JPH0324132A - Dyed silk fibroin powder and production thereof - Google Patents
Dyed silk fibroin powder and production thereofInfo
- Publication number
- JPH0324132A JPH0324132A JP1158548A JP15854889A JPH0324132A JP H0324132 A JPH0324132 A JP H0324132A JP 1158548 A JP1158548 A JP 1158548A JP 15854889 A JP15854889 A JP 15854889A JP H0324132 A JPH0324132 A JP H0324132A
- Authority
- JP
- Japan
- Prior art keywords
- silk fibroin
- fibroin powder
- dyed
- volatile organic
- dyeing
- 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.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 62
- 108010022355 Fibroins Proteins 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000004043 dyeing Methods 0.000 claims abstract description 21
- 239000010931 gold Substances 0.000 claims abstract description 18
- 229910052737 gold Inorganic materials 0.000 claims abstract description 18
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 2
- 238000007654 immersion Methods 0.000 abstract description 2
- 238000011161 development Methods 0.000 description 10
- 230000018109 developmental process Effects 0.000 description 10
- 239000000049 pigment Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- -1 copper-ethylene diane Chemical compound 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- HNMCSUXJLGGQFO-UHFFFAOYSA-N hexaaluminum;hexasodium;tetrathietane;hexasilicate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].S1SSS1.S1SSS1.[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] HNMCSUXJLGGQFO-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000009123 Fibrin Human genes 0.000 description 1
- 108010073385 Fibrin Proteins 0.000 description 1
- BWGVNKXGVNDBDI-UHFFFAOYSA-N Fibrin monomer Chemical compound CNC(=O)CNC(=O)CN BWGVNKXGVNDBDI-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241000220259 Raphanus Species 0.000 description 1
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- UHHXUPJJDHEMGX-UHFFFAOYSA-K azanium;manganese(3+);phosphonato phosphate Chemical compound [NH4+].[Mn+3].[O-]P([O-])(=O)OP([O-])([O-])=O UHHXUPJJDHEMGX-UHFFFAOYSA-K 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000012730 carminic acid Nutrition 0.000 description 1
- 239000004106 carminic acid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940080423 cochineal Drugs 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229950003499 fibrin Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 238000001155 isoelectric focusing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000010299 mechanically pulverizing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Peptides Or Proteins (AREA)
- Coloring (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
金コロイドで染色されていることを特徴とする染色絹フ
ィブロイン粉末とその製造方法に関する．更に詳しくは
発色性．耐光性，耐熱性に優れた顔料として用いること
のできる染色絹フィブロイン粉末とその製造方法に関す
る．
〔従来の技術と発明が解決しようとする課題〕＃料は、
化粧料，塗料などに使用されているが、従来は本発明で
得られるようなワインカラー（赤紫色）を単独で出せる
顔料は知られていない。ワインカラーを作るためには、
いくつかの顔料を混合Ｌ５て用いていた．従来の顔料の
中では本発明で得られる染色絹フィブ０インー粉末の色
であるワインカラーに比較的近い赤紫系統の顔料として
、無機間科ではウルトラマリンバイオレット（群青），
マンガンバイオレットが知られているが、酸・アルカリ
に対する化学的安定性が悪いというｙ点を有するもので
あった。また、有機顔料としては、天然系の紫根やコチ
ニールが知られでいるが、いずれも光や熱に対する安定
性が悪いという欠点を有するものであった。[Detailed Description of the Invention] [Industrial Application Field] This invention relates to a dyed silk fibroin powder characterized by being dyed with gold colloid and a method for producing the same. For more details, see color development. This article relates to a dyed silk fibroin powder that can be used as a pigment with excellent light resistance and heat resistance, and a method for producing the same. [Problems to be solved by conventional technology and invention]
Although it is used in cosmetics, paints, etc., there is no known pigment that can produce the wine color (reddish-purple) obtained by the present invention by itself. To create a wine color,
Several pigments were used in a mixture L5. Among conventional pigments, ultramarine violet (ulmarine), ultramarine violet,
Manganese violet is known, but it has a y point of poor chemical stability against acids and alkalis. Also, natural pigments such as purple root and cochineal are known as organic pigments, but both have the disadvantage of poor stability against light and heat.
