JP2000023711A - Deodorant antibacterial shoes insole - Google Patents

Deodorant antibacterial shoes insole

Info

Publication number
JP2000023711A
JP2000023711A JP10201709A JP20170998A JP2000023711A JP 2000023711 A JP2000023711 A JP 2000023711A JP 10201709 A JP10201709 A JP 10201709A JP 20170998 A JP20170998 A JP 20170998A JP 2000023711 A JP2000023711 A JP 2000023711A
Authority
JP
Japan
Prior art keywords
antibacterial
nonwoven fabric
compound
salt
composition
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
JP10201709A
Other languages
Japanese (ja)
Inventor
Haruyoshi Funae
晴芳 船江
Mitsuo Yoshida
光男 吉田
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.)
Mitsubishi Paper Mills Ltd
Original Assignee
Mitsubishi Paper Mills 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 Mitsubishi Paper Mills Ltd filed Critical Mitsubishi Paper Mills Ltd
Priority to JP10201709A priority Critical patent/JP2000023711A/en
Publication of JP2000023711A publication Critical patent/JP2000023711A/en
Pending legal-status Critical Current

Links

Abstract

PROBLEM TO BE SOLVED: To provide a shoe insole which is effective both for antibacterial and mildewproofing aspects and also better in deodorizing performance. SOLUTION: In this deodorant antibacterial shoes insoles, a nonwoven fabric is stuck on at least one side of a wet type nonwoven fabric that has as requisite components a fibrous substance containing a antibacterial/mildewproofing agent as a metal salt of an organic compound containing at least either a nitrogen containing heterocyclic compound or a sulfur atom, organic fibers and an adsorbing substance and preferably, a composition of mainly composed of a high molecular compound is applied on the surface of the nonwoven fabric. In place of the fibrous substance containing the antibacterial/mildewproofing agent of the wet type nonwoven fabric, it is possible to apply an antibacterial/mildewprooing agent composition containing an antibacterial/mildewproofing agent A and a nonwater soluble polymer compound D with a ratio by weight A/D of 0.05-5 on the wet type nonwoven fabric or impregnate the wet type nonwoven fabric with the antibacterial/mildewproofing agent composition or to apply the composition on the nonwoven fabric to be stuck thereon or impregnate the fabric with the composition. The metal salt herein used is preferably at least one of a silver salt, a copper salt and a zinc salt and the adsorbing substance is preferably zinc alminosilicate. The nonwater soluble high molecular compound is preferably at least one of a urethane based, styrene-butadiene based or acrylic based compound.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、脱臭抗菌性靴中敷
きに関し、詳しくは、抗菌、防黴の双方に極めて効果的
であって、汗等による臭気や湿気を吸収する、安全性の
高い抗菌防黴剤を含有する靴中敷きであり、長期間に渡
り優れた脱臭抗菌効果を有する抗菌防黴性靴中敷きに関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorizing and antibacterial shoe insole, and more particularly to a highly safe antibacterial which is extremely effective for both antibacterial and antifungal, and absorbs odor and moisture caused by sweat and the like. The present invention relates to an antibacterial and antifungal insole which contains an antifungal agent and has an excellent deodorizing and antibacterial effect over a long period of time.

【０００２】[0002]

【従来の技術】靴の中は汗による湿気が多く、菌類が繁
殖しやすく臭気の発生原因となるが、近年、清潔志向が
高まっており、靴の中の臭い、抗菌と湿気の改良を望む
人が増えている。2. Description of the Related Art In shoes, there is a lot of moisture due to sweat, and fungi are easy to propagate and cause odor. However, in recent years, the tendency to cleanliness has been increased, and it is desired to improve odor, antibacterial and moisture in shoes. People are increasing.

【０００３】このような目的で使用される靴中敷きに
は、臭いと湿気を取り、菌類の繁殖を抑えることが要求
されるが、安全性が高く、抗菌性の有る、脱臭除湿効果
の大きい靴中敷きが無いのが現状である。特に、脱臭に
関しては銅化合物、第４級アンモニウム塩化合物、金属
フタロシアニン化合物、椿や針葉樹抽出物質等での試み
がなされたが必ずしも充分な消臭効果が得られなかっ
た。[0003] Shoe insoles used for such a purpose are required to remove odors and moisture and to suppress the growth of fungi, but they are highly safe, have antibacterial properties, and have a large deodorizing and dehumidifying effect. At present, there is no insole. In particular, with respect to deodorization, attempts have been made with a copper compound, a quaternary ammonium salt compound, a metal phthalocyanine compound, a camellia or a softwood extract material, but a sufficient deodorizing effect has not always been obtained.

【０００４】[0004]

【発明が解決しようとする課題】本発明の目的は、長期
に渡り靴の中の臭いと湿気を取り、充分な強度が有り、
快適な履き心地を提供する靴中敷きを提供することであ
る。SUMMARY OF THE INVENTION An object of the present invention is to remove odors and moisture from shoes for a long period of time, and have sufficient strength.
The purpose of the present invention is to provide an insole that provides comfortable wearing comfort.

【０００５】[0005]

【課題を解決するための手段】[Means for Solving the Problems]

【０００６】本発明は、含窒素複素環、硫黄原子の少な
くともいずれかを含む有機化合物の金属塩である抗菌防
黴剤Ａを含有する繊維状物質、有機繊維及び吸着性物質
を必須成分とする湿式不織布Ｂの少なくとも片面に不織
布Ｃを貼り合わせた脱臭抗菌性靴中敷きである。The present invention comprises a fibrous substance, an organic fiber and an adsorbent substance containing an antibacterial and fungicide A which is a metal salt of an organic compound containing at least one of a nitrogen-containing heterocycle and a sulfur atom. It is a deodorant antibacterial insole in which a nonwoven fabric C is bonded to at least one surface of a wet nonwoven fabric B.

【０００７】本発明は、繊維状物質が、イオン交換繊維
である脱臭抗菌性靴中敷きである。[0007] The present invention is a deodorant antibacterial shoe insole whose fibrous substance is ion exchange fiber.

【０００８】本発明は、イオン交換繊維が、ポリスチレ
ン、ポリアクリル、ポリアミド、ポリエステル、ポリエ
チレン、およびセルロースから選ばれる少なくとも１種
であって、スルホン酸基、ホスホン酸基、カルボン酸基
の少なくとも１種を有する脱臭抗菌性靴中敷きである。According to the present invention, the ion exchange fiber is at least one selected from polystyrene, polyacryl, polyamide, polyester, polyethylene, and cellulose, and at least one of sulfonic acid group, phosphonic acid group and carboxylic acid group. It is a deodorant antibacterial shoe insole having:

【０００９】本発明は、イオン交換繊維がカルボキシメ
チル変性セルロースである脱臭抗菌性靴中敷きである。The present invention is a deodorant antibacterial shoe insole in which the ion exchange fiber is carboxymethyl-modified cellulose.

【００１０】本発明は、有機繊維と吸着性物質を必須成
分とする湿式不織布Ｅと不織布Ｆを貼り合わせた構造で
あり、含窒素複素環、硫黄原子の少なくともいずれかを
含む有機化合物の金属塩である抗菌防黴剤Ａと水不溶性
高分子化合物Ｄを含有し、重量比Ａ／Ｄが０．０５〜５
である抗菌防黴剤組成物Ｇを湿式不織布Ｅ又は不織布Ｆ
に塗布又は含浸させた脱臭抗菌性靴中敷きである。The present invention has a structure in which a wet nonwoven fabric E containing an organic fiber and an adsorptive substance as essential components and a nonwoven fabric F are bonded to each other, and a metal salt of an organic compound containing at least one of a nitrogen-containing heterocycle and a sulfur atom. Containing an antimicrobial fungicide A and a water-insoluble polymer compound D having a weight ratio A / D of 0.05 to 5
Nonwoven fabric E or nonwoven fabric F
It is a deodorant antibacterial shoe insole coated or impregnated on a shoe.

【００１１】本発明は、不織布Ｃ又はＦの少なくとも片
面に高分子化合物を主体とする組成物Ｈを塗布又は含浸
加工した脱臭抗菌性靴中敷きである。The present invention is a deodorant antibacterial shoe insole obtained by applying or impregnating a composition H mainly composed of a high molecular compound on at least one surface of a nonwoven fabric C or F.

【００１２】本発明は、含窒素複素環、硫黄原子の少な
くともいずれかを含有する有機化合物が、ベンズイミダ
ゾール化合物、メルカプトピリジン−Ｎ−オキシド化合
物、イソチアゾロン化合物、ベンゾチアゾール化合物も
しくはベンゾチアゾロン化合物から選ばれる少なくとも
１種の化合物である脱臭抗菌性靴中敷きである。In the present invention, the organic compound containing at least one of a nitrogen-containing heterocycle and a sulfur atom is at least one selected from a benzimidazole compound, a mercaptopyridine-N-oxide compound, an isothiazolone compound, a benzothiazole compound and a benzothiazolone compound. It is a deodorant antibacterial shoe insole which is one kind of compound.

【００１３】本発明は、金属塩が銀塩、銅塩、亜鉛塩の
少なくともいずれか１種である脱臭抗菌性靴中敷きであ
る。The present invention is a deodorant antibacterial shoe insole in which the metal salt is at least one of a silver salt, a copper salt and a zinc salt.

【００１４】本発明は、金属塩が銀塩、銅塩および亜鉛
塩の３種が複合されたものである脱臭抗菌性靴中敷きで
ある。The present invention is a deodorizing antibacterial shoe insole in which the metal salt is a composite of three kinds of silver salt, copper salt and zinc salt.

【００１５】本発明は、吸着性物質がアルミノケイ酸亜
鉛である脱臭抗菌性靴中敷きである。The present invention is a deodorant antibacterial shoe insole in which the adsorptive substance is zinc aluminosilicate.

【００１６】本発明は、水不溶性高分子化合物Ｄがウレ
タン系高分子化合物、スチレン−ブタジェン系高分子化
合物、アクリル系高分子化合物から選ばれる少なくとも
１種である脱臭抗菌性靴中敷きである。The present invention is a deodorant antibacterial shoe insole in which the water-insoluble polymer compound D is at least one selected from urethane polymer compounds, styrene-butadiene polymer compounds, and acrylic polymer compounds.

【００１７】本発明は、水不溶性高分子化合物Ｄの少な
くとも１種が自己乳化型である脱臭抗菌性靴中敷きであ
る。The present invention is a deodorant antibacterial shoe insole in which at least one of the water-insoluble polymer compounds D is a self-emulsifying type.

【００１８】本発明は、高分子化合物を主体とする組成
物Ｈが、界面活性剤を含有する脱臭抗菌性靴中敷きであ
る。The present invention is a deodorant antibacterial shoe insole in which the composition H mainly composed of a polymer compound contains a surfactant.

【００１９】[0019]

【発明の実施の形態】以下、本発明の実施の形態につい
て詳細に説明する。本発明では、靴中敷きとして過酷な
使用に耐えるためには、本発明における抗菌防黴剤Ａを
繊維構造内もしくは表面に形成させた繊維状物質か、本
発明の抗菌防黴剤組成物Ｇを繊維表面に強固に固定させ
た靴中敷きであることが必要である。Embodiments of the present invention will be described below in detail. In the present invention, in order to endure severe use as a shoe insole, a fibrous substance in which the antibacterial antifungal agent A of the present invention is formed in or on a fiber structure or the antibacterial antifungal composition G of the present invention is used. It must be a shoe insole firmly fixed to the fiber surface.

【００２０】本発明の抗菌防黴剤Ａで使用する金属塩は
銀、銅、亜鉛、錫、マンガン、コバルト、鉄塩等から選
択される。効果の点で好ましくは銀、銅、亜鉛塩から選
択され、更に２種以上の複合塩で形成され、特に銀、
銅、亜鉛塩の３種が複合されたものがより好ましい。理
由としては、各々の金属塩の水溶解性が異なっており、
亜鉛塩は早く溶解し、銀塩は遅いので抗菌防黴効果を使
用初期から継続して発揮させるためには亜鉛を含む２種
以上、特に銀、銅、亜鉛の３種の複合塩が好ましい。The metal salt used in the antibacterial and antifungal agent A of the present invention is selected from silver, copper, zinc, tin, manganese, cobalt, iron salts and the like. In terms of effect, silver, copper, and zinc salts are preferably selected, and further formed of two or more complex salts.
Those in which three kinds of copper and zinc salts are combined are more preferable. The reason is that the water solubility of each metal salt is different,
Since the zinc salt dissolves quickly and the silver salt is slow, in order to exert the antibacterial and antifungal effect continuously from the initial stage of use, two or more kinds of salts containing zinc, particularly three kinds of salts of silver, copper and zinc are preferable.

【００２１】本発明の抗菌防黴剤Ａで使用する含窒素複
素環、硫黄原子の少なくともいずれかを含有する有機化
合物としては、例えば、ピロール系、ピリジン系、ピリ
ミジン系、ピラゾール系、イミダゾール系、ベンズイミ
ダゾール系、１．３．５−トリアジン系、ヘキサヒドロ
−１．３．５−トリアジン系、トリアゾール系、イソオ
キサゾール系、チアゾール系、ベンゾチアゾール系、チ
アゾロン系、ベンゾチアゾロン系、イソチアゾロン系、
ベンゾイソチアゾロン系、テトラヒドロチアジアジンチ
オン系などを基本骨格とするものが挙げられ、さらに、
それらのアルキルアリル誘導体、メルカプト誘導体など
が挙げられるが、なかでも、ベンズイミダゾール化合
物、メルカルトピリジン−Ｎ−オキシド化合物、イソチ
アゾロン化合物、ベンゾチアゾール化合物、ベンゾチア
ゾロン化合物から選ばれる少なくとも一種の化合物が特
に好ましい。これらの具体例としては、例えば、２−
（４−チアゾリル）−ベンズイミダゾール、２−（カル
ボメトキシアミノ）−ベンズイミダゾール、２−メルカ
ルトピリジン−Ｎ−オキシド、１．２−ベンゾイソチア
ゾリン−３−オン、５−クロロ−２−メチル−４−イソ
チアゾリン−３−オン、２−メチル−４−イソチアゾリ
ン−３−オン、２−ｎ−オクチル−４−イソチアゾリン
−３−オン、１．２−ベンゾチアゾロン、２−（４−チ
オシアノメチルチオ）ベンゾチアゾールなどを挙げるこ
とができる。The organic compound containing at least one of a nitrogen-containing heterocyclic ring and a sulfur atom used in the antibacterial and fungicide A of the present invention includes, for example, pyrrole, pyridine, pyrimidine, pyrazole, imidazole, and the like. Benzimidazole, 1.3.5-triazine, hexahydro-1.3.5-triazine, triazole, isoxazole, thiazole, benzothiazole, thiazolone, benzothiazolone, isothiazolone,
Benzoisothiazolone-based, tetrahydrothiadiazinethione-based and the like as a basic skeleton, and further,
Examples thereof include an alkyl allyl derivative and a mercapto derivative. Among them, at least one compound selected from a benzimidazole compound, a mercartopyridine-N-oxide compound, an isothiazolone compound, a benzothiazole compound, and a benzothiazolone compound is particularly preferable. Examples of these are, for example, 2-
(4-thiazolyl) -benzimidazole, 2- (carbomethoxyamino) -benzimidazole, 2-mercartopyridine-N-oxide, 1.2-benzoisothiazolin-3-one, 5-chloro-2-methyl-4- Isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 1.2-benzothiazolone, 2- (4-thiocyanomethylthio) benzothiazole and the like Can be mentioned.

