JP4526846B2 - Dye solution containing anthocyanin pigment and dyeing method using the same - Google Patents
Dye solution containing anthocyanin pigment and dyeing method using the same Download PDFInfo
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- JP4526846B2 JP4526846B2 JP2004097387A JP2004097387A JP4526846B2 JP 4526846 B2 JP4526846 B2 JP 4526846B2 JP 2004097387 A JP2004097387 A JP 2004097387A JP 2004097387 A JP2004097387 A JP 2004097387A JP 4526846 B2 JP4526846 B2 JP 4526846B2
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- 229930002877 anthocyanin Natural products 0.000 title claims description 38
- 235000010208 anthocyanin Nutrition 0.000 title claims description 38
- 239000004410 anthocyanin Substances 0.000 title claims description 38
- 150000004636 anthocyanins Chemical class 0.000 title claims description 38
- 238000004043 dyeing Methods 0.000 title claims description 33
- 239000000049 pigment Substances 0.000 title claims description 32
- 238000000034 method Methods 0.000 title claims description 22
- 239000004744 fabric Substances 0.000 claims description 29
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 19
- 239000011976 maleic acid Substances 0.000 claims description 18
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 102000004169 proteins and genes Human genes 0.000 claims description 12
- 108090000623 proteins and genes Proteins 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 229940053662 nickel sulfate Drugs 0.000 claims 2
- 238000007654 immersion Methods 0.000 claims 1
- 238000010186 staining Methods 0.000 claims 1
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- 241000196324 Embryophyta Species 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
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- VEVZSMAEJFVWIL-UHFFFAOYSA-O cyanidin Natural products [O+]=1C2=CC(O)=CC(O)=C2C=C(O)C=1C1=CC=C(O)C(O)=C1 VEVZSMAEJFVWIL-UHFFFAOYSA-O 0.000 description 6
- 244000020518 Carthamus tinctorius Species 0.000 description 5
- 235000003255 Carthamus tinctorius Nutrition 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 229930182470 glycoside Natural products 0.000 description 5
- 235000007336 cyanidin Nutrition 0.000 description 4
- 150000002815 nickel Chemical class 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 240000003978 Ipomoea coccinea Species 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 3
- -1 cyanidin glycoside Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 150000002338 glycosides Chemical group 0.000 description 3
- 150000002696 manganese Chemical class 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 244000124853 Perilla frutescens Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- HKUHOPQRJKPJCJ-UHFFFAOYSA-N pelargonidin Natural products OC1=Cc2c(O)cc(O)cc2OC1c1ccc(O)cc1 HKUHOPQRJKPJCJ-UHFFFAOYSA-N 0.000 description 2
- 235000006251 pelargonidin Nutrition 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NZDXSXLYLMHYJA-UHFFFAOYSA-M 4-[(1,3-dimethylimidazol-1-ium-2-yl)diazenyl]-n,n-dimethylaniline;chloride Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1N=NC1=[N+](C)C=CN1C NZDXSXLYLMHYJA-UHFFFAOYSA-M 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- TWCMVXMQHSVIOJ-UHFFFAOYSA-N Aglycone of yadanzioside D Natural products COC(=O)C12OCC34C(CC5C(=CC(O)C(O)C5(C)C3C(O)C1O)C)OC(=O)C(OC(=O)C)C24 TWCMVXMQHSVIOJ-UHFFFAOYSA-N 0.000 description 1
- PLMKQQMDOMTZGG-UHFFFAOYSA-N Astrantiagenin E-methylester Natural products CC12CCC(O)C(C)(CO)C1CCC1(C)C2CC=C2C3CC(C)(C)CCC3(C(=O)OC)CCC21C PLMKQQMDOMTZGG-UHFFFAOYSA-N 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 244000178937 Brassica oleracea var. capitata Species 0.000 description 1
- 240000001548 Camellia japonica Species 0.000 description 1
