臭の特徴的な点は、洗濯し十分に乾燥した後は発生しない、ないしほぼ低減されるが、湿気を帯びるだけで臭いが発生する点にある。再発性の生乾き臭は、長期間タンスなどに収納した場合に生じ易い。また、下着、ハンカチ又はタオルなど、ヒトの肌との接触機会が多く、洗浄−使用サイクルの期間の短い使用頻度の多い繊維製品は、一度この生乾き臭が発生するようになると使用中に臭いが再発してくることが多い。さらには、着用回数が増えるほど生乾き臭の臭い強度が高まる傾向がある。
Underwear, towels, handkerchiefs and other textiles that come into direct contact with human skin, or textiles that may absorb or adhere to sebum-containing sweat or skin, When left in a humid place such as a washing tub for a while, when drying indoors, when wet with rain or sweat, or when drying is insufficient, a specific odor may be generated. This odor is generally called a raw dry odor, and most can be removed by sufficient drying. However, even if the fiber product is sufficiently dried and no longer feels a dry odor, if the fiber product is damp due to sweat or rain, a rag-like raw dry odor may be generated. Once the fiber product once generates this raw dry odor, the dry dry odor can be temporarily removed by sufficient drying after washing, but the raw odor-like raw odor tends to recur during use. Such a dry-dry odor that is likely to recur may occur not only when drying indoors, but also when using a washing machine or dryer equipped with a low-temperature drying function, or even when drying outdoors, even when humid. is there.
A characteristic feature of a recurrent raw dry odor is that it does not occur after washing and is sufficiently dried, or is almost reduced, but odor is generated only by being damp. A recurrent raw dry odor is likely to occur when stored in a chiffon for a long time. In addition, textile products that are frequently used in contact with human skin, such as underwear, handkerchiefs, or towels, and that are frequently used for a short period of the cleaning-use cycle, will smell during use once this dry-dry odor is generated. Often recurs. Furthermore, there is a tendency that the odor intensity of the raw dry odor increases as the number of wears increases.
ところで、これまでに、生乾き臭の指標物質として不飽和結合を有するカルボン酸が提案されている（特許文献１参照）。このうち、４−メチル−３−ヘキセン酸は、天然では、柚子の成分として知られているとともに（非特許文献１参照）、テルペンより微生物によって生成することも知られている（特許文献２参照）。しかし、これらの文献では、生乾き臭発生のメカニズムについて、何ら記載も示唆もされていない。また、不飽和結合を有するカルボン酸と再発性の生乾き臭との関連についても開示するものではない。 By the way, a carboxylic acid having an unsaturated bond has been proposed as an indicator substance for a raw dry odor (see Patent Document 1). Among these, 4-methyl-3-hexenoic acid is known as a component of eggplant in nature (see Non-Patent Document 1) and is also known to be produced by microorganisms from terpenes (see Patent Document 2). ). However, in these documents, there is no description or suggestion about the mechanism of generation of a raw dry odor. In addition, it does not disclose the relationship between a carboxylic acid having an unsaturated bond and a recurring raw dry odor.
一方、繊維製品から発生する異臭等の除去方法としては、香料成分を用いたマスキングや、殺菌又は抗菌剤を用いた異臭の原因となる微生物の抗菌や殺菌による消臭が知られている。
香料成分を用いたマスキング方法としては、香料成分又は香料成分の安定化剤として脂環式ケトン化合物を含有する布帛処理剤を用いたマスキング方法が知られている（例えば、特許文献３及び４参照）。異臭の原因となる微生物の抗菌や殺菌による消臭方法としては、ジケトン化合物や、陽イオン性有機抗菌剤、トリクロサン及びジクロロサンなどの殺菌剤を含有する処理剤を用いた方法などが知られている。例えば、特許文献５には、殺菌剤を用いて生乾き臭を抑制する技術が開示されている。また特許文献６はジケトン化合物を用いて、発汗に伴った悪臭を抑制する技術に関し、非微生物悪臭を抑制する技術が開示されている。その他には、特許文献７には過酸化水素を含有する液体漂白剤自体のマスキングと香調の安定のために、界面活性剤並びにテルペン系炭化水素、脂肪族アルコール及び環状ケトンから選ばれる香料を含有する液体漂白剤組成物が開示されている。
On the other hand, as a method for removing off-flavors and the like generated from textile products, masking using a fragrance component and antibacterial or antibacterial sterilization of microorganisms that cause off-flavor using antibacterial agents are known.
As a masking method using a fragrance component, a masking method using a fabric treatment agent containing an alicyclic ketone compound as a fragrance component or a stabilizer of a fragrance component is known (for example, see Patent Documents 3 and 4). ). Known methods of deodorization by antibacterial and sterilization of microorganisms that cause off-flavors include methods using diketone compounds, cationic organic antibacterial agents, treatment agents containing fungicides such as triclosan and dichlorosan, etc. Yes. For example, Patent Literature 5 discloses a technique for suppressing a raw dry odor using a bactericide. Patent Document 6 discloses a technique for suppressing a non-microbial malodor by using a diketone compound to suppress a malodor associated with sweating. In addition, Patent Document 7 discloses a surfactant and a fragrance selected from terpene hydrocarbons, aliphatic alcohols and cyclic ketones for masking and stabilizing the fragrance of the liquid bleach containing hydrogen peroxide. A liquid bleach composition containing is disclosed.
本発明は、繊維製品から発生する生乾き臭、特に、繊維製品を乾燥後、湿潤（湿気を帯びること）によって生じる再発性の生乾き臭に対して優れた抑制能を有する、生乾き臭抑制剤を提供することを課題とする。また、本発明は、効率的に生乾き臭を抑制する、生乾き臭抑制方法を提供することを課題とする。 The present invention provides a raw dry odor inhibitor having excellent ability to suppress a raw dry odor generated from a textile product, in particular, a repetitive raw dry odor caused by wetting (wetting moisture) after the textile product is dried. The task is to do. Moreover, this invention makes it a subject to provide the method for suppressing a raw dry odor which suppresses a raw dry odor efficiently.
上記課題に鑑み、本発明者等は、生乾き臭の原因物質、原因菌、及び発生のメカニズムの観点から鋭意検討を行った。その結果、新たな知見が得られた。すなわち生乾き臭の原因物質としては、４−メチル−３−ヘキセン酸、５−メチル−２−ヘキセン酸、５−メチル−４−ヘキセン酸などの中級分岐脂肪酸が知られていたが、これらの中でも特に４−メチル−３−ヘキセン酸の閾値が他の物質と比較して特段に低く、主な原因物質であることを見出した。さらに、生乾き臭のうち、繊維製品を十分に乾燥させた後湿気を帯びることによりぶり返す再発性の生乾き臭は、乾燥後、十分に生乾き臭が除去された後であっても、特定の微生物が繊維製品中に生存又はそこで増殖して産生される臭いであること、或いは乾燥によって繊維に囚われていた臭いが、繊維製品の湿潤により再び解放され、低閾値であるため感じられ易いことを見出した。そして再発性の生乾き臭が、前記４−メチル−３−へキセン酸を主とする中級分岐脂肪酸臭であることを見出した。
さらに、このような知見に基づきさらなる検討を行った。その結果、特定数の炭素原子を有する直鎖脂肪族アルデヒドが生乾き臭の抑制に有用であることを見出した。さらには、このような直鎖脂肪族アルデヒドが、生乾き臭の主な原因物質である４−メチル−３−ヘキセン酸の微生物による生成を抑制することを見出した。
本発明はこれらの知見に基づいて完成するに至ったものである。
In view of the above problems, the present inventors have conducted extensive studies from the viewpoints of causative substances, causative bacteria, and generation mechanisms of raw dry odors. As a result, new knowledge was obtained. That is, intermediate branched fatty acids such as 4-methyl-3-hexenoic acid, 5-methyl-2-hexenoic acid and 5-methyl-4-hexenoic acid have been known as causative substances for raw dry odors. In particular, it was found that the threshold value of 4-methyl-3-hexenoic acid was particularly low compared to other substances and was the main causative substance. Furthermore, among the fresh-dry odors, recurring raw-dry odors that rebound by being dampened after the textiles are sufficiently dried are those that have certain microorganisms removed even after they have been sufficiently removed after drying. It was found that the odor was produced by growing or growing in the fiber product, or the odor that was trapped in the fiber by drying was released again by the wetting of the fiber product, and it was easy to feel because it was a low threshold. . And it discovered that recurrent re-dried odor was the intermediate | middle branched fatty-acid odor which mainly has the said 4-methyl-3- hexenoic acid.
Furthermore, further examination was performed based on such knowledge. As a result, the present inventors have found that a linear aliphatic aldehyde having a specific number of carbon atoms is useful for suppressing a dry-dry odor. Furthermore, it has been found that such a linear aliphatic aldehyde suppresses the production of 4-methyl-3-hexenoic acid, which is a main causative substance of a raw dry odor, by microorganisms.
The present invention has been completed based on these findings.
すなわち、本発明は、炭素数８〜１２の直鎖脂肪族アルデヒドを含む、生乾き臭抑制剤、に関する。
また、本発明は、前記生乾き臭抑制剤を含有する、生乾き臭抑制組成物、に関する。
That is, the present invention relates to a raw dry odor inhibitor containing a linear aliphatic aldehyde having 8 to 12 carbon atoms.
Moreover, this invention relates to the raw-dry odor suppression composition containing the said raw-dry odor inhibitor.
さらに、本発明は、前記炭素数８〜１２の直鎖脂肪族アルデヒドを含む、４−メチル−３−ヘキセン酸生成抑制剤、に関する。
また、本発明は、前記４−メチル−３−ヘキセン酸生成抑制剤を含有する、４−メチル−３−ヘキセン酸生成抑制組成物、に関する。
Furthermore, this invention relates to the 4-methyl-3- hexenoic acid production | generation inhibitor containing the said C8-C12 linear aliphatic aldehyde.
The present invention also relates to a 4-methyl-3-hexenoic acid production inhibitor composition containing the 4-methyl-3-hexenoic acid production inhibitor.
さらに、本発明は、前記生乾き臭抑制剤若しくは生乾き臭抑制組成物又は前記４−メチル−３−ヘキセン酸生成抑制剤若しくは４−メチル−３−ヘキセン酸生成抑制組成物を繊維製品と接触させ、該繊維製品からの生乾き臭の発生を抑制する、生乾き臭抑制方法、に関する。 Furthermore, the present invention brings the raw dry odor inhibitor or raw dry odor suppressor composition or the 4-methyl-3-hexenoic acid production inhibitor or the 4-methyl-3-hexenoic acid production inhibitor composition into contact with a textile product, The present invention relates to a method for suppressing a raw dry odor, which suppresses generation of a raw dry odor from the textile product.
本発明の生乾き臭抑制剤は、繊維製品から発生する生乾き臭、特に、乾燥後、湿潤によって生じる再発性の生乾き臭に対して優れた抑制能を有する。また、本発明の生乾き臭抑制方法によれば、効率的に生乾き臭を抑制することができる。 The raw dry odor suppressant of the present invention has an excellent ability to suppress a raw dry odor generated from a textile product, particularly a repetitive raw dry odor caused by wetting after drying. Moreover, according to the raw dry odor control method of this invention, a raw dry odor can be suppressed efficiently.
本発明の生乾き臭抑制剤及び４−メチル−３−ヘキセン酸（本明細書において、４Ｍ３Ｈともいう）生成抑制剤は、炭素数８〜１２の直鎖脂肪族アルデヒドを含むものである。特には、炭素数８〜１２の直鎖脂肪族アルデヒドを有効成分として含む、生乾き臭抑制剤又は４−メチル−３−へキセン酸生成抑制剤、である。なお、本発明の生乾き臭抑制剤及び４Ｍ３Ｈ生成抑制剤は、炭素数８〜１２の直鎖脂肪族アルデヒドの単一化合物そのものからなるものだけでなく、他の化合物との混合物（組成物）の形のものも包含される。さらに、本発明の生乾き臭抑制剤及び４Ｍ３Ｈ生成抑制剤に含まれる炭素数８〜１２の直鎖脂肪族アルデヒドは、１種であっても、２種以上であってもよい。
一般に、生乾き臭等の臭い抑制剤の作用機序としては、繊維製品等に付着した微生物の殺菌、繊維製品に残存する汗、皮脂等の生乾き原因物質への変換を予防、生乾き臭原因物質の無臭物質への分解又は変換、生乾き臭のマスキング等が挙げられる。なお、本発明における「生乾き臭抑制剤」の作用機序は、皮脂汚れ成分が生乾き臭原因物質の１種である４Ｍ３Ｈに変換されるのを予防し４Ｍ３Ｈの生成を抑制するものである。
なお、４Ｍ３Ｈには、下記に示すようにシス・トランス異性体が存在し、本発明においては、シス型、トランス型のいずれの構造の化合物も包含するものである。
The raw dry odor inhibitor and the 4-methyl-3-hexenoic acid (also referred to as 4M3H in this specification) production inhibitor of the present invention contain a linear aliphatic aldehyde having 8 to 12 carbon atoms. In particular, it is a raw dry odor inhibitor or a 4-methyl-3-hexenoic acid production inhibitor containing a linear aliphatic aldehyde having 8 to 12 carbon atoms as an active ingredient. In addition, the raw dry odor inhibitor and 4M3H production | generation inhibitor of this invention are not only what consists of a single compound itself of a C8-C12 linear aliphatic aldehyde, but the mixture (composition) with another compound. Shapes are also included. Further, the straight-chain aliphatic aldehyde having 8 to 12 carbon atoms contained in the raw dry odor inhibitor and the 4M3H production inhibitor of the present invention may be one type or two or more types.
