JP2000026205A - Antibacterial and antifungal agent and its production - Google Patents
Antibacterial and antifungal agent and its productionInfo
- Publication number
- JP2000026205A JP2000026205A JP10194292A JP19429298A JP2000026205A JP 2000026205 A JP2000026205 A JP 2000026205A JP 10194292 A JP10194292 A JP 10194292A JP 19429298 A JP19429298 A JP 19429298A JP 2000026205 A JP2000026205 A JP 2000026205A
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- antifungal
- antifungal agent
- compound
- reaction product
- 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
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、抗菌防黴剤及びそ
の製造方法に関し、特に、抗菌性、防黴性の両効果に優
れると共にその効果の持続性（抗菌防黴効果の徐放性）
に優れ、かつ抗菌防黴性の金属イオンに由来する変色を
抑制し、耐熱性にも優れた抗菌防黴剤及びその製造方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial and antifungal agent and a method for producing the same, and more particularly, it is excellent in both antibacterial and antifungal effects and has a sustained effect (sustained release of antibacterial and antifungal effect).
The present invention relates to an antibacterial and antifungal agent which is excellent in heat resistance, suppresses discoloration derived from metal ions having antibacterial and antifungal properties, and has excellent heat resistance and a method for producing the same.
【０００２】[0002]
【従来の技術】従来から用いられている抗菌抗黴剤は、
大別すると無機系と有機系との２種類がある。前者に
は、銀、銅、亜鉛等の抗菌性金属イオンを、ゼオライ
ト、アパタイト、シリカゲル、モンモリロナイトなどの
層状化合物などに担持させた化合物がある。また、後者
にはチアゾリルベンツイミダゾールなどのイミダゾール
系、２−メチル−イソチアゾリン−３−オンなどのチア
ゾール系、塩化ベンザルコニウムなどの４級アンモニウ
ム系、エチルアルコールなどのアルコール系、ＯＢＰＡ
（ 10 ，10−オキシビスフェノキシアルシン）のような
有機ヒ素化合物や８−オキシキノリン銅などの有機金属
化合物、その他天然系など数多くの化合物がある。2. Description of the Related Art Antibacterial and antifungal agents conventionally used are
Broadly classified, there are two types: inorganic and organic. The former includes compounds in which antibacterial metal ions such as silver, copper, and zinc are supported on layered compounds such as zeolite, apatite, silica gel, and montmorillonite. The latter include imidazoles such as thiazolylbenzimidazole, thiazoles such as 2-methyl-isothiazolin-3-one, quaternary ammoniums such as benzalkonium chloride, alcohols such as ethyl alcohol, and OBPA.
There are many compounds such as organic arsenic compounds such as (10,10-oxybisphenoxyarsine), organic metal compounds such as copper 8-oxyquinoline, and other natural compounds.
【０００３】〔問題点〕しかしながら、従来の無機系抗
菌防黴剤ではイオン交換、インターカレーションなど比
較的強固ではない結合力を利用しているため、層間の金
属イオンが、共存するイオン種によっては容易に脱離し
たり還元することなどによって、変色を引き起こし、意
匠性を失ったりした。また、無機担持体にモンモリロナ
イトなどの層状化合物を用いた場合、イオン交換性の化
合物であるため、そのイオン交換容量が固有であるため
担持量が制限される。[Problems] However, since the conventional inorganic antibacterial and fungicide uses a relatively weak binding force such as ion exchange and intercalation, the metal ions between the layers may vary depending on the coexisting ionic species. Easily dissociated or reduced, causing discoloration and loss of design. When a layered compound such as montmorillonite is used as the inorganic carrier, the amount of the carrier is limited because the compound is an ion-exchangeable compound and has an inherent ion exchange capacity.
【０００４】一方、有機系抗菌防黴剤は有機化合物原体
であるため、耐熱性に劣り、揮発、溶出のため耐久性に
欠け、効果が持続しないなどの不具合があった。特に、
プラスチックや繊維などへの練り混み加工に使用した場
合、有機系抗菌防黴剤の耐熱温度が加工温度より高くて
も処理時間によってはより低温で揮発などが生じ、十分
な抗菌防黴効果が発揮されていなかった。また、親水性
に乏しく、水に対する分散性が良くなかった。On the other hand, since the organic antibacterial and fungicide is a raw material of an organic compound, it has poor heat resistance, lacks durability due to volatilization and elution, and has a problem that the effect is not maintained. In particular,
When used in kneading of plastics and fibers, even if the heat resistance temperature of the organic antibacterial and antifungal agent is higher than the processing temperature, volatilization occurs at lower temperatures depending on the processing time, and a sufficient antibacterial and antifungal effect is exhibited. Had not been. Moreover, the hydrophilicity was poor and the dispersibility in water was not good.
【０００５】また、一般に、無機系抗菌防黴剤は菌に対
して、有機系抗菌防黴剤は黴に対して効果が高く、それ
ぞれ抗菌性、防黴性のどちらかの効果を主として発揮す
るため、抗菌防黴性を備えるためには両者を併用しなけ
ればならなかった。In general, inorganic antibacterial and fungicides are highly effective against fungi, and organic antibacterial and fungicides are effective against fungi. Therefore, both must be used in combination in order to provide antibacterial and antifungal properties.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、上記問題点
に鑑みてなされたものであり、その解決のため具体的に
設定された課題は、抗菌性、防黴性の両方に優れた効果
を示すとともに、変色防止性、抗菌防黴効果の持続性
（抗菌防黴成分の徐放性）、耐熱性等を高め、長期使用
可能な抗菌防黴剤及びその製造方法を提供することにあ
る。DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and the problems specifically set for solving the problems are an effect excellent in both antibacterial properties and antifungal properties. In addition, the present invention provides an antibacterial and antifungal agent which can be used for a long period of time and has a long-term use, and a method for producing the antibacterial and antifungal agent. .
【０００７】[0007]
【課題を解決するための手段】本発明における請求項１
に係る抗菌防黴剤は、抗菌性金属成分と防黴性有機化合
物との反応生成物が多孔質シリカ粒子の表面及び／又は
内部に固着していることを特徴とするものである。Means for Solving the Problems Claim 1 of the present invention
The antibacterial and antifungal agent according to the invention is characterized in that a reaction product of an antibacterial metal component and an antifungal organic compound is fixed on the surface and / or inside of the porous silica particles.
【０００８】請求項２に係る抗菌防黴剤は、抗菌性金属
成分と防黴性有機化合物との反応生成物が多孔質シリカ
により内包されていることを特徴とする。The antibacterial and antifungal agent according to claim 2 is characterized in that a reaction product of an antibacterial metal component and an antifungal organic compound is included in porous silica.
【０００９】請求項３に係る抗菌防黴剤は、請求項１に
係る抗菌防黴剤の粒子径が 0.01 〜１μｍであることを
特徴とする。The antibacterial and antifungal agent according to claim 3 is characterized in that the antibacterial and antifungal agent according to claim 1 has a particle size of 0.01 to 1 μm.
【００１０】請求項４に係る抗菌防黴剤は、請求項２に
係る抗菌防黴剤の粒子径が0.01〜５μｍであることを特
徴とする。According to a fourth aspect of the present invention, there is provided an antibacterial and antifungal agent according to the second aspect, wherein the antibacterial and antifungal agent has a particle size of 0.01 to 5 μm.
【００１１】請求項５に係る抗菌防黴剤は、前記防黴性
有機化合物がイミダゾール系化合物、チアゾール系化合
物、Ｎ−ハロアルキルチオ系化合物、ピリジン系化合
物、イソチアゾロン系化合物からなる群から選ばれた少
なくとも１種であることを特徴とする。[0011] In the antibacterial and fungicide according to claim 5, the fungicidal organic compound is selected from the group consisting of an imidazole compound, a thiazole compound, an N-haloalkylthio compound, a pyridine compound and an isothiazolone compound. It is characterized by at least one kind.
【００１２】請求項６に係る抗菌防黴剤の製造方法は、
抗菌性金属成分と防黴性有機化合物との反応生成物をシ
リカにより処理することを特徴とするものである。[0012] The method for producing an antibacterial and fungicide according to claim 6 comprises:
The reaction product of the antibacterial metal component and the antifungal organic compound is treated with silica.
【００１３】請求項７に係る抗菌防黴剤の製造方法は、
抗菌性金属成分と防黴性有機化合物との反応生成物が分
散したアルカリ金属の珪酸塩の水溶液と、アルカリ金属
の珪酸塩を不溶化する化合物の水溶液とを混合・攪拌す
ることを特徴とする。[0013] The method for producing an antibacterial and antifungal agent according to claim 7 comprises:
An aqueous solution of an alkali metal silicate in which a reaction product of an antibacterial metal component and an antifungal organic compound is dispersed is mixed and stirred with an aqueous solution of a compound that insolubilizes the alkali metal silicate.
【００１４】請求項８に係る抗菌防黴剤の製造方法は、
抗菌性金属成分と防黴性有機化合物との反応生成物が分
散したアルカリ金属の珪酸塩を不溶化する化合物の水溶
液と、アルカリ金属の珪酸塩の水溶液とを混合・攪拌す
ることを特徴とする。[0014] The method for producing an antibacterial and fungicide according to claim 8 comprises:
An aqueous solution of a compound insolubilizing an alkali metal silicate in which a reaction product of an antibacterial metal component and an antifungal organic compound is dispersed, and an aqueous solution of an alkali metal silicate are mixed and stirred.
【００１５】請求項９に係る抗菌防黴剤の製造方法は、
アルコキシシラン中に、抗菌性金属成分と防黴性有機化
合物との反応生成物を粉状または分散した状態で添加
し、加水分解触媒を加え、攪拌しながら前記アルコキシ
シランを加水分解することを特徴とする。[0015] The method for producing an antibacterial and antifungal agent according to claim 9 comprises:
In the alkoxysilane, a reaction product of the antibacterial metal component and the antifungal organic compound is added in a powdery or dispersed state, a hydrolysis catalyst is added, and the alkoxysilane is hydrolyzed with stirring. And
【００１６】請求項１０に係る抗菌防黴剤の製造方法
は、防黴性有機化合物が溶解したアルコキシシラン中
に、抗菌性金属成分塩の水溶液を添加し、加水分解触媒
を加え、攪拌しながら前記アルコキシシラン化合物を加
水分解することを特徴とする。[0016] According to a tenth aspect of the present invention, there is provided a method for producing an antibacterial fungicide, comprising adding an aqueous solution of an antibacterial metal component salt to an alkoxysilane in which a fungicidal organic compound is dissolved, adding a hydrolysis catalyst, and stirring the mixture. The method is characterized in that the alkoxysilane compound is hydrolyzed.
【００１７】請求項１１に係る抗菌防黴剤の製造方法
は、抗菌性金属成分と防黴性有機化合物との反応生成物
を、アルカリ金属の珪酸塩の水溶液に分散する工程Ａ
と、この工程Ａで得られた分散液に水不溶性又は難溶性
の有機溶媒を混合してＷ／Ｏ型エマルジョンとする工程
Ｂと、この工程Ｂで得られたＷ／Ｏ型エマルジョンに、
前記アルカリ金属の珪酸塩を不溶化する化合物の水溶液
を添加して攪拌し、微多孔質カプセル粒子を生成する工
程Ｃとからなることを特徴とする。In the method for producing an antibacterial and antifungal agent according to claim 11, the reaction product of the antibacterial metal component and the antifungal organic compound is dispersed in an aqueous solution of an alkali metal silicate.
Step B of mixing the dispersion obtained in Step A with a water-insoluble or poorly soluble organic solvent to form a W / O emulsion; and W / O emulsion obtained in Step B,
A step C of adding an aqueous solution of the compound for insolubilizing the alkali metal silicate and stirring the mixture to form microporous capsule particles.