- YPXWWSJGANMFFQ-AQAMAIGXSA-O Cyanidin 3-O-(6-O-para-coumaroyl)glucoside-5-O-glucoside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC(C1=C2)=CC(O)=CC1=[O+]C(C=1C=C(O)C(O)=CC=1)=C2O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](COC(=O)\C=C\C=2C=CC(O)=CC=2)O1 YPXWWSJGANMFFQ-AQAMAIGXSA-O 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 240000001549 Ipomoea eriocarpa Species 0.000 description 1
- 235000005146 Ipomoea eriocarpa Nutrition 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 244000273928 Zingiber officinale Species 0.000 description 1
- 235000006886 Zingiber officinale Nutrition 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 235000018597 common camellia Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 235000008397 ginger Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PFOARMALXZGCHY-UHFFFAOYSA-N homoegonol Natural products C1=C(OC)C(OC)=CC=C1C1=CC2=CC(CCCO)=CC(OC)=C2O1 PFOARMALXZGCHY-UHFFFAOYSA-N 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- YPVZJXMTXCOTJN-UHFFFAOYSA-N pelargonidin chloride Chemical compound [Cl-].C1=CC(O)=CC=C1C(C(=C1)O)=[O+]C2=C1C(O)=CC(O)=C2 YPVZJXMTXCOTJN-UHFFFAOYSA-N 0.000 description 1
- 229930015721 peonidin Natural products 0.000 description 1
- 235000006404 peonidin Nutrition 0.000 description 1
- OGBSHLKSHNAPEW-UHFFFAOYSA-N peonidin chloride Chemical compound [Cl-].C1=C(O)C(OC)=CC(C=2C(=CC=3C(O)=CC(O)=CC=3[O+]=2)O)=C1 OGBSHLKSHNAPEW-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
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- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
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Description
本発明は、植物アントシアニン色素の安定した染料溶液及びそれを使用して絹繊維製品など蛋白質物質を鮮麗な赤色に色濃く染色する方法に関する。 The present invention relates to a stable dye solution of a plant anthocyanin pigment and a method for dyeing a protein substance such as a silk fiber product in a bright red color using the same.
植物色素による赤色の染色には、茜、紅花、スオウの色素が利用されている。しかし、花の代表的な色素として、果実、葉、根にも含まれるアントシアニン色素は、それらとは異なる特徴的な鮮麗な色を演じる色素でありながら、食品以外の物質に染色するには技術的困難を伴うとされていた。 For the dyeing of red with plant pigments, the pigments of camellia, safflower and suou are used. However, as a typical pigment of flowers, anthocyanin pigments contained in fruits, leaves, and roots are pigments that produce distinctive and distinctive colors. It was supposed to be accompanied by technical difficulties.
染色に植物色素を利用するには、藍、紅花などに対する特殊な方法を除き、一般に染材を水と共に加熱する煮煎と称する色素抽出が行われており、水不溶性の色素の抽出、あるいは急速抽出の場合には、アルコールなどの有機溶媒も用いられてきた。しかし、染色向けのアントシアニン色素の抽出は、それら何れの方法によっても効果的ではなく、硫酸などの取り扱いが危険な無機酸水溶液を用いても充分ではなく、代わりに酢酸を用いれば、なおいっそう抽出効率が低いので、得られた抽出液で繊維製品等を濃色に染めることはできなった。 In order to use plant pigments for dyeing, except for special methods for indigo, safflower, etc., pigment extraction is generally performed by heating the dyeing material with water to extract water-insoluble pigments or rapidly. In the case of extraction, organic solvents such as alcohol have also been used. However, the extraction of anthocyanin dyes for dyeing is not effective by any of these methods, and it is not enough to use an aqueous solution of inorganic acid that is dangerous to handle, such as sulfuric acid. Since the efficiency is low, it has been impossible to dye textiles and the like darkly with the obtained extract.
なお、サトイモ科サトイモのアントシアニン色素をpH1.5〜4.0の酸水性液で抽出する試みがある(特許文献1参照)が、この方法では、染料溶液として貯蔵安定性ある製品を得難く、また、このような方法で得た色素溶液を用いただけでは、繊維製品を濃色に堅牢度よく染めることは出来なかった。 There is an attempt to extract the anthocyanin pigment of the taro family taro with an acid aqueous solution having a pH of 1.5 to 4.0 (see Patent Document 1), but in this method, it is difficult to obtain a storage-stable product as a dye solution. In addition, using only the dye solution obtained by such a method, the textile product could not be dyed darkly with good fastness.