一方、特開昭６ ２−２ ９ ９ ５ ８ ７には金ヒ
ドロゾルを用いて繊＃ａ威形物を紫色に染伯ずる技術が
開示されているが、織物，編物，不織布，紙および糸の
染色方法に限定されており、金ヒドｌ】ゾルを用いて粉
体を染イムし、ワインカラーの顔料を得る技術は確立さ
れていなかった．
本発明の目的は、発色がよく、耐熱性，耐光性等に優れ
た化学的安定性の良い染色絹フィブロイン粉末及びその
製造方法を提供することにある。On the other hand, Japanese Patent Application Laid-Open No. 62-29995-87 discloses a technique for dyeing textile #a ornaments purple using gold hydrosol, but it is not suitable for textiles, knitted fabrics, non-woven fabrics, paper and yarn. However, the technology for dyeing powder using gold hydride sol to obtain wine-colored pigments had not been established. An object of the present invention is to provide a dyed silk fibroin powder with good color development, excellent heat resistance, light resistance, etc., and good chemical stability, and a method for producing the same.
〔！１題を解決するための手段〕
本発明者らは、前述の問題点に鑑み、鋭意研究を電ねた
結果、絹フィブロイン粉末を陽イオン性界面活性剤を含
有する金ヒドロゾル中に浸漬し２、染色して得られた金
コロイドで染色されている染仏紐フィブロイン粉末が、
鮮やかな赤紫色（ワインカラー）を里すると同時に前述
問題点を解決することを見出し、またその製造方法を確
立して本発明を完威するに至った．
本発明は、金コロイドで染伯されていることを特徴とす
る染色絹フィブロイン粉東及びその製造方法である。[! Means for Solving Problem 1] In view of the above-mentioned problems, the present inventors have conducted extensive research and have found that silk fibroin powder is immersed in gold hydrosol containing a cationic surfactant. , Dyed Buddha String Fibroin Powder is dyed with gold colloid obtained by dyeing.
We have discovered that we can achieve a bright reddish-purple color (wine color) and at the same time solve the above-mentioned problems, and we have also established a manufacturing method and brought the present invention to fruition. The present invention is a dyed silk fibroin powder characterized by being dyed with gold colloid and a method for producing the same.
以下本発明の横戊について詳述する。The cross section of the present invention will be explained in detail below.
本発明に用いる紐フィブロイン粉末は一般に粉砕法や再
生法によって得られたもの等を用いる。The string fibroin powder used in the present invention is generally obtained by a pulverization method or a regeneration method.
粉砕法は天然の紐繊維を脱Ｄ後、アルカリ処理し、機械
的に粉砕する方法である．一方再生法は例えば銅一エチ
レンジアｌン水溶液、水酸化鋼、アンモニア水溶液、水
酸化銅−アルカリーグリセリン水溶液、臭化リチウム水
溶液、カルシウムあるいはマグネシウムまたは亜鉛の塩
化物あるいは硝酸塩またはチオシアン酸塩の水溶液、チ
オシアン酸ナトリウム水溶液よりなる群から選択された
少なくとも一種の溶媒に絹（フィブロイン）を溶解後、
透析して得た３〜２０重置％のフイプ口イン水溶液に凝
固性塩の混合，空気吹きこみ６等電点凝固，超音波処理
および速いずり変形速度で攬ｆｌ等の少なくとも一種の
方法により、フイブロインを凝固析出せしめ、次いで脱
水、乾燥後粉砕する方法であるよ
本発明には、上記製造方法による絹フイブロイン粉末の
いずれをも用いることができるが、純度が高く、形状や
粒度をコントロールしやすいという点において再生法に
よる紐フイプロイン粉末がより好ましい．
本発明に用いる絹フイブロイン粉末の粒度は特に限定さ
れないが、塗料等へ配合する染色絹フイブロイン粉末を
得るためには粉砕法．再生法いずれの方法による場合も
０． １ − ５ ０μの範囲にあるものを用いるのが
好ましく、１〜３０μの範囲にあるものが特に好ましい
