JP2010083937A - India ink-like composition - Google Patents
India ink-like composition Download PDFInfo
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- JP2010083937A JP2010083937A JP2008252401A JP2008252401A JP2010083937A JP 2010083937 A JP2010083937 A JP 2010083937A JP 2008252401 A JP2008252401 A JP 2008252401A JP 2008252401 A JP2008252401 A JP 2008252401A JP 2010083937 A JP2010083937 A JP 2010083937A
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- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 239000000980 acid dye Substances 0.000 claims abstract description 24
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000010446 mirabilite Substances 0.000 claims description 12
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- -1 aliphatic amines Chemical class 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 3
- 239000000975 dye Substances 0.000 abstract description 24
- 229920001778 nylon Polymers 0.000 abstract description 18
- 238000004043 dyeing Methods 0.000 abstract description 17
- 238000005406 washing Methods 0.000 abstract description 6
- 239000003086 colorant Substances 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 description 23
- 239000004677 Nylon Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 210000002268 wool Anatomy 0.000 description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 description 9
- 229920000742 Cotton Polymers 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- HMEKVHWROSNWPD-UHFFFAOYSA-N Erioglaucine A Chemical compound [NH4+].[NH4+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 HMEKVHWROSNWPD-UHFFFAOYSA-N 0.000 description 6
- 230000002421 anti-septic effect Effects 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- 229920000297 Rayon Polymers 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 239000002964 rayon Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 235000012745 brilliant blue FCF Nutrition 0.000 description 4
- 239000004161 brilliant blue FCF Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 4
- 239000000230 xanthan gum Substances 0.000 description 4
- 229920001285 xanthan gum Polymers 0.000 description 4
- 235000010493 xanthan gum Nutrition 0.000 description 4
- 229940082509 xanthan gum Drugs 0.000 description 4
- 239000003429 antifungal agent Substances 0.000 description 3
- 229940121375 antifungal agent Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000004599 antimicrobial Substances 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- OIQPTROHQCGFEF-UHFFFAOYSA-L chembl1371409 Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 OIQPTROHQCGFEF-UHFFFAOYSA-L 0.000 description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 2
- 238000009967 direct dyeing Methods 0.000 description 2
- AOMZHDJXSYHPKS-UHFFFAOYSA-L disodium 4-amino-5-hydroxy-3-[(4-nitrophenyl)diazenyl]-6-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(S([O-])(=O)=O)=C(N=NC=3C=CC=CC=3)C(O)=C2C(N)=C1N=NC1=CC=C([N+]([O-])=O)C=C1 AOMZHDJXSYHPKS-UHFFFAOYSA-L 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 235000012738 indigotine Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005185 salting out Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 235000014347 soups Nutrition 0.000 description 2
- UJMBCXLDXJUMFB-GLCFPVLVSA-K tartrazine Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-GLCFPVLVSA-K 0.000 description 2
- 235000012756 tartrazine Nutrition 0.000 description 2
- 239000004149 tartrazine Substances 0.000 description 2
- XOSXWYQMOYSSKB-LDKJGXKFSA-L water blue Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC(C=C2)=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C(C=C2)=CC=C2S([O-])(=O)=O)=CC(S(O)(=O)=O)=C1N.[Na+].[Na+] XOSXWYQMOYSSKB-LDKJGXKFSA-L 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- LFLZOWIFJOBEPN-UHFFFAOYSA-N nitrate, nitrate Chemical class O[N+]([O-])=O.O[N+]([O-])=O LFLZOWIFJOBEPN-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は、洗濯により落ちる墨汁様組成物に関する。 The present invention relates to an ink-like composition that falls off by washing.
墨汁は、毛筆で書画を書くのに用いる文房具として、広く使用されている。墨汁は、狭義には墨をすった汁であり、黒色の顔料（例えばカーボンブラック）および膠を含む。しかし、最近、黒の色を、顔料でなく、染料で発色させている液体が、墨汁の代わりに使用されつつある。そのような液体は狭義には墨汁ではないという見解もあり、例えば「書道液」、「墨液」等と称されることもある。そのため、本明細書では、顔料および膠を含まないが、書道または水墨画作成のために用いられる、着色された液体を「墨汁様組成物」と称する。 Ink juice is widely used as a stationery for writing calligraphy with a brush. Ink soup is, in a narrow sense, a soup made of ink, and contains black pigment (for example, carbon black) and glue. Recently, however, a liquid in which a black color is developed with a dye instead of a pigment is being used instead of ink. There is a view that such a liquid is not ink ink in a narrow sense, and for example, it may be referred to as “calligraphy liquid”, “ink ink” or the like. Therefore, in the present specification, a colored liquid that does not contain pigments and glue but is used for calligraphy or ink painting is called “ink-like composition”.
