JPH0689507B2 - Antibacterial deodorant for textiles - Google Patents
Antibacterial deodorant for textilesInfo
- Publication number
- JPH0689507B2 JPH0689507B2 JP13205391A JP13205391A JPH0689507B2 JP H0689507 B2 JPH0689507 B2 JP H0689507B2 JP 13205391 A JP13205391 A JP 13205391A JP 13205391 A JP13205391 A JP 13205391A JP H0689507 B2 JPH0689507 B2 JP H0689507B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- alkyl
- antibacterial
- carbon atoms
- represented
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は新規な繊維用抗菌防臭
剤、さらに詳しくは、特にグラム陰性菌に対しても十分
な効果を発揮し、かつ取扱いの容易なシリコーン系第四
級アンモニウム塩に代わる繊維用抗菌防臭剤に関するも
のである。FIELD OF THE INVENTION The present invention relates to a novel antibacterial and deodorant agent for fibers, and more specifically to a silicone-based quaternary ammonium salt which exhibits a sufficient effect particularly on Gram-negative bacteria and is easy to handle. The present invention relates to an alternative antibacterial deodorant for fibers.
【０００２】[0002]
【従来の技術】従来、繊維用抗菌防臭剤としてシリコー
ン系第四級アンモニウム塩が知られている。このシリコ
ーン系第四級アンモニウム塩は、通常反応性シリコーン
樹脂と併用され、繊維処理に用いられるが、このような
併用系で処理された繊維製品においては、黄変、蛍光白
度及び吸水性の低下、加熱による四級アンモニウム塩の
分解それに伴う殺菌性の低下、処理機械の錆発生など、
好ましくない事態を招来するため、繊維用抗菌防臭剤と
しての用途が制限されるのを免れないという欠点を有し
ている。一方、繊維用抗菌防臭剤として、一般式2. Description of the Related Art Conventionally, silicone-based quaternary ammonium salts have been known as antibacterial deodorants for fibers. This silicone-based quaternary ammonium salt is usually used in combination with a reactive silicone resin and used for fiber treatment. In a fiber product treated by such a combined system, yellowing, fluorescent whiteness and water absorption Deterioration, decomposition of quaternary ammonium salt due to heating, deterioration of sterilization accompanying it, generation of rust on processing machines, etc.
Since it causes an unfavorable situation, it has a drawback that its use as an antibacterial deodorant for fibers is unavoidable. On the other hand, as an antibacterial deodorant for fibers, the general formula
【化５】 （式中のＲ1は炭素数８〜２２のアルキル基又はアルケ
ニル基、Ｒ2及びＲ3は炭素数１〜５のアルキル基、Ｒ'
は炭素数２〜４のアルキレン基、ｍは１又は２、ｎは１
〜５の整数、Ｘm-はアルキルリン酸エステルイオンであ
る）で表される第四級アンモニウム塩が開示されている
（特公平１−３３５８９号公報）。しかしながら、この
抗菌防臭剤はグラム陽性菌に対しては十分に効果を発揮
するものの、グラム陰性菌に対しては必ずしも十分に効
果を発揮するとはいえない。[Chemical 5] (Wherein R 1 is an alkyl group or an alkenyl group having 8 to 22 carbon atoms, R 2 and R 3 are alkyl groups having 1 to 5 carbon atoms, R ′
Is an alkylene group having 2 to 4 carbon atoms, m is 1 or 2, and n is 1.
A quaternary ammonium salt represented by an integer of ˜5 and X m − is an alkyl phosphate ester ion is disclosed (Japanese Patent Publication No. 1-33589). However, although this antibacterial deodorant is sufficiently effective against Gram-positive bacteria, it cannot be said that it is sufficiently effective against Gram-negative bacteria.