。The pulverization method involves removing D from natural string fibers, treating them with alkali, and mechanically pulverizing them. On the other hand, regeneration methods include, for example, an aqueous solution of copper-ethylene diane, steel hydroxide, aqueous ammonia solution, aqueous copper hydroxide-alkaline glycerin solution, aqueous lithium bromide solution, aqueous solution of calcium, magnesium or zinc chloride, nitrate or thiocyanate, After dissolving silk (fibroin) in at least one solvent selected from the group consisting of sodium thiocyanate aqueous solution,
By at least one method such as mixing a coagulating salt with a 3 to 20% aqueous solution obtained by dialysis, blowing air, isoelectric focusing, ultrasonic treatment, and immersion at a high shear deformation rate. This method involves coagulating and precipitating fibroin, followed by dehydration, drying, and pulverization. In the present invention, any of the silk fibroin powders produced by the above manufacturing method can be used, but it is preferable to use silk fibroin powders that have high purity and can control the shape and particle size. String fiproin powder produced by the recycling method is more preferable because it is easy to use. The particle size of the silk fibroin powder used in the present invention is not particularly limited, but in order to obtain dyed silk fibroin powder to be blended into paints, etc., a pulverization method may be used. Regeneration method: 0. It is preferable to use one in the range of 1 to 50 μm, and particularly preferably in the range of 1 to 30 μm.
本発明に用いられる賜イオン性界面活性剤は、塩化ステ
アリルトリメチルアンモニウム等のアルキル四級アンモ
ニウム塩や塩化セチルビリジニウム等の環式四級アンモ
ニウＪ、塩のような四級アンモニウム塩型で水溶性の界
面活性剤が適し、金ヒ［′口ゾル中の濃度が０．００１
−１重量％の範囲で用いられる．
本発明に用いられる金ヒドロゾルは、塩化金酸などを原
料とし、その水溶液を水素化ホウ素ナトリウム、クエン
酸ナトリウムなどの水溶性還元剤で処理する従来方法で
得られ陽イオン性界面活性剤は、この還元処理の前また
は後に添加される．金しドロゾル中の金濃度は０． ０
０ １〜０，１重景％の範囲がよい．０．１ｊｌ量％
より多いと安定な金コロイドができず沈澱が生じるため
好ましくないし、０．０１重量％より少ないと染めあが
りの色が好ましいものではない．
本発明に用いられる水は蒸留水，イオン交換水等の精製
水が適用される．
本発明に用いられる水と相溶性のある揮発性有機溶剤は
、沸点が１００゜Ｃ以下であるエタノール，メタノール
，イソブロビルアルコール， ｎ−７”ロビルアルコ
ール ｔｅｒｔ−ブチルアルコール，アセトンなどから
なる群から選ばれる少なくとも一種が適用される．
本発明に用いる上述のような揮発性有機ｌ剤は水溶液と
しても本発明に適用されるが、溶剤の濃度は５０重量％
以上であることが好ましい．濃度が５０重量％未溝の場
合は、水のみを用いた場合も含めて、絹フィブロイン粉
末を均一に分散することができず、染色ムラが生じやす
いと同時に、一定の色調の染色絹フイプロイン粉末を再
現性良く得ることができないために好ましくない．同様
の理由から、水と相溶性のある揮発性有機溶剤もしくは
その水溶液（以下、揮発性，有機溶剤溶液と略記する）
に絹フイブロイン粉末を分散する第一工程を省いて、直
接金ヒドロゾル中に投入攪拌した場合も、満足すべき染
色絹フィブロイン粉末を得ることができない．
揮発性有機溶剤溶液の量は、染色混合液全量に対して５
〜５０重量％の範囲で用いられる，５０重量％より多い
と、金コロイドが急速に不安定化して凝集、沈澱してし
まうために、均一に染色することができない．一方、５
！ｌ量％より少ないとダマにならない程度にシルクパウ
ダーを分散させるためには、おのずと金ヒドロゾル全量
に対して少量のシルクパウダーしか染色できず、過剰の
金コロイドが濾液中に残ってしまって経済性が悪いと同
時に、一定の色調の染色絹フィブロイン粉末を再現性良
く得ることができないために好ましくない．
本発明における、第一工程で得られる分散液を陽イオン
性界面活性剤を含有する金ヒドロゾル中に投入攪拌して
染色する第二工程における染色時間は数分間から数時間
の範囲で選ばれるが、長時間浸漬しても色相に差を生じ
ないことから通常３０分から３時間の範囲が好ましい．
本発明における第三工程とは、第二工程で得られる染色
混合液から染色絹フィブロイン粉末を得る工程である．
具体的には第二工程で得られる染色混合液を濾過し、沈
澱物を乾燥して染色絹フィブロインを得るなどの通常の
方法が用いられる．〔実施例〕
以下実施例について説明する．
なお染色絹フィブロイン粉末及び比較例の耐光性，耐熱
性，発色性（染まり具合）の評価方法は次の通りである
．
（１） 耐光性試験