【００２２】特に、ベンズイミダゾール化合物、メルカ
プトピリジン−Ｎ−オキシド化合物、イソチアゾロン化
合物、ベンゾチアゾール化合物もしくはベンゾチアゾロ
ン化合物のうちの少なくとも１種類が効果の点で好まし
い。In particular, at least one of a benzimidazole compound, a mercaptopyridine-N-oxide compound, an isothiazolone compound, a benzothiazole compound and a benzothiazolone compound is preferred in terms of effect.

【００２３】本発明の抗菌防黴剤Ａを含有させる繊維状
物質として、いわゆるイオン交換繊維が用いられ、例え
ばポリスチレン、ポリアクリル、ポリアミド、ポリエチ
レン、セルロース等のベースポリマーにスルホン酸基、
ホスホン酸基、カルボン酸基等を適度に導入する事によ
って得られる。As the fibrous substance containing the antibacterial and fungicide A of the present invention, so-called ion-exchange fibers are used. For example, sulfonic acid groups, base polymers such as polystyrene, polyacryl, polyamide, polyethylene and cellulose are used.
It can be obtained by appropriately introducing a phosphonic acid group, a carboxylic acid group and the like.

【００２４】また通常パルプと称せられる天然のセルロ
ース系繊維を部分的に化学変性することにより好ましく
利用出来る。化学変性処理としては、硫酸化、リン酸
化、硝酸化、カルボキシメチル化、カルボキシエチル
化、カルボキシプロピル化処理が挙げられる。中でも、
カルボキシメチル化処理はプロセスが容易で、経済性、
安全性も良く、かつ膨潤性、イオン浸透性等に優れてお
り本発明の実施に極めて好適であり、特に該セルロース
系繊維の部変性物の置換度が０．５以下のものが好まし
い。Further, natural cellulose fibers usually called pulp can be preferably used by partially chemically modifying them. Examples of the chemical denaturation treatment include sulfation, phosphorylation, nitration, carboxymethylation, carboxyethylation, and carboxypropylation. Among them,
The carboxymethylation process is easy, economical,
It is excellent in safety and excellent in swelling property, ion permeability and the like, and is very suitable for the practice of the present invention. In particular, it is preferable that the degree of substitution of the partially modified product of the cellulose fiber is 0.5 or less.

【００２５】本発明で繊維状物質としては、適度にカル
ボキシメチル化された木材パルプ（針葉樹パルプ、広葉
樹パルプなど）が、本発明の実施に好適であるが、この
他、レーヨンなどの再生セルロースも同様に使用可能で
ある。さらには、前記主旨に沿って適度に変性されたイ
オン交換能を有する合成繊維、アルギン酸繊維や可溶性
ポリマーの湿式紡糸繊維であっても良い。また、本発明
における抗菌・防黴能を有する有機金属複合塩を含有す
るポリマー液から製造された湿式紡糸繊維であっても良
い。As the fibrous substance in the present invention, suitably carboxymethylated wood pulp (softwood pulp, hardwood pulp, etc.) is suitable for the practice of the present invention. In addition, regenerated cellulose such as rayon is also used. It can be used as well. Further, a synthetic fiber, an alginic acid fiber, or a wet-spun fiber of a soluble polymer, which is appropriately modified according to the above-mentioned purpose and has ion exchange ability, may be used. Further, a wet-spun fiber produced from a polymer solution containing an organic metal complex salt having antibacterial and antifungal properties according to the present invention may be used.

【００２６】本発明における繊維状物質の好ましい一具
体例としては、天然セルロース系繊維のカルボキシメチ
ル化加工によって達成される。A preferred specific example of the fibrous substance in the present invention is achieved by carboxymethylation of a natural cellulosic fiber.

【００２７】所望のカルボキシメチル基置換度を持つ繊
維状物質を得るには、基本的には、セルロース系繊維に
対するモノクロル酢酸ナトリウム量、アルカリ量および
水の量、その他反応条件を調整することによって可能で
ある。A fibrous substance having a desired degree of carboxymethyl group substitution can be basically obtained by adjusting the amount of sodium monochloroacetate, the amount of alkali and water with respect to the cellulosic fiber, and other reaction conditions. It is.

【００２８】一般的に、カルボキシメチル基置換度は、
グルコース単位当たりのカルボキシメチル基の置換度
（ＤＳ）で定義され、その置換率は、一旦、酸型カルボ
キシメチルセルロースに変換後、過剰量のアルカリを加
えて中和した後、酸で逆滴定することによって求められ
る。In general, the degree of carboxymethyl group substitution is
It is defined as the degree of substitution of carboxymethyl groups per glucose unit (DS). The degree of substitution is to convert to acid-type carboxymethylcellulose, neutralize it by adding an excess amount of alkali, and then back titrate with acid. Required by

【００２９】本発明で用いられる各種のカルボキシメチ
ル基置換度を持つ繊維状物質は、置換度が大きくなるに
つれて、金属イオン捕獲能は高まり、したがって、本発
明における抗菌・防黴能を有する有機金属複合塩の充填
密度は高くなるが、高置換度では膨潤が過度に進み、繊
維強度の低下および、ひいては可溶化に至る。一般的
に、置換度はおよそ０．６で可溶性となる。強度低下は
あるが置換度はおよそ０．５が繊維形状が維持できる上
限レベルである。The fibrous substance having various degrees of carboxymethyl group substitution used in the present invention has a higher metal ion capturing ability as the degree of substitution increases, and therefore, the organic metal having antibacterial and antifungal properties according to the present invention. Although the packing density of the composite salt increases, the swelling proceeds excessively at a high degree of substitution, leading to a decrease in fiber strength and, consequently, to solubilization. Generally, the degree of substitution becomes soluble at around 0.6. Although the strength is reduced, the degree of substitution is about 0.5, which is the upper limit level at which the fiber shape can be maintained.

【００３０】本発明における繊維状物質と併用される有
機繊維としては、植物繊維、動物繊維、再成繊維、半合
成繊維および合成繊維から選ばれる繊維を単独あるいは
混合したものが使用される。As the organic fiber used in combination with the fibrous substance in the present invention, a fiber selected from plant fibers, animal fibers, regenerated fibers, semi-synthetic fibers and synthetic fibers alone or in combination is used.

【００３１】植物繊維としては、綿、麻（亜麻、ラミ
ー）が、動物繊維としては、絹、羊毛などの繊維が挙げ
られる。The plant fibers include cotton and hemp (flax, ramie), and the animal fibers include fibers such as silk and wool.

【００３２】再成繊維としては、レーヨン、キュプラ
が、半合成繊維としては、アセテート、トリアセテー
ト、プロミックスが、合成繊維としては、ナイロン、ア
クリル、ビニロン、ビニリデン、ポリ塩化ビニル、ポリ
エステル、ポリエチレン、ポリプロピレン、ベンゾエー
ト、ポリクラール、フェノール系などの繊維が挙げられ
る。Rayon and cupra are used as regenerated fibers, acetate, triacetate and promix are used as semi-synthetic fibers, and nylon, acryl, vinylon, vinylidene, polyvinyl chloride, polyester, polyethylene and polypropylene are used as synthetic fibers. , Benzoate, polychloral, phenol-based fibers and the like.

【００３３】なお、本発明においては、上記の繊維の他
に、植物繊維として、針葉樹パルプ、広葉樹パルプなど
の木材パルプや藁パルプなどの木本類、草本類を含むも
のとする。さらに、古紙、損紙などから得られるパルプ
繊維も含まれる。In the present invention, in addition to the above-mentioned fibers, woody plants such as softwood pulp and hardwood pulp, woody plants such as straw pulp, and herbs are included as plant fibers. Further, pulp fibers obtained from waste paper, broke, and the like are also included.

【００３４】本発明における繊維状物質を他の併用され
る各種繊維と混抄して使用する場合、必要に応じて、各
種のバインダーを用いることができる。When the fibrous substance in the present invention is mixed with various other fibers to be used, various binders can be used as necessary.

【００３５】本発明に用いられる繊維状のバインダー
は、芯鞘タイプ（コアシェルタイプ）、並列タイプ（サ
イドバイサイドタイプ）などの複合繊維が挙げられる。
例えば、ポリプロピレン（芯）とポリエチレン（鞘）の
組み合わせ（商品名：ダイワボウＮＢＦ−Ｈ：大和紡績
社製）、ポリプロピレン（芯）とエチレンビニルアルコ
ール（鞘）の組み合わせ（商品名：ダイワボウＮＢＦ−
Ｅ：大和紡績社製）、ポリプロピレン（芯）とポリエチ
レン（鞘）の組み合わせ（商品名：チッソＥＳＣ：チッ
ソ社製）、高融点ポリエステル（芯）と低融点ポリエス
テル（鞘）の組み合わせ（商品名：メルテイ４０８０：
ユニチカ社製）などが挙げられる。また、ビニロンバイ
ンダー繊維（ＶＰＢ１０７×１：クラレ社製）などの熱
水溶融タイプなども使用できる。The fibrous binder used in the present invention includes conjugate fibers such as a core-sheath type (core-shell type) and a side-by-side type (side-by-side type).
For example, a combination of polypropylene (core) and polyethylene (sheath) (trade name: Daiwabo NBF-H: manufactured by Daiwa Spinning Co.), a combination of polypropylene (core) and ethylene vinyl alcohol (sheath) (trade name: Daiwabo NBF-)
E: Daiwa Spinning Co., Ltd.), a combination of polypropylene (core) and polyethylene (sheath) (trade name: Chisso ESC: made by Chisso), a combination of high melting polyester (core) and low melting polyester (sheath) (trade name: Melty 4080:
Unitika). Further, a hot water melting type such as vinylon binder fiber (VPB107 × 1: manufactured by Kuraray Co., Ltd.) can also be used.

【００３６】湿式不織布は、各種短繊維を水中に分散し
た後、紙と同様の抄紙機で抄造、乾燥され、シート化さ
れるが、本発明の湿式不織布Ｂ及びＥの製造は、丸網抄
紙機、長網抄紙機、傾斜ワイヤー式抄紙機等の単独か組
み合わせにより、単層か多層で抄造される。The wet nonwoven fabric is prepared by dispersing various types of short fibers in water, and then formed and dried by using the same paper machine as paper. The wet nonwoven fabrics B and E of the present invention are produced by round net papermaking. A single-layer or multi-layer paper is made by a single machine, a fourdrinier machine, an inclined wire paper machine, or the like.

【００３７】本発明の湿式不織布Ｂ及びＥの目付は一般
的には３０〜６００ｇ／ｍ2である。好ましくは５０〜
５００ｇ／ｍ2である。６００ｇ／ｍ2より重いと厚くて
曲がりにくくなり、中敷きに加工した時の履き心地が悪
くなる。３０ｇ／ｍ2より軽いと強度や硬さがなくなり
しわになりやすくなる。The basis weight of the wet nonwoven fabrics B and E of the present invention is generally 30 to 600 g / m 2 . Preferably 50 to
500 g / m 2 . If it is heavier than 600 g / m 2 , it will be thick and difficult to bend, and the comfort when processing it into an insole will be poor. If the weight is less than 30 g / m 2 , strength and hardness are lost and wrinkles are liable to occur.

【００３８】本発明の湿式不織布Ｂ及びＥに充填する吸
着性物質は、粘土系、ゼオライト系、酸性白土系、活性
白土系、ベントナイト系、活性炭系等の無機化合物系や
酸性基や塩基性基を有する高分子化合物等が利用出来
る。好ましいのは靴や靴下の汚れる心配の少ない白色系
の無機化合物であり、特に好ましいのは、アンモニア、
トリメチルアミン、硫化水素、エチルメルカプタン等の
吸着に有効である粘土系のアルミノケイ酸亜鉛系であ
る。具体的には水沢化学工業社製のミズカナイトＡＰ、
ミズカナイトＡＧ、ミズカナイトＨＰ、ミズカナイトＨ
Ｇが挙げられる。The adsorptive substance to be filled in the wet nonwoven fabrics B and E of the present invention may be an inorganic compound such as a clay-based, zeolite-based, acid clay-based, activated clay-based, bentonite-based, activated carbon-based, or an acidic or basic group. And the like. Preferred are white inorganic compounds that are less likely to stain shoes and socks, and particularly preferred are ammonia,
It is a clay-based zinc aluminosilicate that is effective for adsorption of trimethylamine, hydrogen sulfide, ethyl mercaptan and the like. Specifically, Mizucanite AP manufactured by Mizusawa Chemical Industries,
MIZUKANITE AG, MIZUKANITE HP, MIZUKANITE H
G.

【００３９】湿式不織布に充填する吸着性物質の量は、
その種類により異なるが、臭気物質の吸着効果からは湿
式不織布の単位面積当たりで５ｇ／ｍ2以上の使用が好
ましく、より好ましくは１０ｇ／ｍ2以上である。一般
的な充填比率は湿式不織布の３〜５０重量％程度であ
る。The amount of the adsorptive substance to be filled in the wet nonwoven fabric is as follows:
Although it depends on the type, it is preferable to use 5 g / m 2 or more per unit area of the wet nonwoven fabric, more preferably 10 g / m 2 or more, from the viewpoint of the adsorption effect of the odorous substance. A typical filling ratio is about 3 to 50% by weight of the wet nonwoven fabric.

【００４０】本発明の不織布Ｃ、及び抗菌防黴剤組成物
Ｇを含浸又は塗布する不織布Ｆは、カード法等による乾
式不織布、スパンボンド、メルトブローン等による不織
布、湿式不織布、及びそれらのスパンレース加工不織布
が使用される。The nonwoven fabric C of the present invention and the nonwoven fabric F impregnated with or coated with the antibacterial and fungicidal composition G can be a dry nonwoven fabric by a card method or the like, a nonwoven fabric by a spun bond, a melt blown or the like, a wet nonwoven fabric, and a spunlace process thereof. Non-woven fabric is used.