【０００３】[0003]
【発明が解決しようとする課題】本発明はこのような従
来の繊維用抗菌防臭剤が有する欠点を克服し、グラム陽
性菌はもちろんのこと、グラム陰性菌に対しても十分な
効果を発揮し、かつ取扱いの容易なシリコーン系第四級
アンモニウム塩に代わる繊維用抗菌防臭剤を提供するこ
とを目的としてなされたものである。The present invention overcomes the drawbacks of the conventional antibacterial and deodorant agents for fibers, and exerts a sufficient effect not only on Gram-positive bacteria but also on Gram-negative bacteria. The purpose of the present invention is to provide an antibacterial and deodorant agent for fibers, which is an alternative to the silicone-based quaternary ammonium salt and is easy to handle.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、従来抗菌
剤として用いられている第四級アンモニウム塩はその対
イオンがハロゲンイオンであり、これが錆発生及び耐熱
性低下の原因となっていること、アニオン性界面活性剤
と不溶性コンプレックスを形成するのはカチオン成分の
みでなく、対イオンのアニオンにも起因することなどに
着目し、先に、耐熱性を向上させ、かつ錆発生がない
上、アニオン性界面活性剤が混入しても不溶性コンプレ
ックスを形成せず、しかも、良好な殺菌活性を有する、
前記一般式［１］で示される第四級アンモニウム塩から
成る繊維用抗菌防臭剤を見い出した（特公平１−３３５
８９号公報）。しかしながら、この抗菌防臭剤は、前記
したようにグラム陰性菌に対する殺菌活性は必ずしも満
足しうるものではないという欠点があった。The present inventors have found that the counter ion of the quaternary ammonium salt conventionally used as an antibacterial agent is a halogen ion, which causes rust generation and heat resistance deterioration. That the insoluble complex forms with the anionic surfactant not only due to the cation component but also due to the anion of the counter ion. First, heat resistance is improved and rust does not occur. Moreover, even if an anionic surfactant is mixed, it does not form an insoluble complex and has good bactericidal activity.
An antibacterial deodorant for fibers comprising a quaternary ammonium salt represented by the general formula [1] was found (Japanese Patent Publication No. 1-335).
No. 89). However, this antibacterial deodorant has a drawback that the bactericidal activity against Gram-negative bacteria is not always satisfactory as described above.
【０００５】本発明者は前記目的を達成するために、さ
らに鋭意研究を進めた結果、対イオンとして有機性で防
錆力及び緩衝能力のあるアニオンを用い、かつ殺菌力を
向上させるために窒素原子にアラルキル基を導入した特
定構造の第四級アンモニウム塩により、その目的を達成
しうることを見い出し、この知見に基づいて本発明を完
成するに至った。すなわち、本発明は、一般式As a result of further intensive research to achieve the above object, the present inventor used an anion having an organic rust preventive and buffering ability as a counter ion, and nitrogen for improving sterilizing ability. It was found that the object can be achieved by a quaternary ammonium salt having a specific structure in which an aralkyl group is introduced into an atom, and the present invention has been completed based on this finding. That is, the present invention has the general formula
【０００６】[0006]
【化６】 [Chemical 6]
【０００７】（式中のＲ1は炭素数８〜２２のアルキル
基又はアルケニル基、Ｒ2及びＲ3はそれぞれ炭素数１〜
５のアルキル基であり、それらは同一であってもよい
し、たがいに異なっていてもよく、Ｒ4は炭素数２〜４
のアルキレン基、Ａｒは置換基を有する若しくは有しな
いアリール基又はアリールオキシ基、Ｘm-はアルキルリ
ン酸エステルイオン、ｍは１又は２である）で表される
第四級アンモニウム塩の中から選ばれた少なくとも１種
から成る繊維用抗菌防臭剤を提供するものである。(In the formula, R 1 is an alkyl or alkenyl group having 8 to 22 carbon atoms, R 2 and R 3 are each 1 to 1 carbon atoms.
5 alkyl groups, which may be the same or different from each other, and R 4 has 2 to 4 carbon atoms.
Alkylene group, Ar is an aryl group or an aryloxy group with or without a substituent, X m- is an alkyl phosphate ester ion, and m is 1 or 2). The present invention provides an antibacterial and deodorant agent for fibers, which comprises at least one selected.
【０００８】以下、本発明を詳細に説明する。前記一般
式［２］におけるＸm-はアルキルリン酸エステルイオン
であり、Ｘm-が硝酸イオン、硫酸イオン、カルボン酸イ
オン、リン酸イオンなどである場合は、錆の発生を防止
することができない。該アルキルリン酸エステルイオン
の形成には、一般式The present invention will be described in detail below. In the general formula [2], X m- is an alkyl phosphate ester ion, and when X m- is a nitrate ion, a sulfate ion, a carboxylate ion, a phosphate ion or the like, it is possible to prevent the generation of rust. Can not. For the formation of the alkyl phosphate ester ion, a general formula is used.