得られた染色絹フィブロイン粉末を金皿に圧縮充填した
試料を２個準備し、１個は太陽光線に３０日間曝射し、
１個は冷暗所に３０日間保存して、３０日後に両試料の
色を肉眼観察により比較して、色の変化の程度から耐光
性を判定した．肉眼で両試料の色の差を判別できない場
合を０３差を感じる場合を×とした．
（２） 耐熱性試験
耐光性試験と同様の試料を２個準備し、１個は内部温度
を１０５℃に調節した乾燥機の中に２４時間収容し、１
個は冷暗所に２４時間保存して、２４時間後に両試料の
色を肉眼観察により比較して、色の変化の程度から耐熱
性を判定した．肉眼で両試料の色の差を判別できない場
合を０，差を感じる場合を×とした．
（３）発色性（染まり具合）試験
染色終了後、染色絹フィブロイン粉末を濾過した後の濾
液が無色透明で、金コロイドがすべて絹フィブロイン粉
末に吸着し、かつ得られた染色絹フィブロイン粉末の色
相に色ムラのない場合をＯとした．濾液中に金コロイド
が残って赤色を呈し、得られた染色絹フィブロイン粉末
に色ムラがあって十分に染色することができなかった場
合を×とした．
実施例ｌ
塩化金酸８ ２ ４ｍｇを純水１００ｍｆに溶解する．
この塩化金酸水溶液２５ｍｊ！に純水９１５ｍｌを加え
、攪拌下に塩化ステアリルトリメチルアンモニウムの１
％水Ｒ ｅ １ ０ ｒｎ ｉを注入する。The ionic surfactants used in the present invention are water-soluble quaternary ammonium salts such as alkyl quaternary ammonium salts such as stearyltrimethylammonium chloride and cyclic quaternary ammonium salts such as cetylviridinium chloride. Suitable surfactants have a concentration of 0.001
It is used in the range of -1% by weight. The gold hydrosol used in the present invention is obtained by the conventional method of using chloroauric acid as a raw material and treating its aqueous solution with a water-soluble reducing agent such as sodium borohydride or sodium citrate. It is added before or after this reduction process. The gold concentration in the gold drop sol is 0. 0
A range of 0.1 to 0.1 deep view% is good. 0.1jl amount%
If it is more than 0.01% by weight, the dyed color will not be desirable, because stable gold colloid will not be formed and precipitation will occur. The water used in the present invention may be purified water such as distilled water or ion-exchanged water. The volatile organic solvents that are compatible with water used in the present invention include those having a boiling point of 100°C or lower, such as ethanol, methanol, isobrobyl alcohol, n-7"robyl alcohol, tert-butyl alcohol, and acetone. At least one selected from the following is applied. The above-mentioned volatile organic agent used in the present invention can be applied to the present invention as an aqueous solution, but the concentration of the solvent is 50% by weight.
The above is preferable. If the concentration is 50% by weight, the silk fibroin powder cannot be uniformly dispersed, even when only water is used, and uneven dyeing tends to occur. This method is undesirable because it cannot be obtained with good reproducibility. For the same reason, volatile organic solvents or their aqueous solutions that are compatible with water (hereinafter abbreviated as volatile organic solvent solutions)
Even if the first step of dispersing silk fibroin powder is omitted and the gold hydrosol is directly added and stirred, a satisfactory dyed silk fibroin powder cannot be obtained. The amount of volatile organic solvent solution is 5% based on the total amount of dyeing mixture.
