JP6270622B2 - Antibacterial and antifungal agent for textile and method for producing antibacterial and antifungal fiber product - Google Patents
Antibacterial and antifungal agent for textile and method for producing antibacterial and antifungal fiber product Download PDFInfo
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- JP6270622B2 JP6270622B2 JP2014104478A JP2014104478A JP6270622B2 JP 6270622 B2 JP6270622 B2 JP 6270622B2 JP 2014104478 A JP2014104478 A JP 2014104478A JP 2014104478 A JP2014104478 A JP 2014104478A JP 6270622 B2 JP6270622 B2 JP 6270622B2
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- Prior art keywords
- antibacterial
- antifungal
- fibers
- fiber product
- antifungal agent
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- 229940121375 antifungal agent Drugs 0.000 title claims description 137
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- 239000003429 antifungal agent Substances 0.000 title claims description 87
- 230000000843 anti-fungal effect Effects 0.000 title claims description 84
- 239000004753 textile Substances 0.000 title claims description 34
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Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明は、繊維用抗菌抗かび剤及び抗菌抗かび性繊維製品の製造方法に関する。より詳しくは特定の繊維用抗菌抗かび剤、及びこれを用いて、繊維製品に抗菌抗かび加工を施すことを特徴とする抗菌抗かび性繊維製品の製造方法に関する。 The present invention relates to an antibacterial and antifungal agent for fibers and a method for producing an antibacterial and antifungal fiber product. More particularly, the present invention relates to a specific antibacterial and antifungal agent for fibers, and a method for producing an antibacterial and antifungal fiber product characterized by applying an antibacterial and antifungal process to a fiber product using the same.
近年、メチシリン耐性黄色ブドウ球菌（ＭＲＳＡ）等による院内感染や病原性大腸菌Ｏ−１５７等による食中毒など、菌を原因とする事故が多発し社会問題化している。また、一般家庭においては、居住空間の気密性の高まりや空調設備の普及により、これまで以上にかびが繁殖しやすい環境となり、かび由来のアレルギーの発生や日用品の変色といった問題が増加している。これらの問題に対応するために抗菌抗かび剤等を配合した各種繊維製品が上市されている。 In recent years, accidents caused by bacteria such as nosocomial infections caused by methicillin-resistant Staphylococcus aureus (MRSA) and food poisoning caused by pathogenic Escherichia coli O-157 and the like have become a social problem. In addition, in ordinary households, the increase in airtightness of living spaces and the spread of air conditioning equipment have made it easier for molds to propagate, and problems such as generation of mold-related allergies and discoloration of daily necessities are increasing. . In order to address these problems, various fiber products containing antibacterial and antifungal agents have been put on the market.
用いられる抗菌抗かび剤としては、まずは塩化ベンザルコニウム、塩化セチルピリジニウム、グルコン酸クロルヘキシジン、５−クロロ−２−［２，４−ジクロロフェノキシ］フェノール等の低分子有機系抗菌抗かび剤が挙げられる。しかしながら、処理された繊維製品は抗菌性及び抗かび性を示すものの、台所、洗面所等の水回りで使用したり、洗濯を繰り返したりした場合に容易に抗菌抗かび剤が脱落し、抗菌性や抗かび性が著しく低下する問題がある。 Antibacterial and antifungal agents used are low molecular organic antibacterial agents such as benzalkonium chloride, cetylpyridinium chloride, chlorhexidine gluconate, and 5-chloro-2- [2,4-dichlorophenoxy] phenol. It is done. However, although the treated textile products exhibit antibacterial and antifungal properties, the antibacterial and antifungal agents easily fall off when used around water in kitchens, washrooms, etc. or when washing is repeated. There is a problem that the antifungal property is remarkably lowered.
そこで、特許文献１〜３において、塩酸ポリヘキサメチレンビグアナイド塩酸塩、ポリ［オキシエチレン（ジメチルイミノ）エチレン（ジメチルイミノ）エチレンジクロライド］、シアノグアニジンとポリエチレンポリアミンの重合物等の高分子有機系抗菌抗かび剤が提案されている。 Therefore, in Patent Documents 1 to 3, high molecular organic antibacterial antimicrobial agents such as polyhexamethylene biguanide hydrochloride, poly [oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride], and a polymer of cyanoguanidine and polyethylene polyamine are disclosed. Molds have been proposed.
また、特許文献４において、ジンクピリチオン、銀ゼオライト、酸化亜鉛等の金属系抗菌抗かび剤において、特定の界面活性剤を用いて分散することによって、処理浴の安定性を向上させることができ、染色加工と同じ処理浴中で抗菌抗かび加工を行う処理（以降、「染色同浴加工」ともいう）においても使用可能であることが提案されている。 Moreover, in patent document 4, in metal type antibacterial antifungal agents, such as a zinc pyrithione, silver zeolite, and zinc oxide, the stability of a processing bath can be improved by disperse | distributing using specific surfactant, dyeing | staining It has been proposed that the antibacterial and antifungal processing can be used in the same processing bath as the processing (hereinafter also referred to as “dyeing bath processing”).
特許文献１〜３に記載の抗菌抗かび剤では、洗濯を繰り返しても性能の低下が少ない（以降、「洗濯耐久性のある」ともいう）抗菌性が得られるものの、洗濯耐久性のある抗かび性を得ることは困難である。また抗菌抗かび性を示す成分がカチオン性化合物であるため、染色同浴加工に適しておらず、染料との凝集による染色不良などのトラブルを起こすという問題がある。 In the antibacterial and antifungal agents described in Patent Documents 1 to 3, antibacterial properties with little deterioration in performance even after repeated washing (hereinafter also referred to as “washing durability”) are obtained, but antibacterial properties with washing durability are obtained. It is difficult to obtain moldiness. In addition, since the component exhibiting antibacterial and antifungal properties is a cationic compound, it is not suitable for the dyeing and bathing process, and there is a problem of causing troubles such as poor dyeing due to aggregation with the dye.
特許文献４に記載の抗菌抗かび剤では、抗菌性については、洗濯耐久性のある十分な性能が得られるものの、より良好な抗かび性が求められていた。さらに満足できる抗かび性とともに、得られる繊維製品のより良好な耐光堅牢性が求められていた。 In the antibacterial and antifungal agent described in Patent Document 4, a sufficient antifungal property has been required for antibacterial properties, although sufficient performance with washing durability can be obtained. In addition to satisfactory antifungal properties, there has been a demand for better light fastness of the resulting fiber product.
本発明は、上記事情を鑑みてなされたものであり、得られる繊維製品の耐光堅牢性を低下させることなく、洗濯耐久性のある抗菌性及び抗かび性を同時に繊維製品に付与することができ、染色同浴加工における染色への阻害の少ない繊維用抗菌抗かび剤及びそれを用いる抗菌抗かび性繊維製品の製造方法を提供することにある。 The present invention has been made in view of the above circumstances, and can simultaneously impart antibacterial and antifungal properties having washing durability to a textile without reducing the light fastness of the resulting textile. Another object of the present invention is to provide an antibacterial and antifungal agent for fibers with less hindrance to dyeing in the dyeing and bathing process and a method for producing an antibacterial and antifungal fiber product using the same.
本発明の態様は、以下のようである。
（１）下記一般式（Ｉ）で表される化合物（Ａ）と、アニオン界面活性剤及び非イオン界面活性剤の中から選ばれる１種又は２種以上の界面活性剤（Ｂ）と、乳化分散媒（Ｃ）と、を含有する乳化分散物であって、下記一般式（Ｉ）で表される化合物（Ａ）１００質量部に対して、アニオン界面活性剤及び非イオン界面活性剤の中から選ばれる１種又は２種以上の界面活性剤（Ｂ）の配合量が１〜９９質量部であることを特徴とする繊維用抗菌抗かび剤。
（２）前記界面活性剤（Ｂ）のアニオン界面活性剤がα−オレフィンスルホン酸塩またはスチレン化フェノールアルキレンオキサイド付加物硫酸エステル塩であり、そして非イオン界面活性剤がスチレン化フェノールアルキレンオキサイド付加物または炭素数１６〜２４のアルコールのアルキレンオキサイド付加物である、（１）に記載の繊維用抗菌抗かび剤。
（３）前記繊維用抗菌抗かび剤を基準として、前記化合物（Ａ）を３質量％以上かつ５０質量％以下含む、（１）または（２）に記載の繊維用抗菌抗かび剤。
（４）（１）〜（３）のいずれか一項に記載の繊維用抗菌抗かび剤を用いて、繊維製品に抗菌抗かび加工を施すことを特徴とする抗菌抗かび性繊維製品の製造方法。
（５）繊維製品に抗菌抗かび加工を施すと同時に、染色加工を施すことを特徴とする（４）記載の抗菌抗かび性繊維製品の製造方法。
Aspects of the present invention are as follows.
(1) Compound (A) represented by the following general formula (I), one or more surfactants (B) selected from anionic surfactants and nonionic surfactants, and emulsification An emulsified dispersion containing a dispersion medium (C), and an anionic surfactant and a nonionic surfactant among 100 parts by mass of the compound (A) represented by the following general formula (I) The antibacterial and antifungal agent for fibers, wherein the amount of one or more surfactants (B) selected from 1 to 99 parts by mass is 1 to 99 parts by mass.
(2) The anionic surfactant of the surfactant (B) is an α-olefin sulfonate or a styrenated phenol alkylene oxide adduct sulfate salt, and the nonionic surfactant is a styrenated phenol alkylene oxide adduct. Alternatively, the antibacterial and antifungal agent for fibers according to (1), which is an alkylene oxide adduct of an alcohol having 16 to 24 carbon atoms.
(3) The antibacterial and antifungal agent for fibers according to (1) or (2), containing 3% by mass to 50% by mass of the compound (A) based on the antibacterial and antifungal agent for fibers.
(4) Production of an antibacterial and antifungal fiber product, characterized by applying an antibacterial and antifungal process to the fiber product using the antibacterial and antifungal agent for fibers according to any one of (1) to (3) Method.
(5) The method for producing an antibacterial and antifungal fiber product according to (4), wherein the fiber product is subjected to an antibacterial and antifungal process at the same time as a dyeing process.
