JP3716966B2 - Antifungal agent - Google Patents

Description

（式中、Ｒは水素原子またはアルキル基である。）
【０００８】
このような化合物としては、例えば、（イ）ビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート、（ロ）ポリ［｛６−（１，１，３，３−テトラメチルブチル）アミノ−１，３，５−トリアジン−２，４−ジイル｝｛（２，２，６，６−テトラメチル−４−ピペリジル）イミノ｝ヘキサメチレン｛（２，２，６，６−テトラメチル−４−ピペリジル）イミノ｝］、（ハ）１，２，３，４−ブタンテトラカルボン酸と、２，２，６，６，−テトラメチル−４−ピペリジノール及び３，９−ビス（２−ヒドロキシ−１，１−ジメチルエチル）−２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカンとの混合エステル化物、（ニ）テトラキス（１，２，２，６，６−ペンタメチル−４−ピペリジル）−１，２，３，４−ブタンテトラカルボキシラート、（ホ）テトラキス（２，２，６，６−テトラメチル−４−ピペリジル）−１，２，３，４−ブタンテトラカルボキシラート等が知られている。上記の内、（ロ）はポリオレフィン等衛生協議会のポジティブリストに記載されており、食品容器及び包装用途への使用が認められていることから、特に安全性に優れた化合物である。
【０００９】
本発明で使用される（ロ）の２，２，６，６−テトラメチル−４−ピペリジン誘導体は、融点及び軟化点が８０〜１３５℃であり、樹脂への分散性に優れ、透明性が高い防黴性樹脂組成物を提供することができる。
【００１０】
本発明で使用される上記（ロ）の２，２，６，６−テトラメチル−４−ピペリジン誘導体は、特に樹脂に対して、耐候性、耐熱性及び耐劣化性を付与することが知られており、従来の有機防黴剤より優れた防黴性樹脂組成物を提供することができる。
【００１１】
本発明の防黴剤の防黴性は以下の機構により発現されるものと推測される。即ち２，２，６，６−テトラメチル−４−ピペリジン構造から第四級アンモニウム塩を形成し、黴に対して細胞膜・細胞壁の損傷、酵素タンパク質の変性・呼吸阻害を引き起こして防黴性を示すものと考えられる。
【００１２】
本発明の防黴性樹脂組成物の製造に使用される樹脂は特に限定されず、例えば、ポリエチレン樹脂、ポリプロピレン樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリスチレン樹脂、ポリ塩化ビニル樹脂、ポリウレタン樹脂、ポリアクリル樹脂、ポリアミド樹脂、ポリビニルアルコール樹脂、セルロース樹脂等が挙げられる（但し、ポリアセタール樹脂は除かれる。）。
【００１３】
本発明の防黴性樹脂組成物における樹脂への上記（ロ）の２，２，６，６−テトラメチル−４−ピペリジン誘導体の添加量は特に限定されないが、樹脂１００重量部に対して０．０５〜５重量部の範囲が好ましい。添加量が０．０５重量部未満になると防黴効果が低くなる。又、添加量が５重量部を越えると樹脂組成物の物性に悪影響を及ぼすおそれがある。
【００１４】
また、本発明の防黴性樹脂組成物には本発明の効果を損わない範囲で顔料、各種添加剤、抗菌剤、他の防黴剤等を加えることができる。本発明の防黴性を有する物品は、本発明の防黴性樹脂組成物からなるものであれば特に限定されないが、例として以下の物品が挙げられる。
【００１５】
（１）防黴性成形品
本発明の防黴性樹脂組成物を射出成形、押出成形、ブロー成形等により成形した物品であり、より具体的には食品容器、ごみ箱、文具、電気器具のハウジング、化粧品容器、車両内装部品、台所用品、浴用製品、衣装収納製品等が挙げられる。
（２）防黴性繊維
本発明の防黴性樹脂組成物を紡糸等により繊維化した物品であり、更にはそれを織布又は不織布としたものである。より具体的には衣服やカーペット等が挙げられる。
（３）防黴性塗料
本発明の防黴性樹脂組成物を溶剤等を使用して塗料とする。
【００１６】
【実施例】
以下に実施例及び比較例を挙げて本発明を詳しく説明する。尚、文中部とあるのは特に断りのない限り重量基準である。
本実施例で使用する防黴剤を以下に示す。
防黴剤ａ：ポリ［｛６−（１，１，３，３−テトラメチルブチル）アミノ−１，３，５−トリアジン−２，４−ジイル｝｛（２，２，６，６テトラメチル−４−ピペリジル）イミノ｝ヘキサメチレン｛（２，２，６，６−テトラメチル−４−ピペリジル）イミノ｝］（ＣＡＳ Ｎｏ．７１８７８−１９−８）
【００１７】
実施例１
本発明の防黴剤ａの０．１％溶液をＰＤＡ培地（ポテト浸出液２０ｇ、デキストロース２ｇ、寒天１．５ｇ／１００ｍｌ、ｐＨ５．６）中に添加し、この培地を直径９ｃｍのシャーレに分注しプレートを作った。このプレートの中央に一白金耳量の供試菌の菌糸を植え付け、２５℃で２週間培養した。成長したコロニーの直径を測定し、下記に示す生育阻止率を算出し、本発明品の黴生育阻止効果を調べた。この結果を表１に示す。
【００１８】