It is used in the range of ~50% by weight; if it exceeds 50% by weight, the gold colloid will rapidly become unstable, coagulate, and precipitate, making it impossible to dye uniformly. On the other hand, 5
! If the amount is less than 1%, in order to disperse the silk powder to the extent that it does not form lumps, it is natural that only a small amount of silk powder can be dyed with respect to the total amount of gold hydrosol, and excess gold colloid will remain in the filtrate, making it uneconomical. Not only is this method undesirable, but it is also unfavorable because dyed silk fibroin powder with a constant color tone cannot be obtained with good reproducibility. In the present invention, the dyeing time in the second step, in which the dispersion obtained in the first step is poured into a gold hydrosol containing a cationic surfactant and stirred for dyeing, is selected in the range of several minutes to several hours. Since there is no difference in hue even if immersed for a long time, a period of 30 minutes to 3 hours is usually preferable. The third step in the present invention is a step of obtaining dyed silk fibroin powder from the dyeing mixture obtained in the second step.
Specifically, a conventional method is used, such as filtering the dyeing mixture obtained in the second step and drying the precipitate to obtain dyed silk fibroin. [Example] An example will be explained below. The methods for evaluating the light resistance, heat resistance, and color development (dyeness of dyeing) of the dyed silk fibroin powder and comparative examples are as follows. (1) Light resistance test Two samples were prepared by compressing and filling the obtained dyed silk fibroin powder in a metal plate, and one was exposed to sunlight for 30 days.
One sample was stored in a cool, dark place for 30 days, and after 30 days, the colors of both samples were compared by visual observation, and the light resistance was determined from the degree of color change. Cases in which the difference in color between the two samples could not be discerned with the naked eye were marked as 0, and cases in which a difference was felt were marked as ×. (2) Heat resistance test Two samples similar to the light resistance test were prepared, one was placed in a dryer with the internal temperature adjusted to 105°C for 24 hours, and one
The samples were stored in a cool, dark place for 24 hours, and after 24 hours, the colors of both samples were compared by visual observation, and the heat resistance was determined from the degree of color change. The score was 0 if the difference in color between the two samples could not be discerned with the naked eye, and the score was × if the difference was felt. (3) Color development (dyeness of dyeing) test After dyeing, the filtrate after filtering the dyed silk fibroin powder is colorless and transparent, all the gold colloids are adsorbed to the silk fibroin powder, and the hue of the obtained dyed silk fibroin powder The case where there was no color unevenness was rated O. A case where colloidal gold remained in the filtrate and exhibited a red color, and the dyed silk fibroin powder obtained had uneven color and could not be dyed sufficiently was rated as ×. Example 1 Dissolve 4 mg of chloroauric acid 82 in 100 mf of pure water.
This chloroauric acid aqueous solution 25 mj! Add 915 ml of pure water to the solution, and add 1 ml of stearyltrimethylammonium chloride while stirring.
% water R e 10 rni is injected.
続いて水素化ホウ素ナＩ・リウム７５、７ｍｇ／５０ｍ
． Ａ！水溶液５ ０ ｍ Ｎを注入して１０分間撹拌
後放置する。Next, sodium boron hydride/lium 75, 7mg/50m
．． A! 50 mN of an aqueous solution was injected, stirred for 10 minutes, and then left to stand.
，二うＬ２て得られた金ヒドロゾルの金イオン濃度は０
． ０ ０ ’３ ８ ５重叛％．界面活性剤濃度は０
６０１敢盟％となる８この金ヒドＩプゾルＩＮに天然の
紺繊禮を機械的に粉砕しで得た粉砕絹フィブ口イ゛．／
粉末ＸＯｇを２００ｇのエタノールに分散させたものを
加える，６０分間攪拌後、濾過、水洗、乾燥し、染色絹
フ４ブロイン粉末を得た。, the gold ion concentration of the gold hydrosol obtained by L2 is 0.
