JPS62162083A - Fixing of phthalocyanine derivative - Google Patents
Fixing of phthalocyanine derivativeInfo
- Publication number
- JPS62162083A JPS62162083A JP61003680A JP368086A JPS62162083A JP S62162083 A JPS62162083 A JP S62162083A JP 61003680 A JP61003680 A JP 61003680A JP 368086 A JP368086 A JP 368086A JP S62162083 A JPS62162083 A JP S62162083A
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- JP
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- Prior art keywords
- phthalocyanine
- derivative
- fixing
- acid
- phthalocyanine derivative
- Prior art date
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Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はパルプ、紙、繊維、織布、不織布等にフタロシ
アニン錯塩誘導体を高率に定着する方法及び得られた固
定化物に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for fixing a phthalocyanine complex salt derivative on pulp, paper, fiber, woven fabric, non-woven fabric, etc. at a high rate, and the resulting immobilized product.
（従来の技術）
フタロシアニンの鉄、コバルト、ニッケル、銅等との錯
塩のカルブキシル基、スルホン酸基を有する誘導体は、
例えば特開昭５６−６３３５５号公報のようにその触媒
作用あるいはその色相に着目してレーヨンあるいはパル
プ、繊維等の表面に担持させて、消臭材料あるいは着色
繊維として用いられている。(Prior art) Derivatives of complex salts of phthalocyanine with iron, cobalt, nickel, copper, etc. having carboxyl groups and sulfonic acid groups are
For example, as disclosed in Japanese Patent Application Laid-Open No. 56-63355, it is used as a deodorizing material or colored fiber by supporting it on the surface of rayon, pulp, fiber, etc., focusing on its catalytic action or its hue.
これらのフタロシアニン錯塩誘導体を担持させる方法と
しては従来、これらのフタロシアニン錯塩誘導体を苛性
アルカリ存在下にアルカリ金属塩の水溶液とし、これに
繊維等を浸漬した後、溶液を酸性にすることによシフタ
ロジアニン錯塩誘導体を繊維に定着する方法が知られて
いた。The conventional method for supporting these phthalocyanine complex salt derivatives is to make these phthalocyanine complex salt derivatives into an aqueous solution of an alkali metal salt in the presence of caustic alkali, immerse fibers, etc. in this solution, and then make the solution acidic. Methods of fixing derivatives to fibers were known.
例、特開昭５６−６３３５５号公報。For example, Japanese Patent Application Laid-open No. 56-63355.
（発明が解決しようとする問題点）
しかしながら、前記の定着方法では、繊維等に定着され
るフタロシアニン錯塩誘導体の量は、繊維に含浸され、
又は繊維の表面に存在するフタロシアニン錯塩誘導体水
溶液中に含まれるフタロシアニン錯塩誘導体が主体であ
るため、使用したフタロシアニン錯塩誘導体の一部分が
定着するのみであシ、他は残液中に沈澱物となシ、利用
されない。又、このような浸漬法による場合、フタロシ
アニン錯塩誘導体による消臭効果は主に繊維等の表面に
定着したものだけが有効であるため、全定着量の内有効
なものは比較的少ない。このように従来法では、フタロ
シアニン錯塩誘導体の定着率及び定着物の有効率が低く
、且これらに用いられるフタロシアニン錯塩誘導体は非
常に高価な物質であるため、実用的に著しい不利益を与
えているなどの欠点を有する。(Problems to be Solved by the Invention) However, in the fixing method described above, the amount of the phthalocyanine complex salt derivative fixed on the fiber etc.
