JP5638908B2 - Reactive dye composition and dyeing method using the same - Google Patents
Reactive dye composition and dyeing method using the same Download PDFInfo
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- 239000000985 reactive dye Substances 0.000 title claims description 272
- 239000000203 mixture Substances 0.000 title claims description 88
- 238000004043 dyeing Methods 0.000 title claims description 38
- 238000000034 method Methods 0.000 title claims description 18
- 239000000975 dye Substances 0.000 claims description 150
- 239000002253 acid Substances 0.000 claims description 48
- 229920003043 Cellulose fiber Polymers 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 238000005562 fading Methods 0.000 claims description 5
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 238000009472 formulation Methods 0.000 description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 description 9
- 235000017550 sodium carbonate Nutrition 0.000 description 9
- UIEBGVDTKLYGTN-UHFFFAOYSA-J tetrasodium;7-[[2-(carbamoylamino)-4-[[4-chloro-6-[3-(2-sulfonatooxyethylsulfonyl)anilino]-1,3,5-triazin-2-yl]amino]phenyl]diazenyl]naphthalene-1,3,6-trisulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].C=1C=C(N=NC=2C(=CC3=CC(=CC(=C3C=2)S([O-])(=O)=O)S([O-])(=O)=O)S([O-])(=O)=O)C(NC(=O)N)=CC=1NC(N=1)=NC(Cl)=NC=1NC1=CC=CC(S(=O)(=O)CCOS([O-])(=O)=O)=C1 UIEBGVDTKLYGTN-UHFFFAOYSA-J 0.000 description 9
- 229920000742 Cotton Polymers 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- GCFAQSYBSUQUPL-UHFFFAOYSA-I pentasodium 5-[[4-chloro-6-[3-(2-sulfonatooxyethylsulfonyl)anilino]-1,3,5-triazin-2-yl]amino]-3-[(1,5-disulfonatonaphthalen-2-yl)diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].Oc1c(N=Nc2ccc3c(cccc3c2S([O-])(=O)=O)S([O-])(=O)=O)c(cc2cc(cc(Nc3nc(Cl)nc(Nc4cccc(c4)S(=O)(=O)CCOS([O-])(=O)=O)n3)c12)S([O-])(=O)=O)S([O-])(=O)=O GCFAQSYBSUQUPL-UHFFFAOYSA-I 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- -1 alkali metal salts Chemical class 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 238000012937 correction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NSDSIQGBHACTLY-UHFFFAOYSA-N Reactive Blue 5 Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=C(S(O)(=O)=O)C=C1NC(C=1)=CC=C(S(O)(=O)=O)C=1NC(N=1)=NC(Cl)=NC=1NC1=CC=CC(S(O)(=O)=O)=C1 NSDSIQGBHACTLY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 229920001407 Modal (textile) Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000013022 formulation composition Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- HFIYIRIMGZMCPC-YOLJWEMLSA-J remazole black-GR Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(S([O-])(=O)=O)=C(\N=N\C=3C=CC(=CC=3)S(=O)(=O)CCOS([O-])(=O)=O)C(O)=C2C(N)=C1\N=N\C1=CC=C(S(=O)(=O)CCOS([O-])(=O)=O)C=C1 HFIYIRIMGZMCPC-YOLJWEMLSA-J 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
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Description
本発明は、セルロース繊維又はセルロース繊維含有繊維の染色に適する特定の赤色用反応染料を含有する反応染料組成物及びそれを用いる染色法に関する。 The present invention relates to a reactive dye composition containing a specific red reactive dye suitable for dyeing cellulose fibers or cellulose fiber-containing fibers, and a dyeing method using the same.
反応染料を用いるセルロース繊維の染色においては、黄色、赤色、及び、青色又は紺色の反応染料を三原色用染料として用い、それらを種々の割合で配合して染色する方法が知られている。 In dyeing cellulose fibers using reactive dyes, methods are known in which yellow, red, and blue or amber reactive dyes are used as dyes for the three primary colors, and they are blended in various proportions for dyeing.
三原色に使用される反応染料に関しては、各染料のビルドアップ性や均染性が優れていること、三原色の染着速度がほぼ等しく温度依存性が揃っていること、三原色の諸堅牢度が優れていることが必要とされてきている。更に、実工程に対応出来ることが特に必要とされる。つまり、一般的に製品に使用する染色には実験室スケール（概ね５〜３０ｇ）、中実験スケール（概ね３〜２０ｋｇ）、工場スケール（概ね１００〜１０００ｋｇ）のステップ段階を踏むが、このスケールに由来する又はセルロース含有材料のセルロース混率による染色浴比を一定にするのは極めて困難である。 Regarding reactive dyes used for the three primary colors, the build-up and leveling properties of each dye are excellent, the dyeing speeds of the three primary colors are almost equal, and the temperature dependence is uniform, and the fastnesses of the three primary colors are excellent. It has been needed. Furthermore, it is particularly necessary to be able to deal with actual processes. In other words, in general, the dyeing used for products is performed in steps of laboratory scale (approximately 5 to 30 g), medium experiment scale (approximately 3 to 20 kg), and factory scale (approximately 100 to 1000 kg). It is extremely difficult to make the dye bath ratio derived from the cellulose content of the derived or cellulose-containing material constant.
しかるに、従来の三原色用染料として使用する各染料のセルロース繊維に対する親和性は異なり、染着挙動が異なるため、染色浴比の変化に伴う濃度や色相の変化による色違いの問題が生じ、色修正・脱色修正が現場では頻繁に行われているのが現状である。その為、同一の染色浴比変化挙動を示す三原色が染色現場では強く望まれている。
又、染色浴比に伴う問題とは別に、アルカリ添加温度による色違いの問題があり、実験室スケールと工場スケールでの再現性不良も起こっている。
However, the affinity of each dye used as a conventional primary color dye to cellulose fibers is different, and the dyeing behavior is different, so there is a problem of color differences due to changes in density and hue due to changes in the dye bath ratio, and color correction・ Currently, decolorization correction is frequently performed on site. Therefore, the three primary colors showing the same dye bath ratio change behavior are strongly desired in the dyeing site.
In addition to the problem associated with the dye bath ratio, there is a problem of color difference due to the alkali addition temperature, resulting in poor reproducibility on the laboratory scale and factory scale.
このような問題を解決するために、例えば下記の特許文献では様々な検討がなされているが、未だ満足な結果は得られていない。 In order to solve such problems, for example, various studies have been made in the following patent documents, but satisfactory results have not yet been obtained.
本発明は、前記の問題を解決し、セルロース繊維又はセルロース繊維含有繊維を再現性よく、均染性もよく、高堅牢度に染色する反応染料組成物及びそれを用いた染色法の開発を目的とする。 The present invention aims to solve the above problems and to develop a reactive dye composition for dyeing cellulose fibers or cellulose fiber-containing fibers with good reproducibility, good levelness and high fastness, and a dyeing method using the same. And
前記目的のために、本発明者等は鋭意研究の結果、特定の赤色用反応染料を含有する反応染料組成物、該反応染料組成物と特定の青色用若しくは紺色用反応染料を含有する反応染料組成物及び／又は特定の黄色用反応染料を含有する反応染料組成物とを組み合わせて含有する反応染料組成物及びそれを用いる染色方法を見出し、本発明を完成させるに至った。 For the above-mentioned purpose, the present inventors, as a result of diligent research, have reacted dye compositions containing a specific reactive dye for red, reactive dyes containing the reactive dye composition and a specific blue or amber reactive dye. A reactive dye composition containing a combination of the composition and / or a reactive dye composition containing a specific yellow reactive dye and a dyeing method using the same have been found, and the present invention has been completed.