【００４１】不織布Ｃ、及び不織布Ｆの目付は３０〜４
００ｇ／ｍ2が一般的であるが、５０〜３００ｇ／ｍ2が
履き心地や強度からは好ましい。The basis weight of the nonwoven fabric C and the nonwoven fabric F is 30 to 4
00 g / m 2 is generally used, but 50 to 300 g / m 2 is preferable from the viewpoint of comfort and strength.

【００４２】本発明で、不織布Ｂと不織布Ｃ、不織布Ｅ
と不織布Ｆとを貼り合わせる場合には、固形、水系、溶
剤系の各種接着剤が使用出来るが、好ましくはポリエチ
レン系、ポリプロピレン系の固形粒子で不織布上にふり
かけ、適度に加熱溶融した後重ね合わせて加圧する方法
が通気性から好ましい。In the present invention, the nonwoven fabric B and the nonwoven fabric C, the nonwoven fabric E
When the non-woven fabric F is bonded to the non-woven fabric, various solid, water-based, and solvent-based adhesives can be used. Pressure is preferred from the viewpoint of air permeability.

【００４３】又、ポリエチレン系やポリプロピレン系等
の網目状のシートであるノリフを、貼り合わせる不織布
の間に入れて加熱加圧して積層する方法も通気性からは
好ましいが、何れも加熱時に溶融して通気性を大きく下
げない不織布や処理温度の選択が必要である。A method of laminating a net-like sheet such as a polyethylene-based or polypropylene-based sheet between nonwoven fabrics to be laminated by heating and pressing is also preferable from the viewpoint of air permeability. It is necessary to select a nonwoven fabric and a processing temperature that do not greatly reduce the air permeability.

【００４４】また、本発明の抗菌防黴剤組成物Ｇで使用
する水不溶性高分子化合物としては、ウレタン系高分子
化合物、スチレン−ブタジェン系高分子化合物、アクリ
ル系高分子化合物、アクリロニトリル−ブタジェン系高
分子化合物、エステル系高分子化合物、スチレン系高分
子化合物、アミド系高分子化合物、塩化ビニル系化合
物、酢酸ビニル系化合物、フッソ系化合物、シリコン系
化合物、エチレン系高分子化合物やプロピレン系高分子
化合物等のオレフィン系高分子化合物等が挙げられる。The water-insoluble polymer compound used in the antibacterial and fungicide composition G of the present invention includes urethane polymer compounds, styrene-butadiene polymer compounds, acrylic polymer compounds, acrylonitrile-butadiene compounds. Polymer compound, ester polymer compound, styrene polymer compound, amide polymer compound, vinyl chloride compound, vinyl acetate compound, fluorine compound, silicon compound, ethylene polymer compound and propylene polymer Examples include olefin-based high molecular compounds such as compounds.

【００４５】水不溶性高分子化合物が好ましい理由は、
それを含有する抗菌防黴剤組成物を各種の材料に塗布ま
たは含浸し、最低造膜温度以上の温度で乾燥することに
より特に耐水性が良好な抗菌防黴性能を持った材料が得
られるからである。更に、水不溶性高分子化合物に自己
乳化性を付与したり、乳化剤で水に分散させたものを乾
燥した場合には膜の不連続部分が発生しやすく、抗菌防
黴剤のような異種のものを加えた場合には特に顕著であ
り、その不連続部分より抗菌防黴剤の成分が移動しやす
くなり、良好な抗菌防黴性が発現すると予想される。The reason why the water-insoluble polymer compound is preferable is as follows.
By coating or impregnating various materials with the antibacterial and fungicide composition containing the same and drying at a temperature higher than the minimum film forming temperature, a material having particularly good water resistance and antibacterial and fungicidal properties can be obtained. It is. Furthermore, when a water-insoluble polymer compound is imparted with self-emulsifying properties, or when dried in water with an emulsifier, a discontinuous portion of the film is liable to occur, and different types of materials such as an antibacterial and fungicide are used. Is particularly remarkable when the compound is added, the components of the antibacterial and antifungal agent are easily transferred from the discontinuous portion, and it is expected that good antibacterial and antifungal properties will be exhibited.

【００４６】本発明で水不溶性高分子化合物Ｄに対する
抗菌防黴剤Ａの重量比Ａ／Ｄが０．０５〜５が好ましい
理由は、５より大きいと耐水性、耐久性に劣り、０．０
５より小さいと抗菌防黴剤Ａを水不溶性高分子化合物Ｂ
が覆う為に内側の抗菌防黴剤Ａの効果が得にくく、又、
抗菌防黴剤の密度が低いので初期の抗菌防黴効果も劣る
ためである。In the present invention, the reason that the weight ratio A / D of the antibacterial and fungicide A to the water-insoluble polymer compound D is preferably 0.05 to 5 is that if it is larger than 5, water resistance and durability are poor, and 0.0
If it is less than 5, the antibacterial and fungicide A is replaced with the water-insoluble polymer compound B
Is difficult to obtain the effect of the antibacterial and antifungal agent A on the inside because
This is because the antibacterial and antifungal agent has a low density, so that the initial antibacterial and antifungal effect is poor.

【００４７】本発明で抗菌防黴剤組成物が塗布または含
浸され、乾燥された後では水不溶性高分子化合物の膜は
耐水性が有り、水分が加えられても安定であり、抗菌防
黴剤成分が水分と共に適度に表面に移動、徐放すること
により継続した良好な抗菌性、防黴性の効果が得られる
と予想される。After the antibacterial and fungicide composition of the present invention has been applied or impregnated and dried, the film of the water-insoluble polymer compound has water resistance, is stable even when added with water, It is anticipated that the components will move to the surface appropriately with moisture and are gradually released, whereby a continuous good antibacterial and antifungal effect will be obtained.

【００４８】耐水性を更に向上させる為には、水不溶性
高分子化合物に架橋剤を添加して適度に架橋させること
も可能である。In order to further improve the water resistance, it is also possible to add a crosslinking agent to the water-insoluble polymer compound so as to appropriately crosslink.

【００４９】耐久性、耐光性、摩擦強度等の特性から、
好ましくは水不溶性高分子化合物としてウレタン系高分
子化合物、スチレン−ブタジェン系高分子化合物、アク
リル系高分子化合物が用いられる。From the characteristics such as durability, light resistance and friction strength,
Preferably, a urethane polymer, a styrene-butadiene polymer, or an acrylic polymer is used as the water-insoluble polymer.

【００５０】好ましくは水不溶性高分子化合物が自己乳
化型である。その理由は水に分散する場合に各種乳化剤
を添加する必要が無いので各物品に塗布または含浸、乾
燥された後の抗菌防黴剤と水不溶性高分子化合物との接
着性が良好となり、耐水性、耐久性に優れる為である。Preferably, the water-insoluble polymer compound is of a self-emulsifying type. The reason is that it is not necessary to add various emulsifiers when dispersing in water, so that the adhesion between the antibacterial fungicide and the water-insoluble polymer compound after being applied or impregnated and dried on each article becomes good, and water resistance It is because of excellent durability.

【００５１】特に、本発明の抗菌防黴剤を水中に分散す
るのには自己乳化型の水不溶性高分子化合物が好まし
く、自己乳化型のウレタン系高分子化合物、スチレン−
ブタジェン系高分子化合物、アクリル系高分子化合物が
好ましい。Particularly, for dispersing the antibacterial and fungicide of the present invention in water, a self-emulsifying water-insoluble polymer compound is preferable, and a self-emulsifying urethane polymer compound and styrene-
Butadiene polymer compounds and acrylic polymer compounds are preferred.

【００５２】具体的にはウレタン系、スチレン−ブタジ
ェン系、アクリル系等の水不溶性高分子化合物が特定量
以上のカルボキシル基、アミノ基、水酸基やエステル類
等のアニオン、ノニオン、カチオン性の親水性の部分を
有するものであり、それにより水中で安定的に分散可能
となるものである。大日本インキ化学工業社製ハイドラ
ンＨＷ３５０、ラックスターＤＳ−４０５、ラックスタ
ーＤＳ−４０７、パテラコートＳＢ−３０１等が挙げら
れる。More specifically, water-insoluble polymer compounds such as urethane, styrene-butadiene, and acryl are used in an amount of a specified amount or more such as anions such as carboxyl groups, amino groups, hydroxyl groups and esters, nonions, and cationic hydrophilicity. , So that it can be stably dispersed in water. Hydran HW350 manufactured by Dainippon Ink and Chemicals, Luck Star DS-405, Luck Star DS-407, Patera Coat SB-301, and the like.

【００５３】好ましくは水不溶性高分子化合物が自己架
橋型である。その理由は、自己架橋により膜が強固にな
り耐水性、耐久性が良好となるためである。自己架橋型
ではない水不溶性高分子化合物に架橋剤を添加する場合
は抗菌防黴剤組成物の液安定性が劣り、抗菌防黴剤同士
が凝集しやすくなるために架橋剤の種類、及び量の選択
が難しい。Preferably, the water-insoluble polymer compound is of a self-crosslinking type. The reason is that the self-crosslinking strengthens the film and improves water resistance and durability. When a crosslinking agent is added to a water-insoluble polymer compound that is not a self-crosslinking type, the liquid stability of the antibacterial and fungicide composition is inferior, and the antibacterial and fungicidal agents are easily aggregated. Is difficult to choose.

【００５４】具体的にはウレタン系、スチレン−ブタジ
ェン系、アクリル系等の水不溶性高分子化合物がビニル
基、アルデヒド基、エポキシ基、等の反応性の高い部分
を有しており、縮合反応や付加反応、開環反応等により
自己架橋するものである。大日本インキ化学工業社製ボ
ンコート３２５６、ラックスターＤＳ−４０７等が挙げ
られる。Specifically, water-insoluble polymer compounds such as urethane, styrene-butadiene, and acrylic have highly reactive parts such as vinyl group, aldehyde group, epoxy group, and the like. Self-crosslinking is carried out by an addition reaction, ring opening reaction or the like. Examples include Bonncoat 3256 and Luckstar DS-407 manufactured by Dainippon Ink and Chemicals, Inc.

【００５５】本発明で抗菌防黴剤組成物Ｇには必要に応
じて各種の接着剤、顔料、染料等を混合することが出来
る。In the present invention, various adhesives, pigments, dyes and the like can be mixed with the antibacterial and fungicidal composition G as required.

【００５６】次に、本発明の抗菌防黴剤Ａ作成の一例と
して、置換度が０．４のＮａ型カルボキシメチルセルロ
ースを使った例を用いて説明する。 １）上記パルプ固形分１００ｇ相当量に攪拌が可能な程
度に水を加える。 ２）硝酸銀１００ｍｍｏｌ／相当量（１７ｇ）を添加す
る。 ３）系のｐＨが５．５〜６．０となるようにアルカリを
添加する。 ４）室温下で３０分攪拌し、十分に置換（吸着）させ
る。 ５）２−メルカプトピリジン−Ｎ−オキシドナトリウム
塩の０．１Ｍ／ｌ液１０００ｍｌを攪拌しながら少しず
つ添加する。銀電極もしくは白金電極を用いて、電位計
測すると、反応終了点を検知することができる。 ６）添加終了後、３０分間攪拌し、十分に反応させる。 ７）０．１Ｍ／ｌの硫酸液を加えて、系のｐＨを約４ま
で下げた後、脱水プレスにて脱水する。Next, as an example of the preparation of the antibacterial and fungicide A of the present invention, an example using Na-type carboxymethylcellulose having a substitution degree of 0.4 will be described. 1) Add water to an amount equivalent to 100 g of the above pulp solid content to such an extent that stirring is possible. 2) Add 100 mmol / equivalent (17 g) of silver nitrate. 3) Add alkali so that the pH of the system is 5.5 to 6.0. 4) Stir at room temperature for 30 minutes to allow sufficient displacement (adsorption). 5) 1000 ml of a 0.1 M / l solution of sodium 2-mercaptopyridine-N-oxide is added little by little with stirring. When the potential is measured using a silver electrode or a platinum electrode, the reaction end point can be detected. 6) After completion of the addition, the mixture is stirred for 30 minutes to allow a sufficient reaction. 7) The pH of the system is lowered to about 4 by adding a 0.1 M / l sulfuric acid solution, and then the system is dehydrated by a dehydration press.

【００５７】上記の手順により、メルカプトピリジン−
Ｎ−オキシド銀塩を含有するパルプが得られる。必要な
らば、再度水中に分散し、水洗することにより、脱落分
をあらかじめ除くことができる。実験結果によれば、一
部脱落はするが９０％以上の高収率で繊維内および表面
固着の形で塩が形成されていることが認められた。According to the above procedure, mercaptopyridine-
A pulp containing a silver N-oxide salt is obtained. If necessary, the fall-off can be removed in advance by dispersing in water again and washing with water. According to the results of the experiment, it was confirmed that salts were formed in the fiber and in the form of surface fixation at a high yield of 90% or more, although some were removed.

【００５８】メルカプトピリジン−Ｎ−オキシド銀塩を
繊維内もしくは表面に収率良く形成させるには、ｐＨコ
ントロール、攪拌、薬品添加濃度および速度などの最適
化が必要である。In order to form the mercaptopyridine-N-oxide silver salt in the fiber or on the surface with a high yield, it is necessary to optimize pH control, stirring, concentration and rate of addition of chemicals.

【００５９】本発明において、最も効果的に抗菌防黴機
能を発揮する有機化合物の複合塩の作製方法について述
べる。In the present invention, a method for preparing a complex salt of an organic compound which exhibits the most effective antibacterial and antifungal function will be described.

【００６０】基本的には、前記の単一金属塩の場合と同
様に、カルボキシメチルセルロースに対して添加する金
属塩組成を、計算量配合することによって達成できる
し、また、銀電極もしくは白金電極を用いた電位計測に
より、各イオンとの反応をモニターできる。Basically, as in the case of the above-described single metal salt, the composition of the metal salt to be added to carboxymethylcellulose can be achieved by mixing the calculated amount, and the silver electrode or the platinum electrode can be used. The reaction with each ion can be monitored by the potential measurement used.