Or, since the phthalocyanine complex salt derivative contained in the phthalocyanine complex salt derivative aqueous solution existing on the surface of the fiber is the main component, only a part of the phthalocyanine complex salt derivative used is fixed, and the rest becomes a precipitate in the residual liquid. , not used. Furthermore, in the case of such a dipping method, the deodorizing effect of the phthalocyanine complex salt derivative is mainly effective only when it is fixed on the surface of the fibers, etc., so that the effective amount of the phthalocyanine complex salt derivative is relatively small out of the total amount fixed. As described above, in the conventional method, the fixing rate of the phthalocyanine complex salt derivative and the effective rate of the fixed product are low, and the phthalocyanine complex salt derivative used in these methods is a very expensive substance, so it has a significant practical disadvantage. It has drawbacks such as:
（問題点を解決するための手段）
本発明者等はこれらの欠点を解決するため、鋭意検討し
た結果、フタロシアニン錯塩誘導体を定着させようとす
る担持用基材（以下、単に基材と略す。）表面にあらか
じめ、キトサン層を設けておくと、フタロシアニン錯塩
誘導体が該キトサン層を介して基材に極めて高率に定着
することを見い出し本発明に到達したものである。(Means for Solving the Problems) In order to solve these drawbacks, the inventors of the present invention have made extensive studies and have developed a supporting substrate (hereinafter simply referred to as the substrate) on which the phthalocyanine complex salt derivative is to be fixed. ) The present invention was achieved by discovering that if a chitosan layer is previously provided on the surface, the phthalocyanine complex salt derivative is fixed to the substrate at an extremely high rate via the chitosan layer.
すなわち、本発明は、基材表面にあらかじめキトサン層
を設けた後フタロシアニン錯塩誘導体分散液に浸漬する
かあるいは粉末状フタロシアニン誘導体と接触させるこ
とを沈着させた後、フタロシアニン錯塩誘導体の定着方
法及びフタロシアニン誘導体を定着せしめた担持体に関
する。That is, the present invention provides a method for fixing a phthalocyanine complex salt derivative, and a method for fixing a phthalocyanine complex salt derivative, in which a chitosan layer is previously provided on the surface of a base material, and then immersed in a phthalocyanine complex derivative dispersion liquid or brought into contact with a powdered phthalocyanine derivative. The present invention relates to a carrier on which is fixed.
本発明に用いられる基材としては、キトサンが定着し得
る素材であればいずれでも良く、例えばクララトノ９ル
プ、サルファイトノ母ルゾ等の木材ノ臂ルゾ等のノクル
グ、マニラ麻、ジーート等の麻、木綿、リンター、コウ
ゾ、ミツマタ等の繊維又はそのノ４’ Ａ／７’化物な
どのセルロース類、セルロースアセテ−）、ＣＭＣ等の
セルロース誘導体、植物ガム、海藻ガム、微生物ガム、
ポリビニルアルコール、ポリアクリル酸、ポリメタアク
リル酸の共重合体、ポリアクリロニトリル、ポリアミド
を含有する粉体、繊維状物、紙、不織布、織物、編物、
シート状物、フィルム状物等が挙けられるがこれらに限
定されるものではない。The base material used in the present invention may be any material as long as chitosan can be fixed on it, such as wood such as Claratono9lupe and Sulfite Tonoluzo, hemp such as Manila hemp, and jeeto; Celluloses such as cotton, linter, mulberry, and mulberry fibers or their 4'A/7' derivatives, cellulose acetate), cellulose derivatives such as CMC, vegetable gums, seaweed gums, microbial gums,
Powder, fibrous material, paper, nonwoven fabric, woven fabric, knitted fabric containing polyvinyl alcohol, polyacrylic acid, polymethacrylic acid copolymer, polyacrylonitrile, polyamide,
Examples include, but are not limited to, sheet-like materials and film-like materials.
又、本発明に用いられるキトサンはキチンを脱アセチル
化することにより得られる塩基性多糖類物質であシ、通
常入手されるグレード品で良い。Furthermore, the chitosan used in the present invention is a basic polysaccharide substance obtained by deacetylating chitin, and any commonly available grade product may be used.