In general, the mechanism of action of odor control agents such as raw dry odor is to sterilize microorganisms adhering to textile products, prevent conversion to raw dry causative substances such as sweat and sebum remaining on textile products, Examples include decomposition or conversion into odorless substances and masking of raw odors. In addition, the mechanism of action of the “raw dry odor inhibitor” in the present invention is to prevent the sebum soil component from being converted to 4M3H, which is one of the raw dry odor causing substances, and suppress the production of 4M3H.
As shown below, cis / trans isomers exist in 4M3H, and in the present invention, both cis-type and trans-type compounds are included.
本明細書において、「皮脂汚れ」とは、衣類等の繊維製品に付着する最も代表的な汚れであり、遊離脂肪酸、グリセリド等の油分を多量に含有しており、それらがほこり中のカーボンや泥、剥離した角質等を閉じ込めたものが、繊維製品等で観察されるものである。また「皮脂汚れ成分」とは、衣類等に通常見られる皮脂汚れの成分であれば特に制限はないが、繊維製品から生じる生乾き臭原因物質の前駆体となり得る物質が好ましい。繊維製品から生じる生乾き臭原因物質の前駆体となり得る物質としては、例えば炭素数９〜２１（好ましくは炭素数１１〜１９、より好ましくは炭素数１７〜１９）の飽和又は不飽和のアンテイソ脂肪酸（例えば、６−メチルオクタン酸、８−メチルデカン酸、１２−メチルテトラデカン酸、１４−メチルヘキサデカン酸、１６−メチルオクタデカン酸、１４−メチルヘキサデセン酸及び１６−メチルオクタデセン酸）、並びにその塩及びエステルが挙げられる。これらの中には、皮脂汚れ中には実際には存在しない化合物も含まれる。 In the present specification, “sebum dirt” is the most typical dirt that adheres to textile products such as clothing, and contains a large amount of oils such as free fatty acids and glycerides. What is trapped in mud, exfoliated keratin, etc. is observed in textile products. The “sebum stain component” is not particularly limited as long as it is a component of sebum stain usually found in clothing and the like, but a substance that can be a precursor of a raw dry odor-causing substance generated from a textile product is preferable. As a substance that can be a precursor of a raw dry odor-causing substance generated from a textile product, for example, a saturated or unsaturated anteiso fatty acid having 9 to 21 carbon atoms (preferably 11 to 19 carbon atoms, more preferably 17 to 19 carbon atoms) ( 6-methyloctanoic acid, 8-methyldecanoic acid, 12-methyltetradecanoic acid, 14-methylhexadecanoic acid, 16-methyloctadecanoic acid, 14-methylhexadecenoic acid and 16-methyloctadecenoic acid), and salts and esters thereof Is mentioned. Among these are compounds that are not actually present in sebum soil.
「生乾き臭」とは、繊維製品を洗濯し乾燥が不十分な場合、又は繊維製品が湿気を帯びた場合、に生じる臭いを言う。しかし、繊維製品を十分に乾燥させることにより生乾き臭を一時的に除去できても、乾燥後すぐ若しくは保管後に再び使用し始めてすぐ若しくは繊維製品を使用し始めてしばらくしてから、又は雨、汗等の湿気などにより、繊維製品から雑巾臭様の生乾き臭が再発することがある。このように、十分に乾燥させることにより生乾き臭を一時的に除去した繊維製品が湿気を帯びることにより再発する雑巾臭様の生乾き臭を本明細書において「再発性の生乾き臭」又は「再発性臭」という場合もある。
繊維製品を洗濯後乾燥が不十分なため生じる生乾き臭としては、Ｓ（含硫化合物）臭、Ｎ（含窒素化合物）臭、アルデヒド臭、低級脂肪酸臭、４Ｍ３Ｈ臭を含む中級分岐脂肪酸臭などの複合臭である。一方、繊維製品を十分に乾燥させて生乾き臭を除去した後、再び雨、汗等の湿気などにより、繊維製品から再発する雑巾様臭の再発性の不快臭は、４Ｍ３Ｈ臭を主とする中級分岐脂肪酸臭が大部分であり、その他のＳ臭、Ｎ臭、アルデヒド臭などの揮発性の高い臭いはほとんど発生しない。
また、「生乾き臭抑制」とは、生乾き臭を抑制すること、生乾き臭生成を予防することを包含するものである。そして本発明では、生乾き臭として前記再発性の生乾き臭、特には４Ｍ３Ｈ臭の抑制を特徴的に指すものとする。
“Dry odor” refers to an odor that occurs when a textile product is washed and dried, or when the textile product is damp. However, even if the dry odor can be temporarily removed by sufficiently drying the textile, it can be used immediately after drying or after storage, or after using the textile for a while, or after rain, sweat, etc. The wet odor like a rag-like odor may reappear from textile products due to moisture, etc. In this specification, the odor-like raw dry odor that recurs when the textile product from which the raw dry odor has been temporarily removed by sufficiently drying is dampened in this specification is referred to as “recurrent raw dry odor” or “recurrent Sometimes called odor.
Raw dry odors generated due to insufficient drying after washing of textile products include S (sulfur-containing compound) odor, N (nitrogen-containing compound) odor, aldehyde odor, lower fatty acid odor, intermediate branched fatty acid odor including 4M3H odor, etc. It is a complex odor. On the other hand, after removing the dry odor by sufficiently drying the textile product, the recurrent unpleasant odor of the rag-like odor recurring from the textile product again due to moisture such as rain, sweat, etc. is an intermediate class mainly 4M3H odor Branched fatty acid odor is the majority, and other highly volatile odors such as S odor, N odor, and aldehyde odor hardly occur.
Moreover, “raw dry odor suppression” includes suppressing raw dry odor and preventing raw dry odor production. In the present invention, the recurrent raw dry odor, particularly the suppression of 4M3H odor, is characteristically indicated as the raw dry odor.
本発明の生乾き臭抑制剤又は４Ｍ３Ｈ生成抑制剤に含まれる炭素数８〜１２の直鎖脂肪族アルデヒドは、直鎖脂肪族アルデヒドのアルキル部が飽和結合からなる直鎖脂肪族アルデヒドであっても、直鎖脂肪族アルデヒドのアルキル部が不飽和結合を有する直鎖脂肪族アルデヒドのいずれであってもよい。また、前記直鎖脂肪族アルデヒドは、炭素数１０〜１２の直鎖脂肪族アルデヒドであることが好ましい。 The straight-chain aliphatic aldehyde having 8 to 12 carbon atoms contained in the raw dry odor inhibitor or the 4M3H production inhibitor of the present invention is a straight-chain aliphatic aldehyde in which the alkyl part of the straight-chain aliphatic aldehyde is a saturated bond. Any of linear aliphatic aldehydes in which the alkyl portion of the linear aliphatic aldehyde has an unsaturated bond may be used. Moreover, it is preferable that the said linear aliphatic aldehyde is a C10-12 linear aliphatic aldehyde.
以下に、本発明に用いる炭素数８〜１２の直鎖脂肪族アルデヒドの具体例を示すが、本発明はこれらに限定されない。 Although the specific example of a C8-C12 linear aliphatic aldehyde used for this invention below is shown, this invention is not limited to these.
本発明に用いる直鎖脂肪族アルデヒドとして、前記例示化合物の中でも、例示化合物（１）（ドデカナール）、例示化合物（２）（ウンデカナール）、例示化合物（３）（10-ウンデセナール）、及び例示化合物（４）（デカナール）がより好ましい。 As the linear aliphatic aldehyde used in the present invention, among the exemplified compounds, exemplified compound (1) (dodecanal), exemplified compound (2) (undecanal), exemplified compound (3) (10-undecenal), and exemplified compound (4) (Decanal) is more preferable.
本発明において、前記直鎖脂肪族アルデヒドとして市販のものを用いてもよい。例えば、前記直鎖脂肪族アルデヒドは、シグマアルドリッチ社、関東化学社、東京化成工業社などから試薬として、入手することができる。また、前記直鎖脂肪族アルデヒドは、通常の製造方法で合成することもできる。例えば、アルコールと酸化剤とを反応させることで合成することができる。 In the present invention, a commercially available linear aliphatic aldehyde may be used. For example, the linear aliphatic aldehyde can be obtained as a reagent from Sigma-Aldrich, Kanto Chemical Co., Tokyo Kasei Kogyo Co., etc. Moreover, the said linear aliphatic aldehyde can also be synthesize | combined with a normal manufacturing method. For example, it can synthesize | combine by making alcohol and an oxidizing agent react.
本発明において、前記生乾き臭抑制剤又は４Ｍ３Ｈ生成抑制剤を含有する組成物として用いてもよい。これら組成物において、炭素数８〜１２の直鎖脂肪族アルデヒドを１種のみを含有させてもよいし、炭素数８〜１２の直鎖脂肪族アルデヒドを２種以上含有させてもよい。本発明において「組成物」とは、本発明の生乾き臭抑制剤又は４Ｍ３Ｈ生成抑制剤、及び１種以上のその他成分を含有する組成物を意味している。該組成物は、繊維製品の生乾き臭及び／又は４Ｍ３Ｈ生成抑制のための繊維製品処理組成物であることが好ましい。 In the present invention, the composition may contain the raw dry odor inhibitor or the 4M3H production inhibitor. In these compositions, the linear aliphatic aldehyde having 8 to 12 carbon atoms may be contained alone or two or more linear aliphatic aldehydes having 8 to 12 carbon atoms may be contained. In the present invention, the “composition” means a composition containing the raw dry odor inhibitor or 4M3H production inhibitor of the present invention and one or more other components. The composition is preferably a textile treatment composition for suppressing the raw dry odor and / or 4M3H production of textiles.
本発明の組成物において、前記直鎖脂肪族アルデヒドを溶媒に可溶化又は乳化して用いることが好ましい。
前記直鎖脂肪族アルデヒドの可溶化又は乳化に用いる溶媒としては、乾燥により繊維製品から除去される低沸点の溶媒が好ましく、１０１３ｈＰａにおいて１１０℃以下の沸点を有する溶媒がより好ましく、１０１３ｈＰａにおいて１０５℃以下の沸点を有する溶媒が特に好ましい。好適な溶媒としては、水；メタノール、エタノール、プロパノール、イソプロパノール等の低級アルコール；アセトン、メチルエチルケトン等のケトン系溶剤；ヘキサン、トルエン等の炭化水素系溶剤；アセトニトリル等が挙げられる。
In the composition of the present invention, the linear aliphatic aldehyde is preferably solubilized or emulsified in a solvent.
The solvent used for solubilization or emulsification of the linear aliphatic aldehyde is preferably a low boiling point solvent removed from the fiber product by drying, more preferably a solvent having a boiling point of 110 ° C. or less at 1013 hPa, and 105 ° C. at 1013 hPa. A solvent having the following boiling point is particularly preferred. Suitable solvents include water; lower alcohols such as methanol, ethanol, propanol and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; hydrocarbon solvents such as hexane and toluene; acetonitrile and the like.
本発明の組成物における前記直鎖脂肪族アルデヒドの濃度は、使用する溶媒、併用する基材及び／又は用途によって適宜決定することができる。 The density | concentration of the said linear aliphatic aldehyde in the composition of this invention can be suitably determined with the solvent to be used, the base material to be used together, and / or a use.