【００１８】[0018]
【発明の実施の形態】以下、本発明の実施の形態を具体
的に説明する。ただし、この実施の形態は、本発明をよ
り良く理解させるため具体的に説明するものであり、特
に指定のない限り、発明内容を限定するものではない。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. However, the embodiments are specifically described for better understanding of the present invention, and do not limit the contents of the invention unless otherwise specified.
【００１９】〔抗菌防黴剤〕この実施の形態における抗
菌防黴剤は、抗菌性金属成分と防黴性有機化合物との反
応生成物がシリカにより処理されて、次の形態となった
ものである。 （ａ）抗菌性金属成分と防黴性有機化合物との反応生成
物が、多孔質シリカ粒子の表面及び／又は内部に固着し
たもの。 （ｂ）抗菌性金属成分と防黴性有機化合物との反応生成
物が、多孔質シリカにより内包されたもの。[Antimicrobial and antifungal agent] The antimicrobial and antifungal agent of this embodiment is obtained by treating a reaction product of an antimicrobial metal component and an antifungal organic compound with silica to form the following form. is there. (A) A product in which a reaction product of an antibacterial metal component and an antifungal organic compound adheres to the surface and / or inside of porous silica particles. (B) A reaction product of an antibacterial metal component and a fungicidal organic compound encapsulated in porous silica.
【００２０】上記のうち、抗菌防黴剤（ａ）は、抗菌性
金属成分と防黴性有機化合物との反応生成物が、シリカ
の網目構造中及び／又は構造端に固着しており、下記に
詳述する第１〜４の製造方法により、粒径が微細な、ま
た、抗菌性金属成分と防黴性有機化合物との反応生成物
の担持量の大きなものが、容易に得られ、また、顕著な
抗菌防黴効果を有する点で特に好ましい。Among the above, the antibacterial and antifungal agent (a) has a reaction product of an antibacterial metal component and an antifungal organic compound fixed to the silica network structure and / or at the structural end thereof. According to the first to fourth production methods described in detail, fine particles having a large particle size, and a large amount of the reaction product of the antibacterial metal component and the antifungal organic compound can be easily obtained. It is particularly preferable in that it has a remarkable antibacterial and antifungal effect.
【００２１】なお、抗菌性金属成分と防黴性有機化合物
との反応生成物の、シリカの網目構造中及び／又は構造
端に固着した状態は、必ずしも明確でないが、図１およ
び図２に示すように、シリカの網目構造中及び／又は構
造端に位置する珪酸基（Ｓｉ−Ｏ- ）を介して結合して
いるものと推定される。The state in which the reaction product of the antibacterial metal component and the antifungal organic compound is fixed in the silica network structure and / or at the structural end is not necessarily clear, but is shown in FIGS. 1 and 2. as silicate group located in a network structure and / or structure end of the silica - is estimated that over a bonded (Si-O).
【００２２】また、抗菌防黴剤（ｂ）は、不溶性のシリ
カを、抗菌性金属成分と防黴性有機化合物との反応生成
物の周囲に沈着させて、抗菌性金属成分と防黴性有機化
合物との反応生成物をシリカからなる多数の微小な孔を
有するカプセルで包み込んだ形態を採る。In addition, the antibacterial and fungicide (b) deposits insoluble silica around the reaction product of the antibacterial metal component and the antifungal organic compound to form an antibacterial metal component and an antifungal organic compound. The reaction product of the compound is encapsulated in a capsule having a large number of fine pores made of silica.
【００２３】前記抗菌防黴剤において、抗菌性金属成分
は特に限定されるものではないが、安全性、抗菌性等の
観点から、例えば銀、銅、亜鉛等が用いられ、特に銀が
好適に用いられる。In the antibacterial and antifungal agent, the antibacterial metal component is not particularly limited, but from the viewpoint of safety, antibacterial properties, etc., for example, silver, copper, zinc or the like is used, and silver is particularly preferable. Used.
【００２４】また防黴性有機化合物も、抗菌性金属成分
と反応して生成物を生成するものであれば特に限定され
るものではないが、安全性、防黴性、汎用性などの観点
から、例えばイミダゾール系、チアゾール系では２−
（４−チアゾリル）−ベンツイミダゾール（以下、ＴＢ
Ｚと略記する）、Ｎ−ハロアルキルチオ系ではＮ−（フ
ルオロジクロロメチルチオ）−フタルイミド、ピリジン
系では２，３，５，６−テトラクロロ−４−（メチルス
ルフォニル）−ピリジン、イソチアゾロン系では１，２
−ベンツイソチアゾロンなどが用いられ、特に、ＴＢＺ
のような、抗菌性金属成分に対して有機配位子になり得
るものが好適に用いられる。The antifungal organic compound is not particularly limited as long as it reacts with the antibacterial metal component to form a product, but from the viewpoints of safety, antifungal properties and versatility. For example, in the case of imidazole and thiazole, 2-
(4-thiazolyl) -benzimidazole (hereinafter referred to as TB
Z), N- (fluorodichloromethylthio) -phthalimide for N-haloalkylthio, 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine for pyridine and 1,1 for isothiazolone 2
-Benzisothiazolone and the like, especially TBZ
Those which can become an organic ligand to the antibacterial metal component are suitably used.
【００２５】抗菌性金属成分と防黴性有機化合物との反
応生成物は、反応生成物中に、抗菌性成分と防黴性成分
とを併せて有していることから、抗菌性、防黴性の双方
に優れた効果を有する。そして、この抗菌防黴剤は、耐
熱性、抗菌・防黴効果の持続性（即ち、抗菌・防黴作用
の徐放性）、耐紫外線性を向上させるという観点等か
ら、抗菌性金属成分と防黴性有機化合物との反応生成物
をシリカにより処理したものである。The reaction product of the antibacterial metal component and the antifungal organic compound contains the antibacterial component and the antifungal component in the reaction product. It has an excellent effect on both properties. The antibacterial and antifungal agent is used in combination with an antibacterial metal component from the viewpoint of improving heat resistance, sustained antibacterial and antifungal effects (that is, sustained release of antibacterial and antifungal effects), and UV resistance. A product obtained by treating a reaction product with an antifungal organic compound with silica.
【００２６】この抗菌防黴剤中の、抗菌性金属成分と防
黴性有機化合物との反応生成物の含有量は、抗菌・防黴
効果の発現性、抗菌・防黴効果の持続性から 0.01 〜 2
0 重量％、好適には 1〜 10 重量％であることが望まし
い。含有量が 0.01 重量％より少ない場合には、抗菌・
防黴効果の発現が不確実となり、一方、 20 重量％を超
えた場合には、抗菌防黴成分の含有量としては過剰とな
り、必要以上の原料コストの増大を招く。The content of the reaction product between the antibacterial metal component and the antifungal organic compound in the antibacterial and antifungal agent is determined by considering the antibacterial and antifungal effect and the durability of the antibacterial and antifungal effect. ~ 2
It is desirably 0% by weight, preferably 1 to 10% by weight. If the content is less than 0.01% by weight,
When the antifungal effect is uncertain, the content of the antibacterial and antifungal component is excessive when the content exceeds 20% by weight, which leads to an unnecessary increase in raw material costs.
【００２７】抗菌防黴剤の粒径は、抗菌防黴剤（ａ）に
あっては 0.01 〜1 μｍ、抗菌防黴剤（ｂ）にあっては
0.01 〜5 μｍであることが、抗菌防黴性を付与する対
象物への分散性が向上し、効果的に抗菌・防黴効果を発
現させる等の点から望ましく、プラスティック、繊維に
対する練り混み加工を考慮した場合、意匠性、強度等を
損なわないためにも、最大粒径は小さいほど望ましい。The particle size of the antibacterial and fungicide (a) is 0.01 to 1 μm, and the particle size of the antibacterial and fungicide (b) is
A particle size of 0.01 to 5 μm is desirable from the viewpoint of improving the dispersibility in an object to which antibacterial and antifungal properties are imparted and effectively exhibiting an antibacterial and antifungal effect. In consideration of the above, the smaller the maximum particle size is, the more desirable it is so as not to impair the design property, strength and the like.
【００２８】この抗菌防黴剤（ａ），（ｂ）を用いて抗
菌防黴性を付与する場合、抗菌防黴剤（ａ），（ｂ）を
対象物に対して添加する。対象物としてはプラスティッ
ク、繊維、セメント、石膏、ゴム、紙、皮革、木材、塗
料、接着剤等が挙げられ、抗菌防黴性が付与される物品
には家電製品、住設機器、建材、雑貨、シーリング材、
アルミやステンレスなどの金属に対する表面コーティン
グフィルム、ガスケット等があり、その他、通常、細菌
や黴の繁殖が懸念される箇所や製品に適用される。When the antibacterial and fungicidal agents (a) and (b) are used to impart antibacterial and fungicidal properties, the antibacterial and fungicidal agents (a) and (b) are added to the object. Examples of objects include plastics, fibers, cement, gypsum, rubber, paper, leather, wood, paints, adhesives, and the like, and articles provided with antibacterial and antifungal properties include home appliances, housing equipment, building materials, and miscellaneous goods. , Sealing materials,
There are surface coating films, gaskets, etc. for metals such as aluminum and stainless steel, and they are usually applied to places and products where there is concern about the propagation of bacteria and mold.
【００２９】〔抗菌防黴剤の製造方法〕この実施の形態
における抗菌防黴剤は、例えば下記のいずれかの方法に
より製造することができる。そして、いずれの製造方法
を用いても、抗菌性金属成分と防黴性有機化合物との反
応生成物の含有量を、その担持形態がイオン交換、イン
ターカレーションによらないため、任意に調整すること
が可能である。[Production method of antibacterial and antifungal agent] The antibacterial and antifungal agent in this embodiment can be produced, for example, by any of the following methods. And, no matter which production method is used, the content of the reaction product between the antibacterial metal component and the antifungal organic compound is arbitrarily adjusted because the supported form does not depend on ion exchange or intercalation. It is possible.
【００３０】〔（ａ）の第１の製造方法〕抗菌防黴剤
（ａ）の第１の製造方法は、抗菌性金属成分と防黴性有
機化合物との反応生成物が分散したアルカリ金属の珪酸
塩水溶液と、このアルカリ金属の珪酸塩を不溶化する化
合物の水溶液とを混合・攪拌して製造する。抗菌防黴剤
の粒径は原料濃度、攪拌条件、熟成温度等を制御して調
節する。[First Production Method of (a)] The first production method of the antibacterial and antifungal agent (a) is a method for preparing an alkali metal in which a reaction product of an antibacterial metal component and an antifungal organic compound is dispersed. A silicate aqueous solution and an aqueous solution of a compound for insolubilizing the alkali metal silicate are mixed and stirred to produce the silicate. The particle size of the antibacterial and antifungal agent is adjusted by controlling the raw material concentration, stirring conditions, aging temperature and the like.
【００３１】また、抗菌性金属成分と防黴性有機化合物
との反応生成物の製法は下記，の方法によるものと
する。これらの実施において、反応生成物が沈殿生成し
ない場合があるが、その際には溶液のｐＨを調整するこ
とにより沈殿生成させることができる場合がある。The reaction product of the antibacterial metal component and the antifungal organic compound is produced by the following method. In these implementations, the reaction product may not form a precipitate, but in that case, precipitation may be possible by adjusting the pH of the solution.
