JPH0949170A - Antimicrobial textile product and its production - Google Patents
Antimicrobial textile product and its productionInfo
- Publication number
- JPH0949170A JPH0949170A JP22847795A JP22847795A JPH0949170A JP H0949170 A JPH0949170 A JP H0949170A JP 22847795 A JP22847795 A JP 22847795A JP 22847795 A JP22847795 A JP 22847795A JP H0949170 A JPH0949170 A JP H0949170A
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- chitosan
- fiber product
- antibacterial
- treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、人体、生物に障害を与
えることなく、親水性繊維もしくは疎水性繊維を含む繊
維製品に着色がなく、かつ耐久性のある抗菌性、保湿
性、pHバランス性等の多機能を付与するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a durable, antibacterial, moisturizing and pH balance that does not damage the human body or organisms, has no coloring in textiles containing hydrophilic fibers or hydrophobic fibers. It imparts multiple functions such as sex.
【0002】[0002]
【従来の技術】繊維製品に耐久性のある抗菌性を付与す
ることは、病院、老人ホームのカーテン、シーツ、寝衣
等の調度品、家庭の寝具、赤ちゃん用品、衣料等におい
て望ましいことであるが、この抗菌性付与は決して容易
なことではない。特に疎水性繊維を含む繊維製品に抗菌
性を付与することは困難であって、古くから殺菌剤、抗
菌剤が繊維処理剤として用いられているにもかかわらず
満足な結果をもたらすものは得られていない。2. Description of the Related Art It is desirable to impart durable antibacterial properties to textiles in hospitals, nursing home curtains, sheets, furnishings such as sleepwear, household bedding, baby products, clothing, etc. However, imparting this antibacterial property is not easy. In particular, it is difficult to impart antibacterial properties to textile products containing hydrophobic fibers, and it has been possible to obtain satisfactory results even though bactericides and antibacterial agents have been used as fiber treatment agents for a long time. Not not.
【0003】特に最近では、MRSAのような耐性菌の
出現により、抗生物質が抗菌性万能とはいえなくなり、
このような耐性菌への配慮も必要となっている。Particularly recently, with the advent of resistant bacteria such as MRSA, antibiotics are no longer universal antibacterial,
It is also necessary to consider such resistant bacteria.
【0004】更に、ジフェニルエーテル系の抗菌剤のよ
うに加工繊維の焼却時に、発がん物質のダイオキシンが
生成する事例が報告されるなど、環境への配慮も必要と
なっている。Further, it is necessary to consider the environment, such as the case where a carcinogen, dioxin, is produced when the processed fiber is incinerated like a diphenyl ether type antibacterial agent.
【0005】耐性菌に対しても強い抗菌性を示し、かつ
発がん物質の生成もない抗菌剤として、ゼオライトの
銀、銅もしくは亜鉛のイオン交換体等の無機化合物が試
みられているが、耐久性に乏しいのが欠点である。Inorganic compounds such as zeolite silver, copper or zinc ion exchangers have been attempted as antibacterial agents showing strong antibacterial properties against resistant bacteria and not producing carcinogens. The shortcoming is that it is poor.
【0006】特公昭57−41950公報には、キトサ
ン銅コンプレックスまたはキトサン銀コンプレックスを
活性成分として特に天然繊維に担持させて、反復使用可
能の殺菌性繊維シートを製造することが記載されてい
る。Japanese Patent Publication No. 57-41950 discloses that a chitosan copper complex or a chitosan silver complex is supported as an active ingredient on a natural fiber in particular to produce a reusable bactericidal fiber sheet.
【0007】上記繊維シート、特に天然繊維または皮革
からなるシートに、キトサン銅コンプレックスまたはキ
トサン銀コンプレックスを担持させることによって耐久
性のある殺菌性、抗菌性を付与することはできるが、問
題点が多い。[0007] By carrying the chitosan copper complex or the chitosan silver complex on the above-mentioned fiber sheet, particularly a sheet made of natural fiber or leather, durable bactericidal property and antibacterial property can be imparted, but there are many problems. .
【0008】問題点のひとつは、綿、羊毛等の親水性繊
維製品や合成繊維等の疎水性繊維製品に施した場合に
は、なお耐久性が不充分なことである。また他の問題点
は、銅または銀のコンプレックスが着色しているため
に、所望の色彩の繊維製品が得られにくいことである。[0008] One of the problems is that the durability is still insufficient when applied to hydrophilic fiber products such as cotton and wool and hydrophobic fiber products such as synthetic fibers. Another problem is that it is difficult to obtain a fiber product having a desired color because the copper or silver complex is colored.
【0009】また特開平4−193275号には、無機
あるいは有機の粉末状物にキトサンを固定化し、その後
に原子番号12〜13、20〜30、38〜51、57
〜83及び88〜89の金属元素からなる群より選ばれ
た一種又は二種以上の金属元素を固定化させて粉末状消
臭材料を得る技術が記載されている。しかし、上記先行
技術では、処理手段は、本発明と似ているが、殺菌性の
付与について、なんらの示唆もなされていない。Further, in Japanese Patent Laid-Open No. 4-193275, chitosan is immobilized on an inorganic or organic powdery substance, and then atomic numbers 12 to 13, 20 to 30, 38 to 51, 57.