従来、水溶性樹脂を使用したタイプでは、消去性向上のために水溶性樹脂を使用しているが、そのため、この組成物を使用して半紙に書いた作品を高湿度の環境下においておくと滲みが生じることがある。顔料を使用したタイプでは、顔料を使用しているため、高湿度下での滲みはおきにくいが、顔料は染料と異なり、溶解ではなく液中に分散した状態で存在するので、分散安定性を考慮する必要がある場合がある。
一方、酸性染料は衣料によく使用される綿・ポリエステルには染着しにくいという性質があるが、本来ポリアミド繊維の染色に用いられる染料のため、ナイロン・ウールには染着しやすい。
Conventionally, the type using water-soluble resin uses water-soluble resin to improve erasability. Therefore, if the composition written on a half-paper using this composition is placed in a high humidity environment, Bleeding may occur. In the type using pigments, since pigments are used, bleeding is difficult to occur under high humidity, but unlike dyes, pigments exist in a state of being dispersed in liquid rather than dissolved. You may need to consider.
On the other hand, acid dyes have a property that they are difficult to dye on cotton and polyester often used in clothing, but are easy to dye on nylon and wool because they are dyes originally used for dyeing polyamide fibers.
しかし、本来、酸性染料は、ポリアミド繊維の染色に用いられる染料の為、カルボニル基とアミノ基の両方を有するナイロン繊維に対しては、親和性が高く、ナイロン繊維へは染着し、洗濯しても落ちにくい。 However, since acid dyes are originally dyes used for dyeing polyamide fibers, they have a high affinity for nylon fibers having both carbonyl groups and amino groups, and are dyed and washed on nylon fibers. Even hard to fall.
本来、インキでは、水性インキは収納管に含まれ、飛び散る危険性が少ないが、墨汁様組成物では筆を剥き出しの墨汁様組成物中へ浸すため、飛散、衣類付着という墨汁様組成物固有の大きな問題がある。 Originally, with ink, water-based ink is contained in the storage tube, and there is little risk of splashing. There is a big problem.
本発明の課題は、着色剤として染料を使用するが、ナイロン繊維への染着を抑制し、またウール繊維への染着をも抑制することができる、洗濯しても落ちる墨汁様組成物を提供するものである。 An object of the present invention is to use a ink-like composition that uses a dye as a colorant, but can suppress dyeing to nylon fibers and can also suppress dyeing to wool fibers, and can be removed even after washing. It is to provide.
上記課題を解決するため鋭意検討した結果、
本発明は、酸性染料、脂肪族アミン、水を含有し、墨汁様組成物のｐＨがアルカリ領域である墨汁様組成物である。
特に、墨汁様組成物全量に対して脂肪族アミンを０．０１〜３重量％含有していることが好ましい。なお、上記脂肪族アミンの中でも、トリエタノールアミンが好適に用いられる。
As a result of intensive studies to solve the above problems,
The present invention is an ink-like composition containing an acid dye, an aliphatic amine, and water, and having a pH of the ink-like composition in the alkaline region.
In particular, it is preferable to contain 0.01 to 3% by weight of an aliphatic amine with respect to the total amount of the ink-like composition. Of the aliphatic amines, triethanolamine is preferably used.
また本発明の墨汁様組成物は、さらに芒硝（無水硫酸ナトリウム）を墨汁様組成物全量に対して１〜２０重量％含有するものである。 The ink-like composition of the present invention further contains 1 to 20% by weight of mirabilite (anhydrous sodium sulfate) with respect to the total amount of the ink-like composition.
