JP2020015706A - Antibacterial and antifungal agent and antibacterial and antifungal product - Google Patents

Antibacterial and antifungal agent and antibacterial and antifungal product Download PDF

Info

Publication number
JP2020015706A
JP2020015706A JP2018141757A JP2018141757A JP2020015706A JP 2020015706 A JP2020015706 A JP 2020015706A JP 2018141757 A JP2018141757 A JP 2018141757A JP 2018141757 A JP2018141757 A JP 2018141757A JP 2020015706 A JP2020015706 A JP 2020015706A
Authority
JP
Japan
Prior art keywords
compound
antibacterial
antifungal
group
carbon atoms
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.)
Pending
Application number
JP2018141757A
Other languages
Japanese (ja)
Inventor
田中　多加志
Takashi Tanaka
多加志 田中
深雪 梅村
Miyuki Umemura
深雪 梅村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nicca Chemical Co Ltd
Original Assignee
Nicca Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nicca Chemical Co Ltd filed Critical Nicca Chemical Co Ltd
Priority to JP2018141757A priority Critical patent/JP2020015706A/en
Priority to PCT/JP2019/018036 priority patent/WO2020021810A1/en
Publication of JP2020015706A publication Critical patent/JP2020015706A/en
Pending legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dentistry (AREA)
  • Dermatology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Epidemiology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Birds (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Abstract

To provide an antibacterial and antifungal agent that has reduced stimulus while having sufficient antibacterial and antifungal performance, and an antibacterial and antifungal product.SOLUTION: The antibacterial and antifungal agent contains a compound represented by general formula (1). [In the formula (1), one or two of R, R, Rand Rindependently represent a C8-22 alkyl group that may have a hydroxyl group, or a C8-22 alkenyl group that may have a hydroxyl group, the remaining three or two of them independently represent a group represented by general formula (2), Xis a counterion. -(AO)-H (2) {In formula (2), Ais a C1-6 alkylene group or a C2-6 alkenylene group, n is an integer of 1-7, the sum total of n in a molecule of the compound is 9 or less, if n is 2 or more, a plurality of Amay be the same or different.}].SELECTED DRAWING: None

Description

本発明は、抗菌抗かび剤及び抗菌抗かび性製品に関する。   The present invention relates to an antibacterial antifungal agent and an antibacterial antifungal product.

近年、メチシリン耐性黄色ブドウ球菌（ＭＲＳＡ）による院内感染や病原性大腸菌Ｏ−１５７による食中毒など、菌に起因する事故が多発し、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、かびが繁殖しやすい環境となっており、かび由来のアレルギーや日用品の変色などの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を配合した各種の製品が上市されている。   In recent years, accidents caused by bacteria, such as hospital-acquired infections caused by methicillin-resistant Staphylococcus aureus (MRSA) and food poisoning caused by pathogenic Escherichia coli O-157, occur frequently and have become social problems. In general households, molds are easily propagated due to the increase in airtightness of living spaces and the spread of air conditioning equipment, and problems such as allergy derived from mold and discoloration of daily necessities are increasing. Various products containing antibacterial and antifungal agents have been put on the market to address these problems.

抗菌抗かび剤としては塩化ベンザルコニウムなどが広く使用されている。その用途は、消毒剤、殺菌剤、消臭剤、洗剤、毛髪用薬剤、医療薬剤、接着剤、繊維製品や紙製品、プラスチック製品、金属製品、木工製品など多岐にわたる。一方で、塩化ベンザルコニウムには皮膚刺激性があり、皮膚・粘膜の刺激症状として、かゆみ、かぶれ、発疹等の報告がある。   Benzalkonium chloride and the like are widely used as antibacterial and antifungal agents. Its applications range from disinfectants, disinfectants, deodorants, detergents, hair agents, medical agents, adhesives, textiles and paper products, plastic products, metal products, wood products, and more. On the other hand, benzalkonium chloride has skin irritation, and itching, rash, rash and the like have been reported as skin / mucosal irritation symptoms.

低刺激性の抗菌抗かび剤の検討はこれまでにもなされており、例えば、下記特許文献１には、トリメチルドデシルアンモニウム、トリメチルテトラデシルアンモニウム、トリメチルヘキサデシルアンモニウム、トリメチルオクタデシルアンモニウム、トリメチルヤシ油アルキルアンモニウム、ジメチルエチルドデシルアンモニウム、ジメチルエチルテトラデシルアンモニウム、ジメチルエチルヘキサデシルアンモニウム、ジメチルエチルオクタデシルアンモニウム、ジメチルエチルヤシ油アルキルアンモニウム、メチルジエチルドデシルアンモニウム、メチルジエチルテトラデシルアンモニウム、メチルジエチルヘキサデシルアンモニウム、メチルジエチルオクタデシルアンモニウム、メチルジエチルヤシ油アルキルアンモニウム、ジメチルジヘキシルアンモニウム、ジメチルジオクチルアンモニウム、ジメチルジデシルアンモニウム、ジメチルジドデシルアンモニウムなどの第４級アンモニウム基を有し、有機カルボン酸を対イオンとする第４級アンモニウム塩を含有することを特徴とする低刺激性抗菌剤組成物が開示されている。   Studies have been made on hypoallergenic antibacterial antifungal agents. For example, Patent Document 1 listed below discloses trimethyldodecylammonium, trimethyltetradecylammonium, trimethylhexadecylammonium, trimethyloctadecylammonium, and trimethyl coco oil alkyl. Ammonium, dimethylethyldodecylammonium, dimethylethyltetradecylammonium, dimethylethylhexadecylammonium, dimethylethyloctadecylammonium, dimethylethyl coconut oil alkyl ammonium, methyl diethyldodecylammonium, methyldiethyltetradecylammonium, methyldiethylhexadecylammonium, methyldiethyl Octadecyl ammonium, methyl diethyl coconut oil alkyl ammonium, dimethyl Low irritation characterized by containing a quaternary ammonium group having a quaternary ammonium group such as hexyl ammonium, dimethyl dioctyl ammonium, dimethyl didecyl ammonium and dimethyl didodecyl ammonium, and having an organic carboxylic acid as a counter ion. An antimicrobial composition is disclosed.

また、下記特許文献２には、トリメチルドデシルアンモニウム、トリメチルテトラデシルアンモニウム、トリメチルヘキサデシルアンモニウム、トリメチルオクタデシルアンモニウム、トリメチルヤシ油アルキルアンモニウム、ジメチルエチルドデシルアンモニウム、ジメチルエチルテトラデシルアンモニウム、ジメチルエチルヘキサデシルアンモニウム、ジメチルエチルオクタデシルアンモニウム、ジメチルエチルヤシ油アルキルアンモニウム、メチルジエチルドデシルアンモニウム、メチルジエチルテトラデシルアンモニウム、メチルジエチルヘキサデシルアンモニウム、メチルジエチルオクタデシルアンモニウム、メチルジエチルヤシ油アルキルアンモニウム、ジメチルジヘキシルアンモニウム、ジメチルジオクチルアンモニウム、ジメチルジデシルアンモニウム、ジメチルジドデシルアンモニウムなどの第４級アンモニウム基を有し、リン酸を対イオンとする第４級アンモニウム塩を含有することを特徴とする低刺激性抗菌剤組成物が開示されている。   Further, Patent Document 2 described below, trimethyl dodecylammonium, trimethyltetradecylammonium, trimethylhexadecylammonium, trimethyloctadecylammonium, alkylammonium trimethyl cocoate, dimethylethyldodecylammonium, dimethylethyltetradecylammonium, dimethylethylhexadecylammonium, Dimethyl ethyl octadecyl ammonium, dimethyl ethyl coconut oil alkyl ammonium, methyl diethyl dodecyl ammonium, methyl diethyl tetradecyl ammonium, methyl diethyl hexadecyl ammonium, methyl diethyl octadecyl ammonium, methyl diethyl coconut oil alkyl ammonium, dimethyl dihexylammonium, dimethyl dioctylammonium A hypoallergenic antibacterial agent composition comprising a quaternary ammonium group having a quaternary ammonium group such as tildidecyl ammonium and dimethyldidodecyl ammonium and having phosphoric acid as a counter ion is disclosed. ing.

特開平９−１３２５０４号公報JP-A-9-132504 特開平９−７７６１０号公報JP-A-9-77610

しかしながら、これらの第４級アンモニウム塩であっても、皮膚や眼などに対する刺激が十分少ないとは言えず、更に低刺激性の抗菌抗かび剤が求められている。   However, even with these quaternary ammonium salts, irritation to the skin, eyes and the like cannot be said to be sufficiently low, and antibacterial antifungal agents having further low irritation are required.

本発明は、上記事情に鑑みてなされたものであり、十分な抗菌抗かび性能を有しつつ、従来よりも低刺激性の抗菌抗かび剤及び抗菌抗かび性製品を提供することを目的とする。   The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide an antibacterial antifungal agent and an antibacterial antifungal product having sufficient antibacterial and antifungal properties, and having a lower irritation than before. I do.

本発明者らは上記課題を解決するため鋭意研究を重ねた結果、特定の置換基を有する第４級アンモニウム塩が、十分な抗菌抗かび性を示すとともに、皮膚刺激性試験において優れた評価結果が得られることを見出し、この知見に基づき本発明を完成させた。   The present inventors have conducted intensive studies to solve the above problems, and as a result, a quaternary ammonium salt having a specific substituent shows sufficient antibacterial and antifungal properties and an excellent evaluation result in a skin irritation test. Were obtained, and the present invention was completed based on this finding.

すなわち、本発明は、下記一般式（１）で示される化合物を含有する、抗菌抗かび剤を提供する。

Figure 2020015706

［式（１）中、Ｒ１、Ｒ２、Ｒ３及びＲ４のうちの１つ又は２つが、それぞれ独立に、ヒドロキシル基を有していてもよい炭素数８〜２２のアルキル基、又はヒドロキシル基を有していてもよい炭素数８〜２２のアルケニル基を示し、残りの３つ又は２つが、それぞれ独立に、下記一般式（２）で示される基を示し、Ｘ−が対イオンを示す。
−（Ａ１Ｏ）ｎ−Ｈ （２）
｛式（２）中、Ａ１は炭素数１〜６のアルキレン基、又は炭素数２〜６のアルケニレン基を示し、ｎは１〜７の整数を示し、上記化合物の分子内におけるｎの総和は９以下であり、ｎが２以上の場合、複数のＡ１は同一であっても、異なっていてもよい。｝］ That is, the present invention provides an antibacterial antifungal agent containing a compound represented by the following general formula (1).
Figure 2020015706
[In the formula (1), one or two of R 1 , R 2 , R 3, and R 4 are each independently an alkyl group having 8 to 22 carbon atoms which may have a hydroxyl group, or an alkenyl group having 8 to 22 carbon atoms which may have a hydroxyl group, but the remaining three or two, each independently represent a group represented by the following general formula (2), X - is a counter ion Is shown.
- (A 1 O) n -H (2)
中 In the formula (2), A 1 represents an alkylene group having 1 to 6 carbon atoms or an alkenylene group having 2 to 6 carbon atoms, n represents an integer of 1 to 7, and the sum of n in the molecule of the compound. Is 9 or less, and when n is 2 or more, a plurality of A 1 may be the same or different. ｝]

本発明の抗菌抗かび剤によれば、上記化合物を含むことにより、従来よりも低刺激性でありながら、十分な抗菌抗かび性能を付与することができる。   According to the antibacterial and antifungal agent of the present invention, by containing the above compound, sufficient antibacterial and antifungal performance can be imparted while being less irritating than before.

本発明はまた、上記本発明の抗菌抗かび剤によって抗菌抗かび性が付与された抗菌抗かび性製品を提供する。   The present invention also provides an antibacterial and antifungal product to which antibacterial and antifungal properties are imparted by the above antibacterial and antifungal agent of the present invention.

本発明の抗菌抗かび性製品は、十分な抗菌抗かび性能を有しつつ、製品が皮膚に触れる場合であっても従来よりも刺激が少ないものになり得る。   The antibacterial and antifungal product of the present invention has sufficient antibacterial and antifungal properties, and can be less irritating than conventional products even when the product touches the skin.

本発明は、上記一般式（１）で示される化合物を含有する皮膚用洗浄剤を提供することができる。   The present invention can provide a skin cleanser containing the compound represented by the general formula (1).

本発明によれば、十分な抗菌抗かび性能を有しつつ、従来よりも低刺激性の抗菌抗かび剤及び抗菌抗かび性製品を提供することができる。   According to the present invention, it is possible to provide an antibacterial antifungal agent and an antibacterial antifungal product which have sufficient antibacterial and antifungal properties and are less irritating than conventional ones.

以下、本発明の好適な実施形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。   Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

［抗菌抗かび剤］
本実施形態の抗菌抗かび剤は、下記一般式（１）で示される化合物（以下、「化合物（１）」という場合もある）を含有する。

Figure 2020015706

［式（１）中、Ｒ１、Ｒ２、Ｒ３及びＲ４のうちの１つ又は２つが、それぞれ独立に、ヒドロキシル基を有していてもよい炭素数８〜２２のアルキル基、又はヒドロキシル基を有していてもよい炭素数８〜２２のアルケニル基を示し、残りの３つ又は２つが、それぞれ独立に、下記一般式（２）で示される基を示し、Ｘ−が対イオンを示す。
−（Ａ１Ｏ）ｎ−Ｈ （２）
｛式（２）中、Ａ１は炭素数１〜６のアルキレン基、又は炭素数２〜６のアルケニレン基を示し、ｎは１〜７の整数を示し、上記化合物の分子内におけるｎの総和は９以下であり、ｎが２以上の場合、複数のＡ１は同一であっても、異なっていてもよい。｝］ [Antibacterial and antifungal agent]
The antibacterial antifungal agent of the present embodiment contains a compound represented by the following general formula (1) (hereinafter, also referred to as “compound (1)”).
Figure 2020015706
[In the formula (1), one or two of R 1 , R 2 , R 3, and R 4 are each independently an alkyl group having 8 to 22 carbon atoms which may have a hydroxyl group, or an alkenyl group having 8 to 22 carbon atoms which may have a hydroxyl group, but the remaining three or two, each independently represent a group represented by the following general formula (2), X - is a counter ion Is shown.
- (A 1 O) n -H (2)
中 In the formula (2), A 1 represents an alkylene group having 1 to 6 carbon atoms or an alkenylene group having 2 to 6 carbon atoms, n represents an integer of 1 to 7, and the sum of n in the molecule of the compound. Is 9 or less, and when n is 2 or more, a plurality of A 1 may be the same or different. ｝]

抗菌抗かび性能及び低皮膚刺激性の観点から、化合物（１）は、上記一般式（２）中のｎが１〜４である基を有することが好ましく、ｎが１である基を有することがより好ましく、上記一般式（２）で示される基として−Ｃ２Ｈ４ＯＨ及び／又は−Ｃ３Ｈ６ＯＨを有することが更に好ましい。 From the viewpoints of antibacterial antifungal performance and low skin irritation, the compound (1) preferably has a group in which n in the general formula (2) is 1 to 4, and has a group in which n is 1. still more preferably, it is more preferred to have a -C 2 H 4 OH and / or -C 3 H 6 OH as the group represented by the general formula (2).

抗菌抗かび性能及び低皮膚刺激性を高水準で両立する観点から、化合物（１）は、分子内のｎの総和が３以下であることが好ましく、Ｒ１、Ｒ２、Ｒ３及びＲ４のうちの３つが−Ｃ２Ｈ４ＯＨ及び／又は−Ｃ３Ｈ６ＯＨであることがより好ましい。 From the viewpoint of achieving high levels of antibacterial and antifungal performance and low skin irritation, compound (1) preferably has a total of n of 3 or less in the molecule, and R 1 , R 2 , R 3 and R 4. more preferably three of the is a -C 2 H 4 OH and / or -C 3 H 6 OH.