本発明の組成物において、可溶化剤を用いて前記直鎖脂肪族アルデヒドを溶媒に可溶化又は乳化させてもよい。可溶化剤としては特に制限はなく、水と油の両方に親和性のある溶剤が好ましい。具体的にはメタノール、エタノール、プロパノール、イソプロパノール等の低級アルコール；アセトン、メチルエチルケトン等のケトン系溶剤；エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、エチレングリコールの炭素数１〜４のモノ又はジアルキルエーテル、プロピレングリコールの炭素数１〜４のモノ又はジアルキルエーテル、ジエチレングリコールの炭素数１〜４のモノ又はジアルキルエーテル（好ましくはジエチレングリコールモノブチルエーテル）、ジプロピレングリコールの炭素数１〜４のモノ又はジアルキルエーテル等のグリコール系溶剤が挙げられる。このような可溶化剤は、前記直鎖脂肪族アルデヒドが水等の溶媒に均一に可溶化又は乳化できる程度の量を用いることが好ましく、例えば、溶媒として水を用いる場合、可溶化剤は液体中に０．０１〜５０質量％、より好ましくは０．０１〜１０質量％、さらに好ましくは０．０１〜５質量％、特に好ましくは０．１〜３質量％含有させるのが好ましい。 In the composition of the present invention, the linear aliphatic aldehyde may be solubilized or emulsified in a solvent using a solubilizer. There is no restriction | limiting in particular as a solubilizer, The solvent which has affinity to both water and oil is preferable. Specifically, lower alcohols such as methanol, ethanol, propanol, and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; mono- or dialkyl ethers having 1 to 4 carbon atoms of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and ethylene glycol , C1-C4 mono or dialkyl ether of propylene glycol, C1-C4 mono or dialkyl ether of diethylene glycol (preferably diethylene glycol monobutyl ether), C1-C4 mono or dialkyl ether of dipropylene glycol, etc. These glycol solvents are mentioned. Such a solubilizer is preferably used in such an amount that the linear aliphatic aldehyde can be uniformly solubilized or emulsified in a solvent such as water. For example, when water is used as the solvent, the solubilizer is liquid. The content is preferably 0.01 to 50% by mass, more preferably 0.01 to 10% by mass, still more preferably 0.01 to 5% by mass, and particularly preferably 0.1 to 3% by mass.
本発明の組成物において、界面活性剤を用いて前記直鎖脂肪族アルデヒドを溶媒に可溶化又は乳化させてもよい。界面活性剤としては特に制限はなく、具体的には、炭素数１０〜１５のアルキルベンゼンスルホン酸又はその塩、炭素数８〜１６のアルキル硫酸エステル塩、アルキレンオキシ基の炭素数が２又は３でありアルキレンオキシ基の平均付加モル数が０．２〜６でありアルキル基の炭素数が８〜１６であるポリオキシアルキレンアルキルエーテル硫酸エステル塩等の陰イオン界面活性剤、アルキレンオキシ基の平均付加モル数が０．２〜６でありアルキル基の炭素数が８〜１６であるポリオキシアルキレンアルキルエーテル、アルキル基の炭素数が８〜１６でありグルコースの平均縮合度が１〜２のアルキルグリコシド等の非イオン界面活性剤、アルキル基の炭素数が８〜１８のアルキルトリメチルアンモニウム塩や総炭素数１６〜３６のジアルキルトリメチルアンモニウム塩等のカチオン界面活性剤等が挙げられる。
本発明の組成物における界面活性剤の含有量は１ｐｐｍ以上が好ましく、２ｐｐｍ以上がより好ましい。また、界面活性剤を５００ｐｐｍ以上含有する場合は、前記直鎖脂肪族アルデヒドを０．２ｐｐｍ以上含有させることが好ましい。
In the composition of the present invention, the linear aliphatic aldehyde may be solubilized or emulsified in a solvent using a surfactant. There is no restriction | limiting in particular as surfactant, Specifically, C10-C15 alkylbenzenesulfonic acid or its salt, C8-C16 alkyl sulfate ester salt, C2 or C2 of an alkyleneoxy group is C2 or C3. Yes Anionic surfactants such as polyoxyalkylene alkyl ether sulfates having an average addition mole number of alkyleneoxy groups of 0.2 to 6 and an alkyl group of 8 to 16 carbon atoms, average addition of alkyleneoxy groups Polyoxyalkylene alkyl ether having a mole number of 0.2 to 6 and an alkyl group having 8 to 16 carbon atoms, an alkyl glycoside having an alkyl group having 8 to 16 carbon atoms and an average degree of glucose condensation of 1 to 2 Nonionic surfactants such as alkyltrimethylammonium salts having an alkyl group of 8 to 18 carbon atoms and dials having a total carbon number of 16 to 36 Cationic surfactants such as Le trimethyl ammonium salts.
The content of the surfactant in the composition of the present invention is preferably 1 ppm or more, and more preferably 2 ppm or more. Moreover, when it contains 500 ppm or more of surfactant, it is preferable to contain the said linear aliphatic aldehyde 0.2 ppm or more.
本発明の組成物は、香料を含有してもよい。本発明に用いることができる香料としては特に制限はないが、炭化水素系香料、アルコール系香料、エーテル系香料、アルデヒド系香料、ケトン系香料、エステル系香料、ラクトン系香料又は環状ケトン系香料等の通常の香料を用いることができる。本発明の組成物における香料成分の含有量は、０．０１〜１０質量％が好ましく、０．０１〜５．０質量％がより好ましく、０．０２〜１．０質量％が特に好ましい。 The composition of the present invention may contain a fragrance. The fragrance that can be used in the present invention is not particularly limited, but hydrocarbon fragrance, alcohol fragrance, ether fragrance, aldehyde fragrance, ketone fragrance, ester fragrance, lactone fragrance, cyclic ketone fragrance, etc. Ordinary fragrances can be used. 0.01-10 mass% is preferable, as for content of the fragrance | flavor component in the composition of this invention, 0.01-5.0 mass% is more preferable, and 0.02-1.0 mass% is especially preferable.
本発明の組成物の２５℃におけるｐＨは、生乾き臭抑制効果の点から、７．０〜９．５が好ましく、７．０〜９．０がより好ましく、７．０〜８．５が特に好ましい。ｐＨに調整するには、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウムなどのアルカリ剤、塩酸、硫酸、燐酸などの無機酸、クエン酸、エチレンジアミン４酢酸、１−ヒドロキシエチル−１，１−ジホスホン酸などの有機酸を用いることができる。 The pH of the composition of the present invention at 25 ° C. is preferably 7.0 to 9.5, more preferably 7.0 to 9.0, and particularly preferably 7.0 to 8.5, from the viewpoint of the effect of suppressing the dry odor. preferable. To adjust to pH, alkali agents such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, citric acid, ethylenediaminetetraacetic acid, 1-hydroxyethyl-1,1 -Organic acids such as diphosphonic acid can be used.
本発明の組成物に、パラトルエンスルホン酸塩、キシレンスルホン酸、クメンスルホン酸塩などのハイドロトロープ剤を配合してもよい。 You may mix | blend hydrotrope agents, such as paratoluenesulfonic acid salt, xylenesulfonic acid, and cumenesulfonic acid salt, with the composition of this invention.
本発明の組成物における各成分の濃度は、目的とする使用用途、処理方法等によって適宜調整することができ、各成分の配合割合は目的とする香調等によって調整することができる。 The density | concentration of each component in the composition of this invention can be suitably adjusted with the intended use use, a processing method, etc., and the mixture ratio of each component can be adjusted with the target fragrance etc.
本発明の生乾き臭抑制方法は、本発明の生乾き臭抑制剤若しくは４Ｍ３Ｈ生成抑制剤、又はこれを含んでなる生乾き臭抑制組成物若しくは４Ｍ３Ｈ組成物を繊維製品と接触させ、該繊維製品からの生乾き臭の発生を抑制する。
本発明における繊維製品の素材としては特に制限はなく、ウール、シルク、木綿等の天然素材、ポリエステル、ポリアミド等の化学繊維、及びこれらの組合せのいずれであってもよい。本発明において、繊維製品の素材は木綿であることが好ましい。繊維製品は未使用であっても、一度以上使用した使用済のものでもよい。本発明の生乾き臭抑制剤若しくは４Ｍ３Ｈ生成抑制剤、又はこれを含んでなる生乾き臭抑制組成物若しくは４Ｍ３Ｈ組成物を接触させる繊維製品は、湿気／水分を含んだものでもよいし、乾燥を十分に行ったものであってもよい。
The method for suppressing raw dry odor of the present invention comprises bringing the raw dry odor suppressor or 4M3H formation inhibitor of the present invention, or the raw dry odor suppressing composition or 4M3H composition comprising the same into contact with a textile product, and then subjecting the textile product to raw drying. Suppresses the generation of odors.
There is no restriction | limiting in particular as a raw material of the textiles in this invention, Any of natural materials, such as wool, silk, and cotton, chemical fibers, such as polyester and polyamide, and these combination may be sufficient. In the present invention, the material of the textile product is preferably cotton. The fiber product may be unused or used once or more. The raw dry odor inhibitor or 4M3H formation inhibitor of the present invention, or the textile product brought into contact with the raw dry odor suppressor composition or 4M3H composition containing the same may contain moisture / moisture, and may be sufficiently dried. It may have been done.
本発明の効果の発現には、処理対象となる繊維製品１ｋｇあたり前記直鎖脂肪族アルデヒドが０．０１ｍｇ以上存在するよう、本発明の生乾き臭抑制剤若しくは４Ｍ３Ｈ生成抑制剤、又はこれを含んでなる生乾き臭抑制組成物若しくは４Ｍ３Ｈ組成物と繊維製品とを接触させることが好ましい。また、繊維製品の質感などに影響しない程度接触させることが好ましく、１ｇ以下がより好ましく、１００ｍｇ以下が特に好ましい。 The manifestation of the effect of the present invention includes the raw dry odor inhibitor or 4M3H production inhibitor of the present invention, or this so that the linear aliphatic aldehyde is present in an amount of 0.01 mg or more per 1 kg of the textile product to be treated. It is preferable to bring the raw dry odor suppressing composition or 4M3H composition into contact with the textile product. Moreover, it is preferable to contact so that the texture of a textile product etc. is not affected, 1 g or less is more preferable, and 100 mg or less is especially preferable.
本発明の生乾き臭抑制剤若しくは４Ｍ３Ｈ生成抑制剤、又はこれを含んでなる生乾き臭抑制組成物若しくは４Ｍ３Ｈ組成物を繊維製品に接触させる方法としては特に制限はないが、例えば、本発明の組成物に繊維製品を含浸する方法、本発明の組成物をスプレー噴霧手段を備えた容器に充填して繊維製品にスプレーする方法、スポンジなどの可撓性材料に含浸させた本発明の組成物を繊維製品にこすり付ける方法などを挙げることができる。簡便性及び本発明の効果を十分引き出す目的から、本発明の組成物をスプレー噴霧手段を備えた容器に充填して繊維製品にスプレーする方法及び本発明の組成物に繊維製品を含浸する方法が好ましい。
スプレー処理を行う場合、噴霧手段としてはスプレーヤーが好ましく、エアロゾールやミスト、又はトリガー式などのポンプタイプのものを挙げることができる。ポンプタイプのスプレーヤーを用いる場合は、ボタ落ちが少ない蓄圧式と呼ばれるものを用いることが好ましい。本発明において、トリガー式スプレーヤーを用いて繊維製品に噴霧する方法がより好ましい。
Although there is no restriction | limiting in particular as a method of making the raw dry odor inhibitor or 4M3H production | generation inhibitor of this invention, or the raw dry odor suppression composition or this containing 4M3H composition contact a textiles, For example, the composition of this invention A method of impregnating a fiber product into a fiber, a method of spraying a fiber product after filling the composition of the present invention into a container equipped with a spraying means, a fiber of the composition of the present invention impregnated with a flexible material such as sponge The method of rubbing on the product can be mentioned. For the purpose of drawing out the effects of the present invention sufficiently for simplicity and convenience, there are a method of filling the composition of the present invention in a container equipped with a spraying means and spraying the fiber product, and a method of impregnating the fiber product into the composition of the present invention. preferable.
In the case of performing the spray treatment, the spray means is preferably a sprayer, and examples thereof include aerosol, mist, or a trigger type pump type. When a pump type sprayer is used, it is preferable to use a so-called pressure accumulation type that causes little dropout. In the present invention, a method of spraying a textile product using a trigger sprayer is more preferable.
本発明の組成物を実際に使用する際、例えば、トリガー式スプレーヤーを用いて本発明の組成物を繊維製品に噴霧する場合には、繊維製品に均一に付着するのに十分な量の組成物を噴霧する必要がある。また、本発明の組成物に繊維製品を含浸させる場合には、含浸後に脱水や濯ぎなどにより有効成分がロスすることも考慮に入れ、本発明の組成物に用いる基剤が繊維製品に十分な量で残留する必要がある。 When the composition of the present invention is actually used, for example, when the composition of the present invention is sprayed onto a textile product using a trigger sprayer, the composition is sufficient to uniformly adhere to the textile product. It is necessary to spray things. In addition, when impregnating a fiber product into the composition of the present invention, taking into account that the active ingredient is lost due to dehydration or rinsing after the impregnation, the base used in the composition of the present invention is sufficient for the fiber product. Need to remain in quantity.