さらに、植物の生きた組織から分離抽出したアントシアニン色素は急速な光退色を受け、酵素などによる経時的な分解を受け易いので、それを防ぐ目的でアントシアニン染色物にアルミニウム、鉄、銅などの塩類による金属媒染をほどこすと、色素がこれらの金属イオンとキレート結合して著しく変色し、アントシアニン特有の鮮麗色の再現が果たせなかった。
本発明は、アントシアニン色素を含む貯蔵安定性に優れた染色溶液を提供すること、すなわち植物からアントシアニン色素を効率よく抽出して、鮮明な実用性ある赤色染料溶液を提供することを課題とするものであり、同時に、アントシアニン色素を用いて蛋白質物質を鮮明な赤色に堅牢度よく染色する方法を提供することをも課題とする。 An object of the present invention is to provide a dyeing solution having an excellent storage stability containing an anthocyanin pigment, that is, to efficiently extract an anthocyanin pigment from a plant and provide a clear and practical red dye solution. At the same time, another object of the present invention is to provide a method for dyeing a protein substance into a bright red with high fastness using an anthocyanin dye.
本発明者は、以下の(1)〜(5)に示す諸条件を満たす技術を開発するように鋭意研究を重ねた。
(1)染色用のアントシアニン色素を植物から容易に抽出する方法。
(2)抽出した色素が染色可能な状態を保持したまま長期間の保存が有効となる方法。
(3)市販のアントシアニン色素を染色に適した状態とする方法。
(4)アントシアニン固有の色を容易に被染物上に再現する染色方法。
(5)染色後のアントシアニンの色安定性を向上する方法。
This inventor repeated earnest research so that the technique which satisfy | fills various conditions shown in the following (1)-(5) may be developed.
(1) A method for easily extracting an anthocyanin pigment for dyeing from a plant.
(2) A method in which long-term storage is effective while maintaining a state in which the extracted pigment can be stained.
(3) A method of bringing a commercially available anthocyanin dye into a state suitable for dyeing.
(4) A dyeing method for easily reproducing the color inherent to anthocyanins on the object to be dyed.
(5) A method for improving the color stability of anthocyanins after dyeing.
本発明では、マレイン酸を含むpH1.2以下の水溶液に、アントシアニン色素を含ませることにより、(1)、(2)、(3)および(4)の条件を満たすことを可能とした。マレイン酸は有機二塩基酸で、水に溶けて強い酸性を示し、0.5%水溶液のpH値は1.1にまで低下する。他の多塩基酸(コハク酸、マロン酸、酒石酸、クエン酸、リンゴ酸、グルタル酸など)が、同濃度で示すpH値は1.7〜2.4であるのに対し、マレイン酸水溶液の酸性度は群を抜いて高い。また、有機酸として最も強い酸である蟻酸は、刺激性、腐食性の強い液体で取り扱いが危険であるが、マレイン酸は、強酸でありながら揮散性が低いために刺激性がほとんどなく、また細粒状であるため、取り扱いが容易で安全性が高い。したがって、このマレイン酸水溶液にアントシアニンを含む植物組織を漬けることによって、色素はその強い酸性のために容易かつ安全に抽出され、(1)の目的が達せられる。 In the present invention, the conditions (1), (2), (3) and (4) can be satisfied by including an anthocyanin dye in an aqueous solution containing maleic acid and having a pH of 1.2 or lower. Maleic acid is an organic dibasic acid that dissolves in water and exhibits strong acidity, and the pH value of a 0.5% aqueous solution decreases to 1.1. While other polybasic acids (succinic acid, malonic acid, tartaric acid, citric acid, malic acid, glutaric acid, etc.) have the same pH value of 1.7 to 2.4, The acidity is by far the highest. Formic acid, which is the strongest organic acid, is a liquid that is highly irritating and corrosive and is dangerous to handle. Maleic acid is a strong acid but has low volatility, so it has little irritation. It is fine and easy to handle and highly safe. Therefore, by soaking a plant tissue containing anthocyanin in this aqueous maleic acid solution, the pigment is easily and safely extracted due to its strong acidity, and the object of (1) is achieved.