即ち、本発明は以下の１）〜１１）に関する。
１）遊離酸の形が式（１）で示される反応染料が１０重量％〜９０重量％、遊離酸の形が式（２）で示される反応染料が１０重量％〜９０重量％である赤色用反応染料を含有する反応染料組成物。
1) Red in which the form of the free acid is 10% by weight to 90% by weight of the reactive dye represented by the formula (1) and the form of the reactive dye represented by the formula (2) is 10% by weight to 90% by weight. A reactive dye composition containing a reactive dye.
２）赤色用反応染料が、遊離酸の形が式（１）で示される反応染料が２０重量％〜５０重量％、遊離酸の形が式（２）で示される反応染料が５０重量％〜８０重量％である前記１）記載の反応染料組成物。
３）前記１）又は２）に記載の赤色用反応染料と、遊離酸の形が式（３）で示される反応染料が１０重量％〜９０重量％で、遊離酸の形が式（４）及び式（５）で示される反応染料からなる群から選ばれる１種以上の反応染料が１０重量％〜９０重量％である青色用反応染料とを含有する反応染料組成物。
3) The reactive dye for red as described in 1) or 2) above, and the reactive dye whose free acid form is represented by the formula (3) is 10% by weight to 90% by weight, and the free acid form is the formula (4) And a reactive dye composition containing at least one reactive dye selected from the group consisting of the reactive dye represented by formula (5) and a blue reactive dye in an amount of 10% to 90% by weight.
４）青色用反応染料が、遊離酸の形が式（３）で示される反応染料が１０重量％〜３０重量％で、遊離酸の形が式（４）及び式（５）で示される反応染料からなる群から選ばれる１種以上の反応染料が７０重量％〜９０重量％である前記３）記載の反応染料組成物。
５）青色用反応染料が、遊離酸の形が式（３）で示される反応染料が１０重量％〜３０重量％、遊離酸の形が式（４）で示される反応染料が５０％〜６０重量％及び遊離酸の形が式（５）で示される反応染料が２０重量％〜３０重量％である前記３）又は４）に記載の反応染料組成物。
4) The reactive dye for blue is a reaction dye whose free acid form is represented by the formula (3) is 10 to 30% by weight, and the free acid form is represented by the formulas (4) and (5). The reactive dye composition as described in 3) above, wherein at least one reactive dye selected from the group consisting of dyes is 70% by weight to 90% by weight.
5) The reactive dye for blue is 10% to 30% by weight of the reactive dye in which the form of the free acid is represented by the formula (3), and 50% to 60% of the reactive dye in which the form of the free acid is represented by the formula (4) The reactive dye composition according to 3) or 4), wherein the reactive dye represented by the formula (5) is 20% by weight to 30% by weight in terms of the weight% and the free acid.
６）前記１）又は２）に記載の赤色反応染料と、遊離酸の形が式（４）で示される反応染料が５重量％〜９５％重量％及び遊離酸の形が式（６）で示される反応染料が５重量％〜９５％重量％である紺色用反応染料とを含有する反応染料組成物。
７）紺色用反応染料が、遊離酸の形が式（４）で示される反応染料が８０重量％〜９５％重量％及び遊離酸の形が式（６）で示される反応染料が５重量％〜２０％重量％である前記６）記載の反応染料組成物。
6) The red reactive dye described in 1) or 2) above, the reactive dye in which the form of the free acid is represented by the formula (4) is 5% by weight to 95% by weight, and the form of the free acid is in the formula (6) A reactive dye composition comprising an amber reactive dye, wherein the reactive dye shown is from 5% to 95% by weight.
7) The reaction dye for fading is 80% to 95% by weight of the reactive dye represented by the formula (4) and 5% by weight of the reactive dye represented by the formula (6). The reactive dye composition according to 6) above, which is -20% by weight.
８）前記１）又は２）に記載の赤色用反応染料と、遊離酸の形が式（７）で示される黄色用反応染料とを含有する反応染料組成物。
９）前記３）〜５）のいずれか一項に記載の反応染料組成物に、更に遊離酸の形が式（７）で示される黄色反応染料を含有する反応染料組成物。
１０）前記６）又は７）に記載の反応染料組成物に、更に遊離酸の形が式（７）で示される黄色反応染料を含有する反応染料組成物。
１１）前記１）〜１０）のいずれか一項に記載の反応染料組成物を用いることを特徴とするセルロース繊維又はセルロース繊維含有繊維の染色方法。
8) A reactive dye composition comprising the reactive dye for red according to the above 1) or 2) and a reactive dye for yellow whose free acid form is represented by formula (7).
9) A reactive dye composition comprising the reactive dye composition according to any one of 3) to 5) above, further containing a yellow reactive dye whose free acid form is represented by formula (7).
10) A reactive dye composition further comprising a yellow reactive dye represented by the formula (7) in the form of a free acid in the reactive dye composition described in 6) or 7) above.
11) A method for dyeing cellulose fibers or cellulose fiber-containing fibers, wherein the reactive dye composition according to any one of 1) to 10) is used.
本発明の反応染料組成物及びそれを用いる染色方法により、染色浴比の変化による色相の変化が無く、且つ、濃度補正をする係数を掛け合わせて染色することで常に同様な濃度、色相を得ることが出来、更に、アルカリ添加温度による色相変化も無く、セルロース繊維又はセルロース繊維含有繊維を再現性よく且つ高堅牢度に染色出来るものである。 By the reactive dye composition of the present invention and the dyeing method using the same, there is no change in hue due to a change in the dye bath ratio, and the same density and hue are always obtained by dyeing by multiplying the coefficient for density correction. Furthermore, there is no hue change due to the alkali addition temperature, and the cellulose fiber or cellulose fiber-containing fiber can be dyed with good reproducibility and high fastness.
本発明は、遊離酸の形が前記式（１）で示される反応染料が１０重量％〜９０重量％、遊離酸の形が前記式（２）で示される反応染料が１０重量％〜９０重量％である赤色用反応染料を含有する反応染料組成物である。該反応染料組成物に含有される遊離酸の形が式（１）で示される反応染料は、例えば特許文献５等に、遊離酸の形が式（２）で示される反応染料は、例えば特公平７−９１４８３号公報等に記載されており、又、商業的に入手可能である。しかしながら、それらの染料を含有する反応染料組成物は知られていない。該反応染料組成物には式（１）で示される反応染料を１０重量％〜９０重量％、式（２）で示される反応染料を１０重量％〜９０重量％含有する。特に式（１）で示される反応染料を２０重量％〜５０重量％、式（２）で示される反応染料を５０重量％〜８０重量％含有するのが好ましい。 In the present invention, the form of the free acid represented by the formula (1) is 10% by weight to 90% by weight, and the form of the free acid represented by the formula (2) is 10% by weight to 90%. % Reactive dye composition containing red reactive dye. Examples of the reactive dye in which the form of the free acid contained in the reactive dye composition is represented by the formula (1) are disclosed in, for example, Patent Document 5 and the like, and the reactive dye in which the form of the free acid is represented by the formula (2) are, for example, It is described in Japanese Patent Publication No. 7-91483, etc., and is commercially available. However, reactive dye compositions containing these dyes are not known. The reactive dye composition contains 10% to 90% by weight of the reactive dye represented by the formula (1) and 10% to 90% by weight of the reactive dye represented by the formula (2). In particular, the reactive dye represented by the formula (1) is preferably contained in an amount of 20 to 50% by weight, and the reactive dye represented by the formula (2) is preferably contained in an amount of 50 to 80% by weight.