．． 0 0 '3 8 5 times %. Surfactant concentration is 0
8. Crushed silk fibres, obtained by mechanically crushing natural navy blue fibers, are added to this golden hydride I-Puzol IN with a strength of 601%. /
Powder XOg dispersed in 200 g of ethanol was added, stirred for 60 minutes, filtered, washed with water, and dried to obtain dyed silk 4-broin powder.
得ｈれた染免絹フィブロイン粉末は第１表から明らかな
如《、耐光性，耐熱性．発色性（染まり奥合）に優れた
ものであった。As is clear from Table 1, the obtained dyed silk fibroin powder has good light resistance and heat resistance. It had excellent color development (dye depth).
実施例２
実施例１と同梯にして得られた金ヒドロゾル１１′！に
絹フィブ口インを溶解後、再析ＩＪｉ Ｌ．て得た再生
絹フィブロイン粉末１０ｇをあらかじめエタノール２０
０ｇに分散させ注入する．６０分間攪拌後、濾過、水洗
、乾燥し、染免紐フィブロイン粉末を得た。Example 2 Gold hydrosol 11' obtained in the same manner as in Example 1! After dissolving the silk fibrin in the IJi L. 10g of the regenerated silk fibroin powder obtained by
Disperse to 0g and inject. After stirring for 60 minutes, the mixture was filtered, washed with water, and dried to obtain dyed string fibroin powder.
得られた染色絹フィブロイン粉末は第１表から明らかな
如く、耐光性，耐熱性．発色性（染まり具合）に優れた
ものであったや
実施例３〜６
水と相溶性のある揮発性有機溶剤の種類を第１表の如く
変化させる他｛大，、実施例２と同様に行なって染色絹
プイブロイン粉末を得た２
得られた染色絹フィブロイン粉末は第１表から明らかな
如く耐光性，耐熱性．発色性（染まり４４合）にイ憂れ
たちのであった．
実施例７〜９
水と相溶性のある揮発性有機溶剤の濃度を第１表に示す
如く変化さセる仙は実施例２と同梯ｒ行なって染免絹フ
ィブロイン粉末を得た。As is clear from Table 1, the obtained dyed silk fibroin powder has light resistance and heat resistance. Examples 3 to 6 The type of volatile organic solvent that is compatible with water was changed as shown in Table 1. As is clear from Table 1, the dyed silk fibroin powder obtained has good light resistance and heat resistance. I was worried about the color development (44 stains). Examples 7 to 9 The concentration of the volatile organic solvent that is compatible with water was changed as shown in Table 1.The same steps as in Example 2 were carried out to obtain dyed silk fibroin powder.
実施例７〜９により得られた染色紐２イブロイン粉末は
第１表から明らかな如く、耐光件．耐熱性。発色性（染
まり具合）に優れたものであった，実施例１０
水と相溶牲のある揮発性有機溶剤溶液の濃度を第１表に
示す如く変化させる他は実施Ｎ２．’：同様に行なって
染色紐フィブロイン粉末を得た．実施例ｌＯにより得ら
れた染偽絹フイブロイン粉末は第１表から明らかな如く
、耐光性．耐熱性．発佑性（染まり具合）に優れたもの
であ，つた。As is clear from Table 1, the dyed cord 2 ibroin powder obtained in Examples 7 to 9 has light resistance. Heat-resistant. Example 10, which had excellent color development (staining quality); Example N2 except that the concentration of the volatile organic solvent solution that is compatible with water was changed as shown in Table 1. ': The dyed string fibroin powder was obtained in the same manner. As is clear from Table 1, the dyed pseudosilk fibroin powder obtained in Example 1O has light resistance. Heat-resistant. It has excellent susceptibility (dyeness of dyeing).
比較例１
紮根１００Ｓを粉砕し、１００ｒｎｆｆｉの水に浸漬し
た後，、４０〜６０℃の水２１を逍加して手もみ踏．み
出し法茫よって免素抽出を行ない、紫根色素１． １
ｇ含有する染液２．０９１を得た。Comparative Example 1 After pulverizing 100S of radish root and immersing it in 100 rnffi of water, 40 to 60°C water 21 was added thereto and the mixture was rubbed by hand. Immune extraction was carried out using the omidashi method, and the purple root pigment 1. 1
A dye liquor containing 2.091 g was obtained.