また、マレイン酸水溶液で抽出したアントシアニン色素液を5℃以下で冷蔵すると、約1〜2年間、異常なく安定に保存できた。
その理由は、強酸性条件下で、低温に保つことによって、アントシアニンの色素本体が安定な状態のカチオン構造を保ち、且つ、共存すると思われる色素分解酵素は失活したままの状態で維持できること、および、マレイン酸の持つ優れた防腐、防黴効果により、色素以外に溶存する他の植物成分の腐敗が防止されるため、(2)の目的が達せられる。なお、ここでいう色素本体とは、色素の配糖体構造から糖を除外したアグリコンのことを指す。
In addition, when the anthocyanin dye solution extracted with an aqueous maleic acid solution was refrigerated at 5 ° C. or lower, it could be stably stored without any abnormality for about 1 to 2 years.
The reason for this is that the anthocyanin dye main body maintains a stable cation structure by keeping it at a low temperature under strongly acidic conditions, and the chromolytic enzyme that seems to coexist can be maintained in an inactivated state. In addition, because of the excellent antiseptic and antifungal effects of maleic acid, it is possible to prevent the decay of other plant components dissolved in addition to the pigment, so that the purpose of (2) is achieved. In addition, the pigment | dye main body here refers to the aglycone which excluded saccharide | sugar from the glycoside structure of a pigment | dye.
また、マレイン酸の水溶液と市販のアントシアニン色素を混合した場合にも、(2)の抽出液と同じ効果を得ることができる。 In addition, when an aqueous solution of maleic acid and a commercially available anthocyanin dye are mixed, the same effect as the extract of (2) can be obtained.
アントシアニン色素のマレイン酸抽出液、またはマレイン酸混合液に被染物を長時間浸けると、被染物がマレイン酸基を吸着して部分的にアニオン化される。一方、配糖体であるアントシアニン色素は強酸による加水分解作用を受けて徐々に糖が分離し、その分、色素はカチオン性の色素本体となり、アニオン化した被染物との間にイオン間の相互作用が生じ、イオン染着することが可能となって、(4)の目的が達せられる。 When the object to be dyed is immersed in a maleic acid extract of anthocyanin dye or a maleic acid mixture for a long time, the object to be dyed adsorbs maleic acid groups and is partially anionized. On the other hand, anthocyanin dyes, which are glycosides, are hydrolyzed by strong acids, and the sugars are gradually separated, and the dyes become cationic dye bodies. An effect | action arises and it becomes possible to ion-stain and the objective of (4) is achieved.
被染物が蛋白物質のような両性物質では、染液のpH値が低いと等電点を超えて+に極性化されることがあり、カチオン性の染料分子との間に同種イオン間の反発力がはたらくためにアントシアニン色素の染着が抑制される。無機酸を用いて酸性にした染液を使うと、その理由で染め着きにくい。しかし、マレイン酸の酸基は炭素原子4個からなる有機性のかなり大きい酸基であるため、有機質の被染物表面に吸着しやすく、吸着した面は−に極性化する。したがって被染物の+極性化を抑え、アントシアニン色素本体に対する同種イオン間に基づく染着抑止力を逓減する。それによって色素本体は蛋白物質の組織に拡散し、染色することが可能となって、(4)の目的が達せられる。 If the dyed substance is an amphoteric substance such as a protein substance, it may be polarized to + beyond the isoelectric point if the pH value of the dyeing solution is low, and repulsion between the same species ions with the cationic dye molecule. Since the force works, dyeing of anthocyanin pigments is suppressed. When using a dyeing solution acidified with an inorganic acid, it is difficult to dye. However, since the acid group of maleic acid is an organic organic acid group consisting of 4 carbon atoms, it is easily adsorbed on the surface of the organic dyed object, and the adsorbed surface is polarized to-. Therefore, + polarization of the object to be dyed is suppressed, and the dyeing deterrence based on the same kind of ions for the anthocyanin dye main body is gradually reduced. As a result, the dye body can be diffused and stained in the tissue of the protein substance, thereby achieving the purpose of (4).