抗菌抗かび性能の観点から、化合物（１）は、炭素数１２〜１８のアルキル基を有することが好ましい。   From the viewpoint of antibacterial and antifungal performance, the compound (1) preferably has an alkyl group having 12 to 18 carbon atoms.

抗菌抗かび性能及び低皮膚刺激性を高水準で両立する観点から、化合物（１）は、Ｒ１、Ｒ２、Ｒ３及びＲ４のうちの１つが、ヒドロキシル基を有していてもよい炭素数１２〜１８のアルキル基、又はヒドロキシル基を有していてもよい炭素数１２〜１８のアルケニル基であり、残りの３つが、上記一般式（２）中のＡ１が炭素数１〜６のアルキレン基であり、ｎが１である基であることが好ましく、Ｒ１、Ｒ２、Ｒ３及びＲ４のうちの１つが、炭素数１２〜１８のアルキル基であり、Ｒ１、Ｒ２、Ｒ３及びＲ４のうちの３つが−Ｃ２Ｈ４ＯＨ及び／又は−Ｃ３Ｈ６ＯＨであることがより好ましい。 From the viewpoint of achieving high levels of antibacterial and antifungal performance and low skin irritation, compound (1) may have one of R 1 , R 2 , R 3 and R 4 having a hydroxyl group. An alkyl group having 12 to 18 carbon atoms, or an alkenyl group having 12 to 18 carbon atoms which may have a hydroxyl group, and the remaining three are such that A 1 in the above general formula (2) has 1 to 1 carbon atoms. 6 is an alkylene group, and n is preferably a group in which one of R 1 , R 2 , R 3 and R 4 is an alkyl group having 12 to 18 carbon atoms, and R 1 , R 2, and more preferably three of R 3 and R 4 is a -C 2 H 4 OH and / or -C 3 H 6 OH.

Ｘ−は、第４級アンモニウム化合物と対イオンを形成することができるアニオンであれば特に制限はなく、例えば、塩化物イオン、臭化物イオンなどのハロゲンアニオン；硫酸イオン、硝酸イオン、リン酸イオンなど無機アニオン；ギ酸イオン、酢酸イオン、プロピオン酸イオン、グルコン酸イオン、乳酸イオン、フマル酸イオン、マレイン酸イオン、アジピン酸イオンなどの一価又は多価カルボン酸に由来するアニオン；ポリオキシアルキレンアルキルエーテルリン酸エステルイオン、アルキル又はアリールリン酸エステルイオンなどのリン酸エステルアニオン；アルキルベンゼンスルホン酸イオン、アルキルスルホン酸イオンなどスルホン酸アニオン；メチルカーボネートイオン、エチルカーボネートイオンなどのアルキルカーボーネートアニオン；アルキル硫酸エステルイオン、アルケニル硫酸エステルイオン、ポリオキシアルキレンアルキルエーテル硫酸エステルイオンなど硫酸エステルアニオンなどを挙げることができる。 X − is not particularly limited as long as it is an anion capable of forming a counter ion with the quaternary ammonium compound, and examples thereof include halogen anions such as chloride ions and bromide ions; sulfate ions, nitrate ions, and phosphate ions. Inorganic anions; anions derived from monovalent or polyvalent carboxylic acids such as formate, acetate, propionate, gluconate, lactate, fumarate, maleate, and adipate; polyoxyalkylene alkyl ethers Phosphate anion such as phosphate ion, alkyl or aryl phosphate ion; Sulfonate anion such as alkylbenzene sulfonate ion or alkyl sulfonate ion; Alkyl carbonate such as methyl carbonate ion or ethyl carbonate ion And a sulfate anion such as an alkyl sulfate ion, an alkenyl sulfate ion, and a polyoxyalkylene alkyl ether sulfate ion.

化合物（１）は、例えば、以下の方法で製造することができる。   Compound (1) can be produced, for example, by the following method.

＜Ｒ１、Ｒ２、Ｒ３及びＲ４のうちの１つが炭素数８〜２２のアルキル基（若しくはアルケニル基）であり、３つが上記一般式（２）で示される基である化合物＞
このような化合物は、例えば、下記に示される方法等により得ることができる。 <Compound in which one of R 1 , R 2 , R 3 and R 4 is an alkyl group (or alkenyl group) having 8 to 22 carbon atoms, and three are groups represented by the above general formula (2)>
Such a compound can be obtained, for example, by the method shown below.

（ｉ）トリエタノールアミンに炭素数８〜２２のアルキル（若しくはアルケニル）ハライドを反応させる方法。
（ｉｉ）トリエタノールアミンにアルキレンオキシドを付加し、その後、炭素数８〜２２のアルキル（若しくはアルケニル）ハライドを反応させる方法。
（ｉｉｉ）炭素数８〜２２のモノアルキル（若しくはモノアルケニル）アミンにアルキレンオキシドを付加し、その後、下記一般式（ａ−１）で示される化合物を用いて４級化する方法。
Ｙ−Ｒ１１−ＯＨ （ａ−１）
［式（ａ−１）中、Ｙはハロゲン原子を示し、Ｒ１１が炭素数２〜６のアルキレン基（若しくはアルケニレン基）を示す。］
（ｉＶ）炭素数８〜２２のモノアルキル（若しくはモノアルケニル）アミンにアルキレンオキシドを付加し、その後、酸で中和した後、アルキレンオキシドを反応させて４級化する方法。 (I) A method in which triethanolamine is reacted with an alkyl (or alkenyl) halide having 8 to 22 carbon atoms.
(Ii) A method in which an alkylene oxide is added to triethanolamine and then reacted with an alkyl (or alkenyl) halide having 8 to 22 carbon atoms.
(Iii) A method in which an alkylene oxide is added to a monoalkyl (or monoalkenyl) amine having 8 to 22 carbon atoms, and then quaternized using a compound represented by the following general formula (a-1).
Y-R 11 -OH (a- 1)
[In the formula (a-1), Y represents a halogen atom, and R 11 represents an alkylene group (or alkenylene group) having 2 to 6 carbon atoms. ]
(Iv) A method of adding an alkylene oxide to a monoalkyl (or monoalkenyl) amine having 8 to 22 carbon atoms, neutralizing the resultant with an acid, and then reacting the alkylene oxide to quaternize the amine.

＜Ｒ１、Ｒ２、Ｒ３及びＲ４のうちの２つが炭素数８〜２２のアルキル基（若しくはアルケニル基）であり、２つが上記一般式（２）で示される基である化合物＞
このような化合物は、例えば、下記に示される方法等により得ることができる。 <Compound in which two of R 1 , R 2 , R 3 and R 4 are an alkyl group (or alkenyl group) having 8 to 22 carbon atoms, and two are groups represented by the above general formula (2)>
Such a compound can be obtained, for example, by the method shown below.

（ｉ）炭素数８〜２２のジアルキル（若しくはジアルケニル）アミンにアルキレンオキシドを付加し、その後、酸で中和した後、アルキレンオキシドを反応させて４級化する方法。
（ｉｉ）炭素数８〜２２のモノアルキル（若しくはモノアルケニル）アミンにアルキレンオキシドを付加し、その後、炭素数８〜２２のアルキル（若しくはアルケニル）ハライドを反応させ４級化する方法。 (I) A method of adding an alkylene oxide to a dialkyl (or dialkenyl) amine having 8 to 22 carbon atoms, neutralizing the resultant with an acid, and then reacting the alkylene oxide to quaternize the amine.
(Ii) A method in which an alkylene oxide is added to a monoalkyl (or monoalkenyl) amine having 8 to 22 carbon atoms, and then quaternized by reacting with an alkyl (or alkenyl) halide having 8 to 22 carbon atoms.

化合物（１）は、単独で又は二種以上を組み合わせて配合することができる。   Compound (1) can be used alone or in combination of two or more.

本実施形態の抗菌抗かび剤は、その用途に応じて、非イオン界面活性剤、アニオン界面活性剤、上記一般式（１）で示される化合物以外のカチオン界面活性剤、両性界面活性剤等の界面活性剤；アクリル樹脂、ウレタン樹脂、エポキシ樹脂、ポリアミド樹脂、シリコーン樹脂等のバインダー樹脂；ヘキシレンジイソシアネート、トルエンジイソシアネート等のイソシアネート化合物等の架橋剤；これらをブロックさせたブロックイソシアネート化合物等の架橋剤、パール剤、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、水等の他の成分を含有することができる。これらは、単独で又は二種以上を組み合わせて配合することができる。   The antibacterial and antifungal agent of the present embodiment may be, for example, a nonionic surfactant, an anionic surfactant, a cationic surfactant other than the compound represented by the general formula (1), an amphoteric surfactant, or the like. Surfactant; binder resin such as acrylic resin, urethane resin, epoxy resin, polyamide resin and silicone resin; crosslinking agent such as isocyanate compound such as hexylene diisocyanate and toluene diisocyanate; crosslinking agent such as blocked isocyanate compound which blocked these. And other components such as pearlescent agents, softening agents, leveling agents, penetrants, leveling agents, antistatic agents, chelating agents, antioxidants, defoamers, solvents, and water. These can be used alone or in combination of two or more.

上記非イオン界面活性剤としては、特に限定されるものではないが、例えば、ポリオキシアルキレンオレイルエーテル、ポリオキシアルキレンラウリルエーテル、モノステアリン酸ポリオキシアルキレングリセリン、モノオレイン酸ポリオキシアルキレンソルビタン、モノラウリン酸ポリオキシアルキレンソルビタン、モノラウリン酸ポリオキシアルキレンソルビット、ポリオキシアルキレン硬化ヒマシ油、ポリオキシアルキレンラノリン、モノオレイン酸ポリアルキレングリコール、セスキオレイン酸ソルビタン、モノステアリン酸アルキレングリコール、ショ糖脂肪酸エステル、ヤシ油脂肪酸ジエタノールアミド等が挙げられる。   Examples of the nonionic surfactant include, but are not particularly limited to, for example, polyoxyalkylene oleyl ether, polyoxyalkylene lauryl ether, polyoxyalkylene glycerin monostearate, polyoxyalkylene sorbitan monooleate, monolauric acid Polyoxyalkylene sorbitan, polyoxyalkylene sorbit monolaurate, polyoxyalkylene hydrogenated castor oil, polyoxyalkylene lanolin, polyalkylene glycol monooleate, sorbitan sesquioleate, alkylene glycol monostearate, sucrose fatty acid ester, coconut fatty acid Diethanolamide and the like.

上記アニオン界面活性剤としては、特に限定されるものではないが、例えば、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、ベヘニン酸、ウンデシレン酸、オキシステアリン酸、リノール酸、ラノリン脂肪酸、イソステアリン酸、イソパルミチン酸、イソトリデカン酸、イソノナン酸、２−エチルヘキサン酸、ヤシ油脂肪酸等の炭素数１２〜２２の高級脂肪酸塩；アルキルスルホン酸塩、アルケニルスルホン酸塩、ポリオキシアルキレンアルキルエーテルのスルホン酸塩、ポリオキシアルキレンアルケニルエーテルのスルホン酸塩、ポリオキシアルキレンアルキルフェニルエーテルのスルホン酸塩、ポリオキシアルキレンアルケニルフェニルエーテルのスルホン酸塩などのスルホン酸塩；アルキル硫酸エステル塩、アルケニル硫酸エステル塩、ポリオキシアルキレンアルキルエーテルの硫酸エステル塩、ポリオキシアルキレンアルケニルエーテルの硫酸エステル塩、ポリオキシアルキレンアルキルフェニルエーテルの硫酸エステル塩、ポリオキシアルキレンアルケニルフェニルエーテルの硫酸エステル塩などの硫酸エステル塩；アルキルリン酸エステル塩、アルケニルリン酸エステル塩、ポリオキシアルキレンアルキルエーテルのリン酸エステル塩、ポリオキシアルキレンアルケニルエーテルのリン酸エステル塩、ポリオキシアルキレンアルキルフェニルエーテルのリン酸エステル塩、ポリオキシアルキレンアルケニルフェニルエーテルのリン酸エステル塩などのリン酸エステル塩等が挙げられる。   The anionic surfactant is not particularly limited, for example, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, undecylenic acid, oxystearic acid, linoleic acid, lanolin fatty acid, Higher fatty acid salts having 12 to 22 carbon atoms such as isostearic acid, isopalmitic acid, isotridecanoic acid, isononanoic acid, 2-ethylhexanoic acid, and coconut oil fatty acids; alkyl sulfonates, alkenyl sulfonates, and polyoxyalkylene alkyl ethers Sulfonates such as sulfonates, polyoxyalkylene alkenyl ether sulfonates, polyoxyalkylene alkyl phenyl ether sulfonates, and polyoxyalkylene alkenyl phenyl ether sulfonates; alkyl sulfates; Sulfuric acid esters such as lucenyl sulfate, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, polyoxyalkylene alkyl phenyl ether sulfate, and polyoxyalkylene alkenyl phenyl ether sulfate Salts: alkyl phosphate salts, alkenyl phosphate salts, polyoxyalkylene alkyl ether phosphate salts, polyoxyalkylene alkenyl ether phosphate salts, polyoxyalkylene alkyl phenyl ether phosphate salts, polyoxy Phosphoric acid ester salts such as a phosphoric acid ester salt of alkylene alkenyl phenyl ether and the like.

上記カチオン界面活性剤としては、特に限定されるものではないが、例えば、アルキルアミンのアルキレンオキシド高モル付加物の塩、アルケニルアミンのアルキレンオキシド高モル付加物の塩、アルキルアミンのアルキレンオキシド高モル付加物の４級アンモニウム塩、アルケニルアミンのアルキレンオキシド高モル付加物の４級アンモニウム塩、高分子ポリカチオン化合物等が挙げられる。   Examples of the cationic surfactant include, but are not particularly limited to, a salt of an alkylamine alkylene oxide high molar adduct of an alkylamine, a salt of an alkylene oxide high molar adduct of an alkenylamine, an alkylamine alkylene oxide high molar Examples include quaternary ammonium salts of adducts, quaternary ammonium salts of high-molar adducts of alkylene oxides of alkenylamine, and high molecular weight polycation compounds.

上記両面界面活性剤としては、特に限定されるものではないが、例えば、ラウリルジメチルアミノ酢酸ベタイン、塩化アルキルジアミノエチルグリシン、β−ラウリルアミノプロピオン酸ナトリウム、２−アルキル−Ｎ−カルボキシメチル−Ｎ−ヒドロキシエチルイミダゾリニウムベタイン等が挙げられる。   The double-sided surfactant is not particularly limited. For example, lauryl dimethylamino acetate betaine, alkyldiaminoethyl glycine chloride, sodium β-laurylaminopropionate, 2-alkyl-N-carboxymethyl-N- Hydroxyethyl imidazolinium betaine and the like.

上記パール剤としては、特に限定されるものではないが、例えば、エチレングリコールのステアリン酸エステル、ジエチレングリコールのステアリン酸エステル、トリエチレングリコールのステアリン酸エステルなどが挙げられる。具体的には、エチレングリコールモノステアレート、エチレングリコールジステアレート、ジエチレングリコールモノステアレート、ジエチレングリコールジステアレート、トリエチレングリコールモノステアレート、トリエチレングリコールジステアレート等が挙げられる。   Examples of the pearling agent include, but are not particularly limited to, ethylene glycol stearic acid ester, diethylene glycol stearic acid ester, and triethylene glycol stearic acid ester. Specific examples include ethylene glycol monostearate, ethylene glycol distearate, diethylene glycol monostearate, diethylene glycol distearate, triethylene glycol monostearate, and triethylene glycol distearate.

上記溶剤としては、特に限定されるものではないが、例えば、メタノール、エタノール、イソプロピルアルコール、ブタノール等の低級アルコール；エチレングリコール、ジエチレングリコール、プロピレングリコール、ヘキサメチレングリコール、ヘキシレングリコール等のグリコール；グリセリン、ソルビトール等の多価アルコールが挙げられる。   Examples of the solvent include, but are not limited to, lower alcohols such as methanol, ethanol, isopropyl alcohol, and butanol; glycols such as ethylene glycol, diethylene glycol, propylene glycol, hexamethylene glycol, and hexylene glycol; glycerin; And polyhydric alcohols such as sorbitol.