詳細に説明すると、本発明は、下記一般式（Ｉ）で表される化合物（Ａ）と、アニオン界面活性剤及び非イオン界面活性剤の中から選ばれる１種又は２種以上の界面活性剤（Ｂ）と、乳化分散媒（Ｃ）と、を含有する乳化分散物であって、下記一般式（Ｉ）で表される化合物（Ａ）１００質量部に対して、アニオン界面活性剤及び非イオン界面活性剤の中から選ばれる１種又は２種以上の界面活性剤（Ｂ）の配合量が１〜９９質量部であることを特徴とする繊維用抗菌抗かび剤を提供する。 More specifically, the present invention relates to a compound (A) represented by the following general formula (I) and one or more surfactants selected from anionic surfactants and nonionic surfactants. An emulsified dispersion containing (B) and an emulsified dispersion medium (C), and an anionic surfactant and a non-emulsifying agent with respect to 100 parts by mass of the compound (A) represented by the following general formula (I) Provided is an antibacterial and antifungal agent for fibers, wherein the amount of one or more surfactants (B) selected from ionic surfactants is 1 to 99 parts by mass.
本発明の繊維用抗菌抗かび剤によれば、得られる繊維製品の耐光堅牢性を低下させることなく、洗濯耐久性のある抗菌性及び抗かび性を同時に繊維製品に付与することができる。また、染色阻害が少ないため、これまで困難だった染色同浴加工においても使用することができる。 According to the antibacterial and antifungal agent for fibers of the present invention, antibacterial and antifungal properties having washing durability can be simultaneously imparted to a fiber product without reducing the light fastness of the resulting fiber product. Moreover, since there is little dyeing | staining inhibition, it can be used also in the dyeing bath processing which was difficult until now.
本発明はまた、下記一般式（Ｉ）で表される化合物（Ａ）と、アニオン界面活性剤及び非イオン界面活性剤の中から選ばれる１種又は２種以上の界面活性剤（Ｂ）と、乳化分散媒（Ｃ）と、を含有する乳化分散物であって、下記一般式（Ｉ）で表される化合物（Ａ）１００質量部に対して、アニオン界面活性剤及び非イオン界面活性剤の中から選ばれる１種又は２種以上の界面活性剤（Ｂ）の配合量が１〜９９質量部である繊維用抗菌抗かび剤を用いて、繊維製品に抗菌抗かび加工を施すことを特徴とする抗菌抗かび性繊維製品の製造方法を提供する。 The present invention also includes a compound (A) represented by the following general formula (I), and one or more surfactants (B) selected from anionic surfactants and nonionic surfactants. And an emulsified dispersion medium (C), an anionic surfactant and a nonionic surfactant with respect to 100 parts by mass of the compound (A) represented by the following general formula (I) Using an antibacterial and antifungal agent for fibers in which the blending amount of one or more surfactants (B) selected from 1 to 99 parts by mass is applied to the textile product. Provided is a method for producing a characteristic antibacterial and antifungal fiber product.
本発明はさらに、繊維製品に抗菌抗かび加工を施すと同時に、染色加工を施すことを特徴とする抗菌抗かび性繊維製品の製造方法を提供する。 The present invention further provides a method for producing an antibacterial and antifungal fiber product, wherein the fiber product is subjected to an antibacterial and antifungal process and a dyeing process at the same time.
本発明の抗菌抗かび性繊維製品の製造方法によれば、本発明に係る繊維用抗菌抗かび剤を用いることによって、耐光堅牢性に優れ、洗濯耐久性のある抗菌抗かび性繊維製品を安定して製造することができる。また、染色加工と同じ処理浴中で抗菌抗かび加工でも使用することができるため、工程短縮、コスト低減を図ることもできる。 According to the method for producing an antibacterial and antifungal fiber product of the present invention, by using the antibacterial and antifungal agent for fibers according to the present invention, the antibacterial and antifungal fiber product having excellent light fastness and washing durability can be stabilized. Can be manufactured. In addition, since it can be used in antibacterial and antifungal processing in the same treatment bath as the dyeing processing, the process can be shortened and the cost can be reduced.
本発明の繊維用抗菌抗かび剤は、各種繊維製品に処理することにより、得られる繊維製品の耐光堅牢性を低下させることなく、様々な菌やかびに対する優れた抗菌性及び抗かび性を同時に付与することができる。また、洗濯を繰り返した場合においても、その効果を充分に維持することができる。さらには、繊維製品に処理する際に、本発明の繊維用抗菌抗かび剤の単独処理での使用は勿論のこと、染色阻害が少ないため、染色同浴加工にも使用することができる。 The antibacterial and antifungal agent for fibers according to the present invention simultaneously exhibits excellent antibacterial and antifungal properties against various fungi and fungi without lowering the light fastness of the resulting fiber product by treating various fiber products. Can be granted. Further, even when washing is repeated, the effect can be sufficiently maintained. Furthermore, when processing into a textile product, the antibacterial and antifungal agent for fibers of the present invention can be used not only in a single process but also in dyeing and bathing because of less dyeing inhibition.
本発明の繊維用抗菌抗かび剤は、下記一般式（Ｉ）で表される化合物（Ａ）と、アニオン界面活性剤及び非イオン界面活性剤の中から選ばれる１種又は２種以上の界面活性剤（Ｂ）と、乳化分散媒（Ｃ）と、を含有する乳化分散物であり、下記一般式（Ｉ）で表される化合物（Ａ）１００質量部に対して、アニオン界面活性剤及び非イオン界面活性剤の中から選ばれる１種又は２種以上の界面活性剤（Ｂ）の配合量が１〜９９質量部である。 The antibacterial and antifungal agent for fibers of the present invention is a compound (A) represented by the following general formula (I), and one or more interfaces selected from anionic surfactants and nonionic surfactants An emulsified dispersion containing an activator (B) and an emulsified dispersion medium (C), with respect to 100 parts by mass of the compound (A) represented by the following general formula (I), an anionic surfactant and The compounding quantity of 1 type, or 2 or more types of surfactant (B) chosen from nonionic surfactant is 1-99 mass parts.
（式中、Ｙはハロゲン原子及びアセチル基からなる群から選択され、Ｙが複数である場合は、同一であっても、異なっていてもよい。ｍ及びｎはそれぞれ独立して、０〜２の整数である。） Wherein Y is selected from the group consisting of a halogen atom and an acetyl group, and when Y is plural, they may be the same or different. M and n are each independently 0-2. Is an integer.)
本発明の繊維用抗菌抗かび剤に用いられる上記一般式（Ｉ）で表される化合物（Ａ）としては、サリチルアニリド、５−クロロサリチルアニリド、４−クロロサリチルアニリド、３’，４’−ジクロロサリチルアニリド、３’，４’，５−トリクロロサリチルアニリド、５−アセチルサリチルアニリド、４−アセチルサリチルアニリド等が挙げられる。得られる繊維製品の抗菌性及び抗かび性の点で、サリチルアニリド（一般式（Ｉ）：ｍ、ｎ＝０）または一般式（Ｉ）におけるＹがハロゲン原子である置換体（一般式（Ｉ）：Ｙ＝ハロゲン原子、ｍ及びｎが０でない）が好ましく、サリチルアニリド及び５−クロロサリチルアニリドや４−クロロサリチルアニリドのような置換体（一般式（Ｉ）：Ｙ＝ハロゲン原子、ｍ＝１、ｎ＝０）がより好ましく、サリチルアニリドがさらに好ましい。これらの化合物は、例えば、特開昭６０−１３６５４７号公報に記載の方法により、アニリンもしくは、ハロゲン原子又はアセチル基で置換されたアニリンに、サリチル酸もしくは、ハロゲン原子又はアセチル基で置換されたサリチル酸を１５０℃以上で反応させ、溶媒で再結晶することにより得ることができる。また市販品を用いることもできる。 Examples of the compound (A) represented by the general formula (I) used for the antibacterial and antifungal agent for fibers of the present invention include salicylanilide, 5-chlorosalicylanilide, 4-chlorosalicylanilide, 3 ′, 4′- Examples include dichlorosalicylanilide, 3 ′, 4 ′, 5-trichlorosalicylanilide, 5-acetylsalicylanilide, 4-acetylsalicylanilide, and the like. In terms of antibacterial and antifungal properties of the resulting fiber product, salicylanilide (general formula (I): m, n = 0) or a substituent in which Y in general formula (I) is a halogen atom (general formula (I ): Y = halogen atom, m and n are not 0), and salicylanilide and substituted products such as 5-chlorosalicylanilide and 4-chlorosalicylanilide (general formula (I): Y = halogen atom, m = 1, n = 0) is more preferable, and salicylanilide is more preferable. These compounds are prepared by, for example, converting aniline or aniline substituted with a halogen atom or acetyl group to salicylic acid or salicylic acid substituted with a halogen atom or acetyl group by the method described in JP-A-60-136547. It can be obtained by reacting at 150 ° C. or higher and recrystallizing with a solvent. Commercial products can also be used.
本発明の繊維用抗菌抗かび剤が染色同浴加工においても使用可能な理由の一つとして、上記一般式（Ｉ）で表される化合物（Ａ）が、従来の高分子有機系抗菌抗かび剤に含まれるカチオン性の抗菌抗かび成分と比較して、染料との凝集を起こしにくく、染色同浴加工における染色阻害が少ないことが考えられる。 As one of the reasons that the antibacterial and antifungal agent for fibers of the present invention can be used in dyeing and bathing treatment, the compound (A) represented by the above general formula (I) is a conventional high molecular organic antibacterial and antifungal agent. Compared with the cationic antibacterial and antifungal component contained in the agent, it is considered that aggregation with the dye is less likely to occur and there is less dyeing inhibition in the dyeing and bathing process.
また、本発明の繊維用抗菌抗かび剤に用いられる上記一般式（Ｉ）で表される化合物（Ａ）の配合量は、特に限定されるものではないが、得られる繊維製品の抗菌性及び抗かび性と繊維用抗菌抗かび剤の貯蔵安定性の点で、繊維用抗菌抗かび剤全体を基準として、１質量%以上が好ましく、３質量％以上がより好ましく、５質量％以上がさらに好ましい。かつ５０質量％以下が好ましく、４０質量％以下がより好ましく、３０質量％以下がさらに好ましい。１質量％未満であると、繊維用抗菌抗かび剤を大量に使用しなければ十分な抗菌性及び抗かび性が得られないおそれがある。５０質量％を超えると、上記一般式（Ｉ）で表される化合物（Ａ）の乳化分散状態を安定に保つ効果が低下し、繊維用抗菌抗かび剤の貯蔵安定性が不十分となる傾向がある。 Further, the compounding amount of the compound (A) represented by the above general formula (I) used in the antibacterial and antifungal agent for fibers of the present invention is not particularly limited, but the antibacterial properties of the resulting fiber product and In terms of antifungal property and storage stability of the antibacterial and antifungal agent for fibers, based on the whole antibacterial and antifungal agent for fibers, preferably 1% by mass or more, more preferably 3% by mass or more, and further more preferably 5% by mass or more. preferable. And 50 mass% or less is preferable, 40 mass% or less is more preferable, and 30 mass% or less is further more preferable. If the amount is less than 1% by mass, sufficient antibacterial and antifungal properties may not be obtained unless a large amount of antibacterial and antifungal agent for fibers is used. When it exceeds 50% by mass, the effect of stably maintaining the emulsified dispersion state of the compound (A) represented by the above general formula (I) is lowered, and the storage stability of the antibacterial and antifungal agent for fibers tends to be insufficient. There is.