又、本発明に用いられるフタロシアニン・金属錯塩誘導
体としては、フタロシアニンの鉄、コバルト、ニッケル
、クロム、銅、亜鉛、白金、ツヤラジウム、バナジウム
錯塩等の酸に対しても安定な錯塩のカルゲン酸基、スル
ホン酸基を導入したものが挙けられ、中でも例えば鉄フ
タロシアニン、オクタカルデン酸、コバルトフタロシア
ニンオフタカルデン酸、ニッケルフタロシアニンオクタ
カルボン酸、銅フタロシアニンオクタカル？ン酸、鉄フ
タロシアニンテトラスルホン酸、コバルトフタロシアニ
ンテトラスルホン酸、ニッケルフタロシアニンテトラス
ルホン酸、鋼フタロシアニンテトラスルホン酸等が好適
に用いられる。In addition, the phthalocyanine/metal complex salt derivatives used in the present invention include the calgenic acid group of complex salts of phthalocyanine that are stable against acids such as iron, cobalt, nickel, chromium, copper, zinc, platinum, glossy radium, and vanadium complex salts; Examples include those with a sulfonic acid group introduced, such as iron phthalocyanine, octacaldic acid, cobalt phthalocyanine octacardic acid, nickel phthalocyanine octacarboxylic acid, and copper phthalocyanine octacaldic acid. Preferred examples include iron phthalocyanine tetrasulfonic acid, cobalt phthalocyanine tetrasulfonic acid, nickel phthalocyanine tetrasulfonic acid, and steel phthalocyanine tetrasulfonic acid.
以下に本発明のフタロシアニン錯塩誘導体の定着方法に
ついて説明する。The method for fixing the phthalocyanine complex salt derivative of the present invention will be explained below.
キトサンを酢酸、塩酸等の酸の存在下に所定量の水に溶
解したキトサン水溶液に基材を浸漬した後苛性カリ等の
苛性アルカリを加えて、−を７．５〜１０．０．好まし
くは７．５〜８．５程度に調節する。After immersing the base material in a chitosan aqueous solution prepared by dissolving chitosan in a predetermined amount of water in the presence of an acid such as acetic acid or hydrochloric acid, a caustic alkali such as caustic potash is added, and -7.5 to 10.0. Preferably it is adjusted to about 7.5 to 8.5.
これによシキトサンは基材表面に高率に沈着される。使
用するキトサンの量は、基材の量、形状及び定着すべき
フタロシアニン錯塩誘導体の量によシ任意に決定される
が、例えば基材がパルプの場合、その重量に対し５％以
下で十分である。As a result, cychitosan is deposited on the surface of the substrate at a high rate. The amount of chitosan to be used is arbitrarily determined depending on the amount and shape of the substrate and the amount of the phthalocyanine complex salt derivative to be fixed, but for example, if the substrate is pulp, 5% or less of the weight of the substrate is sufficient. be.
次イでこの浸漬液に所定量のフタロシアニン錯塩誘導体
粉末あるいは若干の水を加えた水分散液として添加し、
基材と混合径長時間、例えば１〜１６時間放置する。Next, add a predetermined amount of phthalocyanine complex salt derivative powder or an aqueous dispersion with a small amount of water to this immersion liquid,
The base material and the mixed diameter are left for a long time, for example, 1 to 16 hours.
フタロシアニン錯塩誘導体の童は、基材の量、形状及び
目的とする用途により任意に決定されるが例えば基材が
１？ルゾの場合基材重量の１％程度以下で十分である。The size of the phthalocyanine complex derivative is arbitrarily determined depending on the amount, shape, and intended use of the base material, but for example, if the base material is 1? In the case of Luso, about 1% or less of the weight of the base material is sufficient.
フタロシアニン誘導体が基材表面への担持が終了した基
材（以下単に固定化物という）は、水、好ましくはイオ
ン交換水のような不純物の少ない水で水洗した後希望の
程度逸脱水・乾燥する。The substrate on which the phthalocyanine derivative has been supported on the surface of the substrate (hereinafter simply referred to as an immobilized product) is washed with water, preferably water with few impurities such as ion-exchanged water, and then dried to a desired degree.
（実施例）
以下に実施例により具体的に説明するが、本発明はこれ
らに限定されるものではない。(Example) The present invention will be specifically explained below using Examples, but the present invention is not limited thereto.
尚、本実施例の中で用い几フタロシアニン錯塩誘導体の
定着量及び固定化物の消臭活性の評価は以下の方法によ
った。The amount of fixed phthalocyanine complex salt derivative used in this example and the deodorizing activity of the immobilized product were evaluated by the following method.