更に本発明は、前記の赤色用反応染料と、遊離酸の形が前記式（３）で示される反応染料が１０重量％〜９０重量％で、遊離酸の形が前記式（４）及び前記式（５）で示される反応染料からなる群から選ばれる１種以上の反応染料が１０重量％〜９０重量％である青色用反応染料とを含有する反応染料組成物である。該青色用反応染料に含有される遊離酸の形が式（３）で示される反応染料は、例えば特許文献２等に、遊離酸の形が式（４）で示される反応染料は、例えば特許文献３及び４等に、遊離酸の形が式（５）で示される反応染料は、例えば特公平３−１０６６９号公報等に記載されており、又、商業的に入手可能である。該青色用反応染料に含有される式（３）〜式（５）で示される反応染料は、式（３）で示される反応染料を１０重量％〜９０重量％、式（４）及び式（５）で示される反応染料からなる群から選ばれる１種以上の反応染料を１０重量％〜９０重量％含有する。式（３）で示される反応染料を１０重量％〜３０重量％、式（４）及び式（５）で示される反応染料からなる群から選ばれる１種以上の反応染料を７０重量％〜９０重量％含有するのが好ましく、式（３）で示される反応染料を１０重量％〜３０重量％、式（４）で示される反応染料を５０重量％〜６０重量％及び式（５）で示される反応染料を２０％重量％〜３０重量％含有するのが殊更好ましい。 Further, according to the present invention, the reactive dye for red and the reactive dye whose free acid form is represented by the formula (3) are 10% to 90% by weight, and the free acid is the formula (4) and It is a reactive dye composition containing one or more reactive dyes selected from the group consisting of reactive dyes represented by formula (5) and a blue reactive dye in an amount of 10 to 90% by weight. For example, Patent Document 2 discloses a reactive dye in which the form of the free acid contained in the blue reactive dye is represented by Formula (3), and examples of the reactive dye in which the form of the free acid is represented by Formula (4) In References 3 and 4, etc., reactive dyes whose free acid form is represented by the formula (5) are described in, for example, Japanese Patent Publication No. 3-10669 and are commercially available. The reactive dyes represented by the formulas (3) to (5) contained in the blue reactive dye are 10% to 90% by weight of the reactive dye represented by the formula (3), the formulas (4) and ( 5% to 90% by weight of one or more reactive dyes selected from the group consisting of the reactive dyes shown in 5). 10 to 30% by weight of the reactive dye represented by the formula (3), and 70 to 90% by weight of one or more reactive dyes selected from the group consisting of the reactive dyes represented by the formulas (4) and (5) It is preferable to contain 10% by weight to 30% by weight of the reactive dye represented by the formula (3), 50% to 60% by weight of the reactive dye represented by the formula (4), and the formula (5). It is particularly preferred to contain 20% to 30% by weight of the reactive dye.
更に本発明には、前記の赤色反応染料と、遊離酸の形が前記式（４）で示される反応染料が５重量％〜９５％重量％及び遊離酸の形が前記式（６）で示される反応染料が５重量％〜９５％重量％である紺色用反応染料とを含有する反応染料組成物である。式（４）で示される反応染料は前記の通りである。式（６）で示される反応染料はＣ．Ｉ．Ｒｅａｃｔｉｖｅ Ｂｌａｃｋ ５として知られる化合物であり、商業的に入手可能である。該紺色用反応染料には式（４）で示される反応染料が５重量％〜９５重量％、式（６）で示される反応染料が５重量％〜９５重量％含有する。式（４）で示される反応染料を８０重量％〜９５重量％、式（６）で示される反応染料を５重量％〜２０重量％含有するのが好ましい。 Further, the present invention provides the above-mentioned red reactive dye, the reactive dye whose free acid form is represented by the above formula (4) by 5 to 95% by weight, and the free acid form by the above formula (6). A reactive dye composition containing 5% by weight to 95% by weight of the reactive dye. The reactive dye represented by the formula (4) is as described above. The reactive dye represented by the formula (6) is C.I. I. A compound known as Reactive Black 5, which is commercially available. The amber reactive dye contains 5% to 95% by weight of the reactive dye represented by the formula (4) and 5% to 95% by weight of the reactive dye represented by the formula (6). The reactive dye represented by the formula (4) is preferably contained in an amount of 80 to 95% by weight, and the reactive dye represented by the formula (6) is preferably contained in an amount of 5 to 20% by weight.
更に本発明は、前記の赤色反応染料と、遊離酸の形が前記式（７）で示される黄色用反応染料とを含有する反応染料組成物である。該式（７）で示される黄色反応染料は、例えば特許文献６等に記載されており、又、商業的に入手可能である。 Furthermore, this invention is a reactive dye composition containing the said red reactive dye and the reactive dye for yellow whose form of a free acid is shown by the said Formula (7). The yellow reactive dye represented by the formula (7) is described in, for example, Patent Document 6 and is commercially available.
更に本発明の反応染料組成物には、前記の赤色用反応染料と前記の青色用反応染料と前記の黄色用反応染料とを含有する反応染料組成物、又は、前記の赤色用反応染料と前記の紺色用反応染料と前記の黄色用反応染料とを含有する反応染料組成物を含む。 Furthermore, in the reactive dye composition of the present invention, the reactive dye composition containing the reactive dye for red, the reactive dye for blue and the reactive dye for yellow, or the reactive dye for red and the aforementioned A reactive dye composition containing the above-mentioned reactive dye for fading and the above-mentioned reactive dye for yellow.
本発明の反応染料組成物に含有される式（１）〜式（７）で示される反応染料において、Ｙ１、Ｙ２、Ｙ３、Ｙ４、Ｙ５、Ｙ６、Ｙ７、Ｙ８はＳＯ２ＣＨ＝ＣＨ２又はＳＯ２ＣＨ２ＣＨ２Ｚであり、Ｚはアルカリで脱離する基である。Ｚがアルカリで脱離するとＳＯ２ＣＨ＝ＣＨ２となる。Ｚとしては脱離基として知られる各種の基が使用可能であるが、例えば、ＯＳＯ３Ｈ等が挙げられる。 In the reactive dyes represented by the formulas (1) to (7) contained in the reactive dye composition of the present invention, Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8. Is SO 2 CH═CH 2 or SO 2 CH 2 CH 2 Z, and Z is a group leaving with an alkali. When Z is eliminated by alkali, SO 2 CH═CH 2 is obtained. As Z, various groups known as leaving groups can be used, and examples thereof include OSO 3 H.
本発明の反応染料組成物に含有される式（３）で示される反応染料において、Ｒ１は水素原子、ハロゲン原子又は（Ｃ１〜Ｃ４）アルコキシ基を表す。該ハロゲン原子としては塩素原子、臭素原子等が挙げられる。該（Ｃ１〜Ｃ４）アルコキシ基としてはメトキシ基、エトキシ基、ｎ−プロポキシ基、ｎ−ブトキシ基、イソブトキシ基等が挙げられる。Ｒ１としては水素原子が好ましい。 In the reactive dye represented by the formula (3) contained in the reactive dye composition of the present invention, R 1 represents a hydrogen atom, a halogen atom or a (C1-C4) alkoxy group. Examples of the halogen atom include a chlorine atom and a bromine atom. Examples of the (C1-C4) alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, and an isobutoxy group. R 1 is preferably a hydrogen atom.