The technique for obtaining a powdery deodorant material by immobilizing one or more kinds of metal elements selected from the group consisting of metal elements of ~ 83 and 88-89 is described. However, in the above-mentioned prior art, although the treatment means is similar to that of the present invention, there is no suggestion of imparting bactericidal property.
【0010】[0010]
【発明が解決しようとする課題】本発明は、前述した従
来の抗菌性繊維製品の欠点を改良して、耐洗濯性が卓越
し、着色がなく、しかも人体、生物等に障害のない抗菌
性繊維製品を得るものであり、合わせて耐久性のある保
湿性、吸水性、pHバランス性等を付与することを目的
とする。DISCLOSURE OF THE INVENTION The present invention has improved the above-mentioned drawbacks of conventional antibacterial textiles, has excellent washing resistance, is free from coloration, and has no antibacterial properties against human bodies, organisms, etc. The purpose of the present invention is to obtain a textile product, and also to impart durable moisture retention, water absorption, pH balance and the like.
【0011】[0011]
【課題を解決するための手段】本発明は、親水性繊維も
しくは疎水性繊維を含む繊維製品であって、カルシウ
ム、亜鉛、マグネシウム及びアルミニウムよりなる群か
ら選択された少くとも1種の金属の水溶性塩とキトサン
を必須成分とする混合物もしくは複合体が該繊維製品に
対してキトサン含有率として0.01〜7重量%、金属
塩の金属換算含有率として0.02〜3重量%含有され
ていることを特徴とする。ここに複合体とは、塩、錯塩
を形成したり、物理的に結合されたものを意味する。SUMMARY OF THE INVENTION The present invention is a fiber product containing hydrophilic or hydrophobic fibers, which is an aqueous solution of at least one metal selected from the group consisting of calcium, zinc, magnesium and aluminum. A mixture or complex containing essential salt and chitosan as essential components is contained in the fiber product at a chitosan content of 0.01 to 7% by weight and a metal salt content of 0.02 to 3% by weight. It is characterized by being Here, the complex means a salt, a complex salt formed or physically bound.
【0012】本発明の繊維製品は、上述した特公昭57
−41950公報で示された銅または銀のキトサンコン
プレックスによる処理と比較して親水性繊維、疎水性繊
維を問わず、着色せず、耐洗濯性が優れており、特にこ
れまで耐洗濯性のある抗菌性を付与するのが困難であっ
た合成繊維のような疎水性繊維を含む繊維製品に対し
て、卓越した耐洗濯性を付与することができ、しかも着
色がないという優れた利点がある。The textile product of the present invention is the above-mentioned Japanese Patent Publication Sho-57.
-41950 gazette, compared with the treatment with the chitosan complex of copper or silver, regardless of hydrophilic fiber or hydrophobic fiber, it is not colored and has excellent wash resistance, and particularly it has been wash resistant up to now. There is an excellent advantage that excellent washing resistance can be imparted to a fiber product containing hydrophobic fibers such as synthetic fibers, which have been difficult to impart antibacterial properties, and that coloring is not caused.
【0013】また本発明と前記特開平4−193275
号とを比較すれば分かるように、偶々共通の金属はある
ものの、効果は一致せず、被処理物に含有させるキトサ
ン及び金属塩の量も異なっている。The present invention and the above-mentioned JP-A-4-193275
As can be seen from a comparison with No. 1, although there are chances that there is a common metal, the effects do not match, and the amounts of chitosan and metal salt contained in the object to be treated also differ.
【0014】例えば、鉄は悪臭ガス吸収能は優れている
が、殺菌性は乏しい。また本発明では、繊維製品に含有
されるキトサン含有率は0.01〜7重量%、金属換算
金属化合物含有率は0.02〜3重量%であるのに対
し、前記先行技術では、該技術の実施例によれば、キト
サン含有率で9.1〜15.1重量%、金属化合物の金
属換算含有率で3.6〜5.3重量%となっていて、本
発明においては付着量が低いところにあることが分か
る。また、キトサン有機酸塩は、抗菌性を示すことは知
られているが、これのみでは充分な抗菌性は得られな
い。特にアルカリ性条件下では酸が脱離し、抗菌性の基
となるアミノ基の4級化塩が消失して、抗菌性を喪失す
る欠点がある。しかし、本発明のようにキトサンが金属
と複合体を形成して被処理体表層に皮膜を形成すると、
アルカリ性条件下でも抗菌性は消滅しない。For example, iron has an excellent ability to absorb malodorous gas, but has poor bactericidal property. Further, in the present invention, the content of chitosan contained in the textile product is 0.01 to 7% by weight, and the content of metal compound in terms of metal is 0.02 to 3% by weight. According to the examples, the chitosan content is 9.1 to 15.1% by weight, and the metal conversion content of the metal compound is 3.6 to 5.3% by weight. You can see that it is in a low place. Moreover, although it is known that chitosan organic acid salt shows antibacterial property, sufficient antibacterial property cannot be obtained by this alone. Particularly under alkaline conditions, there is a disadvantage that the acid is eliminated and the quaternized salt of the amino group serving as an antibacterial group disappears, and the antibacterial property is lost. However, when chitosan forms a complex with a metal to form a film on the surface layer of the object to be treated as in the present invention,
Antibacterial properties do not disappear even under alkaline conditions.