アントシアニン色素は金属イオンとキレート結合することによって安定性が増すが、著しい変色を伴うおそれがある。しかし、本発明によるアントシアニン染色物をコバルト、マンガン、ニッケルの何れかの塩を含む溶液で処理すると、変色の度合いが小さく、さらに、マレイン酸を含む色素溶液で再染色すれば、アントシアニン特有の鮮麗な色を回復して色濃度が増し、鮮麗、且つ安定性の増強された染色物を得ることが出来るので、(5)の目的が達せられる。 Anthocyanin dyes have increased stability by chelating with metal ions, but may be accompanied by significant discoloration. However, when the anthocyanin dyed product according to the present invention is treated with a solution containing any one of cobalt, manganese, and nickel salts, the degree of discoloration is small. Therefore, the purpose of (5) can be achieved.
アントシアニン色素を含む植物組織をマレイン酸水溶液に室温で長時間漬けることにより、染色用のアントシアニン色素を容易に且つ安全で効率よく抽出することができ、得られた抽出液は長期間保存することができる。
また、植物アントシアニン色素とマレイン酸を共存させた染液に、被染物を長時間浸けることによって鮮麗なアントシアニンの色を容易に染め着けることができ、コバルト、ニッケル、マンガンの何れかの塩で処理して再染すれば、さらに安定した濃色に染めることができるので、従来の植物染では得られなかった濃色のアントシアニンの色を容易に再現できるという独特の染色分野を開拓することが可能となった。
なお、かかる本発明は、花や葉、果皮などアントシアニン色素を有する植物(例えば、寒椿、サザンカ、朝顔、紫蘇、茄子、赤キャベツ、紅葉等)からアントシアニン色素を抽出して安定して美麗な赤色染色溶液となしうるだけでなく、市販のアントシアニン色素の使用にも非常に効率よく適用できる。
また、本発明の方法で染色される蛋白質物質には、生糸、絹布などの蛋白質繊維製品、蛋白質物質からなるフィルム、コーティング物など、蛋白質からなるもので、被染物となりうるものは全て含まれる。
By soaking plant tissue containing anthocyanin pigments in maleic acid aqueous solution at room temperature for a long time, the anthocyanin pigments for dyeing can be extracted easily, safely and efficiently, and the resulting extract can be stored for a long period of time. it can.
In addition, by immersing the dyed product for a long time in a dye liquor in which plant anthocyanin pigment and maleic acid coexist, the color of fresh anthocyanin can be easily dyed and treated with any salt of cobalt, nickel, or manganese. If it is re-dyed, it can be dyed to a more stable dark color, so it is possible to develop a unique dyeing field that can easily reproduce the color of dark anthocyanins that could not be obtained by conventional plant dyeing It became.
In the present invention, an anthocyanin pigment is extracted from a plant having an anthocyanin pigment, such as a flower, a leaf, and a skin (eg, kansui, sasanqua, morning glory, shiso, eggplant, red cabbage, autumn leaves, etc.), and a beautiful and beautiful red color is extracted. Not only can it be used as a dyeing solution, it can also be applied very efficiently to the use of commercially available anthocyanin dyes.
In addition, the protein substances dyed by the method of the present invention include all protein substances that can be dyed, such as protein fiber products such as raw silk and silk cloth, films made of protein substances, and coatings.