【０００９】[0009]
【化７】 [Chemical 7]
【００１０】（式中のＲ5は炭素数１〜８のアルキル
基、ｍは１又は２である）で表されるモノアルキルリン
酸エステル及びジアルキルリン酸エステルの中から選ば
れた少なくとも１種が用いられる。前記一般式［３］で
表されるモノアルキルリン酸エステル及びジアルキルリ
ン酸エステルとしては、例えばモノメチルリン酸エステ
ル、モノエチルリン酸エステル、モノ−ｎ−プロピルリ
ン酸エステル、モノイソプロピルリン酸エステル、モノ
−ｎ−ブチルリン酸エステル、モノイソブチルリン酸エ
ステル、モノ−ｓｅｃ−ブチルリン酸エステルなどのモ
ノアルキルリン酸エステル、ジメチルリン酸エステル、
ジエチルリン酸エステル、ジ−ｎ−プロピルリン酸エス
テル、ジイソプロピルリン酸エステル、ジ−ｎ−ブチル
リン酸エステル、ジイソブチルリン酸エステル、ジ−ｓ
ｅｃ−ブチルリン酸エステルなどのジアルキルリン酸エ
ステルが挙げられる。これらのアルキルリン酸エステル
BR>は１種用いてもよいし、２種以上を組み合わせて用
いてもよい。本発明の第四級アンモニウム塩において
は、殺菌力を向上させるために、モノ長鎖アルキル又は
アルケニルジ低級アルキルアミンに第４の置換基として
アリール基を有するオキシアルキレン基を導入すること
が必要である。このようなオキシアルキレン基を導入す
るには、例えば一般式At least one selected from monoalkyl phosphates and dialkyl phosphates represented by the formula (R 5 is an alkyl group having 1 to 8 carbon atoms and m is 1 or 2) Is used. Examples of the monoalkyl phosphate ester and dialkyl phosphate ester represented by the general formula [3] include monomethyl phosphate ester, monoethyl phosphate ester, mono-n-propyl phosphate ester, monoisopropyl phosphate ester, mono- n-butyl phosphate, monoisobutyl phosphate, mono-sec-butyl phosphate and other monoalkyl phosphates, dimethyl phosphate,
Diethyl phosphate, di-n-propyl phosphate, diisopropyl phosphate, di-n-butyl phosphate, diisobutyl phosphate, di-s
Dialkyl phosphates such as ec-butyl phosphate may be mentioned. These alkyl phosphates
BR> may be used alone or in combination of two or more. In the quaternary ammonium salt of the present invention, in order to improve bactericidal activity, it is necessary to introduce an oxyalkylene group having an aryl group as a fourth substituent into a mono long-chain alkyl or alkenyldi-lower alkylamine. . To introduce such an oxyalkylene group, for example, the general formula
【００１１】[0011]
【化８】 [Chemical 8]
【００１２】（式中のＡｒは置換基を有する若しくは有
しないアリール基又はアリールオキシ基、ｋは０又は１
である）で表されるスチレンオキシドやフェニルグリシ
ジルエーテルなどの芳香族エポキシ化合物が好ましく挙
げられる。このスチレンオキシドやフェニルグリシジル
エーテルの芳香環には低級アルキル基、低級アルコキシ
基、ハロゲン原子などの置換基が１種以上導入されてい
てもよい。前記モノ長鎖アルキル又はアルケニルジ低級
アルキルアミンとしては、例えばオクチルジメチルアミ
ン、オクチルジエチルアミン、デシルジメチルアミン、
デシルジエチルアミン、ラウリルジメチルアミン、ラウ
リルジエチルアミン、ミリスチルジメチルアミン、ミリ
スチルジエチルアミン、パルミチルジメチルアミン、パ
ルミチルジエチルアミン、ステアリルジメチルアミン、
ステアリルジエチルアミン、オレイルジメチルアミン、
オレイルジエチルアミンなどが挙げられる。(In the formula, Ar is an aryl group or an aryloxy group with or without a substituent, k is 0 or 1
Aromatic epoxy compounds such as styrene oxide and phenylglycidyl ether represented by One or more substituents such as a lower alkyl group, a lower alkoxy group and a halogen atom may be introduced into the aromatic ring of styrene oxide or phenylglycidyl ether. Examples of the mono-long-chain alkyl or alkenyldi-lower alkylamine include octyldimethylamine, octyldiethylamine, decyldimethylamine,
Decyldiethylamine, lauryldimethylamine, lauryldiethylamine, myristyldimethylamine, myristyldiethylamine, palmityldimethylamine, palmityldiethylamine, stearyldimethylamine,
Stearyldiethylamine, oleyldimethylamine,
Examples thereof include oleyldiethylamine.