（１）生育阻止率（％）＝１００−｛（防黴剤添加培地上のコロニー直径（ｃｍ）／添加培地上のコロニー直径（ｃｍ）｝×１００
（２）クラドスポリウム：クラドスポリウムクラドスポリオイデス
【００１９】
実施例２
１／８に希釈したＰＤＡ培地を直径９ｃｍのシャーレに分注してプレートを作った。このプレートの中央に、本発明の防黴剤ａを１％を練り込んだ硬質ポリエチレンブロック（１ｃｍ×１ｃｍ×１ｃｍ）を置いた。滅菌済みの０．００５％スルホコハク酸ジオクチルナトリウム水溶液１０ｍｌを用意し、供試黴の５白金耳量をこの溶液に懸濁させた。この菌糸懸濁液１０ｍｌを硬質ポリエチレンブロックを置いたプレート上に散布して供試菌を接種した。このプレートを２５℃で２週間培養した後、プレート上に生じたブロック周辺のハローゾーン形成を観察し、本発明品の防黴効果を調べた。
対照には発明品試料と同サイズの防黴剤無添加の硬質ポリエチレンブロックを用いた。
【００２０】

（１）＋＋：ハローゾーンの直径１ｃｍ以上
＋：ハローゾーンの直径１ｃｍ程度
−：ハローゾーンの形成無し
（２）発明品ａ：１％の防黴剤ａを練り込んだ硬質ポリエチレンブロック
（３）対照品：防黴剤無添加の硬質ポリエチレンブロック
【００２１】
【発明の効果】
本発明の防黴剤は上述のように、優れた防黴性を発現しつつ、安全性、透明性、耐熱性、耐劣化性に優れており、又、該防黴剤を用いた樹脂組成物、更にはその樹脂組成物を用いた物品も同様に優れた上記特性を有する。[0001]
BACKGROUND OF THE INVENTION
The present invention combines the heat resistance and weather resistance, and ensure transparency when kneaded resin relates to antifungal agents excellent in more safety.
[0002]
[Prior art]
In the past, relatively strong toxic agents such as halogen compounds and organic arsenic compounds have been used for antifungal agents in view of their efficacy.
However, as occupational safety and health problems are often pointed out and the growing awareness of environmental protection is emerging, the safety of these antifungal agents is often regarded as a problem, and the environmentally friendly low The development of toxic fungicides is highly desired.
[0003]
[Problems to be solved by the invention]
In the market, antibacterial agents are generally understood to mean agents that suppress the generation of bacteria, and antifungal agents are understood to mean agents that prevent the occurrence of wrinkles.
Bacterial cells are prokaryotic cells, do not have a nuclear membrane structure in the cells, DNA is bare and spreads near the center, and does not contain mitochondria or chloroplasts. Ribosome is 70S type consisting of 30S and 50S subunits, and cell division is amitosis.
On the other hand, sputum cells are eukaryotic cells, have nuclei enveloped in the nuclear membrane, and DNA is also contained therein. In addition, it has organelles such as mitochondria and chloroplasts, ribosome is 80S type consisting of 40S and 60S subunits, and takes the form of mitosis during cell division. Eukaryotic cells in acupuncture can be said to be cells that have evolved in a complex manner with a more functional structure than prokaryotic cells in bacteria.
[0004]
Therefore, generally, anti-fungal agents are more toxic than antibacterial agents. However, this also causes the safety of the antifungal agent to be regarded as a problem, and creates a current situation in which a safe antifungal agent is awaited.
Moreover, when applying an antifungal agent to an individual material, it is necessary to consider compatibility with material properties in addition to antifungal performance. For example, when used for resins, synthetic fibers, paints, etc., an antifungal agent having heat resistance, transparency, weather resistance, deterioration resistance and the like must be used.
[0005]
The present invention has been made in view of the above circumstances, and an object of the present invention is to have safety, excellent transparency, heat resistance, weather resistance, and deterioration resistance with respect to resins and synthetic fibers. It is to provide an antifungal agent that imparts the above.
The present inventors have, as a result of intensive studies to achieve the above object, Po Li [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine -2, 4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino} ] is a resin or synthetic fiber Thus, the present invention has been completed by finding that it is possible to stably impart antifungal properties, etc., and to impart excellent safety, transparency, heat resistance, weather resistance and deterioration resistance.
[0006]
[Means for Solving the Problems]
The above object is achieved by the present invention described below. That is, the present invention is, Po Li [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] (hereinafter “2,2,6,6-tetramethyl-4-piperidine derivative” sometimes referred to as "a antifungal agent characterized by comprising a there).
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Next, the present invention will be described in more detail with reference to preferred embodiments of the present invention.
The 2,2,6,6-tetramethyl-4-piperidine derivative used in the present invention is a compound having the following structure in the molecular skeleton.