【0015】本発明に使用する疎水性繊維としては、セ
ルロースアセテートのような半合成繊維、ポリアミド、
ポリアクリロニトリル等の合成繊維等が挙げられ、疎水
性繊維単独もしくは綿、羊毛、レイヨン等の親水性繊維
との複合による繊維、糸、織物、編物、不織布、紙等が
疎水性繊維を含む繊維製品として挙げられる。The hydrophobic fibers used in the present invention include semi-synthetic fibers such as cellulose acetate, polyamide,
Synthetic fibers such as polyacrylonitrile, etc. are mentioned, and the fiber products including hydrophobic fibers alone or composites with hydrophilic fibers such as cotton, wool, rayon, yarns, woven fabrics, knitted fabrics, non-woven fabrics, papers and the like include hydrophobic fibers. As.
【0016】また親水性繊維としては、綿、羊毛、麻の
ような天然繊維、レイヨン、キュプラのような再生繊
維、PVA繊維のような合成繊維等が挙げられ、親水性
繊維単独もしくはポリエステル、ポリアミド、ポリアク
リロニトリル等の疎水性繊維との複合による繊維、糸、
織物、編物、不織布、紙等が親水性繊維を含む繊維製品
として挙げられる。Examples of hydrophilic fibers include natural fibers such as cotton, wool and hemp, regenerated fibers such as rayon and cupra, and synthetic fibers such as PVA fibers. Hydrophilic fibers alone or polyester, polyamide Fibers, yarns made of composites with hydrophobic fibers such as polyacrylonitrile,
Woven fabrics, knitted fabrics, non-woven fabrics, papers and the like are mentioned as fiber products containing hydrophilic fibers.
【0017】本発明を適用する繊維製品を構成する繊維
は、表面を酸化層にすることが極めて有効である。即
ち、酸化層にすることによって抗菌性の耐洗濯性が飛躍
的に向上する。The fibers constituting the textile product to which the present invention is applied are extremely effective when the surface thereof is an oxidized layer. That is, the antibacterial washing resistance is dramatically improved by forming the oxide layer.
【0018】酸化層を形成させる手段としては、硫酸、
苛性ソーダ等の薬品によって化学的に繊維表面を酸化す
る方法、またはプラズマ処理、コロナ放電処理、紫外線
照射処理、X線、電子線、γ線等の高エネルギー線照射
処理等の物理的処理により酸化する方法がある。As a means for forming an oxide layer, sulfuric acid,
Chemically oxidize the fiber surface with chemicals such as caustic soda, or physical treatment such as plasma treatment, corona discharge treatment, ultraviolet irradiation treatment, high-energy ray irradiation treatment of X-rays, electron rays, γ rays, etc. There is a way.
【0019】酸化層は、形成手段によって構造的に相違
があると見られるが、特に物理的処理による酸化層が有
効であり、特にプラズマ処理、コロナ放電処理または紫
外線照射による酸化層が効果的であって、抗菌性の耐洗
濯性が飛躍的に向上する。The oxide layer is structurally different depending on the forming means, but an oxide layer formed by physical treatment is particularly effective, and an oxide layer formed by plasma treatment, corona discharge treatment or ultraviolet irradiation is particularly effective. Therefore, the antibacterial washing resistance is dramatically improved.
【0020】紫外線照射処理もしくはコロナ放電処理、
プラズマ処理により酸化層を設けることは、繊維表面の
接着性、印刷性等を向上させるために、しばしば採られ
る手段であり、油性、即ち疎水性の溶剤を主体とした媒
体を用いた接着剤、インク等を疎水性の対象物に付与す
ると耐久性のある加工結果が得られることは知られてい
るが、親水性溶剤、例えば水系溶媒を用いた処理剤で処
理する場合には耐久性のある加工結果は得られない。Ultraviolet irradiation treatment or corona discharge treatment,
Providing an oxide layer by plasma treatment is a means often taken in order to improve the adhesiveness of the fiber surface, printability, etc., and is an oily, that is, an adhesive using a medium mainly composed of a hydrophobic solvent, It is known that durable processing results can be obtained by applying ink or the like to a hydrophobic object, but it is durable when treated with a treatment agent using a hydrophilic solvent such as an aqueous solvent. No processing result is obtained.
【0021】特に親水性繊維もしくは疎水性繊維を含む
繊維製品の表面に酸化層を設けると、水系溶媒を用いた
処理剤では、酸化層を設けない場合よりも更に加工効果
が低下する。例えば、澱粉糊などの親水性接着剤では接
着性が反って低下し、酸性染料のような親水性染料では
染色性が反って低下する。In particular, when an oxidation layer is provided on the surface of a fiber product containing hydrophilic fibers or hydrophobic fibers, the processing effect of the treatment agent using an aqueous solvent is lower than that in the case where no oxidation layer is provided. For example, hydrophilic adhesives such as starch paste warp and decrease the adhesiveness, and hydrophilic dyes such as acid dyes warp and decrease the dyeability.
【0022】高分子化合物を繊維表面に付与する場合も
同様であって、例えばポリアクリル酸ソーダ水溶液を前
に述べた酸化層を設けた疎水性繊維製品表面に付与して
も耐洗濯性のある加工効果は得られない。The same applies to the case where the polymer compound is applied to the surface of the fiber. For example, even if the aqueous solution of sodium polyacrylate is applied to the surface of the hydrophobic fiber product provided with the above-mentioned oxidation layer, it has washing resistance. No processing effect can be obtained.