（１） フタロシアニン錯塩誘導体の定着量の測定法
まず、０．０ Ｉ Ｎ苛性カリ水溶液１００ＴＬｌ及び
これにフタロシアニン錯塩誘導体を１即溶解し。(1) Method for measuring the amount of fixed phthalocyanine complex salt derivative First, 100 TLl of a 0.0 IN caustic potassium aqueous solution and the phthalocyanine complex salt derivative were immediately dissolved therein.
それぞれの溶液について原子吸光法によるそれぞれの錯
体を構成している金属の量を定量して検量線を求め、各
サンプルに付着している量は上記と同じ方法で苛性カリ
水溶液に溶解してその金属量から算出した。A calibration curve was obtained by quantifying the amount of metals constituting each complex using atomic absorption spectroscopy for each solution. Calculated from the amount.
（２）臭気ガス減少効果測定方法（気相法）基材にフタ
ロシアニン錯塩誘導体を定着した固定化物１．０ｇを長
さ８０鯨、内径１５１１の試料管にほぼ均一に充填し、
その一端のガス導入口より所定濃度の臭気ガスを含有す
る空気を５ノを導入し、他端の出口よシ出た空気を空の
空気袋に収容した。この空気袋中の空気の臭気ガス濃度
を測定し、この処理前後の臭気ガス濃度差を臭気ガス減
少効果とした。(2) Method for measuring odor gas reduction effect (gas phase method) Fill a sample tube with a length of 80 mm and an inner diameter of 1511 mm approximately uniformly with 1.0 g of an immobilized substance in which a phthalocyanine complex salt derivative is fixed on a base material.
Five volumes of air containing a predetermined concentration of odor gas were introduced through the gas inlet at one end, and the air coming out through the outlet at the other end was stored in an empty air bag. The odor gas concentration of the air in this air bag was measured, and the odor gas concentration difference before and after this treatment was defined as the odor gas reduction effect.
（３）臭気ガス、減少効果測定方法（水溶液法）基材に
フタロシアニン錯塩誘導体を定着した担持体１． Ｏｇ
を所定濃度の臭気ガスを溶解している水溶液１１に分散
し、ゆっくシ攪拌しながら５時間放置した後、水溶液内
の臭気ガス濃度を測定し、処理前後の臭気ガス濃度差を
臭気ガス減少効果とした。(3) Method for measuring odor gas reduction effect (aqueous solution method) Support with phthalocyanine complex salt derivative fixed on the base material 1. Og
is dispersed in an aqueous solution 11 in which a predetermined concentration of odor gas is dissolved, and left to stand for 5 hours while stirring slowly.The odor gas concentration in the aqueous solution is measured, and the odor gas concentration difference before and after treatment is calculated as odor gas reduction. It was considered an effect.
実施例１
キトサン１重量％、酢酸１重量％を含有する水溶液２０
０．９’ｅよくほぐしたＮＢＫＰ （針葉樹材クラフト
パルプ） １００．９に加え、系が均一状になるまでよ
く混練した後、１重量％苛性カリ水溶液２７０１！を加
えて系を弱アルカリ性として更に攪拌した。次いで微粉
末状の鉄フタロシアニンオクタカルがン酸０，２Ｉを添
加し、更に酢酸を加え−を８６５に調整した後、更に４
時間攪拌した。Example 1 Aqueous solution 20 containing 1% by weight of chitosan and 1% by weight of acetic acid
In addition to 0.9'e well loosened NBKP (softwood kraft pulp) 100.9, after kneading well until the system becomes homogeneous, add 1% by weight caustic potassium aqueous solution 2701! was added to make the system slightly alkaline and further stirred. Next, fine powdered iron phthalocyanine octacal was added with 0.2I of phosphoric acid, and then acetic acid was added to adjust the temperature to 865, and then 4
Stir for hours.
この後パルプをｒ別し、脱水後、１１の水で洗浄し、６
“０℃に調節した通風乾燥機によシ１４時間乾燥してパ
ルプ上鉄フタロシアニンオクタカルデン酸の固定化物を
得た。After that, the pulp was separated, dehydrated, washed with water in step 11, and washed with water in step 6.