(In the formula, R is a hydrogen atom or an alkyl group.)
[0008]
Examples of such compounds include (i) bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, (b) poly [{6- (1,1,3,3-tetramethyl Butyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetra Methyl-4-piperidyl) imino}], (c) 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis (2 -Hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, (d) tetrakis (1,2,2,6,6-pentamethyl) -4-piperidyl) -1,2,3,4-bu Emissions tetra carboxylate, it is known (e) tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetra-carboxylate and the like. Among the above , ( B) is a compound with particularly excellent safety because it is described in the positive list of the Sanitation Council for Polyolefins and is approved for use in food containers and packaging .
[0009]
2,2,6,6-tetramethyl-4-piperidine derivatives that are used in the present invention (b) has a melting point and softening point are 80 to 135 ° C., excellent dispersibility in resins, transparency A high antifungal resin composition can be provided.
[0010]
2,2,6,6-tetramethyl-4-piperidine derivative of the above SL (B) used in the present invention, particularly for the resin, the weather resistance, knowledge to impart heat resistance and resistance to deterioration Thus, it is possible to provide an antifungal resin composition superior to conventional organic antifungal agents.
[0011]
The antifungal property of the antifungal agent of the present invention is presumed to be expressed by the following mechanism. That is, quaternary ammonium salt is formed from 2,2,6,6-tetramethyl-4-piperidine structure, causing damage to cell membranes and cell walls, denaturation of enzyme protein, and respiratory inhibition to sputum. It is thought to show.
[0012]
Resin used for manufacture of the anti-mold resin composition of this invention is not specifically limited, For example, polyethylene resin, polypropylene resin, polycarbonate resin, polyester resin, polystyrene resin, polyvinyl chloride resin, polyurethane resin, polyacrylic resin , Polyamide resin, polyvinyl alcohol resin, cellulose resin and the like (however, polyacetal resin is excluded).
[0013]
The addition amount of 2,2,6,6-tetramethyl-4-piperidine derivatives of the above Symbol of the resin in the anti-mold resin composition of the present invention (B) is not particularly limited, with respect to 100 parts by weight of the resin The range of 0.05-5 weight part is preferable. When the addition amount is less than 0.05 parts by weight, the anti-mold effect is lowered. Moreover, when the addition amount exceeds 5 parts by weight, the physical properties of the resin composition may be adversely affected.
[0014]
In addition, pigments, various additives, antibacterial agents, other antifungal agents, and the like can be added to the antifungal resin composition of the present invention as long as the effects of the present invention are not impaired. Although the article | item which has the antifungal property of this invention will not be specifically limited if it consists of the antifungal resin composition of this invention, The following articles | goods are mentioned as an example.
[0015]
(1) Anti-molding molded article An article obtained by molding the anti-mold resin composition of the present invention by injection molding, extrusion molding, blow molding or the like. , Cosmetic containers, vehicle interior parts, kitchenware, bath products, costume storage products, and the like.