トリガー式スプレーヤーを用いて繊維製品に噴霧する場合、噴霧後の組成物の液滴の体積平均粒径が、噴射口から噴射方向に１０ｃｍ離れた地点において１０〜２００μｍであり、２００μｍを越える液滴が噴霧液滴の総数に対して１体積％以下、１０μｍに満たない液滴が噴霧液滴の総数に対して１体積％以下になるような噴霧手段を具備するものが好ましい。このような粒子径分布は、例えば、レーザー回折式粒度分布計（日本電子製）により測定することができる。このような噴霧粒径を制御する方法としては、手動式トリガー型スプレーヤーを用いることが好ましく、噴霧口径が好ましくは１ｍｍ以下、より好ましくは０．５ｍｍ以下の吐出孔を有しているものを用いることで容易に達成することができる。また、吐出孔の形状、材質等は特に限定されるものではない。
トリガー式スプレーヤーを用いて繊維製品に噴霧する場合、組成物の２０℃における粘度が１５ｍＰａ・ｓ以下が好ましく、１〜１０ｍＰａ・ｓがより好ましい。なお、組成物の粘度調整は、組成物濃度の調整、市販の増粘剤の使用等によって行うことができる。なお、本発明の組成物の粘度は、以下のようにして測定されたものである。まず、東京計器社製Ｂ型粘度計モデル形式ＢＭに、ローター番号Ｎｏ．１のローターを備え付けたものを準備する。試料をトールビーカーに充填し、２０℃の恒温槽内にて２０℃に調整する。恒温に調製された試料を粘度計にセットする。ローターの回転数を６０ｒｐｍに設定し、回転を始めてから６０秒後の粘度を水性組成物の粘度とする。
When spraying on a textile product using a trigger sprayer, the volume average particle diameter of the droplets of the composition after spraying is 10 to 200 μm at a point 10 cm away from the injection port in the injection direction, and a liquid exceeding 200 μm It is preferable to have a spraying means in which droplets are 1% by volume or less with respect to the total number of sprayed droplets, and droplets with less than 10 μm are 1% by volume or less with respect to the total number of sprayed droplets. Such a particle size distribution can be measured by, for example, a laser diffraction particle size distribution meter (manufactured by JEOL Ltd.). As a method for controlling the spray particle size, it is preferable to use a manual trigger sprayer, and the spray port diameter is preferably 1 mm or less, more preferably 0.5 mm or less. This can easily be achieved. Moreover, the shape, material, etc. of a discharge hole are not specifically limited.
When spraying on textiles using a trigger sprayer, the viscosity of the composition at 20 ° C. is preferably 15 mPa · s or less, and more preferably 1 to 10 mPa · s. The viscosity of the composition can be adjusted by adjusting the composition concentration or using a commercially available thickener. The viscosity of the composition of the present invention is measured as follows. First, the rotor number no. Prepare one equipped with one rotor. The sample is filled in a tall beaker and adjusted to 20 ° C. in a constant temperature bath at 20 ° C. A sample prepared at a constant temperature is set in a viscometer. The rotational speed of the rotor is set to 60 rpm, and the viscosity 60 seconds after the start of rotation is taken as the viscosity of the aqueous composition.
トリガー式スプレーヤー等を用いて本発明の組成物を繊維製品に噴霧する場合、繊維製品４００ｃｍ2当りの本発明の組成物の噴霧量は、０．１〜３．０ｇが好ましく、０．２〜２．０ｇがより好ましく、０．５〜１．０ｇが特に好ましい。また、前記直鎖脂肪族アルデヒドの噴霧量は、繊維製品４００ｃｍ2当り０．０２〜５０ｍｇが好ましく、０．１〜２０ｍｇがより好ましく、０．２〜１０ｍｇが特に好ましい。トリガー式スプレーヤーを用いて繊維製品に噴霧する場合、本発明の生乾き抑制剤又は４Ｍ３Ｈ生成抑制剤の前記直鎖脂肪族アルデヒドの含有量はその匂いによる製品への影響を考えない限りは特に配合濃度は制限されないが、例えば製品としての香料設計の自由度が低下することが懸念されるため、組成物中１ｐｐｍ〜１０００ｐｐｍが好ましい。
本発明の組成物に繊維製品を含浸させる場合、繊維製品に対する組成物の含浸量は、質量比で繊維製品／組成物＝１／１〜１／３０が好ましく、１／２〜１／２０がより好ましく、１／３〜１／１０がさらに好ましい。含浸する場合の組成物の温度は５〜４０℃が好ましく、１０〜３５℃がより好ましい。含浸時間は１〜３０分が好ましく、５〜１５分程度がより好ましい。本発明の組成物には前記直鎖脂肪族アルデヒドを１〜１００００ｐｐｍ含有させることが好ましい。また、繊維製品を組成物そのものに含浸させても、濃厚溶液組成物を水道水などで希釈した希釈液に繊維製品を含浸させてもよい。
When the composition of the present invention is sprayed on the fiber product using a trigger sprayer or the like, the spray amount of the composition of the present invention per 400 cm 2 of the fiber product is preferably 0.1 to 3.0 g, 0.2 -2.0g is more preferable, and 0.5-1.0g is especially preferable. The spray amount of the linear aliphatic aldehyde is preferably 0.02 to 50 mg, more preferably 0.1 to 20 mg, and particularly preferably 0.2 to 10 mg per 400 cm 2 of the fiber product. When spraying on a textile product using a trigger sprayer, the content of the linear aliphatic aldehyde in the raw drying inhibitor or 4M3H production inhibitor of the present invention is particularly blended unless the influence of the odor on the product is considered. Although a density | concentration is not restrict | limited, since there is a concern that the freedom degree of the fragrance | flavor design as a product falls, for example, 1 ppm-1000 ppm in a composition are preferable.
When the fiber product is impregnated into the composition of the present invention, the amount of impregnation of the composition with respect to the fiber product is preferably fiber product / composition = 1/1 to 1/30, and 1/2 to 1/20 in mass ratio. More preferred is 1/3 to 1/10. The temperature of the composition when impregnated is preferably 5 to 40 ° C, more preferably 10 to 35 ° C. The impregnation time is preferably 1 to 30 minutes, more preferably about 5 to 15 minutes. The composition of the present invention preferably contains 1 to 10,000 ppm of the linear aliphatic aldehyde. Further, the textile product may be impregnated with the textile product itself, or the textile product may be impregnated with a diluted solution obtained by diluting the concentrated solution composition with tap water or the like.
本発明において、４Ｍ３Ｈの検出・定量方法について特に制限はないが、ヒトの生活に実際に使用される繊維製品において、４Ｍ３Ｈは、多数の他の有機物質と混ざった状態で存在する。しかも、４Ｍ３Ｈの閾値は非常に低いものである一方、共存する有機物質の種類によって閾値と検出強度は異なる。そのため、例えば下記方法により、４Ｍ３Ｈを測定することができる。しかし、本発明はこれに制限するものではない。
衣類などの繊維製品５０ｇ程度を裁断し、ジクロロメタン５００ｍＬによりニオイ成分を抽出後減圧濃縮する。さらに、１Ｍ水酸化ナトリウム水溶液２００ｍＬを抽出溶液に添加し、回収した水層に２Ｍ塩酸２００ｍＬ添加し酸性にする。この溶液に、ジクロロメタン２００ｍＬを加え有機層を減圧濃縮し、酸性成分の濃縮物を１ｍＬに定容する。
続いてアジレント社製ガスクロマトグラフィーにゲステル社製Preparative Fraction Collector（PFC）装置を接続したものを用い、濃縮物を以下の条件においてGC保持時間で分画し、目的成分周辺のＧＣ３０回分を内径６ｍｍ、長さ１１７ｍｍのガラス管に充填したＴＥＮＡＸ ＴＡ（商品名、ジーエルサイエンス社製）２００ｍｇに捕集する。
以下に、ガスクロマトグラフィーの条件を示す。
（ＧＣ−ＰＦＣ条件）
ＧＣ：Ａｇｉｌｅｎｔ６８９０Ｎ（商品名、アジレント社製）
カラム：ＤＢ−１（商品名、J&W社製）、長さ３０ｍ、内径０．５３ｍｍ、膜厚１μｍ
４０℃ １ｍｉｎ．ｈｏｌｄ→６℃／ｍｉｎ．ｔｏ ６０℃→４℃／ｍｉｎ．ｔｏ ３００℃
Ｉｎｊｅｃｔｉｏｎ ｖｏｌｕｍｅ：２μＬ
ＰＦＣ（ゲステル社製）：ｔｒａｐ ｔｉｍｅ １８ｍｉｎ．ｔｏ ２４ ｍｉｎ.，３０ ｔｉｍｅｓ
ｔｒａｐ：Ｔｅｎａｘ ＴＡ（商品名、ジーエルサイエンス社製）２００ ｍｇ
In the present invention, there is no particular limitation on the detection and quantification method of 4M3H. However, 4M3H exists in a mixed state with many other organic substances in the textile products actually used in human life. Moreover, while the threshold value of 4M3H is very low, the threshold value and the detection intensity differ depending on the type of coexisting organic substance. Therefore, for example, 4M3H can be measured by the following method. However, the present invention is not limited to this.
About 50 g of textile products such as clothing are cut, extracted with 500 mL of dichloromethane, and concentrated under reduced pressure. Further, 200 mL of 1M aqueous sodium hydroxide solution is added to the extraction solution, and 200 mL of 2M hydrochloric acid is added to the recovered aqueous layer to make it acidic. To this solution, 200 mL of dichloromethane is added, the organic layer is concentrated under reduced pressure, and the concentrated acidic component is made up to 1 mL.
Subsequently, using a gas chromatograph manufactured by Agilent connected to a preparative fraction collector (PFC) manufactured by GUSTER, the concentrate was fractionated by GC retention time under the following conditions, and 30 GCs around the target component were 6 mm in inner diameter. , And collected in 200 mg of TENAX TA (trade name, manufactured by GL Sciences Inc.) filled in a glass tube having a length of 117 mm.
The gas chromatography conditions are shown below.
(GC-PFC conditions)
GC: Agilent 6890N (trade name, manufactured by Agilent)
Column: DB-1 (trade name, manufactured by J & W), length 30 m, inner diameter 0.53 mm, film thickness 1 μm
40 ° C. for 1 min. hold → 6 ° C./min. to 60 ° C. → 4 ° C./min. to 300 ℃
Injection volume: 2μL
PFC (Gestel): trap time 18 min. to 24 min., 30 times
trap: Tenax TA (trade name, manufactured by GL Sciences Inc.) 200 mg
後述の実施例でも示すように、生乾き臭は、特定の微生物が繊維製品中に生存又はそこで増殖して産生される臭いであること、或いは乾燥によって繊維に囚われていた臭いが、繊維製品の湿潤により再び解放され、低閾値であるため感じられ易いことを見出した。そして再発性の生乾き臭が、４Ｍ３Ｈを主とする中級分岐脂肪酸臭であることを見出した。さらに、本発明の生乾き臭抑制剤及び４Ｍ３Ｈ生成抑制剤が、生乾き臭の主な原因物質である４Ｍ３Ｈの微生物による生成を抑制すること及び生乾き臭を抑制することを見出した。したがって、本発明によれば、生乾き臭発生の原因菌を殺菌しなくとも本発明の課題を達成することができると共に、香料によるマスキングに頼らずとも十分な効果を得ることができる。但し、本発明の組成物に殺菌剤や香料等の配合を否定するものではなく、これらを含有してもよい。
生乾き臭の原因菌となる４Ｍ３Ｈ生成能を有する微生物としては、モラクセラ（Moraxella）属細菌、アシネトバクター（Acinetobacter）属細菌、シェードモナス（Pseudomonas）属細菌、バチルス（Bacillus）属細菌、スフィンゴモナス（Sphingomonas）属細菌、ラルストニア（Ralstonia）属細菌、キュープリアビダス（Cupriavidus）属細菌、サイクロバクター（Psychorobacter）属細菌、セラチア（Serratia）属細菌、エシェリキア（Escherichia）属細菌、スタフィロコッカス（Staphylococcus）属細菌、ブルクホルデリア（Burkholderia）属細菌、サッカロマイセス（Saccaromyces）属酵母、及びロドトルラ（Rhodotorula）属酵母等が挙げられる。具体的には、モラクセラ・エスピー（Moraxella sp．）、モラクセラ・オスロエンシス（Moraxella osloensis）、アシネトバクター・レイディオレジステンス（Acinetobacter radioresistens）、アシネトバクター・ジュニイ（Acinetobacter junii）、アシネトバクター・カルコアセティカス（Acinetobacter calcoaceticus）、セラチア・マルセセンス（Serratia marcescens）、エシェリキア・コーライ（Escherichia coli）、スタフィロコッカス・アウレウス（Staphylococcus aureus）、シュードモナス・アルカリゲネス（Pseudomonas alcaligenes）、バチルス・セレウス（Bacillus cereus）、バチルス・サブティリス（Bacillus subtilis）、サイクロバクター・パシフィセンシス（Psychrobacter pacificensis）、サイクロバクター・グラシンコラ（Psychrobacter glacincola）、スフィンゴモナス・ヤノイクヤエ（Sphingomonas yanoikuyae）、ラルストニア エスピー（Ralstonia sp.）、サッカロマイセス・セレビジエ（Saccaromyces cerevisiae）、ロドトルラ・ムシラギノーサ（Rhodotorula mucilaginosa）、ロドトルラ・スルーフィエ（Rhodotorula slooffiae）、キュープリアビダス・オキサラティカス（Cupriavidus oxalaticus）及びブルクホルデリア・セパシア（Burkholderia cepacia）等が挙げられる。
As shown in the examples described later, a raw dry odor is an odor produced by a specific microorganism that survives or grows in a textile product, or an odor that is trapped in the fiber by drying is a wetness of the textile product. It was released again and found that it was easy to feel because of the low threshold. Then, it was found that the recurring raw dry odor is an intermediate branched fatty acid odor mainly composed of 4M3H. Furthermore, it discovered that the raw dry odor inhibitor and 4M3H production | generation inhibitor of this invention suppressed the production | generation by the microorganisms of 4M3H which are the main causative substances of raw dry odor, and suppressed raw dry odor. Therefore, according to the present invention, the object of the present invention can be achieved without sterilizing the causative bacteria of the generation of a raw dry odor, and a sufficient effect can be obtained without relying on masking with a fragrance. However, the composition of the present invention does not deny the blending of bactericides and fragrances, and may contain these.