The product was dried for 14 hours in a ventilation dryer adjusted to 0°C to obtain an immobilized product of iron phthalocyanine octacardic acid on pulp.
この固定化物５！ｉをとって、鉄フタロシアニンオクタ
カルボン酸付着量を測定したところ、０．１９５チであ
った。This immobilized object 5! When i was taken and the amount of iron phthalocyanine octacarboxylic acid deposited was measured, it was 0.195 h.
このパルプ１．９’にとり、前記臭気ガス減少効果測定
方法（気相法）Ｖｒ−よシ硫化水素ガス減少効果を測定
した。Using this pulp 1.9', the effect of reducing hydrogen sulfide gas was measured using the aforementioned method for measuring the effect of reducing odor gas (vapor phase method).
以上の結果を別表１に示した。The above results are shown in Attached Table 1.
実施例２〜４
実施例１で得られたパルプを用いて臭気ガス減少効果測
定方法（水溶液法）によシそれぞれ、メチルメルカプタ
ン、ホルマリン、二硫化水素について臭気ガス減少効果
を測定し、その結果を別表１に示した。Examples 2 to 4 Using the pulp obtained in Example 1, the odor gas reduction effect was measured for methyl mercaptan, formalin, and hydrogen disulfide using a method for measuring odor gas reduction effect (aqueous solution method), and the results were are shown in Attached Table 1.
実施例５〜９
キトサン１．５重量％、酢酸１．０重量％を含有する水
溶液２００ｇを、よく水洗し、解繊した別表１に示した
繊維１００９に添加して系が均一になる迄混練し、次い
で１重量％苛性カリ水溶液２７０ｙを加えて系を弱アル
カリ性とし、次いでそれぞれ別表１に示した種類及び童
の粉末状フタロシアニン錯塩誘導体を５ ｃｃの水に分
散した状態で添加し、更に別表１に示した−に調整した
後、静かに攪拌しながら放置した。次いで実施例１と同
様にして、繊維をＦ別し、水洗・乾燥してそれぞれ、フ
タロシアニン錯体誘導体の担持体を得た。Examples 5 to 9 200 g of an aqueous solution containing 1.5% by weight of chitosan and 1.0% by weight of acetic acid was added to the well-washed and defibrated fiber 1009 shown in Attached Table 1, and kneaded until the system became uniform. Then, 270 y of a 1% by weight aqueous potassium hydroxide solution was added to make the system weakly alkaline, and then powdered phthalocyanine complex salt derivatives of the types and types shown in Attached Table 1 were added in a dispersed state in 5 cc of water. After adjusting to - as shown in , it was left to stand while being gently stirred. Next, in the same manner as in Example 1, the fibers were separated by F, washed with water, and dried to obtain carriers of phthalocyanine complex derivatives.
コレラの担持体についてそれぞれフタロシアニン錯体誘
導体の付着量、それらによる二硫化水素ガスの減少効果
を測定した。The amount of phthalocyanine complex derivatives attached to each cholera carrier and their effect on reducing hydrogen disulfide gas were measured.
以上の処理条件及び測定結果を別表１に示した。The above processing conditions and measurement results are shown in Attached Table 1.
比較例１
水２００ｄに水酸化カリウム７２０■、鉄フタロシアニ
ン錯塩オクタカルぎン酸１．０６．ｌｉ＋を加えて溶解
し、この水溶液に実施例１と同じパルプ７００７Ｑの鉄
フタロシアニン錯塩オクタカルボン酸が含まれていた。Comparative Example 1 200 d of water, 720 ml of potassium hydroxide, 1.06 ml of iron phthalocyanine complex octacarginic acid. li+ was added and dissolved, and this aqueous solution contained the same iron phthalocyanine complex salt octacarboxylic acid of pulp 7007Q as in Example 1.
これに０．０２規定濃度の塩酸水溶液４００１１／’ｉ
加えて１時間放置した。声は約１．７であった。Add to this a 0.02 normal concentration hydrochloric acid aqueous solution 40011/'i
In addition, it was left to stand for 1 hour. The voice was about 1.7.