この染液４ ０ ０＋ｎｊ！に、実，ＳｔｉＮ２の再生
絹フイブロイン粉末１０ｇを分散し、４０〜・６０℃で
２時間染色した後、濾過、水洗、乾煙し、染色絹フィブ
ロイン粉末を得た。This dye liquid 400+nj! Then, 10 g of regenerated silk fibroin powder of StiN2 was dispersed and dyed at 40 to 60°C for 2 hours, followed by filtration, washing with water, and drying to obtain dyed silk fibroin powder.
得られた染仏紐フィブロイン粉末は第１表から明らかな
如く、耐光性１耐熱性が不良であった．実施例ｌ１
金巴ドロゾルを金イオン濃度が０． ０ ０ ５％トナ
るようにｔｌｌ製する表同時に金ヒドロゾルの量を５ｌ
に変化させる他は実施例２と同様に行なって染急組フィ
ブロイン粉末を得た、
得られた染偽絹フィブロイン粉末は第１表から明らかな
如く、耐光性，耐熱性，発色性（染まり具合）に価れた
ものであった．
実施例ｌ２
金ヒドロゾル中の界面活性剤濃度を第１表に示す如く変
化させる他は、実施例２と同様に行なって染色絹フィブ
ロイン粉末を得た。As is clear from Table 1, the obtained dyed Buddhist string fibroin powder had poor light resistance and heat resistance. Example 11 Gold Tomoe Drosol was prepared with a gold ion concentration of 0. 0 0 At the same time, add 5 liters of gold hydrosol to 5% toner.
The dyed pseudo-silk fibroin powder was obtained in the same manner as in Example 2, except that the dyed pseudosilk fibroin powder was changed to ) It was worth it. Example 12 A dyed silk fibroin powder was obtained in the same manner as in Example 2, except that the surfactant concentration in the gold hydrosol was changed as shown in Table 1.
得られた染色紐フィブロイン粉末は第１表から明らかな
如く、耐光性，耐熱性，発色性（染まり具合）に優れた
ものであった。As is clear from Table 1, the obtained dyed string fibroin powder was excellent in light resistance, heat resistance, and color development (dyeness).
実施例１３，比較例２・−３
界面活性剤の種類を第ｔ表の如く変化させる他は、実施
例２と同様の操作を行なった．実施例１３により得られ
た染色絹フィブロイン粉末は、第１表から明らかな如く
、耐光性，耐熱性．発色性（染まり具合）に優れたもの
であった。Example 13, Comparative Examples 2 and -3 The same operations as in Example 2 were carried out, except that the type of surfactant was changed as shown in Table t. As is clear from Table 1, the dyed silk fibroin powder obtained in Example 13 has light resistance, heat resistance. It had excellent color development (dyeness of dyeing).
一方、界面活性剤とＬ７てノニオン界面活性剤を用いた
比較例２やアニオン界面活性剤を用いた比較例３は、濾
液中に金コロイドが残，でしまい、染色することができ
なかった．
実施例１４．１５
絹フィブロイン粉末の染色時間を第１表の如く変化させ
る他は、実施例２と同様の操作を行なった．
得られた染色絹フィブロイン粕末は、第１表より明らか
な如く、耐光性，耐熱性．発色性（染ま〔発明の効果〕
以上記載のごとく、本発明の方法によって染色絹フィブ
ロイン粉末を得ることができ、得られた染色絹フィブロ
イン粉末が耐光性や耐熱性に優れたものであることは明
らかである．On the other hand, in Comparative Example 2 in which a nonionic surfactant was used as surfactant and L7, and Comparative Example 3 in which an anionic surfactant was used, colloidal gold remained in the filtrate and dyeing could not be carried out. Examples 14 and 15 The same operations as in Example 2 were carried out, except that the dyeing time of silk fibroin powder was changed as shown in Table 1. As is clear from Table 1, the obtained dyed silk fibroin lees has light resistance and heat resistance. Color development (dying [effects of the invention]) As described above, dyed silk fibroin powder can be obtained by the method of the present invention, and the obtained dyed silk fibroin powder has excellent light resistance and heat resistance. it is obvious.