The microorganisms having 4M3H capability of producing the bacteria causing half-dried odor, Moraxella (Moraxella) bacteria, Acinetobacter (Acinetobacter) bacteria, shade MONAS (Pseudomonas) bacteria, Bacillus (Bacillus) bacteria, Sphingomonas (Sphingomonas) bacteria belonging to the genus Ralstonia (Ralstonia) bacteria belonging to the genus, queue pre-Avi Das (Cupriavidus) bacteria belonging to the genus, cyclo Enterobacter (Psychorobacter) bacteria belonging to the genus Serratia (Serratia) bacteria belonging to the genus Escherichia (Escherichia) bacteria, Staphylococcus (Staphylococcus) bacteria belonging to the genus , Burkholderia bacteria, Saccaromyces yeasts, Rhodotorula yeasts, and the like. Specifically, Moraxella sp (Moraxella sp.), Moraxella Osuroenshisu (Moraxella osloensis), Acinetobacter Radio Regis Tense (Acinetobacter radioresistens), Acinetobacter Junii (Acinetobacter JuNii), Acinetobacter calcoaceticus (Acinetobacter calcoaceticus ), Serratia marcescens (Serratia marcescens), Escherichia Korai (Escherichia coli), Staphylococcus aureus (Staphylococcus aureus), Pseudomonas Alcaligenes (Pseudomonas alcaligenes), Bacillus cereus (Bacillus cereus), Bacillus subtilis (Bacillus subtilis), cyclo Arthrobacter Pasi Fi forsythensis (Psychrobacter pacificensis), cyclo Arthrobacter Gurashinkora (Psychrobacter glacincola), Sphingomonas Yanoi Yae (Sphingomonas yanoikuyae), Ralstonia sp (Ralstonia sp.), Saccharomyces cerevisiae (Saccaromyces cerevisiae), Rhodotorula Mushiraginosa (Rhodotorula mucilaginosa), Rhodotorula Surufie (Rhodotorula slooffiae), queue pre-Avi Das oxa Ratih dregs (Cupriavidus oxalaticus) And Burkholderia cepacia .
以下、本発明を実施例に基づきさらに詳細に説明するが、本発明はこれに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to this.
試験例１ 生乾き臭原因物質の特定
洗濯乾燥の後に生乾き臭が強く発生した木綿のタオルを家庭より回収して５０ｇを裁断し、ジクロロメタン５００ｍＬよりニオイ成分を抽出後減圧濃縮した。さらに、１Ｍ水酸化ナトリウム水溶液２００ｍＬを抽出溶液に添加し、水層を回収し、２Ｍ塩酸２００ｍＬ添加し酸性にした。この溶液に、ジクロロメタン２００ｍＬを加え有機層を減圧濃縮し、酸性成分の濃縮物を１ｍＬに定容した。
Test Example 1 Identification of causative substance of raw dry odor A cotton towel having a strong raw dry odor after washing and drying was collected from a household, cut into 50 g, extracted from 500 mL of dichloromethane, and concentrated under reduced pressure. Furthermore, 200 mL of 1M sodium hydroxide aqueous solution was added to the extraction solution, the aqueous layer was recovered, and 200 mL of 2M hydrochloric acid was added to make it acidic. To this solution, 200 mL of dichloromethane was added, the organic layer was concentrated under reduced pressure, and the acidic component concentrate was made up to 1 mL.
続いて、アジレント社製ガスクロマトグラフィーにゲステル社製Preparative Fraction Collector（ＰＦＣ）装置を接続したものを用い、濃縮物を下記の条件下でＧＣ保持時間により分画し、目的成分周辺のＧＣ３０回分を内径６ｍｍ、長さ１１７ｍｍのガラス管に充填した充填剤（商品名：TENAX TA、ジーエルサイエンス社製）２００ｍｇに捕集した。
（ＧＣ−ＰＦＣ条件）
ＧＣ：Agilent 6890N（商品名、アジレント社製）
カラム：DB-1（商品名、J&W社製）、長さ３０ｍ、内径０．５３ｍｍ、膜厚１μｍ
４０℃１ｍｉｎ．hold→６℃／ｍｉｎ．to ６０℃→４℃／ｍｉｎ．to ３００℃
Injection volume：２μＬ
ＰＦＣ(ゲステル社製)：trap time １８ｍｉｎ．to ２４ｍｉｎ.、３０ｔｉｍｅｓ
trap：TENAX TA（商品名、ジーエルサイエンス社製）２００ｍｇ
Subsequently, using a gas chromatograph manufactured by Agilent with a Gestel Preparative Fraction Collector (PFC) device connected, the concentrate was fractionated by the GC retention time under the following conditions, and the GC around the target component was divided into 30 batches. It was collected in 200 mg of a filler (trade name: TENAX TA, manufactured by GL Sciences) filled in a glass tube having an inner diameter of 6 mm and a length of 117 mm.
(GC-PFC conditions)
GC: Agilent 6890N (trade name, manufactured by Agilent)
Column: DB-1 (trade name, manufactured by J & W), length 30 m, inner diameter 0.53 mm, film thickness 1 μm
40 ° C. for 1 min. hold → 6 ° C / min. to 60 ° C. → 4 ° C./min. to 300 ℃
Injection volume: 2μL
PFC (Gestel): trap time 18 min. to 24min., 30times
trap: TENAX TA (trade name, manufactured by GL Sciences Inc.) 200mg
最後にTENAXに捕集した目的成分をゲステル社製Thermal Desorption system（ＴＤＳ）をアジレント社製ＧＣ−ＭＳに接続した装置にて、下記条件下で分析した。
（ＴＤＳ−ＧＣ−ＭＳ条件）
GC：Agilent 6890N（商品名、アジレント社製）
MS：Agilent 5973（商品名、アジレント社製）
TDS脱着条件：２５０℃、パージ流量５０ｍＬ／ｍｉｎ、パージ時間 ３ｍｉｎ．
カラム：DB-FFAP（商品名、アジレント社製）、長さ３０ｍ、内径２５０μｍ、膜厚０．２５μｍ
４０℃１ｍｉｎ．hold→６℃／ｍｉｎ．to ６０℃→２℃／ｍｉｎ．to ２４０℃
Finally, the target component collected in TENAX was analyzed under the following conditions with a device in which a Thermal Desorption system (TDS) manufactured by GUSTER Co. was connected to GC-MS manufactured by Agilent.
(TDS-GC-MS conditions)
GC: Agilent 6890N (trade name, manufactured by Agilent)
MS: Agilent 5973 (trade name, manufactured by Agilent)
TDS desorption conditions: 250 ° C., purge flow rate 50 mL / min, purge time 3 min.
Column: DB-FFAP (trade name, manufactured by Agilent), length 30 m, inner diameter 250 μm, film thickness 0.25 μm
40 ° C. for 1 min. hold → 6 ° C / min. to 60 ° C. → 2 ° C./min. to 240 ℃
解析の結果、生乾き臭主原因物質は４Ｍ３Ｈをはじめとする中級分岐脂肪酸であることが明らかとなった。 As a result of the analysis, it was revealed that the raw dry odor main causative substances are intermediate branched fatty acids including 4M3H.
試験例２ 生乾き臭原因菌の特定
（１）菌株の単離
洗濯乾燥の後に生乾き臭が発生した木綿のタオル又はバスタオルを裁断し、ＬＰ希釈液（日本製薬社製）を添加後、攪拌した溶液０．１ｍｌをレシチン・ポリソルベート添加ソイビーン・カゼイン・ダイジェスト（本明細書においてＳＣＤ−ＬＰともいう）寒天培地（日本製薬社製）に塗沫し、３５℃、２４時間培養後、得られたコロニーから微生物を単離した。単離した細菌株の同定は、１６Ｓ ｒＤＮＡ遺伝子の上流領域約５００ｂｐの塩基配列、酵母株の同定は、ＬＳＵのＤ２領域の約２００〜５００ｂｐ領域の塩基配列を決定し、当該塩基配列と基準株との同一性に基づき行なった。塩基配列の同一性は、遺伝子情報処理ソフトウェアＣｌｕｓｔａｌＷを用いて算出した。なおモラクセラ・エスピーに関してはモラクセラ・オスロエンシスＡＴＣＣ１９９７６の塩基配列を決定し、その塩基配列と比較することで同定した。
各タオル又はバスタオルから単離された菌株を表１に示す。
Test Example 2 Identification of causative bacterium causing dry odor (1) Isolation of strain After washing and drying, a cotton towel or bath towel that had ran dry odor was cut, and LP diluent (manufactured by Nippon Pharmaceutical Co., Ltd.) was added and stirred. A 0.1 ml solution was smeared on a lecithin-polysorbate-added soybean casein digest (also referred to herein as SCD-LP) agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.), cultured at 35 ° C. for 24 hours, and then obtained colonies Microorganisms were isolated from. The isolated bacterial strain is identified by determining the base sequence of about 500 bp upstream of the 16S rDNA gene, and the yeast strain is identified by determining the base sequence of the approximately 200-500 bp region of the D2 region of LSU. And based on the identity. The identity of the base sequence was calculated using genetic information processing software ClustalW. Moraxella sp. Was identified by determining the base sequence of Moraxella osloensis ATCC 19976 and comparing it with that base sequence.
The strains isolated from each towel or bath towel are shown in Table 1.
（２）繊維製品での生乾き臭再現試験
上記で単離された各種菌株をそれぞれ生乾き臭が発生した木綿のタオル、あるいは使用後洗濯して保管していた木綿のタオルを滅菌処理したものに接種し、３５℃で２４時間加湿条件下（湿度１００％）で培養後、生乾き臭の発生の有無を下記基準に基づいて、香料評価の訓練を受けた専門評価者（Ｎ＝３）により、合意により判定した。
１：生乾き臭の発生が非常に強い
２：生乾き臭の発生が強い
３：生乾き臭の発生が弱い
４：生乾き臭が全くしない
その結果を表１に示す。
(2) Raw dry odor reproduction test on textile products Each strain isolated above was inoculated into a cotton towel that had a raw dry odor, or a cotton towel that had been sterilized after washing after use. After culturing at 35 ° C for 24 hours in a humidified condition (humidity 100%), an agreement was made by a professional evaluator (N = 3) who was trained in perfume evaluation based on the following criteria for the occurrence of a fresh odor. Judged by.
1: Generation of a raw dry odor is very strong 2: Generation of a raw dry odor is strong 3: Generation of a raw dry odor is weak 4: No raw dry odor is generated The results are shown in Table 1.
表１の結果から、すべての生乾き臭発生タオル・バスタオルから、モラクセラ・エスピーが単離された。また、単離されたモラクセラ・エスピーは、その菌数も多かった。さらに、単離したモラクセラ・エスピーを生乾き臭が発生したタオルを滅菌処理したものに接種したところ、非常に強い生乾き臭が発生することが確認された。
したがって、生乾き臭には本菌種などの特定の微生物が関与していることが明らかとなった。
From the results in Table 1, Moraxella sp. Was isolated from all freshly dried odor generating towels and bath towels. The isolated Moraxella sp. Also had a large number of bacteria. Furthermore, when the isolated Moraxella sp. Was inoculated into a sterilized towel with a fresh odor, it was confirmed that a very strong fresh odor was generated.
Therefore, it was clarified that specific microorganisms such as this species are involved in the raw dry odor.