[実施例1]
シアニジン配糖体を主成分とするアントシアニンを多量に含む寒椿の花弁を、重量比で約5倍の0.5%マレイン酸水溶液(pH1.1)に室温で1昼夜以上浸漬して、色素を抽出した。抽出液は5℃の冷蔵庫内で2年間の保存に耐えた。
また、絹布を、この抽出液(重量比率で絹布の25〜50倍量)に、室温下で1昼夜浸け、食塩を0.5%溶液になるように添加してさらに室温下で1昼夜浸けて水洗した。その後、染色布を、硫酸コバルトの0.2%水溶液に室温下で1時間以上浸し、その後水洗してさらに染色残液に2昼夜浸けて再染し水洗した。再染後の染色布はシアニジン特有の鮮麗なワイン・レッドの色を呈した。
硫酸コバルトの代わりに、硫酸ニッケル又は酢酸マンガンを使用した場合にも、同様の効果が得られた。
[Example 1]
Immerse the petals of agar with a large amount of anthocyanin, the main component of which is a cyanidin glycoside, in a 0.5% maleic acid aqueous solution (pH 1.1) approximately 5 times by weight at room temperature for one day or more. Extracted. The extract endured storage for 2 years in a refrigerator at 5 ° C.
In addition, the silk cloth is soaked in this extract (25-50 times the weight of the silk cloth in weight ratio) at room temperature for one day and night, and salt is added to make a 0.5% solution, and further soaked at room temperature for one day and night. And washed with water. Thereafter, the dyed cloth was immersed in a 0.2% aqueous solution of cobalt sulfate at room temperature for 1 hour or longer, then washed with water, further immersed in the dyeing residual liquid for 2 days and nights, re-dyed and washed with water. The dyed fabric after re-dyeing exhibited a vivid wine red color characteristic of cyanidin.
Similar effects were obtained when nickel sulfate or manganese acetate was used instead of cobalt sulfate.
日光堅牢度を測定すると、露光前後の色差ΔEは次のようになった(このΔEは国際照明委員会およびJISに基づくLAB表色系の色差単位を用いており、値が小さいほど退色が少ない)。なお、露光第一段階を冬期晴天直射日光の連続5時間、第二段階を連続15時間とした。
露光第一段階 露光第二段階
JISブルースケール1級 15 23
. 〃 2級 11 18
. 〃 3級 6 10
. 〃 4級 - 2
寒椿花弁色素染色布 7 13
同上、コバルト塩処理後再染布 4 7
同上、ニッケル塩処理後再染布 4 7
同上、マンガン塩処理後再染布 4 6
When the fastness to sunlight was measured, the color difference ΔE before and after exposure was as follows (this ΔE uses the color difference unit of the LAB color system based on the International Lighting Commission and JIS, and the smaller the value, the less the color fading: ). Note that the first stage of exposure was continuous 5 hours of direct sunlight in winter and the second stage was continuous 15 hours.
First exposure stage Second exposure stage JIS Blue Scale Level 15 23
. 〃 Level 2 11 18
.級 Grade 3 6 10
.級 Level 4-2
Kangaro petal pigmented cloth 7 13
Same as above, re-dyed cloth after cobalt salt treatment 4 7
Same as above, re-dyed after nickel salt treatment 4 7
Same as above, re-dyed after treatment with manganese salt 4 6
本発明の方法による寒椿花弁色素抽出液で浸け染めした染色布の日光堅牢度は通常2〜3級程度と判定されるが、コバルト、ニッケル、マンガンなどの塩で処理して再染すると3級以上となり、染色堅牢度が向上することがわかる。 The fastness to sunlight of a dyed fabric soaked with a koji petal pigment extract according to the method of the present invention is usually determined to be about 2 to 3 grades, but when treated with a salt such as cobalt, nickel, manganese, etc., it is grade 3 From the above, it can be seen that the color fastness is improved.
また、昔から実用されている赤色系植物色素の紅花やスオウによる染色物と、露光第一段階における耐日光性を比較した場合の色差ΔEは次のようになった。
寒椿花弁色素染色布、コバルト塩処理後再染布 3
同上、 ニッケル塩処理後再染布 3
同上、 マンガン塩処理後再染布 3
紅花染め 12
スオウ染め(アルミニウム塩媒染) 5
. 〃 (銅塩媒染) 2
In addition, the color difference ΔE obtained by comparing the dyeing of red plant pigments, which have been practically used for a long time, with safflower and suou, and the sun resistance in the first stage of exposure was as follows.