【0023】ところが、キトサン塩の水溶液を用いた場
合に限り、親水性繊維、疎水性繊維を問わず、繊維表面
に酸化層を設けることにより一層強固なキトサン被膜を
形成することができる。However, only when an aqueous solution of chitosan salt is used, a stronger chitosan coating can be formed by providing an oxidation layer on the surface of the fiber regardless of hydrophilic fiber or hydrophobic fiber.
【0024】コロナ放電処理は、通常10〜25kHz
の発振周波数で電極間距離数mmでコロナ放電させ、そ
の間を被処理物を通過させることによって行う。Corona discharge treatment is usually 10 to 25 kHz
Corrosion discharge is performed at a distance between electrodes of several millimeters at an oscillation frequency of, and an object to be processed is passed between them.
【0025】紫外線処理は、好ましくは150〜300
mmの比較的短波長の紫外線を繊維製品に照射すること
によって達成される。照射時間は光源の種類、強度に左
右されるが10〜60秒間程度である。The UV treatment is preferably 150 to 300.
It is achieved by irradiating the textile with a relatively short wavelength of UV light of mm. The irradiation time depends on the type and intensity of the light source, but is about 10 to 60 seconds.
【0026】本発明に使用されるカルシウム、亜鉛、マ
グネシウムもしくはアルミニウムの水溶性塩は、中性も
しくは中性に近いこと、酸化性もしくは還元性が少ない
こと、着色が少ないものが好ましい。その理由は繊維製
品の着色、変色または劣化を防ぐために重要だからであ
る。またキトサンと結合して錯塩を形成しやすい金属塩
が好ましい。これによって金属塩を繊維製品に強固に接
着させることができる。The water-soluble salt of calcium, zinc, magnesium or aluminum used in the present invention is preferably neutral or close to neutral, less oxidizing or reducing, and less colored. The reason is that it is important to prevent coloration, discoloration or deterioration of the textile product. Further, a metal salt that is easy to combine with chitosan to form a complex salt is preferable. This allows the metal salt to be firmly adhered to the textile product.
【0027】これらの条件を充たす塩類としては、有機
酸の塩類が好ましい。有機酸の例としては、酢酸、修
酸、乳酸、酒石酸、りんご酸等が挙げられる。また止む
を得ず無機酸塩を使用する時には、揮発性酸の塩、即ち
塩化物を使用するのがよい。特に好ましい水溶性塩とし
ては酢酸塩、修酸塩、乳酸塩が挙げられる。Salts satisfying these conditions are preferably salts of organic acids. Examples of organic acids include acetic acid, oxalic acid, lactic acid, tartaric acid, malic acid and the like. When it is unavoidable to use an inorganic acid salt, it is preferable to use a salt of a volatile acid, that is, a chloride. Particularly preferred water-soluble salts include acetate, oxalate and lactate.
【0028】上記金属の水溶性塩の繊維製品に対する付
着量は、金属換算含有率で0.02〜3重量%、好まし
くは0.1〜2重量%である。金属塩の量が多すぎると
着色、変色、劣化等の障害が多いのみでなく、金属塩の
脱落も多く、脱落金属塩による弊害も起こる。The amount of the above-mentioned metal water-soluble salt attached to the fiber product is 0.02 to 3% by weight, preferably 0.1 to 2% by weight, in terms of metal content. If the amount of the metal salt is too large, not only there are many obstacles such as coloring, discoloration, deterioration, etc., but also many metal salts are dropped off, and the harmful effects of the dropped metal salts occur.
【0029】本発明に使用するキトサンは蟹等の甲殻類
や「きのこ」等から得られるキチンを高濃度のアルカリ
で処理して脱アセチル化して得られる遊離アミノ基を有
するものであり、脱アセチル化度は30%以上が好まし
い。Chitosan used in the present invention has a free amino group obtained by deacetylating chitin obtained from crustaceans such as crabs and "mushrooms" with a high concentration of alkali. The degree of conversion is preferably 30% or more.
【0030】また上記キトサンは、通常有機酸塩として
使用されるが、該有機酸としては、酢酸、修酸、乳酸、
蟻酸、りんご酸等が例示される。特に好ましい酸は、酢
酸、修酸、乳酸である。The above-mentioned chitosan is usually used as an organic acid salt, and as the organic acid, acetic acid, oxalic acid, lactic acid,
Examples include formic acid and malic acid. Particularly preferred acids are acetic acid, oxalic acid and lactic acid.
【0031】キトサンの繊維製品への付着量は、0.0
1〜7重量%であって、0.1〜5重量%が好ましい。
付着量が大きすぎると繊維が黄変したり、風合が硬化す
る障害が生ずる。従って上記金属塩とキトサンとの混合
物もしくは複合体の繊維に対する含有量は0.03〜8
重量%であることが好ましい。The amount of chitosan attached to the textile product is 0.0
It is 1 to 7% by weight, preferably 0.1 to 5% by weight.
If the amount of adhesion is too large, the fibers will turn yellow and the hand will be hardened. Therefore, the content of the mixture or composite of the metal salt and chitosan in the fiber is 0.03 to 8
It is preferably in the weight%.