本実施形態の抗菌抗かび剤によれば、上記一般式（１）で示される化合物を含むことにより、従来よりも低刺激性でありながら、十分な抗菌抗かび性能を付与することができる。   According to the antibacterial and antifungal agent of the present embodiment, by including the compound represented by the general formula (1), sufficient antibacterial and antifungal performance can be imparted while being less irritating than before.

本実施形態の抗菌抗かび剤がこのような効果を奏することができる理由について本発明者らは以下のとおり考えている。まず、上記一般式（１）で示される化合物は、皮膚刺激性のある塩化ベンザルコニウムやジデシルジメチルアンモニウム塩などの従来の第４級アンモニウム塩が有している短鎖アルキル基若しくは短鎖アルケニル基やベンジル基を有していない。その一方で、上記一般式（１）で示される化合物は、第４級アンモニウム基の置換基として、特定の炭素数のアルキル基若しくはアルケニル基と上記一般式（２）で示される基とを所定の置換数で有している。これにより、第４級アンモニウム塩としての抗菌抗かび性能は十分維持されつつ、従来よりも皮膚に対する刺激が一層少ない特性が得られたものと本発明者らは推察する。   The present inventors consider the reason why the antibacterial antifungal agent of the present embodiment can exert such an effect as follows. First, the compound represented by the general formula (1) is a short-chain alkyl group or a short-chain alkyl group of a conventional quaternary ammonium salt such as benzalkonium chloride or didecyldimethylammonium salt having skin irritation. Has no alkenyl or benzyl group. On the other hand, in the compound represented by the general formula (1), an alkyl group or an alkenyl group having a specific carbon number and a group represented by the general formula (2) are specified as substituents of the quaternary ammonium group. With the number of substitutions. Thus, the present inventors speculate that the antibacterial and antifungal properties of the quaternary ammonium salt were sufficiently maintained, and the property of causing less irritation to the skin than before was obtained.

＜抗菌抗かび性製品＞
本実施形態の抗菌抗かび性製品は、上記本実施形態の抗菌抗かび剤によって抗菌抗かび性が付与されている。なお、抗菌抗かび剤によって抗菌抗かび性が付与されているとは、製品が抗菌抗かび剤を含むこと、及び、製品が抗菌抗かび剤によって処理されていることの意味を包含する。本実施形態の抗菌抗かび性製品は、例えば、液状洗剤；固体洗剤；消毒剤；殺菌剤；噴霧用液体等に本実施形態の抗菌抗かび剤を配合したり、本実施形態の抗菌抗かび剤を用いて繊維製品等の表面に化合物（１）を付着させたり、樹脂製品等に本実施形態の抗菌抗かび剤を配合して化合物（１）を練りこむことなどによって得ることができる。すなわち、本実施形態の抗菌抗かび性製品は、化合物（１）を含むものであってもよい。 <Antibacterial and antifungal products>
The antibacterial and antifungal product of this embodiment is provided with antibacterial and antifungal properties by the antibacterial and antifungal agent of the above embodiment. The expression that the antifungal agent is imparted with the antifungal agent includes that the product contains the antifungal agent and that the product is treated with the antifungal agent. The antibacterial / antifungal product of the present embodiment may be, for example, a liquid detergent; a solid detergent; a disinfectant; a germicide; The compound (1) can be obtained by attaching the compound (1) to the surface of a fiber product or the like using an agent, compounding the compound (1) with the antibacterial antifungal agent of the present embodiment mixed with a resin product or the like. That is, the antibacterial and antifungal product of the present embodiment may contain the compound (1).

本実施形態の抗菌抗かび性製品は、本実施形態に係る抗菌抗かび剤に含まれる化合物（１）によって抗菌抗かび性が付与され、十分な抗菌抗かび性能を有しつつ、皮膚に直接触れる場合であっても刺激が少ないものになり得る。   The antibacterial and antifungal product of the present embodiment is provided with antibacterial and antifungal properties by the compound (1) contained in the antibacterial and antifungal agent according to the present embodiment, and has a sufficient antibacterial and antifungal performance while being directly applied to the skin Even when touching, it can be less irritating.

抗菌抗かび性製品としては、例えば、液状洗剤；固体洗剤；消毒剤；殺菌剤；噴霧用液体；その他の液状製品；ゲル状製品；コーティング剤；樹脂用添加剤；繊維製品；紙製品及び樹脂製品が挙げられる。   Antibacterial and antifungal products include, for example, liquid detergents; solid detergents; disinfectants; disinfectants; sprayable liquids; other liquid products; gel-like products; coatings; Products.

本実施形態に係る液状洗剤又は固体洗剤は、本実施形態の抗菌抗かび剤を、化合物（１）の含有量が液状洗剤又は固体洗剤全量に対して０．０１〜２０質量％となる割合で含むことができる。抗菌抗かび性及び経済性の観点から、液状洗剤又は固体洗剤における化合物（１）の含有量は、液状洗剤又は固体洗剤全量に対して０．１〜５質量％となることが好ましい。   The liquid detergent or the solid detergent according to the present embodiment comprises the antibacterial antifungal agent according to the present embodiment in a ratio such that the content of the compound (1) is 0.01 to 20% by mass based on the total amount of the liquid detergent or the solid detergent. Can be included. From the viewpoints of antibacterial and antifungal properties and economy, the content of the compound (1) in the liquid detergent or solid detergent is preferably 0.1 to 5% by mass based on the total amount of the liquid detergent or solid detergent.

本実施形態に係る液状洗剤又は固体洗剤によれば、家庭用洗濯、工業用洗濯、台所、浴室、洗面所及びトイレ等の水回り、洗濯機、並びに、洗顔、手洗い（ハンドソープ、消毒用スプレー）及び身体洗浄（ボディソープ、シャンプー、リンスなど）等の皮膚用洗浄などに使用され、種々の細菌やかびの発生を抑制することができる。また、使用の際の手荒れを抑制することができる。低皮膚刺激性の点で、本実施形態の液状洗剤又は固体洗剤は皮膚用洗浄剤であることが好ましい。   According to the liquid detergent or the solid detergent according to the present embodiment, household laundry, industrial laundry, kitchen, bathroom, lavatory and toilet, etc., water washing machine, face washing, hand washing (hand soap, spray for disinfection) ) And body washing (body soap, shampoo, rinse, etc.) and the like, and can suppress the occurrence of various bacteria and mold. In addition, rough hands during use can be suppressed. From the viewpoint of low skin irritation, the liquid detergent or solid detergent of the present embodiment is preferably a skin detergent.

本実施形態に係る液状洗剤又は固体洗剤は、液状洗剤又は固体洗剤に使われる従来公知の成分を含むことができる。そのような成分としては、例えば、界面活性剤、柔軟剤、漂白剤、パール剤、保湿剤及び安定剤等が挙げられる。   The liquid detergent or the solid detergent according to the present embodiment may include a conventionally known component used in the liquid detergent or the solid detergent. Such components include, for example, surfactants, softeners, bleaches, pearlescent agents, humectants, stabilizers, and the like.

本実施形態に係る医療用などの消毒剤及び殺菌剤は、本実施形態の抗菌抗かび剤を水、メタノール、エタノール及びイソプロパノールなどの低級アルコールなどの有機溶剤、並びにこれらの混合溶媒などにより希釈して使用することができる。消毒性及び殺菌性の観点から、消毒剤及び殺菌剤における化合物（１）の含有量は、消毒剤及び殺菌剤全量に対して０．０００１〜５質量％となることが好ましく、０．００１〜１質量％となることが更に好ましい。   The disinfectant and disinfectant for medical use according to the present embodiment is obtained by diluting the antibacterial antifungal agent of the present embodiment with water, an organic solvent such as a lower alcohol such as methanol, ethanol and isopropanol, and a mixed solvent thereof. Can be used. From the viewpoint of disinfectant and bactericidal properties, the content of the compound (1) in the disinfectant and the bactericide is preferably 0.0001 to 5% by mass based on the total amount of the disinfectant and the bactericide, and 0.001 to 5% by mass. More preferably, it is 1% by mass.

本実施形態に係る噴霧用液体は、本実施形態の抗菌抗かび剤を、化合物（１）の含有量が噴霧用液体全量に対して０．０１〜１００質量％となる割合で含むことができる。抗菌抗かび性の観点から、噴霧用液体における化合物（１）の含有量は、０．１〜９０質量％となることが好ましい。   The liquid for spraying according to the present embodiment can contain the antibacterial and antifungal agent of the present embodiment at a ratio where the content of the compound (1) is 0.01 to 100% by mass relative to the total amount of the liquid for spraying. . From the viewpoint of antibacterial and antifungal properties, the content of the compound (1) in the spray liquid is preferably 0.1 to 90% by mass.

本実施形態に係る噴霧用液体は、化合物（１）を、単独で、又は水、メタノール、エタノール若しくはイソプロパノール等の低級アルコール、又はこれらの混合溶媒などで希釈することによって得ることができる。本実施形態の噴霧用液体を、台所、浴室、洗面所及びトイレ等の水回りの壁、床並びにそれらにある物品、寝具、衣類、カーペット、靴、紙、プラスチック製品、陶器、並びに、フィルターなどの細菌やかびが発生する可能性がある箇所に適量噴霧することによって、細菌やかびの発生を抑制することができる。また、本実施形態の噴霧用液体によれば、対象物に抗菌抗かび加工を施すことができる。さらに消毒用に手に適量噴霧することによって、細菌やかびの発生を抑制することができる。また、使用の際の手荒れを抑制することができる。   The liquid for spraying according to the present embodiment can be obtained by diluting the compound (1) alone or with water, a lower alcohol such as methanol, ethanol or isopropanol, or a mixed solvent thereof. The liquid for spraying of the present embodiment may be applied to kitchen, bathroom, lavatory, toilet and other water-around walls, floors and the articles, bedding, clothing, carpet, shoes, paper, plastic products, pottery, filters, etc. By spraying an appropriate amount on a place where there is a possibility that the germs and mold will occur, the occurrence of germs and mold can be suppressed. Further, according to the spray liquid of the present embodiment, an antibacterial and antifungal process can be applied to the target object. Furthermore, by spraying an appropriate amount on the hand for disinfection, the occurrence of bacteria and mold can be suppressed. In addition, rough hands during use can be suppressed.

本実施形態に係るゲル状製品としては、例えば、ゲル状芳香剤、ゲル状消臭剤、湿布薬及びゲル状石けんが挙げられる。これらのゲル状製品は、本実施形態の抗菌抗かび剤を、化合物（１）の含有量がゲル状製品全量に対して０．００１〜２０質量％となる割合で含むことができる。抗菌抗かび性及び経済性の観点から、ゲル状製品における化合物（１）の含有量は、０．０１〜５質量％となることが好ましい。   Examples of the gel-like product according to the present embodiment include a gel-like fragrance, a gel-like deodorant, a poultice, and a gel-like soap. These gel-like products can contain the antibacterial antifungal agent of the present embodiment at a ratio where the content of the compound (1) is 0.001 to 20% by mass relative to the total amount of the gel-like products. From the viewpoints of antibacterial and antifungal properties and economy, the content of the compound (1) in the gel product is preferably 0.01 to 5% by mass.

本実施形態に係るゲル状製品は、種々の細菌やかびに対し有効な抗菌性及び抗かび性を有し、細菌やかびに起因する変色や異臭が発生しにくいものになり得る。また、本実施形態に係るゲル状製品は、皮膚に直接触れる場合であっても刺激が少ないものになり得る。   The gel-like product according to the present embodiment has effective antibacterial and antifungal properties against various bacteria and molds, and may be less likely to cause discoloration and odor due to the bacteria and molds. Further, the gel-like product according to the present embodiment can be less irritating even when directly touching the skin.

本実施形態に係るコーティング剤は、本実施形態の抗菌抗かび剤を、化合物（１）の含有量がコーティング剤全量に対して０．０１〜９５質量％となる割合で含むことができる。抗菌抗かび性の観点から、コーティング剤における化合物（１）の含有量は、０．１〜９０質量％となることが好ましい。   The coating agent according to the present embodiment can contain the antibacterial and antifungal agent of the present embodiment at a ratio such that the content of the compound (1) is 0.01 to 95% by mass based on the total amount of the coating agent. From the viewpoint of antibacterial and antifungal properties, the content of the compound (1) in the coating agent is preferably 0.1 to 90% by mass.

本実施形態のコーティング剤に含まれる他の成分としては、例えば、アクリル樹脂及びウレタン樹脂等のバインダー、増粘剤、制電剤、酸化防止剤及び分散剤が挙げられる。   Other components included in the coating agent of the present embodiment include, for example, binders such as acrylic resins and urethane resins, thickeners, antistatic agents, antioxidants, and dispersants.

本実施形態に係るコーティング剤によれば、繊維製品、紙製品及びプラスチックや陶器などの硬質材料表面にコーティングされることで、対象物に抗菌抗かび加工を施すことができ、対象物における細菌やかびの発生を抑制することができる。コーティング方法としては、従来公知の方法を採用することができ、例えば、ロールコーティング、刷毛塗り及び噴霧が挙げられる。   According to the coating agent according to the present embodiment, by coating the surface of a hard material such as textiles, paper products, plastics, and ceramics, the object can be subjected to antibacterial and antifungal processing, and bacteria and the like in the object can be treated. The occurrence of mold can be suppressed. As the coating method, a conventionally known method can be adopted, and examples thereof include roll coating, brushing, and spraying.

本実施形態の抗菌抗かび剤を含む本実施形態に係る樹脂用添加剤は、添加剤が添加される樹脂組成物全量に対する化合物（１）の割合が０．０１〜１０質量％となるように用いることができる。抗菌抗かび性及び経済性の観点から、樹脂用添加剤は、樹脂組成物全量に対する化合物（１）の割合が０．０１〜１質量％となるように添加することが好ましく、０．０１〜０．５質量％となるように添加することがより好ましい。   The additive for a resin according to the present embodiment including the antibacterial antifungal agent of the present embodiment is such that the ratio of the compound (1) to the total amount of the resin composition to which the additive is added is 0.01 to 10% by mass. Can be used. From the viewpoints of antibacterial and antifungal properties and economy, the resin additive is preferably added so that the ratio of the compound (1) to the total amount of the resin composition is 0.01 to 1% by mass, and 0.01 to 1% by mass. More preferably, it is added so as to be 0.5% by mass.

本実施形態に係る樹脂用添加剤に含まれる他の成分としては、例えば、制電剤、酸化防止剤及び分散剤が挙げられる。   Other components included in the resin additive according to the present embodiment include, for example, an antistatic agent, an antioxidant, and a dispersant.

本実施形態に係る樹脂用添加剤によれば、樹脂類を含む樹脂組成物に練り込む等の方法によって、樹脂製品に抗菌及び抗かび加工を施すことができる。用いる樹脂としては特に制限されず、例えば、アクリル樹脂、スチレン樹脂、メラミン樹脂、ウレタン樹脂、フェノール樹脂、ポリプロピレン樹脂、ポリアセタール、フッ素樹脂、シリコーン樹脂、酢酸ビニル樹脂、塩化ビニル樹脂、エポキシ樹脂、ポリエステル樹脂、ポリアミド樹脂、ＡＢＳ樹脂、ポリカーボネート樹脂及び酢酸セルロースが挙げられる。   According to the resin additive according to the present embodiment, the resin product can be subjected to antibacterial and antifungal processing by a method such as kneading into a resin composition containing resins. The resin used is not particularly limited. For example, acrylic resin, styrene resin, melamine resin, urethane resin, phenol resin, polypropylene resin, polyacetal, fluorine resin, silicone resin, vinyl acetate resin, vinyl chloride resin, epoxy resin, polyester resin , Polyamide resins, ABS resins, polycarbonate resins and cellulose acetate.