次いでこの塩酸水浸漬浴よりｒ別して湿潤ノ９ルプ６７
．３ ｆｉを得た。この湿潤ノ９ルゾを６０℃で通風乾
燥して乾燥した鉄フタロシアニン錯塩オクタカルがン酸
固定化物１９．８．！ｉ’を得た。Then, from this hydrochloric acid water immersion bath, separate the water into a wet bath.
．． Got 3 fi. Iron phthalocyanine complex octacal acid fixed product 19.8. ! I got i'.
得られた固定化物について実施例１と同様にしてフタロ
シアニン錯塩オクタカルボン酸付着量及び二硫化水素ガ
ス減少効果を測定した。Regarding the obtained immobilized product, the amount of attached phthalocyanine complex octacarboxylic acid and the hydrogen disulfide gas reduction effect were measured in the same manner as in Example 1.
以上の処理条件及び測定結果を別表１に示した。The above processing conditions and measurement results are shown in Attached Table 1.
実施例１０
実施例１と全く同様にして作製した鉄７りロシアニンオ
クタカルデン酸固定化ノＪ？ルゾ３０部と、未処理のカ
ットレーヨン（３ｄＸ５ｍｍ長）とを混合し、湿式抄紙
法によシ坪量３０ｇ／ｍ”の混抄紙を作製した。この混
抄紙から巾６０朋の短冊全作シ、合せて長さ３ｍ分を長
さ６０ｍｘ、外径１４ｍ＋！になるように棒状にほぼ均
一に巻き、これを前記の臭気ガス減少効果測定法（気相
法）の試料管に充填し、その他は前記の測定法（気相法
）に従がい、実施例１と同様にして硫化水素ガスの減少
効果を測定した。Example 10 Iron-7 lycyanine octacaldic acid-immobilized J? produced in exactly the same manner as in Example 1. 30 parts of Ruso and untreated cut rayon (3d x 5mm length) were mixed to make a mixed paper with a basis weight of 30g/m'' by a wet papermaking method.From this mixed paper, a complete strip of paper with a width of 60mm was made. , Wrap the total length of 3 m almost uniformly into a rod shape so that the length is 60 m x and the outer diameter is 14 m +!, and fill it into the sample tube of the above-mentioned odor gas reduction effect measurement method (gas phase method), etc. The effect of reducing hydrogen sulfide gas was measured in the same manner as in Example 1 according to the measurement method described above (gas phase method).
その結果を表２に示した。The results are shown in Table 2.
実施例１１
鉄フタロシアニン錯クタカルデン酸の添加ｉｔＯ，１８
ｇとした他は実施例１と全く同様にしてＮＢＫＰの鉄フ
タロシアニンオクタカルがン酸固定化物を作成した。こ
のパルプの鉄フタロシアニンオクタカルがン酸の付着量
は０．０５７ ％であった。Example 11 Addition of iron phthalocyanine complex cutacardic acid itO,18
A product of iron phthalocyanine octacal acid immobilized with NBKP was prepared in exactly the same manner as in Example 1, except that g was used. The amount of iron phthalocyanine octacarboxylic acid deposited on this pulp was 0.057%.
このノクルｆを用いて実施例１０と同様にして坪量３０
ｇ／ｍ２のパルプ紙を作成し、硫化水素ガス減少効果（
気相法〕を測定した。Using this nockle f, the basis weight was 30 in the same manner as in Example 10.
g/m2 pulp paper with hydrogen sulfide gas reduction effect (
[vapor phase method] was used.
その結果を表２に示した。The results are shown in Table 2.
実施例１２
カットレーヨン（３ｄＸ３８朋長）を用いたレーヨン糸
３０／１ ’に用いて編織した目付３０，９／ｍ２の編
地５０ｇを折たたみ、キトサン１重量％、酢酸１重量％
ヲ含有する水溶液１００ｇに浸漬し、圧搾、含浸を繰フ
返した後、浸漬浴中に苛性カリ１チ水溶液１３５ｇを加
え再び圧搾・含浸を繰り返した。次いで微粉状鉄７りロ
シアニンオクタカルぎン酸０．０９Ｆ’ｔ−添加し、更
に酢酸を加えｐＨ’に８、５ Ｋ調整した後、再び編地
の圧搾・含浸全２０回繰返した。Example 12 50 g of knitted fabric with a fabric weight of 30.9/m2 knitted using rayon yarn 30/1' using cut rayon (3dX38 Tomocho) was folded, and 1% by weight of chitosan and 1% by weight of acetic acid were added.