【００１３】前記一般式［２］で表される第四級アンモ
ニウム塩の製造方法については特に制限はなく、従来公
知の方法を用いることができる。例えば前記モノ長鎖ア
ルキル又はアルケニルジ低級アルキルアミンに、中和当
量の前記一般式［３］で表されるモノアルキルリン酸エ
ステル及び／又はジアルキルリン酸エステルを加えて中
和して、一般式、The method for producing the quaternary ammonium salt represented by the general formula [2] is not particularly limited, and a conventionally known method can be used. For example, the mono-long-chain alkyl or alkenyl di-lower alkyl amine is neutralized by adding a neutralization equivalent of a mono-alkyl phosphate ester and / or a di-alkyl phosphate ester represented by the general formula [3],
【００１４】[0014]
【化９】 [Chemical 9]
【００１５】（式中のＲ1、Ｒ2、Ｒ3及びｍは前記と同
じ意味をもち、ＸＨmはアルキルリン酸エステルであ
る）で表される第三級アミンのアルキルリン酸エステル
塩を形成させたのち、その水溶液を通常５０〜１５０
℃、好ましくは１００℃前後の温度に加熱し、次いでこ
れに前記一般式［４］で表される芳香族エポキシ化合物
を該アミンに対し約当量の割合で添加し、反応させるこ
とにより、所望の第四級アンモニウム塩が得られる。(Wherein R 1 , R 2 , R 3 and m have the same meanings as described above, and XH m is an alkyl phosphate), an alkyl phosphate salt of a tertiary amine represented by After being formed, the aqueous solution is usually added to 50 to 150
By heating to a temperature of about 100 ° C., preferably about 100 ° C., and then adding an aromatic epoxy compound represented by the above general formula [4] to the amine in a ratio of about an equivalent amount, and reacting, A quaternary ammonium salt is obtained.
【００１６】このようにして得られた第四級アンモニウ
ム塩は、グラム陽性菌はもちろんのこと、グラム陰性菌
に対する殺菌活性に優れる上に、耐黄変性、耐熱性、防
錆性及びアニオン性界面活性剤との相溶性にも優れてお
り、繊維用抗菌防臭剤として、例えば綿、ポリエステル
／綿、ポリエステル、アクリル、ナイロンなどのあらゆ
る繊維の処理に用いられる。この処理方法については特
に制限はなく、従来繊維の処理に慣用されている方法、
例えば連続処理、浸漬処理、スプレー処理などの方法の
中から任意の方法を選択して用いることができる。The quaternary ammonium salt thus obtained is excellent in bactericidal activity against not only Gram-positive bacteria but also Gram-negative bacteria, and also has resistance to yellowing, heat resistance, rust prevention and anionic interface. It has excellent compatibility with activators and is used as an antibacterial deodorant for fibers in the treatment of all fibers such as cotton, polyester / cotton, polyester, acrylic, nylon. There is no particular limitation on this treatment method, a method which is conventionally used for treating fibers,
For example, an arbitrary method can be selected and used from continuous treatment, immersion treatment, spray treatment and the like.
【００１７】本発明の抗菌防臭剤の好適な使用濃度は、
通常被処理繊維に対し、０.０５〜１％ｏ.ｗ.ｆの範囲
で選ばれる。この濃度が０.０５ｏ.ｗ.ｆ未満では実用
性に欠けるし、１％ｏ.ｗ.ｆを超えると量の割には抗菌
性の向上効果がみられない。このようにして、本発明の
抗菌防臭剤で処理された繊維は耐洗たく性を有し、かつ
黄変がない上、優れた抗菌性を示す。The preferred use concentration of the antibacterial deodorant of the present invention is
Usually, it is selected in the range of 0.05 to 1% owf with respect to the fiber to be treated. If this concentration is less than 0.05 owf, it is not practical, and if it exceeds 1% owf, the effect of improving the antibacterial property is not seen for the amount. Thus, the fibers treated with the antibacterial and deodorant of the present invention have wash resistance, no yellowing and excellent antibacterial properties.
【００１８】[0018]
【実施例】次に、実施例により本発明をさらに詳細に説
明するが、本発明はこれらの例によってなんら限定され
るものではない。なお、抗菌防臭剤の性能は次のように
して評価した。The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. The performance of the antibacterial deodorant was evaluated as follows.
【００１９】（１）抗菌性 供試試料を肺炎桿菌を植種した寒天培地上に置き、３７
℃で２４時間、菌の培養を行い、試料周辺の肺炎桿菌の
生育の有無により、抗菌効果を、次の基準に従い判定し
た。 判定基準 ○：試料周辺での細菌の生育が認められず、ハローが発
生する。 △：試料周辺にはハローが発生しないが、試料表面又は
裏面には細菌の生育が認められない。 ×：試料表面又は裏面に細菌の生育が認められる。(1) Antibacterial property The test sample was placed on an agar medium in which Klebsiella pneumoniae was inoculated, and 37
The bacteria were cultivated at 24 ° C. for 24 hours, and the antibacterial effect was judged according to the following criteria based on the presence or absence of Klebsiella pneumoniae growth around the sample. Judgment Criteria ◯: No halo is generated because no bacterial growth is observed around the sample. Δ: No halo is generated around the sample, but no bacterial growth is observed on the front or back surface of the sample. X: Bacterial growth is observed on the front or back surface of the sample.