試験例３ ４Ｍ３Ｈ生成能を有する微生物の選定
前記試験例２に準じて単離、同定した菌株、環境（土壌、住居内）より定法によりソイビーン・カゼイン・ダイジェスト（本明細書においてＳＣＤともいう）寒天培地又はＰＤＡ培地を用いて分離した後、単離同定した菌株、及び微生物供託機関から入手した微生物の４Ｍ３Ｈ生成能を測定した。
なお、微生物供託機関から入手した菌株は下記の通りである。
モラクセラ・オスロエンシスNCIMB10693株（NCIMB（National Collection of Industrial，Marine and Food Bacteria）から購入）
モラクセラ・オスロエンシスATCC19976株（ATCC（American Type Culture Collection）から購入）
サイクロバクター・インモビリス（Psychrobacter immobilis）NBRC15733株、サイクロバクター・パシフィセンシスNBRC103191株、サイクロバクター・グラシンコラNBRC101053株、シュードモナス・エルギノーサ（Pseudomonas aeruginosa）NBRC13275株、シュードモナス・プチダ（Pseudomonas putida）NBRC14164株、スフィンゴモナス・ヤノイクヤエNBRC15102株、ミクロコッカス・ルテウス（Micrococcus luteus）NBRC3333株、ブレブンディモナス・ディミヌタ（Brevundimonas diminuta）NBRC12697株、ロゼオモナス・エリラタ（Roseomonas aerilata）NBRC106435株、キュープリアビダス・オキサラティカスNBRC13593株、シュードキサントモナス・エスピー（Pseudoxanthomonas sp．）NBRC101033株、セラチア・マルセセンスNBRC12648株、エンテロバクター・クロアカ（Enterobacter cloacae）NBRC3320株、コリネバクテリウム・エフィシエンス（Corynebacterium efficiens）NBRC100395株、エシェリキア・コーライNBRC3972株、スタフィロコッカス・アウレウスNBRC13276株、サッカロマイセス・セレビジエNBRC1661株、カンジダ・アルビカンス（Candida albicans）NBRC1061株、アルガリゲネス・フェカリス（Alcaligenes faecalis）NBRC13111株、ブルクホルデリア・セパシアNBRC15124株及びロドトルラ・ムシラギノサNBRC0909株（いずれもNBRC（NITE Biological Resource Center）から購入）
バチルス・セレウスJCM2152株、バチルス・サブティリスJCM1465株及びラクトバチルス・プランタルム（Lactobacillus plantarum）JCM1149株（JCM(Japan Collection of Microorganisms)から購入）
Test Example 3 Selection of Microorganisms Capable of Generating 4M3H Soybean / Casein Digest (also referred to as SCD in the present specification) agar by a standard method from the strain and environment (soil, house) isolated and identified according to Test Example 2 After separation using a medium or a PDA medium, the 4M3H production ability of the strains isolated and identified and the microorganisms obtained from the microorganism depository were measured.
The strains obtained from the microorganism depository are as follows.
Moraxella Oslo Ensis NCIMB10693 (purchased from NCIMB (National Collection of Industrial, Marine and Food Bacteria))
Moraxella Oslo Ensis ATCC19976 (purchased from ATCC (American Type Culture Collection))
Cyclo Arthrobacter Inmobirisu (Psychrobacter immobilis) NBRC15733 share, cyclo Arthrobacter Pasi Fi forsythensis NBRC103191 share, cyclo Arthrobacter Gurashinkora NBRC101053 strain, Pseudomonas aeruginosa (Pseudomonas aeruginosa) NBRC13275 strain, Pseudomonas putida (Pseudomonas putida) NBRC14164 share, Sphingomonas Yanoikuyae NBRC15102, Micrococcus luteus NBRC3333, Brevundimonas diminuta NBRC12697, Roseomonas aerilata NBRC106435, Cupriavidas oxalaticas 593 sp (Pseudoxanthomonas sp.) NBRC101033 strain, Serratia marcescens NBRC12648 share, Enterobacter cloacae (Enterobacter cloacae) NBRC3320 shares, Korinebakuteriu · Efficiens (Corynebacterium efficiens) NBRC100395 strain, Escherichia Korai NBRC3972 shares, NBRC13276 shares Staphylococcus aureus, Saccharomyces cerevisiae NBRC1661 strain, Candida albicans (Candida albicans) NBRC1061 shares, Arugarigenesu faecalis (Alcaligenes faecalis) NBRC13111 shares, Petersburg Holderia cepacia NBRC15124 and Rhodotorula mushiraginosa NBRC0909 (both purchased from NITE Biological Resource Center)
Bacillus cereus JCM2152 strain, Bacillus subtilis JCM1465 strain and Lactobacillus plantarum JCM1149 strain (purchased from JCM (Japan Collection of Microorganisms))
さらに、モラクセラ属細菌については、１６Ｓ ｒＤＮＡ遺伝子領域の塩基配列について、配列番号１、配列番号２又は配列番号３に示す塩基配列との同一性について決定した。なお、配列番号１、配列番号２又は配列番号３に示す塩基配列は、それぞれ、モラクセラ・エスピー4-1株、モラクセラ・エスピー4-4株及びモラクセラ・オスロエンシスATCC19976株の１６Ｓ ｒＤＮＡ遺伝子領域の塩基配列を示す。さらに、塩基配列の同一性は、遺伝子情報処理ソフトウェアＣｌｕｓｔａｌＷを用いて算出した。なお、モラクセラ・エスピー4-1株は、２０１０年１０月１４日付で、独立行政法人産業技術総合研究所特許生物寄託センター（茨城県つくば市東１−１−１つくばセンター中央第６）に、受託番号ＦＥＲＭ Ｐ-22030として寄託された。
その結果を表２に示す。
Further, for Moraxella bacteria, the identity of the base sequence of the 16S rDNA gene region with the base sequence shown in SEQ ID NO: 1, SEQ ID NO: 2 or SEQ ID NO: 3 was determined. The base sequences shown in SEQ ID NO: 1, SEQ ID NO: 2 or SEQ ID NO: 3 are the bases of the 16S rDNA gene region of Moraxella sp. 4-1 strain, Moraxella sp. 4-4 strain and Moraxella osloensis ATCC 19976 strain, respectively. Indicates the sequence. Furthermore, the identity of the base sequence was calculated using genetic information processing software ClustalW. Moraxella Sp. 4-1 shares were commissioned on October 14, 2010 to the National Institute of Advanced Industrial Science and Technology Patent Biological Depositary Center (1-1-1 Tsukuba Center Central, Tsukuba City, Ibaraki Prefecture). Deposited under the number FERM P-22030.
The results are shown in Table 2.
１．使用済み繊維製品を用いた選抜
入手した菌株をＳＣＤ液体培地（日本製薬社製）５ｍＬに一白金耳接種し、３５℃で２４時間振とう培養（１６０ｒｐｍ）を行なった。培養後の菌体を遠心（８０００×ｇ、１０分）して上清を取り除いた後、生理食塩水５ｍＬに懸濁し、再度遠心（８０００×ｇ、１０分）した後上清を取り除き、生理食塩水を用いてＯＤ600＝１．０となるように菌液を調製した。
家庭生活の中で使用と洗濯を繰り返した木綿の中古タオルを５ｃｍ×５ｃｍの正方形に切断し滅菌したものに前記各種菌液０．１ｍＬを植菌し、加湿条件下で３７℃で２４時間静置した。
専門評価者（Ｎ=３）により、２４時間静置後の前記木綿の中古タオルの生乾き臭の有無を合意により判定した。評価基準は、生乾き臭が強く感じられる試料を◎、生乾き臭が感じられる試料を○、生乾き臭が若干感じられる試料を△、生乾き臭が全くない試料を×とした。その結果を表３に示す。
1. Selection using used textile products One platinum loop of the obtained strain was inoculated into 5 mL of SCD liquid medium (manufactured by Nippon Pharmaceutical Co., Ltd.) and cultured with shaking (160 rpm) at 35 ° C. for 24 hours. The cultured cells are centrifuged (8000 × g, 10 minutes) to remove the supernatant, suspended in 5 mL of physiological saline, centrifuged again (8000 × g, 10 minutes), the supernatant is removed, and the physiological A bacterial solution was prepared using saline so that OD 600 = 1.0.
A used cotton towel that has been used and washed in daily life is cut into a 5cm x 5cm square and sterilized, and 0.1 mL of the various bacterial solutions are inoculated and allowed to stand at 37 ° C for 24 hours under humidified conditions. I put it.
An expert evaluator (N = 3) determined by agreement whether or not the cotton used towels had been left for 24 hours had a dry odor. The evaluation criteria were ◎ for a sample that felt a strong odor, ◯ for a sample that felt a odor, Δ for a sample that felt a little odor, and x for a sample that did not have any odor at all. The results are shown in Table 3.
２．皮脂汚れ成分を塗布した繊維製品を用いた選抜
特開２００９−１４９５４６号公報に準じて、１４−メチルヘキサデカン酸を下記の２工程の反応で合成した。
（ａ）工程
１２−ドデカノリド１１．９ｇ（６０．０ｍｍｏｌ）、３２％臭化水素/酢酸溶液２４．３ｇ（９６．０ｍｍｏｌ、１．６当量）を、テフロン（登録商標）で保護された１００ｍＬオートクレーブに入れ、窒素置換した後密閉し、６０℃のオイルバスを用いて、１６時間マグネチックスターラーで攪拌した。冷却後、水１４ｍＬを加え、熱ヘキサン２００ｍＬを用い、分液ロートに移送した。イオン交換水で洗浄後、硫酸マグネシウムで乾燥し、ろ過、ｎ−ヘキサンで晶析することで、１２−ブロモドデカン酸１４．４ｇ（収率８６％）を得た。
（ｂ）工程
次に、還流冷却管、５０ｍＬ滴下ロート、マグネチックスターラー、温度センサーを備えた１００ｍＬの４口フラスコに、１２−ブロモドデカン酸５．０ｇ（１７．９ｍｍｏｌ）及びトリフェニルホスフィン（関東化学社製）２８．２ｍｇ（０．００６ｅｑ）を入れ、減圧乾燥した。アルゴン雰囲気下、臭化銅（Ｉ）（アルドリッチ社製）７７．１ｍｇ（０．０３当量）、無水テトラヒドロフラン１０ｍＬを加えた。室温下、２−メチルブチルマグネシウムブロミド３９．５ｍＬ（３当量、１．３６Ｎテトラヒドロフラン溶液）を、１時間で滴下した。１時間攪拌した後、１Ｎ塩酸水溶液５０ｍＬを加え、ヘキサン１００ｍＬで２回抽出した。イオン交換水５０ｍＬで２回洗浄した後、硫酸マグネシウムで乾燥した。ろ過、減圧濃縮して、粗生成物３．９ｇを得た。
ガスクロマトグラフィー（カラム：アジレント社製、商品名：Ｕｌｔｒａ−２、３０ｍ×０．２ｍｍ×０．３３μｍ、ＤＥＴ３００℃、ＩＮＪ３００℃、カラム温度１００℃→３００℃、１０℃／分）で、内標にオクタデカンを用い、定量した結果、収率７９％であった。
このようにして、１２−ドデカノリドから１４−メチルヘキサデカン酸を全収率６８％で得た。また純度は９８％であった。
2. Selection using fiber product coated with sebum stain component According to JP 2009-149546 A, 14-methylhexadecanoic acid was synthesized by the following two-step reaction.
(A) Step 12-dodecanolide 11.9 g (60.0 mmol), 32% hydrogen bromide / acetic acid solution 24.3 g (96.0 mmol, 1.6 eq) were added to a Teflon-protected 100 mL autoclave. The mixture was purged with nitrogen, sealed, and stirred with a magnetic stirrer for 16 hours using an oil bath at 60 ° C. After cooling, 14 mL of water was added, and the mixture was transferred to a separatory funnel using 200 mL of hot hexane. After washing with ion-exchanged water, drying with magnesium sulfate, filtration, and crystallization with n-hexane gave 14.4 g (yield 86%) of 12-bromododecanoic acid.
Step (b) Next, to a 100 mL four-necked flask equipped with a reflux condenser, a 50 mL dropping funnel, a magnetic stirrer, and a temperature sensor, 5.0 g (17.9 mmol) of 12-bromododecanoic acid and triphenylphosphine (Kanto) 28.2 mg (0.006 eq) was added and dried under reduced pressure. Under an argon atmosphere, 77.1 mg (0.03 equivalent) of copper (I) bromide (Aldrich) and 10 mL of anhydrous tetrahydrofuran were added. At room temperature, 39.5 mL (3 equivalents, 1.36N tetrahydrofuran solution) of 2-methylbutylmagnesium bromide was added dropwise over 1 hour. After stirring for 1 hour, 50 mL of 1N aqueous hydrochloric acid was added, and the mixture was extracted twice with 100 mL of hexane. After washing twice with 50 mL of ion exchange water, it was dried over magnesium sulfate. Filtration and concentration under reduced pressure gave 3.9 g of a crude product.