本発明の反応染料組成物に含有される式（５）で示される反応染料において、Ｒ２は水素原子又は（Ｃ１〜Ｃ４）アルキル基を表す。該（Ｃ１〜Ｃ４）アルキル基としてはメチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、イソブチル基等が挙げられる。Ｒ２としてはエチル基が好ましい。
Ｙ１、Ｙ３、Ｙ４、Ｙ５、Ｙ６、Ｙ８、Ｒ１の置換位置は置換可能な位置であれば特に限定されない。
In the reactive dye represented by the formula (5) contained in the reactive dye composition of the present invention, R 2 represents a hydrogen atom or a (C1-C4) alkyl group. Examples of the (C1 to C4) alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an isobutyl group. R 2 is preferably an ethyl group.
The substitution position of Y 1 , Y 3 , Y 4 , Y 5 , Y 6 , Y 8 , R 1 is not particularly limited as long as it can be substituted.
本発明の反応染料組成物に含有される式（１）〜（７）で示される反応染料は遊離酸の形で示しているが、塩であってもよく、その対カチオンは特に限定されない。中でもアルカリ金属塩又はアルカリ土類金属塩が好ましく、特にナトリウム塩、カリウム塩、リチウム塩が好ましい。 The reactive dyes represented by formulas (1) to (7) contained in the reactive dye composition of the present invention are shown in the form of a free acid, but may be a salt, and the counter cation is not particularly limited. Of these, alkali metal salts or alkaline earth metal salts are preferable, and sodium salts, potassium salts, and lithium salts are particularly preferable.
本発明の反応染料組成物において各反応染料の配合方法は特に限定されない。例えば、それぞれの反応染料を別々に製造し、その後に配合する方法；製造時生成した各反応染料を含有した反応液を混合し、その後に乾燥して組成物とする方法；染色浴にそれぞれの反応染料を溶解し、染色浴中で各組成物と同じ組成とする方法等を採ることが出来る。その際に、各反応染料組成物の混合割合は、所望の色調に応じて適宜行われる。又、必要に応じて、本発明の組成物中には公知の添加剤、例えば、濃度調整剤、分散剤、均染剤、沈殿防止剤、金属イオン封鎖剤、還元防止剤等を含有させてもよい。 The method for blending each reactive dye in the reactive dye composition of the present invention is not particularly limited. For example, a method in which each reactive dye is produced separately and then blended; a reaction solution containing each reactive dye produced at the time of production is mixed and then dried to form a composition; A method of dissolving a reactive dye and making it the same composition as each composition in a dyeing bath can be employed. In that case, the mixing ratio of each reactive dye composition is suitably performed according to a desired color tone. If necessary, the composition of the present invention may contain a known additive such as a concentration adjusting agent, a dispersing agent, a leveling agent, a suspending agent, a sequestering agent, a reducing inhibitor, and the like. Also good.
染浴、パディング浴、捺染糊に本発明の反応染料組成物を構成する各染料及び必要に応じて前記の添加剤等を加え、染浴等を調製して染色する場合に、各染料、添加剤等を溶解する順序は任意の順序でよい。使用する各構成成分の使用量も公知の方法を参考にして決めればよい。 Add each dye that constitutes the reactive dye composition of the present invention to the dyeing bath, padding bath, and printing paste and the above-mentioned additives, etc., if necessary. The order of dissolving the agent and the like may be any order. What is necessary is just to determine the usage-amount of each structural component to be used with reference to a well-known method.
本発明の反応染料組成物を用いた染色法においてそれらの使用量は通常、繊維重量に対して０．０００５〜１５重量％程度である。 In the dyeing method using the reactive dye composition of the present invention, the amount used is usually about 0.0005 to 15% by weight based on the fiber weight.
本発明の反応染料組成物はセルロース繊維やそれを含有する繊維に有用である。対象となる繊維としては、例えば、木綿、麻、レーヨン、ポリノジック、キュプラ、リヨセル等のセルロース繊維、又は、これら同士の混合繊維が挙げられる。更にはこれらの繊維又は混合繊維と他の繊維、例えば、ポリエステル繊維、アセテート繊維、ポリアクリルニトリル繊維、羊毛、絹、ナイロン等のポリアミド繊維等との混紡、又は、交織品等が挙げられる。 The reactive dye composition of the present invention is useful for cellulose fibers and fibers containing the same. Examples of the target fiber include cellulose fibers such as cotton, hemp, rayon, polynosic, cupra, and lyocell, or mixed fibers of these. Furthermore, these fibers or mixed fibers and other fibers, for example, polyester fibers, acetate fibers, polyacrylonitrile fibers, blended fibers of wool, silk, nylon, and the like, or woven fabrics can be mentioned.
本発明には前記の反応染料組成物を用いることを特徴とするセルロース繊維又はセルロース繊維含有繊維の染色方法も含まれる。
該反応染料組成物を用いる染色は、例えば、それ自体は公知の下記のような方法に従って行うことが出来るが、これらに限定されるものではない。例えば、木綿等のセルロース繊維の染色においては所望の色相及び濃度に応じた本発明の反応染料組成物を染浴に加え、無機中性塩、例えば、無水芒硝、食塩等と、酸結合剤、例えば、炭酸ナトリウム、重炭酸ナトリウム、苛性ソーダ、第三燐酸ナトリウム等をそれぞれ単独に、又は、併用して行う。この時用いる無機中性塩や酸結合剤の使用量についても特に制限はない。又、無機中性塩や酸結合剤の染浴への投入は一度に行ってもよいし、分割して投入してもよい。
染色工程終了後、水洗、湯染の後、常法により、市販のソーピング剤を含むソーピング浴にて洗浄を行い、染色を終了する。
The present invention also includes a method for dyeing cellulose fibers or cellulose fiber-containing fibers, characterized by using the reactive dye composition described above.
Dyeing using the reactive dye composition can be carried out, for example, according to the following methods known per se, but is not limited thereto. For example, in the dyeing of cellulose fibers such as cotton, the reactive dye composition of the present invention according to the desired hue and concentration is added to the dyeing bath, an inorganic neutral salt such as anhydrous sodium sulfate, sodium chloride, an acid binder, For example, sodium carbonate, sodium bicarbonate, caustic soda, sodium triphosphate and the like are used alone or in combination. There are no particular restrictions on the amount of inorganic neutral salt or acid binder used at this time. In addition, the inorganic neutral salt or the acid binder may be added to the dye bath at once or dividedly.
After completion of the dyeing step, washing with water and hot water dyeing are followed by washing in a soaping bath containing a commercially available soaping agent by a conventional method, and dyeing is completed.
以下、本発明を実施例により更に詳細に説明する。
本実施例では本発明の式（１）〜（７）で示される反応染料として、以下の式（Ａ）〜（Ｇ）で示される反応染料を用いた。
尚、本文中「部」は特別な記載がない限り重量部を表わす。表中、Ｃ．Ｉ．Ｒｅａｃｔｉｖｅはカラーインデックスジェネリックネームを意味する。
Hereinafter, the present invention will be described in more detail with reference to examples.
In this example, reactive dyes represented by the following formulas (A) to (G) were used as reactive dyes represented by the formulas (1) to (7) of the present invention.
In the text, “parts” represents parts by weight unless otherwise specified. In the table, C.I. I. Reactive means a color index generic name.
実施例１
反応染料の配合組成
表１に反応染料の組み合わせ及びそれらの使用量を記した。
［表１］配合組成
本発明配合例１ Ｂｒｏｗｎ
赤色用反応染料
式（１）の染料 ０．１０部
式（２）の染料 ０．１８部
青色用反応染料
式（３）の染料 ０．１０部
式（５）の染料 ０．２８部
黄色用反応染料
式（７）の染料 １．１２部
Example 1
Composition of reactive dyes Table 1 shows combinations of reactive dyes and their amounts used.