これにより、本発明は酸性染料を使用して作製した墨汁様組成物に、脂肪族アミンを添加することで、墨汁様組成物のｐＨが酸性染料が染まり難いアルカリ領域にあり、酸性染料にアミンが吸着することで、染料のポリアミド繊維のアミノ基への吸着を抑制して、酸性染料のポリアミド繊維、特にナイロンへの吸着が妨害され、墨汁様組成物が布（衣類）に付着した時の洗濯落ちをよくし、洗濯性を向上できる。墨汁様組成物のｐＨがアルカリ領域にあっても、苛性ソーダ添加では洗濯性は向上しない。 Accordingly, the present invention adds an aliphatic amine to the ink-like composition prepared using an acid dye, so that the pH of the ink-like composition is in an alkaline region where the acid dye is difficult to be dyed. By adsorbing, the adsorption of the dye to the amino group of the polyamide fiber is suppressed, the adsorption of the acid dye to the polyamide fiber, particularly nylon, is obstructed, and the ink-like composition adheres to the cloth (clothing). Improves washability and improves washability. Even if the pH of the ink-like composition is in the alkaline region, the addition of caustic soda does not improve the washability.
また芒硝は染料の増量剤としてポピュラーであるが、洗濯性を出す為に墨汁様組成物に添加した例は無い。これにより、本発明は酸性染料を使用して作製した墨汁様組成物に、芒硝（無水硫酸ナトリウム）を添加することで、酸性染料の会合を促進し、酸性染料が繊維特にウール繊維に吸着しにくくする。従って、墨汁様組成物が布（衣類）に付着した時の洗濯落ちをよくし、洗濯性を向上できる。 In addition, although mirabilite is popular as a dye extender, there is no example of adding it to the ink-like composition in order to provide washability. As a result, the present invention promotes association of the acid dyes by adding mirabilite (anhydrous sodium sulfate) to the ink-like composition prepared using the acid dyes, and the acid dyes adsorb to fibers, particularly wool fibers. Make it harder. Therefore, the washing-off can be improved when the ink-like composition adheres to the cloth (clothing), and the washability can be improved.
＜酸性染料＞
本発明で用いられる酸性染料としては、綿・ポリエステルに対する直染性がない又は弱い染料が用いられる。なお、直染性がない又は弱い染料とは、親和力が小さい染料を指す。直染性が弱い染料は、繊維に吸着されにくく、染色の際に媒染等の特別な処理を施さなければ、直接染料溶液に繊維をした浸すだけでは、繊維に吸着されにくい。そのような染料が付着してできる染みは、洗濯すれば、退色させることができる。
例えば、C.I.Acid Red 18、C.I.Acid Blue 9、C.I.Acid Blue 90、C.I.Acid Yellow 17、C.I.Acid Yellow 23、C.I.Acid Yellow 40が用いられ、中でも、C.I.Acid Red 18、C.I.Acid Blue 9、C.I.Acid Blue 90、C.I.Acid Yellow 17、C.I.Acid Yellow 23が好適である。
<Acid dye>
As the acid dye used in the present invention, a dye having no or weak direct dyeing property to cotton / polyester is used. The dye having no direct dyeability or weak dye refers to a dye having a low affinity. A dye having a low direct dyeing property is difficult to be adsorbed to the fiber. Unless special treatment such as mordanting is performed at the time of dyeing, it is difficult to adsorb to the fiber only by immersing the fiber directly in the dye solution. A stain formed by such a dye attached can be faded if washed.
For example, CIAcid Red 18, CIAcid Blue 9, CIAcid Blue 90, CIAcid Yellow 17, CIAcid Yellow 23, CIAcid Yellow 40 are used, among them, CIAcid Red 18, CIAcid Blue 9, CIAcid Blue 90, CIAcid Yellow 17, CIAcid Yellow 23 Is preferred.
本発明において、酸性染料の実施可能な範囲は、墨汁様組成物全量に対して０．１〜２０．０重量％、好適な範囲は墨汁様組成物全量に対して０．５〜１０．０重量％である。より好適な範囲は墨汁様組成物全量に対して２．０〜８．０重量％である。酸性染料が過剰な場合は、綿・レーヨン・ポリエステルへの染着を抑制できるが、ナイロン・ウール・絹への染着については洗濯で落ち難くなる。酸性染料が過小の場合は、発色が弱くなる。 In the present invention, the feasible range of the acid dye is 0.1 to 20.0% by weight with respect to the total amount of the ink-like composition, and the preferred range is 0.5 to 10.0 with respect to the total amount of the ink-like composition. % By weight. A more preferable range is 2.0 to 8.0% by weight based on the total amount of the ink-like composition. When the acid dye is excessive, dyeing on cotton, rayon, and polyester can be suppressed, but dyeing on nylon, wool, and silk is difficult to wash off. When the acid dye is too small, color development becomes weak.