本実施形態に係る繊維製品は、コーティング、噴霧、浸漬処理、パディング（ｄｉｐ−ｎｉｐ）処理などの公知の方法で、本実施形態の抗菌抗かび剤を繊維に付着させて抗菌抗かび加工をすることによって、製造することができる。本実施形態に係る繊維製品としては、各種素材、各種形態の繊維製品等が挙げられる。素材としては、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）等の再生セルロース繊維；アセテート、プロミックス等の半合成繊維；ポリアミド繊維、ポリエステル繊維、アクリル繊維、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、ポリウレタン繊維等の合成繊維；これらの繊維の複合繊維などが挙げられる。また、繊維製品の形態としては、例えば、短繊維、長繊維、糸、織物、編物、不織布、わた、スライバー及びトップが挙げられる。   The antibacterial and antifungal processing of the fiber product according to the present embodiment is performed by attaching the antibacterial and antifungal agent of the present embodiment to the fiber by a known method such as coating, spraying, dipping, and padding (dip-nip) processing. Thus, it can be manufactured. Examples of the fiber products according to the present embodiment include various materials, various forms of fiber products, and the like. Examples of the material include natural fibers such as cotton, hemp, wool, and silk; regenerated cellulose fibers such as rayon, cupra, and Tencel (trademark); semi-synthetic fibers such as acetate and promix; polyamide fibers, polyester fibers, and acrylic fibers And synthetic fibers such as polyolefin fibers, polyvinyl chloride fibers, polyimide fibers, and polyurethane fibers; and composite fibers of these fibers. Examples of the form of the fiber product include short fiber, long fiber, yarn, woven fabric, knitted fabric, nonwoven fabric, cotton, sliver, and top.

上記繊維製品の抗菌抗かび加工がコーティングの場合、例えば、化合物（１）をウレタン樹脂やアクリル樹脂等のバインダー、増粘剤等に混合した繊維用処理剤で処理することができる。この場合、本実施形態に係る繊維用処理剤は、本実施形態の抗菌抗かび剤を、化合物（１）の含有量が繊維用処理剤全量に対して０．０１〜９５質量％となる割合で含んでよく、０．１〜１０質量％となる割合で含むことが好ましい。   In the case where the antibacterial and antifungal treatment of the above fiber product is a coating, for example, the fiber product can be treated with a fiber treating agent obtained by mixing the compound (1) with a binder such as a urethane resin or an acrylic resin, a thickener, or the like. In this case, the treating agent for fibers according to the present embodiment is obtained by adding the antibacterial antifungal agent of the present embodiment to the composition in which the content of the compound (1) is 0.01 to 95% by mass based on the total amount of the treating agent for fibers. , And preferably 0.1 to 10% by mass.

上記抗菌抗かび加工が噴霧の場合、例えば、本実施形態の抗菌抗かび剤として、化合物（１）の濃度が０．０１〜９５質量％の溶液を用意し、この溶液で噴霧処理することができる。噴霧しやすさと抗菌抗かび性の観点から、化合物（１）の濃度が５〜９０質量％の溶液で噴霧処理することが好ましい。このときの溶媒としては、水、メタノール、エタノール、イソプロピルアルコール、ブタノール等の低級アルコール；エチレングリコール、ジエチレングリコール、プロピレングリコール、ヘキサメチレングリコール、ヘキシレングリコール等のグリコール；グリセリン、ソルビトール等の多価アルコール；アセトン、メチルエチルケトン等のケトン類が挙げられる。   When the antibacterial and antifungal processing is spraying, for example, a solution having a concentration of compound (1) of 0.01 to 95% by mass is prepared as the antibacterial and antifungal agent of the present embodiment, and spraying is performed with this solution. it can. From the viewpoint of ease of spraying and antibacterial and antifungal properties, it is preferable to carry out spraying treatment with a solution having a compound (1) concentration of 5 to 90% by mass. Examples of the solvent at this time include water, lower alcohols such as methanol, ethanol, isopropyl alcohol and butanol; glycols such as ethylene glycol, diethylene glycol, propylene glycol, hexamethylene glycol and hexylene glycol; polyhydric alcohols such as glycerin and sorbitol; Ketones such as acetone and methyl ethyl ketone;

本実施形態の抗菌抗かび剤を繊維製品にコーティング又は噴霧する場合、対象物に対する化合物（１）の付着量が０．０１〜１００ｇ／ｍ２となることが好ましく、抗菌抗かび性及び経済性の観点から、０．１〜２０ｇ／ｍ２となることがより好ましい。 When the antibacterial and antifungal agent of the present embodiment is coated or sprayed on a fiber product, the amount of the compound (1) attached to the target object is preferably 0.01 to 100 g / m 2, and the antibacterial and antifungal property and economy are high. In light of the above, it is more preferable that the amount be 0.1 to 20 g / m 2 .

また、上記繊維製品の抗菌抗かび加工が浸漬処理又はパディング処理の場合、例えば、本実施形態の抗菌抗かび剤として、化合物（１）を含む処理浴を作製し、この処理浴を用いて抗菌抗かび加工する方法が挙げられる。処理浴中の化合物（１）の濃度は、抗菌抗かび性及び経済性の観点から、対象物に対する化合物（１）の付着量が０．１〜２０ｇ／ｍ２となるように設定することが好ましい。 When the antibacterial and antifungal processing of the textile product is a dipping treatment or a padding treatment, for example, a treatment bath containing the compound (1) is prepared as the antibacterial and antifungal agent of the present embodiment, and the antibacterial treatment is performed using this treatment bath. An anti-mold processing method may be used. The concentration of the compound (1) in the treatment bath may be set so that the amount of the compound (1) attached to the object is 0.1 to 20 g / m 2 from the viewpoints of antibacterial and antifungal properties and economy. preferable.

本実施形態に係る紙製品は、例えば、抄紙工程などの紙を製造する工程において本実施形態の抗菌抗かび剤を添加する方法や、本実施形態の抗菌抗かび剤を含む紙用処理剤を調製し、該処理剤を出来上がった紙にコーティング、噴霧、含浸処理、パディング処理などの方法によって、紙に化合物（１）を含有させる又は付着させる方法等が挙げられる。抗菌性及び抗かび性がより優れるという観点から、本実施形態の紙製品の製造方法としては、本実施形態の抗菌抗かび剤を含む紙用処理剤を調製し、紙にコーティング、噴霧、含浸処理、パディング処理などの方法で、化合物（１）を付着させる方法が好ましい。上記紙用処理剤としては、例えば上述の液状製品が挙げられる。   The paper product according to the present embodiment includes, for example, a method of adding the antibacterial antifungal agent of the present embodiment in a paper manufacturing process such as a papermaking process, and a paper treating agent including the antibacterial antifungal agent of the present embodiment. A method in which the compound (1) is contained or adhered to the prepared paper by a method such as coating, spraying, impregnating treatment, padding treatment, or the like, on the finished paper, and the like. From the viewpoint of better antibacterial and antifungal properties, the method for producing a paper product of the present embodiment includes preparing a paper treating agent containing the antibacterial and antifungal agent of the present embodiment, and coating, spraying, and impregnating the paper. A method of attaching the compound (1) by a method such as treatment or padding treatment is preferable. Examples of the paper treating agent include the liquid products described above.

紙の製造工程において本実施形態の抗菌抗かび剤を添加する場合、化合物（１）がパルプ全量に対して０．０１〜１０質量％となるように添加することが好ましく、０．１〜５質量％となるように添加することがより好ましい。また、紙にコーティング、噴霧、含浸処理又はパディング処理を施す場合、化合物（１）がパルプ全量に対して０．０１〜１０質量％となるように処理することが好ましく、０．０１〜２質量％となるように処理することがより好ましい。処理方法が紙へのコーティングの場合、コーティングに用いられる装置としては特に限定されず、例えば、エアナイフコーター、ロールコーター、ブレードコーター、リバースロールコーター、バーコーター、サイズプレスコーター、カーテンコーター及びゲートロールコーターが挙げられる。   When the antibacterial antifungal agent of the present embodiment is added in the paper manufacturing process, it is preferable to add the compound (1) in an amount of 0.01 to 10% by mass relative to the total amount of pulp, and 0.1 to 5% by mass. More preferably, it is added so as to be in mass%. When the paper is subjected to coating, spraying, impregnating treatment or padding treatment, it is preferable to treat the compound (1) in an amount of 0.01 to 10% by mass relative to the total amount of pulp, and 0.01 to 2% by mass. % Is more preferable. When the treatment method is coating on paper, the apparatus used for coating is not particularly limited, and examples thereof include an air knife coater, a roll coater, a blade coater, a reverse roll coater, a bar coater, a size press coater, a curtain coater, and a gate roll coater. Is mentioned.

本実施形態の紙製品に使用するパルプは特に制限はなく、例えば、広葉樹及び針葉樹等から得られる木材パルプ、バガス、ケナフ及び竹パルプ等の植物繊維、レーヨン及びポリエステル等の合成高分子繊維、繊維状無機材料、並びに、古紙再生パルプが挙げられる。   The pulp used for the paper product of the present embodiment is not particularly limited.For example, wood pulp obtained from hardwood and coniferous wood, plant fiber such as bagasse, kenaf and bamboo pulp, synthetic polymer fiber such as rayon and polyester, fiber Inorganic material, and recycled paper pulp.

以下、実施例により本発明を更に詳しく説明するが、本発明はこれらの実施例により何ら制限されるものではない。   Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

＜第４級アンモニウム塩の調製＞
下記式（３）で表される第４級アンモニウム塩について、表１及び２に示されるように第４級アンモニウム基の置換基や対イオンの種類を変更した化合物をそれぞれ調製した。

Figure 2020015706
<Preparation of quaternary ammonium salt>
With respect to the quaternary ammonium salt represented by the following formula (3), compounds having different quaternary ammonium group substituents and counter ion types as shown in Tables 1 and 2, respectively, were prepared.
Figure 2020015706

なお、表１及び２中、ＥＯ及びＰＯは、それぞれ、エチレンオキシ基及びプロピレンオキシ基を示し、数字は付加モル数(又は平均付加モル数)を示す。また、表１及び２中で、例えば、化合物（Ｅ４）のようにＲ２、Ｒ３及びＲ４の項目にまたいで−（ＥＯ）４Ｈという記載がある場合は、結合手を３つ有する窒素原子１モルに対して、合計で４モルのＥＯが付加した構造を表す。すなわち、Ｒ２、Ｒ３及びＲ４のうちの１つが−（ＥＯ）２Ｈであり、残りの２つがそれぞれ−（ＥＯ）１Ｈである。化合物（Ｅ５）のようにＲ２及びＲ３の項目にまたいで−（ＥＯ）２−（ＰＯ）２Ｈという表記がある場合は、結合手を２つ有する窒素原子１モルに対して、合計で２モルのＥＯ及び２モルのＰＯがそれぞれブロックで付加した構造を表す。 In Tables 1 and 2, EO and PO indicate an ethyleneoxy group and a propyleneoxy group, respectively, and the numbers indicate the number of moles added (or the average number of moles added). In addition, in Tables 1 and 2, for example, when there is a description of-(EO) 4 H across the items of R 2 , R 3, and R 4 as in the case of the compound (E4), the compound has three bonds. A structure in which a total of 4 moles of EO is added to 1 mole of a nitrogen atom. That is, one of R 2 , R 3 and R 4 is — (EO) 2 H, and the other two are each — (EO) 1 H. In the case where — (EO) 2 — (PO) 2 H is described across R 2 and R 3 as in the compound (E5), the total is based on 1 mol of a nitrogen atom having two bonds. Represents a structure in which 2 moles of EO and 2 moles of PO are added in blocks.

Figure 2020015706
Figure 2020015706

Figure 2020015706
Figure 2020015706

（調製例１）
耐圧反応容器（オートクレーブ）にラウリルアミンを１モル当量仕込み、オートクレーブを窒素置換した後、１２０〜１３０℃でエチレンオキシド２モル当量を吹き込んだ。その後、４時間の熟成を行い、ラウリルアミンのエチレンオキシド２モル付加物である中間体化合物を得た。中間体化合物と重量比で同量の蒸留水を中間体化合物に添加し、さらにパラトルエンスルホン酸を０．９７モル当量混合し中和した。オートクレーブを窒素置換した後、これに再度８５〜９５℃でエチレンオキシド１．１モル当量を吹き込んだ。４時間の熟成を行うことで４級化反応を進行させ化合物（Ｅ１）を得た。得られた化合物（Ｅ１）の酸価は０であった。１Ｈ−ＮＭＲ及び１３Ｃ−ＮＭＲ［ＪＭＮ−ＥＣＺ５００Ｒ（日本電子（株）］を用いて中間体化合物及び化合物（Ｅ１）を分析し、化合物（Ｅ１）が、一般式（１）中、Ｒ１がラウリル基、Ｒ２、Ｒ３及びＲ４が−（ＥＯ）１Ｈである化合物を含むことを確認した。 (Preparation Example 1)
1 mol equivalent of laurylamine was charged into a pressure-resistant reaction vessel (autoclave), and the autoclave was purged with nitrogen, and then 2 mol equivalent of ethylene oxide was blown at 120 to 130 ° C. Thereafter, aging was performed for 4 hours to obtain an intermediate compound which is an adduct of laurylamine with 2 mol of ethylene oxide. The same amount of distilled water as the weight ratio of the intermediate compound was added to the intermediate compound, and 0.97 mole equivalent of paratoluenesulfonic acid was further mixed and neutralized. After the autoclave was purged with nitrogen, 1.1 mol equivalents of ethylene oxide was blown into the autoclave again at 85 to 95 ° C. After aging for 4 hours, the quaternization reaction was allowed to proceed to obtain a compound (E1). The acid value of the obtained compound (E1) was 0. The intermediate compound and the compound (E1) were analyzed using 1 H-NMR and 13 C-NMR [JMN-ECZ500R (JEOL Ltd.)], and the compound (E1) was represented by R 1 in the general formula (1). Included a compound in which R 2 , R 3 and R 4 were — (EO) 1 H.

（調製例２）
耐圧反応容器（オートクレーブ）にステアリルアミンを１モル当量仕込み、オートクレーブを窒素置換した後、１２０〜１３０℃でエチレンオキシド２モル当量を吹き込んだ。その後、４時間の熟成を行い、ステアリルアミンのエチレンオキシド２モル付加物である中間体化合物を得た。中間体化合物と重量比で倍量の蒸留水を中間体化合物に添加し、さらに塩酸を０．９７モル当量混合し中和した。オートクレーブを窒素置換した後、これに再度８５〜９５℃でエチレンオキシド１．１モル当量を吹き込んだ。４時間の熟成を行うことで４級化反応を進行させ化合物（Ｅ２）を得た。得られた化合物（Ｅ２）の酸価は０．２であった。１Ｈ−ＮＭＲ及び１３Ｃ−ＮＭＲを用いて中間体化合物及び化合物（Ｅ２）を分析し、化合物（Ｅ２）が、一般式（１）中、Ｒ１がステアリル基、Ｒ２、Ｒ３及びＲ４が−（ＥＯ）１Ｈである化合物を含むことを確認した。 (Preparation Example 2)
After 1 mol equivalent of stearylamine was charged into a pressure-resistant reaction vessel (autoclave), and the autoclave was replaced with nitrogen, 2 mol equivalent of ethylene oxide was blown at 120 to 130 ° C. Thereafter, aging was performed for 4 hours to obtain an intermediate compound which was a 2 mol addition product of stearylamine and ethylene oxide. Distilled water was added to the intermediate compound in an amount twice that of the intermediate compound in a weight ratio, and 0.97 molar equivalent of hydrochloric acid was further mixed and neutralized. After the autoclave was purged with nitrogen, 1.1 mol equivalents of ethylene oxide was blown into the autoclave again at 85 to 95 ° C. After aging for 4 hours, the quaternization reaction was allowed to proceed to obtain a compound (E2). The acid value of the obtained compound (E2) was 0.2. The intermediate compound and the compound (E2) are analyzed using 1 H-NMR and 13 C-NMR, and the compound (E2) is represented by the general formula (1), wherein R 1 is a stearyl group, R 2 , R 3 and R 4 - (EO) was confirmed to contain the compound is 1 H.