【００６１】一例として、２−メルカプトピリジン−Ｎ
−オキシドの複合塩の作製方法を例示すれば、銀、銅、
亜鉛の複合系に２−メルカプトピリジン−Ｎ−オキシド
を添加することにより得られる。銀５０モル％、銅２５
モル％、亜鉛５０モル％と２−メルカプトピリジン−Ｎ
−オキシドの複合塩を形成させるための具体例を挙げれ
ば、 Ｎａ型カルボキシメチルセルロース（ＤＳ＝０．４）固形分 １００ｇ 水 ５０００ｇ 硝酸銀 ５０ｍｍｏｌ 硫酸銅 ２５ｍｍｏｌ 硝酸亜鉛 ５０ｍｍｏｌ 水 １０００ｇ ２−メルカプトピリジン−Ｎ−オキシドナトリウム０．
２ｍｏｌ／ｌ溶液１０００ｇとなる。As an example, 2-mercaptopyridine-N
Illustrating a method for producing a composite salt of an oxide, silver, copper,
It is obtained by adding 2-mercaptopyridine-N-oxide to a composite system of zinc. 50 mol% silver, 25 copper
Mol%, zinc 50 mol% and 2-mercaptopyridine-N
Specific examples for forming a complex salt of -oxide include: Na-type carboxymethylcellulose (DS = 0.4) solid content 100 g water 5000 g silver nitrate 50 mmol copper sulfate 25 mmol zinc nitrate 50 mmol water 1000 g 2-mercaptopyridine-N-oxide Sodium 0.
It becomes 1000 g of a 2 mol / l solution.

【００６２】次に、本発明における抗菌防黴剤組成物Ｇ
の作成例として銀、銅、亜鉛の複合系の抗菌防黴剤およ
びポリウレタン系高分子化合物について述べる。一例と
して、自己乳化型ポリウレタン系高分子化合物を使った
例を用いて説明する。 １）水５００ｇを用意する。 ２）硝酸銀１００ｍｍｏｌ相当量を添加する。 ３）硫酸銅５０ｍｍｏｌ相当量を添加する。 ４）硝酸亜鉛１００ｍｍｏｌ相当量を添加する。 ５）室温下で十分に攪拌する。 ６）２−メルカプトピリジン−Ｎ−オキシドナトリウム
塩の４００ｍｍｏｌ／ｌ液１０００ｇを攪拌しながら少
しずつ添加する。銀電極もしくは白金電極を用いて、電
位計測すると、反応終了点を検知することができる。 ７）添加終了後、３０分間攪拌し、十分に反応させる。 ８）自己乳化型ポリウレタン系高分子化合物の４０重量
％水分散液を２００ｇ添加する。Next, the antibacterial and antifungal composition G according to the present invention.
As an example of the preparation, a composite antibacterial fungicide of silver, copper and zinc and a polyurethane polymer compound will be described. As an example, an example using a self-emulsifying polyurethane polymer compound will be described. 1) Prepare 500 g of water. 2) Add an amount equivalent to 100 mmol of silver nitrate. 3) Add 50 mmol of copper sulfate equivalent. 4) Add an amount equivalent to 100 mmol of zinc nitrate. 5) Stir well at room temperature. 6) 1000 g of a 400 mmol / l solution of 2-mercaptopyridine-N-oxide sodium salt is added little by little with stirring. When the potential is measured using a silver electrode or a platinum electrode, the reaction end point can be detected. 7) After completion of the addition, the mixture is stirred for 30 minutes to be sufficiently reacted. 8) 200 g of a 40% by weight aqueous dispersion of a self-emulsifying polyurethane polymer compound is added.

【００６３】上記の手順により、本発明における抗菌防
黴剤組成物Ｇであるメルカプトピリジン−Ｎ−オキシド
の銀塩、銅塩および亜鉛塩と水不溶性高分子化合物より
なる分散液が得られる。そのままの液状でも抗菌防黴剤
組成物の塗料として不織布に含浸、塗布等が可能であ
る。According to the above procedure, a dispersion comprising a silver salt, a copper salt and a zinc salt of mercaptopyridine-N-oxide, which is the antibacterial and fungicide composition G of the present invention, and a water-insoluble polymer compound is obtained. Even when the liquid is used as it is, it can be impregnated and applied to the nonwoven fabric as a paint for the antibacterial and antifungal composition.

【００６４】尚、最初に自己乳化型ポリウレタン系高分
子化合物水分散液中に硝酸銀、硫酸銅及び硝酸亜鉛を添
加し、２−メルカプトピリジン−Ｎ−オキシドナトリウ
ム塩を添加してもメルカプトピリジン−Ｎ−オキシド銀
塩を合成することが可能で同様な抗菌防黴剤組成物が得
られるが、粒径が不均一になりやすい。Incidentally, first, silver nitrate, copper sulfate and zinc nitrate were added to an aqueous dispersion of a self-emulsifying polyurethane-based polymer compound, and 2-mercaptopyridine-N-oxide sodium salt was added. -A similar antibacterial and fungicide composition can be obtained by synthesizing an oxide silver salt, but the particle size tends to be non-uniform.

【００６５】抗菌防黴剤の粒径は電子顕微鏡や光散乱法
により測定が可能であるが、好ましくは０．１μｍ以上
の粒子を５０重量％以上含有するものである。微粒の粒
子が多いと塗料中で凝集する為に不織布等へ塗布、含浸
した場合に均一に分布しにくい他、水洗処理等により脱
落しやすい。The particle size of the antibacterial and antifungal agent can be measured by an electron microscope or a light scattering method, and preferably contains 50% by weight or more of particles of 0.1 μm or more. If the number of fine particles is large, they are agglomerated in the paint, so that they are difficult to be uniformly distributed when coated or impregnated on a nonwoven fabric or the like.

【００６６】本発明の抗菌防黴剤Ａの単位面積当たりの
靴中敷きに対する含有量は、一般的には０．０５ｇ／ｍ
2以上であるが、０．１ｇ／ｍ2以上が好ましい。The content of the antibacterial and antifungal agent A of the present invention based on the insole per unit area is generally 0.05 g / m 2.
Although 2 or more, 0.1 g / m 2 or more.

【００６７】抗菌防黴剤Ａが０．０５ｇ／ｍ2より少な
いと使用の初期から充分な抗菌性、防黴性が得られにく
い。抗菌防黴性の必要持続期間により適宜含有量を選択
出来るが、数日以上の使用では０．１ｇ／ｍ2以上が必
要である。When the amount of the antibacterial and antifungal agent A is less than 0.05 g / m 2 , it is difficult to obtain sufficient antibacterial and antifungal properties from the beginning of use. The content can be appropriately selected depending on the required duration of the antibacterial and antifungal properties, but when used for several days or more, 0.1 g / m 2 or more is required.

【００６８】本発明の抗菌防黴剤組成物Ｇは、作成した
ものをそのまま不織布等に塗布又は含浸しても良いが、
抗菌防黴剤組成物の安定性向上や接着性を高めるため
に、塗布する前に各種接着剤を付与することや着色のた
めの少量の顔料や染料の付与も可能である。The antibacterial and fungicidal composition G of the present invention may be coated or impregnated on a nonwoven fabric or the like as it is.
In order to improve the stability and adhesiveness of the antibacterial and antifungal composition, it is possible to apply various adhesives before application and to apply a small amount of pigment or dye for coloring.

【００６９】接着剤としては、本発明の水不溶性高分子
化合物以外に各種水溶性高分子化合物、例えば、ポリビ
ニルアルコール、カルボキシメチルセルロース、ヒドロ
キシエチルセルロース、澱粉などが挙げられ、これらを
単独、もしくは架橋剤と併用しても使用できる。Examples of the adhesive include various water-soluble polymer compounds such as polyvinyl alcohol, carboxymethylcellulose, hydroxyethylcellulose and starch in addition to the water-insoluble polymer compound of the present invention. Can be used in combination.

【００７０】抗菌防黴剤組成物に付与する接着剤量は、
本発明における抗菌防黴剤組成物固形分に対して５０重
量％未満が好ましい。５０重量％を超えると、接着性は
強くなるものの抗菌防黴性が低下する。The amount of the adhesive provided to the antibacterial and antifungal composition is
It is preferably less than 50% by weight based on the solid content of the antibacterial and antifungal agent composition in the present invention. If it exceeds 50% by weight, the adhesiveness is increased, but the antibacterial and antifungal properties are reduced.

【００７１】本発明の不織布Ｃ又はＦの、他の不織布と
貼り合わせていない、足と接触する面に高分子化合物主
体の組成物Ｈを含浸又は塗布することにより靴中敷きの
耐久性や、美装性が向上するので好ましい。The nonwoven fabric C or F of the present invention is impregnated or coated with the composition H mainly composed of a high molecular compound on the surface which is not bonded to another nonwoven fabric and which comes into contact with the foot, so that the durability and beauty of the insole can be improved. This is preferable because the mountability is improved.

【００７２】高分子化合物主体の組成物Ｈで使用する高
分子化合物は、本発明の抗菌防黴剤組成物Ｇで使用する
水不溶性高分子化合物Ｄと同様のものが使用出来る。例
えば、ウレタン系高分子化合物、スチレン−ブタジェン
系高分子化合物、アクリル系高分子化合物、アクリロニ
トリル−ブタジェン系高分子化合物、エステル系高分子
化合物、スチレン系高分子化合物、アミド系高分子化合
物、塩化ビニル系化合物、酢酸ビニル系化合物、フッソ
系化合物、シリコン系化合物、エチレン系高分子化合物
やプロピレン系高分子化合物等のオレフィン系高分子化
合物等が挙げられる。As the high molecular compound used in the composition H mainly composed of a high molecular compound, the same compound as the water-insoluble high molecular compound D used in the antibacterial and fungicidal composition G of the present invention can be used. For example, urethane polymer compounds, styrene-butadiene polymer compounds, acrylic polymer compounds, acrylonitrile-butadiene polymer compounds, ester polymer compounds, styrene polymer compounds, amide polymer compounds, vinyl chloride And olefin-based polymer compounds such as ethylene-based polymer compounds and propylene-based polymer compounds.

【００７３】本発明の高分子化合物主体の組成物Ｈには
発泡剤として各種の界面活性剤を添加するほうが好まし
い。その理由は、靴中敷き表面から内部へ汗等の水分や
臭いが透過するように通気性を向上させる為である。添
加量は、固形で組成物Ｈの０．５〜２０重量％が一般的
である。発泡は撹拌や空気吹き込み等により行う。It is preferable to add various surfactants as a foaming agent to the polymer compound-based composition H of the present invention. The reason is to improve the air permeability so that moisture and odor such as sweat permeate from the surface of the insole to the inside. The amount of addition is generally 0.5 to 20% by weight of the composition H in a solid form. Foaming is performed by stirring or blowing air.

【００７４】発泡剤として使用される界面活性剤として
は、フッ素系、脂肪酸塩系、スルホン酸塩系、硫酸エス
テル塩系、アクリル系等が挙げられる。具体例として
は、大日本インキ化学工業社製、メガファックＦ−８２
４、Ｆ−１、住友化学工業社製、ネオペレックスＦ−２
５、カネボウ・エヌエスシー社製、ＦＲ−２０、ＬＡ−
９３が挙げられる。Examples of the surfactant used as a foaming agent include fluorine-based, fatty acid salt-based, sulfonate-based, sulfate ester-based, and acrylic surfactants. As a specific example, manufactured by Dainippon Ink and Chemicals, Megafac F-82
4, F-1, manufactured by Sumitomo Chemical Co., Ltd., Neoperex F-2
5. Kanebo NSC, FR-20, LA-
93.

【００７５】本発明の高分子化合物主体の組成物Ｈの各
不織布へ塗布又は含浸する量は、固形で５〜１００ｇ／
ｍ2、好ましくは１０〜７０ｇ／ｍ2である。The amount of the composition H mainly comprising the polymer compound of the present invention to be applied or impregnated to each nonwoven fabric is 5 to 100 g / solid.
m 2 , preferably 10 to 70 g / m 2 .

【００７６】[0076]

【実施例】以下に実施例を挙げて本発明を具体的に説明
するが、本発明は実施例に限定されるものではない。な
お、実施例中の「部」および「％」は、それぞれ「重量
部」および「重量％」を示す。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples. In the examples, “parts” and “%” indicate “parts by weight” and “% by weight”, respectively.

【００７７】製造例Ａ 前記の発明の実施の形態の記載に準じて、カルボキシメ
チル基置換度０．２２（ＤＳ＝０．２２）の変性ＮＢＫ
Ｐに、銀／２−メルカプトピリジン−Ｎ−オキシドを吸
着させた有機化合物の金属塩よりなる抗菌防黴剤を含有
する繊維状物質を作製した（以下、ＣＰ２２ＡｇＭＰと
略記する）。上記の変性ＮＢＫＰ分散液に硝酸銀を加
え、ｐＨを５．５に調節してから、３０分間攪拌する。
０．１Ｍ／ｌの２−メルカプトピリジン−Ｎ−オキシド
ナトリウム液を、変性ＮＢＫＰ分散液に加えられた硝酸
銀と等モル相当量を添加した。３０分間攪拌してから、
硫酸でｐＨを４まで下げた後、脱水した。脱水パルプ
に、再び５００ｍｌの水を加え、攪拌水洗して脱水し
た。これを、銀／２−メルカプトピリジン−Ｎ−オキシ
ドを吸着させた有機化合物の金属塩よりなる抗菌防黴剤
を含有するカルボキシメチル基置換度０．２２（ＤＳ＝
０．２２）の変性ＮＢＫＰとした。 比較例１ ２ｍ3の分散タンクにアクリル酸ソーダ系アニオン性界
面活性剤（日本アクリル化学社製、プライマル８５０）
を全繊維に対して１％になるように添加し、ＮＢＫＰ
（カナダ標準濾水度４８０ｍｌ）、ＰＥＴ繊維（０．５
デニール×５ｍｍ）、ポリエステルバインダー繊維（メ
ルティー４０８０；２デニール×５ｍｍ、ユニチカ社
製）、高叩解ＮＢＫＰ（カナダ濾水度１５０ｍｌ）を各
々４０：１０：４５：５の比率で配合し、分散濃度０．
２％で３０分間分散した後、乾燥重量で３００g/ｍ2に
なるように円網抄紙機で抄紙後、表面温度１３０℃のシ
リンダードライヤーで乾燥し、比較例１で使用する靴中
敷き下層用シートを得た。 比較例２ 比較例１で内填剤としてアルミノケイ酸亜鉛系脱臭剤
（ミズカナイトＡＰ、水沢化学工業社製）を全繊維の２
０％になるように添加した以外は同様にして比較例２で
使用する靴中敷き下層用シートを得た。 実施例１〜５ 比較例２のＮＢＫＰの一部を、上記製造例Ａで得られた
本発明における繊維状物質であるＣＰ２２ＡｇＭＰに、
表１記載の配合量で置き換えた外は、比較例１と同様に
して、実施例１〜５で使用する靴中敷き下層用シートを
得た。Production Example A Modified NBK having a carboxymethyl group substitution degree of 0.22 (DS = 0.22) according to the description of the above embodiment of the invention.
A fibrous substance containing an antibacterial and fungicide composed of a metal salt of an organic compound having silver / 2-mercaptopyridine-N-oxide adsorbed on P was prepared (hereinafter abbreviated as CP22AgMP). Silver nitrate is added to the modified NBKP dispersion to adjust the pH to 5.5, and then the mixture is stirred for 30 minutes.
A 0.1 M / l sodium 2-mercaptopyridine-N-oxide solution was added in an equimolar amount to the silver nitrate added to the modified NBKP dispersion. After stirring for 30 minutes,
After the pH was lowered to 4 with sulfuric acid, it was dehydrated. To the dehydrated pulp, 500 ml of water was again added, and the mixture was washed with stirring and dehydrated. This was replaced with a carboxymethyl group substitution degree of 0.22 (DS = DS) containing an antibacterial and antifungal agent comprising a metal salt of an organic compound adsorbed with silver / 2-mercaptopyridine-N-oxide.
0.22). Comparative Example 1 A sodium acrylate-based anionic surfactant (Nippon Acrylic Chemical Co., Primal 850) was placed in a 2 m 3 dispersion tank.
Is added so as to be 1% with respect to all fibers, and NBKP is added.
(Canada standard freeness 480 ml), PET fiber (0.5
Denier × 5 mm), polyester binder fiber (Melty 4080; 2 denier × 5 mm, manufactured by Unitika), and high-beaten NBKP (Canada freeness 150 ml) were blended at a ratio of 40: 10: 45: 5, respectively, and the dispersion concentration was 0. .
After being dispersed at 2% for 30 minutes, the paper is made with a circular paper machine so as to have a dry weight of 300 g / m 2 , dried with a cylinder dryer having a surface temperature of 130 ° C., and used for the lower layer of the shoe insole used in Comparative Example 1. I got Comparative Example 2 In Comparative Example 1, a zinc aluminosilicate-based deodorant (Mizukanite AP, manufactured by Mizusawa Chemical Industry Co., Ltd.) was used as a filler in all fibers.
A shoe insole lower layer sheet used in Comparative Example 2 was obtained in the same manner, except that it was added so as to be 0%. Examples 1 to 5 A part of NBKP of Comparative Example 2 was added to CP22AgMP which is a fibrous substance in the present invention obtained in Production Example A above,
Except for replacing with the compounding amount shown in Table 1, in the same manner as in Comparative Example 1, sheets for insole lower layers used in Examples 1 to 5 were obtained.