本発明の繊維用抗菌抗かび剤に用いられるアニオン界面活性剤及び非イオン界面活性剤の中から選ばれる１種又は２種以上の界面活性剤（Ｂ）としては、特に限定されるものではなく、公知のものが挙げられる。 One or more surfactants (B) selected from the anionic surfactants and nonionic surfactants used in the antibacterial and antifungal agent for fibers of the present invention are not particularly limited. And known ones.
アニオン界面活性剤としては、例えば、脂肪酸セッケン等のカルボン酸塩型アニオン界面活性剤；高級アルコール硫酸エステル塩、高級アルキルポリアルキレングリコールエーテル硫酸エステル塩、スチレン化アルキルフェノールアルキレンオキサイド付加物硫酸エステル塩、スチレン化フェノールアルキレンオキサイド付加物硫酸エステル塩、ベンジル化フェノールアルキレンオキサイド付加物硫酸エステル塩、硫酸化油、硫酸化脂肪酸エステル、硫酸化脂肪酸、硫酸化オレフィン等の硫酸エステル塩型アニオン界面活性剤；スチレン化アルキルフェノールアルキレンオキサイド付加物スルホン酸塩、スチレン化フェノールアルキレンオキサイド付加物スルホン酸塩、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、クレゾールスルホン酸塩やナフタレンスルホン酸塩等のホルマリン縮合物、α−オレフィンスルホン酸塩、パラフィンスルホン酸塩、スルホコハク酸ジエステル塩等のスルホン酸塩型アニオン界面活性剤；高級アルコールリン酸エステル塩、スチレン化アルキルフェノールアルキレンオキサイド付加物リン酸エステル塩、スチレン化フェノールアルキレンオキサイド付加物リン酸エステル塩、ベンジル化フェノールアルキレンオキサイド付加物リン酸エステル塩等のリン酸エステル塩型アニオン界面活性剤；Ｎ−メチルタウリンオレイン酸塩、Ｎ−メチルタウリンステアリン酸塩等のアニオン界面活性剤が挙げられる。 Examples of the anionic surfactant include carboxylate-type anionic surfactants such as fatty acid soaps; higher alcohol sulfates, higher alkyl polyalkylene glycol ether sulfates, styrenated alkylphenol alkylene oxide adduct sulfates, styrene Sulfate anion surfactants such as sulfated phenol alkylene oxide adduct sulfate, benzylated phenol alkylene oxide adduct sulfate, sulfated oil, sulfated fatty acid ester, sulfated fatty acid, sulfated olefin; Alkylphenol alkylene oxide adduct sulfonate, styrenated phenol alkylene oxide adduct sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, Formalin condensates such as sol sulfonate and naphthalene sulfonate, sulfonate anionic surfactants such as α-olefin sulfonate, paraffin sulfonate, sulfosuccinic acid diester salt; higher alcohol phosphate ester salt, styrene N-methyltaurine phosphate ester type anionic surfactants such as phosphorylated alkylphenol alkylene oxide adduct phosphate salt, styrenated phenol alkylene oxide adduct phosphate ester salt, and benzylated phenol alkylene oxide adduct phosphate ester salt Anionic surfactants such as oleate and N-methyl taurate stearate are mentioned.
その中でも、上記一般式（Ｉ）で表される化合物（Ａ）の乳化分散状態を安定に保つ効果の点で、α−オレフィンスルホン酸塩やスチレン化フェノールアルキレンオキサイド付加物硫酸エステル塩が好ましい。α−オレフィンスルホン酸塩としては、炭素数８〜１８のα−オレフィンスルホン酸塩がより好ましく、対塩はナトリウムがより好ましい。スチレン化フェノールアルキレンオキサイド付加物硫酸エステル塩としては、スチレンの付加モル数は２〜４、アルキレンオキサイドの炭素数は２〜４、アルキレンオキサイドの付加モル数は１〜３０のスチレン化フェノールアルキレンオキサイド付加物硫酸エステル塩がより好ましく、対塩はナトリウムがより好ましい。 Among these, α-olefin sulfonates and styrenated phenol alkylene oxide adduct sulfates are preferred from the viewpoint of stably maintaining the emulsified dispersion state of the compound (A) represented by the general formula (I). As the α-olefin sulfonate, an α-olefin sulfonate having 8 to 18 carbon atoms is more preferable, and the counter salt is more preferably sodium. Styrenated phenol alkylene oxide adduct sulfate ester salt, styrene addition phenol number of styrene addition 2-4, alkylene oxide carbon number 2-4, alkylene oxide addition mol number 1-30 The sulfate salt is more preferable, and the counter salt is more preferably sodium.
非イオン界面活性剤としては、例えば、高級アルコールアルキレンオキサイド付加物、アルキルフェノールアルキレンオキサイド付加物、炭素数１６〜２４のアルコールのアルキレンオキサイド付加物、スチレン化アルキルフェノールアルキレンオキサイド付加物、スチレン化フェノールアルキレンオキサイド付加物、ベンジルフェノールアルキレンオキサイド付加物、高級アルキルアミンアルキレンオキサイド付加物等のエーテル型非イオン界面活性剤；脂肪酸アルキレンオキサイド付加物、油脂のアルキレンオキサイド付加物等のエーテルエステル型非イオン界面活性剤；ポリプロピレングリコールエチレンオキサイド付加物等のポリアルキレングリコール型非イオン界面活性剤；グリセロールの脂肪酸エステル、ペンタエリスリトールの脂肪酸エステル、ソルビトールの脂肪酸エステル、ソルビタンの脂肪酸エステル、ショ糖の脂肪酸エステル等のエステル型非イオン界面活性剤；多価アルコールのアルキルエーテル、アルカノールアミン類の脂肪酸アミド等の非イオン界面活性剤が挙げられる。 Nonionic surfactants include, for example, higher alcohol alkylene oxide adducts, alkylphenol alkylene oxide adducts, alkylene oxide adducts of alcohols having 16 to 24 carbon atoms, styrenated alkylphenol alkylene oxide adducts, and styrenated phenol alkylene oxide adducts. , Benzylphenol alkylene oxide adduct, higher alkylamine alkylene oxide adduct, etc. ether type nonionic surfactants; fatty acid alkylene oxide adducts, oil and fat alkylene oxide adducts, etc., ether ester type nonionic surfactants; polypropylene Polyalkylene glycol type nonionic surfactants such as glycol ethylene oxide adducts; fatty acid esters of glycerol, pentaerythritol Nonionic surfactants such as fatty acid esters, fatty acid esters of sorbitol, fatty acid esters of sorbitan, fatty acid esters of sucrose, etc .; alkyl ethers of polyhydric alcohols, fatty acid amides of alkanolamines, etc. It is done.
その中でも、上記一般式（Ｉ）で表される化合物（Ａ）の乳化分散状態を安定に保つ効果の点で、スチレン化フェノールアルキレンオキサイド付加物または炭素数１６〜２４のアルコールのアルキレンオキサイド付加物が好ましく、染色同浴処理における染色阻害が少ない点でスチレン化フェノールアルキレンオキサイド付加物がより好ましい。スチレン化フェノールアルキレンオキサイド付加物としては、スチレンの付加モル数は２〜４、アルキレンオキサイドの炭素数は２〜４、アルキレンオキサイドの付加モル数は１〜３０がより好ましい。炭素数１６〜２４のアルコールのアルキレンオキサイドの付加物としては、アルキレンオキサイドの炭素数は２〜４、アルキレンオキサイドの付加モル数は１〜３０がより好ましい。アルコールの炭素数は、１６〜２４であり、１６〜２０がより好ましい。 Among them, a styrenated phenol alkylene oxide adduct or an alkylene oxide adduct of an alcohol having 16 to 24 carbon atoms is effective in that the emulsified dispersion state of the compound (A) represented by the general formula (I) is stably maintained. A styrenated phenol alkylene oxide adduct is more preferable in terms of less dyeing inhibition in the dyeing and bath treatment. As the styrenated phenol alkylene oxide adduct, the addition mole number of styrene is 2 to 4, the carbon number of alkylene oxide is 2 to 4, and the addition mole number of alkylene oxide is more preferably 1 to 30. As the adduct of an alkylene oxide of an alcohol having 16 to 24 carbon atoms, the alkylene oxide preferably has 2 to 4 carbon atoms, and the alkylene oxide has an addition mole number of 1 to 30. Carbon number of alcohol is 16-24, and 16-20 are more preferable.
アニオン界面活性剤及び非イオン界面活性剤の中から選ばれる１種又は２種以上の界面活性剤（Ｂ）として、得られる繊維製品の抗菌性および抗かび性の点で、アニオン界面活性剤の使用が好ましく、本発明の抗菌抗かび剤の貯蔵安定性を向上する目的で、非イオン界面活性剤を併用することができる。 As one or more surfactants (B) selected from anionic surfactants and nonionic surfactants, an anionic surfactant is used in terms of antibacterial and antifungal properties of the resulting fiber product. It is preferably used, and a nonionic surfactant can be used in combination for the purpose of improving the storage stability of the antibacterial and antifungal agent of the present invention.