（調製例３）
耐圧反応容器（オートクレーブ）にラウリルアミンを１モル当量仕込み、オートクレーブを窒素置換した後、１２０〜１３０℃でプロピレンオキシド２モル当量を吹き込んだ。その後、４時間の熟成を行い、ラウリルアミンのプロピレンオキシド２モル付加物である中間体化合物を得た。中間体化合物と重量比で同量の蒸留水を中間体化合物に添加し、さらにパラトルエンスルホン酸を０．９７モル当量混合し中和した。オートクレーブを窒素置換した後、これに再度８５〜９５℃でエチレンオキシド１．１モル当量を吹き込んだ。４時間の熟成を行うことで４級化反応を進行させ化合物（Ｅ３）を得た。得られた化合物（Ｅ３）の酸価は０．１であった。１Ｈ−ＮＭＲ及び１３Ｃ−ＮＭＲを用いて中間体化合物及び化合物（Ｅ３）を分析し、化合物（Ｅ３）が、一般式（１）中、Ｒ１がラウリル基、Ｒ２及びＲ３が−（ＰＯ）１Ｈ、Ｒ４が−（ＥＯ）１Ｈである化合物を含むことを確認した。 (Preparation Example 3)
1 mol equivalent of laurylamine was charged into a pressure-resistant reaction vessel (autoclave), and the autoclave was purged with nitrogen. Then, 2 mol equivalent of propylene oxide was blown at 120 to 130 ° C. Thereafter, aging was performed for 4 hours to obtain an intermediate compound which was a 2-mol adduct of propylene oxide of laurylamine. The same amount of distilled water as the weight ratio of the intermediate compound was added to the intermediate compound, and 0.97 mole equivalent of paratoluenesulfonic acid was further mixed and neutralized. After the autoclave was purged with nitrogen, 1.1 mol equivalents of ethylene oxide was blown into the autoclave again at 85 to 95 ° C. After aging for 4 hours, the quaternization reaction was allowed to proceed to obtain a compound (E3). The acid value of the obtained compound (E3) was 0.1. The intermediate compound and the compound (E3) are analyzed using 1 H-NMR and 13 C-NMR, and the compound (E3) is represented by the general formula (1) in which R 1 is a lauryl group, and R 2 and R 3 are — (PO) 1 H, R 4 is - (EO) was confirmed to contain the compound is 1 H.

（調製例４）
耐圧反応容器（オートクレーブ）にトリエタノールアミンを１モル当量仕込み、オートクレーブを窒素置換した後、１２０〜１３０℃でエチレンオキシド１モル当量を吹き込んだ。４時間の熟成を行い、トリエタノールアミンのエチレンオキシド１モル付加物である中間体化合物を得た。この中間体化合物１モル当量と、中間体化合物と重量比で倍量の蒸留水とを還流コンデンサー付きの４つ口フラスコに仕込んだ。その後、８５〜９５℃でステアリルクロリド０．８８モル当量と、オレイルクロリド０．２２モル当量との混合物を４つ口フラスコに徐々に仕込んだ。仕込み終了後、４時間の熟成を行うことで４級化反応を進行させ化合物（Ｅ４）を得た。得られた化合物（Ｅ４）のアミン価は０．４であった。１Ｈ−ＮＭＲ及び１３Ｃ−ＮＭＲを用いて中間体化合物及び化合物（Ｅ４）を分析し、化合物（Ｅ４）は、一般式（１）中、Ｒ１がステアリル基又はオレイル基（ステアリル基とオレイル基との割合は、モル比でステアリル基：オレイル基＝８：２）であり、Ｒ２、Ｒ３及びＲ４が、結合手を３つ有する窒素原子１モルに対して合計で４モルのＥＯが付加した構造である化合物を含むことを確認した。 (Preparation Example 4)
One molar equivalent of triethanolamine was charged into a pressure-resistant reaction vessel (autoclave), and the autoclave was purged with nitrogen, followed by blowing 1 molar equivalent of ethylene oxide at 120 to 130 ° C. Aging was performed for 4 hours to obtain an intermediate compound which was a 1 mol ethylene oxide adduct of triethanolamine. One mole equivalent of this intermediate compound and distilled water in a weight ratio twice that of the intermediate compound were charged into a four-necked flask equipped with a reflux condenser. Thereafter, a mixture of 0.88 molar equivalent of stearyl chloride and 0.22 molar equivalent of oleyl chloride was gradually charged into a four-neck flask at 85 to 95 ° C. After completion of the charging, the mixture was aged for 4 hours to advance a quaternization reaction, thereby obtaining a compound (E4). The amine value of the obtained compound (E4) was 0.4. The intermediate compound and the compound (E4) were analyzed using 1 H-NMR and 13 C-NMR. In the compound (E4), in the general formula (1), R 1 represents a stearyl group or an oleyl group (a stearyl group and an oleyl group). The ratio with the group is a stearyl group: oleyl group = 8: 2) in a molar ratio, and R 2 , R 3 and R 4 have a total of 4 moles per mole of a nitrogen atom having three bonds. It was confirmed that a compound having a structure to which EO was added was included.

（調製例５）
耐圧反応容器（オートクレーブ）にセチルアミン１モル当量仕込み、オートクレーブを窒素置換した後、１２０〜１３０℃でエチレンオキシド２モル当量を吹き込んだ。その後、４時間の熟成を行った。さらに触媒として水酸化ナトリウムをセチルアミンの５／１０００質量分を仕込み、減圧脱水し、オートクレーブを窒素置換した。その後、１２０〜１３０℃でプロピレンオキシド２モル当量を吹き込み、４時間の熟成を行い、セチルアミンのエチレンオキシド２モル、プロピレンオキシド２モル付加物である中間体化合物を得た。中間体化合物と重量比で倍量の蒸留水を中間体化合物に添加し、さらにラウリルスルホン酸を０．９７モル当量混合し中和した。これに再度８５〜９５℃でエチレンオキシド１．１モル当量を吹き込み、４時間の熟成を行うことで４級化反応を進行させ化合物（Ｅ５）を得た。得られた化合物（Ｅ５）の酸価は０．２であった。１Ｈ−ＮＭＲ及び１３Ｃ−ＮＭＲを用いて中間体化合物及び化合物（Ｅ５）を分析し、化合物（Ｅ５）が、一般式（１）中、Ｒ１がセチル基であり、Ｒ２及びＲ３が、結合手を２つ有する窒素原子１モルに対して合計で２モルのＥＯ及び２モルのＰＯがそれぞれブロックで付加した構造であり、Ｒ４が−（ＥＯ）１Ｈである化合物を含むことを確認した。 (Preparation Example 5)
After 1 mol equivalent of cetylamine was charged into a pressure-resistant reaction vessel (autoclave), and the autoclave was replaced with nitrogen, 2 mol equivalent of ethylene oxide was blown at 120 to 130 ° C. Thereafter, aging was performed for 4 hours. Further, sodium hydroxide was charged as a catalyst in an amount of 5/1000 mass of cetylamine, dehydrated under reduced pressure, and the autoclave was purged with nitrogen. Thereafter, 2 mole equivalents of propylene oxide were blown at 120 to 130 ° C., and aging was performed for 4 hours to obtain an intermediate compound which is an adduct of cetylamine with 2 moles of ethylene oxide and 2 moles of propylene oxide. Distilled water was added to the intermediate compound in a weight ratio twice that of the intermediate compound, and 0.97 molar equivalent of lauryl sulfonic acid was further mixed and neutralized. 1.1 mol equivalents of ethylene oxide was again blown into the mixture at 85 to 95 ° C., and aging was performed for 4 hours to advance the quaternization reaction, thereby obtaining a compound (E5). The acid value of the obtained compound (E5) was 0.2. The intermediate compound and the compound (E5) are analyzed using 1 H-NMR and 13 C-NMR, and the compound (E5) is a compound of the general formula (1) in which R 1 is a cetyl group, R 2 and R 3 Has a structure in which 2 moles of EO and 2 moles of PO are respectively added by blocks to 1 mole of a nitrogen atom having two bonds, and includes a compound in which R 4 is — (EO) 1 H. It was confirmed.

（調製例６）
耐圧反応容器（オートクレーブ）にジデシルアミンを１モル当量仕込み窒素置換後１２０〜１３０℃でエチレンオキシド１モル当量を吹き込みんだ。その後、４時間の熟成を行いジデシルアミンのエチレンオキシド１モル付加物である中間体化合物を得た。中間体化合物と重量比で倍量の蒸留水を中間体化合物に混合し、さらに塩酸を０．９７モル当量混合し中和した。オートクレーブを窒素置換した後、これに再度８５〜９５℃でエチレンオキシド１．１モル当量を吹き込んだ。４時間の熟成を行うことで４級化反応を進行させ化合物（Ｅ６）を得た。得られた化合物（Ｅ６）の酸価は０．２であった。１Ｈ−ＮＭＲ及び１３Ｃ−ＮＭＲを用いて中間体化合物及び化合物（Ｅ６）を分析し、化合物（Ｅ６）が、一般式（１）中、Ｒ１及びＲ２がデシル基、Ｒ３及びＲ４が−（ＥＯ）１Ｈである化合物を含むことを確認した。 (Preparation Example 6)
1 molar equivalent of didecylamine was charged into a pressure-resistant reaction vessel (autoclave), and after nitrogen substitution, 1 molar equivalent of ethylene oxide was blown at 120 to 130 ° C. Thereafter, aging was performed for 4 hours to obtain an intermediate compound which was a 1 mol addition product of didecylamine with ethylene oxide. The intermediate compound and a double amount of distilled water in a weight ratio were mixed with the intermediate compound, and 0.97 molar equivalent of hydrochloric acid was further mixed and neutralized. After the autoclave was purged with nitrogen, 1.1 mol equivalents of ethylene oxide was blown into the autoclave again at 85 to 95 ° C. After aging for 4 hours, the quaternization reaction was allowed to proceed to obtain a compound (E6). The acid value of the obtained compound (E6) was 0.2. The intermediate compound and the compound (E6) are analyzed using 1 H-NMR and 13 C-NMR, and the compound (E6) is a compound represented by the general formula (1) in which R 1 and R 2 are a decyl group, R 3 and R 4 - (EO) was confirmed to contain the compound is 1 H.

（調製例７）
耐圧反応容器（オートクレーブ）にジデシルアミンを１モル当量仕込み、及び触媒として水酸化ナトリウムをジデシルアミンの５／１０００質量分を仕込んだ。そして、オートクレーブ内を減圧脱水し、窒素置換後１２０〜１３０℃でエチレンオキシド４モル当量吹き込み熟成を４時間行ってジデシルアミンのエチレンオキシド４モル付加物である中間体化合物を得た。中間体化合物に中間体化合物と重量比で倍量の蒸留水を添加し、さらにりん酸を０．９７モル当量混合し中和した。オートクレーブを窒素置換した後、これに再度８５〜９５℃でエチレンオキシド１．１モル当量を吹き込んだ。その後、４時間の熟成を行うことで４級化反応を進行させ化合物（Ｅ７）を得た。得られた化合物（Ｅ７）の酸価は０．２であった。１Ｈ−ＮＭＲ及び１３Ｃ−ＮＭＲを用いて中間体化合物及び化合物（Ｅ７）を分析し、化合物（Ｅ７）が、一般式（１）中、Ｒ１及びＲ２がデシル基、Ｒ３が−（ＥＯ）４Ｈ、Ｒ４が−（ＥＯ）１Ｈである化合物を含むことを確認した。 (Preparation Example 7)
A pressure-resistant reaction vessel (autoclave) was charged with 1 molar equivalent of didecylamine, and sodium hydroxide as a catalyst was charged at 5/1000 mass of didecylamine. Then, the inside of the autoclave was dehydrated under reduced pressure, and after purging with nitrogen, aging was performed by blowing 4 mole equivalents of ethylene oxide at 120 to 130 ° C. for 4 hours to obtain an intermediate compound which was an adduct of didecylamine with 4 moles of ethylene oxide. Distilled water was added to the intermediate compound in an amount twice that of the intermediate compound in a weight ratio, and 0.97 molar equivalent of phosphoric acid was further mixed and neutralized. After the autoclave was purged with nitrogen, 1.1 mol equivalents of ethylene oxide was blown into the autoclave again at 85 to 95 ° C. Thereafter, aging was performed for 4 hours to advance the quaternization reaction, thereby obtaining a compound (E7). The acid value of the obtained compound (E7) was 0.2. The intermediate compound and the compound (E7) are analyzed using 1 H-NMR and 13 C-NMR, and the compound (E7) is represented by the formula (1) in which R 1 and R 2 represent a decyl group, and R 3 represents — (EO) 4 H, It was confirmed that R 4 contained a compound in which — (EO) 1 H was present.

（調製例８）
耐圧反応容器（オートクレーブ）にベヘニルアミンを１モル当量仕込み窒素置換後１２０〜１３０℃でエチレンオキシド２モル当量吹き込み熟成を４時間行ってベヘニルアミンのエチレンオキシド２モル付加物である中間体化合物を得た。中間体化合物に中間体化合物と重量比で倍量の蒸留水を添加し、さらに塩酸を０．９７モル当量混合し中和した。オートクレーブを窒素置換した後、これに再度８５〜９５℃でエチレンオキシド１．１モル当量を吹き込んだ。その後、４時間の熟成を行うことで４級化反応を進行させ化合物（Ｅ８）を得た。得られた化合物（Ｅ８）の酸価は０．２であった。１Ｈ−ＮＭＲ及び１３Ｃ−ＮＭＲを用いて中間体化合物及び化合物（Ｅ８）を分析し、化合物（Ｅ８）が、一般式（１）中、Ｒ１がベヘニル基、Ｒ２、Ｒ３及びＲ４が−（ＥＯ）１Ｈである化合物を含むことを確認した。 (Preparation Example 8)
1 molar equivalent of behenylamine was charged into a pressure-resistant reaction vessel (autoclave), and after substituting with nitrogen, 2 molar equivalents of ethylene oxide were blown at 120 to 130 ° C. and ripening was performed for 4 hours to obtain an intermediate compound which is an adduct of ethylene oxide of behenylamine with 2 mol. To the intermediate compound, distilled water was added in an amount twice that of the intermediate compound in a weight ratio, and 0.97 molar equivalent of hydrochloric acid was further mixed and neutralized. After the autoclave was purged with nitrogen, 1.1 mol equivalents of ethylene oxide was blown into the autoclave again at 85 to 95 ° C. Thereafter, aging was performed for 4 hours to advance the quaternization reaction, thereby obtaining a compound (E8). The acid value of the obtained compound (E8) was 0.2. The intermediate compound and the compound (E8) are analyzed using 1 H-NMR and 13 C-NMR, and the compound (E8) is a compound represented by the general formula (1), wherein R 1 is a behenyl group, R 2 , R 3 and R 4 - (EO) was confirmed to contain the compound is 1 H.