Gas chromatography (column: manufactured by Agilent, trade name: Ultra-2, 30 m × 0.2 mm × 0.33 μm, DET 300 ° C., INJ 300 ° C., column temperature 100 ° C. → 300 ° C., 10 ° C./min) As a result of quantification using octadecane, the yield was 79%.
In this way, 14-methylhexadecanoic acid was obtained from 12-dodecanolide in a total yield of 68%. The purity was 98%.
１６-メチルオクタデカン酸を、上記に示す１４−メチルヘキサデカン酸の合成工程の（ａ）工程において、１２−ドデカノリドを１５−ペンタドデカノリドに換え、（ｂ）工程にて２−メチルブチルマグネシウムブロミドをｓｅｃ−ブチルマグネシウムブロミドに換えて同様の操作で合成し、１５−ペンタドデカノリドから１６−メチルオクタデカン酸を全収率８４％で得た。また純度は９５％であった。 16-methyloctadecanoic acid was replaced with 15-pentadodecanolide in step (a) of the 14-methylhexadecanoic acid synthesis step shown above, and 2-methylbutylmagnesium bromide in step (b). Was replaced by sec-butylmagnesium bromide in the same manner, and 16-methyloctadecanoic acid was obtained from 15-pentadodecanolide in a total yield of 84%. The purity was 95%.
各菌株をＳＣＤ液体培地（日本製薬社製）５ｍＬに一白金耳接種し、３５℃で２４時間振とう培養（１６０ｒｐｍ）を行なった。培養後の菌体を遠心（８０００×ｇ、１０分）して上清を取り除いた後、生理食塩水５ｍＬに懸濁し、再度遠心（８０００×ｇ、１０分）した後上清を取り除き、生理食塩水を用いてＯＤ600＝１．０となるように菌液を調製した。
２ｃｍ×２ｃｍの正方形に切断した木綿の平織り布に、皮脂汚れ成分として、前述の方法で合成した１４−メチルヘキサデカン酸又は１６−メチルオクタデカン酸０．５ｍｇをメタノール０．１ｍＬに溶解した溶液を塗布し、その後メタノールの乾固を行った。
上記木綿の平織り布に、前記各種菌液０．１ｍＬを植菌し、加湿条件下で３７℃で２４時間静置し、下記の４Ｍ３Ｈの定量及び生乾き臭の官能評価を行った。
Each strain was inoculated into 5 mL of SCD liquid medium (manufactured by Nippon Pharmaceutical Co., Ltd.), and cultured with shaking (160 rpm) at 35 ° C. for 24 hours. The cultured cells are centrifuged (8000 × g, 10 minutes) to remove the supernatant, suspended in 5 mL of physiological saline, centrifuged again (8000 × g, 10 minutes), the supernatant is removed, and the physiological A bacterial solution was prepared using saline so that OD 600 = 1.0.
Apply a solution of 0.5 mg of 14-methylhexadecanoic acid or 16-methyloctadecanoic acid synthesized by the above-mentioned method as a sebum stain component to a plain weave cloth of cotton cut into 2 cm x 2 cm squares in 0.1 mL of methanol. Then, methanol was dried up.
The above-mentioned cotton plain weave cloth was inoculated with 0.1 mL of the various bacterial solutions and allowed to stand at 37 ° C. for 24 hours under humidified conditions, and the following 4M3H determination and sensory evaluation of the live-dry odor were performed.
（１）４Ｍ３Ｈの定量
２４時間静置後の前記タオルに、メタノール１０ｍＬを添加し、そのうちの１ｍＬとＡＤＡＭ（9-Anthrydiazomethanene、フナコシ社製、０．１ｗ/ｖ％）１ｍＬとを混合し、室温で６０分放置し、誘導体化を行なった。
その後、１０μＬ溶液について、ＬＣ−ＦＬ（液体クロマトグラフィー装置：HITACHI ELITE LaChrom（商品名、日立社製）、カラム：Lichrospher 100 RP-8(e)（商品名、アジレント社製、５μｍ×１２５ｍｍ×４ｍｍφ）、カラム温度：４０℃、溶離剤：アセトニトリル／水＝７／３（体積比）の混合溶液、流速：１．０ｍＬ／ｍｉｎ、検出器：励起波長（３６５ｎｍ）、測定波長（４１２ｎｍ））を用いて解析を行うことで、生成した４Ｍ３Ｈの定量を行った。４Ｍ３Ｈの生成量について、生成した４Ｍ３Ｈの量が１μｇより多かった試料を◎、０.１μｇより多く１μｇ以下の試料を○、０μｇより多く０．１μｇ以下の試料を△、全く検出されなかった試料を×として評価した。１４−メチルヘキサデカン酸を塗布した場合の結果を表４に、１６−メチルオクタデカン酸を塗布した場合の結果を表５にそれぞれ示す。
（２）生乾き臭の官能評価
専門評価者（Ｎ=３）により、２４時間静置後の前記木綿平織り布の生乾き臭の有無を判定した。評価基準は、生乾き臭が強く感じられる試料を◎、生乾き臭が感じられる試料を○、生乾き臭が若干感じられる試料を△、生乾き臭が全くない試料を×とした。ヘキサデカン酸を塗布した場合の結果を表４に、１６−メチルオクタデカン酸を塗布した場合の結果を表５にそれぞれ示す。
(1) Quantification of 4M3H 10 mL of methanol was added to the towel after standing for 24 hours, 1 mL of which was mixed with 1 mL of ADAM (9-Anthrydiazomethanene, Funakoshi, 0.1 w / v%), and room temperature And left for 60 minutes for derivatization.
Then, about 10 μL solution, LC-FL (liquid chromatography device: HITACHI ELITE LaChrom (trade name, manufactured by Hitachi), column: Lichrospher 100 RP-8 (e) (trade name, manufactured by Agilent, 5 μm × 125 mm × 4 mmφ) ), Column temperature: 40 ° C., eluent: acetonitrile / water = 7/3 (volume ratio) mixed solution, flow rate: 1.0 mL / min, detector: excitation wavelength (365 nm), measurement wavelength (412 nm)) The generated 4M3H was quantified by using the analysis. Regarding the amount of 4M3H produced, the sample in which the amount of 4M3H produced was greater than 1 μg, ◎ the sample greater than 0.1 μg and 1 μg or less, ◯ the sample greater than 0 μg and 0.1 μg or less, and the sample not detected at all Was evaluated as x. Table 4 shows the results when 14-methylhexadecanoic acid was applied, and Table 5 shows the results when 16-methyloctadecanoic acid was applied.
(2) Sensory evaluation of raw dry odor The expert evaluator (N = 3) determined the presence or absence of the raw dry odor of the cotton plain weave fabric after standing for 24 hours. The evaluation criteria were ◎ for a sample that felt a strong odor, ◯ for a sample that felt a odor, Δ for a sample that felt a little odor, and x for a sample that did not have any odor at all. Table 4 shows the results when hexadecanoic acid was applied, and Table 5 shows the results when 16-methyloctadecanoic acid was applied.
表３、４及び５の結果から、種々の微生物の中でも、モラクセラ属細菌、アシネトバクター属細菌、シュードモナス属細菌、バチルス属細菌、スフィンゴモナス属細菌、キュープリアビダス属細菌、ラルストニア属細菌、サイクロバクター属細菌、セラチア属細菌、エシェリキア属細菌、スタフィロコッカス属細菌、ブルクホルデリア属細菌、サッカロマイセス属酵母、ロドトルラ属酵母等、特定の微生物が４Ｍ３Ｈ生成能を有することがわかる。さらには、このような４Ｍ３Ｈ生成能を有する微生物が生乾き臭の発生に関与していることが明らかとなった。 From the results of Tables 3, 4 and 5, among various microorganisms, among the various microorganisms, Moraxella bacteria, Acinetobacter bacteria, Pseudomonas bacteria, Bacillus bacteria, Sphingomonas bacteria, Cupriavidas bacteria, Ralstonia bacteria, Cyclobacter It can be seen that specific microorganisms such as genus bacteria, Serratia bacteria, Escherichia bacteria, Staphylococcus bacteria, Burkholderia bacteria, Saccharomyces yeasts, Rhodotorula yeasts and the like have 4M3H producing ability. Furthermore, it has been clarified that such a microorganism having 4M3H generating ability is involved in the generation of a raw dry odor.
実施例１
ＳＣＤ−ＬＰ寒天培地（和光純薬社製）に、モラクセラ・エスピー４−１株を供試細菌として接種し、常温にて１〜２週間培養し、これを前培養プレートとした。前培養プレートからコンラージでコロニー表面を掻き取り、生理食塩水５ｍＬに懸濁し、ＯＤ600＝１．０（約１０8ＣＦＵ／ｍＬ）に調整した。
Example 1
A SCD-LP agar medium (manufactured by Wako Pure Chemical Industries, Ltd.) was inoculated with Moraxella sp. Strain 4-1 as a test bacterium and cultured at room temperature for 1 to 2 weeks to prepare a preculture plate. The surface of the colony was scraped from the preculture plate with congeal, suspended in 5 mL of physiological saline, and adjusted to OD 600 = 1.0 (about 10 8 CFU / mL).
滅菌処理し、２５℃、４０％ＲＨで乾燥して一定状態にした綿メリヤス布（色染社、木綿メリヤス、未シルケット加工）を２ｃｍ×２ｃｍの正方形に切断し、皮脂汚れ成分として前述の方法で合成した１４−メチルヘキサデカン酸０．５ｍｇをメタノール０．１ｍＬに溶解した溶液を塗布した。その後メタノールの乾固を行い、モデル試験布を作成した。 A cotton knitted fabric (color dyeing company, cotton knitted fabric, non-silquette processed) that has been sterilized and dried to a constant state at 25 ° C. and 40% RH is cut into 2 cm × 2 cm squares and used as a sebum stain component as described above. A solution prepared by dissolving 0.5 mg of 14-methylhexadecanoic acid synthesized in 1 in 0.1 mL of methanol was applied. Thereafter, methanol was dried to prepare a model test cloth.
下記表６に示す化合物のメタノール溶液を調製し、モデル試験布１ｇに対して表６に示す化合物（シグマアルドリッチ社、関東化学社、東京化成工業社などから試薬として入手）の塗布量が１０μｇとなるように、前記メタノール溶液を前記モデル試験布に２０℃で塗布し、室温で２時間乾燥させ、メタノール乾固した。上記モデル試験布に前記細菌懸濁液０．１ｍＬを塗布し、シャーレ中で３７℃、相対湿度７０％の培養庫において２４時間培養を行い、細菌定着布を調製した。 A methanol solution of the compound shown in Table 6 below was prepared, and the coating amount of the compound shown in Table 6 (obtained as a reagent from Sigma Aldrich, Kanto Chemical Co., Tokyo Kasei Kogyo Co., Ltd., etc.) per 1 g of model test cloth was 10 μg. Thus, the methanol solution was applied to the model test cloth at 20 ° C., dried at room temperature for 2 hours, and dried to methanol. 0.1 mL of the bacterial suspension was applied to the model test cloth, and cultured in a petri dish at 37 ° C. and a relative humidity of 70% for 24 hours to prepare a bacterial fixing cloth.
生乾き臭の嗅ぎ分けが可能な専門評価者により、モデル試験布の官能評価を行った。評価基準は、生乾き臭抑制効果のあるものを○、判断が難しいもの又は生乾き臭抑制効果が弱いものを△、生乾き臭抑制効果が全くないものを×として評価した。その結果を表６に示す。 Sensory evaluation of the model test cloth was performed by a professional evaluator who can sniff out the raw odor. The evaluation criteria were evaluated as ◯ for those having a raw dry odor suppressing effect, △ for those that were difficult to judge or those having a weak raw dry odor suppressing effect, and × for those having no raw dry odor suppressing effect. The results are shown in Table 6.
表６の結果から、炭素数８〜１２の直鎖脂肪族アルデヒドに明確な生乾き臭抑制効果が見られた。 From the results shown in Table 6, a clear effect of suppressing the dry odor was observed in the linear aliphatic aldehyde having 8 to 12 carbon atoms.
実施例２
下記表７に示す化合物を用い、モデル試験布１ｇに対して塗布する化合物の量が１０μｇとなるよう、実施例１と同様に細菌定着布を作成した。作成した細菌定着布について試験例３と同様に４Ｍ３Ｈ量を定量し、化合物を添加しない場合の４Ｍ３Ｈ生成量に対する比を算出し、４Ｍ３Ｈ生成抑制率を測定した。その結果を表７に示す。
Example 2
Using the compounds shown in Table 7 below, a bacterial fixing cloth was prepared in the same manner as in Example 1 so that the amount of the compound applied to 1 g of the model test cloth was 10 μg. The amount of 4M3H was quantified in the same manner as in Test Example 3 for the prepared bacterial fixing cloth, the ratio to the amount of 4M3H produced when no compound was added was calculated, and the 4M3H production inhibition rate was measured. The results are shown in Table 7.