また、本発明の繊維用抗菌抗かび剤におけるアニオン界面活性剤及び非イオン界面活性剤の中から選ばれる１種又は２種以上の界面活性剤（Ｂ）の配合量は、上記一般式（Ｉ）で表される化合物（Ａ）１００質量部に対して、１〜９９質量部である。好ましくは５〜８０質量部であり、より好ましくは１０〜７０質量部である。上記範囲内であると、上記一般式（Ｉ）で表される化合物（Ａ）の乳化分散状態を安定に保つ効果に優れ、染色同浴処理での染着濃度の低下などの染色阻害を起こしにくい。１質量部未満であると、上記一般式（Ｉ）で表される化合物（Ａ）の乳化分散状態を安定に保つ効果が低下し、繊維用抗菌性抗かび剤の貯蔵安定性が低下する傾向にある。９９質量部を超えると、上記一般式（Ｉ）で表される化合物（Ａ）の乳化分散状態を過剰に安定化させ、繊維製品への付着を阻害し、得られる繊維製品の抗菌性及び抗かび性を低下させる傾向にある。さらには、染色同浴加工にて、染料の分散状態も過剰に安定化させ、染着濃度の低下などの染色阻害を起こす傾向にある。 Moreover, the compounding quantity of 1 type, or 2 or more types of surfactant (B) chosen from the anionic surfactant and nonionic surfactant in the antibacterial antifungal agent for fibers of this invention is the said general formula (I). ) To 100 parts by mass of the compound (A) represented by 1) to 99 parts by mass. Preferably it is 5-80 mass parts, More preferably, it is 10-70 mass parts. Within the above range, the compound (A) represented by the general formula (I) is excellent in the effect of stably maintaining the emulsified dispersion state, and causes dyeing inhibition such as a decrease in the dyeing concentration in the dyeing and bathing treatment. Hateful. When the amount is less than 1 part by mass, the effect of stably maintaining the emulsified dispersion state of the compound (A) represented by the above general formula (I) is lowered, and the storage stability of the antibacterial antifungal agent for fibers tends to be lowered. It is in. When it exceeds 99 parts by mass, the emulsified and dispersed state of the compound (A) represented by the above general formula (I) is excessively stabilized, the adhesion to the fiber product is inhibited, and the antibacterial and antibacterial properties of the resulting fiber product are prevented. It tends to reduce moldability. Furthermore, in the dyeing and bathing process, the dispersion state of the dye is excessively stabilized, and there is a tendency to cause dyeing inhibition such as a decrease in dyeing density.
本発明の繊維用抗菌抗かび剤に用いられる乳化分散媒（Ｃ）としては、水や、メタノール、エタノール、イソプロピルアルコール、３−メトキシ−３−メチル−１−ブタノール等のアルコール系溶剤や、モノメチルグリコール、モノメチルジグリコール、モノエチレングリコール、ジエチレングリコール、トリエチレングリコール、ブチルグリコール、ブチルジグリコール、ブチルトリグリコール、イソブチルグリコール、イソブチルジグリコール、イソブチルトリグリコール、メチルプロピレングリコール、メチルプロピレンジグリコール、メチルプロピレントリグリコール等のグリコール系溶剤、などが挙げられる。得られる繊維製品の洗濯や摩擦に対する堅牢性の点で、水、エタノール、ブチルグリコールが好ましい。さらに繊維用抗菌抗かび剤のハンドリング性の点で、水がより好ましい。
本発明においては、繊維用抗菌抗かび剤中において、上記化合物（Ａ）、上記界面活性剤（Ｂ）および下記の任意選択的添加剤に対して、残余を占める量で加えることができる。
Examples of the emulsified dispersion medium (C) used in the antibacterial and antifungal agent for fibers of the present invention include water, alcohol solvents such as methanol, ethanol, isopropyl alcohol, 3-methoxy-3-methyl-1-butanol, and monomethyl. Glycol, monomethyl diglycol, monoethylene glycol, diethylene glycol, triethylene glycol, butyl glycol, butyl diglycol, butyl triglycol, isobutyl glycol, isobutyl diglycol, isobutyl triglycol, methyl propylene glycol, methyl propylene diglycol, methyl propylene tri Examples thereof include glycol solvents such as glycol. Water, ethanol, and butyl glycol are preferable in terms of fastness to washing and friction of the obtained fiber product. Furthermore, water is more preferable from the viewpoint of the handleability of the antibacterial and antifungal agent for fibers.
In the present invention, in the antibacterial and antifungal agent for fibers, the compound (A), the surfactant (B) and the following optional additives can be added in an amount occupying the remainder.
本発明の繊維用抗菌抗かび剤の形態は、乳化分散物であり、処理浴への展開性が良く、抗菌抗かび加工時のハンドリング性に優れる。例えば、処理浴に添加した場合に、すばやく処理浴全体に拡散し、一般式（Ｉ）で表される化合物（Ａ）を繊維製品に均一に付着させることができ、無駄の少ない効率的な抗菌抗かび性の付与が可能となる。 The form of the antibacterial and antifungal agent for fibers according to the present invention is an emulsified dispersion, has a good developability to a treatment bath, and is excellent in handling property during antibacterial and antifungal processing. For example, when added to the treatment bath, it diffuses quickly throughout the treatment bath and allows the compound (A) represented by the general formula (I) to be uniformly attached to the textile product, and is an efficient antibacterial with little waste. It is possible to impart antifungal properties.
本発明の繊維用抗菌抗かび剤には、必要に応じて、添加剤として、上記アニオン界面活性剤及び非イオン界面活性剤以外の各種界面活性剤、本発明以外の抗菌剤及び抗かび剤、柔軟剤、平滑剤、浸透剤、均染剤、制電剤、キレート剤、酸化防止剤、消泡剤、溶剤、合成樹脂、架橋剤、粘度調整剤、ｐＨ調整剤等を、本発明の効果を阻害しない範囲において、配合しても良い。 In the antibacterial and antifungal agent for fibers of the present invention, as necessary, various surfactants other than the above anionic surfactants and nonionic surfactants, antibacterial agents and antifungal agents other than the present invention, Softening agent, smoothing agent, penetrating agent, leveling agent, antistatic agent, chelating agent, antioxidant, antifoaming agent, solvent, synthetic resin, crosslinking agent, viscosity modifier, pH adjuster, etc. You may mix | blend in the range which does not inhibit.
本発明の繊維用抗菌抗かび剤の製造方法については、特に限定されるものではなく、例えば、上記一般式（Ｉ）で表される化合物（Ａ）と、アニオン界面活性剤及び非イオン界面活性剤の中から選ばれる１種又は２種以上の界面活性剤（Ｂ）と、乳化分散媒（Ｃ）とを混合し、乳化分散することにより得ることができる。必要に応じて、ビーズミル、ボールミル、サイドグラインダー等のメディアミル、高圧ホモジナイザー、超高圧ホモジナイザー等の圧力式乳化分散機、超音波乳化分散機、及び薄膜旋回型乳化分散機を使用しても良い。 The method for producing the antibacterial and antifungal agent for fibers of the present invention is not particularly limited. For example, the compound (A) represented by the above general formula (I), an anionic surfactant and a nonionic surfactant It can be obtained by mixing and emulsifying and dispersing one or more surfactants (B) selected from the agents and the emulsifying dispersion medium (C). If necessary, a media mill such as a bead mill, a ball mill, or a side grinder, a pressure type emulsifying disperser such as a high pressure homogenizer, or an ultra high pressure homogenizer, an ultrasonic emulsifying disperser, and a thin film swirl type emulsifying disperser may be used.
上記メディアミル等を用いて湿式分散する場合には、５０％積算粒径が０．０５〜１０μｍであることが好ましく、０．１〜５μｍであることがより好ましく、０．１〜３μｍであることがさらに好ましい。５０％積算粒径が０．０５μｍ未満であると、繊維用抗菌抗かび剤の貯蔵安定性の向上効果が少なく、また、微粒子化に時間がかかるため経済的に不利となる傾向にある。一方、１０μｍを超えると、繊維用抗菌抗かび剤の貯蔵安定性が低下する傾向にある。さらに、本発明の繊維用抗菌抗かび剤としては、繊維用抗菌抗かび剤の貯蔵安定性がさらに向上する傾向にあるという点から、９０％積算粒径が１０μｍ以下であることが好ましい。 When wet dispersion is performed using the media mill or the like, the 50% cumulative particle size is preferably 0.05 to 10 μm, more preferably 0.1 to 5 μm, and 0.1 to 3 μm. More preferably. When the 50% cumulative particle size is less than 0.05 μm, the effect of improving the storage stability of the antibacterial and antifungal agent for fibers is small, and it takes time to make fine particles, which tends to be economically disadvantageous. On the other hand, when it exceeds 10 μm, the storage stability of the antibacterial and antifungal agent for fibers tends to be lowered. Furthermore, the antibacterial / antifungal agent for fibers of the present invention preferably has a 90% cumulative particle size of 10 μm or less from the viewpoint that the storage stability of the antibacterial / antifungal agent for fibers tends to be further improved.
本発明において、５０％積算粒径及び９０％積算粒径は、レーザ回折／散乱式粒度分布測定装置ＬＡ−９２０（株式会社堀場製作所製）を用い、繊維用抗菌抗かび剤の粒径の百分率積算値が小粒径側から５０％の粒径を５０％積算粒径。百分率積算値の小粒径側から９０％の粒径を９０％積算粒径とすることで測定することができる。 In the present invention, the 50% cumulative particle size and the 90% cumulative particle size are percentages of the particle size of the antibacterial and antifungal agent for fibers using a laser diffraction / scattering particle size distribution measuring device LA-920 (manufactured by Horiba, Ltd.). The integrated value is 50% of the particle size of 50% from the small particle size side. It can be measured by setting 90% of the particle size from the small particle size side of the percentage integrated value to 90% integrated particle size.
本発明の繊維用抗菌抗かび剤を適用できる繊維製品の素材としては、特に限定されるものではなく、例えば、綿、麻、羊毛、絹等の天然繊維、レーヨン、キュプラ、テンセル（商標）等の半合成繊維、ポリエステル繊維、カチオン可染ポリエステル繊維、ナイロン繊維、アクリル繊維、ポリアミド繊維、ポリオレフィン繊維、ポリ塩化ビニル繊維、ポリイミド繊維、ウレタン繊維等の合成繊維、及びこれらの繊維を含む混紡繊維や複合繊維を挙げることができる。また、素材の形態としても、特に限定されるものではなく、例えば、短繊維、長繊維、糸、織物、編物、不織布等が挙げられる。これらの繊維の太さ、断面形状や繊維の減量工程等の表面処理の有無など特に限定されるものではない。 The material of the fiber product to which the antibacterial and antifungal agent for fibers of the present invention can be applied is not particularly limited. For example, natural fibers such as cotton, hemp, wool, silk, rayon, cupra, Tencel (trademark), etc. Semi-synthetic fibers, polyester fibers, cationic dyeable polyester fibers, nylon fibers, acrylic fibers, polyamide fibers, polyolefin fibers, polyvinyl chloride fibers, polyimide fibers, urethane fibers, and blended fibers containing these fibers A composite fiber can be mentioned. Moreover, it does not specifically limit as a form of a raw material, For example, a short fiber, a long fiber, a thread | yarn, a textile fabric, a knitted fabric, a nonwoven fabric etc. are mentioned. There is no particular limitation on the thickness of these fibers, the cross-sectional shape, and the presence or absence of surface treatment such as a fiber weight reduction process.
本発明の抗菌抗かび性繊維製品の製造方法について説明する。
本発明の繊維用抗菌抗かび剤を用いて、繊維製品に抗菌抗かび加工を施すということは、基材となる繊維製品に本発明の繊維用抗菌抗かび剤を処理して、上記一般式（Ｉ）で表される化合物（Ａ）を付着させ（以降、「付着工程」ともいう）、熱処理を加えることによって、上記一般式（Ｉ）で表される化合物（Ａ）を繊維製品に吸尽（固着）させる（以降、「吸尽工程」ともいう）ことである。
A method for producing the antibacterial and antifungal fiber product of the present invention will be described.