[Table 1] Blending composition of the present invention Blending Example 1 Brown
Red reactive dye
0.10 parts of the dye of formula (1)
0.18 parts of the dye of formula (2)
Blue reactive dye
0.10 parts of dye of formula (3)
0.28 parts of dye of formula (5)
Yellow reactive dye
Dye of formula (7) 1.12 parts
本発明配合例２ Ｂｒｏｗｎ
赤色用反応染料
式（１）の染料 ０．１２部
式（２）の染料 ０．１４部
紺色用反応染料
式（４）の染料 ０．３７部
式（６）の染料 ０．０４部
黄色用反応染料
式（７）の染料 １．１４部
Invention Formulation Example 2 Brown
Red reactive dye
0.12 parts of dye of formula (1)
0.14 parts of the dye of formula (2)
Amber reactive dye
0.37 parts of dye of formula (4)
Dye of formula (6) 0.04 part
Yellow reactive dye
Dye of formula (7) 1.14 parts
本発明配合例３ Ｇｒｅｙ
赤色用反応染料
式（１）の染料 ０．１２部
式（２）の染料 ０．３３部
青色用反応染料
式（３）の染料 ０．２６部
式（４）の染料 ０．７１部
式（５）の染料 ０．３５部
黄色用反応染料
式（７）の染料 ０．７５部
Invention Formulation Example 3 Gray
Red reactive dye
0.12 parts of dye of formula (1)
0.33 parts of dye of formula (2)
Blue reactive dye
0.26 parts of dye of formula (3)
0.71 part of the dye of formula (4)
0.35 parts of dye of formula (5)
Yellow reactive dye
0.75 parts of dye of formula (7)
本発明配合例４ Ｇｒｅｙ
赤色用反応染料
式（１）の染料 ０．０９部
式（２）の染料 ０．２６部
紺色用反応染料
式（４）の染料 ０．９３部
式（６）の染料 ０．１１部
黄色用反応染料
式（７）の染料 ０．６０部
Invention Formulation Example 4 Gray
Red reactive dye
0.09 parts of dye of formula (1)
0.26 parts of dye of formula (2)
Amber reactive dye
0.93 parts of dye of formula (4)
Dye of formula (6) 0.11 part
Yellow reactive dye
0.60 parts of dye of formula (7)
比較例１
比較配合例１ Ｂｒｏｗｎ
赤色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｒｅｄ １９５ ０．５０部
青色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｂｌｕｅ ２２０ ０．４０部
黄色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｙｅｌｌｏｗ １４５ １．２１部
Comparative Example 1
Comparative Formulation Example 1 Brown
Red reactive dye C.I. I. Reactive Red 195 0.50 part
Blue reactive dye C.I. I. Reactive Blue 220 0.40 part
Yellow reactive dye C.I. I. Reactive Yellow 145 1.21 parts
比較配合例２ Ｇｒｅｙ
赤色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｒｅｄ １９５ ０．５０部
青色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｂｌｕｅ ５ ０．７０部
黄色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｙｅｌｌｏｗ １４５ ０．６４部
Comparative Formulation Example 2 Gray
Red reactive dye C.I. I. Reactive Red 195 0.50 part
Blue reactive dye C.I. I. Reactive Blue 5 0.70 parts
Yellow reactive dye C.I. I. Reactive Yellow 145 0.64 parts
比較配合例３ Ｂｒｏｗｎ
赤色用反応染料
式（２）の染料 ０．４０部
青色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｂｌｕｅ ２２０ ０．３５部
黄色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｙｅｌｌｏｗ １４５ ０．６８部
Comparative Blending Example 3 Brown
Red reactive dye
Dye of formula (2) 0.40 part
Blue reactive dye C.I. I. Reactive Blue 220 0.35 part
Yellow reactive dye C.I. I. Reactive Yellow 145 0.68 parts
比較配合例４ Ｇｒｅｙ
赤色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｒｅｄ １９５ ０．４０部
青色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｂｌｕｅ ２２１ ０．２８部
黄色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｙｅｌｌｏｗ １４５ ０．６８部
Comparative Formulation Example 4 Gray
Red reactive dye C.I. I. Reactive Red 195 0.40 part
Blue reactive dye C.I. I. Reactive Blue 221 0.28 parts
Yellow reactive dye C.I. I. Reactive Yellow 145 0.68 parts
比較配合例５ Ｂｒｏｗｎ
赤色用反応染料
式（２）の染料 ０．４０部
青色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｂｌｕｅ ２２１ ０．３５部
黄色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｙｅｌｌｏｗ １４５ ０．６８部
Comparative Formulation Example 5 Brown
Red reactive dye
Dye of formula (2) 0.40 part
Blue reactive dye C.I. I. Reactive Blue 221 0.35 parts
Yellow reactive dye C.I. I. Reactive Yellow 145 0.68 parts
浴比依存性試験法について説明する。
（１）浴比１：１０での染色
表１に示す各配合組成の染料及び無水硫酸ナトリウム１０部に水を加えて全量４９０部の染浴を調製した。この染浴に木綿メリヤス５０部を投入し、６０℃で１５分間処理後、炭酸ナトリウム１０部を投入し、同温度で６０分間染色した。次いで、水洗、湯洗の後、市販のソーピング剤（スコアロールＣ−１２００ 北広ケミカル（株）１ｇ／Ｌ）を含む水溶液１０００部中で１００℃にて１５分間のソーピングをし、次いで水洗、乾燥して染色物を得た。
The bath ratio dependency test method will be described.
(1) Dyeing at a bath ratio of 1:10 A dye bath having a total amount of 490 parts was prepared by adding water to 10 parts of the dyes of each composition shown in Table 1 and anhydrous sodium sulfate. 50 parts of cotton knitted fabric was added to this dye bath, treated at 60 ° C. for 15 minutes, then 10 parts of sodium carbonate was added, and dyed at the same temperature for 60 minutes. Next, after washing with water and hot water, soaping is performed at 100 ° C. for 15 minutes in 1000 parts of an aqueous solution containing a commercially available soaping agent (Scorerol C-1200 Kitahiro Chemical Co., Ltd. 1 g / L), then washed with water and dried. As a result, a dyed product was obtained.
（２）浴比１：３０での染色
表１に示す各配合組成の染料及び無水硫酸ナトリウム３０部に水を加えて全量１４７０部の染浴を調製した。この染浴に木綿メリヤス５０部を投入し、６０℃で１５分間処理後、炭酸ナトリウム３０部を投入し、同温度で６０分間染色した。次いで、水洗、湯洗の後、前記ソーピング剤を含む水溶液１０００部中で１００℃にて１５分間のソーピングをし、次いで水洗、乾燥して染色物を得た。
(2) Dyeing at a bath ratio of 1:30 A dye bath having a total amount of 1470 parts was prepared by adding water to the dyes of each formulation shown in Table 1 and 30 parts of anhydrous sodium sulfate. 50 parts of cotton knitted fabric was added to this dye bath, treated at 60 ° C. for 15 minutes, then 30 parts of sodium carbonate was added, and dyed at the same temperature for 60 minutes. Then, after washing with water and hot water, soaping was performed at 1000 ° C. for 15 minutes in 1000 parts of an aqueous solution containing the soaping agent, and then washed with water and dried to obtain a dyed product.