【００３２】 抗菌性金属成分塩、例えば硝酸塩、硫
酸塩、酢酸塩の水溶液と防黴性有機化合物のアルコール
溶液とを混合して反応生成物を得る方法。 酸性または塩基性水溶液、各種有機溶剤に防黴性有
機化合物を溶解し、抗菌性金属成分塩、例えば硝酸塩、
硫酸塩、酢酸塩の水溶液を添加して反応生成物を得る方
法。A method of obtaining a reaction product by mixing an aqueous solution of an antibacterial metal component salt, for example, a nitrate, a sulfate, or an acetate, and an alcohol solution of an antifungal organic compound. Acidic or basic aqueous solutions, dissolving fungicide-resistant organic compounds in various organic solvents, antibacterial metal component salts, such as nitrates,
A method of obtaining a reaction product by adding an aqueous solution of sulfate or acetate.
【００３３】このようなシリカ処理において、前記反応
生成物は分散状態のものを用いる必要がある。これは抗
菌性金属成分塩の水溶液を直接アルカリ金属の珪酸塩水
溶液に加えた場合、金属コロイドが析出したり、酸化
物、水酸化物等が生成して安定化するため、反応生成物
を形成しない場合があるためである。前記反応生成物は
粉体状では比較的分散しにくいため、アルコール、セル
ロース類などを添加することにより分散性を高める。In such a silica treatment, it is necessary to use the reaction product in a dispersed state. This is because when an aqueous solution of an antibacterial metal component salt is directly added to an aqueous solution of a silicate of an alkali metal, a metal colloid is precipitated, and an oxide or a hydroxide is formed and stabilized, thereby forming a reaction product. This is because they may not. Since the reaction product is relatively difficult to disperse in powder form, the dispersibility is enhanced by adding alcohol, cellulose, or the like.
【００３４】シリカ処理された最終反応生成物を沈殿さ
せるには、アルカリ金属の珪酸塩を不溶化する化合物、
例えば硫酸アンモニウム、炭酸アンモニウム、炭酸水素
アンモニウム、炭酸水素ナトリウム、塩化カルシウム塩
等の水溶液を添加することが望ましく、好適には硫酸ア
ンモニウム水溶液を当量より過剰量、好ましくは３倍程
度添加する。In order to precipitate the silica-treated final reaction product, a compound which insolubilizes an alkali metal silicate,
For example, it is desirable to add an aqueous solution of ammonium sulfate, ammonium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, calcium chloride salt or the like, and the ammonium sulfate aqueous solution is preferably added in excess of the equivalent amount, preferably about 3 times.
【００３５】その得られた沈殿物を（例えば温度 35 ℃
にて２時間程度）熟成し、そして、濾過後、十分に蒸留
水で洗浄し、遊離した各種のイオンを洗浄除去し（例え
ば温度 130℃にて２時間程度）乾燥することにより、抗
菌防黴剤（ａ）を得る。[0035] The resulting precipitate (for example, at a temperature of 35 ° C)
Aging for about 2 hours), and after filtration, washing thoroughly with distilled water, washing and removing various released ions (for example, at a temperature of 130 ° C. for about 2 hours), and drying. Agent (a) is obtained.
【００３６】〔（ａ）の第２の製造方法〕抗菌防黴剤
（ａ）の第２の製造方法は、抗菌性金属成分と防黴性有
機化合物との反応生成物が分散した、アルカリ金属の珪
酸塩を不溶化する化合物の水溶液と、アルカリ金属の珪
酸塩水溶液とを混合・攪拌して製造する。その他の条件
については、第１の製造方法に準ずればよい。[Second Production Method of (a)] The second production method of the antibacterial and antifungal agent (a) is a method for preparing an alkali metal dispersion in which a reaction product of an antibacterial metal component and an antifungal organic compound is dispersed. And an aqueous solution of an alkali metal silicate are mixed and stirred to produce the compound. Other conditions may be based on the first manufacturing method.
【００３７】〔（ａ）の第３の製造方法〕抗菌防黴剤
（ａ）の第３の製造方法は、アルコキシシラン中に、抗
菌性金属成分と防黴性有機化合物との反応生成物を粉状
または分散した状態で添加し、加水分解触媒を加え、攪
拌しながら前記アルコキシシランを加水分解して製造す
る。[Third Production Method of (a)] In a third production method of the antibacterial and fungicide (a), a reaction product of an antibacterial metal component and an antifungal organic compound is added to an alkoxysilane. It is added in a powdered or dispersed state, a hydrolysis catalyst is added, and the alkoxysilane is hydrolyzed with stirring to produce.
【００３８】アルコキシシランとしては、比較的安価で
あること、加水分解反応を触媒により制御しやすい等の
理由からテトラメトキシシラン（ＴＭＯＳ）、テトラエ
トキシシラン（ＴＥＯＳ）が好適に用いられる。また、
加水分解触媒としては、各種の無機系、有機系の酸や、
アルカリ性物質等が用いられるが、アルカリ触媒下では
バルク状に加水分解が進み、粒子が大きくなるため、酸
性触媒下で加水分解させるのが望ましく、好適にはｐＨ
2〜5 にて行う。抗菌防黴剤の粒径を望ましい値である
0.01 〜１μｍとするには、原料濃度、触媒のｐＨ、反
応温度等を適宜選定して制御すればよい。その他の条件
については、第１の製造方法に準ずればよい。As the alkoxysilane, tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS) are preferably used because they are relatively inexpensive and the hydrolysis reaction is easily controlled by a catalyst. Also,
As the hydrolysis catalyst, various inorganic and organic acids,
Although an alkaline substance or the like is used, hydrolysis proceeds in a bulk under an alkali catalyst, and the particles become large.
Perform steps 2-5. Desirable value of particle size of antibacterial and fungicide
In order to make it 0.01 to 1 μm, the concentration of the raw material, the pH of the catalyst, the reaction temperature and the like may be appropriately selected and controlled. Other conditions may be based on the first manufacturing method.
【００３９】〔（ａ）の第４の製造方法〕抗菌防黴剤
（ａ）の第４の製造方法は、防黴性有機化合物が溶解し
たアルコキシシラン中に、銀、銅、亜鉛等の抗菌性金属
成分の水溶液を添加し、加水分解触媒を加えて前記アル
コキシシラン化合物を加水分解して抗菌防黴剤を製造す
る。その他の条件については、第３の製造方法に準ずれ
ばよい。[Fourth Production Method of (a)] The fourth production method of the antibacterial and antifungal agent (a) is a method for dissolving antibacterial agents such as silver, copper and zinc in an alkoxysilane in which a fungicidal organic compound is dissolved. An aqueous solution of a reactive metal component is added, and a hydrolysis catalyst is added to hydrolyze the alkoxysilane compound to produce an antibacterial and antifungal agent. Other conditions may be based on the third manufacturing method.
【００４０】〔（ｂ）の製造方法〕抗菌防黴剤（ｂ）の
製造方法は、下記の３工程からなる。 (1) 抗菌性金属成分と防黴性有機化合物との反応生成物
を、アルカリ金属の珪酸塩、例えば珪酸ナトリウムの水
溶液に分散する分散工程Ａ。 (2) 分散工程Ａで得られた分散液に水不溶性又は難溶性
の有機溶媒を混合しＷ／Ｏ型エマルジョンとするエマル
ジョン化工程Ｂ。 (3) エマルジョン化工程Ｂで得られたＷ／Ｏ型エマルジ
ョンに、前記アルカリ金属の珪酸塩を不溶化し得る化合
物の水溶液を添加して攪拌し、微多孔質カプセル粒子を
生成するカプセル粒子生成工程Ｃ。[Production method of (b)] The production method of the antibacterial and antifungal agent (b) comprises the following three steps. (1) Dispersion step A in which a reaction product of an antibacterial metal component and a fungicidal organic compound is dispersed in an aqueous solution of an alkali metal silicate, for example, sodium silicate. (2) An emulsification step B in which a water-insoluble or poorly soluble organic solvent is mixed with the dispersion obtained in the dispersion step A to form a W / O emulsion. (3) Capsule particle forming step of adding an aqueous solution of the compound capable of insolubilizing the alkali metal silicate to the W / O emulsion obtained in the emulsifying step B and stirring to form microporous capsule particles. C.
【００４１】水不溶性または難溶性の有機溶媒として
は、ｎ−ヘキサン、イソヘキサン、ｎ−ヘプタン、イソ
ヘプタン等の脂肪族炭化水素類、シクロペンタン、シク
ロヘキサン等の脂環式炭化水素類、ベンゼン、トルエ
ン、キシレン等の芳香族炭化水素類、プロピルエーテ
ル、イソプロピルエーテル等のエーテル類、酢酸エチ
ル、酢酸−ｎ−プロピル等のエステル類等が好適に用い
られる。Examples of the water-insoluble or sparingly soluble organic solvent include aliphatic hydrocarbons such as n-hexane, isohexane, n-heptane and isoheptane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, benzene, toluene, and the like. Aromatic hydrocarbons such as xylene, ethers such as propyl ether and isopropyl ether, and esters such as ethyl acetate and n-propyl acetate are preferably used.
【００４２】有機溶媒の使用量は、得られるエマルジョ
ンがＷ／Ｏ型になる限り、特に限定されないが、通常エ
マルジョンの 50 重量％以上、好ましくは 70 〜 90 重
量％とするのがよい。エマルジョンとする方法は、攪拌
方法、振盪方法、ホモジナイザーの使用等の常法に従え
ばよい。エマルジョン化に際しては公知の乳化剤を添加
してもい。乳化剤としては、好ましくはＨＬＢが 3.5〜
6.0 の範囲にある非イオン性界面活性剤を単独で用いる
か、複数の非イオン性界面活性剤を配合してＨＬＢを
3.5〜6.0 に調整して使用できる。The amount of the organic solvent used is not particularly limited as long as the obtained emulsion is of the W / O type, but it is usually 50% by weight or more, preferably 70 to 90% by weight of the emulsion. The emulsion may be formed by a conventional method such as a stirring method, a shaking method, or a homogenizer. At the time of emulsification, a known emulsifier may be added. As the emulsifier, preferably HLB is 3.5 to
The nonionic surfactant in the range of 6.0 alone may be used alone, or a plurality of nonionic surfactants may be blended to form an HLB.
Adjustable to 3.5-6.0.
【００４３】また、アルカリ金属の珪酸塩を不溶化する
化合物としては、硫酸アンモニウム、炭酸アンモニウ
ム、炭酸水素アンモニウム、炭酸水素ナトリウム、塩化
カルシウム等が使用できる。抗菌防黴剤の粒径を望まし
い値である 0.01 〜5 μｍとするには、攪拌速度、攪拌
時間、乳化剤等適宜選定すればよい。なお、この製造方
法によれば、真球状の抗菌防黴剤が得られやすい。As the compound for insolubilizing the alkali metal silicate, ammonium sulfate, ammonium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, calcium chloride and the like can be used. In order to adjust the particle size of the antibacterial and fungicide to a desirable value of 0.01 to 5 μm, the stirring speed, the stirring time, the emulsifier and the like may be appropriately selected. In addition, according to this manufacturing method, a true spherical antibacterial and antifungal agent is easily obtained.
【００４４】[0044]
【実施例】以下に実施の例を詳説する。 「実施例１」 〔抗菌防黴剤Ａの製造〕ＴＢＺ 2.5ｇをメチルアルコー
ル 320ｍｌに完全に溶解し、この溶液に 10 重量％硝酸
銀水溶液 10 ｍｌを加えて、銀とＴＢＺとの反応生成物
（以下、銀−ＴＢＺと略記）の白色沈殿を得た。この白
色沈殿を濾別し、メチルアルコールと蒸留水にて充分洗
浄後、温度 130℃にて乾燥し、乳鉢にて微粉砕した。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments will be described below in detail. [Example 1] [Production of antibacterial and antifungal agent A] 2.5 g of TBZ was completely dissolved in 320 ml of methyl alcohol, and 10 ml of a 10% by weight aqueous solution of silver nitrate was added to this solution to form a reaction product of silver and TBZ ( Hereinafter, a white precipitate of silver-TBZ) was obtained. The white precipitate was separated by filtration, sufficiently washed with methyl alcohol and distilled water, dried at a temperature of 130 ° C., and pulverized in a mortar.