After immersing the sample in 100 g of an aqueous solution containing 100 g of water, squeezing and impregnating were repeated, 135 g of a caustic potash 1-trich aqueous solution was added to the immersion bath, and the squeezing and impregnating were repeated again. Next, 0.09 F't of pulverized iron 7 and cyanine octacarginic acid was added, and acetic acid was further added to adjust the pH to 8.5 K, and the knitted fabric was again compressed and impregnated 20 times.
この後、編地を圧搾ロールで脱水し、更に水洗した後、
６０℃に調節した通風乾燥機によシ乾燥した。After this, the knitted fabric was dehydrated with a pressure roll, and then washed with water.
It was dried in a ventilation dryer adjusted to 60°C.
得られた編地（鉄フタロシアニンオクタカルデン酸固定
化物）の鉄フタロシアニンオクタカルぎン酸の付着量は
０．０５４％であった。The amount of iron phthalocyanine octacarginic acid adhered to the obtained knitted fabric (iron phthalocyanine octacardic acid fixed product) was 0.054%.
この絹地を用いて実施例１０と同様にして硫化水素ガス
の減少効果を測定した。Using this silk fabric, the effect of reducing hydrogen sulfide gas was measured in the same manner as in Example 10.
その結果を表２に示した。The results are shown in Table 2.
（作用及び効果）
以上の方法のように、本発明においては、繊維等の担体
の表面に７タロシアニン錯塩誘導体を定着させる際、あ
らかじめ担体の表面にキトサン被覆を設けであるため、
きわめて高価なフタロシアニン錯塩誘導体がキトサン被
覆表面に選択的に沈着されるため、沈着後の残浴中の７
タロシアニン錯塩誘導体は殆んど残らず、定着率は著し
く高く、経済的に有利である。(Functions and Effects) As in the above method, in the present invention, when fixing the 7-talocyanine complex salt derivative on the surface of a carrier such as fiber, the surface of the carrier is coated with chitosan in advance.
Because the extremely expensive phthalocyanine complex salt derivative is selectively deposited on the chitosan-coated surface, the
Almost no talocyanine complex salt derivative remains, the fixation rate is extremely high, and it is economically advantageous.
又、本発明の方法で得られた７タロシアニン錯塩誘導体
の固定化物を消臭剤として用いる場合、従来技術である
比較例１の場合に比べ、定着量が少いにもかかわらず臭
気ガス減少効果は著しく高いことがわかる。Furthermore, when the immobilized product of the 7-thalocyanine complex salt derivative obtained by the method of the present invention is used as a deodorant, the effect of reducing odor gas is lower than that of Comparative Example 1, which is the conventional technology, despite the smaller amount of fixation. is found to be significantly high.
又、本発明の定着方法によって得られる固定化物はその
固定が堅牢であるため、例えば固定化繊維状物は、その
後加工として抄紙、紡績、絨布工程によってもフタロシ
アニン錯塩誘導体が脱落しないため、固定化物又は固定
化物を一部含有して抄紙、紡績、織布等の加工を行なっ
ても、すぐれた消臭効果を示す。In addition, since the immobilized product obtained by the fixing method of the present invention is firmly fixed, for example, the phthalocyanine complex salt derivative does not fall off from the immobilized fibrous material even during subsequent processing such as paper making, spinning, and carpet fabrication. Alternatively, even when a part of the immobilized product is contained and processed into paper making, spinning, weaving, etc., it exhibits an excellent deodorizing effect.