Using the antibacterial and antifungal agent for fibers of the present invention, the antibacterial and antifungal process is applied to the fiber product, and the above general formula By adhering the compound (A) represented by (I) (hereinafter also referred to as “adhesion step”) and applying heat treatment, the compound (A) represented by the above general formula (I) is absorbed into the fiber product. It is exhausted (fixed) (hereinafter also referred to as “exhaust process”).
付着工程に用いる方法としては、特に限定されるものではなく、例えば、本発明の繊維用抗菌抗かび剤をそのままあるいは適宜希釈して処理液とし、織物や編物等を浸漬等により接触させることにより、上記一般式（Ｉ）で表される化合物（Ａ）を付着させることができる。接触させる方法としては、浸漬処理、パディング（ｄｉｐ−ｎｉｐ）処理、コーティング処理、スプレー処理等が挙げられる。 The method used in the attaching step is not particularly limited. For example, the antibacterial and antifungal agent for fibers according to the present invention is used as it is or appropriately diluted to obtain a treatment liquid, and contacted with fabric or knitted fabric by dipping or the like. The compound (A) represented by the general formula (I) can be attached. Examples of the contact method include immersion treatment, padding (dip-nip) treatment, coating treatment, and spray treatment.
浸漬処理としては、例えば、染色仕上機器総覧（昭和５６年、繊維社発行）の１９６〜２４７頁に記載のバッチ式染色機を用いる方法が挙げられ、液流染色機、気流染色機、ドラム染色機、ウインス染色機、ワッシャー染色機、チーズ染色機等を用いて、繊維製品を処理液に浸漬した後、脱水することにより上記一般式（Ｉ）で表される化合物（Ａ）を付着させることができる。パディング処理としては、例えば、繊維染色加工辞典（昭和３８年、日刊工業新聞社発行）の３９６〜３９７頁や色染化学III （１９７５年、実教出版株式会社発行）の２５６〜２６０頁に記載のパディング装置を用いた方法が挙げられ、繊維製品を処理液に浸漬し、マングル、ロール等を用いて所定のピックアップ量に調整することにより上記一般式（Ｉ）で表される化合物（Ａ）を付着させることができる。コーティング処理としては、例えば、染色仕上機器総覧（昭和５６年、繊維社発行）の４７３〜４７７頁に記載のコーティング機を用いる方法が挙げられ、繊維製品に処理液を塗布することにより上記一般式（Ｉ）で表される化合物（Ａ）を付着させることができる。スプレー処理としては、例えば、圧搾空気で処理液を霧状にして吹き付けるエアースプレーや、液圧霧化方式のエアースプレーを用いた方法が挙げられ、繊維製品に処理液を噴霧することにより上記一般式（Ｉ）で表される化合物（Ａ）を付着させることができる。 Examples of the dipping treatment include a method using a batch dyeing machine described on pages 196 to 247 of the dyeing and finishing equipment overview (published by Textile Co., Ltd., 1981), including a liquid dyeing machine, an airflow dyeing machine, and drum dyeing. After immersing the fiber product in the treatment liquid using a machine, a wine dyeing machine, a washer dyeing machine, a cheese dyeing machine, etc., the compound (A) represented by the above general formula (I) is adhered by dehydration. Can do. Examples of the padding process are described in pages 396 to 397 of the Textile Dyeing Dictionary (published by Nikkan Kogyo Shimbun, 1963) and pages 256 to 260 of Color Dye Chemistry III (1975, published by Jikkyo Publishing Co., Ltd.). The method using the padding apparatus of (1), the compound (A) represented by the above general formula (I) by immersing the fiber product in the treatment liquid and adjusting to a predetermined pickup amount using a mangle, a roll or the like Can be attached. Examples of the coating treatment include a method using the coating machine described on pages 473 to 477 of the dyeing and finishing equipment overview (published in 1986, issued by Textile Co., Ltd.). The compound (A) represented by (I) can be attached. Examples of the spray treatment include an air spray that sprays the treatment liquid in a mist form with compressed air, and a method using a hydraulic atomization type air spray. The compound (A) represented by the formula (I) can be attached.
パディング処理やコーティング処理にて付着工程を行う場合、処理液を加工に適した粘度に調整して用いることができる。使用可能な粘度調整剤は特に限定されるものではないが、例えば、グアーガム、ヒドロキシエチルグアーガム、ヒドロキシプロピルグアーガム、ヒドロキシエチルセルロース、メチルセルロース、エチルセルロース、ヒドロキシプロピルメチルセルロース、ヒドロキシプロピルエチルセルロース、ポリビニルアルコール、デキストラン、デキストリン、ポリオキシエチレンポリオキシプロピレングリコールなどの非イオン性高分子化合物や、カルボキシメチルセルロース、カルボキシエチルセルロース、キサンタンガム、カラギーナン、ポリアクリル酸、ポリアクリルアミド、アルギン酸などのアニオン性高分子化合物を挙げることができる。 When the adhesion process is performed by padding or coating, the treatment liquid can be adjusted to a viscosity suitable for processing. The viscosity modifier that can be used is not particularly limited. Nonionic polymer compounds such as polyoxyethylene polyoxypropylene glycol, and anionic polymer compounds such as carboxymethyl cellulose, carboxyethyl cellulose, xanthan gum, carrageenan, polyacrylic acid, polyacrylamide, and alginic acid can be used.
吸尽工程については、上記一般式（Ｉ）で表される化合物（Ａ）が付着した繊維製品に熱処理を加え、上記一般式（Ｉ）で表される化合物（Ａ）を吸尽できれば良く、付着工程と同時に実施しても、付着工程の後に施しても良い。 About the exhaustion process, it is only necessary to add heat treatment to the fiber product to which the compound (A) represented by the general formula (I) is attached, and exhaust the compound (A) represented by the general formula (I). It may be performed simultaneously with the attaching step or after the attaching step.
付着工程と吸尽工程とを同時に施す方法としては、高温吸尽法が挙げられる。高温吸尽法としては、上記一般式（Ｉ）で表される化合物（Ａ）を浸漬処理により繊維製品の素材に付着させ、同処理浴中にて、８０〜１３５℃の温度範囲で熱処理することが好ましく、１００〜１３０℃の温度範囲で熱処理することがより好ましい。８０℃未満では、上記一般式（Ｉ）で表される化合物（Ａ）が繊維に充分に吸尽されずに得られる繊維製品の抗菌性及び抗かび性を低下させる傾向にある。１３５℃を超えると、得られる繊維製品の脆化や変色等が起こる傾向にある。 As a method of performing the adhesion step and the exhaustion step at the same time, a high temperature exhaustion method can be mentioned. As the high temperature exhaustion method, the compound (A) represented by the above general formula (I) is attached to the material of the fiber product by dipping treatment and heat-treated in a temperature range of 80 to 135 ° C. in the same treatment bath. It is preferable to heat-treat in a temperature range of 100 to 130 ° C. If it is less than 80 degreeC, it exists in the tendency for the antibacterial property and antifungal property of the textiles obtained by the compound (A) represented by the said general formula (I) not to be exhausted fully to a fiber to be reduced. When it exceeds 135 ° C., the resulting fiber product tends to become brittle or discolored.
付着工程の後に吸尽工程を施す方法としては、上記一般式（Ｉ）で表される化合物（Ａ）を繊維製品の素材に付着させる付着工程の後、ドライヤー等での乾燥処理や飽和常圧スチーム処理、加熱スチーム処理、高圧スチーム処理等の蒸熱処理を施すことによって、上記一般式（Ｉ）で表される化合物（Ａ）を吸尽させる方法が挙げられる。乾燥処理及び蒸熱処理のいずれにおいても、素材によって異なるが、通常８０〜２１０℃の範囲内であることが好ましく、１００〜１９０℃の範囲内であることがより好ましい。８０℃未満では、上記一般式（Ｉ）で表される化合物が繊維製品に充分に吸尽されずに得られる繊維製品の抗菌性及び抗かび性を低下させる傾向にある。１３５℃を超えると、得られる繊維製品の脆化や変色等が起こる傾向にある。 As a method of performing the exhaustion process after the adhesion process, after the adhesion process in which the compound (A) represented by the above general formula (I) is adhered to the material of the textile product, drying treatment with a dryer or the saturated normal pressure Examples of the method include exhausting the compound (A) represented by the general formula (I) by performing steam heat treatment such as steam treatment, heating steam treatment, and high-pressure steam treatment. In both the drying process and the steaming process, although it varies depending on the material, it is usually preferably in the range of 80 to 210 ° C, more preferably in the range of 100 to 190 ° C. If it is less than 80 degreeC, it exists in the tendency for the antibacterial property and antifungal property of the fiber product obtained by the compound represented with the said general formula (I) not to be exhausted enough to a fiber product to be reduced. When it exceeds 135 ° C., the resulting fiber product tends to become brittle or discolored.
付着工程及び吸尽工程を施す際の処理液の濃度や熱処理等の処理条件は、その目的や要求性能等の諸条件を考慮して、適宜調整することができる。しかしながら、得られる繊維製品において、上記一般式（Ｉ）で表される化合物（Ａ）の吸尽量が素材重量に対して０．０１〜１０質量％であることが好ましい。０．０１質量％未満であると、抗菌抗かび性が十分に得られない傾向にある。１０質量％を越えると、得られる繊維の風合等の繊維物性が低下したり、粉吹き等の製造上のトラブルにつながったりする傾向にある。 The treatment conditions such as the concentration of the treatment liquid and the heat treatment during the adhesion step and the exhaust step can be appropriately adjusted in consideration of various conditions such as the purpose and required performance. However, in the obtained fiber product, the exhaust amount of the compound (A) represented by the general formula (I) is preferably 0.01 to 10% by mass with respect to the material weight. If it is less than 0.01% by mass, antibacterial and antifungal properties tend not to be sufficiently obtained. If it exceeds 10% by mass, the physical properties of the resulting fiber, such as the feel of the fiber, tend to be reduced, or manufacturing problems such as powder blowing tend to occur.