【００４５】ＪＩＳ１号水ガラスを蒸留水を用い体積比
で１：１に希釈した珪酸ナトリウム水溶液 10 ｍｌに、
前記銀―ＴＢＺ 0.25 ｇ、カルボキシメチルセルロース
0.7ｇ、変性エチルアルコール１〜２滴を加え、５分
間、超音波により分散処理し、引き続きマグネチックス
ターラにて完全に分散させた。JIS No. 1 water glass was diluted with distilled water to a volume ratio of 1: 1 to 10 ml of an aqueous sodium silicate solution,
0.25 g of the above silver-TBZ, carboxymethyl cellulose
0.7 g and 1-2 drops of denatured ethyl alcohol were added, and the mixture was ultrasonically dispersed for 5 minutes, and then completely dispersed with a magnetic stirrer.
【００４６】別に用意した 1.5ｍｏｌ／ｌの硫酸アンモ
ニウム水溶液 110ｍｌをマグネチックスターラで攪拌し
つつ、この水溶液中に前記銀―ＴＢＺが分散した前記珪
酸ナトリウム水溶液を添加し、温度 30 ℃にて２時間攪
拌しながら熟成し、沈殿生成物を得た。この沈殿生成物
を濾別し、蒸留水にて充分洗浄後、温度 130℃にて乾燥
し、乳鉢にて解砕して抗菌防黴剤Ａを得た。While separately stirring 110 ml of a 1.5 mol / l aqueous ammonium sulfate solution with a magnetic stirrer, the aqueous solution of sodium silicate in which the silver-TBZ was dispersed was added to the aqueous solution, and the mixture was stirred at a temperature of 30 ° C. for 2 hours. While aging, a precipitate product was obtained. The precipitated product was separated by filtration, sufficiently washed with distilled water, dried at a temperature of 130 ° C., and crushed in a mortar to obtain an antibacterial and antifungal agent A.
【００４７】この抗菌防黴剤Ａは、銀―ＴＢＺがシリカ
の表面および内部に固着していることが赤外線吸収スペ
クトル法（ＩＲ）により確認された。また、シリカは多
孔質であること、および平均粒子径 0.2μｍの微細粒子
であることが走査型電子顕微鏡観察により確認された。
この粒子性状を図３の写真に示した。また、この抗菌防
黴剤Ａ中の、銀―ＴＢＺの含有量を、銀はプラズマ発光
分析法（ＩＣＰ法）で、ＴＢＺ量は熱分析法（ＴＧ法）
による減量値から算出した。その結果を表１に示した。It was confirmed by infrared absorption spectroscopy (IR) that this antibacterial and fungicide A had silver-TBZ fixed to the surface and inside of the silica. In addition, it was confirmed by scanning electron microscope observation that the silica was porous and fine particles having an average particle diameter of 0.2 μm.
The properties of the particles are shown in the photograph of FIG. The content of silver-TBZ in the antibacterial and antifungal agent A was determined by plasma emission spectrometry (ICP method), and the amount of TBZ was determined by thermal analysis (TG method).
Was calculated from the weight loss value. The results are shown in Table 1.
【００４８】〔耐熱性評価〕抗菌防黴剤Ａの耐熱性を評
価した。評価方法として、熱分析手法を用い、加熱減量
の開始温度を測定する方法を採用した。その結果を表２
に示した。[Evaluation of Heat Resistance] The heat resistance of the antibacterial and antifungal agent A was evaluated. As an evaluation method, a method of measuring the onset temperature of weight loss by heating using a thermal analysis technique was adopted. Table 2 shows the results.
It was shown to.
【００４９】〔徐放性評価〕抗菌防黴剤Ａの徐放性を評
価した。評価方法として、ｐＨ3.5 とした硝酸水溶液に
抗菌防黴剤Ａを分散して分散液とし、この分散液中の銀
イオン濃度を銀イオン電極を用いて測定する手法を採用
した。その結果を図４に示す。[Evaluation of sustained release] The sustained release of the antibacterial and fungicide A was evaluated. As an evaluation method, a method was employed in which an antibacterial and fungicide A was dispersed in a nitric acid aqueous solution having a pH of 3.5 to form a dispersion, and the silver ion concentration in the dispersion was measured using a silver ion electrode. FIG. 4 shows the results.
【００５０】〔抗菌性評価〕抗菌防黴剤Ａの抗菌性を、
下記、の方法で評価した。 石膏に抗菌防黴剤Ａを１重量％添加し、水と混練
し、硬化させた硬化体を得、この硬化体の抗菌性を条件
（ａ）〜（ｄ）の下で評価し、その結果を表３に示し
た。 （ａ）温水負荷（温度 60 ℃の温水中に 24 時間浸漬） （ｂ）塩水負荷（１重量％の塩水中に 24 時間浸漬） （ｃ）ＵＶ負荷（中心波長 352ｎｍのブラックライトを
７日間照射） （ｄ）負荷なし[Evaluation of antibacterial activity]
The following method evaluated. 1% by weight of an antibacterial and fungicide A was added to gypsum, kneaded with water to obtain a cured product, and the cured product was evaluated for its antibacterial properties under conditions (a) to (d). Are shown in Table 3. (A) Hot water load (immersed in warm water at a temperature of 60 ° C for 24 hours) (b) Salt water load (immersed in 1% by weight of salt water for 24 hours) (c) UV load (irradiation with black light with a central wavelength of 352 nm for 7 days) (D) No load
【００５１】なお、この硬化体には金属イオンに由来す
る変色は認められなかった。また、この硬化体の抗菌性
の評価方法は、シェイクフラスコ法に準拠した。シェイ
クフラスコ法の概要は以下のとおりである。「三角フラ
スコにリン酸緩衝液を入れ、滅菌する。これに試験菌液
を加え順次希釈し、 10 倍希釈系列を作る。試験試料を
加え、温度 25 ℃にて１時間（330rpm）振盪（しんと
う）した後、生存菌数を寒天平板法にて測定する。」The cured product did not show any discoloration due to metal ions. The method for evaluating the antibacterial property of this cured product was based on the shake flask method. The outline of the shake flask method is as follows. "Put a phosphate buffer solution in an Erlenmeyer flask and sterilize. Add the test bacterial solution to this and dilute it sequentially to make a 10-fold dilution series. Add the test sample and shake at 330C for 1 hour at a temperature of 25 ° C. ), And then determine the number of surviving bacteria by the agar plate method. "
【００５２】 市販の水性アクリルエマルジョン塗料
に抗菌防黴剤Ａを１重量％添加し、これをガラス基板上
に硬化後の膜厚が 1.0ｍｍとなるよう塗布して抗菌性塗
膜を得、この抗菌性塗膜の抗菌性を、上記（ａ）〜
（ｄ）の条件下で評価した。その結果を表４に示した。1% by weight of an antibacterial and fungicide A was added to a commercially available water-based acrylic emulsion paint, and this was applied on a glass substrate so that the film thickness after curing became 1.0 mm to obtain an antibacterial coating film. The antibacterial property of the antibacterial coating film is determined by the above (a) to
The evaluation was made under the condition (d). Table 4 shows the results.
【００５３】なお、抗菌性塗膜には金属イオンに由来す
る変色は認められなかった。また、この塗膜の抗菌性の
評価方法は、銀等無機抗菌材研究会制定のフィルム密着
法に準拠した。フィルム密着法の概要は以下のとおりで
ある。No discoloration due to metal ions was observed in the antibacterial coating film. The antibacterial property of this coating film was evaluated in accordance with the film adhesion method established by the Research Group for Inorganic Antibacterial Materials such as Silver. The outline of the film adhesion method is as follows.
【００５４】「試験体に、 1／500 に希釈した普通ブイ
ヨンを含み、菌濃度 105ｃｆｕ／ｍｌに調整した菌液を
25 ｃｍ2 当たり 0.5ｍｌ接種し、この菌液の上に試験
製品と同一形状のポリエチレン製フィルムを載せる。こ
れを温度 35 ℃にて 24 時間培養した後、生存菌数を寒
天平板法にて測定する。」[0054] The "test body comprises a nutrient broth diluted to 1/500, bacterial solution was adjusted to a cell concentration 10 5 cfu / ml of
Inoculate 0.5 ml per 25 cm 2, and place a polyethylene film of the same shape as the test product on the bacterial solution. After culturing the cells at 35 ° C for 24 hours, the number of surviving bacteria is measured by the agar plate method. "
【００５５】〔防黴性評価〕抗菌防黴剤Ａの防黴性を、
上記，の方法で評価した。なお、上記条件（ａ）〜
（ｄ）のほか、次の条件（ｅ）をも加えた。 （ｅ）加熱負荷（温度 320℃で 30 分間加熱） その結果を表５、表６に示した。なお、防黴性の評価方
法は、ポテトデキスロース寒天培地を用い、温度 27 ℃
にて14日培養した後、ＪＩＳ Ｚ−２９１１の表示方法
により評価する方法を用いた。[Evaluation of antifungal property]
The evaluation was performed by the method described above. Note that the above conditions (a) to
In addition to (d), the following condition (e) was also added. (E) Heating load (heating at 320 ° C. for 30 minutes) The results are shown in Tables 5 and 6. The antifungal property was evaluated using potato dextrose agar at a temperature of 27 ° C.
After culturing for 14 days, the method of evaluation according to the display method of JIS Z-2911 was used.
【００５６】黴抵抗の表示基準は次のとおりである。 １：菌糸の発育部分の面積が１／３を超える。 ２：菌糸の発育部分の面積が１／３を超えない。 ３：菌糸の発育が認められない。The display criteria for mold resistance are as follows. 1: The area of the hyphal growth part exceeds 1/3. 2: The area of the hyphal growth part does not exceed 1/3. 3: No hyphal growth was observed.
【００５７】「実施例２」 〔抗菌防黴剤Ｂの製造〕ＴＢＺ 0.3ｇをテトラメトキシ
シラン 20 ｍｌに溶解し、この溶液に 0.15 重量％の硝
酸銀水溶液 100ｍｌを加え、マグネチックスターラで攪
拌しながら２時間熟成を行った。静置後、上澄みを除去
して沈殿生成物を回収し、得られた沈殿生成物を真空デ
シケータ内にて乾燥して抗菌防黴剤Ｂを得た。Example 2 [Production of antibacterial and antifungal agent B] 0.3 g of TBZ was dissolved in 20 ml of tetramethoxysilane, and 100 ml of a 0.15% by weight aqueous solution of silver nitrate was added to this solution, and the mixture was stirred with a magnetic stirrer. Aging was performed for 2 hours. After standing, the supernatant was removed to recover the precipitate, and the obtained precipitate was dried in a vacuum desiccator to obtain an antibacterial and fungicide B.
【００５８】この抗菌防黴剤Ｂは、銀―ＴＢＺがシリカ
の表面および内部に固着していることが赤外線吸収スペ
クトル法（ＩＲ）により確認された。また、シリカは多
孔質であること、および平均粒子径 0.2μｍの微細粒子
であることが走査型電子顕微鏡観察により確認された。
この粒子性状を図５の写真に示した。また、この抗菌防
黴剤Ｂ中の、銀―ＴＢＺの含有量を、実施例１に準じて
算出した。その結果を表１に示した。It was confirmed by infrared absorption spectroscopy (IR) that this antibacterial and fungicide B had silver-TBZ fixed to the surface and inside of the silica. In addition, it was confirmed by scanning electron microscope observation that the silica was porous and fine particles having an average particle diameter of 0.2 μm.