＜脂肪族アミン＞
本発明は主にナイロンへの染着を阻止するために脂肪族アミンを用いる。アミンは、染料の染着に関与する官能基にナイロン繊維のアミドより先に吸着することにより、染料が繊維に染着するのを防ぐため、アミンの添加によりナイロンの洗濯性が向上する。
換言すれば、アミンは主にナイロン繊維のイオン性に関与し、ｐＨをアルカリ性とし、酸性染料にアミンが吸着することで酸性染料の繊維への吸着が妨害される。すなわち、脂肪族アミンの末端アミン（＋）が、染料とナイロンが結びつく前に、染料の末端官能基であるＣＯＯ−、などの（―）に対して擬似染着座席を占有する。またアミンを加えることによって、墨汁様組成物のｐＨは高くなる（塩基性になる）が、アミノ基とカルボキシル基を両方有する繊維では、カルボキシル基がＣＯＯ−になるとともに、アミノ基は帯電せず不活性になる。
アミン類は脂肪族アミンと芳香族アミンに大別されるが、芳香族アミンは一般に水に対する溶解性が低いため、水を基材とした墨汁様組成物には使用できない。
脂肪族アミンとしては、第一級アミン、第二級アミン、第三級アミンのどれでもよく、１分子内にアミノ基やイミノ基を一つ持つものでも複数持つものでもよい。中でも、トリエタノールアミン、プロパノールアミン、ジプロパノールアミン、トリプロパノールアミン、ジプロピルアミン、トリエチレンテトラミンが好適に使用でき、トリエタノールアミンが好適である。
本発明において用いられる脂肪族アミンとしては、実施可能な範囲は墨汁様組成物全量に対して０．０１〜３．０重量％、好適な範囲は墨汁様組成物全量に対して０．１重量％以上、より好適には０．３重量％以上である。また好適な範囲は墨汁様組成物全量に対して１．５重量％以下、より好ましくは墨汁様組成物全量に対して１．０重量％以下である。脂肪族アミンが過剰な場合は墨汁様組成物pHがあがりすぎて染料を分解してしまうなど、墨汁様組成物の安定性が悪化する。脂肪族アミンが過小の場合は、主にナイロンへの染着を阻止することができず、洗濯性向上効果が薄れる。
<Aliphatic amine>
The present invention uses aliphatic amines primarily to prevent dyeing on nylon. The amine is adsorbed before the amide of the nylon fiber to the functional group involved in dyeing of the dye, thereby preventing the dye from dyeing on the fiber. Therefore, the addition of the amine improves the washability of the nylon.
In other words, the amine is mainly involved in the ionicity of the nylon fiber, makes the pH alkaline, and the amine is adsorbed on the acid dye, thereby preventing the acid dye from adsorbing on the fiber. That is, the terminal amine (+) of the aliphatic amine occupies the pseudo-dyeing seat for (−) such as COO − , which is the terminal functional group of the dye, before the dye and nylon are combined. By adding amine addition, pH of India ink-like composition (became basic) made high, the fibers having both an amino group and a carboxyl group, a carboxyl group COO - with becomes, the amino group is not charged Become inactive.
Amines are roughly classified into aliphatic amines and aromatic amines, but aromatic amines generally have low solubility in water and cannot be used in ink-like compositions based on water.
The aliphatic amine may be a primary amine, a secondary amine, or a tertiary amine, and may have one or more amino groups or imino groups in one molecule. Among these, triethanolamine, propanolamine, dipropanolamine, tripropanolamine, dipropylamine, and triethylenetetramine can be preferably used, and triethanolamine is preferable.
As the aliphatic amine used in the present invention, the feasible range is 0.01 to 3.0% by weight with respect to the total amount of the ink-like composition, and the preferred range is 0.1% with respect to the total amount of the ink-like composition. % Or more, and more preferably 0.3% by weight or more. Moreover, a suitable range is 1.5 weight% or less with respect to the total amount of ink-like composition, More preferably, it is 1.0 weight% or less with respect to the total amount of ink-like composition. When the aliphatic amine is excessive, the stability of the ink-like composition deteriorates, for example, the pH of the ink-like composition is excessively increased and the dye is decomposed. When the aliphatic amine is too small, dyeing to nylon cannot be mainly prevented, and the effect of improving the washability is reduced.