さらに、本発明の製造方法においては、吸尽工程の後に、通常の公知方法によってソーピング処理を行い、繊維製品に吸尽されずに表面に付着しているに過ぎない余剰の抗菌抗かび性付与成分や染料を除去することが好ましい。余剰の抗菌抗かび性付与成分や染料は、得られる繊維製品の洗濯や摩擦に対する堅牢性を低下させる傾向にある。このようなソーピング処理に用いられるソーピング剤としては、例えば、アニオン性、非イオン性、両性界面活性剤、及びこれらが配合されたソーピング剤を用いることができ、また、サンモールＲＣ−７００Ｅ（日華化学株式会社製）、エスクードＦＲＮ（日華化学株式会社製）、エクスードＦＺ（日華化学株式会社製）等の市販品を用いることができる。 Furthermore, in the production method of the present invention, after the exhausting step, a soaping process is performed by a conventional known method, and the excess antibacterial and antifungal properties imparted only to the surface without being exhausted by the textiles are imparted. It is preferable to remove components and dyes. Excess antibacterial and antifungal properties and dyes tend to reduce the fastness of the resulting textile product to washing and friction. As a soaping agent used for such a soaping treatment, for example, anionic, nonionic, amphoteric surfactants, and a soaping agent in which these are blended can be used. Commercially available products such as Hua Chemical Co., Ltd., Esucudo FRN (Nikka Chemical Co., Ltd.), and EXudo FZ (Nikka Chemical Co., Ltd.) can be used.
また、本発明の製造方法においては、本発明の効果を阻害しない範囲において、帯電防止剤、撥水撥油剤、防汚剤、硬仕上げ剤、風合調整剤、柔軟剤、吸水剤、スリップ防止剤、耐光向上剤等の機能性薬剤を併用することができる。得られる繊維製品の抗菌抗かび性の持続性向上のために、ウレタン樹脂、シリコーン樹脂、メラニン樹脂、グリオキザール系樹脂などの樹脂成分を併用することができる。さらに、繊維製品の表面ｐＨを４〜８に調整するために、クエン酸やリンゴ酸などの揮発性の低い酸を併用することができる。 Further, in the production method of the present invention, an antistatic agent, a water / oil repellent, an antifouling agent, a hard finish agent, a texture adjusting agent, a softening agent, a water absorbing agent, and an antislip can be used as long as the effects of the present invention are not impaired. A functional agent such as an agent and a light resistance improver can be used in combination. Resin components such as urethane resin, silicone resin, melanin resin, and glyoxal resin can be used in combination for improving the durability of the antibacterial and antifungal properties of the resulting fiber product. Furthermore, in order to adjust the surface pH of a textile product to 4-8, acids with low volatility, such as a citric acid and malic acid, can be used together.
本発明の繊維用抗菌抗かび剤は、染着濃度の低下などの染色阻害を起こしにくく、抗菌抗かび加工を施すと同時に、染色加工を施すことができる。つまり染色同浴加工でも使用することができる。例えば、ポリエステル繊維製品に上記染色機を用いて、繊維製品の抗菌抗かび加工を染色加工と同じ処理浴中で同時に施す場合、本発明の繊維用抗菌抗かび剤と、分散染料と、分散均染剤とを含む処理浴に、繊維製品を浸漬し、１１０〜１４０℃にて１５〜６０分間の加熱処理を施すことにより、抗菌抗かび加工と染色加工とが同時に施された繊維製品を得ることができる。このような加工が施されたポリエステル繊維を、ソーピング又は水洗し、未固着の抗菌抗かび成分や染料などを洗い落として脱水した後、１００〜１８０℃で乾燥してもよい。 The antibacterial and antifungal agent for fibers of the present invention hardly causes dyeing inhibition such as a decrease in dyeing concentration, and can be dyed simultaneously with antibacterial and antifungal processing. In other words, it can also be used in dyeing bath processing. For example, when the above-mentioned dyeing machine is used for a polyester fiber product and the antibacterial and antifungal processing of the fiber product is simultaneously performed in the same treatment bath as the dyeing processing, the antibacterial and antifungal agent for fibers of the present invention, a disperse dye, The textile product is immersed in a treatment bath containing a dye and subjected to heat treatment at 110 to 140 ° C. for 15 to 60 minutes to obtain a textile product on which antibacterial and antifungal processing and dyeing processing are simultaneously performed. be able to. The polyester fiber that has been subjected to such processing may be soaped or washed with water, washed away unfixed antibacterial and antifungal components and dyes, and then dehydrated, and then dried at 100 to 180 ° C.
以下に、実施例及び比較例を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例により何ら限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.
＜繊維用抗菌抗かび性繊維製品の評価項目＞
（１）抗菌性
社団法人繊維評価技術協議会（以下、繊技協という）の抗菌性の評価方法及び基準に準拠して、以下のように試験を行った。
洗濯前（Ｌ−０）及び洗濯１０回後（Ｌ−１０）の繊維製品の抗菌性について、ＪＩＳ Ｌ １９０２（２００８）の定量方法である菌吸収法に準拠して、黄色ブドウ球菌（ＮＢＲＣ１３９４２）を供試菌として、繊技協が認証している抗菌防臭加工を想定した静菌活性値にて評価を行った。
なお、洗濯については、繊技協が定める洗濯方法マニュアル（ＪＩＳ Ｌ ０２１７（１９９５）付表１の１０３法）に準拠した。繊技協基準として静菌活性値が洗濯前（Ｌ−０）及び洗濯１０回後（Ｌ−１０）の繊維製品について２．２より大きい場合には効果があると判定した。
<Evaluation items for antibacterial and antifungal fiber products for textiles>
(1) Antibacterial properties In accordance with the antibacterial evaluation methods and standards of the Japan Fiber Evaluation Technology Council (hereinafter referred to as the Textile Technology Association), tests were conducted as follows.
About the antibacterial property of the textile product before washing (L-0) and after 10 washings (L-10), in accordance with the bacteria absorption method which is a quantitative method of JIS L 1902 (2008), Staphylococcus aureus (NBRC13942) Was evaluated as a bacteriostatic activity value assuming antibacterial and deodorant processing certified by the Sengikyo.
In addition, about washing, it conformed to the washing method manual (JIS L 0217 (1995) Appendix 103 method 103) defined by the Japan Textile Technology Association. It was determined that there was an effect when the bacteriostatic activity value was greater than 2.2 for textile products before washing (L-0) and 10 times after washing (L-10) as a textile technology cooperative standard.
（２）抗かび性（ＪＩＳ法）
洗濯前（Ｌ−０）及び洗濯１０回後（Ｌ−１０）の繊維製品の抗かび性（ＪＩＳ法）について、ＪＩＳ Ｚ ２９１１（２０１０）のかび抵抗性試験「７．繊維製品の試験方法」に準拠して行った。７．ｃ）２）の水道水による注水濯ぎ工程は行わなかった。
なお、洗濯については、繊技協が定める洗濯方法マニュアル「ＪＩＳ Ｌ ０２１７（１９９５）付表１の１０３法」に準拠した。洗濯前（Ｌ−０）及び洗濯１０回後（Ｌ−１０）の繊維製品について、結果表示が０又は１である場合には効果があると判定した。
(2) Antifungal property (JIS method)
About antifungal property (JIS method) of textile products before washing (L-0) and 10 times after washing (L-10), JIS Z 2911 (2010) fungus resistance test “7. Testing method of textile products” In accordance with 7). c) The water rinsing step with tap water of 2) was not performed.
In addition, about washing, it conformed to the washing method manual “JIS L 0217 (1995) Attached Table 103 method” defined by the Japan Science and Technology Association. About the textile product before washing (L-0) and 10 times after washing (L-10), when the result display was 0 or 1, it determined with having an effect.
（３）抗かび性（繊技協法）
洗濯前（Ｌ−０）及び洗濯１０回後（Ｌ−１０）の繊維製品の抗かび性（繊技協法）について、繊技協のＪＥＣＦ３０１の「抗かび加工繊維製品認証基準」に準拠して行った。黒コウジカビを供試菌として、繊技協が認証しているＡ．ｎに対する抗かび活性値を求めた。
なお、洗濯については、繊技協が定める洗濯方法マニュアル（ＪＩＳ Ｌ ０２１７（１９９５）付表１の１０３法）に準拠した。洗濯前（Ｌ−０）及び洗濯１０回後（Ｌ−１０）の繊維製品について、抗かび活性値が２．０以上の場合には効果があると判定した。
(3) Anti-fungal property (Textile Technology Cooperation Act)
The anti-fungal property (textile technology law) of textile products before washing (L-0) and 10 times after washing (L-10) conforms to the “Justification of anti-fungal processed textile products” of FECF 301 I went. B. koji mold is used as a test bacterium and is certified by the Japan Textile Technology Association. The antifungal activity value for n was determined.
In addition, about washing, it conformed to the washing method manual (JIS L 0217 (1995) Appendix 103 method 103) defined by the Japan Textile Technology Association. The textile product before washing (L-0) and after 10 washings (L-10) was judged to be effective when the antifungal activity value was 2.0 or more.
（４）耐光堅牢度
洗濯前（Ｌ−０）の繊維製品の耐光堅牢度について、ＪＩＳ Ｌ ０８４２（２００４）の日光に対する染色堅ろう度試験方法の第５露光法の２級に準拠して行い、変退色用グレースケール（一般社団法人 日本規格協会製）を基準として１級〜５級の判定を行った。５級が最も変退色が少なく、１級が最も変退色が多く、３級以上を耐光堅牢性が良好と判定した。
(4) Light fastness About the light fastness of the textile before washing (L-0), it is performed in accordance with the second exposure method class 2 of the dyeing fastness test method for sunlight of JIS L 0842 (2004), First to fifth grades were determined based on a gray scale for color fading (manufactured by Japan Standards Association). Grade 5 has the least discoloration and color, Grade 1 has the most discoloration, and grade 3 and above were judged to have good light fastness.