The properties of the particles are shown in the photograph of FIG. Further, the content of silver-TBZ in this antibacterial and fungicide B was calculated according to Example 1. The results are shown in Table 1.
【００５９】〔耐熱性評価〕抗菌防黴剤Ｂの耐熱性を実
施例１に準じて評価した。その結果を表２に示した。[Evaluation of Heat Resistance] The heat resistance of the antibacterial and antifungal agent B was evaluated in the same manner as in Example 1. The results are shown in Table 2.
【００６０】〔徐放性評価〕抗菌防黴剤Ｂの徐放性を実
施例１に準じて評価した。その結果を図４に示した。[Evaluation of sustained release property] The sustained release property of the antibacterial and antifungal agent B was evaluated in the same manner as in Example 1. The result is shown in FIG.
【００６１】〔抗菌性評価〕抗菌防黴剤Ｂの抗菌性を実
施例１に準じて評価した。その結果を表３、表４に示し
た。なお、硬化体、塗膜とも金属イオンに由来する変色
は認められなかった。[Evaluation of Antibacterial Property] The antibacterial property of the antibacterial and fungicide B was evaluated in accordance with Example 1. The results are shown in Tables 3 and 4. In addition, discoloration derived from metal ions was not observed in both the cured product and the coating film.
【００６２】〔防黴性評価〕抗菌防黴剤Ｂの防黴性を実
施例１に準じて評価した。その結果を表５、表６に示し
た。[Evaluation of antifungal property] The antifungal property of the antibacterial antifungal agent B was evaluated in accordance with Example 1. The results are shown in Tables 5 and 6.
【００６３】「実施例３」 〔抗菌防黴剤Ｃの製造〕ＪＩＳ１号水ガラスを蒸留水を
用い体積比で１：１に希釈した珪酸ナトリウム水溶液 1
0 ｍｌに、前記銀―ＴＢＺ 0.25 ｇ、カルボキシメチル
セルロース 0.7ｇ、変性エチルアルコール１〜２滴を添
加し、分散した分散液を、非イオン系界面活性剤を加え
たベンゼンに添加し、エマルジョン化した。別に用意し
た 1.5ｍｏｌ／ｌの硫酸アンモニウム水溶液 110ｍｌ中
に前記エマルジョン液を添加し、温度 30 ℃にて２時間
攪拌しながら熟成し、沈殿生成物を得た。この沈殿生成
物を遠心分離して油相を除いた後、濾別し、蒸留水にて
充分に洗浄した後、温度 130℃にて乾燥し、乳鉢にて解
砕して抗菌防黴剤Ｃを得た。[Example 3] [Production of antibacterial and antifungal agent C] An aqueous solution of sodium silicate obtained by diluting JIS No. 1 water glass with distilled water to a volume ratio of 1: 1.
To 0 ml, 0.25 g of the silver-TBZ, 0.7 g of carboxymethylcellulose, and 1 to 2 drops of denatured ethyl alcohol were added, and the dispersed liquid was added to benzene to which a nonionic surfactant was added to emulsify. . The emulsion was added to 110 ml of a separately prepared 1.5 mol / l aqueous ammonium sulfate solution, and the mixture was aged at 30 ° C. for 2 hours with stirring to obtain a precipitate. The precipitate is centrifuged to remove the oil phase, filtered, washed thoroughly with distilled water, dried at a temperature of 130 ° C., crushed in a mortar, and treated with an antibacterial and fungicide C. I got
【００６４】この抗菌防黴剤Ｃは、銀―ＴＢＺがシリカ
により内包されていることが赤外線吸収スペクトル法
（ＩＲ）により確認された。また、平均粒子径４μｍの
微細カプセル粒子であることが走査型電子顕微鏡観察に
より確認された。この粒子性状を図６の写真に示した。
また、この抗菌防黴剤Ｃ中の銀―ＴＢＺの含有量を、実
施例１に準じて算出した。その結果を表１に示した。It was confirmed by infrared absorption spectroscopy (IR) that this antibacterial and fungicide C contained silver-TBZ in silica. Further, it was confirmed by scanning electron microscope observation that the particles were fine capsule particles having an average particle diameter of 4 μm. The properties of the particles are shown in the photograph of FIG.
Further, the content of silver-TBZ in this antibacterial and fungicide C was calculated according to Example 1. The results are shown in Table 1.
【００６５】〔耐熱性評価〕抗菌防黴剤Ｃの耐熱性を実
施例１に準じて評価した。その結果を表１に示した。[Evaluation of Heat Resistance] The heat resistance of the antibacterial and fungicide C was evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００６６】〔徐放性評価〕抗菌防黴剤Ｃの徐放性を実
施例１に準じて評価した。その結果を図４に示した。[Evaluation of sustained release property] The sustained release property of the antibacterial and fungicide C was evaluated in the same manner as in Example 1. The result is shown in FIG.
【００６７】〔抗菌性評価〕抗菌防黴剤Ｃの抗菌性を実
施例１に準じて評価した。その結果を表３、表４に示し
た。なお、硬化体、塗膜とも金属イオンに由来する変色
は認められなかった。[Evaluation of Antibacterial Property] The antibacterial property of the antibacterial and fungicide C was evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 4. In addition, discoloration derived from metal ions was not observed in both the cured product and the coating film.
【００６８】〔防黴性評価〕抗菌防黴剤Ｃの防黴性を実
施例１に準じて評価した。その結果を表５、表６に示し
た。[Evaluation of antifungal property] The antifungal property of the antibacterial and antifungal agent C was evaluated in the same manner as in Example 1. The results are shown in Tables 5 and 6.
【００６９】「実施例４」 〔抗菌防黴剤Ｄの製造〕Ｎ−（フルオロジクロロメチル
チオ）−フタルイミド（以下、フタルイミドと略記）
2.5ｇをメチルアルコール 300ｍｌに完全に溶解し、こ
の溶液に 10 重量％硝酸銀水溶液 10 ｍｌを加えて、銀
とフタルイミドとの反応生成物（以下、銀−フタルイミ
ドと略記）を得た。この沈殿物を濾別し、メチルアルコ
ールと蒸留水にて充分洗浄後、温度 130℃にて乾燥し、
乳鉢にて微粉砕した。Example 4 [Production of antibacterial and antifungal agent D] N- (fluorodichloromethylthio) -phthalimide (hereinafter abbreviated as phthalimide)
2.5 g was completely dissolved in 300 ml of methyl alcohol, and 10 ml of a 10% by weight aqueous solution of silver nitrate was added to this solution to obtain a reaction product of silver and phthalimide (hereinafter abbreviated as silver-phthalimide). This precipitate was separated by filtration, sufficiently washed with methyl alcohol and distilled water, and then dried at a temperature of 130 ° C.
It was pulverized in a mortar.
【００７０】ＪＩＳ１号水ガラスを蒸留水を用い体積比
で１：１に希釈した珪酸ナトリウム水溶液 10 ｍｌに、
前記銀−フタルイミド 0.25 ｇ、変性エチルアルコール
１〜２滴を加え、５分間、超音波により分散処理し、引
き続きマグネチックスターラにて完全に分散させた。別
に用意した 1.5ｍｏｌ／ｌの硫酸アンモニウム水溶液 1
10ｍｌをマグネチックスターラで攪拌しつつ、この水溶
液中に前記銀−フタルイミドが分散した前記珪酸ナトリ
ウム水溶液を添加し、温度 30 ℃にて２時間攪拌しなが
ら熟成し、沈殿生成物を得た。この沈殿生成物を濾別
し、蒸留水にて充分に洗浄後、温度 130℃にて乾燥し、
乳鉢にて解砕して抗菌防黴剤Ｄを得た。JIS No. 1 water glass was diluted with distilled water to a volume ratio of 1: 1 to 10 ml of an aqueous sodium silicate solution,
0.25 g of the above-mentioned silver-phthalimide and 1 to 2 drops of denatured ethyl alcohol were added, and the mixture was subjected to a dispersion treatment with ultrasonic waves for 5 minutes, and then completely dispersed with a magnetic stirrer. 1.5 mol / l aqueous solution of ammonium sulfate prepared separately 1
While stirring 10 ml with a magnetic stirrer, the above-mentioned aqueous solution of sodium silicate in which the above-mentioned silver-phthalimide was dispersed was added to this aqueous solution, and the mixture was aged at 30 ° C for 2 hours with stirring to obtain a precipitate product. This precipitated product was separated by filtration, washed sufficiently with distilled water, and dried at a temperature of 130 ° C.
This was crushed in a mortar to obtain an antibacterial and fungicide D.
【００７１】この抗菌防黴剤Ｄは、平均粒子径 0.2μｍ
の微細粒子であった。また、この抗菌防黴剤Ｄ中の、
銀、フタルイミドの含有量を、実施例１に準じて算出し
た。その結果を表１に示した。The antibacterial and fungicide D has an average particle size of 0.2 μm
Of fine particles. Also, in this antibacterial and fungicide D,
The contents of silver and phthalimide were calculated according to Example 1. The results are shown in Table 1.
【００７２】〔耐熱性評価〕抗菌防黴剤Ｄの耐熱性を実
施例１に準じて評価した。その結果を表２に示した。[Evaluation of Heat Resistance] The heat resistance of the antibacterial and antifungal agent D was evaluated in the same manner as in Example 1. The results are shown in Table 2.
【００７３】〔徐放性評価〕抗菌防黴剤Ｄの徐放性を実
施例１に準じて評価した。その結果を図７に示した。[Evaluation of sustained release] The sustained release of the antibacterial and antifungal agent D was evaluated in the same manner as in Example 1. The result is shown in FIG.
【００７４】〔抗菌性評価〕抗菌防黴剤Ｄの抗菌性を実
施例１に準じて評価した。その結果を表３、表４に示し
た。なお、硬化体、塗膜とも金属イオンに由来する変色
は認められなかった。[Evaluation of Antibacterial Property] The antibacterial property of the antibacterial and fungicide D was evaluated in accordance with Example 1. The results are shown in Tables 3 and 4. In addition, discoloration derived from metal ions was not observed in both the cured product and the coating film.
【００７５】〔防黴性評価〕抗菌防黴剤Ｄの防黴性を実
施例１に準じて評価した。その結果を表５、表６に示し
た。[Evaluation of antifungal property] The antifungal property of the antibacterial antifungal agent D was evaluated according to Example 1. The results are shown in Tables 5 and 6.
【００７６】「実施例５」 〔抗菌防黴剤Ｅの製造〕２，３，５，６−テトラクルロ
−４−メチルスルフォニル−ピリジン（以下、ピリジン
と略記） 1.2ｇをメチルアルコール 300ｍｌに完全に溶
解し、この溶液に 10 重量％硝酸銀水溶液 10 ｍｌを加
えて、銀とピリジンとの反応生成物（以下、銀−ピリジ
ンと略記）を得た。この沈殿を濾別し、メチルアルコー
ルと蒸留水にて充分に洗浄後、温度 130℃にて乾燥し、
乳鉢にて微粉砕した。[Example 5] [Production of antibacterial and antifungal agent E] 1.2 g of 2,3,5,6-tetrachloro-4-methylsulfonyl-pyridine (hereinafter abbreviated as pyridine) was completely dissolved in 300 ml of methyl alcohol. Then, 10 ml of a 10% by weight aqueous solution of silver nitrate was added to this solution to obtain a reaction product of silver and pyridine (hereinafter abbreviated as silver-pyridine). This precipitate was separated by filtration, thoroughly washed with methyl alcohol and distilled water, and dried at a temperature of 130 ° C.