表７から明らかなように、比較化合物には４Ｍ３Ｈ生成抑制効果は見られないのに対し、本発明の４Ｍ３Ｈ生成抑制剤は４Ｍ３Ｈ生成抑制率が高く、優れた４Ｍ３Ｈ生成抑制効果を有することがわかる。さらには、本発明の４Ｍ３Ｈ生成抑制剤の中でも、炭素数１０〜１２の直鎖脂肪族アルデヒドは４Ｍ３Ｈ生成抑制率が特に高いことがわかる。 As is clear from Table 7, the 4M3H production inhibitory effect of the present invention is high in the comparative compound, whereas the 4M3H production inhibitory effect of the present invention has a high 4M3H production inhibition rate, and has an excellent 4M3H production inhibitory effect. . Furthermore, it can be seen that among the 4M3H production inhibitors of the present invention, a linear aliphatic aldehyde having 10 to 12 carbon atoms has a particularly high 4M3H production inhibition rate.
実施例３
複数回洗濯と使用を繰り返した２０代〜４０代の成人男子の肌着のうち、乾燥時は臭わないが、湿り気を帯びたときに、同じ臭気の生乾き臭を発する肌着（綿１００％）を、５ｃｍ×５ｃｍに裁断し、同じ臭いレベルであると専門評価者により確認されたピースを実衣料試験布とした。なお、同じ臭気の生乾き臭について定性的に分析したところ、４Ｍ３Ｈ臭を主とする中級分岐脂肪酸臭であることが確認された。
前記実衣料試験布を十分に洗濯し、直ちに２５℃、相対湿度３５％環境下で２４時間放置し、十分に乾燥させた。乾燥後の実衣料試験布の臭気強度は、同専門評価者により後述の評価基準１であることを確認した。
次に、表８に示す組成の組成物１〜６を市販のポリエチレン製スプレー容器に入れ、上記実衣料試験布１枚辺り、０．０５ｇ噴霧した。
このようにして調製した実衣料試験布について、下記の臭気強度評価試験（臭気強度評価Ａ〜Ｃ）を行った。
Example 3
Of the underwear of adult men in their 20s to 40s who repeated washing and use multiple times, underwear (100% cotton) that does not smell when dry, but emits a dry odor of the same odor when damp. A piece that was cut into 5 cm × 5 cm and confirmed by a professional evaluator as having the same odor level was used as an actual clothing test cloth. In addition, when qualitatively analyzing the raw odor of the same odor, it was confirmed to be a middle-branched fatty acid odor mainly having a 4M3H odor.
The actual clothing test cloth was thoroughly washed and immediately left in an environment of 25 ° C. and a relative humidity of 35% for 24 hours to be sufficiently dried. The odor intensity | strength of the actual clothing test cloth after drying confirmed that it was the below-mentioned evaluation criteria 1 by the same expert evaluator.
Next, Compositions 1 to 6 having the compositions shown in Table 8 were put in a commercially available polyethylene spray container, and 0.05 g was sprayed around one actual clothing test cloth.
The following odor intensity evaluation tests (odor intensity evaluations A to C) were performed on the actual clothing test cloths thus prepared.
＜臭気強度評価Ａ（生乾き状態の繊維製品から発生する再発性の生乾き臭の評価）＞
組成物１〜６を噴霧した実衣料試験布を、生乾き臭の発生し易い環境下である３７℃、相対湿度７０％の培養庫において２４時間保管した。保管後の実衣料試験布について、専門評価者５人により生乾き臭（Ｓ臭、Ｎ臭、アルデヒド臭、低級脂肪酸臭、４Ｍ３Ｈ臭等の中級分岐脂肪酸臭を含む複合臭）の官能評価を行った。
＜臭気強度評価Ｂ（乾燥状態の繊維製品から発生する再発性の生乾き臭の評価）＞
前記臭気強度評価Ａを行った実衣料試験布を２５℃、相対湿度３５％の環境下に一昼夜放置して乾燥処理を行ない、実衣料試験布を十分に乾燥させた。乾燥後の実衣料試験布について、同専門評価者５人により生乾き臭（Ｓ臭、Ｎ臭、アルデヒド臭、低級脂肪酸臭、４Ｍ３Ｈ臭等の中級分岐脂肪酸臭を含む複合臭）の官能評価を行った。
＜臭気強度評価Ｃ（繊維製品を再度湿潤させることによって発生する再発性の生乾き臭の評価）＞
前記臭気強度評価Ｂで用いた実衣料試験布に、スプレー容器を用いて水道水０．１ｇ噴霧した。水道水を噴霧した直後、再度湿潤させた実衣料試験布について、同専門評価者５人により再発性の生乾き臭（４Ｍ３Ｈ臭を主とする中級分岐脂肪酸臭）の官能評価を行った。
<Odor intensity evaluation A (evaluation of recurrent dry odor generated from fiber products in the dry state)>
The actual clothing test cloth sprayed with the compositions 1 to 6 was stored for 24 hours in an incubator with a relative humidity of 70% at 37 ° C. in an environment where a raw dry odor is likely to occur. The sensory evaluation of raw dry odors (complex odors including intermediate branched fatty acid odors such as S odor, N odor, aldehyde odor, lower fatty acid odor, 4M3H odor) was conducted by five expert evaluators on the actual clothing test cloth after storage. .
<Odor intensity evaluation B (evaluation of recurrent raw dry odor generated from dry textile products)>
The actual clothing test cloth subjected to the odor intensity evaluation A was left to stand in an environment of 25 ° C. and a relative humidity of 35% for 24 hours to dry the actual clothing test cloth sufficiently. Sensory evaluation of raw odor (complex odor including intermediate-branched fatty acid odors such as S odor, N odor, aldehyde odor, lower fatty acid odor, 4M3H odor) is performed on the actual clothing test cloth after drying by five expert evaluators. It was.
<Odor strength evaluation C (evaluation of recurrent dry odor generated by rewetting the textile product)>
The actual clothing test cloth used in the odor intensity evaluation B was sprayed with 0.1 g of tap water using a spray container. Immediately after the tap water was sprayed, the actual clothing test cloth wetted again was subjected to sensory evaluation of a recurrent raw dry odor (intermediate branched fatty acid odor mainly consisting of 4M3H odor) by five expert evaluators.
前記臭気強度評価Ａ〜Ｃの評価結果は、下記評価基準に基づいて、専門評価者の合意により決定した。
（評価基準）
１：まったく臭わない
２：ほぼ臭わない
３：なんとなくわかる臭い
４：よく嗅ぐとわかる臭い
５：はっきりとわかる臭い
前記臭気強度評価Ａ〜Ｃの結果を表８に示す。
The evaluation results of the odor intensity evaluations A to C were determined by agreement of professional evaluators based on the following evaluation criteria.
(Evaluation criteria)
1: No odor at all 2: Almost no odor 3: Somehow odors 4: Some odors that can be understood by sniffing 5: All odors clearly understood
The results of the odor intensity evaluations A to C are shown in Table 8.
表８の結果から明らかなように、比較例の組成物５及び６には生乾き状態の繊維製品から発生する生乾き臭の抑制効果は全く見られなかった（臭気強度評価Ａ）。ここで、臭気強度評価Ａにおいて、組成物５及び６を噴霧した繊維製品から発生した生乾き臭は、４Ｍ３Ｈ臭を含む複合臭であった。なお、繊維製品を十分に乾燥させると臭気強度が低下するのは一般的で、比較例の組成物５及び６を用いた場合も乾燥状態の繊維製品から発生する生乾き臭の臭気強度は一時的に低下した（臭気強度評価Ｂ）。しかし、完全に乾燥させた繊維製品を再度湿潤させた場合、比較例の組成物５及び６を噴霧した繊維製品からは４Ｍ３Ｈ臭等の中級分岐脂肪酸臭が主たる臭いの生乾き臭としてぶり返した（臭気強度評価Ｃ）。
これに対し、本発明の組成物には優れた生乾き臭及び再発性の生乾き臭の抑制効果を有することがわかる。具体的には、生乾き状態であっても、本発明の組成物１〜４を接触させた繊維製品において中級分岐脂肪酸臭を含む複合臭である生乾き臭が抑制された（臭気強度評価Ａ）。さらに、完全に乾燥させた繊維製品を再度湿潤させた場合であっても、本発明の組成物１〜４を接触させた繊維製品において４Ｍ３Ｈ臭を主とする中級分岐脂肪酸臭が大部分である再発性の生乾き臭が抑制された（臭気強度評価Ｃ）。
As is clear from the results in Table 8, the compositions 5 and 6 of the comparative examples did not show any effect of suppressing the raw dry odor generated from the fiber product in the raw dry state (odor intensity evaluation A). Here, in the odor intensity evaluation A, the raw dry odor generated from the fiber product sprayed with the compositions 5 and 6 was a composite odor containing a 4M3H odor. In addition, it is common that odor intensity | strength will fall if textiles are fully dried, and also when using the composition 5 and 6 of a comparative example, the odor intensity | strength of the freshly dried odor generated from the textile product in a dry state is temporary. (Odor intensity evaluation B). However, when the completely dried fiber product was wetted again, the fiber product sprayed with the compositions 5 and 6 of the comparative example reappeared as an intermediate dry fatty acid odor such as 4M3H odor as the main odor (odor) Strength evaluation C).
On the other hand, it can be seen that the composition of the present invention has an excellent effect of suppressing fresh and dry recurrent odors. Specifically, even in the freshly dried state, the freshly dried odor, which is a complex odor containing intermediate-branched fatty acid odors, was suppressed in the textiles brought into contact with the compositions 1 to 4 of the present invention (odor intensity evaluation A). Furthermore, even when the fiber product that has been completely dried is re-moistened, the intermediate branched fatty acid odor mainly consisting of 4M3H odor is predominant in the fiber product contacted with the compositions 1 to 4 of the present invention. Recurrent raw dry odor was suppressed (odor intensity evaluation C).
Claims (8)
４−メチル−３−ヘキセン酸生成能を有する前記微生物が、モラクセラ（Moraxella）属細菌、アシネトバクター（Acinetobacter）属細菌、スフィンゴモナス（Sphingomonas）属細菌、ラルストニア（Ralstonia）属細菌、キュープリアビダス（Cupriavidus）属細菌、サイクロバクター（Psychorobacter）属細菌、セラチア（Serratia）属細菌、スタフィロコッカス（Staphylococcus）属細菌、ブルクホルデリア（Burkholderia）属細菌、サッカロマイセス（Saccaromyces）属酵母、及びロドトルラ（Rhodotorula）属酵母からなる群より選ばれる、生乾き臭抑制剤。 A raw dry odor causative substance adhering to textiles by microorganisms having one or more selected from the group consisting of dodecanal, undecanal, 10-undecenal and decanal, and having 4-methyl-3-hexenoic acid producing ability suppressing the formation of 4-methyl-3-hexenoic acid from the precursor inhibits the recurrent half-dry odor that occurs when it moist again after drying the textile, with the half-dried odor inhibitor There,
The microorganism having 4-methyl-3-hexenoic acid producing ability is selected from the group consisting of Moraxella bacterium, Acinetobacter bacterium, Sphingomonas bacterium, Ralstonia bacterium, Cupriavidas ( Cupriavidus, Psychorobacter, Serratia, Staphylococcus, Burkholderia, Saccaromyces, and Rhodotorula Raw dry odor suppressor selected from the group consisting of genus yeast .
４−メチル−３−ヘキセン酸生成能を有する前記微生物が、モラクセラ（Moraxella）属細菌、アシネトバクター（Acinetobacter）属細菌、スフィンゴモナス（Sphingomonas）属細菌、ラルストニア（Ralstonia）属細菌、キュープリアビダス（Cupriavidus）属細菌、サイクロバクター（Psychorobacter）属細菌、セラチア（Serratia）属細菌、スタフィロコッカス（Staphylococcus）属細菌、ブルクホルデリア（Burkholderia）属細菌、サッカロマイセス（Saccaromyces）属酵母、及びロドトルラ（Rhodotorula）属酵母からなる群より選ばれる、４−メチル−３−ヘキセン酸の生成を抑制する剤。 4 from a precursor of a raw dry odor-causing substance by a microorganism having 4-methyl-3-hexenoic acid producing ability, including one or more selected from the group consisting of dodecanal, undecanal, 10-undecenal and decanal An agent that suppresses the formation of methyl-3-hexenoic acid ,
The microorganism having 4-methyl-3-hexenoic acid producing ability is selected from the group consisting of Moraxella bacterium, Acinetobacter bacterium, Sphingomonas bacterium, Ralstonia bacterium, Cupriavidas ( Cupriavidus, Psychorobacter, Serratia, Staphylococcus, Burkholderia, Saccaromyces, and Rhodotorula The agent which suppresses the production | generation of 4-methyl-3- hexenoic acid chosen from the group which consists of a genus yeast .
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