【００２０】（２）防錆性 薬剤４重量％を含有する水溶液を調製し、これをガーゼ
に浸し、この上にアセトン洗浄した虫ピン１０本を置
き、４０℃で４８時間放置した後の錆の発生本数を百分
率で表した。(2) Anticorrosive property An aqueous solution containing 4% by weight of a chemical was prepared, dipped in gauze, 10 acetone-washed insect pins were placed on the aqueous solution, and rust was allowed to stand at 40 ° C. for 48 hours. The number of occurrence of was expressed as a percentage.
【００２１】（３）黄変性 綿、Ｔ／Ｃ（ポリエステル／綿混紡）及びＰＥＴ（ポリ
エチレンテレフタレート）の３種について、次のように
して試料を作成し、熱黄変テスト（１８０℃、２分間処
理）、耐光堅牢度テスト［フェード・オ・メータ（スガ
試験機製）にて、６３℃で２０時間処理］及び酸化窒素
ガス堅牢度テスト（ＪＩＳ Ｌ-０８５５に準拠）を行
い、黄変性を求めた。以上の処理布はＪＩＳ Ｌ-０８０
４（変退色用グレースケール）に準じ、測色機（Ｍａｃ
ｂｅｔｈ ＣＯＬＯＲ−Ｍ２０２０）にて反射率を測定
し、級数をつけた。(3) Yellow Decoloration Samples were prepared for the three types of cotton, T / C (polyester / cotton blend) and PET (polyethylene terephthalate) in the following manner, and subjected to a thermal yellowing test (180 ° C., 2 minutes). Treatment), light fastness test [fade o meter (manufactured by Suga Test Instruments Co., Ltd., 20 hours at 63 ° C)] and nitric oxide gas fastness test (according to JIS L-0855) to determine yellowing. It was The above treated cloth is JIS L-080
4 (Gray scale for fading)
The reflectance was measured with a beth COLOR-M2020) and a series was assigned.
【００２２】（４）グラム陰性菌に対する殺菌効力 被検菌としてＫｌｅｂｓｉｅｌｌａ ｐｎｅｕｍｏｎｉ
ａｅ ＩＦＯ−１３２７７を用いた。試験法は一般的に
利用されている液状培地希釈法を用い、菌との接触時間
による殺菌剤の効果を調べ、次の判定基準に従い、殺菌
効力を求めた。 判定基準 −：菌の発育が認められない。 ＋：菌の発育が認められる。(4) Bactericidal efficacy against Gram-negative bacteria Klebsiella pneumoni was used as a test organism.
ae IFO-13277 was used. As the test method, a generally used liquid medium dilution method was used, and the effect of the bactericide on the contact time with the bacteria was examined, and the bactericidal effect was determined according to the following criteria. Criteria-: No growth of bacteria is observed. +: Growth of bacteria is recognized.
【００２３】実施例１ イソプロパノール１８重量部と無水リン酸１４重量部と
から得られたモノ体／ジ体の混合比が重量基準で約１／
１のイソプロピルリン酸エステル３２重量部と水１４０
重量部を反応器に仕込み、ラウリルジメチルアミン３４
重量部を加えて中和したのち、これにフェニルグリシジ
ルエーテル１５重量部を添加し、１００℃で３時間反応
させて繊維用抗菌防臭剤（１）を得た。このものは、ラ
ウリル硫酸塩との相溶性がよく、カチオン性界面活性剤
でありながら、両性界面活性剤の性質を示すという優れ
た機能を備えている。Example 1 The mixing ratio of mono-form / di-form obtained from 18 parts by weight of isopropanol and 14 parts by weight of phosphoric anhydride was about 1 / by weight.
32 parts by weight of isopropyl phosphate 1 and 140 parts of water
Part by weight was charged into a reactor, and lauryldimethylamine 34 was added.
After neutralizing by adding 1 part by weight, 15 parts by weight of phenyl glycidyl ether was added thereto and reacted at 100 ° C. for 3 hours to obtain an antibacterial deodorant for fibers (1). This compound has a good compatibility with lauryl sulfate and has an excellent function of exhibiting the properties of an amphoteric surfactant even though it is a cationic surfactant.