It was pulverized in a mortar.
【００７７】ＪＩＳ１号水ガラスを蒸留水を用い体積比
で１：１に希釈した珪酸ナトリウム水溶液 10 ｍｌに、
前記銀−ピリジンの化合物 0.25 ｇ、変性エチルアルコ
ール１〜２滴を加え、５分間、超音波により分散処理
し、引き続きマグネチックスターラにて完全に分散させ
た。別に用意した 1.5ｍｏｌ／ｌの硫酸アンモニウム水
溶液 110ｍｌをマグネチックスターラで攪拌しつつ、こ
の水溶液中に前記銀−ピリジンが分散した前記珪酸ナト
リウム水溶液を添加し、温度 30 ℃にて２時間攪拌しな
がら熟成し、沈殿生成物を得た。この沈殿生成物を濾別
し、蒸留水にて充分洗浄後、温度 130℃にて乾燥し、乳
鉢にて解砕して抗菌防黴剤Ｅを得た。JIS No. 1 water glass was diluted with distilled water to a volume ratio of 1: 1 to 10 ml of an aqueous sodium silicate solution,
0.25 g of the silver-pyridine compound and 1-2 drops of denatured ethyl alcohol were added, and the mixture was subjected to ultrasonic dispersion treatment for 5 minutes, and then completely dispersed with a magnetic stirrer. While separately stirring 110 ml of a 1.5 mol / l aqueous solution of ammonium sulfate with a magnetic stirrer, the aqueous solution of sodium silicate in which the silver-pyridine was dispersed was added to the aqueous solution, and the mixture was aged while stirring at a temperature of 30 ° C. for 2 hours. Then, a precipitated product was obtained. The precipitated product was separated by filtration, sufficiently washed with distilled water, dried at a temperature of 130 ° C., and crushed in a mortar to obtain an antibacterial and antifungal agent E.
【００７８】この抗菌防黴剤Ｅは、平均粒子径 0.2μｍ
の微細粒子であった。また、この抗菌防黴剤Ｅ中の、
銀、ピリジンの化合物の含有量を、実施例１に準じて算
出し、その結果を表１に示した。This antibacterial and fungicide E has an average particle size of 0.2 μm
Of fine particles. Further, in this antibacterial and fungicide E,
The contents of the silver and pyridine compounds were calculated according to Example 1, and the results are shown in Table 1.
【００７９】〔耐熱性評価〕抗菌防黴剤Ｅの耐熱性を実
施例１に準じて評価した。その結果を表２に示した。[Evaluation of Heat Resistance] The heat resistance of the antibacterial and antifungal agent E was evaluated in the same manner as in Example 1. The results are shown in Table 2.
【００８０】〔徐放性評価〕抗菌防黴剤Ｅの徐放性を実
施例１に準じて評価した。その結果を図７に示した。[Evaluation of sustained release property] The sustained release property of the antibacterial and fungicide E was evaluated in the same manner as in Example 1. The result is shown in FIG.
【００８１】〔抗菌性評価〕抗菌防黴剤Ｅの抗菌性を実
施例１に準じて評価した。その結果を表３、表４に示し
た。なお、硬化体、塗膜とも金属イオンに由来する変色
は認められなかった。[Evaluation of Antibacterial Property] The antibacterial property of the antibacterial and fungicide E was evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 4. In addition, discoloration derived from metal ions was not observed in both the cured product and the coating film.
【００８２】〔防黴性評価〕抗菌防黴剤Ｅの防黴性を実
施例１に準じて評価した。その結果を表５、表６に示し
た。[Evaluation of antifungal property] The antifungal property of the antibacterial antifungal agent E was evaluated in the same manner as in Example 1. The results are shown in Tables 5 and 6.
【００８３】「実施例６」 〔抗菌防黴剤Ｆの製造〕１，２−ベンツイソチアゾロン
（以下、ＢＩＴと略記） 1.2ｇを蒸留水 300ｍｌに完全
に溶解し、この溶液に 10 重量％硝酸銀水溶液 10 ｍｌ
を加えて、銀とＢＩＴとの反応生成物（以下、銀−ＢＩ
Ｔと略記）を得た。この沈殿を濾別し、蒸留水にて充分
に洗浄後、温度 130℃にて乾燥し、乳鉢にて微粉砕し
た。Example 6 [Production of antibacterial and fungicide F] 1.2 g of 1,2-benzisothiazolone (hereinafter abbreviated as BIT) was completely dissolved in 300 ml of distilled water, and a 10% by weight aqueous solution of silver nitrate was added to this solution. 10 ml
To the reaction product of silver and BIT (hereinafter referred to as silver-BI
T). This precipitate was separated by filtration, washed sufficiently with distilled water, dried at a temperature of 130 ° C., and pulverized in a mortar.
【００８４】ＪＩＳ１号水ガラスを蒸留水を用い体積比
で１：１に希釈した珪酸ナトリウム水溶液 10 ｍｌに、
前記銀−ＢＩＴ 0.25 ｇ、変性エチルアルコール 1〜2
滴を加え、５分間、超音波により分散処理し、引き続き
マグネチックスターラにて完全に分散させた。別に用意
した 1.5ｍｏｌ／ｌの硫酸アンモニウム水溶液 110ｍｌ
をマグネチックスターラで攪拌しつつ、この水溶液中に
前記銀−ＢＩＴが分散した前記珪酸ナトリウム水溶液を
添加し、温度 30 ℃にて２時間攪拌しながら熟成し、沈
殿生成物を得た。この沈殿生成物を濾別し、蒸留水にて
充分洗浄後、温度 130℃にて乾燥し、乳鉢にて解砕して
抗菌防黴剤Ｆを得た。JIS No. 1 water glass was diluted with distilled water to a volume ratio of 1: 1 in 10 ml of an aqueous sodium silicate solution,
0.25 g of the silver-BIT, denatured ethyl alcohol 1-2
Drops were added, and the mixture was dispersed with ultrasonic waves for 5 minutes, and then completely dispersed with a magnetic stirrer. 110 ml of 1.5 mol / l ammonium sulfate aqueous solution prepared separately
Was stirred with a magnetic stirrer, the aqueous solution of sodium silicate in which the silver-BIT was dispersed was added to the aqueous solution, and the mixture was aged at 30 ° C. for 2 hours to obtain a precipitate. This precipitated product was separated by filtration, sufficiently washed with distilled water, dried at a temperature of 130 ° C., and crushed in a mortar to obtain an antibacterial and antifungal agent F.
【００８５】この抗菌防黴剤Ｆは、平均粒子径 0.2μｍ
の微細粒子であった。また、この抗菌防黴剤Ｆ中の、
銀、ＢＩＴの含有量を実施例１に準じて算出した。その
結果を表１に示した。This antibacterial and fungicide F has an average particle size of 0.2 μm
Of fine particles. Further, in this antibacterial and antifungal agent F,
The contents of silver and BIT were calculated according to Example 1. The results are shown in Table 1.
【００８６】〔耐熱性評価〕抗菌防黴剤Ｆの耐熱性を実
施例１に準じて評価した。その結果を表２に示した。[Evaluation of Heat Resistance] The heat resistance of the antibacterial and antifungal agent F was evaluated in the same manner as in Example 1. The results are shown in Table 2.
【００８７】〔徐放性評価〕抗菌防黴剤Ｆの徐放性を実
施例１に準じて評価した。その結果を図７に示した。[Evaluation of sustained release property] The sustained release property of the antibacterial and antifungal agent F was evaluated in the same manner as in Example 1. The result is shown in FIG.
【００８８】〔抗菌性評価〕抗菌防黴剤Ｆの抗菌性を実
施例１に準じて評価した。その結果を表３、表４に示し
た。なお、硬化体、塗膜とも金属イオンに由来する変色
は認められなかった。[Evaluation of Antibacterial Property] The antibacterial property of the antibacterial and antifungal agent F was evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 4. In addition, discoloration derived from metal ions was not observed in both the cured product and the coating film.
【００８９】〔防黴性評価〕抗菌防黴剤Ｆの防黴性を実
施例１に準じて評価した。その結果を表５、表６に示し
た。[Evaluation of antifungal property] The antifungal property of the antibacterial antifungal agent F was evaluated in accordance with Example 1. The results are shown in Tables 5 and 6.
【００９０】「比較例１」銀−ＴＢＺの耐熱性、抗菌
性、防黴性を実施例１に準じて評価した。その結果を表
２、表３、表４、表５、表６に示した。Comparative Example 1 The heat resistance, antibacterial property and antifungal property of silver-TBZ were evaluated in the same manner as in Example 1. The results are shown in Table 2, Table 3, Table 4, Table 5, and Table 6.
【００９１】「比較例２」ＴＢＺの耐熱性、抗菌性、防
黴性を実施例１に準じて評価した。その結果を表２、表
３、表４、表５、表６に示した。Comparative Example 2 The heat resistance, antibacterial property and antifungal property of TBZ were evaluated in the same manner as in Example 1. The results are shown in Table 2, Table 3, Table 4, Table 5, and Table 6.
【００９２】「比較例３」フタルイミドの耐熱性、抗菌
性、防黴性を実施例１に準じて評価した。その結果を表
２、表３、表４、表５、表６に示した。Comparative Example 3 The phthalimide was evaluated for heat resistance, antibacterial property and antifungal property in the same manner as in Example 1. The results are shown in Table 2, Table 3, Table 4, Table 5, and Table 6.
【００９３】「比較例４」ピリジンの耐熱性、抗菌性、
防黴性を実施例１に準じて評価した。その結果を表２、
表３、表４、表５、表６に示した。Comparative Example 4 Heat resistance and antibacterial properties of pyridine
The antifungal property was evaluated according to Example 1. Table 2 shows the results.
The results are shown in Tables 3, 4, 5, and 6.
【００９４】「比較例５」ＢＩＴの耐熱性、抗菌性、防
黴性を実施例１に準じて評価した。その結果を表２、表
３、表４、表５、表６に示した。Comparative Example 5 The BIT was evaluated for heat resistance, antibacterial property and antifungal property in the same manner as in Example 1. The results are shown in Table 2, Table 3, Table 4, Table 5, and Table 6.
【００９５】「比較例６」銀−フタルイミド、銀−ピリ
ジン、銀−ＢＩＴの徐放性を実施例１に準じて評価し
た。その結果を図７に示した。Comparative Example 6 The sustained release of silver-phthalimide, silver-pyridine and silver-BIT was evaluated in the same manner as in Example 1. The result is shown in FIG.
【００９６】[0096]
【表１】 [Table 1]
【００９７】[0097]
【表２】 [Table 2]
【００９８】[0098]
【表３】 [Table 3]
【００９９】[0099]
【表４】 [Table 4]
【０１００】[0100]
【表５】 [Table 5]
【０１０１】[0101]
【表６】 [Table 6]
【０１０２】表１、表３、表４、表５、表６の結果よ
り、実施例１〜６の抗菌防黴剤Ａ〜Ｆは、充分な量の抗
菌防黴成分（銀と防黴性有機化合物）を担持し、抗菌効
果と防黴効果を併せて有していることが判る。なかで
も、抗菌防黴剤Ａ，Ｂは、抗菌防黴剤Ｃよりも、多量の
抗菌性金属成分と防黴性有機化合物とを担持しており、
抗菌性金属成分と防黴性有機化合物の担持性に優れてい
る。From the results shown in Tables 1, 3, 4, 5 and 6, the antibacterial and antifungal agents A to F of Examples 1 to 6 show a sufficient amount of antibacterial and antifungal components (silver and antifungal agent). It can be seen that the compound has an organic compound) and has both an antibacterial effect and an antifungal effect. Above all, the antibacterial and fungicides A and B carry a larger amount of an antibacterial metal component and an antifungal organic compound than the antibacterial and fungicide C,
It has excellent carrying properties of antibacterial metal components and antifungal organic compounds.