＜芒硝＞
本発明は主にウール繊維への染着を阻止するために芒硝（無水硫酸ナトリウム）を用いることができる。適当な量の芒硝を加えると、沈降しないぎりぎりの範囲で酸性染料が会合して分子が大きくなるので、酸性染料が繊維間に取り込まれにくくなる。また染料の末端基であるＣＯＯ−、ＳＯ３ −は、芒硝のＳＯ４ ２−よりも繊維組織と結びつくのが遅い。芒硝の硝酸イオンなどが、ウール繊維の染着座席を占有するものである。
本発明において、芒硝は、実施可能な範囲は墨汁様組成物全量に対して１〜２０重量％、好適な範囲は墨汁様組成物全量に対して２〜１５重量％、より好ましくは墨汁様組成物全量に対して３〜１０重量％である。芒硝が過剰な場合は染料の析出が起こる。芒硝が過小の場合は、洗濯性向上効果が薄れる。
<Shizo Glass>
The present invention can use mirabilite (anhydrous sodium sulfate) mainly to prevent dyeing on wool fibers. When an appropriate amount of mirabilite is added, the acid dye associates within a marginal range where it does not settle and the molecule becomes large, so that it becomes difficult for the acid dye to be taken in between the fibers. Further, COO − and SO 3 − which are end groups of the dye are slower to associate with the fiber structure than SO 4 2− of mirabilite. Nitrate nitrates occupy the wool fiber dyeing seat.
In the present invention, mirabilite can be used in an effective range of 1 to 20% by weight based on the total amount of the ink-like composition, and a preferable range is 2 to 15% by weight, more preferably an ink-like composition. It is 3-10 weight% with respect to the whole quantity. If the salt is excessive, dye deposition occurs. When the mirabilite is too small, the effect of improving the washability is reduced.
＜水溶性樹脂＞
本発明では粘度調整のため水溶性樹脂を用いることができる。例えば、ポリビニルアルコール（ＰＶＡ）、ポリビニルピロリドン（PVP）、カルボキシメチルセルロース（CMC）、ヒドロキシエチルセルロース（HEC）、ポリエチレンオキサイト（PEO）、ポリアクリル酸、キサンタンガム、ラムザンガム、サクシノグルカンなどである。好ましくは、ポリビニルアルコール（ＰＶＡ）、ポリビニルピロリドン（PVP）、カルボキシメチルセルロース（CMC）、キサンタンガムである。
本発明において水溶性樹脂を用いる場合、実施可能な範囲は墨汁様組成物全量に対して０．０１〜１０．０重量％、好適な範囲は墨汁様組成物全量に対して０．０４〜８．０重量％、より好ましくは墨汁様組成物全量に対して０．０５〜５重量％である。例えばより好ましくはキサンタンガムの場合０．０５〜０．３０重量％、ＣＭＣの場合は０．３〜３．０重量％、ＰＶＡでも２．０〜７．０重量％である。水溶性樹脂が過剰な場合、粘度が上がりすぎ、墨汁様組成物として使用し難くなる。水溶性樹脂が過小の場合は粘度が低すぎ、墨汁様組成物として使用し難くなる。
また特に、芒硝を用いた場合、芒硝が過剰であるなら、ポリビニルアルコール（ＰＶＡ）、ポリビニルピロリドン（ＰＶＰ）が入っていると塩析凝集がおこる。キサンタンガム、サクシノグルカン、ラムザン、ＣＭＣなどは上記０．０４〜８．０重量％の範囲内であると塩析凝集しない。
<Water-soluble resin>
In the present invention, a water-soluble resin can be used for viscosity adjustment. For example, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), polyethylene oxide (PEO), polyacrylic acid, xanthan gum, lambzan gum, succinoglucan and the like. Polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), carboxymethyl cellulose (CMC), and xanthan gum are preferable.
When a water-soluble resin is used in the present invention, the practicable range is 0.01 to 10.0% by weight with respect to the total amount of ink-like composition, and the preferred range is 0.04 to 8 with respect to the total amount of ink-like composition. 0.0% by weight, more preferably 0.05 to 5% by weight based on the total amount of the ink-like composition. For example, more preferably 0.05 to 0.30% by weight for xanthan gum, 0.3 to 3.0% by weight for CMC, and 2.0 to 7.0% by weight for PVA. When the water-soluble resin is excessive, the viscosity increases too much and it becomes difficult to use it as a ink-like composition. When the water-soluble resin is too small, the viscosity is too low and it becomes difficult to use as a ink-like composition.
In particular, when mirabilite is used, if the mirabilite is excessive, salting out aggregation occurs when polyvinyl alcohol (PVA) or polyvinylpyrrolidone (PVP) is contained. Xanthan gum, succinoglucan, rhamsan, CMC, and the like do not undergo salting out aggregation when they are within the range of 0.04 to 8.0% by weight.