【００２４】実施例２ イソプロパノール１８重量部と無水リン酸１４重量部と
から得られたモノ体／ジ体の混合比が重量基準で約１／
１のイソプロピルリン酸エステル３２重量部と水１５６
重量部を反応器に仕込み、ラウリルジメチルアミン３４
重量部を加えて中和したのち、これにスチレンオキシド
１２重量部を添加し、１００℃で３時間反応させて繊維
用抗菌防臭剤（２）を得た。このものは、ラウリル硫酸
塩との相溶性がよく、カチオン性界面活性剤でありなが
ら、両性界面活性剤の性質を示すという優れた機能を備
えている。Example 2 The mixing ratio of mono-form / di-form obtained from 18 parts by weight of isopropanol and 14 parts by weight of phosphoric anhydride was about 1 / by weight.
32 parts by weight of isopropyl phosphate 1 and water 156
Part by weight was charged into a reactor, and lauryldimethylamine 34 was added.
After neutralizing by adding 1 part by weight, 12 parts by weight of styrene oxide was added thereto and reacted at 100 ° C. for 3 hours to obtain an antibacterial and deodorant (2) for fibers. This compound has a good compatibility with lauryl sulfate and has an excellent function of exhibiting the properties of an amphoteric surfactant even though it is a cationic surfactant.
【００２５】実施例３ メチルアルコール１０重量部と無水リン酸１４重量部と
から得られたモノ体／ジ体の混合比が重量基準で約１／
１のメチルリン酸エステル２４重量部と水１４６重量部
を反応器に仕込み、ラウリルジメチルアミン３４重量部
を加えて中和したのち、これにフェニルグリシジルエー
テル１５重量部を添加し、１００℃で３時間反応させて
繊維用抗菌防臭剤（３）を得た。このものは、ラウリル
硫酸塩との相溶性がよく、カチオン性界面活性剤であり
ながら、両性界面活性剤の性質を示すという優れた機能
を備えている。Example 3 The mixing ratio of mono-form / di-form obtained from 10 parts by weight of methyl alcohol and 14 parts by weight of phosphoric anhydride was about 1 / by weight.
24 parts by weight of the methyl phosphate ester of 1 and 146 parts by weight of water were charged into a reactor, and after adding 34 parts by weight of lauryldimethylamine for neutralization, 15 parts by weight of phenylglycidyl ether was added thereto, and the mixture was added at 100 ° C. for 3 hours. The reaction was performed to obtain an antibacterial deodorant for fibers (3). This compound has a good compatibility with lauryl sulfate and has an excellent function of exhibiting the properties of an amphoteric surfactant even though it is a cationic surfactant.
【００２６】実施例４ ブチルアルコール２２重量部と無水リン酸１４重量部と
から得られたモノ体／ジ体の混合比が重量基準で約１／
１のブチルリン酸エステル３６重量部と水１７０重量部
を反応器に仕込み、ラウリルジメチルアミン３４重量部
を加えて中和したのち、これにフェニルグリシジルエー
テル１５重量部を添加し、１００℃で３時間反応させて
繊維用抗菌防臭剤（４）を得た。このものは、ラウリル
硫酸塩との相溶性がよく、カチオン性界面活性剤であり
ながら、両性界面活性剤の性質を示すという優れた機能
を備えている。Example 4 The mixing ratio of mono-form / di-form obtained from 22 parts by weight of butyl alcohol and 14 parts by weight of phosphoric anhydride was about 1 / by weight.
36 parts by weight of butyl phosphate ester of 1 and 170 parts by weight of water were charged into a reactor, and after adding 34 parts by weight of lauryldimethylamine for neutralization, 15 parts by weight of phenylglycidyl ether was added thereto, and the mixture was added at 100 ° C. for 3 hours. The reaction was performed to obtain an antibacterial deodorant (4) for fibers. This compound has a good compatibility with lauryl sulfate and has an excellent function of exhibiting the properties of an amphoteric surfactant even though it is a cationic surfactant.