【００７８】製造例Ｂ 製造例Ａと同様であるが、前記の発明の実施の形態の記
載に準じて、ＣＰ２２ＡｇＭＰの代わりに、カルボキシ
メチル基置換度０．４０（ＤＳ＝０．４０）の変性ＮＢ
ＫＰに銅／１，２−ベンズイソチアゾリン−３−オンを
吸着させた有機化合物の金属塩よりなる抗菌防黴剤を含
有する繊維状物質を作製した（以下、ＣＰ４０ＣｕＢＩ
Ｔと略記する）。 実施例６〜８ 比較例２のＮＵＫＰの一部を、上記製造例Ｂで得られた
本発明における繊維状物質であるＣＰ４０ＣｕＢＩＴ
に、表１記載の配合量で置き換えた外は、比較例２と同
様にして、実施例６〜１０で使用する靴中敷き下層用シ
ートを得た。Production Example B The same as Production Example A, but modified according to the description of the above embodiment of the invention, instead of CP22AgMP, with a degree of carboxymethyl group substitution of 0.40 (DS = 0.40). NB
A fibrous material containing an antibacterial and fungicide made of a metal salt of an organic compound in which copper / 1,2-benzisothiazolin-3-one was adsorbed on KP was prepared (hereinafter referred to as CP40CuBI).
T). Examples 6 to 8 A part of NUKP of Comparative Example 2 was replaced with the fibrous substance CP40CuBIT of the present invention obtained in Production Example B above.
In the same manner as in Comparative Example 2 except that the amount was replaced with the compounding amount shown in Table 1, a sheet for an insole lower layer used in Examples 6 to 10 was obtained.

【００７９】製造例Ｃ 製造例Ａと同様であるが、前記の発明の実施の形態の記
載に準じて、ＣＰ２２ＡｇＭＰの代わりに、カルボキシ
メチル基置換度０．４０（ＤＳ＝０．４０）の変性ＮＢ
ＫＰに（銀、銅、亜鉛）／２−メルカプトピリジン−Ｎ
−オキシドを吸着させた有機化合物の３種の金属塩より
なる抗菌防黴剤を含有する繊維状物質を作製した（以
下、ＣＰ４０Ａｇ２５Ｃｕ２５Ｚｎ５０ＭＰと略記す
る）。なお、括弧内金属原子の次の数字は、モル％比を
表わす。 実施例９〜１３ 比較例２のＮＢＫＰの一部を、上記製造例Ｃで得られた
本発明における繊維状物質であるＣＰ４０Ａｇ２５Ｃｕ
２５Ｚｎ５０ＭＰに、表１記載の配合量で置き換えた外
は、比較例２と同様にして、実施例１１〜１５で使用す
る靴中敷き下層用シートを得た。Preparation Example C Same as Preparation Example A, but according to the description of the above embodiment of the present invention, a modified compound having a carboxymethyl group substitution degree of 0.40 (DS = 0.40) instead of CP22AgMP. NB
KP with (silver, copper, zinc) / 2-mercaptopyridine-N
-A fibrous substance containing an antibacterial and fungicide consisting of three metal salts of an organic compound to which an oxide was adsorbed was prepared (hereinafter abbreviated as CP40Ag25Cu25Zn50MP). In addition, the number following the metal atom in parenthesis represents a mol% ratio. Examples 9 to 13 A part of the NBKP of Comparative Example 2 was replaced with the fibrous substance CP40Ag25Cu of the present invention obtained in Production Example C above.
Except having replaced with 25Zn50MP by the compounding quantity of Table 1, it carried out similarly to the comparative example 2, and obtained the sheet for the insole lower layer used in Examples 11-15.

【００８０】実施例１４ 実施例１１で、アルミノケイ酸亜鉛系脱臭剤（ミズカナ
イトＡＰ）の添加量を全繊維の３０％とした以外は同様
にして実施例１４で使用する靴中敷き下層用シートを得
た。Example 14 A sheet for a shoe insole lower layer used in Example 14 was obtained in the same manner as in Example 11, except that the amount of the zinc aluminosilicate-based deodorant (Mizukanite AP) was changed to 30% of the total fiber. Was.

【００８１】実施例１５ 実施例１１と同様であるが、アルミノケイ酸亜鉛系脱臭
剤（ミズカナイトＡＰ）に替えてゼオライト系脱臭剤
（シルトンＢ、水沢化学工業社製）を同量添加した以外
は同様にして実施例１５で使用する靴中敷き下層用シー
トを得た。Example 15 The same as Example 11, except that the same amount of a zeolite-based deodorant (Silton B, manufactured by Mizusawa Chemical Industry) was added instead of the zinc aluminosilicate-based deodorant (Mizukanite AP). Thus, a sheet for an insole lower layer used in Example 15 was obtained.

【００８２】実施例１６ 実施例１１と同様であるが、アルミノケイ酸亜鉛系脱臭
剤（ミズカナイトＡＰ）に替えて酸性白土（ミズカエー
ス３００、水沢化学工業社製）を同量添加した以外は同
様にして実施例１６で使用する靴中敷き下層用シートを
得た。Example 16 The same as Example 11, except that the same amount of acid clay (Mizuka Ace 300, manufactured by Mizusawa Chemical Industries) was added in place of the zinc aluminosilicate deodorant (Mizukanite AP). A sheet for a shoe insole lower layer used in Example 16 was obtained.

【００８３】比較例３ 実施例１１と同様であるが、本発明における３金属塩併
用系のＣＰ４０Ａｇ２５Ｃｕ２５Ｚｎ５０ＭＰ含有繊維
状物質の代わりに、塩化ベンザルコニウム含有繊維状物
質１０％を使用して、比較例３で使用する靴中敷き下層
用シートを得た。なお、塩化ベンザルコニウム含有繊維
状物質は、製造例Ｃで用いたカルボキシメチル基置換度
０．４０（ＤＳ＝０．４０）の変性ＮＢＫＰ１０グラム
に対して、０.１Ｍ/ｌの塩化ベンザルコニウム液１００
ｍｌを加え、ｐＨ５.５に調整後、攪拌し、脱水、水洗
した後、再び脱水を行って作製した。Comparative Example 3 The same procedure as in Example 11 was carried out except that 10% of a benzalkonium chloride-containing fibrous substance was used instead of the CP40Ag25Cu25Zn50MP-containing fibrous substance according to the present invention. The insole lower layer sheet used in Step 3 was obtained. In addition, the benzalkonium chloride-containing fibrous substance was obtained by adding 0.1 M / l of benzalkonium chloride to 10 g of modified NBKP having a carboxymethyl group substitution degree of 0.40 (DS = 0.40) used in Production Example C. Nium liquid 100
After adjusting the pH to 5.5, the mixture was stirred, dehydrated, washed with water, and then dehydrated again to prepare a product.

【００８４】製造例Ｄ 前記の発明の実施の形態の記載に準じて、銀／２−メル
カプトピリジン−Ｎ−オキシドを含有させた、有機化合
物の金属塩よりなる抗菌防黴剤とウレタン系高分子化合
物とアクリル系高分子化合物を含む抗菌防黴剤組成物を
作製した（以下、ＡｇＭＰ−ＵＡ０．３と略記する）。
即ち、水に硝酸銀０．１ｍｏｌを加え、撹拌する。０．
１ｍｏｌ／ｌの２−メルカプトピリジン−Ｎ−オキシド
ナトリウム液を、加えられた硝酸銀と等モル相当量を添
加し、３０分間攪拌する。これに自己乳化型ウレタン系
高分子化合物（大日本インキ化学工業社製、ハイドラン
ＨＷ−３５０）の水分散液を加え、５分間撹拌した後、
同重量の自己架橋型アクリル系高分子化合物（大日本イ
ンキ化学工業社製、ボンコート３２５６）の水分散液を
加え、銀／２−メルカプトピリジン−Ｎ−オキシドの抗
菌防黴剤のウレタン系高分子化合物に対する重量比を
０．３とした。尚、括弧内金属原子の次の数字は、モル
％比を表わし、最後尾の数字は水不溶性高分子化合物に
対する抗菌防黴剤の重量比を表わす。Production Example D An antibacterial antifungal agent comprising a metal salt of an organic compound containing silver / 2-mercaptopyridine-N-oxide and a urethane-based polymer according to the description of the above embodiment of the invention An antibacterial and fungicide composition containing the compound and an acrylic polymer compound was prepared (hereinafter abbreviated as AgMP-UA0.3).
That is, 0.1 mol of silver nitrate is added to water and stirred. 0.
A 1 mol / l sodium 2-mercaptopyridine-N-oxide solution is added in an equimolar amount to the added silver nitrate and stirred for 30 minutes. An aqueous dispersion of a self-emulsifying urethane polymer compound (Hydran HW-350, manufactured by Dainippon Ink and Chemicals, Inc.) was added thereto, and the mixture was stirred for 5 minutes.
An aqueous dispersion of the same weight of a self-crosslinkable acrylic polymer compound (Boncoat 3256, manufactured by Dainippon Ink and Chemicals, Inc.) was added thereto, and a urethane polymer as an antibacterial and antifungal agent of silver / 2-mercaptopyridine-N-oxide was added. The weight ratio to the compound was 0.3. The number following the metal atom in the parenthesis indicates the mole% ratio, and the last number indicates the weight ratio of the antibacterial and fungicide to the water-insoluble polymer compound.

【００８５】製造例Ｅ 製造例Ｄと同様であるが、前記の発明の実施の形態の記
載に準じて、ＡｇＭＰ−ＵＡ０．３の代わりに、（銀、
銅）／１，２−ベンズイソチアゾリン−３−オンの抗菌
防黴剤を含有した自己乳化型ウレタン系高分子化合物
（ハイドランＨＷ−３５０）と自己架橋型アクリル系高
分子化合物（ボンコート３２５６）水分散液を作製し
た。即ち、硝酸銀０．５０ｍｏｌ、硫酸銅０．５０ｍｏ
ｌ及びそれらの総モル相当量である１．５ｍｏｌの１，
２−ベンズイソチアゾリン−３−オンのアルコール液を
添加、撹拌し、自己乳化型ウレタン系高分子化合物を添
加、撹拌後同高分子化合物と同量の自己架橋型アクリル
系高分子化合物の水分散液を添加、撹拌して、（銀、
銅）／１，２−ベンズイソチアゾリン−３−オンの抗菌
防黴剤と水不溶性高分子化合物との重量比を０．３とし
た（以下、Ａｇ５０Ｃｕ５０ＢＩＴ−ＵＡ０．３と略記
する）。尚、括弧内金属原子の次の数字は、モル％比を
表わし、最後尾の数字は水不溶性高分子化合物に対する
抗菌防黴剤の重量比を表わす。Production Example E The same as Production Example D, but according to the description of the above-mentioned embodiment of the present invention, instead of AgMP-UA0.3, (silver,
Copper) / 1,2-benzisothiazolin-3-one antibacterial and antifungal agent containing self-emulsifying urethane polymer (Hydran HW-350) and self-crosslinking acrylic polymer (Boncoat 3256) dispersed in water A liquid was prepared. That is, silver nitrate 0.50 mol, copper sulfate 0.50 mol
l and their total molar equivalent of 1.5 mol of 1,
An alcohol solution of 2-benzisothiazolin-3-one is added and stirred, a self-emulsifying urethane polymer compound is added, and after stirring, an aqueous dispersion of the same amount of the self-crosslinking acrylic polymer compound as the polymer compound. , And stirred, (silver,
The weight ratio of the antibacterial fungicide of (copper) / 1,2-benzisothiazolin-3-one to the water-insoluble polymer compound was 0.3 (hereinafter abbreviated as Ag50Cu50BIT-UA0.3). The number following the metal atom in the parenthesis indicates the mole% ratio, and the last number indicates the weight ratio of the antibacterial and fungicide to the water-insoluble polymer compound.