＜その他＞
その他必要に応じて添加する成分として、容器の口部での乾燥防止のため水溶性有機溶剤のほか、無機塩類（食塩、硫酸マグネシウム）、防腐剤・防黴剤があげられる。ただし、酸性染料、脂肪族アミン、水を含有し、苛性ソーダ及び湿潤剤を含有しないで、墨汁様組成物全量に対して脂肪族アミンを０．０１〜３．０重量％含有し、墨汁様組成物のｐＨがアルカリ領域である墨汁様組成物が好ましい。水は溶媒として残部用いることができ、実施可能な範囲は特に限定しないが、墨汁様組成物全量に対して例えば１〜９０重量％、好ましくは２０〜８０重量％である。
<Others>
In addition to water-soluble organic solvents for preventing drying at the mouth of the container, inorganic salts (sodium chloride, magnesium sulfate), preservatives, and antifungal agents are included as other components added as necessary. However, it contains an acid dye, an aliphatic amine, and water, does not contain caustic soda and a wetting agent, contains 0.01 to 3.0% by weight of an aliphatic amine based on the total amount of the ink-like composition, and produces an ink-like composition. Ink-like compositions in which the pH of the product is in the alkaline region are preferred. The remaining amount of water can be used as a solvent, and the practicable range is not particularly limited, but is, for example, 1 to 90% by weight, preferably 20 to 80% by weight, based on the total amount of the ink-like composition.
＜製造方法＞
例えば水に水溶性樹脂及び水溶性有機溶剤を必要に応じて投入し、加熱攪拌して、水溶性樹脂の完溶を確認後、脂肪族アミン、または脂肪族アミン及び芒硝を投入し攪拌する。その後、酸性染料を加えて攪拌し、必要に応じて防腐・防黴剤を投入して攪拌する。
<Manufacturing method>
For example, a water-soluble resin and a water-soluble organic solvent are added to water as necessary, and the mixture is heated and stirred, and after confirming the complete dissolution of the water-soluble resin, an aliphatic amine or an aliphatic amine and sodium sulfate are added and stirred. Thereafter, an acid dye is added and stirred, and if necessary, an antiseptic / antifungal agent is added and stirred.
表１に示す組成にて、上記の方法にて各実施例及び比較例の試験サンプル（墨汁様組成物）を作製した。ｐＨは実施例がアルカリ領域、比較例が酸性領域である。この実施例及び比較例にはいずれも苛性ソーダ及び湿潤剤を含有されていない。 With the compositions shown in Table 1, test samples (inkbrush-like compositions) of each Example and Comparative Example were prepared by the above method. As for pH, an Example is an alkali area | region and a comparative example is an acidic area | region. Neither this example nor the comparative example contains caustic soda and a wetting agent.
［表注］
成分：
食用青色１号 Acid Blue 9
食用赤色１０２号 Acid Red 18
食用黄色５号 Food Yellow 3
Water Blue 116 Acid Blue 90
Water Blue 9 Acid Blue 9
Water Yellow 1 Acid Yellow 23
Water Black R-455 Acid Black 2
PVA-203 PVA
サンアイバックSA 防腐・防カビ剤
コートサイドH 防腐・防カビ剤
[Table note]
component:
Food Blue 1 Acid Blue 9
Food Red 102 Acid Red 18
Food Yellow 3
Water Blue 116 Acid Blue 90
Water Blue 9 Acid Blue 9
Water Yellow 1 Acid Yellow 23
Water Black R-455 Acid Black 2
PVA-203 PVA
Sun Eye Back SA Antiseptic and mildewproofing agent
Coatside H Antiseptic and mildewproofing agent
次に、各実施例及び比較例の墨汁様組成物を染色堅牢度試験用白布（交織１号）（ＪＩＳ Ｌ０８０３−２００５）に筆で塗布し、３時間乾燥した。続いて、洗剤、漂白剤を溶かした液に２時間浸漬した。のちに、洗剤で１５分洗濯し、１５分すすぎ、乾燥した。 Next, the ink-like compositions of each Example and Comparative Example were applied to a white cloth for dyeing fastness test (Kyogi No. 1) (JIS L0803-2005) with a brush and dried for 3 hours. Then, it was immersed in the liquid which melt | dissolved the detergent and the bleach for 2 hours. Later, it was washed with detergent for 15 minutes, rinsed for 15 minutes and dried.