【００２７】実施例５ 綿ブロード（４０番）を０.１wt％塩化ベンザルコニウ
ム液、実施例１〜４で得た繊維用抗菌防臭剤（１）〜
（４）の０.１wt％液及び１.０wt％シリコーン系第四級
アンモニウム塩をそれぞれ用い、絞り率１００％で処理
し、１０５℃で３分間乾燥したのち、１６０℃で２分間
キュアリングを行った。このものについて、未洗たく、
１０回洗たく、２０回洗たく、３０回洗たくの場合の抗
菌性を調べた。その結果を第１表に示す。なお、洗たく
は次のようにして行った。すなわち、家庭用電気洗たく
機を用い、中性洗剤ニュービーズ［花王(株)製］２ｇ／
リットルを含有する４０℃の水溶液で５分間、洗たくし
たのち、流水洗を２分間行い脱水し、さらに流水洗を２
分間行い脱水乾燥する。この操作を所定回数繰返し、実
施する。Example 5 A 0.1 wt% benzalkonium chloride solution of cotton broad (No. 40), the antibacterial and deodorant agent for fibers (1) obtained in Examples 1 to 4
The 0.1 wt% liquid of (4) and the 1.0 wt% silicone-based quaternary ammonium salt were treated with a squeezing ratio of 100%, dried at 105 ° C for 3 minutes, and then cured at 160 ° C for 2 minutes. went. About this thing, unwashed,
The antibacterial properties were examined for 10 times, 20 times and 30 times. The results are shown in Table 1. The washing was performed as follows. That is, using a household electric washing machine, Neutral detergent New beads [manufactured by Kao Corporation] 2 g /
After washing with an aqueous solution containing 40 liters at 40 ° C. for 5 minutes, washing with running water for 2 minutes for dehydration, and further washing with running water for 2 minutes
Do it for a minute and dehydrate and dry. This operation is repeated a predetermined number of times.
【００２８】実施例６ 実施例５において、綿ブロードの代わりに、ポリエステ
ル／綿（６５／３５重量比）ブロードを用いた以外は、
実施例５と同様にして抗菌性を調べた。その結果を第１
表に示す。Example 6 In Example 5, except that polyester / cotton (65/35 weight ratio) broad was used instead of cotton broad,
The antibacterial property was examined in the same manner as in Example 5. The result is first
Shown in the table.
【００２９】実施例７ 実施例５において、綿ブロードの代わりに、ポリエステ
ルジャージを用い、かつキュアリングを１８０℃で３０
秒間行った以外は、実施例５と同様に実施して抗菌性を
調べた。その結果を第１表に示す。Example 7 In Example 5, polyester jersey was used instead of cotton broad and curing was performed at 180 ° C. for 30 minutes.
The antibacterial property was examined by the same method as in Example 5 except that the operation was performed for 2 seconds. The results are shown in Table 1.
【００３０】[0030]
【表１】 [Table 1]
【００３１】注 Ｌ−０、１０、２０、３０は洗たく回
数を示す。Note L-0, 10, 20, 30 indicates the number of times of washing.
【００３２】実施例８ 各薬剤の防錆性を調べた。その結果を次に示す。 薬剤 錆発生率（％） 塩化ベンザルコニウム １００ 本発明抗菌防臭剤（１） ０ 本発明抗菌防臭剤（２） ０ 本発明抗菌防臭剤（３） ０ 本発明抗菌防臭剤（４） ０ シリコーン系第四級アンモニウム塩 １００Example 8 The anticorrosive property of each chemical was examined. The results are shown below.Drug Rust occurrence rate (%) Benzalkonium chloride 100 Antibacterial deodorant of the present invention (1) 0 Antibacterial deodorant of the present invention (2) 0 Antibacterial deodorant of the present invention (3) 0 Antibacterial deodorant of the present invention (4) 0 Silicone quaternary ammonium salt 100
【００３３】実施例９ 各薬剤について、熱黄変テスト、耐光堅牢度テスト及び
酸化窒素ガス堅牢度テストを行い、黄変性を調べた。結
果を第２表に示す。Example 9 Each drug was subjected to a thermal yellowing test, a light fastness test and a nitric oxide gas fastness test to examine yellowing. The results are shown in Table 2.
【００３４】[0034]
【表２】 [Table 2]
【００３５】注 Ｔ／Ｃ：ポリエステル／綿混紡 ＰＥＴ：ポリエチレンテレフタレートNote T / C: polyester / cotton blend PET: polyethylene terephthalate
【００３６】実施例１０ 各薬剤のグラム陰性菌に対する殺菌効力を求めた。その
結果を第３表に示す。Example 10 The bactericidal efficacy of each drug against Gram-negative bacteria was determined. The results are shown in Table 3.
【００３７】[0037]
【表３】 [Table 3]
【００３８】[0038]
【発明の効果】本発明の繊維用抗菌防臭剤は、取扱いが
容易で、かつグラム陽性菌はもちろんのことグラム陰性
菌に対する殺菌活性に優れる上、耐黄変性、耐熱性、防
錆性及びアニオン性界面活性剤との相溶性にも優れてお
り、シリコーン系第四級アンモニウム塩に代わって、
綿、ポリエステル綿、ポリエステル、アクリル、ナイロ
ンなどのあらゆる繊維に対し、抗菌防臭効果を付与する
のに好適に用いられる。INDUSTRIAL APPLICABILITY The antibacterial and deodorant agent for textiles of the present invention is easy to handle and has excellent bactericidal activity against Gram-negative bacteria as well as Gram-negative bacteria. It also has excellent compatibility with hydrophilic surface-active agents, replacing the silicone-based quaternary ammonium salt,
It is preferably used for imparting an antibacterial and deodorant effect to all fibers such as cotton, polyester cotton, polyester, acrylic and nylon.