Kangaro petal dyed cloth, re-dyed cloth after cobalt salt treatment 3
Same as above, re-dyed after nickel salt treatment 3
Same as above, re-dyed fabric after manganese salt treatment 3
Safflower dyeing 12
Suo dyeing (aluminum salt mordanting) 5
. 〃 (Copper salt mordanting) 2
本発明による染色法では、ΔEがスオウ染めのアルミニウム塩媒染と銅塩媒染のほぼ中間程度で、紅花染めよりも優れた耐日光性を有する実用性ある染色布を得ることができることが認められた。
なお、寒椿の花弁の代わりに赤色サザンカの花弁を用いて、実施例1と同様の方法を実施した場合にも、同様の結果が得られた。
In the dyeing method according to the present invention, it was confirmed that ΔE is approximately halfway between the aluminum salt mordanting and the copper salt mordanting, and a practical dyeing cloth having better sunlight resistance than safflower dyeing can be obtained. .
In addition, the same result was obtained also when the same method as Example 1 was implemented using the petal of a red sasanqua instead of the petal of a cold ginger.
[実施例2]
シアニジン、およびペオニジンの配糖体であるアントシアニンを多量に含んでいるムラサキイモ色素のエキス製品(台糖研究所製:色価800unit)を4%水溶液とし、マレイン酸を0.5%になるように加え、この液を絹布重量の25倍〜50倍用意し、以下は実施例1と同じ方法で絹布を染めて、赤臙脂色の染色布を得た。
[Example 2]
An extract product of Murasaki potato pigment containing a large amount of anthocyanin which is a glycoside of cyanidin and peonidin (manufactured by Taisho Laboratories: color unit 800 unit) is made into a 4% aqueous solution, so that maleic acid becomes 0.5%. In addition, 25 to 50 times the weight of the silk cloth was prepared, and the following was used to dye the silk cloth in the same manner as in Example 1 to obtain a red greave-dyed cloth.
[実施例3]
赤色朝顔の花弁(ペラルゴニジン配糖体を主成分とするアントシアニンを多量に含む)を重量比で約5倍の0.5%マレイン酸水溶液に室温で1昼夜以上浸漬し、色素を抽出した。抽出液は5℃の冷蔵庫内で2年間の保存に耐えた。
絹布を、この抽出液(重量比率で絹布の25〜50倍量)に、室温下で1昼夜浸け、食塩を0.5%溶液になるように添加して、さらに室温下で1昼夜浸けて水洗した。その後、染色布を、実施例1と同様にコバルト、ニッケル、マンガンのいずれかの塩の水溶液で処理し、水洗後、さらに染色残液に2昼夜浸けて再染し水洗した。再染後の染色布はペラルゴニジン特有の鮮麗なルビー・レッドの色を呈した。
[Example 3]
A red morning glory petal (containing a large amount of anthocyanin containing pelargonidin glycoside as a main component) was immersed in a 0.5% maleic acid aqueous solution of about 5 times by weight at room temperature for one day or more to extract a pigment. The extract endured storage for 2 years in a refrigerator at 5 ° C.
The silk cloth is immersed in this extract (25-50 times the weight of the silk cloth by weight) at room temperature for one day and night, salt is added to make a 0.5% solution, and further immersed at room temperature for one day and night. Washed with water. Thereafter, the dyed fabric was treated with an aqueous solution of any one of cobalt, nickel, and manganese in the same manner as in Example 1, washed with water, further immersed in the dyeing residual solution for two days and nights, re-dyed and washed with water. The dyed fabric after the re-dyeing exhibited a vivid ruby red color peculiar to pelargonidin.
この染色布の日光堅牢度を、実施例1と同様な方法で調べると露光前後の色差ΔEは次のようになった。
. 露光第一段階 露光第二段階
JISブルースケール1級 14 28
. 〃 2級 9 20
. 〃 3級 6 14
. 〃 4級 - 3
赤色朝顔花弁色素染色布 3 9
同上、コバルト塩処理後再染布 2 5
同上、ニッケル塩処理後再染布 3 6
同上、マンガン塩処理後再染布 2 6
When the fastness to sunlight of this dyed fabric was examined by the same method as in Example 1, the color difference ΔE before and after exposure was as follows.