＜評価＞
墨汁様組成物の塗布などしていない交換布８種の繊維（綿、レーヨン、ポリエステル、ナイロン、ウール、アクリル、アセテート、絹）それぞれを顕微式色差計にて測色し、ブランクとする。
次に、各実施例及び比較例の墨汁様組成物を塗布し洗濯し乾燥したＪＩＳ交換布８種を顕微式色差計にて測色する。
続いて、ブランクと試験片のΔＥ（デルタＥ）を各繊維毎に算出する。綿、レーヨン、ポリエステル、ナイロン、ウール、アクリル、アセテート、絹の８種の繊維のΔＥ（デルタＥ）値の平均値を算出する。
<Evaluation>
Each of the eight types of fibers (cotton, rayon, polyester, nylon, wool, acrylic, acetate, silk) not coated with the ink-like composition is measured with a micro colorimeter to obtain a blank.
Next, eight kinds of JIS exchange cloths, which are coated with the ink-like composition of each Example and Comparative Example, washed, and dried, are measured with a micro colorimeter.
Subsequently, ΔE (delta E) of the blank and the test piece is calculated for each fiber. An average value of ΔE (delta E) values of eight kinds of fibers of cotton, rayon, polyester, nylon, wool, acrylic, acetate, and silk is calculated.
表１より、実施例は、比較例と同じく、綿、レーヨン、ポリエステル、ウール、アクリル、アセテートいずれにおいても洗濯性（墨汁様組成物の色が洗濯により落ちる）が良好であるが、特にナイロンは比較例と比べて格別顕著に効果を奏していることが認められる。 From Table 1, the Examples have good washability (the color of the ink-like composition drops by washing) in any of cotton, rayon, polyester, wool, acrylic, and acetate, as in the comparative example, but especially nylon is It is recognized that the effect is particularly remarkable as compared with the comparative example.
次に、表２に示す組成にて、各実施例及び比較例の試験サンプル（墨汁様組成物）を作製した。すなわち、水に水溶性樹脂を投入し、加熱攪拌して、水溶性樹脂の完溶を確認後、脂肪族アミンまたは脂肪族アミン及び芒硝を投入し攪拌する。その後、酸性染料を加えて攪拌し、必要に応じて防腐・防黴剤を投入して攪拌する。 Next, test samples (inkbrush-like compositions) of each Example and Comparative Example were prepared with the compositions shown in Table 2. That is, a water-soluble resin is added to water and heated and stirred, and after confirming complete dissolution of the water-soluble resin, an aliphatic amine or an aliphatic amine and sodium sulfate are added and stirred. Thereafter, an acid dye is added and stirred, and if necessary, an antiseptic / antifungal agent is added and stirred.
［表注］
成分：
食用青色１号 Acid Blue 9
食用赤色１０２号 Acid Red 18
食用黄色５号 Food Yellow 3
Water Blue 116 Acid Blue 90
Water Blue 9 Acid Blue 9
Water Yellow 1 Acid Yellow 23
Water Black R-455 Acid Black 2
PVA-203 PVA
サンアイバックSA 防腐・防カビ剤
コートサイドH 防腐・防カビ剤
[Table note]
component:
Food Blue 1 Acid Blue 9
Food Red 102 Acid Red 18
Food Yellow 3
Water Blue 116 Acid Blue 90
Water Blue 9 Acid Blue 9
Water Yellow 1 Acid Yellow 23
Water Black R-455 Acid Black 2
PVA-203 PVA
Sun Eye Back SA Antiseptic and mildewproofing agent
Coatside H Antiseptic and mildewproofing agent
同様に、各実施例及び比較例の墨汁様組成物を染色堅牢度試験用白布（交織１号）（ＪＩＳ Ｌ０８０３−２００５）に筆で塗布し、３時間乾燥した。続いて、洗剤、漂白剤を溶かした液に２時間浸漬した。のちに、洗剤で１５分洗濯し、１５分すすぎ、乾燥した。 Similarly, the ink-like compositions of each Example and Comparative Example were applied to a white cloth for dyeing fastness test (Kyozai No. 1) (JIS L0803-2005) with a brush and dried for 3 hours. Then, it was immersed in the liquid which melt | dissolved the detergent and the bleach for 2 hours. Later, it was washed with detergent for 15 minutes, rinsed for 15 minutes and dried.