Claims (1)
後、フタロシアニン誘導体の粉末あるいは分散液と接触
させることを特徴とするフタロシアニン誘導体の定着方
法。 ２、フタロシアニン誘導体が金属フタロシアニンカルボ
ン酸誘導体であることを特徴とする特許請求の範囲第１
項のフタロシアニン誘導体の定着方法。 ３、担持用基材をキトサンの酸性水溶液に浸漬した後、
液を弱アルカリ性にすることにより担持用基材表面にキ
トサンを沈着させることを特徴とする特許請求の範囲第
１項のフタロシアニン誘導体の定着方法。 ４、担持用基材がセルロースあるいはその誘導体又はポ
リビニルアルコールあるいはその誘導体から成ることを
特徴とする特許請求の範囲第１項のフタロシアニン誘導
体の定着方法。 ５、フタロシアニン誘導体分散液をｐＨ＝７〜９に設定
することを特徴とする特許請求の範囲第一項のフタロシ
アニン誘導体の定着方法。 ６、担持用基材表面にキトサン層を介してフタロシアニ
ン誘導体を定着せしめたフタロシアニン誘導体の固定化
物。[Claims] 1. A method for fixing a phthalocyanine derivative, which comprises depositing chitosan on the surface of a supporting substrate in advance and then contacting the surface with a powder or dispersion of the phthalocyanine derivative. 2. Claim 1 characterized in that the phthalocyanine derivative is a metal phthalocyanine carboxylic acid derivative
Method for fixing phthalocyanine derivatives. 3. After immersing the supporting base material in an acidic aqueous solution of chitosan,
A method for fixing a phthalocyanine derivative according to claim 1, characterized in that chitosan is deposited on the surface of a supporting substrate by making the liquid slightly alkaline. 4. The method for fixing a phthalocyanine derivative according to claim 1, wherein the supporting substrate is made of cellulose or a derivative thereof, or polyvinyl alcohol or a derivative thereof. 5. The method for fixing a phthalocyanine derivative according to claim 1, which comprises setting the pH of the phthalocyanine derivative dispersion to 7 to 9. 6. An immobilized product of a phthalocyanine derivative in which the phthalocyanine derivative is fixed on the surface of a supporting substrate via a chitosan layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61003680A JPH0635713B2 (en) | 1986-01-13 | 1986-01-13 | Method for fixing phthalocyanine derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61003680A JPH0635713B2 (en) | 1986-01-13 | 1986-01-13 | Method for fixing phthalocyanine derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62162083A true JPS62162083A (en) | 1987-07-17 |
| JPH0635713B2 JPH0635713B2 (en) | 1994-05-11 |
Family
ID=11564120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61003680A Expired - Lifetime JPH0635713B2 (en) | 1986-01-13 | 1986-01-13 | Method for fixing phthalocyanine derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0635713B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994012034A1 (en) * | 1992-12-01 | 1994-06-09 | Minnesota Mining And Manufacturing Company | Durable anti-microbial agents |
| JP2018071022A (en) * | 2016-10-31 | 2018-05-10 | ダイワボウホールディングス株式会社 | Fiber aggregate and manufacturing method thereof |
| CN108503726A (en) * | 2018-04-19 | 2018-09-07 | 福州大学 | A kind of phthalocyanine-chitosan oligosaccharide conjugate and the preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109160957B (en) * | 2018-07-03 | 2020-06-12 | 福州大学 | Zinc phthalocyanine-chitosan oligosaccharide conjugate and preparation method and application thereof |
-
1986
- 1986-01-13 JP JP61003680A patent/JPH0635713B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994012034A1 (en) * | 1992-12-01 | 1994-06-09 | Minnesota Mining And Manufacturing Company | Durable anti-microbial agents |
| CN1083693C (en) * | 1992-12-01 | 2002-05-01 | 明尼苏达州采矿和制造公司 | Durable antimicrobial agents |
| JP2018071022A (en) * | 2016-10-31 | 2018-05-10 | ダイワボウホールディングス株式会社 | Fiber aggregate and manufacturing method thereof |
| CN108503726A (en) * | 2018-04-19 | 2018-09-07 | 福州大学 | A kind of phthalocyanine-chitosan oligosaccharide conjugate and the preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0635713B2 (en) | 1994-05-11 |
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