【0032】上記金属塩とキトサンは、少なくとも一部
が複合体を形成して被処理繊維上に耐洗濯性の優れた皮
膜を形成し、特にキトサン塩は繊維に対して親和性が強
いために耐洗濯性の優れた抗菌性繊維を得ることができ
る。At least a part of the above-mentioned metal salt and chitosan forms a complex to form a film having excellent washing resistance on the fiber to be treated. Especially, the chitosan salt has a strong affinity for the fiber. An antibacterial fiber having excellent wash resistance can be obtained.
【0033】上記繊維製品に上記金属塩とキトサン塩と
を付与する手段としては、常法に従って上記両薬剤の水
溶液もしくは水分散液をパッディング法、浸漬法等の手
段を用いて施せばよい。ただし、この際、キトサン塩濃
度は20%以下で、pHは3〜6の範囲にあることが好
ましい。これは上記金属塩とキトサン塩とが複合体を作
って、耐久性が発現する条件である。As a means for applying the metal salt and chitosan salt to the fiber product, an aqueous solution or water dispersion of the both agents may be applied by a padding method, a dipping method or the like according to a conventional method. However, in this case, the chitosan salt concentration is preferably 20% or less and the pH is preferably in the range of 3 to 6. This is a condition under which the metal salt and chitosan salt form a complex and durability is exhibited.
【0034】更に、該複合体が繊維製品上で形成される
ことが、耐久性の点で最も好ましいことであり、そのた
めに上記金属塩とキトサン塩とを別々に繊維製品に付与
して(順序は問わない)、該製品上で複合体を形成する
のが好ましい。Further, it is most preferable in terms of durability that the composite is formed on a fiber product, for which purpose the above metal salt and chitosan salt are separately applied to the fiber product (sequence). However, it is preferable to form a complex on the product.
【0035】なお、この処理とともに染料、蛍光漂白
剤、帯電防止剤、柔軟剤、風合調節剤等を適宜添加して
もさしつかえない。Incidentally, dyes, fluorescent bleaching agents, antistatic agents, softening agents, texture adjusting agents and the like may be added appropriately along with this treatment.
【0036】次に実施例について、本発明を更に詳細に
説明する。なお、実施例中、抗菌性、吸水性、保湿性等
の試験は次の方法で行った。Next, the present invention will be described in more detail with reference to Examples. In the examples, tests for antibacterial properties, water absorption properties, moisturizing properties, etc. were conducted by the following methods.
【0037】抗菌性:シェークフラスコ法で試験菌(黄
色ブドウ状球菌)1〜2×104/mlの懸濁液を調整
したのち、生菌数を測定する。次に0.75gの試験片
を加えて25℃、320rpmで1時間振盪したのち、
再度生菌数を測定して次式により滅菌率を求めた。 Antibacterial property: After a suspension of test bacteria (Staphylococcus aureus) of 1 to 2 × 10 4 / ml was prepared by the shake flask method, the number of viable bacteria was measured. Next, after adding 0.75 g of the test piece and shaking at 320 rpm at 25 ° C. for 1 hour,
The viable cell count was measured again, and the sterilization rate was calculated by the following formula.
【0038】保湿性:試験片を20℃、65%RHの雰
囲気で48時間放置した後の水分率(1)及び20℃、
95%RHの雰囲気で60分間放置した後の水分率
(2)によって示した。Moisture retention: Moisture content (1) after leaving the test piece in an atmosphere of 20 ° C. and 65% RH for 48 hours and 20 ° C.
It was shown by the water content (2) after standing for 60 minutes in an atmosphere of 95% RH.
【0039】滅菌率、保湿性の耐洗濯性:各々JIS
L 0217−103号の方法によって洗濯を30回繰
返したのちの滅菌率及び保湿性で示した。Sterilization rate, moisture retention and washing resistance: JIS
The sterilization rate and the moisturizing property after the washing was repeated 30 times by the method of L 0217-103 were shown.
【0040】キトサン塩の耐洗濯性:キトサン塩のアミ
ノ基と酸性側で反応する酸性染料(カヤノールフロキシ
ンNK 保土谷化学社製)の1重量%水溶液の1:20
の浴比の染浴で100℃、10分間染色し、呈色濃度に
よって判定する。即ち洗濯前の呈色濃度を5として、グ
レースケールの5段階法で比色し、濃度が濃い程、耐洗
濯性が良好と判定する。Washing resistance of chitosan salt: 1:20 of a 1% by weight aqueous solution of an acid dye (Kayanol Phloxine NK Hodogaya Chemical Co., Ltd.) which reacts with the amino group of chitosan salt on the acidic side.
It is dyed at 100 ° C. for 10 minutes in a dyeing bath having a bath ratio of, and judged by the color density. That is, the color density before washing is set to 5, and color comparison is performed by a gray scale 5-step method. The higher the density, the better the wash resistance.
【0041】実施例1 下記3種の試験布を常法に従い、各々精練、過酸化水素
漂白した。一部をそのまま残し(以下、試験布(B)と
いう)、他の漂白布に低電圧水銀ランプが放射する紫外
線(装置:セン特殊光源(株)、フォト・サーフェイス
・プロセッサー、185mm〜315mm波長)で約6
0秒間照射処理を施した(以下、試験布(A)とい
う)。Example 1 The following three kinds of test cloths were scoured and bleached with hydrogen peroxide according to a conventional method. Part of it is left as it is (hereinafter referred to as test cloth (B)), and ultraviolet light emitted from the low-voltage mercury lamp to other bleaching cloth (apparatus: Sen Special Light Source Co., Ltd., Photo Surface Processor, 185 mm to 315 mm wavelength) About 6
Irradiation treatment was performed for 0 seconds (hereinafter referred to as test cloth (A)).