(2) Anti-mold fiber An article obtained by fiberizing the anti-mold resin composition of the present invention by spinning or the like, and further, a woven fabric or a non-woven fabric. More specifically, clothes and carpets can be mentioned.
(3) Antifungal paint The antifungal resin composition of the present invention is used as a paint using a solvent or the like.
[0016]
【Example】
Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. In addition, unless there is particular notice, what is in the middle of a sentence is a basis of weight.
The antifungal agents used in this example are shown below.
Antifungal a: Po Li [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl Methyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] (CAS No. 71878-19-8)
[0017]
Example 1
A 0.1% solution of the antifungal agent a of the present invention was added to a PDA medium (potato leaching solution 20 g, dextrose 2 g, agar 1.5 g / 100 ml, pH 5.6), and this medium was dispensed into a petri dish having a diameter of 9 cm. And made a plate. One platinum loop of mycelium of the test bacteria was planted in the center of this plate and cultured at 25 ° C. for 2 weeks. The diameter of the grown colony was measured, the growth inhibition rate shown below was calculated, and the effect of inhibiting the growth of cocoons of the present invention was examined. The results are shown in Table 1.
[0018]

(1) Growth inhibition rate (%) = 100 − {(colony diameter on the antifungal agent-added medium (cm) / colony diameter on the added medium (cm)} × 100
(2) Cladosporium: Cladosporium cladosporioides [0019]
Example 2
A plate was prepared by dispensing PDA medium diluted to 1/8 into a petri dish having a diameter of 9 cm. In the center of the plate, a hard polyethylene block (1 cm × 1 cm × 1 cm) in which 1% of the antifungal agent a of the present invention was kneaded was placed. 10 ml of a sterilized 0.005% sodium dioctyl sulfosuccinate aqueous solution was prepared, and 5 platinum loops of a test tube were suspended in this solution. 10 ml of this mycelial suspension was sprayed on a plate on which a hard polyethylene block was placed to inoculate the test bacteria. After culturing the plate at 25 ° C. for 2 weeks, the formation of a halo zone around the block formed on the plate was observed to examine the antifungal effect of the product of the present invention.
For control, a hard polyethylene block having the same size as that of the inventive sample and without an antifungal agent was used.
[0020]

(1) ++: Hello zone diameter 1cm or +: Hello zone diameter 1cm about - Formation None of halo zone (2) invention product a: 1% of the hard polyethylene block (3) kneaded antifungal agent a Control product: Rigid polyethylene block with no antifungal agent [0021]
【The invention's effect】
As described above, the antifungal agent of the present invention exhibits excellent antifungal properties and is excellent in safety, transparency, heat resistance, and deterioration resistance, and a resin composition using the antifungal agent Articles, and articles using the resin composition also have excellent characteristics as described above.

Claims (1)

Po Li [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4 piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] or antifungal agent characterized by Ranaru.