（調製例９）
耐圧反応容器（オートクレーブ）にノルマルオクチルアミンを１モル当量仕込み窒素置換後１２０〜１３０℃でエチレンオキシド２モル当量吹き込み熟成を４時間行ってオクチルアミンのエチレンオキシド２モル付加物である中間体化合物を得た。中間体化合物に中間体化合物と重量比で同量の蒸留水を添加し、さらに硫酸を０．９７モル当量混合し中和した。オートクレーブを窒素置換した後、これに再度８５〜９５℃でエチレンオキシド１．１モル当量を吹き込んだ。４時間の熟成を行うことで４級化反応を進行させ化合物（Ｅ９）を得た。得られた化合物（Ｅ９）の酸価は０．１であった。１Ｈ−ＮＭＲ及び１３Ｃ−ＮＭＲを用いて中間体化合物及び化合物（Ｅ９）を分析し、化合物（Ｅ９）が、一般式（１）中、Ｒ１がオクチル基、Ｒ２、Ｒ３及びＲ４が−（ＥＯ）１Ｈである化合物を含むことを確認した。 (Preparation Example 9)
1 mol equivalent of normal octylamine was charged into a pressure-resistant reaction vessel (autoclave), and after purging with nitrogen, 2 mol equivalent of ethylene oxide was blown at 120 to 130 ° C. and ripening was performed for 4 hours to obtain an intermediate compound which was an adduct of octylamine with 2 mol of ethylene oxide. . The same amount of distilled water as the weight ratio of the intermediate compound was added to the intermediate compound, and 0.97 mole equivalent of sulfuric acid was further mixed and neutralized. After the autoclave was purged with nitrogen, 1.1 mol equivalents of ethylene oxide was blown into the autoclave again at 85 to 95 ° C. After aging for 4 hours, the quaternization reaction was allowed to proceed to obtain a compound (E9). The acid value of the obtained compound (E9) was 0.1. The intermediate compound and the compound (E9) are analyzed using 1 H-NMR and 13 C-NMR, and the compound (E9) is represented by the general formula (1), wherein R 1 is an octyl group, R 2 , R 3 and R 4 - (EO) was confirmed to contain the compound is 1 H.

（調製例１０）
耐圧反応容器（オートクレーブ）にジノルマルオクチルアミンを１モル当量仕込み窒素置換後１２０〜１３０℃でエチレンオキシド１モル当量吹き込み熟成を４時間行ってジノルマルオクチルアミンのエチレンオキシド１モル付加物である中間体化合物を得た。中間体化合物に中間体化合物と重量比で同量の蒸留水を添加し、さらに塩酸を０．９７モル当量混合し中和した。オートクレーブを窒素置換した後、これに再度８５〜９５℃でエチレンオキシド１．１モル当量を吹き込んだ。４時間の熟成を行うことで４級化反応を進行させ化合物（Ｅ１０）を得た。得られた化合物（Ｅ１０）の酸価は０．２であった。１Ｈ−ＮＭＲ及び１３Ｃ−ＮＭＲを用いて中間体化合物及び化合物（Ｅ１０）を分析し、化合物（Ｅ１０）が、一般式（１）中、Ｒ１及びＲ２がノルマルオクチル基、Ｒ３及びＲ４が−（ＥＯ）１Ｈである化合物を含むことを確認した。 (Preparation Example 10)
1 mol equivalent of dinormal octylamine was charged into a pressure-resistant reaction vessel (autoclave), and after purging with nitrogen, 1 mol equivalent of ethylene oxide was blown at 120 to 130 ° C. and ripened for 4 hours to perform an intermediate compound as an adduct of 1 mol of dinormal octylamine with ethylene oxide. I got Distilled water was added to the intermediate compound in the same amount as the intermediate compound in a weight ratio, and 0.97 molar equivalent of hydrochloric acid was further mixed and neutralized. After the autoclave was purged with nitrogen, 1.1 mol equivalents of ethylene oxide was blown into the autoclave again at 85 to 95 ° C. After aging for 4 hours, the quaternization reaction was allowed to proceed to obtain a compound (E10). The acid value of the obtained compound (E10) was 0.2. The intermediate compound and the compound (E10) are analyzed using 1 H-NMR and 13 C-NMR, and the compound (E10) is a compound represented by the general formula (1), wherein R 1 and R 2 are each a normal octyl group, R 3 and It was confirmed that R 4 contained a compound having — (EO) 1 H.

（調製例１１）
耐圧反応容器（オートクレーブ）に２−エチルヘキシルアミン１モル当量仕込み窒素置換後１２０〜１３０℃でエチレンオキシド２モル当量吹き込み熟成を４時間行った。さらに触媒として水酸化ナトリウムを２エチルヘキシルアミンの５／１０００質量分を仕込み、減圧脱水し、オートクレーブを窒素置換した後、１２０〜１３０℃にてエチレンオキシド２モル当量吹き込み熟成を４時間行って、２エチルヘキシルアミンのエチレンオキシド４モル付加物である中間体化合物を得た。この中間体化合物１モル当量と中間体化合物と重量比で倍量の蒸留水を還流コンデンサー付きの４つ口フラスコに仕込み、８５〜９５℃にてラウリルクロリド１．１モル当量を徐々に仕込んだ。仕込み終了後、４時間の熟成を行うことで４級化反応を進行させ化合物（Ｅ１１）を得た。得られた化合物（Ｅ１１）のアミン価は０．２であった。１Ｈ−ＮＭＲ及び１３Ｃ−ＮＭＲを用いて中間体化合物及び化合物（Ｅ１１）を分析し、化合物（Ｅ１１）が、一般式（１）中、Ｒ１がオクチル基であり、Ｒ２がラウリル基であり、Ｒ３及びＲ４が、結合手を２つ有する窒素原子１モルに対して合計で４モルのＥＯが付加した構造である化合物（Ｅ１１）を含むことを確認した。 (Preparation Example 11)
One pressure equivalent of 2-ethylhexylamine was charged into a pressure-resistant reaction vessel (autoclave), and after purging with nitrogen, 2 mole equivalents of ethylene oxide were blown at 120 to 130 ° C., followed by ripening for 4 hours. Further, sodium hydroxide was charged as a catalyst in an amount of 5/1000 mass of 2-ethylhexylamine, dehydrated under reduced pressure, and the autoclave was purged with nitrogen. An intermediate compound was obtained which was an ethylene oxide 4 mol adduct of an amine. 1 mole equivalent of this intermediate compound and twice the amount of distilled water in a weight ratio to the intermediate compound were charged into a four-necked flask equipped with a reflux condenser, and 1.1 mole equivalent of lauryl chloride was gradually charged at 85 to 95 ° C. . After completion of the charging, the mixture was aged for 4 hours to advance a quaternization reaction, thereby obtaining a compound (E11). The amine value of the obtained compound (E11) was 0.2. The intermediate compound and the compound (E11) were analyzed using 1 H-NMR and 13 C-NMR. In the compound (E11), in the general formula (1), R 1 was an octyl group, and R 2 was a lauryl group. It was confirmed that R 3 and R 4 contained a compound (E11) having a structure in which a total of 4 mols of EO was added to 1 mol of a nitrogen atom having two bonds.

（比較調製例１）
環流コンデンサー付きの４つ口フラスコにラウリルジメチルアミンを１モル当量及び重量比で倍量の蒸留水を仕込み、８５〜９５℃で塩化ベンジルを１．１モル当量滴下した。滴下終了後、４時間の熟成を行うことで４級化反応を進行させ化合物（ＣＥ１）を得た。得られた化合物（ＣＥ１）のアミン価０．３であった。１Ｈ−ＮＭＲ及び１３Ｃ−ＮＭＲを用いて化合物（ＣＥ１）を分析し、化合物（ＣＥ１）が、一般式（１）中、Ｒ１がラウリル基、Ｒ２及びＲ３がメチル基、Ｒ４がベンジル基である化合物であることを確認した。
（比較調製例２）
環流コンデンサー付きの４つ口フラスコにリン酸３９部と蒸留水３００部を仕込み、８０〜９０℃に保ちながらジデシルジメチルアンモニウムメチルカーボネートのメタノール溶液２３０部（メタノール６９部含有）を２時間かけて徐々に加えた。発生する二酸化炭素を留去し、還流コンデンサー外し、さらに減圧を行うことでメタノールを留去し、化合物（ＣＥ２）を得た。得られた化合物（ＣＥ２）のアミン価０であった。１Ｈ−ＮＭＲ及び１３Ｃ−ＮＭＲを用いて化合物（ＣＥ２）を分析し、化合物（ＣＥ２）が、一般式（１）中、Ｒ１及びＲ２がデシル基、Ｒ３及びＲ４がメチル基である化合物であることを確認した。 (Comparative Preparation Example 1)
Into a four-necked flask equipped with a reflux condenser, 1 mol equivalent of lauryl dimethylamine and twice the amount of distilled water in a weight ratio were charged, and 1.1 mol equivalent of benzyl chloride was added dropwise at 85 to 95 ° C. After completion of the dropwise addition, the mixture was aged for 4 hours to advance the quaternization reaction, thereby obtaining a compound (CE1). The amine value of the obtained compound (CE1) was 0.3. The compound (CE1) is analyzed using 1 H-NMR and 13 C-NMR, and the compound (CE1) is a compound represented by the general formula (1), wherein R 1 is a lauryl group, R 2 and R 3 are methyl groups, and R 4 Was a benzyl group.
(Comparative Preparation Example 2)
A four-necked flask equipped with a reflux condenser is charged with 39 parts of phosphoric acid and 300 parts of distilled water, and 230 parts of a methanol solution of didecyldimethylammonium methyl carbonate (containing 69 parts of methanol) is added over 2 hours while maintaining the temperature at 80 to 90 ° C. Slowly added. The generated carbon dioxide was distilled off, the reflux condenser was removed, and methanol was distilled off by further reducing the pressure to obtain a compound (CE2). The amine value of the obtained compound (CE2) was 0. The compound (CE2) is analyzed using 1 H-NMR and 13 C-NMR, and the compound (CE2) is a compound represented by the formula (1) in which R 1 and R 2 are decyl groups, and R 3 and R 4 are methyl groups. It was confirmed that it was a compound.

（比較調製例３）
環流コンデンサー付きの４つ口フラスコに５０％グルコン酸水溶液１５７部（純分換算０．４０モル）と蒸留水３００部を８０〜９０℃に保ちながらジデシルジメチルアンモニウムメチルカーボネートのメタノール溶液２３０部（メタノール６９部含有）を２時間かけて徐々に加えた。発生する二酸化炭素を留去し、還流コンデンサーを外し、さらに減圧を行うことでメタノールを留去し、化合物（ＣＥ３）を得た。得られた化合物（ＣＥ３）のアミン価０であった。１Ｈ−ＮＭＲ及び１３Ｃ−ＮＭＲを用いて化合物（ＣＥ３）を分析し、化合物（ＣＥ３）が、一般式（１）中、Ｒ１及びＲ２がデシル基、Ｒ３及びＲ４がメチル基である化合物であることを確認した。 (Comparative Preparation Example 3)
In a four-necked flask equipped with a reflux condenser, 230 parts of a methanol solution of didecyldimethylammonium methyl carbonate (157 parts of a 50% aqueous gluconic acid solution (0.40 mol in terms of a pure content) and 300 parts of distilled water were kept at 80 to 90 ° C.) Methanol (containing 69 parts) was gradually added over 2 hours. The generated carbon dioxide was distilled off, the reflux condenser was removed, and the pressure was further reduced, whereby methanol was distilled off to obtain a compound (CE3). The amine value of the obtained compound (CE3) was 0. The compound (CE3) is analyzed using 1 H-NMR and 13 C-NMR, and the compound (CE3) is a compound represented by the formula (1) in which R 1 and R 2 are decyl groups, and R 3 and R 4 are methyl groups. It was confirmed that this was a compound.

（比較調製例４）
環流コンデンサー付きの４つ口フラスコにラウリルジメチルアミンを１モル当量と重量比で倍量の蒸留水を仕込み、８５〜９５℃にてジメチル硫酸を１．１モル当量滴下した。滴下終了後、４時間の熟成を行うことで４級化反応を進行させ化合物（ＣＥ４）を得た。得られた化合物（ＣＥ４）のアミン価０．２であった。１Ｈ−ＮＭＲ及び１３Ｃ−ＮＭＲを用いて化合物（ＣＥ４）を分析し、化合物（ＣＥ４）が、一般式（１）中、Ｒ１がラウリル基、Ｒ２、Ｒ３及びＲ４がメチル基である化合物であることを確認した。 (Comparative Preparation Example 4)
Into a four-necked flask equipped with a reflux condenser, lauryl dimethylamine was charged with 1 mole equivalent of distilled water in a weight ratio twice as much as 1 mole equivalent, and 1.1 mole equivalent of dimethyl sulfuric acid was added dropwise at 85 to 95 ° C. After completion of the dropwise addition, the mixture was aged for 4 hours to advance the quaternization reaction, thereby obtaining a compound (CE4). The amine value of the obtained compound (CE4) was 0.2. The compound (CE4) is analyzed using 1 H-NMR and 13 C-NMR, and the compound (CE4) is a compound represented by the general formula (1) in which R 1 is a lauryl group and R 2 , R 3 and R 4 are methyl groups. It was confirmed that this was a compound.

（比較調製例５）
耐圧反応容器（オートクレーブ）にラウリルジメチルアミンを１モル当量と重量比で同量の蒸留水を仕込み、パラトルエンスルホン酸を０．９７モル当量混合し中和した。オートクレーブを窒素置換した後、８５〜９５℃でエチレンオキシド１．１モル当量を吹き込んだ。４時間の熟成を行うことで４級化反応を進行させ化合物（ＣＥ５）を得た。得られた合成物の酸価は０．２であった。１Ｈ−ＮＭＲ及び１３Ｃ−ＮＭＲを用いて化合物（ＣＥ５）を分析し、化合物（ＣＥ５）が、一般式（１）中、Ｒ１がラウリル基、Ｒ２及びＲ３がメチル基、Ｒ４が−（ＥＯ）１Ｈである化合物を含むことを確認した。 (Comparative Preparation Example 5)
A pressure-resistant reaction vessel (autoclave) was charged with 1 mole equivalent of lauryl dimethylamine and the same amount of distilled water in a weight ratio, and 0.97 mole equivalent of paratoluenesulfonic acid was mixed and neutralized. After purging the autoclave with nitrogen, 1.1 molar equivalents of ethylene oxide were blown in at 85 to 95 ° C. After aging for 4 hours, the quaternization reaction was allowed to proceed to obtain a compound (CE5). The acid value of the obtained synthesized product was 0.2. The compound (CE5) is analyzed using 1 H-NMR and 13 C-NMR, and the compound (CE5) is a compound represented by the general formula (1), wherein R 1 is a lauryl group, R 2 and R 3 are methyl groups, R 4 There - (EO) was confirmed to contain the compound is 1 H.

（比較調製例６）
耐圧反応容器（オートクレーブ）にステアリルアミンを１モル当量仕込み、その後オートクレーブを窒素置換した。次いで、１２０〜１３０℃でエチレンオキシド２モル当量を吹き込んだ。そして、４時間の熟成を行うことでステアリルアミンのエチレンオキシド２モル付加物である中間体化合物を得た。この中間体化合物１モル当量と中間体化合物と重量比で倍量の蒸留水を還流コンデンサー付きの４つ口フラスコに仕込み、８５〜９５℃でジメチル硫酸を１．１モル当量滴下した。滴下終了後、４時間の熟成を行うことで４級化反応を進行させ化合物（ＣＥ６）を得た。得られた化合物（ＣＥ６）のアミン価０．２であった。１Ｈ−ＮＭＲ及び１３Ｃ−ＮＭＲを用いて中間体化合物及び化合物（ＣＥ６）を分析し、化合物（ＣＥ６）が、一般式（１）中、Ｒ１がステアリル基、Ｒ２及びＲ３が−（ＥＯ）１Ｈ、Ｒ４がメチル基である化合物を含むことを確認した。 (Comparative Preparation Example 6)
One molar equivalent of stearylamine was charged into a pressure-resistant reaction vessel (autoclave), and then the autoclave was purged with nitrogen. Then, at 120-130 ° C, 2 molar equivalents of ethylene oxide were blown. Then, aging was performed for 4 hours to obtain an intermediate compound which was an adduct of stearylamine with 2 mol of ethylene oxide. 1 mole equivalent of this intermediate compound and twice the amount of distilled water in a weight ratio to the intermediate compound were charged into a four-necked flask equipped with a reflux condenser, and 1.1 mole equivalent of dimethyl sulfate was added dropwise at 85 to 95 ° C. After completion of the dropwise addition, the mixture was aged for 4 hours to advance the quaternization reaction, thereby obtaining a compound (CE6). The amine value of the obtained compound (CE6) was 0.2. The intermediate compound and the compound (CE6) are analyzed using 1 H-NMR and 13 C-NMR, and the compound (CE6) is represented by the formula (1) in which R 1 is a stearyl group, and R 2 and R 3 are — (EO) It was confirmed that 1 H and R 4 included a compound in which a methyl group was contained.