【0042】上記3種の試験布(A)及び3種の試験布
(B)を、次の処方の処理液によってパッディング(絞
り率100%)し、100℃で2分間乾燥し、120℃
で2分間熱処理した。The above-mentioned 3 kinds of test cloths (A) and 3 kinds of test cloths (B) were padded (squeeze ratio 100%) with a treatment liquid of the following formulation, dried at 100 ° C. for 2 minutes, and then 120 ° C.
And heat treated for 2 minutes.
【0043】試験布 (1) 30番手の綿糸使い天竺組織編布(試験布
(1)) (2) ポリエステル、綿混紡(混紡率60:40)3
0番手糸使い天竺丸編布(試験布(2)) (3) ポリエステル100% 30番手糸使い天竺丸
編布(試験布(3))Test cloth (1) 30-count cotton thread using a plain cloth knitted fabric (test cloth (1)) (2) polyester, cotton blended spinning (blending ratio 60:40) 3
Tenjiku-maru knitted fabric using No. 0 yarn (test cloth (2)) (3) 100% polyester Tenjiku-maru knitted fabric using No. 30 yarn (test cloth (3))
【0044】処方 キトサン乳酸塩* 0.5重量% 乳酸亜鉛 0.3重量% * 脱アセチル化度80%のキトサンの乳酸(48%水
溶液)1:1溶液Prescription Chitosan Lactate * 0.5% by weight Zinc lactate 0.3% by weight * 1: 1 solution of chitosan lactic acid (48% aqueous solution) with a deacetylation degree of 80%
【0045】なお、比較例1として試験布B(2)を用
い、キトサン乳酸塩0.5重量%のみの処方、及び比較
例2として乳酸亜鉛0.3重量%のみの処方によって実
施例1と同様に処理を行った。As Comparative Example 1, test cloth B (2) was used, and as Comparative Example 2, only 0.5% by weight of chitosan lactate was prepared, and as Comparative Example 2, 0.3% by weight of zinc lactate was prepared. The same process was performed.
【0046】得られた処理布について、抗菌性、耐洗濯
性、保湿性、pHバランス性を測定した。その結果は、
表1及び表2のとおりである。また各試験布とも着色は
なかった。With respect to the obtained treated cloth, antibacterial property, washing resistance, moisturizing property and pH balance property were measured. The result is
It is as shown in Table 1 and Table 2. Further, each test cloth was not colored.
【表1】 [Table 1]
【0047】[0047]
【表2】 [Table 2]
【0048】また試験布をpHが4,5,8,11の液
の各々に浸して、浴から取出し、30分後の試料布のp
Hを測ったが、pHは7付近でpHバランスが良好であ
ることが分かった。Further, the test cloth was dipped in each of the solutions having pHs of 4, 5, 8 and 11 and taken out from the bath.
When H was measured, it was found that the pH balance was good when the pH was around 7.
【0049】実施例2 下記3種の試験布を、常法に従って各々精練、過酸化水
素漂白した。次に、一部をそのまま残し(以下、試験布
(B)という)、他の漂白布に高周波コロナ放電処理
(発生器:発生周波数20kHz,交流100V)を施
した。上記3種の試験布(A)及び3種の試験布(B)
を、次の処方の処理液によってパッディング処理(絞り
率100%)し、100℃で2分間乾燥し、120℃で
2分間熱処理した。Example 2 The following three kinds of test cloths were scoured and bleached with hydrogen peroxide according to a conventional method. Next, a part of the cloth was left as it is (hereinafter referred to as test cloth (B)), and the other bleached cloth was subjected to high-frequency corona discharge treatment (generator: generation frequency 20 kHz, AC 100 V). The above 3 kinds of test cloths (A) and 3 kinds of test cloths (B)
Was subjected to a padding treatment (squeezing ratio: 100%) with a treatment liquid having the following formulation, dried at 100 ° C. for 2 minutes, and heat-treated at 120 ° C. for 2 minutes.
【0050】試験布 (1) 30番手の綿糸使い天竺組織編布(試験布
(4)) (2) ポリエステル長繊維、綿繊維複合糸使い天竺丸
編布(試験布(5)) (3) ポリエステル100%30番手紡績糸使い天竺
丸編布(試験布(6))Test cloth (1) 30th count cotton thread using a plain cloth knitted fabric (test cloth (4)) (2) Polyester filament, cotton fiber composite thread using a plain cloth circular knit cloth (test cloth (5)) (3) Tenjiku circular knitted fabric with 100% polyester and 30th spun yarn (test cloth (6))
【0051】 処方 第1パッド浴 乳酸カルシウム 1.0重量% 第2パッド浴 キトサン乳酸塩* 0.5重量% * 脱アセチル化度50%のキトサンの乳酸(48%水溶液)1:1溶液Prescription 1st pad bath Calcium lactate 1.0% by weight 2nd pad bath Chitosan lactate * 0.5% by weight * 1: 1 lactic acid (48% aqueous solution) solution of chitosan with 50% deacetylation degree
【0052】更に試験布(5)を用い、乳酸カルシウム
1.0重量%とキトサン乳酸塩0.5重量%とを含む浴
で1浴パッディング処理をした例についても行った。Further, the test cloth (5) was subjected to a one-bath padding treatment in a bath containing 1.0% by weight of calcium lactate and 0.5% by weight of chitosan lactate.