（３）浴比１：６０での染色
表１に示す各配合組成の染料及び無水硫酸ナトリウム６０部に水を加えて全量２９４０部の染浴を調製した。この染浴に木綿メリヤス５０部を投入し、６０℃で１５分間処理後、炭酸ナトリウム６０部を投入し、同温度で６０分間染色した。次いで、水洗、湯洗の後、前記ソーピング剤を含む水溶液１０００部中で１００℃にて１５分間のソーピングをし、次いで水洗、乾燥して染色物を得た。
(3) Dyeing at a bath ratio of 1:60 A dye bath having a total amount of 2940 parts was prepared by adding water to 60 parts of the dyes of each composition shown in Table 1 and anhydrous sodium sulfate. 50 parts of cotton knitted fabric was put into this dye bath, treated at 60 ° C. for 15 minutes, and then 60 parts of sodium carbonate was added and dyed at the same temperature for 60 minutes. Then, after washing with water and hot water, soaping was performed at 1000 ° C. for 15 minutes in 1000 parts of an aqueous solution containing the soaping agent, and then washed with water and dried to obtain a dyed product.
（４）浴比１：６０で濃度補正した染色
（３）の浴比１：６０の条件で表１に示す各配合組成の染料を１．３３倍使用して染色し染色物を得た。浴比を１：３０から１：６０にすると濃度が３／４になるので染料を１．３３倍使用して濃度補正した。
(4) Dyeing Corrected at a Density Ratio of 1:60 Bath Ratio Dyeing was carried out by using 1.33 times the dye composition shown in Table 1 under the condition of (3) bath ratio 1:60 to obtain a dyed product. When the bath ratio was changed from 1:30 to 1:60, the density became 3/4. Therefore, the density was corrected by using 1.33 times the dye.
（５）判定方法
（１）の浴比１：１０で得られた染色物を基準にそれぞれの条件で得られた染色物の色相差を、測色機カラ−アイＣＥ７１００（マクベス社製）、Ｄ６５光源下、Ｃ．Ｉ．Ｅ色差式を使用して求め、色相差ΔＥａ＊ｂ＊及び色差ΔＥを表２に示した。
(5) Judgment method The color difference of the dyed product obtained under each condition on the basis of the dyed product obtained at a bath ratio of 1:10 in (1) is measured by a colorimeter Color Eye CE7100 (manufactured by Macbeth), Under the D65 light source, C.I. I. Table 2 shows the hue difference ΔEa * b * and the color difference ΔE obtained using the E color difference formula.
［表２］
１：６０濃度補正後のΔＥは、０．７以下であれば相当優れた水準である。
[Table 2]
If ΔE after 1:60 density correction is 0.7 or less, it is an excellent level.
実施例２
反応染料の配合組成
表３に反応染料の組み合わせ及びそれらの使用量を記した。
［表３］配合組成
本発明配合例５ Ｂｒｏｗｎ
赤色用反応染料
式（１）の染料 ０．２９部
式（２）の染料 ０．８５部
青色用反応染料
式（３）の染料 ０．３１部
式（４）の染料 ０．８３部
式（５）の染料 ０．３９部
黄色用反応染料
式（７）の染料 ３．７８部
Example 2
Composition of reactive dyes Table 3 shows the combinations of reactive dyes and their amounts used.
[Table 3] Blending composition Present invention blending example 5 Brown
Red reactive dye
0.29 parts of dye of formula (1)
0.85 parts of dye of formula (2)
Blue reactive dye
0.31 parts of dye of formula (3)
0.83 parts of dye of formula (4)
0.39 parts of the dye of formula (5)
Yellow reactive dye
Dye of formula (7) 3.78 parts
本発明配合例６ Ｂｒｏｗｎ
赤色用反応染料
式（１）の染料 ０．２０部
式（２）の染料 ０．７２部
青色用反応染料
式（３）の染料 ０．４０部
式（５）の染料 １．１９部
黄色用反応染料
式（７）の染料 ３．５８部
Invention Formulation Example 6 Brown
Red reactive dye
0.20 parts of dye of formula (1)
0.72 parts of dye of formula (2)
Blue reactive dye
0.40 parts of dye of formula (3)
Dye of formula (5) 1.19 parts
Yellow reactive dye
Dye of formula (7) 3.58 parts
本発明配合例７ Ｂｒｏｗｎ
赤色用反応染料
式（１）の染料 ０．２６部
式（２）の染料 ０．８０部
紺色用反応染料
式（４）の染料 １．１０部
式（６）の染料 ０．１３部
黄色用反応染料
式（７）の染料 ３．４２部
Invention Formulation Example 7 Brown
Red reactive dye
0.26 parts of dye of formula (1)
0.80 parts of dye of formula (2)
Amber reactive dye
Dye of formula (4) 1.10 parts
0.13 parts of the dye of formula (6)
Yellow reactive dye
3.42 parts of dye of formula (7)
本発明配合例８ Ｇｒｅｙ
赤色用反応染料
式（１）の染料 ０．３２部
式（２）の染料 １．００部
青色用反応染料
式（３）の染料 ０．７９部
式（４）の染料 ２．１４部
式（５）の染料 １．０３部
黄色用反応染料
式（７）の染料 ２．２５部
Invention Formulation Example 8 Gray
Red reactive dye
0.32 parts of dye of formula (1)
Dye of formula (2) 1.00 parts
Blue reactive dye
0.79 parts of dye of formula (3)
2.14 parts of dye of formula (4)
Dye of formula (5) 1.03 parts
Yellow reactive dye
2.25 parts of dye of formula (7)
本発明配合例９ Ｇｒｅｙ
赤色用反応染料
式（１）の染料 ０．２９部
式（２）の染料 ０．９０部
青色用反応染料
式（３）の染料 ０．７９部
式（４）の染料 ２．８２部
黄色用反応染料
式（７）の染料 ２．１２部
Invention Formulation Example 9 Gray
Red reactive dye
0.29 parts of dye of formula (1)
0.90 parts of dye of formula (2)
Blue reactive dye
0.79 parts of dye of formula (3)
Dye of formula (4) 2.82 parts
Yellow reactive dye
Dye of formula (7) 2.12 parts
本発明配合例１０ Ｇｒｅｙ
赤色用反応染料
式（１）の染料 ０．２７部
式（２）の染料 ０．９０部
紺色用反応染料
式（４）の染料 ２．８０部
式（６）の染料 ０．３２部
黄色用反応染料
式（７）の染料 １．８０部
Invention Formulation Example 10 Gray
Red reactive dye
0.27 parts of dye of formula (1)
0.90 parts of dye of formula (2)
Amber reactive dye
2.80 parts of dye of formula (4)
0.32 parts of dye of formula (6)
Yellow reactive dye
Dye of formula (7) 1.80 parts
比較例２
比較配合例６ Ｂｒｏｗｎ
赤色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｒｅｄ １９５ １．５０部
青色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｂｌｕｅ ２２１ １．２０部
黄色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｙｅｌｌｏｗ １４５ ３．６３部
Comparative Example 2
Comparative Formulation Example 6 Brown
Red reactive dye C.I. I. Reactive Red 195 1.50 parts
Blue reactive dye C.I. I. Reactive Blue 221 1.20 parts
Yellow reactive dye C.I. I. Reactive Yellow 145 3.63 parts
比較配合例７ Ｂｒｏｗｎ
赤色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｒｅｄ １９５ １．６２部
青色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｂｌｕｅ ２２０ １．８８部
黄色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｙｅｌｌｏｗ １４５ ３．７０部
Comparative Formulation Example 7 Brown
Red reactive dye C.I. I. Reactive Red 195 1.62 parts
Blue reactive dye C.I. I. Reactive Blue 220 1.88 parts
Yellow reactive dye C.I. I. Reactive Yellow 145 3.70 parts
比較配合例８ Ｂｒｏｗｎ
赤色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｒｅｄ １９５ １．４４部
青色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｂｌｕｅ ５ ０．８４部
黄色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｙｅｌｌｏｗ １４５ ３．９０部
Comparative Formulation Example 8 Brown
Red reactive dye C.I. I. Reactive Red 195 1.44 parts
Blue reactive dye C.I. I. Reactive Blue 5 0.84 parts
Yellow reactive dye C.I. I. Reactive Yellow 145 3.90 parts
比較配合例９ Ｇｒｅｙ
赤色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｒｅｄ １９５ １．８９部
青色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｂｌｕｅ ２２１ ３．０５部
黄色用反応染料
Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｙｅｌｌｏｗ １４５ １．８３部
Comparative Formulation Example 9 Gray
Red reactive dye C.I. I. Reactive Red 195 1.89 parts
Blue reactive dye C.I. I. Reactive Blue 221 3.05 parts
Yellow reactive dye C.I. I. Reactive Yellow 145 1.83 parts
アルカリ添加温度依存性試験法について説明する。
（１）アルカリ（炭酸ナトリウム） ６０℃添加での染色
表３に示す各配合組成の染料及び無水硫酸ナトリウム４０部に水を加えて全量４９０部の染浴を調製した。この染浴に木綿メリヤス５０部を投入し、２０分間で６０℃へ昇温した。６０℃で１０分間処理後、炭酸ナトリウム１０部を投入し、同温度で６０分間染色した。次いで、水洗、湯洗の後、市販のソーピング剤（スコアロールＣ−１２００ 北広ケミカル（株）１ｇ／Ｌ）を含む水溶液１０００部中で１００℃にて１５分間のソーピングをし、次いで水洗、乾燥して染色物を得た。
The alkali addition temperature dependency test method will be described.