＜浸漬処理によるポリエステル繊維製品の染色同浴抗菌抗かび加工における性能評価＞
実施例１
サリチルアニリド１０ｇとα−オレフィン（Ｃ１４−１６）スルホン酸ナトリウム（ネオゲンＡＯ−９０、第一工業製薬株式会社製）５ｇにエタノール８５ｇを加えながら乳化し、抗菌抗かび剤１を得た。
ミニカラー染色機（テキサム技研製）を用いて、上記抗菌抗かび剤１を表１記載の所定の使用濃度、分散染料ダイアニックスレッドＡＣＥ（ダイスタージャパン株式会社製）を０．５％ｏ．ｗ．ｆ．、ニッカサンソルトＲＭ−３４０６（分散均染剤、日華化学株式会社製）を１ｇ／Ｌ、８０質量％の酢酸を０．５ｇ／Ｌ、となるように水に希釈し処理液とし、浴比（ポリエステルニット白布：処理液）１：１５にて、ポリエステルニット白布（ポリエステル１００％、目付：１８０ｇ／ｍ２、未染色）を入れ、１３０℃にて３０分間加熱処理し、８０℃まで冷却し、処理液を排出した。次いで、サンモールＲＣ−７００Ｅ（ソーピング剤、日華化学株式会社製）を１ｇ／Ｌ、ハイドロサルファイトを１ｇ／Ｌ、ソーダ灰を１ｇ／Ｌとなるように水に希釈した処理液を、浴比１：２０になるように加え、８０℃にて１０分間加熱処理し、水洗した後、１２０℃にて３分間乾燥した。得られた抗菌抗かび性繊維製品の性能評価を行い、評価結果を表１に示す。
<Performance evaluation in dyeing bath antibacterial and antifungal processing of polyester fiber products by immersion treatment>
Example 1
Antibacterial and antifungal agent 1 was obtained by emulsifying 85 g of ethanol in 10 g of salicylanilide and 5 g of sodium α-olefin (C14-16) sulfonate (Neogen AO-90, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
Using a mini-color dyeing machine (manufactured by Texam Giken), the above antibacterial and antifungal agent 1 was used at the prescribed concentration shown in Table 1, and the disperse dye Dynic Thread ACE (manufactured by Dystar Japan Co., Ltd.) was 0.5% o. w. f. Nikkasan Salt RM-3406 (dispersion leveling agent, manufactured by Nikka Chemical Co., Ltd.) is diluted with water to 1 g / L and 80% by mass of acetic acid to 0.5 g / L to form a treatment liquid, In a ratio (polyester knit white cloth: treatment liquid) 1:15, a polyester knit white cloth (100% polyester, basis weight: 180 g / m 2 , undyed) is added, heat-treated at 130 ° C. for 30 minutes, and cooled to 80 ° C. Then, the treatment liquid was discharged. Next, a treatment solution diluted with water so that Sunmol RC-700E (soaping agent, manufactured by Nikka Chemical Co., Ltd.) is 1 g / L, hydrosulfite is 1 g / L, and soda ash is 1 g / L The mixture was added so that the ratio was 1:20, heat-treated at 80 ° C. for 10 minutes, washed with water, and dried at 120 ° C. for 3 minutes. The performance of the obtained antibacterial and antifungal fiber product was evaluated, and the evaluation results are shown in Table 1.
実施例２
サリチルアニリド１０ｇとα−オレフィン（Ｃ１４−１６）スルホン酸ナトリウム（ネオゲンＡＯ−９０、第一工業製薬株式会社製）５ｇにブチルグリコール４０ｇと水４５ｇを加えながら乳化し、抗菌抗かび剤２を得た。
抗菌抗かび剤１の代わりに、抗菌抗かび剤２を用いた以外は、実施例１と同様の方法で加工し、得られた抗菌抗かび性繊維製品の性能評価を行い、評価結果を表１に示す。
Example 2
Antibacterial antifungal agent 2 is obtained by emulsifying 10 g of salicylanilide and 5 g of sodium α-olefin (C14-16) sulfonate (Neogen AO-90, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) while adding 40 g of butyl glycol and 45 g of water. It was.
The antibacterial and antifungal agent 2 was processed in the same manner as in Example 1 except that the antibacterial and antifungal agent 2 was used, and the performance of the obtained antibacterial and antifungal fiber product was evaluated. It is shown in 1.
実施例３
サリチルアニリド１０ｇ、α−オレフィン（Ｃ１４−１６）スルホン酸ナトリウム（ネオゲンＡＯ−９０、第一工業製薬株式会社製）５ｇと水８５ｇの混合物を、直径０．５ｍｍガラスビーズを用いてビーズミル（アイメックス株式会社製）にて湿式分散し、抗菌抗かび剤３を得た。５０％積算粒径は０．４５μｍであった。
抗菌抗かび剤１の代わりに、抗菌抗かび剤３を用いた以外は、実施例１と同様の方法で加工し、得られた抗菌抗かび性繊維製品の性能評価を行い、評価結果を表１に示す。
Example 3
A mixture of 10 g of salicylanilide, 5 g of sodium α-olefin (C14-16) sulfonate (Neogen AO-90, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and water 85 g is bead milled using glass beads with a diameter of 0.5 mm (IMEX Co., Ltd.) The antibacterial and antifungal agent 3 was obtained by wet dispersion. The 50% cumulative particle size was 0.45 μm.
The antibacterial and antifungal agent 3 was processed in the same manner as in Example 1 except that the antibacterial and antifungal agent 3 was used, and the resulting antibacterial and antifungal fiber product was evaluated for performance. It is shown in 1.
実施例４
サリチルアニリド１０ｇ、α−オレフィン（Ｃ１４−１６）スルホン酸ナトリウム（ネオゲンＡＯ−９０、第一工業製薬株式会社製）３．５ｇとトリスチレン化フェノールのエチレンオキサイド１６モル付加物３．５ｇに、ブチルジグリコール４０ｇと水４３ｇを加えながら乳化し、抗菌抗かび剤４を得た。抗菌抗かび１の代わりに、抗菌抗かび剤４を用いた以外は、実施例１と同様の方法で加工し、得られた抗菌抗かび性繊維製品の性能評価を行い、評価結果を表１に示す。
Example 4
To 10 g of salicylanilide, 3.5 g of sodium α-olefin (C14-16) sulfonate (Neogen AO-90, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 3.5 g of trioxide-phenol ethylene oxide 16 mol adduct, butyl An antibacterial and antifungal agent 4 was obtained by emulsifying while adding 40 g of diglycol and 43 g of water. The antibacterial and antifungal agent 4 was processed in the same manner as in Example 1 except that the antibacterial and antifungal agent 4 was used. The performance of the obtained antibacterial and antifungal fiber product was evaluated. Shown in
実施例５
５−クロロサリチルアニリド１０ｇとトリスチレン化フェノールのエチレンオキサイド２０モル付加物硫酸エステルナトリウム塩５ｇにエタノール８５ｇを加えながら乳化し、抗菌抗かび剤５を得た。
抗菌抗かび剤１の代わりに、抗菌抗かび剤５を用いた以外は、実施例１と同様の方法で加工し、得られた抗菌抗かび性繊維製品の性能評価を行い、評価結果を表１に示す。
Example 5
Antibacterial and antifungal agent 5 was obtained by emulsifying 85 g of ethanol with 10 g of 5-chlorosalicylanilide and 5 g of an ethylene oxide 20 mol adduct of tristyrenated phenol and sodium sulfate.
The antibacterial and antifungal agent 5 was processed in the same manner as in Example 1 except that the antibacterial and antifungal agent 5 was used, and the performance of the obtained antibacterial and antifungal fiber product was evaluated. It is shown in 1.
実施例６
５−クロロサリチルアニリド１０ｇ、α−オレフィン（Ｃ１４−１６）スルホン酸ナトリウム（ネオゲンＡＯ−９０、第一工業製薬株式会社製）３．５ｇとステアリルアルコールエチレンオキサイド８モル付加物３．５ｇにブチルグリコール４０ｇと水４３ｇを加えながら乳化し、抗菌抗かび剤６を得た。
抗菌抗かび剤１の代わりに、抗菌抗かび剤６を用いた以外は、実施例１と同様の方法で加工し、得られた抗菌抗かび性繊維製品の性能評価を行い、評価結果を表１に示す。
Example 6
10 g of 5-chlorosalicylanilide, 3.5 g of α-olefin (C14-16) sodium sulfonate (Neogen AO-90, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 3.5 g of stearyl alcohol ethylene oxide 8 mol adduct, butyl glycol The mixture was emulsified while adding 40 g and 43 g of water to obtain antibacterial and antifungal agent 6.
The antibacterial and antifungal agent 6 was processed in the same manner as in Example 1 except that the antibacterial and antifungal agent 6 was used, and the resulting antibacterial and antifungal fiber product was evaluated for performance. It is shown in 1.
比較例１
１０％塩化ベンザルコニウム水溶液を抗菌抗かび剤７とした。
抗菌抗かび剤１の代わりに、抗菌抗かび剤７を用いた以外は、実施例１と同様の方法で加工し、得られた抗菌抗かび性繊維製品の性能評価を行い、評価結果を表１に示す。
Comparative Example 1
The 10% aqueous benzalkonium chloride solution was used as the antibacterial and antifungal agent 7.
The antibacterial and antifungal agent 7 was processed in the same manner as in Example 1 except that the antibacterial and antifungal agent 7 was used, and the resulting antibacterial and antifungal fiber product was evaluated for performance. It is shown in 1.
比較例２
ジンクピリチオン１０ｇ、α−オレフィン（Ｃ１４−１６）スルホン酸ナトリウム（ネオゲンＡＯ−９０、第一工業製薬株式会社製）５ｇと水８５ｇの混合物を、直径０．５ｍｍガラスビーズを用いてビーズミル（アイメックス株式会社製）にて湿式分散し、抗菌抗かび剤８を得た。５０％積算粒径は０．４６μｍであった。
抗菌抗かび剤１の代わりに、抗菌抗かび剤８を用いた以外は、実施例１と同様の方法で加工し、得られた抗菌抗かび性繊維製品の性能評価を行い、評価結果を表１に示す。
Comparative Example 2
A mixture of 10 g of zinc pyrithione, 5 g of α-olefin (C14-16) sodium sulfonate (Neogen AO-90, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 85 g of water was added to a bead mill (Imex Corporation) using glass beads with a diameter of 0.5 mm. The antibacterial and antifungal agent 8 was obtained by wet dispersion. The 50% cumulative particle size was 0.46 μm.
The antibacterial and antifungal agent 8 was processed in the same manner as in Example 1 except that the antibacterial and antifungal agent 8 was used, and the performance of the obtained antibacterial and antifungal fiber product was evaluated. It is shown in 1.
比較例３
サリチルアニリド１０ｇとα−オレフィン（Ｃ１４−１６）スルホン酸ナトリウム（ネオゲンＡＯ−９０、第一工業製薬株式会社製）１５ｇにエタノール７５ｇを加えながら乳化し、抗菌抗かび剤９を得た。
抗菌抗かび剤１の代わりに、抗菌抗かび剤９を用いた以外は、実施例１と同様の方法で加工し、得られた抗菌抗かび性繊維製品の性能評価を行い、評価結果を表１に示す。
Comparative Example 3
The antibacterial and antifungal agent 9 was obtained by emulsifying 75 g of ethanol in 10 g of salicylanilide and 15 g of sodium α-olefin (C14-16) sulfonate (Neogen AO-90, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
The antibacterial and antifungal agent 9 was processed in the same manner as in Example 1 except that the antibacterial and antifungal agent 9 was used, and the performance evaluation of the obtained antibacterial and antifungal fiber product was performed. It is shown in 1.