続いて、墨汁様組成物の塗布などしていない交換布８種の繊維（綿、レーヨン、ポリエステル、ナイロン、ウール、アクリル、アセテート、絹）それぞれを顕微式色差計にて測色し、ブランクとする。
次に、各実施例及び比較例の墨汁様組成物を塗布し洗濯し乾燥したＪＩＳ交換布８種を顕微式色差計にて測色する。
続いて、ブランクと試験片のΔＥ（デルタＥ）を各繊維毎に算出する。表２はその結果を示している。
Subsequently, each of the eight types of fibers (cotton, rayon, polyester, nylon, wool, acrylic, acetate, silk) not coated with the ink-like composition was measured with a micro colorimeter, and the blank and To do.
Next, eight kinds of JIS exchange cloths, which are coated with the ink-like composition of each Example and Comparative Example, washed, and dried, are measured with a micro colorimeter.
Subsequently, ΔE (delta E) of the blank and the test piece is calculated for each fiber. Table 2 shows the results.
表２より、ナイロン繊維について、ブランクである比較例が１２．０であるのに対し、実施例４〜１０のいずれについても７．４〜５．９であり、脂肪族アミンである実施例のプロパノールアミン、ジプロパノールアミン、トリプロパノールアミン、ジプロピルアミン、トリエチレンテトラミン、トリエタノールアミンを含む墨汁様組成物のいずれについても洗濯性（墨汁様組成物の色が洗濯により落ちる）が良好である。またさらに芒硝を加えた実施例１０はウール繊維についても洗濯性（墨汁様組成物の色が洗濯により落ちる）が良好である。
From Table 2, for nylon fiber, the comparative example which is a blank is 12.0, whereas all of Examples 4 to 10 are 7.4 to 5.9, which is an aliphatic amine. The ink-like composition containing propanolamine, dipropanolamine, tripropanolamine, dipropylamine, triethylenetetramine, and triethanolamine has good washability (the color of the ink-like composition drops by washing). . Further, Example 10 with addition of mirabilite also has good washability (the color of the ink-like composition drops by washing) for the wool fiber.
Claims (6)
墨汁様組成物のｐＨがアルカリ領域である
墨汁様組成物。 Contains acid dyes, aliphatic amines, water,
A ink-like composition in which the pH of the ink-like composition is in the alkaline region.
墨汁様組成物全量に対して脂肪族アミンを０．０１〜３．０重量％含有し、
墨汁様組成物のｐＨがアルカリ領域である請求項１記載の
墨汁様組成物。 Contains acid dyes, aliphatic amines, water, no caustic soda and wetting agents,
Containing 0.01 to 3.0% by weight of an aliphatic amine with respect to the total amount of the ink-like composition,
2. The ink-like composition according to claim 1, wherein the pH of the ink-like composition is in an alkaline region.
6. The ink-like composition according to claim 5, wherein the aliphatic amine is triethanolamine.
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| JP2010024287A (en) * | 2008-07-16 | 2010-02-04 | Sakura Color Prod Corp | Indian ink-like composition |
| JP2010083936A (en) * | 2008-09-30 | 2010-04-15 | Sakura Color Prod Corp | India ink-like composition |
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2008
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|---|---|---|---|---|
| JPS55155071A (en) * | 1979-05-23 | 1980-12-03 | Dainichi Seika Kogyo Kk | Marking agent |
| JPH107957A (en) * | 1996-06-24 | 1998-01-13 | Sakura Color Prod Corp | Erasable colorant composition |
| JP2006057084A (en) * | 2004-07-21 | 2006-03-02 | Sakura Color Prod Corp | Coloring material composition erasable by washing |
| JP2006219680A (en) * | 2006-05-12 | 2006-08-24 | Sakura Color Prod Corp | Black writing fluid |
| JP2006274268A (en) * | 2006-05-12 | 2006-10-12 | Sakura Color Prod Corp | Ink composition for erasable marking pen |
| JP2009263563A (en) * | 2008-04-28 | 2009-11-12 | Sakura Color Prod Corp | India ink-like composition |
| JP2010024287A (en) * | 2008-07-16 | 2010-02-04 | Sakura Color Prod Corp | Indian ink-like composition |
| JP2010083936A (en) * | 2008-09-30 | 2010-04-15 | Sakura Color Prod Corp | India ink-like composition |
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| 化学大辞典, JPN6014019528, 1987, pages 626, ISSN: 0002810957 * |
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