. First exposure stage Second exposure stage JIS Blue Scale Level 14 28
. 〃 Grade 2 9 20
.級 Grade 3 6 14
.級 Level 4-3
Red morning glory petal pigmented cloth 3 9
Same as above, re-dyed cloth after cobalt salt treatment 2 5
Same as above, re-dyed after nickel salt treatment 3 6
Same as above, re-dyed fabric after manganese salt treatment 2 6
本発明の方法による赤色朝顔花弁抽出液で浸け染めした染色布の日光堅牢度は3〜4級と判定される。コバルト、ニッケル、マンガンなどの塩で処理して再染した染色布も、堅牢度の等級としては同程度であるがΔEはさらに小さく、耐日光性が向上する傾向を示した。 The fastness to sunlight of the dyed cloth soaked with the red morning glory petal extract according to the method of the present invention is determined to be 3 to 4 grades. The dyed fabric treated with a salt of cobalt, nickel, manganese, etc. and re-dyed also had the same fastness rating but a smaller ΔE and showed a tendency to improve sunlight resistance.
[実施例4]
シアニジン配糖体のシソニンと称するアントシアニンを多量に含む赤紫蘇の葉を集め、この葉を同重量の0.5%マレイン酸水溶液に室温で1昼夜以上浸漬し、色素を抽出した。抽出液は5℃の冷蔵庫内で2年間の保存に耐えた。また、この抽出液を用いて、実施例1と同様の方法で、絹布を染色した。その結果、鮮麗なワイン・レッド色の染色絹布を得た。
[Example 4]
Red shiso leaves containing a large amount of anthocyanin called shisonin, a cyanidin glycoside, were collected, and the leaves were immersed in a 0.5% maleic acid aqueous solution of the same weight at room temperature for one day or more to extract the pigment. The extract endured storage for 2 years in a refrigerator at 5 ° C. Moreover, silk cloth was dye | stained by the method similar to Example 1 using this extract. As a result, a fresh wine-red dyed silk cloth was obtained.
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JPS60246884A (en) * | 1984-05-16 | 1985-12-06 | 工業技術院長 | Dyeing of silk fiber |
JPH03213588A (en) * | 1990-01-10 | 1991-09-18 | Nippon Paint Co Ltd | Dyeing of yarn |
JPH06136669A (en) * | 1992-10-27 | 1994-05-17 | Yuko Teramura | Method for dyeing wool with plant |
JPH06264055A (en) * | 1993-03-16 | 1994-09-20 | K I Kasei Kk | Method for stabilizing carotenoid pigment, stabilized composition of carotenoid pigment, and feed containing carotenoid pigment stabilized thereby |
JPH07166480A (en) * | 1993-12-15 | 1995-06-27 | Cosmo Kaihatsu Kk | Dyeing with phycocyanin |
JP2004091758A (en) * | 2002-09-04 | 2004-03-25 | Gumma Prefecture | Colored particle and method for producing the same |
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JPS60246884A (en) * | 1984-05-16 | 1985-12-06 | 工業技術院長 | Dyeing of silk fiber |
JPH03213588A (en) * | 1990-01-10 | 1991-09-18 | Nippon Paint Co Ltd | Dyeing of yarn |
JPH06136669A (en) * | 1992-10-27 | 1994-05-17 | Yuko Teramura | Method for dyeing wool with plant |
JPH06264055A (en) * | 1993-03-16 | 1994-09-20 | K I Kasei Kk | Method for stabilizing carotenoid pigment, stabilized composition of carotenoid pigment, and feed containing carotenoid pigment stabilized thereby |
JPH07166480A (en) * | 1993-12-15 | 1995-06-27 | Cosmo Kaihatsu Kk | Dyeing with phycocyanin |
JP2004091758A (en) * | 2002-09-04 | 2004-03-25 | Gumma Prefecture | Colored particle and method for producing the same |
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