【0053】得られた処理布について抗菌性、耐洗濯
性、保湿性を測定した結果は表3、表4のとおりであ
る。なお、各試験布とも着色はなかった。Tables 3 and 4 show the results obtained by measuring the antibacterial property, the washing resistance and the moisturizing property of the obtained treated cloth. In addition, each test cloth was not colored.
【0054】[0054]
【表3】 [Table 3]
【0055】[0055]
【表4】 [Table 4]
【0056】表3、表4の結果から明らかなように、抗
菌性、保湿性、紫外線遮断性のいずれにおいても優れた
耐久性が見られた。特にコロナ放電処理により酸化層を
形成させた試験布Aについては、各測定項目の洗濯耐久
性が極めて優れていることがわかる。また各試験布とも
着色はなかった。As is clear from the results of Tables 3 and 4, excellent durability was observed in all of antibacterial properties, moisturizing properties and ultraviolet blocking properties. In particular, it is understood that the test cloth A having the oxide layer formed by the corona discharge treatment has extremely excellent washing durability in each measurement item. Further, each test cloth was not colored.
【0057】実施例3 実施例1で使用した試験布A3種類及び試験布B3種類
を用い、各々を次の処方の処理液でパッディング処理し
(絞り率100%)、100℃で2分間乾燥し、120
℃で2分間熱処理した。 処方 キトサン酢酸塩* 0.5重量% 酢酸アルミニウム 1.0重量% * 脱アセチル化度50%のキトサンの酢酸(48%)
1:1溶液Example 3 Using 3 kinds of test cloth A and 3 kinds of test cloth B used in Example 1, each was padded with a processing solution having the following formulation (squeezing ratio 100%) and dried at 100 ° C. for 2 minutes. Then 120
It heat-processed at 2 degreeC for 2 minutes. Prescription Chitosan acetate * 0.5% by weight Aluminum acetate 1.0% by weight * Acetate of chitosan with 48% deacetylation (48%)
1: 1 solution
【0058】なお、比較例3として試験布(2)を用
い、キトサン酢酸塩0.5重量%のみの処方、及び比較
例4として酢酸アルミニウム1.0重量%のみの処方に
よって実施例1と同様に処理を行った。Similar to Example 1, the test cloth (2) was used as Comparative Example 3 and the formulation of only chitosan acetate of 0.5% by weight and the formulation of Comparative Example 4 of 1.0% by weight of aluminum acetate were used. Was processed.
【0059】得られた処理布について、抗菌性、耐洗濯
性を測定した。その結果は、下記表5のとおりであり、
優れた耐洗濯性を示すことが分かる。特に紫外線照射処
理を施した試験布は特に優秀な耐洗濯性を示している。Antibacterial properties and washing resistance of the obtained treated cloth were measured. The results are shown in Table 5 below.
It can be seen that it exhibits excellent wash resistance. In particular, the test cloth which has been subjected to the ultraviolet irradiation treatment shows particularly excellent wash resistance.
【0060】[0060]
【表5】 [Table 5]
【0061】実施例4 実施例1で使用した試験布A3種類及び試験布B3種類
を用い、各々を次の処方の処理液でパッディング(絞り
率100%)処理し、100℃で2分間乾燥し、120
℃で2分間熱処理した。 処方 キトサン酢酸塩* 0.5重量% 酢酸マグネシウム 0.3重量% * 脱アセチル化度50%のキトサンの酢酸(48%)
1:1溶液Example 4 Using 3 kinds of test cloth A and 3 kinds of test cloth B used in Example 1, each was padded with a treatment liquid having the following formulation (squeeze ratio 100%) and dried at 100 ° C. for 2 minutes. Then 120
It heat-processed at 2 degreeC for 2 minutes. Prescription Chitosan acetate * 0.5% by weight Magnesium acetate 0.3% by weight * Acetate of chitosan (48%) with 50% deacetylation degree
1: 1 solution
【0062】なお、比較例5として試験布(8)を用
い、キトサン酢酸塩0.5重量%のみの処方、及び比較
例6として酢酸マグネシウム1.0重量%のみの処方に
よって実施例1と同様に処理を行った。As Comparative Example 5, the test cloth (8) was used, and the same procedure as in Example 1 was carried out except that only 0.5% by weight of chitosan acetate was used and Comparative Example 6 was 1.0% by weight of magnesium acetate. Was processed.
【0063】得られた処理布について、抗菌性、耐洗濯
性を測定した。その結果は、表6のとおりであって、先
の実施例と同じく特に紫外線照射処理をしたものが優れ
た耐洗濯性を示すことが分かる。また各試験布とも着色
はなかった。The antibacterial property and the washing resistance of the obtained treated cloth were measured. The results are shown in Table 6, and it can be seen that particularly those subjected to the ultraviolet irradiation treatment, as in the previous example, exhibit excellent wash resistance. Further, each test cloth was not colored.
【0064】[0064]
【表6】 [Table 6]
【0065】[0065]
【発明の効果】実施例で示したように、本発明の繊維製
品は、着色がなく、耐洗濯性が優れた抗菌性を示し、特
に酸化層を設けた繊維製品では、更に卓越した耐洗濯性
のある抗菌性が得られる。As shown in the examples, the textile products of the present invention are not colored and exhibit excellent anti-bacterial properties with excellent washing resistance. Particularly, the textile products provided with an oxidation layer have more excellent washing resistance. Antibacterial properties are obtained.