Claims (6)
色絹フィブロイン粉末。(1) A dyed silk fibroin powder characterized by being dyed with gold colloid.
含有する金ヒドロゾル中に浸漬して、染色することを特
徴とする染色絹フィブロイン粉末の製造方法。(2) A method for producing dyed silk fibroin powder, which comprises dyeing silk fibroin powder by immersing it in gold hydrosol containing a cationic surfactant.
機溶剤もしくはその水溶液に分散する第一工程と、第一
工程で得られる分散液を陽イオン性界面活性剤を含有す
る金ヒドロゾル中に投入攪拌して染色する第二工程と、
第二工程で得られる染色混合液から染色絹フィブロイン
粉末を得る第三工程からなる請求項（２）の染色絹フィ
ブロイン粉末の製造方法。(3) A first step of dispersing silk fibroin powder in a volatile organic solvent compatible with water or its aqueous solution, and dispersing the dispersion obtained in the first step into a gold hydrosol containing a cationic surfactant. A second step of dyeing by stirring,
The method for producing dyed silk fibroin powder according to claim 2, comprising a third step of obtaining dyed silk fibroin powder from the dyeing mixture obtained in the second step.
、エタノール、ｎ−プロピルアルコール、イソプロピル
アルコール、ｔｅｒｔ−ブチルアルコール、アセトンの
少なくとも一種からなる請求項（３）の染色絹フィブロ
イン粉末の製造方法。(4) The production of dyed silk fibroin powder according to claim (3), wherein the volatile organic solvent compatible with water comprises at least one of methanol, ethanol, n-propyl alcohol, isopropyl alcohol, tert-butyl alcohol, and acetone. Method.
溶液における揮発性有機溶剤の濃度が５０重量％以上で
ある請求項（３）の染色絹フィブロイン粉末の製造方法
。(5) The method for producing dyed silk fibroin powder according to claim (3), wherein the concentration of the volatile organic solvent in the water-compatible volatile organic solvent or the volatile organic solvent in the aqueous solution is 50% by weight or more.
液全量に対して５〜５０重量％の範囲にある請求項（３
）の染色絹フィブロイン粉末の製造方法。(6) Claim (3) wherein the amount of the volatile organic solvent that is compatible with water is in the range of 5 to 50% by weight based on the total amount of the dyeing mixture.
) method for producing dyed silk fibroin powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1158548A JPH0655830B2 (en) | 1989-06-21 | 1989-06-21 | Dyeed silk fibroin powder and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1158548A JPH0655830B2 (en) | 1989-06-21 | 1989-06-21 | Dyeed silk fibroin powder and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0324132A true JPH0324132A (en) | 1991-02-01 |
| JPH0655830B2 JPH0655830B2 (en) | 1994-07-27 |
Family
ID=15674116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1158548A Expired - Lifetime JPH0655830B2 (en) | 1989-06-21 | 1989-06-21 | Dyeed silk fibroin powder and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0655830B2 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5839452A (en) * | 1981-09-02 | 1983-03-08 | 米良 勅夫 | Board sheet |
| JPS5943448A (en) * | 1982-09-06 | 1984-03-10 | Nippon Telegr & Teleph Corp <Ntt> | Remote patch system |
| JPS61293907A (en) * | 1985-06-21 | 1986-12-24 | Kanebo Ltd | Makeup cosmetic |
| JPS62299587A (en) * | 1986-06-17 | 1987-12-26 | 工業技術院長 | Dyeing method by gold hydrosol |
-
1989
- 1989-06-21 JP JP1158548A patent/JPH0655830B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5839452A (en) * | 1981-09-02 | 1983-03-08 | 米良 勅夫 | Board sheet |
| JPS5943448A (en) * | 1982-09-06 | 1984-03-10 | Nippon Telegr & Teleph Corp <Ntt> | Remote patch system |
| JPS61293907A (en) * | 1985-06-21 | 1986-12-24 | Kanebo Ltd | Makeup cosmetic |
| JPS62299587A (en) * | 1986-06-17 | 1987-12-26 | 工業技術院長 | Dyeing method by gold hydrosol |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0655830B2 (en) | 1994-07-27 |
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