（比較調製例７）
耐圧反応容器（オートクレーブ）にラウリルメチルアミンを１モル当量及び触媒として水酸化ナトリウムをラウリルメチルアミンの５／１０００質量分を仕込んだ。そして、オートクレーブ内を減圧脱水し、窒素置換した。次いで、１２０〜１３０℃でエチレンオキシド５モル当量吹き込み、４時間の熟成を行うことでラウリルメチルアミンのエチレンオキシド５モル付加物である中間体化合物を得た。環流コンデンサー付きの４つ口フラスコに中間体化合物の１モル当量と重量比で同量の蒸留水を仕込み、８５〜９５℃でジメチル硫酸を１．１モル当量滴下した。滴下終了後、４時間の熟成を行うことで４級化反応を進行させ化合物（ＣＥ７）を得た。得られた化合物（ＣＥ７）のアミン価０．３であった。１Ｈ−ＮＭＲ及び１３Ｃ−ＮＭＲを用いて中間体化合物及び化合物（ＣＥ７）を分析し、化合物（ＣＥ７）が一般式（１）中、Ｒ１がラウリル基、Ｒ２が−（ＥＯ）５−Ｈ、Ｒ３及びＲ４がメチル基である化合物を含むことを確認した。 (Comparative Preparation Example 7)
A pressure-resistant reaction vessel (autoclave) was charged with 1 molar equivalent of laurylmethylamine and 5/1000 mass of sodium hydroxide as a catalyst as laurylmethylamine. Then, the inside of the autoclave was dehydrated under reduced pressure and replaced with nitrogen. Subsequently, 5 mole equivalents of ethylene oxide were blown in at 120 to 130 ° C., and aging was performed for 4 hours to obtain an intermediate compound which was an adduct of laurylmethylamine with 5 moles of ethylene oxide. To a four-necked flask equipped with a reflux condenser was charged distilled water in the same amount as 1 mol equivalent of the intermediate compound in a weight ratio, and 1.1 mol equivalent of dimethyl sulfuric acid was added dropwise at 85 to 95 ° C. After completion of the dropwise addition, the mixture was aged for 4 hours to advance the quaternization reaction, thereby obtaining a compound (CE7). The amine value of the obtained compound (CE7) was 0.3. The intermediate compound and the compound (CE7) are analyzed using 1 H-NMR and 13 C-NMR, and the compound (CE7) is a compound represented by the general formula (1), wherein R 1 is a lauryl group, and R 2 is — (EO) 5. It was confirmed that -H, R 3 and R 4 included a compound having a methyl group.

＜抗菌抗かび剤の調製＞
（実施例１〜１１）
抗菌抗かび剤として、調製例１〜１１で得られた化合物（Ｅ１）〜（Ｅ１１）をそれぞれ用意した。 <Preparation of antibacterial and antifungal agent>
(Examples 1 to 11)
Compounds (E1) to (E11) obtained in Preparation Examples 1 to 11 were prepared as antibacterial and antifungal agents, respectively.

（比較例１〜７）
抗菌抗かび剤として、比較調製例１〜７で得られた化合物（ＣＥ１）〜（ＣＥ７）をそれぞれ用意した。 (Comparative Examples 1 to 7)
Compounds (CE1) to (CE7) obtained in Comparative Preparation Examples 1 to 7 were prepared as antibacterial and antifungal agents, respectively.

＜評価１．抗菌抗かび剤の最小発育阻止濃度試験＞
実施例１〜１１で用意した化合物（Ｅ１）〜（Ｅ１１）、及び比較例１〜７で用意した化合物（ＣＥ１）〜（ＣＥ７）をそれぞれ、２．５、５、１０、２５、５０、１２５、２５０、５００及び１０００ｍｇ／Ｌの濃度となるように水で希釈して試験液を調製した。これらの調製した試験液について、「わかりやすい真菌（かび） 検査法と汚染防止対策（株式会社テクノシステム １９９１年 第一版）、第ＩＩ編わかりやすい真菌（かび） 検査法、第６章抗かび試験、第４節防かび剤の効力試験」に準拠して、下記の試験菌と試験かびに対する最小発育阻止濃度（ｍｇ／Ｌ）を測定した。最小発育阻止濃度が小さいほど、抗菌抗かび性があることを表す。試験菌又は試験かびの種類、培養条件は下記のようにした。結果を表３〜５に示す。
試験菌：黄色ブドウ球菌、肺炎桿菌、大腸菌、緑膿菌
試験かび：黒かび菌、黒かび、青かび、白癖菌
培養条件：（菌）３７℃、４８時間、普通寒天培地
（かび）２５℃、２又は７日間、ポテト・デキストロース寒天培地
<Evaluation 1. Minimum growth inhibitory concentration test of antibacterial antifungal agent>
Compounds (E1) to (E11) prepared in Examples 1 to 11 and compounds (CE1) to (CE7) prepared in Comparative Examples 1 to 7, respectively, were 2.5, 5, 10, 25, 50, and 125, respectively. , 250, 500, and 1000 mg / L, and diluted with water to prepare test solutions. These prepared test solutions are described in “Easy-to-understand fungus (mold) inspection method and contamination prevention measures (Techno System Co., Ltd., 1991 first edition), Part II. The minimum inhibitory concentration (mg / L) for the following test bacteria and test fungi was measured in accordance with "Section 4 Efficacy test of fungicide". The smaller the minimum inhibitory concentration, the more antibacterial and antifungal. The kind of test bacteria or test mold and culture conditions were as follows. The results are shown in Tables 3 to 5.
Test bacteria: Staphylococcus aureus, Klebsiella pneumoniae, Escherichia coli, Pseudomonas aeruginosa Test mold: Black mold, black mold, blue mold, white mold fungus Culture conditions: (fungi) 37 ° C, 48 hours, ordinary agar
(Mold) 25 ° C, potato dextrose agar medium for 2 or 7 days

Figure 2020015706
Figure 2020015706

Figure 2020015706
Figure 2020015706

Figure 2020015706
Figure 2020015706


＜評価２．抗菌抗かび剤の皮膚刺激性試験（クロ−ズド・パッチ試験）＞
実施例１〜１１で用意した化合物（Ｅ１）〜（Ｅ１１）、及び比較例１〜７で用意した化合物（ＣＥ１）〜（ＣＥ７）をそれぞれ、０．５質量％、２．０質量％、及び５．０質量％の濃度となるように水で希釈して、試験液を調製した。得られた試験液を絞り率１００％となるように２ｃｍ×２ｃｍの綿のガーゼにそれぞれしみこませた。試験液をしみこませたガーゼを男女各１０名（合計２０名）の上腕の内側に４８時間貼り続けた後、目視で観察を行って下記の判定基準に従い評価した。２０名の合計ポイントを表６及び７に示すまた、第４級アンモニウム塩を含まない水のみの結果も合わせて示す。
［判定基準］
０ポイント：紅い斑が発生しなかった
１ポイント：軽い紅い斑が発生した。
２ポイント：明らかな紅い斑が発生した。
<Evaluation 2. Skin irritation test of antibacterial antifungal agent (closed patch test)>
The compounds (E1) to (E11) prepared in Examples 1 to 11 and the compounds (CE1) to (CE7) prepared in Comparative Examples 1 to 7 were respectively 0.5% by mass, 2.0% by mass, and A test solution was prepared by diluting with water to a concentration of 5.0% by mass. Each of the obtained test solutions was soaked in cotton gauze of 2 cm × 2 cm so as to have a squeezing ratio of 100%. Gauze impregnated with the test solution was continuously applied to the inside of the upper arm of each of 10 men and women (20 persons in total) for 48 hours, and then visually observed and evaluated according to the following criteria. The total points of the 20 persons are shown in Tables 6 and 7, and the results of water alone without quaternary ammonium salts are also shown.
[Criteria]
0 point: Red spot was not generated. 1 point: Light red spot was generated.
2 points: Apparent red spots occurred.

Figure 2020015706
Figure 2020015706

Figure 2020015706
Figure 2020015706


＜評価３．抗菌抗かび加工したポリエステルフィルムの抗菌性及び抗かび性試験＞
実施例１〜１１で用意した化合物（Ｅ１）〜（Ｅ１１）、及び比較例１〜７で用意した化合物（ＣＥ１）〜（ＣＥ７）をそれぞれ、２．０、８．０、及び２０．０質量％の濃度となるようにイソプロピルアルコールで希釈し、処理液を調製した。ポリエステルフィルム（帝人デュポンフィルム（株）社製、商品名：テイジンテトロンフィルム、銘柄Ｇ２）に対して、得られた処理液をスプレー塗布した。このとき、ポリエステルフィルム１平方メートルあたりの化合物の付着量は、２．０、８．０、及び２０．０質量％の処理液でそれぞれ０．５ｇ／ｍ２、２．０ｇ／ｍ２、及び５．０ｇ／ｍ２となった。スプレー塗布後、ポリエステルフィルムを室温にて１００℃で３０分間乾燥し、加工ポリエステルフィルムを得た。 <Evaluation 3. Antibacterial and antifungal test of antibacterial and antifungal polyester film>
The compounds (E1) to (E11) prepared in Examples 1 to 11 and the compounds (CE1) to (CE7) prepared in Comparative Examples 1 to 7 were 2.0, 8.0, and 20.0 masses, respectively. %, And diluted with isopropyl alcohol to prepare a treatment solution. The obtained treatment liquid was spray-coated on a polyester film (manufactured by Teijin Dupont Film Co., Ltd., trade name: Teijin Tetron Film, brand G2). At this time, the adhesion amount of the compound per square meter of the polyester film was 0.5 g / m 2 , 2.0 g / m 2 , and 5 g for 2.0, 8.0, and 20.0% by mass of the treatment liquid, respectively. 0.0 g / m 2 . After spraying, the polyester film was dried at room temperature at 100 ° C. for 30 minutes to obtain a processed polyester film.

得られた加工ポリエステルフィルム及び未加工ポリエステルフィルムの黄色ブドウ球菌に対する抗菌活性値を、ＪＩＳ Ｚ ２８０１（２０１０）に従って求め、抗菌性を調べた。抗菌活性値が２．０より大きい場合に抗菌効果があると判定した。また、黒麹黴に対する抗かび活性値を社団法人繊維評価技術協議会（以下、繊技協という）のＪＥＣＦ３０１「抗かび加工繊維製品認証基準」に準拠して、抗かび性を調べた。抗かび活性値が２．０より大きい場合に抗かび効果があると判定した。
The antibacterial activity value of the obtained processed polyester film and unprocessed polyester film against Staphylococcus aureus was determined in accordance with JIS Z 2801 (2010), and the antibacterial properties were examined. When the antibacterial activity value was greater than 2.0, it was determined that there was an antibacterial effect. In addition, the antifungal activity against black mold was evaluated for antifungal activity based on JECF301 “Certification Standard for Antifungal Processed Textile Products” of the Japan Textile Evaluation Technology Association (hereinafter referred to as Sengikyo). When the antifungal activity value was greater than 2.0, it was determined that there was an antifungal effect.

Figure 2020015706
Figure 2020015706

Figure 2020015706
Figure 2020015706


＜評価４．抗菌抗かび性ハンドソープの最小発育阻止濃度試験＞
実施例１で用意した化合物（Ｅ１）を配合して、表１０に示す組成（数値の単位は質量％）を有するハンドソープ１〜８を得た。次に、ハンドソープ１〜８の濃度が１質量％となるようにイオン交換水で希釈し、試験液１〜８をそれぞれ調製した。試験液１〜８を用いて、評価１．抗菌抗かび剤の最小発育阻止濃度試験と同様にして、抗菌抗かび性ハンドソープの最小発育阻止濃度試験を行った。なお、試験液１〜８は、抗菌抗かび性が発現した場合、それぞれ２．５ｍｇ／Ｌ、５ｍｇ／Ｌ、１０ｍｇ／Ｌ、２５ｍｇ／Ｌ、５０ｍｇ／Ｌ、１２５ｍｇ／Ｌ、２５０ｍｇ／Ｌ、５００ｍｇ／Ｌの最小発育阻止濃度に相当する。 <Evaluation 4. Antibacterial and antifungal hand soap minimum growth inhibitory concentration test>
The compounds (E1) prepared in Example 1 were blended to obtain Hand Soaps 1 to 8 having the compositions shown in Table 10 (units of numerical values are% by mass). Next, test liquids 1 to 8 were prepared by diluting with ion-exchanged water so that the concentrations of the hand soaps 1 to 8 were 1% by mass. Evaluation using test liquids 1 to 8 The minimum growth inhibitory concentration test of the antibacterial antifungal hand soap was performed in the same manner as the test for the minimum growth inhibitory concentration of the antibacterial antifungal agent. In addition, when the antibacterial and antifungal properties were developed, the test liquids 1 to 8 each contained 2.5 mg / L, 5 mg / L, 10 mg / L, 25 mg / L, 50 mg / L, 125 mg / L, 250 mg / L, and 500 mg. / L corresponding to the minimum inhibitory concentration.

化合物（Ｅ１）に代えて、実施例２、４、６〜９で用意した化合物（Ｅ２）、（Ｅ４）、（Ｅ６）〜（Ｅ９）又は比較例１〜７で用意した化合物（ＣＥ１）〜（ＣＥ７）を用いたこと以外は、上記と同様にして抗菌抗かび性ハンドソープの最小発育阻止濃度試験を行った。   Instead of the compound (E1), the compounds (E2), (E4), (E6) to (E9) prepared in Examples 2, 4, 6 to 9 or the compounds (CE1) to (E1) prepared in Comparative Examples 1 to 7 A minimum growth inhibitory concentration test of an antibacterial and antifungal hand soap was performed in the same manner as described above except that (CE7) was used.

これらの結果を表１１及び１２に示す。
The results are shown in Tables 11 and 12.

Figure 2020015706
Figure 2020015706

Figure 2020015706
Figure 2020015706



Figure 2020015706
Figure 2020015706



＜評価５．抗菌抗かび性ボディソープの最小発育阻止濃度試験＞
実施例１で用意した化合物（Ｅ１）を配合して、表１３に示す組成（数値の単位は質量％）を有するボディソープ１〜８を得た。次に、ボディソープ１〜８の濃度が１質量％となるようにイオン交換水で希釈し、試験液１〜８をそれぞれ調製した。試験液１〜８を用いて、評価１．抗菌抗かび剤の最小発育阻止濃度試験と同様にして、抗菌抗かび性ボディソープの最小発育阻止濃度試験を行った。なお、試験液１〜８は、抗菌抗かび性が発現した場合、それぞれ２．５ｍｇ／Ｌ、５ｍｇ／Ｌ、１０ｍｇ／Ｌ、２５ｍｇ／Ｌ、５０ｍｇ／Ｌ、１２５ｍｇ／Ｌ、２５０ｍｇ／Ｌ、５００ｍｇ／Ｌの最小発育阻止濃度に相当する。 <Evaluation 5. Test for minimum inhibitory concentration of antibacterial and antifungal body soap>
The compound (E1) prepared in Example 1 was blended to obtain body soaps 1 to 8 having the compositions shown in Table 13 (units of numerical values are% by mass). Next, test solutions 1 to 8 were prepared by diluting with body water so that the concentrations of body soaps 1 to 8 would be 1% by mass. Evaluation using test liquids 1 to 8 A minimum inhibitory concentration test of an antibacterial antifungal body soap was performed in the same manner as in the test of the minimum inhibitory concentration of the antibacterial antifungal agent. In addition, when the antibacterial and antifungal properties were developed, the test liquids 1 to 8 each contained 2.5 mg / L, 5 mg / L, 10 mg / L, 25 mg / L, 50 mg / L, 125 mg / L, 250 mg / L, and 500 mg. / L corresponding to the minimum inhibitory concentration.