(1) Dyeing with alkali (sodium carbonate) added at 60 ° C. Water was added to 40 parts of the dyes and the anhydrous sodium sulfate shown in Table 3 to prepare a dyeing bath having a total amount of 490 parts. 50 parts of cotton knitted fabric was added to this dye bath, and the temperature was raised to 60 ° C. in 20 minutes. After treatment at 60 ° C. for 10 minutes, 10 parts of sodium carbonate was added and dyed at the same temperature for 60 minutes. Next, after washing with water and hot water, soaping is performed at 100 ° C. for 15 minutes in 1000 parts of an aqueous solution containing a commercially available soaping agent (Scorerol C-1200 Kitahiro Chemical Co., Ltd. 1 g / L), then washed with water and dried. As a result, a dyed product was obtained.
（２）アルカリ（炭酸ナトリウム） ４０℃添加での染色
表３に示す各配合組成の染料及び無水硫酸ナトリウム４０部に水を加えて全量４９０部の染浴を調製した。この染浴に木綿メリヤス５０部を投入し、４０℃で２０分間処理後、炭酸ナトリウム１０部を投入し、２０分間で６０℃へ昇温した。同温度で６０分間染色し、次いで、水洗、湯洗の後、前記のソーピング剤を含む水溶液１０００部中で１００℃にて１５分間のソーピングをし、次いで水洗、乾燥して染色物を得た。
(2) Dyeing by adding alkali (sodium carbonate) at 40 ° C. Dye baths having a total amount of 490 parts were prepared by adding water to 40 parts of the dyes having the blending compositions shown in Table 3 and anhydrous sodium sulfate. 50 parts of cotton knitted fabric was added to this dye bath, treated at 40 ° C. for 20 minutes, 10 parts of sodium carbonate was added, and the temperature was raised to 60 ° C. over 20 minutes. Dyeing at the same temperature for 60 minutes, followed by washing with water and hot water, soaping in 1000 parts of an aqueous solution containing the above-mentioned soaping agent at 100 ° C. for 15 minutes, then washing with water and drying to obtain a dyed product .
（３）判定方法
６０℃添加で得られた染色物を基準に、４０℃添加で得られた染色物の色相差を、測色機カラ−アイＣＥ７１００（マクベス社製）、Ｄ６５光源下、Ｃ．Ｉ．Ｅ色差式を使用して求め、色差ΔＥを表４に示した。
(3) Judgment method Based on the dyed product obtained by adding 60 ° C, the hue difference of the dyed product obtained by adding 40 ° C was measured using a colorimeter Color Eye CE7100 (manufactured by Macbeth), under the D65 light source, C . I. The color difference ΔE was determined using the E color difference formula and is shown in Table 4.
［表４］
表２及び表４から明らかなように、本発明の配合例１、２、３、４、５、６、７、８、９、１０の組み合わせで染色を行った場合、赤色用反応染料、青色用反応染料若しくは紺色用反応染料、黄色用反応染料の親和性が一致しており、浴比が大きく変動した場合でも濃度補正をしても色相変化が極めて小さく、又、アルカリ添加温度が変動した場合でも色相変化が極めて小さく、染色再現性が極めて優れている。 As is apparent from Tables 2 and 4, when dyeing is carried out with combinations of Formulation Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 of the present invention, a reactive dye for red, blue The affinity of the reactive dye for amber, the reactive dye for amber, and the reactive dye for yellow matches, and even if the bath ratio fluctuates greatly, the hue change is extremely small even if the concentration is corrected, and the alkali addition temperature fluctuates. Even in this case, the hue change is extremely small, and the dyeing reproducibility is extremely excellent.
実施例３〜実施例１２
実施例１の配合例の組み合わせ及び使用量に替えて、表５に示す染料の組み合わせ及び使用量を用い、無水硫酸ナトリウム１５部に水を加えて全量４９０部の染浴をそれぞれ調製した。この染浴に木綿メリヤス５０部を投入し、２０分間で６０℃へ昇温した。６０℃で１０分間処理後、炭酸ナトリウム１０部を投入し、同温度で６０分間染色した。次いで、水洗、湯洗の後、市販のソーピング剤（スコアロールＣ−１２００ 北広ケミカル（株）１ｇ／Ｌ）を含む水溶液５００部中で１００℃にて１５分間のソーピングをし、次いで水洗、乾燥して染色物を得た。
Examples 3 to 12
Instead of the combination and usage amount of the formulation example of Example 1, water was added to 15 parts of anhydrous sodium sulfate using the dye combinations and usage amounts shown in Table 5 to prepare a total amount of 490 parts of dye bath. 50 parts of cotton knitted fabric was added to this dye bath, and the temperature was raised to 60 ° C. in 20 minutes. After treatment at 60 ° C. for 10 minutes, 10 parts of sodium carbonate was added and dyed at the same temperature for 60 minutes. Next, after washing with water and hot water, soaping is performed for 15 minutes at 100 ° C. in 500 parts of an aqueous solution containing a commercially available soaping agent (Scorerol C-1200 Kitahiro Chemical Co., Ltd. 1 g / L), followed by washing with water and drying. As a result, a dyed product was obtained.