【０１０３】また、抗菌防黴剤Ａ，Ｂ，Ｄ〜Ｆ（いずれ
も平均粒径 0.2μｍ）は、抗菌防黴剤Ｃ（平均粒径４μ
ｍ）に比較して微細であることから、優れた抗菌防黴効
果が期待され、抗菌防黴性を付与する対象物への分散性
に優れたものとなる。更に、表２の結果より、抗菌防黴
剤Ａ〜Ｆは優れた耐熱性を備えていることが、また、図
４，７の結果より抗菌防黴効果の持続性（徐放性）に優
れていることが判る。更にまた、抗菌防黴剤Ａ〜Ｆは、
抗菌防黴性を付与する対象物を変色せしめることがな
い。The antibacterial and fungicides A, B, and D to F (all having an average particle size of 0.2 μm) are the same as the antibacterial and fungicides C (with an average particle size of 4 μm).
Since it is finer than that of m), an excellent antibacterial and antifungal effect is expected, and it is excellent in dispersibility in an object imparting antibacterial and antifungal properties. Furthermore, from the results in Table 2, it can be seen that the antibacterial and fungicidal agents A to F have excellent heat resistance, and from the results in FIGS. You can see that Furthermore, the antibacterial and antifungal agents A to F are
It does not discolor the object imparting antibacterial and antifungal properties.
【０１０４】[0104]
【発明の効果】以上のように本発明では、請求項１に係
る抗菌防黴剤では、抗菌性金属成分と防黴性有機化合物
との反応生成物が、多孔質シリカ粒子の表面及び／又は
内部に固着していることにより、前記反応生成物の担持
量が大きなもの、粒径の微細なものが容易に得られ、抗
菌防黴性を付与する対象物への分散性が向上し、抗菌防
黴性を付与された物品の表面に変色を生じさせることが
なく、耐熱性が高くなり、抗菌防黴効果が持続し、長期
使用を可能にすることができる。As described above, according to the present invention, in the antibacterial and antifungal agent according to the first aspect, the reaction product of the antibacterial metal component and the antifungal organic compound is formed on the surface of the porous silica particles and / or By being fixed inside, a product having a large amount of the reaction product, a product having a small particle size can be easily obtained, and dispersibility in an object imparting antibacterial and antifungal properties is improved. Discoloration does not occur on the surface of the article provided with the antifungal property, the heat resistance is increased, the antibacterial and antifungal effect is maintained, and long-term use can be achieved.
【０１０５】請求項２に係る抗菌防黴剤では、抗菌性金
属成分と防黴性有機化合物との反応生成物が、多孔質シ
リカにより内包されていることにより、抗菌防黴性を付
与する対象物への分散性が向上し、抗菌防黴性を付与さ
れた物品の表面に変色を生じさせることがなく、耐熱性
が高くなり、抗菌防黴効果が持続し、長期使用を可能に
することができる。In the antibacterial and antifungal agent according to the second aspect, the reaction product of the antibacterial metal component and the antifungal organic compound is encapsulated by porous silica, thereby imparting antibacterial and antifungal properties. The dispersibility in the product is improved, the discoloration does not occur on the surface of the article provided with the antibacterial and fungicidal properties, the heat resistance is increased, the antibacterial and fungicidal effect is maintained, and long-term use is possible. Can be.
【０１０６】請求項３に係る抗菌防黴剤では、粒子径が
0.01〜１μｍであることにより、抗菌防黴性を付与する
対象物への分散性が向上し、意匠性や強度等を向上させ
ることができる。The antibacterial and antifungal agent according to claim 3 has a particle diameter of
When the thickness is from 0.01 to 1 μm, the dispersibility of the antibacterial and antifungal property in an object is improved, and the design property, strength, and the like can be improved.
【０１０７】請求項４に係る抗菌防黴剤では、粒子径が
0.01〜５μｍであることにより、担持量を増加させると
ともに抗菌防黴性を付与する対象物への分散性が向上
し、意匠性や強度等を向上させることができる。The antibacterial and antifungal agent according to claim 4 has a particle diameter of
When the particle size is from 0.01 to 5 μm, the dispersibility in an object to be imparted with antibacterial and antifungal properties is improved while the amount of the carrier to be carried is increased, and the design property and strength can be improved.
【０１０８】請求項５に係る抗菌防黴剤では、前記防黴
性有機化合物がイミダゾール系化合物、チアゾール系化
合物、Ｎ−ハロアルキルチオ系化合物、ピリジン系化合
物、イソチアゾロン系化合物からなる群から選ばれた少
なくとも１種であることにより、抗菌性金属成分に対し
て有機配位子になり得て、抗菌防黴効果を向上させると
ともに安全性および汎用性を向上させることができる。In the antibacterial and fungicide according to claim 5, the fungicidal organic compound is selected from the group consisting of imidazole compounds, thiazole compounds, N-haloalkylthio compounds, pyridine compounds and isothiazolone compounds. By being at least one kind, it can be an organic ligand to the antibacterial metal component, and the antibacterial and antifungal effect can be improved, and the safety and versatility can be improved.
【０１０９】請求項６に係る抗菌防黴剤の製造方法で
は、抗菌性金属成分と防黴性有機化合物との反応生成物
がシリカにより処理されたことにより、抗菌性および防
黴性の両方に優れた効果を有し、持続性および耐熱性を
向上させるとともに物品表面の色調への影響がなく、長
期使用に耐える抗菌防黴剤を容易に得ることができる。In the method for producing an antibacterial and antifungal agent according to claim 6, the reaction product of the antibacterial metal component and the antifungal organic compound is treated with silica, so that both antibacterial and antifungal properties are obtained. An antibacterial and antifungal agent which has excellent effects, improves durability and heat resistance, does not affect the color tone of the article surface, and can withstand long-term use can be easily obtained.
【０１１０】請求項７に係る抗菌防黴剤の製造方法で
は、抗菌性金属成分と防黴性有機化合物との反応生成物
が分散したアルカリ金属の珪酸塩の水溶液と、アルカリ
金属の珪酸塩を不溶化する化合物の水溶液とを混合・攪
拌することにより、請求項１記載の抗菌防黴剤を製造す
ることができ、水系での反応により粒子径が 0.01 〜1
μｍの微細な抗菌防黴剤を容易に得ることができる。In the method for producing an antibacterial and fungicide according to claim 7, an aqueous solution of an alkali metal silicate in which a reaction product of an antibacterial metal component and an antifungal organic compound is dispersed, and an alkali metal silicate are used. By mixing and stirring with an aqueous solution of the compound to be insolubilized, the antibacterial and fungicidal agent according to claim 1 can be produced, and the particle diameter of the antibacterial and fungicidal agent is 0.01 to 1 by an aqueous reaction.
A fine antimicrobial and antimicrobial agent having a size of μm can be easily obtained.
【０１１１】請求項８に係る抗菌防黴剤の製造方法で
は、抗菌性金属成分と防黴性有機化合物との反応生成物
が分散した、アルカリ金属の珪酸塩を不溶化する化合物
の水溶液と、アルカリ金属の珪酸塩の水溶液とを混合・
攪拌することにより、請求項１記載の抗菌防黴剤を製造
することができ、水系での反応により粒子径が 0.01 〜
1 μｍの微細な抗菌防黴剤を容易に得ることができる。In the method for producing an antibacterial and antifungal agent according to claim 8, an aqueous solution of a compound insolubilizing an alkali metal silicate in which a reaction product of an antibacterial metal component and an antifungal organic compound is dispersed is provided. Mix with an aqueous solution of metal silicate
By stirring, the antibacterial and fungicidal agent according to claim 1 can be produced, and the particle diameter of the antibacterial and fungicide according to claim 1 is 0.01 to 0.01 due to an aqueous reaction.
A fine antibacterial and antifungal agent of 1 μm can be easily obtained.
【０１１２】請求項９に係る抗菌防黴剤の製造方法で
は、アルコキシシラン中に、抗菌性金属成分と防黴性有
機化合物との反応生成物を粉状または分散した状態で添
加し、加水分解触媒を加え、攪拌しながら前記アルコキ
シシランを加水分解することにより、予め合成された前
記反応生成物をシリカ処理して請求項１記載の抗菌防黴
剤を製造することができ、有機系での反応により粒子径
が 0.01 〜1 μｍの微細な抗菌防黴剤を容易に得ること
ができる。In the method for producing an antibacterial and antifungal agent according to the ninth aspect, a reaction product of an antibacterial metal component and an antifungal organic compound is added to alkoxysilane in a powdery or dispersed state, and hydrolysis is carried out. By adding a catalyst and hydrolyzing the alkoxysilane with stirring, the previously synthesized reaction product can be treated with silica to produce the antibacterial fungicide according to claim 1, which can be used in an organic system. By the reaction, a fine antibacterial and fungicide having a particle size of 0.01 to 1 μm can be easily obtained.
【０１１３】請求項１０に係る抗菌防黴剤の製造方法で
は、防黴性有機化合物が溶解したアルコキシシラン中
に、抗菌性金属成分塩の水溶液を添加し、加水分解触媒
を加え、攪拌しながら前記アルコキシシラン化合物を加
水分解することにより、前記反応生成物の合成とシリカ
処理とを略同時に行って請求項１記載の抗菌防黴剤を製
造することができ、有機系での反応により粒子径が 0.0
1 〜1 μｍの微細な抗菌防黴剤を容易に得ることができ
る。In the method for producing an antibacterial and fungicide according to claim 10, an aqueous solution of an antibacterial metal component salt is added to an alkoxysilane in which an antifungal compound is dissolved, a hydrolysis catalyst is added, and the mixture is stirred. By hydrolyzing the alkoxysilane compound, the synthesis of the reaction product and the silica treatment can be performed almost simultaneously to produce the antibacterial and antifungal agent according to claim 1, and the particle size is determined by an organic reaction. Is 0.0
A fine antibacterial and antifungal agent of 1 to 1 μm can be easily obtained.
【０１１４】請求項１１に係る抗菌防黴剤の製造方法で
は、抗菌性金属成分と防黴性有機化合物との反応生成物
を、アルカリ金属の珪酸塩の水溶液に分散する工程Ａ
と、この工程Ａで得られた分散液に水不溶性又は難溶性
の有機溶媒を混合してＷ／Ｏ型エマルジョンとする工程
Ｂと、この工程Ｂで得られたＷ／Ｏ型エマルジョンに、
前記アルカリ金属の珪酸塩を不溶化する化合物の水溶液
を添加して攪拌し、微多孔質カプセル粒子を生成する工
程Ｃとからなるから、前記反応生成物をアルカリ金属の
珪酸塩水溶液に分散したＷ／Ｏ型エマルジョンに、アル
カリ金属の珪酸塩を不溶化する化合物の水溶液を添加し
て、請求項２記載の抗菌防黴剤を製造することができ、
粒子径が 0.01 〜5 μｍの微細な真球状の抗菌防黴剤を
得ることができる。In the method for producing an antibacterial and antifungal agent according to the eleventh aspect, a step A of dispersing a reaction product of the antibacterial metal component and the antifungal organic compound in an aqueous solution of an alkali metal silicate.
Step B of mixing the dispersion obtained in Step A with a water-insoluble or sparingly soluble organic solvent to form a W / O emulsion; and W / O emulsion obtained in Step B,
A step C of adding an aqueous solution of the compound for insolubilizing the alkali metal silicate and stirring to form microporous capsule particles. Therefore, the reaction product is dispersed in an aqueous solution of the alkali metal silicate in W / The antibacterial fungicide according to claim 2 can be produced by adding an aqueous solution of a compound that insolubilizes an alkali metal silicate to the O-type emulsion,
A fine spherical antibacterial fungicide having a particle size of 0.01 to 5 μm can be obtained.