【００８６】製造例Ｆ 製造例Ｄと同様であるが、前記の発明の実施の形態の記
載に準じて、ＡｇＭＰ−ＵＡ０．３の代わりに、（銀、
銅、亜鉛）／２−メルカプトピリジン−Ｎ−オキシドの
抗菌防黴剤を含有した自己乳化型ウレタン系高分子化合
物（ハイドランＨＷ−３５０）と自己架橋型アクリル系
高分子化合物（ボンコート３２５６）の水分散液を作製
した。即ち、硝酸銀０．２５ｍｏｌ、硫酸銅０．２５ｍ
ｏｌ、硝酸亜鉛０．５ｍｏｌ及びそれらの総モル相当量
である１．７５ｍｏｌの２−メルカプトピリジン−Ｎ−
オキシドナトリウム水溶液を添加、撹拌し、自己乳化型
ウレタン系高分子化合物水分散液を添加、撹拌後、自己
架橋型アクリル系化合物水分散液を添加、撹拌して、
（銀、銅、亜鉛）／２−メルカプトピリジン−Ｎ−オキ
シドの抗菌防黴剤と自己乳化型ウレタン系高分子化合物
と自己架橋型アクリル系高分子化合物との重量比を０．
３とした（以下、Ａｇ２５Ｃｕ２５Ｚｎ５０ＭＰ−ＵＡ
０．３と略記する）。尚、括弧内金属原子の次の数字
は、モル％比を表わし、最後尾の数字は水不溶性高分子
化合物に対する抗菌防黴剤の重量比を表す。Production Example F The same as Production Example D, but according to the description of the above-mentioned embodiment of the present invention, instead of AgMP-UA0.3, (silver,
Water of a self-emulsifying urethane polymer compound (Hydran HW-350) and a self-crosslinking acrylic polymer compound (Boncoat 3256) containing an antibacterial and fungicide of (copper, zinc) / 2-mercaptopyridine-N-oxide A dispersion was prepared. That is, 0.25 mol of silver nitrate and 0.25 m of copper sulfate
ol, 0.5 mol of zinc nitrate and 1.75 mol of 2-mercaptopyridine-N-
Aqueous sodium oxide solution was added and stirred, a self-emulsifying urethane polymer aqueous dispersion was added and stirred, and then a self-crosslinking acrylic compound aqueous dispersion was added and stirred.
The weight ratio of the antibacterial and antifungal agent of (silver, copper, zinc) / 2-mercaptopyridine-N-oxide, the self-emulsifying urethane polymer compound and the self-crosslinking acrylic polymer compound to 0.1.
3 (hereinafter, Ag25Cu25Zn50MP-UA)
0.3). The number following the metal atom in the parenthesis indicates the mole% ratio, and the last number indicates the weight ratio of the antibacterial and fungicide to the water-insoluble polymer compound.

【００８７】製造例Ｇ〜Ｊ 製造例Ｆで（銀、銅、亜鉛）／２−メルカプトピリジン
−Ｎ−オキシドの抗菌防黴剤と自己乳化型ウレタン系高
分子化合物と自己架橋型アクリル系高分子化合物との重
量比を表２に示すように０．０５から５迄の範囲で変え
た以外は同様にして本発明の抗菌防黴剤組成物を製造し
た。Production Examples G to J In Production Example F, an antibacterial antifungal agent of (silver, copper, zinc) / 2-mercaptopyridine-N-oxide, a self-emulsifying urethane polymer compound and a self-crosslinking acrylic polymer An antibacterial and antifungal composition of the present invention was produced in the same manner except that the weight ratio to the compound was changed in the range of 0.05 to 5 as shown in Table 2.

【００８８】実施例１７〜２５ ７デニールのポリエステル繊維５０重量％と１０デニー
ルのポリエチレン−ポリプロピレン複合繊維５０重量％
からなる混合ウエブを熱処理した乾式不織布（目付１５
０ｇ／ｍ2、厚さ３０００μｍ）に上記実施例Ｄ〜Ｊで
得られた本発明の抗菌防黴剤組成物を表２に記載の乾燥
塗布量になるようにロールコーターで塗布し、１１０℃
で乾燥して実施例１７〜２５で使用する靴中敷き上層用
用シートを得た。尚、塗布適性を向上させるために抗菌
防黴剤組成物にセルロースエーテル（信越化学工業社
製、メトローズＳＨ３００００）水溶液を適量添加して
塗布した。以下の実施例、比較例でも同様にしてセルロ
ースエーテルを適量添加して塗布した。Examples 17 to 250 50% by weight of 7 denier polyester fiber and 50% by weight of 10 denier polyethylene-polypropylene composite fiber
Dry non-woven fabric obtained by heat-treating a mixed web consisting of
0 g / m 2 , thickness 3000 μm) and the antibacterial and fungicide compositions of the present invention obtained in Examples D to J were applied by a roll coater so as to obtain the dry coating amount shown in Table 2.
To obtain sheets for the upper layer of the insole used in Examples 17 to 25. In order to improve the coating suitability, an appropriate amount of an aqueous solution of cellulose ether (manufactured by Shin-Etsu Chemical Co., Ltd., Metroose SH30000) was added to the antibacterial and fungicidal composition and applied. In the following Examples and Comparative Examples, a suitable amount of cellulose ether was added and applied in the same manner.

【００８９】実施例２６ 比較例２で得られた靴中敷き下層用シートの片面に製造
例Ｆで得られたＡｇ２５Ｃｕ２５Ｚｎ５０ＭＰ−ＵＡ
０．３を乾燥塗布量が１ｇ／ｍ2になるようにロールコ
ーターで塗布し、１１０℃で乾燥して実施例２６で使用
する靴中敷き下層用シートを得た。Example 26 The Ag25Cu25Zn50MP-UA obtained in Production Example F was applied on one side of the sheet for the lower layer of an insole obtained in Comparative Example 2.
0.3 was applied by a roll coater so that the dry coating amount was 1 g / m 2 , and dried at 110 ° C. to obtain a sheet for a shoe insole lower layer used in Example 26.

【００９０】比較例４ 実施例２０で、Ａｇ２５Ｃｕ２５Ｚｎ５０ＭＰ−ＵＡ
０．３の代わりに、塩化ベンザルコニウム含有したアク
リル系高分子化合物（ボンコート３２５６）を使用して
乾燥塗布量が１．０ｇ／ｍ2になるように塗布、乾燥し
て比較例４で使用する靴中敷き上層用シートを得た。な
お、塩化ベンザルコニウム含有アクリル系高分子化合物
は、製造例Ｆで用いた自己乳化型ウレタン系高分子化合
物と自己架橋型アクリル系高分子化合物を固形で１０ｇ
に対して、０.１ｍｏｌ/ｌの塩化ベンザルコニウム液１
２０ｍｌを加え、ｐＨ５.５に調整後、攪拌して作製し
た。Comparative Example 4 In Example 20, Ag25Cu25Zn50MP-UA
Instead of using 0.3, an acrylic polymer compound containing benzalkonium chloride (Boncoat 3256) was used so that the dry coating amount was 1.0 g / m 2 , and then dried and used in Comparative Example 4. The insole insole upper sheet was obtained. The benzalkonium chloride-containing acrylic polymer compound is 10 g of the self-emulsifying urethane polymer compound and the self-crosslinking acrylic polymer compound used in Production Example F as solids.
0.1 mol / l benzalkonium chloride solution 1
After adding 20 ml and adjusting the pH to 5.5, the mixture was stirred and prepared.

【００９１】製造例Ｋ、Ｌ 製造例Ｆで、（銀、銅、亜鉛）／２−メルカプトピリジ
ン−Ｎ−オキシドの抗菌防黴剤と自己乳化型ウレタン系
高分子化合物と自己架橋型アクリル系高分子化合物との
重量比を０．０３とした製造例ＫによりＡｇ２５Ｃｕ２
５Ｚｎ５０ＭＰ−ＵＡ０．０３の抗菌防黴剤組成物を、
重量比を６．０とした製造例ＬによりＡｇ２５Ｃｕ２５
Ｚｎ５０ＭＰ−ＵＡ６．０の抗菌防黴剤組成物を比較用
として製造した。Production Examples K and L In Production Example F, an antibacterial and antifungal agent of (silver, copper, zinc) / 2-mercaptopyridine-N-oxide, a self-emulsifying urethane polymer compound and a self-crosslinking acrylic Ag25Cu2 according to Production Example K in which the weight ratio to the molecular compound was 0.03.
5Zn50MP-UA0.03 antibacterial fungicide composition,
Ag25Cu25 according to Production Example L with a weight ratio of 6.0
An antibacterial and fungicide composition of Zn50MP-UA6.0 was produced for comparison.

【００９２】比較例５ 実施例２０と同様であるが、本発明における３金属塩併
用系のＡｇ２５Ｃｕ２５Ｚｎ５０ＭＰ−ＵＡ０．０５の
代わりに、製造例Ｋで得られたＡｇ２５Ｃｕ２５Ｚｎ５
０ＭＰ−ＵＡ０．０３を使用して乾燥塗布量が１．０ｇ
／ｍ2になるように塗布、１１０℃で乾燥して比較例５
で使用する靴中敷き上層用シートを得た。Comparative Example 5 The same as Example 20 except that the Ag25Cu25Zn50MP-UA0.05 of the trimetal salt combination system of the present invention was replaced with the Ag25Cu25Zn5 obtained in Production Example K
The dry coating amount is 1.0 g using 0MP-UA0.03.
/ M 2 and dried at 110 ° C. to obtain Comparative Example 5.
To obtain a sheet for the upper layer of the shoe insole used in the above.

【００９３】比較例６ 実施例２０と同様であるが、本発明における３金属塩併
用系のＡｇ２５Ｃｕ２５Ｚｎ５０ＭＰ−ＵＡ５．０の代
わりに、製造例Ｌで得られたＡｇ２５Ｃｕ２５Ｚｎ５０
ＭＰ−ＵＡ６．０を使用して乾燥塗布量が１．０ｇ／ｍ
2になるように塗布、１１０℃で乾燥して比較例６で使
用する靴中敷き上層用シートを得た。Comparative Example 6 Same as Example 20, except that the Ag25Cu25Zn50 MP-UA5.0 of the present invention, which was used in combination with a three-metal salt, was replaced with the Ag25Cu25Zn50 obtained in Production Example L.
1.0 g / m2 dry coating weight using MP-UA 6.0
2 and dried at 110 ° C. to obtain a shoe insole upper layer sheet used in Comparative Example 6.

【００９４】ウレタン系高分子化合物（ハイドランＨＷ
３２５、大日本インキ化学工業社製）と発泡剤としてメ
ガファックＦ−１（大日本インキ化学工業社製）を固形
重量比１０：１で混合し、体積が２〜３倍になるまで撹
拌により発泡させて表層用塗布液Ｘとした。Urethane polymer compounds (Hydran HW
325, manufactured by Dainippon Ink and Chemicals, Inc.) and Megafac F-1 (manufactured by Dainippon Ink and Chemicals, Inc.) as a foaming agent at a solid weight ratio of 10: 1, and stirred until the volume becomes 2-3 times. The mixture was foamed to obtain a coating solution X for a surface layer.

【００９５】７デニールのポリエステル繊維５０重量％
と１０デニールのポリエチレン−ポリプロピレン複合繊
維５０重量％からなる混合ウエブを熱処理した乾式不織
布（目付１５０ｇ／ｍ2、厚さ３０００μｍ）の片面に
上記表層用塗布液Ｘをロッドコーターにより固形で３０
ｇ／ｍ2塗布し、１２０℃で乾燥して、靴中敷き上層用
シートＹを得た。同様にして実施例１７〜２５及び比較
例４〜６で得られた靴中敷き上層用シートの抗菌防黴剤
組成物未塗布面上に表層用塗布液Ｘを塗布、乾燥した。50% by weight of 7 denier polyester fiber
And a 10-denier polyethylene-polypropylene composite fiber of 50% by weight and a heat-treated dry nonwoven fabric (basis weight: 150 g / m 2 , thickness: 3000 μm).
g / m 2 was applied and dried at 120 ° C. to obtain a shoe insole upper layer sheet Y. Similarly, the coating solution X for surface layer was applied to the surface of the upper insole sheet obtained in Examples 17 to 25 and Comparative Examples 4 to 6 on which the antibacterial and fungicide composition was not applied, and dried.

【００９６】実施例１〜１６、比較例１〜３で得られた
靴中敷き下層用シートの片面上に粒状ポリエチレン系接
着剤（住友精化社製、フローバックＱＨ４０１１Ｎ）を
１０ｇ／ｍ2ふりかけ、加熱後靴中敷き上層用シートＹ
の未塗布面を重ねて加圧し積層した。得られた積層シー
トを型抜き機で足形に抜いて実施例１〜１６、比較例３
の靴中敷きを作成し、抗菌性、耐久抗菌性、防黴性、脱
臭性及び耐久性を下記の方法で測定した。得られた結果
を表３に示す。Sprinkle 10 g / m 2 of a granular polyethylene adhesive (Sumitomo Seika Co., Ltd., Flowback QH4011N) on one surface of the shoe insole lower layer sheet obtained in Examples 1 to 16 and Comparative Examples 1 to 3. Heated shoe insole upper sheet Y after heating
The uncoated surfaces were overlaid and pressurized. Examples 1 to 16 and Comparative Example 3 were obtained by removing the obtained laminated sheet into a footprint with a die-cutting machine.
Was prepared, and the antibacterial property, the antibacterial property, the antifungal property, the deodorizing property and the durability were measured by the following methods. Table 3 shows the obtained results.

【００９７】比較例２で得られた靴中敷き下層用シート
の片面上に粒状ポリエチレン系接着剤（住友精化社製、
フローバックＱＨ４０１１Ｎ）を１０ｇ／ｍ2ふりか
け、加熱後実施例１７〜２５、比較例４〜６で得られた
靴中敷き上層用シートの表層用塗布液Ｘ未塗布面を重ね
て加圧し積層して実施例１７〜２５、比較例４〜６の靴
中敷きを作成した。同様に、実施例２６の抗菌防黴剤組
成物を塗布した面上に粒状ポリエチレン系接着剤（住友
精化社製、フローバックＱＨ４０１１Ｎ）を１０ｇ／ｍ
2ふりかけ、加熱後靴中敷き上層用シートＹの未塗布面
を重ねて加圧し積層した。抗菌性、耐久抗菌性、防黴
性、脱臭性及び耐久性を下記の方法で測定した。得られ
た結果を表４に示す。A granular polyethylene adhesive (Sumitomo Seika Co., Ltd.) was applied on one surface of the shoe insole lower layer sheet obtained in Comparative Example 2.
Flowback QH4011N) was sprinkled with 10 g / m 2 , and after heating, the surface of the shoe insole upper layer sheets obtained in Examples 17 to 25 and Comparative Examples 4 to 6 was coated with the surface coating solution X uncoated surface, and then pressurized and laminated. The insoles of Examples 17 to 25 and Comparative Examples 4 to 6 were prepared. Similarly, a granular polyethylene-based adhesive (Flowback QH4011N, manufactured by Sumitomo Seika Co., Ltd.) was applied at 10 g / m on the surface to which the antibacterial and fungicide composition of Example 26 was applied.
2 sprinkling, after heating, the uncoated surface of the upper layer sheet Y of the shoe insole was overlaid and pressed to laminate. Antibacterial properties, durability antibacterial properties, antifungal properties, deodorizing properties and durability were measured by the following methods. Table 4 shows the obtained results.