Claims (4)
ニル基、Ｒ2及びＲ3はそれぞれ炭素数１〜５のアルキル
基であり、それらは同一であってもよいし、たがいに異
なっていてもよく、Ｒ4は炭素数２〜４のアルキレン
基、Ａｒは置換基を有する若しくは有しないアリール基
又はアリールオキシ基、Ｘm-はアルキルリン酸エステル
イオン、ｍは１又は２である）で表される第四級アンモ
ニウム塩の中から選ばれた少なくとも１種から成る繊維
用抗菌防臭剤。1. A general formula: (In the formula, R 1 is an alkyl group or an alkenyl group having 8 to 22 carbon atoms, R 2 and R 3 are each an alkyl group having 1 to 5 carbon atoms, and they may be the same or different from each other. R 4 is an alkylene group having 2 to 4 carbon atoms, Ar is an aryl group or an aryloxy group having or not having a substituent, X m − is an alkyl phosphate ion, and m is 1 or 2. ) An antibacterial deodorant for fibers comprising at least one selected from the quaternary ammonium salts represented by
ニル基、Ｒ2及びＲ3はそれぞれ炭素数１〜５のアルキル
基であり、それらは同一であってもよいし、たがいに異
なっていてもよく、ＸＨmはアルキルリン酸エステル、
ｍは１又は２である）で表される第三級アミンのアルキ
ルリン酸エステル塩を四級化して得られたものである請
求項１記載の繊維用抗菌防臭剤。2. A quaternary ammonium salt is represented by: (In the formula, R 1 is an alkyl group or an alkenyl group having 8 to 22 carbon atoms, R 2 and R 3 are each an alkyl group having 1 to 5 carbon atoms, and they may be the same or different from each other. XH m is an alkyl phosphate ester,
The antibacterial and deodorant agent for fibers according to claim 1, which is obtained by quaternizing an alkyl phosphate ester salt of a tertiary amine represented by m is 1 or 2.
を構成するアルキルリン酸エステルが、一般式 【化３】 （式中のＲ5は炭素数１〜８のアルキル基、ｍは１又は
２である）で表されるモノアルキルリン酸エステル及び
ジアルキルリン酸エステルの中から選ばれた少なくとも
１種である請求項２記載の繊維用抗菌防臭剤。3. An alkyl phosphoric acid ester which constitutes an alkyl phosphoric acid ester salt of a tertiary amine is represented by the general formula: (Wherein R 5 is an alkyl group having 1 to 8 carbon atoms and m is 1 or 2) is at least one selected from monoalkyl phosphates and dialkyl phosphates. Item 2. The antibacterial deodorant for fibers according to item 2.
ル基又はアリールオキシ基、ｋは０又は１である）で表
されるエポキシ化合物により四級化されたものである請
求項１、２又は３記載の繊維用抗菌防臭剤。4. A quaternary ammonium salt is represented by the general formula: The compound is quaternized with an epoxy compound represented by the formula (wherein Ar is an aryl group or an aryloxy group having or not having a substituent, and k is 0 or 1). The antibacterial deodorant for fibers described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13205391A JPH0689507B2 (en) | 1991-05-08 | 1991-05-08 | Antibacterial deodorant for textiles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13205391A JPH0689507B2 (en) | 1991-05-08 | 1991-05-08 | Antibacterial deodorant for textiles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04333665A JPH04333665A (en) | 1992-11-20 |
| JPH0689507B2 true JPH0689507B2 (en) | 1994-11-09 |
Family
ID=15072423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13205391A Expired - Fee Related JPH0689507B2 (en) | 1991-05-08 | 1991-05-08 | Antibacterial deodorant for textiles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0689507B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111534905A (en) * | 2020-06-04 | 2020-08-14 | 席梦思床褥家具（苏州）有限公司 | Antibacterial anti-mite organic cotton composite fiber fabric and processing technology thereof |
-
1991
- 1991-05-08 JP JP13205391A patent/JPH0689507B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111534905A (en) * | 2020-06-04 | 2020-08-14 | 席梦思床褥家具（苏州）有限公司 | Antibacterial anti-mite organic cotton composite fiber fabric and processing technology thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04333665A (en) | 1992-11-20 |
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