【図１】本発明の実施の形態における抗菌性金属成分と
防黴性有機化合物との反応生成物のシリカ網目構造への
固着モデルを示す模式図である。FIG. 1 is a schematic diagram showing a model for fixing a reaction product of an antibacterial metal component and an antifungal organic compound to a silica network structure in an embodiment of the present invention.
【図２】本発明の実施の形態における抗菌性金属成分と
防黴性有機化合物との反応生成物のシリカ構造の珪酸基
への固着モデルを示す模式図である。FIG. 2 is a schematic diagram showing a model of a reaction product of an antibacterial metal component and an antifungal organic compound according to an embodiment of the present invention fixed to a silicate group of a silica structure.
【図３】本発明の実施例１における抗菌防黴剤Ａの粒子
性状を示す電子顕微鏡写真である。FIG. 3 is an electron micrograph showing the particle properties of the antibacterial and fungicide A in Example 1 of the present invention.
【図４】本発明の実施例１〜３における抗菌防黴剤Ａ，
Ｂ，Ｃの銀イオン濃度を時間経過を追って示すグラフで
ある。FIG. 4 shows the antibacterial and fungicide A in Examples 1 to 3 of the present invention.
5 is a graph showing silver ion concentrations of B and C with time.
【図５】本発明の実施例２における抗菌防黴剤Ｂの粒子
性状を示す電子顕微鏡写真である。FIG. 5 is an electron micrograph showing the particle properties of the antibacterial and fungicide B in Example 2 of the present invention.
【図６】本発明の実施例３における抗菌防黴剤Ｃの粒子
性状を示す電子顕微鏡写真である。FIG. 6 is an electron micrograph showing the particle properties of the antibacterial and fungicide C in Example 3 of the present invention.
【図７】本発明の実施例４〜６における抗菌防黴剤Ｄ，
Ｅ，Ｆの銀イオン濃度を比較例とともに時間経過を追っ
て示すグラフである。FIG. 7 shows antibacterial and fungicide D in Examples 4 to 6 of the present invention.
It is a graph which shows silver ion concentration of E and F with a comparative example over time.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ａ０１Ｎ 43/80 １０２ Ａ０１Ｎ 43/80 １０２ 59/16 59/16 Ａ Ａ６１Ｌ 2/16 Ａ６１Ｌ 2/16 Ａ Ｆターム(参考） 4C058 AA01 AA02 AA23 BB07 JJ02 JJ03 JJ04 JJ05 JJ08 4H011 AA02 AA03 BA01 BA06 BB09 BB10 BB11 BB18 BC18 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) A01N 43/80 102 A01N 43/80 102 59/16 59/16 A A61L 2/16 A61L 2/16 AF Terms (reference) 4C058 AA01 AA02 AA23 BB07 JJ02 JJ03 JJ04 JJ05 JJ08 4H011 AA02 AA03 BA01 BA06 BB09 BB10 BB11 BB18 BC18
Claims (11)
応生成物が、多孔質シリカ粒子の表面及び／又は内部に
固着していることを特徴とする抗菌防黴剤。1. An antibacterial and antifungal agent comprising a reaction product of an antibacterial metal component and an antifungal organic compound fixed to the surface and / or inside of porous silica particles.
応生成物が、多孔質シリカにより内包されていることを
特徴とする抗菌防黴剤。2. An antibacterial and antifungal agent characterized in that a reaction product of an antibacterial metal component and an antifungal organic compound is encapsulated by porous silica.
する請求項１記載の抗菌防黴剤。3. The antibacterial and antifungal agent according to claim 1, wherein the particle size is 0.01 to 1 μm.
する請求項２記載の抗菌防黴剤。4. The antibacterial and antifungal agent according to claim 2, wherein the particle size is 0.01 to 5 μm.
合物、チアゾール系化合物、Ｎ−ハロアルキルチオ系化
合物、ピリジン系化合物、イソチアゾロン系化合物から
なる群から選ばれた少なくとも１種であることを特徴と
する請求項１または２記載の抗菌防黴剤。5. The method according to claim 1, wherein the fungicidal organic compound is at least one selected from the group consisting of an imidazole compound, a thiazole compound, an N-haloalkylthio compound, a pyridine compound, and an isothiazolone compound. The antibacterial and antifungal agent according to claim 1 or 2.
応生成物をシリカにより処理することを特徴とする抗菌
防黴剤の製造方法。6. A method for producing an antibacterial and antifungal agent, comprising treating a reaction product of an antibacterial metal component with an antifungal organic compound with silica.
応生成物が分散したアルカリ金属の珪酸塩の水溶液と、
アルカリ金属の珪酸塩を不溶化する化合物の水溶液とを
混合・攪拌することを特徴とする請求項６記載の抗菌防
黴剤の製造方法。7. An aqueous solution of an alkali metal silicate in which a reaction product of an antibacterial metal component and an antifungal organic compound is dispersed,
The method for producing an antibacterial and antifungal agent according to claim 6, wherein an aqueous solution of a compound for insolubilizing an alkali metal silicate is mixed and stirred.
応生成物が分散したアルカリ金属の珪酸塩を不溶化する
化合物の水溶液と、アルカリ金属の珪酸塩の水溶液とを
混合・攪拌することを特徴とする請求項６記載の抗菌防
黴剤の製造方法。8. An aqueous solution of a compound insolubilizing an alkali metal silicate in which a reaction product of an antibacterial metal component and an antifungal organic compound is dispersed, and an aqueous solution of an alkali metal silicate are mixed and stirred. The method for producing an antibacterial and antifungal agent according to claim 6, characterized in that:
防黴性有機化合物との反応生成物を粉状または分散した
状態で添加し、加水分解触媒を加え、攪拌しながら前記
アルコキシシランを加水分解することを特徴とする請求
項６記載の抗菌防黴剤の製造方法。9. A reaction product of an antibacterial metal component and a fungicidal organic compound in a powdery or dispersed state is added to alkoxysilane, a hydrolysis catalyst is added, and the alkoxysilane is hydrolyzed with stirring. 7. The method for producing an antibacterial and antifungal agent according to claim 6, wherein the agent is decomposed.
シラン中に、抗菌性金属成分塩の水溶液を添加し、加水
分解触媒を加え、攪拌しながら前記アルコキシシラン化
合物を加水分解することを特徴とする請求項６記載の抗
菌防黴剤の製造方法。10. An alkoxysilane in which a fungicidal organic compound is dissolved, an aqueous solution of an antibacterial metal component salt is added, a hydrolysis catalyst is added, and the alkoxysilane compound is hydrolyzed with stirring. A method for producing an antibacterial and antifungal agent according to claim 6.
反応生成物を、アルカリ金属の珪酸塩の水溶液に分散す
る工程Ａと、この工程Ａで得られた分散液に水不溶性又
は難溶性の有機溶媒を混合してＷ／Ｏ型エマルジョンと
する工程Ｂと、この工程Ｂで得られたＷ／Ｏ型エマルジ
ョンに、前記アルカリ金属の珪酸塩を不溶化する化合物
の水溶液を添加して攪拌し、微多孔質カプセル粒子を生
成する工程Ｃとからなることを特徴とする請求項６記載
の抗菌防黴剤の製造方法。11. A step A in which a reaction product of an antibacterial metal component and an antifungal organic compound is dispersed in an aqueous solution of an alkali metal silicate, and water-insoluble or hardly soluble in the dispersion obtained in the step A. A step B of mixing a soluble organic solvent to form a W / O emulsion, and adding an aqueous solution of the compound for insolubilizing the alkali metal silicate to the W / O emulsion obtained in the step B, followed by stirring. 7. The method for producing an antibacterial and antifungal agent according to claim 6, comprising a step C of producing microporous capsule particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10194292A JP2000026205A (en) | 1998-07-09 | 1998-07-09 | Antibacterial and antifungal agent and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10194292A JP2000026205A (en) | 1998-07-09 | 1998-07-09 | Antibacterial and antifungal agent and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000026205A true JP2000026205A (en) | 2000-01-25 |
Family
ID=16322176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10194292A Pending JP2000026205A (en) | 1998-07-09 | 1998-07-09 | Antibacterial and antifungal agent and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000026205A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007026004A2 (en) * | 2005-09-02 | 2007-03-08 | Thor Gmbh | Synergetic silver-containing biocide composition |
| DE102007009450A1 (en) * | 2007-02-27 | 2008-08-28 | Clariant International Ltd. | Composition useful for producing an antimicrobial finish on substrates, e.g. medical instruments or textiles, comprises silver or a silver compound and an isothiazoline biocide |
| WO2008104310A2 (en) * | 2007-02-27 | 2008-09-04 | Clariant Finance (Bvi) Limited | Antimicrobial compositions |
| JP2008544953A (en) * | 2005-05-10 | 2008-12-11 | チバ ホールディング インコーポレーテッド | Antibacterial porous silicon oxide particles |
| JP2011057855A (en) * | 2009-09-10 | 2011-03-24 | Univ Of Tokushima | Active energy ray-curable composition, coating agent and resin film |
| WO2015045942A1 (en) * | 2013-09-30 | 2015-04-02 | 株式会社Ｌｉｘｉｌ | Fiber board |
| JP2015066901A (en) * | 2013-09-30 | 2015-04-13 | 株式会社Ｌｉｘｉｌ | Fiber board |
| JP2015520732A (en) * | 2012-04-16 | 2015-07-23 | ブンゲ アモルプヒク ソルトイオンス エルエルシー | Antibacterial chemical composition |
-
1998
- 1998-07-09 JP JP10194292A patent/JP2000026205A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008544953A (en) * | 2005-05-10 | 2008-12-11 | チバ ホールディング インコーポレーテッド | Antibacterial porous silicon oxide particles |
| WO2007026004A2 (en) * | 2005-09-02 | 2007-03-08 | Thor Gmbh | Synergetic silver-containing biocide composition |
| WO2007026004A3 (en) * | 2005-09-02 | 2007-05-18 | Thor Gmbh | Synergetic silver-containing biocide composition |
| DE102007009450A1 (en) * | 2007-02-27 | 2008-08-28 | Clariant International Ltd. | Composition useful for producing an antimicrobial finish on substrates, e.g. medical instruments or textiles, comprises silver or a silver compound and an isothiazoline biocide |
| WO2008104310A2 (en) * | 2007-02-27 | 2008-09-04 | Clariant Finance (Bvi) Limited | Antimicrobial compositions |
| WO2008104310A3 (en) * | 2007-02-27 | 2009-06-04 | Clariant Finance Bvi Ltd | Antimicrobial compositions |
| DE102007009450B4 (en) * | 2007-02-27 | 2012-11-15 | Clariant International Ltd. | Antimicrobial compositions |
| US8496952B2 (en) | 2007-02-27 | 2013-07-30 | Clariant Finance (Bvi) Limited | Antimicrobial compositions comprising silver chloride and benzoisothiazoline |
| JP2011057855A (en) * | 2009-09-10 | 2011-03-24 | Univ Of Tokushima | Active energy ray-curable composition, coating agent and resin film |
| JP2015520732A (en) * | 2012-04-16 | 2015-07-23 | ブンゲ アモルプヒク ソルトイオンス エルエルシー | Antibacterial chemical composition |
| WO2015045942A1 (en) * | 2013-09-30 | 2015-04-02 | 株式会社Ｌｉｘｉｌ | Fiber board |
| JP2015066901A (en) * | 2013-09-30 | 2015-04-13 | 株式会社Ｌｉｘｉｌ | Fiber board |
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