［表５］配合組成
実施例３ グリーン
赤色用反応染料
式（１）の染料 ０．０８部
式（２）の染料 ０．１８部
青色用反応染料
式（３）の染料 ０．１６部
式（５）の染料 ０．６４部
黄色用反応染料
式（７）の染料 ０．８部
[Table 5] Formulation Composition Example 3 Green
Red reactive dye
0.08 parts of dye of formula (1)
0.18 parts of the dye of formula (2)
Blue reactive dye
0.16 parts of dye of formula (3)
0.64 parts of the dye of formula (5)
Yellow reactive dye
0.8 parts of the dye of formula (7)
実施例４ バイオレット
赤色用反応染料
式（１）の染料 ０．２０部
式（２）の染料 ０．５５部
青色用反応染料
式（３）の染料 ０．２０部
式（４）の染料 ０．５０部
黄色用反応染料
式（７）の染料 ０．２０部
Example 4 Violet
Red reactive dye
0.20 parts of dye of formula (1)
0.55 parts of dye of formula (2)
Blue reactive dye
0.20 parts of dye of formula (3)
0.50 parts of dye of formula (4)
Yellow reactive dye
Dye of formula (7) 0.20 part
実施例５ エンジ色
赤色用反応染料
式（１）の染料 ０．３０部
式（２）の染料 ０．８５部
青色用反応染料
式（３）の染料 ０．０４部
式（４）の染料 ０．１１部
式（５）の染料 ０．０６部
黄色用反応染料
式（７）の染料 ０．３５部
Example 5 Engine color
Red reactive dye
0.30 parts of dye of formula (1)
0.85 parts of dye of formula (2)
Blue reactive dye
Dye of formula (3) 0.04 part
0.11 part of dye of formula (4)
Dye of formula (5) 0.06 part
Yellow reactive dye
0.35 parts of the dye of formula (7)
実施例６ カーキー色
赤色用反応染料
式（１）の染料 ０．０９部
式（２）の染料 ０．２１部
青色用反応染料
式（３）の染料 ０．０６部
式（４）の染料 ０．２０部
式（５）の染料 ０．０９部
黄色用反応染料
式（７）の染料 ０．１０部
Example 6 Car key color
Red reactive dye
0.09 parts of dye of formula (1)
0.21 parts of dye of formula (2)
Blue reactive dye
0.06 parts of dye of formula (3)
0.20 parts of dye of formula (4)
Dye of formula (5) 0.09 part
Yellow reactive dye
0.10 parts of dye of formula (7)
実施例７ ネービー
赤色用反応染料
式（１）の染料 ０．２０部
式（２）の染料 ０．５８部
青色用反応染料
式（３）の染料 ０．４４部
式（４）の染料 ０．８８部
式（５）の染料 ０．３５部
黄色用反応染料
式（７）の染料 ０．８０部
Example 7 Navy
Red reactive dye
0.20 parts of dye of formula (1)
0.58 parts of dye of formula (2)
Blue reactive dye
0.44 parts of dye of formula (3)
0.88 parts of dye of formula (4)
0.35 parts of dye of formula (5)
Yellow reactive dye
0.80 parts of dye of formula (7)
実施例８ グリーン
赤色用反応染料
式（１）の染料 ０．０４部
式（２）の染料 ０．１２部
紺色用反応染料
式（４）の染料 ０．７０部
式（６）の染料 ０．１０部
黄色用反応染料
式（７）の染料 ０．８０部
Example 8 Green
Red reactive dye
0.04 parts of dye of formula (1)
0.12 parts of dye of formula (2)
Amber reactive dye
0.70 parts of the dye of formula (4)
Dye of formula (6) 0.10 parts
Yellow reactive dye
0.80 parts of dye of formula (7)
実施例９ バイオレット
赤色用反応染料
式（１）の染料 ０．１５部
式（２）の染料 ０．４２部
紺色用反応染料
式（４）の染料 ０．５２部
式（６）の染料 ０．０８部
黄色用反応染料
式（７）の染料 ０．２０部
Example 9 Violet
Red reactive dye
0.15 parts of dye of formula (1)
0.42 parts of dye of formula (2)
Amber reactive dye
0.52 parts of dye of formula (4)
0.08 parts of dye of formula (6)
Yellow reactive dye
Dye of formula (7) 0.20 part
実施例１０ エンジ色
赤色用反応染料
式（１）の染料 ０．２６部
式（２）の染料 ０．７７部
紺色用反応染料
式（４）の染料 ０．１０５部
式（６）の染料 ０．０１５部
黄色用反応染料
式（７）の染料 ０．３０部
Example 10 Engine color
Red reactive dye
0.26 parts of dye of formula (1)
0.77 parts of dye of formula (2)
Amber reactive dye
0.105 parts of dye of formula (4)
0.015 part of the dye of formula (6)
Yellow reactive dye
Dye of formula (7) 0.30 part
実施例１１ カーキー色
赤色用反応染料
式（１）の染料 ０．０８部
式（２）の染料 ０．２０部
紺色用反応染料
式（４）の染料 ０．１７部
式（６）の染料 ０．０３部
黄色用反応染料
式（７）の染料 ０．９０部
Example 11 Car key color
Red reactive dye
0.08 parts of dye of formula (1)
0.20 parts of dye of formula (2)
Amber reactive dye
0.17 parts of dye of formula (4)
Dye of formula (6) 0.03 part
Yellow reactive dye
0.90 parts of dye of formula (7)
実施例１２ ネービー
赤色用反応染料
式（１）の染料 ０．１６部
式（２）の染料 ０．５５部
紺色用反応染料
式（４）の染料 １．７５部
式（６）の染料 ０．２０部
黄色用反応染料
式（７）の染料 ０．６５部
Example 12 Navy
Red reactive dye
0.16 parts of dye of formula (1)
0.55 parts of dye of formula (2)
Amber reactive dye
1.75 parts of the dye of formula (4)
Dye of formula (6) 0.20 part
Yellow reactive dye
0.65 parts of dye of formula (7)
試験結果
実施例３〜１２で得られた染色物について浴比依存性試験及びアルカリ添加温度依存性試験を行ったところ、いずれの反応染料の組み合わせにおいても浴比が大きく変動した場合でも色相変化が極めて小さく、又、アルカリ添加温度が変動した場合でも色相変化が極めて小さく、染色再現性が極めて優れていた。
Test results When the bath ratio dependency test and the alkali addition temperature dependency test were performed on the dyed products obtained in Examples 3 to 12, the hue change was observed even when the bath ratio varied greatly in any combination of reactive dyes. It was very small, and even when the alkali addition temperature fluctuated, the hue change was extremely small, and the dyeing reproducibility was extremely excellent.
Claims (11)
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| JPS56118974A (en) * | 1980-02-16 | 1981-09-18 | Sumitomo Chemical Co | Cheese dyeing of cellulosic fiber |
| JPH0668083B2 (en) * | 1987-07-22 | 1994-08-31 | 三菱化成株式会社 | Water-soluble dye mixture |
| JP3168624B2 (en) * | 1991-08-02 | 2001-05-21 | 住友化学工業株式会社 | Reactive dye composition and method for dyeing or printing fiber material using the same |
| JP4218101B2 (en) * | 1998-12-21 | 2009-02-04 | 住友化学株式会社 | Reactive dye mixture and dyeing or printing method using the same |
| JP2003055570A (en) * | 2001-08-21 | 2003-02-26 | Dystar Japan Ltd | Reactive dye composition and method for dying using the same |
| JP4614671B2 (en) * | 2003-02-21 | 2011-01-19 | 日本化薬株式会社 | Reactive dye composition and dyeing method using the same |
| KR20060124717A (en) * | 2004-03-03 | 2006-12-05 | 니폰 가야꾸 가부시끼가이샤 | Reactive dye compositions and method for dyeing with the same |
| JP2006037051A (en) * | 2004-07-30 | 2006-02-09 | Sumitomo Chemical Co Ltd | Reactive dye composition and its application to fiber |
| JP4576924B2 (en) * | 2004-08-09 | 2010-11-10 | 住友化学株式会社 | Reactive dye composition and dyeing or printing method using the composition |
| JP5682947B2 (en) * | 2009-05-28 | 2015-03-11 | 日本化薬株式会社 | Reactive dye composition and dyeing method using the same |
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