【００９８】実施例２７ 実施例２０で、靴中敷き上層用シートに表層用塗布液Ｘ
を塗布しない以外は同様にして比較例２の靴中敷き下層
用シートと積層して靴中敷きを作成した。評価結果を表
４に示す。Example 27 In Example 20, the coating solution X for the surface layer was applied to the upper layer sheet insole.
Was applied in the same manner as above, except that it was not applied. Table 4 shows the evaluation results.

【００９９】比較例７ 実施例１１で得られた靴中敷き下層用シートのみで靴中
敷きを作成した。評価結果を表４に示す。＜抗菌性＞ 大腸菌（Ｅ−ｃｏｌｉ ＩＦＯ３３０１）を液体培地
（ペプトン・イースト）で２４時間前培養し、希釈して
試験液を調整した。上記実施例および比較例により得ら
れた各靴中敷きから試験片２ｃｍ×２ｃｍを切り取って
用意し、それぞれをペトリ皿上に上層用シートが上にな
るように配置し、上記試験液を５滴（約０．１ｍｌ）滴
下し、乾燥しないようにカバーして、２５℃で２４時間
経時した。経時後、試験片のそれぞれをＮｕｔｒｉｅｎ
ｔ Ｂｒｏｔｈ寒天培地上に押し当て、試験片上の菌を
転写させて剥離し、３８℃で２４時間培養し、観察し
た。評価は、次のとおりとした。 評価グレード −− 殆ど完全に殺菌し、菌の成育がない。 − ２ｃｍ×２ｃｍ転写面に５コロニー以下の成育
はあるが、殆ど完全に殺菌。 ＋ ２ｃｍ×２ｃｍ転写面に100コロニー以下で良
好な抗・殺菌作用。 ＋＋ ２ｃｍ×２ｃｍ転写面に効果は認められるが、
弱いか、少ない。 ＋＋＋ ２ｃｍ×２ｃｍ転写面に実質的効果なし。Comparative Example 7 A shoe insole was prepared using only the sheet for the lower layer of the shoe insole obtained in Example 11. Table 4 shows the evaluation results. <Antibacterial Property> Escherichia coli (E-coli IFO3301) was pre-cultured in a liquid medium (peptone yeast) for 24 hours and diluted to prepare a test solution. A test piece of 2 cm × 2 cm was cut out from each shoe insole obtained in the above Examples and Comparative Examples, prepared and placed on a Petri dish with the upper layer sheet facing upward, and 5 drops of the test liquid ( (Approximately 0.1 ml) was added dropwise, covered so as not to dry, and aged at 25 ° C. for 24 hours. After a lapse of time, each of the test pieces was Nutrien.
The strain was pressed onto a t-Broth agar medium to transfer the bacteria on the test piece, peeled off, cultured at 38 ° C. for 24 hours, and observed. The evaluation was as follows. Evaluation grade --- Almost completely sterilized, with no growth of bacteria. -Growth of 5 colonies or less on the 2cm x 2cm transfer surface, but almost completely sterilized. + Good anti-bacterial effect with less than 100 colonies on the 2cm x 2cm transfer surface. ++ 2cm × 2cm Although the effect is recognized on the transfer surface,
Weak or less. ++++ 2cm × 2cm No substantial effect on transfer surface.

【０１００】＜耐久抗菌性＞上記実施例および比較例に
より得られた各靴中敷きを４０℃、９０％ＲＨの環境条
件で７日間放置する。取り出した靴中敷きから試験片２
ｃｍ×２ｃｍを切り取り、抗菌性の評価と同様にして、
それぞれをペトリ皿上に上層用シートが上になるように
配置し、上記試験液を５滴（約０．１ｍｌ）滴下し、乾
燥しないようにカバーして、２５℃で２４時間経時し
た。経時後、試験片のそれぞれをＮｕｔｒｉｅｎｔ Ｂ
ｒｏｔｈ寒天培地上に押し当て、試験片上の菌を転写さ
せて剥離し、３８℃で２４時間培養し、観察した。評価
は、次のとおりとした。 評価グレード −− 殆ど完全に殺菌し、菌の成育がない。 − ２ｃｍ×２ｃｍ転写面に５コロニー以下の成育
はあるが、殆ど完全に殺菌。 ＋ ２ｃｍ×２ｃｍ転写面に100コロニー以下で良
好な抗・殺菌作用。 ＋＋ ２ｃｍ×２ｃｍ転写面に効果は認められるが、
弱いか、少ない。 ＋＋＋ ２ｃｍ×２ｃｍ転写面に実質的効果なし。<Durable Antibacterial Property> Each shoe insole obtained in the above Examples and Comparative Examples is allowed to stand at 40 ° C. and 90% RH for 7 days. Test piece 2 from the insole taken out
cm × 2cm, and in the same manner as the evaluation of antibacterial properties,
Each was placed on a Petri dish with the upper layer sheet facing upward, 5 drops (approximately 0.1 ml) of the test solution was dropped, covered so as not to dry, and aged at 25 ° C. for 24 hours. After a lapse of time, each of the test pieces was replaced with Nutrient B
The cells were pressed onto a roth agar medium, the bacteria on the test piece were transferred, peeled off, cultured at 38 ° C. for 24 hours, and observed. The evaluation was as follows. Evaluation grade --- Almost completely sterilized, with no growth of bacteria. -There is growth of 5 colonies or less on the transfer surface of 2 cm x 2 cm, but almost completely sterilized. + Good anti-bacterial effect with less than 100 colonies on the 2cm x 2cm transfer surface. ++ 2cm × 2cm Although the effect is recognized on the transfer surface,
Weak or less. ++++ 2cm × 2cm No substantial effect on transfer surface.

【０１０１】＜防黴性＞試験菌株として、黒カビ（Ａｓ
ｐｅｒｇｉｌｌｕｓ ｎｉｇｅｒ）を用いた。斜面培地
から胞子を採り、少量の湿潤剤（スルホコハク酸ジオク
チルナトリウム液）を加え、激しく振って胞子を分散さ
せ、ガーゼで濾過し、全量を５０ｍｌに調整した。１．
５％の寒天を加えたＧＰ培地（日本製薬社製）を作り、
上記菌液を均一に噴霧し、一旦、表面を乾燥させた。各
実施例、比較例で得られた靴中敷きから試験片２ｃｍ×
２ｃｍに切り取ったものを乗せ、十分に圧着させ、再度
試験菌を全面に噴霧して、２８℃で経時培養し、最高１
週間まで経時観察した。評価は、次のとおりとした。 評価グレード −− 黴の生育を完全に阻害。 − 黴の生育か否か判断がつきかねる。 ＋ かなり良好な制御力を示すが表面積1/5以下に
カビの生育を認める。 ＋＋ 表面積１／３位にカビの生育が認められる。 ＋＋＋ 全面に黴が生育する。<Mold resistance> As a test strain, black mold (As
pergillus niger) was used. The spores were collected from the slant medium, a small amount of a wetting agent (dioctyl sodium sulfosuccinate solution) was added, and the spores were dispersed by shaking vigorously, and filtered with gauze to adjust the total volume to 50 ml. 1.
Make a GP medium (Nippon Pharmaceutical Co., Ltd.) with 5% agar,
The bacterial solution was sprayed uniformly and the surface was once dried. Test piece 2 cm x from shoe insole obtained in each example and comparative example
A piece cut into 2 cm is placed, pressed sufficiently, and the test bacterium is sprayed again on the entire surface and cultured at 28 ° C. over time.
Observed over time for up to a week. The evaluation was as follows. Evaluation grade --- Completely inhibits mold growth. -It is difficult to judge whether mold is growing or not. + Shows fairly good controllability, but shows mold growth below 1/5 of the surface area. ++ Mold growth is observed at 1/3 of the surface area. ++ Mold grows on the entire surface.

【０１０２】＜脱臭性＞各実施例、比較例で得られた靴
中敷きを２ｃｍ×５ｃｍに切り、１０枚を１．８リット
ルのガラス瓶に入れて密閉し、アンモニアが２５０ｐｐ
ｍになるようにガスを注入し、６時間放置後瓶内の気体
を１００ｍｌ取り出し、官能評価を行った。 評価グレード ３：楽に感知される臭い。 ２：何の臭いか判別可能な臭い。 １：やっと感知出来る臭い。 ０：無臭。<Deodorizing property> The shoe insole obtained in each of the examples and comparative examples was cut into 2 cm × 5 cm pieces, and 10 pieces were placed in a 1.8 liter glass bottle and sealed, and ammonia was added at 250 pp.
After injecting a gas so as to reach m, 100 ml of the gas in the bottle was taken out after standing for 6 hours, and the sensory evaluation was performed. Evaluation grade 3: Odor easily perceived. 2: An odor that can be distinguished from what odor. 1: A smell that can be finally sensed. 0: Odorless.

【０１０３】＜耐久性＞各実施例、比較例で得られた靴
中敷きを１０名が９時間／一日程度で３０日試着後の靴
中敷き表面と裏面の摩耗、剥がれ及びしわの様子を観察
した。摩耗、剥がれ、しわを５段階で評価し、１０名の
平均を取った。 評価グレード １：摩耗、剥がれ又はしわが大きくもう使用できない状
態。 ２：摩耗、剥がれ又はしわがやや大きいがまだ使用可能
の状態。 ３：摩耗、剥がれ又はしわがはっきり分かる状態。 ４：摩耗、剥がれ又はしわが分かる状態。 ５：摩耗、剥がれ及びしわがほとんど無い状態。<Durability> Observation of abrasion, peeling and wrinkling on the front and back surfaces of the shoe insole after 10 days of trying on the shoe insole obtained in each of Examples and Comparative Examples for about 9 hours / day for about 30 days. did. Abrasion, peeling, and wrinkles were evaluated on a five-point scale, and the average of ten persons was taken. Evaluation Grade 1: A condition in which abrasion, peeling or wrinkles are so large that it cannot be used anymore. 2: Abrasion, peeling or wrinkles are somewhat large, but still usable. 3: A state in which abrasion, peeling or wrinkles are clearly visible. 4: A state where wear, peeling or wrinkles are recognized. 5: A state with almost no wear, peeling and wrinkles.

【０１０４】[0104]

【表１】 （註）表１中の添加量は靴中敷き下層用シートの全繊維
に対する％[Table 1] (Note) The amount of addition in Table 1 is% to the total fiber of the sheet for the lower layer of the shoe insole.

【０１０５】[0105]

【表２】 （註）表２の実施例、比較例の靴中敷きは吸着性物質と
してミズカナイトＡＰを下層用不織布シートの全繊維に
対して２０％使用している。[Table 2] (Note) The insoles of Examples and Comparative Examples in Table 2 use 20% of mizucanite AP as an adsorptive substance with respect to all the fibers of the nonwoven fabric sheet for the lower layer.

【０１０６】[0106]

【表３】 [Table 3]

【０１０７】[0107]

【表４】 [Table 4]

【０１０８】表３、表４の結果から、次のことが解る。From the results in Tables 3 and 4, the following can be understood.

【０１０９】製造例Ａ〜Ｃで製造した本発明の抗菌防黴
剤を含有した繊維状物質を用いた実施例１〜１２までの
靴中敷きの抗菌性、耐久抗菌性、防黴性は繊維状物質の
添加量が増すに従って向上するが、同一添加量で比較し
た場合は、銀塩又は銅塩単独よりも銀塩、銅塩、亜鉛塩
を用いた製造例Ｃが最も良好である。吸着性物質の比較
では、脱臭性は実施例１１のアルミノケイ酸亜鉛は無臭
であるが実施例１６の酸性白土は殆ど無臭、実施例１５
のゼオライト系は感知出来る程度であり、アルミノケイ
酸亜鉛が最も優れている。不織布目付３００ｇ／ｍ2で
の添加量は、効果の点では３％が臭いが識別出来る程度
であり、効果の出る下限に近い。抗菌防黴剤を含まない
比較例１、２では抗菌性、防黴性が非常に悪い。塩化ベ
ンザルコニウムを使用した比較例３では耐久抗菌性が無
くなっている。吸着性物質を含まない比較例１は脱臭性
が非常に悪い。The antibacterial, durable antibacterial and antifungal properties of the insoles of Examples 1 to 12 using the fibrous substance containing the antibacterial and antifungal agent of the present invention produced in Production Examples A to C are fibrous. It increases as the added amount of the substance increases, but when compared at the same added amount, Production Example C using silver salt, copper salt or zinc salt is the best than silver salt or copper salt alone. In comparison of the adsorptive substances, the deodorizing property was that the zinc aluminosilicate of Example 11 was odorless, but the acid clay of Example 16 was almost odorless, and Example 15
The zeolite system is perceptible and zinc aluminosilicate is the best. The addition amount at a nonwoven fabric basis weight of 300 g / m 2 is close to the lower limit at which the effect is attained, since 3% is such that the odor can be recognized in terms of the effect. In Comparative Examples 1 and 2 containing no antibacterial and antifungal agent, the antibacterial property and the antifungal property are very poor. Comparative Example 3 using benzalkonium chloride has no durable antibacterial property. Comparative Example 1, which does not contain an adsorbing substance, has a very poor deodorizing property.

【０１１０】本発明の抗菌防黴剤組成物を塗布又は含浸
した実施例１７〜２６の靴中敷きは、抗菌性、耐久抗菌
性、防黴性は良好である。同一塗布量で比較すると、実
施例１７の銀塩を用いた場合、実施例１８の銀塩と銅塩
を用いた場合、実施例２０の銀塩、銅塩および亜鉛塩を
用いた場合の順に良くなる。実施例１９は抗菌防黴剤組
成物の塗布量が０．２ｇ／ｍ2、抗菌防黴剤として０．
０４６ｇ／ｍ2で耐久抗菌性からは下限に近いと予想さ
れる。実施例２２の、水不溶性高分子化合物Ｄに対する
抗菌防黴剤Ａの重量比が０．０５では抗菌性、特に耐久
抗菌性が劣り、比較例５の０．０３では耐久抗菌性が無
くなっている。逆に実施例２５の重量比５．０では初期
の抗菌性は良好であるが、水不溶性高分子化合物がすく
ないために耐久抗菌性は劣っており、比較例６の重量比
６．０では耐久抗菌性は無くなっている。塩化ベンザル
コニウムを用いた比較例４では耐久抗菌性は無くなって
いる。The insoles of Examples 17 to 26 coated with or impregnated with the antibacterial and antifungal agent composition of the present invention have good antibacterial properties, durable antibacterial properties and antifungal properties. Comparing with the same coating amount, in the case of using the silver salt of Example 17, the case of using the silver salt and copper salt of Example 18, and the case of using the silver salt, copper salt and zinc salt of Example 20 Get better. In Example 19, the amount of the antibacterial and fungicide composition applied was 0.2 g / m 2 , and the amount of the antibacterial and fungicide was 0.1 g.
046 g / m 2 is expected to be close to the lower limit from the viewpoint of durability and antibacterial properties. When the weight ratio of the antibacterial and fungicide A to the water-insoluble polymer compound D in Example 22 was 0.05, the antibacterial properties, particularly the durable antibacterial properties, were inferior. In Comparative Example 5, 0.03, the durable antibacterial properties were lost. . Conversely, when the weight ratio of Example 25 was 5.0, the initial antibacterial property was good, but the water-insoluble polymer compound was so small that the antimicrobial durability was inferior. Antibacterial properties are gone. In Comparative Example 4 using benzalkonium chloride, durability antibacterial properties were lost.