Claims (9)
維製品であって、カルシウム、亜鉛、マグネシウム、及
びアルミニウムよりなる群から選択された少くとも1種
の金属の水溶性塩とキトサンを必須成分とする混合物も
しくは複合体が、該繊維製品に対してキトサン含有率と
して0.01重量%〜7重量%、水溶性金属塩の金属換
算含有率として0.02重量%〜3重量%含有されてい
ることを特徴とする抗菌性繊維製品。1. A fiber product containing hydrophilic or hydrophobic fibers, wherein a chitosan and a water-soluble salt of at least one metal selected from the group consisting of calcium, zinc, magnesium, and aluminum are essential components. And a mixture or complex containing 0.01 to 7% by weight as a chitosan content and 0.02 to 3% by weight as a metal-equivalent content of a water-soluble metal salt in the fiber product. An antibacterial textile product characterized by
維製品を構成する繊維の表面が酸化層となっていること
を特徴とする請求項1記載の抗菌性繊維製品。2. The antibacterial fiber product according to claim 1, wherein the surface of the fiber forming the fiber product containing the hydrophilic fiber or the hydrophobic fiber is an oxidized layer.
しくは2記載の抗菌性繊維製品。3. The antibacterial fiber product according to claim 1, wherein the fiber product contains a hydrophobic fiber.
求項1ないし3記載の抗菌性繊維製品。4. The antibacterial fiber product according to claim 1, wherein the oxide layer is formed by physical treatment.
もしくは紫外線照射によるものである請求項1ないし4
記載の抗菌性繊維製品。5. The oxide layer is formed by corona discharge treatment, plasma treatment or ultraviolet irradiation.
The described antibacterial textile product.
維製品にカルシウム、亜鉛、マグネシウム及びアルミニ
ウムよりなる群から選択された少くとも1種の金属の水
溶性塩とキトサンを、水系媒体中で、該繊維製品に対し
てキトサン含有率として0.01重量%〜7重量%、水
溶性金属塩の金属換算含有率として0.02重量%〜3
重量%含有されるように、上記繊維製品に付与し、繊維
上に該水溶性金属塩とキトサンの複合体を形成すること
を特徴とする抗菌性繊維製品の製造法。6. A water-soluble salt of at least one metal selected from the group consisting of calcium, zinc, magnesium and aluminum and chitosan are added to a fiber product containing hydrophilic fibers or hydrophobic fibers in an aqueous medium, The content of chitosan in the fiber product is 0.01% to 7% by weight, and the content of the water-soluble metal salt in terms of metal is 0.02% to 3% by weight.
A method for producing an antibacterial fiber product, which comprises adding to the above-mentioned fiber product so as to contain it in a weight percentage and forming a complex of the water-soluble metal salt and chitosan on the fiber.
しくは疎水性繊維を含む繊維製品に付与するに先立っ
て、該繊維製品に酸化処理を施すことを特徴とする請求
項6記載の抗菌性繊維製品の製造法。7. The antibacterial property according to claim 6, wherein the fiber product is subjected to an oxidation treatment before the water-soluble metal salt and chitosan are applied to the fiber product containing hydrophilic fibers or hydrophobic fibers. Textile manufacturing method.
しくは7記載の抗菌性繊維製品の製造法。8. The method for producing an antibacterial fiber product according to claim 6, wherein the oxidation treatment is a physical treatment.
理もしくは紫外線照射処理である請求項6ないし8記載
の抗菌性繊維製品の製造法。9. The method for producing an antibacterial fiber product according to claim 6, wherein the oxidation treatment is corona discharge treatment, plasma treatment or ultraviolet irradiation treatment.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP22847795A JPH0949170A (en) | 1995-08-01 | 1995-08-01 | Antimicrobial textile product and its production |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP22847795A JPH0949170A (en) | 1995-08-01 | 1995-08-01 | Antimicrobial textile product and its production |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0949170A true JPH0949170A (en) | 1997-02-18 |
Family
ID=16877091
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP22847795A Pending JPH0949170A (en) | 1995-08-01 | 1995-08-01 | Antimicrobial textile product and its production |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0949170A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001034897A1 (en) * | 1999-11-11 | 2001-05-17 | Moritoshi Co., Ltd. | Fiber-treating agent and fiber |
CN1085216C (en) * | 1999-09-23 | 2002-05-22 | 青岛海洋大学 | Alkaline aluminium salt of chitose |
CN115287897A (en) * | 2022-07-25 | 2022-11-04 | 武汉纺织大学 | Antibacterial finishing method for micro-nano silver loaded uncooked and bleached pure cotton non-woven fabric |
-
1995
- 1995-08-01 JP JP22847795A patent/JPH0949170A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1085216C (en) * | 1999-09-23 | 2002-05-22 | 青岛海洋大学 | Alkaline aluminium salt of chitose |
WO2001034897A1 (en) * | 1999-11-11 | 2001-05-17 | Moritoshi Co., Ltd. | Fiber-treating agent and fiber |
CN115287897A (en) * | 2022-07-25 | 2022-11-04 | 武汉纺织大学 | Antibacterial finishing method for micro-nano silver loaded uncooked and bleached pure cotton non-woven fabric |
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