化合物（Ｅ１）に代えて、実施例２、６〜８、１０で用意した化合物（Ｅ２）、（Ｅ６）〜（Ｅ８）、（Ｅ１０）又は比較例１〜７で用意した化合物（ＣＥ１）〜（ＣＥ７）を用いたこと以外は、上記と同様にして抗菌抗かび性ボディソープの最小発育阻止濃度試験を行った。   Instead of the compound (E1), the compounds (E2), (E6) to (E8) and (E10) prepared in Examples 2, 6 to 8, and 10 or the compounds (CE1) to 7 prepared in Comparative Examples 1 to 7 The minimum growth inhibitory concentration test of the antibacterial and antifungal body soap was carried out in the same manner as described above, except that (CE7) was used.

これらの結果を表１４及び１５に示す。
The results are shown in Tables 14 and 15.

Figure 2020015706
Figure 2020015706

Figure 2020015706
Figure 2020015706



Figure 2020015706
Figure 2020015706


＜評価６．抗菌抗かび性ハンドソープの皮膚刺激性試験（クロ−ズド・パッチ試験）＞
実施例１で用意した化合物（Ｅ１）を配合して、下記に示す組成を有するハンドソープ１を調製した。次いで、ハンドソープ１の濃度が１０、２０、又は５０質量％となるようにイオン交換水で希釈し、試験液１〜３を得た。得られた試験液１〜３を用い、評価２．抗菌抗かび剤の皮膚刺激性試験と同様にして、抗菌抗かび性ハンドソープの皮膚刺激性試験を行った。 <Evaluation 6. Skin irritation test of antibacterial and antifungal hand soap (closed patch test)>
Compound (E1) prepared in Example 1 was blended to prepare Hand Soap 1 having the following composition. Then, it was diluted with ion-exchanged water so that the concentration of the hand soap 1 was 10, 20, or 50% by mass, to obtain Test Solutions 1 to 3. Evaluation 2 using the obtained test liquids 1 to 3. The skin irritation test of the antibacterial antifungal hand soap was performed in the same manner as the skin irritation test of the antibacterial antifungal agent.

（配合成分） （質量％）
ヤシ油脂肪酸カリウム １６
ラウリルジメチルベタイン ４
トリエタノールアミン ４
ジエチレングリコールジステアレート １
化合物（Ｅ１） ２
イオン交換水 ７３
合計 １００ (Blend components) (% by mass)
Coconut oil fatty acid potassium 16
Lauryl dimethyl betaine 4
Triethanolamine 4
Diethylene glycol distearate 1
Compound (E1) 2
Ion exchange water 73
Total 100

化合物（Ｅ１）に代えて、実施例２、４、６〜９で用意した化合物（Ｅ２）、（Ｅ４）、（Ｅ６）〜（Ｅ９）又は比較例１〜７で用意した化合物（ＣＥ１）〜（ＣＥ７）を用いたこと以外は、上記と同様にして抗菌抗かび性ハンドソープの皮膚刺激性試験を行った。   Instead of the compound (E1), the compounds (E2), (E4), (E6) to (E9) prepared in Examples 2, 4, 6 to 9 or the compounds (CE1) to (E1) prepared in Comparative Examples 1 to 7 A skin irritation test of an antibacterial and antifungal hand soap was performed in the same manner as described above, except that (CE7) was used.

これらの結果を表１６及び１７に示す。また、第４級アンモニウム塩を含まないハンドソープの結果も合わせて示す。
The results are shown in Tables 16 and 17. The results of hand soap containing no quaternary ammonium salt are also shown.

Figure 2020015706
Figure 2020015706

Figure 2020015706
Figure 2020015706


＜評価７．抗菌抗かび性ボディソープを使った抗菌抗かび試験の皮膚刺激性試験（クロ−ズド・パッチ試験）＞
実施例１で用意した化合物（Ｅ１）を配合して、下記に示す組成を有するボディソープ１を調製した。次いで、ボディソープ１の濃度が１０、２０、又は５０質量％となるようにイオン交換水で希釈し、試験液１〜３を得た。得られた試験液１〜３を用い、評価２．抗菌抗かび剤の皮膚刺激性試験と同様にして、抗菌抗かび性ボディソープの皮膚刺激性試験を行った。 <Evaluation 7. Skin irritation test of antibacterial antifungal test using antibacterial antifungal body soap (closed patch test)>
The compound (E1) prepared in Example 1 was blended to prepare a body soap 1 having the following composition. Next, the body soap 1 was diluted with ion-exchanged water so that the concentration of the body soap 1 became 10, 20, or 50% by mass, to obtain Test Solutions 1 to 3. Evaluation 2 using the obtained test liquids 1 to 3. The skin irritation test of the antibacterial antifungal body soap was performed in the same manner as the skin irritation test of the antibacterial antifungal agent.

（配合成分） （質量％）
ポリオキシエチレン（２）ラウリルエーテル硫酸 １６
エステルナトリウム
ラウリルジメチルベタイン ３
化合物（Ｅ１） １
イオン交換水 ８０
合計 １００ (Blend components) (% by mass)
Polyoxyethylene (2) lauryl ether sulfate 16
Sodium ester lauryl dimethyl betaine 3
Compound (E1) 1
Ion exchange water 80
Total 100

化合物（Ｅ１）に代えて、実施例２、６〜８、１０で用意した化合物（Ｅ２）、（Ｅ６）〜（Ｅ８）、（Ｅ１０）又は比較例１〜７で用意した化合物（ＣＥ１）〜（ＣＥ７）を用いたこと以外は、上記と同様にして抗菌抗かび性ボディソープの皮膚刺激性試験を行った。   Instead of the compound (E1), the compounds (E2), (E6) to (E8) and (E10) prepared in Examples 2, 6 to 8, and 10 or the compounds (CE1) to 7 prepared in Comparative Examples 1 to 7 A skin irritation test of an antibacterial and antifungal body soap was performed in the same manner as described above, except that (CE7) was used.

これらの結果を表１８及び１９に示す。また、第４級アンモニウム塩を含まないボディソープの結果も合わせて示す。
The results are shown in Tables 18 and 19. In addition, the results of a body soap containing no quaternary ammonium salt are also shown.

Figure 2020015706
Figure 2020015706

Figure 2020015706
Figure 2020015706

本発明によれば、十分な抗菌抗かび性能を有しつつ、従来よりも低刺激性の抗菌抗かび剤及び抗菌抗かび性製品を提供することができる。
According to the present invention, it is possible to provide an antibacterial antifungal agent and an antibacterial antifungal product which have sufficient antibacterial and antifungal properties and are less irritating than conventional ones.

Claims (3)

下記一般式（１）で示される化合物を含有する、抗菌抗かび剤。
Figure 2020015706
［式（１）中、Ｒ１、Ｒ２、Ｒ３及びＲ４のうちの１つ又は２つが、それぞれ独立に、ヒドロキシル基を有していてもよい炭素数８〜２２のアルキル基、又はヒドロキシル基を有していてもよい炭素数８〜２２のアルケニル基を示し、残りの３つ又は２つが、それぞれ独立に、下記一般式（２）で示される基を示し、Ｘ−が対イオンを示す。
−（Ａ１Ｏ）ｎ−Ｈ （２）
｛式（２）中、Ａ１は炭素数１〜６のアルキレン基又は炭素数２〜６のアルケニレン基を示し、ｎは１〜７の整数を示し、前記化合物の分子内におけるｎの総和は９以下であり、ｎが２以上の場合、複数のＡ１は同一であっても、異なっていてもよい。｝］ An antibacterial and antifungal agent comprising a compound represented by the following general formula (1).
Figure 2020015706
[In the formula (1), one or two of R 1 , R 2 , R 3, and R 4 are each independently an alkyl group having 8 to 22 carbon atoms which may have a hydroxyl group, or an alkenyl group having 8 to 22 carbon atoms which may have a hydroxyl group, but the remaining three or two, each independently represent a group represented by the following general formula (2), X - is a counter ion Is shown.
- (A 1 O) n -H (2)
｛In Formula (2), A 1 represents an alkylene group having 1 to 6 carbon atoms or an alkenylene group having 2 to 6 carbon atoms, n represents an integer of 1 to 7, and the total sum of n in the molecule of the compound is When n is 9 or less and n is 2 or more, a plurality of A 1 may be the same or different. ｝] 請求項１に記載の抗菌抗かび剤によって抗菌抗かび性が付与された、抗菌抗かび性製品。   An antibacterial and antifungal product provided with antibacterial and antifungal properties by the antibacterial and antifungal agent according to claim 1. 下記一般式（１）で示される化合物を含有する、皮膚用洗浄剤。
Figure 2020015706
［式（１）中、Ｒ１、Ｒ２、Ｒ３及びＲ４のうちの１つ又は２つが、それぞれ独立に、ヒドロキシル基を有していてもよい炭素数８〜２２のアルキル基、又はヒドロキシル基を有していてもよい炭素数８〜２２のアルケニル基を示し、残りの３つ又は２つが、それぞれ独立に、下記一般式（２）で示される基を示し、Ｘ−が対イオンを示す。
−（Ａ１Ｏ）ｎ−Ｈ （２）
｛式（２）中、Ａ１は炭素数１〜６のアルキレン基又は炭素数２〜６のアルケニレン基を示し、ｎは１〜７の整数を示し、前記化合物の分子内におけるｎの総和は９以下であり、ｎが２以上の場合、複数のＡ１は同一であっても、異なっていてもよい。｝］
A skin cleanser comprising a compound represented by the following general formula (1).
Figure 2020015706
[In the formula (1), one or two of R 1 , R 2 , R 3, and R 4 are each independently an alkyl group having 8 to 22 carbon atoms which may have a hydroxyl group, or an alkenyl group having 8 to 22 carbon atoms which may have a hydroxyl group, but the remaining three or two, each independently represent a group represented by the following general formula (2), X - is a counter ion Is shown.
- (A 1 O) n -H (2)
｛In Formula (2), A 1 represents an alkylene group having 1 to 6 carbon atoms or an alkenylene group having 2 to 6 carbon atoms, n represents an integer of 1 to 7, and the total sum of n in the molecule of the compound is When n is 9 or less and n is 2 or more, a plurality of A 1 may be the same or different. ｝]
JP2018141757A 2018-07-27 2018-07-27 Antibacterial and antifungal agent and antibacterial and antifungal product Pending JP2020015706A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2018141757A JP2020015706A (en) 2018-07-27 2018-07-27 Antibacterial and antifungal agent and antibacterial and antifungal product
PCT/JP2019/018036 WO2020021810A1 (en) 2018-07-27 2019-04-26 Antibacterial/antifungal agent and antibacterial/antifungal product

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2018141757A JP2020015706A (en) 2018-07-27 2018-07-27 Antibacterial and antifungal agent and antibacterial and antifungal product

Publications (1)

Publication Number Publication Date
JP2020015706A true JP2020015706A (en) 2020-01-30

Family

ID=69182278

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2018141757A Pending JP2020015706A (en) 2018-07-27 2018-07-27 Antibacterial and antifungal agent and antibacterial and antifungal product

Country Status (2)

Country Link
JP (1) JP2020015706A (en)
WO (1) WO2020021810A1 (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5323378B1 (en) * 1965-05-28 1978-07-14
JPS594695A (en) * 1982-06-30 1984-01-11 ジヨンソン株式会社 Detergent composition
JPS5988494A (en) * 1982-10-06 1984-05-22 チバ−ガイギ−・アクチエンゲゼルシヤフト Ammonium stannate-(iv), manufacture and organism killing agent
JPS6481900A (en) * 1987-09-24 1989-03-28 Shiseido Co Ltd Cleaning agent composition
JPH08283779A (en) * 1995-04-10 1996-10-29 Nikka Chem Co Ltd Disinfecting detergent with chelating capability and its production
JPH10226797A (en) * 1997-02-14 1998-08-25 Asahi Denka Kogyo Kk Detergent composition for use in kitchen and for clothing and body
JP2003160402A (en) * 2001-11-21 2003-06-03 Sds Biotech:Kk Wood preserving agent and method for treating wood
JP2009149574A (en) * 2007-12-21 2009-07-09 Kao Corp Antimicrobial agent
JP2013517249A (en) * 2010-01-18 2013-05-16 ビーエーエスエフ ソシエタス・ヨーロピア Composition comprising a pesticide and an alkoxylate of 2-propylheptylamine

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5323378B1 (en) * 1965-05-28 1978-07-14
JPS594695A (en) * 1982-06-30 1984-01-11 ジヨンソン株式会社 Detergent composition
JPS5988494A (en) * 1982-10-06 1984-05-22 チバ−ガイギ−・アクチエンゲゼルシヤフト Ammonium stannate-(iv), manufacture and organism killing agent
JPS6481900A (en) * 1987-09-24 1989-03-28 Shiseido Co Ltd Cleaning agent composition
JPH08283779A (en) * 1995-04-10 1996-10-29 Nikka Chem Co Ltd Disinfecting detergent with chelating capability and its production
JPH10226797A (en) * 1997-02-14 1998-08-25 Asahi Denka Kogyo Kk Detergent composition for use in kitchen and for clothing and body
JP2003160402A (en) * 2001-11-21 2003-06-03 Sds Biotech:Kk Wood preserving agent and method for treating wood
JP2009149574A (en) * 2007-12-21 2009-07-09 Kao Corp Antimicrobial agent
JP2013517249A (en) * 2010-01-18 2013-05-16 ビーエーエスエフ ソシエタス・ヨーロピア Composition comprising a pesticide and an alkoxylate of 2-propylheptylamine

Also Published As

Publication number Publication date
WO2020021810A1 (en) 2020-01-30

Similar Documents

Publication Publication Date Title
EP3500102B1 (en) Anti-microbial composition
CN107466207A (en) Antimicrobial compositions
JP4610144B2 (en) Antibacterial siloxane quat formulation, its production and use
CN111876272A (en) Laundry detergent
US6620854B2 (en) Surface-active preparations
JP6614848B2 (en) Liquid softener composition
JP4750499B2 (en) Ionic liquid and antibacterial agent and antibacterial fiber using the same
WO2011148950A1 (en) Antibacterial and antifungal agent, and antibacterial and antifungal product
KR20130093014A (en) Liquid bleaching composition for garment
JP5165362B2 (en) Antibacterial agent
KR101489128B1 (en) Heated moist towelette and method for producing heated moist towelette
JP6802068B2 (en) Liquid antibacterial agents, including water-soluble polymers and water-soluble antibacterial agents
JP2020015706A (en) Antibacterial and antifungal agent and antibacterial and antifungal product
JP6231617B2 (en) Liquid detergent composition for clothing
JP6739772B2 (en) Antibacterial/antiviral composition, aqueous solution, soap, hygiene product, household detergent, kitchen detergent, laundry detergent, residential antibacterial/antiviral agent, kitchen antibacterial/antiviral agent, clothing antibacterial/antiviral agent , Cosmetics, wet tissues and hand towels
EP3420063A1 (en) Detergent or cleaning agent having an improved antimicrobial effect
JP5165363B2 (en) Antibacterial agent
WO2021079798A1 (en) Wipe material
CN114501991B (en) Deodorant composition
KR100828023B1 (en) Fabric softener composition
JP2003535047A (en) Use of 3-iodine-2-propynyl carbamate as an antimicrobial active agent
WO2022181457A1 (en) Wipe sheet and aqueous composition for impregnating wipe sheet
KR910003655B1 (en) Preparation of polyester fibers having excellent antibacterial and decorizing properties
SU349133A1 (en)
JP2023048363A (en) Antiviral agent composition for fiber

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20210521

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20220517

A02 Decision of refusal

Free format text: JAPANESE INTERMEDIATE CODE: A02

Effective date: 20221115