比較例４
抗菌抗かび剤を添加しなかったこと以外は、実施例１と同様の方法で加工し、得られた抗菌抗かび性繊維製品の性能評価を行い、評価結果を表１に示す。
Comparative Example 4
Except that no antibacterial and antifungal agent was added, the performance of the obtained antibacterial and antifungal fiber product was evaluated by the same method as in Example 1, and the evaluation results are shown in Table 1.
＜パディング処理によるポリエステル繊維製品の抗菌抗かび加工における性能評価＞
実施例７
実施例１記載の抗菌抗かび剤１を表２記載の所定の使用濃度、ベッカミンＭ−３（メラニン系樹脂、ＤＩＣ株式会社製）を３ｇ／Ｌ、キャタリストＭ（金属塩系触媒、ＤＩＣ株式会社製）を３ｇ／Ｌとなるように水に希釈し処理液とし、その処理液をパッド浴として、ポリエステルニット白布（ポリエステル１００％、目付：１８０ｇ／ｍ２、未染色）を通し、マングルにて絞り率１００質量％になるように絞り、１２０℃にて３分間乾燥し、さらに１８０℃にて３０秒間乾燥した。得られた抗菌抗かび性繊維製品の性能評価を行い、評価結果を表２に示す。
<Performance evaluation of antibacterial and antifungal processing of polyester fiber products by padding>
Example 7
Antibacterial and antifungal agent 1 described in Example 1 was used at a predetermined concentration described in Table 2, Becamine M-3 (melanin resin, manufactured by DIC Corporation) was 3 g / L, Catalyst M (metal salt catalyst, DIC stock) Company) is diluted to 3 g / L in water to make a treatment liquid, and the treatment liquid is used as a pad bath, and a polyester knit white cloth (100% polyester, basis weight: 180 g / m 2 , undyed) is passed through the mangle. The squeezing rate was 100% by mass, dried at 120 ° C. for 3 minutes, and further dried at 180 ° C. for 30 seconds. The obtained antibacterial and antifungal fiber product was evaluated for performance, and the evaluation results are shown in Table 2.
実施例８〜１１、比較例５〜７
抗菌抗かび剤１の代わりに、各々表２記載の所定の抗菌抗かび剤を用いた以外は、実施例７と同様の方法で加工し、得られた抗菌抗かび性繊維製品の性能評価を行い、評価結果を表２に示す。
Examples 8-11, Comparative Examples 5-7
In place of the antibacterial and antifungal agent 1, each was processed in the same manner as in Example 7 except that the predetermined antibacterial and antifungal agents listed in Table 2 were used. The evaluation results are shown in Table 2.
＜パディング処理による綿繊維製品の抗菌抗かび加工における性能評価＞
実施例１２
実施例１記載の抗菌抗かび剤１を表３記載の所定の使用濃度、ベッカミンＮＳ−１１（グリオキザール系樹脂、ＤＩＣ株式会社製）を５０ｇ／Ｌ、キャタリストＡＣＸ（アミン系触媒、ＤＩＣ株式会社製）を２０ｇ／Ｌとなるように水に希釈し処理液とし、その処理液をパッド浴として、綿ニット白布（綿１００％、目付：１５０ｇ／ｍ２、未染色）を通し、マングルにて絞り率１００質量％になるように絞り、１２０℃にて３分間乾燥し、さらに１５０℃にて６０秒間乾燥した。得られた抗菌抗かび性繊維製品の性能評価を行い、評価結果を表３に示す。
<Performance evaluation in antibacterial and antifungal processing of cotton fiber products by padding>
Example 12
The antibacterial and antifungal agent 1 described in Example 1 was used at a predetermined concentration shown in Table 3, Becamine NS-11 (glyoxal resin, manufactured by DIC Corporation) was 50 g / L, and catalyst ACX (amine catalyst, DIC Corporation). The product is diluted with water to 20 g / L to give a treatment solution, and the treatment solution is used as a pad bath, with a cotton knit white cloth (100% cotton, basis weight: 150 g / m 2 , undyed) passed through a mangle. The squeezing rate was 100% by mass, dried at 120 ° C. for 3 minutes, and further dried at 150 ° C. for 60 seconds. The performance of the obtained antibacterial and antifungal fiber product was evaluated, and the evaluation results are shown in Table 3.
実施例１３〜１６、比較例８〜１０
抗菌抗かび剤１の代わりに、各々表３記載の所定の抗菌抗かび剤を使用した以外は実施例１２と同様の方法で加工を行い、得られた抗菌抗かび性繊維製品の性能評価を行い、評価結果を表３に示す。
Examples 13-16, Comparative Examples 8-10
In place of the antibacterial and antifungal agent 1, each was processed in the same manner as in Example 12 except that the prescribed antibacterial and antifungal agents listed in Table 3 were used, and the performance evaluation of the obtained antibacterial and antifungal fiber product was performed. The evaluation results are shown in Table 3.
表１〜３に示すように、本発明の繊維用抗菌抗かび剤を用いた実施例１〜１６の抗菌抗かび性繊維製品は、抗菌性及び抗かび性を有しており、洗濯１０回後でも充分にその効果が得られている。また、耐光堅牢性の低下も無く、良好な結果であった。つまり本発明の繊維用抗菌抗かび剤は得られる繊維製品の耐光堅牢性を低下させることなく、洗濯耐久性のある抗菌性及び抗かび性を繊維製品に付与することができる。また、実施例１〜６のように浸漬処理における染色同浴加工においても洗濯耐久性のある抗菌性及び抗かび性を付与できており、本発明の繊維用抗菌抗かび剤は、染色同浴加工においても使用可能である。 As shown in Tables 1 to 3, the antibacterial and antifungal fiber products of Examples 1 to 16 using the antibacterial and antifungal agent for fibers of the present invention have antibacterial and antifungal properties and are washed 10 times. Even after that, the effect is sufficiently obtained. Further, the light fastness was not deteriorated, and the result was good. That is, the antibacterial and antifungal agent for fibers of the present invention can impart antibacterial and antifungal properties having durability to washing to the fiber product without reducing the light fastness of the resulting fiber product. Moreover, the antibacterial and antifungal properties having washing durability can be imparted even in the dyeing and bathing process in the immersion treatment as in Examples 1 to 6, and the antibacterial and antifungal agent for fibers of the present invention is dyed and bathing. It can also be used in processing.
一方、従来の低分子有機系抗菌抗かび剤を浸漬処理による染色同浴加工に用いた比較例１では、処理浴中に凝集物が発生し、評価しうる抗菌抗かび性繊維を得ることができなかった。また、パディング処理による加工に用いた比較例５及び８では、洗濯耐久性のある抗かび性が得られなかった。 On the other hand, in Comparative Example 1 in which a conventional low molecular weight organic antibacterial antifungal agent was used for dyeing and bathing processing by dipping, aggregates were generated in the treatment bath, and an antibacterial antifungal fiber that can be evaluated was obtained. could not. Moreover, in Comparative Examples 5 and 8 used for processing by padding treatment, antifungal property having washing durability was not obtained.
従来の金属系抗菌抗かび剤を用いた比較例２、６、９では、洗濯耐久性のある抗かび性が得られず、耐光堅牢性が劣る結果であった。 In Comparative Examples 2, 6, and 9 using conventional metal antibacterial and antifungal agents, antifungal properties having durability for washing could not be obtained, and the light fastness was inferior.
一般式（Ｉ）で表される化合物（Ａ）に対する界面活性剤（Ｂ）の配合量が本発明の請求の範囲外である比較例３の抗菌抗かび性繊維製品は、全体的に抗菌性及び抗かび性が劣り、洗濯耐久性も得られない結果であった。
抗菌抗かび剤を使用せずに加工を施した比較例４、７、１０では、抗菌性及び抗かび性ともに得られなかった。
The antibacterial and antifungal fiber product of Comparative Example 3 in which the blending amount of the surfactant (B) with respect to the compound (A) represented by the general formula (I) is outside the scope of the present invention is generally antibacterial. In addition, the antifungal property was inferior and the washing durability was not obtained.
In Comparative Examples 4, 7, and 10 that were processed without using an antibacterial and antifungal agent, neither antibacterial or antifungal properties were obtained.
本発明の繊維用抗菌抗かび剤は、各種繊維製品に対し、得られる繊維製品の耐光堅牢性を低下させることなく、洗濯耐久性のある抗菌性及び抗かび性を付与することができ、本発明の抗菌抗かび性繊維製品の製造方法によると、耐光堅牢性に優れ、洗濯耐久性のある抗菌抗かび性繊維製品を安定して製造することができる。さらに、本発明の繊維用抗菌抗かび剤は、染色阻害を起こしにくく、染色同浴加工においても使用することができ、工程短縮や加工コストの低減を図ることができる。 The antibacterial and antifungal agent for fibers of the present invention can impart antibacterial and antifungal properties having durability to washing to various fiber products without reducing the light fastness of the resulting fiber products. According to the method for producing an antibacterial and antifungal fiber product of the invention, it is possible to stably produce an antibacterial and antifungal fiber product having excellent light fastness and durability for washing. Furthermore, the antibacterial and antifungal agent for fibers according to the present invention hardly causes dyeing inhibition, and can be used in dyeing and bathing processes, thereby shortening the process and reducing the processing cost.
Claims (3)
前記界面活性剤（Ｂ）のアニオン界面活性剤がα−オレフィンスルホン酸塩またはスチレン化フェノールアルキレンオキサイド付加物硫酸エステル塩であり、そして非イオン界面活性剤がスチレン化フェノールアルキレンオキサイド付加物または炭素数１６〜２４のアルコールのアルキレンオキサイド付加物であり、
前記繊維用抗菌抗かび剤を基準として、前記化合物（Ａ）を３質量％以上かつ１０質量％以下含む、繊維用抗菌抗かび剤。 A compound (A) represented by the following general formula (I), one or more surfactants (B) selected from an anionic surfactant and a nonionic surfactant, an emulsifying dispersion medium ( C) and an emulsified dispersion containing 100 parts by weight of the compound (A) represented by the following general formula (I), selected from anionic surfactants and nonionic surfactants The antibacterial and antifungal agent for fibers, wherein the amount of one or more surfactants (B) is 1 to 99 parts by mass,
The anionic surfactant of the surfactant (B) is an α-olefin sulfonate or a styrenated phenol alkylene oxide adduct sulfate salt, and the nonionic surfactant is a styrenated phenol alkylene oxide adduct or carbon number. An alkylene oxide adduct of 16 to 24 alcohols,
Wherein, based on the fiber for antibacterial and antifungal agents, the compounds comprising (A) a 3 mass% or more and 1 0% by weight or less, for fibers antibacterial and antifungal agents.
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