【０１１１】耐久性は表層用塗布液Ｘを塗布した実施例
１〜２６及び比較例１〜５は良好であるが、塗布しなか
った実施例２７ではやや耐久性に劣り、湿式不織布のみ
の比較例７では一ヶ月の試着に耐えなかった。実施例２
２、２３では、抗菌防黴剤組成物の水不溶性高分子化合
物の比率が高く、表層用塗布液Ｘの塗布により耐久性は
非常に優れた靴中敷きになる。The durability was good in Examples 1 to 26 and Comparative Examples 1 to 5 in which the coating liquid X for surface layer was applied, but in Example 27 in which the coating liquid X was not applied, the durability was slightly inferior. Example 7 did not withstand one month of fitting. Example 2
In Nos. 2 and 23, the ratio of the water-insoluble polymer compound in the antibacterial and fungicide composition is high, and the application of the surface layer coating liquid X results in a shoe insole with extremely excellent durability.

【０１１２】[0112]

【発明の効果】本発明に使用される抗菌防黴剤を含有す
る繊維状物質、有機繊維及び吸着性物質を必須成分とす
る湿式不織布と不織布の貼り合わせた脱臭送金性靴中敷
きは、長期の抗菌、防黴の双方に効果が有り、脱臭効果
にも優れている。The deodorizing and remittance-shoe insole in which the wet nonwoven fabric and the nonwoven fabric containing the fibrous substance, the organic fiber and the adsorbent substance containing the antibacterial and fungicide used in the present invention as essential components are bonded for a long time. It is effective for both antibacterial and antifungal, and has excellent deodorizing effect.

【０１１３】特に効果的に機能を発揮するのは、繊維状
物質がイオン交換繊維であり、吸着性物質がアルミノケ
イ酸亜鉛であれば長期に渡る効果が得られる。Particularly effective functions are exhibited when the fibrous substance is ion-exchange fiber and the adsorptive substance is zinc aluminosilicate.

【０１１４】本発明に使用される抗菌防黴剤と水不溶性
高分子物質の重量比が０．０５〜５である抗菌防黴剤組
成物は、水不溶性高分子物質により抗菌防黴剤を覆うこ
とで耐水性を持たせる為、塗布等の加工により抗菌・防
黴性を付与したものであって、それ故、菌捕捉性が良
く、また、各種のイオン拡散性も良好である。さらに、
本発明で使用される抗菌防黴剤は、適度な解離性を有し
ているために、水不溶性高分子化合物の膜の間隙を通っ
て徐放される。それ故、抗菌防黴効果が持続されて、ポ
ットライフが長く、耐水性、耐久性に優れている。The antibacterial fungicide composition having a weight ratio of the antibacterial fungicide to the water-insoluble polymer substance of 0.05 to 5 used in the present invention covers the antibacterial fungicide with the water-insoluble polymer substance. In order to impart water resistance, antibacterial and antifungal properties are imparted by processing such as coating, so that the bacteria-trapping property is good and various ion diffusivities are also good. further,
Since the antibacterial and antifungal agent used in the present invention has an appropriate dissociation property, it is gradually released through the gap of the membrane of the water-insoluble polymer compound. Therefore, the antibacterial and antifungal effect is maintained, the pot life is long, and the water resistance and durability are excellent.

【０１１５】また、本発明において、抗菌防黴剤を担持
して最も効果的に機能を発揮する高分子化合物は、ウレ
タン系高分子化合物、スチレン−ブタジェン系高分子化
合物、アクリル系高分子化合物である。このような水不
溶性高分子化合物を用いると、耐久性、耐水性が優れ、
抗菌防黴剤が過度に解離するのを押さえ、抗菌防黴効果
が持続する。Further, in the present invention, the polymer compounds which exhibit the most effective function by carrying the antibacterial and fungicide are urethane polymer compounds, styrene-butadiene polymer compounds, and acrylic polymer compounds. is there. When such a water-insoluble polymer compound is used, durability and water resistance are excellent,
Excessive dissociation of the antibacterial and antifungal agent is suppressed, and the antibacterial and antifungal effect is maintained.

【０１１６】抗菌防黴剤の金属塩が銀塩、銅塩、亜鉛塩
の何れか１種であれば抗菌性から好ましく、特に３種が
複合されたものであれば、使用直後から長期にわたって
の抗菌、防黴性が得られるので好ましい。If the metal salt of the antibacterial and antifungal agent is at least one of silver salt, copper salt and zinc salt, it is preferable from the viewpoint of antibacterial properties. It is preferable because antibacterial and antifungal properties can be obtained.

【０１１７】しかも、本発明に使用される抗菌防黴剤が
含有された水不溶性高分子化合物は、シート状物に塗
布、含浸等で加工する場合でも、生産性は良好である。Further, the water-insoluble polymer compound containing the antibacterial and antifungal agent used in the present invention has good productivity even when it is processed by coating or impregnating a sheet.

【０１１８】靴中敷きの表面層には高分子化合物主体の
組成物を塗布又は含浸することで耐久性と見た目の美装
性の改良になる。特に、発泡剤を添加することで通気性
が良化するので臭気、汗等の水分が通過しやすく好まし
い。By coating or impregnating a composition mainly composed of a high molecular compound on the surface layer of the insole, the durability and the appearance can be improved. In particular, the addition of a foaming agent improves air permeability, so that moisture such as odor and sweat easily passes therethrough, which is preferable.

Claims (13)

【特許請求の範囲】[Claims] 【請求項１】 含窒素複素環、硫黄原子の少なくともい
ずれかを含む有機化合物の金属塩である抗菌防黴剤
（Ａ）を含有する繊維状物質、有機繊維及び吸着性物質
を必須成分とする湿式不織布（Ｂ）の少なくとも片面に
不織布（Ｃ）を貼り合わせたことを特徴とする脱臭抗菌
性靴中敷き。An essential component is a fibrous substance, an organic fiber and an adsorptive substance containing an antibacterial and fungicide (A) which is a metal salt of an organic compound containing at least one of a nitrogen-containing heterocycle and a sulfur atom. A deodorizing and antibacterial shoe insole, characterized by laminating a nonwoven fabric (C) on at least one surface of a wet nonwoven fabric (B). 【請求項２】 繊維状物質が、イオン交換繊維であるこ
とを特徴とする請求項１記載の脱臭抗菌性靴中敷き。2. The deodorant antibacterial insole according to claim 1, wherein the fibrous substance is an ion exchange fiber. 【請求項３】 イオン交換繊維が、ポリスチレン、ポリ
アクリル、ポリアミド、ポリエステル、ポリエチレン、
およびセルロースから選ばれる少なくとも１種であっ
て、スルホン酸基、ホスホン酸基、カルボン酸基の少な
くとも１種を有することを特徴とする請求項２記載の脱
臭抗菌性靴中敷き。3. The method according to claim 1, wherein the ion exchange fiber is polystyrene, polyacryl, polyamide, polyester, polyethylene,
3. The deodorant antibacterial insole according to claim 2, wherein the shoe has at least one selected from the group consisting of sulfonic acid group, phosphonic acid group and carboxylic acid group. 【請求項４】 イオン交換繊維がカルボキシメチル変性
セルロースであることを特徴とする請求項２記載の脱臭
抗菌性靴中敷き。4. The deodorant antibacterial insole according to claim 2, wherein the ion exchange fiber is carboxymethyl-modified cellulose. 【請求項５】 有機繊維と吸着性物質を必須成分とする
湿式不織布（Ｅ）の少なくとも片面に不織布（Ｆ）を貼
り合わせた構造であり、含窒素複素環、硫黄原子の少な
くともいずれかを含む有機化合物の金属塩である抗菌防
黴剤（Ａ）と水不溶性高分子化合物（Ｄ）を含有し、重
量比（Ａ／Ｄ）が０．０５〜５である抗菌防黴剤組成物
（Ｇ）が湿式不織布（Ｅ）又は不織布（Ｆ）の少なくと
も片面に塗布又は含浸加工されていることを特徴とする
脱臭抗菌性靴中敷きシート。5. A structure in which a nonwoven fabric (F) is bonded to at least one surface of a wet nonwoven fabric (E) containing an organic fiber and an adsorptive substance as essential components, and contains at least one of a nitrogen-containing heterocycle and a sulfur atom. An antibacterial fungicide composition (G) containing an antibacterial fungicide (A) which is a metal salt of an organic compound and a water-insoluble polymer compound (D) and having a weight ratio (A / D) of 0.05 to 5 ) Is coated or impregnated on at least one surface of the wet nonwoven fabric (E) or the nonwoven fabric (F). 【請求項６】 不織布（Ｃ）又は（Ｆ）の、他の不織布
と貼り合わせていない面に高分子化合物主体の組成物
（Ｈ）を塗布又は含浸加工したことを特徴とする請求項
１又は５記載の脱臭抗菌性靴中敷き。6. The non-woven fabric (C) or (F), which has been coated or impregnated with a composition (H) mainly composed of a polymer compound on a surface not bonded to another non-woven fabric. 5. The deodorant antibacterial shoe insole according to 5. 【請求項７】 含窒素複素環、硫黄原子の少なくともい
ずれかを含有する有機化合物が、ベンズイミダゾール化
合物、メルカプトピリジン−Ｎ−オキシド化合物、イソ
チアゾロン化合物、ベンゾチアゾール化合物もしくはベ
ンゾチアゾロン化合物から選ばれる少なくとも１種の化
合物であることを特徴とする請求項１又は５記載の脱臭
抗菌性靴中敷き。7. The organic compound containing at least one of a nitrogen-containing heterocyclic ring and a sulfur atom is at least one selected from benzimidazole compounds, mercaptopyridine-N-oxide compounds, isothiazolone compounds, benzothiazole compounds and benzothiazolone compounds. The deodorant antibacterial shoe insole according to claim 1 or 5, which is a compound of the formula (1). 【請求項８】 金属塩が銀塩、銅塩、亜鉛塩の少なくと
もいずれか１種であることを特徴とする請求項１又は５
記載の脱臭抗菌性靴中敷き。8. The method according to claim 1, wherein the metal salt is at least one of a silver salt, a copper salt and a zinc salt.
The deodorant antibacterial shoe insole described. 【請求項９】 金属塩が銀塩、銅塩および亜鉛塩の３種
が複合されたものであることを特徴とする請求項１又は
５記載の脱臭抗菌性靴中敷き。9. The deodorant antibacterial insole according to claim 1, wherein the metal salt is a composite of three kinds of silver salt, copper salt and zinc salt. 【請求項１０】 吸着性物質がアルミノケイ酸亜鉛であ
ることを特徴とする請求項１又は５記載の脱臭抗菌性靴
中敷き。10. The deodorant antibacterial shoe insole according to claim 1, wherein the adsorptive substance is zinc aluminosilicate. 【請求項１１】 水不溶性高分子化合物（Ｄ）がウレタ
ン系高分子化合物、スチレン−ブタジェン系高分子化合
物、アクリル系高分子化合物から選ばれる少なくとも１
種であることを特徴とする請求項５記載の脱臭抗菌性靴
中敷き。11. The water-insoluble polymer compound (D) is at least one selected from urethane polymer compounds, styrene-butadiene polymer compounds, and acrylic polymer compounds.
The deodorant antibacterial insole according to claim 5, which is a seed. 【請求項１２】 水不溶性高分子化合物（Ｄ）の少なく
とも１種が自己乳化型であることを特徴とする請求項５
記載の脱臭抗菌性靴中敷き。12. The method according to claim 5, wherein at least one of the water-insoluble polymer compounds (D) is of a self-emulsifying type.
The deodorant antibacterial shoe insole described. 【請求項１３】 高分子化合物を主体とする組成物
（Ｈ）が、発泡剤を含有することを特徴とする請求項８
記載の脱臭抗菌性靴中敷き。13. The composition (H) mainly comprising a polymer compound, comprising a foaming agent.
The deodorant antibacterial shoe insole described.
JP10201709A 1998-07-16 1998-07-16 Deodorant antibacterial shoes insole Pending JP2000023711A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP10201709A JP2000023711A (en) 1998-07-16 1998-07-16 Deodorant antibacterial shoes insole

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP10201709A JP2000023711A (en) 1998-07-16 1998-07-16 Deodorant antibacterial shoes insole

Publications (1)

Publication Number Publication Date
JP2000023711A true JP2000023711A (en) 2000-01-25

Family

ID=16445637

Family Applications (1)

Application Number Title Priority Date Filing Date
JP10201709A Pending JP2000023711A (en) 1998-07-16 1998-07-16 Deodorant antibacterial shoes insole

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Country Link
JP (1) JP2000023711A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030013987A (en) * 2001-08-10 2003-02-15 제이티엘주식회사 A headrest have a function of ativation
USD903268S1 (en) 2019-02-06 2020-12-01 S. C. Johnson & Son, Inc. Insole
USD906658S1 (en) 2019-02-19 2021-01-05 S. C. Johnson & Son, Inc. Insole
CN113502005A (en) * 2021-07-30 2021-10-15 苏州远浩新纺织科技有限公司 Antibacterial and deodorant lining material for shoes and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030013987A (en) * 2001-08-10 2003-02-15 제이티엘주식회사 A headrest have a function of ativation
USD903268S1 (en) 2019-02-06 2020-12-01 S. C. Johnson & Son, Inc. Insole
USD906658S1 (en) 2019-02-19 2021-01-05 S. C. Johnson & Son, Inc. Insole
USD935758S1 (en) 2019-02-19 2021-11-16 S. C. Johnson & Son, Inc. Insole
CN113502005A (en) * 2021-07-30 2021-10-15 苏州远浩新纺织科技有限公司 Antibacterial and deodorant lining material for shoes and preparation method thereof

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